JPH10323619A - Cured body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating method by which it is possible to simply apply a coating to a substrate such as metal, an inorganic ceramic base, a resin molding, plastic film, wood, paper or glass and also, to an existing coat deteriorated qualitatively to be replaced with a new one, and make the coating fast durably for a long time. SOLUTION: This cured material is obtained by applying to a substrate a composition containing a hydrolyzed product of organosilane expressed by formula R<1> n Si(OR<2> )4-n (in the formula, R<1> is a 1-8C organic group; R<2> is a 1-5C alkyl group or a 1-4C acyl group; and n is 0-3) and/or the partial condensation product of the hydrolyzed product and a vinyl resin solution containing a silyl group with a silyl group having a silicon atom bonded with a hydrolyzable group and/or a hydroxylic group on the terminal or the side chain, and drying the composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention provides a coating film which is excellent in weather resistance, stain resistance and chemical resistance and which is excellent in versatility such as curability, drying property and workability. Metals such as stainless steel; inorganic ceramic base materials including cement, concrete, ALC, flexible board, mortar, slates, gypsum, ceramics, bricks, etc .; phenol,
Epoxy, polyester, polyethylene, polypropylene, polycarbonate, ABS and other resin molded products; polyethylene, polycarbonate, polyethylene terephthalate, polypropylene, polyimide, polyurethane,
The present invention relates to a coating method for coating a plastic film such as polyvinyl alcohol; a substrate such as wood, paper, glass, etc., and a deteriorated coating film for repainting.

[0002]

2. Description of the Related Art In recent years, there has been a demand for a coating composition having excellent weather resistance, stain resistance, and chemical resistance and capable of forming a coating film having high hardness. Is required. Heretofore, compositions comprising a silyl group-containing vinyl resin and an organosilane compound have been disclosed in JP-A-01-69673 and JP-A-01-696.
There are 74, but all of them have limited substrates, and there are JP-A-04-108172 and JP-A-04-117473, but the target substrates are all wide, but the coating specifications are not specifically described. There is no example that has been generalized.

[0003]

SUMMARY OF THE INVENTION The present invention has been made on the background of the above-mentioned conventional technical problems, and comprises an organosilane and a hydrolyzable silyl group-containing vinyl-based resin as essential components. In addition to base materials such as inorganic ceramics base materials, resin molded products, plastic films, wood, paper, and glass, coatings that can be easily applied to deteriorated coatings for repainting and have long-term durability adhesion The aim is to provide a method.

[0004]

The present invention SUMMARY OF THE INVENTION may, (a) the general formula R ¹ _n Si (OR ²⁾ in _4-n (wherein, R ¹ is 1 to 8 carbon atoms
R ² represents an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms, and n represents 0 to 3), and a hydrolyzate of an organosilane represented by the formula: A composition comprising a condensate, and (b) a silyl group-containing vinyl resin solution having a silyl group having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group at a terminal or a side chain thereof is used as a base material. It is to provide a cured product which is applied and dried.

[0005]

Next, the composition of the present invention will be described in detail for each constituent element. Component (a) component (a) is a general formula _{^{R 1 n Si (OR 2)}} 4-n represent organosilane hydrolysis is, the hydrolyzate obtained by condensation and / or partial condensate, In the composition used in the present invention, it functions as a binder. R ¹ in the organosilane has 1 to 1 carbon atoms.
8 organic groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, n-hexyl, n-heptyl, etc. Alkyl group, other γ-chloropropyl group,
Vinyl group, 3,3,3-trifluoropropyl group, γ-glycidoxypropyl group, γ-methacryloxypropyl group, γ-mercaptopropyl group, phenyl group, 3,4-
An epoxycyclohexylethyl group; R ² in the organosilane is an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a n-propyl group, an i-propyl group,
-Butyl group, sec-butyl group, tert-butyl group,
Examples include an acetyl group, a propionyl group, and a butyryl group.

Specific examples of these organosilanes include tetraethoxysilane, tetramethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetraacetyloxysilane and tetraphenoxysilane. (N = 0); methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i -Propyltriethoxysilane, n-butyltrimethoxysilane, i-butyltrimethoxysilane, i
-Butyltriethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-pentyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, N- (2-
Aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, vinyltrimethoxysilane, Vinyltriethoxysilane, vinyltriacetoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane,
3,3,3-trifluoropropyltrimethoxysilane,
3,3,3-trifluoropropyltriethoxysilane,
3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2
-Hydroxypropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ- (meth) acryloxy Propyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3,4-epoxycyclohexylethyl Trimethoxysilane, 3,4-epoxycyclohexylethyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-u Id propyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 1,
3,5-N-tris (trimethoxysilylpropyl) isocyanurate, bis (trimethoxysilylpropyl)
Amine (n = 1); dimethyldimethoxysilane;
Dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-i-propyldimethoxysilane, di-i-propyldiethoxysilane, di- n-butyldimethoxysilane, di-n-butyldiethoxysilane, n-pentylmethyldimethoxysilane, n-pentylmethyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane Silane, di-n
-Pentyldimethoxysilane, di-n-pentyldiethoxysilane, di-n-hexyldimethoxysilane, di-
n-hexyldiethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxysilane, di-n-octyldimethoxysilane, di-n-octyldiethoxysilane, dicyclohexyldimethoxysilane,
Examples include dicyclohexyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane (n = 2); and trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane (n = 3) and the like. Preferred are methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane and dimethyldiethoxysilane.

These organosilanes can be used alone or in combination of two or more. The weight average molecular weight of the component (a) is preferably from 800 to 100,000, more preferably 1,000.
~ 50,000. The commercially available products of component (a) include MKC silicate manufactured by Mitsubishi Chemical Corporation, silicate manufactured by Tama Chemical Co., Ltd., silicon resin and silicon oligomer manufactured by Toray Dow Corning Co., Ltd., and Toshiba Silicone Co., Ltd. ), And a silicone oligomer manufactured by Nippon Yunika Co., Ltd., and these may be used. Such a hydrolyzate and / or a partial condensate thereof may be either a linear one or a three-dimensional one. These can be prepared and used in advance, but in the present invention, when the silane compound of the component (a) and the components (b) to (g) described later are blended, an appropriate amount of water is usually added. By the addition, the component (a) can be hydrolyzed and condensed during the preparation of the composition.

