TW202006076A - Self-healing coating agent, cured product and film including hydroxyl-containing (meth) acrylic resin, hydroxyl-containing polysiloxane, polyisocyanates and polycarbonate polyols - Google Patents

Abstract

The present invention provides a self-healing coating agent, a cured product, and a film. The present invention provides a self-healing coating agent, a cured product thereof, and a film containing the cured product, wherein the self-healing coating agent includes a hydroxyl-containing (meth) acrylic resin, a hydroxyl-containing polysiloxane, a polyisocyanates and a polycarbonate polyols. In one embodiment, the polyisocyanates of the self-healing coating agent include two or more selected from an adduct of the polyisocyanates, an allophanate body of the polyisocyanates, a biuret body of the polyisocyanates, and an isocyanurate body of the polyisocyanates.

Description

Self-healing coating agent, hardened material and film

The invention relates to a self-healing coating agent, hardened material and film.

Plastic substrates such as 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 performed with coating agents. Among these coating agents, the self-healing coating agent will disappear with time due to the damage generated, so it is an ideal coating agent in protecting various substrates.

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

【Prior Technical Literature】 【Patent Literature】

[Patent Document 1] Japanese Patent No. 6241571

Patent Document 1 describes that it is excellent in self-healing property and contamination resistance, but it can be further improved in workability.

The technical problem to be solved by the present invention is to provide a self-healing coating agent for manufacturing hardened materials and films with excellent processability; and to provide a self-repairing coating material for manufacturing hardened materials and films with excellent transparency and good appearance. Repairing coating agent; providing a self-repairing coating agent for manufacturing anti-fouling hardened materials and films.

The inventors conducted intensive studies and found that the above-mentioned technical problems can be solved by using self-healing coating agents containing specific ingredients.

With the present invention, the following items are provided.

(Item 1)

A self-healing coating agent characterized by containing hydroxyl-containing (meth)acrylic resin, hydroxyl-containing silicone, polyisocyanate and polycarbonate polyol.

(Item 2)

The self-healing coating agent as described in the above item, wherein the polyisocyanate contains an isocyanate selected from polyisocyanate, allophanate of polyisocyanate, biuret of polyisocyanate and isocyanate of polyisocyanate Two or more of cyanurate.

(Item 3)

The self-healing coating agent as described in the above item 1 or 2, wherein the glass transition temperature of the hydroxyl group-containing (meth)acrylic resin is 40 to 100°C.

(Item 4)

The self-healing coating agent as described in 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)

The self-healing coating agent according to any one of items 1 to 4 above, wherein the aforementioned hydroxyl-containing (meth)acrylic resin, hydroxyl-containing polysiloxane, polyisocyanate and polycarbonate polyol When the total content is set to 100% by mass, the content of hydroxyl-containing (meth)acrylic resin is 30 to 70% by mass, the content of hydroxyl-containing polysiloxane is 1 to 10% by mass, and the content of polyisocyanate is 10 ~50% by mass, and the content of polycarbonate polyol is 15~40% by mass.

(Item 6)

A hardened product characterized in that it is a hardened product of the self-healing coating agent described in any one of items 1 to 5 above.

(Item 7)

A film characterized by containing the hardened product described in item 6 above.

In the present invention, the one or more features described above can be provided in combination in addition to the combinations explicitly described.

By using the self-healing coating agent of the present invention, a cured product and a film with excellent processability and good elongation, a cured product and a film with excellent transparency and a good coating appearance, and a cured product and a film with good antifouling properties can be obtained .

In the whole of the present invention, the numerical range of each physical property value, content, etc. can be appropriately set (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 can be exemplified by A1, A2, A3, etc., and the lower limit of the value α can be exemplified by B1, B2, B3, etc., the range of the value α can be exemplified by A1 or less, A2 Below, below A3, above B1, above B2, above B3, above A1~B1, A1~B2, A1~B3, A2~B1, A2~B2, A2~B3, A3~B1, A3~B2, A3~B3, etc. .

[Self-repairing coating agent]

The invention provides a self-healing coating agent containing hydroxyl-containing (meth)acrylic resin, hydroxyl-containing polysiloxane, polyisocyanate and polycarbonate polyol.

<Hydroxy-containing (meth)acrylic resin>

The hydroxyl group-containing (meth)acrylic resin may, for example, be a copolymer containing a constitutional unit derived from a hydroxyl-free alkyl (meth)acrylate and a hydroxyl group-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 invention, "(meth)acrylic acid" means "at least one selected from the group consisting of acrylic acid and methacrylic acid". Similarly, "(meth)acrylate" means "at least one selected from the group consisting of acrylate and methacrylate". In addition, "(meth)acryloyl" means "at least one selected from the group consisting of acryloyl and methacryloyl".

(Hydroxy-free alkyl (meth)acrylate)

The alkyl (meth)acrylate not containing a hydroxyl group is represented by the following general formula.

【Chemistry 1】

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

The alkyl (meth) acrylate which does not contain a hydroxyl group can be used individually or in combination of 2 or more types.

The alkyl group can be exemplified by straight chain alkyl groups, branched chain alkyl groups, cycloalkyl groups, and the like.

The linear alkyl group is represented by the general formula -C _n H _2n+1 (n is an integer of 1 or more). Examples of straight-chain alkyl groups include methyl, ethyl, propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decylmethyl groups.

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

Examples of cycloalkyl groups include monocyclic cycloalkyl groups, bridged cycloalkyl groups, and condensed ring cycloalkyl groups.

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

Examples of bridged cycloalkyls include tricyclodecyl, adamantyl, and norbornyl.

Examples of the fused ring cycloalkyl include bicyclodecyl.

Alkyl (meth)acrylates that do not contain hydroxyl groups can be exemplified by linear alkyl (meth)acrylates that do not contain hydroxyl groups, branched alkyl (meth)acrylates that do not contain hydroxyl groups, and (meth) groups that do not contain hydroxyl groups Naphthenic acrylate, etc.

Straight-chain alkyl (meth)acrylates that do not contain hydroxyl groups can be exemplified by methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, (Meth) hexyl acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, cetyl (meth) acrylate, dodecyl (meth) acrylate, deca (meth) acrylate Octane, arachidyl (meth)acrylate, behenyl (meth)acrylate, etc.

Branched alkyl (meth)acrylates without hydroxyl groups, exemplified by isopropyl (meth)acrylate, isobutyl (meth)acrylate, secondary butyl (meth)acrylate, tri(meth)acrylate Grade butyl ester, 2-ethylhexyl (meth)acrylate, etc.

Cycloalkyl (meth)acrylates that do not contain hydroxyl groups can be exemplified by cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, (Meth) acrylate, etc.

In one embodiment, from the viewpoint of contributing to leveling and adhesion of the self-healing coating agent, it is desirable to be an alkyl (meth)acrylate having about 1 to 20 carbon atoms in the alkyl group. In addition, by using a combination of alkyl (meth)acrylates having different alkyl groups with different carbon atoms, it is possible to adjust physical properties such as the glass transition temperature of the hydroxyl-containing (meth)acrylic resin.

In one embodiment, among the alkyl (meth)acrylates that do not contain hydroxyl groups, it is desirable from the viewpoint of abrasion resistance, leveling property, and adhesion of the self-healing coating agent in particular. It is methyl (meth)acrylate and butyl (meth)acrylate.

