TW202012558A - Thermosetting coating agent, cured product and film - Google Patents

Abstract

Provided herein is a thermosetting coating agent, a cured material and a film. The present invention provides a thermosetting coating agent, containing: a polyol (A) having a hydroxyl value of 200 mgKOH/g or more and a molecular weight of 1,000 or less; a carbamate polyol (B); a hydroxyl-containing silicone-modified resin (C); an allophanate form of polyisocyanate (D); and a biuret form (E1) and/or isocyanurate form (E2) of polyisocyanate. This film coated with a coating agent has excellent properties in self-repairing, abrasion resistance, antifouling, elongation at break, and steel wool resistance.

Description

Thermosetting coating agent, hardened material and film

The present invention relates to thermosetting coating agents, cured products and films.

Plastic materials such as acrylonitrile-butadiene-styrene (ABS) and polycarbonate are used in various industrial products such as electronic equipment and automotive parts. In order to protect such plastic substrates, surface treatment is carried out with coating agents.

Among the coating agents, there are coating agents that have been provided with self-healing properties for the purpose of eliminating the generated damage over time (Patent Document 1 to Patent Document 2). [Prior Technical Literature] (Patent Literature)

Patent Document 1: Japanese Patent Application Publication No. 2010-043261 Patent Document 2: Japanese Patent Laid-Open No. 2016-033175

[Technical problems to be solved by the invention] However, when the coating agent described in the above-mentioned patent document is used, there is a problem that the resistance to damage caused by strength (steel wool, etc.) is low. In addition, such a self-healing coating agent needs to have various physical properties depending on the application. The technical problem to be solved by the present invention is to provide a coating agent for manufacturing a film with good self-healing properties, abrasion resistance, stain resistance, elongation at break, and steel wool resistance. [Technical means to solve technical problems]

The present inventors conducted intensive studies and found that the thermosetting coating agent containing specific components can solve the above-mentioned technical problems.

According to the present invention, the following items are provided. (Item 1) A thermosetting coating agent, the thermosetting coating agent contains: Polyol (A) with a hydroxyl value of 200 mgKOH/g or more and a molecular weight of 1000 or less; Urethane polyol (B); hydroxyl-containing silicone modified resin (C); Allophanate form (D) of polyisocyanates; and, The biuret form (E1) and/or isocyanurate form (E2) of the polyisocyanate. (Item 2) The thermosetting coating agent according to the above item, wherein the urethane polyol (B) contains 35 to 70% by mass of a structural unit derived from a polymer polyol. (Item 3) The thermosetting coating agent according to any one of the above items, wherein the thermosetting coating agent is a self-healing coating agent. (Item 4) A hardened product is the hardened product of the thermosetting coating agent according to any one of the above items. (Item 5) A film containing the hardened product described in the above item.

In the present invention, in addition to the combinations explicitly described, one or more of the above features may be further combined. [Beneficial effect]

By using the thermosetting coating agent of the present invention, it is possible to obtain a film having good self-healing properties, abrasion resistance, stain resistance, elongation at break, and steel wool resistance. In addition, it can also be applied to the application of decorative films.

Throughout the present invention, the ranges of numerical values such as physical property values and contents can be set appropriately (for example, selected from the values of the upper limit and the lower limit described in the following items). Specifically, for the value α, when the upper limit of the value α is exemplified by A1, A2, A3, etc., and the lower limit of the value α is exemplified by B1, B2, B3, etc., the range of the value α is exemplified by 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 Wait.

[Thermosetting coating agent: also called coating agent] The present invention provides a thermosetting coating agent containing: a polyol (A) having a hydroxyl value of 200 mgKOH/g or more and a molecular weight of 1,000 or less; a carbamate polyol (B); Hydroxy-containing silicone-modified resin (C); allophanate form of polyisocyanate (D); and biuret form of polyisocyanate (E1) and/or isocyanurate form (E2).

>Polyol (A) with a hydroxyl value of 200 mgKOH/g or more and a molecular weight of 1000 or less: also called (A) component> In the present invention, "polyol" refers to, for example, a compound having two or more hydroxyl groups (-OH).

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

(A) The upper limit of the molecular weight of the component is exemplified by 1000, 900, 750, 500, 400, 250, 200, 100, 90, etc.; the lower limit is exemplified by 900, 750, 500, 400, 250, 200, 100, 90, 50 etc. In one embodiment, the molecular weight of the component (A) is preferably 1,000 or less, and more preferably 50 to 1,000.

In the present invention, when only "molecular weight" is described, it means one of the formula weight or the number average molecular weight. When a specific chemical formula can be used to uniquely represent the structure of a compound (ie, the molecular weight distribution is 1), the above molecular weight means the amount of formula. On the other hand, when the structure of the compound cannot be uniquely expressed by a specific chemical formula (that is, the molecular weight distribution is greater than 1), the above molecular weight means the number average molecular weight.

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

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

>alkylene polyol> The alkylene polyol may be used alone or in combination of two or more. Examples of alkylene polyols include alkylene glycols and alkylene triols.

In the present invention, "alkylene polyol" refers to a compound formed of alkylene and two or more hydroxyl groups.

Examples of alkylene glycols include linear alkylene glycols, branched alkylene glycols, and the like.

Examples of linear alkylene glycols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,7-heptanediol Alcohol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, etc.

Examples of branched alkylene glycols include 1,2-propanediol, 1,3-butanediol, 1,2-butanediol, 1,4-pentanediol, 1,3-pentanediol, and 1, 2-pentanediol, 1,5-hexanediol, 1,4-hexanediol, 1,3-hexanediol, 1,2-hexanediol, 1,2-heptanediol, 1,2- Octanediol, 1,2-nonanediol, 1,2-decanediol, etc.

Examples of alkylene triols include glycerin, butanetriol, pentatriol, and trimethylolpropane.

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

>Polyether polyol> In the present invention, "polyether polyol" refers to, for example, a compound continuously having two or more hydroxyl groups and two or more repeating units containing an ether bond. The polyether polyol may be used alone or in combination of two or more.

In one embodiment, the polyether polyol is represented by the following structural formula: HO-(R ^Ether -O-) _n H where R ^Ether is alkylene, cycloalkylene, arylene, or arylalkylene Base aryl group, n is an integer of 2 or more.

Examples of the alkylene extension include linear alkylene extension, branched alkylene extension, and the like.

