JP2003226740A - Silicone-containing thermosetting composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silicone-containing thermosetting composition that gives a cured product having excellent chemical performance, physical performance, scuffing resistance, weatherability, acid resistance and appearance, and gives, in particular, a cured product having good water repellent property, oil repellent property, stain resistance, and stain removing ability. <P>SOLUTION: This silicone-containing thermosetting composition comprises a silicone compound (component A) having one or more reactive functional groups in a molecule, a compound (component B) having, in a molecule, two or more chemically blocked carboxyl groups represented by formula (1) (wherein R<SB>1</SB>, R<SB>2</SB>and R<SB>3</SB>are, each, a hydrogen atom or a 1-18C organic group, and R<SB>4</SB>is a 1-18C organic group, where R<SB>3</SB>and R<SB>4</SB>may be bonded with each other to form a heterocyclic ring with Y<SB>1</SB>being an oxygen or sulfur atom as a hetero atom), and a compound (component C) having two or more epoxy groups in a molecule. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel silicone-containing thermosetting composition, more specifically, good chemical performance,
It is possible to give a cured product having physical performance, acid resistance, abrasion resistance, weather resistance, and appearance, and particularly excellent in water repellency, oil repellency, stain resistance, stain removability, for example,
The present invention relates to a silicone-containing thermosetting composition suitable for paints, inks, adhesives, molded articles and the like.

[0002]

2. Description of the Related Art Topcoat paints are applied in order to impart design and appearance to the article to be coated. In addition to these characteristics, the resulting coating film has weather resistance, water resistance and acid resistance. Functions such as alkali resistance and chemical resistance have been demanded. However, in recent years, as weather-resistant paints such as fluororesin paints, silicone resin paints, and urethane paints have become widespread and the lifespan of paint films has been extended, the paint films have resistance to contaminants such as stain resistance and decontamination properties. Sex has come to be required.

Factors that influence the resistance to pollutants are 1. Contact angle of water or oil, 2. Weather resistance, 3. Acid resistance,
4. Surface hardness, 5. Crosslink density etc. are mentioned. A coating film having high water repellency and oil repellency has high resistance to contaminants because it is difficult for oil and water to come into contact with it. A coating film having good weather resistance and acid resistance maintains the initial resistance to contaminants because the surface performance is stable for a long period of time. Also, when the dirt is solid, if the coating film has a high hardness, the dirt is hard to attach,
Dirt is reduced. When the dirt is liquid or gas, the dirt diffuses and permeates into the coating film and is fixed. If the coating film has a high cross-linking density, it prevents the diffusion of dirt and enhances the resistance to contaminants.

Conventionally, the thermosetting coating compositions containing polyol and melamine resin as the main components, which have been generally used, do not have sufficient acid resistance and have a problem that they are eroded by acid rain and their stain resistance is lowered. . As a technique for imparting stain resistance and stain removability to a coating film, a coating material having water repellency obtained by blending a fluororesin is used. However, there is a problem that lipophilic stains cannot be removed only by water repellency.

[0005]

The present invention solves the above problems and provides a cured product having excellent chemical performance, physical performance, scratch resistance, weather resistance, acid resistance and appearance, and in particular, It is an object of the present invention to provide a silicone-containing thermosetting composition that gives a cured product that is excellent in water repellency and oil repellency, and has good stain resistance and stain removability.

[0006]

Means for Solving the Problems As a result of intensive research to develop a silicone-containing thermosetting composition having the above-mentioned preferable properties, the present inventors have found that one or more reactive functional groups in a molecule. A silicone compound having, a compound having two or more carboxyl groups chemically blocked in the molecule, and a compound having two or more epoxy groups in the molecule as essential components, and, in some cases, exhibiting activity during heat curing By using a silicone-containing thermosetting composition containing a heat-latent catalyst, in particular, acid resistance, water repellency,
It was found that a cured product having excellent oil repellency, stain resistance, and stain removability, and having good chemical performance, physical performance, scratch resistance, weather resistance, and excellent appearance can be provided, and the present invention It came to completion.

That is, the present invention is as follows (1) to (5)
Specified by. (1) Silicone compound having one or more reactive functional groups in the molecule (component (A)), formula (1) (Chemical Formula 3) in the molecule
The chemically blocked carboxyl group represented by 2
A compound having one or more (component (B)),

[0008]

[Chemical 3] (In the formula, R ₁ , R ₂ and R ₃ are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, R ₄ is an organic group having 1 to 18 carbon atoms, and R ₃ and R ₄ are bonded to each other. A heterocycle having Y ₁ as a hetero atom may be formed, and Y ₁ is an oxygen atom or a sulfur atom) and an epoxy group in the molecule is 2
A silicone-containing thermosetting composition, characterized in that it comprises a compound having at least one component (component (C)).

