Surface protective coatings, cured products and laminates

Abstract

To provide a surface protective coating agent, a cured product and a laminate.SOLUTION: A surface protective coating agent contains (A) a hydroxy group-containing (meth)acrylic resin, (B) a polyisocyanate and (C) a hydroxy group-containing fluororesin.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to surface protective coatings, cured products, and laminates. [Background technology]

[0002] Plastic substrates such as thermoplastic polyurethane are used for protective films for various industrial products such as electronic devices and automotive parts. Such plastic substrates are at risk of losing their appearance and physical properties due to scratches and dirt, so they are surface-treated with a coating agent to achieve a lasting effect.

[0003] As such a coating agent, an ultraviolet-curable hard coating agent is known (Patent Document 1). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Special Publication No. 6-029382 Summary of the Invention [Problem to be solved by the invention]

[0005] However, the ultraviolet-curable hard coating agent has a problem that the elongation of the cured product is low due to the high hardness. From this viewpoint, coating agents other than the ultraviolet-curable hard coating agent have been considered. In addition, the coating film may deteriorate due to ultraviolet light, and a coating agent capable of producing a cured product having sufficient weather resistance is required. However, the above-mentioned UV-curable paint, EB-curable paint, and silica-based hard coating agent are prone to problems such as reduced adhesion to the material and cracks due to the use of hard monomers to achieve high hardness and increased distortion during curing shrinkage caused by increasing crosslink density. The problem to be solved by the present invention is to provide a coating agent capable of producing a cured product that has stain resistance, high elongation, and can maintain high elongation even after weather resistance testing. [Means for solving the problem]

[0006] As a result of extensive investigation, the present inventors have found that the above problems can be solved by a specific surface protective coating agent.

[0007] The present disclosure provides the following: (Item 1) (A) Hydroxyl group-containing (meth)acrylic resin (B) Polyisocyanates and (C) Hydroxyl-containing fluororesin A surface protective coating agent comprising: (Item 2) (D) The surface protective coating agent according to the above item, which comprises an organically modified silicone. (Item 3) A cured product of the surface protective coating agent according to any one of the preceding items. (Item 4) A laminate comprising the cured product described above and a substrate.

[0008] In the present disclosure, one or more of the above-described features may be provided in further combinations in addition to the combinations explicitly stated. Effect of the Invention

[0009] By using the surface protective coating agent according to this embodiment, a cured product having good stain resistance, elongation, and elongation after weather resistance testing can be produced. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] Throughout this disclosure, the range of the values ​​of the physical properties, contents, etc. may be set as appropriate (for example, by selecting from the upper and lower limit values ​​described in each item below). Specifically, when A4, A3, A2, A1 (where A4>A3>A2>A1) are exemplified as the upper and lower limits of the value α, the range of the value α is exemplified as A4 or less, A3 or less, A2 or less, A1 or more, A2 or more, A3 or more, A1 to A2, A1 to A3, A1 to A4, A2 to A3, A2 to A4, A3 to A4, etc.

[0011] [Surface protective coating agent: Also called coating agent] The present disclosure provides a surface protective coating agent comprising (A) a hydroxyl group-containing (meth)acrylic resin, (B) a polyisocyanate, and (C) a hydroxyl group-containing fluororesin.

[0012] <Hydroxyl group-containing (meth)acrylic resin (A): Also referred to as component (A).> The component (A) may be used alone or in combination of two or more types.

[0013] Examples of the component (A) include copolymers containing structural units derived from a non-hydroxyl group-containing alkyl (meth)acrylate and structural units derived from a hydroxyl group-containing monomer.

[0014] In the present disclosure, "(meth)acrylic" means "at least one selected from the group consisting of acrylic and methacrylic". Similarly, "(meth)acrylate" means "at least one selected from the group consisting of acrylate and methacrylate". In addition, "(meth)acryloyl" means "at least one selected from the group consisting of acryloyl and methacryloyl".

[0015] (Non-hydroxyl group-containing alkyl (meth)acrylate) The non-hydroxyl group-containing alkyl (meth)acrylate is [ka] (In the formula, R a1 is a hydrogen atom or a methyl group, and R a2 is an alkyl group. The non-hydroxyl group-containing alkyl (meth)acrylates may be used alone or in combination of two or more.

[0016] R a2 The upper and lower limits of the number of carbon atoms in R are exemplified as 22, 21, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, etc. a2 The number of carbon atoms is preferably 1 to 22.

[0017] Examples of the alkyl group include a straight-chain alkyl group, a branched alkyl group, and a cycloalkyl group.

[0018] A straight chain alkyl group is -C n H 2n+1 (n is an integer of 1 or more). Examples of linear alkyl groups include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl (lauryl), tridecyl, tetradecyl (myristyl), pentadecyl, hexadecyl (palmityl), heptadecyl, octadecyl (stearyl), nonadecyl, icosyl, henicosyl, and docosyl groups.

[0019] A branched alkyl group is a group in which at least one hydrogen atom of a linear alkyl group is replaced by an alkyl group. Examples of branched alkyl groups include an i-propyl group, an i-butyl group, an s-butyl group, a t-butyl group, a diethylpentyl group, a trimethylbutyl group, a trimethylpentyl group, a trimethylhexyl group, and a 2-ethylhexyl group.

[0020] Examples of the cycloalkyl group include a monocyclic cycloalkyl group, a bridged ring cycloalkyl group, and a condensed ring cycloalkyl group.

[0021] In the present disclosure, a monocyclic ring refers to a ring structure formed by a carbon covalent bond and having no internal bridge structure. A fused ring refers to a ring structure in which two or more monocyclic rings share two atoms (i.e., each ring shares only one side (fused) with each other). A bridged ring refers to a ring structure in which two or more monocyclic rings share three or more atoms.

[0022] Examples of the monocyclic cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclodecyl group, and a 3,5,5-trimethylcyclohexyl group.

[0023] Examples of the bridged ring cycloalkyl group include a tricyclodecyl group, an adamantyl group, and a norbornyl group.

[0024] The condensed ring cycloalkyl group is exemplified by a bicyclodecyl group.

[0025] Examples of the non-hydroxyl group-containing alkyl (meth)acrylate include non-hydroxyl group-containing linear alkyl (meth)acrylate, non-hydroxyl group-containing branched alkyl (meth)acrylate, and non-hydroxyl group-containing cycloalkyl (meth)acrylate.

[0026] Examples of non-hydroxyl group-containing linear alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, hexadecyl (meth)acrylate, dodecyl (meth)acrylate, octadecyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, octadecyl (meth)acrylate, nonadecyl (meth)acrylate, icosyl (meth)acrylate, henicosyl (meth)acrylate, and docosyl (meth)acrylate.

[0027] Examples of non-hydroxyl group-containing branched alkyl (meth)acrylates include isopropyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate.

[0028] Examples of hydroxyl group-free cycloalkyl (meth)acrylates include cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, cyclopentanyl (meth)acrylate, and isobornyl (meth)acrylate.

[0029] Among these, alkyl(meth)acrylates having an alkyl group with a carbon number of about 1 to 20 are preferred because they contribute to leveling properties and adhesion to plastic substrates. In addition, by using in combination non-hydroxyl group-containing alkyl(meth)acrylates having alkyl groups with different carbon numbers, it becomes possible to adjust the physical properties of component (A), such as the glass transition temperature.