The linear alkylene group can be represented by the structural formula -(CH ₂ ) _n- (n is an integer of 1 or more). Examples of straight-chain alkylene include methylene, ethylidene, propylidene, n-butylidene, n-pentylidene, n-hexylidene, n-heptylidene, n-octylidene, n-nonylidene, and n-decylmethylene ( n-decamethylene) etc.

A branched alkylene group is a group in which at least one hydrogen of a linear alkylene group is substituted with an alkyl group. Examples of branched alkylene include diethylpentyl, trimethylbutyl, trimethylpentyl, trimethylhexyl, and the like.

Examples of the cycloalkylene include monocyclic cycloalkylene, bridged cycloalkylene, and condensed cycloalkylene. In addition, one or more hydrogens of the cycloalkylene group may be substituted with a linear or branched alkyl group.

In the present invention, a single ring means a ring structure formed by carbon covalent bonds and having no bridge structure inside. In addition, a fused ring means a cyclic structure in which two or more single rings share two atoms (that is, only one side of each ring is shared (condensed) with each other). A bridged ring means a ring structure in which more than 2 single rings share 3 or more atoms.

Examples of the monocyclic cycloalkylene include cyclopentyl, cyclohexyl, cycloheptyl, cyclodecyl, 3,5,5-trimethylcyclohexyl, and the like.

Examples of the bridged cycloalkylene include tricyclodecyl, adamantyl, norbornyl and the like.

Examples of the fused ring cycloalkylene include bicyclodecyl and the like.

Examples of arylene groups include phenylene groups, naphthyl groups, and fluorenyl groups.

Arylalkylene The ^{alkylenearylene} group is a group represented by the following formula: -R ^arylene -R ^alkylene -R ^arylene -where R ^arylene represents an arylene group and R ^alkylene represents an ^alkylene group.

Examples of the arylene group and the arylene group are phenyldimethylene and phenylene.

Examples of polyether polyols include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and alkylene oxide adducts of polyols.

(Alkylene oxide adduct of polyol) The alkylene oxide adduct of polyhydric alcohol may be used alone or in combination of two or more. Examples of the alkylene oxide adducts of polyhydric alcohols include alkylene oxide adducts of alkylene glycols and alkylene oxide adducts of alkylene triols.

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

Examples of the alkylene oxide adducts include ethylene oxide adducts and propylene oxide adducts.

>Polyester polyol> In the present invention, “polyester polyol” refers to, for example, a compound having two or more hydroxyl groups and two or more repeating units containing an ester bond continuously. The polyester polyol may be used alone, or two or more kinds may be used in combination. In addition, polycaprolactone polyol is a 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 where R ^aEster , R ^bEster and R ^cEster are each independently alkylene or cycloalkylene, and m is an integer of 2 or more.

The polyester polyol exemplifies a reaction product of a polycarboxylic acid or its anhydride and a polyol.

Examples of polycarboxylic acids include dicarboxylic acids.

Examples of dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 2-methylsuccinic acid Acid, 2-methyladipic acid, 3-methyladipic acid, 3-methylglutaric acid, 2-methyl suberic acid, 3,8-dimethyl sebacic acid, 3,7-di Dicarboxylic acids such as methyl sebacic acid, phthalic acid, terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid and cyclohexane dicarboxylic acid.

Examples of polycarboxylic acid anhydrides include acetic anhydride, propionic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride, and the like.

The polyol is exemplified by the above-mentioned alkylene polyol and the like.

>Polycarbonate polyol> In the present invention, "polycarbonate polyol" refers to, for example, a compound having two or more hydroxyl groups and two or more repeating units containing a carbonate bond. The polycarbonate polyol may be used alone or in combination of two 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 (wherein, R ^aCarbo and R ^bCarbo are each independently extended Alkyl or cycloalkyl, p is an integer of 2 or more).

Examples of the polycarbonate polyol include a reactant of a polyol and phosgene, a ring-opening polymer of a cyclic carbonate (alkylene carbonate, etc.), and the like.

The polyol is exemplified by the above-mentioned alkylene polyol and the like.

Examples of alkylene carbonate include ethylidene 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 exemplified by 15% by mass, 14% by mass, 13% by mass, 11% by mass, 10% by mass, 9% by mass, 7% by mass, and 5% by mass. , 4% by mass, 3% by mass, 2% by mass, etc.; the lower limit is exemplified by 14% by mass, 13% by mass, 11% by mass, 10% by mass, 9% by mass, 7% by mass, 5% by mass, 4% by mass, 3% by mass, 2% by mass, 1% by mass, etc. In one embodiment, the content of the component (A) in the thermosetting coating agent is preferably 1% by mass to 15% by mass.

>Carbamate polyol (B): also known as (B) component> In one embodiment, the urethane polyol is a reactant of polyol and polyisocyanate.

(Polyol) Examples of polyols include alkylene polyols, polymer polyols, and the like.

The alkylene polyol may be used alone or in combination of two or more. The alkylene polyol exemplifies the above-mentioned substances and the like.

The upper limit of the content of the structural unit derived from the alkylene 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, and 15 Mass %, etc.; the lower limit is exemplified by 25 mass %, 20 mass %, 15 mass %, 10 mass %, etc. In one embodiment, the content of the structural unit derived from the alkylene polyol is preferably 10 to 30% by mass relative to 100% by mass of the structural unit derived from the polyol of the urethane polyol.

The polymer polyol may be used alone or in combination of two or more. Examples of polymer polyols include polyether polyols, polyester polyols, polycarbonate polyols, and the like.

In addition, the structural units of the polyether polyol, polyester polyol, and polycarbonate polyol are exemplified by the aforementioned structural units and the like.

The upper limit of the content of the structural unit derived from the polymer polyol relative 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, and 15% by mass %, etc.; the lower limit exemplifies 25% by mass, 20% by mass, 15% by mass, 10% by mass, etc. In one embodiment, the content of the structural unit derived from the polymer polyol is preferably 10 to 30% by mass relative to 100% by mass of the structural unit derived from the polyol in 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% by mass, 65% by mass, 60% by mass, 55% by mass, 50% by mass, 45% by mass, and 40% by mass Etc.; the lower limit exemplifies 65% by mass, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass, etc. In one embodiment, the urethane polyol (B) contains 35 to 70% by mass of structural units 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 exemplified by 2000, 1900, 1750, 1500, 1250, 1000, 900, 750, 600, etc.; the lower limit is exemplified 1900, 1750, 1500, 1250, 1000, 900, 750, 600, 500, etc. are shown. 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, etc.; the lower limit is exemplified 1900, 1750, 1500, 1250, 1000, 900, 750, 600, 500, etc. are shown. 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 obtained as polystyrene conversion values measured by gel permeation chromatography (GPC) under 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, etc.; the lower limit is 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 99% by mass, 95% by mass, 90% by mass, 80% by mass, 70% by mass with respect to 100% by mass of all the structural units of the urethane polyol. 60% by mass, 55% by mass, etc.; the lower limit is exemplified by 95% by mass, 90% by mass, 80% by mass, 70% by mass, 60% by mass, 55% by mass, 50% by mass, etc. In one embodiment, the content of the structural unit derived from the polyol is preferably 50% to 99% by mass relative to 100% by mass of all the structural units of the urethane polyol.

