(19)
(11)EP 3 464 480 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
04.11.2020 Bulletin 2020/45

(21)Application number: 17732637.8

(22)Date of filing:  25.05.2017
(51)International Patent Classification (IPC): 
C09D 5/00(2006.01)
B43L 1/10(2006.01)
C09D 183/16(2006.01)
B43L 1/00(2006.01)
(86)International application number:
PCT/US2017/034367
(87)International publication number:
WO 2017/205562 (30.11.2017 Gazette  2017/48)

(54)

1K 100% SOLIDS DRY-ERASE COATING COMPOSITION

TROCKENLÖSCHBARE 1K-BESCHICHTUNGSZUSAMMENSETZUNG AUS 100 % FESTSTOFFEN

COMPOSITION DE REVÊTEMENT D'ESSUYAGE À SEC 1K À 100 % DE MATIÈRES SOLIDES


(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

(30)Priority: 27.05.2016 US 201662342225 P

(43)Date of publication of application:
10.04.2019 Bulletin 2019/15

(73)Proprietor: SWIMC LLC
Cleveland, OH 44115 (US)

(72)Inventors:
  • MARKOVITZ II, Frank, F.
    Lakewood OH 44107 (US)
  • MAKOWSKI, Brian
    Warrensville Heights OH 44128 (US)
  • REIMANN, Jay, A.
    Mentor OH 44060 (US)
  • SHAH, Shailesh, S.
    Westlake OH 44145 (US)

(74)Representative: Dannenberger, Oliver Andre et al
Abitz & Partner Patentanwälte mbB Arabellastrasse 17
81925 München
81925 München (DE)


(56)References cited: : 
EP-A2- 2 208 766
US-A- 4 988 778
WO-A1-2013/110046
US-A1- 2010 234 497
  
      
    Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


    Description


    [0001] This application claims benefit of of co-pending U.S. Provisional Application No.: 62/342,225 filed May 27, 2016.

    TECHNICAL FIELD



    [0002] The disclosure relates generally to a dry-erase coating composition suitable for many applications including coating interior wall surfaces. Upon coating an interior wall surface with the coating composition, the composition will cure to form a dry-erase coating on the interior wall surface.

    BACKGROUND



    [0003] Dry-erase boards, also referred to as whiteboards, have been manufactured commercially for many years. Dry-erase surfaces provide a writing surface with a non-porous character that prevents the penetration of dry-erase marker ink through the surface. Conventional dry-erase marker ink formulations include a hydrophobic, oily release agent that inhibits permanent marking or staining of the whiteboard. The non-porous nature of the whiteboard combined with the oily, quick drying marker ink in dry erase markers allow the marker ink to be easily removed from the whiteboard on the top of the hydrophobic coating, and allows the ink to be removed easily.

    [0004] To manufacture a whiteboard, the manufacturer coats a dry-erase coating composition onto a substrate, and allows the substrate to dry. A number of dry-erase coating compositions are known. Traditional dry-erase coating compositions are created using two components, which must be mixed together immediately prior to coating the composition onto the substrate. Such coatings are referred to as "2K" coating compositions. Many dry-erase coating compositions are formulated using organic solvents, which impart a high level of volatile organic compounds ("VOCs"), such as ethylene glycol, formaldehyde, or benzene, many of which are hazardous. In addition, the cure time for these coating compositions can be several days. In light of these attributes, such 2K dry-erase coating compositions are intended only for professional commercial application. In addition, some known dry-erase coating compositions include isocyanate compounds or epoxies. Isocyanates are hazardous, and epoxies are prone to yellowing over time.

    [0005] It would be desirable to provide a dry-erase coating composition that is suitable for consumer application. For example, a homeowner, school, or office manager might wish to coat an interior wall surface with such a coating composition to thereby create a dry-erase "wall," or portion of a wall surface. Ideally, such a dry-erase coating composition would have a low VOC concentration (less than 150 grams/liter), and would be a single-component (or "1K") composition that did not require pre-mixing by the consumer. The coaling composition ideally would be suitable for interior architectural surfaces such as wood, drywall, cement, metal, and plaster, or over a primer coating. The dry-erase coating composition should cure at ambient temperature and without ancillary equipment such as ultraviolet lights. Upon curing, the coating composition should form a smooth, hard dry-erase coating that is resistant to interior moisture and humidity, and that is compatible with conventional dry-erase markers.

    SUMMARY



    [0006] The subject matter of the present invention is defined in claims 1-15 as attached. Embodiments described herein which are not covered by the claims merely serve to illustrate the technical context of the present invention.

    [0007] In various nonexclusive embodiments, the present application provides a coating composition, a method for making a coating composition, a method of applying a coating composition, a cured coating, and a method of marking a surface.

    [0008] It has now been discovered that a dry erase coating composition may be made by providing an aminoalkoxysilane and, in the substantial absence of water and in any suitable order, reacting a portion of the aminoalkoxysilane with a carbonate and reacting a portion of the aminoalkoxysilane with an epoxy compound. These reactions will yield a mixture of alkoxysilylamines and alkoxysilylcarbamates. An alkylamine is also provided in an amount effective to catalytically deprotect alkoxy groups in the alkoxysilylamines and alkoxysilylcarbamates to yield silanol groups.