The upper limit of the content of the structural unit derived from the (meth)acrylic acid alkyl ester which does not contain a hydroxyl group in 100 mol% of all the structural units of a (meth)acrylic resin containing a hydroxyl group can be exemplified by 98 mol%, 95 mol Ear%, 90 mole%, 85 mole%, 80 mole%, 75 mole%, 70 mole%, 65 mole%, etc., the lower limit can be exemplified by 95 mole%, 90 mole%, 85 mole %, 80 mol%, 75 mol%, 70 mol%, 65 mol%, 62 mol%, etc. In one embodiment, the content range of the structural unit derived from the (meth)acrylic acid alkyl ester which does not contain a hydroxyl group in 100 mol% of all the structural units of the (meth)acrylic resin containing a hydroxyl group is ideally About 62 mole% to 98 mole%.

The upper limit of the content of the structural unit derived from the (meth)acrylic acid alkyl ester not containing a hydroxyl group in 100% by mass of all the structural units of the (meth)acrylic resin containing a hydroxyl group can be exemplified by 98% by mass, 95% by mass, 90% by mass, 85% by mass, 80% by mass, 75% by mass, 70% by mass, etc., the lower limit can be exemplified by 95% by mass, 90% by mass, 85% by mass, 80% by mass, 75% by mass, 70% by mass, 65% by mass %Wait. In one embodiment, the range of the content of the structural units derived from the (meth)acrylic acid alkyl ester not containing a hydroxyl group in 100% by mass of all the structural units of the (meth)acrylic resin containing a hydroxyl group is desirably about 65% by mass to 98% by mass.

(Hydroxy-containing alkyl (meth)acrylate)

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

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

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

The alkylene group may, for example, be a linear alkylene group, a branched alkylene group, or a cycloalkylene group.

Hydroxy-containing alkyl (meth)acrylates, exemplified by linear alkyl (meth)acrylates containing hydroxyl, branched alkyl (meth)acrylates containing hydroxyl, cycloalkyl (meth)acrylates containing hydroxyl Wait.

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

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

Examples of the hydroxyl group-containing cycloalkyl (meth)acrylate include hydroxycyclohexyl (meth)acrylate and 4-(hydroxymethyl)cyclohexyl methyl (meth)acrylate.

The hydroxyl group-containing alkyl (meth)acrylate is preferably a hydroxyl group-containing (methyl) group having about 1 to 4 carbon atoms from the viewpoint of the curability of the self-healing coating agent and the shelf life. Alkyl acrylate.

In one embodiment, the hydroxyl group-containing alkyl (meth)acrylate is preferably 2-hydroxyethyl (meth)acrylate from the viewpoint of the hardenability and storage life of the self-healing coating agent.

The upper limit of the content of the constituent units derived from the hydroxyl group-containing (meth)acrylic acid alkyl ester in 100 mole% of all the constituent units of the hydroxyl group-containing (meth)acrylic resin can be exemplified by 38 mole% and 35 mole %, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, 5 mol%, 2.5 mol%, etc., the lower limit can be exemplified by 35 mol%, 30 mol% , 25 mol%, 20 mol%, 15 mol%, 10 mol%, 5 mol%, 2.5 mol%, 1.5 mol%, etc. In one embodiment, the content range of the constituent units derived from the hydroxyl group-containing (meth)acrylic acid alkyl ester in 100 mole% of all the constituent units of the hydroxyl group-containing (meth)acrylic resin is desirably about 1.5 mole% to 38 mole%.

The upper limit of the content of the constituent units derived from the hydroxyl group-containing (meth)acrylic acid alkyl ester in 100% by mass of all the constituent units of the hydroxyl group-containing (meth)acrylic resin can be exemplified by 35% by mass, 30% by mass, and 25 Mass%, 20 mass%, 15 mass%, 10 mass%, 5 mass%, 2.5 mass%, etc., the lower limit can be exemplified by 30 mass%, 25 mass%, 20 mass%, 15 mass%, 10 mass%, 5 mass% , 2.5% by mass, 2% by mass, etc. In one embodiment, the content range of the structural units derived from the hydroxyl group-containing (meth)acrylic acid alkyl ester in 100% by mass of all the structural units of the hydroxyl group-containing (meth)acrylic resin is desirably about 2 Mass%~35 mass%.

Ratio of the amount of the constituent unit derived from the (meth)acrylic acid alkyl group not containing a hydroxyl group to the constituent unit derived from the (meth)acrylic acid alkyl group containing a hydroxyl group in the (meth)acrylic resin containing a hydroxyl group ( The upper limit of hydroxy-free (meth)acrylic acid alkyl ester _mol /hydroxy-containing (meth)acrylic acid alkyl ester _mol ) can be exemplified by 57, 50, 40, 30, 20, 15, 10, 5, 2, etc., the lower limit can be Examples 55, 50, 40, 30, 20, 15, 10, 5, 2, 1.6, etc. In one embodiment, in the hydroxyl-containing (meth)acrylic resin, the structural unit derived from the non-hydroxyl-containing (meth)acrylic acid alkyl ester and the structural unit derived from the hydroxyl-containing (meth)acrylic acid alkyl ester ratio (no hydroxyl (meth) acrylic acid alkyl ester _mol / hydroxyl group-containing (meth) acrylic acid alkyl ester _mol) amount of a substance over about 1.6 to 57, more preferably from 5 to 15.

Mass ratio of the structural unit derived from the (meth)acrylic acid alkyl group which does not contain a hydroxyl group to the structural unit derived from the (meth)acrylic acid alkyl group which contains a hydroxyl group (hydroxyl group-free) the upper limit of the (meth) acrylic acid alkyl ester _mass / hydroxyl group-containing (meth) acrylic acid alkyl ester _Mass) 49,40,30,20,15,10,5,2 the like may be exemplified, lower limit can be exemplified 45,40, 30, 20, 15, 10, 5, 2, 1.8 etc. In one embodiment, in the hydroxyl-containing (meth)acrylic resin, the structural unit derived from the non-hydroxyl-containing (meth)acrylic acid alkyl ester and the structural unit derived from the hydroxyl-containing (meth)acrylic acid alkyl ester mass ratio (no hydroxyl (meth) acrylic acid alkyl ester _mass / hydroxyl group-containing (meth) acrylic acid alkyl ester _mass), desirably from about 1.8 to 49, more preferably from 5 to 15.

(Monomers other than hydroxyl-free alkyl (meth)acrylate and hydroxyl-containing alkyl (meth)acrylate: also known as other monomers)

When producing a hydroxyl-containing (meth)acrylic resin, a monomer that does not belong to any of the hydroxyl-free alkyl (meth)acrylate and the hydroxyl-containing alkyl (meth)acrylate may also be used. Two or more monomers may be used in combination.

Other monomers can be exemplified by (meth)acrylic acid, α,β-unsaturated carboxylic acids, styrenes, α-olefins, unsaturated alcohols and their salts, dialkylaminoalkyl (meth)propene Acetamide and its salts, chain transfer monomers, (meth)acrylonitrile, (meth)acrylamides, vinylamine, bis(meth)acrylamide, di(meth)acrylate, Divinyl ester, difunctional monomers other than the above, trifunctional monomers, tetrafunctional monomers, etc.

The upper limit of the content of the structural units derived from other monomers in 100 mol% of all the structural units of the hydroxyl-containing (meth)acrylic resin can be exemplified by 13 mol%, 10 mol%, 9 mol%, 5 mol%, 4 mol%, 1 mol%, etc., the lower limit can be exemplified by 12 mol%, 10 mol%, 9 mol%, 5 mol%, 4 mol%, 1 mol%, 0 Moore% etc. In one embodiment, the content range of the structural units derived from other monomers in 100 mol% of all the structural units of the (meth)acrylic resin containing hydroxyl groups is desirably about 0 mol% to 13 mol ear%.