(2) The silicone-containing thermosetting composition as described in (1), which further contains a thermal latent catalyst (component (D)) which is active during heat curing. (3) The silicone-containing thermosetting composition according to (1) or (2), wherein the reactive functional group of the component (A) is an epoxy group. (4) The silicone-containing thermosetting composition according to (1) or (2), wherein the reactive functional group of the component (A) is a carboxyl group. (5) The reactive functional group of the component (A) is represented by the formula (2)
The silicone-containing thermosetting composition according to (1) or (2), which is a chemically blocked carboxyl group represented by:

[0010]

[Chemical 4] (Wherein R ₅ , R ₆ and R ₇ are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, R ₈ is an organic group having 1 to 18 carbon atoms, and R ₇ and R ₈ are bonded to each other. May form a heterocycle having Y ₂ as a hetero atom, and Y ₂ is an oxygen atom or a sulfur atom)

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
Examples of the silicone compound having one or more reactive functional groups in the molecule of the component (A) include compounds represented by the formula (5)
Having a polyorganosiloxane structure having a structure represented by, further, a hydroxyl group, a carboxyl group, an epoxy group,
It is a compound having at least one functional group such as an amino group, a vinyl group, an isocyanate group, a carbamate group, an oxazolidine group or a block thereof. Of these, the functional group is preferably a carboxyl group, a hydroxyl group, or a chemically blocked carboxyl group represented by the formula (2).

[0012]

[Chemical 5] (In the formula, R ₉ and R ₁₀ are each independently a carbon number of 1 to 1.
6 represents an alkyl group or a phenyl group)

Specific examples of the above-mentioned compound having a functional group include commercially available products shown below. Examples of the silicone compound having one or more hydroxyl groups in the molecule include trade names X-22-160AS and KF-6 manufactured by Shin-Etsu Chemical Co., Ltd.
Examples thereof include both-end reactive silicone compounds such as 001, KF-6002 and KF-6003, and one-end reactive silicone compounds such as X-22-170DX manufactured by Shin-Etsu Chemical Co., Ltd.

As the silicone compound having one or more epoxy groups in the molecule, a trade name KF manufactured by Shin-Etsu Chemical Co., Ltd.
-105, X-22-163A, X-22-163B,
X-22-163C, Toray Dow Corning
Examples of such silicones include BY16-855D manufactured by Silicone Co., Ltd., which is reactive at both ends.

Examples of silicone compounds having one or more carboxyl groups in the molecule include BY16-750 manufactured by Toray Dow Corning Silicone Co., Ltd. and trade name X-22-162C manufactured by Shin-Etsu Chemical Co., Ltd. Both end reactive silicones are included. These commercially available products may be used alone or in combination of two or more.

The compound having the above functional group may be a synthetic product of a reactive silicone and another compound. A synthetic compound of a silicone compound having one or more epoxy groups in the molecule is prepared by reacting a compound having two or more epoxy groups in the molecule with a silicone compound having a carboxyl group,
Alternatively, it can be obtained by reacting a silicone compound having an epoxy group at both ends with a compound having a carboxyl group. In addition, a copolymer of a reactive silicone compound having a vinyl group and an α, β-unsaturated monomer having an epoxy group, or a reactive silicone compound having a vinyl group, an α, β-unsaturated monomer having a hydroxyl group. It is obtained by copolymerization with a monomer and another α, β-unsaturated monomer having no hydroxyl group.

Synthetic products of silicone compounds having one or more carboxyl groups in the molecule include, for example, 1) reacting a polyvalent carboxylic acid with a reactive silicone having a hydroxyl group or an epoxy group, and 2) adding a hydroxyl group in the molecule. Half-esterify a compound having two or more with an acid anhydride, leaving one or more carboxyl groups generated per molecule, and reacting the remaining carboxyl group with a silicone compound having a hydroxyl group or an epoxy group. 3) In the molecule A compound having two or more hydroxyl groups and a silicone compound having a carboxyl group are reacted so that one or more hydroxyl groups remain in one molecule, and the remaining hydroxyl groups are half-esterified with an acid anhydride. 4) Polyisocyanate compound and hydroxy Addition of carboxylic acid or amino acid, leaving one or more carboxyl groups generated per molecule Reacting a silicone compound to the remaining carboxyl group with a hydroxyl group or epoxy group,
5) A polyisocyanate compound and a silicone compound having a hydroxyl group or an amino group are added so that one or more isocyanate groups remain in one molecule, and the remaining isocyanate group and a hydroxycarboxylic acid or amino acid are added, 6) In the molecule To react a compound having a hydroxyl group and a carboxyl group with a silicone compound having a hydroxyl group,
7) A carboxyl group-containing α, β-unsaturated monomer is homopolymerized or copolymerized with another α, β-unsaturated monomer,
React with a silicone compound so that one or more carboxyl groups remain in one molecule, 8) React with a polyol having one or more hydroxyl groups in the molecule, and a silicone compound having carboxyl groups at both ends, 9) Carboxyl Α, β-Unsaturated monomer having functional group capable of reacting with a group is homopolymerized or copolymerized with other α, β-unsaturated monomer to react with silicone compound having carboxyl group at both ends. , And the like.