    [0009] The mixture of alkoxysilylamines and alkoxysilylcarbamates when blended with the alkylamine may together constitute a coating composition that, upon curing by exposure to water in air, forms a dry-erase coating. The coating composition can be formulated such that the dry-erase coating that is formed is smooth, hard, moisture-resistant, durable, and compatible with conventional dry-erase ink formulations.

    [0010] In some embodiments, the aminoalkoxysilane can have a structure represented by the following formula (1):

    where A1, A2, and A3 are the same or different and comprise hydrogen or C1-C4 alkyl, with the proviso that at least one of A1, A2, and A3 comprises C1-C4 alkyl, where B1 and B2 are the same or different and comprise hydrogen or C1-C4 alkyl, with the proviso that at least one of B1 and B2 is hydrogen, and where R1 is C1-C4 alkyl.

    [0011] In accordance with the invention, the carbonate has a formula according to the following formula (2):

    R2 and R3 each independently including an alkyl group, or R2 and R3 forming a cyclic structure that may include any one or more of an alkyl group, a hydroxyalkyl group, and a hydroxyl group as substituents.

    [0012] In some embodiments, the epoxy compound can have the following formula (8)

    wherein A4 - A6 are the same or different and comprise hydrogen or a carbon-containing group with one to three carbon atoms, A7 is a carbonyl-containing linking group, and R19 is an aliphatic group having at least four carbon atoms.

    [0013] In one aspect, a coating composition prepared in accordance with the above method is provided. In another aspect, not mutually exclusive, the mixture of alkoxysilylamines and alkoxysilyl carbamates of the coating composition comprises at least two of (10), (11), and (12):





    where A1, A2, and A3 are the same or different and comprise hydrogen or C1-C4 alkyl, with the proviso that at least one of A1, A2, and A3 comprises C1-C4 alkyl, where R1 is C1-C4 alkyl, and wherein R20 is a hydroxyalkyl carbamate. The composition may be a 100% solids composition, i.e., solvent-free or essentially so.

    [0014] As described in more detail below, the coating compositions will cure to form a coating composition, the cured coating composition being within another aspect of the present application. Also provided herein are methods of applying a coating composition and methods of marking a surface. These methods employ the novel coating composition and cured coating provided herein respectively, and are otherwise conventional.

    DETAILED DESCRIPTION



    [0015] When prepared in accordance with the present teachings, it is possible to provide a dry-erase coating composition that has several desirable attributes. The coating composition can be an aqueous 1K coating composition that can have a low VOC content (less than 150 grams/liter; in some embodiments less than 125 grams/liter; in some embodiments less than 100 grams/liter; in some embodiments less than 75 grams/liter; in some embodiments less than 50 grams/liter; in some embodiments less than 25 grams/liter) and in some instances essentially zero VOC content (less than 5 grams/liter). The composition can be a 100% solids composition, by which is contemplated that the composition is free or essentially free of solvents. The cure time of the composition can be on the order of 24 hours or less. Upon curing, the cured coating can exhibit excellent marker appearance and marker removal property, with minimal ghosting. The coating will be resistant to acetone and isopropanol, which are common whiteboard cleaning solvents, and also will be resistant to water. The composition can be formulated to have at least a 12-month shelf life. Notably, these attributes are not limiting and it is possible to formulate a coating composition in accordance with the present teachings that lacks some or all of the above attributes.

    [0016] The coating compositions described herein are based on alkoxysilane technology. When used at high levels, alkoxysilanes can create a low surface energy film that reduces the chances of foreign bodies adhering to the surface. Alkoxysilanes also advantageously promote adhesion to multiple types of surfaces, and incorporate substantial crosslinking to resist penetration of marker ink. The crosslinked cured composition results in a non-porous layer on a surface on which the coating is applied.

    [0017] Generally, in preparing a coating composition, an aminoalkoxysilane, a carbonate, and an epoxy compound are provided, wherein a portion of the aminoalkoxysilane reacts with the carbonate and a portion of the aminoalkoxysilane reacts with the epoxy compound. These reactions, which may occur in any suitable order, yield a mixture of alkoxysilylamines and alkoxysilylcarbamates. The reactions may occur in the substantial absence of water or any other solvent to produce a coating composition having a solids content of 80% or more, 85% or more, 90% or more, 95% or more, 97% or more, 98% or more, 99% or more, and substantially 100%, based on the total amount of the coating composition.

    [0018] The reactions may generally occur in any order and/or simultaneously. For example, the method may comprise combining the epoxy compound and the aminoalkoxysilane to form a reacted blend, and then subsequently combining the carbonate with the blend. Alternatively, the method may include combining the carbonate and the aminoalkoxysilane to form a reacted blend, and then combining the epoxy compound and the blend. In yet other instances, the method may include simultaneously combining the carbonate, the aminoalkoxysilane, and the epoxy compound to form a reacted blend.

    [0019] In exemplary methods, the reaction between the aminoalkoxysilane and the carbonate may occur for 45 to 180 minutes, 90 to 160 minutes, or 110 to 130 minutes, and the reaction between the aminoalkoxysilane and the epoxy compound may occur for 15 to 165 minutes, 60 to 120 minutes, or 75 to 90 minutes. The reactants may be mixed during the reactions. Generally, the reactions between the aminoalkoxysilane and the carbonate and between the aminoalkoxysilane and the epoxy compound may both occur at a suitable temperature and pressure, and in practice, it has desirably been found that satisfactory results can be obtained at room temperature (20-25° C) and at approximately 101 kPa.

