阅读说明：本技术 热固化型涂覆剂、固化物以及膜 (Heat-curable coating agent, cured product, and film ) 是由 桥本祐希 久米启太 山崎彰宽 东本徹 于 2019-07-18 设计创作，主要内容包括：提供热固化型涂覆剂、固化物和膜。本公开提供热固化型涂覆剂,所述热固化型涂覆剂含有：羟值为200mgKOH/g以上且分子量为1000以下的多元醇(A)；氨基甲酸酯多元醇(B)；含羟基的硅酮改性树脂(C)；和多异氰酸酯的脲基甲酸酯形式(D)；以及多异氰酸酯的缩二脲形式(E1)和/或异氰脲酸酯形式(E2)。(Provided are a thermosetting coating agent, a cured product and a film. The present disclosure provides a heat-curable coating agent containing: a polyol (A) having a hydroxyl value of 200mgKOH/g or more and a molecular weight of 1000 or less; a urethane polyol (B); a hydroxyl group-containing silicone-modified resin (C); and allophanate form (D) of a polyisocyanate; and the biuret form (E1) and/or the isocyanurate form (E2) of the polyisocyanate.)

1. A heat-curable coating agent containing:

a polyol (A) having a hydroxyl value of 200mgKOH/g or more and a molecular weight of 1000 or less;

a urethane polyol (B); a hydroxyl group-containing silicone-modified resin (C); and

allophanate form (D) of a polyisocyanate; and

the biuret form (E1) and/or the isocyanurate form (E2) of the polyisocyanate.

2. The heat-curable coating agent according to claim 1, wherein the urethane polyol (B) contains 35 to 70 mass% of a structural unit derived from a polymer polyol.

3. The heat-curable coating agent according to claim 1 or 2, which is a self-healing coating agent.

4. A cured product of the heat-curable coating agent according to any one of claims 1 to 3.

5. A film comprising the cured product according to claim 4.

Technical Field

The present disclosure relates to a heat-curable coating agent, a cured product, and a film.

Background

Plastic substrates such as ABS and polycarbonate are used for various industrial products such as electronic devices and automobile parts. In order to protect such plastic substrates, surface treatment is carried out by a coating agent.

Among coating agents, there are coating agents that impart self-repairability for the purpose of eliminating the generated damage over time (patent documents 1 to 2).

Disclosure of Invention

Technical problem to be solved by the invention

However, when the coating agent described in the above patent document is used, there is a problem that the resistance to damage caused by a strong force (steel wool (スチールウール) or the like) is low. Further, such a self-healing coating agent is required to have various physical properties depending on the use. The invention aims to provide a coating agent for producing a film having excellent self-repairability, wear resistance, stain resistance, elongation at break and steel wool resistance (スチールウール resistance).

Means for solving the problems

The present inventors have conducted extensive studies and, as a result, have found that the above-mentioned problems can be solved by a heat-curable coating agent containing a specific component.

The following items are provided in accordance with the present disclosure.

(item 1)

A heat-curable coating agent containing:

a polyol (A) having a hydroxyl value of 200mgKOH/g or more and a molecular weight of 1000 or less;

a urethane polyol (ウレタンポリオール) (B); a hydroxyl group-containing silicone modified resin (water acid based curable resin containing シリコーン) (C); and

allophanate form (D) of a polyisocyanate; and

the biuret form (E1) and/or the isocyanurate form (E2) of the polyisocyanate.

(item 2)

The heat-curable coating composition according to the above item, wherein the urethane polyol (B) contains 35 to 70 mass% of a structural unit derived from a polymer polyol.

(item 3)

The heat-curable coating agent according to any one of the above items, which is a self-repairable coating agent.

(item 4)

A cured product of the heat-curable coating agent according to any one of the above items.

(item 5)

A film comprising the cured product as described above.

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

Advantageous effects

By using the heat-curable coating agent of the present invention, a film having excellent self-repairability, abrasion resistance, antifouling property, elongation at break and steel wool resistance can be obtained. Further, the present invention can be applied to coating of a decorative film and the like.

Detailed Description

Specifically, for the value α, when the upper limit of the value α shows a1, a2, A3, and the like, and the lower limit of the value α shows B1, B2, B3, and the like, the ranges of the value α show a1 or less, a2 or less, A3 or less, B1 or more, B2 or more, B3 or more, B1 to a1, B2 to a1, B3 to a1, B1 to a2, B2 to a2, B3 to a2, B1 to A3, B2 to A3, B3 to A3, and the like.

[ heat-curable coating agent: also referred to as coating agent ]

The present disclosure provides a heat-curable coating agent containing: a polyol (A) having a hydroxyl value of 200mgKOH/g or more and a molecular weight of 1000 or less; a urethane polyol (B); a hydroxyl group-containing silicone-modified resin (C); and allophanate form (D) of a polyisocyanate; and the biuret form (E1) and/or the isocyanurate form (E2) of the polyisocyanate.

< polyol (A) having a hydroxyl value of 200mgKOH/g or more and a molecular weight of 1000 or less: also referred to as component (A) >

In the present disclosure, "polyol" refers to, for example, a compound having two or more hydroxyl groups (-OH).

(A) Examples of the upper limit of the hydroxyl value of the component include 2000mgKOH/g, 1900mgKOH/g, 1750mgKOH/g, 1500mgKOH/g, 1250mgKOH/g, 1000mgKOH/g, 900mgKOH/g, 750mgKOH/g, 500mgKOH/g, 300mgKOH/g, and the like; examples of the lower limit include 1900mgKOH/g, 1750mgKOH/g, 1500mgKOH/g, 1250mgKOH/g, 1000mgKOH/g, 900mgKOH/g, 750mgKOH/g, 500mgKOH/g, 300mgKOH/g, 200mgKOH/g and the like. In one embodiment, the hydroxyl value of the component (A) is preferably 200mgKOH/g or more, and more preferably 200mgKOH/g to 2000 mgKOH/g.

(A) The upper limit of the molecular weight of the component (a) is exemplified by 1000, 900, 750, 500, 400, 250, 200, 100, 90, etc.; the lower limits are exemplified by 900, 750, 500, 400, 250, 200, 100, 90, 50, etc. In one embodiment, the molecular weight of the component (a) is preferably 1000 or less, and more preferably 50 to 1000.

In the present disclosure, when only "molecular weight" is recited, it means one of formula weight or number average molecular weight. When the structure of a compound can be uniquely represented by a specific chemical formula (i.e., molecular weight distribution of 1), the above molecular weight means the formula weight. On the other hand, when the structure of the compound cannot be uniquely represented by a specific chemical formula (i.e., molecular weight distribution is more than 1), the above molecular weight means a number average molecular weight.

As long as the component (A) has a hydroxyl value of 200mgKOH/g or more and a molecular weight of 1000 or less, various known components can be used.

(A) Examples of the component (a) include alkylene polyols, polyether polyols, polyester polyols, polycarbonate polyols, and the like.