Component (A) has 1 reactive functional group in the molecule.
Examples of the compound having two or more hydroxyl groups in the molecule used when producing a silicone compound having two or more
For example, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,2-butanediol, 1,6-hexanediol, diethylene glycol, pentane. Diol, dimethylbutanediol,
Hydrogenated bisphenol A, cyclohexane-1,4-diol, resorcin, glycerin, sorbitol, neopentyl glycol, 1,8-octanediol, 1,
Polyhydric alcohols such as 3,6-hexanetriol, 1,2,4-butanetriol, trimethylolethane, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol and tripentaerythritol, and polyhydric alcohols thereof. γ−
Examples thereof include ring-opening adducts with lactone compounds such as butyrolactone and ε-caprolactone, and polyesters containing these polyhydric alcohols.

Component (A) has 1 reactive functional group in the molecule.
Examples of the compound having a carboxyl group used in the case of producing a silicone compound having not less than, for example,
Formic acid, acetic acid, propionic acid, octylic acid, lauric acid,
Monovalent carboxylic acids such as myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, succinic acid, glutaric acid, azelaic acid, sebacic acid, decamethylenedicarboxylic acid, phthalic acid, maleic acid, trimellitic acid , Polyvalent carboxylic acids such as pyromellitic acid, tetrahydrophthalic acid, and hexahydrophthalic acid, compounds containing these carboxylic acid compounds, and acrylic acid and methacrylic acid, which are carboxyl group-containing α, β-unsaturated monomers. Examples thereof include polymers of crotonic acid, isocrotonic acid, itaconic acid, maleic acid, fumaric acid, and copolymers with other α, β-unsaturated monomers. It can also be obtained by half-esterifying a compound having two or more hydroxyl groups in the molecule and an acid anhydride of a polyvalent carboxylic acid.

Component (A) has 1 reactive functional group in the molecule.
Examples of the acid anhydride used in the case of producing a silicone compound having more than one, for example, succinic acid, itaconic acid, citraconic acid, glutaric acid, azelaic acid, sebacic acid, decamethylenedicarboxylic acid, phthalic acid, maleic acid, triacid Examples thereof include acid anhydrides of polyvalent carboxylic acids such as mellitic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid and methylhexahydrophthalic acid.

Component (A) has 1 reactive functional group in the molecule.
Examples of the compound having a hydroxyl group and a carboxyl group in the molecule used in the case of producing a silicone compound having more than one, for example, hydroxybenzoic acid, hydroxyisophthalic acid, hydroxynaphthoic acid, hydroxyphenylacetic acid, hydroxyphenylpropionic acid, dimethylolbutane Examples thereof include acids, polyester compounds having a hydroxyl group and a carboxyl group, and acrylic compounds having a hydroxyl group and a carboxyl group.

Component (A) has 1 reactive functional group in the molecule.
As the reactive silicone compound having a vinyl group, which is used in the case of producing a silicone compound having two or more, trade names X-24-8201 and X-2 manufactured by Shin-Etsu Chemical Co., Ltd.
2-174DX, X-22-2426, trade name Cilaplane FM-0711, FM-07 manufactured by Chisso Corporation
21, FM-0725, TM-0701, TM-070
5 and the like.

Component (A) has 1 reactive functional group in the molecule.
As an α, β-unsaturated monomer having a hydroxyl group, which is used in the case of producing a silicone compound having two or more
Examples thereof include hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate.

Component (A) has 1 reactive functional group in the molecule.
As the α, β-unsaturated monomer having no hydroxyl group, which is used in the case of producing a silicone compound having one or more,
For example, methyl (meth) acrylate, ethyl (meth)
Acrylate, propyl (meth) acrylate, normal butyl (meth) acrylate, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, normal lauryl (meth) acrylate, stearyl (meth)
C1-C18 of (meth) acrylic acid such as acrylate
(Meth), such as alkyl ester, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate
Cycloalkyl ester of acrylic acid, aromatic hydrocarbon alkyl ester such as benzyl (meth) acrylate, alkoxyalkyl (meth) acrylate such as 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, styrene, α -Vinyl aromatic compounds such as methylstyrene, aminoalkyl esters of (meth) acrylates such as dimethylaminoethyl (meth) acrylate, acrylamide, acrylonitrile and the like.

