KR20200001522A - Thermosetting coating agent, cured product and film - Google Patents

Abstract

The present invention relates to a thermosetting coating agent, a cured product and a film. The thermosetting coating agent comprises: (A) a hydroxyl group containing (meth)acrylic resin having the glass transition temperature of less than -20°C; (B) an organic modified silicone containing a hydroxyl group; and (C) an allophanate and/or burette body of polyisocyanate. In one embodiment, the thermosetting coating agent comprises a diol having a hydroxyl value of 200 mgKOH/g or more and molecular weight of 500 or less.

Description

Thermosetting Coatings, Cured Products and Films {THERMOSETTING COATING AGENT, CURED PRODUCT AND FILM}

The present disclosure relates to a thermosetting coating agent, a cured product, and a film.

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

When surface protection is performed using a hard coating agent, there is a problem that cracking occurs or is not suitable for protecting the curved surface.

On the other hand, in the case of surface protection using a self-healing coating agent, a coating film can be formed that can be restored to its original shape even when it is deformed under an external force, and since the flexibility is high, cracking occurs. It is difficult.

Patent Literature 1 discloses a coating agent comprising a copolymer of a polyfunctional acrylate compound containing a 3 to 6 functional acrylate monomer and a caprolactone group and an inorganic fine particle.

In patent document 2, the urethane acrylate using the polyhydric isocyanate type compound containing two or more allophanate groups is described.

Japanese Patent No. 6114413 Japanese Patent Laid-Open No. 2015-124265

However, in the case of Patent Literature 1, the film thickness after curing requires about 50 µm to 150 µm for self-repairing expression, and there is a problem that productivity is poor because the amount of coating agent required is large, and as a result, energy required for curing increases. In addition, there is a problem that a photopolymerizable coating agent such as Patent Document 1 or a coating agent containing inorganic particles is likely to cause cracking in the coating film.

Moreover, in the case of patent document 2, there existed a problem that it needs heat and a long time until it receives an external force and deform | transforms and returns to an original shape.

The problem to be solved by the present invention is to provide a coating agent having good self-healing properties, abrasion resistance, anti-fouling property, and tensile properties of the cured product.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining, the present inventors discovered that the said subject was solved by the coating agent containing a specific component.

The following items are provided by the present disclosure.

(Item 1)

(A) hydroxyl-containing (meth) acrylic resin having a glass transition temperature of less than -20 ° C,

(B) hydroxyl-containing organic modified silicone and

(C) allophanate and / or biuret body of polyisocyanate

Thermosetting coating comprising a.

(Item 2)

(D) The thermosetting coating agent described in the said item containing the diol whose hydroxyl value is 200 mggOH / g or more and molecular weight is 500 or less.

(Item 3)

(E) The thermosetting coating of any one of the above items containing a curing catalyst.

(Item 4)

(F) The thermosetting coating agent of any one of the said items containing an organic solvent.

(Item 5)

The thermosetting coating of any one of the preceding items, which is a self-healing coating.

(Item 6)

Hardened | cured material of the thermosetting coating agent of any one of said items.

(Item 7)

A film comprising the cured product described in the above item.

In the present disclosure, one or more of the features described above may be provided in addition to and in combination with the specified combination.

The self-healing, abrasion resistance, antifouling and tensile properties of the cured product of the thermosetting coating of the present invention are good. Therefore, by using the thermosetting coating of the present invention, a film having good self-healing, abrasion resistance, antifouling property and tensile properties can be produced. It is also applicable to coatings on decorative films.

Throughout the present disclosure, a range of numerical values such as physical property values, content, and the like can be appropriately set (for example, by selecting from upper and lower values described in the following items). Specifically, with respect to the numerical value α, when the upper limit of the numerical value α is exemplified by A1, A2, A3, etc., and the lower limit of the numerical value α is exemplified by B1, B2, B3 or the like, 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, B1 to A1, B2 to A1, B3 to A1, B1 to A2, B2 to A2, B3 to A2, B1 to A3, B2 to A3, B3 to A3, etc. Is illustrated.

[Thermosetting coating: Also called coating]

The present disclosure includes an allophanate and / or biuret of (A) a hydroxyl-containing (meth) acrylic resin having a glass transition temperature of less than -20 ° C, (B) a hydroxyl-containing organic modified silicone and (C) a polyisocyanate. It provides a thermosetting coating.

<(A) component: hydroxyl-containing (meth) acrylic resin>

(A) component: The copolymer etc. which contain the structural unit derived from hydroxyl-containing alkyl (meth) acrylate, and the structural unit derived from hydroxyl-containing alkyl (meth) acrylate are illustrated as hydroxyl-containing (meth) acrylic resin. The hydroxyl group-containing (meth) acrylic resins may be used alone or in combination of two or more thereof.

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 1 selected from the group which consists of an acrylate and a methacrylate." In addition, "(meth) acryloyl" means "at least 1 chosen from the group which consists of acryloyl and methacryloyl."

(Hydroxy group-free alkyl (meth) acrylate)

The hydroxyl-free alkyl (meth) acrylate is,

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

Is represented. The hydroxyl-free alkyl (meth) acrylates may be used alone or in combination of two or more.

Examples of the alkyl group include a straight chain alkyl group, a branched alkyl group, a cycloalkyl group and the like.

The straight chain alkyl group is represented by the structural formula of -C _n H _{2n + 1} (n is an integer of 1 or more). Examples of the linear alkyl group 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 and the like.

The branched alkyl group is a group in which at least one hydrogen of the linear alkyl group is substituted with an alkyl group. Examples of the branched alkyl group include isobutyl group, sec-butyl group, ether-butyl group, diethylpentyl group, trimethylbutyl group, trimethylpentyl group, and trimethylhexyl group.

Examples of the cycloalkyl group include monocyclic cycloalkyl groups, provisional-exchange cycloalkyl groups, and condensed cyclic cycloalkyl groups.

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

Tricyclodecyl group, adamantyl group, norbornyl group, etc. are illustrated as a temporary exchange cycloalkyl group.

A bicyclodecyl group etc. are illustrated as a condensed cyclic cycloalkyl group.

Examples of the hydroxyl group-free alkyl (meth) acrylate include a hydroxyl-free straight chain alkyl (meth) acrylate, a hydroxyl-free branched alkyl (meth) acrylate, a hydroxyl-free cycloalkyl (meth) acrylate, and the like.

The hydroxyl-free linear alkyl (meth) acrylate is methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, hexyl (meth) acrylate, (meth) acrylic acid Heptyl, octyl (meth) acrylate, hexadecyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, ecosilyl (meth) acrylate, docosyl (meth) acrylate, etc. are mentioned.

