JP2022137861A - Surface protective coating agent, cured product and laminate - Google Patents

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

The present disclosure relates to surface protective coatings, cured products and laminates.

Plastic substrates such as thermoplastic polyurethanes are used as protective films for various industrial products such as electronic devices and automobile parts. Such plastic substrates are likely to lose their appearance and physical properties due to scratches and adhesion of dirt, and are surface-treated with a coating agent so as to exhibit a lasting effect.

As such a coating agent, an ultraviolet curable hard coating agent is known (Patent Document 1).

Japanese Patent Publication No. 6-029382

However, the UV-curable hard coating agent has a problem in that the elongation of the cured product is low due to the high hardness. From this point of view, coating agents other than UV-curable hard coating agents are being investigated. Moreover, the coating film may be deteriorated by ultraviolet rays, and there is a demand for a coating agent capable of producing a cured product having sufficient weather resistance. However, in the above UV curable paints, EB curable paints, and silica-based hard coating agents, the use of hard monomers to increase hardness and the increase in distortion during curing shrinkage due to the increase in cross-linking density can cause material It is easy to cause problems such as a decrease in adhesion to the surface and the occurrence of cracks. The problem to be solved by the present invention is to provide a coating agent that can produce a cured product that has stain resistance, high elongation, and can maintain high elongation even after a weather resistance test.

As a result of intensive studies, the present inventors have found that the above problems can be solved by a specific surface protective coating agent.

The following items are provided by this disclosure.
(Item 1)
A surface protective coating agent comprising (A) a hydroxyl group-containing (meth)acrylic resin (B) a polyisocyanate and (C) a hydroxyl group-containing fluororesin.
(Item 2)
(D) The surface protective coating agent according to the above items, which contains an organically modified silicone.
(Item 3)
A cured product of the surface protective coating agent according to any one of the above items.
(Item 4)
A laminate comprising the cured product and a base material according to the above items.

In the present disclosure, one or more of the features described above may be provided in further combinations in addition to the explicit combinations.

By using the surface protective coating agent according to the present embodiment, a cured product having good stain resistance, elongation, and elongation after a weather resistance test can be produced.

Throughout the present disclosure, the range of numerical values for each physical property value, content, etc. can be set as appropriate (for example, by selecting from the upper and lower limit values described in each item below). Specifically, regarding the numerical value α, when A4, A3, A2, A1 (with A4>A3>A2>A1), etc. are exemplified as the upper and lower limits of the numerical value α, the range of the numerical value α is A4 or less, Examples include 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.

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

<Hydroxyl group-containing (meth)acrylic resin (A): Also referred to as component (A). ＞
(A) A component can be used individually or in 2 or more types.

Component (A) is exemplified by copolymers containing structural units derived from hydroxyl-free alkyl (meth)acrylates and structural units derived from hydroxyl-containing monomers.

In the present disclosure, "(meth)acryl" means "at least one selected from the group consisting of acryl and methacryl." Similarly, "(meth)acrylate" means "at least one selected from the group consisting of acrylate and methacrylate". "(Meth)acryloyl" means "at least one selected from the group consisting of acryloyl and methacryloyl".

（式中、Ｒ^ａ１は水素原子、又はメチル基であり、Ｒ^ａ２はアルキル基である。）
で表わされる。水酸基非含有アルキル（メタ）アクリレートは、単独又は２種以上で使用され得る。 (Hydroxyl group-free alkyl (meth) acrylate)
The hydroxyl-free alkyl (meth)acrylate is

(In the formula, R ^a1 is a hydrogen atom or a methyl group, and R ^a2 is an alkyl group.)
is represented by A hydroxyl group-free alkyl (meth)acrylate may be used alone or in combination of two or more.

The upper and lower limits of the carbon number of R ^a2 are 22, 21, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3 , 2, 1, etc. are exemplified. In one embodiment, R ^a2 preferably has 1 to 22 carbon atoms.

Alkyl groups are exemplified by linear alkyl groups, branched alkyl groups, cycloalkyl groups and the like.

A straight-chain alkyl group is represented by a general formula of -C _n H _2n+1 (n is an integer of 1 or more). Linear alkyl groups include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group and n-decyl. group, undecyl group, dodecyl group (lauryl group), tridecyl group, tetradecyl group (myristyl group), pentadecyl group, hexadecyl group (palmityl group), heptadecyl group, octadecyl group (stearyl group), nonadecyl group, icosyl group, henicosyl group , a docosyl group, and the like.

Branched alkyl groups are groups in which at least one hydrogen atom of a straight chain alkyl group has been replaced by an alkyl group. Examples of branched alkyl groups include i-propyl, i-butyl, s-butyl, t-butyl, diethylpentyl, trimethylbutyl, trimethylpentyl, trimethylhexyl, and 2-ethylhexyl groups. .

The cycloalkyl group is exemplified by a monocyclic cycloalkyl group, a bridged ring cycloalkyl group, a condensed ring cycloalkyl group and the like.

In the present disclosure, monocyclic means a cyclic structure with no internal bridging structure formed by covalent carbon bonds. Fused rings also refer to cyclic structures in which two or more single rings share two atoms (ie, each ring shares (condenses) only one edge with each other). Bridged ring means a cyclic structure in which two or more single rings share three or more atoms.

Monocyclic cycloalkyl groups are exemplified by cyclopentyl, cyclohexyl, cycloheptyl, cyclodecyl and 3,5,5-trimethylcyclohexyl groups.

The bridging ring cycloalkyl group is exemplified by a tricyclodecyl group, an adamantyl group, a norbornyl group and the like.

The condensed ring cycloalkyl group is exemplified by a bicyclodecyl group and the like.

Examples of hydroxyl-free alkyl (meth)acrylates include hydroxyl-free linear alkyl (meth)acrylates, hydroxyl-free branched alkyl (meth)acrylates, and hydroxyl-free cycloalkyl (meth)acrylates.

Linear alkyl (meth)acrylates not containing hydroxyl groups include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, and hexyl (meth)acrylate. , heptyl (meth)acrylate, octyl (meth)acrylate, hexadecyl (meth)acrylate, dodecyl (meth)acrylate, octadecyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, (Meth) undecyl acrylate, (meth) dodecyl acrylate, (meth) tridecyl acrylate, (meth) tetradecyl acrylate, (meth) pentadecyl acrylate, (meth) hexadecyl acrylate, (meth) heptadecyl acrylate, ( Octadecyl meth)acrylate, nonadecyl (meth)acrylate, icosyl (meth)acrylate, henicosyl (meth)acrylate, docosyl (meth)acrylate and the like are exemplified.