[0030] The upper and lower limits of the content of structural units derived from non-hydroxyl group-containing alkyl (meth)acrylate relative to 100 mol % of all structural units of the component (A) are, for example, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10 mol %, etc. In one embodiment, the content is preferably 10 to 90 mol %.

[0031] The upper and lower limits of the content of structural units derived from non-hydroxyl group-containing alkyl (meth)acrylates in which the non-hydroxyl group-containing alkyl group has 1 to 7 carbon atoms relative to 100 mol % of all structural units of the component (A) are, for example, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10 mol %, etc. In one embodiment, the content is preferably 10 to 90 mol %.

[0032] The upper and lower limits of the content of structural units derived from non-hydroxyl group-containing alkyl (meth)acrylates in which the non-hydroxyl group-containing alkyl group has 8 to 22 carbon atoms relative to 100 mol % of all structural units of the component (A) are, for example, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10 mol %, etc. In one embodiment, the content is preferably 10 to 90 mol %.

[0033] Examples of upper and lower limits for the content of structural units derived from non-hydroxyl group-containing alkyl (meth)acrylate relative to 100 mass% of all structural units of the component (A) are 95, 94.5, 94, 93, 92, 91, 90, 89, 88.5, 88, 87, 86, 85, 84, 83, 82, 81, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20 mass%, etc. In one embodiment, the content is preferably 20 to 95 mass%, and more preferably 80 to 95 mass%.

[0034] Examples of upper and lower limits for the content of structural units derived from non-hydroxyl group-containing alkyl (meth)acrylates in which the non-hydroxyl group-containing alkyl group has 1 to 7 carbon atoms relative to 100 mass% of all structural units of the component (A) are 95, 94.5, 94, 93, 92, 91, 90, 89, 88.5, 88, 87, 86, 85, 84, 83, 82, 81, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20 mass%, etc. In one embodiment, the content is preferably 20 to 95 mass%, more preferably 20 to 85 mass%.

[0035] Examples of upper and lower limits for the content of structural units derived from non-hydroxyl group-containing alkyl (meth)acrylates in which the non-hydroxyl group-containing alkyl group has 8 to 22 carbon atoms relative to 100 mass% of all structural units of the component (A) are 95, 94.5, 94, 93, 92, 91, 90, 89, 88.5, 88, 87, 86, 85, 84, 83, 82, 81, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20 mass%, etc. In one embodiment, the content is preferably 20 to 95 mass%, and more preferably 30 to 65 mass%.

[0036] (Hydroxyl Group-Containing Monomer) The hydroxyl group-containing monomers may be used alone or in combination of two or more.

[0037] The hydroxyl group-containing monomer has the following structural formula: [ka] [In the formula, R a3 is a hydrogen atom or a methyl group, R a4 NHR a4A’ OR a4B’ and R a4A’ is a hydroxyl group-containing alkyl group, R a4B’ (R a4B1’ O) n H (R a4B1’ is an alkylene group, and n is an integer of 1 or more. or R a4B2’O(C(=O)(CH 2 ) 5 O) m H (R a4B2’ is an alkylene group, and m is an integer of 1 or more. It is.] It is expressed as:

[0038] In the present disclosure, a "hydroxyl-containing alkyl group" is a group in which one hydrogen atom of an alkyl group is replaced by a hydroxyl group. Examples of the hydroxyl-containing alkyl group include a hydroxyl-containing linear alkyl group, a hydroxyl-containing branched alkyl group, and a hydroxyl-containing cycloalkyl group.

[0039] Examples of the alkylene group include a straight-chain alkylene group, a branched alkylene group, and a cycloalkylene group.

[0040] A straight chain alkylene group has the general formula: -(CH 2 ) n - (n is an integer of 1 or more). Examples of the linear alkylene group include a methylene group, an ethylene group, a propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group, an n-octylene group, an n-nonylene group, and an n-decamethylene group.

[0041] A branched alkylene group is a linear alkylene group in which at least one hydrogen atom is substituted with an alkyl group. Examples of branched alkylene groups include a diethylpentylene group, a trimethylbutylene group, a trimethylpentylene group, and a trimethylhexylene group (trimethylhexamethylene group).

[0042] Examples of the cycloalkylene group include a monocyclic cycloalkylene group, a bridged ring cycloalkylene group, a condensed ring cycloalkylene group, etc. In addition, the cycloalkylene group may have one or more hydrogen atoms substituted with a straight-chain or branched alkyl group.

[0043] Examples of the monocyclic cycloalkylene group include a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclodecylene group, and a 3,5,5-trimethylcyclohexylene group.

[0044] Examples of the bridged ring cycloalkylene group include a tricyclodecylene group, an adamantylene group, and a norbornylene group.

[0045] The condensed ring cycloalkylene group is exemplified by a bicyclodecylene group.

[0046] In the present disclosure, examples of the upper and lower limits of the number of carbon atoms in a hydrocarbon group (such as an alkyl group, an alkylene group, an arylene group, an arylene alkylene arylene group, etc.) that is not specified include 30, 29, 25, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, etc.

[0047] Examples of the hydroxyl group-containing monomer include hydroxyl group-containing (meth)acrylic esters, polyalkylene glycol mono(meth)acrylates, caprolactone-modified hydroxyalkyl (meth)acrylates, and hydroxyl group-containing (meth)acrylamides.

[0048] The hydroxyl group-containing (meth)acrylic ester is R a4 OR a4B1’ OH, i.e. R a4B’ is a monomer in which the hydroxyl group-containing alkyl group is present. The symbols have the same meanings as above. The hydroxyl group-containing alkyl group preferably has 1 to 4 carbon atoms.

[0049] Examples of hydroxyl group-containing (meth)acrylic esters include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, and 1,4-cyclohexanedimethanol mono(meth)acrylate.

[0050] Polyalkylene glycol mono(meth)acrylate is R a4 is O(R a4B1’ O) n H. The meanings of the symbols are the same as above. In one embodiment, n is preferably 1 or more, more preferably 1 to 60, and R a4B1’ is preferably an ethylene group or a propylene group.

[0051] Examples of commercially available polyalkylene glycol mono(meth)acrylates include Blemmer PE-90, Blemmer 200, Blemmer 350, Blemmer PME-400, Blemmer AE-400, Blemmer PME-1000, and Blemmer PME-2000 (manufactured by NOF Corporation).

[0052] Caprolactone-modified hydroxyalkyl (meth)acrylate is R a4 OR a4B2’ O(C(=O)(CH 2 ) 5 O) m H. The meanings of the symbols are the same as above. In one embodiment, m is preferably 1 or more, more preferably 1 to 6, and even more preferably 1 to 3. R a4B2’ is preferably an alkylene group having 2 to 6 carbon atoms, and more preferably an ethylene group.

[0053] Examples of commercially available caprolactone-modified hydroxyalkyl (meth)acrylate products include "PLAXEL FM1", "PLAXEL FM2", "PLAXEL FM1D", "PLAXEL FM2D", "PLAXEL FM3", "PLAXEL FM3X", "PLAXEL FM4", "PLAXEL FM-5", "PLAXEL FA1", "PLAXEL FA2", "PLAXEL FA1D", "PLAXEL FA1DDM", "PLAXEL FA2D", "PLAXEL FA3", "PLAXEL FA4", and "PLAXEL FA5" (all manufactured by Daicel Corporation).