[0008] (b) Silyl group-containing vinyl resin (b) The silyl group-containing vinyl resin has a main chain composed of a vinyl polymer, and has a terminal or side chain bonded to a hydrolyzable group and / or a hydroxyl group. A polymer containing at least one, and preferably two or more, silyl groups having atoms (hereinafter, simply referred to as "silyl group") in one molecule of the polymer;
It is represented by the following general formula. The content of the silyl group in the component (b) is usually 0.001 to 20% by weight in terms of the amount of silicon atom, based on the polymer before the introduction of the silyl group. The component (b) includes a silyl group (hereinafter simply referred to as "silyl group") having a main chain composed of a vinyl polymer and having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group at a terminal or a side chain. At least one in one molecule of the merging,
Preferably, it contains two or more and further has at least one kind of functional group. In the present invention, the silyl group is generally represented by the following general formula. —Si (R ⁶ ) _3-m X _m (wherein X is a halogen atom, an alkoxy group, an acyloxy group, an aminoxy group, a phenoxy group, a thioalkoxy group,
A hydrolyzable group such as an amino group and / or a hydroxyl group;
⁶ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aralkyl group having 1 to 10 carbon atoms, and m is an integer of 1 to 3. )

The component (b) may be produced by reacting (a) a hydrosilane compound with a vinyl resin having a carbon-carbon double bond, and (b) a hydrolysis represented by the following general formula. The polymer may be produced by polymerizing a vinyl compound having a functional group and / or a hydroxyl group with various vinyl compounds, and the production method is not limited. R ⁷ -Si (R ⁶ ) _3-m X _m (where X, R ⁶ and m are the same as above, and R ⁷ is an organic group having a polymerizable double bond.)

Here, as the hydrosilane compound used in the production method shown in the above (a), for example, halogenated silanes such as methyldichlorosilane, trichlorosilane and phenyldichlorosilane; methyldiethoxysilane, methyl Alkoxysilanes such as dimethoxysilane, phenyldimethoxysilane, trimethoxysilane and triethoxysilane; acyloxysilanes such as methyldiacetoxysilane, phenyldiacetoxysilane and triacetoxysilane; methyldiaminoxysilane, triaminoxysilane; Examples include aminosilanes such as dimethylaminoxysilane and triaminosilane. These hydrosilane compounds can be used alone or in combination of two or more.

The unsaturated vinyl polymer used in the method (a) is not particularly limited as long as it is not a polymer having a hydroxyl group. For example, the following (a-1) and (a)
It can be manufactured by the method 2) or a combination thereof. That is, (a-1) a functional group (hereinafter, referred to as “functional group (α)”).
After a (co) polymerization of a vinyl monomer having the above formula, the functional group (i) in the (co) polymer is replaced with a functional group capable of reacting with the functional group (α) (hereinafter referred to as “functional group (β ) ") And an unsaturated compound having a carbon-carbon double bond to produce an unsaturated vinyl polymer having a carbon-carbon double bond in a side chain of the polymer molecular chain. Can be. (A-2) A radical polymerization initiator having a functional group (α) (for example, 4,4-azobis-4-cyanovaleric acid or the like) is used, or a functional group ( a) (for example, 4,4-azobis-4-cyanovaleric acid and dithioglycolic acid), and (co) polymerizing a vinyl monomer to form one end of the polymer molecular chain or After synthesizing a (co) polymer having a functional group (α) derived from a radical polymerization initiator or a chain transfer agent at both ends, a functional group (β) is added to the functional group (α) in the (co) polymer. ) Is reacted with an unsaturated compound having a carbon-carbon double bond to produce an unsaturated vinyl polymer having a carbon-carbon double bond at one or both ends of the polymer molecular chain. it can.

Examples of the reaction between the functional group (α) and the functional group (β) in the methods (a-1) and (a-2) include:
Esterification reaction between carboxyl group and hydroxyl group, ring-opening esterification reaction between carboxylic anhydride group and hydroxyl group, esterification reaction between carboxyl group and epoxy group, amidation reaction between carboxyl group and amino group, carboxylic acid anhydride A ring-opening amidation reaction between a substance group and an amino group, a ring-opening addition reaction between an epoxy group and an amino group, a urethanation reaction between a hydroxyl group and an isocyanate group, a combination of these reactions, and the like.

Examples of the vinyl monomer having a functional group (α) include unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid;
Unsaturated carboxylic anhydrides such as maleic anhydride and itaconic anhydride; 2-hydroxyethyl (meth) acrylate;
Hydroxyl-containing vinyl monomers such as 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, N-methylol (meth) acrylamide, and 2-hydroxyethyl vinyl ether; 2-aminoethyl (meth) acrylate; 2-aminopropyl (meth) acrylate, 3-aminopropyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-diethylaminoethyl (meth) acrylate,
2-dimethylaminopropyl (meth) acrylate, 3
-Dimethylaminopropyl (meth) acrylate, 2-
Amino group-containing vinyl monomers such as aminoethyl vinyl ether, N, N-dimethylamino (meth) acrylamide, N, N-diethylamino (meth) acrylamide;
1,1,1-trimethylamine (meth) acrylimide, 1-methyl-1-ethylamine (meth) acrylimide, 1,1-dimethyl-1- (2-hydroxypropyl) amine (meth) acrylimide, 1,1 -Dimethyl-1- (2'-phenyl-2'-hydroxyethyl) amine (meth) acrylimide, 1,1-dimethyl-1-
Amine-containing vinyl monomers such as (2'-hydroxy-2'-phenoxypropyl) amine (meth) acrylimide and epoxy-containing vinyl monomers such as glycidyl (meth) acrylate and allyl glycidyl ether. Can be mentioned. These vinyl monomers having a functional group (α) can be used alone or in combination of two or more.

Other vinyl monomers to be copolymerized with a vinyl monomer having a functional group (α) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate,
N-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylic acid Cyclohexyl,
(Meth) acrylamide, crotonamide, maleic diamide, fumaric diamide, itaconic diamide, α
-Ethylacrylamide, N-butoxymethyl (meth)
Examples include acrylamide, (meth) acrylonitrile, styrene, α-methylstyrene, vinyl chloride, vinyl acetate, and vinyl propionate. These other vinyl monomers can be used alone or in combination of two or more.