Hydroxyl group-free branched alkyl (meth)acrylates include isopropyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, and 2-(meth)acrylate. Ethylhexyl and the like are exemplified.

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

Among these, alkyl (meth)acrylates having an alkyl group with about 1 to 20 carbon atoms are preferable because they contribute to leveling properties and adhesion to plastic substrates. In addition, by using a hydroxyl group-free alkyl (meth)acrylate having a different number of carbon atoms in the alkyl group, it is possible to adjust the physical properties of the component (A) such as the glass transition temperature.

The upper and lower limits of the content of structural units derived from hydroxyl-free alkyl (meth)acrylate in 100 mol% of all structural units of component (A) are 90, 85, 80, 75, 70, 65, 60, 55, Examples include 50, 45, 40, 35, 30, 25, 20, 15, 10 mol %. In one embodiment, the content is preferably 10 to 90 mol%.

The upper and lower limits of the content of structural units derived from hydroxyl-free alkyl (meth)acrylates having 1 to 7 carbon atoms in the hydroxyl-free alkyl groups in 100 mol% of all structural units of component (A) are 90, Examples include 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10 mol%. In one embodiment, the content is preferably 10 to 90 mol%.

The upper limit and the lower limit of the content of structural units derived from hydroxyl-free alkyl (meth)acrylate in which the hydroxyl-free alkyl group has 8 to 22 carbon atoms in 100 mol% of all structural units of component (A) are 90, Examples include 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10 mol%. In one embodiment, the content is preferably 10 to 90 mol%.

The upper and lower limits of the content of structural units derived from hydroxyl-free alkyl (meth)acrylate in 100% by mass of all structural units of 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% by mass, etc. are exemplified. In one embodiment, the content is preferably 20 to 95% by mass, more preferably 80 to 95% by mass.

The upper limit and the lower limit of the content of structural units derived from hydroxyl-free alkyl (meth)acrylate, in which the hydroxyl-free alkyl group has 1 to 7 carbon atoms in 100% by mass of all structural units of 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% by mass and the like are exemplified. In one embodiment, the content is preferably 20 to 95% by mass, more preferably 20 to 85% by mass.

The upper and lower limits of the content of structural units derived from hydroxyl-free alkyl (meth)acrylates, in which the hydroxyl-free alkyl group has 8 to 22 carbon atoms in 100% by mass of all structural units of 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% by mass and the like are exemplified. In one embodiment, the content is preferably 20 to 95% by mass, more preferably 30 to 65% by mass.

(Hydroxyl group-containing monomer)
A hydroxyl-containing monomer may be used individually or in 2 or more types.

［式中、Ｒ^ａ３は水素原子又はメチル基であり、Ｒ^ａ４はＮＨＲ^ａ４Ａ’又はＯＲ^ａ４Ｂ’であり、
Ｒ^ａ４Ａ’は水酸基含有アルキル基であり、
Ｒ^ａ４Ｂ’は（Ｒ^{ａ４Ｂ１’}Ｏ）_ｎＨ
（Ｒ^{ａ４Ｂ１’}はアルキレン基であり、ｎは１以上の整数である。）
又は
Ｒ^{ａ４Ｂ２’}Ｏ（Ｃ（＝Ｏ）（ＣＨ_２）_５Ｏ）_ｍＨ
（Ｒ^{ａ４Ｂ２’}はアルキレン基であり、ｍは１以上の整数である。）
である。］
で表わされる。 The hydroxyl group-containing monomer has the following structural formula

[Wherein, R ^a3 is a hydrogen atom or a methyl group, R ^a4 is NHR ^a4A′ or OR ^a4B′ ,
R ^a4A' is a hydroxyl group-containing alkyl group,
R ^a4B′ is (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.)
is. ]
is represented by

In the present disclosure, a "hydroxyl-containing alkyl group" is a group in which one hydrogen atom of an alkyl group is substituted with a hydroxyl group. The hydroxyl-containing alkyl group is exemplified by a hydroxyl-containing linear alkyl group, a hydroxyl-containing branched alkyl group, a hydroxyl-containing cycloalkyl group, and the like.

The alkylene group is exemplified by a linear alkylene group, a branched alkylene group, a cycloalkylene group and the like.

A linear alkylene group is represented by the general formula: -(CH ₂ ) _n - (n is an integer of 1 or more). Straight-chain alkylene group includes methylene group, ethylene group, propylene group, n-butylene group, n-pentylene group, n-hexylene group, n-heptylene group, n-octylene group, n-nonylene group, n-decamethylene group, etc. are exemplified.

A branched alkylene group is a straight-chain alkylene group in which at least one hydrogen atom has been replaced by an alkyl group. The branched alkylene group is exemplified by a diethylpentylene group, trimethylbutylene group, trimethylpentylene group, trimethylhexylene group (trimethylhexamethylene group) and the like.

The cycloalkylene group is exemplified by a monocyclic cycloalkylene group, a bridged ring cycloalkylene group, a condensed ring cycloalkylene group and the like. A cycloalkylene group may also have one or more hydrogen atoms replaced by a straight or branched alkyl group.

The monocyclic cycloalkylene group is exemplified by a cyclopentylene group, cyclohexylene group, cycloheptylene group, cyclodecylene group, 3,5,5-trimethylcyclohexylene group and the like.

The bridging ring cycloalkylene group is exemplified by a tricyclodecylene group, an adamantylene group, a norbornylene group and the like.

The condensed ring cycloalkylene group is exemplified by a bicyclodecylene group and the like.

In the present disclosure, the upper and lower limits of the carbon number of the hydrocarbon group (alkyl group, alkylene group, arylene group, arylenealkylenearylene group, etc.) not mentioned are 30, 29, 25, 20. , 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, and the like.

Examples of hydroxyl group-containing monomers include hydroxyl group-containing (meth)acryl esters, polyalkylene glycol mono(meth)acrylates, caprolactone-modified hydroxyalkyl(meth)acrylates, and hydroxyl group-containing (meth)acrylamides.

The hydroxyl group-containing (meth)acrylic ester is a monomer in which R ^a4 in the above structural formula is OR ^a4B1′ OH, that is, R ^a4B′ is a hydroxyl group-containing alkyl group. The meaning of the symbols is the same as above. The number of carbon atoms in the hydroxyl group-containing alkyl group is preferably 1-4.

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 ( Examples include meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate and the like.