    [0020] In exemplary coating compositions, the aminoalkoxysilane can be present in an amount of 1.0 to 3.0 parts, 1.5 to 2.5 parts, or 1.75 to 2.25 parts, the epoxy compound can be present in an amount of 0.25 to 2.0 parts, 0.5 to 1.5 parts, or 0.75 to 1.25 parts, and the carbonate can be present in an amount of 0.5 to 2.5 parts, 1.0 to 2.0 parts, or 1.25 to 1.75 parts, relative to one another in the reaction blend.

    [0021] Any suitable aminoalkoxysilane may be employed, and for example, the aminoalkoxysilane may have a structure represented by the following general formula (1):

    where A1, A2, and A3 are the same or different and comprise hydrogen or C1-C4 alkyl, with the proviso that at least one of A1, A2, and A3 comprises C1-C4 alkyl, where B1 and B2 are the same or different and comprise hydrogen or C1-C4 alkyl, with the proviso that at least one of B1 and B2 is hydrogen, and where R1 is C1-C4 alkyl. In some aspects, A1, A2, and A3 each comprises C1-C4 alkyl. For example, the aminoalkoxysilane may comprise an aminopropyl trialkoxysilane, such as aminopropyl trimethoxysilane (sold as Dynasylan® AMMO from Evonik Industries).

    [0022] The carbonate has a general formula according to the following formula (2):

    R2 and R3 each independently including an alkyl group (with or without terminal hydroxyl groups), or R2 and R3 forming a cyclic structure that may include any one or more of an alkyl group, a hydroxyalkyl group, and a hydroxyl group as substituents. In some embodiments, the cyclic carbonate may have an empirical formula of C(3+y)H(4+2y)O4, where y is an integer of up to four. The carbonate may, for example, comprise a carbonate having the following formula:

    where A4 indicates an alkyl group, a hydroxyalkyl group, or a hydroxyl group. An example of a suitable carbonate is glycerol carbonate:



    [0023] The epoxy compound has a structure represented by the following general formula (8):

    wherein A4 - A6 are the same or different and comprise hydrogen or a carbon-containing group with one to three carbon atoms, A7 is a carbonyl-containmg linking group, and R19 is an aliphatic group having at least four carbon atoms.

    [0024] In some embodiments, the epoxy compound may comprise a glycidyl aliphatic ester. An exemplary glycidyl aliphatic ester can have the following general formula (9):

    wherein R19 is an aliphatic group having at least four carbon atoms. For example, a glycidyl aliphatic ester useful in preparing the coating composition has the following formula:

    which is sold as Cardura™ E10-P by Hexion, Inc.

    [0025] Also disclosed are compositions, wherein the epoxy compound may comprise a glycidyl aliphatic ether. An exemplary glycidyl aliphatic ether has the following formula:

    which is sold as Erisys® GE-5 by CVC Thermoset Specialties.

    [0026] The reactions between the aminoalkoxysilane and the carbonate and between the aminoalkoxysilane and the epoxy compound can yield a mixture of alkoxysilylamines and alkoxysilylcarbamates. In some instances, the method of making the coating composition can yield a mixture of alkoxysilylamines and alkoxysilylcarbamates comprising at least two of the following compounds (10), (11), and (12):





    where A1, A2, and A3 are the same or different and comprise hydrogen or C1-C4 alkyl, with the proviso that at least one of A1, A2, and A3 comprises C1-C4 alkyl, where R1 is C1-C4 alkyl, and R20 is a hydroxyalkylcarbamate. A1, A2, and A3 may each comprise the same or different C1-C4 alkyl, such as methyl. In some instances, R20 comprises a derivative from reacting an amino group with glycerol carbonate. The method is also capable of yielding a coating composition comprising a mixture of alkoxysilylamines and alkoxysilylcarbamates comprising all three of general formulas (10), (11), and (12).

    [0027] In the coating composition, compound (10) may be present, for example, in an amount of 0.7 to 1.3 parts, compound (11) may be present in an amount of 1.0 to 1.3 parts, and compound (12) may be present in an amount of 0.0 to 0.5 parts, relative to one another. In some embodiments, the coating composition consists essentially of two or more of (10), (11), and (12), optionally including pigments and other modifiers, but without substantial amounts of water or other solvents.

    [0028] In an embodiment of the method making the coating composition, a portion of aminopropyl trimethoxysilane reacts with Cardura™ E10-P and a portion of aminopropyl trimethoxysilane reacts with glycerol carbonate to produce a mixture of alkoxysilylamines and carbamates comprising at least two of (13), (14), (15):



    and

    These components are believed to function as crosslinkers in the 1K coating composition.

    [0029] The coating composition is a 1K technology that has long term shelf stability, yet that is capable of forming siloxane bonds effectively. Insofar as the present application discloses aspects other than the method for preparing the coating composition, it should be noted that the above reactions are not limiting, however, because there are other ways to create the above crosslinkers.