The hydroxyl group-free branched alkyl (meth) acrylate is isopropyl (meth) acrylate, isobutyl (meth) acrylate, seb-butyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate Etc. are illustrated.

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

Among them, hydroxyl group-free alkyl (meth) acrylates having about 1 to 20 carbon atoms in the alkyl group are preferable because they contribute to wear resistance, leveling properties and adhesion in the coating agent. Moreover, by using together the hydroxyl-free alkyl (meth) acrylate from which the carbon number of an alkyl group differs, physical properties, such as glass transition temperature, of a hydroxyl-containing (meth) acrylic resin can be adjusted.

The upper limit of content of the structural unit derived from the hydroxyl-free alkyl (meth) acrylate which occupies for 100 mol% of all structural units in (A) component is 98, 95, 90, 85, 80, 75, 70, 65 mol% Etc. are illustrated, and a lower limit is illustrated at 95, 90, 85, 80, 75, 70, 65, 62 mol% and the like. In one embodiment, the range of content of the structural unit derived from the hydroxyl-free alkyl (meth) acrylate which occupies for 100 mol% of the precursor units in (A) component is 62- from a viewpoint of self-recoverability and abrasion resistance. About 98 mol% is preferable.

As for the upper limit of content of the structural unit derived from the hydroxyl-free alkyl (meth) acrylate which occupies for 100 mass% of the precursor units in (A) component, 98, 95, 90, 85, 80, 75, 70 mass% etc. are illustrated. 95, 90, 85, 80, 75, 70, 65 mass% etc. are illustrated as a minimum. In one embodiment, the range of content of the structural unit derived from the hydroxyl-free alkyl (meth) acrylate which occupies for 100 mass% of protonic units in (A) component is 65 from a viewpoint of self-recoverability and abrasion resistance, About 98 mass% is preferable.

(Hydroxyl group-containing alkyl (meth) acrylate)

The hydroxyl group-containing alkyl (meth) acrylate has the following structural formula

(Wherein R ^a3 is a hydrogen atom or a methyl group, and R ^a4 is a straight chain alkylene group, a branched alkylene group or a cyclo alkylene group.)

It is represented by The hydroxyl group-containing alkyl (meth) acrylates may be used alone or in combination of two or more. Examples of the linear alkylene group, the branched alkylene group, and the cycloalkylene group include the groups described below.

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

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

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

Examples of the hydroxyl group-containing cycloalkyl (meth) acrylate include (meth) acrylic acid hydroxycyclohexyl, (meth) acrylic acid 4- (hydroxymethyl) cyclohexylmethyl, and the like.

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

The upper limit of content of the structural unit derived from hydroxyl-containing alkyl (meth) acrylate which occupies for 100 mol% of precursor units in (A) component is 38, 35, 30, 25, 20, 15, 10, 5, 2.5 mol%, etc. These are illustrated and the minimum is 35, 30, 25, 20, 15, 10, 5, 2.5, 1.5 mol%, etc. are illustrated. In one embodiment, the range of content of the structural unit derived from the hydroxyl-containing alkyl (meth) acrylate which occupies for 100 mol% of the precursor units in (A) component is self-repairing property, abrasion resistance, coating film appearance, and pot life. From a viewpoint of about 1.5-38 mol% is preferable.

As for the upper limit of content of the structural unit derived from the hydroxyl-containing alkyl (meth) acrylate which occupies for 100 mass% of the precursor units in (A) component, 35, 30, 25, 20, 15, 10, 5, 2.5 mass%, etc. As a minimum, 30, 25, 20, 15, 10, 5, 2.5, 2 mass% etc. are illustrated. In one embodiment, the range of content of the structural unit derived from the hydroxyl-containing alkyl (meth) acrylate which occupies for 100 mass% of protonic units in (A) component is self-repairing property, abrasion resistance, coating film appearance, and pot From a viewpoint of life, about 2-35 mass% is preferable.

(A) Component-weight 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 (The hydroxyl-free alkyl (meth) acrylate _molecule / hydroxyl-containing group) The upper limit of the alkyl (meth) acrylate _molecule ) is exemplified by 65, 60, 50, 40, 30, 20, 10, 5, 2, etc., and the lower limit is 60, 50, 40, 30, 20, 10, 5, 2 , 1.6 and the like are exemplified. In one embodiment, the mass ratio of the structural unit derived from the hydroxyl-free alkyl (meth) acrylate in the component (A) and the structural unit derived from the hydroxyl-containing alkyl (meth) acrylate (hydroxyl-free alkyl (meth) ) acrylate _{mol /} hydroxyl group-containing alkyl (meth) acrylates _mol) is, from the number of self-redundancy, wear resistance, coating film appearance and pot life point of view, it is preferable that 1.6 to 65 degree.

_Mass ratio of the structural unit derived from the hydroxyl-free alkyl (meth) acrylate in (A) component, and the structural unit derived from the hydroxyl-containing alkyl (meth) acrylate (hydroxyl-free alkyl (meth) acrylate _MACS / hydroxyl-containing alkyl) 49, 40, 30, 20, 10, 5, 2, etc. are illustrated for the upper limit of (meth) acrylate _MACs , and 45, 40, 30, 20, 10, 5, 2, 1.8, etc. are illustrated for the minimum. In one embodiment, mass ratio (hydroxyl group-free alkyl (meth)) of the structural unit derived from the hydroxyl-free alkyl (meth) acrylate in (A) component, and the structural unit derived from the hydroxyl-containing alkyl (meth) acrylate. As for acrylate _mass / hydroxyl group-containing alkyl (meth) acrylate _mass , about 1.8-49 are preferable from a viewpoint of self-repairing property, abrasion resistance, coating film appearance, and pot life.

(The monomer which is neither hydroxyl-containing alkyl (meth) acrylate nor hydroxyl-containing alkyl (meth) acrylate: also called other monomers)

When manufacturing a hydroxyl-containing (meth) acrylic resin, you may use the monomer which does not correspond to either hydroxyl-containing alkyl (meth) acrylate and hydroxyl-containing alkyl (meth) acrylate. Other monomers may be used alone or in combination of two or more thereof.

Other monomers include (meth) acrylic acid, α, β-unsaturated carboxylic acid, styrenes, α-olefins, unsaturated alcohols and salts thereof, dialkylaminoalkyl (meth) acrylamides and salts thereof, chain transfer monomers, (meth) Acrylonitrile, (meth) acrylamide, vinylamine, bis (meth) acrylamide, di (meth) acrylic ester, divinyl ester, bifunctional monomers other than the above, trifunctional monomers, tetrafunctional monomers, etc. This is illustrated.

