JP7151649B2 - Self-healing coating agents, cured products and films - Google Patents

Description

The present disclosure relates to self-healing coating agents, cured products and films.

Plastic substrates such as ABS and polycarbonate are used in various industrial products such as electronic devices and automobile parts. In order to protect such plastic substrates, surface treatment is performed with a coating agent. Among these coating agents, the self-repairing coating agents are preferred for protecting various substrates, since the resulting scratches disappear over time.

As a prior art related to these coating agents, for example, Patent Document 1, which discloses a coating agent containing a urethane (meth)acrylate resin (a), a fluorine compound (b), and a photopolymerization initiator (d), is known. It is

Japanese Patent No. 6241571

In Patent Document 1, it is described that the self-healing property and stain resistance are excellent, but it is possible to further improve the workability.

The problem to be solved by the present invention is to provide a self-healing coating agent for producing cured products and films with excellent workability, and to produce cured products and films with excellent transparency and good coating appearance. and to provide a self-repairing coating agent for producing cured products and films having antifouling properties.

As a result of intensive studies, the present inventors have found that the above problems can be solved by a self-repairing coating agent containing specific components.

The following items are provided by this disclosure.
(Item 1)
A self-healing coating agent comprising a hydroxyl group-containing (meth)acrylic resin, a hydroxyl group-containing silicone, a polyisocyanate and a polycarbonate polyol.
(Item 2)
The self-healing coating agent according to the above items, wherein the polyisocyanate contains two or more selected from a polyisocyanate adduct, a polyisocyanate allophanate, a polyisocyanate biuret, and a polyisocyanurate isocyanurate.
(Item 3)
3. The self-healing coating agent according to item 1 or 2 above, wherein the hydroxyl group-containing (meth)acrylic resin has a glass transition temperature of 40 to 100°C.
(Item 4)
4. The self-healing coating agent according to any one of items 1 to 3 above, wherein the polycarbonate polyol has a number average molecular weight of 800 to 1,000.
(Item 5)
When the total content of the hydroxyl group-containing (meth)acrylic resin, hydroxyl group-containing silicone, polyisocyanate and polycarbonate polyol is 100% by mass, the content of the hydroxyl group-containing (meth)acrylic resin is 30 to 70% by mass, and the hydroxyl group-containing silicone content of 1 to 10 mass%, polyisocyanate content of 10 to 50 mass%, and polycarbonate polyol content of 15 to 40 mass%. agent.
(Item 6)
A cured product of the self-healing coating agent according to any one of items 1 to 5 above.
(Item 7)
A film comprising the cured product according to Item 6 above.

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

By using the self-healing coating agent of the present invention, cured products and films with excellent workability and good elongation, cured products and films with excellent transparency and good coating appearance, and cured products with good antifouling properties. or film can be obtained.

Throughout the present disclosure, the range of numerical values for each physical property value, content, etc. can be set as appropriate (for example, by selecting from the upper and lower limit values described in each item below). Specifically, for the numerical value α, when the upper limit of the numerical value α is A1, A2, A3, etc., and the lower limit of the numerical value α is B1, B2, B3, etc., the range of the numerical value α is A1 or less, A2 or less, A3 or less, B1 or more, B2 or more, B3 or more, A1-B1, A1-B2, A1-B3, A2-B1, A2-B2, A2-B3, A3-B1, A3-B2, A3-B3 etc. are exemplified.

[Self-healing coating agent]
The present disclosure provides self-healing coating agents comprising hydroxyl-containing (meth)acrylic resins, hydroxyl-containing silicones, polyisocyanates and polycarbonate polyols.

<Hydroxyl group-containing (meth)acrylic resin>
The hydroxyl-containing (meth)acrylic resin is exemplified by a copolymer containing structural units derived from a hydroxyl-free alkyl (meth)acrylate and a structural unit derived from a hydroxyl-containing alkyl (meth)acrylate. The hydroxyl group-containing (meth)acrylic resin may be used alone or in combination of two or more.

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

(Hydroxyl group-free alkyl (meth) acrylate)
A hydroxyl group-free alkyl (meth)acrylate is represented by the following general formula.

（式中、
Ｒ^ａ１は水素原子、又はメチル基であり、
Ｒ^ａ２はアルキル基である。）

(In the formula,
R ^a1 is a hydrogen atom or a methyl group,
R ^a2 is an alkyl group. )

A hydroxyl group-free alkyl (meth)acrylate may be used alone or in combination of two or more.

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

A straight-chain alkyl group is represented by a general formula of -C _n H _2n+1 (n is an integer of 1 or more). Linear alkyl groups include methyl group, ethyl group, propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decamethyl group, etc. are exemplified.

A branched alkyl group is a group in which at least one hydrogen of a straight-chain alkyl group has been replaced by an alkyl group. Branched alkyl groups are exemplified by diethylpentyl, trimethylbutyl, trimethylpentyl, trimethylhexyl and the like.

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

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

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

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

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

Linear alkyl (meth)acrylates not containing hydroxyl groups include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, and hexyl (meth)acrylate. , heptyl (meth)acrylate, octyl (meth)acrylate, hexadecyl (meth)acrylate, dodecyl (meth)acrylate, octadecyl (meth)acrylate, icosyl (meth)acrylate, docosyl (meth)acrylate, etc. are exemplified.

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

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

In one embodiment, an alkyl (meth)acrylate having an alkyl group with about 1 to 20 carbon atoms is preferable because it contributes to the leveling property and adhesion of the self-healing coating agent. In addition, by using hydroxyl-free alkyl (meth)acrylates having different numbers of carbon atoms in the alkyl group, physical properties such as the glass transition temperature of the hydroxyl-containing (meth)acrylic resin can be adjusted.

In one embodiment, among hydroxyl group-free alkyl (meth)acrylates, methyl (meth)acrylate and (meth)acrylic acid are particularly useful because they contribute to the wear resistance, leveling properties, and adhesion of self-healing coating agents. Butyl acid is preferred.

The upper limit of the content of structural units derived from hydroxyl-free alkyl (meth)acrylate in 100 mol% of the total structural units of the hydroxyl-containing (meth)acrylic resin is 98, 95, 90, 85, 80, 75, 70, 65. Examples include mol % and the like, and the lower limit is exemplified by 95, 90, 85, 80, 75, 70, 65, 62 mol % and the like. In one embodiment, the content of structural units derived from hydroxyl-free alkyl (meth)acrylate in 100 mol% of all structural units of the hydroxyl-containing (meth)acrylic resin is preferably about 62 to 98 mol%.

The upper limit of the content of structural units derived from hydroxyl-free alkyl (meth)acrylates in 100% by mass of the total structural units of the hydroxyl-containing (meth)acrylic resin is 98, 95, 90, 85, 80, 75, 70% by mass. etc., and the lower limit is exemplified by 95, 90, 85, 80, 75, 70, 65% by mass. In one embodiment, the content of structural units derived from hydroxyl-free alkyl (meth)acrylate in 100% by mass of the total structural units of the hydroxyl-containing (meth)acrylic resin is preferably about 65 to 98% by mass.

(hydroxy group-containing alkyl (meth) acrylate)
A hydroxyl group-containing alkyl (meth)acrylate is represented by the following general formula.

（式中、
Ｒ^ａ３は水素原子、又はメチル基であり、
Ｒ^ａ４はアルキレン基である。）

(In the formula,
R ^a3 is a hydrogen atom or a methyl group,
R ^a4 is an alkylene group. )

Two or more kinds of hydroxyl group-containing alkyl (meth)acrylates may be used in combination.

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

Examples of hydroxyl group-containing alkyl (meth)acrylates include hydroxyl group-containing linear alkyl (meth)acrylates, branched hydroxyl group-containing alkyl (meth)acrylates, hydroxyl group-containing cycloalkyl (meth)acrylates, and the like.

Examples of hydroxyl group-containing linear alkyl (meth)acrylates include hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.

Examples of branched hydroxyl group-containing alkyl (meth)acrylates include 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 3-hydroxybutyl (meth)acrylate.