Component (A) has 1 reactive functional group in the molecule.
Examples of the compound having two or more epoxy groups in a molecule used for producing a silicone compound having two or more epoxy compounds include sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, and triglycidyl tris isocyanurate. , Polyepoxy compounds such as glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, resorcin diglycidyl ether, neopentyl glycol diglycidyl ether,
1,6-hexanediol diglycidyl ether, bisphenol S diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, adipic acid diglycidyl ester,
Examples include diepoxy compounds such as diglycidyl phthalate.

Component (A) has 1 reactive functional group in the molecule.
As the polyisocyanate compound used when producing a silicone compound having more than one, tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, hydrogenated methylene cyclohexyl isocyanate,
Examples thereof include hydrogenated methylcyclohexane diisocyanate, hydrogenated isocyanate methylcyclohexane, isophorone diisocyanate, and trimethylhexamethylene diisocyanate, which may be isocyanurate bodies, allophanate bodies, or adduct bodies of these polyisocyanates.

Component (A) has 1 reactive functional group in the molecule.
Examples of the α, β-unsaturated monomer having an epoxy group used when producing a silicone compound having one or more epoxy compounds include epoxy group-containing (meth) acrylates such as glycidyl (meth) acrylate and methylglycidyl (meth) acrylate. Examples include monomers.

Component (A) has 1 reactive functional group in the molecule.
Examples of the carboxyl group-containing α, β-unsaturated monomer used when producing a silicone compound having one or more of them include acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, itaconic acid, maleic acid and fumaric acid. .

Component (A) has 1 reactive functional group in the molecule.
Examples of the other α, β-unsaturated monomer used in the case of producing a silicone compound having at least one are, for example,
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, normal butyl (meth) acrylate, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, normal lauryl ( C1-C18 alkyl esters of (meth) acrylic acid such as (meth) acrylate and stearyl (meth) acrylate, cycloalkyl esters of (meth) acrylic acid such as cyclohexyl (meth) acrylate and isobornyl (meth) acrylate, benzyl (meth) ) Aromatic hydrocarbon alkyl ester such as acrylate, 2-methoxyethyl (meth) acrylate, alkoxyalkyl (meth) acrylate such as 3-methoxybutyl (meth) acrylate, styrene , Alpha-methyl styrene and vinyl aromatic compounds, (meth) aminoalkyl esters of acrylates such as dimethylaminoethyl (meth) acrylate, acrylamide, and acrylonitrile and the like. Each of the compounds described above may be used alone or in combination of two or more.

The silicone compound having at least one chemically blocked carboxyl group represented by the formula (2) (Chemical Formula 6) in the molecule is a silicone compound having at least one carboxyl group in the molecule. By blocking by reacting the carboxyl group of the compound with a vinyl ether compound, a vinyl thioether compound of the formula (3) (Chemical formula 7), or a heterocyclic compound having a vinyl double bond having an oxygen atom or a sulfur atom as a hetero atom. , Easily obtained.

[0031]

[Chemical 6]

[0032]

[Chemical 7] (In the formulas (2) and (3), R₅, R₆And R₇
Is a hydrogen atom or an organic group having 1 to 18 carbon atoms, R
₈Is an organic group having 1 to 18 carbon atoms, and R₇And R ₈flag
Combine with galleries and Y_TwoForm a heterocycle with
May be Y _TwoIs an oxygen atom or a sulfur atom
)

The reaction between the carboxyl group and the compound represented by the above formula (3) is usually carried out at room temperature to 10 in the presence of an acidic catalyst.
It is carried out at temperatures in the range of 0 ° C.

In the above formulas (2) and (3), R ₅ ,
Preferred as R ₆ and R ₇ are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and an aryl group, and preferred examples of R ₈ are an alkyl group having 1 to 10 carbon atoms and an aryl group.

Specific examples of the compound represented by the above formula (3) include methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, sec-butyl vinyl ether and ter-.
Examples thereof include aliphatic vinyl ether compounds such as butyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, and corresponding aliphatic vinyl thioether compounds.

In the present invention, the component (B) is a compound having two or more chemically blocked carboxyl groups represented by the formula (1) (formula 8) in the molecule.

[Chemical 8] (In the formula, R ₁ , R ₂ and R ₃ are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, R ₄ is an organic group having 1 to 18 carbon atoms, and R ₃ and R ₄ are bonded to each other. A heterocycle having Y ₁ as a hetero atom may be formed, and Y ₁ is an oxygen atom or a sulfur atom.)

The blocked carboxyl group of the formula (1) is a carboxyl group and a vinyl ether compound or vinyl thioether compound represented by the formula (4) (formula 9), or a vinyl double compound having an oxygen atom or a sulfur atom as a hetero atom. It can be easily formed by reaction with a heterocyclic compound having a bond.