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

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

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

Examples of the aliphatic polyisocyanate include linear aliphatic polyisocyanate, branched aliphatic polyisocyanate, and alicyclic polyisocyanate.

Examples of the straight-chain aliphatic group include the straight-chain alkylene groups described above.

Examples of linear aliphatic polyisocyanates include methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, and hepta Methylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, etc.

The branched aliphatic group is exemplified by the aforementioned branched alkylene group and the like.

Examples of the branched aliphatic polyisocyanate include diethylpentyl diisocyanate, trimethylpentyl diisocyanate, trimethylpentyl diisocyanate, trimethylhexamethylene diisocyanate, and the like.

The alicyclic group is exemplified by the above-mentioned monocyclic cycloalkylene, bridged cycloalkylene, condensed cycloalkylene and the like.

Examples of the alicyclic polyisocyanate include monocyclic cycloalkyl polyisocyanate, bridged cycloalkyl polyisocyanate, condensed ring cycloalkyl polyisocyanate, and the like.

Examples of monocyclic cycloalkylated polyisocyanates include hydrogenated xylene diisocyanate, isophorone diisocyanate, cyclopentyl diisocyanate, cyclohexyl diisocyanate, cycloheptyl diisocyanate, cyclodecyl diisocyanate , 3,5,5-trimethylcyclohexyl diisocyanate, dicyclohexylmethane diisocyanate, etc.

Examples of the bridged cycloalkyl polyisocyanate include tricyclodecyl diisocyanate, adamantane diisocyanate, norbornene diisocyanate, and the like.

Examples of the fused ring cycloalkyl polyisocyanate include bicyclodecyl diisocyanate.

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

The aromatic group is exemplified by the above-mentioned arylene group, arylene group, alkylene group, etc.

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

The upper limit of the content of the structural unit derived from polyisocyanate is 50% by mass, 45% by mass, 40% by mass, 30% by mass, 20% by mass with respect to 100% by mass of all the structural units of the urethane polyol. 15% by mass, etc.; the lower limit is exemplified by 45% by mass, 40% by mass, 30% by mass, 20% by mass, 15% by mass, 10% by mass, etc. In one embodiment, the content of the structural unit derived from polyisocyanate is preferably 10% by mass to 50% by mass relative to 100% by mass of all the structural units of the urethane polyol.

The upper limit of the mass ratio of structural units derived from alkylene polyol to structural units derived from polyisocyanate (structural units derived from alkylene polyol/structural units derived from polyisocyanate) in the urethane polyol is exemplified 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.; examples of the lower limit are 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 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 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, etc.; examples of the lower limit are 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 It is preferably 0.2 to 3.

(Other monomers) The urethane polyol described above may contain structural units derived from monomers (also referred to as other monomers) that are neither polymer polyols, nor alkylene polyols, nor polyisocyanates.

Examples of other monomers include arylene polyol and the like.

In one embodiment, with respect to 100% by mass of all structural units of the urethane polyol, the content of structural units derived from other monomers is exemplified by less than 5% by mass, less than 1% by mass, and less than 0.9% by mass. Less than 0.5% by mass, less than 0.1% by mass, 0% by mass, etc.

In one embodiment, the content of structural units from other monomers is less than 5 mol%, less than 1 mol%, and less than 0.9 relative to 100 mol% of all structural units of the urethane polyol. Molar %, less than 0.5 Molar%, less than 0.1 Molar%, 0 Molar%, etc.

>Physical properties of carbamate polyols, etc.> The upper limit of the acid value of the carbamate polyol is exemplified by 1 mgKOH/g, 0.9 mgKOH/g, 0.7 mgKOH/g, 0.5 mgKOH/g, 0.3 mgKOH/g, 0.1 mgKOH/g, etc.; the lower limit is 0.9 mgKOH/g, 0.7mgKOH/g, 0.5mgKOH/g, 0.3mgKOH/g, 0.1mgKOH/g, 0mgKOH/g, etc. In one embodiment, the acid value of the carbamate polyol is preferably 0 mgKOH/g to 1 mgKOH/g.

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

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

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

The upper limit of the weight average molecular weight (Mw) of the urethane polyol is exemplified by 80000, 75000, 70000, 60000, 55000, etc.; the lower limit is exemplified by 75000, 70000, 60000, 55000, 50,000, etc. In one embodiment, the weight average molecular weight (Mw) of the urethane polyol is more preferably about 50,000 to 80,000.

The upper limit of the number average molecular weight (Mn) of the carbamate polyol is exemplified by 30000, 25000, 20,000, 15000, etc.; the lower limit is exemplified by 25000, 20,000, 15000, 10000, etc. In one embodiment, the number average molecular weight (Mn) of the urethane polyol is more preferably about 10,000 to 30,000.

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 limit is exemplified by 3.5, 3.0, 2.0, 1.5, 1.0, etc. In one embodiment, the molecular weight distribution (Mw/Mn) of the urethane polyol is preferably 1.0 to 4.0.

The urethane polyol can be produced by various well-known methods for reacting the polyol and the polyisocyanate. Examples of the organic solvent used when manufacturing the urethane polyol are the solvents described below.

The upper limit of the content of the urethane polyol in the above coating agent is exemplified by 30% by mass, 25% by mass, 20% by mass, 15% by mass, 10% by mass, etc.; the lower limit is illustrated by 25% by mass, 20% by mass %, 15% by mass, 10% by mass, 5% by mass, etc. In one embodiment, the content of the urethane polyol in the coating agent is preferably 5% by mass to 30% by mass.

