(19)
(11)EP 3 318 615 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
17.06.2020 Bulletin 2020/25

(21)Application number: 16817993.5

(22)Date of filing:  29.06.2016
(51)International Patent Classification (IPC): 
C09D 201/00(2006.01)
C09D 5/20(2006.01)
C09D 7/40(2018.01)
B05D 7/24(2006.01)
C09D 167/08(2006.01)
(86)International application number:
PCT/JP2016/069349
(87)International publication number:
WO 2017/002885 (05.01.2017 Gazette  2017/01)

(54)

SURFACE LAYER-PEELABLE COMPOSITE COATING FILM, COATING COMPOSITION FOR FORMING COMPOSITE COATING FILM, AND METHOD

VERBUNDBESCHICHTUNGSFILM MIT ABZIEHBARER OBERFLÄCHENSCHICHT, BESCHICHTUNGSZUSAMMENSETZUNG ZUR HERSTELLUNG EINES ZUSAMMENGESETZTEN BESCHICHTUNGSFILMS UND VERFAHREN

FILM DE REVÊTEMENT COMPOSITE À COUCHE DE SURFACE PELABLE, COMPOSITION DE REVÊTEMENT POUR FORMER LE FILM DE REVÊTEMENT COMPOSITE ET PROCÉDÉ


(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: 01.07.2015 JP 2015132782

(43)Date of publication of application:
09.05.2018 Bulletin 2018/19

(73)Proprietor: Nippon Paint Holdings Co., Ltd.
Osaka-shi, Osaka 531-8511 (JP)

(72)Inventors:
  • URABE, Kengo
    Tokyo 140-8675 (JP)
  • IGA, Mika
    Tokyo 140-8675 (JP)
  • MINATO, Yasunori
    Tokyo 140-8675 (JP)

(74)Representative: Mewburn Ellis LLP 
Aurora Building Counterslip
Bristol BS1 6BX
Bristol BS1 6BX (GB)


(56)References cited: : 
CN-A- 101 386 770
JP-A- H0 299 566
JP-A- H02 170 877
JP-A- 2003 138 214
JP-A- 2015 189 792
CN-A- 103 937 393
JP-A- S6 420 274
JP-A- H02 500 450
JP-A- 2008 038 123
  
      
    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

    TECHNICAL FIELD



    [0001] The present invention provides a surface layer-peelable composite coating film, a coating composition for forming such a composite coating film, and a method thereof.

    BACKGROUND ART



    [0002] An alkyd resin is an oxidative polymerization resin synthesized from a polybasic acid or a polybasic acid anhydride, a polyhydric alcohol, and a fatty acid, and the oxidative polymerization resin undergoes ester oxidation polymerization due to oxygen in air at ordinary temperature to form a three-dimensional network structure, resulting in a coating film with high solvent resistance and water resistance. An alkyd resin-based coating material is usable for various materials and is inexpensive and therefore useful for a wide range of applications from indoor wall coating to coating of large structures such as buildings, ships, and vehicles.

    [0003] For a coating material containing an alkyd resin, Patent Document 1 discloses a radically curable resin composition and a covering material that are useful as a civil engineering and building material retaining low-temperature flexibility with high low-temperature curing property. This resin composition contains (A) a polyether acryl urethane resin, (B) an air-drying property imparting type polymer using a drying oil and/or a fatty acid-based compound thereof, and (C) an ethylenically unsaturated monomer. The component (B) is preferably an alkyd resin. For the purpose of improving a drying property, paraffin and/or wax (D) may be used together in this resin composition in addition to the components (A) to (C).

    [0004] Patent Document 2 discloses a radically curable resin composition and a covering material that are suitable for a wide range of civil engineering and building material applications as in Patent Document 1. This resin composition contains (A) a resin having a (meth)acryloyl group at a molecular end, (B) an air-drying property imparting type polymer using a drying oil and/or a fatty acid-based compound thereof, and (C) an ethylenically unsaturated monomer having a (meth)acryloyl group with a molecular weight of 160 or more. The component (B) is preferably an alkyd resin. For the purpose of improving a drying property, paraffin and/or wax (D) may be used together in this resin composition in addition to the components (A) to (C).

    [0005] Patent Document 3 discloses a coating composition having a thermosetting film formability and based on wax or a wax-like compound (e.g., polyethylene wax, paraffin wax) or a natural drying oil or an alkyd resin. This coating composition is used for preventing corrosion of a metal base material of a vehicle body, and an additive gelling at a relatively high temperature (e.g., polyvinyl chloride, and C1-8 alkyl ester of methacrylic acid or acrylic acid) can be added in a small amount so as to completely prevent coating from flowing or dripping.
    Patent Document 4 describes a gelled varnish and the gelled coating material comprise a synthetic resin and/or fats and oils, a solvent, and a thickening agent as the essential components, and the above solvent contains a high boiling point solvent having a boiling point of 200-400 °C and the weight of the high boiling point solvent based on the total weight of the varnish or the coating material is 10-80%.
    Patent Document 5 describes a lead-free catalyst alkyd resin finish comprising 55-75% alkyd resin, 10-20% pigment, 3-5% of a film forming additive, 3-5% of a drier, 0.3-1.0% of an anti-skinning agent and the balance being a petroleum solvent, based on 100% of the total weight.
    Patent Document 6 describes a phenolic aldehyde modified alcohol acid antirust coating comprising 30-45% parts of phenolic aldehyde modified alcohol acid resin (the percentage by weight of solids is 70%+/-3%), 10-15 parts chromium-free polyphosphoric acid aluminium zinc, 10-15 parts low-lead zinc phosphate, 0.5-1.5 parts of carbon black, 5-10 parts titanium dioxide, 10-15 parts precipitated barium sulfate, 5-10 parts talcum powder, 0.5-1.0 parts bentonite BE-828, 0.2-1.0 partd high-efficiency dispersant EDL-4020, 0.5-1.0 parts cobalt iso-octoate (4%), 2-3 parts rare earth drier for coating, 0.5-1.0 parts anti- sagging additive, 0.1-0.3 parts anti-skinning agent and 5-10 parts of heavy aromatics.

    PRIOR ART DOCUMENTS


    PATENT DOCUMENTS



    [0006] 

    Patent Document 1: Japanese Laid-Open Patent Publication No.: 8-259643

    Patent Document 2: Japanese Laid-Open Patent Publication No.: 8-283357

    Patent Document 3: Japanese Unexamined Patent Application Publication (Translation of PCT Application) No.: 8-503987

    Patent Document 4: JP2003138214 A

    Patent Document 5: CN101386770A

    Patent Document 6: CN103937393A


    SUMMARY OF THE INVENTION


    PROBLEM TO BE SOLVED BY THE INVENTION



    [0007] When a surface of a coating film is scratched or soiled, or when the function imparted to the coating film is deactivated, recoating is required. The recoating is more difficult in places where the recoating is more required, such as hospital rooms and precision equipment rooms that must always be kept clean, windscreens on roads frequently damaged or contaminated, high humidity places, and factories.

    [0008] Since conventional typical coating films are designed to be completely cured, difficult recoating is necessary when a coating film surface is damaged or contaminated or the function thereof is deactivated.

    [0009] This leads to a problem of development of a coating composition, for example, a highly versatile alkyd resin-based coating composition, capable of forming a coating film that can be renewed a number of times by peeling a coating-film surface layer.

    MEANS FOR SOLVING PROBLEM



    [0010] As a result of intensive studies for solving the problem, the present inventors found that by using a certain coating composition containing a flow-inhibitory and polymerization-reaction-inhibitory substance, a dryer, and an oxidative polymerization inhibitor for an oxidative polymerization resin, a composite coating film made up of a cured film layer and an uncured inner layer can be formed. The film layer of this composite coating film can be peeled off and the surface of the uncured inner layer allowed to appear by peeling is exposed to oxygen so that a surface layer is dried and cured to form a film layer.

    [0011] The present invention provides a coating composition comprising a base resin composition containing an oxidative polymerization resin; an organic compound having a melting point of 5 to 150 °C; a dryer; and an oxidative polymerization inhibitor containing at least one of a dryer protectant and a radical inhibitor, which comprises the 10 to 100 wt% organic compound based on the 100 wt% base resin composition and a content of metal elements in the dryer is 0.001 to 1.5 wt% based on 100 wt% solid content of the oxidative polymerization resin, wherein if the oxidative polymerization inhibitor contains any one of the dryer protectant and the radical inhibitor, 0.5 to 4 moles of the dryer protectant is contained per mole of metal elements in the dryer; or the 0.01 to 2.0 wt% radical inhibitor is contained based on 100 wt% solid content of the oxidative polymerization resin; or if the oxidative polymerization inhibitor contains both the dryer protectant and the radical inhibitor, when 0.5 to 4 moles of the dryer protectant is contained per mole of metal elements in the dryer, the 2.0 wt% or less radical inhibitor is contained based on 100 wt% solid content of the oxidative polymerization resin; or when less than 0.5 moles of the dryer protectant is contained per mole of metal elements in the dryer, the 0.01 to 2.0 wt% radical inhibitor is contained based on 100 wt% solid content of the oxidative polymerization resin.

    [0012] Additionally, the present invention provides a composite coating film comprising a film layer; and an inner layer, wherein the inner layer is an uncured body of the coating composition of the present invention, while the film layer is a cured body of the coating composition formed in a peelable manner on a surface of the inner layer, and wherein a surface layer of the inner layer exposed to air by peeling the film layer formed on the inner layer is curable due to oxidative polymerization so that another film layer is formable in a peelable manner.