[Chemical 9] (In the formula, R ₁ , R ₂ and R ₃ are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, R ₄ is an organic group having 1 to 18 carbon atoms, and R ₃ and R ₄ are bonded to each other. A heterocycle having Y ₁ as a hetero atom may be formed, and Y ₁ is an oxygen atom or a sulfur atom.)

The reaction between the carboxyl group and the compound represented by the above formula (4) is usually carried out at room temperature to 10 in the presence of an acidic catalyst.
It is carried out at temperatures in the range of 0 ° C.

In the above formulas (1) and (4), R ₁ ,
Preferred as R ₂ and R ₃ are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and an aryl group, and preferred ones as R ₄ are an alkyl group having 1 to 10 carbon atoms and an aryl group.

Specific examples of the compound represented by the above formula (4) include methyl vinyl ether, ethyl vinyl ether,
Aliphatic vinyl ether compounds such as isopropyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, sec-butyl vinyl ether, ter-butyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether and corresponding aliphatic vinyl thioether compounds Is mentioned.

Examples of the compound having two or more carboxyl groups in the molecule used when producing the component (B) include aliphatic polycarboxylic acids having 2 to 22 carbon atoms such as succinic acid and adipic acid, and phthalic acid. Aromatic polycarboxylic acid such as acid,
Examples thereof include alicyclic polycarboxylic acids such as hexahydrophthalic acid, and polyester resins having two or more carboxyl groups in the molecule, acrylic resins, maleated polybutadiene resins, and the like. The compound having two or more carboxyl groups in the molecule is, for example, 1) half-esterified with a polyol compound having two or more hydroxyl groups per molecule and an acid anhydride, and 2) isocyanate per molecule. 3) Addition of a polyisocyanate compound having two or more groups to a hydroxycarboxylic acid or an amino acid, 3) homopolymerization of a carboxyl group-containing α, β-unsaturated monomer or other α, β-unsaturated monomer It can also be obtained by a method of copolymerizing, 4) synthesizing a carboxyl group-terminated polyester, or the like. Of these,
1) A half ester of a polyol compound having two or more hydroxyl groups per molecule and an acid anhydride, and 3) a homopolymerization of a carboxy-containing α, β-unsaturated monomer or other α Those copolymerized with a .beta.-unsaturated monomer are preferable.

Here, examples of the polyol compound used in the method 1) include ethylene glycol, 1,
2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,2-butanediol, 1,6-hexanediol, diethylene glycol, pentanediol, dimethylbutanediol, water Bisphenol A, cyclohexane-1,4-diol, glycerin, sorbitol,
Neopentyl glycol, 1,8-octane diol,
Polyhydric alcohols such as 1,3,6-hexanetriol, 1,2,4-butanetriol, trimethylolethane, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol and tripentaerythritol, and polyhydric alcohols thereof. Alcohol and γ
Examples thereof include ring-opening adducts with lactone compounds such as butyrolactone and ε-caprolactone. Examples of the acid anhydride to be reacted with the polyol include succinic acid, glutaric acid, azelaic acid, sebacic acid, decamethylenedicarboxylic acid, phthalic acid, maleic acid, trimellitic acid, pyromellitic acid, tetrahydrophthalic acid, and tetrahydrophthalic acid. And acid anhydrides of polyvalent carboxylic acids such as hexahydrophthalic acid.

Examples of the carboxyl group-containing α, β-unsaturated monomer used in the method 3) include acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, itaconic acid, maleic acid and fumaric acid. . Examples of other α, β-unsaturated monomers include methyl (meth) acrylate, ethyl (meth) acrylate,
Propyl (meth) acrylate, normal butyl (meth) acrylate, isobutyl (meth) acrylate,
Tertiary butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, normal lauryl (meth) acrylate, stearyl (meth) acrylate,
C1-C18 alkyl ester of (meth) acrylic acid such as, cycloalkyl ester of (meth) acrylic acid such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, aromatic hydrocarbon alkyl such as benzyl (meth) acrylate Esters, alkoxyalkyl (meth) acrylates such as 2-methoxyethyl (meth) acrylate and 3-methoxybutyl (meth) acrylate, vinyl aromatic compounds such as styrene and α-methylstyrene, and dimethylaminoethyl (meth) acrylate. Examples thereof include aminoalkyl ester of (meth) acrylate, acrylamide, and acrylonitrile. The above compounds may be used alone or in combination of two or more. As the polyisocyanate and hydroxycarboxylic acid used in the method 2), the polyisocyanate and hydroxycarboxylic acid used for producing the component (A) are used.