    [0030] It is generally believed that, during a process of curing the coating composition, the alkyoxy groups present in the crosslinkers at least partially hydrolyze when exposed to water in air. As these hydrolysis reactions occur, the alkoxy groups convert to silanol groups. It is also believed that at least a portion of the silanol groups cross-link together to form siloxane linkages. This curing process produces a highly cross-linked cured coating that exhibits dry-erase properties. The hydrolysis reactions may also produce water and one or more types of alcohol, which may evaporate from the coating composition. While alcohol may be considered VOC, it is generally believed that the amount of alcohol produced during the curing process is substantially lower than the amounts of VOCs that are produced during curing of an organic solvent-based coating composition.

    [0031] It is generally believed that the crosslinkers may, in some instances, include hydrophobic structures that slow the progress of a hydrolysis reaction between water and the alkoxy groups. To resolve this problem, an alkylamine may also be provided in the coating composition in an amount effective to catalytically deprotect alkoxy groups in the alkoxysilylamines and alkoxycarbamates to yield silanol groups. The alkylamine can accelerate the production of the silanol groups during curing of the coating composition. For example, without intending to be bound by any particular theory, it is believed that the alkylamine may catalytically deprotect the alkoxy groups according to the following reaction:



    [0032] Any suitable alkylamine may be provided in the coating composition. Exemplary secondary and tertiary amines include di and trimethyl amine, di and triethyl amine, di and tripropyl amine, di and tributyl amine, di and tripentyl amine, di and trihexyl amine, n-ethylmethylamine, n-ethylpropylamine, n-ethylbutylamine, n-ethylpentylamine, n-methylpropylamine, n-propylbutylamine, n-pentylpropylamirte, n-butylmethylamine, n-butylpentylamine, n-butylhexylamine, n-pentylhexylamine, n-isopropylmethylamine, n-methylisobutylamine, ethylisobutylamine, diisobutyl amine, and diisopropyl amine. In exemplary coating compositions, the alkylamine can be included in an amount of 0.15 wt% based on the total amount of the coating composition.

    [0033] The coating composition may include other functional ingredients in amounts intended for their effective purposes. For example, the coating composition may contain a colorant, such as a pigment. Desirably, when the coating composition is intended for use as a whiteboard paint, the pigment may be titanium dioxide. The colorant may be present in any amount suitable to impart color and covering effect to the finished coating; for example, when the pigment is titanium dioxide, it may be present in an amount ranging from 5 to 30% by weight of the composition. Other suitable pigments include any suitable pigment particles, such as azo pigments, anazurite, aluminum silicate, aluminum potassium silicate, aluminum paste, anthraquinone pigments, antimony oxide, barium metaborate, barium sulfate, calcium carbonate, calcium metaborate, calcium metasilicate, carbon black, chromium oxides, clay, copper oxides, copper oxychloride, dioxazine pigments, feldspar, hansa yellows, iron oxides such as yellow and red iron oxides, isoindoline pigments, kaolinite, lithopone, magnesium silicates, metallic flakes, mica, napthol pigments such as napthol reds, nitroso pigments, nepheline syenite, perinone pigments, perylene pigments, polycyclic pigments, pyrropyrrol pigments, pthalocyanines such as copper pthalocyanine blue and copper pthalocyanine green, quinacridones such as quinacridone violets, quinophthalone pigments, silicates, sulfides, talc, titanium dioxide, ultramarine, zinc chromate, zinc oxide, and zinc phosphate. In addition, pearlescents, optical brighteners, ultraviolet stabilizers, and the like may be employed. Colored pigments ordinarily would not be employed for whiteboard paint, but could be used in other applications.

    [0034] The composition further may include a plasticizer to improve water sensitivity. It is believed that exposure of the cured coating to water may tend to increase crosslinking via post-core drift, thus hardening the film and making the film susceptible to cracking. A flexible plasticizer or spacer may be added to at least partially inhibit additional silanol crosslinking. One suitable spacer is polyethylene glycol (such as PEG8000). The spacer may be used in any amount ranging up to about 10% by weight of the coating composition. Above this amount, the film may dissolve when exposed to water or may become undesirably soft. The coating composition also may include any one or more of dispersants, surfactants, wetting agents, synergists, and rheology modifiers. Any suitable dispersant, such as any one or more of anionic dispersants, cationic dispersants, amphoteric dispersants, or nonionic dispersants may be used in conjunction with a pigment vehicle. Other known dispersants believed to be suitable include Nuosperse® 657 and Nuosperse® FA 196 available from Elementis Specialties, Disperbyk 108 available from Altana AG, and Solsperse™M387 available from Lubrizol Corporation. Similarly, any suitable wetting agents such as any one or more of anionic wetting agents, cationic wetting agents, amphoteric wetting agents, or nonionic wetting agents may be used. An exemplary synergist is Solsperse™ 5000 available from Lubrizol Corporation. Exemplary rheology modifiers include Suspeno 201-MS available from Poly-Resyn, Inc. and Aerosil® available from Evonik Industries.

    [0035] Once formed, the coating composition may be applied immediately to a substrate, but the coating composition also may be dispensed into a suitable container, such as a paint can, and sealed. It is believed that the coating composition will have a shelf life of at least twelve months.