Examples of hydroxyl group-containing cycloalkyl (meth)acrylates include hydroxycyclohexyl (meth)acrylate and 4-(hydroxymethyl)cyclohexylmethyl (meth)acrylate.

The hydroxyl group-containing alkyl (meth)acrylate preferably has an alkyl group with about 1 to 4 carbon atoms from the viewpoint of curability and pot life of the self-repairing coating agent.

In one embodiment, among the hydroxyl group-containing alkyl (meth)acrylates, 2-hydroxyethyl (meth)acrylate is preferred from the viewpoint of the curability of the self-repairing coating agent, pot life, and the like.

The upper limit of the content of the structural unit derived from the hydroxyl group-containing alkyl (meth)acrylate in 100 mol% of the total structural units of the hydroxyl group-containing (meth)acrylic resin is 38, 35, 30, 25, 20, 15, 10, 5, Examples include 2.5 mol %, and the lower limits include 35, 30, 25, 20, 15, 10, 5, 2.5, 1.5 mol % and the like. In one embodiment, the content of the structural unit derived from the hydroxyl group-containing alkyl (meth)acrylate in 100 mol % of the total structural units of the hydroxyl group-containing (meth)acrylic resin is preferably in the range of about 1.5 to 38 mol %.

The upper limit of the content of the structural unit derived from the hydroxyl group-containing alkyl (meth)acrylate in 100% by mass of the total structural units of the hydroxyl group-containing (meth)acrylic resin is 35, 30, 25, 20, 15, 10, 5, 2. Examples include 5% by mass, and the lower limit is 30, 25, 20, 15, 10, 5, 2.5, 2% by mass, and the like. In one embodiment, the content of the structural unit derived from the hydroxyl group-containing alkyl (meth)acrylate in 100% by weight of the total structural units of the hydroxyl group-containing (meth)acrylic resin is preferably in the range of about 2 to 35% by weight.

Substance amount ratio of structural units derived from hydroxyl-free alkyl (meth)acrylate and hydroxyl-containing alkyl (meth)acrylate-derived structural units in hydroxyl-containing (meth)acrylic resin (hydroxyl-free alkyl (meth)acrylate _mol / hydroxyl group The upper limit of the content alkyl (meth)acrylate _mol ) is exemplified by 57, 50, 40, 30, 20, 10, 5, 2, etc., and the lower limit is 55, 50, 40, 30, 20, 10, 5, 2. , 1.6 and the like are exemplified. In one embodiment, the substance amount ratio of the structural unit derived from the hydroxyl-free alkyl (meth)acrylate and the structural unit derived from the hydroxyl-containing alkyl (meth)acrylate in the hydroxyl-containing (meth)acrylic resin (the hydroxyl-free alkyl ( The meth)acrylate _mol /hydroxyl group-containing alkyl (meth)acrylate _mol ) is preferably about 1.6 to 57, more preferably 5 to 15.

Mass ratio of structural units derived from hydroxyl-free alkyl (meth)acrylate to hydroxyl-containing alkyl (meth)acrylate-derived structural units in the hydroxyl-containing (meth)acrylic resin (hydroxyl-free alkyl (meth)acrylate _mass / hydroxyl-containing The upper limit of alkyl (meth)acrylate _mass ) is 49, 40, 30, 20, 10, 5, 2, etc., and the lower limit is 45, 40, 30, 20, 10, 5, 2, 1.8, etc. are exemplified. In one embodiment, the mass ratio of structural units derived from hydroxyl-free alkyl (meth)acrylate to hydroxyl-containing alkyl (meth)acrylate-derived structural units in the hydroxyl-containing (meth)acrylic resin (hydroxyl-free alkyl (meth) ) acrylate _mass /hydroxy group-containing alkyl (meth)acrylate _mass ) is preferably about 1.8 to 49, more preferably 5 to 15.

(Monomers other than hydroxyl-free alkyl (meth)acrylates and hydroxyl-containing alkyl (meth)acrylates: also referred to as other monomers)
When producing a hydroxyl group-containing (meth)acrylic resin, a monomer that does not fall under any of hydroxyl group-containing alkyl (meth)acrylates and hydroxyl group-containing alkyl (meth)acrylates may be used. Other monomers may be used in combination of two or more.

Other monomers include (meth)acrylic acid, α,β-unsaturated carboxylic acids, styrenes, α-olefins, unsaturated alcohols and their salts, dialkylaminoalkyl (meth)acrylamides and their salts, chain transfer Monomers, (meth)acrylonitrile, (meth)acrylamides, vinylamine, bis(meth)acrylamide, di(meth)acryl esters, divinyl esters, bifunctional monomers other than the above, trifunctional monomers, tetrafunctional monomers, etc. exemplified.

The upper limit of the content of other monomer-derived structural units in 100 mol% of the total structural units of the hydroxyl group-containing (meth)acrylic resin is exemplified by 13, 10, 9, 5, 4, 1 mol%, etc., and the lower limit is , 12, 10, 9, 5, 4, 1, 0 mol %, and the like. In one embodiment, the range of the content of structural units derived from other monomers in 100 mol % of the total structural units of the hydroxyl group-containing (meth)acrylic resin is preferably about 0 to 13 mol %.

The upper limit of the content of other monomer-derived structural units in 100% by mass of the total structural units of the hydroxyl group-containing (meth)acrylic resin is exemplified by 10, 9, 5, 4, 1% by mass, etc., and the lower limit is 9. , 5, 4, 1, 0% by mass, and the like. In one embodiment, the range of the content of structural units derived from other monomers in 100% by weight of the total structural units of the hydroxyl group-containing (meth)acrylic resin is preferably about 0 to 10% by weight.

Substance amount ratio of structural units derived from hydroxyl-free alkyl (meth)acrylate and structural units derived from other monomers in hydroxyl-containing (meth)acrylic resin (other monomer _mol /hydroxyl-free alkyl (meth)acrylate _mol ) The upper limit is exemplified by 0.22, 0.20, 0.15, 0.10, 0.05, etc., and the lower limit is 0.20, 0.15, 0.10, 0.05, 0, etc. exemplified. In one embodiment, the substance amount ratio of structural units derived from hydroxyl-free alkyl (meth)acrylate and structural units derived from other monomers in the hydroxyl-containing (meth)acrylic resin (other monomer _mol / hydroxyl-free alkyl (Meth)acrylate _mol ) is preferably about 0 to 0.22.

Mass ratio of structural units derived from hydroxyl-free alkyl (meth)acrylates and structural units derived from other monomers in the hydroxyl-containing (meth)acrylic resin ( _mass of other monomers/ _mass of hydroxyl-free alkyl (meth)acrylates) The upper limit is exemplified by 0.19, 0.15, 0.10, 0.05, etc., and the lower limit is exemplified by 0.15, 0.10, 0.05, 0, etc. In one embodiment, the mass ratio of structural units derived from hydroxyl-free alkyl (meth)acrylate and structural units derived from other monomers in the hydroxyl-containing (meth)acrylic resin (other monomer _mass / hydroxyl-free alkyl ( Meth) acrylate _mass ) is preferably about 0 to 0.19.

Upper limit of the substance amount ratio of the structural unit derived from the hydroxyl group-containing alkyl (meth)acrylate and the structural unit derived from the other monomer in the hydroxyl group-containing (meth)acrylic resin (other monomer _mol /hydroxyl group-containing alkyl (meth)acrylate _mol ) is exemplified by 8.0, 7.0, 6.0, 5.0, 4.0, 3.0, 2.0, 1.0, 0.5, etc., and the lower limit is 7.5, 7 .0, 6.0, 5.0, 4.0, 3.0, 2.0, 1.0, 0.5, 0 and the like are exemplified. In one embodiment, the substance amount ratio of the structural unit derived from the hydroxyl group-containing alkyl (meth)acrylate and the structural unit derived from the other monomer in the hydroxyl group-containing (meth)acrylic resin (other monomer _mol / hydroxyl group-containing alkyl (meth) ) acrylate _mol ) is preferably about 0 to 8.0.

