AN OMNIPHOBIC AND BIOCIDE SOL-GEL COATING COMPOSITION

Description

[0001] This application claims the benefit of European Patent Application EP19383186.4 filed on December 23rd 2019.

[0002] The present invention relates to sol-gel coatings, particularly to repellent, omniphobic and biocide sol-gel coating compositions useful as non-stick surfaces. The repellent, omniphobic and biocide sol-gel coating compositions of the present invention are useful to prepare antiadhesive, easy-to-clean, antifogging, anti-icing and antifouling surfaces, for having a durable low interfacial energy and non-leaching antibacterial activity also with low roughness and anticorrosion properties. The present invention also relates to a process for the preparation of the sol-gel coated substrate and the coated substrate obtainable by the process.

Background Art

[0003] The surface energy is an important property that influences the material's wettability, adhesion and friction properties and therefore, it may be modulated to reduce adherence of undesirable agents such as water, oil, grease, soiling, dust or ice during its life service. In particular, the wetting behaviour of a surface by a liquid is governed by both the surface free energy and its topography. Perfluorinated polymers are known for being materials with extremely low surface free energy, which results in an antiadhesive behaviour for polar and non-polar substances. Furthermore, the high strength of the carbon-fluoro bond grants excellent thermal, chemical, photochemical and hydrolytic stability, which are relevant features for outdoor application and weathering resistance.

[0004] Besides, it is also well known that the wetting of a surface by a liquid is affected by its roughness. Indeed, an effective way to enhance the hydrophobic properties of a coating is to increase its surface roughness with a given topography. For example, coatings prepared with the highly inert and non-polar material polytetrafluoroethylene (i.e. perfluorinated polymer) known for having an intrinsic low surface free energy have disclosed in the state of the art water contact angle values between 90-100° for surfaces with low roughness in the order of 8 nm root mean square (rms). However, the same material with a surface roughness in the order of 100 nm root mean square (rms) has presented superhydrophobic properties, thus water contact angle value higher than 150°. However, the application of coatings of well-known dirt repellent materials like polytetrafluroethylene requires high process temperatures which exceed the maximum allowable temperature of several substrates. On the other hand, a high surface roughness can have an undesirable remarkable effect in the attainment of easy-to-clean surfaces. Prevention of dirt and soiling sticking as well as organic materials that promote biofilm growth can be encouraged by minimizing the contact area between surface and contaminants, by means of very smooth surfaces.

[0005] Apart from inert soiling, substances of biological origin are the root cause of the formation of biofilm and biofouling in most industrial systems. A biofilm is an agglomeration of bacteria on a surface that is surrounded by extracellular polysaccharide polymeric substances, which are produced by the bacteria themselves to help them get attached to the surfaces and bind to one another. The formation of a biofilm of microorganisms usually results in the establishment of a macroscopic community of living organisms on a (submerged) surface with devastating effects on engineered materials (also known as biofouling). The biofouling affects a wide range of sectors (for instance marine applications, sanitary/medical field, household and other industrial sectors such as food packaging, heat transfer and air-conditioning systems, among others) creating problems such as microbially influenced corrosion, product contamination, anti-hygienic conditions and the spread of infections and diseases causing threats to public health.

[0006] In particular, biofouling is a very dynamic process which implies firstly, the formation of a layer of proteins from bacteria adsorbed to a pristine surface, that may happen within seconds to minutes after immersion and it is strongly influenced by both the topographical morphology and chemical properties of the surface. Protein conformation defines functionality with respect to cell adhesion. In fact, this first protein layer acts as a conditioning film for the settlement of micro-organisms such as diatoms.

[0007] In order to avoid the formation of a biofilm, the surface should ease the detachment of the protein layer or kill the bacteria. In fact, in marine applications two main approaches are usually followed for attaining antifouling properties: (i) preventing biofoulings from attaching to the surface (foul-release property), through coatings with controlled low interfacial energy; or (ii) killing the biofouling (bactericidal activity), by incorporating species with controlled release of enzymatic natural biocide in the coatings. Regarding the first strategy, foul-release property is attributed to a surface with low interfacial energy, low elastic modulus, low glass transition temperature and low roughness, resulting in weak adhesion with the adhesives secreted by biofoulings. A correlation between adhesion of organisms and the interfacial energy of a surface is given by the Baier curve. This relationship has been demonstrated in several marine and biomedical environments. A key characteristic of the Baier curve is that minimal adhesion is typically achieved at a critical surface tension of 22-24 mJ/m² (or mN/m). This surface tension, often referred to as surface energy, is approximately equal to the dispersive component for water. Regarding the strategy to kill the bacteria, traditionally, in marine environments, coatings containing biocide agents have been used to prevent the growth of potential fouling organisms such as bacteria, fungi, algae, plants and molluscs. However, the use of biocides is problematic because they can leach into the environment and cause harm to living organisms other than the ones they were intended to kill. In addition, cells in biofilm might become resistant to antibacterial agents. For this reason, world-wide legislation is imposing increasing limitations on the use of biocides to combat biofouling (particularly in marine applications).

[0008] Active biocidal chemicals are essential in some applications and indeed have been used for hundreds of years in antisepsis, disinfection, and preservation. Antiseptics are biocides or products that destroy or inhibit the growth of microorganisms in or on living tissue (e.g. health care personnel handwashes and surgical scrubs) and disinfectants are similar but generally are products or biocides that are used on inanimate objects or surfaces.

[0009] Antimicrobial surfaces can be designed in several ways to kill microbes in the vicinity by conjugating polymer with agents such as antibiotics or antimicrobial peptides or complexed with biocide agents such as silver. However, the bactericidal action of biocide agents relies to a certain extent on the leaching of the ions, which in addition may cause certain environmental issues. An alternative way to create contact-active surfaces is to immobilize polymers conjugated with antimicrobial proteins, although the antimicrobial activity of these proteins decreases after immobilization in many reported studies. A new promising class of antimicrobial polymeric surfaces is based on the immobilization of the bactericidal polymer chain to kill the bacteria upon contact. Some of these biocide polymer chains are those containing cationic groups, such as quaternary ammonium or phosphonium groups.

[0010] In particular, quaternary ammonium compounds (QAC) are highly effective antiseptics and disinfectants and have been used for a variety of clinical disinfection purposes. QACs are considered as excellent antibacterial agents due to their effective biocidal activity, long term durability and environmentally friendly performance and they are membrane active agents (i.e., with a target site predominantly at the cytoplasmic inner membrane in bacteria or the plasma membrane in yeasts). The following sequence of events occurs with microorganisms exposed to cationic agents: (i) adsorption and penetration of the agent into the cell wall; (ii) reaction with the cytoplasmic membrane (lipid or protein) followed by membrane disorganization; (iii) leakage of intracellular low-molecular-weight material; (iv) degradation of proteins and nucleic acids; and (v) wall lysis caused by autolytic enzymes. This implies a loss of structural organization and integrity of the cytoplasmic membrane in bacteria, together with other damaging effects to the bacterial cell.

[0011] The deposition of organic monolayers containing quaternary ammonium groups has been shown by many authors to confer biocidal properties on a large variety of solid surfaces. However, unfortunately, leaks of QACs to the environment are still observed.

[0012] Therefore, from what it is known in the state of the art, there is still the need of providing environmentally friendly, versatile and stable coatings with low roughness and permanent multi-repellent and antimicrobial activity, without biocide agent leaching, capable to reduce dirt, soiling, grease and ice adherence as well as biofilm growth.

Summary of Invention

[0013] Inventors have provided a stable sol-gel composition useful for preparing repellent coatings with low interfacial energy comprising a specific mixture of inorganic and organic precursors that lead to the formation of a functionalized hybrid organic-inorganic material at molecular level, even some of them having biocide activity. Furthermore, inventors have also provided a stable sol-gel composition useful for preparing omniphobic coatings with low interfacial energy comprising a specific mixture of inorganic and organic precursors that lead to the formation of a functionalized hybrid organic-inorganic material at molecular level.

[0014] The use of metal or semimetal organo-alkoxide compounds as sol-gel precursors in which the organic moiety is linked to the central atom by a non-hydrolysable carbon-metal or carbon-semimetal bond (particularly a C-Si bond), permits to design a sol-gel material with the desired functionalization covalently linked to the inorganic network. In particular, the sol-gel composition of the present invention is a versatile composition which allows attaining permanent repellent, omniphobic, biocide or repellent-biocide functionalities thanks to the presence of appropriate moieties covalently bonded to the network through metal-C or semimetal-C bonds (particularly C-Si bonds). This fact will avoid leaching of the functional moieties and will guarantee the durability, stability and homogeneity of the wettability, surface energy and biocide properties also provided by the perfect adhesion of the sol-gel coating to a huge variety of substrates such as metal, metal alloys, glass and plastic surfaces.

[0015] Particularly, the sol-gel coating composition of the invention comprises a hybrid matrix functionalized with covalently bonded polyfluoroalkyl chain, alkyl chain, quaternary ammonium compound or mixture thereof which are introduced in the sol-gel network by means of fluoroalkyl silane (FAS), alkyl silane (CAS) quaternary ammonium silane (QAS), or a mixture thereof respectively, without compromising the integrity of the hybrid matrix and permitting having the desired repellent and omniphobic properties with a low interfacial energy as well as a permanent and non-leaching biocide activity. It is remarkable that this repellent omniphobic, biocide or dual effects is achieved by the incorporation of extremely low quantities of polyfluoroalkyl (FAS-based), alkyl (CAS-based), quaternary ammonium silane (QAS-based) or a mixture thereof. On the one hand, the polyfluoroalkyl chains (FAS-based) chemically bonded to the coating network lead to durability of the omniphobic property as the polyfluoro-carbon moiety does not migrate out of the coating due to its covalent bonding to the structure. On the other hand, the quaternary ammonium silanes (QAS-based), are the perfect candidates to prepare materials with immobilized biocide organic moiety due to the presence of the non-hydrolysable Si-C bond, thus permitting to obtain non-leaching biocides with permanent activity. The hydrolysis and condensation of the alkoxy groups let to obtain quaternary ammonium moiety chemically bonded to the coating matrix.

[0016] Furthermore, the inventors have also surprisingly found that sol-gel coating compositions of the invention which are prepared by incorporating acrylate or methacrylate organic precursors (i.e. an organic precursors of formula (VI) and (VII)) compatible with organo-alkoxysilanes and zirconium alkoxide without the need of the presence of functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof. Furthermore, these sol-gel coating compositions also add a high levelling ability to the coating. It is advantageous because these sol-gel coating compositions allows obtaining super-smooth surfaces decreasing the intrinsic original roughness of the substrate.

[0017] As it is shown in the experimental section, the sol-gel coating compositions of the present invention are useful as repellent or multi-repellent surfaces for having low interfacial energy, or as antifouling surfaces for having low interfacial energy combined with bactericide activity. Particularly, the coating surfaces prepared with sol-gel coating compositions of the present invention comprising at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof showed water contact angle values higher than 90° and hexadecane contact angle values higher than 90°, which makes them hydrophobic and oleophobic surfaces with an interfacial free energy tailored between 8 to 30 mJ/m² even showing an extremely low roughness. Furthermore, the coating surfaces prepared with sol-gel coating compositions of the present invention showed a biocidal activity. Particularly, they killed all colony forming units (CFU) of Escherichia Coli after 24 h of contact according to ISO22196 standard, showing roughness values as low as 2.4 nm. On the other hand, the coating surfaces prepared with sol-gel coating compositions of the present invention prepared by an acrylate or methacrylate organic precursors (i.e. an organic precursor of formula (VI) or (VII)) compatible with organo-alkoxysilanes and zirconium alkoxide showed water contact angle values higher than 90°, interfacial free energy < 30 mJ/m² and Escherichia Coli CFU were totally went away after 24 h of contact according to ISO22196 standard, showing roughness values as low as nm.

[0018] Furthermore, the sol-gel coatings of the present invention have also shown excellent homogeneity and adhesion on a wide variety of substrates such as aluminium alloy, glass and plastic (for instance polyetherimide -PEI), as well as excellent corrosion protection of aluminium alloys.

[0019] Thus, the first aspect of the inventio relates to a process for preparing a sol-gel coated substrate comprising:

1) firstly, depositing a sol-gel coating composition selected from the group consisting of sol1 and sol3 over the substrate

2) secondly, curing the coating obtained in step 1);

wherein the sol1 is a sol-gel coating composition obtainable by a process which comprises:

a) preparing a mixture A comprising:

at least one alkoxide selected from the group consisting of a metal alkoxide, a semimetal alkoxide, an organo-alkoxysilane and a mixture thereof;

at least one acid catalyst in aqueous solution having a pH lower than 5;

optionally, at least one (C₁-C₈)alcohol;

optionally, at least one organic precursor;

optionally, at least one polymerization initiator; and

optionally, at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, fluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof;

at a temperature from 15 °C to 90 °C for an appropriate period of time to obtain sol1; and

optionally ageing the resulting mixture sol1 by stirring at a temperature from 15 °C to 30 °C for a period of time from 24 h to 72 h to obtain sol1;
and

wherein the sol3 is a sol-gel coating composition obtainable by a process which comprises:

b) preparing a mixture A comprising:

at least one alkoxide selected from the group consisting of a metal alkoxide, a semimetal alkoxide, an organo-alkoxysilane and a mixture thereof;

at least one acid catalyst in aqueous solution having a pH lower than 5

optionally, at least one organic precursor;

optionally, at least one polymerization initiator;

optionally, at least one (C₁-C₈)alcohol; and

optionally, at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof;

at a temperature from 15 °C to 90 °C to obtain sol1; and

optionally ageing the resulting mixture sol1 by stirring at a temperature from 15 °C to 30 °C from 24 h to 72 h;

c) preparing a mixture B comprising:

at least one metal alkoxide;

at least one complexing agent;

optionally, at least one acid catalyst in aqueous solution or water having a pH lower than 7;

optionally, one or more (C₁-C₈) alcohol; and

optionally, at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof,

at a temperature from 15 °C to 30 °C for an appropriate period of time to obtain sol2; and optionally ageing the resulting mixture sol2 by stirring at a temperature from 15 °C to 30 °C from 24 h to 72 h; and

d) mixing the sol 1 with the sol 2; optionally adding to the mixture obtained in step d) at least one acid catalyst in aqueous solution or water having a pH lower than 7; and ageing the resulting mixture by stirring at a temperature from 15 °C to 30 °C from 24 h to 72 h;

with the proviso that the sol-gel coating composition of step 1) comprises at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof;

or alternatively,

a process for preparing a sol-gel coated substrate comprising:

1) firstly, depositing a sol-gel coating composition selected from the group consisting of sol3 over the substrate; and

2) secondly, curing the coating obtained in step 1);

wherein the sol3 is a sol-gel coating composition obtainable by a process which comprises:

b) preparing a mixture A comprising:

at least one alkoxide selected from the group consisting of a metal alkoxide, a semimetal alkoxide, an organo-alkoxysilane and a mixture thereof;

at least one acid catalyst in aqueous solution having a pH lower than 5;

at least one organic precursor;

at least one polymerization initiator; and

optionally, at least one (C₁-C₈)alcohol;

at a temperature from 15 °C to 90 °C to obtain sol1; and

optionally ageing the resulting mixture sol1 by stirring at a temperature from 15 °C to 90 °C from 24 h to 72 h;

c) preparing a mixture B comprising:

at least one metal alkoxide;

at least one complexing agent;

optionally one or more (C₁-C₈) alcohol; and

optionally at least one acid catalyst in aqueous solution or water having a pH lower than 7;

at a temperature from 15 °C to 30 °C to obtain sol2; optionally ageing the resulting mixture sol2 by stirring at a temperature from 15 °C to 30 °C from 24 h to 72 h; and

d) mixing the sol 1 with the sol 2; optionally adding to the mixture obtained in step d) at least one acid catalyst in aqueous solution or water having a pH lower than 7; and ageing the resulting mixture by stirring at a temperature from 15 °C to 30 °C from 24 h to 72 h;
wherein, the organic precursor is a compound selected from the group consisting of a compound of formula (VI)

, a compound of formula (VII)

and a mixture thereof
wherein:

R₂₇ are independently selected from (C₁-C₆)alkyl;

R₄₀ and R₄₁ are independently selected from the group consisting of H and (C₁-C₆)alkyl;

X₂ is selected from the group consisting of a compound of formula (VIII)

and a compound of formula (IX);

and a mixture thereof;
wherein:

R₄₂ is selected from the group consisting of H and (C₁-C₆)alkyl;

p is an integer from 1 to 8; and

n' is an integer from 1 to 6.

[0020] And, the second aspect of the invention relates to a coated substrate comprising a sol-gel layer obtainable by the process as defined in the first aspect of the invention.

Brief Description of Drawings

[0021] Fig. 1 shows a graphical representation of contact angle and surface tension in the solid-liquid, solid-vapour, and liquid-vapour interfaces.

Detailed description of the invention

[0022] All terms as used herein in this application, unless otherwise stated, shall be understood in their ordinary meaning as known in the art. More specific definitions for certain terms as used in the present application are as set forth below and are intended to apply uniformly throughout the specification and claims unless an otherwise expressly set out definition provides a broader definition.

[0023] For purposes of the present invention, the given ranges include both the lower and the upper end-points. Ranges such as temperatures, times, and the like, should be considered approximate, unless specifically stated.

[0024] For the purpose of the invention, the term "sol-gel" or "solution sol-gel" or "SG" process have the same meaning and are used interchangeably. They refer to a chemical process that is used for the synthesis of single- or multiple-component materials, including glasses, in the form of thin solid films, ultrafine powders, high surface area porous materials, dense abrasive minerals, and continuous ceramic and glass fibres. In particular, a sol-gel coating is prepared by a sol-gel process that involves the preparation of one or more precursor mixtures (also called "sol"), which is converted into intermediate product (also called "gel") and thereof into a specified material by a process that may involve chemical reactions, product forming, jellification, drying, and curing.

[0025] The term "sol" refers to either a dispersion of colloidal particles of one phase in a fluid medium or a solution prepared by hydrolysis and polycondensation of semimetal or metalorganic derivatives compounds or inorganic salts in alcoholic solution. The term "gel" refers to a material consisting of a three-dimensional network of a solid phase interwoven with an entrapped and immobilized continuous liquid phase.

[0026] The terms "percentage (%) by weight" or "% by weight" are used interchangeably and they refer to the percentage of each component in relation to the total weight of the composition.

[0027] The term "metal alkoxide" refers to a compound characterized by a metal central atom that forms covalent bonds to organic groups, but not directly to a carbon atom, though an oxygen atom instead, namely metal-oxygen-carbon bonds. The term "metal atom" refers to elements that form materials in which the valence and the conduction band is overlapped. It refers to chemical elements defined as metal in the periodic table of elements. Metallic elements are subdivided in alkali metals, alkaline earth metals, transition metals, post-transition metals, lanthanides and actinides. Examples of metals appropriate for the present invention include, without limitation, Al, Ti, Zr and Y.

[0028] The term "semimetal alkoxide" refers to a compound characterized by a semimetal central atom that forms covalent bonds to organic groups, but not directly to a carbon atom, though an oxygen atom instead, namely semimetal-oxygen-carbon bonds. The term "semimetal atom" refers to chemical elements defined as "metalloid" in the periodic table of elements. Examples of semimetals appropriate for the present invention include, without limitation, Si, Ge, B, As, Sb, Te, Po and At.

[0029] The term "organo-alkoxysilane" refers to a semimetal-organic compound in which the central atom is silicon that forms two types of covalent bonding systems. One of them is silicon-oxygen-carbon and the other is silicon-carbon.

[0030] The term "molar ratio" refers to the relation of mols between the different components of the sol-gel coating compositions.

[0031] The terms "coating" or "layer" have the same meaning and are used interchangeably. They refer to the surface that remains after the deposition of a "coating composition" directly onto the bare surface of a substrate or alternatively onto a substrate which already has one or more layers.

[0032] For the purposes of the invention the expressions "obtainable", "obtained" and equivalent expressions are used interchangeably, and in any case, the expression "obtainable" encompasses the expression "obtained".

[0033] The term "alkyl" refers to a saturated straight, or branched hydrocarbon chain which contains the number of carbon atoms specified in the description or claims. Examples include, among others, the group methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, and n-hexyl.

[0034] The term "alkylene" refers to a bivalent alkyl group which contains the number of carbon atoms specified in the description or claims.

[0035] The term "alkenyl" refers to a saturated straight or branched alkyl chain which contains f the number of carbon atoms specified in the description or claims and that also contains one or more double bonds. Examples include, among others, ethenyl, 1-propen-1-yl, 1-propen-2-yl, 3-propen-1-yl, 1-buten-1-yl, 1-buten-2-yl, 3-buten-1-yl, 3-buten-2-yl, 2-buten-1-yl, 2-buten-2-yl, 2-methyl-1-propen-1-yl, 2-methyl-2-propen-1-yl, 1,3-butadien-1-yl, 1,3-butadien-2-yl, and 2-hexenyl.

[0036] The term "alkynyl" refers a saturated straight or branched alkyl chain which contains the number of carbon atoms specified in the description or claims and that also contains one or more triple bonds. Examples include, among others, ethynyl, 1-propynyl, 2-butynyl, 1,3-butadinyl, 4-pentynyl, and 1-hexynyl.

[0037] The term "aryl" refers to a membered ring, saturated, partially or totally unsaturated, optionally bridged or fused to a 5 to 6 membered ring, wherein the number of the members of the rings is that specified in the description or claims and the members of the rings are independently selected from C, CH, CH₂, O, N, NH, and S; being one or more of the hydrogen atoms of the members optionally substituted by a radical selected from the group consisting of (C₁-C₆)alkyl, (C₁-C₆)alkyl-halogen, halogen, (C₁-C₆)alkyl-O, (C₁-C₆)alkyl-CO-, (C₁-C₆)alkyl-O-CO-, -NO₂ and -CN.

[0038] The term "polyfluoro-alkyl" refers to a saturated straight, or branched hydrocarbon wherein at least one hydrogen atom is substituted by a fluorine atom and which contains from 1 to 20 carbon atoms. Examples include, among others, the group trifluoromethyl/perfluoro methyl, perfluoro ethyl, perfluoro propyl, perfluoro isopropyl, perfluoro butyl, perfluoro isobutyl, perfluoro-sec-butyl, perfluoro-tert-butyl, perfluoro-n-pentyl, perfluoro-hexyl, perfluoro-octyl, perfluoro-dodecyl perfluoro-decyl.

[0039] The term "halogen" refers to fluorine, chlorine, bromine and iodine.

[0040] As mentioned above, an aspect of the present invention refers to a process for preparing a sol-gel coating composition useful for the preparation of a repellent coating on a substrate having durable omniphobicity and antibacterial activity over a wide range of substrates obtainable by the process of the invention.

[0041] As it is shown above, the sol-gel coating composition of the invention are useful to prepare omniphobic, repellent, antiadhesive, easy-to-clean, antifogging, anti-icing and antifouling surfaces, for having a durable low interfacial energy and non-leaching antibacterial activity also in combination with low roughness and anticorrosion properties.

[0042] For the purpose of the invention, the term "repellent" refers to a material or a coating or a surface that can repel at least a substance such as water, oil or organic solvents. The repellence capability can be measured by any method known in the state of the art. Examples of appropriate methods for determining the repellence capability include the determination of contact angle formed by a test liquid in the interface. The measurement of contact angle with more than one test liquid allows calculating the dispersive and polar components of the surface free energy by Owens-Wendt method. The total surface free energy corresponds to the sum of both components. A material can be considered repellent when shows a contact angle value > 90° for at least one test liquid. The repellence capability can also be attributed to a material with low surface free energy < 30 mJ/m².

[0043] For the purpose of the invention, the terms "omniphobic" and "multi-repellent" have the same meaning and are used interchangeable. They refer to a material or a coating or a surface that exhibit omniphobic functionality since they are able to repel substances of different nature such as water, oil and/or organic solvents.

[0044] For the purpose of the invention, the term "biocide" and "antibacterial" have the same meaning and are used interchangeable. They refer to a material, coating or surface capable of destroying a harmful organism; or counteracting, neutralizing, or avoiding the action of a harmful organism; or exercise any control over a harmful organism, by chemical or biological means.

[0045] The first alternative of the first aspect of the invention refers to a process for preparing a sol-gel coated substrate comprising:

1) firstly, depositing a sol-gel coating composition selected from the group consisting of sol1 and sol3 over the substrate

2) secondly, curing the coating obtained in step 1);

wherein the sol1 is a sol-gel coating composition obtainable by a process which comprises:

a) preparing a mixture A comprising:

at least one alkoxide selected from the group consisting of a metal alkoxide, a semimetal alkoxide, an organo-alkoxysilane and a mixture thereof;

at least one acid catalyst in aqueous solution having a pH lower than 5

optionally, at least one (C₁-C₈)alcohol;

optionally, at least one organic precursor;

optionally, at least one polymerization initiator; and

optionally, at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, fluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof;

at a temperature from 15 °C to 90 °C for an appropriate period of time to obtain sol1; and

optionally ageing the resulting mixture sol1 by stirring at a temperature from 15 °C to 30 °C for a period of time from 24 h to 72 h to obtain sol1;
and

wherein the sol3 is a sol-gel coating composition obtainable by a process which comprises:

b) preparing a mixture A comprising:

at least one alkoxide selected from the group consisting of a metal alkoxide, a semimetal alkoxide, an organo-alkoxysilane and a mixture thereof;

at least one acid catalyst in aqueous solution having a pH lower than 5

optionally, at least one organic precursor;

optionally, at least one polymerization initiator;

optionally, at least one (C₁-C₈)alcohol; and

optionally, at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof;

at a temperature from 15 °C to 90 °C to obtain sol1; and

optionally ageing the resulting mixture sol1 by stirring at a temperature from 15 °C to 30 °C from 24 h to 72 h;

c) preparing a mixture B comprising:

at least one metal alkoxide;

at least one complexing agent;

optionally, at least one acid catalyst in aqueous solution or water having a pH lower than 7;

optionally, one or more (C₁-C₈) alcohol; and

optionally, at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof,

at a temperature from 15 °C to 30 °C for an appropriate period of time to obtain sol2; and optionally ageing the resulting mixture sol2 by stirring at a temperature from 15 °C to 30 °C from 24 h to 72 h; and

d) mixing the sol 1 with the sol 2; optionally adding to the mixture obtained in step d) at least one acid catalyst in aqueous solution or water having a pH lower than 7; and ageing the resulting mixture by stirring at a temperature from 15 °C to 30 °C from 24 h to 72 h;

with the proviso that the sol-gel coating composition of step 1) comprises at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof.

[0046] In an embodiment, the process comprises:

1) firstly, depositing a sol-gel coating composition sol1 over the substrate; and

2) secondly, curing the coating obtained in step 1);

wherein the sol1 is a sol-gel coating composition obtainable by a process which comprises:

a) preparing a mixture A comprising:

at least one alkoxide selected from the group consisting of a metal alkoxide, a semimetal alkoxide, an organo-alkoxysilane and a mixture thereof;

at least one acid catalyst in aqueous solution having a pH lower than 5

optionally, at least one (C₁-C₈)alcohol;

optionally, at least one organic precursor;

optionally, at least one polymerization initiator; and

at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof;

at a temperature from 15 °C to 90 °C for an appropriate period of time; particularly for a period of time from 30 min to 4 h to obtain sol1; and

optionally ageing the resulting mixture sol1 by stirring at a temperature from 15 °C to 30 °C for a period of time from 24 h to 72 h to obtain ageing sol1.

[0047] In an embodiment, the process comprises depositing a sol1 sol-gel coating composition obtainable by a process which comprises:
a1) preparing a mixture A1 comprising:

at least one semimetal alkoxide;

at least one organo-alkoxysilane;

at least one acid catalyst in aqueous solution having a pH lower than 5; and

optionally at least one (C₁-C₈)alcohol; and

at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof;
by:

a1') mixing the semimetal alkoxide; the organo-alkoxysilane; optionally at least one (C₁-C₈)alcohol; an aqueous solution of at least one acid catalyst in aqueous solution having a pH lower than 5; and at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof at a temperature from 15 °C to 90 °C for an appropriate period of time to obtain the sol1-1; and

a1") optionally ageing the resulting mixture by stirring at a temperature from 15 °C to 30 °C from 24 h to 72 h to obtain the ageing sol1-1.

[0048] In an embodiment, the process comprises depositing a sol1 sol-gel coating composition obtainable by a process which comprises:
a2) preparing a mixture A2 comprising:

at least one semimetal alkoxide;

at least one organo-alkoxysilane;

at least one acid catalyst in aqueous solution having a pH lower than 5

at least one organic precursor;

optionally, at least one polymerization initiator;

optionally, at least one (C₁-C₈)alcohol; and

at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof;
by:

a2') preparing a first mixture comprising the semimetal alkoxide; the organo-alkoxysilane; optionally at least one (C₁-C₈)alcohol; an aqueous solution of at least one acid catalyst in aqueous solution having a pH lower than 5; and optionally at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof at a temperature from 15 °C to 90 °C;

a2") preparing a second mixture comprising at least one organic precursor; optionally, at least one polymerization initiator or a mixture thereof; optionally an aqueous solution of at least one acid catalyst in aqueous solution having a pH lower than 5; optionally at least one (C₁-C₈) alcohol; and optionally at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof at a temperature from 15 °C to 30 °C;

a2‴) mixing the second mixture and the first mixture at a temperature from 15°C to 30°C; and stirring the resulting mixture at a temperature from 15 °C to 90 °C for an appropriate period of time to obtain the sol1-2; and

a2ʺʺ) optionally ageing the resulting mixture by stirring at a temperature from 15 °C to 30 °C from 24 h to 72 h to obtain the ageing sol1-2;

with the proviso that the sol1-2 comprises at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof.

[0049] In an embodiment, the process comprises depositing the sol1-2 as defined above obtainable by a process wherein the at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof is present in step a2'. In an embodiment, the process comprises depositing the sol1-2 as defined above obtainable by a process wherein the at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof is present in step a2".

[0050] In an embodiment, the process comprises depositing a sol1 sol-gel coating composition obtainable by a process which comprises:
a3) preparing a mixture A3 comprising:

at least one semimetal alkoxide;

at least one organo-alkoxysilane;

at least one acid catalyst in aqueous solution having a pH lower than 5

at least one organic precursor;

optionally, at least one polymerization initiator;

at least one (C₁-C₈)alcohol; and

at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof;
by:

a3') preparing a first mixture comprising the organo-alkoxysilane; optionally at least one (C₁-C₈)alcohol; an aqueous solution of at least one acid catalyst in aqueous solution having a pH lower than 5; and optionally at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof at a temperature from 15 °C to 90 °C;

a3") optionally, adding at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl;

a3‴) adding at least one semimetal alkoxide; and stirring the resulting mixture at a temperature from 15 °C to 90 °C for an appropriate period of time;

a3ʺʺ) preparing a second mixture comprising at least one organic precursor; optionally, at least one polymerization initiator; optionally at least one (C₁-C₈)alcohol; optionally, an aqueous solution of at least one acid catalyst in aqueous solution having a pH lower than 5; or a mixture thereof; and optionally at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof at a temperature from 15 °C to 30 °C;

a3^v) mixing the second mixture with the mixture obtained in step a3ʺʺ) at a temperature from 15 °C to 90 °C to obtain the sol1-3; and

a3^vi) optionally ageing the resulting mixture by stirring at a temperature from 15 °C to 30 °C from 24 h to 72 h to obtain the ageing sol1-3.

with the proviso that the sol1-3 comprises at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof.