[0054] Examples of hydroxyl group-containing (meth)acrylamides include N-(2-hydroxyethyl)acrylamide and N-(1-methyl-2-hydroxyethyl)acrylamide.

[0055] An example of the monomer having two or more hydroxyl groups is glycerin mono(meth)acrylate.

[0056] The upper and lower limits of the content of structural units derived from hydroxyl group-containing alkyl (meth)acrylate relative to 100 mol % of all structural units of the component (A) are, for example, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10 mol %, etc. In one embodiment, the content is preferably 10 to 90 mol %.

[0057] Examples of upper and lower limits for the content of structural units derived from hydroxyl group-containing alkyl (meth)acrylate relative to 100 mass% of all structural units of the component (A) are 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11.5, 11, 10, 9, 8, 7, 6, 5.5, 5 mass%, etc. In one embodiment, the content is preferably 5 to 80 mass%, and more preferably 5 to 25 mass%.

[0058] The molar ratio of the structural units derived from a non-hydroxyl group-containing alkyl (meth)acrylate to the structural units derived from a hydroxyl group-containing alkyl (meth)acrylate in the component (A) (non-hydroxyl group-containing alkyl (meth)acrylate mol / Hydroxyl-containing alkyl (meth)acrylate mol ) are exemplified by upper and lower limits such as 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, etc. In one embodiment, the molar ratio is preferably 0.1 to 9.

[0059] The mass ratio of the structural units derived from a non-hydroxyl group-containing alkyl (meth)acrylate to the structural units derived from a hydroxyl group-containing alkyl (meth)acrylate in the component (A) (non-hydroxyl group-containing alkyl (meth)acrylate mass / Hydroxyl-containing alkyl (meth)acrylate mass ) are exemplified by upper and lower limits such as 19, 18, 17.5, 17.2, 17, 16, 15, 13, 11, 10, 9, 8, 7.9, 7.7, 7.5, 7, 6, 5, 4.9, 4.7, 4.5, 4.3, 4.1, 4, 3, 2, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.25, etc. In one embodiment, the above mass ratio is preferably 0.25 to 19.

[0060] (Monomers other than non-hydroxyl group-containing alkyl (meth)acrylates and hydroxyl group-containing alkyl (meth)acrylates: also referred to as other monomers) When producing the component (A), a monomer that does not fall into either the non-hydroxyl group-containing alkyl (meth)acrylate or the hydroxyl group-containing alkyl (meth)acrylate may be used. The other monomers may be used alone or in combination of two or more kinds.

[0061] Examples of other monomers include (meth)acrylic acid, α,β-unsaturated carboxylic acids, epoxy group-containing (meth)acrylates, styrenes, α-olefins, unsaturated alcohols, aryl (meth)acrylates, dialkylaminoalkyl (meth)acrylates and salts thereof, dialkylaminoalkyl (meth)acrylamides and salts thereof, chain transfer monomers, (meth)acrylamides, vinylamine, (meth)acrylonitrile, monofunctional monomers other than those mentioned above, bis(meth)acrylamides, di(meth)acrylic esters, divinyl esters, difunctional monomers other than those mentioned above, trifunctional monomers, tetrafunctional monomers, and the like.

[0062] The upper and lower limits of the content of structural units derived from other monomers relative to 100 mol % of all structural units of the component (A) are, for example, 20, 15, 10, 9, 5, 4, 1, 0.9, 0.5, 0.1, 0 mol %, etc. In one embodiment, the content is preferably 0 to 20 mol %.

[0063] Examples of upper and lower limits for the content of structural units derived from other monomers relative to 100% by mass of all structural units of the component (A) are 20, 15, 10, 9, 5, 4, 1, 0.9, 0.5, 0.1, 0% by mass, etc. In one embodiment, the content is preferably 0 to 20% by mass.

[0064] The molar ratio of the structural units derived from the non-hydroxyl group-containing alkyl (meth)acrylate in the component (A) to the structural units derived from other monomers (other monomers mol / Non-hydroxyl group-containing alkyl (meth)acrylate mol ) may be 0.30, 0.25, 0.20, 0.15, 0.10, 0.05, 0, etc. In one embodiment, the molar ratio is preferably 0 to 0.30.

[0065] The mass ratio of the structural units derived from the non-hydroxyl group-containing alkyl (meth)acrylate in the component (A) to the structural units derived from other monomers (other monomers mass / Non-hydroxyl group-containing alkyl (meth)acrylate mass ) may be 0.29, 0.25, 0.20, 0.15, 0.10, 0.05, 0, etc. In one embodiment, the above mass ratio is preferably 0 to 0.29.

[0066] The molar ratio of the structural units derived from the hydroxyl group-containing alkyl (meth)acrylate in the component (A) to the structural units derived from other monomers (other monomers mol / Hydroxyl-containing alkyl (meth)acrylate mol ) may be 4, 3, 2, 1, 0.9, 0.7, 0.5, 0.3, 0.1, 0, etc. In one embodiment, the molar ratio is preferably 0 to 4.

[0067] The mass ratio of the structural units derived from the hydroxyl group-containing alkyl (meth)acrylate in the component (A) to the structural units derived from other monomers (other monomers mass / Hydroxyl-containing alkyl (meth)acrylate mass) may be 3.3, 3, 2, 1, 0.7, 0.5, 0.3, 0.1, 0, etc. In one embodiment, the above mass ratio is preferably 0 to 3.3.

[0068] <Physical properties of component (A)> Examples of upper and lower limits of the glass transition temperature of the component (A) are 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 0, -5, -10, -15, -20, -22, -25, -30, -35, -40, -45, -50, -55, -60°C, etc. In one embodiment, the glass transition temperature is preferably -60 to 60°C, and more preferably -30 to 30°C.

[0069] The glass transition temperature is calculated by the Fox equation. Fox formula: 1 / Tg = (Wa / Tga) + (Wb / Tgb) + ··· + (Wn / Tgn) Tg: Glass transition temperature of the copolymer (K) Wa: mass% of monomer A Tga: Glass transition temperature of homopolymer of monomer A (K) Wb: mass% of monomer B Tgb: Glass transition temperature of homopolymer of monomer B (K) Wn: mass% of monomer N Tgn: Glass transition temperature of homopolymer of monomer N (K)

[0070] Examples of upper and lower limits of the hydroxyl value of the (A) component include 200, 190, 180, 170, 160, 150, 140, 130, 120, 110, 100, 90, 85, 82, 80, 75, 70, 60, 55, 50, 45, 40, 30, 25, 20, and 10 mgKOH / g. In one embodiment, the hydroxyl value is preferably 10 to 200 mgKOH / g, and more preferably 20 to 100 mgKOH / g.

[0071] The hydroxyl value is measured by a method in accordance with JIS K1557-1.

[0072] The upper and lower limits of the hydroxyl equivalent of the component (A) are exemplified as 2.4, 2, 1.9, 1.7, 1.5, 1.3, 1.0, 0.9, 0.7 meq / g, etc. In one embodiment, the hydroxyl equivalent is preferably 0.7 to 2.4 meq / g.

[0073] In the present disclosure, the hydroxyl equivalent is the amount of hydroxyl groups present in 1 g of a solid.

[0074] The upper and lower limits of the acid value of the component (A) are exemplified as 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0 meq / g, etc. In one embodiment, the acid value is preferably 0 to 0.7 meq / g, particularly in consideration of curability.

[0075] The acid value is measured by a method in accordance with JIS K0070.