The upper limit of the content of constituent units derived from other monomers in 100% by mass of all constituent units of the hydroxyl-containing (meth)acrylic resin can be exemplified by 10% by mass, 9% by mass, 5% by mass, 4% by mass, 1% by mass, etc., the lower limit can be exemplified by 9% by mass, 5% by mass, 4% by mass, 1% by mass, 0% by mass, etc. In one embodiment, the content range of the constituent units derived from other monomers in 100% by mass of all the constituent units of the hydroxyl-containing (meth)acrylic resin is desirably about 0% by mass to 10% by mass.

Ratio of the amount of the constituent unit derived from other monomers to the constituent unit derived from the (meth)acrylic acid alkyl group not containing hydroxyl groups in the hydroxyl-containing (meth)acrylic resin (other monomers _mol /excluded) The upper limit of the hydroxyl (alkyl) (meth)acrylate ( _mol ) can be exemplified by 0.22, 0.20, 0.15, 0.10, 0.05, etc., and the lower limit can be exemplified by 0.20, 0.15, 0.10, 0.05, 0, etc. In one embodiment, the ratio of the amounts of the constituent units derived from other monomers to the constituent units derived from the (meth)acrylic acid alkyl group not containing hydroxyl groups in the hydroxyl-containing (meth)acrylic resin ( The other monomer _mol /hydroxy-free alkyl (meth)acrylate _mol ) is ideally about 0~0.22.

Mass ratio of structural units derived from other monomers to structural units derived from (meth)acrylic acid alkyl groups not containing hydroxyl groups in (meth)acrylic resins containing hydroxyl groups (other monomer _mass /hydroxyl group-free ( The upper limit of the alkyl meth) acrylate _mass ) can be exemplified by 0.19, 0.15, 0.10, 0.05, etc., and the lower limit can be exemplified by 0.15, 0.10, 0.05, 0, etc. In one embodiment, the mass ratio of structural units derived from other monomers in the hydroxyl-containing (meth)acrylic resin to structural units derived from alkyl (meth)acrylates not containing hydroxyl groups (other monomers) _mass /hydroxy-free (meth)acrylate ( _mass ) is ideally about 0~0.19.

The ratio of the amount of the constituent unit derived from other monomers to the constituent unit derived from the hydroxyl-containing (meth)acrylic acid resin in the hydroxyl-containing (meth)acrylic resin (other monomer _mol / hydroxyl-containing The upper limit of (meth)acrylic acid _mol ) can be 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 can be exemplified by 7.5, 7.0, 6.0, 5.0, 4.0, 3.0, 2.0, 1.0 , 0.5, 0, etc. In one embodiment, the ratio of the amount of substances derived from the constituent units of other monomers in the hydroxyl-containing (meth)acrylic resin to the constituent units derived from the hydroxyl-containing (meth)acrylic acid alkyl ester (other The monomer _mol /hydroxy-containing alkyl (meth)acrylate _mol ) is ideally about 0 to 8.0.

Mass ratio of structural units derived from other monomers in hydroxyl-containing (meth)acrylic resin to structural units derived from hydroxyl-containing (meth)acrylic acid alkyl ester (other monomer _mass / hydroxyl-containing (methyl ) The upper limit of alkyl acrylate _mass ) can be exemplified by 5.0, 4.0, 3.0, 2.0, 1.0, 0.5, etc., and the lower limit can be exemplified by 4.5, 4.0, 3.0, 2.0, 1.0, 0.5, 0, etc. In one embodiment, the mass ratio of the structural unit derived from other monomers to the structural unit derived from hydroxyl-containing (meth)acrylic acid in the hydroxyl-containing (meth)acrylic resin (other monomer _mass / (Hydroxyl-containing (meth) acrylate ( _mass )) is ideally about 0 to 5.0.

In one embodiment, as the hydroxyl group-containing (meth)acrylic resin, from the viewpoint of self-healing and antifouling properties, it is preferably a resin containing a hydroxyl group-containing monomer and a hydroxyl group-free monomer, more preferably It is a resin containing hydroxyl-containing monomers. In addition, in one embodiment, the hydroxyl-containing (meth)acrylic resin preferably contains one or more kinds selected from methyl (meth)acrylate, butyl (meth)acrylate, and (meth)acrylic acid 2- Hydroxyethyl resin.

<Physical properties of hydroxyl-containing (meth)acrylic resin, etc.>

The upper limit of the glass transition temperature of the hydroxyl group-containing (meth)acrylic resin can be exemplified by 100°C, 90°C, 80°C, 70°C, 60°C, etc., and the lower limit can be exemplified by 90°C, 80°C, 70°C, 60°C, 50°C , 40 ℃ and so on. In one embodiment, the glass transition temperature of the hydroxyl group-containing (meth)acrylic resin is preferably from 40 to 100°C from the viewpoint of excellent processability of the film and cured product. In addition, in one embodiment, the glass transition temperature of the hydroxyl-containing (meth)acrylic resin is ideally 40 to 90°C from the viewpoint that both the self-healing properties and the workability of the film and the cured product are particularly excellent. More desirably 40 to 80°C, further more desirably 40 to 70°C, particularly desirably 50 to 70°C, even more desirably 50 to 60°C.

The glass transition temperature is calculated by the Fox formula.

Fox formula: 1/Tg=(Wa/Tga)+(Wb/Tgb)+...+(Wn/Tgn)

Tg: glass transition temperature of the copolymer (K)

Wa: Mass% of monomer A

Tga: Glass transition temperature of homopolymer of monomer A (K)

Wb: mass% of monomer B

Tgb: glass transition temperature of homopolymer of monomer B (K)

Wn: mass% of monomer N

Tgn: glass transition temperature of homopolymer of monomer N (K)

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

In the present invention, the hydroxyl equivalent is the amount of the hydroxyl group present in 1 g of the solid.

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

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-containing (meth)acrylic resin can be exemplified by 100,000, 90,000, 80,000, 70,000, 60,000, 50,000, 40,000, 30000, 20000, 10000, 5000, 4000, etc., and the lower limit can be exemplified by 90,000, 80000, 70000, 60000, 50000, 40000, 30000, 20000, 10000, 5000, 4000, 3000, etc. In one embodiment, the weight-average molecular weight (Mw) of the hydroxyl-containing (meth)acrylic resin is considered from the viewpoints of the blocking resistance, initial adhesion, and moisture and heat resistance of the self-healing coating agent. Ideally, it is about 3,000 to 100,000, and more preferably about 10,000 to 80,000.

The upper limit of the number average molecular weight (Mn) of the hydroxyl-containing (meth)acrylic resin can be exemplified by 100,000, 90,000, 80000, 70000, 60000, 50,000, 40,000, 30000, 20,000, 10000, 5000, 4000, etc., and the lower limit can be exemplified by 90,000, 80000, 70000, 60000, 50000, 40000, 30000, 20000, 10000, 5000, 4000, 3000, etc. In one embodiment, the number-average molecular weight (Mn) of the hydroxyl-containing (meth)acrylic resin is from the viewpoint of the blocking resistance, initial adhesion and moisture-heat adhesion of the self-healing coating agent Ideally, it is about 3,000 to 100,000, and more preferably about 10,000 to 80,000.