< alkylene polyol >

The alkylene polyols may be used alone or in combination of 2 or more. Examples of the alkylene polyol include alkylene glycol and alkylene triol.

In the present disclosure, "alkylene polyol" refers to a compound formed from an alkylene group and two or more hydroxyl groups.

The alkylene glycol is exemplified by a straight chain alkylene glycol, a branched chain alkylene glycol, and the like.

Examples of the straight chain alkylene glycol include ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol, and the like.

Examples of the branched alkylene glycol include 1, 2-propanediol, 1, 3-butanediol, 1, 2-butanediol, 1, 4-pentanediol, 1, 3-pentanediol, 1, 2-pentanediol, 1, 5-hexanediol, 1, 4-hexanediol, 1, 3-hexanediol, 1, 2-heptanediol, 1, 2-octanediol, 1, 2-nonanediol, and 1, 2-decanediol.

Examples of the alkylene triol include glycerin, butanetriol, pentanetriol, and trimethylolpropane.

The number of carbon atoms of the alkylene polyol is not particularly limited, and in one embodiment, the number of carbon atoms of the alkylene polyol is preferably 2 to 6.

< polyether polyol >

In the present disclosure, "polyether polyol" means, for example, a compound having 2 or more hydroxyl groups and 2 or more repeating units containing an ether bond in succession. The polyether polyols may be used alone or in combination of 2 or more.

In one embodiment, the polyether polyol is represented by the following structural formula:

HO-(R^Ether-O-)_nH

(in the formula, R^EtherIs alkylene, cycloalkylene, arylene or arylenealkylenearylene, and n is an integer of 2 or more).

Examples of the alkylene group include a linear alkylene group, a branched alkylene group and the like.

The linear alkylene group may be represented by the formula- (CH)₂)_n- (n is an integer of 1 or more). The straight-chain alkylene group is exemplified by methylene, ethylene, propylene, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, n-nonylene, n-decamethylene (group n- デカメチレン), etc.

Branched alkylene is a group in which at least 1 hydrogen of a linear alkylene group is substituted with an alkyl group. Examples of the branched alkylene group include diethylpentylene, trimethylbutylene, trimethylpentylene, trimethylhexylene and the like.

Examples of cycloalkylene include monocyclic cycloalkylene, bridged cycloalkylene, fused cycloalkylene and the like. Further, 1 or more hydrogens of the cycloalkylene group may be substituted with a linear or branched alkyl group.

In the present disclosure, monocyclic means a cyclic structure formed by covalent bonds of carbon and having no bridging structure inside. Further, a condensed ring means a cyclic structure in which 2 or more monocyclic rings share 2 atoms (i.e., only one side of each ring is shared (condensed) with each other). Bridged ring means a cyclic structure in which 2 or more monocyclic rings have 3 or more atoms in total.

Monocyclic cycloalkylene is exemplified by cyclopentylene, cyclohexylene, cycloheptylene, cyclodecylene, 3,5, 5-trimethylcyclohexylene, and the like.

Examples of the bridged cycloalkylene group include tricyclodecylene, adamantylene (アダマンチレン group), norbornylene (ノルボルニレン group), and the like.

Examples of the fused cycloalkylene group include bicyclodecylene (ビシクロデシレン -yl group) and the like.

The arylene group is exemplified by phenylene, naphthylene, fluorenylene (フルオニレン group), etc.

Arylenealkylenearylene is a group represented by the formula:

-R^arylene-R^alkylene-R^arylene-

(in the formula, R^aryleneRepresents an arylene group, R^alkyleneRepresents an alkylene group).

The arylene alkylene arylene group is exemplified by phenylenedimethylmethylenephenylene and the like.

Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, alkylene oxide adducts (アルキレンオキサイド adducts) of polyhydric alcohols, and the like.

(alkylene oxide adduct of polyhydric alcohol)

The alkylene oxide adducts of polyhydric alcohols may be used alone or in combination of 2 or more. Examples of the alkylene oxide adduct of a polyhydric alcohol include alkylene oxide adducts of alkylene glycols, alkylene oxide adducts of alkylene triols, and the like.

The alkylene glycol and alkylene triol are exemplified by the above-mentioned ones and the like.

The alkylene oxide adducts include, for example, ethylene oxide adducts, propylene oxide adducts and the like.

< polyester polyol >

In the present disclosure, "polyester polyol" refers to, for example, a compound having 2 or more hydroxyl groups and 2 or more repeating units containing an ester bond in succession. The polyester polyols may be used alone or in combination of 2 or more. In addition, polycaprolactone polyol is 1 type of polyester polyol.

In one embodiment, the polyester polyol is represented by the following structural formula:

HO-{R^aEster-OC(＝O)-R^bEster-C(＝O)O}_m-R^cEster-OH

(in the formula, R^aEster、R^bEsterAnd R^cEsterEach independently is an alkylene group or cycloalkylene group, and m is an integer of 2 or more).

The polyester polyol is exemplified by a reaction product of a polycarboxylic acid or an anhydride thereof and a polyol, and the like.

The polycarboxylic acids include dicarboxylic acids.

Examples of the dicarboxylic acid include dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 2-methylsuccinic acid, 2-methyladipic acid, 3-methylglutaric acid, 2-methyladipic acid, 3, 8-dimethylsebacic acid, 3, 7-dimethylsebacic acid, phthalic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, and cyclohexanedicarboxylic acid.

Examples of the polycarboxylic acid anhydride include acetic anhydride, propionic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride (water トリメリト acid), and the like.

Examples of the polyol include the alkylene polyols described above.

< polycarbonate polyol >

In the present disclosure, "polycarbonate polyol" refers to, for example, a compound having 2 or more hydroxyl groups and 2 or more repeating units containing a carbonate bond. The polycarbonate polyols may be used alone or in combination of 2 or more.

In one embodiment, the polycarbonate polyol is represented by the following structural formula:

HO-{R^aCarbo-OC(＝O)O}_p-R^bCarbo-OH

(in the formula, R^aCarboAnd R^bCarboEach independently is an alkylene group or cycloalkylene group, and p is an integer of 2 or more).

The polycarbonate polyol includes, for example, a reactant of a polyol and phosgene (ホスゲン), a ring-opened polymer of a cyclic carbonate (alkylene carbonate, etc.), and the like.

Examples of the polyol include the alkylene polyols described above.

The alkylene carbonate is exemplified by ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, hexamethylene carbonate, and the like.

The upper limit of the content of the component (a) in the thermosetting coating agent is, for example, 15 mass%, 14 mass%, 13 mass%, 11 mass%, 10 mass%, 9 mass%, 7 mass%, 5 mass%, 4 mass%, 3 mass%, 2 mass%, or the like; examples of the lower limit include 14 mass%, 13 mass%, 11 mass%, 10 mass%, 9 mass%, 7 mass%, 5 mass%, 4 mass%, 3 mass%, 2 mass%, 1 mass%, and the like. In one embodiment, the content of the component (a) in the thermosetting coating agent is preferably 1 to 15% by mass.