    [0013] Furthermore, the present invention provides a method of manufacturing a composite coating film made up of a film layer and an inner layer such that the film layer is formed in a peelable manner on a surface of the inner layer, the method comprising the steps of applying the coating composition of the present invention onto a basal plate to form a coating film made up of an uncured body of the coating composition; and forming a film layer by exposing the coating film made up of the uncured body to air to cure a surface layer thereof due to oxidative polymerization while maintaining a portion under the film layer in an uncured state as an inner layer.

    [0014] In some cases, the composite coating film has a rebound resilience of 11 to 55%.

    [0015] In some instances, the film layer has a thickness in a range of 10 µm to 5 mm, and wherein the inner layer has a thickness equal to or greater than the thickness of the film layer.

    [0016] In some instances, the other film layer has a thickness in a range of 10 µm to 5 mm.

    EFFECT OF THE INVENTION



    [0017] The composite coating film according to the present invention can be formed by applying the coating composition of the present invention onto a base material and exposing the coating composition to oxygen in air and, when the surface thereof is damaged or contaminated or a function imparted thereto is deactivated, only the film layer can be peeled off to renew the surface layer one or more times.

    [0018] Furthermore, the composite coating film according to the present invention can be used as an underlayer with a top coating material applied, or with an interior material such as an exterior material and a wallpaper material applied, thereon to form an upper layer, and the upper layer can easily be renewed by peeling the composite film layer of the present invention.

    BRIEF DESCRIPTION OF DRAWINGS



    [0019] 

    Fig. 1 is a schematic of a composite coating film of the present invention and peeling of a film layer thereof.

    Fig. 2 is a schematic of steps of formation of the composite coating film of the present invention.

    Fig. 3 is a schematic for explaining a measurement method of rebound resilience.

    Fig. 4 is a schematic for explaining a peeling test.


    MODES FOR CARRYING OUT THE INVENTION



    [0020] The present invention will now be described in detail with preferred embodiments.

    1. Coating Composition



    [0021] A coating composition of the present invention comprises a base resin composition containing an oxidative polymerization resin; an organic compound having a melting point of 5 to 150 °C; a dryer; and an oxidative polymerization inhibitor containing at least one of a dryer protectant and a radical inhibitor, and comprises 10 to 100 wt% organic compound based on the 100 wt% base resin composition and a content of metal elements in the dryer is 0.001 to 1.5 wt% based on 100 wt% solid content of the oxidative polymerization resin, and
    if the oxidative polymerization inhibitor contains any one of the dryer protectant and the radical inhibitor,
    0.5 to 4 moles of the dryer protectant is contained per mole of metal elements in the dryer; or
    the 0.01 to 2.0 wt% radical inhibitor is contained based on 100 wt% solid content of the oxidative polymerization resin; or
    if the oxidative polymerization inhibitor contains both the dryer protectant and the radical inhibitor,
    when 0.5 to 4 moles of the dryer protectant is contained per mole of metal elements in the dryer, the 2.0 wt% or less radical inhibitor is contained based on 100 wt% solid content of the oxidative polymerization resin; or
    when less than 0.5 moles of the dryer protectant is contained per mole of metal elements in the dryer, the 0.01 to 2.0 wt% radical inhibitor is contained based on 100 wt% solid content of the oxidative polymerization resin.

    [0022] In the present invention, the base resin composition is a resin composition containing at least an oxidative polymerization resin and may further contain an oxidative polymerization compound, and a coating resin without an oxidative polymerization group.

    [0023] In the present invention, the oxidative polymerization resin contained in the base resin composition is a resin containing an oxidative polymerization group undergoing an oxidative polymerization reaction due to a reaction with oxygen in air to be three-dimensionally crosslinked, and examples thereof include, an alkyd resin that is a reaction product of a polybasic acid or polybasic acid anhydride, a fatty acid, and a polyhydric alcohol, a reaction product of an acrylic resin or a urethane resin and a fatty acid.

    [0024] Examples of the polybasic acid or polybasic acid anhydride in the alkyd resin usable in the present invention include, compounds having two or more carboxyl groups in molecules of dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, itaconic acid, maleic acid , fumaric acid, phthalic acid, isophthalic acid, and terephthalic acid; tricarboxylic acids such as trimellitic acid; and tetracarboxylic acids such as pyromellitic acid, and acid anhydrides thereof.

    [0025] Examples of the fatty acid in the alkyd resin usable in the present invention include, a fatty acid contained in drying oil having an iodine value of 130 or more selected from the group consisting of linseed oil, tung oil, poppy-seed oil, perilla oil, sunflower oil, and safflower oil; a fatty acid contained in semi-drying oil having an iodine value of 100 to 130 selected from the group consisting of soybean oil, rice bran oil, cottonseed oil, and sesame oil; a fatty acid contained in non-drying oil having an iodine value of less than 100 selected from the group consisting of olive oil, almond oil, peanut oil, coconut oil, camellia oil, rapeseed oil, and castor oil. Examples of such fatty acids include, unsaturated fatty acids such as palmitoleic acid, oleic acid, linoleic acid, and linolenic acid.

    [0026] Examples of the polyhydric alcohol in the alkyd resin usable in the present invention include, diols selected from the group consisting of ethylene glycol, diethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2-diethyl-1,3-propanediol, neopentyl glycol; trivalent or higher polyols selected from the group consisting of triethylene glycol, trimethylol propane, trimethylol ethane, glycerine, and pentaerythritol; and hydroxycarboxylic acid selected from the group consisting of 2,2-dimethylolpropionic acid, 2,2-dimethylol butanoic acid, 2,2-dimethylol pentanoic acid, 2,2-dimethylol-hexanoic acid, and 2,2-dimethylol octanoic acid.

    [0027] The fatty acid in the reaction product of the acrylic resin or urethane resin and the fatty acid usable in the present invention is the same as the fatty acid in the alkyd resin usable in the present invention.

    [0028] The solid content of the oxidative polymerization resin is 70 to 100 wt%, preferably 85 to 100 wt%, more preferably 95 to 100 wt% in the solid content of the total base resin composition. When the content of the oxidative polymerization resin is within the range, the drying property of the coating film is ensured.

    [0029] The oxidative polymerization compound allowed to be contained in the base resin composition in the present invention is a compound containing an oxidative polymerization group undergoing an oxidative polymerization reaction due to a reaction with oxygen in air to be three-dimensionally crosslinked, and examples thereof include, fatty acids contained in drying oil having an iodine value of 130 or more selected from the group consisting of linseed oil, tung oil, poppy seed oil, perilla oil, sunflower oil, and safflower oil; and fatty acids contained in semi-drying oil having an iodine value of 100 to 130 selected from the group consisting of soybean oil, rice bran oil, cottonseed oil, and sesame oil. Examples of such fatty acids include, but are not limited to, unsaturated fatty acids such as palmitoleic acid, oleic acid, linoleic acid, and linolenic acid.

    [0030] In the present invention, examples of the coating resin without an oxidative polymerization group allowed to be contained in the base resin composition are common coating resins including acrylic resin, urethane resin, epoxy resin, polyester resin, etc.

    [0031] In the present invention, the organic compound having a melting point of 5 to 150 °C is a compound that can be kneaded with the base resin composition at a temperature not lower than the melting point such that an obtained mixture forms a coating film structure without flowing at a temperature of usage environment of the coating film. Therefore, an inner layer of the composite coating film made up of an uncured body can form and maintain the coating film structure without flowing in the usage environment due to the action of the organic compound. Additionally, the organic compound has a function of intervening between components of the oxidative polymerization resin so as to hinder the approach between the oxidative polymerization resins and thereby inhibit a dry curing reaction due to an oxidative polymerization reaction. Therefore, in the present invention, the organic compound can be regarded as a flow-inhibitory and polymerization-reaction-inhibitory substance.

    [0032] In the present invention, if the melting point of the organic compound is 5 °C or higher, the coating film structure can be formed in usual usage environment. If the melting point is 150 °C or less, excessive heating is not required at the time of kneading with the base resin composition.

    [0033] Examples of the organic compound usable in the present invention include, but not limited to, liquid paraffin, paraffin wax, microcrystalline wax, polyethylene, polyacrylamide, polyacrylate, animal wax, vegetable wax, higher fatty acid, higher alcohol, amines, ketones, esters, etc. These organic compounds can be used singly or as a mixture of two or more compounds. Paraffins are alkanes represented by CnH2n+2, and include paraffins in the forms of liquid and solid at ordinary temperature depending on the carbon number or molecular weight. Paraffins in the form of liquid are referred to as liquid paraffin, while paraffins in the form of solid are referred to as paraffin wax. The paraffin wax is generally classified by the melting point rather than the carbon number or molecular weight. The paraffin wax includes, for example, those having a low melting point (about 42 °C) to a high melting point (about 70 °C), and those having a higher melting point. In the present invention, paraffin wax, polyethylene, or a combination thereof is preferable.

    [0034] The content of the organic compound is 10 to 100 wt% based on the 100 wt% base resin composition. The content less than the lower limit leads to vulnerability to a change in temperature of the usage environment, and the content larger than the upper limit leads to an increase in time required for forming the film layer. To improve workability of peeling and ensure the number of times of peeling, the content is more preferably 15 to 50 wt%, further preferably 20 to 40 wt%.

    [0035] In the present invention, the dryer is a compound promoting oxidative polymerization of the oxidative polymerization resin such as an alkyd resin, and mainly promotes generation of a peroxide through hydrogen abstraction of an α-methylene group of a double bond in the presence of oxygen, and generation of oxygen radicals due to decomposition of the generated peroxide. The polymerization proceeds due to a radical chain reaction to form a coating film with a three-dimensional network structure.