In the present invention, the weight average molecular weight and the number average molecular weight are measured by gel permeation chromatography (GPC) as a polystyrene conversion value measured in an appropriate solvent.

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

The hydroxyl-containing (meth)acrylic resin can be produced by various conventional methods. An example of a method for producing a hydroxyl-containing (meth)acrylic resin is to use a non-hydroxyl-containing (meth)acrylic acid alkyl ester, a hydroxyl-containing (meth)acrylic acid alkyl ester, and other monomers as needed in a solvent-free In a low temperature or organic solvent, a method of performing a copolymerization reaction at about 80° C. to 180° C. for about 1 hour to 10 hours in the presence of a polymerization initiator is generally used. Examples of organic solvents and polymerization initiators used when producing hydroxyl-containing (meth)acrylic resins include various conventional organic solvents and polymerization initiators, and/or organic solvents and polymerization initiators described below.

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

<Hydroxy-containing polysiloxane>

The hydroxyl-containing polysiloxane can be used alone or in combination of two or more. In the present invention, the hydroxyl-containing polysiloxane refers to a polymer having a hydroxyl group in the molecule and a main chain having a siloxane bond. Hydroxy-containing polysiloxane, exemplified by acrylic polymer modified hydroxyl-containing polysiloxane, polyester modified hydroxyl-containing polysiloxane, polyether modified hydroxyl-containing polysiloxane, methanol modification Hydroxy-containing polysiloxane and other organically modified hydroxyl-containing polysiloxane. In addition, from the viewpoint of good reactivity, the hydroxyl group is preferably included in the modified site. Among various polysiloxanes, by using hydroxyl-containing polysiloxanes, the cured products and films obtained by hardening the self-healing coating agent of the present invention are excellent in transparency.

Commercial products of acrylic polymer-modified hydroxyl-containing polysiloxanes can be exemplified by ZX-028-G (manufactured by T & K TOKA Co., Ltd.), BYK-SILCLEAN 3700 (manufactured by BYK Chemical Co., Ltd. of Japan), SYMAC US-270 (manufactured by East Asia Synthetic Co., Ltd.), etc.

Commercial products of polyether-modified hydroxyl-containing polysiloxane or polyester-modified hydroxyl-containing polysiloxane can be exemplified by BYK-370, BYK-375, BYK-377, BYK-SILCLEAN3720 (Bike Chemical. Made in Japan Co., Ltd.), X-22-4952, KF-6123 (made by Shin-Etsu Chemical Industry Co., Ltd.), etc.

Commercial products of methanol-modified hydroxyl-containing polysiloxanes can be exemplified by 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-DA26 (manufactured by JNC Corporation), etc.

In one embodiment, the content of the hydroxyl-containing polysiloxane in the self-healing coating agent is ideally 1-10% by mass.

In one embodiment, the mass ratio of hydroxyl-containing (meth)acrylic resin to hydroxyl-containing polysiloxane in the self-healing coating agent (hydroxyl-containing (meth)acrylic resin _mass /hydroxyl-containing silicon _Mass poly siloxane), over 10 to 30, more preferably from 15 to 25.

<polyisocyanate>

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

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

The straight-chain aliphatic group may, for example, be a straight-chain alkylene group. Linear alkylene group, which can be represented by the general formula -(CH ₂ ) _n- (n is an integer of 1 or more), exemplified by methylene, ethylene, propylene, n-butylene, n-pentylene, N-hexylene, n-heptylene, n-octylene, n-nonylene, n-decyl methylene, etc.

Linear aliphatic polyisocyanate, exemplified by methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, Heptamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, etc.

The branched aliphatic group may be exemplified by a branched alkylene 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. Specific examples include diethylpentylene, trimethylbutylene, trimethylpentylene, tri Methylhexylene (trimethylhexamethylene), etc.

Examples of branched aliphatic polyisocyanates include diethylpentyl diisocyanate, trimethylbutylene diisocyanate, trimethylpentylene diisocyanate, and trimethylhexamethylene diisocyanate.

The alicyclic group may be exemplified by a monocyclic alicyclic group, a bridged alicyclic group, a condensed alicyclic group, and the like. In addition, the cycloalkylene group may be substituted with more than one hydrogen by a linear or branched alkyl group.

In the present invention, a single ring refers to a ring structure that does not have a bridge structure inside a covalent bond of carbon. In addition, a fused ring refers to a cyclic structure in which two or more single rings share two atoms (that is, each ring shares (fused) only one side with each other). A bridge ring refers to a ring structure in which more than two single rings share more than three atoms.

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

Examples of the bridged alicyclic group include tricyclodecylene, adamantylene, and norbornylene.

Examples of the fused cycloaliphatic group include bicyclodecylene.

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

Monocyclic alicyclic polyisocyanate, exemplified by hydrogenated xylylene diisocyanate, isophorone diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, cycloheptyl diisocyanate, cyclodecene Diisocyanate, 3,5,5-trimethylcyclohexylene diisocyanate, dicyclohexylmethane diisocyanate, etc.

Examples of bridged cycloaliphatic polyisocyanates include tricyclodecyl diisocyanate, adamantane diisocyanate, norbornene diisocyanate, and the like.

Examples of the fused cycloaliphatic polyisocyanate include bicyclodecyl diisocyanate.

The number of carbon atoms of the aliphatic group is not particularly limited, and the upper limit may be exemplified by 30, 29, 25, 20, 16, 12, 10, 9, 8, 7, 7, 6, 5, 4, 3, 2, etc., the lower limit may be Examples are 29, 25, 20, 16, 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 desirably 1-30, more desirably 1-20, further desirably 1-16, and particularly desirably 1-12.

Examples of the aromatic group include phenylene and naphthylene.

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

In one embodiment, the polyisocyanate is preferably an aliphatic polyisocyanate from the viewpoint of weather resistance and self-healing properties, and more preferably a linear aliphatic polyisocyanate.

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

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

In one embodiment, the total content of one or more of the self-healing coating agents selected from the group consisting of hydroxyl-containing (meth)acrylic resins and hydroxyl-containing polysiloxanes and polyisocyanates mass ratio of (total content _maas resin, hydroxyl group-containing poly-silicon and siloxane groups in the one or more selected from the group consisting of hydroxyl group-containing (meth) acrylate / polyisocyanate _mass) over 1 / 0.2 to 1/20.

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

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

In one embodiment, the polyisocyanate in the above-mentioned self-healing coating agent is desirably an urea containing an adduct selected from polyisocyanate and a polyisocyanate, because of its excellent antifouling properties and processability. Two or more of carbamate body, polyisocyanate biuret body and polyisocyanate isocyanurate body; more preferably, polyisocyanate adducts and polyisocyanate isocyanurate body, Polyisocyanate allophanate body and polyisocyanate biuret body, or polyisocyanate adduct and polyisocyanate biuret body. Among these combinations, from the viewpoint of being particularly excellent in both antifouling properties and processability, it is most desirable to include a polyisocyanate adduct and a polyisocyanate biuret.

In one embodiment, in the case where the above-mentioned self-healing coating agent contains two polyisocyanates, the total content of the two polyisocyanates is 100% by mass, and the content of each polyisocyanate is ideally 20 to 80% by mass. It is more preferably 30 to 80% by mass, further more preferably 30 to 70% by mass, particularly ideal 35 to 70% by mass, further particularly ideal 35 to 65% by mass, and most preferably 40 to 60% by mass. When the two kinds of polyisocyanates are within the above-mentioned range, the self-healing property and processability become better than those outside the range.