< urethane polyol (B): also referred to as (B) component >

In one embodiment, the urethane polyol is a reactant of a polyol and a polyisocyanate.

(polyhydric alcohol)

Examples of the polyol include alkylene polyols, polymer polyols, and the like.

The alkylene polyols may be used alone or in combination of 2 or more. The alkylene polyols described above are exemplified.

The upper limit of the content of the structural unit derived from an alkylene polyol with respect to 100% by mass of the structural unit derived from a polyol of a urethane polyol is, for example, 30% by mass, 25% by mass, 20% by mass, 15% by mass, or the like; examples of the lower limit include 25 mass%, 20 mass%, 15 mass%, 10 mass%, and the like. In one embodiment, the content of the structural unit derived from the alkylene polyol is preferably 10 to 30% by mass with respect to 100% by mass of the structural unit derived from the polyol of the urethane polyol.

The polymer polyol may be used alone, or 2 or more kinds may be used in combination. The polymer polyol is exemplified by polyether polyol, polyester polyol, polycarbonate polyol and the like.

The structural units of the polyether polyol, polyester polyol and polycarbonate polyol are exemplified by the above-mentioned structural units.

The upper limit of the content of the structural unit derived from the polymer polyol with respect to 100% by mass of the structural unit derived from the polyol of the urethane polyol is exemplified by 30% by mass, 25% by mass, 20% by mass, 15% by mass, and the like; examples of the lower limit include 25 mass%, 20 mass%, 15 mass%, 10 mass%, and the like. In one embodiment, the content of the structural unit derived from the polymer polyol is preferably 10% by mass to 30% by mass with respect to 100% by mass of the structural unit derived from the polyol of the urethane polyol.

The upper limit of the content of the structural unit derived from the polymer polyol in the urethane polyol is exemplified by 70 mass%, 65 mass%, 60 mass%, 55 mass%, 50 mass%, 45 mass%, 40 mass%, and the like; examples of the lower limit include 65 mass%, 60 mass%, 55 mass%, 50 mass%, 45 mass%, 40 mass%, 35 mass%, and the like. In one embodiment, the urethane polyol (B) contains 35 to 70 mass% of a structural unit derived from a polymer polyol.

The upper limit of the weight average molecular weight (Mw) of the polymer polyol contained as a structural unit in the urethane polyol is, for example, 2000, 1900, 1750, 1500, 1250, 1000, 900, 750, 600, or the like; the lower limits are shown by way of example as 1900, 1750, 1500, 1250, 1000, 900, 750, 600, 500, etc. In one embodiment, the weight average molecular weight (Mw) of the polymer polyol contained as a structural unit in the urethane polyol is preferably 500 to 2000.

The upper limit of the number average molecular weight (Mn) of the polymer polyol contained as a structural unit in the urethane polyol is exemplified by 2000, 1900, 1750, 1500, 1250, 1000, 900, 750, 600, and the like; the lower limits are shown by way of example as 1900, 1750, 1500, 1250, 1000, 900, 750, 600, 500, etc. In one embodiment, the number average molecular weight (Mn) of the polymer polyol contained as a structural unit in the urethane polyol is preferably 500 to 2000.

The weight average molecular weight and the number average molecular weight can be determined as polystyrene equivalent values measured by Gel Permeation Chromatography (GPC) in an appropriate solvent, for example.

The upper limit of the molecular weight distribution (Mw/Mn) of the polymer polyol contained as a structural unit in the urethane polyol is exemplified by 1.5, 1.4, 1.3, 1.2, 1.1, and the like; the lower limits are exemplified by 1.4, 1.3, 1.2, 1.1, 1.0, etc. In one embodiment, the molecular weight distribution (Mw/Mn) of the polymer polyol contained as a structural unit in the urethane polyol is preferably 1.0 to 1.5.

The upper limit of the content of the structural unit derived from the polyol is, for example, 99 mass%, 95 mass%, 90 mass%, 80 mass%, 70 mass%, 60 mass%, 55 mass%, or the like, with respect to 100 mass% of the total structural units of the urethane polyol; examples of the lower limit include 95 mass%, 90 mass%, 80 mass%, 70 mass%, 60 mass%, 55 mass%, 50 mass%, and the like. In one embodiment, the content of the structural unit derived from the polyol is preferably 50 to 99% by mass with respect to 100% by mass of the total structural units of the urethane polyol.

The upper limit of the mass ratio of the structural unit derived from the alkylene polyol to the structural unit derived from the polymer polyol in the urethane polyol is, for example, 3, 2.9, 2.5, 2, 1.9, 1.5, 1.1, etc.; the lower limits are exemplified by 2.9, 2.5, 2, 1.9, 1.5, 1.1, 1, etc. In one embodiment, the mass ratio of the structural unit derived from the alkylene polyol to the structural unit derived from the polymer polyol in the urethane polyol is preferably 1 to 3.

(polyisocyanate)

In the present disclosure, a "polyisocyanate" is a compound having 2 or more isocyanate groups (-N ═ C ═ O). The polyisocyanate may be used alone or in combination of 2 or more.

Examples of the polyisocyanate include aliphatic polyisocyanates, aromatic polyisocyanates, and the like.

Examples of the aliphatic polyisocyanate include a straight-chain aliphatic polyisocyanate, a branched-chain aliphatic polyisocyanate, and an alicyclic polyisocyanate.

Examples of the linear aliphatic group include the above-mentioned linear alkylene groups.

The linear aliphatic polyisocyanate is exemplified by methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, and the like.

Examples of the branched aliphatic group include the branched alkylene groups described above.

Examples of the branched aliphatic polyisocyanate include diethylpentylene diisocyanate, trimethylbutylene diisocyanate, trimethylpentylene diisocyanate, trimethylhexamethylene diisocyanate, and the like.

Examples of the alicyclic group include the monocyclic cycloalkylene group, bridged cycloalkylene group, fused cycloalkylene group and the like described above.

The alicyclic polyisocyanate is exemplified by monocyclic alkylene polyisocyanate, bridged cyclic alkylene polyisocyanate, fused cyclic alkylene polyisocyanate, and the like.

Monocyclic alkylene polyisocyanate shows, for example, hydrogenated xylene diisocyanate, isophorone diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, cycloheptylene diisocyanate, cyclodecylene diisocyanate, 3,5, 5-trimethylcyclohexylene diisocyanate, dicyclohexylmethane diisocyanate and the like.

Examples of the bridged cyclic alkylene polyisocyanate include tricyclodecylidene diisocyanate, adamantane diisocyanate, norbornene diisocyanate, and the like.

Examples of the fused alkylene polyisocyanate include dicyclodecylene diisocyanate and the like.

The number of carbon atoms of the aliphatic group is not particularly limited, and examples of the upper limit thereof include 30, 29, 25, 20, 16, 15, 12, 10, 9, 8, 7, 6, 5, 4, 3, 2 and the like; the lower limits are exemplified by 29, 25, 20, 15, 12, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, etc. In one embodiment, the aliphatic group has preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, still more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms.