Polyalkylene glycol mono(meth)acrylates are monomers where R ^a4 is O(R ^a4B1′ O) _n H. The meaning of the symbols is 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.

Commercially available polyalkylene glycol mono(meth)acrylates include BLEMMER PE-90, BLEMMER 200, BLEMMER 350, BLEMMER PME-400, BLEMMER AE-400, BLEMMER PME-1000, BLEMMER PME-2000 (manufactured by NOF Corporation). ) and the like are exemplified.

Caprolactone-modified hydroxyalkyl (meth)acrylates are monomers in which R ^a4 is OR ^a4B2′ O(C(═O)(CH ₂ ) ₅ O) _m H. The meaning of the symbols is the same as above. In one embodiment, m is preferably 1 or more, more preferably 1 to 6, even more preferably 1 to 3. R ^a4B2′ is preferably an alkylene group having 2 to 6 carbon atoms, more preferably an ethylene group.

Commercially available caprolactone-modified hydroxyalkyl (meth)acrylates include “PLAXEL FM1,” “PLAXEL FM2,” “PLAXEL FM1D,” “PLAXEL FM2D,” “PLAXEL FM3,” “PLAXEL FM3X,” “PLAXEL FM4,” and “PLAXEL FM. -5” “Plaxel FA1”, “Plaxel FA2”, “Plaxel FA1D”, “Plaxel FA1DDM”, “Plaxel FA2D”, “Plaxel FA3”, “Plaxel FA4”, “Plaxel FA5” (all manufactured by Daicel Corporation ) and the like are exemplified.

The hydroxyl group-containing (meth)acrylamide is exemplified by N-(2-hydroxyethyl)acrylamide, N-(1-methyl-2-hydroxyethyl)acrylamide and the like.

Examples of monomers having two or more hydroxyl groups include glycerin mono(meth)acrylate.

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

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

(A) molar ratio of structural units derived from hydroxyl-free alkyl (meth)acrylate to hydroxyl-containing alkyl (meth)acrylate-derived structural units (hydroxyl-free alkyl (meth)acrylate _mol / hydroxyl-containing alkyl (meth) ) acrylate _mol ) is 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 and the like are exemplified. In one embodiment, the molar ratio is preferably 0.1-9.

(A) Mass ratio of structural units derived from hydroxyl-free alkyl (meth)acrylate and hydroxyl-containing alkyl (meth)acrylate-derived structural units in component (hydroxyl-containing alkyl (meth)acrylate _mass / hydroxyl-containing alkyl (meth) ) acrylate _mass ) is 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 and the like are exemplified. In one embodiment, the mass ratio is preferably 0.25-19.

(Monomers other than hydroxyl-free alkyl (meth)acrylates and hydroxyl-containing alkyl (meth)acrylates: also referred to as other monomers)
When manufacturing component (A), a monomer that does not correspond to any of hydroxyl-free alkyl (meth)acrylates and hydroxyl-containing alkyl (meth)acrylates may be used. Other monomers may be used singly or in combination of two or more.

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 their salts, dialkylaminoalkyl (meth)acrylamides and their salts, chain transfer monomers, (meth)acrylamides, vinylamine, (meth)acrylonitrile, monofunctional monomers other than the above, bis(meth)acrylamide , di(meth)acrylic esters, divinyl esters, bifunctional monomers other than the above, trifunctional monomers, tetrafunctional monomers, and the like.

The upper and lower limits of the content of structural units derived from other monomers in 100 mol% of all structural units of component (A) are 20, 15, 10, 9, 5, 4, 1, 0.9, and 0.5. , 0.1, 0 mol % and the like are exemplified. In one embodiment, the above content is preferably 0 to 20 mol %.

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

The upper and lower limits of the molar ratio of structural units derived from hydroxyl-free alkyl (meth)acrylate and structural units derived from other monomers in component (A) (other monomer _mol /hydroxyl-free alkyl (meth)acrylate _mol ) is exemplified by 0.30, 0.25, 0.20, 0.15, 0.10, 0.05, 0, and the like. In one embodiment, the molar ratio is preferably 0-0.30.

(A) The upper and lower limits of the mass ratio of structural units derived from hydroxyl-free alkyl (meth)acrylates and structural units derived from other monomers in component (other monomer _mass /hydroxyl-free alkyl (meth)acrylate _mass ) is exemplified by 0.29, 0.25, 0.20, 0.15, 0.10, 0.05, 0, and the like. In one embodiment, the mass ratio is preferably 0 to 0.29.

The upper and lower limits of the molar ratio of structural units derived from hydroxyl group-containing alkyl (meth)acrylate and structural units derived from other monomers in component (A) ( _mol of other monomer/ _mol of hydroxyl group-containing alkyl (meth)acrylate) are 4, 3, 2, 1, 0.9, 0.7, 0.5, 0.3, 0.1, 0 and the like are exemplified. In one embodiment, the molar ratio is preferably 0-4.

The upper and lower limits of the mass ratio of the structural unit derived from the hydroxyl group-containing alkyl (meth)acrylate and the structural unit derived from the other monomer in the component (A) (other monomer _mass / hydroxyl group-containing alkyl (meth)acrylate _mass ) are 3.3, 3, 2, 1, 0.7, 0.5, 0.3, 0.1, 0 and the like are exemplified. In one embodiment, the mass ratio is preferably 0 to 3.3.

<Physical properties of component (A)>
The upper and lower limits of the glass transition temperature of 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 and the like are exemplified. In one embodiment, the glass transition temperature is preferably -60 to 60°C, more preferably -30 to 30°C.

The glass transition temperature is calculated from the Fox formula.
Fox's formula: 1/Tg=(Wa/Tga)+(Wb/Tgb)+...+(Wn/Tgn)
Tg: glass transition temperature of the copolymer (K)
Wa: % by mass of monomer A
Tga: glass transition temperature of homopolymer of monomer A (K)
Wb: % by mass of monomer B
Tgb: glass transition temperature of homopolymer of monomer B (K)
Wn: % by mass of monomer N
Tgn: glass transition temperature of homopolymer of monomer N (K)

The upper and lower limits of the hydroxyl value of component (A) are 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, 10 mgKOH/g, and the like. In one embodiment, the hydroxyl value is preferably 10-200 mgKOH/g, more preferably 20-100 mgKOH/g.

The hydroxyl value is measured according to JIS K1557-1.

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

In the present disclosure, the hydroxyl equivalent is the physical amount of hydroxyl groups present in 1 g of solid.