[0051] In an embodiment, the process comprises depositing the sol1-3 as defined above obtainable by a process wherein the at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof is present in step a3'). In an embodiment, the process comprises depositing the sol1-3 as defined above obtainable by a process wherein the at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof is present in step a3"). In an embodiment, the process comprises depositing the sol1-3 as defined above obtainable by a process wherein the at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof is present in step a3ʺʺ).

[0052] In an embodiment, the process comprises depositing a sol1 sol-gel coating composition obtainable by a process which comprises:
a4) preparing a mixture A4 comprising:

at least one organo-alkoxysilane;

at least one acid catalyst in aqueous solution having a pH lower than 5

at least one organic precursor;

optionally, at least one polymerization initiator; and

at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof;
by:

a4') preparing a first mixture comprising the organo-alkoxysilane; an aqueous solution of at least one acid catalyst in aqueous solution having a pH lower than 5; and optionally at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof at a temperature from 15 °C to 90 °C;

a4") optionally, adding at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof at a temperature from 15 °C to 30 °C; and stirring the resulting mixture at a temperature from 15 °C to 90 °C; and

a4‴) preparing a second mixture comprising at least one organic precursor; optionally, at least one polymerization initiator or a mixture thereof; optionally, an aqueous solution of at least one acid catalyst in aqueous solution having a pH lower than 5; and optionally at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof at a temperature from 15 °C to 30 °C;

a4ʺʺ) mixing the second mixture with the mixture obtained in step a4‴) and stirring at a temperature from 15 °C to 90 °C to obtain the sol1-4; and

a4^v) optionally ageing the resulting mixture by stirring at a temperature from 15 °C to 30 °C from 24 h to 72 h to obtain the ageing sol1-4;

with the proviso that the sol1-4 comprises at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof.

[0053] In an embodiment, the process comprises depositing the sol1-4 as defined above obtainable by a process wherein the at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof is present in step a4'). In an embodiment, the process comprises depositing the sol1-4 as defined above obtainable by a process wherein the at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof is present in step a4"). In an embodiment, the process comprises depositing the sol1-4 as defined above obtainable by a process wherein the at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof is present in step a4‴).

[0054] In an embodiment, the process comprises depositing a sol1 sol-gel coating composition obtainable by a process which comprises:
a5) preparing a mixture A5 comprising:

at least one semimetal alkoxide;

at least one organo-alkoxysilane;

at least one acid catalyst in aqueous solution having a pH lower than 5

at least one organic precursor;

optionally, at least one polymerization initiator; and

at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof;
by:

a5') preparing a first mixture comprising the organo-alkoxysilane; an aqueous solution of at least one acid catalyst in aqueous solution having a pH lower than 5; and optionally at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof at a temperature from 15 °C to 90 °C;

a5") optionally, adding at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof at a temperature from 15 °C to 30 °C;

a5‴) adding at least one semimetal alkoxide at a temperature from 15 °C to 30 °C;

a5ʺʺ) mixing the resulting mixture at a temperature from 15 °C to 90 °C; and stirring the resulting mixture at a temperature from 15 °C to 90 °C; and

a5^v) preparing a second mixture comprising at least one organic precursor; optionally, at least one polymerization initiator or a mixture thereof; optionally, one acid catalyst in aqueous solution having a pH lower than 5; and optionally at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof at a temperature from 15 °C to 30 °C;

a5^vi) mixing the second mixture with the mixture obtained in step a5‴) at a temperature from 15 °C to 90 °C to obtain the sol1-5; and

a5^vii) optionally ageing the resulting mixture by stirring at a temperature from 15 °C to 30 °C from 24 h to 72 h to obtain the ageing sol1-5; and

with the proviso that the sol1-5 comprises at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof.

[0055] In an embodiment, the process comprises depositing the sol1-5 as defined above obtainable by a process wherein the at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof is present in step a5'). In an embodiment, the process comprises depositing the sol1-4 as defined above obtainable by a process wherein the at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof is present in step a5"). In an embodiment, the process comprises depositing the sol1-4 as defined above obtainable by a process wherein the at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof is present in step a5^v).

[0056] In an embodiment, the process comprises depositing a sol3 sol-gel coating composition obtainable by a process which comprises:

1) firstly, depositing a sol-gel coating composition sol3 over the substrate; and

2) secondly, curing the coating obtained in step 1);

wherein the sol3 is a sol-gel coating composition obtainable by a process which comprises:

b) preparing a mixture A comprising:

at least one alkoxide selected from the group consisting of a metal alkoxide, a semimetal alkoxide, an organo-alkoxysilane and a mixture thereof;

at least one acid catalyst in aqueous solution having a pH lower than 5;

at least one organic precursor;

optionally, at least one polymerization initiator;

optionally, at least one (C₁-C₈)alcohol; and

optionally, at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof;

at a temperature from 15 °C to 90 °C to obtain sol1; and

optionally ageing the resulting mixture sol1 by stirring at a temperature from 15 °C to 30 °C from 24 h to 72 h;

c) preparing a mixture B comprising:

at least one metal alkoxide;

at least one complexing agent;

optionally one or more (C₁-C₈) alcohol; and

optionally at least one acid catalyst in aqueous solution or water having a pH lower than 7;

optionally at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof,

at a temperature from 15 °C to 30 °C to obtain sol2; optionally ageing the resulting mixture sol2 by stirring at a temperature from 15 °C to 30 °C from 24 h to 72 h; and

d) mixing the sol 1 with the sol 2; optionally adding to the mixture obtained in step d) at least one acid catalyst in aqueous solution or water having a pH lower than 7; and ageing the resulting mixture by stirring at a temperature from 15 °C to 30 °C from 24 h to 72 h;

with the proviso that the sol3 comprises at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof.

[0057] In an embodiment, the process comprises depositing the sol3 as defined above obtainable by a process wherein the at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof is present in sol1.

[0058] In an embodiment, the process comprises depositing the sol3 as defined above obtainable by a process wherein the at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof is present in sol2.

[0059] In an embodiment, the process comprises depositing the sol3 as defined above obtainable by a process which comprises:

b) preparing a sol1 selected from the group consisting of sol1-1, sol1-2, sol1-3, sol1-4, sol1-5, ageing sol1-1, ageing sol1-2, ageing sol1-3, ageing sol1-4 and ageing sol1-5 as defined above;

c) preparing a sol2 by preparing a mixture B by mixing at least one metal alkoxide; at least one complexing agent; optionally one or more (C₁-C₈) alcohol; optionally, at least one acid catalyst in aqueous solution or water having a pH lower than 7; and optionally at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof, at a temperature from 15 °C to 90 °C to obtain sol2; optionally ageing the resulting mixture sol2 by stirring at a temperature from 15 °C to 30 °C from 24 h to 72 h to obtain ageing sol2; and

d) mixing the sol 1 with the sol 2, optionally adding to the mixture obtained in step d) at least one acid catalyst in aqueous solution or water having a pH lower than 7; and ageing the resulting mixture by stirring at a temperature from 15 °C to 30 °C from 24 h to 72 h to obtain sol3 selected from the group consisting of sol3-1, sol3-2, sol3-3, sol3-4, sol3-5, ageing sol3-1, ageing sol3-2, ageing sol3-3, ageing sol3-4 and ageing sol3-5, respectively.

[0060] In an embodiment, the process comprises depositing the sol3 as defined above obtainable by a process wherein when the sol1 is a sol1-1, then sol1-1 is obtainable by a process wherein step a1') mixing the semimetal alkoxide; the organo-alkoxysilane; optionally at least one (C₁-C₈)alcohol; an aqueous solution of at least one acid catalyst in aqueous solution having a pH lower than 5; and at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof at a temperature from 15 °C to 90 °C for an appropriate period of time to obtain the sol1-1; and a1") optionally ageing the resulting mixture by stirring at a temperature from 15 °C to 30 °C from 24 h to 72 h.

[0061] In an embodiment, the process comprises depositing the sol3 as defined above obtainable by a process wherein when the sol1 is a sol1-2, then sol1-2 is obtainable by a process wherein step a2') preparing a first mixture comprising the semimetal alkoxide; the organo-alkoxysilane; at least one (C₁-C₈)alcohol; an aqueous solution of at least one acid catalyst in aqueous solution having a pH lower than 5; and optionally at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof at a temperature from 15 °C to 90 °C; a2") preparing a second mixture comprising at least one organic precursor; at least one polymerization initiator or a mixture thereof; and optionally at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof at a temperature from 15 °C to 90 °C; a2‴) mixing the second mixture and the first mixture at a temperature from 15°C to 30°C; and stirring the resulting mixture at a temperature from 15 °C to 90 °C for an appropriate period of time to obtain the sol1-2; and a2ʺʺ) optionally ageing the resulting mixture by stirring at a temperature from 15 °C to 30 °C from 24 h to 72 h.

[0062] In an embodiment, the process comprises depositing the sol3 as defined above obtainable by a process wherein when the sol1 is a sol1-3, then sol1-3 is obtainable by a process wherein step a3') preparing a first mixture comprising the organo-alkoxysilane; optionally at least one (C₁-C₈)alcohol; an aqueous solution of at least one acid catalyst in aqueous solution having a pH lower than 5; and optionally at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof at a temperature from 15 °C to 90 °C;

a3") optionally, adding at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl at a temperature from 15 °C to 30 °C;

a3‴) adding at least one semimetal alkoxide at a temperature from 15 °C to 30 °C;

a3ʺʺ^v) preparing a second mixture comprising at least one organic precursor; optionally, at least one polymerization initiator; optionally, an aqueous solution of at least one acid catalyst in aqueous solution having a pH lower than 5; or a mixture thereof; and optionally at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof at a temperature from 15 °C to 30 °C;

a3^v) mixing the second mixture with the mixture obtained in step a3‴) at a temperature from 15 °C to 30 °C to obtain the sol1-3; and

a3^vi) optionally ageing the resulting mixture by stirring at a temperature from 15 °C to 30 °C from 24 h to 72 h.

[0063] In an embodiment, the process comprises depositing the sol3 as defined above obtainable by a process wherein when the sol1 is a sol1-4, then sol1-4 is obtainable by a process wherein step a4') preparing a first mixture comprising the organo-alkoxysilane; an aqueous solution of at least one acid catalyst in aqueous solution having a pH lower than 5; and optionally at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof at a temperature from 15 °C to 90 °C;

a4") optionally, adding at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof at a temperature from 15 °C to 30 °C; and stirring the resulting mixture at a temperature from 15 °C to 90 °C; and

a4‴) preparing a second mixture comprising at least one organic precursor; optionally, at least one polymerization initiator or a mixture thereof; optionally, an aqueous solution of at least one acid catalyst in aqueous solution having a pH lower than 5; and optionally at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof at a temperature from 15 °C to 30 °C;

a4ʺʺ) mixing the second mixture with the mixture obtained in step a4‴) and stirring at a temperature from 15 °C to 90 °C to obtain the sol1-4; and

a4^v) optionally ageing the resulting mixture by stirring at a temperature from 15 °C to 30 °C from 24 h to 72 h.

[0064] In an embodiment, the process comprises depositing the sol3 as defined above obtainable by a process wherein when the sol1 is a sol1-5, then sol1-5 is obtainable by a process wherein stepa5') preparing a first mixture comprising the organo-alkoxysilane; an aqueous solution of at least one acid catalyst in aqueous solution having a pH lower than 5; and optionally at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof at a temperature from 15 °C to 90 °C;

a5") optionally, adding at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof at a temperature from 15 °C to 30 °C;

a5‴) adding at least one semimetal alkoxide at a temperature from 15 °C to 30 °C;

a5ʺʺ) mixing the resulting mixture at a temperature from 15 °C to 90 °C; and stirring the resulting mixture at a temperature from 15 °C to 90 °C; and

a5^v) preparing a second mixture comprising at least one organic precursor; optionally, at least one polymerization initiator or a mixture thereof; optionally, one acid catalyst in aqueous solution having a pH lower than 5; and optionally at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof at a temperature from 15 °C to 30 °C;

a5^vi) mixing the second mixture with the mixture obtained in step a5‴) at a temperature from 15 °C to 90 °C to obtain the sol1-5; and

a5^vii) optionally ageing the resulting mixture by stirring at a temperature from 15 °C to 30 °C from 24 h to 72 h.

[0065] As it is mentioned above, the first alternative process of the first aspect of the invention comprises depositing a sol-gel coating composition comprising at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof.

[0066] The term "functional organo-alkoxysilane" refers to a compound consisting of a silicon central atom containing some functional organic moiety directly bonded to a carbon and some organic groups not directly bonded to carbon, though an oxygen atom instead, thus alkoxy groups. The functional organic moiety adds new functionality to a final formed material, such as hydrophobicity, oleophobicity or biocidal action.

[0067] The term "functional organo-halosilane" refers to a compound consisting of a silicon central atom containing some functional organic moiety directly bonded to a carbon and some direct bonds to halogen atoms. The functional organic moiety adds new functionality to a final formed material, such as hydrophobicity, oleophobicity or biocidal action.

[0068] The term "functional organosilyl moiety" refers to an organic moiety containing a carbon to silicon bond. The functional organic moiety adds new functionality to a final formed material, such as hydrophobicity, oleophobicity or biocidal action.

[0069] In an embodiment, the process comprises depositing a sol-gel coating composition comprising at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of: quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, which is selected from the group consisting of: one or more quaternary ammonium alkoxysilanes; one or more quaternary ammonium halosilanes; one or more polyfluoro-(C₁-C₂₀)alkyl alkoxysilanes; one or more polyfluoro-(C₁-C₂₀) halosilanes; one or more (C₁-C₄₀)alkyl alkoxysilanes; one or more (C₁-C₄₀)alkyl halosilanes; a mixture of one or more quaternary ammonium alkoxysilane and one or more polyfluoro-(C₁-C₂₀)alkyl alkoxysilanes; a mixture of one or more quaternary ammonium alkoxysilane and one or more polyfluoro-(C₁-C₂₀) halosilanes; a mixture of one or more quaternary ammonium halosilanes and one or more polyfluoro-(C₁-C₂₀)alkyl alkoxysilanes; a mixture of one or more polyfluoro-(C₁-C₂₀)alkyl alkoxysilanes and one or more (C₁-C₄₀)alkyl alkoxysilane; a mixture of one or more polyfluoro-(C₁-C₂₀)alkyl alkoxysilanes and one or more (C₁-C₄₀)alkyl halosilanes; a mixture of one or more polyfluoro-(C₁-C₂₀) halosilanes and one or more (C₁-C₄₀)alkyl alkoxysilane; a mixture of one or more polyfluoro-(C₁-C₂₀) halosilanes and one or more (C₁-C₄₀)alkyl halosilanes; a mixture of one or more quaternary ammonium alkoxysilane and one or more (C₁-C₄₀)alkyl alkoxysilane; a mixture of one or more quaternary ammonium alkoxysilane and one or more (C₁-C₄₀)alkyl halosilanes; a mixture of one or more quaternary ammonium halosilanes and one or more (C₁-C₄₀)alkyl alkoxysilane; a mixture of one or more quaternary ammonium alkoxysilane, one or more polyfluoro-(C₁-C₂₀)alkyl alkoxysilane and one or more (C₁-C₄₀)alkyl alkoxysilane; a mixture of one or more quaternary ammonium alkoxysilane, one or more polyfluoro-(C₁-C₂₀) halosilanes and one or more (C₁-C₄₀)alkyl alkoxysilane; a mixture of one or more quaternary ammonium alkoxysilane, one or more polyfluoro-(C₁-C₂₀)alkyl alkoxysilane and one or more (C₁-C₄₀)alkyl halosilanes; a mixture of one or more quaternary ammonium alkoxysilane, one or more polyfluoro-(C₁-C₂₀) halosilanes and one or more (C₁-C₄₀)alkyl halosilanes; and a mixture of one or more quaternary ammonium halosilanes, one or more polyfluoro-(C₁-C₂₀)alkyl silane and one or more (C₁-C₄₀)alkyl alkoxysilane.

[0070] In an embodiment, the process comprises depositing a sol-gel coating composition comprising at least one functional organo-alkoxysilane or organo-halosilane having a quaternary ammonium silyl as a functional organosilyl moiety, thereby being a quaternary ammonium alkoxysilane or a quaternary ammonium halosilane. For the purpose of the invention, the term functional organo-alkoxysilane or organo-halosilane having a quaternary ammonium silyl as a functional organosilyl moiety refers to a quaternary ammonium alkoxysilane or a quaternary ammonium halosilane. The terms "quaternary ammonium silane" and "silylated quaternary ammonium salt" have the same meaning and are used interchangeable. Particularly, the "quaternary ammonium alkoxysilane" refers to a salt consisting of a cation formed by a silicon central atom containing i) a quaternary ammonium moiety linked to Si by an alkyl chain and ii) alkyl groups linked to Si by an oxygen atom, thus Si-O-C, thus forming alkoxy groups; in combination with an halide anion; and the term "quaternary ammonium halosilane" refers to a salt consisting of a cation formed by a silicon central atom containing i) a quaternary ammonium moiety linked to Si by an alkyl chain and ii) direct bonds between Si to halogen atoms, Si-X; in combination with an halide anion.

[0071] In an embodiment, the process comprises depositing a sol-gel coating composition comprising at least one quaternary ammonium alkoxysilane of formula (XIV)

wherein X is an halogen selected from the group consisting of chlorine, bromine and iodine; each R⁵⁷ is independently a (C₁-C₆)alkyl, particularly selected form methyl, ethyl, n-propyl, isopropyl and butyl; R⁵⁸ is a (C₁-C₂₀)alkylene, R⁵⁹ is (C₁-C₂₀)alkyl, R⁶⁰ is (C₁-C₂₀)alkyl and R⁶¹ is (C₁-C₂₀)alkyl.

[0072] In an embodiment, the process comprises depositing a sol-gel coating composition comprising at least one quaternary ammonium alkoxysilane selected from the group consisting of dimethyl octadecyl[-3-(trimethoxy silyl)propyl]ammonium chloride, dimethyl octadecyl[-3-(triethoxy silyl)propyl]ammonium chloride, diethyl octadecyl[-3-(trimethoxy silyl)propyl]ammonium chloride, dimethyl octadecyl[-3-(trimethoxy silyl)propyl]ammonium fluoride, dimethyl tetradecyl (3-trimethoxysilylpropyl)ammonium chloride, dimethyl tetradecyl (3-triethoxysilylpropyl)ammonium chloride, dimethyl hexadecyl[-3-(trimethoxy silyl)propyl]ammonium chloride, dimethyl hexadecyl[-3-(triethoxy silyl)propyl]ammonium chloride and a mixture thereof. In an embodiment, the process comprises depositing a sol-gel coating composition comprising at least one quaternary ammonium alkoxysilane or a quaternary ammonium halosilane is dimethyl octadecyl[3-(trimethoxysilyl) propyl] ammonium chloride.

[0073] In an embodiment, the process comprises depositing a sol-gel coating composition comprising at least one functional organo-alkoxysilane or organo-halosilane having a polyfluoro-(C₁-C₂₀)alkyl silyl as a functional organosilyl moiety, thereby being polyfluoro-(C₁-C₂₀)alkyl alkoxysilanes or a polyfluoro-(C₁-C₂₀) halosilanes; particularly a polyfluoro-(C₁-C₁₂)alkyl alkoxysilane or a polyfluoro-(C₁-C₁₂)alkyl halosilane. For the purpose of the invention, the term polyfluoro-(C₁-C₂₀)alkyl alkoxysilane" refers to a compound formed by silicon central atom containing some polyfluoroalkyl moiety linked to Si by an alkyl (or polyfluoroalkyl) chain and some alkyl groups linked to Si by an oxygen atom, thus Si-O-C, thus forming alkoxy groups; and the term "polyfluoro-(C₁-C₂₀) halosilane" refers to a compound formed by silicon central atom containing some polyfluoroalkyl moiety linked to Si by an alkyl (or polyfluoroalkyl) chain and some halogen atoms linked to Si by a Si-X bond.

[0074] In an embodiment, the process comprises depositing a sol-gel coating composition comprising at least one polyfluoro-(C₁-C₂₀)alkyl alkoxysilane or a polyfluoro-(C₁-C₂₀)alkyl halosilane selected from the group consisting of a compound of formula (XV)

        [CF₃-(CF₂)_v(CH₂)_u]_w-Si(OR⁴⁷)_y     (XV)

wherein each R⁴⁷ is independently (C₁-C₂₀)alkyl; u and v are independently an integer from 0 to 20, w is an integer selected from 1, 2 and 3; y is an integer selected from 1, 2, and 3; and the sum of w+y is 4;
and a compound of formula (XVI)

        [CF₃-(CF₂)_v(CH₂)_u]_w-SiX_y     (XVI)

wherein each X is independently an halogen independently selected from the group consisting of chlorine, bromine and iodine; u and v are independently an integer from 0 to 20, w is an integer selected from 1, 2 and 3; y is an integer selected from 1, 2, and 3; and the sum of w+y is 4.

[0075] In an embodiment, the process comprises depositing a sol-gel coating composition comprising at least one polyfluoro-(C₁-C₂₀)alkyl alkoxysilane or a polyfluoro-(C₁-C₂₀)alkyl halosilane, selected from the group consisting of a compound of formula (XV-A):

        CF₃-(CF₂)_v(CH₂)_u-Si(OR⁴⁸)(OR⁴⁹)(OR⁵⁰)     (XV-A)

wherein: each one of R⁴⁸, R⁴⁹ and R⁵⁰ are independently selected from the group consisting of a substituted or un-substituted (C₁-C₁₄)alkyl and u and v are independently an integer from 0 to 20;
and a compound of formula (XVI-A)

        CF₃-(CF₂)_v(CH₂)_u-SiX₃     (XVI-A)

wherein X is a halogen independently selected from the group consisting of chlorine, bromine and iodine; preferably chlorine; and u and v are independently an integer from 0 to 20.

[0076] In an embodiment, the process comprises depositing a sol-gel coating composition comprising at least one polyfluoro-(C₁-C₂₀)alkyl alkoxysilane or a polyfluoro-(C₁-C₂₀)alkyl halosilane selected from the group consisting of (1H,1H,2H,2H-perfluorododec-1-yl) triethoxy silane (1H,1H,2H,2H-perfluorododecyl) trimethoxy silane, (1H,1H,2H,2H-perfluorodecyl) triethoxy silane (FAS17), (1H,1H,2H,2H-perfluorodecyl) trimethoxy silane, (1H,1H,2H,2H-perfluorooctyl) triethoxy silane (FAS13), (1H,1H,2H,2H-perfluorooctyl) trimethoxy silane (3,3,3-trifluoropropyl) triethoxy silane, (3,3,3-trifluoropropyl) trimethoxy silane; preferably (1H,1H,2H,2H-perfluorodecyl) triethoxy silane, 1H,1H,2H,2H-perfluorododecyltrichlorosilane, 1H,1H,2H,2H-perfluorodecyltrichlorosilane, 1H,1H,2H,2H-perfluorooctyltrichlorosilane, and trichloro(3,3,3-trifluoropropyl)silane; preferably 1H,1H,2H,2H-perfluorodecyltrichlorosilane and a mixture thereof. In an embodiment, the process comprises depositing a sol-gel coating composition comprising at least one polyfluoro-(C₁-C₂₀)alkyl alkoxysilane or a polyfluoro-(C₁-C₂₀)alkyl halosilane is (1H,1H,2H,2H-perfluorodecyl) triethoxy silane (FAS17).

[0077] In an embodiment, the process comprises depositing a sol-gel coating composition comprising at least one functional organo-alkoxysilane or organo-halosilane having a (C₁-C₄₀)alkyl silyl as a functional organosilyl moiety, thereby being a (C₁-C₄₀)alkyl alkoxysilanes or a (C₁-C₄₀)alkyl halosilanes. For the purpose of the invention, the term "(C₁-C₄₀)alkyl alkoxysilane" refers to a compound formed by silicon central atom containing some alkyl moiety directly linked to Si, thus a Si-C bond, and some alkyl groups linked to Si by an oxygen atom, thus Si-O-C, thus forming alkoxy groups; and the term "(C₁-C₄₀)alkyl halosilane" refers to a compound formed by silicon central atom containing some alkyl moiety directly linked to Si, thus a Si-C bond, and some halogen atoms linked to Si by a Si-X bond.

[0078] In an embodiment, the process comprises depositing a sol-gel coating composition comprising at least one (C₁-C₄₀)alkyl alkoxysilanes or a (C₁-C₄₀)alkyl halosilanes selected from the group consisting of a compound of formula (XVII)

        (R⁵¹)_aSi(OR⁵²)_b     (XVII)

wherein each R⁵¹ is independently a (C₁-C₄₀)alkyl; each R⁵² is independently a (C₁-C₂₀)alkyl; w is an integer selected from 1, 2 and 3; y is an integer selected from 1, 2, and 3; and the sum of w+y is 4;
and a compound of formula (XVII)

        [CH₃-(CH₂)_u]_w-SiX_y     (XVIII)

wherein each X is an halogen independently selected from the group consisting of chlorine, bromine and iodine; u is an integer from 0 to 40, w is an integer selected from 1, 2 and 3; y is an integer selected from 1, 2, and 3; and the sum of w+y is 4.

[0079] In an embodiment, the process comprises depositing a sol-gel coating composition comprising at least one (C₁-C₄₀)alkyl alkoxysilanes or a (C₁-C₄₀)alkyl halosilanes selected from the group consisting of a compound of formula (XVII-A)

        R⁵³Si(OR⁵⁴)(OR⁵⁵)(OR⁵⁶)     (XVII-A)

wherein each R⁵³ is independently a (C₁-C₄₀)alkyl; each R^54, R⁵⁵ and R⁵⁶ are independently a (C₁-C₂₀)alkyl;
and a compound of formula (XVIII-A)

        CH₃-(CH₂)_u-SiX₃     (XVIII-A)

wherein X is an halogen independently selected from the group consisting of chlorine, bromine and iodine; preferably chlorine and u is an integer from 0 to 40.

[0080] In an embodiment, the process comprises depositing a sol-gel coating composition comprising at least one (C₁-C₄₀)alkyl alkoxysilanes or a (C₁-C₄₀)alkyl halosilanes selected from the group consisting of n-octadecyltriethoxysilane, n-octadecyltrimethoxysilane, n-hexadecyltriethoxysilane, n-hexadecyltrimethoxysilane, n-dodecyltriethoxysilane (C12), n-dodecyltrimethoxysilane, n-octyltriethoxysilane and n-octyltrimethoxysilane; preferably n-dodecyltriethoxysilane (C12), , of n-octadecyltrichlorosilane, n-hexadecyltrichlorosilane, n-dodecyltrichlorosilane (C12), n- n-octyltriethoxysilane and n-octyltrimchlorosilane;; preferably n-octadecyltrichlorosilane and a mixture thereof. In an embodiment, the process comprises depositing a sol-gel coating composition comprising at least one (C₁-C₄₀)alkyl alkoxysilane or a (C₁-C₄₀)alkyl halosilane is n-dodecyltriethoxysilane (C12).

[0081] In an embodiment, the process comprises depositing a sol-gel coating composition comprising a mixture selected from the group consisting of (1H,1H,2H,2H-perfluorodecyl) triethoxy silane (FAS17) and dimethyl octadecyl[3-(trimethoxysilyl) propyl] ammonium chloride; and (1H,1H,2H,2H-perfluorodecyl) triethoxy silane (FAS17) and n-dodecyltriethoxysilane (C12).

[0082] In an embodiment, the process comprises depositing a sol-gel coating composition comprising at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof in a molar ratio between it and the organo-silicon alkoxide from 0.001 to 2 moles for one mole of the organo-silicon alkoxide. In an embodiment, the process comprises depositing a sol-gel coating composition comprising at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof in a molar ratio between it and the organo-silicon alkoxide from 0.01 to 0.5 moles for one mole of the organo-silicon alkoxide.

[0083] In an embodiment, the process comprises depositing a sol-gel coating composition comprising a mixture of one or more quaternary ammonium alkoxysilane and one or more polyfluoro-(C₁-C₂₀)alkyl alkoxysilanes as defined in the present invention, wherein the molar ratio between them is from 1:0.1 to 1:10 (i.e. from 0.1 to 10 moles of polyfluoro-(C₁-C₂₀)alkyl alkoxysilanes for one mole of quaternary ammonium alkoxysilane). In an embodiment, the process comprises depositing a sol-gel coating composition comprising a mixture of one or more quaternary ammonium alkoxysilanes and one or more polyfluoro-(C₁-C₂₀)alkyl halosilanes as defined in the present invention, wherein the molar ratio between them is from 1:0.1 to 1:10. In an embodiment, the process comprises depositing a sol-gel coating composition comprising a mixture of one or more polyfluoro-(C₁-C₂₀)alkyl alkoxysilanes and one or more (C₁-C₄₀)alkyl alkoxysilane as defined in the present invention, wherein the molar ratio between them is from 1:0.1 to 1:10. In an embodiment, the process comprises depositing a sol-gel coating composition comprising a mixture of one or more quaternary ammonium alkoxysilane and one or more (C₁-C₄₀)alkyl alkoxysilane as defined in the present invention, wherein the molar ratio between them is from 1:0.1 to 1:10. In an embodiment, the process comprises depositing a sol-gel coating composition comprising a mixture of one or more quaternary ammonium alkoxysilanes and one or more (C₁-C₄₀)alkyl halosilane as defined in the present invention, wherein the molar ratio between them is from 1:0.1 to 1:10. In an embodiment, the process comprises depositing a sol-gel coating composition comprising a mixture of one or more quaternary ammonium alkoxysilane, one or more polyfluoro-(C₁-C₂₀)alkyl silane and one or more (C₁-C₄₀)alkyl alkoxysilane as defined in the present invention, wherein the molar ratio between them is from 1:0.1:0.1 to 1:10:10. In an embodiment, the process comprises depositing a sol-gel coating composition comprising a mixture of one or more quaternary ammonium alkoxysilanes, one or more polyfluoro-(C₁-C₂₀)halosilane and one or more (C₁-C₄₀)alkyl halosilane as defined in the present invention, wherein the molar ratio between them is from 1:0.1:0.1 to 1:10:10.