The upper limit of the content ratio of (A) component in the coating agent to the mass of urethane polyol ((A) component/urethane polyol) is exemplified by 3, 2.9, 2.5, 2, 1.5 , 1, 0.9, 0.5, 0.1, 0.09, 0.05, etc.; the lower limit is 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 above-mentioned quality is relatively preferably 0.03 to 3.

>Hydroxy-containing silicone modified resin (C): also known as (C) component> In the present invention, the "hydroxyl group-containing silicone-modified resin" means, for example, a resin having a hydroxyl group-containing silicone portion.

The hydroxyl group-containing silicone-modified resin may be used alone or in combination of two or more. Examples of hydroxyl-containing silicone-modified resins include hydroxyl-containing silicone-modified acrylic resins, hydroxyl-containing silicone-modified polyester resins, hydroxyl-containing silicone-modified polyether resins, and hydroxyl-containing silicone-modified silicone resins. Quality methanol resin, etc. In addition, the resin portion may be introduced into any one of the one end, both ends, and the side chain of the silicone chain.

Examples of commercial products of hydroxyl-modified silicone-modified acrylic resin include ZX-028-G (manufactured by T&K TOKA Co., Ltd.), BYK-SILCLEAN3700 (manufactured by BYK Japan Co., Ltd.), and SYMAC US-270 (East Asia Synthesizer) Co., Ltd.) etc.

Examples of commercially available products of hydroxyl-containing silicone-modified polyester resin or hydroxyl-containing silicone-modified polyether resin are BYK-370, BYK-375, BYK-377, and BYK-SILCLEAN3720 (manufactured by BYK Japan Co., Ltd.) ); X-22-4952, KF-6123 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), etc.

Examples of commercially available products of hydroxyl-containing silicone-modified methanol resin are 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 Industry Co., Ltd.); Silaplane FM-4411, Silaplane FM-4421, Silaplane FM- 4425, Silaplane FM-0411, Silaplane FM-0421, Silaplane FM-DA11, Silaplane FM-DA21, Silaplane FM-DA21, Silaplane FM-DA26 (manufactured by JNC Corporation), etc.

The upper limit of the content of the hydroxyl group-containing silicone modified resin in the coating agent is exemplified by 3.0% by mass, 2.5% by mass, 2.0% by mass, 1.5% by mass, 1.0% by mass, etc.; the lower limit is exemplified by 2.5% by mass, 2.0 Mass%, 1.5 mass%, 1.0 mass%, 0.5 mass%, etc. In one embodiment, the content of the hydroxyl-containing silicone modified resin in the coating agent is preferably 0.5% by mass to 3.0% by mass.

The upper limit of the content ratio of (A) component in the coating agent to the hydroxyl-containing silicone modified resin ((A) component/hydroxy-containing silicone modified resin) is exemplified by 30, 29, 25, 20 , 19, 17, 15, 13, 10, 9, 7, 5, 3, etc.; the lower limit is exemplified by 29, 25, 20, 19, 17, 15, 13, 10, 9, 7, 5, 3, 2, etc. . In one embodiment, the above-mentioned quality is preferably 2-30.

The upper limit of the mass ratio of the urethane polyol to the hydroxyl-containing silicone-modified resin in the above coating agent (urethane polyol/hydroxy-containing silicone-modified resin) is exemplified by 60, 59 , 50, 40, 30, 20, 10, 9, 5, 4, 2, etc.; the lower limit is 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-containing silicone-modified resin in the coating agent (urethane polyol/hydroxy-containing silicone-modified resin) is preferred It is 1～60.

> Allophanate form of polyisocyanate (D): also known as (D) component> The allophanate form of polyisocyanate may be used alone or in combination of two or more. When manufacturing the allophanate form of polyisocyanate, the polyisocyanate may be used alone or in combination of two or more. The polyisocyanate exemplifies the above-mentioned substances and the like.

式中，n^a 為0以上的整數；R^aA 為烷基或芳基；R^aB ～R^aG 各自獨立地為伸烷基或伸芳基；R^aα ～R^aγ 各自獨立地為異氰酸酯基或下述基。就每個結構單元各自而言，R^aB ～R^aE 、R^aα ～R^aβ 的基團也可以不同。

n^a1 為0以上的整數；R^a1 ～R^a6 各自獨立地為伸烷基或伸芳基；R^a ’～R^a ’’’各自獨立地為異氰酸酯基或R^aα ～R^aγ 自身的基團。就每個結構單元各自而言，R^a1 ～R^a4 、R^a ’～R^a ’’的基團也可以不同。The allophanate form of polyisocyanate exemplifies compounds represented by the following structural formulas, etc.:

In the formula, n ^a is an integer of 0 or more; R ^aA is an alkyl group or an aryl group; R ^aB to R ^aG are each independently an alkylene or aryl group; R ^aα to R ^aγ are each independently an isocyanate group or the following述基。 The base. For each on each structural ^{unit, R aB ~ R aE, R} aα ~ R aβ groups may be different.

n ^a1 is an integer of 0 or more; R ^a1 to R ^a6 are each independently an alkylene or aryl group; R ^a ′ to R ^{a ″} are each independently an isocyanate group or a group of R ^aα to R ^aγ itself . For each on each structural ^{unit, R a1 ~ R a4, R} a '~ R a'' groups may be different.

Examples of commercial products in the allophanate form of polyisocyanates include TAKENATE D-178NL (manufactured by Mitsui Chemicals Co., Ltd.), CORONATE 2770 (manufactured by Tosoh Corporation), CORONATE 2793 (manufactured by Tosoh Corporation) , DURANATE A201H (manufactured by Asahi Kasei Corporation), etc.

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

The upper limit of the number average molecular weight (Mn) of the allophanate form of polyisocyanate is exemplified by 3000, 2900, 2750, 2500, 2250, 2000, 1750, 1500, 1250, 1000, 900, 800, etc.; the lower limit is exemplified by 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 700-3000.

The upper limit of the molecular weight distribution (Mw/Mn) of the allophanate form of polyisocyanate is exemplified by 1.5, 1.4, 1.3, 1.2, 1.1, etc.; the lower limit is 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 1.0 to 1.5.

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

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

The upper limit of the mass ratio of the content of (A) component in the above coating agent to the allophanate form of polyisocyanate ((A) component/allophanate form of polyisocyanate) is exemplified by 15, 13, 10 , 9, 5, 4, 1, 0.9, 0.5, 0.1, 0.09, 0.05, 0.02, etc.; examples of lower limits are 13, 10, 9, 5, 4, 1, 0.9, 0.5, 0.1, 0.09, 0.05, 0.02, 0.01 etc. In one embodiment, the above-mentioned quality is preferably 0.01 to 15.

