JPH0748540A - Curable resin composition for top coating - Google Patents

Abstract

PURPOSE:To obtain a top coating composition excellent in adhesion to architectural materials, weatherability, etc., by incorporating a specific silicon compound, a curing catalyst and an adhesion improver in an acrylic copolymer having specific reactive silyl groups. CONSTITUTION:A curable resin composition is prepared by incorporating 2-70 pts.wt. of a silicon compound of formula II (wherein R<3> and R<4> are each a monovalent hydrocarbon such as a 1-10C alkyl; and b is 0 or 1), 0.1-20 pts.wt. of a curing catalyst comprising a monovalent organic carboxylic acid and an organic tertiary amine, and 0.1-20 pts.wt. of an adhesion improver (silane coupling agent, etc.) in 100 pts.wt. of an acrylic copolymer having reactive silyl groups of formula I (wherein R<1> is H or a 1-10C alkyl; R<2> is H or a monovalent hydrocarbon such as a 1-10C alkyl; and a is 0-2). It is preferable for the acrylic copolymer to contain n-butyl methacrylate as a polymer component and has a number average molecular weight of 3,000-25,000 in view of the durability of coating film. The resin composition can be used preferably for the top coating of buildings.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a curable resin composition for a topcoat paint. More specifically, for example, curability for top coatings that can be suitably used for coating metal, ceramics, glass, cement, ceramic moldings, buildings made of plastic, wood, paper, fibers, etc., home appliances, industrial equipment, etc. It relates to a resin composition.

[0002]

2. Description of the Related Art Conventionally, the surfaces of ceramic moldings, buildings made of concrete and steel, industrial products such as building materials, etc. are coated with paints such as fluororesin paints, acrylic urethane paints and acrylic silicone resin paints. By doing so, the appearance of buildings and the like is improved and corrosion resistance and weather resistance are improved.

[0003]

However, in recent years,
Due to the deterioration of the environment centering on urban areas and the improvement of aesthetic and landscape retention awareness, there is an increasing demand for stain resistance of the above paints.

Among the above-mentioned paints, acrylic silicone resin paints have excellent stain resistance, but they are still insufficient in severe environments.

[0005]

Means for Solving the Problems As a result of intensive studies in view of the above circumstances, the present inventors have found that an acrylic copolymer containing a specific reactive silyl group, a specific silicon compound, and The composition containing the curing catalyst and the adhesion-improving component in a specific ratio has curability at room temperature, and the coating film from the composition has excellent weather resistance as well as the coating film from the acrylic silicone resin paint. They finally found that they have excellent stain resistance and adhesion at the same time, and have completed the present invention.

That is, the present invention has the general formula (I):

[0007]

[Chemical 3]

(In the formula, R ¹ is a hydrogen atom or a carbon number of 1 to
10 alkyl groups, R ² is a hydrogen atom or 1 to 1 carbon atoms
A monovalent hydrocarbon group selected from an alkyl group, an aryl group and an aralkyl group of 0, a represents an integer of 0 to 2), and an acrylic copolymer containing a reactive silyl group bonded to a carbon atom. General formula (II):

[0009]

[Chemical 4]

(In the formula, R ³ is a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group and an aralkyl group, and R ⁴ is an alkyl group having 1 to 10 carbon atoms, an aryl group and A monovalent hydrocarbon group selected from aralkyl groups, b represents 0 or 1) and / or a silicon compound represented by the formula (B)
70 parts, 0.1 to 20 parts of at least one curing catalyst (C) selected from organic carboxylic acids, a combination of organic carboxylic acids and organic amines, and an organometallic compound, and an adhesion improving component (D ) 0.1-20 parts by weight of the curable resin composition for top coating composition (Invention 1), and the acrylic copolymer (A) in Invention 1 have the general formula (I) in the molecule.
The monomer unit containing a reactive silyl group represented by
The composition (Invention 2), which is a copolymer containing 90 to 90% (% by weight, the same hereinafter), and the acrylic copolymer (A) in Invention 1 or Invention 2 contain an n-butyl methacrylate unit as a polymerization component. A composition (invention 3) which is a copolymer of the present invention, and a composition in which the combination of the organic carboxylic acid and the organic amine in the invention 1 is composed of a saturated or unsaturated monovalent carboxylic acid and a tertiary amine ( Invention 4), Invention 1
Or a composition (invention 5) in which the organic amines in invention 4 contain a reaction product of an aminosilane compound and / or an aminosilane compound, and the organic carboxylic acids and organic amines in invention 1, invention 4 or invention 5. In the composition (Invention 6), the combination product of the above is a composition (Invention 6) in which the ratio of the carboxyl groups of the organic carboxylic acids and the amino groups of the organic amines (ratio of amino group / carboxyl group) is 0.2 to 3. A composition in which the organometallic compound is dibutyltin alkyl ester (Invention 7), a composition in which the adhesion-improving component (D) in Invention 1 is a silane coupling agent and / or a reaction product thereof (Invention 8), in Invention 8 The silane coupling agent and / or the reactant thereof has an amino group or a glycidoxy group. Composition) is the reaction about (invention 9).

[0011]

Functions and Examples The curable resin composition for top coating of the present invention has the general formula (I) as a base resin curable at room temperature in the presence of moisture:

[0012]

[Chemical 5]

(In the formula, R ¹ is a hydrogen atom or a carbon number of 1 to
10 alkyl groups, R ² is a hydrogen atom or 1 to 1 carbon atoms
A monovalent hydrocarbon group selected from an alkyl group, an aryl group and an aralkyl group of 0, a represents an integer of 0 to 2), and an acrylic copolymer containing a reactive silyl group bonded to a carbon atom. Combined (A) is contained.

The acrylic copolymer (A) has a main chain substantially composed of a main chain copolymerized with an acrylic monomer (hereinafter, the main chain is also substantially composed of an acrylic copolymer chain. Since it is a copolymer, the coating film formed from the obtained curable resin composition for top coating composition of the present invention has excellent weather resistance and chemical resistance.

Incidentally, the fact that the main chain of the acrylic copolymer (A) is substantially composed of the acrylic copolymer chain means that 50% of the units constituting the main chain of the acrylic copolymer (A).
The above means that 70% or more is formed from acrylic monomer units.