As for the upper limit of content of the structural unit derived from the other monomer which occupies for 100 mol% of precursors in (A) component, 13, 10, 9, 5, 4, 1 mol% etc. are illustrated, and a minimum is 12, 10, 9, 5, 4, 1, 0 mol% etc. are illustrated. In one embodiment, about 0-13 mol% is preferable in the range of content of the structural unit derived from the other monomer which occupies for 100 mol% of the precursor units in (A) component from a viewpoint of self-recoverability and abrasion resistance. .

10, 9, 5, 4, 1 mass% etc. are illustrated for the upper limit of content of the structural unit derived from the other monomer which occupies for 100 mass% of the electroconductive units in (A) component, and the lower limit is 9, 5, 4, 1, 0 mass% etc. are illustrated. In one embodiment, the range of content of the structural unit derived from the other monomer which occupies for 100 mass% of the precursor units in (A) component is about 0-10 mass% from a viewpoint of self-recoverability and abrasion resistance. desirable.

Component (A) and other monomers alkyl-containing structural unit with a hydroxyl group ratio of the origin of the (meth) of the structural units of the acrylate derivative weight ratio (other monomer _{mol /} hydroxyl group-free (meth) acrylate _mol) The upper limit of Is 0.22, 0.20, 0.15, 0.10, 0.05, etc., and a lower limit is 0.20, 0.15, 0.10, 0.05, 0, etc. are illustrated. In one embodiment, (A) component and other monomer-derived constituent unit and the hydroxyl group-free (meth) water mass ratio of the structural unit of acrylate-derived (or other monomer _{mol /} hydroxyl group-free (meth of ) acrylate _mol) is, from the number of self-redundancy, and the point of view of abrasion resistance, a degree of from 0 to 0.22 are preferred.

The upper limit of the _mass ratio of the structural unit derived from the other monomer in (A) component, and the structural unit derived from the hydroxyl-free alkyl (meth) acrylate (other monomer _mals / hydroxyl-containing alkyl (meth) acrylate _MACs ) is 0.19, 0.15, 0.10, 0.05, etc. are illustrated, and a lower limit is 0.15, 0.10, 0.05, 0, etc. are illustrated. In one embodiment, the mass ratio of the structural unit derived from the other monomer in (A) component, and the structural unit derived from the hydroxyl-free alkyl (meth) acrylate (other monomer _MASS / hydroxyl-free alkyl (meth) acrylate _mass) is, from the number of self-redundancy, and the point of view of abrasion resistance, a degree of from 0 to 0.19 are preferred.

(A) The upper limit of the contained structural units of the other monomers derived from the hydroxyl (meth) water mass ratio of the structural unit of acrylate-derived (or other monomer _{mol /} hydroxyl group-containing alkyl (meth) acrylates _mol) of the component is 8.0 , 7.0, 6.0, 5.0, 4.0, 3.0, 2.0, 1.0, 0.5 and the like are exemplified, 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. In one embodiment, (A) component the structural unit of other monomer derived from a hydroxyl-containing alkyl (meth) water mass ratio of the structural units of the acrylate resulting in the (other monomer _{mol /} hydroxyl group-containing (meth) acrylate rate _mol) is, from the number of self-redundancy, and the point of view of abrasion resistance, a degree of from 0 to 8.0 is preferred.

The upper limit of the _mass ratio of the structural unit derived from the other monomer in (A) component, and the structural unit derived from the hydroxyl-containing alkyl (meth) acrylate (other monomer _macros / hydroxyl-containing alkyl (meth) acrylates) is 5.0, 4.0, 3.0, 2.0, 1.0, 0.5, etc. are illustrated, and a lower limit is illustrated with 4.5, 4.0, 3.0, 2.0, 1.0, 0.5, 0, etc. In one embodiment, mass ratio of the structural unit derived from the other monomer in (A) component, and the structural unit derived from the hydroxyl group containing alkyl (meth) acrylate (other monomer _maxs / hydroxyl group containing alkyl (meth) acrylate _{As for mass} , about 0-5.0 are preferable from a viewpoint of self-recoverability and abrasion resistance.

<Physical properties of hydroxyl group-containing (meth) acrylic resin>

As for the upper limit of the glass transition temperature of (A) component, -20, -20.1, -21, -23, -25, -30, -31, -35, -39 degreeC etc. are illustrated, and the minimum is -20.1, -21 , -23, -25, -30, -31, -35, -39, -40 deg. In one embodiment, the glass transition temperature of the component (A) is preferably less than -20 ° C, more preferably -40 ° C or more and less than -20 ° C from the viewpoint of self-healing properties, abrasion resistance, and tensile properties.

The glass transition temperature is calculated from the equation of F0.

Formula of フ ｏｘ: 1 / Ｔｇ = (Ｗａ / Ｔｇａ) + (Ｗｂ / Ｔｇｂ) + ·· + (Ｗｎ / Ｔｇｎ)

TA: glass transition temperature of the copolymer (K)

Ｗa: Mass% of monomer A

TgA: glass transition temperature (K) of the homopolymer of monomer A

Ｗｂ: mass% of monomer B

Tg: glass transition temperature (K) of the homopolymer of monomer B.

Ｗｎ: Mass% of monomer N

Tg n: Glass transition temperature (K) of monomer N homopolymer.

The upper limit of the hydroxyl equivalent of (A) component is illustrated with 2.7, 2.5, 2.0, 1.8, 1.5, 1.0, 0.5, 0.25 mE / g, etc., and the lower limit is 2.5, 2.0, 1.8, 1.5, 1.0, 0.5, 0.25, 0.17 Mire / g etc. are illustrated. In one embodiment, as for the hydroxyl equivalent of (A) component, about 0.17-2.7 milli / g is preferable from a viewpoint of self-repair, abrasion resistance, coating film appearance, and pot life, and about 0.5-1.8 milli / g More preferred.

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

The upper limit of the hydroxyl value (solid content conversion) of (A) component is 150, 140, 130, 120, 110, 100, 90, 80, 70, 60, 50, 40, 30, 20, 15 mg gOH / g etc. This is illustrated and the lower limit is exemplified by 140, 130, 120, 110, 100, 90, 80, 70, 60, 50, 40, 30, 20, 15, 10 mggOH / g and the like. In one embodiment, as for the hydroxyl value (solid content conversion) of (A) component, about 10-150 mggOH / g is preferable from a viewpoint of self-healing property, abrasion resistance, coating film appearance, and pot life.