In one embodiment, when the above-mentioned self-healing coating agent contains two polyisocyanates, the mass ratio of the two polyisocyanates (one polyisocyanate _mass /another polyisocyanate _mass ) is ideally 0.1 to 5, More preferably, it is 0.5~3, and further more preferably, it is 0.7~2. When the two kinds of polyisocyanates are within the above-mentioned range, the self-healing property and processability become better than those outside the range.

<adduct of polyisocyanate>

The polyisocyanate adduct may be used alone or in combination of two or more. When manufacturing the polyisocyanate adduct, the polyisocyanate may be used alone or in combination of two or more. The polyisocyanate can be exemplified by the above-mentioned polyisocyanates and the like.

The polyisocyanate adducts can be exemplified: the adducts of trimethylolpropane and polyisocyanate represented by the following general formula,

^(Wherein, R adA ~ R adE are each independently an alkylene group or an arylene ^group, R adD ~ R adE in the unit constituting the respective groups may be different .n ^ad is an integer of 0 or more is over 0 ~ .n ^ad 3); The adduct of glycerin and polyisocyanate represented by the following general formula,

(In the formula, R ^adα ~ R ^adε are each independently an alkylene group or an arylene group, and R ^adδ ~ R ^adε may be different in each constituent unit. n ^ad1 is an integer of 0 or more. n ^{ad1 is} ideally 0 ~ 3) Wait.

^And, R adα ~ R adε radicals ^R adA ~ R adE the above formula and the above formula may have various functional groups are more than one ester group, an ether group or a carbonyl group.

Commercial products of polyisocyanate adducts can be exemplified: Duranate P301-75E (manufactured by Asahi Kasei Corporation), Duranate E402-80B (manufactured by Asahi Kasei Corporation), Duranate E405-70B (manufactured by Asahi Kasei Corporation), Coronate HL (manufactured by Tosoh Corporation), Burnock D-750 (manufactured by DIC Corporation), etc.

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

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

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

In one embodiment, the NCO content (NCO%) of the polyisocyanate adduct is ideally 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 total content of one or more of the self-healing coating agents selected from the group consisting of hydroxyl-containing (meth)acrylic resins and hydroxyl-containing polysiloxanes and polyisocyanates The mass ratio of the adduct (a total content of more than one _mass /polyisocyanate adduct _mass selected from the group consisting of hydroxyl-containing (meth)acrylic resin and hydroxyl-containing polysiloxane) is ideally 1 /0.2~1/20.

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

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

<Allophanate body of polyisocyanate>

The polyisocyanate allophanate can be used alone or in combination of two or more. When manufacturing the allophanate body of polyisocyanate, the polyisocyanate may be used alone or in combination of two or more. The polyisocyanate can be exemplified by the above-mentioned polyisocyanates and the like.

Examples of the allophanate body of polyisocyanate include compounds represented by the following general formula.

【Chemical 5】

[In the formula, 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 ~ R ^AL6 are each independently an alkylene group or an arylene group, and R ^AL '~R ^AL ''' are independently an isocyanate group or a group of R ^ALα ~ R ^Alγ itself group.

"R ^AL1 ~ R ^{AL4 "} , R ^AL '~ R ^AL " may be different in each constituent unit.).

The groups of R ^ALB ~R ^ALE and R ^ALα ~R ^ALβ may be different in each constituent unit. ]

Commercial products of polyisocyanate allophanate bodies can be exemplified by Takenate D-178N (Mitsui Chemical Co., Ltd.), Coronate 2770 (Tosoh Co., Ltd.), Coronate 2793 (Tosoh Co., Ltd.) , Duranate A201H (made by Asahi Kasei Corporation), etc.

In one embodiment, the weight-average molecular weight (Mw) of the allophanate body of polyisocyanate is ideally 800 to 3500.

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

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

Examples of the upper limit of the NCO content (NCO%) of the allophanate body of polyisocyanate include 30% by mass, 25% by mass, 20% by mass, and 15% by mass. Examples of the lower limit include 25% by mass and 20% by mass. Mass%, 15 mass%, 10 mass%, 5 mass%, etc. In one embodiment, the NCO content (NCO%) of the allophanate body of polyisocyanate is desirably 5 to 30% by mass.

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

In one embodiment, the total content of one or more of the self-healing coating agents selected from the group consisting of hydroxyl-containing (meth)acrylic resins and hydroxyl-containing polysiloxanes and polyisocyanates Mass ratio of allophanate body (all selected from the group consisting of hydroxyl-containing (meth)acrylic resin and hydroxyl-containing polysiloxane) total content of _mass /polyisocyanate allophanate Body _mass ) Ideally 2/5~15/1.

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

In one embodiment, the mass ratio of the hydroxyl-containing polysiloxane to the polyisocyanate allophanate body in the self-healing coating agent (hydroxyl-containing polysiloxane _mass /polyisocyanate urea The carbamate _mass ) is ideally 0.1/1 to 1/1.

<polyisocyanate biuret>

The polyisocyanate biuret may be used alone or in combination of two or more. In the production of a polyisocyanate biuret, the polyisocyanate may be used alone or in combination of two or more. The polyisocyanate can be exemplified by the above-mentioned polyisocyanates and the like.

Examples of the polyisocyanate biuret include compounds represented by the following general formula.

[In the formula, n ^b is an integer of 0 or more, R ^bA to R ^bE are each independently an alkylene group or an arylene group, and 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, and R ^b ′ to R ^b ”are each independently an isocyanate group or a group of R ^bα to R ^bβ itself.

R ^b4 ~R ^b5 and R ^b ”may be different in each constituent unit.).

The groups of R ^bD ~R ^bE and R ^bβ may be different in each constituent unit. ]

Polyisocyanate biuret can be exemplified by Duranate 24A-100, Duranate 22A-75P, Duranate 21S-75E (above manufactured by Asahi Kasei Corporation), Desmodur N3200A (biuret of hexamethylene diisocyanate) ( The above is manufactured by Sumitomo Bayer Polyurethane Co., Ltd.).

In one embodiment, the weight average molecular weight (Mw) of the polyisocyanate biuret is ideally 500 to 1500.

In one embodiment, the polyisocyanate biuret has a number average molecular weight (Mn) of 500 to 1500.

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

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

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

In one embodiment, the total content of one or more of the self-healing coating agents selected from the group consisting of hydroxyl-containing (meth)acrylic resins and hydroxyl-containing polysiloxanes and polyisocyanates The mass ratio of the biuret body (the total content of more than one _mass /polyisocyanate biuret _mass selected from the group consisting of (meth)acrylic resins containing hydroxyl groups and polysiloxanes containing hydroxyl groups) is ideal It is 1/0.1~1/10.

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

In one embodiment, the mass ratio of the hydroxyl-containing polysiloxane to the polyisocyanate biuret in the self-healing coating agent (hydroxyl-containing polysiloxane _mass /polyisocyanate biuret Body _mass ) is ideally 0.1/1~0.3/1.

In one embodiment, the mass ratio of the polyisocyanate allophanate body to the polyisocyanate biuret body in the above-mentioned self-healing coating agent (polyisocyanate allophanate body _mass /polyisocyanate The biuret _mass ) is ideally 1/6~1/1.

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

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

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 body of polyisocyanate>

The isocyanurate body of the polyisocyanate may be used alone, or two or more kinds may be used in combination. When producing an isocyanurate body of polyisocyanate, the polyisocyanate may be used alone or in combination of two or more. The polyisocyanate can be exemplified by the above-mentioned polyisocyanates and the like.