Since the acrylic copolymer (A) contains a reactive silyl group bonded to a carbon atom, the coating film has excellent water resistance, alkali resistance and acid resistance. Become.

In the acrylic copolymer (A), the number of reactive silyl groups bonded to the carbon atom represented by the general formula (I) is 2 or more per 1 molecule of the acrylic copolymer (A), preferably Is preferably 3 or more because the coating film formed from the composition of the present invention has excellent durability such as weather resistance and solvent resistance.

The reactive silyl group represented by the above general formula (I) may be bonded to the end of the main chain of the acrylic copolymer (A) or may be bonded to the side chain thereof. It may be attached to the chain ends and side chains.

In the above general formula (I), R ¹ is a hydrogen atom or has 1 to 10 carbon atoms, preferably, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-
It is an alkyl group having 1 to 4 carbon atoms such as a butyl group and an i-butyl group. If the number of carbon atoms in the alkyl group exceeds 10, the reactivity of the reactive silyl group will decrease. Also, when R ¹ is a group other than an alkyl group such as a phenyl group or a benzyl group, the reactivity of the reactive silyl group is lowered.

In the general formula (I), R ² is a hydrogen atom or a C 1-10 alkyl group, preferably, for example, a C 1-4 alkyl group exemplified in the R ¹ .
For example, it is a monovalent hydrocarbon group selected from an aryl group having preferably 6 to 25 carbon atoms such as a phenyl group and an aralkyl group having preferably 7 to 12 carbon atoms such as a benzyl group. Among these, an alkyl group having 1 to 4 carbon atoms is preferable from the viewpoint that the composition of the present invention has excellent curability.

In the general formula (I), (R ¹ O)
_3-a is such that 3-a is 1 or more and 3 or less, that is, a
Is selected to be 0 to 2, but a is preferably 0 or 1 from the viewpoint that the curability of the acrylic copolymer (A) is improved. Therefore, the number of bonds of R ² is preferably 0 to 1.

(R ¹ O) _3-a present in the general formula (I)
Or

[0023]

[Outer 1]

When the number of is 2 or more, R ¹ or R ² contained in 2 or more may be the same or different.

Specific examples of the reactive silyl group bonded to the carbon atom represented by the general formula (I) include groups contained in a monomer containing a reactive silyl group described later.

The acrylic copolymer (A) has the general formula (I) in its molecule from the viewpoint of ease of synthesis.
Those containing a monomer unit containing a reactive silyl group bonded to a carbon atom represented by are preferred. The content ratio of the monomer unit in the acrylic copolymer (A) is such that the coating film formed by using the composition of the present invention has excellent durability and high strength. 3 to 90
%, More preferably 11 to 70%, and particularly preferably 11 to 50%.

The monomer units other than the monomer unit containing the reactive silyl group bonded to the carbon atom represented by the general formula (I) contained in the acrylic copolymer (A) will be described later. The unit derived from the acrylic monomer, and the units derived from other monomers optionally used as described later are included.

The acrylic copolymer (A) has a number average molecular weight of 1,000 to 300 from the viewpoint of excellent physical properties such as durability of a coating film formed using the composition of the present invention.
00, especially 3000-25000 is preferable.

Acrylic copolymer (A) as described above
May be used alone or in combination of two or more.

Next, an example of the method for producing the acrylic copolymer (A) will be described.

The acrylic copolymer (A) is, for example, a monomer having a polymerizable double bond and a reactive silyl group bonded to a carbon atom (hereinafter referred to as monomer (A-1)), (meth). It can be produced by polymerizing acrylic acid and / or its derivative (hereinafter referred to as monomer (A-2)) and optionally other monomer.

Specific examples of the monomer (A-1) include, for example,

[0033]

[Chemical 6]

General formula (III) such as:

[0035]

[Chemical 7]

(Wherein R ¹ , R ² and a are the same as above,
⁵ represents a hydrogen atom or a methyl group);

[0037]

[Chemical 8]

General formula (IV) such as:

[0039]

[Chemical 9]

A compound represented by the formula: wherein R ¹ , R ² , R ⁵ and a are the same as defined above, and n is an integer of 1 to 12;

[0041]

[Chemical 10]

General formula (V) such as:

[0043]

[Chemical 11]

A compound represented by the formula (wherein R ¹ , R ² , R ⁵ , a and n are the same as defined above);

[0045]

[Chemical 12]

General formula (VI) such as:

[0047]

[Chemical 13]

A compound represented by the formula: wherein R ¹ , R ² , R ⁵ and a are the same as defined above, and m is an integer of 1 to 14;

[0049]

[Chemical 14]

(Wherein p represents an integer of 0 to 20) such as general formula (VII):

[0051]

[Chemical 15]

(Wherein R ¹ , R ² , R ⁵ and a are the same as above, q is an integer of 0 to 22), or a reactive silyl group bonded to a carbon atom is a urethane bond. Or having at the end via a siloxane bond (meth)
Examples include acrylate. Among these, the compound represented by the general formula (IV) is preferable from the viewpoint of excellent copolymerizability and polymerization stability, and curability and storage stability of the obtained composition.

These monomers (A-1) may be used alone or in combination of two or more kinds.

As described above, the monomer (A-1) is a monomer containing a reactive silyl group bonded to a carbon atom represented by the general formula (I) in the obtained acrylic copolymer (A). 3 to 90% of the unit of mer, further 11 to 7
It is preferable to use it so as to contain 0%, particularly 11 to 50%.