A hydroxyl value is measured by the method (acetyl method) based on JISK1557-1.

As for the upper limit of the acid value of (A) component, 10, 5, 1, 0.1 mggOH / g etc. are illustrated, and a minimum is 5, 1, 0.1, 0 mggOH / g, etc. are illustrated. In one embodiment, when the acid value of (A) component especially considers sclerosis | hardenability, about 0-10 mggOH / g is preferable, and about 0-1 mggOH / g is more preferable.

An acid value is measured by the method based on JISK0070.

As for the upper limit of the weight average molecular weight (MV) of (A) component, 300000, 200000, 100000, 90000, 80000, 70000, 60000, 50000, 40000, 30000, 20000 etc. are illustrated, and the lower limit is 200000, 100000, 90000, 80000, 70000, 60000, 50000, 40000, 30000, 20000, 10000 and the like are exemplified. In one embodiment, from the viewpoint of self-healing property, abrasion resistance, tensile property and antifouling property of the coating agent, the weight average molecular weight (MV) of the component (A) is preferably about 10000 to 300,000, more preferably about 50000 to 300,000. desirable.

As for the upper limit of the number average molecular weight (Mn) of (A) component, 100000, 90000, 80000, 70000, 60000, 50000, 40000, 30000, 20000, 10000, etc. are illustrated, and the lower limit is 90000, 80000, 70000, 60000, 50000, 40000, 30000, 20000, 10000, 5000, etc. are illustrated. In one embodiment, the number average molecular weight (Mn) of (A) component is preferable about 5000-100000 from the viewpoint of the self-repairing property, abrasion resistance, tensile property, and antifouling property of a coating agent, and about 10000-100000 is more preferable. desirable.

10, 7.5, 5, 2.5, 2, etc. are illustrated for the upper limit of the molecular weight distribution (Mw / Mn) of (A) component, and 9.5, 7.5, 5, 2.5, 2, 1.5, etc. are illustrated for the minimum. In one embodiment, as for the molecular weight distribution (MV / Mn) of (A) component, about 1.5-10 are preferable from a viewpoint of self-repair, abrasion resistance, tensile property, and contamination prevention property.

(A) component can be manufactured by various well-known methods. The method for producing a hydroxyl group-containing (meth) acrylic resin includes a hydroxyl group-free alkyl (meth) acrylate and a hydroxyl group-containing alkyl (meth) acrylate and other monomers, if necessary, in a solvent-free or organic solvent, usually with a polymerization initiator. The method of copolymerizing about 1 to 10 hours at about 70-180 degreeC in presence of the following is illustrated. The thing mentioned later is mentioned as an organic solvent used when manufacturing a hydroxyl-containing (meth) acrylic resin. Examples of the polymerization initiator include azo initiators such as azobisisobutyronitrile (AIEN).

90, 80, 70, 60, 50, 40, 30, 20 mass% etc. are illustrated for the upper limit of content (solid content conversion) of the said (A) component in the said coating agent, and a lower limit is 80, 70, 60, 50, 40 , 30, 20, 10 mass%, etc. are illustrated. In one embodiment, 10-90 mass% of content (solid content conversion) of (A) component in the said coating agent is preferable from a viewpoint of self-recoverability, abrasion resistance, tensile characteristics, and antifouling property.

<(B) component: hydroxyl-containing organic modified silicone>

In the present disclosure, "hydroxyl group-containing organic modified silicone" means silicon having, for example, a hydroxyl group-containing organic group. Component (B): The hydroxyl-containing organic modified silicone may be used alone or in combination of two or more thereof. Containing a hydroxyl group reacts with the polyisocyanate and is fixed in the cured product, thus preventing contamination in the long term. Examples of the component (B) include acrylic polymer-modified hydroxyl group-containing organic modified silicone, polyester-modified hydroxyl-containing organic modified silicone, polyether-modified hydroxyl-containing organic modified silicone, and carbinol-modified hydroxyl-containing organic modified silicone. Moreover, the said modified site should just be introduce | transduced into either one terminal, both terminal, and side chain of a silicone chain.

Commercially available products of the acrylic polymer-modified hydroxyl group-containing organic modified silicone include V-028-V (manufactured by T & V TOHA), V-SIL CLAANN 3700 (manufactured by BIC Chemi Japan Co., Ltd.), and SYMAC (SYMAC). ) US-270 (made by TOAGOSEI CO., LTD.) Etc. are illustrated.

Commercially available products of the polyether-modified hydroxyl group-containing organic modified silicone or the polyester-modified hydroxyl group-containing organic modified silicone include VIII-370, VIII-375, V-377, V-SILCLAEN3720 (manufactured by BICKEE JAPAN), V-22 -4952, WF-6123 (made by Shin-Etsu Chemical Co., Ltd.), etc. are illustrated.

Commercially available products of carbinol-modified hydroxyl group-containing organic modified silicones include V-22-4039, V-22-4015, V-22-4952, V-22-4272, V-22-170 V, V-22-170DV and VF- 6000, PF-6001, PF-6002, PF-6003, PF-6123, JP-22-176F (Shin-Etsu Chemical Co., Ltd.), Silaplane MF-4411, Silaplane MF-4421, Silaplane FM-4425, Sila Plain FM-0411, Sila Plain FM-0421, Sila Plain FM-D11, Sila Plain FM-DA21, Sila Plain FM-Da26 (manufactured by NC Corporation), and others. Is illustrated.

As for the upper limit of content (solid content conversion) of (B) component in the said coating agent, 5, 4, 3, 2, 1, 0.9, 0.5, 0.2 mass% etc. are illustrated, and a minimum is 4, 3, 2, 1, 0.9 , 0.5, 0.2, 0.1 mass%, etc. are illustrated. In one embodiment, 0.1-5.0 mass% of content (solid content conversion) of (B) component in the said coating agent is preferable from a pollution prevention viewpoint.

<(C) component: Allophanate body and / or biuret body of polyisocyanate>

(C) component: The allophanate body and / or biuret body of polyisocyanate can be used individually or in combination of 2 or more types. In the present disclosure, "polyisocyanate" is a compound having two or more isocyanate groups (-N = C = O). When producing the allophanate or biuret body of polyisocyanate, polyisocyanate may be used alone or in combination of two or more.

Examples of the polyisocyanate include aliphatic polyisocyanates and aromatic polyisocyanates.

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

Examples of the linear aliphatic group include a linear alkylene group and the like. The linear alkylene group can be represented by the structural formula of-(Ch ₂ ) _n- (n is an integer of 1 or more), methylene group, ethylene group, propylene group, n-butylene group, n-pentylene group, n-hexylene group, n-heptylene group, n-octylene group, n-nonylene group, n-decamethylene group, etc. are illustrated.