The upper limit of the mass ratio of the carbamate polyol to the polyisocyanate in the allophanate form of the above coating agent (carbamate polyol/polyisocyanate in the allophanate form) is exemplified by 30 , 29, 25, 20, 19, 15, 10, 9, 5, 4, 1, 0.9, 0.5, 0.1, 0.09, etc.; examples of lower limits are 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 carbamate polyol to the allophanate form of the polyisocyanate in the above coating agent (carbamate polyol/polyisocyanate allophanate form) Preferably it is 0.05-30.

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

>The biuret form of polyisocyanate (E1): also known as (E1) ingredient> The biuret form of polyisocyanate may be used alone or in combination of two or more. When manufacturing the biuret form of polyisocyanate, the polyisocyanate may be used alone or in combination of two or more. The polyisocyanate exemplifies the above-mentioned substances and the like.

式中，n^b 為1以上的整數；R^bA ～R^bE 各自獨立地為伸烷基或伸芳基；R^bα ～R^bβ 各自獨立地為異氰酸酯基或下述基。就每個結構單元各自而言，R^bD ～R^bE 、R^bβ 的基團也可以不同。

n^b1 為0以上的整數；R^b1 ～R^b5 各自獨立地為伸烷基或伸芳基；R^b ’～R^b ’’各自獨立地為異氰酸酯基或R^bα ～R^bβ 自身的基團。就每個結構單元各自而言，R^b4 ～R^b5 、R^b ’’的基團也可以不同。The biuret form of polyisocyanate exemplifies compounds represented by the following structural formulas, etc.:

In the formula, n ^b is an integer of 1 or more; R ^bA to R ^bE are each independently an alkylene group or an aryl group; R ^bα to R ^bβ are each independently an isocyanate group or the following group. For each structural unit, the groups of R ^bD to R ^bE and R ^bβ may be different.

n ^b1 is an integer of 0 or more; R ^b1 to R ^b5 are each independently an alkylene or aryl group; R ^b ′ to R ^{b ″} are each independently an isocyanate group or a group of R ^bα to R ^bβ itself. For each structural unit, the groups of R ^b4 to R ^b5 and R ^{b ″} may be different.

Examples of commercially available products in the form of polyisocyanates in biuret include DURANATE 24A-100, DURANATE 22A-75P, DURANATE 21S-75E (above manufactured by Asahi Kasei Co., Ltd.); Desmodur N3200A (diethylene hexamethylene diisocyanate Urea form) (above manufactured by Sumitomo Bayer Urethane Co., Ltd.), etc.

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 limit is exemplified by 1400, 1250, 1100, 1000, 900, 750, 600, 500, etc. In one embodiment, the weight average molecular weight (Mw) of the polyisocyanate in biuret form is preferably 500 to 1500.

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

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

The upper limit of the NCO content rate (NCO%) of the biuret form of polyisocyanate is exemplified by 30% by mass, 25% by mass, 20% by mass, 15% by mass, 10% by mass, etc.; the lower limit is illustrated by 25% by mass, 20 Mass%, 15 mass%, 10 mass%, 5 mass%, etc. In one embodiment, the NCO content (NCO%) of the polyisocyanate in biuret form 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% by mass, 95% by mass, 93.5% by mass, 90% by mass, 85% by mass, 80% by mass, 75% by mass, and 70% by mass , 65% by mass, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 15% by mass, 10% by mass, 5% by mass Mass%, 2 mass%, 1 mass%, etc.; the lower limit exemplifies 95 mass%, 93.5 mass%, 90 mass%, 85% mass, 80 mass%, 75 mass%, 70 mass%, 65 mass%, 60 mass %, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 15% by mass, 10% by mass, 5% by mass, 2% by mass, 1% by mass, 0% by mass, etc. In one embodiment, the content of the polyisocyanate in the biuret form of 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 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 shows 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 above-mentioned quality is preferably 0 to 99.

The upper limit of the mass ratio of the content of the polyisocyanate biuret form of the coating agent to (A) component (polyisocyanate biuret form/(A) component) 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 above-mentioned quality is preferably 0 to 99.

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

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

>Isocyanurate form of polyisocyanate (E2): also known as (E2) ingredient> The isocyanurate form of polyisocyanate may be used alone or in combination of two or more. When producing the isocyanurate form of the polyisocyanate, the polyisocyanate may be used alone, or two or more kinds may be used in combination. The polyisocyanate exemplifies the above-mentioned substances and the like.

式中，nⁱ 為0以上的整數；R^iA ～R^iE 各自獨立地為伸烷基或伸芳基；R^iα ～R^iβ 各自獨立地為異氰酸酯基或下述基。就每個結構單元各自而言，R^iD ～R^iE 、R^iβ 的基團也可以不同。

nⁱ¹ 為0以上的整數；Rⁱ¹ ～Rⁱ⁵ 各自獨立地為伸烷基或伸芳基；Rⁱ ’～Rⁱ ’’各自獨立地為異氰酸酯基或R^iα ～R^iβ 自身的基團。就每個結構單元各自而言，Rⁱ⁵ 、Rⁱ ’’的基團也可以不同。The isocyanurate form of the polyisocyanate exemplifies compounds represented by the following structural formulas, etc.:

In the formula, n ⁱ is an integer of 0 or more; R ^iA to R ^iE are each independently an alkylene group or an aryl group; R ^iα to R ^iβ are each independently an isocyanate group or the following group. The groups of R ^iD to R ^iE and R ^iβ may be different for each structural unit.

n ⁱ¹ is an integer of 0 or more; R ⁱ¹ to R ⁱ⁵ are each independently an alkylene group or an aryl group; R ⁱ ′ to R ^{i ″} are each independently an isocyanate group or a group of R ^iα to R ^iβ itself. For each structural unit, the groups of R ⁱ⁵ and R ^{i ″} may also be different.

Examples of commercially available products in isocyanurate form of polyisocyanate include DURANATE TPA-100, DURANATE TKA-100, DURANATE MFA-75B, DURANATE MHG-80B (above manufactured by Asahi Kasei Corporation); CORONATE HXR (Liuya Isocyanurate form of methyl diisocyanate (above manufactured by Tosoh Corporation); TAKENATE D-127N (isocyanurate form of hydrogenated xylene diisocyanate) (above manufactured by Mitsui Chemicals Co., Ltd.) ); VESTANAT T1890/100 (isocyanurate form of isophorone diisocyanate) (above manufactured by EVONIK Japan Co., Ltd.), etc.