In the present invention, the component (C) is obtained by homopolymerizing an α, β-unsaturated monomer having an epoxy group or optionally by copolymerizing another α, β-unsaturated monomer. can get. The α, β-unsaturated monomer having an epoxy group is not particularly limited as long as it has an unsaturated group at the terminal and has one or more epoxy groups in one molecule. Specific examples of the α, β-unsaturated monomer having one or more epoxy groups in one molecule include, for example, epoxy group-containing (meth) s such as glycidyl (meth) acrylate and methylglycidyl (meth) acrylate. An acrylate monomer may be used. These may be used alone or in combination of two or more. Examples of the other α, β-unsaturated monomer include the same as those described in the explanation of the component (A) and the component (B).

The average molecular weight of the compound as the component (C) can be used without limitation. The epoxy equivalent of the compound as the component (C) is preferably 200 to 2000 g / mol,
It is preferably 250 to 1000 g / mol. In the thermosetting composition of the present invention, the compound as the component (C) may be used alone or in combination of two or more.

In the thermosetting composition of the present invention, (A)
The molar ratio of the chemically blocked carboxyl groups of formulas (1) and (2) in the component (B) and the total amount of the carboxyl groups to the epoxy group in the component (C) is 0.
It is desirable that each component be contained in a ratio of 2: 1.0 to 1.0: 0.2. If the ratio is out of the above range, the crosslinking reaction will be insufficient and the coating performance will be deteriorated. Further, the functional group of the component (A) is an epoxy group, a carboxyl group,
Alternatively, in the case of the chemically blocked carboxyl group represented by the formula (2), the components (A) and (B) + (C)
The ratio of the components is preferably 0.01: 1 to 1: 0.1 by weight. When the weight ratio of the component (A) to the component (B) + the component (C) is less than 0.01: 1, sufficient water repellency and oil repellency cannot be obtained. When the weight ratio of the component (A) to the component (B) + the component (C) is larger than 1: 0.1,
Cross-linking becomes insufficient and coating film performance deteriorates. further,
When the component (A) has a functional group other than the epoxy group, the carboxyl group, or the chemically blocked carboxyl group represented by the formula (2), the component (A) and the component (B) + (C) The weight ratio is preferably 0.01: 1 to 1: 1. When the weight ratio of the component (A) to the component (B) + the component (C) is less than 0.01: 1, sufficient water repellency and oil repellency cannot be obtained. Further, the component (A) is the component (B) +
If the weight ratio to the component (C) is greater than 1: 1 then crosslinking will be insufficient and the coating performance will be impaired.

As the component (D), a thermal latentizing catalyst which is active during heat curing may be contained. The thermal latent catalyst is preferably a compound that exhibits acid catalytic activity at a temperature of 80 ° C. or higher. Examples of the thermal latent catalyst for the component (D) include a proton acid, a Lewis acid, a compound obtained by neutralizing a proton acid with a Lewis acid base, a compound obtained by neutralizing a Lewis acid with a Lewis base, and a Lewis acid and a trialkylphosphite. blend,
Preferable examples include a mixture of Lewis acid and dialkyl sulfide, sulfonic acid esters, phosphoric acid esters, and onium compounds. These may be used alone or in combination. The blending amount of component (D) is
The range of 0.01 to 10 parts by weight is preferable per 100 parts by weight of the total of the components (A), (B) and (C).

In addition to the above-mentioned components, the thermosetting composition of the present invention contains a UV absorber such as a benzotriazole-based UV absorber, a triazine-based UV absorber, an anilide oxalate-based UV absorber, and a hindered amine-based light absorber. Light stabilizers such as stabilizers, phenolic antioxidants, phosphite antioxidants, antioxidants such as thioether antioxidants,
Organic resin fine particles, fatty acid amide wax, polyamide wax, polyethylene wax, polyethylene oxide wax, silica, organic bentonite, viscosity modifiers such as urea compound viscosity modifiers, silicone surface treatment agents, vinyl compound surface conditioning A surface modifier such as a defoaming agent, a defoaming agent such as a silicone-based defoaming agent, a vinyl compound-based defoaming agent, and the like can be appropriately added. Further, as the color pigment, titanium oxide, zinc oxide, yellow iron oxide, red iron oxide, inorganic color pigments such as carbon black, phthalocyanine blue, slene blue, phthalocyanine green, insoluble azo, soluble azo, perylene, quinacridone red, thio. Organic color pigments such as indigo red, dioxazine violet, anthrapyrimidine yellow, quinophthalone yellow and the like, and aluminum powder, nickel powder, pearl mica and the like as a brightening agent can be appropriately mixed.