The aromatic group is exemplified by the above-mentioned arylene group, arylenealkylenearylene group, and the like.

Examples of the aromatic polyisocyanate include xylylene diisocyanate and the like.

The upper limit of the content of the structural unit derived from the polyisocyanate is, for example, 50 mass%, 45 mass%, 40 mass%, 30 mass%, 20 mass%, 15 mass%, or the like, with respect to 100 mass% of the total structural units of the urethane polyol; examples of the lower limit include 45 mass%, 40 mass%, 30 mass%, 20 mass%, 15 mass%, 10 mass%, and the like. In one embodiment, the content of the structural unit derived from the polyisocyanate is preferably 10 to 50% by mass with respect to 100% by mass of the total structural units of the urethane polyol.

The upper limit of the mass ratio of the structural unit derived from the alkylene polyol to the structural unit derived from the polyisocyanate in the urethane polyol (structural unit derived from the alkylene polyol/structural unit derived from the polyisocyanate) is, for example, 3, 2.9, 2.5, 2.3, 2, 1.9, 1.7, 1.5, 1.4, 1.2, 1, 0.9, 0.7, 0.5, 0.3, etc.; the lower limits are exemplified by 2.9, 2.5, 2.3, 2, 1.9, 1.7, 1.5, 1.4, 1.2, 1, 0.9, 0.7, 0.5, 0.3, 0.2, etc. In one embodiment, the mass ratio of the alkylene polyol-derived structural unit to the polyisocyanate-derived structural unit (alkylene polyol-derived structural unit/polyisocyanate-derived structural unit) in the urethane polyol is preferably 0.2 to 3.

The upper limit of the mass ratio of the structural unit derived from the polymer polyol to the structural unit derived from the polyisocyanate (structural unit derived from the polymer polyol/structural unit derived from the polyisocyanate) in the urethane polyol is exemplified by 3, 2.9, 2.5, 2.3, 2, 1.9, 1.7, 1.5, 1.4, 1.2, 1, 0.9, 0.7, 0.5, 0.3 and the like; the lower limits are exemplified by 2.9, 2.5, 2.3, 2, 1.9, 1.7, 1.5, 1.4, 1.2, 1, 0.9, 0.7, 0.5, 0.3, 0.2, etc. In one embodiment, the mass ratio of the structural unit derived from the polymer polyol to the structural unit derived from the polyisocyanate in the urethane polyol (structural unit derived from the polymer polyol/structural unit derived from the polyisocyanate) is preferably 0.2 to 3.

(other monomers)

The urethane polyol may contain a structural unit derived from a monomer (also referred to as another monomer) that is neither a polymer polyol nor an alkylene polyol nor a polyisocyanate.

Other monomers are exemplified by arylene polyols and the like.

In one embodiment, the content of the structural unit derived from another monomer is, for example, less than 5 mass%, less than 1 mass%, less than 0.9 mass%, less than 0.5 mass%, less than 0.1 mass%, 0 mass%, or the like, with respect to 100 mass% of the total structural units of the urethane polyol.

In one embodiment, the content of the structural unit derived from another monomer is, for example, less than 5 mol%, less than 1 mol%, less than 0.9 mol%, less than 0.5 mol%, less than 0.1 mol%, 0 mol%, or the like, relative to 100 mol% of the total structural units of the urethane polyol.

< physical Properties of urethane polyol and the like >

The upper limit of the acid value of the urethane polyol is exemplified by 1mgKOH/g, 0.9mgKOH/g, 0.7mgKOH/g, 0.5mgKOH/g, 0.3mgKOH/g, 0.1mgKOH/g, etc.; the lower limits are, for example, 0.9mgKOH/g, 0.7mgKOH/g, 0.5mgKOH/g, 0.3mgKOH/g, 0.1mgKOH/g, 0mgKOH/g and the like. In one embodiment, the acid value of the urethane polyol is preferably 0mgKOH/g to 1 mgKOH/g.

In the present disclosure, the acid value is measured, for example, by a method based on JIS K0070.

The upper limit of the hydroxyl value of the urethane polyol is exemplified by 130mgKOH/g, 120mgKOH/g, 110mgKOH/g, 100mgKOH/g, 90mgKOH/g, 80mgKOH/g, 75mgKOH/g, 50mgKOH/g, etc.; the lower limits are, for example, 120mgKOH/g, 110mgKOH/g, 100mgKOH/g, 90mgKOH/g, 80mgKOH/g, 75mgKOH/g, 50mgKOH/g, 45mgKOH/g, etc. In one embodiment, the hydroxyl value of the urethane polyol is preferably from 45mgKOH/g to 130 mgKOH/g.

In the present disclosure, the hydroxyl value is measured, for example, by a method based on JIS K1557-1.

The upper limit of the weight average molecular weight (Mw) of the urethane polyol is exemplified by 80000, 75000, 70000, 60000, 55000, and the like; examples of the lower limit include 75000, 70000, 60000, 55000, 50000 and the like. In one embodiment, the weight average molecular weight (Mw) of the urethane polyol is more preferably about 50000 to 80000.

The upper limit of the number average molecular weight (Mn) of the urethane polyol is exemplified by 30000, 25000, 20000, 15000, etc.; examples of the lower limit include 25000, 20000, 15000, 10000, and the like. In one embodiment, the number average molecular weight (Mn) of the urethane polyol is more preferably about 10000 to 30000.

The upper limit of the molecular weight distribution (Mw/Mn) of the urethane polyol is exemplified by 4.0, 3.5, 3.0, 2.0, 1.5, etc.; the lower limits are exemplified by 3.5, 3.0, 2.0, 1.5, 1.0, etc. In one embodiment, the urethane polyol preferably has a molecular weight distribution (Mw/Mn) of 1.0 to 4.0.

The urethane polyol can be produced by various known methods of reacting a polyol with a polyisocyanate. Examples of the organic solvent used in the production of the urethane polyol include a solvent described later.

The upper limit of the content of the urethane polyol in the coating agent is, for example, 30 mass%, 25 mass%, 20 mass%, 15 mass%, 10 mass%, or the like; examples of the lower limit include 25 mass%, 20 mass%, 15 mass%, 10 mass%, 5 mass%, and the like. In one embodiment, the content of the urethane polyol in the coating agent is preferably 5 to 30% by mass.

The upper limit of the mass ratio of the component (a) to the urethane polyol in the coating agent (component (a)/urethane polyol) is, for example, 3, 2.9, 2.5, 2, 1.5, 1, 0.9, 0.5, 0.1, 0.09, 0.05, etc.; the lower limits are exemplified by 2.9, 2.5, 2, 1.5, 1, 0.9, 0.5, 0.1, 0.09, 0.05, 0.03, etc. In one embodiment, the mass ratio is preferably 0.03 to 3.

< hydroxyl group-containing silicone modified resin (C): also referred to as component (C) >

In the present disclosure, "hydroxyl group-containing silicone modified resin" refers to, for example, a resin having a hydroxyl group-containing silicone moiety.