Specific examples of the monomer (A-2) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-
Ethylhexyl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, trifluoroethyl (meth) acrylate, pentafluoropropyl (meth) acrylate, perfluorocyclohexyl (meth) acrylate, (meth ) Acrylonitrile, glycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, (meth) acrylamide, α-ethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N- Dimethyl (meth) acrylamide, N-methyl (meth) acrylamide, (meth) acryloylmorpholine, 2-hydroxyethyl (meth) acrylate, 2-hydro Shipuropiru (meth) acrylate, N- methylol (meth) acrylamide, Aronikusu M-5700, is a macromonomer AS-6, A
Compounds such as N-6, AA-6, AB-6, AK-5 (above, Toa Gosei Chemical Industry Co., Ltd.), Placcel
FA-1, Placcel FA-4, Placce
l FM-1, Placcel FM-4 (above, manufactured by Daicel Chemical Industries, Ltd.), phosphate ester groups such as condensation products of hydroxyalkyl esters of (meth) acrylic acid and phosphoric acid or phosphate esters Inclusion (meta)
Examples thereof include acrylic compounds, (meth) acrylates containing urethane bonds and siloxane bonds. Among these, the obtained acrylic copolymer (A) has excellent compatibility with the silicon compound represented by the general formula (II) described below and / or its partially hydrolyzed condensate (B). Therefore, it is preferable to contain n-butyl methacrylate.

These monomers (A-2) may be used alone or in combination of two or more kinds.

The acrylic copolymer (A) contains 3 to 90% of a monomer unit containing a reactive silyl group bonded to a carbon atom represented by the general formula (I) in the molecule,
If it contains n-butyl methacrylate units,
Any effect obtained when these are contained can be obtained.

The amount of the monomer (A-2) to be used may be appropriately adjusted depending on the type and amount of the monomer (A-1) used, but it is usually 5 to 90 of the total amount of the polymerization components usually used.
%, More preferably 30 to 85%, especially 50 to 85%. In addition, as the monomer (A-2), n-
When butyl methacrylate is used, the amount used is 20 to 50% of the total amount of the monomers used, and the silicon compound represented by the general formula (II) described below and / or its partial hydrolysis condensation is used. It is preferable from the viewpoint that the compatibility with the substance (B) and the various properties of the coating film formed from the resulting curable resin composition are excellent.

Further, in the present invention, for the purpose of further improving the weather resistance of the coating film formed from the composition of the present invention obtained, for example, a segment or a monomer (having a urethane bond or a siloxane bond in the main chain) A-1),
A segment derived from a monomer other than the monomer (A-2) may be introduced during the production of the acrylic copolymer (A) within a range not exceeding 50%.

The above-mentioned monomer (A-1) and monomer (A-
Specific examples of monomers other than 2) include aromatic hydrocarbon vinyl compounds such as styrene, α-methylstyrene, chlorostyrene, styrenesulfonic acid, 4-hydroxystyrene and vinyltoluene; maleic acid and fumaric acid. Acids, unsaturated carboxylic acids such as itaconic acid, salts thereof such as alkali metal salts, ammonium salts and amine salts;
Acid anhydrides of unsaturated carboxylic acids such as maleic anhydride, esters of unsaturated carboxylic acids such as diesters or half esters of these acid anhydrides with linear or branched alcohols having 1 to 20 carbon atoms; acetic acid Vinyl, vinyl propionate, vinyl ester and allyl compounds such as diallyl phthalate; vinyl group-containing vinyl compounds such as vinyl pyridine and aminoethyl vinyl ether; itaconic acid diamide, crotonic acid amide, maleic acid diamide, fumaric acid diamide, N-vinyl Amide group-containing vinyl compounds such as pyrrolidone; 2-hydroxyethyl vinyl ether, methyl vinyl ether, cyclohexyl vinyl ether, vinyl chloride, vinylidene chloride, chloroprene, propylene, butadiene, isoprene, fluoroolefin male De, N- vinylimidazole, and other vinyl compounds such as vinyl sulfonic acid.

These may be used alone or in combination of two or more.

The acrylic copolymer (A) may contain a group such as a carboxyl group or an amino group. In this case, the curability and adhesion are improved, but the group is bonded to the polymer chain. In the case of a carboxyl group or an amino group, the activity is weak, and a cured product having good properties cannot be obtained even if these are used instead of a curing catalyst to cure.

The acrylic copolymer (A) can be obtained, for example, from JP-A-54-36395 and JP-A-57-559.
It can be produced by the hydrosilylation method described in JP-A No. 54 or the like or a solution polymerization method using a monomer containing a reactive silyl group, but it contains a reactive silyl group from the viewpoint of ease of synthesis and the like. It is particularly preferable to use a monomer and a solution polymerization method using an azo radical polymerization initiator such as azobisisobutyronitrile.

The solvent used in the solution polymerization method is not particularly limited as long as it is a non-reactive solvent. For example, hydrocarbons such as toluene, xylene, n-hexane and cyclohexane; ethyl acetate, butyl acetate. Acetate esters such as; cellosolves such as ethyl cellosolve and butyl cellosolve; ether esters such as cellosolve acetate; methyl ethyl ketone, ethyl acetoacetate,
Examples include ketones such as acetylacetone, methyl isobutyl ketone, and acetone.

In the solution polymerization, if necessary, for example, n-dodecyl mercaptan, t-dodecyl mercaptan, n-butyl mercaptan, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, (CH ₃ O) ₃ Si—S—S—Si (O
_{CH 3) 3, (CH 3} O) 3 Si-S 8 -Si (OCH
₃ ) The molecular weight of the resulting acrylic copolymer (A) may be adjusted by using a chain transfer agent such as ₃ alone or in combination of two or more kinds. In particular, when a chain transfer agent having an alkoxysilyl group in the molecule such as γ-mercaptopropyltrimethoxysilane is used, a reactive silyl group should be introduced at the end of the acrylic copolymer (A). It is possible to do so, which is preferable. The amount of the chain transfer agent used is preferably 0.05 to 10%, and more preferably 0.1 to 8% of the total amount of the polymerization components used.

In the present invention, the acrylic copolymer (A) described above is used to improve the stain resistance of the coating film formed from the composition of the present invention, and to improve the adhesion between the coating film and the article to be coated. The general formula (I
I):

[0067]

[Chemical 16]

(In the formula, R ³ is a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group and an aralkyl group, and R ⁴ is an alkyl group having 1 to 10 carbon atoms, an aryl group and A silicon compound represented by a monovalent hydrocarbon group selected from aralkyl groups, b represents 0 or 1, and / or a partial hydrolysis-condensation product (B) thereof (hereinafter also referred to as a silicon compound or the like (B)) ) Is used.
A mixture of a silicone compound or the like (B) with an acrylic copolymer (A) gives a composition having a room temperature curability, and a coating film formed using the composition has excellent stain resistance. However, the reason why the coating film has excellent stain resistance is not yet clear. Presumably, the difference in relative curing rate between the acrylic copolymer (A) and the silicon compound etc. (B) and the compatibility are attributed to the improvement in surface hardness and hydrophilicity.