[0084] In an embodiment, the process comprises depositing a sol-gel coating composition comprising an organo-alkoxysilane selected from the group consisting of:

a compound of formula (I);

        [R4]_s-Si(OR¹)_t(OR²)(OR³)     (I)

a compound of formula (II);

        [R⁸-(CH₂)_m]-Si(OR⁵)_qR⁶_r     (II)

a compound of formula (III)

        (⁹RO)(¹⁰RO)(¹¹RO)Si-X_i-Si(OR¹²)(OR¹³)(OR¹⁴)     (III)

a mixture of at least a compound of formula (I) wherein R⁴ is (C₁-C₄)alkenyl and at least a compound of formula (I) wherein R⁴ is (C₂-C₂₀)alkyl-CH=CH-;

a mixture of at least a compound of formula (I) and at least a compound of formula (II);

a mixture of at least a compound of formula (I) and at least a compound of formula (III);

a mixture of at least a compound of formula (II) and at least a compound of formula (III);

wherein:

each one of R¹, R² and R³ are independently a substituted or un-substituted (C₁-C₁₄)alkyl;

R⁴ is selected from the group consisting of a substituted or un-substituted (C₂-C₁₄)alkenyl, (C₅-C₆)aryl, (C₂-C₁₄)alkynyl; and (C₂-C₂₀)alkyl-CH=CH-;

R⁵, R⁶, R⁹, R¹⁰, R¹¹, R¹², R¹³ and R¹⁴ are independently selected from the group consisting of a substituted or

un-substituted (C₁-C₁₄)alkyl, (C₅-C₆)aryl, (C₂-C₁₄)alkenyl, and (C₂-C₁₄)alkyl-CH=CH-;

R⁸ is selected from the group consisting of H, -SH, substituted or un-substituted (C₁-C₁₂)alkyl, substituted or

un-substituted (C₅-C₆)aryl, -(CF₂)_b-CF₃, -NR¹⁵R¹⁶, a compound of formula (IV)

and a compound of formula (V)

R¹⁵ and R¹⁶ are independently selected from the group consisting of H, substituted or un-substituted (C₁-C₁₂)alkyl, -CO, and substituted or un-substituted (C₅-C₆)aryl;

R¹⁷ is selected from the group consisting of H and substituted or un-substituted (C₁-C₁₂)alkyl;

X₁ is selected from the group consisting of substituted or unsubstituted -(C₁-C₁₂)alkylene-, -(C₁-C₁₂)alkylene-NH-(C₁-C₁₂)alkylene-, and -(C₁-C₁₂)alkylene-(S)_n-(C₁-C₁₂)alkylene-;

m is an integer from 0 to 20;

n is an integer from 1 to 4;

q is an integer from 2 to 3;

r is an integer from 0 to 1;

s is an integer from 1 to 2;

t is an integer from 0 to 1;

the sum of q + r is 3;

the sum of s + t is 2; and

b is an integer from 0 to 12.

[0085] In an embodiment, the process comprises depositing a sol-gel coating composition comprising an organo-alkoxysilane of formula (I) as defined above. In an embodiment, the process comprises depositing a sol-gel coating composition comprising an organo-alkoxysilane of formula (I) selected from the group consisting of vinyltriethoxysilane (VTES), vinyltrimethoxysilane (VTMS), allyltriethoxysilane, allyltrimethoxysilane, isopropenyltriethoxysilane, isopropenyltrimethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, (2-phenylethyl)triethoxysilane, (2-phenylethyl)trimethoxysilane and a mixture thereof.

[0086] In an embodiment, the process comprises depositing a sol-gel coating composition comprising an organo-alkoxysilane of formula (II) as defined above. In an embodiment, the process comprises depositing a sol-gel coating composition comprising an organo-alkoxysilane of formula (II) selected from the group consisting of (3-glycidyloxypropyl)trimethoxy silane (GPTMS), (3-glycidyloxypropyl)triethoxysilane (GPTES), (3-glycidoxypropyl)dimethoxymethylsilane, [3-(methacryloyloxy)propyl]trimethoxysilane (MAPTMS), [3-(methacryloyloxy)propyl]triethoxysilane (MAPTES), [3-(phenylamino)propyl]trimethoxy silane (PAPTMS), [3-(phenylamino)propyl]triethoxy silane (PAPTES), (3-mercaptopropyl)trimethoxy silane (MPTMS), (3-mercaptopropyl)triethoxy silane (MPTES), (3-isocyanatopropyl)triethoxysilane (ICPTES), 1-[3-(trimethoxy silyl)propyl]ureido (UPS) and a mixture thereof.

[0087] In an embodiment, the process comprises depositing a sol-gel coating composition comprising an organo-alkoxysilane of formula (III) as defined above. In an embodiment, the process comprises depositing a sol-gel coating composition comprising an organo-alkoxysilane of formula (III) selected from the group consisting of bis-silylfunctional precursors, bis-[triethoxysilylpropyl] tetrasulfide silane (BTESTP) and bis-1,2(triethoxysilyl)ethane (BTSE) bis-[3-(trimethoxysilyl)propyl]amine.

[0088] In an embodiment, the process comprises depositing a sol-gel coating composition comprising [3-(methacryloyloxy)propyl]trimethoxysilane (MAPTMS), [3-(methacryloyloxy)propyl]triethoxysilane (MAPTES), (3-glycidyloxypropyl)triethoxy silane (GPTES) or (3-glycidyloxypropyl)trimethoxy silane (GPTMS) as organo-alkoxysilane.

[0089] In an embodiment, the process comprises depositing a sol-gel coating composition comprising an organic precursor selected from the group consisting of:
compound of formula (VI)

, a compound of formula (VII)

and a mixture thereof
wherein:

R₂₇ are independently selected from (C₁-C₆)alkyl;

R₄₀ and R₄₁ are independently selected from the group consisting of H and (C₁-C₆)alkyl;

X₂ is selected from the group consisting of a compound of formula (VIII)

and a compound of formula (IX);

and a mixture thereof;
wherein:

R₄₂ is selected from the group consisting of H and (C₁-C₆)alkyl;

p is an integer from 1 to 8; and

n' is an integer from 1 to 6.

[0090] In an embodiment, the process comprises depositing a sol-gel coating composition comprising an organic precursor of formula (VI)

wherein R₂₇ are independently selected from (C₁-C₆)alkyl.

[0091] In an embodiment, the process comprises depositing a sol-gel coating composition comprising an organic precursor of formula (VI) wherein all R₂₇ are methyl.

[0092] In an embodiment, the process comprises depositing a sol-gel coating composition comprising an organic precursor of formula (VI) selected from the group consisting of methyl methacrylate, ethyl methacrylate and propyl methacrylate.

[0093] In an embodiment, the process comprises depositing a sol-gel coating composition comprising an organic precursor of formula (VII)

wherein:

R₄₀ and R₄₁ are independently selected from the group consisting of H and (C₁-C₆)alkyl;

X₂ is selected from the group consisting of a compound of formula (VIII)

and a compound of formula (IX);

and a mixture thereof;
wherein:

R₄₂ is selected from the group consisting of H and (C₁-C₆)alkyl;

p is an integer from 1 to 8; and

n' is an integer from 1 to 6.

[0094] In an embodiment, the process comprises depositing a sol-gel coating composition comprising an organic precursor is a compound of formula (VII) as defined above wherein both R₄₀ and R₄₁ are H. In an embodiment, the process comprises depositing a sol-gel coating composition comprising an organic precursor is a compound of formula (VII) as defined above wherein both R₄₀ and R₄₁ are (C₁-C₆)alkyl; preferably methyl.

[0095] In an embodiment, the process comprises depositing a sol-gel coating composition comprising an organic precursor is a compound of formula (VII) as defined above wherein X₂ is a compound of formula (VIII) as defined above; particularly X₂ is a compound of formula (VIII) and n is from 1 to 5.

[0096] In an embodiment, the process comprises depositing a sol-gel coating composition comprising an organic precursor is a compound of formula (VII) as defined above wherein X₂ is a compound of formula (IX) as defined above. In an embodiment, the process comprises depositing a sol-gel coating composition comprising an organic precursor is a compound of formula (IX) as defined above wherein X₂ is a compound of formula (IX) and R₄₂ is H. In an embodiment, the process comprises depositing a sol-gel coating composition comprising an organic precursor is a compound of formula (VII) as defined above wherein X₂ is a compound of formula (IX) and R₄₂ is (C₁-C₆)alkyl; preferably methyl. In an embodiment, the process comprises depositing a sol-gel coating composition comprising an organic precursor is a compound of formula (VII) as defined above wherein X₂ is a compound of formula (IX) and p is from 1 to 4.

[0097] In an embodiment, the process comprises depositing a sol-gel coating composition comprising an organic precursor is a compound of formula (VII) selected from the group consisting of ethylene glycol dimethacrylate, di(ethylene glycol) dimethacrylate, tri(ethylene glycol) dimethacrylate, tetra(ethylene glycol) dimethacrylate, ethylene glycol diacrylate, di(ethylene glycol) diacrylate, 1,3-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, and mixture thereof. In an embodiment, optionally in combination with one or more features of the various embodiments described above or below, the organic precursor is selected from the group consisting of ethylene glycol dimethacrylate (EGDMA), di(ethylene glycol) dimethacrylate, tri(ethylene glycol) dimethacrylate, tetra(ethylene glycol) dimethacrylate, ethylene glycol diacrylate, di(ethylene glycol) diacrylate, tri(ethylene glycol) diacrylate, tetra(ethylene glycol) diacrylate, 1,3-butanediol dimethacrylate, 1,3-butanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,6-hexanediol diacrylate and a mixture thereof. In an embodiment, the process comprises depositing a sol-gel coating composition comprising ethylene glycol dimethacrylate (EGDMA) as the organic precursor of formula (VII).

[0098] In an embodiment, the process comprises depositing a sol-gel coating composition comprising at least one organic precursor as defined above and at least one alkoxide being an organo-alkoxysilane as defined above. In an embodiment, the process comprises depositing a sol-gel coating composition comprising at least one organic precursor as defined above and at least one alkoxide being an organo-alkoxysilane as defined above, wherein the molar ratio between the organic precursor and the organo-alkoxysilane is from 0.1 to 10.

[0099] In an embodiment, the process comprises depositing a sol-gel coating composition comprising at least one metal alkoxide, at least one semimetal alkoxide or a mixture thereof being independently selected from a compound of formula (XIII)

        (OR⁴³)(OR⁴⁴)(OR⁴⁵)(OR⁴⁶)Z     (XIII)

wherein:

each one of R⁴³, R⁴⁴, R⁴⁵ and R⁴⁶ are independently selected from the group consisting of substituted or un-substituted (C₁-C₁₄)alkyl, (C₅-C₆)aryl, (C₂-C₁₄)alkenyl and (C₂-C₁₄)alkynyl group; and

Z is selected from the group consisting of the metal and semimetal atoms.

[0100] In an embodiment, the process comprises depositing a sol-gel coating composition comprising a metal alkoxide, wherein the metal atom is selected from the group consisting of Al, Ti, Zr and Y; particularly Zr and Ti. In an embodiment, the process comprises depositing a sol-gel coating composition comprising a metal alkoxide, wherein the metal atom is Zr. In an embodiment, the process comprises depositing a sol-gel coating composition comprising a metal alkoxide is selected from the group consisting of zirconium (IV) n-propoxide (TPOZ), zirconium (IV) isopropoxide, zirconium (IV) n-butoxide, zirconium (IV) isobutoxide, and mixtures thereof; particularly zirconium (IV) n-propoxide (TPOZ). In an embodiment, the process comprises depositing a sol-gel coating composition comprising a metal alkoxide, wherein the metal atom is Ti. In an embodiment, the process comprises depositing a sol-gel coating composition comprising a metal alkoxide is selected from the group consisting of titanium n-propoxide, titanium isopropoxide, titanium n-butoxide, titanium isobutoxide, and mixtures thereof; particularly titanium n-propoxide and titanium isopropoxide (TISP).

[0101] In an embodiment, the process comprises depositing a sol-gel coating composition comprising a semimetal alkoxide, wherein the semimetal atom is selected from the group consisting of Si, Ge, B, As, Sb, Te, Po and At. In an embodiment, the process comprises depositing a sol-gel coating composition comprising a semimetal alkoxide, wherein the semimetal atom is Si. In an embodiment, the process comprises depositing a sol-gel coating composition comprising a semimetal alkoxide is selected from the group consisting of tetraethylorthosilicate (TEOS), tetramethyl orthosilicate (TMOS), and mixtures thereof; particularly tetraethylorthosilicate (TEOS).

[0102] In an embodiment, the process comprises depositing a sol-gel coating composition comprising an alkoxide selected from at least zirconium (IV) n-propoxide (TPOZ) as a metal alkoxide, at least tetraethylorthosilicate (TEOS) as a semimetal alkoxide, and [3-(methacryloyloxy)propyl]trimethoxysilane (MAPTMS) or [3-(methacryloyloxy)propyl]triethoxysilane (MAPTES) as an organo-alkoxysilane.

[0103] In an embodiment, the process comprises depositing a sol-gel coating composition comprising an alkoxide selected from at least zirconium (IV) n-propoxide (TPOZ) as a metal alkoxide, at least tetraethylorthosilicate (TEOS) as a semimetal alkoxide, and (3-glycidyloxypropyl)trimethoxy silane (GPTMS) or (3-glycidyloxypropyl)triethoxy silane (GPTES) as an organo-alkoxysilane.

[0104] In an embodiment, the process comprises depositing a sol-gel coating composition comprising an alkoxide selected from at least zirconium (IV) n-propoxide (TPOZ) as a metal alkoxide, at least tetraethylorthosilicate (TEOS) as a semimetal alkoxide, and [3-(methacryloyloxy)propyl]trimethoxysilane (MAPTMS) as an organo-alkoxysilane; and ethylene glycol dimethacrylate (EGDMA) as an organic precursor.

[0105] In an embodiment, the process comprises depositing a sol-gel coating composition comprising at least one polymerization initiator. In an embodiment, the process comprises depositing a sol-gel coating composition comprising at least one polymerization initiator selected from the group consisting of azo compounds, peroxide compounds, imidazole compounds, aliphatic amines, phenylenediamines, carboxylic acids and their anhydrides and a mixture thereof. Examples of appropriate azo compounds include, without limitation azobisisobutyronitrile or 2,2'-azobis(2-methylpropionitrile) (AIBN) and 1,1'-azobis(cyclohexane carbonitrile) (ACHN). Examples of appropriate peroxide compounds include benzoyl peroxide and lauroyl peroxide. Examples of appropriate imidazole compounds for the present invention include, without limitation, (1-methylimidazole (1-MI), 2-methylimidazole (2-MI), 2-phenylimidazole (2-Phl), 1,2-dimethylimidazole (1,2-DMI), 2-ethyl-4-methylimidazole (2,4-EMI), 1-benzyl-2-methylimidazole (1,2-BMI). Examples of appropriate aliphatic amine include, without limitation, ethylenediamine (EDA), tris(2-aminoethyl)amine (TAEA), triethylenetetramine (TETA), or diethylenetriamine (DETA). Examples of phenylenediamines include without limitation, o-phenylenediamine (o-PDA), m-phenylenediamine (m-PDA), or p-phenylenediamine (p-PDA). Examples of appropriate carboxylic acids include, without limitation, phthalic acid (PA), hexahydro phthalic acid (HHPA), or tetrahydro phthalic acid (THPA). Examples of appropriate anhydrides of carboxylic acids include, without limitation phthalic anhydride (PA), hexahydro phthalic anhydride (HHPA), or tetrahydro phthalic anhydride (THPA). In an embodiment, the process comprises depositing a sol-gel coating composition comprising at least 2,2'-azobis(2-methylpropionitrile) (AIBN) as polymerization initiator. In an embodiment, the process comprises depositing a sol-gel coating composition comprising at least one polymerization initiator in a molar ratio between the organo-alkoxysilane and the polymerization initiator from 50 to 150; particularly from 50 to 100.

[0106] In an embodiment, the process comprises depositing a sol-gel coating composition comprising at least one complexing agent. In an embodiment, the process comprises depositing a sol-gel coating composition comprising at least one complexing agent selected from the group consisting of acetyl acetone (AcAc), methacrylic acid (MAc), acetic acid, isobutyric acid, bipyridine, and a mixture thereof. In an embodiment, the process comprises depositing a sol-gel coating composition comprising at least methacrylic acid (MAc) as complexing agent. In an embodiment, the process comprises depositing a sol-gel coating composition comprising at least one complexing agent in a molar ratio between the metal alkoxide, and the complexing agent from 0.5 to 4; from 0.7 to 3; particularly from 0.7 to 2.

[0107] In an embodiment, the process comprises depositing a sol-gel coating composition comprising at least one (C₁-C₈)alcohol. In an embodiment, the process comprises depositing a sol-gel coating composition comprising at least one (C₁-C₈)alcohol selected from the group consisting of ethanol, butanol, propanol, and a mixture thereof. The term "alcohol" refers to an "alkane" wherein at least one hydrogen atom is substituted by a hydroxyl group and that contains the number of carbon atoms specified in the description or claims. The term "alkane" refers to a saturated, branched or linear hydrocarbon that contains the number of carbon atoms specified in the description or claims. Examples include methanol, ethanol, n-propanol, iso-propanol, butanol, iso-butanol, and sec-butanol. In an embodiment, the process comprises depositing a sol-gel coating composition comprising at least ethanol as (C₁-C₈)alcohol. In an embodiment, the process comprises depositing a sol-gel coating composition comprising at least one (C₁-C₈)alcohol in a molar ratio between the organo-silicon alkoxide, and the (C₁-C₈)alcohol from 0.1 to 10.

[0108] In an embodiment, the process comprises depositing a sol-gel coating composition comprising an acid catalyst in aqueous solution. In an embodiment, the process comprises depositing a sol-gel coating composition comprising an acid catalyst in aqueous solution is an inorganic acid selected from the group consisting of H₂SO₄, HCl, HNO₃, and a mixture thereof; particularly HNO₃. The acid catalyst is in form of an aqueous solution having a pH lower than 5; preferably the pH is from 0 to 3. In an embodiment, the process comprises depositing a sol-gel coating composition comprising an acid catalyst in aqueous solution as defined above in a molar ratio between the sum of moles of alkoxides; particularly the sum of metal alkoxide plus semimetal alkoxide plus organo-silicon alkoxide plus functional organo-silicon alkoxide presents in the formulation; and moles of water of the aqueous acidic solution is from 0.01 to 100; preferable from 0.10 to 10.

[0109] In an embodiment, the process comprises depositing a sol-gel coating composition comprising:

an inorganic acid catalyst in aqueous solution independently selected from the group consisting of H₂SO₄, HCl, HNO₃, and a mixture thereof;

an (C₁-C₈)alcohol independently selected from the group consisting of methanol, ethanol, butanol, n-propanol, isopropanol, and a mixture thereof; and

a complexing agent selected from the group consisting of acetyl acetone, methacrylic acid, acetic acid, isobutyric acid, bipyridine, and a mixture thereof.

[0110] In an embodiment, the process comprises depositing a sol-gel coating composition comprising:

a polymerization initiator selected from the group consisting of azo compounds and a mixture thereof;

an inorganic acid catalyst in aqueous solution independently selected from the group consisting of H₂SO₄, HCl, HNO₃, and a mixture thereof;

an (C₁-C₈)alcohol independently selected from the group consisting of methanol, ethanol, butanol, n-propanol, isopropanol, and a mixture thereof; and

a complexing agent selected from the group consisting of acetyl acetone, methacrylic acid, acetic acid, isobutyric acid, bipyridine, and a mixture thereof.

[0111] In an embodiment, the process comprises depositing a sol-gel coating composition comprising:

2'-azobis(2-methylpropionitrile) (AIBN) as polymerization initiator;

HNO₃ as an acid catalyst in aqueous solution;

methanol, ethanol and/or n-propanol as (C₁-C₈)alcohols; and

methacrylic acid as complexing agent.

[0112] In an embodiment, the process comprises depositing a sol-gel coating composition comprising a alkoxide selected from at least zirconium (IV) n-propoxide (TPOZ) as a metal alkoxide, at least tetraethylorthosilicate (TEOS) as a semimetal alkoxide, [3-(methacryloyloxy)propyl]trimethoxysilane (MAPTMS) as an organo-alkoxysilane; 2'-azobis(2-methylpropionitrile) (AIBN) as polymerization initiator; HNO₃ as an acid catalyst in aqueous solution;
methanol, ethanol and/or n-propanol as (C₁-C₈)alcohols; and methacrylic acid as complexing agent.

[0113] In an embodiment, the process comprises depositing a sol-gel coating composition comprising a alkoxide selected from at least zirconium (IV) n-propoxide (TPOZ) as a metal alkoxide, at least tetraethylorthosilicate (TEOS) as a semimetal alkoxide, and [3-(methacryloyloxy)propyl]trimethoxysilane (MAPTMS) as an organo-alkoxysilane; ethylene glycol dimethacrylate (EGDMA) as an organic precursor; 2'-azobis(2-methylpropionitrile) (AIBN) as polymerization initiator; HNO₃ as an acid catalyst in aqueous solution; methanol, ethanol and/or n-propanol as (C₁-C₈)alcohols; and methacrylic acid as complexing agent.

[0114] For the purposes of the invention, the term "substrate" refers to any material susceptible to be spoiled. In an embodiment, the substrate is selected from the group consisting of metal, polymeric substrate, glass, and ceramic. In an embodiment, substrate is metal; preferably the metal is selected from the group consisting of aluminium, aluminium alloy, magnesium, magnesium alloy, carbon steel, stainless steel, as well as these metals and metallic alloys treated with conventional coatings that are commonly applied such as galvanising, electroplating, electroless plating, electrophoretic deposition, anodising, chemical conversion treatments, thermochemical surface treatments, thin films applied by dry techniques (e.g. Plasma Vapour Deposition, Chemical Vapour Deposition, thermal spraying), plasma based surface treatments. In an embodiment, the substrate is glass. In an embodiment, the substrate is a polymeric substrate. In an embodiment, the substrate is ceramic. In an embodiment, the substrate is aluminium alloy.

[0115] The term "glass" refers to a non-crystalline amorphous solid that is often transparent. The term "glass" is often defined in a broader sense, encompassing every solid that possesses a non-crystalline structure at the atomic scale and that exhibits a glass transition when heated towards the liquid state. In any case, the term "glass" encompasses the terms "silica glass" and "oxide glass". In particular, the term "silica glass" refers to any silica-based glass and combination thereof known in the state of the art. And, the term "oxide glass" refers to a glass that comprises oxide selected from the group consisting of Aluminum oxide, Antimony trioxide, Arsenic trioxide, Barium oxide, Bismuth(III) oxide, Boron trioxide, Calcium oxide, Cerium(lll) oxide, Chromium(III) oxide, Gadolinium oxide, Germanium oxide, Iron(III) oxide, Lanthanum oxide, Lead(II) oxide, Lithium oxide, Magnesium oxide, Niobium pentoxide, Phosphorus pentoxide, Potassium oxide, Silicon dioxide, Sodium oxide, Strontium oxide, Sulphur dioxide, Tin dioxide, Titanium dioxide, Zinc oxide, Zirconium dioxide and combination therefore.

[0116] Step 1) of depositing the sol-gel composition over a substrate can be performed using the known techniques of the state of the art for depositing sol-gel coating compositions. In an embodiment, step 1) is performed by depositing the sol-gel layer over the substrate using a technique selected from the group consisting of spin-coating, web-coating, dip-coating, spray-coating, doctor blade coating, flow-coating, roll-coating, printing such as screen-printing, ink-jet printing, flexographic printing, gravure printing, and micro-gravure printing. In an embodiment, the sol-gel coating composition of the invention is deposited over the substrate (step 1) by dipping the substrate in the sol-gel coating composition as defined in the present invention to obtain a coated substrate having one or more of the permanent properties selected from hydrophobicity, oleophobicity and antibacterial activity.

[0117] In an embodiment, step 1) of the process of the invention is performed by dipping the substrate in the sol-gel coating composition as disclosed in the present invention at a deposition rate from 1 cm/min to 40 cm/min.

[0118] In an embodiment, the process of the present invention further comprises a previous step prior to step 1) which comprises conditioning the substrate. The conditioning step of the substrate facilitates the deposition and/or coating steps. Regarding the nature of the substrate, the conditioning step is performed by using the corresponding technics known in the state of the art such as for example degreasing, cleaning, etching and/or blasting the substrate. The appropriate preparation/pre-treatment conditions can readily be determined by those skilled in the art according to the type of substrate being used. In a particular embodiment, when the substrate is an aluminium-based substrate the conditioning steps comprises an alkaline cleaning followed by acidic etching.

[0119] In a particular embodiment, when the substrate is polymer-based substrate the conditioning steps comprises activation of the surface to form free radicals on the surface by means of processes that break covalent bonds between stable C-C bonds, thus offering sites to promote adhesion of coatings. Example of known technics used for performing the conditioning step of the substrate can be, among others, plasma treatment, UV-Ozone treatment, wet-chemical etching.

[0120] As it is mentioned above, the process for preparing the coated substrate of the present invention comprises a curing step 2) after the deposition of the sol-gel coating composition over the substrate. Step 2) of the process of the invention can be performed using the known techniques of the state of the art for curing a coating on a substrate. In an embodiment, step 2) is performed by a technique selected from the group consisting of thermal curing; photochemical curing such as ultraviolet curing and infrared curing; microwave induced curing; other options include latent heat curing when substrate undergoes previous processes generating residual heat. In an embodiment, curing step (step 2) is performed by thermal curing at a temperature from 80 °C to 220 °C for an appropriate period of time; particularly from 0.1 h to 48 h. In an embodiment, curing step (step 2) is performed by thermal curing at a temperature from 80 °C to 200 °C for 30 min to 12 h.

[0121] In an embodiment, the process for preparing the coated substrate of the present invention further comprises adding one or more additives for the preparation of the sol1 or alternatively the sol3 as defined in the present invention. In an embodiment, the additive is selected from the group consisting of a corrosion inhibitor, an ink and a photoinitiator. Examples of appropriate corrosion inhibitors for the present invention include, without limitation, inorganic salts of Cerium, Yttrium, Manganese, Lanthanum, Lithium; organic compounds such as benzotriazole and benzothiazole derivatives, propargyl alcohol, 8-hydroxyquinoline; ceramic or metallic nanoparticles optionally doped with the corrosion inhibitor. Examples of appropriate inks for the present invention include, without limitation, inorganic and organic inks. Examples of organic inks include, without limitation, erythrosine B, calcien, fluoroscein, trypan blue, and brilliant green. Examples of appropriate photoinitiator for the present invention include, without limitation, cationic UV curing photoinitiators such as diaryliodonium or triarylsulfonium salts; and UV radical photoinitiators such as 2-benzyl-2-N,N-dimethylamino-1-(4- morpholino phenyl) butanone, 2,2-dimethoxy-2- phenyl acetophenone, 2-hydroxy-2-methylpropiophenone and 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone.

[0122] The sol-gel coated substrates of the invention may be defined by its preparation process as defined above and therefore, those coated substrates obtainable by the process above is considered the second aspect of the invention. Thus, a coated substrate obtainable by a process of the first aspect of the invention is also part of the invention.

[0123] As it is mentioned above, the coated substrate obtained by the process of the invention comprising the sol-gel coating composition disclosed in the present invention have permanent hydrophobicity, oleophobicity and/or antibacterial activity. Furthermore, the coated substrates are also advantageous because allow having a permanent hydrophobicity, oleophobicity and/or antibacterial activity including a low amount of the functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl and a mixture thereof.

[0124] All the embodiments disclosed above for the steps of the process including the components of the sol-gel composition as well as the experimental conditions of each step of the process also apply for the coated substrates obtainable by the process. The coated substrates of the present invention are specially advantageous to obtain super-smooth surfaces and to prevent or retard adherence of undesirable agents such as substances dissolved in water, oil, grease, soiling, dust, ice, fingerprints, fog, fouling, biofouling or biofilm growth during its life service, as well as facilitate the surface cleaning in case of attachment.

[0125] The second alternative of the first aspect of the invention refers to a process for preparing a sol-gel coated substrate comprising:

1) firstly, depositing a sol-gel coating composition selected from the group consisting of sol3 over the substrate; and

2) secondly, curing the coating obtained in step 1);

wherein the sol3 is a sol-gel coating composition obtainable by a process which comprises:

b) preparing a mixture A comprising:

at least one alkoxide selected from the group consisting of a metal alkoxide, a semimetal alkoxide, an organo-alkoxysilane and a mixture thereof;

at least one acid catalyst in aqueous solution having a pH lower than 5

at least one organic precursor;

at least one polymerization initiator; and

optionally, at least one (C₁-C₈)alcohol;

at a temperature from 15 °C to 90 °C to obtain sol1; and

optionally ageing the resulting mixture sol1 by stirring at a temperature from 15 °C to 90 °C from 24 h to 72 h;

c) preparing a mixture B comprising:

at least one metal alkoxide;

at least one complexing agent;

optionally one or more (C₁-C₈) alcohol; and

optionally at least one acid catalyst in aqueous solution or water having a pH lower than 7;

at a temperature from 15 °C to 30 °C to obtain sol2; optionally ageing the resulting mixture sol2 by stirring at a temperature from 15 °C to 30 °C from 24 h to 72 h; and

d) mixing the sol 1 with the sol 2; optionally adding to the mixture obtained in step d) at least one acid catalyst in aqueous solution or water having a pH lower than 7; and ageing the resulting mixture by stirring at a temperature from 15 °C to 30 °C from 24 h to 72 h;

wherein, the organic precursor is a compound selected from the group consisting of a compound of formula (VI)

, a compound of formula (VII)

and a mixture thereof
wherein:

R₂₇ are independently selected from (C₁-C₆)alkyl;

R₄₀ and R₄₁ are independently selected from the group consisting of H and (C₁-C₆)alkyl;

X₂ is selected from the group consisting of a compound of formula (VIII)

and a compound of formula (IX);

and a mixture thereof;
wherein:

R₄₂ is selected from the group consisting of H and (C₁-C₆)alkyl;

p is an integer from 1 to 8; and

n' is an integer from 1 to 6.

[0126] A coated substrate obtainable by the process of the third aspect of the invention is also part of the invention. All the embodiments disclosed above for the process of the first aspect of the invention, such as the steps of the process, the components of the sol-gel composition as well as the experimental conditions of each step also apply for the process of the third aspect of the invention and for the coated substrates obtainable by this process. These coated substrates are specially advantageous to obtain super-smooth surfaces and to prevent or retard the formation of fouling, biofouling or biofilm growth during its life service, as well as facilitate the surface cleaning in case of attachment.

[0127] Throughout the description and claims the word "comprise" and variations of the word, are not intended to exclude other technical features, additives, components, or steps. Furthermore, the word "comprise" encompasses the case of "consisting of". Additional objects, advantages and features of the invention will become apparent to those skilled in the art upon examination of the description or may be learned by practice of the invention. The following examples and drawings are provided by way of illustration, and they are not intended to be limiting of the present invention. Reference signs related to drawings and placed in parentheses in a claim, are solely for attempting to increase the intelligibility of the claim and shall not be construed as limiting the scope of the claim. Furthermore, the present invention covers all possible combinations of particular and preferred embodiments described herein.