    [0036] A method of applying a coating composition can comprise applying the coating composition to a substrate, and allowing the coating composition to cure. Once applied to the substrate, the coating composition will cure as the composition crosslinks. The curing process does not require additional equipment (e.g., a UV source), but rather the curing occurs when the coating composition is exposed to air containing water.

    [0037] The coating composition may be employed for any suitable purpose. In certain embodiments, the coating composition may be applied to a surface in order to impart dry-erase characteristics. For example, the surface may be a wall, which may have paint or a primer already applied to the surface of the wall, over which the coating can be applied. The coating composition may be applied with brush, roller, sponge, or spray gun, or other conventional painting tool. The cured coating may have any suitable thickness, such as a thickness ranging from 0.05 - 2 mm with preferred thickness around 0.1 mm.

    [0038] The high amount of crosslinking that occurs during curing of the coating composition is believed to provide a coating that has a low porosity. The low porosity increases the durability of the coating, the resistance of the coating to water, and the resistance of the coating to marker ghosting.

    [0039] When the coating composition is applied to a surface, and allowed to successfully cure, a dry-erase marker may be used to mark the surface of the coating. As the siloxane linkage (via self-crosslinking) has lower surface energy than that of the marker ink, and the porosity of the coating is greatly reduced through crosslinking, the ink from the dry-erase marker does not penetrate into the cured coating.

    [0040] Accordingly, the dry-erase marker ink can be successfully removed by wiping without a cleaning solution or using a commercially available dry-erase cleaner that includes chemicals (e.g., water, propylene glycol n-butyl ether, and/or isopropyl alcohol). In addition, the coating may be able to resist a ghosting effect when marker ink is left on the surface for up to nine days, due to the low porosity.

    EXAMPLES


    Example 1



    [0041] A mixture of alkoxysilylamines and alkoxysilylcarbamates was produced by reacting 48% of Dynasylan® AMMO and 30% of Cardura™ E10-P in a flask, mixing and reacting the contents of the flask for 120 minutes, and then adding 22% of glycerol carbonate to the flask and further mixing and reacting the contents of the flask for an additional 120 minutes. After the addition of the glycerol carbonate, an exothermic reaction was observed and the viscosity of the contents of the flask began to increase over the 120 minute reaction period.

    Example 2



    [0042] A mixture of alkoxysilylamines and alkoxysilylcarbamates was produced by reacting 48% of Dynasylan® AMMO and 22% of glycerol carbonate in a flask, mixing and reacting the contents of the flask for 120 minutes, and then adding 30% of Cardura™ E10-P to the flask and further mixing and reacting the contents of the flask for an additional 120 minutes.

    Examples 3 and 4



    [0043] Examples 1 and 2 are repeated, except that 0.15 wt% of dibutyl amine is Example 1 to form Example 3, and 0.15 of dibutyl amine is added to Example 2 to form Example 4.

    Example 5



    [0044] A mixture of alkoxysilylamines and alkoxysilylcarbamates is produced by reacting 47% of Dynasylan® AMMO and 22% of glycerol carbonate in a flask, mixing and reacting the contents of the flask for 120 minutes, and then adding 30% of Erisys® GE-5 to the flask and further mixing and reacting the contents of the flask for an additional 120 minutes. Subsequently, 0.15% of dibutyl amine is added to the flask.

    Curing Time



    [0045] Films of Examples 1 and 2 were applied to separate Leneta testing charts and allowed to cure. A minimum curing period of 3 days was required before testing. However, an optimal curing period of 7 days was allowed before testing the water sensitivity and dry-erase properties of the cured coatings of Examples 1 and 2.

    Water Resistance Test 1



    [0046] At laboratory temperature (ambient conditions (25C +/- 3 degrees) and humidity was 50% +/- 5%., water was dropped onto a horizontal Leneta chart covered with the cured coatings of Examples 1-2, and the tested areas were covered with a medicine cup to prevent evaporation for a duration 1 to 24 hours. The cured films of Examples 1-2 demonstrated no blushing or degradation after exposure to water for up to 24 hours. Upon removal of water from the films of Examples 1-2, the films remained hard with no blistering, cracking, or delamination.

    [0047] Example 5 was tested in the same manner as Examples 1-2, but Example 5 provided inferior water resistance properties when compared with Examples 1-2, which is due to the shorter hydrophobic aliphatic tails compared to Examples 1-2.

    Water Resistance Test 2



    [0048] At laboratory temperature (ambient conditions (25C +/- 3 degrees) and humidity was 50% +/- 5%, water was sprayed onto a vertical surface (Leneta chart) covered with the cured coatings of Examples 1-2, and the sprayed coatings were immediately allowed to dry. The cured films of Examples 1-4 displayed no blushing, degradation, blistering, cracking, or delamination after a period of 24 hours had lapsed from the time of spraying.

    [0049] Example 5 was tested in the same manner as Examples 1-2, but Example 5 provided inferior water resistance properties when compared with Examples 1-2, which is due to the shorter hydrophobic aliphatic tails compared to Examples 1-2.

    Dry-Erase Performance Test



    [0050] An Expo® Dry-Erase Marker, sold by Newell Brands Company, was used to mark the cured coatings of Examples 1-5. The marking applied to the cured films could immediately be removed with the touch of a finger or by wiping with a paper towel. However, after a period of 4 hours passed from the time of applying the markings, removal of the markings from the cured films of Examples 1, 2, and 5 required rubbing with isopropanol and acetone. It is believed that the markings are drawn to the soft tail of the structure derived from Cardura™ E10-P. It was also observed that the linear structure provided by Erisys® GE-5 did not increase the dry erase performance of the cured film of Example 5 relative to Examples 1-4.