Examples of the isocyanurate body of the polyisocyanate include compounds represented by the following general formula.

[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 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, and R ⁱ ′ to R ⁱ ”are each independently an isocyanate group or a group of R ^iα to R ^iβ itself.

R ⁱ⁴ ~R ⁱ⁵ and R ⁱ ”may be different in each constituent unit.).

R ^iD ~R ^iE and R ^iβ may be different in each constituent unit. ]

Isocyanurate body of polyisocyanate, such as Duranate TPA-100, Duranate TKA-100, Duranate MFA-75B, Duranate MHG-80B (above manufactured by Asahi Kasei Corporation), Coronate HXR (hexamethylene diisocyanate (Isocyanurate body) (the above is manufactured by Tosoh Corporation), Takenate D-127N (isocyanurate body of hydrogenated xylylene diisocyanate) (the above is manufactured by Mitsui Chemicals Co., Ltd.) , VESTANAT T1890/100 (isocyanurate body of isophorone diisocyanate (above manufactured by Evonik Japan Co., Ltd.), etc.

In one embodiment, the isocyanurate body of the polyisocyanate preferably has a weight average molecular weight (Mw) of 500 to 1500.

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

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

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

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

In one embodiment, the total content of one or more of the self-healing coating agents selected from the group consisting of hydroxyl-containing (meth)acrylic resins and hydroxyl-containing polysiloxanes and polyisocyanates Mass ratio of isocyanurate body (isocyanurate of total content of more than one kind selected from the group consisting of (meth)acrylic resin containing hydroxyl group and polysiloxane containing hydroxyl group _mass /polyisocyanate The body _mass ) is ideally 1/0.1~1/5.

In one embodiment, the mass ratio of the hydroxyl-containing (meth)acrylic resin to the polyisocyanate isocyanurate body (hydroxyl-containing (meth)acrylic resin _mass / The isocyanurate _{mass of} polyisocyanate is ideally 1/0.1~1/2.

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

In one embodiment, the mass ratio of the polyisocyanate adduct to the polyisocyanate isocyanurate body in the above-mentioned self-healing coating agent (polyisocyanate adduct _mass /polyisocyanate isocyanurate The acid ester _mass ) is ideally 1/6~1/0.5.

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

In one embodiment, the self-healing coating agent is selected from the group consisting of polyisocyanate adducts, polyisocyanate allophanate bodies, polyisocyanate biuret bodies, and polyisocyanate isocyanurates The total content of two or more types in the ester body is preferably 10 to 60% by mass.

<polycarbonate polyol>

In the present invention, "polycarbonate polyol" is a compound having two or more carbonate groups (-O-(C=O)-O-) and having two or more hydroxyl groups. Examples of polycarbonate polyols include polycarbonate diols, polycarbonate triols, and polycarbonate tetraols. The polycarbonate polyol may be used alone or in combination of two or more. In addition, when the polycarbonate polyol is used in the self-healing coating agent of the present invention, the compatibility is better than when the polyether polyol is used. As the reason why the film using the self-healing coating agent of the present invention is excellent in hardness and antifouling property, although the precise mechanism is not clear, it is considered to be related to the good compatibility.

Polycarbonate polyols are synthesized by conventional methods such as phosgene method and transesterification reaction. For example, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1, Polyols such as 5-pentanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,10-decanediol, and diphenyl carbonate, Carbonic acid derivatives such as dimethyl carbonate, diethyl carbonate, diethylene carbonate, and phosgene are reacted to obtain polycarbonate polyols.

Examples of commercially available polycarbonate diols include BENEBiOL (manufactured by Mitsubishi Chemical Corporation), NIPPOLLAN 981 (manufactured by Tosoh Corporation), Duranol G3450J (manufactured by Asahi Kasei Corporation), and Duranol G3452 (Asahi Chemical Co., Ltd.) (Made by the company), Duranol T5652 (made by Asahi Kasei Corporation), KURARAY POLYOL C-590 (made by Kuraray Co., Ltd.), KURARAY POLYOL C-1090 (made by Kuraray Co., Ltd.), etc.

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

Examples of the aliphatic polycarbonate polyol include linear aliphatic polycarbonate polyol, branched aliphatic polycarbonate polyol, and alicyclic polycarbonate polyol.

In one embodiment, from the viewpoint of weather resistance and self-healing properties, the polycarbonate polyol is preferably an aliphatic polycarbonate polyol, and more preferably a linear aliphatic polycarbonate polyol.

In one embodiment, the content of the polycarbonate polyol in the self-healing coating agent is ideally 10-40% 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. By setting the hydroxyl value of the polycarbonate polyol 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. By making the weight average molecular weight of the polycarbonate polyol within the above range, the processability becomes better.

In one embodiment, the number average molecular weight (Mn) of the polycarbonate polyol is preferably 500-1000, and 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 molecular weight distribution (Mw/Mn) of the polycarbonate polyol is ideally 1.0 to 1.5.

In one embodiment, the total content of the self-healing coating agent selected from the group consisting of hydroxyl-containing (meth)acrylic resin, hydroxyl-containing polysiloxane, and polyisocyanate and Mass ratio of polycarbonate polyol (a total content of one or more selected from the group consisting of hydroxyl-containing (meth)acrylic resin, hydroxyl-containing polysiloxane, and polyisocyanate _mass /polycarbonate polyol _mass ), ideally 0.01~70, more ideally 0.05~4.

In one embodiment, from the viewpoint of good compatibility between the hydroxyl-containing (meth)acrylic resin and polycarbonate polyol, and excellent transparency of the coating film, the hydroxyl-containing The mass ratio of (meth)acrylic resin to polycarbonate polyol (hydroxyl-containing (meth)acrylic resin _mass /polycarbonate polyol _mass ) is preferably _3/1 to 1/4, further preferably 3/ 1~1/1.

In one embodiment, the mass ratio of hydroxyl-containing polysiloxane to polycarbonate polyol (hydroxyl-containing polysiloxane _mass /polycarbonate polyol _mass ) in the above-mentioned self-healing coating agent is ideal It is 0.05~10.

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

In one embodiment, the total content of the hydroxyl-containing (meth)acrylic resin, hydroxyl-containing polysiloxane, polyisocyanate, and polycarbonate polyol in the above-mentioned self-healing coating agent is set to 100 mass %, the content of hydroxyl-containing (meth)acrylic resin is ideally 30 to 70% by mass, more preferably 40 to 70% by mass, further more preferably 40 to 60% by mass, and particularly preferably 40 to 55% by mass; The content of hydroxyl-containing polysiloxane is ideally 1 to 10% by mass, more preferably 1 to 5% by mass, further more preferably 2 to 5% by mass, and particularly ideally 2 to 3% by mass; the content of polyisocyanate is ideal 10 to 50% by mass, more preferably 10 to 45% by mass, further more preferably 10 to 40% by mass, particularly preferably 15 to 35% by mass; the content of polycarbonate polyol is ideally 15 to 40% by mass, It is more desirably 15 to 35% by mass, further more desirably 20 to 35% by mass, and particularly desirably 20 to 30% by mass.

<hardening catalyst>

In one embodiment, the self-healing coating agent may contain a hardening catalyst. The hardening catalyst may be contained alone or in combination of two or more.

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

Examples of the organometallic catalyst include organic typical metal catalysts, organic transition metal catalysts, and the like.