The linear aliphatic polyisocyanate is methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, nona methylene diisocyanate, Decamethylene diisocyanate etc. are illustrated.

Examples of the branched aliphatic group include a branched alkylene group. The branched alkylene group is a group in which at least one hydrogen of a straight chain alkylene group is substituted with an alkyl group, and specific examples thereof include a diethylpentylene group, trimethylbutylene group, trimethylpentylene group, trimethylhexylene group (trimethylhexamethylene group), and the like. This is illustrated.

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

Examples of the alicyclic group include monocyclic alicyclic groups, temporary-substituted alicyclic groups, and condensed-cyclic alicyclic groups. Moreover, one or more hydrogen may be substituted by the linear or branched alkyl group in a cycloalkylene group.

In the present disclosure, the monocyclic means a ring structure having no bridged structure inside formed by covalent bonds of carbon. Condensed ring also means a ring structure in which two or more monocycles share two atoms (that is, only one side of each ring is shared (condensed) with each other).

Provisional exchange means the ring-shaped structure in which two or more monocycles share three or more atoms.

Examples of the monocyclic alicyclic group include a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclodecylene group, a 3,5,5-trimethylcyclohexylene group, and the like.

Tricyclodecylene group, an adamantylene group, a norbornylene group, etc. are illustrated as a temporary exchange alicyclic group.

A bicyclodecylene group etc. are illustrated as a condensed cyclic alicyclic group.

Examples of the alicyclic polyisocyanate include monocyclic alicyclic polyisocyanates, temporary exchange alicyclic polyisocyanates, and condensed ring alicyclic polyisocyanates.

Monocyclic alicyclic polyisocyanate is hydrogenated xylene diisocyanate, isophorone diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, cycloheptylene diisocyanate, cyclodecylene diisocyanate, 3,5,5-trimethylcyclohexylene Diisocyanate, dicyclohexyl methane diisocyanate, etc. are illustrated.

Tricyclodecylene diisocyanate, adamantane diisocyanate, norbornene diisocyanate, etc. are illustrated as a temporary exchange alicyclic polyisocyanate.

Bicyclodecylene diisocyanate etc. are illustrated as a condensed cyclic alicyclic polyisocyanate.

Although the carbon number of an aliphatic group is not specifically limited, The upper limit is 30, 29, 25, 20, 16, 15, 12, 10, 9, 8, 7, 6, 5, 4, 3, 2, etc. are illustrated, The lower limit is exemplified by 29, 25, 20, 15, 12, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1 and the like. In one embodiment, the carbon number of the aliphatic group is preferably 1 to 30, more preferably 1 to 20, still more preferably 1 to 16, and 1 to 1 from the viewpoint of self-healing properties, abrasion resistance, and tensile properties. 12 is particularly preferred.

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

As an aromatic polyisocyanate, xylene diisocyanate etc. are illustrated.

The allophanate body of polyisocyanate,

The following structural formula:

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

(n1 is an integer of 0 or more, R ¹ ~R ⁶ is independently an alkylene group or arylene group, respectively, R ^{'~R' ''} are each independently a group of isocyanate group or R ^α ~R ^γ own. R ¹ ~R ^4, R ^{'~R' 'is} a group may be different for each unit. a). R ^B ~R ^{E, α} R ^β is ~R or different groups each unit.] Is exemplified by a compound such as represented.

Commercially available products of allophanate of polyisocyanate include, for example, CORONATE 2793 (manufactured by Tosoh Corporation) and Takeate D-178N (Mitsui Chemicals, Inc.). Is illustrated.

The biuret body of polyisocyanate,

The following structural formula:

[In the meal,

ｎ ^ｂ is an integer of 1 or more,

^RBA to ^RVE are each independently an alkylene group or an arylene group,

R ^bα ~R ^bβ is an isocyanate group or each independently

(ｎ ^ｂ1 is an integer greater than or equal to 0,

R ^ｂ1 to R ^ｂ5 are each independently an alkylene group or an arylene group,

R <^b>' -R <^b>" is respectively independently an isocyanate group or R ^{< b>} -R < ^{b >} itself group.

^{R b4 ~R b5, R b '} ' is the group may be different for each unit.).

R ^bD ~R ^bE, R is ^bβ or different groups each unit.]

The compound etc. which are represented by are illustrated.

The biuret body of polyisocyanate is DURANATE 24A-100, DURANATE 22A-75P, DURANATE 21S-75E (above, Asahi Kasei Corp. make), Death module N3200A (hexamethylene Biuret body of diisocyanate) (Similar to Sumitomo Bayer Urethane Co., Ltd.), etc. are illustrated.

Examples of the upper limit of the NC content (NCO% in the solid content) of the component (C) include 30, 25, 20, and 15 mass%, and examples of the lower limit include 25, 20, 15, and 10 mass%. In one embodiment, 10-30 mass% is preferable for the NCO content rate (NCO% in solid content) of (C) component from a viewpoint of self-healing property, abrasion resistance, and a tensile property.

The upper limit of content (solid content conversion) of the (C) component in the said coating agent is 80, 70, 60, 50, 40, 30, 20, 15 mass%, etc. are illustrated, and a minimum is 70, 60, 50, 40, 30 , 20, 15, 10 mass%, etc. are illustrated. In one embodiment, 10-80 mass% of content (solid content conversion) of (C) component in the said coating agent is preferable from a viewpoint of self-recoverability, abrasion resistance, and tensile characteristics.

The upper limit of the mass ratio ((A) component / (C) component) between (A) component and (C) component in the said coating agent is illustrated with 5, 4, 3, 2, 1, 0.9, 0.5, 0.3, etc., 4, 3, 2, 1, 0.9, 0.5, 0.3, 0.2 etc. are illustrated for a minimum. In one embodiment, the mass ratio ((A) component / (C) component) of (A) component and (C) component in the said coating agent is 0.2- from a viewpoint of self-recoverability, abrasion resistance, and tensile characteristics. 5.0 is preferred.

<(D) component: Diol whose hydroxyl value is 200 mggOH / g or more and molecular weight 500 or less>

In one embodiment, the said coating agent may contain the diol whose (D) hydroxyl value is 200 mggOH / g or more and molecular weight 500 or less. By including the component (D), the self-healing property, abrasion resistance and tensile properties are improved. (D) component can be used individually or in combination of 2 or more types.