Examples

Abbreviation

[0128] 

TEOS: tetraethylorthosilicate

MAPTMS: [3-(methacryloyloxy)propyl]trimethoxysilane

GPTES: (3-glycidyloxypropyl)triethoxy silane

BPA: bisphenol A

IS: isosorbide

EDGMA: ethylene glycol dimethacrylate

AIBN: azobisisobutyronitrile or 2,2'-azobis(2-methylpropionitrile)

TPOZ: zirconium (IV) n-propoxide

TISP: titanium (IV) isopropoxide

MAAH: methacrylic acid

FAS13: (1H,1H,2H,2H-perfluorooctyl) triethoxy silane (C₈H₄F₁₃)

FAS17: (1H,1H,2H,2H-perfluorodecyl) triethoxy silane (C₁₀H₄F₁₇)

CAS12: n-dodecyltriethoxysilane (C₁₂H₂₅)

QAS: dimethyl octadecyl[3-(trimethoxysilyl) propyl] ammonium chloride

MeOH: methanol

EtOH: ethanol

1-PropOH: 1-propanol

1. Sol-gel coating composition

1.A- Composition

[0129] First alternative composition comprising functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl

SOL1

[0130] Table 1 shows the quantitative components of SOL1 comprising a functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof that intervene in the preparation of the coated substrates of the present invention by the depositing of these SOL1 over the substrate. The amount of the ingredients is expressed in molar ratio. Table 1 also discloses the process used for the preparation of the SOL1.

Table 1A

Ingredients		Sol-gel coating composition (Ex.)
		Process A
Description	Name	Ex.1	Ex.2	Ex.3	Ex. 4
Semi-metal alkoxide	TEOS	1	1	1	1
Organo-alkoxysilane	MAPTMS	1	1	1	-
	GPTES	-	-	-	1
Acid aqueous solution	HNO3 0.01 N	4	4	4	4
(C1-C8)alcohol	EtOH	10	10	10	10
	MeOH	-	-	-	-
Functional organo-alkoxysilane	Type	FAS13	FAS17	FAS17	FAS17
	Amount	0.01	0.01	0.05	0.01

Table 1B

Ingredients		Sol-gel coating composition (Ex.)
		Process B
Description	Name	Ex.5	Ex.6	Ex.7	Ex.8	Ex.9
Semi-metal alkoxide	TEOS	1	1	1	1	1
Organo-alkoxysilane	MAPTMS	1	1	1	1	1
Organic precursor	EDGMA	0.25	0.25	0.25	0.25	0.25
Polymerization precursor	AIBN	0.015	0.015	0.015	0.015	0.015
Acid aqueous solution	HNO3 0.01N	4	4	4	4	4
(C1-C8)alcohol	EtOH	10	10	10	10	7.86
	MeOH	-	-	-	-	2.14
Functional organo-alkoxysilane	Type	FAS13	FAS13	FAS17	FAS17	FAS17: QAS
	Amount	0.01	0.05	0.01	0.05	0.01:0.1

[0131] Table 2 shows the quantitative components of comparative SOL1 which does not comprise a functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof that intervene in the preparation of the comparative coated substrates falling outside of the present invention by the depositing of comparative SOL1 over the substrate. The amount of the ingredients is expressed in molar ratio. Table 2 also discloses the process used for the preparation of the comparative SOL1.

Table 2

Ingredients		Comparative Sol-gel coating composition
		Process A		Process B
Description	Name	Comparative Ex.1	Comparative Ex.2	Comparative Ex.3
Semi-metal alkoxide	TEOS	1	1	1
Organo-alkoxysilane	MAPTMS	1	-	1
	GPTES	-	1	-
Organic precursor	EDGMA	-	-	0.25
Polymerization initiator	AIBN	-	-	0.015
Acid aqueous solution	HNO3 0.01 N	4	4	4
(C1-C8)alcohol	EtOH	10	10	10

SOL3

[0132] Table 3 shows the quantitative components of SOL3 comprising a functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof that intervene in the preparation of the coated substrates of the present invention by the depositing of these SOL3 over the substrate.

[0133] Particularly, Table 3 shows the quantitative components of SOL1 and SOL2. The amount of the ingredients is expressed in molar ratio. Table 3 also discloses the process used for the preparation of the SOL1 and SOL2.

Table 3

Ingredients		Sol-gel coating composition (Ex.)
		Sol	Process C					Process D
Description	Name		10	11	12	13	14	15	16	17
Semi-metal alkoxide	TEOS	1	0.5	0.5	0.5	0.5	0.5	0.125	0.125	0.125
Organo-silicon alkoxide	MAPTM S		1	1	1	1	1	1	1	1
Organic precursor	EDGMA		0.25	0.25	0.25	0.25	0.25	0.25	0.25	0.25
Polymerizatio n initiator	AIBN		0.015	0.015	0.015	0.015	0.015	0.015	0.015	0.015
Acid aqueous solution	HNO3 0.01N		3.5	3.5	3.5	3.5	3.5	1.03	1.08	1.03
(C1-C8)alcohol	EtOH		9.42	9.42	9.42	9.42	9.42	1	1	-
Functional organo-alkoxysilane	Type		FAS13	FAS17	FAS17	FAS17	FAS17: CAS12	FAS17	FAS17: CAS12	FAS17: QAS
	Amount		0.075	0.01	0.05	0.075	0.1:0.1	0.02	0.05: 0.05	0.02:0.05
Metal alkoxide	TPOZ	2	0.5	0.5	0.5	0.5	0.5	0.125	0.125	0.125
Complexing agent	MAAH		0.5	0.5	0.5	0.5	0.5	0.125	0.125	0.125
C1-C0)alcohol	1-PropOH		1.15	1.15	1.15	1.15	1.15	0.3	0.3	0.3
	MeOH		-	-	-	-	-	-	-	1
Acid aqueous solution	HNO3 0.01 N		1	1	1	1	1	1	1	1

Second alternative composition comprising an organic precursor of formula (VII)

[0134] Table 4 shows the quantitative components of SOL3 which comprises an organic precursor of formula (VII) but do not comprises a functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof that intervene in the preparation of the coated substrates of the third aspect of the invention by the depositing of these SOL3 over the substrate. The amount of the ingredients is expressed in molar ratio. Table 4 also discloses the process used for the preparation of the comparative SOL1 and SOL2.

Table 4

Ingredients		Sol-gel coating composition (Ex.)
		Sol	Process C	Process D
Description	Name		Ex.18	Ex.19	Ex. 20
Semi-metal alkoxide	TEOS	SOL1	0.5	0.125	0.125
Organo-alkoxysilane	MAPTMS		1	1	1
Organic precursor	EDGMA		0.25	0.25	0.25
Polymerization initiator	AIBN		0.015	0.015	0.015
Aqueous solution of at least on acid catalyst	HNO3 0.01N		3.5	1.03	1.03
(C1-C8)alcohol	EtOH		9.42	1	1
Metal alkoxide	TPOZ	SOL2	0.5	0.125	-
	TISP		-	-	0.125
Complexing agent	MAAH		0.5	0.125	0.2
C1-C8)alcohol	1-PropOH		1.15	0.3	0.004
Aqueous solution of at least on acid catalyst	HNO3 0.01 N		1	1	1

1.B- Preparation Process

Process A. General procedure for the preparation of Examples 1-4 (SOL1)

[0135] TEOS, organo-alkoxysilane selected from the group consisting of MAPTMS and GPTES and at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl of 42% weight in methanol, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof were mixed in alcohol media, and aqueous solution HNO₃ 0.01 N was added. The resultant solution was stirred during 3 h at 80 °C to obtain SOL1.

[0136] The amount of components for the preparation of SOL1 are those disclosed in the above-mentioned Table 1.

[0137] The comparative Ex.1 and comparative Ex.2 were prepared following the process A using the components and amounts disclosed in Table 2 but without the addition of the functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, or a mixture thereof.

Process B. General procedure for the preparation of Examples 5-9 (SOL1)

Preparation of SOL1

Preparation of the first mixture

[0138] TEOS, MAPTMS and at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl of 42% weight in methanol, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof were mixed in alcohol media, and aqueous solution HNO₃ 0.01 N was added. The resultant solution was stirred during 3 h at 80 °C to obtain a first mixture.

Preparation of the second mixture

[0139] Separately and simultaneously, EGDMA and AIBN were mixed and stirred during 10 min at room temperature.

Combination of the first and the second mixture

[0140] After cooling the first mixture until reaching room temperature, the second mixture was added to the first mixture; and then, the resulting mixture was stirred for 30 min at room temperature to obtain SOL1.

[0141] The amount of components for the preparation of SOL1 are those disclosed in the above-mentioned Table 1.

[0142] The comparative Ex.3 was prepared following the process B using the components and amounts disclosed in Table 2 but without the addition of the functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, or a mixture thereof.

Process C. General procedure for the preparation of Examples 10-14 and 18

Preparation of SOL1

SOL1 was prepared following the Process B.

Preparation of SOL2

[0143] Separately and simultaneously, TPOZ of 70% weight in n-propanol and MAAH were mixed and stirred during for 30 min at room temperature to obtain SOL2.

Preparation of SOL3

[0144] SOL2 was poured in SOL1, and admixed. Then, aqueous HNO₃ 0.01 N was added and stirred during 30 in to form the SOL3.

[0145] The Example 18 of the present invention was prepared following the process C using the components and amounts disclosed in Table 5, particularly the organic precursor EDGMA of formula (VII) but without the addition of one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl of 42% weight in methanol, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof.

Process D. General procedures for the preparation of Examples 15-17 and 19

Preparation of SOL1

Preparation of the first mixture

[0146] MAPTMS was added to EtOH and the aqueous solution HNO₃ 0.01 N was added. The resultant solution was stirred during 30 minutes at room temperature.

[0147] Then, at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl of 42% weight in methanol, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof were added. Then, TEOS was added and finally an aqueous solution HNO₃ 0.01 N was added. The resultant solution was stirred during 1 h at 80°C to obtain a first mixture.

Preparation of the second mixture

[0148] Separately and simultaneously, EGDMA and AIBN were mixed and stirred during 10 min at room temperature.

Combination of the first and the second mixture

[0149] After cooling the first mixture until reaching room temperature, the second mixture was added to the first mixture; and then, the resulting mixture was stirred for 30 min at room temperature to obtain SOL1.

Preparation of SOL2

[0150] Separately and simultaneously, TPOZ of 70% weight in n-propanol or TISP of 97% in isopropanol and MAAH were mixed and stirred during for 30 min at room temperature to obtain SOL2.

Preparation of SOL3

[0151] SOL2 was poured in SOL1 under stirring. Then, aqueous HNO₃ 0.01 N was added and stirred during 30 in to form the SOL3.

[0152] The Example 19 of the present invention was prepared following the process D using the components and amounts disclosed in Table 5, particularly the organic precursor EDGMA of formula (VII) but without the addition of one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl of 42% weight in methanol, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof.

2. Composition of coated substrate of the present invention

2A. Preparation process

- Surface preparation

[0153] Polymeric substrates were degreased with a cloth soaked in acetone.

[0154] Glass substrates were degreased with a cloth soaked in acetone and introduced in ethanol solution under ultrasonication.

[0155] Aluminium alloys were degreased with a cloth soaked in acetone followed by chemical or mechanical pre-treatments.

[0156] Then, the preparation of the surface was performed by i) chemical pre-treatment after acetone decreasing consisting in alkaline degreasing followed by acid etching, in order to activate the surface and improve the adherence with the sol-gel coating, as disclosed below:

Alkaline degreasing consisted of introducing the substrate in a solution of composition: 45 g/L of Turco 4215 NC LT and 2.5 ml/L of Turco 4215 NC LT at 50°C during 15 min.

Acid etching consisted of introducing the substrate in a solution of composition: 120 g/L of Turco SMUT GO NC and 14.4 ml/L HNO3 (>65%) at room temperature during 5 min.

Or alternatively the surface preparation was performed by ii) mechanical pre-treatment after acetone degreasing through shot blasting with two different types of corundum particles the aluminium surface:

Blasting 1: Shot blasting the degreased substrate using white corundum particles being equal to or higher than 50% of them diameter sized from 50 to 56 µm, at 3 bar and at a distance from 7 to 30 cm;

Blasting 2: Shot blasting the degreased substrate using white corundum particles being equal to or higher than 97% of them diameter sized from 425 to 600 µm, at 3 bar and at a distance from 7 to 30 cm;

- Coating deposition and curing

[0157] The degreased, cleaned and pre-treated substrates obtained in the previous step were introduced in the corresponding sol-gel coating composition of the invention or alternatively, in the comparative sol-gel coating composition and then, they were withdrawn at 15 cm/min, followed by a thermal treatment at 150 °C during 2 h.

2.B. Coating compositions of the invention and substrates.

[0158] The composition of the mono-layer coated substrate of the present invention is disclosed in Table 5. Table 6 discloses the sol-gel composition used for each substrate: glass (G), the aluminum alloy 2024-T3 (A), and polyetherimide (P).

Table 5

Coated substrate	Substrate	Coated substrate	Substrate	Coated substrate	Substrate	Sol-gel coating composition	Thickness (µm)
M1G	Glass	M1A	AA2024	-	-	Ex.1	1.3
M2G	Glass	M2A	AA2024	-	-	Ex.2	1.6
M3G	Glass	M3A	AA2024	-	-	Ex.3	1.8
M4G	Glass	M4A	AA2024	-	-	Ex. 4	0.8
M5G	Glass	M5A	AA2024	-	-	Ex.5	1.7
M6G	Glass	M6A	AA2024	-	-	Ex.6	1.7
M7G	Glass	M7A	AA2024	-	-	Ex.7	1.5
M8G	Glass	M8A	AA2024	-	-	Ex.8	1.5
M9G	Glass	M9A	AA2024	M9P	PEI	Ex.9	1
M10G	Glass	M10A	AA2024			Ex.10	1.7
M11G	Glass	M11A	AA2024	-	-	Ex. 11	1.5
M12G	Glass	M12A	AA2024	-	-	Ex.12	1.7
M13G	Glass	M13A	AA2024	-	-	Ex.13	1.8
M14G	Glass	M14A	AA2024	-	-	Ex.14	2.1
M15G	Glass	M15A	AA2024	-	-	Ex.15	5.5
M16G	Glass	M16A	AA2024	-	-	Ex.16	6.5
M17G	Glass	M17A	AA2024	-	-	Ex.17	7.5
M18G	Glass	M18A	AA2024	-	-	Ex.18	1
M19G	Glass	M19A	AA2024	-	-	Ex.19	3

ND: not determined

2.C. Coating comparative compositions and substrates.

[0159] The composition of the comparative coated substrate of the falling outside the present invention is disclosed in Table 6. Table discloses the sol-gel composition used for each substrate glass (G) and aluminum alloy 2024-T3 (A).

Table 6

Coated substrate	Substrate	Coated substrate	Substrate	Sol-gel coating composition	Thickness (µm)
Comp. M1G	Glass	Comp. M1A	AA2024	Comparative Ex.1	1
Comp. M2G	Glass	Comp. M2A	AA2024	Comparative Ex.2	0.5
Comp. M3G	Glass	Comp. M3A	AA2024	Comparative Ex.3	1

ND: not determined

3. Characterization methods

Contact angle

[0160] The contact angle was determined by the static drop method, using Digidrop Contact Angle Meter (GBX Instruments). Ten measurements of the apparent contact angle were taken for water (

) and hexadecane (

) by placing drops of each liquid on the horizontal and flat coating surface and measuring the angle at the liquid-solid-air boundary. θ_c corresponds to the angle formed at the solid-liquid interface as presented in the Figure 1.

Surface free energy (SFE)

[0161] The SFE was determined by Owens-Wendt method, which considers two types of interaction in a solid-liquid interface. In particular, weak dispersive van der Waals forces, called dispersion component, and the stronger hydrogen-bonding forces associated with the polar interactions, as represented in Equation 1.

where θ_c is the contact angle; γ is the surface tension; subscripts sl, sv, and lv refer to the solid-liquid, solid-vapour, and liquid-vapour interfaces, respectively; superscripts d and p refer to dispersive and polar components, respectively.

[0162] For solving equation, the contact angle must be measured using at least two liquids wherein at least one of them must have a polar part > 0. In particular, the SFE has been determined based on the measurements of the contact angle of the surface with water (

;

) and n-hexadecane (

;

).

[0163] The determination of polar and dispersive surface energy components was calculated from slope (

) and y-intercept (

) of the regression line when plotting

versus

using experimental contact angle data as well as polar and dispersive theoretical surface tension values of each of the test liquids. The total surface free energy corresponds to the sum of polar and dispersive components.

Surface roughness

[0164] The roughness of coatings was measured using profilometer Dektak 150 according to ISO 4288 standard. Five 4.8-mm length scans were taken on each sample using a 2-µm radius stylus, 1 mg force and lengthwise resolution of 0.32 µm. Arithmetic average roughness, Ra, was calculated from the central 4 mm of the scan using short and long pass filter cut off of 800 µm. Mean Ra of the five scans for each sample was calculated.

Antimicrobial activity

[0165] The biocide activity was determined under antimicrobial tests conducted according to the ISO 22196:2011 standard: Measurement of antibacterial activity on plastics and other non-porous surfaces. Assessment of colony forming units of Escherichia coli CECT 516 and Staphylococcus aureus CECT 240 were performed at time 0 h and after 24 h of contact.

Adhesion test

[0166] The adherence of the sol-gel coatings of the present invention to the plastic substrate was evaluated by means of cross-cut tape adhesion tests, following the indications of Section 6 in the ISO 2409:2013(E). The test was performed in accordance with ISO 2409:2013(E) using hand-held, multi-blade cutting tool. A lattice pattern with several cuts in each direction was made in the coated substrate. Evaluation and designation of the results is performed according to Sections 7 and 8 in the ISO 2409:2013(E). Dry adherence test was performed on fresh coated PEI.

Corrosion test: Test of Neutral Salt Spray Foq Test (NSST).

[0167] The samples were tested in a C&W SF/1000/CCT corrosion chamber that met the conditions of the ASTM B-117-16 standard. According to Sections 8.1 and 10.1, the salt solution consisted of 5±1 part of NaCl in 95±1 part by mass of deionised water and the temperature in the exposure zone was maintained at 35±2 °C. Aluminium specimens were supported at 6° from the vertical in accordance with aeronautic specifications MIL-DTL-5541F (page 6, 11 July 2006) and MIL-DTL-81706B:2006 (page 11, 2 May 2006). The borders of the specimens were masked using a tape in order to cover the edges.

Cytotoxicity

[0168] The cytotoxicity was determined according to the UNE-EN ISO 10993-5:2009. The sample and reference preparation followed the protocol described in UNE-EN ISO 10993-12:2009. Discs of i) high density polyethylene discs and ii) polyurethane loaded with 0.1% of zinc diethyldithiocarbamate were tested in parallel as negative and positive references, respectively.

[0169] The tested cells were CCL 171 (ATCC) which were prepared in growth medium supplemented with 10% of fetal bovine serum and 1 % of antibiotic penicillin/streptomycin, at 37± 2°C and atmosphere of 5% de CO₂ up to obtain a confluent monolayer.

[0170] After 24 h, different dilutions of the samples and references extracts which were in Eagle's Minimum Essential Medium (EMEM) were prepared and added to the cells. The blank test consisting of only EMEM and 10% of fetal bovine serum was also added to the cells. After 24 h of incubation at 37± 2°C and atmosphere of 5% de CO₂ the qualitative and quantitative assessment of the cultured cells was done. The cell viability was analysed by colorimetric method WST-1.

4. Results

4.A. Homogeneity and stability of the obtained sols

[0171] The sol-gel coating compositions of the present invention consisted in one-phase, homogeneous and totally transparent liquid, with a stable viscosity value at least along one month. Therefore, the sol-gel coating compositions of the present invention were useful to prepare homogeneous and repetitive coatings on several substrates.

4.B. Contact angle and surface free energy of coated substrates

[0172] The contact angle with water and hexadecane and the surface free energy of coated glass and aluminium alloy substrates (chemically pre-treated) of the present invention are disclosed in the Table 7.

Table 7

Coated substrate			SFE (mJ/m2)	Coated substrate			SFE (mJ/m2)
M1G	96.8±2.8	34.5±1.1	24.7	M1A	88.7±1.4	33.1±1.1	27.5
M2G	109.9±1.6	75.2±1.0	12.3	M2A	108.3±0.5	70.0±2.3	13.8
M3G	113.7±0.5	91.8±2.5	8.4	M3A	111.4±0.7	75.1±1.1	12.0
M4G	98.5±1.3	46.0±0.4	21.8	M4A	106.7±0.7	62.5±2.1	15.9
M5G	102.6±1.9	51.6±2.5	19.5	M5A	89.1±0.7	35.8±0.1	26.8
M6G	105.6±0.2	53.0±1.2	18.6	M6A	103.1±1.0	51.4±1.6	19.5
M7G	108.7±1.2	65.1±0.3	14.9	M7A	104.1±0.8	58.4±0.4	17.5
M8G	108.8±0.7	66.2±3.0	14.6	M8A	107.9±0.6	65.1±1.4	15.1
M9G	91.4±0.6	35.6±0.7	26.1	M9A	90.4±2.0	33.4±1.7	26.8
M10G	95.4±1.0	45.2±1.8	22.8	M10A	97.3±2.2	49.6±1.3	21.3
M11G	99.7±1.1	47.2±1.6	21.2	M11A	98.6±0.2	45.0±0.1	22.0
M12G	103.4±0.9	53.7±0.9	18.8	M12A	103.0±0.8	53.2±0.8	19.0
M13G	100.5±1.6	49.5±0.6	20.5	M13A	101.0±0.9	50.4±0.6	20.2
M14G	99.6±2.2	47.6±2.5	21.2	M14A	105.2±1.7	58.9±1.8	17.2
M15G	107.4±1.9	60.8±1.7	16.3	M15A	102.6±1.6	54.7±1.2	18.8
M16G	101.7±0.9	53.1±0.4	19.4	M16A	105.0±0.4	62.6±0.4	16.3
M17G	102.5±1.4	54.7±1.2	18.8	M17A	98.4±0.8	45.0±1.2	22.1
M18G	91.2±7.9	8.9±2.7	29.7	M18A	ND	ND	ND

ND: not determined

[0173] The contact angle with water and hexadecane and the surface free energy of coated glass and aluminium alloy substrates (chemically pre-treated) of the comparative examples of present invention are disclosed in the Table 8.

Table 8

Coated substrate			SFE (mJ/m2)	Coated substrate			SFE (mJ/m2)
Comp. M1G	63.9±0.7	6.5±1.1	42.7	Comp. M1A	74.1±3.4	9.1±2.5	36.6
Comp. M2G	62.9±0.4	5.4±0.8	43.4	Comp. M2A	68.7±0.8	6.7±0.1	39.8
Comp. M3G	68.8±0.4	10.1±0.8	39.6	Comp. M3A	65.3±0.8	10.5±0.5	41.7

4.C. Roughness of pre-treated and coated substrates

[0174] The roughness of the substrate before and after its treatment with the sol-gel coating compositions of the present invention (Ex. 17) are disclosed in the Table 9.

Table 9

Substrate	Pre-treated substrate	Roughness Ra (nm) of pre-treated substrate	Coated substrate	Roughness Ra (nm) of coated substrate
Glass	Acetone degreasing	< 5	M15G	2.4±0.6
AA2024T3	Alkaline and acid pre-treatments	445±75	M15A	50±5
AA2024T3	Blasting 1	555±15	M15A	110±12
AA2024T3	Blasting 2 + Blasting 1	3350±400	M15A	355±40
Glass	Acetone degreasing	< 5	M16G	4.7±0.7
AA2024T3	Alkaline and acid pre-treatments	445±75	M16A	80±20
AA2024T3	Blasting 1	555±15	M16A	120±15
AA2024T3	Blasting 2 + Blasting 1	3350±400	M16A	730±60
Glass	Acetone degreasing	< 5	M17G	20±5
Glass	Acetone degreasing	< 5	M19G	3.0±0.5

[0175] The roughness of the substrate before and after its treatment with the comparative sol-gel coating compositions falling outside of the scope of the present invention (comparative Ex. 1-3) are disclosed in the Table 10.

Table 10

Substrate	Pre-treated substrate	Roughness Ra (nm) of pre-treated substrate	Coated substrate	Roughness Ra (nm) of coated substrate
Glass	Acetone degreasing	< 10	Comp. M1G	70±30
AA2024T3	Alkaline and acid pretreatments	445±75	Comp. M1A	160±40
AA2024T3	Alkaline and acid pretreatments	445±75	Comp. M2A	260±10
Glass	Acetone degreasing	< 10	Comp. M3G	50±10
AA2024T3	Alkaline and acid pretreatments	445±75	Comp. M3A	190±15

ND: not determined

4.D. Antimicrobial activity coated substrates

[0176] The antimicrobial activity of the coated substrates after the treatment of the substrate with the sol-gel coating compositions of the present invention and the comparative sol-gel coating compositions falling outside the scope of the invention are disclosed in the Table 11.

Table 11

Coated substrate	Escherichia coli		Staphylococcus aureus
	CFU t = 0	CFU t = 24 h	CFU t = 0	CFU t = 24 h
Comp. M3G	2.82 × 105	6.7 × 106	2.68 × 105	ND
M9G		6.7		ND
M15G		1.1 × 103		139
M17G		0		383
M19G		0		ND
M20G		ND		3

ND: not determined

4.F. Adherence on plastic substrate

[0177] The adherence on plastic substrate after the treatment of the substrate with the sol-gel coating compositions of the present invention are disclosed in the Table 12.

Table 12

Coated substrate	Dry adherence
M9P	Score 0 (excellent adherence)

4.G. Corrosion protection of AA2024-T3

[0178] The results of the corrosion protection of the sol-gel coating compositions of the present invention deposited on AA2024-T3 after exposure in the Neutral Salt Spray Test (NSST) are shown in Table 13.

Table 13

Tested samples	Naked eye assessment
M15A	No corrosion evidence after 168 h of exposure in NSST

4.H. Cytotoxicity

[0179] The Table 14 shows the results of cell viability (CCL-171) in contact with the sample extract of the highest concentration with respect to the blank test.

Table 14

Coated substrate	Cell viability (%)
M9G	74 ± 3
M17G	112 ± 3
M19G	115 ± 7
M20G	112 ± 2
Comp. M3G	101 ± 4

[0180] According to UNE-EN-ISO 10993-5:2009, a sample is considered cytotoxic when the cell viability for the sample extract of the highest concentration is lower than 70% with respect to the blank test. Therefore, the tested coatings are not considered cytotoxic.

5. Conclusion

[0181] The above-mentioned results clearly show that chemical precursor combination and synthesis conditions which derive in homogeneous, one-phase, transparent and stables sols have been found. In comparison with the sol-gel coating compositions disclosed in the state of the art, the sol-gel coating compositions of the present invention allow obtaining a repellent, omniphobic or multi-repellent coated substrate having hydrophobic, oleophobic and/or biocide properties appropriate for being used in a wide variety of uses such as for example the preparation of antiadhesive, easy-to-clean, antifogging, anti-icing and antifouling surfaces, having a low interfacial energy, low roughness and antibacterial activity also with anticorrosion properties.

[0182] In particular, the specific experimental conditions of the process of the present invention in combination with the reactants used for the preparation are important for attaining stable, homogenous, one-phase sols useful for obtaining repellent, repellent-biocide or omniphobic coated substrates having hydrophobic, oleophobic and/or biocide properties with low roughness.

Citation List

[0183] 

1. ASTM B117-16

2. ISO 22196 2011

3. ISO 2409 2013

4. MIL-DTL-5541F

5. MIL-DTL-81706B

6. UNE-EN ISO-42881998

7. UNE-EN ISO 10993-5:2009.

8. UNE-EN ISO 10993-12:2009

Claims

1. A process for preparing a sol-gel coated substrate comprising:

1) firstly, depositing a sol-gel coating composition selected from the group consisting of sol1 and sol3 over the substrate

2) secondly, curing the coating obtained in step 1);

wherein the sol1 is a sol-gel coating composition obtainable by a process which comprises:

a) preparing a mixture A comprising:

at least one alkoxide selected from the group consisting of a metal alkoxide, a semimetal alkoxide, an organo-alkoxysilane and a mixture thereof;

at least one acid catalyst in aqueous solution having a pH lower than 5;

optionally, at least one (C₁-C₈)alcohol;

optionally, at least one organic precursor;

optionally, at least one polymerization initiator; and

optionally, at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, fluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof;

at a temperature from 15 °C to 90 °C for an appropriate period of time to obtain sol1; and

optionally ageing the resulting mixture sol1 by stirring at a temperature from 15 °C to 30 °C for a period of time from 24 h to 72 h to obtain sol1;

and

wherein the sol3 is a sol-gel coating composition obtainable by a process which comprises:

b) preparing a mixture A comprising:

at least one alkoxide selected from the group consisting of a metal alkoxide, a semimetal alkoxide, an organo-alkoxysilane and a mixture thereof;

at least one acid catalyst in aqueous solution having a pH lower than 5

optionally, at least one organic precursor;

optionally, at least one polymerization initiator;

optionally, at least one (C₁-C₈)alcohol; and

optionally, at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-Cao)alkyl silyl, and a mixture thereof;

at a temperature from 15 °C to 90 °C to obtain sol1; and

optionally ageing the resulting mixture sol1 by stirring at a temperature from 15 °C to 30 °C from 24 h to 72 h;

c) preparing a mixture B comprising:

at least one metal alkoxide;

at least one complexing agent;

optionally, at least one acid catalyst in aqueous solution or water having a pH lower than 7;

optionally, one or more (C₁-C₈) alcohol; and

optionally, at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-Cao)alkyl silyl, and a mixture thereof,

at a temperature from 15 °C to 30 °C for an appropriate period of time to obtain sol2; and optionally ageing the resulting mixture sol2 by stirring at a temperature from 15 °C to 30 °C from 24 h to 72 h; and

d) mixing the sol 1 with the sol 2; optionally adding to the mixture obtained in step d) at least one acid catalyst in aqueous solution or water having a pH lower than 7; and ageing the resulting mixture by stirring at a temperature from 15 °C to 30 °C from 24 h to 72 h;

with the proviso that the sol-gel coating composition of step 1) comprises at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof;

or alternatively,

a process for preparing a sol-gel coated substrate comprising:

1) firstly, depositing a sol-gel coating composition selected from the group consisting of sol3 over the substrate; and

2) secondly, curing the coating obtained in step 1);

wherein the sol3 is a sol-gel coating composition obtainable by a process which comprises:

b) preparing a mixture A comprising:

at least one alkoxide selected from the group consisting of a metal alkoxide, a semimetal alkoxide, an organo-alkoxysilane and a mixture thereof;

at least one acid catalyst in aqueous solution having a pH lower than 5;

at least one organic precursor;

at least one polymerization initiator; and

optionally, at least one (C₁-C₈)alcohol;

at a temperature from 15 °C to 90 °C to obtain sol1; and

optionally ageing the resulting mixture sol1 by stirring at a temperature from 15 °C to 90 °C from 24 h to 72 h;

c) preparing a mixture B comprising:

at least one metal alkoxide;

at least one complexing agent;

optionally one or more (C₁-C₈) alcohol; and

optionally at least one acid catalyst in aqueous solution or water having a pH lower than 7;

at a temperature from 15 °C to 30 °C to obtain sol2; optionally ageing the resulting mixture sol2 by stirring at a temperature from 15 °C to 30 °C from 24 h to 72 h; and

d) mixing the sol 1 with the sol 2; optionally adding to the mixture obtained in step d) at least one acid catalyst in aqueous solution or water having a pH lower than 7; and ageing the resulting mixture by stirring at a temperature from 15 °C to 30 °C from 24 h to 72 h;

wherein, the organic precursor is a compound selected from the group consisting of a compound of formula (VI)

, a compound of formula (VII)

and a mixture thereof
wherein:

R₂₇ are independently selected from (C₁-C₆)alkyl;

R₄₀ and R₄₁ are independently selected from the group consisting of H and (C₁-C₆)alkyl;

X₂ is selected from the group consisting of a compound of formula (VIII)

and a compound of formula (IX);

and a mixture thereof;
wherein:

R₄₂ is selected from the group consisting of H and (C₁-C₆)alkyl;

p is an integer from 1 to 8; and

n' is an integer from 1 to 6.