The upper and lower limits of the acid value of component (A) are exemplified by 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1 and 0 meq/g. In one embodiment, the acid value is preferably 0 to 0.7 meq/g, especially considering curability.

The acid value is measured according to JIS K0070.

The upper and lower limits of the weight average molecular weight (Mw) of component (A) are exemplified by 100,000, 90,000, 80,000, 70,000, 60,000, 50,000, 40,000, 30,000, 20,000, 10,000, 5,000, 4,000, and 3,000. In one embodiment, the weight average molecular weight (Mw) is preferably 3,000 to 100,000, more preferably 10,000 to 80,000.

The upper and lower limits of the number average molecular weight (Mn) of component (A) are exemplified by 100,000, 90,000, 80,000, 70,000, 60,000, 50,000, 40,000, 30,000, 20,000, 10,000, 5,000, 4,000, and 3,000. In one embodiment, the number average molecular weight (Mn) is preferably 3,000 to 100,000, more preferably 3,000 to 80,000.

The weight-average molecular weight and number-average molecular weight can be determined, for example, as polystyrene-equivalent values measured under 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" (manufactured by Agilent Technology) × 2 Developing solvent, flow rate: tetrahydrofuran, 1.0 mL / min Measurement temperature: 40 ° C.
Detector: RI
Standard: monodisperse polystyrene polymer Concentration: 0.2%

The upper and lower limits of the molecular weight distribution (Mw/Mn) of component (A) are exemplified by 10, 9, 7.5, 5, 2.5, 2, 1.5 and the like. In one embodiment, the molecular weight distribution (Mw/Mn) is preferably 1.5-10.

(A) A component can be manufactured by various well-known methods. The method for producing component (A) comprises adding a hydroxyl-free alkyl (meth)acrylate and a hydroxyl-containing alkyl (meth)acrylate, and optionally other monomers in the absence of a solvent or in an organic solvent, usually a polymerization initiator. and a method of conducting a copolymerization reaction for about 1 to 10 hours at about 80 to 180° C. in the presence of. Examples of the organic solvent and polymerization initiator used in producing the component (A) are those described below.

The upper and lower limits of the content of component (A) in 100% by mass of the solid content of the coating agent are 65, 64, 63, 62, 61, 60, 59, 55, 50, 49, 48, 46, 45, 40, 35, 30% by mass and the like are exemplified. In one embodiment, the content is preferably 30 to 95% by mass, more preferably 40 to 80% by mass.

<Polyisocyanate (B): Also referred to as component (B). ＞
Polyisocyanates may be used singly or in combination of two or more.

In the present disclosure, "polyisocyanate" is a compound having two or more isocyanate groups (-N=C=O).

Examples of polyisocyanates include linear aliphatic polyisocyanates, branched aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and biuret, isocyanurate, allophanate, and adducts thereof.

Linear aliphatic polyisocyanates include methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, and the like. be.

Branched aliphatic polyisocyanates are exemplified by diethylpentylene diisocyanate, trimethylbutylene diisocyanate, trimethylpentylene diisocyanate, trimethylhexamethylene diisocyanate and the like.

The alicyclic polyisocyanate is exemplified by monocyclic alicyclic polyisocyanate, crosslinked alicyclic polyisocyanate, condensed alicyclic polyisocyanate and the like.

Monocyclic alicyclic polyisocyanates include hydrogenated xylene diisocyanate, isophorone diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, cycloheptylene diisocyanate, cyclodecylene diisocyanate, 3,5,5-trimethylcyclohexylene diisocyanate, dicyclohexylmethane Diisocyanate and the like are exemplified.

Examples of the crosslinked cycloaliphatic polyisocyanate include tricyclodecylene diisocyanate, adamantane diisocyanate, and norbornene diisocyanate.

The condensed ring alicyclic polyisocyanate is exemplified by bicyclodecylylene diisocyanate and the like.

The aromatic group is exemplified by a monocyclic aromatic group, a condensed ring aromatic group and the like. An aromatic group may also have one or more hydrogen atoms replaced by a straight or branched alkyl group.

The monocyclic aromatic group is exemplified by a phenyl group (phenylene group), a tolyl group (tolylene group), a mesityl group (mesitylene group) and the like. Further, the condensed ring aromatic group is exemplified by a naphthyl group (naphthylene group) and the like.

Aromatic polyisocyanates are exemplified by monocyclic aromatic polyisocyanates, condensed ring aromatic polyisocyanates, and the like.

Monocyclic aromatic polyisocyanates include dialkyldiphenylmethane diisocyanates such as 4,4′-diphenyldimethylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanates such as 4,4′-diphenyltetramethylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, 4, Examples include 4'-dibenzylisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, m-tetramethylxylylene diisocyanate and the like.

The condensed ring aromatic polyisocyanate is exemplified by 1,5-naphthylene diisocyanate.

［式中、ｎ^ｂは、０以上の整数であり、Ｒ^ｂＡ～Ｒ^ｂＥはそれぞれ独立に、アルキレン基又はアリーレン基であり、Ｒ^ｂα～Ｒ^ｂβはそれぞれ独立に、イソシアネート基又は

（ｎ^ｂ１は、０以上の整数であり、Ｒ^ｂ１～Ｒ^ｂ５はそれぞれ独立に、アルキレン基又はアリーレン基であり、Ｒ^ｂ’～Ｒ ^ｂ’’はそれぞれ独立に、イソシアネート基又はＲ^ｂα～Ｒ^ｂβ自身の基である。Ｒ^ｂ４～Ｒ^ｂ５、Ｒ ^ｂ’’は、各構成単位ごとに基が異なっていてもよい。）である。Ｒ^ｂＤ～Ｒ^ｂＥ、Ｒ^ｂβは、各構成単位ごとに基が異なっていてもよい。］で表される化合物等が例示される。 The biuret form of polyisocyanate is
Structural formula below:

[Wherein, n ^b is an integer of 0 or more, R ^bA to R ^bE are each independently an alkylene group or an arylene group, R ^bα to R ^bβ are each independently an isocyanate group or

(n ^b1 is an integer of 0 or more, R ^b1 to R ^b5 are each independently an alkylene group or an arylene group, R ^b ' to R ^b '' are each independently an isocyanate group or R ^bα to R ^bβ itself, and R ^b4 to R ^b5 and R ^b ″ may be different groups for each structural unit.). R ^bD to R ^bE and R ^bβ may have different groups for each structural unit. ] and the like are exemplified.