Examples of the unsaturated compound having a functional group (β) and a carbon-carbon double bond include, for example, vinyl monomers similar to vinyl monomers having a functional group (α) and the above-mentioned hydroxyl group. Examples thereof include an isocyanate group-containing unsaturated compound obtained by reacting a vinyl monomer and a diisocyanate compound in equimolar amounts.

On the other hand, examples of the vinyl compound having a hydrolyzable group and / or a hydroxyl group used in the production method shown in (b) include, for example, CH ₂ ＣＨCH (CH ₃ ) Si (OCH
₃ ) ₂ , CH ₂ ＣＨCHSi (OCH ₃ ) ₃ , CH ₂ ＣＨCH (C
H ₃ ) SiCl ₂ , CH ₂ ＣＨCHSiCl ₃ , CH ₂ ＣＨCH
COO (CH ₂ ) ₃ Si (OCH ₃ ) ₂ , CH ₂ ＣＨCHCO
O (CH ₂ ) ₃ Si (CH ₃ ) (OCH ₃ ) ₃ , CH ₂ ＣＨCH
COO (CH ₂ ) ₃ Si (CH ₃ ) Cl ₂ , CH ₂ ＣＨCHC
OO (CH ₂ ) ₃ SiCl ₃ , CH ₂ ＣC (CH ₃ ) COO
(CH ₂ ) ₃ Si (CH ₃ ) (OCH ₃ ) ₂ , CH ₂ ＣC (C
_{H 3) COO (CH2) 3} Si (CH 3) (OCH 3) 2,
CH ₂ ＣC (CH ₃ ) COO (CH ₂ ) ₃ SiCl ₂ , CH ₂
ＣC (CH ₃ ) COO (CH ₂ ) ₃ SiCl ₃ ,

[0013]

Embedded image

And the like. Examples of the vinyl compound used in the production method shown in (b) include a vinyl monomer having a functional group (α) exemplified in the method (a) and other vinyl monomers. Or more. Specific examples of (b) the silyl group-containing vinyl resin as described above include, for example, a trialkoxysilyl group-containing acrylic polymer represented by the following general formula.

[0015]

Embedded image

Wherein R ⁸ is a hydrogen atom or a methyl group;
R ⁹ is an alkyl group having 1 to 6 carbon atoms such as methyl group, ethyl group, n-propyl group, n-butyl group, i-butyl group, n-pentyl group, n-hexyl group, and R ¹⁰ is R ⁸ Similarly, R ¹¹ is a methylene group, an ethylene group, a propylene group,
An alkylene group having 1 to 4 carbon atoms such as a butylene group, R ¹² is the same as R ⁹ , and t / (s + t) = 0.01 to 0.1.
4, preferably 0.02 to 0.2. The number average molecular weight of the silyl group-containing vinyl resin (b) is preferably from 2,000 to 100,000, and more preferably from 4,000 to 50,000. here,
The proportion of the solvent in the component (b) is 50% by weight or more.

Among the solvents, examples of the alcohols include monohydric alcohols and dihydric alcohols, and among them, saturated aliphatic alcohols having 1 to 8 carbon atoms are preferable. Specific examples of these alcohols include methanol, ethanol, n-propanol, i-propanol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, ethylene glycol, diethylene glycol,
Examples thereof include triethylene glycol, ethylene glycol monobutyl ether, and ethylene glycol monoethyl ether acetate. Examples of ethers include tetrahydrofuran and dioxane.Examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, and diisobutyl ketone.Examples of esters include ethyl acetate and propyl acetate. Butyl acetate, propylene carbonate and the like, and specific examples of aromatic hydrocarbons include xylene and toluene. (B) The ratio of the silyl group-containing vinyl resin (solid content) in the composition is determined based on the content of the organosilane 10 as a raw material of the component (a).
4 to 500 parts by weight, preferably 7 to 2 parts by weight with respect to 0 parts by weight
The amount is 50 parts by weight, more preferably 10 to 100 parts by weight. When the amount is less than 4 parts by weight, the alkali resistance of the obtained coating film is low, while when it exceeds 500 parts by weight, the weather resistance of the obtained coating film is deteriorated.

Further, the composition used in the present invention includes:
The following components (c) to (f) can be blended.

(C) Organometallic Compound The component (c) is considered to act to form a co-condensate of the component (a) and the component (b). A preferred compound as the component (c) can be represented by the general formula M (OR ³ ) _p (R ⁴ COCH ₂ COR ⁵ ) _q . R ³ and R in component (c)
⁴ is the same or different alkyl group having 1 to 6 carbon atoms, specifically, an ethyl group, an n-propyl group, an i-propyl group,
n-butyl group, sec-butyl group, t-butyl group, n-
Examples include a pentyl group and a phenyl group. R ⁵ is an alkyl group having 1 to 6 carbon atoms as described above,
And 16 alkoxy groups, for example, methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, sec-butoxy, t-butoxy, lauryl, stearyl and the like. Also, p in component (c)
-Q shows the integer of 0-4.

Specific examples of the component (c) include zirconium tetrabutoxyzirconium, zirconium tri-n-butoxyethylacetoacetate, zirconium di-n-butoxybis (ethylacetoacetate), and n-butoxytris (ethylacetoacetate). Zirconium compounds such as zirconium, tetrakis (n-propylacetoacetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium; diisopropoxybis (ethylacetoacetate) titanium, diisopropoxybis ( Acetyl acetate) titanium, diisopropoxy bis (acetyl acetate) titanium, tetra-i-propoxy titanium, tetra-n-butoxy titanium, tetra t- butoxy, tetrakis (2-ethylhexyl oxy) titanium compounds such as titanium; diisopropoxy ethyl acetoacetate aluminum, diisopropoxy acetylacetonate aluminum, diisopropoxy bis (ethylacetoacetate)
Aluminum compounds such as aluminum, isopropoxybis (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonate) aluminum, and monoacetylacetonate bis (ethylacetoacetate) aluminum are exemplified. Preferred among these (c) organometallic compounds are zirconium tri-n-butoxyethyl acetoacetate, titanium diisopropoxybis (acetylacetonate), aluminum diisopropoxyethyl acetoacetate, and aluminum tris (ethylacetoacetate). It is. These (c)
The organometallic compounds can be used alone or in combination of two or more. Further, as the component (c),
Partial hydrolysates of these organometallic compounds can also be used.