In the above general formula (II), R ³ has 1 to 10 carbon atoms, preferably, for example, methyl group, ethyl group, n
-C1-C4 alkyl group such as propyl group, i-propyl group, n-butyl group, i-butyl group, aryl group,
Preferably, it is a monovalent hydrocarbon group selected from an aryl group having 6 to 9 carbon atoms such as a phenyl group and an aralkyl group, and preferably an aralkyl group having 7 to 9 carbon atoms such as a benzyl group. The alkyl group has 1 carbon atom
When it exceeds 0, the reactivity of the silicon compound or the like (B) is lowered. Further, when R ³ is a group other than the above alkyl group, aryl group and aralkyl group, the reactivity is lowered.

In the general formula (II), R ⁴ has 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms similar to R ^3.
Alkyl group, aryl group, preferably an aryl group having 6 to 9 carbon atoms similar to R ³ and an aralkyl group, preferably a monovalent hydrocarbon selected from aralkyl group having 7 to 9 carbon atoms similar to R ^3. It is a base.

In the general formula (II), (R ³ O)
_4-b is such that 4-b is 3 or more, that is, b is 0
Although it is selected to be 1, b is preferably 0 from the viewpoint that the curability of the coating film formed from the composition of the present invention is improved.

(R ³ O) _4-b existing in the general formula (II)
When the number of is 2 or more, R ³ contained in 2 or more may be the same or different.

Specific examples of the silicon compound include, for example, tetramethyl silicate, tetraethyl silicate, tetra n-propyl silicate, tetra i-propyl silicate, tetra n-butyl silicate and tetra i.
-Tetraalkyl silicates such as butyl silicate;
Methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, octadecyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, methyltrise
Examples thereof include trialkoxysilanes such as c-octyloxysilane, methyltriphenoxysilane, methyltriisopropoxysilane, and methyltributoxysilane.

Specific examples of the partially hydrolyzed condensate of the silicon compound include those obtained by condensing water by adding water to the tetraalkyl silicate or trialkoxysilane by a conventional method. MSI51, ESI28, ESI40, HAS-1, H
Partial hydrolysis-condensation products of tetraalkyl silicates such as AS-10 (all manufactured by Colcoat Co., Ltd.), and partial hydrolysis-condensation products of trialkoxysilanes such as AFP-1 (manufactured by Shin-Etsu Chemical Co., Ltd.). Can be given.

The above silicon compounds (B) may be used alone or in combination of two or more kinds.

Among the above silicon compounds and the like (B),
MSI51 (Tetra) is preferred because it has good compatibility with the acrylic copolymer (A), the curability of the obtained composition of the present invention is good, and the hardness of the coating film formed using the composition is excellent. Partial hydrolysis condensate of methyl silicate) and ESI
40 (partially hydrolyzed condensate of tetraethyl silicate)
It is preferable to use a partially hydrolyzed condensate of tetraalkyl silicate such as

In the composition of the present invention, an organic carboxylic acid or a combination of an organic carboxylic acid and an organic amine, which is a component that aids the curing of the acrylic copolymer (A) and the silicon compound (B), is used. And at least one curing catalyst (C) selected from organometallic compounds.

The organic carboxylic acids are saturated or unsaturated (monovalent or polyvalent) carboxylic acids and / or
An acid anhydride of a saturated or unsaturated (monovalent or polyvalent) carboxylic acid.

Specific examples of the saturated or unsaturated (monovalent or polyvalent) carboxylic acid include butanoic acid,
Examples include pentanoic acid, hexanoic acid, 2-ethylhexanoic acid, maleic acid, adipic acid, azelaic acid, sebacic acid, itaconic acid, citric acid, succinic acid, phthalic acid, trimellitic acid, pyromellitic acid and benzoic acid. . Further, specific examples of the acid anhydride of the saturated or unsaturated (monovalent or polyvalent) carboxylic acid include, for example, the organic carboxylic acids listed as the specific examples of the saturated or unsaturated (monovalent or polyvalent) carboxylic acid. Acid anhydride of.

The combination of organic carboxylic acids and organic amines is a saturated or unsaturated (monovalent or polyvalent) carboxylic acid and / or a saturated or unsaturated (monovalent or polyvalent) carboxylic acid. Is a mixture or reaction product of an acid anhydride and an organic amine, and specific examples thereof include the above-mentioned butanoic acid, pentanoic acid, hexanoic acid, 2-ethylhexanoic acid, maleic acid, adipic acid, Azelaic acid, sebacic acid, itaconic acid, citric acid, succinic acid, phthalic acid, trimellitic acid, pyromellitic acid, benzoic acid, mixtures or reaction products of organic carboxylic acids and organic amines such as acid anhydrides can give.

Specific examples of the organic amines include primary amines such as hexylamine, myristylamine and dodecylamine, and secondary amines such as N, N-dimethylamine, distearylamine and di (2-ethylhexyl) amine. Tertiary amines such as amine, dimethyloctylamine, dimethyldecylamine, dimethylmyristylamine, dimethylpalmitylamine, dimethylstearylamine, dimethyldodecylamine, triethylamine, trioctylamine, hexamethylenediamine, tetramethylhexamethylenediamine, tetramethyl Polyamines such as propylenediamine and triethyldiamine, piperazine, N-methylmorpholine, N-ethylmorpholine,
Organic amines such as N, N ′, N ″ -tris (3-dimethylaminopropyl) hexahydro S-triazine, trimethylaminoethylpiperazine, N-trioxyethylene, triethylenediamine and cyclic amines, and aminoethylaminopropyltriazine Aminosilane compounds such as methoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyldimethoxysilane, γ-aminopropyltriethoxysilane and γ-aminopropyldiethoxysilane, and further epoxy compounds such as γ-
Glycidoxypropyltrimethoxysilane, Epicoat 828, Epicoat 10 manufactured by Yuka Shell Epoxy Co., Ltd.
Examples thereof include a reaction product of 01 and the like with an aminosilane compound.