    [0036] Examples of the dryer usable in the present invention include a metal soap composed of bonding between a metal and a long chain fatty acid. Examples of the metal usable for the metal soap include, but not limited to, metals such as cobalt, barium, vanadium, manganese, cerium, lead, iron, calcium, zinc, zirconium, nickel, tin, and strontium, preferably cobalt and manganese having a favorable surface drying property, more preferably cobalt. Examples of the long-chain fatty acid usable for the metal soap include, but not limited to, organic acids such as propionic acid, octylic acid, naphthenic acid, neodecanoic acid, tung oil acid, linseed oil acid, soybean oil acid, and resin acid, preferably propionic acid, naphthenic acid, and octylic acid, more preferably naphthenic acid and octylic acid. The metal soap usable in the present invention is preferably a cobalt salt of naphthenic acid or octylic acid, more preferably a naphthenic acid cobalt salt.

    [0037] The content of the dryer is an amount in which the content of metal elements in the dryer is 0.001 to 1.5 wt% based on 100 wt% solid content of the oxidative polymerization resin. The content less than the lower limit leads to an increase in time required for forming the film layer, and the content larger than the upper limit tends to cause a defect in appearance such as shrinkage in the film layer. To improve workability of peeling and ensure the number of times of peeling, the content is more preferably 0.01 to 1.0 wt%, further preferably 0.05 to 0.5 wt%.

    [0038] In the present invention, the oxidative polymerization inhibitor is an agent inhibiting the oxidative polymerization reaction due to a reaction with oxygen in air by the oxidative polymerization resin and the oxidative polymerization compound contained in the base resin composition, and contains a dryer protectant and a radical inhibitor. The dryer protectant and the radical inhibitor can be used singly or in combination.

    [0039] In the present invention, the dryer protectant is a substance inhibiting the oxidative polymerization promoting effect of the dryer when coexisting with the dryer. Since a volatile dryer protectant is used in the coating composition of the present invention, the dryer protectant disappears due to volatilization in the vicinity of the surface of the coating film, and the oxidative polymerization promoting effect of the dryer is exerted. Consequently, only the surface layer of the coating film is cured to form a film layer. This film layer suppresses the volatilization of the inner dryer protectant and the oxidative polymerization promoting effect of the dryer is inhibited, so that the inner layer is maintained uncured.

    [0040] The dryer protectant usable in the present invention is a volatile substance having a boiling point of 300 °C or less, and example thereof include, methyl ethyl ketoxime, acetone oxime, butyl aldoxime, cyclohexanone oxime, dialkyl hydroxylamine, ammonia, hydroxylamine, triethylamine, and dimethylethanolamine. The dryer protectant is preferably methyl ethyl ketoxime and cyclohexanone oxime.

    [0041] The content of the dryer protectant is preferably 0.5 to 4 moles per mole of metal elements in the dryer. The content less than the lower limit makes the film layer thicker, and the content larger than the upper limit leads to an increase in time required for forming the film layer. To improve workability of peeling and ensure the number of times of peeling, the content is more preferably 1 to 3 moles, further preferably 1.5 to 2.5 moles. When a plurality of dryer protectants is used in combination, the total amount may be within the range described above.

    [0042]  In the present invention, unlike the dryer protectant, the radical inhibitor is not a substance inhibiting the promotion of oxidative polymerization of the dryer and is a substance directly inhibiting the oxidative polymerization initiation function of radicals present in a system. Since the volatile radical inhibitor is used in the coating composition of the present invention, the radical inhibitor disappears due to volatilization in the vicinity of the surface of the coating film, and the oxidative polymerization initiation function of the radicals is exerted. Consequently, only the surface layer of the coating film is cured to form a film layer. This film layer suppresses the volatilization of the inner radical inhibitor and the oxidative polymerization initiation function of the radicals is inhibited, so that the inner layer is maintained uncured.

    [0043] The radical inhibitor usable in the present invention is a volatile substance having a boiling point of 300 °C or less, and example thereof include, phenolic substances such as eugenol, butylated hydroxytoluene, and butylated hydroxyanisole; and phosphite substances such as trimethyl phosphite, triethyl phosphite, and tributyl phosphite. The radical inhibitor is preferably eugenol and tributyl phosphite.

    [0044] The content of the radical inhibitor is preferably 0.01 to 2.0 wt% based on 100 wt% solid content of the oxidative polymerization resin. The content less than the lower limit makes the film layer thicker, and the content larger than the upper limit leads to an increase in time required for forming the film layer. To improve workability of peeling and ensure the number of times of peeling, the content is more preferably 0.03 to 1.0 wt%, further preferably 0.05 to 0.5 wt%. When a plurality of radical inhibitors is used in combination, the total amount may be within the range described above.

    [0045] When the dryer protectant and the radical inhibitor are used in combination, the dryer protectant can be contained in an amount of 4 moles or less per mole of metal elements in the dryer, and the radical inhibitor can be contained in a range of 2.0 wt% or less based on 100 wt% solid content of the oxidative polymerization resin. However, the dryer protectant in the range of less than 0.5 moles per mole of metal elements in the dryer and the radical inhibitor in the range of less than 0.01 wt% based on 100 wt% solid content of the oxidative polymerization resin are excluded since the oxidative polymerization inhibition effect cannot sufficiently be exerted.

    [0046] Because of the composition described above, the coating composition of the present invention can be applied onto a basal plate to form a coating film made up of an uncured body of the coating composition and, by exposing the coating film to air, the surface layer thereof can be cured due to oxidative polymerization to form a composite coating film made up of a cured film layer and an inner layer in an uncured state under the film layer. Since the inner layer of the obtained composite coating film is maintained in the uncured state, the film layer can be peeled off, and the surface layer of the inner layer exposed to air by peeling the film layer is cured due to oxidative polymerization, so that another film layer is newly formed. As long as the inner layer in the uncured state exists, the film layer can be peeled off a number of times to renew the surface layer of the coating film.

    [0047] To the coating composition of the present invention, a pigment component can generally be added in addition to the essential components described above. Examples of the pigment component usable in the present invention include, color pigments such as titanium dioxide, carbon black, red iron oxide, and phthalocyanine blue, extender pigments such as calcium carbonate, talc, mica, and clay, and antirust pigments. The content of the pigment component in the coating material is preferably 0.1 to 70 %, more preferably 0.1 to 50 %, in terms of the pigment weight concentration (PWC) based on the solid content of the coating composition. If the PWC is too low, the concealing property of the coating film may not be sufficient, and if the PWC is too high, the film layer may become difficult to form.

    [0048] The coating composition of the present invention can further contain commonly used coating additives. Examples of the coating additives usable in the coating composition of the present invention can include, ultraviolet absorbers, light stabilizers, viscosity modifiers, surface conditioners, antioxidants, fungicides, plasticizers, nd antifoamers. The coating additives are generally used in an amount of 0.01 to 10 wt% based on the 100 wt% coating composition.

    [0049] An organic solvent can also be contained in the coating composition of the present invention to the extent that the effects of the present invention are not affected.

    2. Composite Coating Film



    [0050] As shown in Fig. 1, the composite coating film of the present invention is a composite coating film made up of a film layer 3 and an inner layer 2 formed by using the coating composition of the present invention, and the film layer 3 formed on the inner layer 2 is peelable. The surface layer of the inner layer 2 allowed to appear by peeling the film layer 3 is exposed to air and cured due to oxidative polymerization to separately form the new film layer 3.

    [0051] For a coating method, any suitable method can be adopted depending on a type of base material. Although not particularly limited, examples of the method include application with a brush, a trowel, a roller, air spray, and airless spray.

    [0052] In the composite coating film of the present invention, the inner layer 2 is an uncured body of the coating composition of the present invention, and the film layer 3 is a cured body of the coating composition formed in a peelable manner on the surface of the inner layer 2. As described above, only the film layer 3 is cured and therefore can be peeled off and, since the inner layer 2 is not cured, the surface layer of the inner layer 2 exposed to air by peeling the film layer 3 is cured so that the surface layer of the coating film can be renewed (Fig. 1).

    [0053] In the composite coating film of the present invention, when the coating film surface layer is determined as being surface-dry based on the definition of JIS K 5600-3-2 (Ballotini method described later) under an atmosphere at 23 °C, it is judged that the film layer 3 is formed.

    [0054] In the composite coating film of the present invention, the inner layer must be maintained in an uncured state. Therefore, it is necessary to confirm that the inner layer is uncured for the composite coating film when it is judged that the film layer is formed.

    [0055] In the present invention, as shown in Fig. 3, a rubber ball is dropped onto the composite coating film to obtain rebound resilience from the rebound height of the ball. In the present invention, when the rebound resilience under an atmosphere at 23 °C is 11 to 55%, it is judged that the inner layer is uncured.

    [0056] Even though being within the range described above, if the rebound resilience subsequently goes out of the range, this means that the curing of the inner layer is proceeding. Therefore, once the rebound resilience within the range is exhibited, the rebound resilience is desirably within the range after long-term aerial exposure, for example, after six-month aerial exposure at 23 °C.

    [0057] The thickness of the film layer 3 as described above is in the range of 10 µm to 5 mm. Since the film layer 3 having a thickness within the range of 10 µm to 5 mm is newly formed in the surface layer of the inner layer 2 by peeling the film layer 3, the film layer 3 can be peeled off one or more times when the inner layer 2 has a thickness equal to or greater than the thickness of the film layer 3.

    [0058] The composite coating film of the present invention can be used as a single-layer coating film or can be used as an underlayer with a top coating material applied, or with an interior material such as an exterior material and a wallpaper material applied, to an upper surface thereof to form an upper layer. The top coating material, the interior material such as an exterior material and a wallpaper material, etc. are not particularly limited and those generally used are usable.

    3. Method of Manufacturing Composite Coating Film



    [0059] A method of manufacturing the composite coating film of the present invention comprises
    a step of applying the coating composition of the present invention onto a basal plate 1 to form a coating film made up of an uncured body of the coating composition (Fig. 2a); and
    a step of exposing the coating film made up of an uncured body to air to cure the surface layer thereof due to oxidative polymerization so as to form the film layer 3 while maintaining a portion under the film layer 3 in an uncured state as the inner layer 2 (Figs. 2b and 2c).