In the present disclosure, when simply described as "molecular weight", it means either a food or a number average molecular weight. When the structure of a compound can be uniquely represented by a specific chemical formula (ie, the molecular weight distribution is 1), the molecular weight means food. On the other hand, when the structure of the compound cannot be expressed uniquely (ie, the molecular weight distribution is greater than 1) by a specific chemical formula, the molecular weight means a number average molecular weight.

Examples of the component (D) include alkylene diols, polyether diols, and the like. Examples of the alkylenediol include linear alkylenediol, branched alkylenediol, cycloalkylenediol and the like.

Straight chain alkylene diols include ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, etc. are illustrated.

Branched alkylene diols are neopentyl glycol, 2,4-diethyl-1,5-pentanediol, 2,4-dibutyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 1 -Methylethylene glycol, 1-ethylethylene glycol, etc. are illustrated.

Examples of the cycloalkylenediol include monocyclic cycloalkylenediol and temporary-substituted cycloalkylenediol.

Examples of the monocyclic cycloalkylenediol include 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 2,2'-bis (4-hydroxycyclohexyl) propane, and the like.

Tricyclodecane dimethanol etc. are illustrated as a temporary exchange cycloalkylene diol.

Examples of the polyetherdiol include diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, polytetramethylene ether glycol, and the like.

20, 19, 15, 10, 9, 5, 3, 1 mass% etc. are illustrated for the upper limit of content (solid content conversion) of the said (D) component in the said coating agent, and a lower limit is 19, 15, 10, 9, 5 , 3, 1, 0 mass%, etc. are illustrated. In one embodiment, 0-20 mass% of content (solid content conversion) of the (D) component in the said coating agent is preferable.

The upper limit of the mass ratio ((D) component / (A) component) of (D) component and (A) component in the said coating agent is illustrated with 1.0, 0.9, 0.7, 0.5, 0.4, 0.2, 0.1, etc. 0.9, 0.7, 0.5, 0.4, 0.2, 0.1, 0, etc. are illustrated. In one embodiment, the mass ratio ((D) component / (A) component) of (D) component and (A) component in the said coating agent is 0-1.0 from a viewpoint of self-repair, wear resistance, and leveling property. This is preferred.

0.5, 0.4, 0.2, 0.1 etc. are illustrated for the upper limit of the mass ratio ((D) component / (C) component) of (D) component and (C) component in the said coating agent, and a lower limit is 0.4, 0.2, 0.1, 0 and the like are exemplified. In one embodiment, 0-0.5 are preferable for mass ratio ((D) component / (C) component) of (D) component and (C) component in the said coating agent.

The upper limit of the molar ratio (NCO / OH) of the isocyanate group of (A) component, (B) component, (D) component, and other components and the hydroxyl group of (C) component is 10, 9, 8, 7, 6, 5, 4 , 3, 2, 1.5, 1, 0.8, 0.6, 0.4, 0.1 and the like, and the lower limit is 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.5, 0.1, 0.05 and the like. . The range of the molar ratio (NCO / OH) can be appropriately set (for example, by selecting from the values of the upper limit and the lower limit). In one embodiment, the molar ratio (NCO / OH) of the isocyanate group of (A) component, (B) component, (D) component, and the other component, and the hydroxyl group of (C) component is self-repairing, abrasion resistance, and contamination From a viewpoint of prevention property and a tensile property, about 0.05-10 are preferable.

The upper limit of the hydroxyl value of (D) component is 1600, 1500, 1250, 1100, 1090, 1080, 1070, 1060, 1050, 1000, 990, 975, 950, 900, 750, 500, 250 mggOH / g, etc. are illustrated, Examples of the lower limit include 1500, 1250, 1100, 1090, 1080, 1070, 1060, 1050, 1000, 990, 975, 950, 900, 750, 500, 250, and 200 mg / OH / g. In one embodiment, as for the hydroxyl value of (D) component, 200-1600 mggOH / g is preferable.

The upper limit of the molecular weight of (D) component is 500, 490, 450, 400, 350, 300, 250, 200, 150, 120, 119, 115, 110, 109, 105, 100, 75, etc., and a lower limit is 490 , 450, 400, 350, 300, 250, 200, 150, 120, 119, 115, 110, 109, 105, 100, 75, 50 and the like. In one embodiment, 50-500 are preferable for the molecular weight of (D) component.

<(E) Component: Curing Catalyst>

In one embodiment, the said coating agent may contain (E) component: a curing catalyst. The component (E) may be used alone or in combination of two or more thereof.

Examples of the component (E) include an organometallic catalyst and an organoamine catalyst.

As an organometallic catalyst, an organic typical metal catalyst, an organic transition metal catalyst, etc. are illustrated.

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

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

Examples of the organic bismuth catalyst include bismuth octyl acid and the like.

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

Titanium ethyl acetoacetate etc. are illustrated as an organic titanium catalyst.

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

Examples of the organic iron catalyst include iron acetylacetonate and the like.

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

1, 0.9, 0.75, 0.5, 0.25, 0.1, 0.09, 0.05, 0.02 mass% etc. are illustrated as an upper limit of content (solid content conversion) of the said (E) component in the said coating agent, and a lower limit is 0.9, 0.75, 0.5, 0.25 , 0.1, 0.09, 0.05, 0.02, 0.01, 0 mass%, etc. are illustrated. In one embodiment, about 0-1 mass% of content (solid content conversion) of (E) component in the said coating agent is preferable from a viewpoint of sclerosis | hardenability and a pot life.

<(F) Component: Organic Solvent>

In one embodiment, the said coating agent can contain (F) component: an organic solvent. (F) A component can be used individually or in combination of 2 or more types. (F) component is ketone solvent, such as methyl ethyl ketone, acetyl acetone, methyl isobutyl ketone, and cyclohexanone; Aromatic solvents such as toluene and xylene; Alcohol solvents such as methanol, ethanol, n-propanol, isopropanol and butanol; Glycol ether solvents such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and propylene glycol monomethyl ether acetate; Ester solvents such as ethyl acetate, butyl acetate, methyl cellosolve acetate, and cellosolve acetate; Petroleum solvents such as Solvesso # 100 and Solvesso # 150 (both trade names, manufactured by Exxon Mobil Corporation); Haloalkane solvents such as chloroform; Amide solvents, such as dimethylformamide, etc. are illustrated. Among these, a ketone solvent is preferable from a viewpoint of the pot life of the coating agent of this invention, and acetylacetone is preferable also in a ketone solvent.