Specific examples of the combination of the organic carboxylic acids and the organic amines include, for example, propionic acid / laurylamine, butyric acid / monomethyllaurylamine, hexanoic acid / triethylamine, octylic acid / dimethyllaurylamine, 2-ethylhexane. Acid / triethylamine,
A combination of a saturated or unsaturated monovalent carboxylic acid such as hexenoic acid / dimethylstearylamine and a primary amine to a tertiary amine; for example, propionic acid / hexamethylenediamine, butyric acid / N, N, N ′, N′-tetra A combination of a saturated or unsaturated monovalent carboxylic acid such as methylpropylenediamine and hexenoic acid / N, N, N ', N'-tetramethylhexamethylenediamine and a polyvalent amine; for example, 2-
Ethylhexanoic acid / pyridine, hexanoic acid / pyridine,
Saturated or unsaturated monovalent such as 2-ethylhexanoic acid / piperazine, hexanoic acid / piperazine, propionic acid / N-methylmorpholine, octylic acid / triethylenediamine, lauric acid / trimethylaminoethylpiperazine, hexenoic acid / N-ethylmorpholine Combination of carboxylic acid and cyclic amine; for example, propionic acid / 3-aminopropyltriethoxysilane, butyric acid / 3- (2-aminoethyl) aminopropyltrimethoxysilane, hexanoic acid / 3-ureidopropyltriethoxysilane ( NH
₂ CONHC ₃ H ₆ Si (OC ₂ H ₅ ) ₃ ), 2-ethylhexanoic acid / γ-aminopropyltriethoxysilane, hexenoic acid / 3- (2-aminoethyl) aminopropyltrimethoxysilane, etc. A combination of a saturated monovalent carboxylic acid and an aminosilane compound; a 2: 1 condensate of 2-ethylhexanoic acid / 3-aminopropyltriethoxysilane and a diglycidyl ether of bisphenol A, hexenoic acid / 3- (2- Aminoethyl) aminopropyltrimethoxysilane and 3-glycidoxypropyltrimethoxysilane, such as a 1: 2.2 condensation product of a saturated or unsaturated monovalent carboxylic acid and a reaction product such as an aminosilane compound and an epoxy compound. Combination products; for example, maleic acid / laurylamine, maleic acid / monomethyllaurylamine, male In-acid / dimethyllaurylamine, fumaric acid / laurylamine, fumaric acid / monomethyllaurylamine, fumaric acid / dimethyllaurylamine,
Succinic acid / laurylamine, succinic acid / monomethyllaurylamine, succinic acid / dimethyllaurylamine, phthalic acid / laurylamine, phthalic acid / monomethyllaurylamine, phthalic acid / dimethyllaurylamine, trimellitic acid / laurylamine, etc. Combination of unsaturated polycarboxylic acid and primary amine to tertiary amine; for example, maleic acid / hexamethylenediamine, fumaric acid / hexamethylenediamine, phthalic acid / hexamethylenediamine, trimellitic acid / hexamethylenediamine, itacone Acid / propylenediamine, succinic acid / hydrazine / saturated polyunsaturated carboxylic acid and polyvalent amine in combination; eg maleic acid / piperazine, fumaric acid /
A combination of a saturated or unsaturated polyvalent carboxylic acid such as N-methylmorpholine, phthalic acid / triethylenediamine, trimellitic acid / trimethylaminoethylpiperazine, succinic acid / N-ethylmorpholine and a cyclic amine; for example, maleic acid / 3-aminopropyltriethoxysilane, maleic acid / 3- (2-aminoethyl) aminopropyltrimethoxysilane, phthalic acid / 3-ureidopropyltrimethoxysilane, trimellitic acid / γ-aminopropyltriethoxysilane, succinic acid / 3- (2-
Aminoethyl) aminopropyltrimethoxysilane, such as a combination of a saturated or unsaturated polycarboxylic acid and an aminosilane compound; for example, a 2: 1 ratio of maleic acid / γ-aminopropyltriethoxysilane and a diglycidyl ether of bisphenol A. Condensate, 2: 1 condensate of phthalic acid / γ-aminopropyltriethoxysilane and diglycidyl ether of bisphenol A, trimellitic acid / 3- (2-aminoethyl) aminopropyltrimethoxysilane and 3-glycine Examples thereof include a combination of a saturated or unsaturated polyvalent carboxylic acid such as a condensate of 1: 2.2 with cidoxypropyltrimethoxysilane and a reactant such as an aminosilane compound and an epoxy compound.

An aminosilane compound may be further mixed in the combination product (mixture or reaction product) of the organic carboxylic acids and the organic amines.

Among the above-mentioned combinations of organic carboxylic acids and organic amines, combinations of saturated or unsaturated monovalent carboxylic acids and tertiary amines are preferable from the viewpoint of the balance between curability and pot life. In addition, a combination of a monovalent or polyvalent organic carboxylic acid and a reaction product of an aminosilane compound and / or an aminosilane compound and an epoxy compound is preferable from the viewpoint of curability and adhesion. The tertiary amine in the combination product of the saturated or unsaturated monovalent carboxylic acid and the tertiary amine is not curable even when it is a reaction product of an aminosilane compound and / or an aminosilane compound and an epoxy compound. It is preferable in terms of excellent adhesion.

In the combination of the organic carboxylic acids and the organic amines, 2-ethylhexanoic acid, hexanoic acid, etc. are used as the organic carboxylic acids, and dimethyldodecylamine, dodecylamine, etc. are used as the organic amines. It is preferable because the solubility is good and the water resistance of the formed coating film is good.

The ratio of the organic carboxylic acids (carboxyl group) to the organic amines (amino group) in the combination of the organic carboxylic acids and organic amines (ratio of amino group / carboxyl group) is 0.3 to 3 , About 0.5 ~
It is preferably 2.5. When the ratio is out of the above range, the curing rate of the acrylic copolymer (A) and the silicon compound (B) tends to be low, and the pot life tends to be short. This tendency occurs in the whole combination of organic carboxylic acids and organic amines, and is saturated or unsaturated.
In the case of a combination of a carboxylic acid and a tertiary amine, an organic carboxylic acid and an aminosilane compound and / or
In the case of a combination with an aminosilane compound-containing reaction product, furthermore, the tertiary amine in the combination of a saturated or unsaturated monovalent carboxylic acid and a tertiary amine is an aminosilane compound and / or aminosilane. It also occurs when it contains a reactant of a compound.