    Stability Test



    [0051] The cured coatings of Examples 1, 2, and 5 each demonstrated good stability after storage both at room temperature (4 weeks, ambient conditions (25C +/- 3 degrees) and humidity was 50% +/- 5%, and in an oven at (4 weeks at 120 F). The cured coatings of Examples 1, 2, and 5 remained clear with a slightly yellow translucent coloration. The cured coatings displayed no visual evidence of precipitation.

    [0052] Although the above description has focused on the disclosed coating compositions as dry-erase compositions, the compositions are contemplated to have many other uses. For example, the coating composition may be applied to a metal surface, in particular a ferrous surface, to form a rust-resistant or other protective coating layer on the metal surface. The composition may be applied to other surfaces such as concrete, painted or unpainted drywall, or plastics. It is also contemplated that the coating composition may be used as a coalescent aid in water-based paints.

    [0053] All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or language describing an example (e.g., "such as") provided herein, is intended to illuminate the invention and does not pose a limitation on the scope of the invention. Any statement herein as to the nature or benefits of the invention or of the preferred embodiments is not intended to be limiting. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the invention unless otherwise indicated herein or otherwise clearly contradicted by context. The description herein of any reference or patent, even if identified as "prior," is not intended to constitute a concession that such reference or patent is available as prior art against the present invention. No unclaimed language should be deemed to limit the invention in scope. Any statements or suggestions herein that certain features constitute a component of the claimed invention are not intended to be limiting unless reflected in the appended claims. Neither the marking of the patent number on any product nor the identification of the patent number in connection with any service should be deemed a representation that all embodiments described herein are incorporated into such product or service.


    Claims

    1. A method of making a dry-erase coating composition, the method comprising:

    providing an aminoalkoxysilane;

    in the substantial absence of water, reacting a portion of said aminoalkoxysilane with a carbonate, the carbonate having a formula according to the following formula (2):

    wherein R2 and R3 each independently include an alkyl group, or R2 and R3 form a cyclic structure that may include any one or more of an alkyl group, a hydroxyalkyl group, and a hydroxyl group as substituents;

    and reacting a portion of said aminoalkoxysilane with an epoxy compound of the following formula (8)

    wherein A4 - A6 are the same or different and comprise hydrogen or a carbon-containing group with one to three carbon atoms, A7 is a carbonyl-containing linking group, and R19 is an aliphatic group having at least four carbon atoms; and

    the reactions yielding a mixture of alkoxysilylamines and alkoxysilylcarbamates;

    the method including providing an alkylamine in an amount effective to catalytically deprotect alkoxy groups in said alkoxysilylamines to yield silanol groups.


     
    2. The method according to claim 1, the method comprising:

    adding said epoxy compound to said aminoalkoxysilane to form a reacted blend, and

    subsequently adding said carbonate to said blend.


     
    3. The method according to claim 1 or claim 2, said aminoalkoxysilane being present in an amount of 1.5 to 2.5 parts, said epoxy compound being present in an amount of 0.5 to 1.5 parts, and said carbonate being present in an amount of 1.0 to 2.0 parts, relative to one another.
     
    4. The method according to any one of claims 1 to 3, said epoxy compound comprising a glycidyl aliphatic ester.
     
    5. The method according to claim 4, the glycidyl aliphatic ester having the following formula (9)

    wherein R19 is an aliphatic group having at least four carbon atoms.
     
    6. The method according to any one of claims 1 to 5, the aminoalkoxysilane having a structure represented by the following formula (1):

    where A1, A2, and A3 are the same or different and comprise hydrogen or C1-C4 alkyl, with the proviso that at least one of A1, A2, and A3 comprises C1-C4 alkyl, where B1 and B2 are the same or different and comprise hydrogen or C1-C4 alkyl, with the proviso that at least one of B1 and B2 is hydrogen, and where R1 is C1-C4 alkyl.
     
    7. The method according to claim 6, the aminoalkoxysilane comprising an aminopropyl trialkoxysilane.
     
    8. The method according to claim 7, the aminoalkoxysilane comprising aminopropyl trimethoxysilane.
     
    9. The method according to any one of claims 1 to 8, said mixture of alkoxysilylamines and alkoxylsilylcarbamates comprising at least two of (10), (11), and (12):





    where A1, A2, and A3 are the same or different and comprise hydrogen or C1-C4 alkyl, with the proviso that at least one of A1, A2, and A3 comprises C1-C4 alkyl, where R1 is C1-C4 alkyl, and wherein R20 is a hydroxyalkylcarbamate.
     
    10. The method according to claim 9, said mixture of alkoxysilylamines and alkoxylsilylcarbamates comprising a mixture of all three of (10), (11), and (12).
     
    11. The method according to claim 9, said mixture of alkoxysilylamines and alkoxysilylcarbamates comprising at least two of (13), (14), (15):



    and


     
    12. The method according to claim 1, the carbonate comprising glycerol carbonate.
     
    13. The method according to any one of claims 1 to 12, the alkylamine comprising dibutyl amine.
     
    14. The method according to any one of claims 1 to 13, further including adding a spacer, wherein preferably said spacer comprises polyethylene glycol.
     