The upper limit of the weight average molecular weight (Mw) of the isocyanurate form of polyisocyanate is exemplified by 1500, 1400, 1250, 1100, 1000, 900, 750, 600, etc.; the lower limit is exemplified by 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 limit is exemplified by 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 limit is 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 rate (NCO%) of the isocyanurate form of the polyisocyanate is exemplified by 30% by mass, 25% by mass, 20% by mass, 15% by mass, 10% by mass, etc.; the lower limit is illustrated by 25% by mass , 20% by mass, 15% by mass, 10% by mass, 5% by mass, etc. In one embodiment, the NCO content rate (NCO%) of the isocyanurate form of the polyisocyanate is preferably 5% by mass to 30% by mass.

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

The upper limit of the mass ratio of the isocyanurate form of the polyisocyanate to the content of (A) component (isocyanurate form of polyisocyanate/(A) component) in the above 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 shows 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 above-mentioned quality 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 the polyisocyanate/carbamate polyol) is exemplified by 20 , 19, 15, 10, 5, 2, 1, etc.; the lower limit exemplifies 19, 15, 10, 5, 2, 1, 0, etc. In one embodiment, the above-mentioned quality is preferably 0-20.

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

>hardening catalyst> In one embodiment, the coating agent may contain a hardening catalyst. The curing catalyst may be contained alone, or two or more kinds may be contained.

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

Examples of organometallic catalysts include organic main group metal catalysts, organic transition metal catalysts, and the like.

Examples of organic main group metal catalysts include organic tin catalysts, organic bismuth catalysts, and the like.

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

Examples of organic bismuth catalysts include bismuth octoate and the like.

Examples of organic transition metal catalysts include organic titanium catalysts, organic zirconium catalysts, organic iron catalysts, and the like.

Examples of organic titanium catalysts include ethyl acetoacetate and titanium.

Examples of organic zirconium catalysts include zirconium tetraacetone acetone and the like.

The organic iron catalyst is exemplified by acetoacetone iron and the like.

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

When the coating agent contains a hardening catalyst, the upper limit of the content of the hardening catalyst in the coating agent is exemplified by 1% by mass, 0.9% by mass, 0.75% by mass, 0.5% by mass, 0.25% by mass, 0.1% by mass, and 0.09 Mass%, 0.05 mass%, 0.02 mass%, etc.; the lower limit is exemplified by 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 %Wait. 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% by mass to 1% by mass.

>Organic solvents> In one embodiment, the coating agent may contain an organic solvent. The organic solvent may be contained alone, or two or more kinds may be contained. Examples of organic solvents include ketone solvents such as methyl ethyl ketone, acetone acetone, methyl isobutyl ketone and cyclohexanone; aromatic solvents such as toluene and xylene; methanol, ethanol, n-propanol, isopropanol and butyl alcohol Alcohol solvents such as alcohol; ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether and Glycol ether solvents such as propylene glycol monomethyl ether acetate; ester solvents such as ethyl acetate, butyl acetate, methyl cellosolve acetate and cellosolve acetate; SOLVESSO#100 and SOLVESSO#150 (both are Trade name, manufactured by Exxon Mobil Company) and other petroleum-based solvents; chloroform and other halogenated alkane solvents; dimethylformamide and other amide solvents. Among them, from the viewpoint of the pot life of the coating agent of the present invention, it is preferable to contain a ketone-based organic solvent, and it is preferable to contain acetone in the ketone-based organic solvent.

When the above coating agent contains an organic solvent, the upper limit of the content of the organic solvent in the above coating agent is exemplified by 90% by mass, 80% by mass, 70% by mass, 60% by mass, 55% by mass, etc.; the lower limit is exemplified by 85 mass%, 80 mass%, 70 mass%, 60 mass%, 55 mass%, 50 mass%, etc. 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. In addition, the organic solvent contained in the coating agent may include the hydroxyl group-containing silicone modified resin, the allophanate form of the polyisocyanate, and the organic solvent contained in the curing catalyst.

>Additives> The coating agent may contain reagents other than the aforementioned (A) component, (B) component, (C) component, (D) component, (E1) component, (E2) component, curing catalyst, and organic solvent as additives. Examples of additives include polymerization inhibitors, antioxidants, light stabilizers, defoamers, surface modifiers, pigments, antistatic agents, metal oxide fine particle dispersions, organic fine particle dispersions, and the like. In one embodiment, as an example of the additive content, the coating agent is exemplified by 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, about 0% by mass, etc. .

The coating agent may include (A) component, (B) component, (C) component, (D) component, (E1) component and/or (E2) component, and a hardening catalyst, if necessary, by various well-known means. The method of the step of mixing the organic solvent and/or additives is obtained.

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

[Hardened] The present invention provides a cured product of the coating agent. The conditions at the time of manufacturing the above-mentioned hardened material are exemplified below and the like.

[film] The present invention provides a film containing the above-mentioned cured product.

Various well-known base materials can be used for a base material. Examples of the substrate include polycarbonate film, acrylic film (polymethyl methacrylate film, etc.), polystyrene film, polyester film, polyolefin film, epoxy resin film, melamine resin film, triethyl cellulose Film, ABS film, acrylonitrile-styrene (AS) film, norbornene-based resin film, cycloolefin film, polyvinyl alcohol film, etc. The thickness of the substrate is not particularly limited, but is preferably about 50 μm to 200 μm. In addition, the thickness of the undercoat layer is not particularly limited, but is preferably about 0.1 μm to 5 μm.

The above-mentioned film can be manufactured by various well-known methods. In one embodiment, a method of manufacturing a thin film includes a step of applying the coating agent on at least one surface of a substrate (coating step); and a step of thermally curing to form a coating agent cured product layer (thermosetting step).

(Coating process) Examples of coating methods include bar coater coating, wire bar coating, Meyer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, and screen printing methods.

The coating amount is not particularly limited. The coating amount is preferably about 0.1 g/m ² to 30 g/m ² after drying, and more preferably about 1 g/m ² to 20 g/m ² .

(Thermosetting process) The drying method is exemplified by drying using a loop dryer or the like. Examples of drying conditions include standing at 120° C. for 30 seconds.