The hydroxyl group-containing silicone-modified resin may be used alone or in combination of 2 or more. Examples of the hydroxyl group-containing silicone-modified resin include a hydroxyl group-containing silicone-modified acrylic resin, a hydroxyl group-containing silicone-modified polyester resin, a hydroxyl group-containing silicone-modified polyether resin, and a hydroxyl group-containing silicone-modified carbinol resin (カルビノール resin). The resin moiety may be introduced into any one of one end, both ends and a side chain of the silicone chain.

Commercially available products of the hydroxyl group-containing silicone-modified acrylic resin include, for example, ZX-028-G (manufactured by T & K TOKA, Inc.), BYK-SILCLEAN3700 (manufactured by ビックケミー & ジャパン, Inc.), サイマック US-270 (manufactured by Toyo Seisaku Co., Ltd.), and the like.

Commercially available products of the hydroxyl group-containing silicone-modified polyester resin or hydroxyl group-containing silicone-modified polyether resin include, for example, BYK-370, BYK-375, BYK-377, BYK-SILCLEAN3720 (manufactured by ビックケミー & ジャパン); x-22-4952, KF-6123 (manufactured by shin-Etsu chemical Co., Ltd.), and the like.

Commercially available products of the hydroxyl group-containing silicone-modified carbinol resin include, for example, 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.); サイラプレーン FM-4411, サイラプレーン FM-4421, サイラプレーン FM-4425, サイラプレーン FM-0411, サイラプレーン FM-0421, サイラプレーン FM-DA11, サイラプレーン FM-DA21, サイラプレーン FM-DA26 (manufactured by JNC Co., Ltd.), and the like.

The upper limit of the content of the hydroxyl group-containing silicone modified resin in the coating agent is, for example, 3.0 mass%, 2.5 mass%, 2.0 mass%, 1.5 mass%, 1.0 mass%, or the like; examples of the lower limit include 2.5 mass%, 2.0 mass%, 1.5 mass%, 1.0 mass%, 0.5 mass%, and the like. In one embodiment, the content of the hydroxyl group-containing silicone modified resin in the coating agent is preferably 0.5 to 3.0 mass%.

The upper limit of the mass ratio of the content of the component (a) to the hydroxyl group-containing silicone-modified resin in the coating agent (component (a)/hydroxyl group-containing silicone-modified resin) is, for example, 30, 29, 25, 20, 19, 17, 15, 13, 10, 9, 7, 5, 3, etc.; the lower limits are exemplified by 29, 25, 20, 19, 17, 15, 13, 10, 9, 7, 5, 3, 2, etc. In one embodiment, the mass ratio is preferably 2 to 30.

The upper limit of the mass ratio of the urethane polyol to the hydroxyl group-containing silicone modified resin in the above coating agent (urethane polyol/hydroxyl group-containing silicone modified resin) is exemplified by 60, 59, 50, 40, 30, 20, 10, 9, 5, 4, 2, etc.; the lower limits are exemplified by 59, 50, 40, 30, 20, 10, 9, 5, 4, 2, 1, etc. In one embodiment, the mass ratio of the urethane polyol to the hydroxyl group-containing silicone modified resin in the coating agent (urethane polyol/hydroxyl group-containing silicone modified resin) is preferably 1 to 60.

< allophanate form (D) of polyisocyanate: also referred to as (D) component >

The allophanate form of the polyisocyanate may be used alone or in combination of 2 or more. In the production of the allophanate form of the polyisocyanate, the polyisocyanate may be used alone or in combination of 2 or more. The polyisocyanate includes the above-mentioned ones, for example.

The allophanate form of the polyisocyanate is exemplified by the compounds represented by the following structural formula:

[ solution 1]

{ formula (II) wherein n^aIs an integer of 0 or more; r^aAIs alkyl or aryl; r^aB～R^aGEach independently is alkylene or arylene; r^aα～R^aγEach independently is an isocyanate group or

[ solution 2]

(n^a1Is 0 or moreThe above integer; r^a1～R^a6Each independently is alkylene or arylene; r^a’～R^a"' are each independently an isocyanate group or R^aα～R^aγA group of itself. For each structural unit, R^a1～R^a4、R^a’～R^aThe "groups may also be different. ) For each structural unit, R^aB～R^aE、R^aα～R^aβThe groups of (a) may also be different. }

Examples of commercially available allophanate forms of polyisocyanates include TAKENATE (タケネート) D-178NL (manufactured by Mitsui chemical Co., Ltd.), CORONATE (コロネート)2770 (manufactured by Chinese imperial sciences, Inc. ソー Co., Ltd.), CORONATE 2793 (manufactured by Chinese imperial sciences, Inc. ソー Co., Ltd.), DURANATE (デュラネート) A201H (manufactured by Asahi chemical synthesis Co., Ltd.), and the like.

The upper limit of the weight average molecular weight (Mw) of the allophanate form of the polyisocyanate is illustrated by way of example 3500, 3300, 3100, 3000, 2900, 2750, 2500, 2250, 2000, 1750, 1500, 1250, 1000, 900, etc.; the lower limits are exemplified by 3300, 3100, 3000, 2900, 2750, 2500, 2250, 2000, 1750, 1500, 1250, 1000, 900, 800, etc. In one embodiment, the weight average molecular weight (Mw) of the allophanate form of the polyisocyanate is preferably from 800 to 3500.

The upper limit of the number average molecular weight (Mn) of the allophanate form of the polyisocyanate is illustrated by 3000, 2900, 2750, 2500, 2250, 2000, 1750, 1500, 1250, 1000, 900, 800, etc.; lower limits are exemplified 2900, 2750, 2500, 2250, 2000, 1750, 1500, 1250, 1000, 900, 800, 700, etc. In one embodiment, the number average molecular weight (Mn) of the allophanate form of the polyisocyanate is preferably from 700 to 3000.

The upper limit of the molecular weight distribution (Mw/Mn) of the allophanate form of the polyisocyanate is illustrated by 1.5, 1.4, 1.3, 1.2, 1.1, etc.; the lower limits are exemplified by 1.4, 1.3, 1.2, 1.1, 1.0, etc. In one embodiment, the molecular weight distribution (Mw/Mn) of the allophanate form of the polyisocyanate is preferably from 1.0 to 1.5.

The upper limit of the NCO content (NCO%) in the allophanate form of the polyisocyanate is exemplified by 30 mass%, 25 mass%, 20 mass%, 15 mass%, 10 mass%, and the like; examples of the lower limit include 25 mass%, 20 mass%, 15 mass%, 10 mass%, 5 mass%, and the like. In one embodiment, the NCO content (NCO%) in the allophanate form of the polyisocyanate is preferably 5% by mass to 30% by mass.