    15. The method according to any one of claims 1 to 14, further including adding a pigment, wherein preferably the pigment includes titanium dioxide.
     


    Ansprüche

    1. Ein Verfahren zur Herstellung einer Whiteboard-Beschichtungszusammensetzung, wobei das Verfahren umfasst:

    Bereitstellen eines Aminoalkoxysilans,

    Umsetzen, im Wesentlichen in Abwesenheit von Wasser, eines Teils des Aminoalkoxysilans mit einem Carbonat, wobei das Carbonat eine Formel gemäß der folgenden Formel (2) besitzt:

    wobei R2 und R3 jeweils unabhängig eine Alkylgruppe beinhalten, oder R2 und R3 eine cyclische Struktur bilden, die eine oder mehrere von einer Alkylgruppe, einer Hydroxyalkylgruppe und einer Hydroxylgruppe als Substituenten enthalten kann,

    und Umsetzen eines Teils des Aminoalkoxysilans mit einer Epoxidverbindung der folgenden Formel (8)

    wobei A4 - A6 gleich oder verschieden sind und Wasserstoff oder eine kohlenstoffhaltige Gruppe mit einem bis drei Kohlenstoffatomen umfassen, A7 eine carbonylhaltige verbindende Gruppe ist, und R19 eine aliphatische Gruppe mit wenigstens vier Kohlenstoffatomen ist, und

    die Umsetzungen eine Mischung aus Alkoxysilylaminen und Alkoxysilylcarbamaten ergeben,

    wobei das Verfahren das Bereitstellen eines Alkylamins in einer wirksamen Menge, um Alkoxygruppen in den Alkoxysilylaminen katalytisch zu entschützen, so dass Silanolgruppen erhalten werden, umfasst.


     
    2. Das Verfahren gemäß Anspruch 1, wobei das Verfahren umfasst:

    Hinzugeben der Epoxidverbindung zu dem Aminoalkoxysilan, um eine umgesetzte Mischung zu bilden, und

    anschließend Hinzugeben des Carbonats zu der Mischung.


     
    3. Das Verfahren gemäß Anspruch 1 oder Anspruch 2, wobei das Aminoalkoxysilan in einer Menge von 1,5 bis 2,5 Teilen vorliegt, die Epoxidverbindung in einer Menge von 0,5 bis 1,5 Teilen vorliegt, und das Carbonat in einer Menge von 1,0 bis 2,0 Teilen vorliegt, relativ zueinander.
     
    4. Das Verfahren gemäß einem der Ansprüche 1 bis 3, wobei die Epoxidverbindung einen aliphatischen Glycidylester umfasst.
     
    5. Das Verfahren gemäß Anspruch 4, wobei der aliphatische Glycidylester die folgende Formel (9) besitzt

    wobei R19 eine aliphatische Gruppe mit wenigstens vier Kohlenstoffatomen ist.
     
    6. Das Verfahren gemäß einem der Ansprüche 1 bis 5, wobei das Aminoalkoxysilan eine Struktur besitzt, die durch die folgende Formel (1) dargestellt wird:

    wobei A1, A2 und A3 gleich oder verschieden sind und Wasserstoff oder C1-C4-Alkyl umfassen, mit der Maßgabe, dass wenigstens eines von A1, A2 und A3 C1-C4-Alkyl umfasst, wobei B1 und B2 gleich oder verschieden sind und Wasserstoff oder C1-C4-Alkyl umfassen, mit der Maßgabe, dass wenigstens eines von B1 und B2 Wasserstoff ist, und wobei R1 C1-C4-Alkyl ist.
     
    7. Das Verfahren gemäß Anspruch 6, wobei das Aminoalkoxysilan ein Aminopropyltrialkoxysilan umfasst.
     
    8. Das Verfahren gemäß Anspruch 7, wobei das Aminoalkoxysilan Aminopropyltrimethoxysilan umfasst.
     
    9. Das Verfahren gemäß einem der Ansprüche 1 bis 8, wobei die Mischung aus Alkoxysilylaminen und Alkoxysilylcarbamaten wenigstens zwei von (10), (11) und (12) umfasst:





    wobei A1, A2 und A3 gleich oder verschieden sind und Wasserstoff oder C1-C4-Alkyl umfassen, mit der Maßgabe, dass wenigstens eines von A1, A2 und A3 C1-C4-Alkyl umfasst, wobei R1 C1-C4-Alkyl ist, und wobei R20 ein Hydroxyalkylcarbamat ist.
     
    10. Das Verfahren gemäß Anspruch 9, wobei die Mischung aus Alkoxysilylaminen und Alkoxysilylcarbamaten eine Mischung aus allen dreien von (10), (11) und (12) umfasst.
     
    11. Das Verfahren gemäß Anspruch 9, wobei die Mischung aus Alkoxysilylaminen und Alkoxysilylcarbamaten wenigstens zwei von (13), (14), (15) umfasst:



    und


     
    12. Das Verfahren gemäß Anspruch 1, wobei das Carbonat Glycerincarbonat umfasst.
     
    13. Das Verfahren gemäß einem der Ansprüche 1 bis 12, wobei das Alkylamin Dibutylamin umfasst.
     
    14. Das Verfahren gemäß einem der Ansprüche 1 bis 13, ferner beinhaltend das Hinzugeben eines Spacers, wobei vorzugsweise der Spacer Polyethylenglycol umfasst.
     