    [0060] More specifically, for example, the coating film made up of an uncured body is exposed to air at 5 to 150 °C for one day or 20 minutes or longer to cure the surface layer thereof due to oxidative polymerization so as to form the film layer 3. Since the oxidative polymerization inhibitor present in the vicinity of the uncured surface layer volatilizes, the oxidative polymerization reaction promoting effect of the dryer is exerted, or the oxidative polymerization initiation function of the radicals present in the system is exhibited, so that only the surface layer is cured. On the other hand, since the oxidative polymerization inhibitor is present in the inner layer 2 under the film layer, the oxidative polymerization reaction promoting effect of the dryer is inhibited, or the oxidative polymerization initiation function of the radicals present in the system is suppressed and, additionally, penetration of oxygen is prevented by the film layer of the cured surface layer. Furthermore, due to the effect of the organic compound inhibiting the approach between the oxidative polymerization resins, so that the inner layer 2 is maintained uncured. Drying conditions can appropriately be adjusted such that only the surface layer cures.

    EXAMPLES



    [0061] The present invention will hereinafter more specifically be described based on Examples and Comparative Examples; however, the present invention is not limited to the following Examples.

    1. Preparation of Coating Composition


    [Example 1]



    [0062] In a preparatory stage, alkyd resin varnish (BECKOSOL P-470-70; DIC Corporation) was wormed to 40 °C, and paraffin (melting point: 42 to 44 °C) (Wako Pure Chemical Industries) and powder polyethylene (Neowax L (melting point: 95 to 115 °C) (Yasuhara Chemical)) were heated to 70 °C and 130 °C, respectively, into a liquid state. Paraffin and polyethylene in a liquid state were mixed while stirring the alkyd resin varnish wormed to 40 °C with a disperser. Subsequently, a dryer protectant (2-butanone oxime (Tokyo Chemical Industry)) and a dryer (cobalt naphthenate mineral spirit solution (Co: 6%)) (Wako Pure Chemical Industries) were sequentially mixed and stirred at 300 rpm for five minutes. The components were combined according to Table 1.

    [0063] From the atomic weight of cobalt: 58.93 and the molecular weight of 2-butanone oxime: 87.12, the number of moles of the dryer protectant per mole of metal elements in the dryer was calculated.

    [0064] After completion of stirring, the mixture was visually confirmed as being homogeneous and used as a coating composition.

    [Example 2]



    [0065] A coating composition was prepared as in Example 1 by combining the components according to Table 1 except that polyethylene was not added.

    [Examples 3 to 5]



    [0066] A coating composition was prepared as in Example 1 by combining the components according to Table 1 except that the polyethylene was not added and that the ratio between the alkyd resin and the paraffin was changed.

    [Examples 6 to 8]



    [0067] A coating composition was prepared as in Example 1 by combining the components according to Table 1 except that the alkyd resin varnish was changed to alkyd resin varnish (BECKOSOL EL-8001; DIC Corporation), alkyd resin varnish (BECKOSOL EL-4501-50; DIC Corporation), or modified alkyd resin varnish (STYRESOL J-719; DIC Corporation).

    [Examples 9 and 10]



    [0068] A coating composition was prepared as in Example 1 by combining the components according to Table 2 except that the alkyd-modified urethane resin (BURNOCK TD-125-HV; DIC Corporation) or acrylic resin (ACRYDIC A-1300; DIC Corporation) was mixed as a resin other than the alkyd resin with the base resin composition.

    [Examples 11 and 12]



    [0069] A coating composition was prepared as in Example 1 by combining the components according to Table 2 except that paraffin (melting point: 50 to 52 °C) (Showa Chemical Industry) and paraffin (melting point: 60 to 62 °C) (Kishida Chemical) were used.

    [Examples 13 to 15]



    [0070] A coating composition was prepared as in Example 1 by combining the components according to Table 2 except that a dryer (cobalt octanoate xylene solution (Co: 6%)) (DIC Corporation) was used or the additive amount of the dryer (cobalt naphthenate mineral spirit solution (Co: 6%)) was changed.

    [Examples 16 to 19]



    [0071] A coating composition was prepared as in Example 1 by combining the components according to Table 3 except that a dryer protectant (cyclohexanone oxime (Wako Pure Chemical Industries)) was used or the additive amount of the dryer protectant (2-butanone oxime (Tokyo Chemical Industry)) was changed.

    [0072] From the atomic weight of cobalt: 58.93, the molecular weight of butanone oxime: 87.12, and the molecular weight of cyclohexanone oxime: 113.16, the number of moles of the dryer protectant per mole of metal elements in the dryer was calculated.

    [Examples 20 to 22]



    [0073] A coating composition was prepared as in Example 1 by combining the components according to Table 3 except that no dryer protectant was added and that eugenol (Wako Pure Chemical Industries) was added as a radical inhibitor.

    [Examples 23 and 24]



    [0074] A coating composition was prepared as in Example 1 by combining the components according to Table 3 except that the dryer protectant was used together with eugenol (Wako Pure Chemical Industries) or tributyl phosphite (Wako Pure Chemical Industries) serving as a radical inhibitor.

    [Example 25]



    [0075] Carbon black (MA 100; Mitsubishi Chemical Corporation) and oil clay (CLAYTONR HY (BYK Additives & Instruments)) were mixed with the alkyd resin varnish (BECKOSOL P-470-70; DIC Corporation) while being stirred with a disperser to prepare a premix paste, which was then dispersed by a sand grind mill to prepare a dispersed paste.

    [0076] In a preparatory stage, paraffin (melting point: 42 to 44 °C) (Wako Pure Chemical Industries) and powder polyethylene (Neowax L (melting point: 95 to 115 ° C) (Yasuhara Chemical Co., Ltd.)) were heated to 70 °C and 130 °C, respectively, into a liquid state.

    [0077] Paraffin and polyethylene in a liquid state were mixed while stirring the dispersed paste wormed to 40 °C with a disperser. Subsequently, a dryer protectant (2-butanone oxime (Tokyo Chemical Industry)) and a dryer (cobalt naphthenate mineral spirit solution (Co: 6%)) (Wako Pure Chemical Industries) were sequentially mixed and stirred at 300 rpm for five minutes. The components were combined according to Table 4.

    [0078] After completion of stirring, the mixture was visually confirmed as being homogeneous and used as a coating composition.

    [Example 26]



    [0079] Titanium oxide (Ti-PURE R-706 (Du Pont)) and oil clay (CLAYTONR HY (BYK Additives & Instruments)) were mixed with the alkyd resin varnish (BECKOSOL P-470-70; DIC Corporation) while being stirred with a disperser to prepare a premix paste, which was then dispersed by a sand grind mill to prepare a dispersed paste.

    [0080] In a preparatory stage, paraffin (melting point: 42 to 44 °C) (Wako Pure Chemical Industries) and powder polyethylene (Neowax L (melting point: 95 to 115 ° C) (Yasuhara Chemical Co., Ltd.)) were heated to 70 °C and 130 °C, respectively, into a liquid state.

    [0081] Paraffin and polyethylene in a liquid state were mixed while stirring the dispersed paste warmed to 40 °C with a disperser. Subsequently, a dryer protectant (2-butanone oxime (Tokyo Chemical Industry)) and a dryer (cobalt naphthenate mineral spirit solution (Co: 6%)) (Wako Pure Chemical Industries) were sequentially mixed and stirred at 300 rpm for five minutes. The components were combined according to Table 4.

    [0082] After completion of stirring, the mixture was visually confirmed as being homogeneous and used as a coating composition.

    [Example 27]



    [0083] A coating composition was prepared as in Example 1.

    [Comparative Example 1]



    [0084] In a preparatory stage, alkyd resin varnish (BECKOSOL P-470-70; DIC Corporation) was warmed to 40 °C, and paraffin (melting point: 42 to 44 °C) (Wako Pure Chemical Industries) was heated to 70 °C into a liquid state. Paraffin in a liquid state was mixed while stirring the alkyd resin varnish warmed to 40 °C with a disperser. Subsequently, a dryer protectant (2-butanone oxime (Tokyo Chemical Industry)) and a dryer (cobalt naphthenate mineral spirit solution (Co: 6%)) (Wako Pure Chemical Industries) were sequentially mixed and stirred at 300 rpm for five minutes. The components were combined according to Table 5.

    [0085] From the atomic weight of cobalt: 58.93 and the molecular weight of 2-butanone oxime: 87.12, the number of moles of the dryer protectant per mole of metal elements in the dryer was calculated.

    [0086] After completion of stirring, the mixture was visually confirmed as being homogeneous and used as a coating composition.

    [Comparative Example 2]



    [0087] A coating composition was prepared as in Example 1 by combining the components according to Table 5 except that the combination ratio of paraffin to the base resin composition containing the alkyd resin varnish was increased.

    [Comparative Example 3]



    [0088] A coating composition was prepared as in Example 1 by combining the components according to Table 5 without using a dryer and an oxidative polymerization inhibitor.

    [Comparative Example 4]



    [0089] A coating composition was prepared as in Example 1 by combining the components according to Table 5 without using an oxidative polymerization inhibitor while using a dryer.