The proportion of the component (c) in the composition is usually 0.01 to 100 parts by weight, preferably 0.1 to 80 parts by weight, per 100 parts by weight of the organosilane used as the raw material of the component (a).
Parts by weight, more preferably 0.5 to 50 parts by weight,
If the amount is less than 0.01 part by weight, the formation of a co-condensate of the component (a) and the component (c) is insufficient, and the weather resistance of the coating film is deteriorated. It is not preferable because storage stability deteriorates and cracks may occur in the obtained coating film.

Component (d) The component (d) is a β-diketone and / or β-ketoester represented by the general formula R ⁴ COCH ₂ COR ⁵ , a carboxylic acid compound, a dihydroxy compound, an amine compound and an oxyaldehyde compound. At least one member selected from the group consisting of: and acts as a stability improver of the composition of the present invention. That is, (a)
(C) present in a composition comprising the component (b) as a main component;
By coordinating to a metal atom in an organometallic compound (zirconium, titanium and / or aluminum compound), it acts to control the condensation reaction of component (a) and / or component (b) by these metal chelate compounds. It is considered that the composition acts to improve the storage stability of the obtained composition. (D) R constituting the component
⁴ and R ⁵ are the same as R ⁴ and R ⁵ constituting the above (c) organometallic compound. Specific examples of the (d) β-diketones and / or β-ketoesters include acetylacetone, methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, and i-acetoacetate.
Propyl, acetoacetic acid-n-butyl, acetoacetic acid-se
c-butyl, t-butyl acetoacetate, 2,4-hexane-dione, 2,4-heptane-dione, 3,5-heptane-dione, 2,4-octane-dione, 2,4-nonane-dione , 5-methyl-hexane-dione, malonic acid, oxalic acid, phthalic acid, glycolic acid, salicylic acid,
Aminoacetic acid, iminoacetic acid, ethylenediaminetetraacetic acid, glycol, catechol, ethylenediamine, 2,2-bipyridine, 1,10-phenanthroline, diethylenetriamine, 2-ethanolamine, dimethylglyoxime, dithizone, methionine, salicylaldehyde, and the like. it can. Of these, ethyl acetoacetate, acetylacetone and 2-ethanolamine are preferred, and acetylacetone is particularly preferred. These β
-Diketones and / or β-ketoesters
Species can be used alone or in combination of two or more. The amount of the component (d) to be used is 2 mol or more, preferably 3 to 20 mol, per 1 mol of the organometallic compound (c). When the amount is less than 2 mol, the obtained composition has poor storage stability. There are cases.

Component (e) In the composition of the present invention, water (e) is usually added to the organosilane constituting component (a). (E) The amount of water used is usually about 0.5 to 3.0 mol, preferably about 0.7 to 2.0 mol, per 1 mol of the organosilane.

(F) Component The total solid content of the composition of the present invention is preferably 50% by weight or less, and the total solid content is adjusted according to the purpose of use. At that time, if necessary, (f) an organic solvent is added. (F) The organic solvent is not particularly limited as long as it mainly mixes the components (a) to (d) uniformly. Examples thereof include alcohols, aromatic hydrocarbons, ethers, ketones, and esters. An organic solvent which can be added and is preferably one kind or a mixture of two or more kinds. For the purpose of impregnating a thin film forming substrate, the total solid content concentration is usually 5 to 30% by weight.
When used for the purpose of forming a thick film or dispersing a filler (g) described later, the total solid content concentration is usually 20 to 5%.
The content is 0% by weight, preferably 30 to 45% by weight, and if it exceeds 50% by weight, the storage stability of the composition deteriorates, which is not preferable.

In the present invention, a metal oxide sol can be added to the composition, if necessary, for the purpose of improving the hardness of the obtained coating film. Examples of the metal oxide sol include organosilica sol, alumina sol, tin sol, zirconium sol, antimony pentoxide sol, and the like.The cocondensation reaction may be performed in the presence of these metal oxide sols, or the mixture may be mixed after the reaction. May be.

Further, in the present invention, the obtained coating film exhibits various properties such as coloring, thickening, heat-resistant ultraviolet absorbing property, antibacterial property, antifungal property, anti-algal property and antistatic property. Therefore, it is also possible to separately add and disperse (g) a filler in the composition. As the filler (g), for example, non-water-soluble pigments such as organic pigments and inorganic pigments, or particles, fibrous or flaky metals and alloys other than pigments, and oxides, hydroxides and carbides thereof. , Nitrides, sulfides and the like. Specific examples of the filler (g) include particles, fibers, and scales of iron, copper, aluminum, nickel, silver, zinc, ferrite, carbon black, stainless steel, silicon dioxide, titanium oxide, and aluminum oxide. , Chromium oxide, manganese oxide, iron oxide, zirconium oxide, cobalt oxide,
Synthetic mullite, aluminum hydroxide, iron hydroxide, silicon carbide, silicon nitride, boron nitride, clay, diatomaceous earth,
Slaked lime, gypsum, talc, barium carbonate, calcium carbonate, magnesium carbonate, barium sulfate, bentonite,
Mica, zinc green, chrome green, cobalt green, viridian, guinea green, cobalt chrome green, shale green, green earth, manganese green, pigment green, ultramarine, navy blue, pigment green, rock ultramarine, cobalt blue, cerulean blue, boric acid Copper, molybdenum blue, copper sulfide, cobalt purple, mars purple,
Manganese purple, Pigment violet, Lead suboxide, Calcium plumbate, Zinc yellow, Lead sulfide, Chrome yellow, Loess,
Cadmium yellow, strontium yellow, titanium yellow, litharge, pigment yellow, cuprous oxide, cadmium red, selenium red, chrome vermillion, bengala, zinc white, antimony white, basic lead sulfate, titanium white, lithopone, lead silicate, Zircon oxide, tungsten white, lead zinc white, bunchesone white, lead phthalate, manganese white, lead sulfate, graphite, bone black, diamond black, thermatomic black, vegetable black, potassium titanate whisker, molybdenum disulfide, etc. be able to. The proportion of the component (g) in the composition is about 10 to 300 parts by weight based on 100 parts by weight of the total solids of the components (a) to (d). Further, in curing the composition of the present invention faster, a curing accelerator may be used depending on the curing conditions, and in order to cure at a relatively low temperature, it is more effective to use a curing accelerator in combination. is there.