2. The process according to claim 1, which comprises depositing a sol1 sol-gel coating composition obtainable by a process which comprises:

a1) preparing a mixture A1 comprising:

at least one semimetal alkoxide;

at least one organo-alkoxysilane;

at least one acid catalyst in aqueous solution having a pH lower than 5; and

optionally at least one (C₁-C₈)alcohol; and

optionally at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-Cao)alkyl silyl, and a mixture thereof;
by:

a1') the semimetal alkoxide; the organo-alkoxysilane; optionally at least one (C₁-C₈)alcohol; mixing an aqueous solution of at least one acid catalyst in aqueous solution having a pH lower than 5; and at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof at a temperature from 15 °C to 90 °C for an appropriate period of time to obtain the sol1-1; and

a1") optionally ageing the resulting mixture by stirring at a temperature from 15 °C to 30 °C from 24 h to 72 h to obtain the ageing sol1-1;

with the proviso that the sol1-1 comprises at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof;

or alternatively;

a2) preparing a mixture A2 comprising:

at least one semimetal alkoxide;

at least one organo-alkoxysilane;

at least one acid catalyst in aqueous solution having a pH lower than 5

at least one organic precursor;

optionally, at least one polymerization initiator;

at least one (C₁-C₈)alcohol; and

at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof;
by:
a2') preparing a first mixture comprising the semimetal alkoxide; the organo-alkoxysilane; at least one (C₁-C₈)alcohol; an aqueous solution of at least one acid catalyst in aqueous solution having a pH lower than 5; and optionally at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-Cao)alkyl silyl, and a mixture thereof at a temperature from 15 °C to 90 °C;

a2") preparing a second mixture comprising an aqueous solution of at least one acid catalyst in aqueous solution having a pH lower than 5; at least one organic precursor; optionally, at least one polymerization initiator or a mixture thereof; at least one (C₁-C₈) alcohol; and optionally at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof at a temperature from 15 °C to 90 °C;

a2‴) mixing the second mixture and the first mixture at a temperature from 15°C to 30°C; and stirring the resulting mixture at a temperature from 15 °C to 90 °C for an appropriate period of time to obtain the sol1-2; and

a2ʺʺ) optionally ageing the resulting mixture by stirring at a temperature from 15 °C to 30 °C from 24 h to 72 h to obtain the ageing sol1-2;

with the proviso that the sol1-2 comprises at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof;

or alternatively;

a3) preparing a mixture A3 comprising:

at least one semimetal alkoxide;

at least one organo-alkoxysilane;

at least one acid catalyst in aqueous solution having a pH lower than 5

at least one organic precursor;

optionally, at least one polymerization initiator;

optionally, at least one (C₁-C₈)alcohol; and

optionally, at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-Cao)alkyl silyl, and a mixture thereof;
by:

a3') preparing a first mixture comprising the organo-alkoxysilane; optionally at least one (C₁-C₈)alcohol; an aqueous solution of at least one acid catalyst in aqueous solution having a pH lower than 5; and optionally at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof at a temperature from 15 °C to 90 °C;

a3") optionally, adding at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl at a temperature from 15 °C to 30 °C;

a3‴) adding at least one semimetal alkoxide at a temperature from 15 °C to 30 °C;

a3ʺʺ^v) preparing a second mixture comprising at least one organic precursor; optionally, at least one polymerization initiator; optionally, an aqueous solution of at least one acid catalyst in aqueous solution having a pH lower than 5; or a mixture thereof; and optionally at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof at a temperature from 15 °C to 30 °C;

a3^v) mixing the second mixture with the mixture obtained in step a3‴) at a temperature from 15 °C to 30 °C to obtain the sol1-3; and

a3^vi) optionally ageing the resulting mixture by stirring at a temperature from 15 °C to 30 °C from 24 h to 72 h to obtain the ageing sol1-3;

with the proviso that the sol1-3 comprises at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof;

or alternatively,

a4) preparing a mixture A4 comprising:

at least one organo-alkoxysilane;

at least one acid catalyst in aqueous solution having a pH lower than 5

at least one organic precursor;

optionally, at least one polymerization initiator; and

optionally, at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-Cao)alkyl silyl, and a mixture thereof;
by:

a4') preparing a first mixture comprising the organo-alkoxysilane; an aqueous solution of at least one acid catalyst in aqueous solution having a pH lower than 5; and optionally at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof at a temperature from 15 °C to 90 °C;

a4") optionally, adding at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof at a temperature from 15 °C to 30 °C;; and stirring the resulting mixture at a temperature from 15 °C to 90 °C; and

a4‴) preparing a second mixture comprising at least one organic precursor; optionally, at least one polymerization initiator or a mixture thereof; optionally, an aqueous solution of at least one acid catalyst in aqueous solution having a pH lower than 5; and optionally at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof at a temperature from 15 °C to 90 °C;

a4ʺʺ) mixing the second mixture with the mixture obtained in step a4‴) at a temperature from 15 °C to 30 °C to obtain the sol1-4; and

a4^v) optionally ageing the resulting mixture by stirring at a temperature from 15 °C to 30 °C from 24 h to 72 h to obtain the ageing sol1-4;

with the proviso that the sol1-4 comprises at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof;

or alternatively,

a5) preparing a mixture A5 comprising:

at least one semimetal alkoxide;

at least one organo-alkoxysilane;

at least one acid catalyst in aqueous solution having a pH lower than 5

at least one organic precursor;

optionally, at least one polymerization initiator; and

optionally, at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-Cao)alkyl silyl, and a mixture thereof;
by:

a5') preparing a first mixture comprising the organo-alkoxysilane; an aqueous solution of at least one acid catalyst in aqueous solution having a pH lower than 5; and optionally at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof at a temperature from 15 °C to 90 °C;

a5") optionally, adding at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof at a temperature from 15 °C to 30 °C;

a5‴) adding at least one semimetal alkoxide at a temperature from 15 °C to 30 °C;

a5ʺʺ) mixing the resulting mixture at a temperature from 15 °C to 90 °C; and stirring the resulting mixture at a temperature from 15 °C to 90 °C; and

a5^v) preparing a second mixture comprising an aqueous solution of at least at least one organic precursor;

optionally, at least one polymerization initiator or a mixture thereof; optionally, one acid catalyst in aqueous solution having a pH lower than 5;and optionally at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof at a temperature from 15 °C to 30 °C;

a5^vi) mixing the second mixture with the mixture obtained in step a5‴) at a temperature from 15 °C to 30 °C to obtain the sol1-5; and

a5^vii) optionally ageing the resulting mixture by stirring at a temperature from 15 °C to 30 °C from 24 h to 72 h to obtain the ageing sol1-5; and

with the proviso that the sol1-5 comprises at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof.

3. The process according to any of the claims 1 or 2, which comprises depositing a sol3 sol-gel coating composition obtainable by a process which comprises:

b) preparing a sol1 selected from the group consisting of sol1-1, sol1-2, sol1-3, sol1-4, sol1-5, ageing sol1-1, ageing sol1-2, ageing sol1-3, ageing sol1-4 and ageing sol1-5 as defined in claim 2;

c) preparing a sol2 by preparing a mixture B by mixing at least one metal alkoxide; at least one complexing agent; optionally one or more (C₁-C₈) alcohol; optionally, at least one acid catalyst in aqueous solution or water having a pH lower than 7; and optionally at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof, at a temperature from 15 °C to 90 °C to obtain sol2; optionally ageing the resulting mixture sol2 by stirring at a temperature from 15 °C to 30 °C from 24 h to 72 h to obtain ageing sol2; and

d) mixing the sol 1 with the sol 2, optionally adding to the mixture obtained in step d) at least one acid catalyst in aqueous solution or water having a pH lower than 7; and ageing the resulting mixture by stirring at a temperature from 15 °C to 30 °C from 24 h to 72 h to obtain sol3 selected from the group consisting of sol3-1, sol3-2, sol3-3, sol3-4, sol3-5, ageing sol3-1, ageing sol3-2, ageing sol3-3, ageing sol3-4 and ageing sol3-5, respectively.

4. The process according to any of the claims 1-3, which comprises depositing a sol-gel coating composition selected from the group consisting of sol1 and sol3 over the substrate, wherein: the sol 1 comprises the organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof.

5. The process according to claim 4, wherein:

when the sol1 is a sol1-1, then sol1-1 is obtainable by a process wherein step a1') mixing the semimetal alkoxide; the organo-alkoxysilane; optionally at least one (C₁-C₈)alcohol; an aqueous solution of at least one acid catalyst in aqueous solution having a pH lower than 5; and at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof at a temperature from 15 °C to 90 °C for an appropriate period of time to obtain the sol1-1; and a1") optionally ageing the resulting mixture by stirring at a temperature from 15 °C to 30 °C from 24 h to 72 h; or alternatively,

when the sol1 is a sol1-2, then sol1-2 is obtainable by a process wherein step a2') preparing a first mixture comprising the semimetal alkoxide; the organo-alkoxysilane; at least one (C₁-C₈)alcohol; an aqueous solution of at least one acid catalyst in aqueous solution having a pH lower than 5; and optionally at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof at a temperature from 15 °C to 90 °C; a2") preparing a second mixture comprising an aqueous solution of at least one acid catalyst in aqueous solution having a pH lower than 5; at least one organic precursor; optionally, at least one polymerization initiator or a mixture thereof; at least one (C₁-C₈) alcohol; and optionally at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-Cao)alkyl silyl, and a mixture thereof at a temperature from 15 °C to 90 °C; a2‴) mixing the second mixture and the first mixture at a temperature from 15°C to 30°C; and stirring the resulting mixture at a temperature from 15 °C to 90 °C for an appropriate period of time to obtain the sol1-2; and a2ʺʺ) optionally ageing the resulting mixture by stirring at a temperature from 15 °C to 30 °C from 24 h to 72 h; or alternatively,

when the sol1 is a sol1-3, then sol1-3 is obtainable by a process wherein step a3') preparing a first mixture comprising the organo-alkoxysilane; optionally at least one (C₁-C₈)alcohol; an aqueous solution of at least one acid catalyst in aqueous solution having a pH lower than 5; and optionally at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof at a temperature from 15 °C to 90 °C;

a3") optionally, adding at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl at a temperature from 15 °C to 30 °C;

a3‴) adding at least one semimetal alkoxide at a temperature from 15 °C to 30 °C;

a3ʺʺ^v) preparing a second mixture comprising at least one organic precursor; optionally, at least one polymerization initiator; optionally, an aqueous solution of at least one acid catalyst in aqueous solution having a pH lower than 5; or a mixture thereof; and optionally at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof at a temperature from 15 °C to 30 °C;

a3^v) mixing the second mixture with the mixture obtained in step a3‴) at a temperature from 15 °C to 30 °C to obtain the sol1-3; and

a3^vi) optionally ageing the resulting mixture by stirring at a temperature from 15 °C to 30 °C from 24 h to 72 h;

or alternatively,

when the sol1 is a sol1-4, then sol1-4 is obtainable by a process wherein step a4') preparing a first mixture comprising the organo-alkoxysilane; an aqueous solution of at least one acid catalyst in aqueous solution having a pH lower than 5; and optionally at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof at a temperature from 15 °C to 90 °C; a4") optionally, adding at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof at a temperature from 15 °C to 30 °C; and stirring the resulting mixture at a temperature from 15 °C to 90 °C; and

a4‴) preparing a second mixture comprising at least one organic precursor; optionally, at least one polymerization initiator or a mixture thereof; optionally, an aqueous solution of at least one acid catalyst in aqueous solution having a pH lower than 5; and optionally at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof at a temperature from 15 °C to 30 °C;

a4ʺʺ) mixing the second mixture with the mixture obtained in step a4‴) and stirring at a temperature from 15 °C to 90 °C to obtain the sol1-4; and

a4^v) optionally ageing the resulting mixture by stirring at a temperature from 15 °C to 30 °C from 24 h to 72 h; or alternatively,

when the sol1 is a sol1-5, then sol1-5 is obtainable by a process wherein step a5') preparing a first mixture comprising the organo-alkoxysilane; an aqueous solution of at least one acid catalyst in aqueous solution having a pH lower than 5; and optionally at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof at a temperature from 15 °C to 90 °C;

a5") optionally, adding at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof at a temperature from 15 °C to 30 °C;

a5‴) adding at least one semimetal alkoxide at a temperature from 15 °C to 30 °C;

a5ʺʺ) mixing the resulting mixture at a temperature from 15 °C to 90 °C; and stirring the resulting mixture at a temperature from 15 °C to 90 °C; and

a5^v) preparing a second mixture comprising at least one organic precursor; optionally, at least one polymerization initiator or a mixture thereof; optionally, one acid catalyst in aqueous solution having a pH lower than 5; and optionally at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, and a mixture thereof at a temperature from 15 °C to 30 °C;

a5^vi) mixing the second mixture with the mixture obtained in step a5‴) at a temperature from 15 °C to 90 °C to obtain the sol1-5; and

a5^vii) optionally ageing the resulting mixture by stirring at a temperature from 15 °C to 30 °C from 24 h to 72 h.

6. The process according to any of the claims 1-5, wherein, the at least one functional organo-alkoxysilane or organo-halosilane having a functional organosilyl moiety selected from the group consisting of:quaternary ammonium silyl, polyfluoro-(C₁-C₂₀)alkyl silyl, (C₁-C₄₀)alkyl silyl, is selected from the group consisting of: one or more quaternary ammonium alkoxysilanes; one or more quaternary ammonium halosilanes; one or more polyfluoro-(C₁-C₂₀)alkyl alkoxysilanes; one or more polyfluoro-(C₁-C₂₀) halosilanes; one or more (C₁-C₄₀)alkyl alkoxysilanes; one or more (C₁-C₄₀)alkyl halosilanes; a mixture of one or more quaternary ammonium alkoxysilane and one or more polyfluoro-(C₁-C₂₀)alkyl alkoxysilanes; a mixture of one or more quaternary ammonium alkoxysilane and one or more polyfluoro-(C₁-C₂₀) halosilanes; a mixture of one or more quaternary ammonium halosilanes and one or more polyfluoro-(C₁-C₂₀)alkyl alkoxysilanes; a mixture of one or more polyfluoro-(C₁-C₂₀)alkyl alkoxysilanes and one or more (C₁-C₄₀)alkyl alkoxysilane; a mixture of one or more polyfluoro-(C₁-C₂₀)alkyl alkoxysilanes and one or more (C₁-C₄₀)alkyl halosilanes; a mixture of one or more polyfluoro-(C₁-C₂₀) halosilanes and one or more (C₁-C₄₀)alkyl alkoxysilane; a mixture of one or more polyfluoro-(C₁-C₂₀) halosilanes and one or more (C₁-C₄₀)alkyl halosilanes; a mixture of one or more quaternary ammonium alkoxysilane and one or more (C₁-C₄₀)alkyl alkoxysilane; a mixture of one or more quaternary ammonium alkoxysilane and one or more (C₁-C₄₀)alkyl halosilanes; a mixture of one or more quaternary ammonium halosilanes and one or more (C₁-C₄₀)alkyl alkoxysilane; a mixture of one or more quaternary ammonium alkoxysilane, one or more polyfluoro-(C₁-C₂₀)alkyl alkoxysilane and one or more (C₁-C₄₀)alkyl alkoxysilane; a mixture of one or more quaternary ammonium alkoxysilane, one or more polyfluoro-(C₁-C₂₀) halosilanes and one or more (C₁-C₄₀)alkyl alkoxysilane; a mixture of one or more quaternary ammonium alkoxysilane, one or more polyfluoro-(C₁-C₂₀)alkyl alkoxysilane and one or more (C₁-C₄₀)alkyl halosilanes; a mixture of one or more quaternary ammonium alkoxysilane, one or more polyfluoro-(C₁-C₂₀) halosilanes and one or more (C₁-C₄₀)alkyl halosilanes; and a mixture of one or more quaternary ammonium halosilanes, one or more polyfluoro-(C₁-C₂₀)alkyl silane and one or more (C₁-C₄₀)alkyl alkoxysilane

7. The process according to any of the claims 1-6, wherein:

the at least one quaternary ammonium silane is a compound of formula (XIV)

wherein each X is an halogen independently selected from the group consisting of chlorine, bromine and iodine; each R⁵⁷ is independently a (C₁-C₆)alkyl, particularly selected form methyl, ethyl, n-propyl, isopropyl and butyl; R⁵⁸ is a (C₁-C₂₀)alkylene, R⁵⁹ is (C₁-C₂₀)alkyl, R⁶⁰ is (C₁-C₂₀)alkyl and R⁶¹ is (C₁-C₂₀)alkyl;

the at least one polyfluoro-(C₁-C₂₀)alkyl alkoxysilane or a polyfluoro-(C₁-C₂₀)alkyl halosilane is selected from the group consisting of a compound of formula (XV)

        [CF₃-(CF₂)_v(CH₂)_u]w-Si(OR⁴⁷)_y     (XV)

wherein each R⁴⁷ is independently (C₁-C₂₀)alkyl; u and v are independently an integer from 0 to 20, w is an integer selected from 1, 2 and 3; y is an integer selected from 1, 2, and 3; and the sum of w+y is 4;

and a compound of formula (XVI)

        [CF₃-(CF₂)_v(CH₂)_u]_w-SiX_y     (XVI)

wherein each X is independently an halogen independently selected from the group consisting of chlorine, bromine and iodine; u and v are independently an integer from 0 to 20, w is an integer selected from 1, 2 and 3; y is an integer selected from 1, 2, and 3; and the sum of w+y is 4;

the at least one (C₁-C₄₀)alkyl alkoxysilanes or a (C₁-C₄₀)alkyl halosilanes is selected from the group consisting of a compound of formula (XVII)

        (R⁵¹)_aSi(OR⁵²)_b     (XVII)

wherein each R⁵¹ is independently a (C₁-C₄₀)alkyl; each R⁵² is independently a (C₁-C₂₀)alkyl; w is an integer selected from 1, 2 and 3; y is an integer selected from 1, 2, and 3; and the sum of w+y is 4;

and a compound of formula (XVII)

        [CH₃-(CH₂)_u]_w-SiX_y     (XVIII)

wherein each X is an halogen independently selected from the group consisting of chlorine, bromine and iodine; u is an integer from 0 to 40, w is an integer selected from 1, 2 and 3; y is an integer selected from 1, 2, and 3; and the sum of w+y is 4.

8. The process according to any of the claims 1-7, wherein the organo-alkoxysilane is selected from the group consisting of:

a compound of formula (I);

        [R⁴]_s-Si(OR¹)_t(OR²)(OR³)     (I)

a compound of formula (II);

        [R⁸-(CH₂)_m]-Si(OR⁵)_qR⁶_r     (II)

a compound of formula (III)

        (⁹RO)(¹⁰RO)(¹¹RO)Si-X₁-Si(OR¹²)(OR¹³)(OR¹⁴)     (III)

a mixture of at least a compound of formula (I) wherein R⁴ is (C₁-C₄)alkenyl and at least a compound of formula (I) wherein R⁴ is (C₂-C₂₀)alkyl-CH=CH-;

a mixture of at least a compound of formula (I) and at least a compound of formula (II);

a mixture of at least a compound of formula (I) and at least a compound of formula (III);

a mixture of at least a compound of formula (II) and at least a compound of formula (III);

wherein:

each one of R¹, R² and R³ are independently a substituted or un-substituted (C₁-C₁₄)alkyl;

R⁴ is selected from the group consisting of a substituted or un-substituted (C₂-C₁₄)alkenyl, (C₅-C₆)aryl, (C₂-C₁₄)alkynyl; and (C₂-C₂₀)alkyl-CH=CH-;

R⁵, R⁶, R⁹, R¹⁰, R¹¹, R¹², R¹³ and R¹⁴ are independently selected from the group consisting of a substituted or

un-substituted (C₁-C₁₄)alkyl, (C₅-C₆)aryl, (C₂-C₁₄)alkenyl, and (C₂-C₁₄)alkyl-CH=CH-;

R⁸ is selected from the group consisting of H, -SH, substituted or un-substituted (C₁-C₁₂)alkyl, substituted or

un-substituted (C₅-C₆)aryl, -(CF₂)_b-CF₃, -NR¹⁵R¹⁶, a compound of formula (IV)

and a compound of formula (V)

R¹⁵ and R¹⁶ are independently selected from the group consisting of H, substituted or un-substituted (C₁-C₁₂)alkyl, -C0, and substituted or un-substituted (C₅-C₆)aryl;

R¹⁷ is selected from the group consisting of H and substituted or un-substituted (C₁-C₁₂)alkyl;

X₁ is selected from the group consisting of substituted or unsubstituted -(C₁-C₁₂)alkylene-, -(C₁-C₁₂)alkylene-NH-(C₁-C₁₂)alkylene-, and -(C₁-C₁₂)alkylene-(S)_n-(C₁-C₁₂)alkylene-;

m is an integer from 0 to 20;

n is an integer from 1 to 4;

q is an integer from 2 to 3;

r is an integer from 0 to 1;

s is an integer from 1 to 2;

t is an integer from 0 to 1;

the sum of q + r is 3;

the sum of s + t is 2; and

b is an integer from 0 to 12.

9. The process according to any of the claims 1-8, wherein the organic precursor is selected from the group consisting of a compound of formula (VI)

, a compound of formula (VII)

and a mixture thereof
wherein:

R₂₇ are independently selected from (C₁-C₆)alkyl;

R₄₀ and R₄₁ are independently selected from the group consisting of H and (C₁-C₆)alkyl;

X₂ is selected from the group consisting of a compound of formula (VIII)

and a compound of formula (IX);

and a mixture thereof;
wherein:

R₄₂ is selected from the group consisting of H and (C₁-C₆)alkyl;

p is an integer from 1 to 8; and

n' is an integer from 1 to 6.

10. The process according to claim 9, wherein the organic precursor is a compound of formula (VII)

wherein:

R₄₀ and R₄₁ are independently selected from the group consisting of H and (C₁-C₆)alkyl;

X₂ is selected from the group consisting of a compound of formula (VIII)

and a compound of formula (IX);

and a mixture thereof;
wherein:

R₄₂ is selected from the group consisting of H and (C₁-C₆)alkyl;

p is an integer from 1 to 8; and

n' is an integer from 1 to 6.

11. The process according to any of the claims 1-10, wherein: the acid catalyst in aqueous solution is an inorganic acid independently selected from the group consisting of H₂SO₄, HCl, HNO₃, and a mixture thereof; the (C₁-C₈)alcohol is independently selected from the group consisting of methanol, ethanol, butanol, n-propanol, isopropanol, and a mixture thereof; and the complexing agent is selected from the group consisting of acetyl acetone, methacrylic acid, acetic acid, isobutyric acid, bipyridine, and a mixture thereof; particularly, the acid is HNO₃, the (C₁-C₈)alcohol is ethanol and the complexing agent is methacrylic acid.

12. The process according to any of the claims 1-11, wherein the metal alkoxide and the semimetal alkoxide are independently a compound of formula (XIII)

        (OR⁴³)(OR⁴⁴)(OR⁴⁵)(OR⁴⁶)Z     (XIII)

wherein:

each one of R⁴³, R⁴⁴, R⁴⁵ and R⁴⁶ are independently selected from the group consisting of substituted or un-substituted (C₁-C₁₄)alkyl, (C₅-C₆)aryl, (C₂-C₁₄)alkenyl and (C₂-C₁₄)alkynyl group; and

Z is selected from the group consisting of the metal and semimetal atoms.

13. A coated substrate comprising a sol-gel layer obtainable by the process as defined in any of the claims 1-12.

Ansprüche

1. Ein Verfahren zur Herstellung eines Sol-Gel-beschichteten Substrats, umfassend:

1) zuerst Abscheiden einer Sol-Gel-Beschichtungszusammensetzung, die aus der Gruppe ausgewählt ist, die aus Sol1 und Sol3 besteht, über dem Substrat

2) zweitens Härten der in Schritt 1) erhaltenen Beschichtung;

wobei das Sol1 eine Sol-Gel-Beschichtungszusammensetzung ist, die durch ein Verfahren erhalten werden kann, das Folgendes umfasst:

a) Herstellen einer Mischung A, umfassend:

mindestens ein Alkoxid, das ausgewählt ist aus der Gruppe bestehend aus einem Metallalkoxid, einem Halbmetallalkoxid, einem Organoalkoxysilan und einer Mischung davon;

mindestens einen sauren Katalysator in wässriger Lösung mit einem pH-Wert von weniger als 5;

wahlweise mindestens einen (C₁-C₈)-Alkohol;

wahlweise mindestens einen organischen Vorläufer;

wahlweise mindestens einen Polymerisationsinitiator; und

wahlweise mindestens ein funktionelles Organoalkoxysilan oder Organohalogensilan mit einem funktionellen Organosilylrest, der ausgewählt ist aus der Gruppe bestehend aus quartärem Ammoniumsilyl, Fluor-(C₁-C₂₀)alkylsilyl, (C₁-C₄₀)-Alkylsilyl und einer Mischung davon;

bei einer Temperatur von 15 °C bis 90 °C für einen angemessenen Zeitraum, um Sol1 zu erhalten; und wahlweise Altern der resultierenden Mischung Sol1 durch Rühren bei einer Temperatur von 15 °C bis 30 °C für einen Zeitraum von 24 h bis 72 h, um Sol1 zu erhalten;
und

wobei das Sol3 eine Sol-Gel-Beschichtungszusammensetzung ist, die durch ein Verfahren erhalten werden kann, das Folgendes umfasst:

b) Herstellen einer Mischung A, umfassend:

mindestens ein Alkoxid, das ausgewählt ist aus der Gruppe bestehend aus einem Metallalkoxid, einem Halbmetallalkoxid, einem Organoalkoxysilan und einer Mischung davon;

mindestens einen sauren Katalysator in wässriger Lösung mit einem pH-Wert von weniger als 5;

wahlweise mindestens einen organischen Vorläufer;

wahlweise mindestens einen Polymerisationsinitiator;

wahlweise mindestens einen (C₁-C₈)-Alkohol; und

wahlweise mindestens ein funktionelles Organoalkoxysilan oder Organohalogensilan mit einem funktionellen Organosilylrest, der ausgewählt ist aus der Gruppe bestehend aus quartärem Ammoniumsilyl, Polyfluor-(C₁-C₂₀)alkylsilyl, (C₁-C₄₀)-Alkylsilyl und einer Mischung davon;

bei einer Temperatur von 15 °C bis 90 °C, um Sol1 zu erhalten; und

wahlweise Altern der resultierenden Mischung Sol1 durch Rühren bei einer Temperatur von 15 °C bis 30 °C von 24 h bis 72 h;

c) Herstellen einer Mischung B, umfassend:

mindestens ein Metallalkoxid;

mindestens einen Komplexbildner;

wahlweise mindestens einen Säurekatalysator in wässriger Lösung oder Wasser mit einem pH-Wert von weniger als 7;

wahlweise einen oder mehrere (C₁-C₈)-Alkohol(e); und

wahlweise mindestens ein funktionelles Organoalkoxysilan oder Organohalogensilan mit einem funktionellen Organosilylrest, der ausgewählt ist aus der Gruppe bestehend aus quartärem Ammoniumsilyl, Polyfluor-(C₁-C₂₀)alkylsilyl, (C₁-C₄₀)-Alkylsilyl und einer Mischung davon;

bei einer Temperatur von 15 °C bis 30 °C für einen angemessenen Zeitraum, um Sol2 zu erhalten; und wahlweise Altern der resultierenden Mischung Sol2 durch Rühren bei einer Temperatur von 15 °C bis 30 °C von 24 h bis 72 h; und

d) Mischen des Sols 1 mit dem Sol 2; wahlweise Zugabe von mindestens einem sauren Katalysator in wässriger Lösung oder Wasser mit einem pH-Wert von weniger als 7 zu der in Schritt d) erhaltenen Mischung; und Altern der resultierenden Mischung durch Rühren bei einer Temperatur von 15 °C bis 30 °C von 24 h bis 72 h;

mit der Maßgabe, dass die Sol-Gel-Beschichtungszusammensetzung von Schritt 1) mindestens ein funktionelles Organoalkoxysilan oder Organohalogensilan mit einem funktionellen Organosilylrest umfasst, der aus der Gruppe ausgewählt ist, die aus quartärem Ammoniumsilyl, Polyfluor-(C₁-C₂₀)-alkylsilyl, (C₁-C₄₀)-Alkylsilyl und einer Mischung davon besteht;

oder ersatzweise,

ein Verfahren zur Herstellung eines Sol-Gel-beschichteten Substrats, umfassend:

1) zuerst Abscheiden einer Sol-Gel-Beschichtungszusammensetzung, die aus der Gruppe ausgewählt ist, die aus Sol3 besteht, über dem Substrat; und

2) zweitens Härten der in Schritt 1) erhaltenen Beschichtung;

wobei das Sol3 eine Sol-Gel-Beschichtungszusammensetzung ist, die durch ein Verfahren erhalten werden kann, das Folgendes umfasst:

b) Herstellen einer Mischung A, umfassend:

mindestens ein Alkoxid, das ausgewählt ist aus der Gruppe bestehend aus einem Metallalkoxid, einem Halbmetallalkoxid, einem Organoalkoxysilan und einer Mischung davon;

mindestens einen sauren Katalysator in wässriger Lösung mit einem pH-Wert von weniger als 5;

mindestens einen organischen Vorläufer;

mindestens einen Polymerisationsinitiator; und

wahlweise mindestens einen (C₁-C₈)-Alkohol;

bei einer Temperatur von 15 °C bis 90 °C, um Sol1 zu erhalten; und

wahlweise Altern der resultierenden Mischung Sol1 durch Rühren bei einer Temperatur von 15 °C bis 90 °C von 24 h bis 72 h;

c) Herstellen einer Mischung B, umfassend:

mindestens ein Metallalkoxid;

mindestens einen Komplexbildner;

wahlweise einen oder mehrere (C₁-C₈)-Alkohol(e); und

wahlweise mindestens einen Säurekatalysator in wässriger Lösung oder Wasser mit einem pH-Wert von weniger als 7;

bei einer Temperatur von 15 °C bis 30 °C, um Sol2 zu erhalten; wahlweise Altern der resultierenden Mischung Sol2 durch Rühren bei einer Temperatur von 15 °C bis 30 °C von 24 h bis 72 h; und

d) Mischen des Sols 1 mit dem Sol 2; wahlweise Zugabe von mindestens einem sauren Katalysator in wässriger Lösung oder Wasser mit einem pH-Wert von weniger als 7 zu der in Schritt d) erhaltenen Mischung; und Altern der resultierenden Mischung durch Rühren bei einer Temperatur von 15 °C bis 30 °C von 24 h bis 72 h;

wobei der organische Vorläufer eine Verbindung ist, die ausgewählt ist aus der Gruppe bestehend aus einer Verbindung der Formel (VI)

eine Verbindung der Formel (VII)

und einer Mischung davon wobei:

R₂₇ unabhängig voneinander ausgewählt sind aus (C₁-C₆)-Alkyl;

R₄₀ und R₄₁ unabhängig voneinander aus der Gruppe ausgewählt sind, die aus H und (C₁-C₆)-Alkyl besteht;

X₂ ausgewählt ist aus der Gruppe bestehend aus einer Verbindung der Formel (VIII)

und eine Verbindung der Formel (IX);

und einer Mischung davon;
wobei:

R₄₂ ausgewählt ist aus der Gruppe bestehend aus H und (C₁-C₆)-Alkyl;

p eine ganze Zahl von 1 bis 8 ist; und

n' eine ganze Zahl von 1 bis 6 ist.