    [Comparative Example 5]



    [0090] A coating composition was prepared as in Example 1 by combining the components according to Table 5 without using paraffin.
    [Table 1]
    componentsNVExample 1 (wt%)Example 2 (wt%)Example 3 (wt%)Example 4 (wt%)Example 5 (wt%)Example 6 (wt%)Example 7 (wt%)Example 8 (wt%)
    base resin composition alkyd resin BECKOSOL P-470-70 70 77.00 77.00 58.10 83.59 88.78 - - 70.21
    BECKOSOL EL-8001 100 - - - - - 70.09 - -
    BECKOSOL EL4501-50 50 - - - - - - 82.44 -
    STYRESOLJ-719 50 - - - - - - - 10.92
    alkyd-modified urethane resin BURNOCK TD-12S-HV 50 - - - - - - - -
    acrylic resin ACRYDICA-1300 60 - - - - - - - -
    organic compound paraffin melting point 42 to 44 °C 100 18.35 21.35 40.64 14.64 9.31 23.86 13.97 18.59
    melting point 50 to 52 °C 100 - - - - - - - -
    melting point 60 to 62 °C 100 - - - - - - - -
    polyethylene Neowax L (melting point 95 to 115 °C) 100 3.00 - - - - 3.90 2.30 3.04
    dryer cobalt naphthenate mineral spirit solution (Co 6%) 68 1.40 1.40 1.06 1.52 1.62 1.82 1.09 1.42
    cobalt octanoate xylene solution (Co 6%) 32 - - - - - - - -
    oxidative polymerization inhibitor dryer protectant 2-butanone oxime 0 0.25 0.25 0.20 0.24 0.29 0.33 0.20 0.25
    cyclohexanone oxime 0 - - - - - - - -
    radical inhibitor eugenol 0 - - - - - - - -
    tributyl phosphite 0 - - - - - - - -
    pigment color pigment Mitsubishi Carbon Black MA 100 100 - - - - - - - -
    Ti-PURE R-706 100 - - - - - - - -
    extender pigment CLAYTONR HY 100 - - - - - - - -
    total 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00
    organic compound with melting point of 5 to 150 °C (wt%)/100 wt% base resin 39.6 39.6 99.9 25.0 15.0 39.6 39.5 39.6
    Co in dryer (wt%)/100 wt% oxidative polymerization resin 0.16 0.16 0.16 0.16 0.16 0.16 0.16 0.16
    dryer protectant (mol)/mole of Co 2.0 2.0 2.1 1.8 2.0 2.0 2.1 2.0
    radical inhibitor (wt%)/100 wt% oxidative polymerization resin - - - - - - - -
    [Table 2]
    componentsNVExample 9 (wt%)Example 10 (wt%)Example 11 (wt%)Example 12 (wt%)Example 13Example 14Example 15 (wt%)
    base resin composition alkyd resin BECKOSOL P-470-70 70 73.73 70.66 77.00 77.00 77.00 78.08 68.31
    BECKOSOL EL-8001 100 - - - - - - -
    BECKOSOL EL-4501-50 50 - - - - - - -
    STYRESOL J-719 50 - - - - -   -
    alkyd-modified urethane resin BURNOCK TD-125-HV 50 10.32 - - - - - - - -
    acrylic resin ACRYDICA-1300 60 - 8.24 - - - - -
    organic compound paraffin melting point 42 to 44 °C 100 17.57 16.84 - 6.12 18.35 18.56 16.28
    melting point 50 to 52 °C 100 - - - 6.12 - - -
    melting point 60 to 62 °C 100 - - 18.35 6.11 - -  
    polyethylene Neowax L (melting point 95 to 115 °C) 100 2.87 2.75 3.00 3.00 3.00 3.04 2.66
    dryer cobalt naphthenate mineral spirit solution (Co 6%) 68 1.34 1.28 1.40 1.40 - 0.27 10.79
    cobalt octanoate xylene solution (Co 6%) 32 - - - - 1.40 - -
    oxidative polymerization inhibitor dryer protectant 2-butanone oxime 0 0.24 0.23 0.25 0.25 0.25 0.05 1.98
    cyclohexanone oxime 0 - - - - - - - -
    radical inhibitor eugenol 0 - - - - - - -
    tributyl phosphite 0 - - - - - - -
    pigment color pigment Mitsubishi Carbon Black MA 100 100 - - - - - - -
    Ti-PURE R-706 100 - - - - - - -
    extender pigment CLAYTONR HY 100 - - - - - - -
    total 100.00 100.00 100.00 100.00 100.00 100.00 100.00
    organic compound with melting point of 5 to 150 °C (wt%)/100 wt% base resin 36.0 36.0 39.6 39.6 39.6 39.5 39.6
    Co in dryer (wt%)/100 wt% oxidative polymerization resin 0.14 0.16 0.16 0.16 0.16 0.03 1.35
    dryer protectant (mol)/mole of Co 2.0 2.0 2.0 2.0 2.0 2.1 2.0
    radical inhibitor (wt%)/100 wt% oxidative polymerization resin - - - - - - -
    [Table 3]
    componentsNVExample 16 (wt%)Example 17 (wt%)Example 18 (wt%)Example 19 (w1%)Example 20 (wt%)Example 21 (wt%)Example 22 (wt%)Example 23 (wt%)Example 24 (wt%)
    base resin composition alkyd resin BECKOSOL P-470-70 70 76.96 76.99 77.13 76.84 77.00 76.45 (wt)% 77.18 76.90 24 (wt%) 76.90
    BECKOSOL EL-8001 100 - - - - - - - -  
    BECKOSOL EL-4501-50 50 - - - - - - - - -
    STYRESOL J-719 50 - - - - - - - - -
    alkyd-modified urethane resin BURNOCK TD-125-HV 50 - - - - - - - - -
    acrylic resin ACRYDIC A-1300 60 - - - - - - - - -
    organic compound paraffin melting point 42 to 44 °C 100 18.31 18.35 18.38 18.31 18.35 18.22 18.39 18.32 18.32
    melting point 50 to 52 °C 100 - - - - - - - - -
    melting point 60 to 62 °C 100 - - - - - - - - -
    polyethylene Neowax L (melting point 95 to 115 °C) 100 3.00 3.00 3.01 2.99 3.00 2.98 3.01 3.00 3.00
    dryer cobalt naphthenate mineral spirit solution (Co 6%) 68 140 1.40 1.40 1.40 1.40 1.39 1.40 1.40 1.40
    cobalt octanoate xylene solution (Co 6%) 32 - - - - - - - - -
    oxidative polymerization inhibitor dryer protectant 2-butanone oxime 0 - 0.20 0.08 0.45 - - - 0.20 0.20
    cyclohexanone oxime 0 0.33 0.06 - - - - - 0.06 0.06
    radical inhibitor eugenol 0 - - - - 0.25 0.96 0.02 0.12 0.08
    tributyl phosphite 0 - - - - - - - - 0.04
    pigment color pigment Mitsubishi Carbon Black MA 100 100 - - - - - - - - -
    Ti-PURE R-706 100 - - - - - - - - -
    extender pigment CLAYTONR HY 100 - - - - - - - - -
    total 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00
    organic compound with melting point of 5 to 150 °C (wt%)/100 wt% base resin 39.6 39.6 39.6 39.6 39.6 39.6 39.6 39.6 39.6
    Co in dryer (wt%)/100 wt% oxidative polymerization resin 0.16 0.16 0.16 0.16 0.16 0.16 0.16 0.16 0.16
    dryer protectant (mol)/mole of Co 2.0 2.0 0.6 3.6 - - - 2.0 2.0
    radical inhibitor (wt%)/100 wt% oxidative polymerization resin - - - - 0.46 1.79 0.04 0.22 0.22
    [Table 4]
    componentsNVExample 25 (wt%)Example 26 (wt%)Example 27 (wt%)
    base resin composition alkyd resin BECKOSOL P-470-70 70 73.37 65.41 77.00
    BECKOSOL EL-8001 100 - - -
    BECKOSOL EL-4501-50 50 - - -
    STYRESOL J-719 50 - - -
    alkyd-modified urethane resin BURNOCK TD-125-HV 50 - - -
    organic compound acrylic resin ACRYDIC A-1300 60 - - -
    paraffin melting point 42 to 44 °C 100 17.48 15.59 18.35
    melting point 50 to 52 °C 100 - - -
    melting point 60 to 62 °C 100 - - -
    polyethylene Neowax L (melting point 95 to 115 °C) 100 2.86 2.55 3.00
    dryer cobalt naphthenate mineral spirit solution (Co 6%) 68 1.33 1.19 1.40
    cobalt octanoate xylene solution (Co 6%) 32 - - -
    oxidative polymerization inhibitor dryer protectant 2-butanone oxime 0 0.24 0.21 0.25
    cyclohexanone oxime 0 - - -
    radical inhibitor eugenol 0 - - -
    tributyl phosphite 0 - - -
    pigment color pigment Mitsubishi Carbon Black MA 100 100 0.18 - -
    Ti-PURE R-706 100 - 11.01 -
    extender pigment CLAYTONR HY 100 4.54 4.04 -
    total 100.00 100.00 100.00
    organic compound with melting point of 5 to 150 °C (wt%)/100 wt% base resin 39.6 39.6 39.6
    Co in dryer (wt%)/100 wt% oxidative polymerization resin 0.16 0.16 0.16
    dryer protectant (mol) mole of Co 2.0 2.0 2.0
    radical inhibitor (wt%)/100 wt% oxidative polymerization resin - - -
    [Table 5]
    componentsNVComparative Example 1 (wt%)Comparative Example 2 (wt%)Comparative Example 3 (wt%)Comparative Example 4 (wt%)Comparative Example 5 (wt%)
    base resin composition alkyd resin BECKOSOL P-470-70 70 96.87 53.70 78.29 77.19 97.90
    BECKOSOL EL-8001 100 - - - - - -
    BECKOSOL EL-4501-50 50 - - - - -
    STYRESOL J-719 50 - - - - -
    alkyd-modified urethane resin BURNOCKTD-125-HV 50 - - - - -
    acrylic resin ACRYDIC A-1300 60 - - - - -
    organic compound paraffin melting point 42 to 44 °C 100 1.00 45.12 21.71 21.40 -
    melting point 50 to 52 °C 100 - - - - - - -
    melting point 60 to 62 °C 100 - - - - - -
    polyethylene Neowax L (melting point 95 to 115 °C) 100 - - - - -
    dryer cobalt naphthenate mineral spirit solution (Co 6%) 68 1.81 1.00 - 1.40 1.78
    cobalt octanoate xylene solution (Co 6%) 32 - - - - -
    oxidative polymerization inhibitor dryer protectant 2-butanone oxime 0 0.32 0.18 - - 0.32
    cyclohexanone oxime 0 - - - - -
    radical inhibitor eugenol 0 - - - - -
    tributyl phosphite 0 - - - - -
    pigment color pigment Mitsubishi Carbon Black MA 100 100 - - - - -
    Ti-PURE R-706 100 - - - - -
    extender pigment CLAYTONR HY 100 - - - - -
    total 100.00 100.00 100.00 100.00 100.00
    organic compound with melting point of 5 to 150 °C (wt%)/100 wt% base resin 1.5 120.0 39.6 39.6 0.0
    Co in dryer (wt%/100 wt% oxidative polymerization resin 0.16 0.16 - 0.16 0.16
    dryer protectant (mol)/mole of Co 2.0 2.0 - - 2.0
    radical inhibitor (wt%)/)00 wt% oxidative polymerization resin - - - - -

    2. Formation of Compatible Coating Film



    [0091] A composite coating film was formed with the following steps.