Typical organic metal catalysts include organic tin catalysts and organic bismuth catalysts.

Examples of organotin catalysts include dibutyltin dilaurate and dioctyltin dilaurate.

Examples of organic bismuth catalysts include bismuth octoate.

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

Examples of organic titanium catalysts include ethyl acetoacetate and titanium.

The organic zirconium catalyst may be exemplified by zirconium tetraacetone acetone.

Examples of organic iron catalysts include acetoacetone iron and the like.

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

When the self-healing coating agent contains a hardening catalyst, the upper limit of the content of the hardening catalyst in the self-healing coating agent can be exemplified by 1% by mass, 0.9% by mass, 0.75% by mass, 0.5% by mass, and 0.25 Mass%, 0.1 mass%, 0.09 mass%, 0.05 mass%, 0.02 mass%, etc., the lower limit can be 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% by mass, 0.01% by mass, etc. In one embodiment, when the self-healing coating agent contains a hardening catalyst, the content of the hardening catalyst in the self-healing coating agent is preferably about 0.01% by mass to 1% by mass.

In one embodiment, the curing catalyst is preferably an organotin catalyst from the viewpoint of curability, shelf life, workability, and coating film appearance, and more preferably dioctyltin dilaurate.

<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. 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; alcohols such as methanol, ethanol, n-propanol, isopropanol and butanol Solvents; glycol ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and propylene glycol monomethyl ether acetate Solvents; ester solvents such as ethyl acetate, butyl acetate, methyl celulose acetate and celulose acetate; Solvesso #100 and Solvesso #150 (both trade names. manufactured by Exxon Corporation) and other petroleum solvents; Halogen solvents such as chloroform; amide solvents such as dimethylformamide, etc. Among them, 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 it is preferable to contain acetone in the ketone-based organic solvent.

In the case where the above-mentioned self-healing coating agent contains an organic solvent, the upper limit of the content of the organic solvent in the above-mentioned self-healing coating agent can be exemplified by 90% by mass, 80% by mass, 70% by mass, 60% by mass, 55 Mass%, etc., the lower limit can be exemplified by 85% by mass, 80% by mass, 70% 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, etc. In one embodiment, when the self-healing coating agent contains an organic solvent, the content of the organic solvent in the self-healing coating agent is desirably about 20% by mass to 90% by mass. In addition, the organic solvent contained in the self-healing coating agent may contain the hydroxyl group-containing (meth)acrylic resin, the hydroxyl group-containing polysiloxane, the polyisocyanate, and the curing catalyst. Organic solvent.

<additive>

The self-healing coating agent may contain reagents other than hydroxyl group-containing (meth)acrylic resin, hydroxyl group-containing polysiloxane, polyisocyanate, polycarbonate polyol, hardening catalyst, and organic solvent as additives. Examples of additives include polymerization inhibitors, antioxidants, light stabilizers, defoamers, surface conditioners, pigments, antistatic agents, metal oxide fine particle dispersions, organic fine particle dispersions, and the like. In one embodiment, as an example of the content of the additive, about 0.1% by mass to 10% by mass, about less than 10 parts by mass, about less than 5 parts by mass, and about less than 1 part by mass of the above-mentioned self-healing coating agent may be exemplified. , About less than 0.1 parts by mass, about less than 0.01 parts by mass, about 0 parts by mass, etc.

The above-mentioned self-healing coating agent may include, by various conventional means, a hydroxyl-containing (meth)acrylic resin, a hydroxyl-containing polysiloxane, a polyisocyanate, a polycarbonate polyol, a hardening catalyst, The method of the step of mixing organic solvents and/or additives is obtained.

[Hardened]

The present invention provides a hardened product of the above-mentioned self-healing coating agent. The conditions at the time of manufacturing the above-mentioned cured product may be exemplified below.

[Film]

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

As the substrate, various conventional substrates are used. Examples of the substrate include polycarbonate film, (meth)acrylic film (poly(meth)acrylate film, etc.), polystyrene film, polyester film, polyolefin film, epoxy resin film, melamine resin film, Cellulose triacetate film, ABS film, AS film, norbornene-based resin film, cyclic olefin film, polyvinyl alcohol film, etc. The thickness of the substrate is also not particularly limited, but it is preferably about 50 μm to 200 μm. In addition, the thickness of the coating layer is not particularly limited, but is preferably about 5 μm to 30 μm.

The above-mentioned film is manufactured by various conventional methods. In one embodiment, the method of manufacturing the film includes a step of applying a self-healing coating agent on at least one side of the substrate (coating step), and a step of thermally curing to form a hardened layer of the self-healing coating agent. (Thermal hardening step).

The film of the present invention can be used as a top coat in various layers of decorative films.

Examples of the types of decorative films include, for example, (1) top coat layer, anchor layer, decorative layer, easy adhesion layer, plastic film, functional layer, and adhesion layer; (2) top coat layer, easy adhesion layer, plastic The order of film, easy adhesion layer, decorative layer, functional layer, and adhesion layer; (3) top coating, anchor layer, decoration layer, functional layer, adhesion layer sequence; (4) top coating, anchor layer, decoration layer 、The order of the next layer; (5) The order of the top coat, decorative layer and the next layer

Composition of decorative films, etc. In addition, the decorative layer may have one or more types selected from a metal layer, a vapor-deposited layer, a colored layer, a printed layer, a multicolor printed layer, and a holographic layer.

The decorative film can be coated and laminated on various layers of the base film by conventional methods such as gravure coating method, roll coating method, spray coating method, comma coating method, lip coating method, gravure printing method, screen printing method, etc. And get. Among the various methods described above, the gravure printing method is desirable from the viewpoint of productivity. In addition, the base film may have a release layer if necessary.

The top coat of the decorative film can be obtained by hardening the self-healing coating agent of the present invention by heat treatment. This heat treatment is ideally heated at a temperature of 80°C to 160°C for 30 seconds to 30 minutes. From the viewpoint of excellent scratch resistance, the thickness of the top coat layer thus obtained is desirably about 5 μm to 30 μm.

The decorative film thus obtained can be formed on the surface of the object to be decorated, such as various electrical products such as mobile phones and televisions, various vehicles such as automobiles and motorcycles.

As a method of attaching the decorative film to the object to be decorated, it may be a primary decoration that attaches the decorative film in the mold for molding the object to be decorated (hereinafter also referred to as "in-mold decoration"), or it may be taken out from the mold The secondary decoration to which the decorative film is attached after being decorated (hereinafter also referred to as "out-of-mold decoration", "post-mold decoration", "overlay molding"). Decoration can be carried out by attaching the substrate film to the object to be decorated together, or by attaching the decoration film to the object to be decorated and transferring the substrate film and the release layer Method. Specific examples of the transfer include in-mold transfer, cover transfer, thermal transfer, water transfer, and pressure-sensitive transfer. Specific examples of the bonding include in-mold bonding and TOM process.

(Coating step)

Examples of the coating method include bar coater coating, wire bar coating, mayer 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. Regarding the coating amount, the mass after drying is usually preferably about 0.1 g/m ² to 30 g/m ² , and more preferably about 1 g/m ² to 20 g/m ² .

(Thermosetting step)

The drying method can be exemplified by drying using a wind 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. As another curing method, photo-curing is known, but from the viewpoint of workability, thermal curing is more desirable.

When manufacturing a film, it is subjected to aging treatment after drying as necessary. As an example, an aging treatment at 40°C for 72 hours and the like can be exemplified.