The upper limit of the mass ratio of structural units derived from hydroxyl group-containing alkyl (meth)acrylates and structural units derived from other monomers in the hydroxyl group-containing (meth)acrylic resin (other monomer _mass / hydroxyl group-containing alkyl (meth)acrylate _mass ) is , 5.0, 4.0, 3.0, 2.0, 1.0, 0.5, etc. are exemplified, and the lower limits are 4.5, 4.0, 3.0, 2.0, 1.0. Examples include 0, 0.5, 0, and the like. In one embodiment, the mass ratio of structural units derived from hydroxyl group-containing alkyl (meth) acrylate and structural units derived from other monomers in the hydroxyl group-containing (meth) acrylic resin (other monomer _mass / hydroxyl group-containing alkyl (meth) Acrylate _mass ) is preferably about 0 to 5.0.

In one embodiment, the hydroxyl-containing (meth)acrylic resin is preferably a resin containing a hydroxyl-containing monomer and a hydroxyl-free monomer from the viewpoint of self-repairability and antifouling properties, and contains a hydroxyl-containing monomer. Resin is more preferred. In one embodiment, the hydroxyl group-containing (meth)acrylic resin contains one or more selected from methyl (meth)acrylate and butyl (meth)acrylate and 2-hydroxyethyl (meth)acrylate. Resin is preferred.

<Physical properties of hydroxyl group-containing (meth)acrylic resin>
The upper limit of the glass transition temperature of the hydroxyl group-containing (meth)acrylic resin is exemplified by 100, 90, 80, 70, 60°C, etc., and the lower limit is exemplified by 90, 80, 70, 60, 50, 40°C, etc. . In one embodiment, the hydroxyl group-containing (meth)acrylic resin preferably has a glass transition temperature of 40 to 100° C. from the viewpoint of excellent workability of the film or cured product. In one embodiment, the glass transition temperature of the hydroxyl group-containing (meth)acrylic resin is preferably 40 to 90° C., preferably 40 to 80, from the viewpoint that the film or cured product is particularly excellent in both self-healing property and workability. C. is more preferred, 40 to 70.degree. C. is even more preferred, 50 to 70.degree. C. is particularly preferred, and 50 to 60.degree.

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

The upper limit of the hydroxyl group equivalent of the hydroxyl group-containing (meth)acrylic resin is exemplified by 2.7, 2.5, 2.0, 1.8, 1.5, 1.0, 0.5, 0.25 meq/g. The lower limit is exemplified by 2.5, 2.0, 1.8, 1.5, 1.0, 0.5, 0.25, 0.17 meq/g. In one embodiment, the hydroxyl group equivalent of the hydroxyl group-containing (meth)acrylic resin is preferably about 0.17 to 2.7 meq/g, more preferably about 0.5 to 1.8 meq/g.

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

The upper limit of the hydroxyl value (in terms of solid content) of the hydroxyl-containing (meth)acrylic resin is 150, 140, 130, 120, 110, 100, 90, 80, 70, 60, 50, 40, 30, 20, 15 mgKOH/g. etc., and the lower limit is exemplified by 140, 130, 120, 110, 100, 90, 80, 70, 60, 50, 40, 30, 20, 15, 10 mgKOH/g. In one embodiment, the hydroxyl value (in terms of solid content) of the hydroxyl-containing (meth)acrylic resin is preferably about 10 to 150 mgKOH/g, more preferably 40 to 100 mgKOH/g, and even more preferably 40 to 90 mgKOH/g. 40-80 mg KOH/g is particularly preferred, 40-70 mg KOH/g is even more preferred, and 40-60 mg KOH/g is most preferred.

The hydroxyl value is measured by the acetylation method according to JIS K1557-1.

The upper limit of the weight average molecular weight (Mw) of the hydroxyl group-containing (meth)acrylic resin is exemplified by 100000, 90000, 80000, 70000, 60000, 50000, 40000, 30000, 20000, 10000, 5000, 4000, etc., and the lower limit is 90000. , 80000, 70000, 60000, 50000, 40000, 30000, 20000, 10000, 5000, 4000, 3000, and the like. In one embodiment, the weight average molecular weight (Mw) of the hydroxyl group-containing (meth)acrylic resin is about 3000 to 100000 from the viewpoint of blocking resistance, initial adhesion, and wet heat resistance adhesion of the self-healing coating agent. It is preferable, and about 10,000 to 80,000 is more preferable.

The upper limit of the number average molecular weight (Mn) of the hydroxyl group-containing (meth)acrylic resin is exemplified by 100000, 90000, 80000, 70000, 60000, 50000, 40000, 30000, 20000, 10000, 5000, 4000, etc., and the lower limit is 90000. , 80000, 70000, 60000, 50000, 40000, 30000, 20000, 10000, 5000, 4000, 3000, and the like. In one embodiment, the number average molecular weight (Mn) of the hydroxyl group-containing (meth)acrylic resin is about 3,000 to 100,000 from the viewpoint of blocking resistance, initial adhesion, and wet heat resistance adhesion of the self-healing coating agent. It is preferable, and about 10,000 to 80,000 is more preferable.

In the present disclosure, the weight-average molecular weight and number-average molecular weight are measured as polystyrene equivalent values measured under an appropriate solvent by gel permeation chromatography (GPC).

The upper limit of the molecular weight distribution (Mw/Mn) of the hydroxyl group-containing (meth)acrylic resin is exemplified by 10, 7.5, 5, 2.5, 2, etc., and the lower limit is 9.5, 7.5, 5, 2.5, 2, 1.5 and the like are exemplified. In one embodiment, the molecular weight distribution (Mw/Mn) of the hydroxyl group-containing (meth)acrylic resin is preferably about 1.5-10.

A hydroxyl group-containing (meth)acrylic resin can be produced by various known methods. A method for producing a hydroxyl group-containing (meth)acrylic resin includes adding a hydroxyl-free alkyl (meth)acrylate and a hydroxyl group-containing alkyl (meth)acrylate, and optionally other monomers in the absence of solvent or in an organic solvent, usually A method of conducting a copolymerization reaction for about 1 to 10 hours at about 80 to 180° C. in the presence of a polymerization initiator is exemplified. Examples of the organic solvent and polymerization initiator used in producing the hydroxyl group-containing (meth)acrylic resin include various known ones and/or those described later.

In one embodiment, the content of the hydroxyl group-containing (meth)acrylic resin in the self-healing coating agent is preferably 20-70% by mass.

<Hydroxyl containing silicone>
The hydroxyl group-containing silicones may be used alone, or two or more of them may be used in combination. In the present disclosure, the hydroxyl group-containing silicone refers to a polymer having hydroxyl groups in the molecule and a main chain of siloxane bonds. Examples of hydroxyl-containing silicones include organic modified hydroxyl-containing silicones such as acrylic polymer-modified hydroxyl-containing silicones, polyester-modified hydroxyl-containing silicones, polyether-modified hydroxyl-containing silicones, and carbinol-modified hydroxyl-containing silicones. From the viewpoint of good reactivity, the hydroxyl group is preferably contained in the modification site. By using a hydroxyl-containing silicone among various silicones, the cured product or film obtained by curing the self-repairing coating agent of the present invention becomes excellent in transparency.

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

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

Commercially available carbinol-modified hydroxyl-containing silicones are X-22-4039, X-22-4015, X-22-4952, X-22-4272, X-22-170BX, X-22-170DX, and KF-6000. , KF-6001, KF-6002, KF-6003, KF-6123, X-22-176F (manufactured by Shin-Etsu Chemical Co., Ltd.), Silaplane FM-4411, Silaplane FM-4421, Silaplane FM-4425, Silaplane FM-0411, Silaplane FM-0421, Silaplane FM-DA11, Silaplane FM-DA21, Silaplane FM-DA26 (manufactured by JNC Corporation) and the like are exemplified.

In one embodiment, the content of hydroxyl group-containing silicone in the self-healing coating agent is preferably 1 to 10% by mass.

In one embodiment, the mass ratio of the hydroxyl-containing (meth)acrylic resin and the hydroxyl-containing silicone in the self-healing coating agent (hydroxyl-containing (meth)acrylic resin _mass /hydroxyl-containing silicone _mass ) is 10 to 30. Preferably, 15-25 is more preferable.