[0076] Examples of upper and lower limits of the weight average molecular weight (Mw) of the component (A) are 100000, 90000, 80000, 70000, 60000, 50000, 40000, 30000, 20000, 10000, 5000, 4000, and 3000. In one embodiment, the weight average molecular weight (Mw) is preferably 3000 to 100000, and more preferably 10000 to 80000.

[0077] Examples of upper and lower limits of the number average molecular weight (Mn) of the component (A) are 100000, 90000, 80000, 70000, 60000, 50000, 40000, 30000, 20000, 10000, 5000, 4000, 3000, etc. In one embodiment, the number average molecular weight (Mn) is preferably 3000 to 100000, and more preferably 3000 to 80000.

[0078] The weight average molecular weight and number average molecular weight can be determined, for example, as a polystyrene equivalent value measured in an appropriate solvent by gel permeation chromatography (GPC). Detailed conditions are exemplified as follows. Model: Product name "HLC-8220" (manufactured by Tosoh Corporation) Column: Product name "PLgel MIXED-C" (Agilent Technology) x 2 Developing solvent, flow rate: tetrahydrofuran, 1.0 mL / min Measurement temperature: 40℃ Detector: RI Standard: Monodisperse polystyrene Polymer concentration: 0.2%

[0079] The upper and lower limits of the molecular weight distribution (Mw / Mn) of the component (A) are, for example, 10, 9, 7.5, 5, 2.5, 2, 1.5, etc. In one embodiment, the molecular weight distribution (Mw / Mn) is preferably 1.5 to 10.

[0080] Component (A) can be produced by various known methods. Examples of the method for producing component (A) include a method in which a hydroxyl-free alkyl (meth)acrylate and a hydroxyl-containing alkyl (meth)acrylate, and other monomers as necessary, are copolymerized in the absence of a solvent or in an organic solvent, usually in the presence of a polymerization initiator, at about 80 to 180°C for about 1 to 10 hours. Examples of the organic solvent and polymerization initiator used in producing component (A) include those described below.

[0081] The upper and lower limits of the content of the (A) component in 100% by mass of the solid content of the coating agent are 95, 90, 85, 80, 75, 74, 73, 72, 71, 70, 69, 68, 67, 66, 65, 64, 63, 62, 61, 60, 59, 55, 50, 49, 48, 46, 45, 40, 35, 30% by mass, etc. In one embodiment, the content is preferably 30 to 95% by mass, more preferably 40 to 80% by mass.

[0082] <Polyisocyanate (B): Also called component (B).> The polyisocyanates may be used alone or in combination of two or more.

[0083] In this disclosure, a "polyisocyanate" is a compound having two or more isocyanate groups (-N=C=O).

[0084] Examples of polyisocyanates include linear aliphatic polyisocyanates, branched aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and biuret forms, isocyanurate forms, allophanate forms, adduct forms, and the like of these.

[0085] Examples of linear aliphatic polyisocyanates include methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, and decamethylene diisocyanate.

[0086] Examples of branched aliphatic polyisocyanates include diethylpentylene diisocyanate, trimethylbutylene diisocyanate, trimethylpentylene diisocyanate, and trimethylhexamethylene diisocyanate.

[0087] Examples of the alicyclic polyisocyanate include monocyclic alicyclic polyisocyanates, crosslinked cyclic alicyclic polyisocyanates, and condensed cyclic alicyclic polyisocyanates.

[0088] Examples of monocyclic alicyclic polyisocyanates include hydrogenated xylene diisocyanate, isophorone diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, cycloheptylene diisocyanate, cyclodecylene diisocyanate, 3,5,5-trimethylcyclohexylene diisocyanate, and dicyclohexylmethane diisocyanate.

[0089] Examples of the crosslinked alicyclic polyisocyanate include tricyclodecylene diisocyanate, adamantane diisocyanate, and norbornene diisocyanate.

[0090] An example of the condensed ring alicyclic polyisocyanate is bicyclodecylene diisocyanate.

[0091] Examples of the aromatic group include a monocyclic aromatic group, a condensed ring aromatic group, etc. Furthermore, the aromatic group may have one or more hydrogen atoms substituted with a linear or branched alkyl group.

[0092] Examples of the monocyclic aromatic group include a phenyl group, a tolyl group, a mesityl group, etc. Examples of the condensed ring aromatic group include a naphthyl group, etc.

[0093] Examples of aromatic polyisocyanates include monocyclic aromatic polyisocyanates and condensed ring aromatic polyisocyanates.

[0094] Examples of monocyclic aromatic polyisocyanates include dialkyl diphenylmethane diisocyanates such as 4,4'-diphenyldimethylmethane diisocyanate, tetraalkyl diphenylmethane diisocyanates such as 4,4'-diphenyltetramethylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dibenzyl isocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, and m-tetramethylxylylene diisocyanate.

[0095] An example of the condensed ring aromatic polyisocyanate is 1,5-naphthylene diisocyanate.

[0096] The biuret form of polyisocyanate is The structural formula: [ka] [where n b is an integer equal to or greater than 0, and R bA ~R bE are each independently an alkylene group or an arylene group; R bα ~R bβ each independently represents an isocyanate group or [ka] (n b1 is an integer equal to or greater than 0, and R b1 ~R b5 are each independently an alkylene group or an arylene group; R b '~R b '' each independently represents an isocyanate group or R bα ~R bβ It is a radical of itself. R b4 ~R b5 , R b '' may be different groups for each structural unit. bD ~R bE , R bβ may be different groups for each structural unit.

[0097] Examples of biuret polyisocyanates include Duranate 24A-100, Duranate 22A-75P, Duranate 21S-75E (all manufactured by Asahi Kasei Corporation), and Desmodur N3200A (biuret of hexamethylene diisocyanate) (all manufactured by Sumitomo Bayer Urethane Co., Ltd.).

[0098] Isocyanurate of polyisocyanate is The structural formula: [ka] [where n i is an integer equal to or greater than 0, and R iA ~R iE are each independently an alkylene group or an arylene group; R iα ~R iβ each independently represents an isocyanate group or [ka] (n i1 is an integer equal to or greater than 0, and R i1 ~R i5 are each independently an alkylene group or an arylene group; R i '~R i'' each independently represents an isocyanate group or R iα ~R iβ It is a radical of itself. R i5 , R i '' may be different groups for each structural unit. iD ~R iE , R iβ may be different groups for each structural unit.

[0099] Commercially available isocyanurate polyisocyanates include Duranate TPA-100, Duranate TKA-100, Duranate MFA-75B, Duranate MHG-80B (all manufactured by Asahi Kasei Corporation), Coronate HXR (isocyanurate of hexamethylene diisocyanate) (all manufactured by Tosoh Corporation), Takenate D-127N (isocyanurate of hydrogenated xylylene diisocyanate) (all manufactured by Mitsui Chemicals, Inc.), VESTANAT T1890 / 100 (isocyanurate of isophorone diisocyanate) (all manufactured by Evonik Japan Co., Ltd.), Takenate D-204EA-1 (isocyanurate of tolylene diisocyanate) (all manufactured by Mitsui Chemicals, Inc.), and Coronate 2037 (all manufactured by Tosoh Corporation).