The organic carboxylic acid and the organic amine in the combination of the organic carboxylic acid and the organic amine are
It is preferable to add them to the acrylic copolymer (A) and the silicon compound (B) after premixing. Even when the acrylic copolymer (A) contains a carboxyl group or an amino group, if the organic carboxylic acids and the organic amines are used after being mixed in advance, the groups in the acrylic copolymer (A) Less susceptible to impact.

The organometallic compound is an organometallic compound used as a general silanol condensation catalyst, and specific examples thereof include organotin compounds, organotitanium compounds, organozirconium compounds, organoaluminum compounds and the like. Can be given.

Specific examples of the organic tin compound include dibutyltin dilaurate, dibutyltin dimaleate, dioctyltin dilaurate, dioctyltin dimaleate, tin octylate, and the like. Specific examples of the organic titanium compound include isopropyltriisostearoyl titanate. , Isopropyl tris (dioctyl pyrophosphate) titanate, bis (dioctyl pyrophosphate) oxyacetate titanate (organic titanate compound), and specific examples of the organic zirconium compound include tetrabutyl zirconate,
Specific examples of the organoaluminum compound such as tetrakis (acetylacetonato) zirconium, tetraisobutylzirconate, butoxytris (acetylacetonato) zirconium include tris (ethylacetoacetate) aluminum, tris (acetylacetonato) aluminum and the like. can give.

Of the above-mentioned organometallic compounds, dibutyltin alkyl ester is preferable because it has good curability, a good balance between pot life and curability, and a small contact angle of the coating film.

Specific examples of the dibutyltin alkyl ester include, for example, dibutyltin bisethylmalate, dibutyltin bisbutylmalate, dibutyltin bisoctylmalate, dibutyltin bisoleyl maleate, dibutyltin dilaurate, dibutyltin fatty acid salt, dibutyltin bisacetylacetate, Examples thereof include dibutyltin diacetate, dibutyltin dioctoate, dibutyltin oxide, dibutyltin bistriethoxysilicate, and reaction products of these.

The curing catalyst (C) may be used alone,
Also, 2 of different type or same type
You may use together 1 or more types.

The composition of the present invention further comprises a silane coupling agent and / or an adhesion improving component (D) which is a reaction product thereof in order to improve the adhesion between the coating film and the organic substance of the substrate. Is contained. For example, acrylic copolymer (A), silicon compound etc. (B) and curing catalyst (C)
When the composition consisting of the above is applied on an epoxy coating film which is generally used as an intermediate coating for construction, there are cases where the adhesion with the epoxy coating film becomes a problem. In this case, the adhesion can be secured by adding a silane coupling agent which is the adhesion improving component (D).

The silane coupling agent as the adhesion improving component (D) has an alkoxysilyl group such as a methoxysilyl group and an ethoxysilyl group as an inorganic functional group, and a halogen group, a vinyl group, as an organic functional group, Those having both a methacryloxy group, a cyclic epoxy group, a glycidoxy group, a mercapto group, an amino group, a diamino group and a ureido group are preferably used. In particular, when a material having an alkoxysilyl group and an amino group or a glycidoxy group is used, the adhesion is excellent.

Specific examples of the silane coupling agent as the adhesion improving component (D) include, for example, aminoethylaminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyldimethoxysilane, γ-amino. Propyltriethoxysilane, γ-
Aminosilane compounds such as aminopropyldiethoxysilane, γ-glycidoxypropylmethoxysilane, β
Examples thereof include epoxysilane compounds such as epoxycyclohexylethyltriethoxysilane, and reaction products of the aminosilane compounds and epoxy compounds.

Specific examples of the epoxy compound reacted with the aminosilane compound include the epoxysilanes, bisphenol A type epoxy resin, and bisphenol F type epoxy resin. These may be used alone or in combination of two or more.

The adhesion improving component (D) may be used alone or in combination of two or more kinds.

The mixing ratio of the acrylic copolymer (A), the silicon compound (B), the curing catalyst (C) and the adhesion improving component (D) is 100% for the acrylic copolymer (A).
2 to 70 parts of the silicon compound (B), 0.1 to 20 parts of the curing catalyst (C), and the adhesion improving component (D)
Is prepared to be 0.1 to 20 parts.

When the amount of the silicon compound or the like (B) is less than 2 parts, the effect of improving the stain resistance of the coating film formed by using the obtained composition becomes insufficient, and 70 parts by weight is used. If it exceeds, appearance properties such as surface gloss of the coating film are deteriorated and cracks are generated.

Further, when the amount of the curing catalyst (C) is less than 0.1 part, the curability of the obtained composition is lowered, and when it exceeds 20 parts, the composition is cured. The appearance properties such as the surface gloss of the coating film formed by using it will be deteriorated.

Further, the amount of the adhesion improving component (D) was 0.
When the amount is less than 1 part, the adhesiveness of the resulting composition is deteriorated, and when it exceeds 20 parts, the appearance such as surface gloss of the coating film formed using the composition is deteriorated. Come to do.

The preferred minimum amount of the silicon compound etc. (B) is 5 parts, more preferably 10 parts, and the preferred maximum amount is 60 parts.
Parts, and further 50 parts, and for example, 5 to 60 parts is mentioned as one of the preferable ranges.

The preferable minimum amount of the curing catalyst (C) is 0.1 part, further 0.5 part, and the preferable maximum amount is 10 parts, further 5 parts, for example, 0.1 to 10 parts. Is one of the preferred ranges.

Further, the preferable minimum amount of the adhesion improving component (D) is 0.2 part or more, further 0.5 part, and the preferable maximum amount is 10 parts, further 6 parts, for example 0.2 part. -10 parts is mentioned as one of the preferable ranges.