The upper limit of the content of the polyisocyanate in the allophanate form in the coating agent is exemplified by 99 mass%, 95 mass%, 93.5 mass%, 90 mass%, 85 mass%, 80 mass%, 75 mass%, 70 mass%, 65 mass%, 60 mass%, 55 mass%, 50 mass%, 45 mass%, 40 mass%, 35 mass%, 30 mass%, 25 mass%, 20 mass%, 15 mass%, 10 mass%, 5 mass%, 2 mass%, and the like; the lower limit includes 95 mass%, 93.5 mass%, 90 mass%, 85 mass%, 80 mass%, 75 mass%, 70 mass%, 65 mass%, 60 mass%, 55 mass%, 50 mass%, 45 mass%, 40 mass%, 35 mass%, 30 mass%, 25 mass%, 20 mass%, 15 mass%, 10 mass%, 5 mass%, 2 mass%, 1 mass%, and the like. In one embodiment, the content of the allophanate form of the polyisocyanate in the coating agent is preferably 1 to 99% by mass.

The upper limit of the mass ratio of the content of the component (a) to the allophanate form of the polyisocyanate in the above-mentioned coating agent ((a) component/allophanate form of polyisocyanate) shows, for example, 15, 13, 10, 9, 5, 4, 1, 0.9, 0.5, 0.1, 0.09, 0.05, 0.02, etc.; examples of the lower limit include 13, 10, 9, 5, 4, 1, 0.9, 0.5, 0.1, 0.09, 0.05, 0.02, 0.01, and the like. In one embodiment, the mass ratio is preferably 0.01 to 15.

The upper limit of the mass ratio of the urethane polyol to the allophanate form of the polyisocyanate in the above-mentioned coating agent (urethane polyol/allophanate form of the polyisocyanate) is exemplified by 30, 29, 25, 20, 19, 15, 10, 9, 5, 4, 1, 0.9, 0.5, 0.1, 0.09 and the like; the lower limits are exemplified by 29, 25, 20, 19, 15, 10, 9, 5, 4, 1, 0.9, 0.5, 0.1, 0.09, 0.05, etc. In one embodiment, the mass ratio of the urethane polyol to the allophanate form of the polyisocyanate (urethane polyol/allophanate form of the polyisocyanate) in the above coating agent is preferably 0.05 to 30.

The upper limit of the mass ratio of the hydroxyl-containing silicone-modified resin to the allophanate form of the polyisocyanate (hydroxyl-containing silicone-modified resin/allophanate form of the polyisocyanate) in the above-mentioned coating agent is exemplified by 3, 2, 1, 0.9, 0.5, 0.1, 0.09, 0.05, 0.01, 0.009, 0.006 and the like; the lower limits are exemplified by 2, 1, 0.9, 0.5, 0.1, 0.09, 0.05, 0.01, 0.009, 0.006, 0.005, etc. In one embodiment, the mass ratio of the hydroxyl-containing silicone modified resin to the allophanate form of the polyisocyanate in the coating agent (hydroxyl-containing silicone modified resin/allophanate form of the polyisocyanate) is preferably 0.005 to 3.

Biuret form of polyisocyanate (E1): also referred to as (E1) ingredient >

The biuret form of the polyisocyanate may be used alone or in combination of 2 or more. In the production of the biuret form of the polyisocyanate, the polyisocyanate may be used alone or 2 or more kinds may be used in combination. The polyisocyanate includes the above-mentioned ones, for example.

The biuret form of the polyisocyanate exemplifies compounds represented by the following structural formula, and the like:

[ solution 3]

{ formula (II) wherein n^bIs an integer of 1 or more; r^bA～R^bEEach independently is alkylene or arylene; r^bα～R^bβEach independently is an isocyanate group or

[ solution 4]

(n^b1Is an integer of 0 or more; r^b1～R^b5Each independently is alkylene or arylene; r^b’～R^b"are each independently an isocyanate group or R^bα～R^bβA group of itself. For each structural unit, R^b4～R^b5、R^bThe "groups may also be different. ) For each structural unit, R^bD～R^bE、R^bβThe groups of (a) may also be different. }

Commercially available biuret forms of polyisocyanates are exemplified by DURANATE24A-100, DURANATE 22A-75P, DURANATE 21S-75E (manufactured by Asahi Kasei corporation, supra); デスモジュール N3200A (biuret form of hexamethylene diisocyanate) (manufactured by Sumitomo バイエルウレタン, Inc.) and the like.

The upper limit of the weight average molecular weight (Mw) of the biuret form of the polyisocyanate is exemplified by 1500, 1400, 1250, 1100, 1000, 900, 750, 600, etc.; the lower limits are shown, for example, as 1400, 1250, 1100, 1000, 900, 750, 600, 500, etc. In one embodiment, the weight average molecular weight (Mw) of the biuret form of the polyisocyanate is preferably 500 to 1500.

The upper limit of the number average molecular weight (Mn) of the biuret form of the polyisocyanate is exemplified by 1500, 1400, 1250, 1100, 1000, 900, 750, 600, etc.; the lower limits are shown, for example, as 1400, 1250, 1100, 1000, 900, 750, 600, 500, etc. In one embodiment, the number average molecular weight (Mn) of the biuret form of the polyisocyanate is preferably 500 to 1500.

The upper limit of the molecular weight distribution (Mw/Mn) of the biuret form of the polyisocyanate is exemplified by 1.5, 1.4, 1.3, 1.2, 1.1, etc.; the lower limits are exemplified by 1.4, 1.3, 1.2, 1.1, 1.0, etc. In one embodiment, the molecular weight distribution (Mw/Mn) of the biuret form of the polyisocyanate is preferably 1.0 to 1.5.

The upper limit of the NCO content (NCO%) in the biuret form of the polyisocyanate is exemplified by 30 mass%, 25 mass%, 20 mass%, 15 mass%, 10 mass%, and the like; examples of the lower limit include 25 mass%, 20 mass%, 15 mass%, 10 mass%, 5 mass%, and the like. In one embodiment, the NCO content (NCO%) of the biuret form of the polyisocyanate is preferably 5% by mass to 30% by mass.

The upper limit of the content of the biuret form of the polyisocyanate in the coating agent is exemplified by 99 mass%, 95 mass%, 93.5 mass%, 90 mass%, 85 mass%, 80 mass%, 75 mass%, 70 mass%, 65 mass%, 60 mass%, 55 mass%, 50 mass%, 45 mass%, 40 mass%, 35 mass%, 30 mass%, 25 mass%, 20 mass%, 15 mass%, 10 mass%, 5 mass%, 2 mass%, 1 mass%, and the like; the lower limit is exemplified by 95 mass%, 93.5 mass%, 90 mass%, 85 mass%, 80 mass%, 75 mass%, 70 mass%, 65 mass%, 60 mass%, 55 mass%, 50 mass%, 45 mass%, 40 mass%, 35 mass%, 30 mass%, 25 mass%, 20 mass%, 15 mass%, 10 mass%, 5 mass%, 2 mass%, 1 mass%, 0 mass%, and the like. In one embodiment, the content of the biuret form of the polyisocyanate in the coating agent is preferably 0% by mass to 99% by mass.