[0100] Allophanate forms of polyisocyanates are The structural formula: [ka] [In the formula, n is an integer of 0 or more, and R A is an alkyl group or an aryl group, R B ~R G are each independently an alkylene group or an arylene group; R α ~R γ each independently represents an isocyanate group or [ka] (n1 is an integer equal to or greater than 0, R 1 ~R 6are each independently an alkylene group or an arylene group, and R' to R''' are each independently an isocyanate group or R α ~R γ It is a radical of itself. R 1 ~R 4 R' to R'' may be different groups for each structural unit. B ~R E , R α ~R β may be different groups for each structural unit.

[0101] Examples of commercially available allophanate polyisocyanate products include Coronate 2793 (manufactured by Tosoh Corporation) and Takenate D-178N (manufactured by Mitsui Chemicals, Inc.).

[0102] The polyisocyanate adduct is The structural formula: [ka] [where n ad is an integer equal to or greater than 0, and R adA ~R adE are each independently an alkylene group or an arylene group; R ad1 ~R ad2 are each independently [ka] (In the formula, n ad’ is an integer equal to or greater than 0, R ad’ ~R ad’’ each independently represents an alkylene group or an arylene group, R ad’’’ is R ad1 ~R ad2 It is the foundation of itself, R ad’ ~R ad’’’ may have different groups for each structural unit. and R adD ~R adE , R ad2may be different for each structural unit.] An adduct of trimethylolpropane and polyisocyanate represented by the formula: The following structural formula [ka] [where n ad1 is an integer equal to or greater than 0, R adα ~R adε each independently represents an alkylene group or an arylene group, R adA ~R adB are each independently [ka] (In the formula, n ad1’ is an integer equal to or greater than 0, R adδ’ ~R adε’ each independently represents an alkylene group or an arylene group, R adB’ is R adA ~R adB It is the foundation of itself, R adδ’ ~R adε’ , R adB’ may have different groups for each structural unit. R adδ ~R adε may be different for each structural unit.] Examples thereof include an adduct of glycerin and polyisocyanate represented by the following formula:

[0103] Examples of polyisocyanate adducts include Duranate P301-75E (both manufactured by Asahi Kasei Corporation), Takenate D-110N, Takenate D-160N (both manufactured by Mitsui Chemicals, Inc.), and Coronate L (both manufactured by Tosoh Corporation).

[0104] The upper and lower limits of the NCO content (NCO%) of the polyisocyanate are, for example, 30, 25, 20, 15, 10%, etc. In one embodiment, the NCO content (NCO%) is preferably 10 to 30%.

[0105] The upper and lower limits of the isocyanate group equivalent of the polyisocyanate are, for example, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1 meq / g, etc. In one embodiment, the isocyanate group equivalent is preferably 1 to 10 meq / g.

[0106] In the present disclosure, the isocyanate group equivalent weight means the amount of isocyanate groups present in 1 g of a solid.

[0107] The upper and lower limits of the ratio (NCO / OH) of the isocyanate group equivalent of the polyisocyanate to the hydroxyl group equivalent of the (A) component are exemplified as 4, 3, 2, 1.75, 1.5, 1.25, 1, 0.75, 0.5, 0.25, 0.1, 0.05, etc. In one embodiment, the ratio (NCO / OH) is preferably 0.05 to 4.

[0108] The upper and lower limits of the amount of consumed OH groups are exemplified as 150, 125, 100, 75, 50, 25, 10 mgKOH / g, etc. In one embodiment, the amount of consumed OH groups is preferably 10 to 150 mgKOH / g.

[0109] In the present disclosure, the amount of consumed OH groups is an index showing how much of the OH groups in the base resin are consumed by adding NCO. The amount of consumed OH groups is calculated by the following formula: Amount of consumed OH groups = isocyanate group equivalent x 56.1 It is calculated as follows.

[0110] The upper and lower limits of the polyisocyanate content in 100% by mass of the coating agent solid content are 45, 43, 41, 40, 39, 36, 35, 30, 29, 28, 27, 26, 25, 24, 23, 22, 21, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10% by mass, etc. In one embodiment, the content is preferably 10 to 45% by mass.

[0111] <Hydroxyl group-containing fluororesin (C): Also referred to as component (C).> The component (C) may be used alone or in combination of two or more types.

[0112] In the present disclosure, "hydroxyl group-containing fluororesin" refers to a resin that contains structural units derived from a fluorine-containing monomer and has one or more hydroxyl groups.

[0113] The fluorine-containing monomer is exemplified by fluoroolefins.

[0114] By "fluoroolefin" in this disclosure is meant an olefin in which one or more of the hydrogen atoms have been replaced with a fluorine atom.

[0115] The fluoroolefins may be used alone or in combination of two or more. The fluoroolefins are CF 2 =CF 2 , C.F. 2 =CFCl, CF 2 =CHF, CF 2 =CH 2 , C.F. 2 =CFCF 3 , C.F. 2 =CHCF 3 , C.F. 3 CH=CHF, CF 3 CF=CH 2 , C.H. 2 =CX(CF 2 ) f Examples include X and Y (wherein X and Y are independently a hydrogen atom or a fluorine atom, and f is an integer of 2 to 10).

[0116] The upper and lower limits of the content of the fluoroolefin-derived structural units relative to 100 mol% of all structural units of the hydroxyl group-containing fluororesin are, for example, 100, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20 mol%, etc. In one embodiment, the content is preferably 20 to 100 mol%, more preferably 30 to 70 mol%, and particularly preferably 40 to 60 mol%.

[0117] The hydroxyl-containing fluororesin contains constitutional units derived from a hydroxyl-containing monomer.

[0118] Examples of the hydroxyl-containing monomer contained in the hydroxyl-containing fluororesin include hydroxyl-containing vinyl ethers, hydroxyl-containing allyl ethers, hydroxyl-containing vinyl esters, hydroxyl-containing allyl esters, hydroxyl-containing (meth)acrylic esters, and allyl alcohols.

[0119] Examples of the hydroxyl group-containing vinyl ether include hydroxyalkyl vinyl ether and polyalkylene glycol monovinyl ether.

[0120] Examples of the hydroxyalkyl vinyl ether include hydroxy linear alkyl vinyl ether, hydroxy branched alkyl vinyl ether, and hydroxycycloalkyl vinyl ether.

[0121] Examples of hydroxy linear alkyl vinyl ethers include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, and 5-hydroxypentyl vinyl ether.

[0122] Examples of hydroxy branched alkyl vinyl ethers include 2-hydroxypropyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, and 4-hydroxy-2-methylbutyl vinyl ether.

[0123] Examples of hydroxycycloalkyl vinyl ethers include 4-hydroxycyclopentyl vinyl ether, 4-hydroxycyclohexyl vinyl ether, and the like.

[0124] Examples of polyalkylene glycol monovinyl ethers include polymethylene glycol monovinyl ether, polyethylene glycol monovinyl ether, and polypropylene glycol monovinyl ether.

[0125] Examples of polymethylene glycol monovinyl ethers include dimethylene glycol monovinyl ether, trimethylene glycol monovinyl ether, tetramethylene glycol monovinyl ether, pentamethylene glycol monovinyl ether, hexamethylene glycol monovinyl ether, heptamethylene glycol monovinyl ether, octamethylene glycol monovinyl ether, nonamethylene glycol monovinyl ether, and decamethylene glycol monovinyl ether.