【Example】

Hereinafter, the present invention will be specifically described by Examples and Comparative Examples. However, the purpose of providing the description of the above-mentioned ideal embodiment and the following embodiments is only for illustration, not for limiting the present invention. Therefore, the scope of the present invention is not limited to the embodiments and examples specifically described in this specification, but only by the scope of the patent application. In addition, in each of the Examples and Comparative Examples, unless otherwise specified, the numerical values of parts, %, and the like are based on mass.

<Preparation of (meth)acrylic resin>

[Resin A]

In a reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen introduction tube, 58 parts of methyl methacrylate (hereinafter also referred to as MMA) and n-butyl acrylate (hereinafter also referred to as BA) 32 were charged Parts, 10 parts of 2-hydroxyethyl acrylate (hereinafter also referred to as HEA) and 412.5 parts of ethyl acetate, and the reaction system was set to 77°C. Next, 2.3 parts of 2,2'-azobisisobutyronitrile was added, and the temperature was kept at 80°C for 5 hours. Next, 3.0 parts of 2,2'-azobisisobutyronitrile was added, and the reaction system was further kept at the same temperature for 4 hours. Then, by cooling the reaction system to room temperature, a solution of resin A having the physical properties described in Table 1 (nonvolatile content 35%) was obtained.

[Resin B, Resin C]

Except that the raw material was changed to the raw material described in Table 1, it was performed in the same manner as the preparation of resin A. Table 1 shows the physical properties of the obtained resin B and resin C. In addition, the acid values of resin A, resin B, and resin C are all 0 mgKOH/g.

Each raw material is a unit of mass.

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 (made by Asahi Kasei Co., Ltd., trade name: Duranol G3450J) (solid content concentration 100%), 27.5 parts of hexamethylene diisocyanate adduct (Made by Asahi Kasei Corporation, trade name: Duranate E402-80B) (solid content concentration 80%), 19.4 parts of biuret of hexamethylene diisocyanate (made by Asahi Kasei Corporation, trade name: Duranate 24A100) (Solid content concentration 100%), 5.1 parts of acrylic polymer modified hydroxyl-containing polysiloxane (Bike Chemical. Japan Co., Ltd., trade name: BYK-SILCLEAN3700) (solid content concentration 25%), 0.13 1 part of dioctyltin dilaurate (solid content concentration 100%) (hereinafter also referred to as DOTDL), 121.5 parts of methyl ethyl ketone (hereinafter also referred to as MEK), and 12.6 parts of acetone (hereinafter also referred to as AcAc) . By thoroughly mixing the above ingredients, a self-healing coating agent with a solid content concentration of 38% was prepared.

Examples 2 to 9 and Comparative Examples 1 to 4

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

【Table 2】

Duranate E402-80B: manufactured by Asahi Kasei Co., Ltd., an adduct of hexamethylene diisocyanate (solid content concentration 80%)

Duranate 24A100: manufactured by Asahi Kasei Corporation, a biuret of hexamethylene diisocyanate (solid content concentration 100%)

Duranate TPA100: manufactured by Asahi Kasei Co., Ltd., isocyanurate body of hexamethylene diisocyanate (solid content concentration 100%)

Coronate 2793: Allophanate body of hexamethylene diisocyanate (solid content concentration 100%) manufactured by Tosoh Corporation

Duranol G3450J: manufactured by Asahi Kasei Co., Ltd., polycarbonate diol (solid content concentration 100%, number average molecular weight 800, hydroxyl value 140 mgKOH/g)

KURARAY POLYOL C-590: manufactured by Kuraray Co., Ltd., polycarbonate diol (solid content concentration 100%, number average molecular weight 500, hydroxyl value 224mgKOH/g)

KURARAY POLYOL C-1090: manufactured by Kuraray Co., Ltd., polycarbonate diol (solid content concentration 100%, number average molecular weight 1000, hydroxyl value 112mgKOH/g)

<Fabrication 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: COMOSHINE A4100, so that the coating film thickness after drying was 10 μm. 100 μm thick), it is heat-cured by drying at 120° C. for 60 seconds.

Evaluation Examples 2 to 9 and Comparative Evaluation Examples 1 to 4

The self-healing coating agents of Examples 2 to 9 and Comparative Examples 1 to 3 were prepared in the same manner as in Evaluation Example 1. In addition, the self-healing coating agent of Comparative Example 4 could not be hardened without forming a thin film.

<Restorability of the film>

At 25°C, a brass brush (manufactured by Azov Co., Ltd.) was used to reciprocate the surface of each film 10 times to form a flaw, and then the time until the flaw of the film disappeared was measured for evaluation. The evaluation criteria are as follows.

○: Recovery within 10 seconds.

△: Recovery within 11 seconds to 1 minute.

×: Repair takes more than 1 minute.

<Antifouling properties of film>

Imprint the mark on the surface of the film with oil-based ink (manufactured by Axel Co., Ltd., trade name: PERMANENT MAKER), and immediately wipe off the mark with a dry nonwoven fabric (made by Asahi Kasei Co., Ltd., trade name: BEMCOT M-3II) To evaluate. The evaluation criteria are as follows.

○: It can be wiped off with 5 times of wiping with a non-woven cloth.

△: Wiping with a non-woven cloth 5 or more times, the traces of the oily ink become lighter.

×: Unable to erase.

<Break elongation of film>

In accordance with the test conditions of JIS K 7127:1999 (Plastics-Test Methods for Tensile Properties-Part 3: Test Conditions for Films and Sheets), the elongation at break of the film alone was measured. As a method for producing the film alone, it is obtained by peeling off the film on the polyethylene terephthalate film produced in Evaluation Example 1 by hand. The shape of the film before the start of the test was set to a width of 5 mm, a thickness of 10 μm, and a length of 25 mm, and the test speed was set to 200 mm/min.

Elongation at break (%)=100×(L-25)/25

L: length of the hardened material when the hardened material is broken

<Appearance of film>

The film was visually confirmed according to the following criteria.

○: Excellent transparency and no foreign matter.

×: There is foreign matter or dirt.

Claims (7)

A self-healing coating agent characterized by containing hydroxyl-containing (meth)acrylic resin, hydroxyl-containing polysiloxane, polyisocyanate and polycarbonate polyol. The self-healing coating agent as described in item 1 of the patent application scope, wherein the polyisocyanate includes an adduct selected from polyisocyanate, an allophanate body of polyisocyanate, a biuret body of polyisocyanate and Two or more of the isocyanurate body of polyisocyanate. The self-healing coating agent as described in item 1 or 2 of the patent application scope, wherein the glass transition temperature of the hydroxyl-containing (meth)acrylic resin is 40 to 100°C. The self-healing coating agent as described in any one of claims 1 to 3, wherein the polycarbonate polyol has a number average molecular weight of 800 to 1,000. The self-healing coating agent as described in any one of claims 1 to 4, wherein the aforementioned hydroxyl-containing (meth)acrylic resin, hydroxyl-containing polysiloxane, polyisocyanate and polycarbonate When the total content of the ester polyol is set to 100% by mass, the content of the hydroxyl group-containing (meth)acrylic resin is 30 to 70% by mass, and the content of the hydroxyl group-containing polysiloxane is 1 to 10% by mass. The content is 10-50% by mass, and the content of the polycarbonate polyol is 15-40% by mass. A hardened product characterized in that it is a hardened product of a self-healing coating agent as described in any one of items 1 to 5 of the patent application. A film characterized by containing a hardened product as described in item 6 of the patent application.