    Step 1: Each of the coating compositions of Examples 1 to 27 and Comparative Examples 1 to 5 was applied to a dish-shaped container (base area: about 34 cm2) of about 3.3 cm in radius and about 7.5 mm in height to a dry film thickness of 2.5 mm (Fig. 2a).

    Step 2: The created coating film was dried under an atmosphere at 23 °C for one day or dried under an atmosphere at 120 °C for 20 minutes to obtain a dry initial coating film (Fig. 2 b).

    Step 3: The coating film was dried under an atmosphere at 23 °C for six months (Fig. 2 c) and a temporal change was observed to confirm formation of a desired composite coating film.


    3. Characteristic Evaluation of Composite Coating Film



    [0092] An evaluation test was performed on each of the obtained composite coating films under the following conditions. The evaluation results are shown in Tables 6 to 11.

    (1) Surface Dryness of Composite Coating Film


    [Purpose]



    [0093] The cured state of the composite coating film surface is confirmed based on a degree of dryness.

    [Test conditions]



    [0094] In accordance with the definition of JIS K 5600-3-2, about 0.5 g of Ballotini (fine glass beads classified such that the beads do not pass through a sieve of 125 µm in nominal (size) aperture and completely pass through a sieve of 250 µm) was dropped from the height of 100 mm onto a coated surface of a horizontally placed coated plate, and the test piece was tilted after 10 seconds and lightly swept with a brush to remove the Ballotini.

    [Evaluation Criteria]



    [0095] +: When the Ballotini can be removed without scratching, it is determined that a surface is dried.

    [0096] -: When the Ballotini cannot be removed since the coating film is scratched or the Ballotini is stuck, it is determined that a surface is undried.

    (2) Surface Tackiness of Composite Coating Film


    [Purpose]



    [0097] The cured state of the composite coating film surface layer is confirmed based on a degree of stickiness.

    [Test conditions]



    [0098] Under an atmosphere at 23 °C, the surface of the coating film was pressed with a finger to evaluate the presence/absence of stickiness (tackiness).

    [Evaluation Criteria]



    [0099] +: sticky.
    -: not sticky.

    (3) Rebound Resilience of Composite Coating Film


    [Purpose]



    [0100] The coating film is made up of a viscous component and an elastic component. The elastic component stores a falling energy (kinetic energy) of this test, while the viscous component causes a loss of the energy. A key point of the technique of allowing peeling multiple times is that only the surface layer is reacted and cured while the inside is in the uncured state, and the rebound resilience in this test is expected to be lower than that of a conventional completely cured coating film. By comparing this value, it is shown that the inside is unreacted.

    [Test conditions]



    [0101] From a position of height H1 (70 cm) under an atmosphere at 23 °C, a rubber ball (made of silicone and having a spherical shape with the diameter of 2 cm, the weight of 5 g, and the hardness of 50 measured in accordance with JIS K 6253-2012 "Rubber, vulcanized or thermoplastic -Determination of hardness-") was allowed to free-fall onto a coating film placed on a marble base, and the rebounding height H2 of the rubber ball in this case was measured (Fig. 3). By using the height H1 as a denominator and the rebound height H2 as a numerator, rebound resilience (%) expressing the value thereof as a percentage is defined to make evaluations based on the magnitude of the value. The test was performed three times and the average value was used. A film thickness of a coating film sample A for the measurement test was standardized to 2.5 mm so as to eliminate the influence of film thickness.

    [Evaluation Criteria]



    [0102] Rebound resilience of 0 to 10%: The surface layer is insufficiently cured.

    [0103] Rebound resilience of 11 to 55%: The surface layer is sufficiently cured and the inner layer is in an uncured state.

    [0104] Rebound resilience of 56 % or more: The inside is excessively cured.

    (4) Internal Flowability of Composite Coating Film


    [Purpose]



    [0105] A coating-film flow suppression effect of a flow suppressing substance is clarified.

    [Test Conditions]



    [0106] Under an atmosphere at 23 °C, a created coated plate was tilted by 90 ° and allowed to stand for one hour, and the presence/absence of flow (deformation) was visually confirmed.

    [Evaluation Criteria]



    [0107] +: No cracks or wrinkles are observed in the film layer and no distortion has occurred in the entire coating film.

    [0108] -: Cracks or wrinkles are observed in the film layer, or distortion has occurred in the entire cording film.

    (5) Peelability of Film Layer


    [Purpose]



    [0109] For the coating film proved as having the cured surface layer in the test described above, it is confirmed whether the film layer can be peeled off.

    [Test Conditions]



    [0110] After the coating film was cut off at a portion adhering to the inner wall of the dish-shaped container with a cutter knife, a cellophane tape (Cellotape CT-24; Nichiban) was attached to a portion of the coating film surface layer and the cellophane tape was pulled up (Fig. 4). A peeled film thickness was measured with an electronic caliper.

    [Evaluation Criteria]



    [0111] ++: When all the film layer can be peeled off from the inner layer without breaking along the way, it is determined as being peelable.

    [0112] +: Even though the film layer is broken along the way, when all the film layer can finally be peeled off from the inner layer, it is determined as being peelable.

    [0113] -: If at least a portion of the film layer cannot be peeled off from the inner layer, it is determined as not being peelable.
    [Table 6]
    evaluation periodevaluation itemsExample 1Example 2Example 3Example 4Example 5Example 6Example 7Example 8
    23 °C×20 min (reference) rebound resilience (%) 9.9 7.0 18.3 4.9 3.7 8.1 12.3 21.7
    surface dryness - - - - - - - -
    surface tackiness - - - - - - + +
    internal flow + + + + + + + +
    23 °C×1 day rebound resilience (%) 33.5 22.8 36.8 18.5 12.3 31.4 35.7 39.1
    surface dryness + + + + + + + +
    surface tackiness + + + + + + + +
    internal flow + + + + + + + +
    peeling ++ ++ ++ ++ ++ ++ ++ ++
    peeled film thickness (µm) 120 220 170 240 280 170 130 150
    23 °C×6 months rebound resilience (%) 40.2 31.0 43.7 27.9 49.9 41.5 41.1 44.0
    surface dryness + + + + + + + +
    surface tackiness + + + + + + + +
    internal flow + + + + + + + +
    peeling ++ ++ ++ ++ ++ ++ ++ ++
    peeled film thickness (µm) 190 320 270 310 850 250 210 230
    [Table 7]
    evaluation periodevaluation itemsExample 9Example 10Example 11Example 12Example 13Example 14Example 15
    23 °C×20 min (reference) rebound resilience (%) 22.9 19.4 29.2 14.3 9.2 9.8 9.2
    surface dryness - - - - - - -
    surface tackiness - - - - - - -
    internal flow + + + + + + +
    23 °C×1 day rebound resilience (%) 38.7 41.1 38.6 35.7 31.9 17.4 36.1
    surface dryness + + + + + + +
    surface tackiness + + + + + + +
    internal flow + + + + + + +
    peeling ++ ++ ++ ++ ++ + ++
    peeled film thickness (µm) 110 130 100 110 120 80 250
    23 °C×6 months rebound resilience (%) 43.8 44.0 46.2 43.0 40.1 24.6 53.1
    surface dryness + + + + + + +
    surface tackiness + + + + + + +
    internal flow + + + + + + +
    peeling ++ ++ ++ ++ ++ ++ ++
    peeled film thickness (µm) 200 220 180 190 200 170 970
    [Table 8]
    evaluation periodevaluation itemsExample 16Example 17Example 18Example 19Example 20Example 21Example 22Example 23Example 24
    23 °C×20 min (reference) rebound resilience (%) 10.0 10.0 9.7 9.9 10.3 10.0 9.8 9.5 9.8
    surface dryness - - - - - - - - -
    surface tackiness - - - - - - - - -
    internal flow + + + + + + + + +
    23 °C×1 day rebound resilience (%) 28.9 29.9 35.2 14.2 31.1 14.7 36.3 26.2 24.3
    surface dryness + + + + + + + + +
    surface tackiness + + + + + + + + +
    internal flow + + + + + + + + +
    peeling ++ ++ ++ + ++ + ++ ++ ++
    peeled film thickness (µm) 100 110 200 70 100 60 190 100 100
    23 °C×6 months rebound resilience (%) 35.2 36.7 43.9 24.0 40.1 23.7 43.1 30.2 27.2
    surface dryness + + + + + + + + +
    surface tackiness + + + + + + + + +
    internal flow + + + + + + + + +
    peeling ++ ++ ++ ++ ++ ++ ++ ++ ++
    peeled film thickness (µm) 180 190 870 170 150 120 820 130 120
    [Table 9]
    evaluation periodevaluation itemsExample 25Example 26
    23 °C×20 min (reference) rebound resilience (%) 30.2 37.5
    surface dryness - -
    surface tackiness - -
    internal flow + +
    23 °C×1 day rebound resilience (%) 43.5 47.2
    surface dryness + +
    surface tackiness + +
    internal flow + +
    peeling ++ ++
    peeled film thickness (µm) 140 130
    23 °C×6 months rebound resilience (%) 49.2 51.5
    surface dryness + +
    surface tackiness + +
    internal flow + +
    peeling ++ ++
    peeled film thickness (µm) 230 220
    [Table 10]
    evaluation periodevaluation itemsExample 27
    120 °C×20 min. rebound resilience (%) 46.0
    surface dryness +
    surface tackiness +
    internal flow +
    peeling ++
    peeled film thickness (µm) 90
    23 °C×6 months rebound resilience (%) 46.4
    surface dryness +
    surface tackiness +
    internal flow +
    peeling ++
    peeled film thickness (µm) 90
    [Table 11]
    evaluation periodevaluation itemsComparative Example 1Comparative Example 2Comparative Example 3Comparative Example 4Comparative Example 5
    23 °C×20 min (reference) rebound resilience (%) 0.0 25.0 6.9 7.1 0.0
    surface dryness - - - - -
    surface tackiness - - - - -
    internal flow - + + + -
    23°C×1 day rebound resilience (%) 0.0 25.4 8.4 35.1 17.5
    surface dryness - - - + +
    surface tackiness - - - + +
    internal flow - - - + -
    peeling not applicable not applicable not applicable ++ ++
    peeled film thickness (µm) - - - 120 360
    23 °C×6 months rebound resilience (%) 68.0 56.2 59.6 69.6 71.3
    surface dryness + + + + +
    surface tackiness + + + + +
    internal flow + + + + +
    peeling (completely cured) (completely cured) (completely cured) (completely cured) (completely cured)
    peeled film thickness (µm) - - - - -