The upper limit of the mass ratio of the biuret form of polyisocyanate to the allophanate form of polyisocyanate (biuret form/allophanate form) in the above-mentioned coating agent shows, by way of example, 99, 95, 93.5, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 2, 1, etc.; the lower limit is exemplified by 95, 93.5, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 2, 1, 0, etc. In one embodiment, the mass ratio is preferably 0 to 99.

The upper limit of the mass ratio of the content of the biuret form of polyisocyanate to the (a) component (the biuret form of polyisocyanate/(a) component) in the above-mentioned coating agent shows, for example, 99, 95, 93.5, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 2, 1, etc.; the lower limit is exemplified by 95, 93.5, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 2, 1, 0, etc. In one embodiment, the mass ratio is preferably 0 to 99.

The upper limit of the mass ratio of the biuret form of polyisocyanate to the urethane polyol (biuret form of polyisocyanate/urethane polyol) in the above coating agent shows by way of example 20, 19, 15, 10, 5, 2, 1, etc.; the lower limit is exemplified by 19, 15, 10, 5, 2, 1, 0, etc. In one embodiment, the mass ratio is preferably 0 to 20.

The upper limit of the mass ratio of the biuret form of polyisocyanate to the hydroxyl group-containing silicone-modified resin (biuret form of polyisocyanate/hydroxyl group-containing silicone-modified resin) in the above-mentioned coating agent shows, for example, 200, 190, 175, 150, 125, 100, 90, 75, 50, 25, 10, 9, 5, 4, 2, 1, etc.; the lower limits are exemplified as 190, 175, 150, 125, 100, 90, 75, 50, 25, 10, 9, 5, 4, 2, 1, 0, etc. In one embodiment, the mass ratio is preferably 0 to 200.

Isocyanurate form of polyisocyanate (E2): also referred to as (E2) ingredient >

The isocyanurate form of the polyisocyanate may be used alone or in combination of 2 or more. In the production of the isocyanurate form of the polyisocyanate, the polyisocyanate may be used alone or in combination of 2 or more. The polyisocyanate includes the above-mentioned ones, for example.

The isocyanurate form of the polyisocyanate illustrates, among other things, compounds represented by the following structural formula:

[ solution 5]

{ formula (II) wherein nⁱIs an integer of 0 or more; r^iA～R^iEEach independently is alkylene or arylene; r^iα～R^iβEach independently is an isocyanate group or

[ solution 6]

(nⁱ¹Is an integer of 0 or more; rⁱ¹～Rⁱ⁵Each of which isIndependently alkylene or arylene; rⁱ’～Rⁱ"are each independently an isocyanate group or R^iα～R^iβA group of itself. For each structural unit, Rⁱ⁵、RⁱThe "groups may also be different. ) For each structural unit, R^iD～R^iE、R^iβThe groups of (a) may also be different. }

Commercially available products of the isocyanurate form of polyisocyanates include DURANATE TPA-100, DURANATETKA-100, DURANATE MFA-75B, DURANATE MHG-80B (manufactured by Asahi Kasei corporation); CORONATE HXR (isocyanurate form of hexamethylene diisocyanate) (manufactured by imperial ソー, Inc.); TAKENATE D-127N (the isocyanurate form of hydrogenated xylene diisocyanate) (manufactured by Mitsui Chemicals, Inc.) above; VESTANAT T1890/100 (isocyanurate form of isophorone diisocyanate) (manufactured by エボニック. ジャパン strain, supra), and the like.

The upper limit of the weight average molecular weight (Mw) of the isocyanurate form of the polyisocyanate is exemplified by 1500, 1400, 1250, 1100, 1000, 900, 750, 600, etc.; the lower limits are shown, for example, as 1400, 1250, 1100, 1000, 900, 750, 600, 500, etc. In one embodiment, the weight average molecular weight (Mw) of the isocyanurate form of the polyisocyanate is preferably 500 to 1500.

The upper limit of the number average molecular weight (Mn) of the isocyanurate form of the polyisocyanate is exemplified by 1500, 1400, 1250, 1100, 1000, 900, 750, 600, etc.; the lower limits are shown, for example, as 1400, 1250, 1100, 1000, 900, 750, 600, 500, etc. In one embodiment, the number average molecular weight (Mn) of the isocyanurate form of the polyisocyanate is preferably 500 to 1500.

The upper limit of the molecular weight distribution (Mw/Mn) of the isocyanurate form of the polyisocyanate is exemplified by 1.5, 1.4, 1.3, 1.2, 1.1, etc.; the lower limits are exemplified by 1.4, 1.3, 1.2, 1.1, 1.0, etc. In one embodiment, the molecular weight distribution (Mw/Mn) of the isocyanurate form of the polyisocyanate is preferably 1.0 to 1.5.

The upper limit of the NCO content (NCO%) in the isocyanurate form of the polyisocyanate is exemplified by 30 mass%, 25 mass%, 20 mass%, 15 mass%, 10 mass%, and the like; examples of the lower limit include 25 mass%, 20 mass%, 15 mass%, 10 mass%, 5 mass%, and the like. In one embodiment, the NCO content (NCO%) in the isocyanurate form of the polyisocyanate is preferably 5% by mass to 30% by mass.

The upper limit of the content of the polyisocyanate in the isocyanurate form in the coating agent is, for example, 99 mass%, 95 mass%, 93.5 mass%, 90 mass%, 85 mass%, 80 mass%, 75 mass%, 70 mass%, 65 mass%, 60 mass%, 55 mass%, 50 mass%, 45 mass%, 40 mass%, 35 mass%, 30 mass%, 25 mass%, 20 mass%, 15 mass%, 10 mass%, 5 mass%, 2 mass%, 1 mass%, or the like; the lower limit is exemplified by 95 mass%, 93.5 mass%, 90 mass%, 85 mass%, 80 mass%, 75 mass%, 70 mass%, 65 mass%, 60 mass%, 55 mass%, 50 mass%, 45 mass%, 40 mass%, 35 mass%, 30 mass%, 25 mass%, 20 mass%, 15 mass%, 10 mass%, 5 mass%, 2 mass%, 1 mass%, 0 mass%, and the like. In one embodiment, the content of the polyisocyanate in the isocyanurate form in the coating agent is preferably 1 to 99% by mass.

The upper limit of the mass ratio of the isocyanurate form of the polyisocyanate to the allophanate form of the polyisocyanate in the above-mentioned coating agent (isocyanurate form/allophanate form) shows, for example, 99, 95, 93.5, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 2, 1, etc.; the lower limit is exemplified by 95, 93.5, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 2, 1, 0, etc. In one embodiment, the mass ratio of the isocyanurate form of the polyisocyanate to the allophanate form of the polyisocyanate (isocyanurate form/allophanate form) in the above-mentioned coating agent is preferably 0 to 99.

The upper limit of the mass ratio of the content of the isocyanurate form of polyisocyanate to the content of the component (a) (isocyanurate form of polyisocyanate/(component (a)) in the above-mentioned coating agent is exemplified by 99, 95, 93.5, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 2, 1, etc.; the lower limit is exemplified by 95, 93.5, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 2, 1, 0, etc. In one embodiment, the mass ratio is preferably 0 to 99.