A solvent may be added to the thermosetting composition of the present invention. Water, an organic solvent or the like can be used as the solvent. Specific examples of the organic solvent include, for example, benzene, toluene, xylene, ethylbenzene, aromatic petroleum naphtha, tetralin, turpentine, Solvesso # 100 (registered trademark of Exxon Chemical Co., Ltd.), Solvesso # 150 (registered by Exxon Chemical Co., Ltd.). (Trademarks), aromatic hydrocarbons such as hexane, heptane and octane, alicyclic hydrocarbons such as cyclohexane, ethers such as dioxane and tetrahydrofuran, methyl acetate, ethyl acetate, n-propyl acetate, Isopropyl acetate, n-butyl acetate, isobutyl acetate, secondary butyl acetate, amyl acetate, methyl ether, methoxybutyl acetate and other esters and ether esters, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclohexanone, isophorone, methyl iso Examples include ketones such as amyl ketone, ethyl amyl ketone, diisobutyl ketone, diethyl ketone, methylpropyl ketone, and diisopropyl, phosphoric acid esters such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, dimethylsulfoxide, N, N-dimethylformamide, and the like. To be These organic solvents may be used alone or in combination of 2
You may combine 2 or more types.

The silicon-containing thermosetting composition of the present invention can be used as an overcoating material applied to a coating material such as a metal material or a resin material. The silicon-containing thermosetting composition of the present invention is applied as it is on the article to be coated as an overcoat paint, or is applied on an undercoat coating film or an intermediate coating film.
As for the coating specifications, it is possible to use a single 1-coat coating, a 2-coat coating in combination with a base coat, a 3-coat coating, or an overcoat coating on the top coating film. The silicon-containing thermosetting composition of the present invention, as a clear coating,
Further, it can be used as an enamel paint containing a pigment or a luster color material.

[0051]

EXAMPLES Next, the present invention will be described more specifically by way of examples. The present invention is not limited to these examples. The components (A), (B), (C), and (D) used in the examples and comparative examples are shown below. Component (A) Component (A-1) Glycerol / X-22-162C (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) Functional group equivalent 2330, both end carboxyl group reactive silicone) = 2/98 (wt%) Butyl acetate solution of the reaction product (solid content 60%)

Component (A-2) glycidyl methacrylate / n-butyl acrylate /
n-butyl methacrylate / X-24-8201 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), functional group equivalent of 2000,
One end vinyl group reactive silicone) = 13/57/20
/ 10 (wt%) copolymer xylene solution (solid content 6
0%)

(A-3) Component X-22-162C (trade name, Shin-Etsu Chemical Co., Ltd.)
Manufactured), a functional group equivalent of 2330, a carboxyl group of both terminal carboxyl group reactive silicone) is chemically blocked with n-butyl vinyl ether in a xylene solution of resin (solid content 45%, equivalent of blocked carboxyl group of resin component: 2430 g / mol)

(Component B) A xylene solution of a resin in which the carboxyl group formed in the reaction product of trimethylolpropane / succinic anhydride = 25/75 (mol%) is chemically blocked with the same molar amount of n-butyl vinyl ether ( Solid content 45
%, Blocked carboxyl group equivalent of resin component 245 g
/ Mol, number average molecular weight 730)

Component (C) Glycidyl Methacrylate / Butyl Acrylate / Butyl Methacrylate / 2-Ethylhexyl Methacrylate / Styrene = 40/20/10/15/15 (wt%)
Xylene solution of copolymer (solid content 60%, epoxy group equivalent of resin component 355 g / mol, number average molecular weight 500
0) 10% xylene solution of component (D) p-toluenesulfonic acid.

A blending amount of each component of the clear coating composition shown in Table 1 (Table 1) was stirred in a homodisper for 20 minutes in a container for producing the clear coating composition.
A clear paint was produced.

[0057]

[Table 1]

Preparation of test plate On the chemically treated dull steel plate, the cationic electrodeposition paint Aqua N
o. 4200 (trade name, manufactured by NOF BASF Coatings Co., Ltd.) was applied to a dry film thickness of 20 μm, baked at 170 ° C. for 20 minutes to cure the coating film, and then used as an intermediate coating material in High Epico No. 500 (trade name, manufactured by NOF BASF Coatings Co., Ltd.) with a dry film thickness of 35
It was coated so as to have a thickness of .mu.m and baked at 140.degree. Then, Bellcoat No. 6000 silver metallic base coat paint (trade name, NOF BA
SF Coatings Co., Ltd.) was coated on the above-mentioned object to be coated so that the dry film thickness was 13 μm. After standing at room temperature for 3 minutes, the clear paint prepared by the above method was applied so that the dry film thickness would be 35 μm. The coated steel sheet was left at room temperature for 10 minutes and then baked at 140 ° C. for 30 minutes to obtain a cured coating film.