Biuret forms of polyisocyanates include Duranate 24A-100, Duranate 22A-75P, Duranate 21S-75E (manufactured by Asahi Kasei Corp.), and Desmodur N3200A (biuret form of hexamethylene diisocyanate) (manufactured by Sumitomo Bayer Urethane Co., Ltd.). ) and the like are exemplified.

［式中、ｎ^ｉは、０以上の整数であり、Ｒ^ｉＡ～Ｒ^ｉＥはそれぞれ独立に、アルキレン基又はアリーレン基であり、Ｒ^ｉα～Ｒ^ｉβはそれぞれ独立に、イソシアネート基又は

（ｎ^ｉ１は、０以上の整数であり、Ｒ^ｉ１～Ｒ^ｉ５はそれぞれ独立に、アルキレン基又はアリーレン基であり、Ｒ^ｉ’～Ｒ ^ｉ’’ はそれぞれ独立に、イソシアネート基又はＲ^ｉα～Ｒ^ｉβ自身の基である。Ｒ^ｉ５、Ｒ^ｉ’’は、各構成単位ごとに基が異なっていてもよい。）である。Ｒ^ｉＤ～Ｒ^ｉＥ、Ｒ^ｉβは、各構成単位ごとに基が異なっていてもよい。］で表される化合物等が例示される。 The isocyanurate form of polyisocyanate is
Structural formula below:

[Wherein, n ⁱ is an integer of 0 or more, R ^iA to R ^iE are each independently an alkylene group or an arylene group, and R ^iα to R ^iβ are each independently an isocyanate group or

(n ⁱ¹ is an integer of 0 or more, R ⁱ¹ to R ⁱ⁵ are each independently an alkylene group or an arylene group, R ⁱ ′ to R ⁱ '' are each independently an isocyanate group or R ^iα to R is a group of ^{iβ itself.R i5} and R ⁱ ″ may be different groups for each structural unit.). R ^iD to R ^iE and R ^iβ may have different groups for each structural unit. ] and the like are exemplified.

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

［式中、ｎは、０以上の整数であり、Ｒ^Ａは、アルキル基又はアリール基であり、Ｒ^Ｂ～Ｒ^Ｇはそれぞれ独立に、アルキレン基又はアリーレン基であり、Ｒ^α～Ｒ^γはそれぞれ独立に、イソシアネート基又は

（ｎ１は、０以上の整数であり、Ｒ^１～Ｒ^６はそれぞれ独立に、アルキレン基又はアリーレン基であり、Ｒ’～Ｒ’’’はそれぞれ独立に、イソシアネート基又はＲ^α～Ｒ^γ自身の基である。Ｒ^１～Ｒ^４、Ｒ’～Ｒ’’は、各構成単位ごとに基が異なっていてもよい。）である。Ｒ^Ｂ～Ｒ^Ｅ、Ｒ^α～Ｒ^βは、各構成単位ごとに基が異なっていてもよい。］で表される化合物等が例示される。 The allophanate form of polyisocyanate is
Structural formula below:

[Wherein, n is an integer of 0 or more, R ^A is an alkyl group or an aryl group, R ^B to R ^G are each independently an alkylene group or an arylene group, and R ^α to R ^γ are each independently, an isocyanate group or

(n1 is an integer of 0 or more, R ¹ to R ⁶ are each independently an alkylene group or an arylene group, R′ to R′″ are each independently an isocyanate group or R ^α to R ^γ themselves The groups of R ¹ to R ⁴ and R′ to R″ may be different for each structural unit.). R ^B to R ^E and R ^α to R ^β may have different groups for each structural unit. ] and the like are exemplified.

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

［式中、ｎ^ａｄは０以上の整数であり、Ｒ^ａｄＡ～Ｒ^ａｄＥは、それぞれ独立にアルキレン基又はアリーレン基であり、Ｒ^ａｄ１～Ｒ^ａｄ２は、それぞれ独立に

（式中、ｎ^ａｄ’は０以上の整数であり、
Ｒ^ａｄ’～Ｒ^ａｄ’’は、それぞれ独立にアルキレン基又はアリーレン基であり、
Ｒ^{ａｄ’’’}は、Ｒ^ａｄ１～Ｒ^ａｄ２自身の基であり、
Ｒ^ａｄ’～Ｒ^{ａｄ’’’}は、各構成単位ごとに基が異なっていてもよい。）
であり、Ｒ^ａｄＤ～Ｒ^ａｄＥ、Ｒ^ａｄ２は、各構成単位ごとに基が異なっていてもよい。］
で示されるトリメチロールプロパンとポリイソシアネートのアダクト体、
下記構造式

［式中、ｎ^ａｄ１は０以上の整数であり、
Ｒ^ａｄα～Ｒ^ａｄεは、それぞれ独立にアルキレン基又はアリーレン基であり、
Ｒ^ａｄＡ～Ｒ^ａｄＢは、それぞれ独立に

（式中、ｎ^ａｄ１’は０以上の整数であり、
Ｒ^ａｄδ’～Ｒ^ａｄε’は、それぞれ独立にアルキレン基又はアリーレン基であり、
Ｒ^ａｄＢ’は、Ｒ^ａｄＡ～Ｒ^ａｄＢ自身の基であり、
Ｒ^ａｄδ’～Ｒ^ａｄε’、Ｒ^ａｄＢ’は、各構成単位ごとに基が異なっていてもよい。）
Ｒ^ａｄδ～Ｒ^ａｄεは、各構成単位ごとに基が異なっていてもよい。］
で示されるグリセリンとポリイソシアネートのアダクト体等が例示される。 The adduct of polyisocyanate is
Structural formula below:

[Wherein, n ^ad is an integer of 0 or more, R ^adA to R ^adE are each independently an alkylene group or an arylene group, and R ^ad1 to R ^ad2 are each independently

(Wherein, n ^{ad '} is an integer of 0 or more,
R ^ad′ to R ^ad″ are each independently an alkylene group or an arylene group,
R ^ad''' is a group of R ^ad1 to R ^ad2 itself,
R ^ad′ to R ^ad′″ may have different groups for each structural unit. )
and R ^adD to R ^adE and R ^ad2 may have different groups for each structural unit. ]
An adduct of trimethylolpropane and polyisocyanate represented by
Structural formula below

[Wherein, n ^ad1 is an integer of 0 or more,
R ^adα to R ^adε are each independently an alkylene group or an arylene group,
R ^adA to R ^adB are each independently

(Wherein, n ^{ad1 '} is an integer of 0 or more,
R ^adδ' to R ^adε' are each independently an alkylene group or an arylene group,
R ^adB' is a group of R ^adA to R ^adB itself,
R ^adδ' to R ^adε' and R ^adB' may have different groups for each structural unit. )
R ^adδ to R ^adε may have different groups for each structural unit. ]
Examples include adducts of glycerin and polyisocyanate represented by.