[0126] Examples of polyethylene glycol monovinyl ethers include diethylene glycol monovinyl ether, triethylene glycol monovinyl ether, tetraethylene glycol monovinyl ether, pentaethylene glycol monovinyl ether, hexaethylene glycol monovinyl ether, heptaethylene glycol monovinyl ether, octaethylene glycol monovinyl ether, nonaethylene glycol monovinyl ether, and decaethylene glycol monovinyl ether.

[0127] Examples of polypropylene glycol monovinyl ethers include dipropylene glycol monovinyl ether, tripropylene glycol monovinyl ether, tetrapropylene glycol monovinyl ether, pentapropylene glycol monovinyl ether, hexapropylene glycol monovinyl ether, heptapropylene glycol monovinyl ether, octapropylene glycol monovinyl ether, nonapropylene glycol monovinyl ether, and decapropylene glycol monovinyl ether.

[0128] The hydroxyl-containing allyl ether is a compound in which the vinyl group of a hydroxyl-containing vinyl ether is replaced with an allyl group.

[0129] In one embodiment, the hydroxyl group-containing monomer contained in the hydroxyl group-containing fluororesin is CH 2 =CHO-CH 2 -cC 6 H 10 -CH 2OH, CH 2 =CHCH 2 O-CH 2 -cC 6 H 10 -CH 2 OH, CH 2 =CHO-CH 2 -cC 6 H 10 -CH 2 -(OCH 2 CH 2 ) 15 OH, CH 2 =CHOCH 2 CH 2 OH, CH 2 =CHCH 2 OCH 2 CH 2 OH, CH 2 =CHOCH 2 CH 2 CH 2 CH 2 OH, CH 2 =CHCH 2 OCH 2 CH 2 CH 2 CH 2 OH is preferred, and CH is preferred from the viewpoint of copolymerizability with fluoroolefin. 2 =CHCH 2 OCH 2 CH 2 OH or CH 2 =CHOCH 2 CH 2 CH 2 CH 2 OH is more preferable. 6 H 10 -" represents a cyclohexylene group, and "-cC 6 H 10 The binding site of - is usually 1,4-.

[0130] The upper and lower limits of the content of the structural units derived from the hydroxyl-containing monomer in 100 mol % of all structural units of the hydroxyl-containing fluororesin are, for example, 35, 30, 25, 20, 15, 10, 5, 4, 3, 2, 1, 0.5, 0.1 mol %, etc. In one embodiment, the content is preferably 0.1 to 35 mol %, more preferably 0.5 to 35 mol %, even more preferably 3 to 25 mol %, even more preferably 5 to 25 mol %, and particularly preferably 5 to 20 mol %.

[0131] Examples of monomers that do not fall into either the fluoroolefin or the hydroxyl group-containing monomer include unsaturated carboxylic acids, alkenes, vinyl ethers, vinyl esters, allyl ethers, allyl esters, and (meth)acrylic esters.

[0132] The upper and lower limits of the content of structural units derived from monomers not corresponding to fluoroolefins or hydroxyl-containing monomers in 100 mol % of all structural units of the hydroxyl-containing fluororesin are, for example, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 4, 3, 2, 1, 0.5, 0.1, 0 mol %, etc. In one embodiment, the content is preferably 0 to 60 mol %, more preferably 5 to 60 mol %, and even more preferably 10 to 50 mol %.

[0133] Examples of hydroxyl-containing fluororesins containing structural units derived from fluoroolefins and structural units derived from non-fluorine-containing monomers include fluoroethylene-vinyl ether copolymers.

[0134] Examples of fluoroethylene-vinyl ether copolymers include fluoroethylene-vinyl ether copolymers, chlorotrifluoroethylene-vinyl ether copolymers, chlorotrifluoroethylene-vinyl ether-vinyl ester copolymers, chlorotrifluoroethylene-vinyl ester-allyl ether copolymers, tetrafluoroethylene-vinyl ester copolymers, tetrafluoroethylene-vinyl ester-allyl ether copolymers, and ethylene-tetrafluoroethylene copolymers.

[0135] Examples of commercially available hydroxyl group-containing fluororesin products include Lumiflon 200F, Lumiflon 710F, Lumiflon 916F, Lumiflon 200, Lumiflon 400, Lumiflon 552, Lumiflon 600X, Lumiflon 800, Lumiflon 810Y, Lumiflon 910LM, Lumiflon 936, Lumiflon 9010, Lumiflon 200MEK, Lumiflon 9716, Lumiflon 9721, Lumiflon FE4300, Lumiflon FE4400, Lumiflon FE4500, and Lumiflon FD1000 (manufactured by AGC Inc.).

[0136] The upper and lower limits of the hydroxyl value of the hydroxyl-containing fluororesin are exemplified as 500, 450, 400, 350, 300, 250, 200, 150, 125, 110, 100, 90, 75, 50, 40, 31, 30, 25, 10 mgKOH / g, etc. In one embodiment, the hydroxyl value is preferably 1 to 500 mgKOH / g.

[0137] Examples of upper and lower limits of the number average molecular weight of the hydroxyl group-containing fluororesin are 30,000, 29,000, 27,500, 25,000, 22,500, 20,000, 19,000, 17,500, 15,000, 12,500, 10,000, 9,000, 7,500, 5,000, 2500, 1,000, 900, 500, and 100. In one embodiment, the number average molecular weight is preferably 100 to 30,000.

[0138] Examples of upper and lower limits of the weight average molecular weight of the hydroxyl group-containing fluororesin are 50,000, 40,000, 30,000, 29,000, 27,500, 25,000, 22,500, 20,000, 19,000, 17,500, 15,000, 12,500, 10,000, 9,000, 7,500, 5,000, 2500, 1000, 900, 500, and 100. In one embodiment, the weight average molecular weight is preferably 100 to 50,000.

[0139] The upper and lower limits of the content of the hydroxyl group-containing fluororesin in 100% by mass of the solid content of the coating agent are, for example, 50, 45, 40, 35, 30, 25, 24, 23, 20, 15, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1% by mass, etc. In one embodiment, the content is preferably 1 to 50% by mass, and more preferably 1 to 10% by mass.

[0140] The upper and lower limits of the mass ratio of the (A) component to the (B) component in the coating agent solid content [mass of the (A) component / mass of the (B) component] are 9.5, 9, 8, 7, 6, 5.5, 5, 4, 3.5, 3, 2.5, 2, 1.5, 1, 0.9, 0.8, 0.7, etc. In one embodiment, the mass ratio is preferably 0.7 to 9.5.

[0141] The upper and lower limits of the mass ratio of the (A) component to the (C) component in the coating agent solid content [mass of the (A) component / mass of the (C) component] are 95, 90, 75, 50, 25, 10, 9, 5, 4, 3, 2, 1.5, 1, 0.9, 0.7, 0.6, etc. are exemplified. In one embodiment, the above mass ratio is preferably 0.6 to 95.

[0142] The upper and lower limits of the mass ratio of the (B) component to the (C) component in the coating agent solid content [mass of the (B) component / mass of the (C) component] are 45, 30, 25, 10, 9, 8, 7, 5, 4.5, 4, 3, 2.5, 2, 1.5, 1, 0.9, 0.5, 0.4, 0.2, etc. In one embodiment, the mass ratio is preferably 0.2 to 45.

[0143] <Organo-modified silicone (D): Also called component (D).> In one embodiment, the coating agent may contain an organic modified silicone. The component (C) may be used alone or in combination of two or more kinds.