<Polyisocyanate>
In the present disclosure, a "polyisocyanate" is a compound with two or more isocyanate groups (-N=C=O). Examples of polyisocyanates include aliphatic polyisocyanates and aromatic polyisocyanates. Polyisocyanate may be used alone or in combination of two or more.

Examples of aliphatic polyisocyanates include linear aliphatic polyisocyanates, branched aliphatic polyisocyanates, and alicyclic polyisocyanates.

A linear alkylene group etc. are illustrated as a linear aliphatic group. A linear alkylene group can be represented by the general formula —(CH ₂ ) _n — (n is an integer of 1 or more), and includes a methylene group, an ethylene group, a propylene group, an n-butylene group, an n-pentylene group, and an n-hexylene group. , n-heptylene group, n-octylene group, n-nonylene group, n-decamethylene group and the like.

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

A branched alkylene group etc. are illustrated as a branched aliphatic group. A branched alkylene group is a group in which at least one hydrogen of a linear alkylene group is substituted with an alkyl group, and specific examples include a diethylpentylene group, a trimethylbutylene group, a trimethylpentylene group, a trimethylhexylene group ( trimethylhexamethylene group) and the like.

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

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

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

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

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

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

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

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

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

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

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

A phenylene group, a naphthylene group, etc. are illustrated as an aromatic group.

Examples of aromatic polyisocyanates include tolylene diisocyanate and xylene diisocyanate.

In one embodiment, among polyisocyanates, aliphatic polyisocyanates are preferred, and straight-chain aliphatic polyisocyanates are more preferred, from the viewpoint of weather resistance and self-healing properties.

In one embodiment, the NCO content (NCO%) of the polyisocyanate is preferably 5-30% by mass.

In one embodiment, the polyisocyanate content in the self-healing coating agent is preferably 5 to 50% by mass.

In one embodiment, the mass ratio of the total content of one or more selected from the group consisting of a hydroxyl group-containing (meth)acrylic resin and a hydroxyl group-containing silicone in the self-healing coating agent to the polyisocyanate (hydroxyl group-containing The total content ( _mass /polyisocyanate _mass ) of one or more selected from the group consisting of (meth)acrylic resins and hydroxyl group-containing silicones is preferably 1/0.2 to 1/20.

In one embodiment, the mass ratio of the hydroxyl group-containing (meth)acrylic resin and the polyisocyanate in the self-healing coating agent (hydroxyl group-containing (meth)acrylic resin _mass / polyisocyanate _mass ) is 1/0.25 to 1/2.4 is preferred.

In one embodiment, the mass ratio of hydroxyl-containing silicone to polyisocyanate (hydroxyl-containing silicone _mass /polyisocyanate _mass ) in the self-healing coating agent is preferably 0.01/1 to 0.2/1.

In one embodiment, the polyisocyanate in the self-healing coating agent is a polyisocyanate adduct, a polyisocyanate allophanate, a polyisocyanate biuret and a polyisocyanate, because both antifouling properties and workability are particularly excellent. It is preferable to include two or more selected from isocyanurate isocyanate, polyisocyanate adduct and polyisocyanurate isocyanurate, polyisocyanate allophanate and polyisocyanate biuret, or polyisocyanate adduct and More preferably, it contains a biuret form of polyisocyanate. Among these combinations, it is most preferable to include a polyisocyanate adduct and a polyisocyanate biuret because both antifouling properties and workability are particularly excellent.

In one embodiment, when two kinds of polyisocyanates are contained in the self-healing coating agent, the content of each polyisocyanate is 20 to 80% by mass out of 100% by mass of the total content of the two kinds of polyisocyanates. Preferably, 30 to 80% by weight is more preferred, 30 to 70% by weight is even more preferred, 35 to 70% by weight is particularly preferred, 35 to 65% by weight is even more preferred, and 40 to 60% by weight is most preferred. When the two kinds of polyisocyanates are within the above range, the self-healing property and workability are further improved as compared with the case where they are out of the range.

In one embodiment, when two kinds of polyisocyanates are contained in the self-healing coating agent, the mass ratio of the two kinds of polyisocyanates (one polyisocyanate _mass / the other polyisocyanate _mass ) is preferably 0.1 to 5. , 0.5 to 3 is more preferred, and 0.7 to 2 is even more preferred. When the two kinds of polyisocyanates are within the above range, the self-healing property and workability are further improved as compared with the case where they are out of the range.

<Adduct of polyisocyanate>
The polyisocyanate adducts may be used alone or in combination of two or more. When producing the polyisocyanate adduct, the polyisocyanate may be used alone or in combination of two or more. Examples of the polyisocyanate include those mentioned above.

（式中、
Ｒ^adＡ～Ｒ^adＥは、それぞれ独立にアルキレン基又はアリーレン基であり、
Ｒ^adＤ～Ｒ^adＥは、各構成単位ごとに基が異なっていてもよい。
ｎ^adは０以上の整数である。ｎ^adは０～３が好ましい。）
で示されるトリメチロールプロパンとポリイソシアネートのアダクト体、
下記一般式

（式中、
Ｒ^adα～Ｒ^adεは、それぞれ独立にアルキレン基又はアリーレン基であり、
Ｒ^adδ～Ｒ^adεは、各構成単位ごとに基が異なっていてもよい。
ｎ^ad1は０以上の整数である。ｎ^ad1は０～３が好ましい。）
で示されるグリセリンとポリイソシアネートのアダクト体等が例示される。 The adduct of polyisocyanate is
The following general formula:

(In the formula,
R ^adA to R ^adE are each independently an alkylene group or an arylene group,
R ^{adD 1} to R ^adE may have different groups for each structural unit.
n ^ad is an integer of 0 or more. n ^ad is preferably 0-3. )
An adduct of trimethylolpropane and polyisocyanate represented by
The following general formula

(In the formula,
R ^adα to R ^adε are each independently an alkylene group or an arylene group,
R ^adδ to R ^adε may have different groups for each structural unit.
n ^ad1 is an integer of 0 or more. n ^ad1 is preferably 0-3. )
Examples include adducts of glycerin and polyisocyanate represented by.

Each of R ^adA to R ^adE in the above general formula and R ^adα to R ^adε in the above general formula may have at least one functional group such as an ester group, an ether group, or a carbonyl group.

Commercially available polyisocyanate adducts include Duranate P301-75E (manufactured by Asahi Kasei Corp.), Duranate E402-80B (manufactured by Asahi Kasei Corp.), Duranate E405-70B (manufactured by Asahi Kasei Corp.), Coronate HL (Tosoh (manufactured by DIC Corporation), Barnock D-750 (manufactured by DIC Corporation), and the like.

In one embodiment, the weight average molecular weight (Mw) of the polyisocyanate adduct is preferably 1,000 to 4,000.

In one embodiment, the number average molecular weight (Mn) of the polyisocyanate adduct is preferably 1,000 to 3,000.

In one embodiment, the molecular weight distribution (Mw/Mn) of the polyisocyanate adduct is preferably 1.2 to 1.5.

In one embodiment, the NCO content (NCO%) of the polyisocyanate adduct is preferably 5 to 30% by mass.

In one embodiment, the content of the polyisocyanate adduct in the self-healing coating agent is preferably 1 to 99% by mass.

In one embodiment, the mass ratio of the total content of one or more selected from the group consisting of a hydroxyl group-containing (meth)acrylic resin and a hydroxyl group-containing silicone in the self-healing coating agent to the polyisocyanate adduct. (Total content _mass of one or more selected from the group consisting of hydroxyl group-containing (meth)acrylic resins and hydroxyl group-containing silicones/adduct _mass of polyisocyanate) is preferably 1/0.2 to 1/20.

In one embodiment, the mass ratio of the hydroxyl group-containing (meth)acrylic resin and the polyisocyanate adduct in the self-healing coating agent (hydroxyl group-containing (meth)acrylic resin _mass / polyisocyanate adduct _mass ) is 1/0.2 to 1/2 is preferred.

In one embodiment, the mass ratio of the hydroxyl group-containing silicone to the polyisocyanate adduct in the self-healing coating agent (hydroxyl group-containing silicone _mass /polyisocyanate adduct _mass ) is preferably 0.05 to 30, 0.05 to 0.25 is more preferred.