Polyisocyanate adducts include Duranate P301-75E (manufactured by Asahi Kasei Corp.), Takenate D-110N, Takenate D-160N (manufactured by Mitsui Chemicals, Inc.), Coronate L (manufactured by Tosoh Corporation), etc. are exemplified.

The upper and lower limits of the NCO content (NCO %) of the polyisocyanate are exemplified by 30, 25, 20, 15, 10% and the like. In one embodiment, the NCO content (NCO %) is preferably 10 to 30%.

The upper and lower limits of the isocyanate group equivalent weight of the polyisocyanate are exemplified by 10, 9, 8, 7, 6, 5, 4, 3, 2, 1 meq/g. In one embodiment, the isocyanate group equivalent is preferably 1 to 10 meq/g.

In the present disclosure, isocyanate group equivalent means the amount of isocyanate groups present in 1 g of solid.

The upper and lower limits of the ratio (NCO/OH) between the isocyanate group equivalent of polyisocyanate and the hydroxyl group equivalent of component (A) are 4, 3, 2, 1.75, 1.5, 1.25, 1, 0. 75, 0.5, 0.25, 0.1, 0.05 and the like are exemplified. In one embodiment, the ratio (NCO/OH) is preferably 0.05-4.

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

In the present disclosure, the amount of OH groups consumed is an index indicating how much NCO that consumes OH groups in the main agent is added. Consumed OH group amount is the following formula: Consumed OH group amount = isocyanate group equivalent x 56.1
Calculated by

The upper and lower limits of the polyisocyanate content in 100% by mass of the solid content of the coating agent are 22, 21, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10% by mass and the like are exemplified. In one embodiment, the content is preferably 10 to 45% by mass.

<Hydroxyl group-containing fluororesin (C): Also referred to as component (C). ＞
(C) A component can be used individually or in 2 or more types.

In the present disclosure, "hydroxyl group-containing fluororesin" means a resin containing structural units derived from a fluorine-containing monomer and having one or more hydroxyl groups.

Fluorine-containing monomers are exemplified by fluoroolefins and the like.

In the present disclosure, "fluoroolefin" means an olefin in which one or more hydrogen atoms have been replaced with fluorine atoms.

Fluoroolefins may be used singly or in combination of two or more. Fluoroolefins include CF2=CF2, CF2= _CFCl , CF2=CHF, CF2 _{= CH2} , CF2 _{= CFCF3 ,} CF2 _{= CHCF3} , _CF3CH =CHF _{, CF3CF = CH2} , CH ₂ ═CX(CF ₂ ) _f Y (wherein X and Y are independently a hydrogen atom or a fluorine atom, and f is an integer of 2 to 10).

The upper and lower limits of the content of structural units derived from fluoroolefins in 100 mol% of the total structural units of the hydroxyl-containing fluororesin are 100, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20 mol % and the like are exemplified. In one embodiment, the content is preferably 20 to 100 mol%, more preferably 30 to 70 mol%, particularly preferably 40 to 60 mol%.

The hydroxyl-containing fluororesin contains structural units derived from hydroxyl-containing monomers.

The hydroxyl-containing monomers 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 acid esters, and allyl alcohol.

Examples of hydroxyl group-containing vinyl ethers include hydroxyalkyl vinyl ethers and polyalkylene glycol monovinyl ethers.

Hydroxy alkyl vinyl ethers are exemplified by hydroxy linear alkyl vinyl ethers, hydroxy branched alkyl vinyl ethers, hydroxy cycloalkyl vinyl ethers and the like.

The hydroxy linear alkyl vinyl ethers are exemplified by 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 5-hydroxypentyl vinyl ether and the like.

Hydroxy-branched alkyl vinyl ethers are exemplified by 2-hydroxypropyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 4-hydroxy-2-methylbutyl vinyl ether and the like.

Hydroxycycloalkyl vinyl ethers are exemplified by 4-hydroxycyclopentyl vinyl ether, 4-hydroxycyclohexyl vinyl ether and the like.

Polyalkylene glycol monovinyl ether is exemplified by polymethylene glycol monovinyl ether, polyethylene glycol monovinyl ether, polypropylene glycol monovinyl ether and the like.

Polymethylene glycol monovinyl ether includes 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, nona Examples include methylene glycol monovinyl ether, decamethylene glycol monovinyl ether, and the like.

Polyethylene glycol monovinyl ether includes 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. Examples include vinyl ether, decaethylene glycol monovinyl ether, and the like.

Polypropylene glycol monovinyl ether includes 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, decapropylene glycol monovinyl ether and the like are exemplified.

A hydroxyl group-containing allyl ether is a compound obtained by substituting a vinyl group of a hydroxyl group-containing vinyl ether with an allyl group.

In one embodiment, the hydroxyl-containing monomer contained in the hydroxyl-containing fluororesin is CH ₂ ═CHO—CH ₂ —cC ₆ H ₁₀ —CH ₂ OH, CH ₂ ═CHCH ₂ O—CH ₂ —cC ₆ H _{10 - CH2OH} , _CH2 =CHO _{- CH2 -} cC6H _{10 -} CH2-( _OCH2CH2 ) _15OH , _{CH2 = CHOCH2CH2OH} , _{CH2 = CHCH2OCH2CH2OH . _ _ _ _ _ _ _ _ _ _ _ _ _ 2OH} or _{CH2 = CHOCH2CH2CH2CH2OH are more} preferred. "-cC ₆ H ₁₀ -" represents a cyclohexylene group, and the binding site of "-cC ₆ H ₁₀ -" is usually 1,4-.

The upper and lower limits of the content of structural units derived from hydroxyl group-containing monomers in 100 mol% of all structural units of the hydroxyl group-containing fluororesin are 35, 30, 25, 20, 15, 10, 5, 4, 3, 2. , 1, 0.5, 0.1 mol %, and the like. 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%, 5 to 20 mol % is particularly preferred.

Examples of monomers that are neither fluoroolefins nor hydroxyl group-containing monomers include unsaturated carboxylic acids, alkenes, vinyl ethers, vinyl esters, allyl ethers, allyl esters, (meth)acrylic acid esters, and the like.