The upper limit of the mass ratio of the isocyanurate form of the polyisocyanate to the urethane polyol in the above coating agent (isocyanurate form of polyisocyanate/urethane polyol) shows, for example, 20, 19, 15, 10, 5, 2, 1, etc.; the lower limit is exemplified by 19, 15, 10, 5, 2, 1, 0, etc. In one embodiment, the mass ratio is preferably 0 to 20.

The upper limit of the mass ratio of the isocyanurate form of polyisocyanate to the hydroxyl group-containing silicone-modified resin in the above-mentioned coating agent (isocyanurate form of polyisocyanate/hydroxyl group-containing silicone-modified resin) shows, for example, 200, 190, 175, 150, 125, 100, 90, 75, 50, 25, 10, 9, 5, 4, 2, 1, etc.; the lower limits are exemplified as 190, 175, 150, 125, 100, 90, 75, 50, 25, 10, 9, 5, 4, 2, 1, 0, etc. In one embodiment, the mass ratio is preferably 0 to 200.

< curing catalyst >

In one embodiment, the coating agent may contain a curing catalyst. The curing catalyst may be contained alone or in an amount of 2 or more.

Examples of the curing catalyst include an organometallic catalyst, an organic amine catalyst, and the like.

Examples of the organometallic catalyst include an organic main group metal catalyst (typical metal catalyst), an organic transition metal catalyst, and the like.

Examples of the organic main group metal catalyst include an organotin catalyst, an organobismuth catalyst, and the like.

Examples of the organotin catalyst include dibutyltin dilaurate, dioctyltin dilaurate and the like.

The organic bismuth catalyst includes, for example, bismuth octoate.

Examples of the organic transition metal catalyst include an organic titanium catalyst, an organic zirconium catalyst, and an organic iron catalyst.

The organic titanium catalyst is exemplified by titanium ethyl acetoacetate (チタンエチルアセトアセテート) and the like.

Examples of the organozirconium catalyst include zirconium tetraacetylacetonate (ジルコニウムテトラアセチルアセトネート) and the like.

Examples of the organic iron catalyst include iron acetylacetonate (iron アセチルアセトネート) and the like.

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

When the coating agent contains a curing catalyst, the upper limit of the content of the curing catalyst in the coating agent is, for example, 1 mass%, 0.9 mass%, 0.75 mass%, 0.5 mass%, 0.25 mass%, 0.1 mass%, 0.09 mass%, 0.05 mass%, 0.02 mass%, or the like; examples of the lower limit include 0.9 mass%, 0.75 mass%, 0.5 mass%, 0.25 mass%, 0.1 mass%, 0.09 mass%, 0.05 mass%, 0.02 mass%, 0.01 mass%, and the like. In one embodiment, when the coating agent contains a curing catalyst, the content of the curing catalyst in the coating agent is preferably about 0.01 to 1% by mass.

< organic solvent >

In one embodiment, the coating agent may contain an organic solvent. The organic solvent may be contained alone or in an amount of 2 or more. Examples of the organic solvent include ketone solvents such as methyl ethyl ketone, acetylacetone, methyl isobutyl ketone, and cyclohexanone; aromatic solvents such as toluene and xylene; alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, and butanol; glycol ether solvents such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and propylene glycol monomethyl ether acetate; ester solvents such as ethyl acetate, butyl acetate, methyl cellosolve acetate, and cellosolve acetate; petroleum solvents such as solvasso (ソルベッソ) #100 and solvasso #150 (both trade names, manufactured by エクソンモービル); halogenated alkane solvents such as chloroform; amide solvents such as dimethylformamide, and the like. Among them, from the viewpoint of pot life (ポットライフ) of the coating agent of the present invention, a ketone organic solvent is preferably contained, and acetylacetone is preferably contained in the ketone organic solvent.

When the coating agent contains an organic solvent, the upper limit of the content of the organic solvent in the coating agent is 90 mass%, 80 mass%, 70 mass%, 60 mass%, 55 mass%, or the like; examples of the lower limit include 85 mass%, 80 mass%, 70 mass%, 60 mass%, 55 mass%, 50 mass%, and the like. In one embodiment, when the coating agent contains an organic solvent, the content of the organic solvent in the coating agent is preferably about 50% by mass to 90% by mass. The organic solvent contained in the coating agent may include the hydroxyl group-containing silicone-modified resin, an allophanate form of the polyisocyanate, and an organic solvent contained in the curing catalyst.

< additives >

The coating agent may contain, as additives, the component (a), the component (B), the component (C), the component (D), the component (E1), the component (E2), a curing catalyst, and a reagent other than an organic solvent. Examples of the additives include polymerization inhibitors, antioxidants, light stabilizers, antifoaming agents, surface control agents, pigments, antistatic agents, metal oxide fine particle dispersions, organic fine particle dispersions, and the like. In one embodiment, as examples of the content of the additive, less than about 5% by mass, less than about 1% by mass, less than about 0.1% by mass, less than about 0.01% by mass, 0% by mass, and the like of the above-described coating agent are illustrated.

The coating agent can be obtained by a method including a step of mixing the component (a), the component (B), the component (C), the component (D), the component (E1) and/or the component (E2) by various known means, and if necessary, a curing catalyst, an organic solvent, an additive, or the like.

The above coating agent can be used as a self-healing coating agent.

[ cured product ]

The present disclosure provides a cured product of the coating agent. The conditions for producing the cured product are exemplified by the conditions described below.

[ film ]

The present disclosure provides a film containing the cured product.

The substrate may be any of various known substrates. Examples of the substrate include a polycarbonate film, an acrylic film (e.g., a polymethyl methacrylate film), a polystyrene film, a polyester film, a polyolefin film, an epoxy resin film, a melamine resin film, a triacetyl cellulose film, an ABS film, an AS film, a norbornene resin film, a cycloolefin film, and a polyvinyl alcohol film. The thickness of the substrate is not particularly limited, and is preferably about 50 μm to 200. mu.m. The thickness of the undercoat layer (アンダーコート body panel) is not particularly limited, but is preferably about 0.1 to 5 μm.

The above-mentioned film can be produced by various known methods. In one embodiment, a method of making a membrane includes: a step (coating step) of coating the coating agent on at least one surface of a base material; and a step of forming a coating agent cured layer by thermal curing (thermal curing step).

(coating Process)

Examples of the coating method include bar coater coating, wire bar coating (ワイヤーバー coating), Meyer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing (フレキソ printing), and screen printing.

The amount of coating is not particularly limited. The coating weight is preferably 0.1g/m in mass after drying²～30g/m²About, more preferably 1g/m²～20g/m²Left and right.

(Heat curing step)

Examples of the drying method include drying with a circulating air dryer. The drying conditions include, for example, standing at 120 ℃ for 30 seconds.

When the film is produced, the film is dried and then aged (エージング) as necessary. The conditions of the aging treatment are shown, for example, at 40 ℃ for 72 hours and the like.