When manufacturing films, aging treatment is performed after drying as needed. Examples of the conditions of the aging treatment are 72 hours at 40°C and the like. [Example]

Hereinafter, the present invention will be specifically described through examples and comparative examples. However, the descriptions in the above preferred embodiments and the following examples are provided for the purpose of illustration only, and not for the purpose of limiting the present invention. Therefore, the scope of the present invention is not limited by the embodiments specifically described in this specification or the embodiments specifically described in this specification, and the scope of the present invention is only limited by the scope of the patent application. In addition, unless otherwise specified, in each Example and Comparative Example, the numerical value of parts, %, etc. is a mass basis.

Production of coating agent>Preparation of raw materials> [urethane polyol] [Resin A] Polyether polyol (trade name "PTMG650" is added to a reaction vessel equipped with a stirrer, thermometer, reflux condenser, and nitrogen introduction pipe) ": 100.0 parts made by Mitsubishi Chemical Co., Ltd., 23.0 parts of trimethylolpropane (hereinafter referred to as TMP), and 4,4'-methylene bis(cyclohexyl isocyanate) (trade name "VESTANAT H ₁₂ MDI": Made by EVONIK, hereinafter referred to as H ₁₂ MDI) 69.9 parts and methyl ethyl ketone 183.7 parts, the reaction system was set to 40°C. Then, 0.16 parts of a catalyst (trade name "NEOSTANN U-830": manufactured by Nitto Kasei Co., Ltd.) was added, and the temperature was kept at 75°C for 8 hours. Then, the reaction system was cooled to room temperature, thereby obtaining a solution of resin A having the physical properties described in Table 1 (nonvolatile content 50%).

The production of resins other than resin A is carried out in the same manner as the production of resin A except that the raw materials are changed to the raw materials described in the following table. In addition, the acid values of resin A to resin G are all 0 mgKOH/g.

PTMG650：三菱化學股份有限公司製造；聚四亞甲基二醇，數均分子量600～700，羥值160mgKOH/g～187mgKOH/g DURANOL T5650E：旭化成股份有限公司製造；聚碳酸酯多元醇，數均分子量500，羥值200mgKOH/g～250mgKOH/g PTMG1000：三菱化學股份有限公司製造；聚四亞甲基二醇，數均分子量950～1050，羥值107mgKOH/g～118mgKOH/g KURARAY POLYOL P-1010：KURARAY股份有限公司製造；聚酯多元醇（聚[(3-甲基-1,5-戊二醇)-alt-(己二酸)]），數均分子量1000[Table 1]

PTMG650: manufactured by Mitsubishi Chemical Corporation; polytetramethylene glycol, number average molecular weight 600 to 700, hydroxyl value 160 mgKOH/g to 187 mgKOH/g DURANOL T5650E: manufactured by Asahi Kasei Corporation; polycarbonate polyol, number average Molecular weight 500, hydroxyl value 200mgKOH/g～250mgKOH/g PTMG1000: manufactured by Mitsubishi Chemical Corporation; polytetramethylene glycol, number average molecular weight 950～1050, hydroxyl value 107mgKOH/g～118mgKOH/g KURARAY POLYOL P-1010 : Made by KURARAY Co., Ltd.; polyester polyol (poly[(3-methyl-1,5-pentanediol)-alt-(adipic acid)]), number average molecular weight 1000

>Preparation of thermosetting coating agent> Example 1 By thoroughly mixing 100 parts of Resin A, BYK-SILCLEAN 3700 (manufactured by BYK Japan Co., Ltd.; hydroxyl-containing acrylic modified silicone resin) (solid content concentration 25%) 5.7 parts, CORONATE 2793 (manufactured by Tosoh Co., Ltd.; VI) Allophanate form of methylene diisocyanate) (solid content concentration 100%) 40.7 parts, DURANATE 24A-100 (manufactured by Asahi Kasei Corporation; biuret form of hexamethylene diisocyanate) (solid content concentration 100%)) 28.6 parts, ADEKA POLYETHER GM-30 (made by ADEKA Corporation; ethylene oxide adduct of trimethylolpropane (solid content concentration 100%)) 25.0 parts, dioctyltin dilaurate (Concentration of solid content 100%; hereinafter referred to as DOTDL) 0.07 parts, methyl ethyl ketone (hereinafter referred to as MEK) 168.5 parts and acetone (hereinafter referred to as AcAc) 14.4 parts, to prepare a thermosetting solid content concentration of 38% Sexual coating agent.

The thermosetting coating agents of Examples and Comparative Examples other than Example 1 were prepared in the same manner as in Example 1 except that the component composition was changed as shown in the following table. In addition, the solid content concentration of the thermosetting coating agent was 38%.

BYK-SILCLEAN3700：（BYK Japan股份有限公司製造；含羥基的矽氧改質丙烯酸樹脂）（固體成分濃度25%） CORONATE 2793：東曹股份有限公司製造；六亞甲基二異氰酸酯的脲基甲酸酯形式（固體成分濃度100%） DURANATE 24A-100：旭化成股份有限公司製造；六亞甲基二異氰酸酯的縮二脲形式（固體成分濃度100%） DURANATE TPA100：旭化成股份有限公司製造；六亞甲基二異氰酸酯的異氰脲酸酯形式（固體成分濃度100%） CORONATE HL：東曹股份有限公司製造；六亞甲基二異氰酸酯的加成物形式（固體成分濃度75%） ADEKA POLYETHER GM-30：ADEKA股份有限公司製造；三羥甲基丙烷的環氧乙烷4加成物（固體成分濃度100%，羥值535mgKOH/g～565mgKOH/g，分子量300） 三羥甲基丙烷（羥值1254.38mgKOH/g、分子量134.17） 乙二醇（羥值1807.70mgKOH/g、分子量62.07） 1,4-丁二醇（羥值1245.01mgKOH/g、分子量90.12） DURANOL T5650E：旭化成股份有限公司製造；聚碳酸酯二醇（羥值200mgKOH/g～250mgKOH/g，數均分子量500） KURARAY POLYOL F-510：KURARAY股份有限公司製造；聚酯多元醇（固體成分濃度100%，羥值319.5mgKOH/g～352.5mgKOH/g，數均分子量500） PLACCEL 303：DAICEL股份有限公司製造；己内酯三醇（固體成分濃度100%，羥值530mgKOH/g～550mgKOH/g，分子量300） PLACCEL 305：DAICEL股份有限公司製造；己内酯三醇（固體成分濃度100%，羥值300mgKOH/g～310mgKOH/g，分子量500） PLACCEL 410：DAICEL股份有限公司製造；己内酯四醇（固體成分濃度100%，羥值216mgKOH/g～232mgKOH/g，分子量1000） PLACCEL 312：DAICEL股份有限公司製造；己内酯三醇（固體成分濃度100%，羥值130mgKOH/g～140mgKOH/g，分子量1250） PTMG650：三菱化學股份有限公司製造；聚四亞甲基二醇（羥值160mgKOH/g～187mgKOH/g，數均分子量600～700）[Table 2]