The upper and lower limits of the content of structural units derived from monomers that are neither fluoroolefins nor hydroxyl group-containing monomers in 100 mol% of the total structural units of the hydroxyl group-containing fluororesin are 60, 55, 50, and 45. , 40, 35, 30, 25, 20, 15, 10, 5, 4, 3, 2, 1, 0.5, 0.1, 0 mol %, and the like. In one embodiment, the content is preferably 0 to 60 mol%, more preferably 5 to 60 mol%, even more preferably 10 to 50 mol%.

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

Fluoroethylene/vinyl ether copolymers include fluoroethylene/vinyl ether copolymers, chlorotrifluoroethylene-vinyl ether copolymers, chlorotrifluoroethylene-vinyl ether-vinyl ester copolymers, and chlorotrifluoroethylene-vinyl ester-allyl ethers. Examples include copolymers, tetrafluoroethylene-vinyl ester copolymers, tetrafluoroethylene-vinyl ester-allyl ether copolymers, ethylene-tetrafluoroethylene copolymers, and the like.

Commercial products of hydroxyl-containing fluororesins 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 916MEK. , Lumiflon 9721, Lumiflon FE4300, Lumiflon FE4400, Lumiflon FE4500, Lumiflon FD1000 (manufactured by AGC Co., Ltd.), and the like.

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

The upper and lower limits of the number average molecular weight of the hydroxyl group-containing fluororesin are 100 and the like are exemplified. In one embodiment, the number average molecular weight is preferably 100-30,000.

The upper and lower limits of the weight average molecular weight of the hydroxyl group-containing fluororesin are 900, 500, 100, etc. are exemplified. In one embodiment, the weight average molecular weight is preferably 100-50,000.

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

The upper and lower limits of the mass ratio [mass of component (A)/mass of component (B)] between component (A) and component (B) in the solid content of the coating agent 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 and the like. In one embodiment, the mass ratio is preferably 0.7-9.5.

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

The upper and lower limits of the mass ratio of component (B) to component (C) in the solid content of the coating agent [mass of component (B)/mass of component (C)] 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 and the like. In one embodiment, the mass ratio is preferably 0.2-45.

<Organically modified silicone (D): Also referred to as component (D). ＞
In one embodiment, the coating agent may include an organomodified silicone. (C) A component can be used individually or in 2 or more types.

In the present disclosure, "organomodified silicone" refers to silicone into which an organic group has been introduced. Examples of the organically modified silicone include side chain type organically modified silicone, both end type organically modified silicone, single end type organically modified silicone, side chain both end type organically modified silicone and the like.

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, carboxyl group-containing organically modified silicones, and the like.

Examples of hydroxyl group-containing organically modified silicones include hydroxyl group-containing acrylic resin-modified silicones, hydroxyl group-containing polyester resin-modified silicones, hydroxyl group-containing polyether resin-modified silicones, hydroxyl group-containing carbinol resin-modified silicones, and the like.

Commercial products of hydroxyl group-containing acrylic resin-modified silicone include ZX-028-G (manufactured by T&K TOKA Co., Ltd.), BYK-SILCLEAN3700 (manufactured by BYK-Chemie Japan Co., Ltd.), and Cymac US-270 (manufactured by Toagosei Co., Ltd.). etc. are exemplified.

Commercial products of hydroxyl-containing polyester resin-modified silicone or hydroxyl-containing polyether resin-modified silicone include BYK-370, BYK-375, BYK-377, BYK-SILCLEAN3720 (manufactured by BYK-Chemie Japan Co., Ltd.), X-22-4952, Examples include KF-6123 (manufactured by Shin-Etsu Chemical Co., Ltd.).

Commercial products of 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, 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).

Commercial products of amino group-containing organomodified silicones are 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, X-22-3939A (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

Commercial products of epoxy group-containing organomodified silicones are X-22-343, KF-101, KF-1001, X-22-2000, X-22-2046, KF-102, X-22-4741, KF-1002. , KF-1005 (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

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

X-22-3701E (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like are examples of commercially available organically modified silicones containing carboxyl groups.

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

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

<Curing catalyst (E): Also referred to as component (E)>
In one embodiment, the coating agent may contain a curing catalyst. A curing catalyst may be contained singly or in combination of two or more.

Examples of curing catalysts include organometallic catalysts and organic amine catalysts.

Examples of organometallic catalysts include organic typical metal catalysts and organic transition metal catalysts.

Examples of organic typical metal catalysts include organic tin catalysts and organic bismuth catalysts.

Examples of organic tin catalysts include dibutyltin dilaurate and dioctyltin dilaurate.

The organic bismuth catalyst is exemplified by bismuth octylate.

Organic transition metal catalysts are exemplified by organic titanium catalysts, organic zirconium catalysts, organic iron catalysts, and the like.

Examples of organic titanium catalysts include titanium ethyl acetoacetate.

Examples of organic zirconium catalysts include zirconium tetraacetylacetonate and the like.

Organic iron catalysts are exemplified by iron acetylacetonate and the like.

Examples of organic amine catalysts include diazabicyclooctane, dimethylcyclohexylamine, tetramethylpropylenediamine, ethylmorpholine, dimethylethanolamine, triethylamine and triethylenediamine.

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 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, Examples include 0.2, 0.1, 0% by mass, and the like. In one embodiment, the content is preferably 0 to 1% by mass.

<Organic solvent (F): Also referred to as component (F). ＞
In one embodiment, the coating agent may contain an organic solvent. An organic solvent can be used individually or in 2 or more types.

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

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

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

<Additive>
The coating agent may contain, as an additive, an agent that does not fall under any of the above components (A) to (F).

Additives include antifoaming agents, antislip agents, preservatives, rust inhibitors, pH adjusters, antioxidants, pigments, dyes, lubricants, leveling agents, conductive agents, polybutadiene, polyisoprene, polychloroprene, polypentadiene, and 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, long-chain alkyl Group-containing alcohols and the like are exemplified.

In one embodiment, the additive content is exemplified by less than 1 part by mass, less than 0.1 part by mass, less than 0.01 part by mass, and 0 part by mass with respect to 100 parts by mass of the coating agent. Further, 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. are exemplified with respect to 100 parts by mass of any one of components (A) to (F).

The above coating agent can be produced by dispersing and mixing components (A) to (C), and optionally components (D) to (F) and additives by various known means. In addition, the addition order of each component is not specifically limited. Moreover, various known apparatuses (emulsification disperser, ultrasonic dispersion apparatus, etc.) can be used as dispersion/mixing means.

The 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.