    [0114] All of the coating films created by using the coating compositions of Examples 1 to 27 exhibited proper rebound resilience (11 to 55 %) and favorable surface dryness and surface tackiness even after one day at 23 °C or 20 minutes at 120 °C and after six months at 23 °C. Internal flowability was favorable after initial coating without cracks or wrinkles formed on the coating film surface, and no deformation had occurred at all.

    [0115] For example, immediately after peeling off the film layers of the composite coating films using the coating compositions of Examples 1 and 2 after six months, the rebound resilience was measured as 7.9 % and 10.1 %, respectively, and it was confirmed that the inner layer was maintained in the uncured state even after being dried for six months.

    [0116] On the other hand, the coating films created by using the coating compositions of Comparative Examples 1 to 5 lacking any of the components contained in the coating composition according to the present invention were completely cured to the inner layer in six months and had the rebound resilience increased to 56 to 70%.

    INDUSTRIAL APPLICABILITY



    [0117] By using the coating composition of the present invention, a composite coating film made up of a cured film layer and an uncured inner layer can be obtained, and this film layer can be peeled off to renew the coating surface layer multiple times. Therefore, by applying the coating composition of the present invention, a state without damage or contamination can always be kept, or the function imparted to the coating film can be maintained, even in a place where recoating is difficult, for example.

    EXPLANATIONS OF LETTERS OR NUMERALS



    [0118] 
    1
    basal plate
    2
    uncured portion of coating film
    3
    cured portion of coating film
    4
    cellophane tape
    A
    coating sample for measurement having coating film thickness of 2.5 mm



    Claims

    1. A coating composition comprising: a base resin composition containing an oxidative polymerization resin; an organic compound having a melting point of 5 to 150 °C; a dryer; and an oxidative polymerization inhibitor containing at least one of a dryer protectant and a radical inhibitor, the coating composition comprising 10 to 100 wt% organic compound based on the 100 wt% base resin composition and a content of metal elements in the dryer is 0.001 to 1.5 wt% based on 100 wt% solid content of the oxidative polymerization resin, wherein

    if the oxidative polymerization inhibitor contains only one of the dryer protectant and the radical inhibitor,

    0.5 to 4 moles of the dryer protectant is contained per mole of metal elements in the dryer; or

    0.01 to 2.0 wt% radical inhibitor is contained based on 100 wt% solid content of the oxidative polymerization resin; or

    if the oxidative polymerization inhibitor contains both the dryer protectant and the radical inhibitor,

    when 0.5 to 4 moles of the dryer protectant is contained per mole of metal elements in the dryer, 2.0 wt% or less radical inhibitor is contained based on 100 wt% solid content of the oxidative polymerization resin; or

    when less than 0.5 moles of the dryer protectant is contained per mole of metal elements in the dryer, 0.01 to 2.0 wt% radical inhibitor is contained based on 100 wt% solid content of the oxidative polymerization resin.


     
    2. The coating composition according to claim 1, wherein the oxidative polymerization resin is an alkyd resin that is a reaction product of a polybasic acid or a polybasic acid anhydride, a fatty acid, and a polyhydric alcohol.
     
    3. The coating composition according to claim 1, wherein the oxidative polymerization inhibitor contains a volatile dryer protectant having a boiling point of 300 °C or less which is selected from a group consisting of methyl ethyl ketoxime, acetone oxime, butyl aldoxime, cyclohexanone oxime, dialkyl hydroxylamine, ammonia, hydroxylamine, triethylamine, and dimethylethanolamine.
     
    4. A composite coating film comprising: a film layer; and an inner layer, wherein

    the inner layer is an uncured body of the coating composition according to any of claims 1 to 3, while the film layer is a cured body of the coating composition formed in a peelable manner on a surface of the inner layer, and wherein

    a surface layer of the inner layer exposed to air by peeling the film layer formed on the inner layer is curable due to oxidative polymerization so that another film layer is formable in a peelable manner.


     
    5. The composite coating film according to claim 4, wherein the film layer is determined as being surface-dry based on the definition of JIS K 5600-3-2, in which about 0.5 g of Ballotini is dropped from the height of 100 mm onto a coated surface of a horizontally placed coated plate, and the test piece is tilted after 10 seconds and lightly swept with a brush to remove the Ballotini, and when the Ballotini can be removed without scratching, it is determined that a surface is dried;
    wherein Ballotini are fine glass beads classified as beads that do not pass through a sieve of 125 µm in nominal size aperture and completely pass through a sieve of 250 µm.
     
    6. The composite coating film according to claim 5, wherein the rebound resilience is 11 to 55 %.
     
    7. The composite coating film according to claim 4, wherein the film layer has a thickness in a range of 10 µm to 5 mm, and wherein the inner layer has a thickness equal to or greater than the thickness of the film layer.
     
    8. The composite coating film according to claim 4, wherein the other film layer has a thickness in a range of 10 µm to 5 mm.
     
    9. A method of manufacturing a composite coating film made up of a film layer and an inner layer wherein the film layer is formed in a peelable manner on a surface of the inner layer, the method comprising the steps of:

    applying the coating composition according to any of claims 1 to 3 onto a basal plate to form a coating film made up of an uncured body of the coating composition; and

    forming a film layer by exposing the coating film made up of the uncured body to air to cure a surface layer thereof due to oxidative polymerization while maintaining a portion under the film layer in an uncured state as an inner layer.


     
    10. The method of manufacturing according to claim 9, wherein the film layer has a thickness in a range of 10 µm to 5 mm, and wherein the inner layer has a thickness equal to or greater than the thickness of the film layer.
     


    Ansprüche

    1. Beschichtungszusammensetzung, die Folgendes umfasst: eine Basisharzzusammensetzung, die ein oxidatives Polymerisationsharz enthält; eine organische Verbindung mit einem Schmelzpunkt von 5 °C bis 150 °C; ein Trockenmittel; und einen oxidativen Polymerisationshemmer, der zumindest eines von einem Trockenmittelschutzmittel und einem Radikalhemmer enthält, wobei die Beschichtungszusammensetzung 10 bis 100 Gew.-% der organischen Verbindung, bezogen auf 100 Gew.-% Basisharzzusammensetzung, umfasst und der Gehalt an Metallelementen in dem Trockenmittel 0,001 bis 1,5 Gew.-%, bezogen auf 100 Gew.-% Feststoffgehalt des oxidativen Polymerisationsharzes, beträgt, wobei
    wenn der oxidative Polymerisationshemmer nur einen aus Trockenmittelschutzmittel und Radikalhemmer enthält,
    0,5 bis 4 mol des Trockenmittelschutzmittels pro Mol Metallelemente in dem Trockenmittel enthalten sind; oder
    0,01 bis 2,0 Gew.-% Radikalhemmer, bezogen auf 100 Gew.-% Feststoffgehalt des oxidativen Polymerisationsharzes, enthalten sind; oder
    wenn der oxidative Polymerisationshemmer sowohl das Trockenschutzmittel als auch den Radikalhemmer enthält,
    wenn 0,5 bis 4 mol des Trockenmittelschutzmittels pro Mol Metallelemente in dem Trockenmittel enthalten sind, 2,0 Gew.-% oder weniger Radikalhemmer, bezogen auf 100 Gew.-% Feststoffgehalt des oxidativen Polymerisationsharzes, enthalten sind; oder
    wenn weniger als 0,5 mol Trockenschutzmittel pro Mol Metallelemente in dem Trockenmittel enthalten sind, 0,01 bis 2,0 Gew.-% Radikalhemmer, bezogen auf 100 Gew.-% Feststoffgehalt des oxidativen Polymerisationsharzes, enthalten sind.
     