The coating performance test of the top coating film obtained by the above method was carried out by the following method. The results are shown in Table 2 (Table 2)
It was shown to. (1) Coating film hardness: The coating film hardness was measured by JIS K5400 8.4.1 tester method, and the coating film was evaluated by scratches. (2) Moisture resistance: A test was carried out for 120 hours by the JIS K5400 9.2.2 rotary method, and after the test was completed, the state of the coating film was visually observed. (3) Adhesion: Adhesion was tested by the JIS K5400 8.5.2 cross-cut tape method, and an evaluation score of 6 or more was passed, and a product not reaching the evaluation score was rejected. (4) Acid resistance: 2 ml of 40% sulfuric acid was placed on the spot on the test plate, left for 30 minutes at 60 ° C., and then abnormalities of the coating film were visually evaluated.

(5) Scratch resistance: 20% water suspension of Kanto loam layer soil (test dust type 8 JIS Z8901) 1 m
1 was applied to a 2 × 2 cm flannel cloth, which was installed in the repetitive motion head of a friction tester (Taiko Machinery), and the coating was scratched 20 times under a load of 50 g on the cured coating. After that, the brightness L * value was measured with a color difference meter (SM-7 type, manufactured by Suga Test Instruments Co., Ltd.), and the brightness difference ΔL * value from the initial value was calculated. The case where the color difference ΔL * was 15 or less was passed, and the case where it exceeded 15 was rejected. (6) Weather resistance: JIS D0205 2.2.1 Accelerated weather resistance test Using the ultraviolet fluorescent lamp weather resistance tester of (3), the presence or absence of cracks in the coating film after 2000 hours of test time was observed. (7) Finished appearance: The appearance of the coating film was visually evaluated. (8) Water repellency: Kyowa Interface Science contact angle meter (CA-Z type)
Was used to measure the contact angle of water, and the case where the contact angle was 85 ° or more was regarded as acceptable. (9) Oil repellency: Kyowa Interface Chemistry contact angle meter (CA-Z type)
Was used to measure the contact angles of xylene and oleic acid. The contact angle was 8 ° or more in the case of xylene and 20 ° or more in the case of oleic acid.

(10) Contamination property: JIS K-5400
(1990) 9.9 According to the weather resistance test, after the outdoor exposure for 3 months, the color of the unwashed surface of the coating film (JIS K-5400
(1990) 7.4.2 measurement method) and L after exposure
The ΔL value was calculated by subtracting the L value at the time of non-exposure from the value and judged based on the following criteria. ◯: ΔL value is less than 3 Δ: ΔL value is 3 or more, less than 6 ×: ΔL value is 6 or more

[0062]

[Table 2]

[0063]

The silicone-containing thermosetting composition of the present invention has excellent chemical performance, physical performance, scratch resistance, weather resistance,
It is possible to give a cured product having acid resistance and appearance, particularly excellent water repellency and oil repellency, and good stain resistance and stain removability. For example, for paints, inks, molded products, adhesives, etc. It is preferably used.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Yasushi Honda             3-4-8 Hino, Konan-ku, Yokohama-shi, Kanagawa             518 F term (reference) 4J036 AB01 AB02 AB03 AK11 AK17                       DA10 DB23 DD01 DD04 DD08                       JA01

Claims (5)

[Claims] 1. A silicone compound having one or more reactive functional groups in the molecule (component (A)), a compound of formula (1) in the molecule.
A compound (component (B)) having two or more chemically blocked carboxyl groups represented by (Chemical Formula 1), (In the formula, R ₁ , R ₂ and R ₃ are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, R ₄ is an organic group having 1 to 18 carbon atoms, and R ₃ and R ₄ are bonded to each other. A heterocycle having Y ₁ as a hetero atom may be formed, and Y ₁ is an oxygen atom or a sulfur atom), and a compound having two or more epoxy groups in the molecule (component (C)) A silicone-containing thermosetting composition comprising: 2. The silicone-containing thermosetting composition according to claim 1, which further comprises a thermal latent catalyst (component (D)) which exhibits activity when cured by heating. 3. The silicone-containing thermosetting composition according to claim 1, wherein the reactive functional group of the component (A) is an epoxy group. 4. The silicone-containing thermosetting composition according to claim 1, wherein the reactive functional group of the component (A) is a carboxyl group. 5. The reactive functional group of the component (A) has the formula (2)
The silicone-containing thermosetting composition according to claim 1 or 2, which is a chemically blocked carboxyl group represented by the formula (2). [Chemical 2] (Wherein R ₅ , R ₆ and R ₇ are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, R ₈ is an organic group having 1 to 18 carbon atoms, and R ₇ and R ₈ are bonded to each other. May form a heterocycle having Y ₂ as a hetero atom, and Y ₂ is an oxygen atom or a sulfur atom)