<Allophanate form of polyisocyanate>
The allophanate form of polyisocyanate may be used alone or in combination of two or more. When producing the allophanate form of polyisocyanate, the polyisocyanate may be used alone or in combination of two or more. Examples of the polyisocyanate include those mentioned above.

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

（ｎ^AL１は、０以上の整数であり、Ｒ^AL１～Ｒ^AL６はそれぞれ独立に、アルキレン基又はアリーレン基であり、Ｒ^AL’～Ｒ ^AL''' はそれぞれ独立に、イソシアネート基又はＲ^ALα～Ｒ^ALγ自身の基である。Ｒ^AL１～Ｒ^AL４、Ｒ^AL’～Ｒ^AL''は、各構成単位ごとに基が異なっていてもよい。）である。Ｒ^ALＢ～Ｒ^ALＥ、Ｒ^ALα～Ｒ^ALβは、各構成単位ごとに基が異なっていてもよい。］で表される化合物等が例示される。 The allophanate form of polyisocyanate is
The following general formula:

[Wherein, n ^AL is an integer of 0 or more, R ^ALA is an alkyl group or an aryl group, R ^ALB to R ^ALG are each independently an alkylene group or an arylene group, and R ^ALα to R ^ALγ are each independently an isocyanate group or

(n ^AL1 is an integer of 0 or more, R ^AL1 to R ^AL6 are each independently an alkylene group or an arylene group, and R ^AL ' to R ^AL ''' are each independently an isocyanate group or R ^ALα to is a group of R ^ALγ itself, and R ^AL1 to R ^AL4 and R ^AL ' to R ^AL '' may be different groups for each structural unit). R ^ALB to R ^ALE and R ^ALα to R ^ALβ may have different groups for each structural unit. ] and the like are exemplified.

Commercially available allophanate forms of polyisocyanates include Takenate D-178N (manufactured by Mitsui Chemicals, Inc.), Coronate 2770 (manufactured by Tosoh Corporation), Coronate 2793 (manufactured by Tosoh Corporation), and Duranate A201H (manufactured by Asahi Kasei Corporation). ) etc. are exemplified.

In one embodiment, the weight average molecular weight (Mw) of the allophanate form of polyisocyanate is preferably 800-3500.

In one embodiment, the number average molecular weight (Mn) of the allophanate form of polyisocyanate is preferably 700-3000.

In one embodiment, the molecular weight distribution (Mw/Mn) of the allophanate form of polyisocyanate is preferably 1.0 to 1.5.

Examples of the upper limit of the NCO content (NCO%) of the allophanate form of the polyisocyanate are 30, 25, 20, 15% by mass, etc., and examples of the lower limit are 25, 20, 15, 10, 5% by mass, etc. mentioned. In one embodiment, the NCO content (NCO%) of the polyisocyanate is preferably 5-30% by mass.

In one embodiment, the content of allophanate form of polyisocyanate in the self-healing coating agent is preferably 1 to 99% by mass.

In one embodiment, the hydroxyl group-containing (meth) acrylic resin in the self-healing coating agent, and the total content of one or more selected from the group consisting of hydroxyl group-containing silicone and the mass ratio of the allophanate body of the polyisocyanate (Total content _mass of one or more selected from the group consisting of hydroxyl group-containing (meth)acrylic resins and hydroxyl group-containing silicones/allophanate body _mass of polyisocyanate) is preferably 2/5 to 15/1.

In one embodiment, the mass ratio of the hydroxyl group-containing (meth)acrylic resin in the self-healing coating agent and the allophanate form of polyisocyanate (hydroxyl group-containing (meth)acrylic resin _mass / allophanate body of polyisocyanate _mass ) is , 5/1 to 15/1.

In one embodiment, the mass ratio of the hydroxyl group-containing silicone to the allophanate form of polyisocyanate in the self-healing coating agent (hydroxyl group-containing silicone _mass / allophanate form of polyisocyanate _mass ) is 0.1/1 to 1/ 1 is preferred.

<Biuret form of polyisocyanate>
The biuret form of polyisocyanate may be used alone or in combination of two or more. When producing a biuret form of polyisocyanate, the polyisocyanate may be used alone or in combination of two or more. Examples of the polyisocyanate include those mentioned above.

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

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

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

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

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

In one embodiment, the weight average molecular weight (Mw) of the biuret form of polyisocyanate is preferably 500-1500.

In one embodiment, the number average molecular weight (Mn) of the biuret form of polyisocyanate is preferably 500-1500.

In one embodiment, the molecular weight distribution (Mw/Mn) of the biuret form of polyisocyanate is preferably 1.0 to 1.5.

In one embodiment, the NCO content (NCO %) of the biuret form of polyisocyanate is preferably 5 to 30% by mass.

In one embodiment, the content of the biuret form of polyisocyanate in the self-healing coating agent is preferably 1 to 99% by mass.

In one embodiment, the mass ratio of the total content of one or more selected from the group consisting of a hydroxyl group-containing (meth)acrylic resin and a hydroxyl group-containing silicone in the self-healing coating agent to the biuret body of the polyisocyanate (Total content _mass of one or more selected from the group consisting of hydroxyl group-containing (meth)acrylic resins and hydroxyl group-containing silicones/biuret body _mass of polyisocyanate) is preferably 1/0.1 to 1/10.

In one embodiment, the mass ratio of the hydroxyl-containing (meth)acrylic resin in the self-healing coating agent to the biuret of polyisocyanate (hydroxyl-containing (meth)acrylic resin _mass /biuret of polyisocyanate _mass ) is , 1/0.1 to 1/2 are preferred.

In one embodiment, the _mass ratio of the hydroxyl-containing silicone to the biuret of polyisocyanate in the self-healing coating agent ( _mass of hydroxyl-containing silicone/biuret of polyisocyanate) is 0.1/1 to 0.1/1. 3/1 is preferred.

In one embodiment, the mass ratio of the polyisocyanate allophanate and the polyisocyanate biuret in the self-healing coating agent (polyisocyanate allophanate _mass /polyisocyanate biuret _mass ) is 1/6 to 1/1 is preferred.

In one embodiment, the total content of the polyisocyanate allophanate and the polyisocyanate biuret in the self-healing coating agent is preferably 8 to 25% by mass.

In one embodiment, the mass ratio of the polyisocyanate adduct and the polyisocyanate biuret in the self-healing coating agent (polyisocyanate adduct _mass /polyisocyanate biuret _mass ) is 1/6 to 1/0.5 is preferred.

In one embodiment, the total content of the polyisocyanate adduct and the polyisocyanate biuret in the self-healing coating agent is preferably 10 to 60% by mass, more preferably 10 to 35% by mass.

<Isocyanurate form of polyisocyanate>
The isocyanurate form of polyisocyanate may be used alone or in combination of two or more. When producing the isocyanurate form of polyisocyanate, the polyisocyanate may be used alone or in combination of two or more. Examples of the polyisocyanate include those mentioned above.

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

（ｎ^ｉ１は、０以上の整数であり、Ｒ^ｉ１～Ｒ^ｉ５はそれぞれ独立に、アルキレン基又はアリーレン基であり、Ｒ^ｉ’～Ｒ ^ｉ'' はそれぞれ独立に、イソシアネート基又はＲ^ｉα～Ｒ^ｉβ自身の基である。Ｒ^ｉ４～Ｒ^ｉ５、Ｒ^ｉ''は、各構成単位ごとに基が異なっていてもよい。）である。Ｒ^ｉＤ～Ｒ^ｉＥ、Ｒ^ｉβは、各構成単位ごとに基が異なっていてもよい。］で表される化合物等が例示される。 The isocyanurate form of polyisocyanate is
The following general formula:

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

(n ⁱ¹ is an integer of 0 or more, R ⁱ¹ to R ⁱ⁵ are each independently an alkylene group or an arylene group, R ⁱ ′ to R ⁱ '' are each independently an isocyanate group or R ^iα to R is a group of ^iβ itself, and R ⁱ⁴ to R ⁱ⁵ and R ⁱ ″ may be different groups for each structural unit). R ^iD to R ^iE and R ^iβ may have different groups for each structural unit. ] and the like are exemplified.