    2. Beschichtungszusammensetzung nach Anspruch 1, wobei das oxidative Polymerisationsharz ein Alkydharz ist, das das Reaktionsprodukt einer mehrbasigen Säure oder eines mehrbasigen Säureanhydrids, einer Fettsäure und eines mehrwertigen Alkohols ist.
     
    3. Beschichtungszusammensetzung nach Anspruch 1, wobei der oxidative Polymerisationshemmer ein flüchtiges Trockenmittelschutzmittel mit einem Siedepunkt von 300 °C oder weniger enthält, das aus der aus Methylethylketoxim, Acetonoxim, Butylaldoxim, Cyclohexanonoxim, Dialkylhydroxylamin, Ammoniak, Hydroxylamin, Triethylamin und Dimethylethanolamin bestehenden Gruppe ausgewählt ist.
     
    4. Verbundbeschichtungsfilm, der Folgendes umfasst: eine Filmschicht und eine innere Schicht, wobei
    die innere Schicht ein ungehärteter Körper aus einer Beschichtungszusammensetzung nach einem der Ansprüche 1 bis 3 ist, während die Filmschicht ein gehärteter Körper aus der Beschichtungszusammensetzung ist, der auf abziehbare Weise auf einer Oberfläche der inneren Schicht ausgebildet ist, und wobei
    eine Oberflächenschicht der inneren Schicht, die durch Abziehen der auf der inneren Schicht ausgebildeten Filmschicht der Luft ausgesetzt wird, durch oxidative Polymerisation härtbar ist, so dass eine weitere Filmschicht auf abziehbare Weise ausbildbar ist.
     
    5. Verbundbeschichtungsfilm nach Anspruch 4, wobei die Filmschicht auf Grundlage der Definition laut JIS K 5600-3-2 als oberflächentrocken festgelegt ist, wobei etwa 0,5 g Ballotini aus einer Höhe von 100 mm auf eine beschichtete Oberfläche einer horizontal angeordneten beschichteten Platte fallen gelassen werden und der Prüfling nach 10 s gekippt und mit einer Bürste vorsichtig abgebürstet wird, um die Ballotini zu entfernen, und wenn die Ballotini entfernt werden können, ohne dass Kratzer entstehen, festgestellt wird, dass die Oberfläche getrocknet ist;
    wobei Ballotini feine Glasperlen sind, die als Perlen klassifiziert sind, die ein Sieb mit 125 µm nomineller Maschenweite nicht und ein 250-µm-Sieb zur Gänze passieren.
     
    6. Verbundbeschichtungsfilm nach Anspruch 5, wobei die Rückprallelastizität 11 % bis 55 % beträgt.
     
    7. Verbundbeschichtungsfilm nach Anspruch 4, wobei die Filmschicht eine Dicke im Bereich von 10 µm bis 5 mm aufweist und wobei die innere Schicht eine Dicke aufweist, die der Dicke der Filmschicht entspricht oder geringer ist.
     
    8. Verbundbeschichtungsfilm nach Anspruch 4, wobei die weitere Filmschicht eine Dicke im Bereich von 10 µm bis 5 mm aufweist.
     
    9. Verfahren zur Herstellung eines Verbundbeschichtungsfilms, der aus einer Filmschicht und einer inneren Schicht besteht, wobei die Filmschicht auf abziehbare Weise auf einer Oberfläche der inneren Schicht ausgebildet ist, wobei das Verfahren folgende Schritte umfasst:

    das Aufbringen einer Beschichtungszusammensetzung nach einem der Ansprüche 1 bis 3 auf eine Basisplatte zur Ausbildung eines Beschichtungsfilms, der aus einem ungehärteten Körper aus der Beschichtungszusammensetzung besteht; und

    das Ausbilden der Filmschicht durch Aussetzen des aus dem ungehärteten Körper bestehenden Beschichtungsfilms gegenüber Luft, um eine Oberflächenschicht durch oxidative Polymerisation zu härten, während der Abschnitt unterhalb der Filmschicht als innere Schicht im ungehärteten Zustand gehalten wird.


     
    10. Herstellungsverfahren nach Anspruch 9, wobei die Filmschicht eine Dicke im Bereich von 10 µm bis 5 mm aufweist und wobei die innere Schicht eine Dicke aufweist, die der Dicke der Filmschicht entspricht oder geringer ist.
     


    Revendications

    1. Composition de revêtement comprenant : une composition de résine de base contenant une résine de polymérisation oxydative ; un composé organique ayant un point de fusion de 5 à 150°C ; un agent de séchage ; et un inhibiteur de polymérisation oxydative contenant au moins un parmi un protecteur d'agent de séchage et un inhibiteur de radicaux, la composition de revêtement comprenant 10 à 100 % en poids de composé organique sur la base de 100 % en poids de la composition de résine de base et une teneur en éléments métalliques dans l'agent de séchage est de 0,001 à 1,5 % en poids sur la base d'une teneur en solides de 100 % en poids de la résine de polymérisation oxydative, dans laquelle
    si l'inhibiteur de polymérisation oxydative ne contient qu'un du protecteur d'agent de séchage et de l'inhibiteur de radicaux,
    0,5 à 4 moles du protecteur d'agent de séchage sont contenues par mole d'éléments métalliques dans l'agent de séchage ; ou
    0,01 à 2,0 % en poids d'inhibiteur de radicaux sont contenus sur la base d'une teneur en solides de 100 % en poids de la résine de polymérisation oxydative ; ou
    si l'inhibiteur de polymérisation oxydative contient à la fois le protecteur d'agent de séchage et l'inhibiteur de radicaux,
    lorsque 0,5 à 4 moles du protecteur d'agent de séchage sont contenues par mole d'éléments métalliques dans l'agent de séchage, 2,0 % en poids ou moins d'inhibiteur de radicaux sont contenus sur la base d'une teneur en solides de 100 % en poids de la résine de polymérisation oxydante ; ou
    lorsque moins de 0,5 mole du protecteur d'agent de séchage est contenue par mole d'éléments métalliques dans l'agent de séchage, 0,01 à 2,0 % en poids d'inhibiteur de radicaux sont contenus sur la base de 100 % en poids de la teneur en solides de la résine de polymérisation oxydative.
     
    2. Composition de revêtement selon la revendication 1, dans laquelle la résine de polymérisation oxydative est une résine alkyde qui est un produit de réaction d'un acide polybasique ou d'un anhydride d'acide polybasique, d'un acide gras et d'un alcool polyhydrique.
     
    3. Composition de revêtement selon la revendication 1, dans laquelle l'inhibiteur de polymérisation oxydative contient un protecteur d'agent de séchage volatil ayant un point d'ébullition de 300°C ou moins qui est choisi dans un groupe comprenant méthyléthylcétoxime, oxime d'acétone, aldoxime de butyle, oxime de cyclohexanone, dialkylhydroxylamine, ammoniac, hydroxylamine, triéthylamine et diméthyléthanolamine.
     
    4. Film de revêtement composite comprenant : une couche de film ; et une couche intérieure, dans lequel
    la couche intérieure est un corps non durci de la composition de revêtement selon l'une quelconque des revendications 1 à 3, tandis que la couche de film est un corps durci de la composition de revêtement formée de manière pelable sur une surface de la couche intérieure, et dans lequel
    une couche de surface de la couche intérieure exposée à l'air par pelage de la couche de film formée sur la couche intérieure est durcissable en raison d'une polymérisation oxydative de sorte qu'une autre couche de film peut être formée d'une manière pelable.
     
    5. Film de revêtement composite selon la revendication 4, dans lequel la couche de film est déterminée comme étant de surface sèche sur la base de la définition de JIS K 5600-3-2, dans laquelle environ 0,5 g de Ballotini tombe d'une hauteur de 100 mm sur une surface revêtue d'une plaque revêtue placée horizontalement, et la pièce de test est inclinée après 10 secondes et légèrement balayée avec une brosse pour retirer les Ballotini, et lorsque les Ballotini peuvent être retirées sans rayure, il est déterminé qu'une surface est séchée ;
    dans lequel les Ballotini sont de fines perles de verre classées comme des perles qui ne passent pas à travers un tamis de 125 µm d'ouverture dimensionnelle et passent complètement à travers un tamis de 250 µm.
     
    6. Film de revêtement composite selon la revendication 5, dans lequel la résilience de rebondissement est de 11 à 55 %.
     
    7. Film de revêtement composite selon la revendication 4, dans lequel la couche de film a une épaisseur dans une plage de 10 µm à 5 mm, et dans lequel la couche intérieure a une épaisseur égale ou supérieure à l'épaisseur de la couche de film.
     
    8. Film de revêtement composite selon la revendication 4, dans lequel l'autre couche de film a une épaisseur dans une plage de 10 µm à 5 mm.
     
    9. Procédé de fabrication d'un film de revêtement composite composé d'une couche de film et d'une couche intérieure dans lequel la couche de film est formée de manière pelable sur une surface de la couche intérieure, le procédé comprenant les étapes consistant à :

    appliquer la composition de revêtement selon l'une quelconque des revendications 1 à 3 sur une plaque de base pour former un film de revêtement composé d'un corps non durci de la composition de revêtement ; et

    former une couche de film en exposant le film de revêtement composé du corps non durci à de l'air pour durcir une couche de surface de celui-ci en raison de la polymérisation oxydative tout en maintenant une partie sous la couche de film dans un état non durci en tant que couche intérieure.


     
    10. Procédé de fabrication selon la revendication 9, dans lequel la couche de film a une épaisseur dans une plage de 10 µm à 5 mm, et dans lequel la couche intérieure a une épaisseur égale ou supérieure à l'épaisseur de la couche de film.
     




    Drawing











    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