When the organic solvent is included in the coating agent, the upper limit of the content of the (F) component in the coating agent is exemplified by 90, 80, 70, 60, 55 mass%, and the lower limit is 85, 80, 70, 60, 55 , 50 mass%, etc. are illustrated. When (F) component is contained in the said coating agent in 1 embodiment, about 50-90 mass% is preferable in content of (F) component in the said coating agent from a pot life viewpoint. Moreover, the organic solvent contained in the said (A) component, the said (B) component, the said (C) component, and the said (E) component may be contained in the (F) component contained in the said coating agent.

<Additive>

The said thermosetting coating agent contains agents other than the said (A) component, the said (B) component, the said (C) component, the said (D) component, the said (E) component, and the said (F) component as an additive. can do. Examples of the additive include triols, tetraols, 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, content of an additive is about 0.1-10 mass%, less than 10 mass%, less than 5 mass%, less than 1 mass%, less than 0.1 mass%, less than 0.01 mass% of the said coating agent , About 0 mass%, etc. (solid content conversion) are illustrated.

The said thermosetting coating agent mixes (A) component, (B) component, and (C) component and (D) component, (E) component, (F) component, and / or additives as needed by various well-known means. It is obtained by the method etc. which include a process.

The thermosetting coating agent may be used as a self-healing thermosetting coating agent, a thermosetting coating agent for a decorative film.

[Hardened]

The present disclosure provides a cured product of the thermosetting coating agent. The conditions at the time of manufacturing the said hardened | cured material are mentioned later, etc. are illustrated.

[film]

The present disclosure provides a film containing the cured product.

As a base material, various well-known thing is employ | adopted. The base material is polycarbonate film, acrylic film (polymethyl methacrylate film, etc.), polystyrene film, polyester film, polyolefin film, epoxy resin film, melamine resin film, triacetylcellulose film, ABS film, AS film, norbornene-based A resin film, a cyclic olefin film, a polyvinyl alcohol film, a thermoplastic polyurethane elastomer (TF) film, etc. are illustrated. Although the thickness of a base material is not specifically limited, About 20-300 micrometers is preferable. Moreover, the thickness of a coating layer is not specifically limited, About 2-30 micrometers is preferable.

The film is produced by various known methods. In one embodiment, the manufacturing method of a film includes the process (coating process) of apply | coating the said coating agent on the at least single side | surface of a base material, and the process (thermal curing process) of thermosetting and forming a coating agent hardened | cured material layer.

(Application Process)

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, flexo printing, screen printing, and the like.

The application amount is not particularly limited. As for application amount, about 0.1-30 g / m <^2> of mass after drying is preferable, and about 1-20 g / m <^2> is more preferable.

(Thermal curing process)

As a drying method, drying by a pure air dryer or the like is illustrated. Drying conditions are illustrated at 120 ° C. for 1 minute.

When manufacturing a film, an aging treatment is performed after drying as needed. As an example, the aging process of 24 hours, etc. are illustrated at 40 degreeC.

EXAMPLE

Hereinafter, the present invention will be described in detail through Examples and Comparative Examples. However, description in the said preferable embodiment and the following example are provided only for the purpose of illustration, and are not provided for the purpose of limiting this invention. Therefore, the scope of the present invention is not limited to the embodiment and examples specifically described herein, but only by the claims. In addition, in each Example and a comparative example, unless otherwise indicated, numerical values, such as a part and%, are mass references | standards.

<Preparation of raw materials>

((Meth) acrylic resin]

[Resin A]

In a reaction vessel equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel and a nitrogen inlet tube, 24.0 parts by mass of methyl methacrylate (hereinafter referred to as MMA) and n-butyl acrylate (hereinafter also referred to as BA) 59.0 parts by mass, 17.0 parts by mass of 2-hydroxyethyl acrylate (hereinafter also referred to as HEA) and 150 parts by mass of methyl ethyl ketone were placed, and the reaction system was set at 80 ° C. Subsequently, 0.5 mass part of azobisisobutyronitrile was put, and it was thermally maintained at 80 degreeC vicinity for 5 hours. Subsequently, 1.0 mass part of azobisisobutyronitrile was put, and the reaction system was further warmed for 4 hours in the vicinity of the same temperature. Thereafter, the reaction system was cooled to room temperature to obtain a solution (A nonvolatile content of 40%) of resin A having the physical properties listed in Table 1.

[Resin B, C]

It carried out similarly to preparation of resin A except having changed the raw material to what is described in Table 1. The physical properties of the obtained resins B and C are shown in Table 1. In addition, all the acid values of resin A-C were 0 mggOH / g.

In the table, the glass transition temperature Tg is a value calculated based on the formula of F0. The resin A was measured by a differential scanning calorimetry (DSC) method at a temperature increase rate of 10 ° C / min under a nitrogen stream, and the glass transition temperature was -23 ° C.

<Preparation of thermosetting coating agent>

Example 1

47.17 parts of resin A as (A) component, and (B) component 1.03 parts of B-SILCLAENA 3700 (made by BICKEI JAPAN CORP .; acrylic polymer modified hydroxyl group containing organic modified silicone) (solid content concentration 25%), (C 6.85 parts of coronate 2793 (made by Tosoh Corporation; the allophanate body of hexamethylene diisocyanate) (solid content concentration 100%) as a component, and dioctyl tin dilaurate (100% of solid content concentration) as (E) component Hereinafter, 0.03 parts of DOTDl and 41.06 parts of methyl ethyl ketone (hereinafter, ME) and 3.86 parts of acetylacetone (hereinafter, AC) were used as the component (F). By mixing the above components well, a coating agent having a solid concentration of 26% was prepared.

Examples 2-6 and Comparative Examples 1-9

The thermosetting coating agents of Examples and Comparative Examples other than Example 1 were prepared in the same manner as in Example 1, except that the composition of the composition was changed as shown in the following table. In addition, the solid content concentration of the coating agent was 26%.