The isocyanurate of polyisocyanate is Duranate TPA-100, Duranate TKA-100, Duranate MFA-75B, Duranate MHG-80B (manufactured by Asahi Kasei Co., Ltd.), Coronate HXR (isocyanurate of hexamethylene diisocyanate) (Tosoh Co., Ltd.), Takenate D-127N (isocyanurate of hydrogenated xylene diisocyanate) (manufactured by Mitsui Chemicals, Inc.), VESTANAT T1890/100 (isocyanurate of isophorone diisocyanate (manufactured by Evonik Japan Co., Ltd.) ) and the like are exemplified.

In one embodiment, the weight average molecular weight (Mw) of the isocyanurate form of polyisocyanate is preferably 500-1500.

In one embodiment, the number average molecular weight (Mn) of the isocyanurate form of polyisocyanate is preferably 500-1500.

In one embodiment, the molecular weight distribution (Mw/Mn) of the isocyanurate form of polyisocyanate is preferably 1.0 to 1.5.

In one embodiment, the NCO content (NCO %) of the isocyanurate form of polyisocyanate is preferably 5 to 30% by mass.

In one embodiment, the content of the isocyanurate form of polyisocyanate in the self-repairing coating agent is preferably 1 to 99% by mass.

In one embodiment, the total content of one or more selected from the group consisting of a hydroxyl group-containing (meth)acrylic resin and a hydroxyl group-containing silicone in the self-healing coating agent and the mass of the isocyanurate body of polyisocyanate The ratio (one or more total content _mass selected from the group consisting of hydroxyl group-containing (meth)acrylic resin and hydroxyl group-containing silicone / isocyanurate body _mass of polyisocyanate) is 1/0.1 to 1/5 preferable.

In one embodiment, the mass ratio of the hydroxyl group-containing (meth)acrylic resin and the isocyanurate polyisocyanate in the self-healing coating agent (hydroxyl group-containing (meth)acrylic resin _mass / isocyanurate _mass of polyisocyanate) is preferably 1/0.1 to 1/2.

In one embodiment, the mass ratio of the hydroxyl group-containing silicone to the isocyanurate of polyisocyanate in the self-healing coating agent (hydroxyl group-containing silicone _mass / isocyanurate of polyisocyanate _mass ) is 0.1/1 to 0.6/1 is preferred.

In one embodiment, the mass ratio of the polyisocyanate adduct and the polyisocyanurate isocyanurate in the self-healing coating agent (polyisocyanate adduct _mass /polyisocyanate isocyanurate _mass ) is 1/ 6 to 1/0.5 is preferred.

In one embodiment, the total content of the polyisocyanate adduct and the polyisocyanurate isocyanurate in the self-healing coating agent is preferably 8 to 25% by mass.

In one embodiment, the total content of two or more selected from a polyisocyanate adduct, a polyisocyanate allophanate, a polyisocyanate biuret, and a polyisocyanurate isocyanurate in the self-healing coating agent is preferably 10 to 60% by mass.

<Polycarbonate polyol>
In the present disclosure, "polycarbonate polyol" is a compound having two or more carbonate groups (-O-(C=O)-O-) and two or more hydroxyl groups. Polycarbonate polyols are exemplified by polycarbonate diols, polycarbonate triols, polycarbonate tetraols and the like. Polycarbonate polyols may be used alone or in combination of two or more. In addition, when polycarbonate polyol is used in the self-repairing coating agent of the present invention, compatibility is better than when polyether polyol is used. Although the exact mechanism is unknown as to why the film using the self-repairing coating agent of the present invention has excellent hardness and antifouling properties, it is believed that this good compatibility is related.

Polycarbonate polyols are synthesized by conventionally known methods such as the phosgene method and transesterification reaction. For example, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octane Polyols such as diols, 1,9-nonanediol, 2-methyl-1,8-octanediol and 1,10-decanediol and carbonic acid derivatives such as diphenyl carbonate, dimethyl carbonate, diethyl carbonate, diethylene carbonate and phosgene A polycarbonate polyol can be obtained by reacting them by a conventionally known method.

Commercially available polycarbonate diols include BENEBiOL (manufactured by Mitsubishi Chemical Corporation), NIPPOLAN 981 (manufactured by Tosoh Corporation), Duranol G3450J (manufactured by Asahi Kasei Corp.), Duranol G3452 (manufactured by Asahi Kasei Corp.), and Duranol T5652 (manufactured by Asahi Kasei Corp.). Asahi Kasei Co., Ltd.), Kuraray Polyol C-590 (Kuraray Co., Ltd.), Kuraray Polyol C-1090 (Kuraray Co., Ltd.), and the like.

Examples of polycarbonate polyols include aliphatic polycarbonate polyols and aromatic polycarbonate polyols.

Examples of aliphatic polycarbonate polyols include linear aliphatic polycarbonate polyols, branched aliphatic polycarbonate polyols, and alicyclic polycarbonate polyols.

In one embodiment, among polycarbonate polyols, aliphatic polycarbonate polyols are preferable, and linear aliphatic polycarbonate polyols are more preferable, from the viewpoint of weather resistance and self-healing properties.

In one embodiment, the content of polycarbonate polyol in the self-healing coating agent is preferably 10 to 40% by mass.

In one embodiment, the polycarbonate polyol preferably has a hydroxyl value of 100 to 250 mgKOH/g, more preferably 100 to 170 mgKOH/g. When the hydroxyl value of the polycarbonate polyol is within the above range, the processability becomes better.

In one embodiment, the weight average molecular weight (Mw) of the polycarbonate polyol is preferably 500-1000, more preferably 800-1000. When the weight-average molecular weight of the polycarbonate polyol is within the above range, the workability becomes better.

In one embodiment, the number average molecular weight (Mn) of the polycarbonate polyol is preferably 500-1000, more preferably 800-1000. When the number-average molecular weight of the polycarbonate polyol is within the above range, the processability becomes better.

In one embodiment, the polycarbonate polyol preferably has a molecular weight distribution (Mw/Mn) of 1.0 to 1.5.

In one embodiment, the mass ratio of the total content of one or more selected from the group consisting of a hydroxyl group-containing (meth)acrylic resin, a hydroxyl group-containing silicone, and a polyisocyanate in the self-healing coating agent to the polycarbonate polyol. (Total content _mass of one or more selected from the group consisting of hydroxyl group-containing (meth)acrylic resin, hydroxyl group-containing silicone, and polyisocyanate/polycarbonate polyol _mass ) is preferably 0.01 to 70 and 0.05 to 4 is more preferred.

In one embodiment, the mass ratio of the hydroxyl group-containing (meth)acrylic resin to the polycarbonate polyol in the self-healing coating agent (hydroxyl group-containing (meth)acrylic resin _mass /polycarbonate polyol _mass ) is the hydroxyl group-containing (meth)acrylic It is preferably 3/1 to 1/4, more preferably 3/1 to 1/1, because the compatibility between the resin and the polycarbonate polyol is improved and the transparency of the coating film is excellent.

In one embodiment, the mass ratio of hydroxyl-containing silicone to polycarbonate polyol in the self-healing coating agent (hydroxyl-containing silicone _mass /polycarbonate polyol _mass ) is preferably 0.05-10.

In one embodiment, the mass ratio of polyisocyanate to polycarbonate polyol (polyisocyanate _mass /polycarbonate polyol _mass ) in the self-healing coating agent is preferably 0.2 to 2.0.

In one embodiment, when the total content of the hydroxyl group-containing (meth) acrylic resin, hydroxyl group-containing silicone, polyisocyanate and polycarbonate polyol in the self-healing coating agent is 100% by mass, the hydroxyl group-containing (meth) acrylic resin The content of is preferably 30 to 70% by mass, more preferably 40 to 70% by mass, even more preferably 40 to 60% by mass, particularly preferably 40 to 55% by mass, and the content of hydroxyl group-containing silicone is 1 to 10 % by mass is preferable, 1 to 5% by mass is more preferable, 2 to 5% by mass is even more preferable, and 2 to 3% by mass is particularly preferable. More preferably 10 to 40% by mass, particularly preferably 15 to 35% by mass, the polycarbonate polyol content is preferably 15 to 40% by mass, more preferably 15 to 35% by mass, 20 to 35% by weight is even more preferred, and 20-30% by weight is particularly preferred.