A paint protection film (PPF) is affixed to the painted surface of the body of an automobile or motorcycle to protect the painted surface of the 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 conform to the curved surface of the vehicle body. Therefore, when the above coating agents are used to produce paint protection films, the produced laminates may be required to have good elongation. Also, as described above, PPF is affixed to the painted surfaces of the bodies of automobiles and motorcycles. Therefore, when the coating agent is used to produce a paint protection film, the produced laminate is required to have good weather resistance because deterioration in weather resistance causes deterioration in physical properties.

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

In one embodiment, the cured product is a thermoset product of the surface protective coating agent. Curing conditions are exemplified by those described later.

[Laminates]
The present disclosure provides a laminate containing the cured product and a substrate.

The base materials include polycarbonate, polymethyl methacrylate, polystyrene, polyethylene terephthalate (PET), polyethylene naphthalate, polyimide, polyolefin, nylon, urethane resin, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, norbornene resin, and the like. and the like are exemplified by base materials made of plastics.

The base material may be surface-treated (corona discharge or the like) as necessary. Also, the substrate may be provided with a layer of a coating agent other than the coating agent of the present disclosure on one or both sides thereof.

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

The coating amount is not particularly limited. The coating amount is preferably such that the mass after drying is about 3 to 25 g/m ² , more preferably 5 to 20 g/m ² .

The heating method is exemplified by drying using a circulation dryer or the like. The drying (curing) conditions are about 90 to 170° C., and the time is about 30 seconds to 2 minutes.

In one embodiment, the laminate manufacturing method includes a curing step. Curing conditions are exemplified by room temperature or heating conditions. When heating, it is exemplified at about 40 to 60° C. for about 1 to 7 days.

Hereinafter, the present invention will be described in detail through examples and comparative examples. However, the above description of preferred embodiments and the following examples are provided for illustrative purposes only and not for the purpose of limiting the invention. Accordingly, the scope of the present invention is not limited to the embodiments or examples specifically described herein, but only by the claims. Further, in each example and comparative example, numerical values such as parts and % are based on mass unless otherwise specified.

Production example 1
24 parts of methyl methacrylate, 59 parts of butyl acrylate, and 17 parts of 2-hydroxyethyl acrylate are added to a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel, and azobis is added as an initiator. 2 parts of isobutyronitrile and 153 parts of ethyl acetate as a solvent are added, the temperature is gradually raised to 77° C., the reaction is performed for 9 hours, and a polymer solution with a solid content concentration of 35% (number average molecular weight: 26,000, weight average molecular weight: 70,000 ).

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

<Explanation of abbreviations>
MMA: methyl methacrylate BA: butyl acrylate LMA: lauryl methacrylate

HEA: 2-hydroxylethyl acrylate HEMA: 2-hydroxylethyl methacrylate

Example 1
100 parts of the polymer of Production Example 1 in terms of solid content, 45 parts of Duranate TPA-100 (manufactured by Asahi Kasei Corporation, hexamethylene diisocyanate nurate, solid content concentration 100%), Lumiflon 916F (manufactured by AGC Corporation, 10 parts of fluoroethylene/vinyl ether alternating copolymer, solid content concentration 100%), 0.17 parts of dioctyltin dilaurate (solid content concentration 100%), and 24 parts of acetylacetone were mixed well, and the solid content concentration was 25 with MEK. A coating agent was prepared by diluting to %.

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

<Explanation of abbreviations>
TPA-100: Duranate TPA-100 (manufactured by Asahi Kasei Co., Ltd., hexamethylene diisocyanate nurate, solid concentration 100%)
24A-100: Duranate 24A-100 (manufactured by Asahi Kasei Co., Ltd., biuret form of hexamethylene diisocyanate, solid content concentration 100%)
D-160N: Takenate D-160N (manufactured by Mitsui Chemicals, Inc., trimethylolpropane adduct of hexamethylene diisocyanate, solid content concentration 75%)

LF916F: Lumiflon 916F (manufactured by AGC Co., Ltd., fluoroethylene/vinyl ether alternating copolymer, hydroxyl value 100 mgKOH/g, solid content concentration 100%)
LF200F: Lumiflon 200F (manufactured by AGC Co., Ltd., fluoroethylene/vinyl ether alternating copolymer, hydroxyl value 31 mgKOH/g, solid content concentration 100%)

BYK3700: BYK-SILCLEAN3700 (manufactured by BYK Chemie Japan Co., Ltd., acrylic-modified silicone, solid content concentration 25%)

Preparation of Laminate The coating agent was applied to a thermoplastic urethane film (185 μm thick) with a bar coater so that the film thickness after drying was 10 μm, and dried at 120° C. for 2 minutes. After that, aging was performed at 40° C. for 5 days to produce a laminate.

Elongation The above test piece was punched out with a JIS-3 dumbbell, and a Tensilon universal material testing machine (trade name "RTC-1250A", manufactured by A&D Co., Ltd.) was used at a tensile speed of 200 mm / min, standard Measurement was performed under the condition that the line-to-line distance was 20 mm.
Breaking elongation (%) = 100 × (L-20) / 20
L: Cured product length when the cured product breaks

Elongation after Weather Resistance Test Using a super-accelerated weather resistance tester (Daipura Metal Weather), the above laminate was subjected to 10 cycles, with the following as one cycle.
4 hours of irradiation (temperature 60°C, humidity 50%, illuminance 90 mW/cm ² )
Condensation 4 hours (Temperature 30°C, Humidity 98%, Shower for 10 seconds before and after)
Darkness for 6 minutes (Temperature 50°C, Humidity 50%)
The elongation of the film after the test was measured in the same manner as described above.

Evaluation of Stain Resistance Magic ink No. 1 was applied to the surface of the laminate. 700 (manufactured by Teranishi Kagaku Kogyo Co., Ltd.), and after 1 minute, the mark was wiped off with a waste cloth for evaluation. Evaluation criteria are as follows.
◎: The mark completely disappears with one round trip wiping ○: The mark completely disappears with wiping within 5 round trips △: The mark is faintly confirmed even after wiping 5 round trips or more ×: Clear even after wiping mark remains

Claims (4)

A surface protective coating agent comprising (A) a hydroxyl group-containing (meth)acrylic resin (B) a polyisocyanate and (C) a hydroxyl group-containing fluororesin. 2. The surface protective coating agent according to claim 1, which contains (D) an organically modified silicone. A cured product of the surface protective coating agent according to claim 1 or 2. A laminate comprising the cured product of claim 3 and a substrate.