Examples of the curing accelerator include alkali metal salts such as naphthenic acid, octylic acid, nitrous acid, sulfurous acid, aluminate, and carbonic acid; alkaline compounds such as sodium hydroxide and potassium hydroxide; acetic acid, hydrochloric acid, sulfuric acid, and alkyl. Acidic compounds such as titanic acid, phosphoric acid, p-toluenesulfonic acid, and phthalic acid; ethylenediamine, hexanediamine,
Diethylenetriamine, triethylenetetramine, tetraethylenepentamine, piperidine, piperazine, m-
Phenylenediamine, p-phenylenediamine, ethanolamine, triethylamine, various modified amines used as curing agents for epoxy resins, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ- (2-aminoethyl)- Amine compounds such as aminopropyltrimethoxysilane, γ- (2-aminoethyl) -aminopropylmethyldimethoxysilane, γ-anilinopropyltrimethoxysilane, zirconium compounds and titanium compounds described in the component (c), Aluminum compound, (C ₄ H ₉ ) ₂ Sn (OCOC
_{11 H 23) 2, (C} 4 H 9) 2 Sn (OCOCH = CHCO
OCH ₃ ) ₂ , (C ₄ H ₉ ) ₂ Sn (OCOCH ＝ CHC)
OOC ₄ H ₉ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (OCOC
_{11 H 23) 2, (C} 8 H 17) 2 Sn (OCOCH = CHC
OOCH ₃ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (OCOCH = C
HCOOC ₄ H ₉ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (OCOC
H = CHCOOC ₈ H ₁₇ ) ₂ , Sn (OCOCC)
Carboxylic acid type organotin compounds such as ₈ H ₁₇ ) ₂ ; (C
_{4 H 9) 2 Sn (SCH} 2 COOC 8 H 17) 2, (C 4 H 9) 2
Sn (SCH ₂ COOC ₈ H ₁₇ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn
(SCH ₂ COOC ₈ H ₁₇ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (SC
H ₂ CH ₂ COOC ₈ H ₁₇ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (SC
H ₂ COOC ₈ H ₁₇ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (SCH ₂ CO
OC ₁₂ H ₂₅ ) ₂ ,

[0028]

Embedded image Mercaptide-type organotin compounds such as;

[0029]

Embedded image (C ₄ H ₉ ) ₂ Sn
O, (C ₈ H ₁₇ ) ₂ SnO, or (C ₄ H ₉ ) ₂ SnO,
An organic tin compound such as a reaction product of an organic tin oxide such as (C ₈ H ₁₇ ) ₂ SnO and an ester compound such as ethyl silicate, dimethyl maleate, diethyl maleate, and dioctyl phthalate is used. The proportion of these curing accelerators in the composition is usually 0.1 to 15 parts by weight per 100 parts by weight of the solid content of the composition of the present invention.
Parts by weight, preferably 0.5 to 10 parts by weight.

In the present invention, other known dehydrating agents such as methyl orthoformate, methyl orthoacetate and tetraethoxysilane, various surfactants, silane coupling agents, titanium coupling agents, dyes, Dispersants, thickeners, leveling agents, or additives for imparting high functionality (light absorption, anticorrosion, antibacterial, antifungal, conductive, insulating) may also be added to the composition. it can.
Anti-absorbing additives include benzophenone, benzotriazole, triazine, phenol-based organic ultraviolet absorbers, zinc oxide, cerium oxide, titanium oxide, etc. Are inorganic antibacterial agents such as silver / zeolite and silver glass, silver-containing phosphorous calcium, amino acid metal soap, silver / zinc calcium phosphate, silver / ceramics, silver / zirconium phosphate, and 2- (4-thiazolyl) -Benzimidazole, N- (fluorodichloromethylthio), 2,
3,5,6-cytochloro-4- (methylthio) -phthalimide, 10,10-oxybisphenoxyarsine,
Trimethoxysyl-propylio-K tadecyl ammonium chloride, 2-N-octyl-4-isothiazolin-3-one, bis (2-pyridylthio-1-oxide)
There are organic antibacterial agents such as zinc. Examples of the conductive agent (antistatic agent) include tin oxide, antimony oxide / tin oxide, antimony-tin tin, and carbon powder. Further, in the present invention, an organic solvent other than the above (f) organic solvent can be contained, and any organic solvent may be used as long as it does not cause precipitation when the above composition is mixed. There is no particular limitation as long as it is used for general paints, coating agents, etc., for example, alcohols, aromatic hydrocarbons, ethers, ketones,
Esters and the like can be mentioned. These organic solvents are usually used in an amount of 10 parts by weight per 100 parts by weight of the composition of the present invention.
It is used in an amount of about 0 parts by weight or less.

In preparing the composition in the present invention, a composition containing the above-mentioned components (a) to (d) may be prepared. For example, the following preparation methods are preferred. To a solution comprising (a) the organosilane constituting the component, (b) a vinyl resin containing a silyl group, and (c) an organometallic compound, 0.1 to 3 mol of water is added to 1 mol of the organosilane, A method comprising forming a composition comprising components (a) to (c), and then adding (d) β-diketones and / or β-ketoesters. (A) 0.1 to 3 mol of water is added to 1 mol of the organosilane constituting the component to carry out a hydrolysis / condensation reaction, and then (b) a silyl group-containing vinyl resin, and (c) an organometallic compound. In addition, mixing, and further performing a condensation reaction,
After forming a composition comprising the components (a) to (c),
(D) A method of adding a component. To a solution obtained by adding the organosilane constituting the component (a), the organometallic compound (c), and the component (d), water is added in an amount of 0.01 to 3 mol per 1 mol of the organosilane to obtain a solution. A method comprising performing a decomposition / condensation reaction to form a composition comprising the components (a) to (c), and then adding the component (d).

Cured Product The cured product of the present invention comprises a substrate / the above-mentioned coating composition or a substrate / primer / the above-mentioned coating composition. The coating method of the coating composition depends on the purpose of coating, such as brush, roll, dipping, flow coating, spray, roll coater, flow coater,
Centrifugal coater, ultrasonic coater, screen process,
There are electrodeposition coating and vapor deposition coating.

Substrates Substrates vary depending on the application. For example, metals such as iron, aluminum, and stainless steel, cement, concrete, ALC, flexible boards, mortar, slates, gypsum, ceramics, bricks, etc. Inorganic ceramic base material including;
Resin molded products such as metal, epoxy, polyester, polyethylene, polypropylene, polycarbonate and ABS;
Plastic films such as polyethylene, polycarbonate, polyethylene terephthalate, polypropylene, polyimide, polyurethane, polyvinyl alcohol; base materials such as wood, paper, glass, etc., and deteriorated coating films for repainting And so on.