[0144] In the present disclosure, "organo-modified silicone" refers to silicone into which an organic group has been introduced. Examples of organo-modified silicone include side-chain type organo-modified silicone, both-end type organo-modified silicone, one-end type organo-modified silicone, and both-end type side-chain organo-modified silicone.

[0145] Examples of organically modified silicones include hydroxyl group-containing organically modified silicones, amino group-containing organically modified silicones, epoxy group-containing organically modified silicones, mercapto group-containing organically modified silicones, and carboxyl group-containing organically modified silicones.

[0146] Examples of hydroxyl-containing organic modified silicones include hydroxyl-containing acrylic resin modified silicones, hydroxyl-containing polyester resin modified silicones, hydroxyl-containing polyether resin modified silicones, and hydroxyl-containing carbinol resin modified silicones.

[0147] Examples of commercially available hydroxyl-containing acrylic resin-modified silicones include ZX-028-G (manufactured by T&K Toka Corporation), BYK-SILCLEAN3700 (manufactured by BYK Japan Co., Ltd.), and Simac US-270 (manufactured by Toagosei Co., Ltd.).

[0148] Examples of commercially available hydroxyl-containing polyester resin-modified silicones or hydroxyl-containing polyether resin-modified silicones include BYK-370, BYK-375, BYK-377, BYK-SILCLEAN3720 (manufactured by BYK Japan K.K.), X-22-4952, and KF-6123 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0149] Examples of commercially available hydroxyl group-containing carbinol resin-modified silicones include X-22-4039, X-22-4015, X-22-4952, X-22-4272, X-22-170BX, X-22-170DX, KF-6000, KF-6001, KF-6002, KF-6003, KF-6123, and X-22-176F (manufactured by Shin-Etsu Chemical Co., Ltd.), Silaplane FM-4411, Silaplane FM-4421, Silaplane FM-4425, Silaplane FM-0411, Silaplane FM-0421, Silaplane FM-DA11, Silaplane FM-DA21, and Silaplane FM-DA26 (manufactured by JNC Corporation).

[0150] Examples of commercially available amino group-containing organic modified silicones include KF-868, KF-865, KF-864, KF-859, KF-393, KF-860, KF-880, KF-8004, KF-8002, KF-8005, KF-867, KF-8021, KF-869, KF-861, KF-877, KF-889, and X-22-3939A (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0151] Examples of commercially available epoxy group-containing organic modified silicones include X-22-343, KF-101, KF-1001, X-22-2000, X-22-2046, KF-102, X-22-4741, KF-1002, and KF-1005 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0152] Examples of commercially available mercapto group-containing organic modified silicones include KF-2001 and KF-2004 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0153] An example of a commercially available carboxyl group-containing organic modified silicone is X-22-3701E (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0154] The upper and lower limits of the hydroxyl value of the organic modified silicone are exemplified as 500, 450, 400, 350, 300, 250, 200, 150, 100, 50, 10, 0 mgKOH / g, etc. In one embodiment, the hydroxyl value is preferably 0 to 500 mgKOH / g.

[0155] The upper and lower limits of the content of the organic modified silicone in 100% by mass of the solid content of the coating agent are exemplified as 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0% by mass, etc. In one embodiment, the content is preferably 0 to 10% by mass.

[0156] <Curing catalyst (E): Also called component (E)> In one embodiment, the coating agent may contain a curing catalyst. The curing catalyst may be contained alone or in combination of two or more kinds.

[0157] Examples of the curing catalyst include an organometallic catalyst and an organoamine catalyst.

[0158] Examples of the organometallic catalyst include organotypical metal catalysts and organotransition metal catalysts.

[0159] Examples of the organotypical metal catalyst include organotin catalysts and organobismuth catalysts.

[0160] Examples of the organotin catalyst include dibutyltin dilaurate and dioctyltin dilaurate.

[0161] An example of the organic bismuth catalyst is bismuth octoate.

[0162] Examples of the organotransition metal catalyst include an organotitanium catalyst, an organozirconium catalyst, and an organoiron catalyst.

[0163] The organic titanium catalyst is exemplified by titanium ethyl acetoacetate.

[0164] The organic zirconium catalyst is exemplified by zirconium tetraacetylacetonate.

[0165] The organic iron catalyst is exemplified by iron acetylacetonate.

[0166] Examples of the organic amine catalyst include diazabicyclooctane, dimethylcyclohexylamine, tetramethylpropylenediamine, ethylmorpholine, dimethylethanolamine, triethylamine, and triethylenediamine.

[0167] The upper and lower limits of the content of the curing catalyst in 100% by mass of the solid content of the coating agent are exemplified as 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0% by mass, etc. In one embodiment, the content is preferably 0 to 1% by mass.

[0168] <Organic solvent (F): Also called component (F).> In one embodiment, the coating agent may contain an organic solvent. The organic solvent may be used alone or in combination of two or more kinds.

[0169] Examples of the organic solvent include methyl ethyl ketone, methyl isobutyl ketone, acetone, ethyl acetate, butyl acetate, toluene, xylene, etc. Among these, from the viewpoint of the solubility of the resin, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, and toluene are preferred.

[0170] The upper and lower limits of the content of the organic solvent in 100% by mass of the coating agent are exemplified as 90, 85, 80, 75, 70, 65, 60% by mass, etc. In one embodiment, the content is preferably 60 to 90% by mass.

[0171] The upper and lower limits of the solid content (non-volatile content) of the coating agent are exemplified as 40, 35, 30, 25, 20, 15, 10%, etc. In one embodiment, the solid content (non-volatile content) is preferably 10 to 40%.

[0172] <Additives> The above coating agent may contain an agent other than any of the above components (A) to (F) as an additive.

[0173] Examples of additives include antifoaming agents, anti-slip agents, preservatives, rust inhibitors, pH adjusters, antioxidants, pigments, dyes, lubricants, leveling agents, conductive agents, polybutadiene, polyisoprene, polychloroprene, polypentadiene, polybutene, polyisobutylene, polystyrene, isoprene-butadiene copolymers, styrene-isoprene copolymers, polyolefins and their derivatives, silicone resins, isocyanate group-containing compounds, epoxy group-containing compounds, amines, carboxylic acid anhydrides, and long-chain alkyl group-containing alcohols.

[0174] In one embodiment, the content of the additive is, for example, less than 1 part by mass, less than 0.1 part by mass, less than 0.01 part by mass, 0 part by mass, etc., relative to 100 parts by mass of the coating agent. Also, for example, the content of the additive is, for example, less than 1 part by mass, less than 0.1 part by mass, less than 0.01 part by mass, 0 part by mass, etc., relative to 100 parts by mass of any of the (A) to (F) components.

[0175] The coating agent can be produced by dispersing and mixing the components (A) to (C), and, if necessary, the components (D) to (F) and additives, by various known means. The order of addition of each component is not particularly limited. As the dispersing and mixing means, various known devices (emulsion disperser, ultrasonic disperser, etc.) can be used.

[0176] The above surface protective coating agent can be used as a thermosetting surface protective coating agent, a surface protective coating agent for paint protection films, a thermosetting surface protective coating agent for paint protection films, and the like.