The curable resin composition for top coating composition of the present invention comprises an acrylic copolymer (A), a silicon compound (B), a curing catalyst (C) and an adhesion improving component (D).
Can be obtained by stirring and mixing so as to obtain a uniform composition using, for example, a stirrer.
By further adding a dehydrating agent or alkyl alcohol to the acrylic copolymer (A) and the silicon compound (B), the storage stability of the composition can be improved over a long period of time. .

Specific examples of the dehydrating agent include hydrolyzable ester compounds such as methyl orthoformate, ethyl orthoformate, methyl orthoacetate, ethyl orthoacetate, methyl silicate and ethyl silicate.

Specific examples of the alkyl alcohol include lower alcohols having 1 to 4 carbon atoms such as methanol and ethanol.

The dehydrating agent and the alkyl alcohol may be added to the components before the acrylic copolymer (A) is polymerized, or may be added during the polymerization of the acrylic copolymer (A). It may be added at the time of mixing the obtained acrylic copolymer (A) with other components, and there is no particular limitation.

The blending amount of the dehydrating agent and the alkyl alcohol is not particularly limited, but the total amount of the dehydrating agent and the alkyl alcohol is usually 0.5 with respect to 100 parts of the resin solid content of the acrylic copolymer (A). It is preferably about 20 to 20 parts, especially about 2 to 10 parts.

Further, the curable resin composition for top coating of the present invention includes, for example, titanium oxide, ultramarine blue, dark blue, zinc white, red iron oxide, yellow lead, lead white, carbon black, transparent iron oxide, which are usually used for coatings. , Inorganic pigments such as aluminum powder, azo pigments, triphenylmethane pigments, quinoline pigments, anthraquinone pigments, phthalocyanine pigments and other organic pigments; diluents, ultraviolet absorbers,
Additives such as light stabilizers, anti-sagging agents, and leveling agents; fibrin such as nitrocellulose and cellulose acetate butyrate; epoxy resins, melamine resins, vinyl chloride resins, fluororesins, chlorinated polypropylene, chlorinated rubber, polyvinyl butyral, A resin such as polysiloxane may be added as appropriate.

The curable resin composition for top-coat paint of the present invention is applied to an object to be coated by a usual method such as dipping, spraying, coating using a brush, etc., and is usually kept at room temperature or at about 30 ° C. Above, it is baked and hardened.

The curable resin composition for a top coating composition of the present invention includes, for example, metal, ceramics, glass, cement,
It is suitably used as a top coat paint for ceramic moldings, constructions made of plastic, wood, paper, fibers, etc., home appliances, industrial equipment, etc.

Next, the curable resin composition for top coating composition of the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

Production Example 1 (Production of Acrylic Copolymer (A)) 40 parts of xylene was charged into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen gas introducing tube and a dropping funnel, and nitrogen was added. The temperature was raised to 110 ° C. while introducing gas. After that, 10 parts of γ-methacryloxypropyltrimethoxysilane, 30 parts of methyl methacrylate, 45 parts of n-butyl methacrylate, 14 parts of n-butyl acrylate, 1 part of acrylamide, 18 parts of xylene and 2,2′-azobisisobutyrate. A mixture consisting of 1 part of ronitrile was added dropwise at a constant rate through a dropping funnel over 5 hours.

After the completion of the dropping, 0.5 part of 2,2'-azobisisobutyronitrile and 8 parts of toluene were added dropwise at a constant rate over 1 hour, followed by aging at 110 ° C for 2 hours and then cooling. Xylene was added to the solution to give a resin solids concentration of 50.
% Acrylic copolymer (A) -1 was obtained.

The number average molecular weight of the obtained acrylic copolymer (A) -1 was 15,000.

Production Example 2 (Production of Acrylic Copolymer (A)) In Production Example 1, 10 parts of γ-methacryloxypropyltrimethoxysilane was added to 12 parts, 30 parts of methyl methacrylate was added to 55 parts, and n-butyl was added. 14 parts of acrylate 3
The resin solid content concentration was 50% in the same manner as in Production Example 1 except that the amount was changed to 2 parts and n-butyl methacrylate was not used.
Acrylic copolymer (A) -2 was obtained.

The number average molecular weight of the obtained acrylic copolymer (A) -2 was 15,000.

Production Example 3 (Production of Acrylic Copolymer (A)) In Production Example 1, 10 parts of γ-methacryloxypropyltrimethoxysilane was added to 50 parts, 30 parts of methyl methacrylate was added to 15 parts, and n-butyl was added. 1 part with 14 parts acrylate
5 parts, 45 parts of n-butyl methacrylate to 20 parts,
1 part of azobisisobutyronitrile was changed to 4 parts, and in the same manner as in Production Example 1, an acrylic copolymer (A) -3 having a resin solid content concentration of 50% was obtained.

The number average molecular weight of the obtained acrylic copolymer (A) -3 was 7,000.

Production Example 4 (Production of Adhesion-improving Component (D)) Epoxy resin (bisphenol A type Epicoat 828 (oilification) was added to a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas introduction tube. 56 parts of Shell Epoxy Co., Ltd.) and 100 parts of xylene were charged and stirred while introducing nitrogen gas. Further, 64 parts of γ-aminopropylethoxysilane was added and mixed at room temperature for 1 hour (2 moles of aminosilane to 1 mole of epoxy resin). after that,
The temperature was raised to 70 ° C., and the reaction was carried out at 70 ° C. for 2 hours. After cooling, it was confirmed by IR analysis that absorption by the epoxy group had disappeared, and a reaction product (adhesion improving component (D) -1) containing 50% of the active ingredient was obtained.

Example 1 100 parts of the resin solid content of the acrylic copolymer (A) -1 obtained in Production Example 1 was used as a silicon compound (B) such as MSI51 (tetramethyl silicate manufactured by Colcoat Co., Ltd.). 40 parts of titanium oxide (CR-90, manufactured by Ishihara Sangyo Co., Ltd.) as a pigment was added to a mixed solution containing 30 parts of the partial hydrolysis condensate), and the mixture was dispersed for 2 hours with a paint conditioner using glass beads. A white enamel having a solid content concentration of 60% was obtained.