Depending on the base material, a surface treatment, a base adjustment, and a treatment for providing design may be performed. For example, in the case of metal, there are polishing, degreasing, plating, chromating, flame treatment, coupling treatment, etc., and in the case of plastic, blasting, chemical treatment, degreasing, flame treatment, oxidation treatment, steam treatment, corona discharge. Treatment, UV irradiation treatment, plasma treatment, ion treatment, etc., polishing, filling, patterning, etc. for ceramic substrates, polishing, filling, insect repellent treatment for wood, filling, insect repellent treatment, etc. for paper In the case of an old coating film for coating, there may be mentioned, for example, keren. The coating specifications differ depending on the condition of the base material and the coating method. For example, in the case of metal, a primer should be used if rust prevention is required, and in the case of ceramic base materials, the characteristics of the base material (surface Roughness, impregnation, alkalinity, etc.)
In general, a primer is used because the concealability differs depending on the type of the primer. In the case of repainting of a deteriorated coating film, use a primer if the old coating film is significantly deteriorated. In the case of other substrates such as plastic, wood, paper, glass, etc., use a primer according to the application. May or may not be present. When there is no primer, it is desirable that the vinyl resin in the organosilane resin contains at least 0.5% by weight of a carboxyl group, a hydroxy group, a carbonyl group, an acid anhydride or a glycidyl group. More preferably, the surface treatment is performed.

[0035] The primer primer layer is not particularly limited, and the base material and the invented core may be used.
Any substance can be used as long as it has a function of adhering to the coating composition, and is selected according to the base material and the purpose of coating. One or two or more primers may be used. The primer may be a paint containing a coloring component such as a pigment, or may be a clear paint that does not contain a coloring component. Further, a dedicated curing accelerator may be used in combination. The type of the primer is, for example, an alkyd resin, an amino alkyd resin, an epoxy resin, a polyester resin, an acrylic resin, a polyurethane resin, or a fluororesin in the case of metal. In ceramics base materials, alkyd resins, amino alkyd resins, epoxy resins, polyurethane resins, acrylic resins,
For polyester resin, acrylic emulsion, epoxy emulsion, polyurethane emulsion, polyester emulsion, plastic, epoxy resin,
Acrylic urethane resin, acrylic resin, polyester resin, acrylic emulsion, epoxy emulsion, polyurethane emulsion, polyester emulsion,
In the case of wood, nitrocellulose-slurker, alkyd resin, aminoalkyd resin, polyester resin, in the case of paper, epoxy resin, polyurethane resin, acrylic resin, polyester resin, acrylic emulsion, epoxy emulsion, polyurethane emulsion, polyester emulsion, polyvinyl alcohol- In the case of an old coating film such as toluene, carboxymethyl cellulose, an epoxy resin, an acrylic resin, an epoxy emulsion, an acrylic emulsion, or a urethane emulsion can be used. The coating composition developed to any of the above primers can be adhered to, but is preferably an epoxy resin, an acrylic resin,
Polyurethane resin and polyester resin. Depending on the application, adhesion under severe conditions such as water or temperature change is required. In this case, the resin can be modified with a functional group. As a functional group or a bonding species, a hydroxy group,
Carboxyl group, carbonyl group, amide group, amine group,
Examples include a glycidyl group, an alkoxysilyl group, an ether bond, and an ester bond.

As the epoxy resin, bisphenol type epoxy resin, phenol novolak type epoxy resin,
Common resins such as cresol novolak type epoxy resin, cycloaliphatic epoxy resin, glycidyl ester epoxy resin, glycidylamine epoxy resin, heterocyclic epoxy resin, brominated epoxy resin, and epoxy group-containing acrylic resin are used. . The epoxy group-containing acrylic resin can be obtained by radical polymerization of a radical polymerizable compound having an epoxy group alone and / or together with another radical polymerizable compound in a solvent. Examples of the radical polymerizable compound having an epoxy group include glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, acrylic acid-3, 4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,
7-epoxyheptyl, 6,7-epoxyheptyl methacrylate, 6,7-epoxyheptyl α-ethylacrylate, N- [4- (2,3-epoxypropoxy)
-3,5-dimethylbenzyl] acrylamide, N-
[4- (2,3-epoxypropoxy) -3,5-dimethylphenylpropyl] acrylamide and the like can be mentioned.

When the above epoxy resin is used as a primer, a curing agent may be used in combination to accelerate the curing of the epoxy resin. As the curing agent, a general epoxy curing agent is used, and specific examples include benzyldimethylamine, trisdimethylaminomethylphenol,
Amines such as tetramethylguanidine, triethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenediamine and diethylaminopropylamine; imidazole, benzimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, -Heptadecylimidazole, 4-methyl-2-phenylimidazole, 1-
Benzyl-2-methylimidazole, 2-ethyl-4-
Methyl-1- (2′-cyanoethyl) imidazole, 2
Imidazole derivatives such as -ethyl-4-methyl-1- [2 '-(3 ", 5" -diaminotriazinyl) ethyl] imidazole; phthalic anhydride, trimellitic anhydride,
Acid anhydrides such as pyromellitic anhydride, maleic anhydride, and benzophenonetetracarboxylic dianhydride; polyamide resins and polyamines.

The acrylic resin includes an acrylic resin obtained by (co) polymerizing a monomer selected from (meth) acrylic acid, (meth) acrylic acid ester and other vinyl monomers. As the (meth) acrylate, isobornyl (meth) acrylate,
Tricyclodecanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 4
-Butylcyclohexyl (meth) acrylate, acryloyl morpholine, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, Propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate,
Tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxyethylene glycol (meth) ) Acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth)
Acrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate,
1,4-butanediol di (meth) acrylate, 1.6
-Hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropanetrioxyethyl (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, tricyclodecanediyldimethyldi ( (Meth) acrylate, di (meth) acrylate of a diol of an adduct of bisphenol A with ethylene oxide or propylene oxide, and di (meth) acrylate of a diol of an adduct of hydrogenated bisphenol A with ethylene oxide or propylene oxide. Examples of other vinyl monomers include styrene, vinyltoluene, divinylbenzene, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinylpyridine, acrylonitrile, triallyl cyanurate and the like.