BYK-SILCLEAN3700: (manufactured by BYK Japan Co., Ltd.; silicone-modified acrylic resin containing hydroxyl groups) (solid content concentration 25%) CORONATE 2793: manufactured by Tosoh Co., Ltd.; urea formic acid of hexamethylene diisocyanate Ester form (solid content concentration 100%) DURANATE 24A-100: manufactured by Asahi Kasei Co., Ltd.; biuret form of hexamethylene diisocyanate (solid content concentration 100%) DURANATE TPA100: manufactured by Asahi Kasei Co., Ltd.; hexamethylene Isocyanurate form of diisocyanate (solid content concentration 100%) CORONATE HL: manufactured by Tosoh Corporation; adduct form of hexamethylene diisocyanate (solid content concentration 75%) ADEKA POLYETHER GM-30 : Made by ADEKA Corporation; ethylene oxide 4 adduct of trimethylolpropane (solid content concentration 100%, hydroxyl value 535mgKOH/g～565mgKOH/g, molecular weight 300) trimethylolpropane (hydroxyl value 1254.38 mgKOH/g, molecular weight 134.17) Ethylene glycol (hydroxyl value 1807.70 mgKOH/g, molecular weight 62.07) 1,4-butanediol (hydroxyl value 1245.01 mgKOH/g, molecular weight 90.12) DURANOL T5650E: manufactured by Asahi Kasei Corporation; polycarbonate Ester diol (hydroxyl value 200mgKOH/g～250mgKOH/g, number average molecular weight 500) KURARAY POLYOL F-510: manufactured by KURARAY Co., Ltd.; polyester polyol (solid content concentration 100%, hydroxyl value 319.5mgKOH/g～352.5 mgKOH/g, number average molecular weight 500) PLACCEL 303: manufactured by DAICEL Co., Ltd.; caprolactone triol (solid content concentration 100%, hydroxyl value 530mgKOH/g～550mgKOH/g, molecular weight 300) PLACCEL 305: DAICEL Co., Ltd. Manufacture; Caprolactone triol (solid content concentration 100%, hydroxyl value 300mgKOH/g～310mgKOH/g, molecular weight 500) PLACCEL 410: manufactured by DAICEL Co., Ltd.; Caprolactone tetraol (solid content concentration 100%, hydroxyl value 216mgKOH/g～232mgKOH/g, molecular weight 1000) PLACCEL 312: manufactured by DAICEL Co., Ltd.; caprolactone triol (solid content concentration 100%, hydroxyl value 130mgKOH/g～140mgKOH/g, molecular weight 1250) PTMG650: Mitsubishi Chemical Corporation Manufactured by a limited company; polytetramethylene glycol (hydroxyl value 160mgKOH/g～187mgKOH/g, number evenly divided Sub-weight 600～700)

>Fabrication of film> The coating agent was applied to a commercially available polyethylene terephthalate film (trade name COMOSHINE A4100, 100 μm thick) so that the coating film thickness after drying was 10 μm, and it was dried at 120° C. for 120 seconds. Heat hardened. Then, 40° C.×2 days aging was performed to produce a coating film.

>Self-healing properties of hardened objects> A brass brush was used to reciprocate 10 times on the film surface, and the time until the scratch disappeared was measured. ◎: Instant recovery ○: Recovery within 10 seconds △: Recovery within 1 minute ×: Do not restore

>Abrasion resistance of hardened products> Measure the haze value before and after the Taber abrasion test using the JIS K 7204 plastic-wear wheel wear test method (Muragami Color Technology Research Institute Co., Ltd., HM-150), and calculate the difference between the haze value before and after the test (ΔH ). The Taber wear test uses a Taber wear tester (manufactured by TESTER Industries Co., Ltd., AB-101 Taber wear tester) to rotate the wear wheel CS-10F 100 times under the conditions of a load of 500 g and a rotation speed of 60 rpm. ○: ΔH value is 1.0 to less than 2.4 △: ΔH value is above 2.4 to less than 10 ×: ΔH value is 10 or more

>Antifouling properties of hardened products> A blot was drawn on the film surface with an oily ink (manufactured by ASKUL Co., Ltd.; trade name PERMANENT MAKER), and the blot was evaluated by wiping the blot with a dry nonwoven fabric (manufactured by Asahi Kasei Co., Ltd.; trade name BEMCOT M-3II). The evaluation criteria are as follows. ○: Can be wiped off ×: Cannot be erased

>Elongation at break of hardened product> The elongation at break of the cured product alone was measured in accordance with the test conditions of JIS K 7204 Plastic-Tensile Properties Test Method. The shape of the cured product was 5 mm wide, 10 μm thick, and 25 mm long, and the test speed was 200 mm/min. Elongation at break (%)=100×(L-25)/25 L: length of the hardened material when the hardened material is broken ○: 150% or more △: 100%～149% ×: 99% or less

>Steel wool (SW) resistance> Press steel wool (#0000) on the surface of the film and reciprocate 10 times under a load of 500g to confirm whether there are scratches. ○: No scratches ×: There are scratches

[table 3]

Domestic storage information (please note in order of storage institution, date, number) no

Overseas hosting information (please note in order of hosting country, institution, date, number) no

Claims (5)

A thermosetting coating agent, the thermosetting coating agent contains: Polyol (A) with a hydroxyl value of 200 mgKOH/g or more and a molecular weight of 1000 or less; Carbamate polyol (B); hydroxyl-containing silicone modified resin (C); Allophanate form (D) of polyisocyanates; and, The biuret form (E1) and/or isocyanurate form (E2) of the polyisocyanate. The thermosetting coating agent according to claim 1, wherein the urethane polyol (B) contains 35 to 70% by mass of a structural unit derived from a polymer polyol. The thermosetting coating agent according to claim 1 or 2, wherein the thermosetting coating agent is a self-healing coating agent. A hardened product which is the cured product of the thermosetting coating agent according to any one of claims 1 to 3. A film containing the hardened product according to claim 4.