<Curing catalyst>
In one embodiment, the self-healing coating agent may contain a curing catalyst. A curing catalyst may be contained singly or in combination of two or more.

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

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

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

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

The organic bismuth catalyst is exemplified by bismuth octylate.

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

Examples of organic titanium catalysts include titanium ethyl acetoacetate.

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

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

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

When the self-repairing coating agent contains a curing catalyst, the upper limit of the content of the curing catalyst in the self-repairing coating agent is 1, 0.9, 0.75, 0.5, 0.25, 0. .1, 0.09, 0.05, 0.02% by mass, etc. are exemplified, and the lower limits are 0.9, 0.75, 0.5, 0.25, 0.1, 0.09, 0.1%. 05, 0.02, 0.01 mass % and the like are exemplified. In one embodiment, when the self-repairing coating agent contains a curing catalyst, the content of the curing catalyst in the self-repairing coating agent is preferably about 0.01 to 1% by mass.

In one embodiment, among curing catalysts, organic tin catalysts are preferable, and dioctyltin dilaurate is more preferable, from the viewpoint of curability, pot life, workability, and coating film appearance.

<Organic solvent>
In one embodiment, the self-healing coating agent may contain an organic solvent. The organic solvent may be contained alone or in combination of two or more. Organic solvents 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 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; Solvesso #100 and Solvesso #150 ( All are trade names, manufactured by Exxon), haloalkane solvents such as chloroform, amide solvents such as dimethylformamide, and the like. Among these, from the viewpoint of the pot life of the self-healing coating agent of the present invention, it is preferable to contain a ketone-based organic solvent, and among the ketone-based organic solvents, it is preferable to include acetylacetone.

When the self-repairing coating agent contains an organic solvent, the upper limit of the content of the organic solvent in the self-repairing coating agent is exemplified by 90, 80, 70, 60, 55% by mass, etc., and the lower limit is 85, 80, 70, 60, 55, 50, 45, 40, 35, 30, 25, 20 mass % and the like are exemplified. In one embodiment, when the self-repairing coating agent contains an organic solvent, the content of the organic solvent in the self-repairing coating agent is preferably about 20 to 90% by mass. The organic solvent contained in the self-healing coating agent may contain the organic solvent contained in the hydroxyl group-containing (meth)acrylic resin, the hydroxyl group-containing silicone, the polyisocyanate, and the curing catalyst.

<Additive>
The self-healing coating agent may contain, as additives, agents other than hydroxyl group-containing (meth)acrylic resins, hydroxyl group-containing silicones, polyisocyanates, polycarbonate polyols, curing catalysts and organic solvents. Examples of additives include polymerization inhibitors, antioxidants, light stabilizers, antifoaming agents, surface conditioners, pigments, antistatic agents, metal oxide fine particle dispersions, organic fine particle dispersions, and the like. In one embodiment, examples of the content of the additive include about 0.1 to 10% by mass, less than about 10 parts by mass, less than about 5 parts by mass, less than about 1 part by mass of the self-healing coating agent, Less than about 0.1 parts by mass, less than about 0.01 parts by mass, about 0 parts by mass, etc. are exemplified.

The above-mentioned self-repairing coating agent includes a step of mixing a hydroxyl group-containing (meth)acrylic resin, a hydroxyl group-containing silicone, a polyisocyanate, a polycarbonate polyol, a curing catalyst, an organic solvent and/or additives by various known means. etc.

[Cured product]
The present disclosure provides a cured product of the self-healing coating agent. Conditions for producing the cured product are exemplified below.

[the film]
The present disclosure provides a film containing the cured product.

Various known substrates are employed as the substrate. Substrates include polycarbonate film, (meth)acrylic film (polymethyl (meth)acrylate film, etc.), polystyrene film, polyester film, polyolefin film, epoxy resin film, melamine resin film, triacetylcellulose film, ABS film, AS film, norbornene. Examples include a system resin film, a cyclic olefin film, a polyvinyl alcohol film, and the like. The thickness of the substrate is also not particularly limited, but is preferably about 50 to 200 μm. Although the thickness of the coating layer is not particularly limited, it is preferably about 5 to 30 μm.

The above films are produced by various known methods. In one embodiment, the method for producing a film includes a step of applying a self-healing coating agent to at least one side of a substrate (coating step), and a step of thermally curing to form a cured self-healing coating agent layer. (Thermal curing step).

The film of the present invention may be used as a topcoat layer among various layers of the decorative film.

Types of decorative films include:
(1) order of top coat layer, anchor layer, decorative layer, easy adhesion layer, plastic film, functional layer, adhesive layer,
(2) order of top coat layer, easy adhesion layer, plastic film, easy adhesion layer, decorative layer, functional layer, adhesion layer,
(3) order of top coat layer, anchor layer, decorative layer, functional layer, adhesive layer,
(4) order of top coat layer, anchor layer, decorative layer, adhesive layer,
(5) order of top coat layer, decorative layer, adhesive layer,
Examples include those composed of In addition, the decorative layer may have one or more selected from a metallic layer, a vapor deposition layer, a colored layer, a printed layer, a multicolor printed layer, a hologram layer, and the like.

The decorative film is formed by coating various layers on the base film by conventionally known methods such as gravure coating, roll coating, spray coating, comma coating, lip coating, gravure printing, and screen printing. It can be obtained by stacking Among these various methods, the gravure printing method is preferable from the viewpoint of productivity. A release layer may be provided on the base film, if necessary.

The top coat layer of the decorative film can be obtained by curing the self-repairing coating agent of the present invention by heat treatment. This heat treatment is preferably performed at a temperature of 80° C. to 160° C. for 30 seconds to 30 minutes. The thickness of the topcoat layer thus obtained is preferably about 5 to 30 μm because it has excellent scratch resistance.

The decorative film thus obtained can be formed on the surfaces of objects to be decorated, such as various electric appliances such as mobile phones and televisions, and various vehicles such as automobiles and motorcycles.

The method of attaching the decorative film to the object to be decorated is primary decoration (hereinafter also referred to as "in-mold decoration") in which the decorative film is attached in a mold for molding the object to be decorated. It is a secondary decoration (hereinafter also referred to as "out-mold decoration", "post-mold decoration", and "overlay molding") in which a decorative film is attached after the object to be decorated is removed from the mold. good too. The decoration may be performed by a lamination method in which the entire base film is attached to the object to be decorated, or by a transfer method in which the base film and the release layer are peeled off after the decorative film is attached to the object to be decorated. may be done. Specific examples of transfer include in-mold transfer, overlay transfer, thermal transfer, water transfer, and pressure-sensitive transfer. Specific examples of lamination include in-mold lamination, TOM method, and the like.

(Coating process)
Examples of the coating method 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.

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

(Thermal curing process)
The drying method is exemplified by drying using a circulation dryer or the like. Examples of drying conditions include heating at a temperature of 80° C. to 160° C. for 30 seconds to 30 minutes. Photocuring is known as another curing method, but heat curing is more preferable from the viewpoint of workability.

When manufacturing a film, aging treatment is performed after drying as needed. An example is aging treatment at 40° C. for 72 hours.

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

<Preparation of (meth)acrylic resin>
[Resin A]
58 parts of methyl methacrylate (hereinafter also referred to as MMA) and 32 parts of n-butyl acrylate (hereinafter also referred to as BA) were added to a reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen inlet tube. , 10 parts of 2-hydroxyethyl acrylate (hereinafter also referred to as HEA) and 412.5 parts of ethyl acetate were charged, and the reaction system was set at 77°C. Next, 2.3 parts of 2,2'-azobisisobutyronitrile was added and the temperature was maintained at around 80°C for 5 hours. Then, 3.0 parts of 2,2'-azobisisobutyronitrile was charged, and the reaction system was kept at about the same temperature for another 4 hours. After that, the reaction system was cooled to room temperature to obtain a solution of Resin A (35% non-volatile content) having the physical properties shown in Table 1.