Examples of the polyurethane resin include a compound of a polyisocyanate and a polyol. Specific examples of the polyisocyanate include tolylene diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, phenylene diisocyanate, diphenylmethane diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate, and methylene bis (4-cyclohexyl isocyanate). Examples include trimethylhexamethylene diisocyanate, lysine diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, tetramethyl xylylene diisocyanate, and the like.

As the polyol, polyether diol, polyester diol and the like are preferably used, and two or more of these polyols can be used in combination. The bonding mode of the structural units in these polyols is not particularly limited, and may be any of a random bond, a block bond, and a graft bond. Specific examples of the polyether diol include diols obtained by ring-opening (co) polymerizing an ionic polymerizable cyclic compound such as tetrahydrofuran, ethylene oxide, propylene oxide, 2-methyltetrahydrofuran, and butene-1-oxide. . Examples of the polyester diol include a diol obtained by reacting a polyhydric alcohol with a polybasic acid. As the above polyhydric alcohol,
For example, ethylene glycol, polyethylene glycol,
Propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 1,9-nonane Diol,
Examples include 2-methyl-1,8-octanediol, and examples of the polybasic acid include phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipic acid, sebacic acid, and the like. Other polyols include polycarbonate polyol, polycaprolactone polyol, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, and 1,4-cyclohexane. Dimethanol, hydrogenated bisphenol A, hydrogenated bisphenol F, a dimethylol compound of dicyclopentadiene, tricyclodecane dimethanol, pentacyclopentadecane dimethanol,
Examples include β-methyl-δ-valerolactone, hydroxy-terminated polybutadiene, hydroxy-terminated hydrogenated polybutadiene, castor oil-modified polyol, polydimethylsiloxane-terminated diol compound, and polydimethylsiloxane carbitol-modified polyol.

Polyester resins include unsaturated dibasic acids such as maleic anhydride, maleic acid and fumaric acid, and saturated dibasic acids such as phthalic anhydride, phthalic acid, isophthalic acid and adipic acid, and ethylene glycol and diethylene glycol. It is obtained by reacting an unsaturated alkyd obtained by polycondensation with glycols with a crosslinking monomer such as styrene, vinyltoluene, divinylbenzene, and acrylate.

When the above-mentioned primer is used, the above-mentioned component (a) or the organosilane used for producing the component (a) may be added to the resin for the purpose of improving adhesion and long-term durability. In this case, the component (a) or the organosilane may be added at any time before, during or after the synthesis of the resin used as the primer.

[0043]

EXAMPLES The present invention will be described more specifically with reference to the following Examples, but it should not be construed that the invention is limited thereto. In the examples, parts and% are by weight unless otherwise specified.

Reference Example 1 [Preparation of silyl group-containing vinyl resin] In a reactor equipped with a reflux condenser and a stirrer, 90 parts of i-propanol was heated to 80 ° C, and 70 parts of methyl methacrylate was added thereto. 15 parts of ethylhexyl methacrylate,
15 parts of γ-methacryloxypropyltrimethoxysilane was added dropwise and mixed well. To this mixture, a solution prepared by dissolving 4 parts of azobisisovaleronitrile in 10 parts of i-propanol was added dropwise over 30 minutes, and further reacted at 80 ° C. for 5 hours to obtain a vinyl-containing silyl group having a solid concentration of 50%. A resin solution was obtained.

Synthesis Examples 1 to 6 and Comparative Synthesis Examples 1 to 2 A reactor equipped with a stirrer and a reflux condenser was charged with 80 parts of methyltrimethoxysilane, 20 parts of dimethyldimethoxysilane,
(B) 40 parts of silyl group-containing vinyl resin [solid content concentration 50%, (A) of Reference Example 1], (c) 8 parts of ethyl acetoacetate aluminum diisopropylate, (f) i-
After adding and mixing 5 parts of propanol, (e) 20 parts of ion-exchanged water was added, and the mixture was reacted at 60 ° C. for 4 hours. After cooling to room temperature, (d) 30 parts of acetylacetone was added. I got Using the same reactor, compositions B to H shown in Tables 1 and 2 were obtained.

[0046]

[Table 1]

[0047]

[Table 2]

Examples 1 to 4 and Comparative Example 1 The compositions A and B obtained in the above Synthesis Examples and Comparative Synthesis Examples
E, F and H were evaluated for adhesion, durable adhesion and weather resistance. The adhesion was measured by a peel test using a 2 mm grid in accordance with JIS K5400. Durability adhesion was confirmed by conducting a test under an atmosphere of 50 ° C. and 98% for 30 days. Evaluation of adhesion is 100/10 grid
0 to 90/100 was rated as ○, 89/100 to 60/100 as Δ, and less than that as ×. Regarding the weather resistance, the color difference (ΔE) and gloss retention (%) were measured using the above-mentioned durable adhesion sample, and those having a color change of 2 or less or those having a gloss retention of 90% or more were evaluated as ○. , And the others were evaluated as x. Table 3 shows the results.

[0049]

[Table 3]

Examples 5 to 10, Comparative Examples 2 to 3 Compositions A to H1 obtained in the above synthesis examples and comparative synthesis examples
To 00 g, 26 g of titanium oxide (white) and 0.5 g of a cellulose-based thickener were added, glass beads were added, and the mixture was stirred with a sand mill to obtain a white paint. A dedicated primer is applied to each base material and dried. An isopropanol solution containing 15% of dibutyltin dilaurate as a curing agent is added to the above composition at 10%, mixed well, and then dried at a dry weight of 50 g / m.
² was applied to a substrate and dried at a plate temperature of 80 ° C. for 10 minutes to prepare a test piece. Using these test pieces, adhesion, durability adhesion and weather resistance were evaluated. The durability was measured by using a sample after an irradiation test of 3,000 hours under the sunshine weather meter. The evaluation method of the adhesion was as described above. Regarding the weather resistance, the color difference (ΔE) and the gloss retention (%) were measured using the above-mentioned durable adhesive sample, and the color change was 2 or less, or the gloss retention was 90% or more. ○, others ×
And The results are shown in Tables 4 and 5.