    15. Das Verfahren gemäß einem der Ansprüche 1 bis 14, ferner beinhaltend das Hinzugeben eines Pigments, wobei vorzugsweise das Pigment Titandioxid beinhaltet.
     


    Revendications

    1. Procédé de fabrication d'une composition de revêtement effaçable à sec, le procédé comprenant les étapes qui consistent à :

    se munir d'un aminoalkoxysilane ;

    en l'absence quasi-totale d'eau, mettre en réaction une portion dudit aminoalkoxysilane avec un carbonate, le carbonate ayant une formule conforme à la formule (2) suivante :

    où R2 et R3 incluent chacun indépendamment un groupement alkyle, ou R2 et R3 forment une structure cyclique qui peut inclure un ou plusieurs quelconques parmi un groupement alkyle, un groupement hydroxyalkyle et un groupement hydroxyle comme substituants ;

    et mettre en réaction une portion dudit aminoalkoxysilane avec un composé époxy de la formule (8) suivante :

    où A4 - A6 sont identiques ou différents et comprennent un hydrogène ou un groupement carboné contenant un à trois atomes de carbone, A7 est un groupement de liaison contenant un carbonyle et R19 est un groupement aliphatique ayant au moins quatre atomes de carbone ; et

    les réactions produisent un mélange d'alkoxysilylamines et d'alkoxysilylcarbamates ;

    le procédé incluant l'étape qui consiste à se munir d'une alkylamine à une quantité efficace pour effectuer une déprotection catalytique des groupements alkoxys dans lesdites alkoxysilylamines pour produire des groupements silanols.


     
    2. Procédé selon la revendication 1, le procédé comprenant :

    l'addition dudit composé époxy au dit aminoalkoxysilane pour former un mélange réagi et

    ensuite l'addition dudit carbonate au dit mélange.


     
    3. Procédé selon la revendication 1 ou la revendication 2, ledit aminoalkoxysilane étant présent à une quantité de 1,5 à 2,5 parties, ledit composé époxy étant présent à une quantité de 0,5 à 1,5 partie et ledit carbonate étant présent à une quantité de 1,0 à 2,0 parties, les uns par rapport aux autres.
     
    4. Procédé selon l'une quelconque des revendications 1 à 3, ledit composé époxy comprenant un ester de glycidyle aliphatique.
     
    5. Procédé selon la revendication 4, l'ester de glycidyle aliphatique ayant la formule (9) suivante :

    où R19 est un groupement aliphatique ayant au moins quatre atomes de carbone.
     
    6. Procédé selon l'une quelconque des revendications 1 à 5, l'aminoalkoxysilane ayant une structure représentée par la formule (1) suivante :

    où A1, A2 et A3 sont identiques ou différents et comprennent un hydrogène ou un alkyle en C1-C4, à condition que un au moins de A1, A2 et A3 comprenne un alkyle en C1-C4, où B1 et B2 sont identiques ou différents et comprennent un hydrogène ou un alkyle en C1-C4, à condition que un au moins de B1 et B2 soit un hydrogène, et où R1 est un alkyle en C1-C4.
     
    7. Procédé selon la revendication 6, l'aminoalkoxysilane comprenant un aminopropyltrialkoxysilane.
     
    8. Procédé selon la revendication 7, l'aminoalkoxysilane comprenant l'aminopropyltriméthoxysilane.
     
    9. Procédé selon l'une quelconque des revendications 1 à 8, ledit mélange d'alkoxysilylamines et d'alkoxysilylcarbamates comprenant deux au moins de (10), (11) et (12) :





    où A1, A2 et A3 sont identiques ou différents et comprennent un hydrogène ou un alkyle en C1-C4, à condition que un au moins de A1, A2 et A3 comprenne un alkyle en C1-C4, où R1 est un alkyle en C1-C4 et où R20 est un (hydroxyalkyl)carbamate.
     
    10. Procédé selon la revendication 9, ledit mélange d'alkoxysilylamines et d'alkoxysilylcarbamates comprenant un mélange des trois (10), (11) et (12).
     
    11. Procédé selon la revendication 9, ledit mélange d'alkoxysilylamines et d'alkoxysilylcarbamates comprenant deux au moins de (13), (14) et (15) :



    et


     
    12. Procédé selon la revendication 1, le carbonate comprenant le carbonate de glycérol.
     
    13. Procédé selon l'une quelconque des revendications 1 à 12, l'alkylamine comprenant la dibutylamine.
     
    14. Procédé selon l'une quelconque des revendications 1 à 13 incluant en outre l'addition d'un espaceur, préférablement où ledit espaceur comprend le polyéthylène glycol.
     
    15. Procédé selon l'une quelconque des revendications 1 à 14 incluant en outre l'addition d'un pigment, préférablement où le pigment inclut le dioxyde de titane.
     






    Cited references

    REFERENCES CITED IN THE DESCRIPTION



    This list of references cited by the applicant is for the reader's convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

    Patent documents cited in the description