2. Das Verfahren nach Anspruch 1, welches das Abscheiden von einer Sol1 Sol-Gel-Beschichtungszusammensetzung umfasst, welche durch ein Verfahren erhalten werden kann, welches Folgendes umfasst:

a1) Herstellen einer Mischung A1, umfassend:

mindestens ein Halbmetallalkoxid;

mindestens ein Organoalkoxysilan;

mindestens einen Säurekatalysator in wässriger Lösung mit einem pH-Wert von weniger als 5; und wahlweise mindestens einen (C₁-C₈)-Alkohol; und

wahlweise mindestens ein funktionelles Organoalkoxysilan oder Organohalogensilan mit einem funktionellen Organosilylrest, der ausgewählt ist aus der Gruppe bestehend aus quartärem Ammoniumsilyl, Polyfluor-(C₁-C₂₀)alkylsilyl, (C₁-C₄₀)-Alkylsilyl und einer Mischung davon;
durch:

a1') das Halbmetallalkoxid; das Organoalkoxysilan; wahlweise mindestens einen (C₁-C₈)-Alkohol; Mischen einer wässrigen Lösung von mindestens einem sauren Katalysator in wässriger Lösung mit einem pH-Wert von weniger als 5; und mindestens einem funktionellen Organoalkoxysilan oder Organohalogensilan mit einem funktionellen Organosilylrest, der ausgewählt ist aus der Gruppe bestehend aus quartärem Ammoniumsilyl, Polyfluor-(C₁-C₂₀)alkylsilyl, (C₁-C₄₀)-Alkylsilyl und einer Mischung davon, bei einer Temperatur von 15 °C bis 90 °C für einen angemessenen Zeitraum, um das Sol1-1 zu erhalten; und

a1") wahlweise Altern der resultierenden Mischung durch Rühren bei einer Temperatur von 15 °C bis 30 °C von 24 h bis 72 h, um das alternde Sol1-1 zu erhalten;

mit die Maßgabe, dass das Sol1-1 mindestens ein funktionelles Organoalkoxysilan oder Organohalogensilan mit einem funktionellen Organosilylrest umfasst, der ausgewählt ist aus der Gruppe bestehend aus quartärem Ammoniumsilyl, Polyfluor-(C₁-C₂₀)alkylsilyl, (C₁-C₄₀)-Alkylsilyl und einer Mischung davon;
oder ersatzweise;

a2) Herstellen einer Mischung A2, umfassend:

mindestens ein Halbmetallalkoxid;

mindestens ein Organoalkoxysilan;

mindestens einen sauren Katalysator in wässriger Lösung mit einem pH-Wert von weniger als 5;

mindestens einen organischen Vorläufer;

wahlweise mindestens einen Polymerisationsinitiator;

mindestens einen (C₁-C₈)-Alkohol; und

wahlweise mindestens ein funktionelles Organoalkoxysilan oder Organohalogensilan mit einem funktionellen Organosilylrest, der ausgewählt ist aus der Gruppe bestehend aus quartärem Ammoniumsilyl, Polyfluor-(C₁-C₂₀)alkylsilyl, (C₁-C₄₀)-Alkylsilyl und einer Mischung davon;
durch:

a2') Herstellen einer ersten Mischung, die das Halbmetallalkoxid; das Organoalkoxysilan; mindestens einen (C₁-C₈)-Alkohol; eine wässrige Lösung von mindestens einem sauren Katalysator in wässriger Lösung mit einem pH-Wert von weniger als 5; und wahlweise mindestens ein funktionelles Organoalkoxysilan oder Organohalogensilan mit einem funktionellen Organosilylrest, der ausgewählt ist aus der Gruppe bestehend aus quartärem Ammoniumsilyl, Polyfluor-(C₁-C₂₀)-alkylsilyl, (C₁-C₄₀)-Alkylsilyl und einer Mischung davon, bei einer Temperatur von 15 °C bis 90 °C, umfasst;

a2") Herstellen einer zweiten Mischung, die eine wässrige Lösung von mindestens einem sauren Katalysator in wässriger Lösung mit einem pH-Wert von weniger als 5; mindestens einen organischen Vorläufer; wahlweise mindestens einen Polymerisationsinitiator oder eine Mischung davon; mindestens einen (C₁-C₈)-Alkohol; und wahlweise mindestens ein funktionelles Organoalkoxysilan oder Organohalogensilan mit einem funktionellen Organosilylrest, der aus der Gruppe ausgewählt ist, die aus quartärem Ammoniumsilyl, Polyfluor-(C₁-C₂₀)-alkylsilyl, (C₁-C₄₀)-Alkylsilyl und einer Mischung davon besteht, bei einer Temperatur von 15 °C bis 90 °C, umfasst;

a2‴) Mischen der zweiten Mischung und der ersten Mischung bei einer Temperatur von 15 °C bis 30 °C; und Rühren der resultierenden Mischung bei einer Temperatur von 15 °C bis 90 °C für einen angemessenen Zeitraum, um das Sol1-2 zu erhalten; und

a2ʺʺ) wahlweise Altern der resultierenden Mischung durch Rühren bei einer Temperatur von 15 °C bis 30 °C von 24 h bis 72 h, um das alternde Sol1-2 zu erhalten;

Mit die Maßgabe, dass das Sol1-2 mindestens ein funktionelles Organoalkoxysilan oder Organohalogensilan mit einem funktionellen Organosilylrest umfasst, der ausgewählt ist aus der Gruppe bestehend aus quartärem Ammoniumsilyl, Polyfluor-(C₁-C₂₀)alkylsilyl, (C₁-C₄₀)-Alkylsilyl und einer Mischung davon;

oder ersatzweise;

a3) Herstellen einer Mischung A3, umfassend:

mindestens ein Halbmetallalkoxid;

mindestens ein Organoalkoxysilan;

mindestens einen sauren Katalysator in wässriger Lösung mit einem pH-Wert von weniger als 5;

mindestens einen organischen Vorläufer;

wahlweise mindestens einen Polymerisationsinitiator;

wahlweise mindestens einen (C₁-C₈)-Alkohol; und

wahlweise mindestens ein funktionelles Organoalkoxysilan oder Organohalogensilan mit einem funktionellen Organosilylrest, der ausgewählt ist aus der Gruppe bestehend aus quartärem Ammoniumsilyl, Polyfluor-(C₁-C₂₀)alkylsilyl, (C₁-C₄₀)-Alkylsilyl und einer Mischung davon;

durch:

a3') Herstellen von einer ersten Mischung umfassend das Organoalkoxysilan; wahlweise mindestens einen (C₁-C₈)Alkohol; eine wässrige Lösung von mindestens einem sauren Katalysator in wässriger Lösung mit einem pH-Wert von weniger als 5; und wahlweise mindestens ein funktionelles Organoalkoxysilan oder Organohalogensilan mit einem funktionellen Organosilylrest, der ausgewählt ist aus der Gruppe bestehend aus quartärem Ammoniumsilyl, Polyfluor-(C₁-C₂₀)alkylsilyl, (C₁-C₄₀)-Alkylsilyl und einer Mischung davon bei einer Temperatur von 15 °C bis 90 °C;

a3") wahlweise, Zugabe von mindestens einem funktionellen Organoalkoxysilan oder Organohalogensilan mit einem funktionellen Organosilylrest, der ausgewählt ist aus der Gruppe bestehend aus quartärem Ammoniumsilyl, Polyfluor-(C₁-C₂₀)alkylsilyl, (C₁-C₄₀)-Alkylsilyl bei einer Temperatur von 15 °C bis 30 °C;

a3‴) Zugeben von mindestens einem Halbmetallalkoxid bei einer Temperatur von 15 °C bis 30 °C;

a3ʺʺ^v) Herstellen von einer zweiten Mischung, die mindestens einen organischen Vorläufer; wahlweise mindestens einen Polymerisationsinitiator; wahlweise eine wässrige Lösung von mindestens einem sauren Katalysator in wässriger Lösung mit einem pH-Wert von weniger als 5; oder eine Mischung davon; und wahlweise mindestens ein funktionelles Organoalkoxysilan oder Organohalogensilan mit einem funktionellen Organosilylrest, der aus der Gruppe ausgewählt ist, die aus quartärem Ammoniumsilyl, Polyfluor-(C₁-C₂₀)-alkylsilyl, (C₁-C₄₀) Alkylsilyl und einer Mischung davon besteht, bei einer Temperatur von 15 °C bis 30 °C, umfasst;

a3^v) Mischen der zweiten Mischung mit der in Schritt a3‴) erhaltenen Mischung bei einer Temperatur von 15 °C bis 30 °C, um das Sol1-3 zu erhalten; und

a3^vi) wahlweise Altern der resultierenden Mischung durch Rühren bei einer Temperatur von 15 °C bis 30 °C von 24 h bis 72 h, um das alternde Sol1-3 zu erhalten;

mit die Maßgabe, dass das Sol1-3 mindestens ein funktionelles Organoalkoxysilan oder Organohalogensilan mit einem funktionellen Organosilylrest umfasst, der ausgewählt ist aus der Gruppe bestehend aus quartärem Ammoniumsilyl, Polyfluor-(C₁-C₂₀)alkylsilyl, (C₁-C₄₀)-Alkylsilyl und einer Mischung davon;

oder ersatzweise,

a4) Herstellen einer Mischung A4, umfassend:

mindestens ein Organoalkoxysilan;

mindestens einen sauren Katalysator in wässriger Lösung mit einem pH-Wert von weniger als 5;

mindestens einen organischen Vorläufer;

wahlweise mindestens einen Polymerisationsinitiator; und

wahlweise mindestens ein funktionelles Organoalkoxysilan oder Organohalogensilan mit einem funktionellen Organosilylrest, der ausgewählt ist aus der Gruppe bestehend aus quartärem Ammoniumsilyl, Polyfluor-(C₁-C₂₀)alkylsilyl, (C₁-C₄₀)-Alkylsilyl und einer Mischung davon;
durch:

a4') Herstellen einer ersten Mischung umfassend das Organoalkoxysilan; eine wässrige Lösung von mindestens einem sauren Katalysator in wässriger Lösung mit einem pH-Wert von weniger als 5; und wahlweise mindestens ein funktionelles Organoalkoxysilan oder Organohalogensilan mit einem funktionellen Organosilylrest, der ausgewählt ist aus der Gruppe bestehend aus quartärem Ammoniumsilyl, Polyfluor-(C₁-C₂₀)alkylsilyl, (C₁-C₄₀)-Alkylsilyl und einer Mischung davon bei einer Temperatur von 15 °C bis 90 °C;

a4") wahlweise, Hinzufügen von mindestens einem funktionellen Organoalkoxysilan oder Organohalogensilan mit einem funktionellen Organosilylrest, der ausgewählt ist aus der Gruppe bestehend aus quartärem Ammoniumsilyl, Polyfluor-(C₁-C₂₀)alkylsilyl, (C₁-C₄₀)-Alkylsilyl und einer Mischung davon, bei einer Temperatur von 15 °C bis 30 °C; und Rühren der resultierenden Mischung bei einer Temperatur von 15 °C bis 90 °C; und

a4‴) Herstellen von einer zweiten Mischung, die mindestens einen organischen Vorläufer; wahlweise mindestens einen Polymerisationsinitiator oder eine Mischung davon; wahlweise eine wässrige Lösung von mindestens einem sauren Katalysator in wässriger Lösung mit einem pH-Wert von weniger als 5; und wahlweise mindestens ein funktionelles Organoalkoxysilan oder Organohalogensilan mit einem funktionellen Organosilylrest, der aus der Gruppe ausgewählt ist, die aus quartärem Ammoniumsilyl, Polyfluor-(C₁-C₂₀)-alkylsilyl, (C₁-C₄₀)-Alkylsilyl und einer Mischung davon besteht, bei einer Temperatur von 15 °C bis 90 °C, umfasst;

a4ʺʺ) Mischen der zweiten Mischung mit der in Schritt a4‴) erhaltenen Mischung bei einer Temperatur von 15 °C bis 30 °C, um das Sol1-4 zu erhalten; und

a4^v) wahlweise Altern der resultierenden Mischung durch Rühren bei einer Temperatur von 15 °C bis 30 °C von 24 h bis 72 h, um das alternde Sol1-4 zu erhalten;

mit die Maßgabe, dass das Sol1-4 mindestens ein funktionelles Organoalkoxysilan oder Organohalogensilan mit einem funktionellen Organosilylrest umfasst, der ausgewählt ist aus der Gruppe bestehend aus quartärem Ammoniumsilyl, Polyfluor-(C₁-C₂₀)alkylsilyl, (C₁-C₄₀)-Alkylsilyl und einer Mischung davon;

oder ersatzweise,

a5) Herstellen einer Mischung A5, umfassend:

mindestens ein Halbmetallalkoxid;

mindestens ein Organoalkoxysilan;

mindestens einen sauren Katalysator in wässriger Lösung mit einem pH-Wert von weniger als 5;

mindestens einen organischen Vorläufer;

wahlweise mindestens einen Polymerisationsinitiator; und

wahlweise mindestens ein funktionelles Organoalkoxysilan oder Organohalogensilan mit einem funktionellen Organosilylrest, der ausgewählt ist aus der Gruppe bestehend aus quartärem Ammoniumsilyl, Polyfluor-(C₁-C₂₀)alkylsilyl, (C₁-C₄₀)-Alkylsilyl und einer Mischung davon;
durch:

a5') Herstellen einer ersten Mischung umfassend das Organoalkoxysilan; eine wässrige Lösung von mindestens einem sauren Katalysator in wässriger Lösung mit einem pH-Wert von weniger als 5; und wahlweise mindestens ein funktionelles Organoalkoxysilan oder Organohalogensilan mit einem funktionellen Organosilylrest, der ausgewählt ist aus der Gruppe bestehend aus quartärem Ammoniumsilyl, Polyfluor-(C₁-C₂₀)alkylsilyl, (C₁-C₄₀)-Alkylsilyl und einer Mischung davon bei einer Temperatur von 15 °C bis 90 °C;

a5") wahlweise, Zugabe von mindestens einem funktionellen Organoalkoxysilan oder Organohalogensilan mit einem funktionellen Organosilylrest, der ausgewählt ist aus der Gruppe bestehend aus quartärem Ammoniumsilyl, Polyfluor-(C₁-C₂₀)alkylsilyl, (C₁-C₄₀)-Alkylsilyl und einer Mischung davon bei einer Temperatur von 15 °C bis 30 °C;

a5‴) Zugeben von mindestens einem Halbmetallalkoxid bei einer Temperatur von 15 °C bis 30 °C;

a5ʺʺ) Mischen der resultierenden Mischung bei einer Temperatur von 15 °C bis 90 °C; und Rühren der resultierenden Mischung bei einer Temperatur von 15 °C bis 90 °C; und

a5^v) Herstellen einer zweiten Mischung, die eine wässrige Lösung von mindestens einem organischen Vorläufer; wahlweise mindestens einen Polymerisationsinitiator oder eine Mischung davon; wahlweise einen sauren Katalysator in wässriger Lösung mit einem pH-Wert von weniger als 5; und wahlweise mindestens ein funktionelles Organoalkoxysilan oder Organohalogensilan mit einem funktionellen Organosilylrest, der aus der Gruppe ausgewählt ist, die aus quartärem Ammoniumsilyl, Polyfluor-(C₁-C₂₀)-alkylsilyl, (C₁-C₄₀)-Alkylsilyl und einer Mischung davon besteht, bei einer Temperatur von 15 °C bis 30 °C, umfasst;

a5^vi) Mischen der zweiten Mischung mit der in Schritt a5‴) erhaltenen Mischung bei einer Temperatur von 15 °C bis 30 °C, um das Sol1-5 zu erhalten; und

a5^vii) wahlweise Altern der resultierenden Mischung durch Rühren bei einer Temperatur von 15 °C bis 30 °C von 24 h bis 72 h, um das alternde Sol1-5 zu erhalten; und

mit die Maßgabe, dass das Sol1-5 mindestens ein funktionelles Organoalkoxysilan oder Organohalogensilan mit einem funktionellen Organosilylrest umfasst, der ausgewählt ist aus der Gruppe bestehend aus quartärem Ammoniumsilyl, Polyfluor-(C₁-C₂₀)alkylsilyl, (C₁-C₄₀)-Alkylsilyl und einer Mischung davon.

3. Das Verfahren nach einem der Ansprüche 1 oder 2, welches das Abscheiden von einer Sol3 Sol-Gel-Beschichtungszusammensetzung umfasst, welche durch ein Verfahren erhalten werden kann, welches Folgendes umfasst:

b) Herstellen eines Sol1 ausgewählt aus der Gruppe bestehend aus Sol1-1, Sol1-2, Sol1-3, Sol1-4, Sol1-5, alterndem Sol1-1, alterndem Sol1-2, alterndem Sol1-3, alterndem Sol1-4 und alterndem Sol1-5 wie in Anspruch 2 definiert;

c) Herstellen eines Sol2 durch Herstellen einer Mischung B durch Mischen von mindestens einem Metallalkoxid; mindestens einem Komplexbildner; wahlweise einem oder mehreren (C₁-C₈)-Alkoholen; wahlweise mindestens einem sauren Katalysator in wässriger Lösung oder Wasser mit einem pH-Wert von weniger als 7; und wahlweise mindestens einem funktionellen Organoalkoxysilan oder Organohalogensilan mit einem funktionellen Organosilylrest, der aus der Gruppe ausgewählt ist, die aus quartärem Ammoniumsilyl, Polyfluor-(C₁-C₂₀)-alkylsilyl, (C₁-C₄₀)-Alkylsilyl und einer Mischung davon besteht, bei einer Temperatur von 15 °C bis 90 °C, um Sol2 zu erhalten; wahlweise Altern der resultierenden Mischung Sol2 durch Rühren bei einer Temperatur von 15 °C bis 30 °C von 24 h bis 72 h, um das alternde Sol2 zu erhalten; und

d) Mischen des Sols 1 mit dem Sol 2, wahlweise Zugeben von mindestens einem sauren Katalysator in wässriger Lösung oder Wasser mit einem pH-Wert von weniger als 7 zu der in Schritt d) erhaltenen Mischung; und Altern der resultierenden Mischung durch Rühren bei einer Temperatur von 15 °C bis 30 °C von 24 h bis 72 h, um das Sol3 zu erhalten, das aus der Gruppe ausgewählt ist, die aus Sol3-1, Sol3-1, Sol3-2, Sol3-3, Sol3-4, Sol3-5, alterndem Sol3-1, alterndem Sol3-2, alterndem Sol3-3, alterndem Sol3-4 bzw. alterndem Sol3-5 besteht.

4. Das Verfahren nach einem der Ansprüche 1 bis 3, welches das Abscheiden von einer Sol-Gel-Beschichtungszusammensetzung, die aus der Gruppe ausgewählt ist, die aus Sol1 und Sol3 besteht, über dem Substrat umfasst, wobei: das Sol 1 das Organoalkoxysilan oder Organohalogensilan mit einem funktionellen Organosilylrest, der aus der Gruppe ausgewählt ist, die aus quartärem Ammoniumsilyl, Polyfluor-(C₁-C₂₀)-alkylsilyl, (C₁-C₄₀)-Alkylsilyl und einer Mischung davon besteht, umfasst.

5. Das Verfahren nach Anspruch 4, wobei:

Wenn das Sol1 ein Sol1-1 ist, dann kann das Sol1-1 durch ein Verfahren erhalten werden, bei dem Schritt a1') das Halbmetallalkoxid; das Organoalkoxysilan; wahlweise mindestens ein (C₁-C₈)-Alkohol; eine wässrige Lösung von mindestens einem sauren Katalysator in wässriger Lösung mit einem pH-Wert von weniger als 5; und mindestens ein funktionelles Organoalkoxysilan oder Organohalogensilan mit einem funktionellen Organosilylrest, der ausgewählt ist aus der Gruppe bestehend aus quartärem Ammoniumsilyl, Polyfluor-(C₁-C₂₀)alkylsilyl, (C₁-C₄₀)-Alkylsilyl und einer Mischung davon bei einer Temperatur von 15 °C bis 90 °C für einen angemessenen Zeitraum zum Erhalten des Sol1-1 gemischt werden; und a1") wahlweise Altern der resultierenden Mischung durch Rühren bei einer Temperatur von 15 °C bis 30 °C von 24 h bis 72 h; oder ersatzweise,

Wenn das Sol1 ein Sol-2 ist, dann kann das Sol1-2 durch ein Verfahren erhalten werden, bei dem Schritt a2') eine erste Mischung hergestellt wird, die das Halbmetallalkoxid; das Organoalkoxysilan; mindestens einen (C₁-C₈)Alkohol; eine wässrige Lösung von mindestens einem sauren Katalysator in wässriger Lösung mit einem pH-Wert von weniger als 5; und wahlweise mindestens ein funktionelles Organoalkoxysilan oder Organohalogensilan mit einem funktionellen Organosilylrest, ausgewählt aus der Gruppe bestehend aus quartärem Ammoniumsilyl, Polyfluor-(C₁-C₂₀)alkylsilyl, (C₁-C₄₀)Alkylsilyl und eine Mischung davon bei einer Temperatur von 15 °C bis 90 °C, umfasst; a2") Herstellen von einer zweiten Mischung, die eine wässrige Lösung von mindestens einem sauren Katalysator in wässriger Lösung mit einem pH-Wert von weniger als 5; mindestens einen organischen Vorläufer; wahlweise mindestens einen Polymerisationsinitiator oder eine Mischung davon; mindestens einen (C₁-C₈) -Alkohol; und wahlweise mindestens ein funktionelles Organoalkoxysilan oder Organohalogensilan mit einem funktionellen Organosilylrest, der ausgewählt ist aus der Gruppe bestehend aus quartärem Ammoniumsilyl, Polyfluor-(C₁-C₂₀)alkylsilyl, (C₁-C₄₀)-Alkylsilyl und eine Mischung davon bei einer Temperatur von 15 °C bis 90 °C; a2‴) Mischen der zweiten Mischung und der ersten Mischung bei einer Temperatur von 15°C bis 30°C; und Rühren der resultierenden Mischung bei einer Temperatur von 15 °C bis 90 °C für einen angemessenen Zeitraum, um das Sol1-2 zu erhalten; und a2ʺʺ) wahlweise Altern der resultierenden Mischung durch Rühren bei einer Temperatur von 15 °C bis 30 °C von 24 h bis 72 h; oder ersatzweise,

Wenn das Sol1 ein Sol1-3 ist, dann kann das Sol1-3 durch ein Verfahren erhalten werden, bei dem Schritt a3') eine erste Mischung hergestellt wird, die das Organoalkoxysilan; wahlweise mindestens einen (C₁-C₈)-Alkohol; eine wässrige Lösung von mindestens einem sauren Katalysator in wässriger Lösung mit einem pH-Wert von weniger als 5; und wahlweise mindestens ein funktionelles Organoalkoxysilan oder Organohalogensilan mit einem funktionellen Organosilylrest, der aus der Gruppe ausgewählt ist, die aus quartärem Ammoniumsilyl, Polyfluor-(C₁-C₂₀)alkylsilyl, (C₁-C₄₀)-Alkylsilyl und einer Mischung davon besteht, bei einer Temperatur von 15 °C bis 90 °C umfasst;

a3") wahlweise, Zugabe von mindestens einem funktionellen Organoalkoxysilan oder Organohalogensilan mit einem funktionellen Organosilylrest, der ausgewählt ist aus der Gruppe bestehend aus quartärem Ammoniumsilyl, Polyfluor-(C₁-C₂₀)alkylsilyl, (C₁-C₄₀)-Alkylsilyl bei einer Temperatur von 15 °C bis 30 °C;

a3‴) Zugeben von mindestens einem Halbmetallalkoxid bei einer Temperatur von 15 °C bis 30 °C;

a3ʺʺ^v) Herstellen von einer zweiten Mischung, die mindestens einen organischen Vorläufer; wahlweise mindestens einen Polymerisationsinitiator; wahlweise eine wässrige Lösung von mindestens einem sauren Katalysator in wässriger Lösung mit einem pH-Wert von weniger als 5; oder eine Mischung davon; und wahlweise mindestens ein funktionelles Organoalkoxysilan oder Organohalogensilan mit einem funktionellen Organosilylrest, der aus der Gruppe ausgewählt ist, die aus quartärem Ammoniumsilyl, Polyfluor-(C₁-C₂₀)-alkylsilyl, (C₁-C₄₀)-Alkylsilyl und einer Mischung davon besteht, bei einer Temperatur von 15 °C bis 30 °C, umfasst;

a3^v) Mischen der zweiten Mischung mit der in Schritt a3‴) erhaltenen Mischung bei einer Temperatur von 15 °C bis 30 °C, um das Sol1-3 zu erhalten; und

a3^vi) wahlweise Altern der resultierenden Mischung durch Rühren bei einer Temperatur von 15 °C bis 30 °C von 24 h bis 72 h; oder ersatzweise,

Wenn das Sol1 ein Sol1-4 ist, dann kann das Sol1-4 durch ein Verfahren erhalten werden, bei dem Schritt a4') eine erste Mischung hergestellt wird, die das Organoalkoxysilan; eine wässrige Lösung von mindestens einem sauren Katalysator in wässriger Lösung mit einem pH-Wert von weniger als 5; und wahlweise mindestens ein funktionelles Organoalkoxysilan oder Organohalogensilan mit einem funktionellen Organosilylrest, der ausgewählt ist aus der Gruppe bestehend aus quartärem Ammoniumsilyl, Polyfluor-(C₁-C₂₀)alkylsilyl, (C₁-C₄₀)-Alkylsilyl und einer Mischung davon, bei einer Temperatur von 15 °C bis 90 °C umfasst;

a4") wahlweise, Hinzufügen von mindestens einem funktionellen Organoalkoxysilan oder Organohalogensilan mit einem funktionellen Organosilylrest, der ausgewählt ist aus der Gruppe bestehend aus quartärem Ammoniumsilyl, Polyfluor-(C₁-C₂₀)alkylsilyl, (C₁-C₄₀)-Alkylsilyl und einer Mischung davon, bei einer Temperatur von 15 °C bis 30 °C; und Rühren der resultierenden Mischung bei einer Temperatur von 15 °C bis 90 °C; und

a4‴) Herstellen von einer zweiten Mischung, die mindestens einen organischen Vorläufer; wahlweise mindestens einen Polymerisationsinitiator oder eine Mischung davon; wahlweise eine wässrige Lösung von mindestens einem sauren Katalysator in wässriger Lösung mit einem pH-Wert von weniger als 5; und wahlweise mindestens ein funktionelles Organoalkoxysilan oder Organohalogensilan mit einem funktionellen Organosilylrest, der aus der Gruppe ausgewählt ist, die aus quartärem Ammoniumsilyl, Polyfluor-(C₁-C₂₀)-alkylsilyl, (C₁-C₄₀)-Alkylsilyl und einer Mischung davon besteht, bei einer Temperatur von 15 °C bis 30 °C, umfasst;

a4ʺʺ) Mischen der zweiten Mischung mit der in Schritt a4‴) erhaltenen Mischung und Rühren bei einer Temperatur von 15 °C bis 90 °C, um das Sol1-4 zu erhalten; und

a4^v) wahlweises Altern der resultierenden Mischung durch Rühren bei einer Temperatur von 15 °C bis 30 °C von 24 h bis 72 h; oder ersatzweise,

Wenn das Sol1 ein Sol1-5 ist, dann kann das Sol1-5 durch ein Verfahren erhalten werden, bei dem Schritt a5') eine erste Mischung hergestellt wird, die das Organoalkoxysilan; eine wässrige Lösung von mindestens einem sauren Katalysator in wässriger Lösung mit einem pH-Wert von weniger als 5; und wahlweise mindestens ein funktionelles Organoalkoxysilan oder Organohalogensilan mit einem funktionellen Organosilylrest, der ausgewählt ist aus der Gruppe bestehend aus quartärem Ammoniumsilyl, Polyfluor-(C₁-C₂₀)alkylsilyl, (C₁-C₄₀)-Alkylsilyl und einer Mischung davon, bei einer Temperatur von 15 °C bis 90 °C umfasst; a5") wahlweise, Zugabe von mindestens einem funktionellen Organoalkoxysilan oder Organohalogensilan mit einem funktionellen Organosilylrest, der ausgewählt ist aus der Gruppe bestehend aus quartärem Ammoniumsilyl, Polyfluor-(C₁-C₂₀)alkylsilyl, (C₁-C₄₀)-Alkylsilyl und einer Mischung davon bei einer Temperatur von 15 °C bis 30 °C;

a5‴) Zugeben von mindestens einem Halbmetallalkoxid bei einer Temperatur von 15 °C bis 30 °C;

a5ʺʺ) Mischen der resultierenden Mischung bei einer Temperatur von 15 °C bis 90 °C; und Rühren der resultierenden Mischung bei einer Temperatur von 15 °C bis 90 °C; und

a5^v) Herstellen von einer zweiten Mischung, die mindestens einen organischen Vorläufer; wahlweise mindestens einen Polymerisationsinitiator oder eine Mischung davon; wahlweise einen sauren Katalysator in wässriger Lösung mit einem pH-Wert von weniger als 5; und wahlweise mindestens ein funktionelles Organoalkoxysilan oder Organohalogensilan mit einem funktionellen Organosilylrest, der aus der Gruppe ausgewählt ist, die aus quartärem Ammoniumsilyl, Polyfluor-(C₁-C₂₀)alkylsilyl, (C₁-C₄₀)-Alkylsilyl und einer Mischung davon besteht, bei einer Temperatur von 15 °C bis 30 °C umfasst;

a5^vi) Mischen der zweiten Mischung mit der in Schritt a5‴) erhaltenen Mischung bei einer Temperatur von 15 °C bis 90 °C, um das Sol1-5 zu erhalten; und

a5^vii) wahlweise Altern der resultierenden Mischung durch Rühren bei einer Temperatur von 15 °C bis 30 °C von 24 h bis 72 h.