[0051]

[Table 4]

[0052]

[Table 5]

The thicknesses of the substrates in Tables 4 and 5 are as follows. Inorganic ceramic base material: 12 mm Aluminum A2024P: 1 mm SUS 304: 1 mm

Reference Example 2 [Preparation of resin for primer (epoxy resin containing silyl group)] Bisphenol A type epoxy resin (epoxy equivalent 25
0) 80 g was dissolved in 200 g of butyl acetate, and 20 g of glycidoxypropyltrimethoxysilane was mixed to obtain a resin a for a primer. Reference Example 3 [Preparation of primer resin (silyl group-containing epoxy resin)] Hydrogenated bisphenol A type epoxy resin (epoxy equivalent 7
00) 80 g was dissolved in 200 g of butyl acetate, and 20 g of aminopropyltrimethoxysilane was added.
The reaction was carried out for a time to obtain a primer resin b.

Reference Example 4 [Preparation of resin for primer (silyl group-containing vinyl resin)] The silyl group-containing vinyl resin obtained in Reference Example 1 was used as primer resin c. Reference Example 5 [Preparation of resin for primer (acrylic resin / epoxy resin)] Bisphenol A was added to 100 g of resin c for primer.
Acetate 5 of epoxy resin (epoxy equivalent 250)
100 g of a 0% by weight solution was added, and the mixture was heated and melted at 80 ° C. for 2 hours to obtain a resin for primer d.

Reference Example 6 [Preparation of Resin for Primer (Acrylic Resin Containing Silyl Group / Polyester Resin)] 30 g of the resin for primer c and 30 g of a polyester resin comprising a saturated dibasic acid and a glycol were mixed.
The resin was heat-melted at 40 ° C. for 2 hours to obtain a resin e for a primer.

Reference Example 7 [Preparation of Primer Resin (Acrylic Resin / Silyl Group-Containing Acrylic Resin)] Acrylic resin composed of 50 g of the above-mentioned primer resin c and glycidyl methacrylate, n-butyl acrylate, methyl methacrylate (Weight average molecular weight 2000
(0, Tg 40 ° C.) and 50 g to obtain a resin f for a primer. Reference Example 8 [Primer resin (silyl group-containing acrylic urethane resin)] 70 g of acrylic polyol (weight average molecular weight 3000)
And 30 g of tolylene diisocyanate were reacted at 120 ° C. for 2 hours to synthesize an acrylic urethane resin. This resin is added to isocyanatopropyltrimethoxysilane 10
g were mixed to obtain a primer resin g.

Reference Example 9 [Primer resin (acrylic urethane resin / silyl group-containing acrylic resin)] 50 g of the acrylic urethane resin, which is an intermediate obtained in Reference Example 8, was mixed with 50 g of the above-mentioned resin for primer c.
The resin was thermally dissolved at 50 ° C. for 2 hours to obtain a primer resin h.

Preparation Example 1 [Preparation of Primer (Brown)] The polycarboxylic acid-based dispersant 0.1% was added to 20 g of the solid content of the primer resins a to h obtained in Reference Examples 2 to 9 above.
g, 8 g of titanium oxide, 6 g of red iron oxide, 6 g of lead chromate and 4 g of carbon, then a diluting solvent was added so that the final solid content concentration became 50% by weight, glass beads were added, and the mixture was stirred with a sand mill to give a brown color. Was obtained. Preparation Example 2 [Preparation of Primer (Clear)] For 30 g of solid content of each of the primer resins, Zn
3 g of O-isopropanol dispersion sol was added to obtain a clear primer composition.

Preparation Example 3 [Preparation of Brown Paint] For 100 g of the solid content of Composition A obtained in Synthesis Example 1, 0.5 g of a cellulose-based thickener, 0.5 g of a polycarboxylic acid-based dispersant, and After adding 40 g of titanium, 30 g of bengara, 10 g of lead chromate and 20 g of carbon, a diluting solvent is added so that the final solid content concentration becomes 50%, glass beads are added, and the mixture is stirred with a sand mill to obtain a brown paint. Was. Preparation Example 4 [Preparation of clear paint] For 100 g of the solid content of composition A obtained in Synthesis Example 1,
If necessary, add ZnO isopropanol dispersion sol to 1
0 g was added.

Example 11 To 100 parts of the primer obtained according to Preparation Example 1 was added 5 parts of a polyamine as a curing agent using the resin a for primer, and the primer was dried at a dry weight of 50 g /
m ² Inorganic ceramic substrate (12 mm thick) was applied and dried. To 100 parts of the coating material obtained in Preparation Example 3, 10 parts of di-n-butoxyethylacetoacetate zirconium was added as a curing agent, and then the coating material was applied to the above substrate at a dry weight of 50 g / m ^2. The specimen was dried at a temperature of 80 ° C. for 10 minutes to prepare a test piece. Using this test piece, weather resistance was evaluated by irradiating a sunshine weather meter for 3,000 hours, and hot water resistance was evaluated by a 60 ° C. hot water immersion test. The number of eyes was 100/100, indicating excellent weather resistance and warm water resistance. Table 6 shows the results. Examples 12 to 26 To the paints obtained in Preparation Examples 3 and 4, a curing agent was added in the same manner as in Example 11, and test pieces were prepared in the same manner as in Example 11 with the formulations shown in Tables 6 to 8. . Using these test pieces, weather resistance and warm water resistance were evaluated in the same manner as in Example 11.
The results are shown in Tables 6 to 8.

[0062]

[Table 6]

[0063]

[Table 7]

[0064]

[Table 8]

The curing agents for the primers in Tables 6 to 8
The following compounds are used. : Polyamine: di-isopropoxyethyl acetoacetate aluminum: 2-aminoethyl-3-aminopropyltrimethoxysilane: di-butyltin dilaurate The deteriorated coating film in Table 8 is obtained by coating and drying an acrylic emulsion. It is a membrane. The thickness of the inorganic ceramics-based substrate in the table is 12 mm.

[0066]

The cured product of the present invention has weather resistance, stain resistance,
Excellent in chemical resistance and long-term durability adhesion.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI // C08J 7/04 C08J 7/04 M

Claims (2)

[Claims] (1) The general formula R ¹ _n Si (OR ² ) _4-n
(Wherein, R ¹ is an organic group having 1 to 8 carbon atoms, and R ² is an organic group having 1 carbon atom.
An alkyl group of 5 to 5 carbon atoms or an acyl group of 1 to 4 carbon atoms, and n is 0 to 3).
A composition comprising a silyl group-containing vinyl resin solution having a silyl group having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group at a terminal or side chain is applied to a substrate and dried. Cured body. 2. The cured product according to claim 1, wherein the substrate is provided with a primer layer.