2-Ethylhexanoic acid (hereinafter referred to as (C) -1) as a curing catalyst (C) was added to the obtained white enamel.
And dodecylamine (hereinafter referred to as (C) -2) are mixed in advance so that each is 0.25 parts with respect to 100 parts of the resin solid content, and the adhesion improving component obtained in Production Example 4. (D) -1 was added to 2 parts with respect to 100 parts of the resin solid content. Further, add thinner and stir for 5 minutes using a stirrer to obtain a solid concentration of 45%.
The composition of

The obtained composition was applied to an aluminum plate (A50
52P) was coated with air spray so that the dry film thickness was about 30 μm, and cured (cured) at 23 ° C. for 7 days.

The surface condition, gloss, stain resistance, weather resistance and contact angle of the obtained coating film were evaluated according to the following methods. Further, the adhesion was evaluated by the following method. The results are shown in Table 1.
Shown in.

(A) Surface condition The coating film surface was visually observed and evaluated according to the following evaluation criteria.

(Evaluation Criteria) A: No cracks were observed and the surface condition was good.

B: Partial or minute cracks are recognized.

C: Cracks are observed on the whole.

(B) Gloss The gloss of the surface of the coating film is measured according to JIS K 5400 on a CD.
It was measured using an X-101 color difference gloss meter (Murakami Color Research Laboratory Co., Ltd.) (60 ° gloss).

(C) Contamination resistance (ΔL value) The color of the coating film surface immediately after formation and the coating film surface after being left outdoors (outdoor exposure) in Settsu City, Osaka Prefecture for 3 months (CDX-10).
The color difference was measured using a 1-color difference gloss meter, and the difference (ΔL value) was determined from the obtained L value (brightness).

(D) Weather resistance (gloss retention) Using a sunshine weatherometer, the gloss on the coating surface immediately after formation and the gloss on the coating surface after 2000 hours were measured, and the gloss retention after 2000 hours was measured. (%) Was calculated.

(E) Contact angle The static contact angle of the coating film surface immediately after molding with water was measured by a contact angle measuring device (CA-S150 type manufactured by Kyowa Interface Science Co., Ltd.).

(F) Adhesiveness A commercially available epoxy intermediate coating (NY Porin K intermediate coating manufactured by Shinto Paint Co., Ltd.) was applied to the steel sheet, and the top coating was applied the next day. Adhesion after one-day curing at room temperature (23 ° C., 55% humidity) was evaluated by measuring cross-cut adhesion according to JIS K5400.

(Evaluation criteria) 10: 100/100 8: 80/100 6: 60/100 4: 40/100 2: 20/100 0: 0/100 Examples 2-8 and Comparative Examples 1-4 A white enamel having a solid content of 60% was prepared in the same manner as in Example 1 except that the composition was changed as shown in Table 1, and a composition having a solid content of 45% was obtained from the white enamel.

The obtained composition was applied to an aluminum plate (A5
The coated film was formed by applying an air spray so that the dry coating film had a thickness of about 30 μm and was cured under the curing conditions shown in Table 1.

The characteristics of the obtained coating film were examined in the same manner as in Example 1. The results are shown in Table 1.

In Table 1, (C) -3 is hexanoic acid,
(C) -4 is γ-aminopropyltrimethoxysilane,
(C) -5 is maleic anhydride, (C) -6 is dibutyltin bisbutyl maleate, (D) -2 is γ-aminopropyltrimethoxysilane, and (D) -3 is γ-glycidoxypropyltrimethoxy. Silane, OcSnM is dioctyl tin malate, and L7607 is a surfactant manufactured by Nippon Unicar Co., Ltd.

[0139]

[Table 1]

From the results shown in Table 1, the compositions obtained in Examples 1 to 8 are those that cure at room temperature, and the coating films formed using the compositions have no cracks and have a glossy appearance. In addition to having a good surface condition and excellent weather resistance, it also has excellent stain resistance and adhesion and a small contact angle.

[0141]

When the composition of the present invention is used, it can be cured at room temperature, and the coating film formed from the composition has good surface condition, gloss, stain resistance, weather resistance and adhesion. , The contact angle also becomes smaller.

Claims (9)

[Claims] 1. A compound represented by the general formula (I): (In the formula, R ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ² is a hydrogen atom or a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group and an aralkyl group, a represents an integer of 0 to 2), based on 100 parts by weight of the acrylic copolymer (A) containing a reactive silyl group bonded to a carbon atom represented by the general formula (II): (In the formula, R ³ is a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group and an aralkyl group,
R ⁴ is a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group and an aralkyl group, b is 0 or 1) and a silicon compound represented by (or) partial hydrolysis condensation thereof. (B) 2 to 70 parts by weight and at least one curing catalyst (C) 0.1 to 20 parts by weight selected from organic carboxylic acids, a combination of organic carboxylic acids and organic amines, and an organometallic compound. And 0.1 to 20 parts by weight of the adhesion improving component (D), which is a curable resin composition for top coating composition. 2. The acrylic copolymer (A) contains 3 to 90% by weight of a monomer unit containing a reactive silyl group bonded to a carbon atom represented by the general formula (I) in the molecule. The composition according to claim 1, which is a copolymer. 3. The composition according to claim 1, wherein the acrylic copolymer (A) is a copolymer containing an n-butyl methacrylate unit as a polymerization component. 4. The composition according to claim 1, wherein the combination product of the organic carboxylic acid and the organic amine is composed of a saturated or unsaturated monovalent carboxylic acid and a tertiary amine. 5. The composition according to claim 1, wherein the organic amine in the combination of the organic carboxylic acid and the organic amine contains an aminosilane compound and / or a reaction product of an aminosilane compound. 6. The combination of the organic carboxylic acid and the organic amine has a ratio of the carboxyl group of the organic carboxylic acid to the amino group of the organic amine (ratio of amino group / carboxyl group) of 0.2 to 3. 6. The method according to claim 1, 4 or 5
The composition as described. 7. The composition of claim 1, wherein the organometallic compound is a dibutyltin alkyl ester. 8. The composition according to claim 1, wherein the adhesion improving component (D) is a silane coupling agent and / or a reaction product thereof. 9. The composition according to claim 8, wherein the silane coupling agent and / or its reaction product is a silane coupling agent having an amino group or a glycidoxy group and / or its reaction product.