6. Das Verfahren nach einem der Ansprüche 1 bis 5, wobei das mindestens eine funktionelle Organoalkoxysilan oder Organohalogensilan mit einem funktionellen Organosilylrest ausgewählt aus der Gruppe bestehend aus: quartärem Ammoniumsilyl, Polyfluor-(C₁-C₂₀)alkylsilyl, (C₁-C₄₀)-Alkylsilyl, ausgewählt ist aus der Gruppe bestehend aus: einem oder mehreren quartären Ammoniumalkoxysilanen; einem oder mehreren quartären Ammoniumhalogensilanen; einem oder mehreren Polyfluor-(C₁-C₂₀)-Alkylalkoxysilanen; einem oder mehreren Polyfluor-(C₁-C₂₀)-Halogensilanen; einem oder mehreren (C₁-C₄₀)-Alkylalkoxysilanen; einem oder mehreren (C₁-C₄₀)-Alkylhalogensilane; einer Mischung aus einem oder mehreren quartären Ammoniumalkoxysilanen und einem oder mehreren Polyfluor-(C₁-C₂₀)-Alkylalkoxysilanen; einer Mischung aus einem oder mehreren quartären Ammoniumalkoxysilanen und einem oder mehreren Polyfluor-(C₁-C₂₀)-Halogensilanen; einer Mischung aus einem oder mehreren quartären Ammoniumhalogensilanen und einem oder mehreren Polyfluor-(C₁-C₂₀)-Alkylalkoxysilanen; einer Mischung aus einem oder mehreren Polyfluor-(C₁-C₂₀)-Alkylalkoxysilanen und einem oder mehreren (C₁-C₄₀)-Alkylalkoxysilanen; einer Mischung aus einem oder mehreren Polyfluor-C₁-C₂₀)-Alkylalkoxysilanen und einem oder mehreren (C₁-C₄₀)-Alkylhalogensilanen; einer Mischung aus einem oder mehreren Polyfluoro-(C₁-C₂₀)-Halogensilanen und einem oder mehreren (C₁-C₄₀)-Alkylalkoxysilanen; einer Mischung aus einem oder mehreren Polyfluoro-(C₁-C₂₀)-Halogensilanen und einem oder mehreren (C₁-C₄₀)-Alkylhalogensilanen; einer Mischung aus einem oder mehreren quartären Ammoniumalkoxysilanen und einem oder mehreren (C₁-C₄₀)-Alkylalkoxysilanen; einer Mischung aus einem oder mehreren quartären Ammoniumalkoxysilanen und einem oder mehreren (C₁-C₄₀)-Alkylhalogensilanen; einer Mischung aus einem oder mehreren quartären Ammoniumhalogensilanen und einem oder mehreren (C₁-C₄₀)-Alkylalkoxysilanen; einer Mischung aus einem oder mehreren quartären Ammoniumalkoxysilanen, einem oder mehreren Polyfluoro-(C₁-C₂₀)-Alkylalkoxysilanen und einem oder mehreren (C₁-C₄₀)-Alkylalkoxysilanen; einer Mischung aus einem oder mehreren quartären Ammoniumalkoxysilanen, einem oder mehreren Polyfluoro-(C₁-C₂₀)-Halogensilanen und einem oder mehreren (C₁-C₄₀)-Alkylalkoxysilanen; einer Mischung aus einem oder mehreren quartären Ammoniumalkoxysilanen, einem oder mehreren Polyfluoro-(C₁-C₂₀)-Alkylalkoxysilanen und einem oder mehreren (C₁-C₄₀)-Alkylhalogensilanen; einer Mischung aus einem oder mehreren quartären Ammoniumalkoxysilanen, einem oder mehreren Polyfluoro-(C₁-C₂₀)-Halogensilanen und einem oder mehreren (C₁-C₄₀)-Alkylhalogensilanen; und einer Mischung aus einem oder mehreren quartären Ammoniumhalogensilanen, einem oder mehreren Polyfluoro-(C₁-C₂₀)alkylsilanen und einem oder mehreren (C₁-C₄₀)-Alkylalkoxysilanen.

7. Das Verfahren nach einem der Ansprüche 1 bis 6, wobei:

das mindestens eine quartäre Ammoniumsilan eine Verbindung der Formel (XIV) ist

wobei jedes X ein Halogen ist, das unabhängig ausgewählt ist aus der Gruppe bestehend aus Chlor, Brom und lod; jedes R⁵⁷ unabhängig ein (C₁-C₆)-Alkyl ist, insbesondere ausgewählt aus Methyl, Ethyl, n-Propyl, Isopropyl und Butyl; R⁵⁸ ein (C₁-C₂₀)-Alkylen ist, R⁵⁹ (C₁-C₂₀)-Alkyl ist, R⁶⁰ (C₁-C₂₀)-Alkyl ist und R⁶¹ (C₁-C₂₀)-Alkyl ist;

das mindestens eine Polyfluor-(C₁-C₂₀)-Alkylalkoxysilan oder ein Polyfluor-(C₁-C₂₀)-Alkylhalogensilan ausgewählt ist aus der Gruppe bestehend aus einer Verbindung der Formel (XV)

        [CF₃-(CF₂)_v(CH₂)_u]_w-Si(OR⁴⁷)_y     (XV)

wobei jedes R⁴⁷ unabhängig voneinander (C₁-C₂₀)-Alkyl ist; u und v unabhängig voneinander eine ganze Zahl von 0 bis 20 sind, w eine ganze Zahl ist, die aus 1, 2 und 3 ausgewählt ist; y eine ganze Zahl ist, die aus 1, 2 und 3 ausgewählt ist; und die Summe aus w+y 4 ist;

und einer Verbindung der Formel (XVI)

        [CF₃-(CF₂)_v(CH₂)_u]_w-SiX_y     (XVI)

wobei jedes X unabhängig ein Halogen ist, das unabhängig aus der Gruppe ausgewählt ist, die aus Chlor, Brom und Jod besteht; u und v unabhängig voneinander eine ganze Zahl von 0 bis 20 sind, w eine ganze Zahl ist, die aus 1, 2 und 3 ausgewählt ist; y eine ganze Zahl ist, die aus 1, 2 und 3 ausgewählt ist; und die Summe von w+y 4 ist;

das mindestens eine (C₁-C₄₀)Alkylalkoxysilan oder ein (C₁-C₄₀)Alkylhalogensilan ausgewählt ist aus der Gruppe bestehend aus einer Verbindung der Formel (XVII)

        (R⁵¹)_aSi(OR⁵²)_b     (XVII)

wobei jedes R⁵¹ unabhängig voneinander ein (C₁-C₄₀)-Alkyl ist; jedes R⁵² unabhängig voneinander ein (C₁-C₂₀)-Alkyl ist; w eine ganze Zahl ist, die aus 1, 2 und 3 ausgewählt ist; y eine ganze Zahl ist, die aus 1, 2 und 3 ausgewählt ist; und die Summe aus w+y 4 ist;

und einer Verbindung der Formel (XVII)

        [CH₃-(CH₂)_u]_w-SiX_y     (XVIII)

wobei jedes X ein Halogen ist, das unabhängig aus der Gruppe ausgewählt ist, die aus Chlor, Brom und Jod besteht; u eine ganze Zahl von 0 bis 40 ist, w eine ganze Zahl ist, die aus 1, 2 und 3 ausgewählt ist; y eine ganze Zahl ist, die aus 1, 2 und 3 ausgewählt ist; und die Summe von w+y 4 ist.

8. Das Verfahren nach einem der Ansprüche 1 bis 7, wobei das Organoalkoxysilan ausgewählt ist aus der Gruppe bestehend aus:

einer Verbindung der Formel (I);

        [R⁴]_s-Si(OR¹)_t(OR²)(OR³)     (I)

einer Verbindung der Formel (II);

        [R⁸-(CH₂)_m]-Si(OR⁵)_qR⁶_r     (II)

einer Verbindung der Formel (III);

        (⁹RO)(¹⁰RO)(¹¹RO)Si-X₁-Si(OR¹²)(OR¹³)(OR¹⁴)      (III)

einer Mischung aus mindestens einer Verbindung der Formel (I), worin R⁴ (C₁-C₄)-Alkenyl ist, und mindestens einer Verbindung der Formel (I), worin R⁴ (C₂-C₂₀)-Alkyl-CH=CH- ist;

einer Mischung aus mindestens einer Verbindung der Formel (I) und mindestens einer Verbindung der Formel (II);

einer Mischung aus mindestens einer Verbindung der Formel (I) und mindestens einer Verbindung der Formel (III);

einer Mischung aus mindestens einer Verbindung der Formel (II) und mindestens einer Verbindung der Formel (III);

wobei:

jeweils eines von R¹, R² und R³ unabhängig voneinander ein substituiertes oder unsubstituiertes (C₁-C₁₄)-Alkyl ist;

R⁴ ausgewählt ist aus der Gruppe bestehend aus einem substituierten oder unsubstituierten (C₂-C₁₄)Alkenyl, (C₅-C₆)Aryl, (C₂-C₁₄)Alkinyl; und (C₂-C₂₀)Alkyl-CH=CH-;

R⁵, R⁶, R⁹, R¹⁰, R¹¹, R¹², R¹³ und R¹⁴ unabhängig voneinander ausgewählt sind aus der Gruppe bestehend aus einem substituierten oder unsubstituierten (C₁-C₁₄)-Alkyl, (C₅-C₆)-Aryl, (C₂-C₁₄)-Alkenyl und (C₂-C₁₄)-Alkyl-CH=CH-;

R⁸ ausgewählt ist aus der Gruppe bestehend aus H, -SH, substituiertem oder unsubstituiertem (C₁-C₁₂)Alkyl, substituiertem oder unsubstituiertem (C₅-C₆)Aryl, -(CF₂)_b-CF₃, -NR¹⁵R¹⁶, einer Verbindung der Formel (IV)

und einer Verbindung der Formel (V)

R¹⁵ und R¹⁶ unabhängig voneinander ausgewählt sind aus der Gruppe bestehend aus H, substituiertem oder unsubstituiertem (C₁-C₁₂)-Alkyl, -CO und substituiertem oder unsubstituiertem (C₅-C₆)-Aryl;

R¹⁷ ausgewählt ist aus der Gruppe bestehend aus H und substituiertem oder unsubstituiertem (C₁-C₁₂)Alkyl;

X₁ ausgewählt ist aus der Gruppe bestehend aus substituiertem oder unsubstituiertem -(C₁-C₁₂)-Alkylen-, - (C₁-C₁₂)-Alkylen-NH-(C₁-C₁₂)-Alkylen- und -(C₁-C₁₂)-Alkylen-(S)_n-(C₁-C₁₂)-Alkylen-,

m eine ganze Zahl von 0 bis 20 ist;

n eine ganze Zahl von 1 bis 4 ist;

q eine ganze Zahl von 2 bis 3 ist;

r eine ganze Zahl von 0 bis 1 ist;

s eine ganze Zahl von 1 bis 2 ist;

t eine ganze Zahl von 0 bis 1 ist;

die Summe von q + r 3 ist;

die Summe von s + t 2 ist; und

b eine ganze Zahl von 0 bis 12 ist.

9. Das Verfahren nach einem der Ansprüche 1 bis 8, wobei der organische Vorläufer ausgewählt ist aus der Gruppe bestehend aus einer Verbindung der Formel (VI)

eine Verbindung der Formel (VII)

und einer Mischung davon
wobei:

R₂₇ unabhängig voneinander ausgewählt sind aus (C₁-C₆)-Alkyl;

R₄₀ und R₄₁ unabhängig voneinander aus der Gruppe ausgewählt sind, die aus H und (C₁-C₆)-Alkyl besteht;

X₂ ausgewählt ist aus der Gruppe bestehend aus einer Verbindung der Formel (VIII)

und eine Verbindung der Formel (IX);



und einer Mischung davon;
wobei:

R₄₂ ausgewählt ist aus der Gruppe bestehend aus H und (C₁-C₆)-Alkyl;

p eine ganze Zahl von 1 bis 8 ist; und

n' eine ganze Zahl von 1 bis 6 ist.

10. Das Verfahren nach Anspruch 9, wobei der organische Vorläufer eine Verbindung der Formel (VII) ist

wobei:

R₄₀ und R₄₁ unabhängig voneinander aus der Gruppe ausgewählt sind, die aus H und (C₁-C₆)-Alkyl besteht;

X₂ ausgewählt ist aus der Gruppe bestehend aus einer Verbindung der Formel (VIII)

und eine Verbindung der Formel (IX);

und einer Mischung davon;
wobei:

R₄₂ ausgewählt ist aus der Gruppe bestehend aus H und (C₁-C₆)-Alkyl;

p eine ganze Zahl von 1 bis 8 ist; und

n' eine ganze Zahl von 1 bis 6 ist.

11. Das Verfahren nach einem der Ansprüche 1 bis 10, wobei: der Säurekatalysator in wässriger Lösung eine anorganische Säure ist, die unabhängig aus der Gruppe ausgewählt ist, die aus H₂SO₄, HCl, HNO₃ und einer Mischung davon besteht;
der (C₁-C₈)-Alkohol unabhängig ausgewählt ist aus der Gruppe bestehend aus Methanol, Ethanol, Butanol, n-Propanol, Isopropanol und einer Mischung davon; und der Komplexbildner ausgewählt ist aus der Gruppe bestehend aus Acetylaceton, Methacrylsäure, Essigsäure, Isobuttersäure, Bipyridin und einer Mischung davon; insbesondere ist die Säure HNO₃, der (C₁-C₈)-Alkohol ist Ethanol und der Komplexbildner ist Methacrylsäure.

12. Das Verfahren nach einem der Ansprüche 1 bis 11, wobei das Metallalkoxid und das Halbmetallalkoxid unabhängig eine Verbindung der Formel (XIII) sind

        (OR⁴³)(OR⁴⁴)(OR⁴⁵)(OR⁴⁶)Z     (XIII)

wobei:

jedes von R⁴³, R⁴⁴, R⁴⁵ und R⁴⁶ unabhängig ausgewählt ist aus der Gruppe bestehend aus substituiertem oder unsubstituiertem (C₁-C₁₄)-Alkyl, (C₅-C₆)-Aryl, (C₂-C₁₄)-Alkenyl und (C₂-C₁₄)-Alkinyl; und

Z ausgewählt ist aus der Gruppe bestehend aus den Metall- und Halbmetallatomen.

13. Ein beschichtetes Substrat, das eine Sol-Gel-Schicht umfasst, die durch das Verfahren wie in einem der Ansprüche 1 bis 12 definiert erhalten werden kann.

Revendications

1. Un procédé de préparation d'un substrat revêtu de sol-gel comprenant :

1) tout d'abord, déposer une composition de revêtement sol-gel choisie dans le groupe constitué par sol1 et sol3 sur le substrat

2) d'autre part, durcir le revêtement obtenu à l'étape 1) ;

dans lequel le sol1 est une composition de revêtement sol-gel pouvant être obtenue par un procédé qui comprend :

a) préparer un mélange A comprenant :

au moins un alcoxyde choisi dans le groupe constitué par un alcoxyde métallique, un alcoxyde semi-métallique, un organo-alcoxysilane et un mélange de ceux-ci ;

au moins un catalyseur acide en solution aqueuse ayant un pH inférieur à 5 ;

facultativement, au moins un alcool en (C₁-C₈) ;

facultativement, au moins un précurseur organique ;

facultativement, au moins un initiateur de polymérisation ; et

facultativement, au moins un organo-alcoxysilane ou organo-halogénosilane fonctionnel ayant un fragment organosilyle fonctionnel choisi dans le groupe constitué par le silyle d'ammonium quaternaire, le fluoro-(Ci-C₂₀) alkylsilyle, l'alkylsilyle en (C₁-C₄₀), et un mélange de ceux-ci ;

à une température de 15 °C à 90 °C pendant une période de temps appropriée pour obtenir le sol1 ; et facultativement faire vieillir le mélange résultant sol1 par agitation à une température de 15 °C à 30 °C pendant une période de temps de 24 h à 72 h pour obtenir le sol1 ;

et

dans lequel le sol3 est une composition de revêtement sol-gel pouvant être obtenue par un procédé qui comprend :

b) préparer un mélange A comprenant :

au moins un alcoxyde choisi dans le groupe constitué par un alcoxyde métallique, un alcoxyde semi-métallique, un organo-alcoxysilane et un mélange de ceux-ci ;

au moins un catalyseur acide en solution aqueuse ayant un pH inférieur à 5

facultativement, au moins un précurseur organique ;

facultativement, au moins un initiateur de polymérisation ;

facultativement, au moins un alcool en (C₁-C₈) ; et

facultativement, au moins un organo-alcoxysilane ou organo-halogénosilane fonctionnel ayant un fragment organosilyle fonctionnel choisi dans le groupe constitué par le silyle d'ammonium quaternaire, le polyfluoro-(alkyl en C₁-C₂₀) silyle, l'alkylsilyle en (C₁-C₄₀), et un mélange de ceux-ci ;

à une température de 15 °C à 90 °C pour obtenir le sol1 ; et

facultativement faire vieillir le mélange résultant sol1 par agitation à une température de 15 °C à 30 °C de 24 h à 72 h;

c) préparer un mélange B comprenant :

au moins un alcoxyde métallique ;

au moins un agent complexant ;

facultativement, au moins un catalyseur acide en solution aqueuse ou de l'eau ayant un pH inférieur à 7 ; facultativement, un ou plusieurs alcools en (C₁-C₈) ; et

facultativement, au moins un organo-alcoxysilane ou organo-halogénosilane fonctionnel ayant un fragment organosilyle fonctionnel choisi dans le groupe constitué par le silyle d'ammonium quaternaire, le polyfluoro-(alkyl en C₁-C₂₀) silyle, l'alkylsilyle en (C₁-C₄₀), et un mélange de ceux-ci,

à une température de 15 °C à 30 °C pendant une période de temps appropriée pour obtenir le sol2 ; et facultativement faire vieillir le mélange résultant sol2 par agitation à une température de 15 °C à 30 °C de 24 h à 72 h ; et

d) mélanger le sol 1 avec le sol 2 ; facultativement ajouter au mélange obtenu à l'étape d) au moins un catalyseur acide en solution aqueuse ou de l'eau ayant un pH inférieur à 7 ; et faire vieillir le mélange résultant par agitation à une température de 15 °C à 30 °C de 24 h à 72 h ;

à condition que la composition de revêtement sol-gel de l'étape 1) comprenne au moins un organo-alcoxysilane ou un organo-halogénosilane fonctionnel ayant un fragment organosilyle fonctionnel choisi dans le groupe constitué par le silyle d'ammonium quaternaire, le polyfluoro-(alkyl en C₁-C₂₀) silyle, l'alkylsilyle en (C₁-C₄₀) et un mélange de ceux-ci ;

ou alternativement,

un procédé de préparation d'un substrat revêtu de sol-gel comprenant :

1) tout d'abord, déposer une composition de revêtement sol-gel choisie dans le groupe constitué par sol3 sur le substrat ; et

2) d'autre part, durcir le revêtement obtenu à l'étape 1) ;

dans lequel le sol3 est une composition de revêtement sol-gel pouvant être obtenue par un procédé qui comprend :

b) préparer un mélange A comprenant :

au moins un alcoxyde choisi dans le groupe constitué par un alcoxyde métallique, un alcoxyde semi-métallique, un organo-alcoxysilane et un mélange de ceux-ci ;

au moins un catalyseur acide en solution aqueuse ayant un pH inférieur à 5 ;

au moins un précurseur organique ;

au moins un initiateur de polymérisation ; et

facultativement, au moins un alcool en (C₁-C₈) ;

à une température de 15 °C à 90 °C pour obtenir le sol1 ; et

facultativement faire vieillir le mélange résultant sol1 par agitation à une température de 15 °C à 90 °C de 24 h à 72 h;

c) préparer un mélange B comprenant :

au moins un alcoxyde métallique ;

au moins un agent complexant ;

facultativement, un ou plusieurs alcools en (C₁-C₈) ; et

facultativement, au moins un catalyseur acide en solution aqueuse ou de l'eau ayant un pH inférieur à 7 ;

à une température de 15 °C à 30 °C pour obtenir le sol2 ; facultativement faire vieillir le mélange résultant sol2 par agitation à une température de 15 °C à 30 °C de 24 h à 72 h ; et

d) mélanger le sol 1 avec le sol 2 ; facultativement ajouter au mélange obtenu à l'étape d) au moins un catalyseur acide en solution aqueuse ou de l'eau ayant un pH inférieur à 7 ; et faire vieillir le mélange résultant par agitation à une température de 15 °C à 30 °C de 24 h à 72 h ;

dans lequel, le précurseur organique est un composé choisi dans le groupe constitué par un composé de formule (VI)

un composé de formule (VII)

et un mélange de ceux-ci
où :

R₂₇ sont indépendamment choisis dans les alkyles (C₁-C₆);

R₄₀ et R₄₁ sont choisi indépendamment dans le groupe constitué par H et alkyle en (C₁-C₆) ;

X₂ est choisi dans le groupe constitué par un composé de formule (VIII)

et un composé de formule (IX) ;

et un mélange de ceux-ci ;
où :

R₄₂ est choisi dans le groupe constitué par H et alkyle en (C₁-C₆) ;

p est un nombre entier de 1 à 8 ; et

n' es un nombre entier de 1 à 6.

2. Le procédé selon la revendication 1, qui comprend le dépôt d'une composition de revêtement sol-gel sol1 pouvant être obtenue par un procédé qui comprend :
a1) préparer un mélange A1 comprenant :

au moins un alcoxyde semi-métallique ;

au moins un organo-alcoxysilane ;

au moins un catalyseur acide en solution aqueuse ayant un pH inférieur à 5 ; et

facultativement au moins un alcool en (C₁-C₈) ; et

facultativement, au moins un organo-alcoxysilane ou organo-halogénosilane fonctionnel ayant un fragment organosilyle fonctionnel choisi dans le groupe constitué par le silyle d'ammonium quaternaire, le polyfluoro-(alkyl en C₁-C₂₀) silyle, l'alkylsilyle en (C₁-C₄₀), et un mélange de ceux-ci ;

en réalisant le suivant :

a1') l'alcoxyde semi-métallique ; l'organo-alcoxysilane ; facultativement au moins un alcool en (C₁-C₈) ; le mélange d'une solution aqueuse d'au moins un catalyseur acide en solution aqueuse ayant un pH inférieur à 5 ; et au moins un organo-alcoxysilane ou organo-halogénosilane fonctionnel ayant un fragment organosilyle fonctionnel choisi dans le groupe constitué par le silyle d'ammonium quaternaire, le polyfluoro-(alkyl en C₁-C₂₀) silyle, l'alkylsilyle en (C₁-C₄₀) et un mélange de ceux-ci à une température de 15 °C à 90 °C pendant une période de temps appropriée pour obtenir le sol1-1 ; et

a1") facultativement faire vieillir le mélange résultant par agitation à une température de 15 °C à 30 °C de 24 h à 72 h pour obtenir le sol 1-1 vieillissant ;

à condition que le sol1-1 comprenne au moins un organo-alcoxysilane ou un organo-halogénosilane fonctionnel ayant un fragment organosilyle fonctionnel choisi dans le groupe constitué par le silyle d'ammonium quaternaire, le polyfluoro-(alkyl en C₁-C₂₀) silyle, l'alkylsilyle en (C₁-C₄₀) et un mélange de ceux-ci ;

ou alternativement ;

a2) préparer un mélange A2 comprenant :

au moins un alcoxyde semi-métallique ;

au moins un organo-alcoxysilane ;

au moins un catalyseur acide en solution aqueuse ayant un pH inférieur à 5 ;

au moins un précurseur organique ;

facultativement, au moins un initiateur de polymérisation ;

au moins un alcool en (C₁-C₈) ; et

facultativement, au moins un organo-alcoxysilane ou organo-halogénosilane fonctionnel ayant un fragment organosilyle fonctionnel choisi dans le groupe constitué par le silyle d'ammonium quaternaire, le polyfluoro-(alkyl en C₁-C₂₀) silyle, l'alkylsilyle en (C₁-C₄₀), et un mélange de ceux-ci ;

en réalisant le suivant :

a2') préparer un premier mélange comprenant l'alcoxyde semi-métallique ; l'organo-alcoxysilane ; au moins un alcool en (C₁-C₈) ; une solution aqueuse d'au moins un catalyseur acide en solution aqueuse ayant un pH inférieur à 5 ; et facultativement au moins un organo-alcoxysilane ou organo-halogénosilane fonctionnel ayant un fragment organosilyle fonctionnel choisi dans le groupe constitué par le silyle d'ammonium quaternaire, le polyfluoro-(alkyl en C₁-C₂₀) silyle, l'alkylsilyle en (C₁-C₄₀), et un mélange de ceux-ci à une température de 15 °C à 90 °C ;

a2") préparer un second mélange comprenant une solution aqueuse d'au moins un catalyseur acide en solution aqueuse ayant un pH inférieur à 5 ; au moins un précurseur organique ; facultativement, au moins un initiateur de polymérisation ou un mélange de ceux-ci ; au moins un alcool en (C₁-C₈) ; et facultativement au moins un organo-alcoxysilane ou organo-halogénosilane fonctionnel ayant un fragment organosilyle fonctionnel choisi dans le groupe constitué par le silyle d'ammonium quaternaire, le polyfluoro-(alkyl en C₁-C₂₀) silyle, l'alkylsilyle en (C₁-C₄₀), et un mélange de ceux-ci à une température de 15 °C à 90 °C ;

a2‴) mélanger le second mélange et le premier mélange à une température de 15 °C à 30 °C ; et agiter le mélange résultant à une température de 15 °C à 90 °C pendant une période de temps appropriée pour obtenir le sol1-2 ; et

a2ʺʺ) facultativement faire vieillir le mélange résultant par agitation à une température de 15 °C à 30 °C de 24 h à 72 h pour obtenir le sol1-2 vieillissant ;

à condition que le sol1-2 comprenne au moins un organo-alcoxysilane ou un organo-halogénosilane fonctionnel ayant un fragment organosilyle fonctionnel choisi dans le groupe constitué par le silyle d'ammonium quaternaire, le polyfluoro-(alkyl en C₁-C₂₀) silyle, l'alkylsilyle en (C₁-C₄₀) et un mélange de ceux-ci ;

ou alternativement ;

a3) préparer un mélange A3 comprenant :

au moins un alcoxyde semi-métallique ;

au moins un organo-alcoxysilane ;

au moins un catalyseur acide en solution aqueuse ayant un pH inférieur à 5 ;

au moins un précurseur organique ;

facultativement, au moins un initiateur de polymérisation ;

facultativement, au moins un alcool en (C₁-C₈) ; et

facultativement, au moins un organo-alcoxysilane ou organo-halogénosilane fonctionnel ayant un fragment organosilyle fonctionnel choisi dans le groupe constitué par le silyle d'ammonium quaternaire, le polyfluoro-(alkyl en C₁-C₂₀) silyle, l'alkylsilyle en (C₁-C₄₀), et un mélange de ceux-ci ;

en réalisant le suivant :

a3') préparer un premier mélange comprenant l'organo-alcoxysilane ; facultativement au moins un alcool en (C₁-C₈) ; une solution aqueuse d'au moins un catalyseur acide en solution aqueuse ayant un pH inférieur à 5 ; et facultativement au moins un organo-alcoxysilane ou organo-halogénosilane fonctionnel ayant un fragment organosilyle fonctionnel choisi dans le groupe constitué par le silyle d'ammonium quaternaire, le polyfluoro-(alkyl en C₁-C₂₀) silyle, l'alkylsilyle en (C₁-C₄₀), et un mélange de ceux-ci à une température de 15 °C à 90 °C ; a3") facultativement, ajouter au moins un organo-alcoxysilane ou un organo-halogénosilane fonctionnel ayant un fragment organosilyle fonctionnel choisi dans le groupe constitué par le silyle d'ammonium quaternaire, le polyfluoro-(alkyl en C₁-C₂₀) silyle, l'alkylsilyle en (C₁-C₄₀) à une température de 15 °C à 30 °C ;

a3‴) ajouter au moins un alcoxyde semi-métallique à une température de 15 °C à 30 °C ;

a3‴^v) préparer un second mélange comprenant au moins un précurseur organique ; facultativement, au moins un initiateur de polymérisation ; facultativement, une solution aqueuse d'au moins un catalyseur acide en solution aqueuse ayant un pH inférieur à 5 ; ou un mélange de ceux-ci ; et facultativement au moins un organo-alcoxysilane ou organo-halogénosilane fonctionnel ayant un fragment organosilyle fonctionnel choisi dans le groupe constitué par le silyle d'ammonium quaternaire, le polyfluoro-(alkyl en C₁-C₂₀) silyle, l'alkylsilyle en (C₁-C₄₀), et un mélange de ceux-ci à une température de 15 °C à 30 °C ;

a3^v) mélanger le second mélange avec le mélange obtenu à l'étape a3‴) à une température de 15 °C à 30 °C pour obtenir le sol1-3 ; et

a3^vi) facultativement faire vieillir le mélange résultant par agitation à une température de 15 °C à 30 °C de 24 h à 72 h pour obtenir le sol1-3 vieillissant ;