[0177] A paint protection film (PPF) is applied to the painted surface of a vehicle body of an automobile or motorcycle to protect the painted surface of the vehicle body from flying stones and dirt. When the PPF is applied to the painted surface of the vehicle body, it is applied while being stretched (deformed) so as to fit the curved surface of the vehicle body. Therefore, when the above-mentioned coating agent is used to manufacture a paint protection film, the manufactured laminate may be required to have good elongation. Also, as mentioned above, the PPF is applied to the painted surface of a vehicle body of an automobile or motorcycle. Therefore, when the above-mentioned coating agent is used to manufacture a paint protection film, the manufactured laminate may be required to have good weather resistance because the physical properties of the manufactured laminate are deteriorated due to weather resistance deterioration.

[0178] [Cured product] The present disclosure provides a cured product of the above-mentioned surface protective coating agent.

[0179] In one embodiment, the cured product is a thermosetting product of the surface protective coating agent. The curing conditions are exemplified as described below.

[0180] [Laminate] The present disclosure provides a laminate comprising the above-mentioned cured product and a substrate.

[0181] Examples of the substrate include substrates made of plastics such as polycarbonate, polymethyl methacrylate, polystyrene, polyethylene terephthalate (PET), polyethylene naphthalate, polyimide, polyolefin, nylon, urethane resin, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, and norbornene resin.

[0182] The substrate may be subjected to a surface treatment (corona discharge, etc.) as necessary. The substrate may also be provided on one or both sides with a layer of a coating agent other than the coating agent of the present disclosure.

[0183] Examples of the coating method include spray, roll coater, reverse roll coater, gravure coater, knife coater, bar coater, dot coater, and the like.

[0184] The coating amount is not particularly limited. The coating amount is 3 to 25 g / m2 after drying. 2 The amount is preferably about 5 to 20 g / m 2 It is more preferable that the amount be such that

[0185] The heating method may be, for example, drying with a circulating air dryer, etc. Drying (curing) conditions may be, for example, about 90 to 170° C., and a time of about 30 seconds to 2 minutes, etc.

[0186] In one embodiment, the method for producing the laminate includes a curing step. The curing conditions are, for example, room temperature or heated conditions. When heated, the curing conditions are, for example, about 40 to 60° C. and about 1 to 7 days. EXAMPLES

[0187] The present invention will be specifically described below through examples and comparative examples. However, the above-mentioned description of the preferred embodiment and the following examples are provided for illustrative purposes only and are not provided for the purpose of limiting the present invention. Therefore, the scope of the present invention is not limited to the embodiments or examples specifically described in this specification, but is limited only by the claims. In each example and comparative example, unless otherwise specified, numerical values ​​such as parts and % are based on mass.

[0188] Manufacturing Example 1 24 parts of methyl methacrylate, 59 parts of butyl acrylate, 17 parts of 2-hydroxyethyl acrylate were added to a four-neck flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel, 2 parts of azobisisobutyronitrile as an initiator, and 153 parts of ethyl acetate as a solvent were added, and the temperature was gradually raised to 77°C. The reaction was carried out for 9 hours to obtain a polymer solution with a solid concentration of 35% (number average molecular weight 26,000, weight average molecular weight 70,000).

[0189] Unless otherwise specified, the Production Examples other than Production Example 1 and the Comparative Production Examples were carried out in the same manner as Production Example 1, except for the changes shown in the table below.

[0190] [Table 1]

[0191] <Explanation of abbreviations> MMA: Methyl methacrylate BA: Butyl acrylate LMA: Lauryl methacrylate HEA: 2-hydroxyethyl acrylate HEMA: 2-hydroxyethyl methacrylate

[0192] Example 1 A coating agent was prepared by thoroughly mixing 100 parts (solids equivalent) of the polymer from Production Example 1, 45 parts of Duranate TPA-100 (manufactured by Asahi Kasei Corporation, nurate form of hexamethylene diisocyanate, solids concentration 100%), 10 parts of Lumiflon 916F (manufactured by AGC Corporation, fluoroethylene-vinyl ether alternating copolymer, solids concentration 100%), 0.17 parts of dioctyltin dilaurate (solids concentration 100%), and 24 parts of acetylacetone, and diluting with MEK to a solids concentration of 25%.

[0193] Unless otherwise specified, the examples and comparative examples other than Example 1 were carried out in the same manner as Example 1, except for the changes shown in the table below.

[0194] [Table 2]

[0195] <Explanation of abbreviations> TPA-100: Duranate TPA-100 (manufactured by Asahi Kasei Corporation, hexamethylene diisocyanate nurate, solids concentration 100%) 24A-100: Duranate 24A-100 (manufactured by Asahi Kasei Corporation, biuret form of hexamethylene diisocyanate, solid content concentration 100%) D-160N: Takenate D-160N (manufactured by Mitsui Chemicals, Inc., hexamethylene diisocyanate trimethylolpropane adduct, solid content 75%) LF916F: Lumiflon 916F (AGC Corporation, fluoroethylene-vinyl ether alternating copolymer, hydroxyl value 100 mg KOH / g, solid content 100%) LF200F: Lumiflon 200F (AGC Corporation, fluoroethylene-vinyl ether alternating copolymer, hydroxyl value 31 mg KOH / g, solids concentration 100%) BYK3700: BYK-SILCLEAN3700 (BYK Japan Co., Ltd., acrylic modified silicone, solid content 25%)

[0196] Preparation of laminates The coating agent was applied to a thermoplastic urethane film (185 μm thick) using a bar coater so that the coating thickness after drying would be 10 μm, and then dried for 2 minutes at 120° C. After that, aging was carried out at 40° C. for 5 days to produce a laminate.

[0197] Elongation The above test pieces were punched out using JIS No. 3 dumbbells, and measurements were made using a Tensilon universal material testing machine (product name "RTC-1250A", manufactured by A&D Co., Ltd.) at a tensile speed of 200 mm / min and a gauge length of 20 mm. Breaking elongation (%) = 100 x (L-20) / 20 L: Length of the cured product at the time of breakage

[0198] Elongation after weathering test The laminate was subjected to 10 cycles of accelerated weathering test using a Daipla Metal Weather machine, with the following cycle being one cycle: Irradiation for 4 hours (temperature 60℃, humidity 50%, illuminance 90mW / cm 2 ) Condensation for 4 hours (temperature 30℃, humidity 98%, 10 second shower before and after) Dark for 6 minutes (temperature 50℃, humidity 50%) After the test, the elongation of the film was measured in the same manner as above.

[0199] Stain resistance evaluation A mark was written on the surface of the laminate with Magic Ink No. 700 (Teranishi Chemical Industry Co., Ltd.), and the mark was wiped off with a cloth after one minute to evaluate the laminate. The evaluation criteria are as follows. ◎: The mark disappears completely after one wipe. ○: The mark disappears completely after 5 wipes or less △: A faint mark is visible even after wiping five times or more. ×: The mark remains clearly even after wiping.

Claims

1. (A) A hydroxyl-containing (meth)acrylic resin having a carboxylic acid content of less than 0.01 mol / kg (B) polyisocyanate and (C) Hydroxyl-containing fluororesin The mass ratio of the (A) component to the (C) component in the coating agent solid content [mass of the (A) component / mass of the (C) component] is 10 or more; The content of the monofunctional isocyanate compound is less than 0.1 parts by mass per 100 parts by mass of the (A) component and the (C) component. Surface protective coating agent.

2. The surface protective coating agent according to claim 1 , comprising (D) an organically modified silicone.

3. A cured product of the surface protective coating agent according to claim 1 or 2.

4. A laminate comprising the cured product according to claim 3 and a substrate.

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