[Resin B, Resin C]
Preparation of Resin A was carried out in the same manner as for Resin A, except that the raw materials were changed to those shown in Table 1. Table 1 shows the physical properties of Resin B and Resin C obtained. Further, the acid values of Resin A, Resin B, and Resin C were all 0 mgKOH/g.

各原料は質量部単位である
ＭＭＡ：メタクリル酸メチル
ＢＭＡ：メタクリル酸ブチル
ＢＡ：アクリル酸ｎ－ブチル
ＨＥＭＡ：メタクリル酸２－ヒドロキシエチル
ＨＥＡ：アクリル酸２－ヒドロキシエチル

MMA: methyl methacrylate BMA: butyl methacrylate BA: n-butyl acrylate HEMA: 2-hydroxyethyl methacrylate HEA: 2-hydroxyethyl acrylate

<Preparation of self-healing coating agent>
Example 1
100.0 parts of resin A, 50.0 parts of polycarbonate diol (manufactured by Asahi Kasei Co., Ltd., product name: Duranol G3450J) (solid concentration: 100%), adduct of hexamethylene diisocyanate (manufactured by Asahi Kasei Co., Ltd., product Name: Duranate E402-80B) (solid concentration 80%) 27.5 parts, biuret form of hexamethylene diisocyanate (manufactured by Asahi Kasei Corporation, trade name: Duranate 24A100) (solid concentration 100%) 19.4 5.1 parts of acrylic polymer-modified hydroxyl-containing silicone (manufactured by BYK-Chemie Japan Co., Ltd., trade name: BYK-SILCLEAN3700) (solid concentration: 25%), dioctyltin dilaurate (solid concentration: 100%) (hereinafter referred to as 0.13 parts of DOTDL), 121.5 parts of methyl ethyl ketone (hereinafter also referred to as MEK), and 12.6 parts of acetylacetone (hereinafter also referred to as AcAc) were used. A self-healing coating agent with a solid content concentration of 38% was prepared by thoroughly mixing the above components.

Examples 2-9 and Comparative Examples 1-4
The self-healing coating agents of Examples 2-9 and Comparative Examples 1-4 were produced in the same manner as in Example 1, except that the component compositions were changed as shown in Table 2 below. The solid content concentration of the self-healing coating agents of Examples 1-9 and Comparative Examples 1-4 was 38%.

デュラネートＥ４０２－８０Ｂ：旭化成（株）製、ヘキサメチレンジイソシアネートのアダクト体（固形分濃度８０％）
デュラネート２４Ａ１００：旭化成（株）製、ヘキサメチレンジイソシアネートのビウレット体（固形分濃度１００％）
デュラネートＴＰＡ１００：旭化成（株）製、ヘキサメチレンジイソシアネートのイソシアヌレート体（固形分濃度１００％）
コロネート２７９３：東ソー（株）製、ヘキサメチレンジイソシアネートのアロファネート体（固形分濃度１００％）
デュラノールＧ３４５０Ｊ：旭化成（株）製、ポリカーボネートジオール（固形分濃度１００％、数平均分子量８００、水酸基価１４０ｍｇＫＯＨ／ｇ）
クラレポリオールＣ－５９０：（株）クラレ製、ポリカーボネートジオール（固形分濃度１００％、数平均分子量５００、水酸基価２２４ｍｇＫＯＨ／ｇ）
クラレポリオールＣ－１０９０：（株）クラレ製、ポリカーボネートジオール（固形分濃度１００％、数平均分子量１０００、水酸基価１１２ｍｇＫＯＨ／ｇ）

Duranate E402-80B: manufactured by Asahi Kasei Co., Ltd., an adduct of hexamethylene diisocyanate (solid content concentration 80%)
Duranate 24A100: manufactured by Asahi Kasei Co., Ltd., biuret form of hexamethylene diisocyanate (solid concentration: 100%)
Duranate TPA100: manufactured by Asahi Kasei Corp., isocyanurate form of hexamethylene diisocyanate (solid concentration: 100%)
Coronate 2793: manufactured by Tosoh Corporation, an allophanate form of hexamethylene diisocyanate (solid content concentration 100%)
Duranol G3450J: manufactured by Asahi Kasei Corp., polycarbonate diol (solid concentration: 100%, number average molecular weight: 800, hydroxyl value: 140 mgKOH/g)
Kuraray Polyol C-590: manufactured by Kuraray Co., Ltd., polycarbonate diol (solid concentration: 100%, number average molecular weight: 500, hydroxyl value: 224 mgKOH/g)
Kuraray Polyol C-1090: manufactured by Kuraray Co., Ltd., polycarbonate diol (solid concentration: 100%, number average molecular weight: 1000, hydroxyl value: 112 mgKOH/g)

<Production of film>
Evaluation example 1
The self-healing coating agent of Example 1 was applied to a commercially available polyethylene terephthalate film (manufactured by Toyobo Co., Ltd., trade name: Cosmoshine A4100, 100 μm thick) so that the film thickness after drying was 10 μm. was heat cured by drying at 120° C. for 60 seconds.

Evaluation Examples 2 to 9 and Comparative Evaluation Examples 1 to 4
Films were produced in the same manner as in Evaluation Example 1 using the self-healing coating agents of Examples 2-9 and Comparative Examples 1-3. The self-healing coating agent of Comparative Example 4 could not be cured and did not form a film.

<Film repairability>
At 25° C., each film surface was scratched with a brass brush (manufactured by AS ONE Co., Ltd.) 10 times, and then evaluated by measuring the time until the scratches disappeared. Evaluation criteria are as follows.
○: Recovered within 10 seconds.
△: Recovered within 11 seconds to 1 minute.
x: It takes 1 minute or more to repair.

<Film antifouling property>
By writing a mark on the surface of the film with an oil-based ink (manufactured by ASKUL Corporation, trade name: PERMANENT MAKER), and immediately after that, the mark is wiped off with a dry nonwoven fabric (manufactured by Asahi Kasei Corp., trade name: BEMCOT M-3II). evaluated. Evaluation criteria are as follows.
○: Can be wiped off by rubbing 5 times with a nonwoven fabric △: Rubbing with a nonwoven fabric 5 times or more makes oily ink traces lighter
&#9747;: Can't be wiped off.

<Breaking elongation of film>
The elongation at break of the film alone was measured according to the test conditions of JIS K 7127:1999 (Plastics &#8722; Testing methods for tensile properties &#8722; Part 3: Test conditions for films and sheets). As a method for producing the film alone, the film on the polyethylene terephthalate film produced in Evaluation Example 1 was peeled off by hand. The shape of the film before the test was started was 5 mm wide, 10 μm thick, and 25 mm long, and the test speed was 200 mm/min.
Breaking elongation (%) = 100 × (L-25) / 25
L: Cured product length when the cured product breaks

<Appearance of film>
The film was visually confirmed according to the following criteria.
○: Excellent transparency, no foreign matter ×: Foreign matter and turbidity are present.

Claims (6)

Including hydroxyl group-containing (meth)acrylic resin, hydroxyl group-containing silicone, polyisocyanate and polycarbonate polyol ,
A self-healing coating agent comprising a polyisocyanate adduct and a polyisocyanate biuret as polyisocyanate . The self-healing coating agent according to claim 1 , wherein the hydroxyl group-containing (meth)acrylic resin has a glass transition temperature of 40 to 100°C. 3. The self-healing coating agent according to claim 1, wherein the polycarbonate polyol has a number average molecular weight of 800-1000. When the total content of the hydroxyl group-containing (meth)acrylic resin, hydroxyl group-containing silicone, polyisocyanate and polycarbonate polyol is 100% by mass, the content of the hydroxyl group-containing (meth)acrylic resin is 30 to 70% by mass, and the hydroxyl group-containing silicone The self-healing coating according to any one of claims 1 to 3 , wherein the content of is 1 to 10% by mass, the content of polyisocyanate is 10 to 50% by mass, and the content of polycarbonate polyol is 15 to 40% by mass. agent. A cured product of the self-healing coating agent according to any one of claims 1 to 4 . A film comprising the cured product according to claim 5 .