à condition que le sol1-3 comprenne au moins un organo-alcoxysilane ou un organo-halogénosilane fonctionnel ayant un fragment organosilyle fonctionnel choisi dans le groupe constitué par le silyle d'ammonium quaternaire, le polyfluoro-(alkyl en C₁-C₂₀) silyle, l'alkylsilyle en (C₁-C₄₀) et un mélange de ceux-ci ;

ou, alternativement ;

a4) préparer un mélange A4 comprenant :

au moins un organo-alcoxysilane ;

au moins un catalyseur acide en solution aqueuse ayant un pH inférieur à 5 ;

au moins un précurseur organique ;

facultativement, au moins un initiateur de polymérisation ; et

facultativement, au moins un organo-alcoxysilane ou organo-halogénosilane fonctionnel ayant un fragment organosilyle fonctionnel choisi dans le groupe constitué par le silyle d'ammonium quaternaire, le polyfluoro-(alkyl en C₁-C₂₀) silyle, l'alkylsilyle en (C₁-C₄₀), et un mélange de ceux-ci ;

en réalisant le suivant :

a4') préparer un premier mélange comprenant l'organo-alcoxysilane ; une solution aqueuse d'au moins un catalyseur acide en solution aqueuse ayant un pH inférieur à 5 ; et facultativement au moins un organo-alcoxysilane ou organo-halogénosilane fonctionnel ayant un fragment organosilyle fonctionnel choisi dans le groupe constitué par le silyle d'ammonium quaternaire, le polyfluoro-(alkyl en C₁-C₂₀) silyle, l'alkylsilyle en (C₁-C₄₀), et un mélange de ceux-ci à une température de 15 °C à 90 °C ;

a4") facultativement, ajouter au moins un organo-alcoxysilane ou un organo-halogénosilane fonctionnel ayant un fragment organosilyle fonctionnel choisi dans le groupe constitué par le silyle d'ammonium quaternaire, le polyfluoro-(alkyl en C₁-C₂₀) silyle, l'alkylsilyle en (C₁-C₄₀), et un mélange de ceux-ci à une température de 15 °C à 30 °C ; et en agitant le mélange résultant à une température de 15 °C à 90 °C ; et

a4‴) préparer un second mélange comprenant au moins un précurseur organique ; facultativement, au moins un initiateur de polymérisation ou un mélange de ceux-ci ; facultativement, une solution aqueuse d'au moins un catalyseur acide en solution aqueuse ayant un pH inférieur à 5 ; et facultativement au moins un organo-alcoxysilane ou organo-halogénosilane fonctionnel ayant un fragment organosilyle fonctionnel choisi dans le groupe constitué par le silyle d'ammonium quaternaire, le polyfluoro-(alkyl en C₁-C₂₀) silyle, l'alkylsilyle en (C₁-C₄₀) et un mélange de ceux-ci à une température de 15 °C à 90 °C ;

a4ʺʺ) mélanger le second mélange avec le mélange obtenu à l'étape a4‴) à une température de 15 °C à 30 °C pour obtenir le sol1-4 ; et

a4^v) facultativement faire vieillir le mélange résultant par agitation à une température de 15 °C à 30 °C de 24 h à 72 h pour obtenir le sol1-4 vieillissant ;

à condition que le sol1-4 comprenne au moins un organo-alcoxysilane ou un organo-halogénosilane fonctionnel ayant un fragment organosilyle fonctionnel choisi dans le groupe constitué par le silyle d'ammonium quaternaire, le polyfluoro-(alkyl en C₁-C₂₀) silyle, l'alkylsilyle en (C₁-C₄₀) et un mélange de ceux-ci ;

ou alternativement,

a5) préparer un mélange A5 comprenant :

au moins un alcoxyde semi-métallique ;

au moins un organo-alcoxysilane ;

au moins un catalyseur acide en solution aqueuse ayant un pH inférieur à 5 ;

au moins un précurseur organique ;

facultativement, au moins un initiateur de polymérisation ; et

facultativement, au moins un organo-alcoxysilane ou organo-halogénosilane fonctionnel ayant un fragment organosilyle fonctionnel choisi dans le groupe constitué par le silyle d'ammonium quaternaire, le polyfluoro-(alkyl en C₁-C₂₀) silyle, l'alkylsilyle en (C₁-C₄₀), et un mélange de ceux-ci ;

en réalisant le suivant :

a5') préparer un premier mélange comprenant l'organo-alcoxysilane ; une solution aqueuse d'au moins un catalyseur acide en solution aqueuse ayant un pH inférieur à 5 ; et facultativement au moins un organo-alcoxysilane ou organo-halogénosilane fonctionnel ayant un fragment organosilyle fonctionnel choisi dans le groupe constitué par le silyle d'ammonium quaternaire, le polyfluoro-(alkyl en C₁-C₂₀) silyle, l'alkylsilyle en (C₁-C₄₀), et un mélange de ceux-ci à une température de 15 °C à 90 °C ;

a5") facultativement, ajouter au moins un organo-alcoxysilane ou organo-halogénosilane fonctionnel ayant un fragment organosilyle fonctionnel choisi dans le groupe constitué par le silyle d'ammonium quaternaire, le polyfluoro-(alkyl en C₁-C₂₀) silyle, l'alkylsilyle en (C₁-C₄₀), et un mélange de ceux-ci à une température de 15 °C à 30 °C ;

a5‴) ajouter au moins un alcoxyde semi-métallique à une température de 15 °C à 30 °C ;

a5ʺʺ) mélanger le mélange résultant à une température de 15 °C à 90 °C ; et agiter le mélange résultant à une température de 15 °C à 90 °C ; et

a5^v) préparer un second mélange comprenant une solution aqueuse d'au moins un précurseur organique ;

facultativement, au moins un initiateur de polymérisation ou un mélange de ceux-ci ; facultativement, un catalyseur acide en solution aqueuse ayant un pH inférieur à 5 ; et facultativement au moins un organo-alcoxysilane ou organo-halogénosilane fonctionnel ayant un fragment organosilyle fonctionnel choisi dans le groupe constitué par le silyle d'ammonium quaternaire, le polyfluoro-(alkyl en C₁-C₂₀) silyle, l'alkylsilyle en (C₁-C₄₀) et un mélange de ceux-ci à une température de 15 °C à 30 °C ;

a5^vi) mélanger le second mélange avec le mélange obtenu à l'étape a5‴) à une température de 15 °C à 30 °C pour obtenir le sol1-5 ; et

a5^vii) facultativement faire vieillir le mélange résultant par agitation à une température de 15 °C à 30 °C de 24 h à 72 h pour obtenir le sol1-5 vieillissant ; et

à condition que le sol1-5 comprenne au moins un organo-alcoxysilane ou un organo-halogénosilane fonctionnel ayant un fragment organosilyle fonctionnel choisi dans le groupe constitué par le silyle d'ammonium quaternaire, le polyfluoro-(alkyl en C₁-C₂₀) silyle, l'alkylsilyle en (C₁-C₄₀) et un mélange de ceux-ci.

3. Le procédé selon l'une quelconque des revendications 1 ou 2, qui comprend le dépôt d'une composition de revêtement sol-gel sol3 pouvant être obtenue par un procédé qui comprend :

b) préparer un sol1 choisi dans le groupe constitué par sol1-1, sol1-2, sol1-3, sol1-4, sol1-5, sol1-1 vieillissant, sol1-2 vieillissant, sol1-3 vieillissant, sol1-4 vieillissant et sol1-5 vieillissant tel que définis dans la revendication 2 ;

c) préparer un sol2 en préparant un mélange B en mélangeant au moins un alcoxyde métallique ; au moins un agent complexant ; facultativement un ou plusieurs alcools en (C₁-C₈) ; facultativement, au moins un catalyseur acide en solution aqueuse ou de l'eau ayant un pH inférieur à 7 ; et facultativement au moins un organo-alcoxysilane ou organo-halogénosilane fonctionnel ayant un fragment organosilyle fonctionnel choisi dans le groupe constitué par le silyle d'ammonium quaternaire, le polyfluoro-(alkyl en C₁-C₂₀) silyle, l'alkylsilyle en (C₁-C₄₀) et un mélange de ceux-ci, à une température de 15 °C à 90 °C pour obtenir le sol2 ; facultativement faire vieillir le mélange résultant sol2 en agitant à une température de 15 °C à 30 °C de 24 h à 72 h pour obtenir le sol2 vieillissant ; et

d) mélanger le sol 1 avec le sol 2, facultativement ajouter au mélange obtenu à l'étape d) au moins un catalyseur acide en solution aqueuse ou de l'eau ayant un pH inférieur à 7 ; et faire vieillir le mélange résultant par agitation à une température de 15 °C à 30 °C de 24 h à 72 h pour obtenir le sol3 choisi dans le groupe constitué par sol3-1, sol3-1, sol3-2, sol3-3, sol3-4, sol3-5, sol3-1 vieillissant, sol3-2 vieillissant, sol3-3 vieillissant, sol3-4 vieillissant et sol3-5 vieillissant, respectivement.

4. Le procédé selon l'une quelconque des revendications 1 à 3, qui comprend le dépôt d'une composition de revêtement sol-gel choisie dans le groupe constitué de sol1 et sol3 sur le substrat, dans lequel : le sol 1 comprend l'organo-alcoxysilane ou l'organo-halogénosilane ayant un fragment organosilyle fonctionnel choisi dans le groupe constitué de silyle d'ammonium quaternaire, polyfluoro-(alkyl en C₁-C₂₀) silyle, alkylsilyle en (C₁-C₄₀), et un mélange de ceux-ci.

5. Le procédé selon la revendication 4, dans lequel :

Lorsque le sol1 est un sol1-1, alors le sol1-1 peut être obtenu par un procédé dans lequel l'étape a1') mélange de l'alcoxyde semi-métallique ; l'organo-alcoxysilane ; facultativement au moins un alcool en (C₁-C₈) ; une solution aqueuse d'au moins un catalyseur acide en solution aqueuse ayant un pH inférieur à 5 ; et au moins un organo-alcoxysilane ou organo-halogénosilane fonctionnel ayant un fragment organosilyle fonctionnel choisi dans le groupe constitué par le silyle d'ammonium quaternaire, le polyfluoro-(alkyl en C₁-C₂₀) silyle, l'alkylsilyle en (C₁-C₄₀) et un mélange de ceux-ci à une température de 15 °C à 90 °C pendant une période de temps appropriée pour obtenir le sol1-1 ; et a1") facultativement faire vieillir le mélange résultant par agitation à une température de 15 °C à 30 °C de 24 h à 72 h ; ou, alternativement,

Lorsque le sol1 est un sol1-2, alors le sol1-2 peut être obtenu par un procédé dans lequel l'étape a2') préparation d'un premier mélange comprenant l'alcoxyde semi-métallique ; l'organo-alcoxysilane ; au moins un alcool en (C₁-C₈) ; une solution aqueuse d'au moins un catalyseur acide en solution aqueuse ayant un pH inférieur à 5 ; et facultativement au moins un organo-alcoxysilane ou organo-halogénosilane fonctionnel ayant un fragment organosilylée fonctionnel choisi dans le groupe constitué par le silyle d'ammonium quaternaire, le polyfluoro-(alkyl en C₁-C₂₀) silyle, l'alkylsilyle (C₁-C₄₀), et un mélange de ceux-ci à une température de 15 °C à 90 °C ; a2") préparation d'un second mélange comprenant une solution aqueuse d'au moins un catalyseur acide en solution aqueuse ayant un pH inférieur à 5 ; au moins un précurseur organique ; facultativement, au moins un initiateur de polymérisation ou un mélange de ceux-ci ; au moins un alcool en (C₁-C₈) ; et

facultativement au moins un organo-alcoxysilane ou organo-halogénosilane fonctionnel ayant un fragment organosilyle fonctionnel choisi dans le groupe constitué par le silyle d'ammonium quaternaire, polyfluoro-(alkyl en C₁-C₂₀) silyle, alkylsilyle en (C₁-C₄₀) et un mélange de ceux-ci à une température de 15 °C à 90 °C ; a2‴) mélange du second mélange et du premier mélange à une température de 15°C à 30°C ; et agitation du mélange résultant à une température de 15 °C à 90 °C pendant une période de temps appropriée pour obtenir le sol1-2 ; et a2ʺʺ) facultativement, faire vieillir le mélange résultant en agitant à une température de 15 °C à 30 °C de 24 h à 72 h; ou, alternativement,

Lorsque le sol1 est un sol1-3, alors le sol1-3 peut être obtenu par un procédé dans lequel l'étape a3') préparation d'un premier mélange comprenant l'organo-alcoxysilane ; facultativement au moins un alcool en (C₁-C₈) ; une solution aqueuse d'au moins un catalyseur acide en solution aqueuse ayant un pH inférieur à 5 ; et facultativement au moins un organo-alcoxysilane ou organo-halogénosilane fonctionnel ayant un fragment organosilyle fonctionnel choisi dans le groupe constitué par le silyle d'ammonium quaternaire, le polyfluoro-(alkyl en C₁-C₂₀) silyle, l'alkylsilyle en (C₁-C₄₀) et un mélange de ceux-ci à une température de 15 °C à 90 °C ; a3") facultativement, ajouter au moins un organo-alcoxysilane ou un organo-halogénosilane fonctionnel ayant un fragment organosilyle fonctionnel choisi dans le groupe constitué par le silyle d'ammonium quaternaire, le polyfluoro-(alkyl en C₁-C₂₀) silyle, l'alkylsilyle en (C₁-C₄₀) à une température de 15 °C à 30 °C ;

a3‴) ajouter au moins un alcoxyde semi-métallique à une température de 15 °C à 30 °C ;

a3‴^v) préparer un second mélange comprenant au moins un précurseur organique ; facultativement, au moins un initiateur de polymérisation ; facultativement, une solution aqueuse d'au moins un catalyseur acide en solution aqueuse ayant un pH inférieur à 5 ; ou un mélange de ceux-ci ; et facultativement au moins un organo-alcoxysilane ou organo-halogénosilane fonctionnel ayant un fragment organosilyle fonctionnel choisi dans le groupe constitué par le silyle d'ammonium quaternaire, le polyfluoro-(alkyl en C₁-C₂₀) silyle, l'alkylsilyle en (C₁-C₄₀), et un mélange de ceux-ci à une température de 15 °C à 30 °C ;

a3^v) mélanger le second mélange avec le mélange obtenu à l'étape a3‴) à une température de 15 °C à 30 °C pour obtenir le sol1-3 ; et

a3^vi) facultativement faire vieillir le mélange résultant en agitant à une température de 15 °C à 30 °C de 24 h à 72 h ; ou, alternativement,

lorsque le sol1 est un sol1-4, alors le sol1-4 peut être obtenu par un procédé dans lequel l'étape a4') préparation d'un premier mélange comprenant l'organo-alcoxysilane ; une solution aqueuse d'au moins un catalyseur acide en solution aqueuse ayant un pH inférieur à 5 ; et facultativement au moins un organo-alcoxysilane ou organo-halogénosilane fonctionnel ayant un fragment organosilyle fonctionnel choisi dans le groupe constitué par le silyle d'ammonium quaternaire, le polyfluoro-(alkyl en C₁-C₂₀) silyle, l'alkylsilyle en (C₁-C₄₀), et un mélange de ceux-ci à une température de 15 °C à 90 °C ;

a4") facultativement, ajouter au moins un organo-alcoxysilane ou un organo-halogénosilane fonctionnel ayant un fragment organosilyle fonctionnel choisi dans le groupe constitué par le silyle d'ammonium quaternaire, le polyfluoro-(alkyl en C₁-C₂₀) silyle, l'alkylsilyle en (C₁-C₄₀), et un mélange de ceux-ci à une température de 15 °C à 30 °C ; et en agitant le mélange résultant à une température de 15 °C à 90 °C ; et

a4‴) préparer un second mélange comprenant au moins un précurseur organique ; facultativement, au moins un initiateur de polymérisation ou un mélange de ceux-ci ; facultativement, une solution aqueuse d'au moins un catalyseur acide en solution aqueuse ayant un pH inférieur à 5 ; et facultativement au moins un organo-alcoxysilane ou organo-halogénosilane fonctionnel ayant un fragment organosilyle fonctionnel choisi dans le groupe constitué par le silyle d'ammonium quaternaire, le polyfluoro-(alkyl en C₁-C₂₀) silyle, l'alkylsilyle en (C₁-C₄₀) et un mélange de ceux-ci à une température de 15 °C à 30 °C ;

a4ʺʺ) mélanger le second mélange avec le mélange obtenu à l'étape a4‴) et agiter à une température de 15 °C à 90 °C pour obtenir le sol1-4 ; et

a4^v) facultativement faire vieillir le mélange résultant en agitant à une température de 15 °C à 30 °C de 24 h à 72 h ; ou, alternativement,

lorsque le sol1 est un sol1-5, alors le sol1-5 peut être obtenu par un procédé dans lequel l'étape a5') préparation d'un premier mélange comprenant l'organo-alcoxysilane ; une solution aqueuse d'au moins un catalyseur acide en solution aqueuse ayant un pH inférieur à 5 ; et facultativement au moins un organo-alcoxysilane ou organo-halogénosilane fonctionnel ayant un fragment organosilyle fonctionnel choisi dans le groupe constitué par le silyle d'ammonium quaternaire, le polyfluoro-(alkyl en C₁-C₂₀) silyle, l'alkylsilyle en (C₁-C₄₀), et un mélange de ceux-ci à une température de 15 °C à 90 °C ;

a5") facultativement, ajouter au moins un organo-alcoxysilane ou organo-halogénosilane fonctionnel ayant un fragment organosilyle fonctionnel choisi dans le groupe constitué par le silyle d'ammonium quaternaire, le polyfluoro-(alkyl en C₁-C₂₀) silyle, l'alkylsilyle en (C₁-C₄₀), et un mélange de ceux-ci à une température de 15 °C à 30 °C ;

a5‴) ajouter au moins un alcoxyde semi-métallique à une température de 15 °C à 30 °C ;

a5ʺʺ) mélanger le mélange résultant à une température de 15 °C à 90 °C ; et agiter le mélange résultant à une température de 15 °C à 90 °C ; et

a5^v) préparer un second mélange comprenant au moins un précurseur organique ; facultativement, au moins un initiateur de polymérisation ou un mélange de ceux-ci ; facultativement, un catalyseur acide en solution aqueuse ayant un pH inférieur à 5 ; et facultativement au moins un organo-alcoxysilane ou organo-halogénosilane fonctionnel ayant un fragment organosilyle fonctionnel choisi dans le groupe constitué par le silyle d'ammonium quaternaire, le polyfluoro-(alkyl en C₁-C₂₀) silyle, l'alkylsilyle en (C₁-C₄₀), et un mélange de ceux-ci à une température de 15 °C à 30 °C ;

a5^vi) mélanger le second mélange avec le mélange obtenu à l'étape a5‴) à une température de 15 °C à 90 °C pour obtenir le sol1-5 ; et

a5^vii) facultativement faire vieillir le mélange résultant par agitation à une température de 15 °C à 30 °C de 24 h à 72 h.

6. Le procédé selon l'une quelconque des revendications 1 à 5, dans lequel l'au moins un organo-alcoxysilane ou organo-halogénosilane fonctionnel ayant un fragment organosilyle fonctionnel choisi dans le groupe constitué par : le silyle d'ammonium quaternaire, le polyfluoro-(alkyl en C₁-C₂₀) silyle, l'alkylsilyle en (C₁-C₄₀), est choisi dans le groupe constitué par : un ou plusieurs alcoxysilanes d'ammonium quaternaire ; un ou plusieurs halogénosilanes d'ammonium quaternaire ; un ou plusieurs polyfluoro-alkyl (C₁-C₂₀) alcoxysilanes ; un ou plusieurs polyfluoro-(C₁-C₂₀) halogénosilanes ; un ou plusieurs alcoxysilanes d'alkyle en C₁ à C₄₀ ; un ou plusieurs halogénosilanes d'alkyle en C₁ à C₄₀ ; un mélange d'un ou plusieurs alcoxysilanes d'ammonium quaternaire et d'un ou plusieurs polyfluoro-alcoxysilanes d'alkyle en C₁ à C₂₀ ; un mélange d'un ou plusieurs alcoxysilanes d'ammonium quaternaire et d'un ou plusieurs polyfluoro-halogénosilanes en C₁ à C₂₀ ; un mélange d'un ou plusieurs halogénosilanes d'ammonium quaternaire et d'un ou plusieurs polyfluoro-alcoxysilanes d'alkyle en C₁ à C₂₀ ; un mélange d'un ou plusieurs polyfluoro-alcoxysilanes d'alkyle en C₁ à C ₂₀)alkylalcoxysilanes et un ou plusieurs (C₁-C₄₀)alkylalcoxysilanes ; un mélange d'un ou plusieurs polyfluoro-(C₁-C-C₂₀)alkyl alcoxysilanes et un ou plusieurs (C₁-C₄₀)alkyl halogénosilanes; un mélange d'un ou plusieurs polyfluoro-(C₁-C₂₀) halogénosilanes et un ou plusieurs alkyl alcoxysilanes en (C₁-C₄₀); un mélange d'un ou plusieurs polyfluoro-(C₁-C₂₀) halogénosilanes et un ou plusieurs alkyl halogénosilanes en (C₁-C₄₀) ; un mélange d'un ou plusieurs alcoxysilanes d'ammonium quaternaire et un ou plusieurs alkyl alcoxysilanes en (C₁-C₄₀) ; un mélange d'un ou plusieurs alcoxysilanes d'ammonium quaternaires et un ou plusieurs halogénosilanes d'alkyle en (C₁-C₄₀) ; un mélange d'un ou plusieurs halogénosilanes d'ammonium quaternaire et un ou plusieurs alcoxysilanes d'alkyle en (C₁-C₄₀) ; un mélange d'un ou plusieurs alcoxysilanes d'ammonium quaternaire, un ou plusieurs alcoxysilanes de polyfluoroalkyle en (C₁-C₂₀) et un ou plusieurs alcoxysilanes d'alkyle en (C₁-C₂₀) ; un mélange d'un ou plusieurs alcoxysilanes d'ammonium quaternaire, un ou plusieurs polyfluoro-(C₁-C₂₀) halogénosilanes et un ou plusieurs alcoxysilanes d'alkyle en (C₁-C₄₀) ; un mélange d'un ou plusieurs alcoxysilanes d'ammonium quaternaire, un ou plusieurs alcoxysilanes de polyfluoroalkyl en (C₁-C₂₀) et un ou plusieurs halogénosilanes d'alkyle en (C₁-C₄₀) ; un mélange d'un ou plusieurs alcoxysilanes d'ammonium quaternaire, un ou plusieurs polyfluoro-(C₁-C₂₀) halogénosilanes et un ou plusieurs halogénosilanes d'alkyle en (C₁-C₄₀) ; et un mélange d'un ou plusieurs halogénosilanes d'ammonium quaternaire, un ou plusieurs silanes de polyfluoroalkyle en (C₁-C₂₀) et un ou plusieurs alcoxysilanes d'alkyle en (C₁-C₄₀).

7. Le procédé selon l'une quelconque des revendications 1 à 6, dans lequel :

le au moins un silane d'ammonium quaternaire est un composé de formule (XIV)

dans laquelle chaque X est un halogène choisi indépendamment dans le groupe constitué par le chlore, le brome et l'iode ; chaque R⁵⁷ est indépendamment un alkyle en (C₁-C₆), en particulier choisi parmi le méthyle, l'éthyle, le n-propyle, l'isopropyle et le butyle ; R⁵⁸ est un alkylène en (C₁-C₂₀), R⁵⁹ est un alkyle en (C₁-C₂₀), R⁶⁰ est un alkyle en (C₁-C₂₀) et R⁶¹ est un alkyle en (C₁-C₂₀) ;

le au moins un alcoxysilane de polyfluoroalkyle en (C₁-C₂₀) ou un halogénosilane de polyfluoroalkyle en (C₁-C₂₀) est choisi dans le groupe constitué par un composé de formule (XV)

        [CF₃-(CF₂)_v(CH₂)_u]_w-Si(OR⁴⁷)_y     (XV)

dans laquelle chaque R⁴⁷ est indépendamment alkyle en (C₁-C₂₀) ; u et v sont indépendamment un nombre entier de 0 à 20, w est un nombre entier choisi parmi 1, 2 et 3 ; y est un nombre entier choisi parmi 1, 2 et 3 ; et la somme de w+y est 4 ;

et un composé de formule (XVI)

        [CF₃-(CF₂)_v(CH₂)_u]_w-SiX_y     (XVI)

dans laquelle chaque X est indépendamment un halogène choisi indépendamment dans le groupe constitué par le chlore, le brome et l'iode ; u et v sont indépendamment un nombre entier de 0 à 20, w est un nombre entier choisi parmi 1, 2 et 3 ; y est un nombre entier choisi parmi 1, 2 et 3 ; et la somme de w+y est 4 ;

l'au moins un alkylalcoxysilane en (C₁-C₄₀) ou un alkylhalogénosilane en (C₁-C₄₀) est choisi dans le groupe constitué par un composé de formule (XVII)

        (R⁵¹)_aSi(OR⁵²)_b     (XVII)

où chaque R⁵¹ est indépendamment un alkyle en (C₁-C₄₀) ; chaque R⁵² est indépendamment un alkyle en (C₁-C₂₀) ; w est un nombre entier choisi parmi 1, 2 et 3 ; y est un nombre entier choisi parmi 1, 2 et 3 ; et la somme de w+y est 4 ;

et un composé de formule (XVII)

        [CH₃-(CH₂)_u]_w-SiX_y     (XVIII)

dans laquelle chaque X est un halogène choisi indépendamment dans le groupe constitué par le chlore, le brome et l'iode ; u est un nombre entier de 0 à 40, w est un nombre entier choisi parmi 1, 2 et 3 ; y est un nombre entier choisi parmi 1, 2 et 3 ; et la somme de w+y est 4.

8. Le procédé selon l'une quelconque des revendications 1 à 7, dans lequel l'organo-alcoxysilane est choisi dans le groupe constitué par :

un composé de formule (I) ;

        [R⁴]_s-Si(OR¹)_t(OR²)(OR³)     (I)

un composé de formule (II) ;

        [R⁸-(CH₂)_m]-Si(OR⁵)_qR⁶_r     (II)

un composé de formule (III)

        (⁹RO)(¹⁰RO)(¹¹RO)Si-X₁-Si(OR¹²)(OR¹³)(OR¹⁴)     (III)

un mélange d'au moins un composé de formule (I) dans laquelle R⁴ est un groupe alcényle en (C₁-C₄) et d'au moins un composé de formule (I) dans laquelle R⁴ est un groupe alkyle en (C₂-C₂₀)-CH=CH- ;

un mélange d'au moins un composé de formule (I) et d'au moins un composé de formule (II) ;

un mélange d'au moins un composé de formule (I) et d'au moins un composé de formule (III) ;

un mélange d'au moins un composé de formule (II) et d'au moins un composé de formule (III) ;
où :

chacun de R¹, R² et R³ sont indépendamment un alkyle en (C₁-C₁₄) substitué ou non substitué ;

R⁴ est choisi dans le groupe constitué par un alcényle en (C₂-C₁₄), aryle en (C₅-C₆), alcynyle en (C₂-C₁₄) substitué ou non substitué ; et alkyl en (C₂-C₂₀)-CH=CH- ;

R⁵, R⁶, R⁹, R¹⁰, R¹¹, R¹², R¹³ et R¹⁴ sont choisi indépendamment dans le groupe constitué par un alkyle en (C₁-C₁₄), un aryle en (C₅-C₆), un alcényle en (C₂-C₁₄) et un alkyle en (C₂-C₁₄)-CH =CH- substitués ou non substitués ;

R⁸ est choisi dans le groupe constitué par H, -SH, alkyle en (C₁-C₁₂) substitué ou non substitué, aryle en (C₅-C₆) substitué ou non substitué, -(CF₂)_b-CF₃, -NR¹⁵R¹⁶, un composé de formule (IV)

et un composé de formule (V)

R¹⁵ et R¹⁶ sont choisi indépendamment dans le groupe constitué par H, alkyle en (C₁-C₁₂) substitué ou non substitué, -CO et aryle en (C₅-C₆) substitué ou non substitué ;

R¹⁷ est choisi dans le groupe constitué par H et alkyle en (C₁-C₁₂) substitué ou non substitué ;

X₁ est choisi dans le groupe constitué par -alkylène en (C₁-C₁₂)-, - alkylène en (C₁ -C ₁₂)-NH- alkylène en (C₁-C₁₂)- et -alkylène en (C₁-C₁₂)-(S)_n-alkylène en (C₁-C₁₂)- substitués ou non substitués ;

m est un nombre entier de 0 à 20 ;

n es un nombre entier de 1 à 4 ;

q est un nombre entier de 2 à 3 ;

r est un nombre entier de 0 à 1 ;

s est un nombre entier de 1 à 2 ;

t est un nombre entier de 0 à 1 ;

la somme de q + r est 3 ;

la somme de s + test 2 ; et

b est un nombre entier de 0 à 12.

9. Le procédé selon l'une quelconque des revendications 1 à 8, dans lequel le précurseur organique est choisi dans le groupe constitué par un composé de formule (VI)

un composé de formule (VII)

et un mélange de ceux-ci
où :

R₂₇ sont indépendamment choisis dans les alkyles (C₁-C₆);

R₄₀ et R₄₁ sont choisi indépendamment dans le groupe constitué par H et alkyle en (C₁-C₆) ;

X₂ est choisi dans le groupe constitué par un composé de formule (VIII)

et un composé de formule (IX) ;

et un mélange de ceux-ci ;
où :

R₄₂ est choisi dans le groupe constitué par H et alkyle en (C₁-C₆) ;

p est un nombre entier de 1 à 8 ; et

n' es un nombre entier de 1 à 6.

10. Le procédé selon la revendication 9, dans lequel le précurseur organique est un composé de formule (VII)

dans laquelle :

R₄₀ et R₄₁ sont choisi indépendamment dans le groupe constitué par H et alkyle en (C₁-C₆) ;

X₂ est choisi dans le groupe constitué par un composé de formule (VIII)

et un composé de formule (IX) ;

et un mélange de ceux-ci ;
où :

R₄₂ est choisi dans le groupe constitué par H et alkyle en (C₁-C₆) ;

p est un nombre entier de 1 à 8 ; et

n' es un nombre entier de 1 à 6.

11. Le procédé selon l'une quelconque des revendications 1 à 10, dans lequel : le catalyseur acide en solution aqueuse est un acide inorganique choisi indépendamment dans le groupe constitué par H₂SO₄, HCl, HNO₃ et un mélange de ceux-ci ;
l'alcool en (C₁-C₈) est choisi indépendamment dans le groupe constitué par le méthanol, l'éthanol, le butanol, le n-propanol, l'isopropanol et un mélange de ceux-ci ; et l'agent complexant est choisi dans le groupe constitué par l'acétylacétone, l'acide méthacrylique, l'acide acétique, l'acide isobutyrique, la bipyridine et un mélange de ceux-ci ; en particulier, l'acide est HNO₃, l'alcool en (C₁-C₈) est l'éthanol et l'agent complexant est l'acide méthacrylique.

12. Le procédé selon l'une quelconque des revendications 1 à 11, dans lequel l'alcoxyde métallique et l'alcoxyde semi-métallique sont indépendamment un composé de formule (XIII)

        (OR⁴³)(OR⁴⁴)(OR⁴⁵)(OR⁴⁶)Z     (XIII)

dans laquelle :

chacun de R⁴³, R⁴⁴, R⁴⁵ et R⁴⁶ sont choisis indépendamment dans le groupe constitué par un groupe alkyle en (C₁-C₁₄), aryle en (C₅-C₆), alcényle en (C₂-C₁₄) et alcynyle en (C₂-C₁₄) substitué ou non substitué ; et

Z est choisi dans le groupe constitué par les atomes métalliques et semi-métalliques.

13. Un substrat revêtu comprenant une couche sol-gel pouvant être obtenue par le procédé tel que défini dans l'une quelconque des revendications 1 à 12.

Drawing