(A) Component (Ｂ) ingredient (C) component (D) component (E) Ingredient (F) ingredient additive Example 1 Susie A
Part 47.17 BYK-
SILCLEAN
3700
1.03 copies Coronate
2793
Part 6.85 (radish) DOTDL
0.03part MEK / AcAc
Part 41.06 / 3.86 (radish) Example 2 Susie A
Part 14.93 BYK-
SILCLEAN
3700
1.03 copies Coronate
2793
Part 16.76 1,5-pentanediol
Part 2.99 DOTDL
0.03part MEK / AcAc
Part 60.40 / 3.86 (radish) Example 3 Susie A
Part 15.09 BYK-
SILCLEAN
3700
1.03 copies Coronate
2793
Part 16.67 Diethylene glycol
Part 3.02 DOTDL
0.03part MEK / AcAc
Part 60.30 / 3.86 (radish) Example 4 Susie A
Part 16.00 BYK-
SILCLEAN
3700
1.03 copies Coronate
2793
Part 16.11 3-methyl-1,5-
Pentanediol
Part 3.20 DOTDL
0.03part MEK / AcAc
Part 59.77 / 3.86 (radish) Example 5 Susie A
Part 51.23 BYK-
SILCLEAN
3700
1.03 copies Duranate
24A-100
Part 5.22 (radish) DOTDL
0.03part MEK / AcAc
Part 38.63 / 3.86 (radish) Example 6 Susie A
Part 20.67 BYK-
SILCLEAN
3700
1.03 copies Coronate
2793
Part 13.32 (radish) DOTDL
0.03part MEK / AcAc
Part 56.96 / 3.86 Adecapolyether
GM-30
Part 4.13 Comparative Example 1 Susie A
Part 45.03 BYK-
SILCLEAN
3700
1.03 copies Takenate
D-140N
Part 10.27 (radish) DOTDL
0.03part MEK / AcAc
Part 39.78 / 3.86 (radish) Comparative Example 2 Susie A
Part 45.65 BYK-
SILCLEAN
3700
1.03 copies Takenate
D-120N
Part 9.94 (radish) DOTDL
0.03part MEK / AcAc
Part 39.49 / 3.86 (radish) Comparative Example 3 Susie A
Part 46.23 BYK-
SILCLEAN
3700
1.03 copies Takenate
D-110N
Part 9.63 (radish) DOTDL
0.03part MEK / AcAc
Part 39.22 / 3.86 (radish) Comparative Example 4 Susie A
Part 45.95 BYK-
SILCLEAN
3700
1.03 copies Takenate D-204EA-1
Part 14.68 (radish) DOTDL
0.03part MEK / AcAc
Part 34.45 / 3.86 (radish) Comparative Example 5 Susie A
Part 50.16 BYK-
SILCLEAN
3700
1.03 copies Coronate
HX
Part 5.65 (radish) DOTDL
0.03part MEK / AcAc
Part 39.27 / 3.86 (radish) Comparative Example 6 Susie A
Part 47.40 BYK-
SILCLEAN
3700
1.03 copies Takenate
D-160N
Part 9.01 (radish) DOTDL
0.03part MEK / AcAc
Part 38.67 / 3.86 (radish) Comparative Example 7 SuzyＢ
Part 47.17 BYK-
SILCLEAN
3700
1.03 copies Coronate
2793
Part 6.85 (radish) DOTDL
0.03part MEK / AcAc
Part 41.06 / 3.86 (radish) Comparative example Resin C
Part 47.17 BYK-
SILCLEAN
3700
1.03 copies Coronate
2793
Part 6.85 (radish) DOTDL
0.03part MEK / AcAc
Part 41.06 / 3.86 (radish) Comparative example Susie A
Part 47.64 (radish) Coronate
2793
Part 6.92 (radish) DOTDL
0.03part MEK / AcAc
Part 41.52 / 3.90 (radish)

Duranate 24A-100: Asahi Kasei Co., Ltd., biuret body of hexamethylene diisocyanate (solid content concentration 100%)

Takenate D-140N: Adduct body of Mitsui Chemicals, isophorone diisocyanate (solid content concentration 75%)

Takeate D-120N: product of Mitsui Chemicals, adduct of hydrogenated xylylene diisocyanate (solid content concentration 75%)

Takeate D-110N: product of Mitsui Chemicals, adduct of xylylene diisocyanate (solid content concentration 75%)

Takeate D-204EA-1: Mitsui Chemicals, isocyanurate of toluene diisocyanate (solid content concentration 50%)

Coronate HX: Isocyanurate body of hexamethylene diisocyanate (the solid content concentration 100%) by Toso Corporation

Takenate D-160N: Mitsui Chemicals, adduct of hexamethylene diisocyanate (solid content concentration 75%)

Adeka polyether WM-30: Made by ADA Co., Ltd., ether triol, hydroxyl group 535-565 mggOH / g

<Production of film>

The obtained thermosetting coating agent was apply | coated to the commercially available polyethylene terephthalate film (brand name Cosmoshine A4100, 100 micrometer thickness) so that the coating film thickness after drying might be set to 10 micrometers, and it thermosetted by drying at 120 degreeC for 60 second.

Self-healing property of hardened materials

The film surface was reciprocated 10 times with a brass brush, and the time until a wound disappeared was measured.

◎: Restore within 1 second

○: Restore within 1 minute

△: restore within 5 minutes

×: not restored in 5 minutes

Wear Resistance of Hardened Materials

The haze value before and after the taper abrasion test performed in accordance with the JIS K 7204 plastic-abrasion test method was measured (MURAKAMI Color Research Institute, HM-150), before and after the test. The difference (ΔH) of the haze value was calculated. The taper abrasion test was carried out using a taper abrasion tester (TESTER SANGYO CO, .LTD.), A-101 taper abrasion tester, under a load of 500 g and a rotation speed of 60 rpm. -10 F was rotated 100 times.

<Contamination Prevention of Hardened Materials>

Nonwoven fabric (made by Asahi Kasei Co., Ltd., product name: bemcot), which is coated with an oil-based marker (made by JEBRA Co., Ltd., product name Maki (red)) and dried on the phosphorus It evaluated by wiping with M-3II). Evaluation criteria are as follows.

○: can be wiped

×: not polished

<Elongation at break of hardened material>

The elongation at break of the cured product alone was measured in accordance with the test conditions of JIS K 7204 plastics-a test method for tensile properties. The shape of hardened | cured material was 5 mm in width, 10 micrometers in thickness, and 25 mm in length, and the test speed was 200 mm / min.

Elongation at break (%) = 100 × (L-25) / 25

L: Cured product length at the time of breaking the cured product

Claims (7)

(A) hydroxyl-containing (meth) acrylic resin having a glass transition temperature of less than -20 ° C,
(B) hydroxyl-containing organic modified silicone and
(C) allophanate and / or biuret body of polyisocyanate
Thermosetting coating comprising a.
The method of claim 1,
(D) A thermosetting coating agent comprising a diol having a hydroxyl value of 200 mggOH / g or more and a molecular weight of 500 or less.
The method according to claim 1 or 2,
(E) A thermosetting coating comprising a curing catalyst.
The method according to any one of claims 1 to 3,
(F) A thermosetting coating comprising an organic solvent.
The method according to any one of claims 1 to 4,
A thermosetting coating that is a self-healing coating.
Hardened | cured material of the thermosetting coating agent of any one of Claims 1-3.
A film comprising the cured product of claim 6.