JP2003253209A - Coating composition and coating member - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coating composition having improved curability and adhesion, good transparency, weather, stain, heat, chemical, corrosion and abrasion resistances and excellent preservation stability by including a specific isocyanurate group- and/or isocyanate group-containing compound. <P>SOLUTION: The coating composition comprises (a) at least one kind selected from the group of a metal alcoholate represented by R<SP>1</SP><SB>m</SB>M(OR<SP>2</SP>)<SB>n</SB>, a hydrolyzate of the metal alcoholate, a condensate of the metal alcoholate, a chelate compound of the metal alcoholate, a hydrolyzate of the metal chelate compound, a condensate of the metal chelate compound, a metal acylate, a hydrolyzate of the metal acylate and a condensate of the metal acylate and (b) a compound having silicon atom bound to hydrolyzable group and/or hydroxy group and isocyanurate groups and/or isocyanate groups. A coating member is obtained by coating a substrate with the composition and forming a film. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a coating composition, and more specifically, it is excellent in storage stability, adhesion and water resistance, and is made of stainless steel, aluminum, alumina, silica, ceramics, plastics, inorganic ceramic substrates and cloths. Coating compositions suitable for coating surfaces such as and the like.

[0002]

2. Description of the Related Art In recent years, heat resistance, water resistance, stain resistance, organic chemical resistance, acid resistance, alkali resistance, corrosion resistance, wear resistance,
There is a demand for a coating composition which is excellent in weather resistance, moisture resistance, adhesion, etc. and can form a coating film having high hardness. As a coating composition satisfying some of such requirements, a composition comprising a partial condensate of organosilane and a dispersion of colloidal silica and a silicone-modified acrylic resin (JP-A-60-135465), organosilane A composition comprising a condensate, a chelate compound of zirconium alkoxide, and a hydrolyzable silyl group-containing vinyl resin (JP-A-64-1769),
A composition (US Pat. No. 4,904,721) comprising a condensate of organosilane, colloidal alumina and a hydrolyzable silyl group-containing vinyl resin has been proposed.

However, the above-mentioned JP-A-60-1354 is used.
Even when a coating film is formed by using the coating composition described in JP-B No. 65 and U.S. Pat. No. 4,904,721, the gloss of the coating film is lowered by irradiation with ultraviolet rays for a long time. The composition described in JP-A-64-1769 is obtained by containing a condensate of organosilane, a chelate compound of zirconium alkoxide, and a hydrolyzable silyl group-containing vinyl resin in a hydrophilic organic solvent. However, the storage stability is not sufficient, and when the solid content concentration is increased, gelation easily occurs in a short period of time. Furthermore, since these compositions are accompanied by a curing reaction in the process of forming a coating film, they require heat treatment at a high temperature or for a long time, which is problematic in terms of practicality. When this heat treatment is performed at low temperature for a short time, the resulting coating film (laminate) is generally likely to have poor adhesion to the substrate or undercoat layer or insufficient hardness. . Further, there is a problem that the adhesion between the overcoat layer and the undercoat layer is significantly impaired when foreign matter such as water adheres to the coating film immediately after the coating film is formed.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned conventional technical problems, and is achieved by incorporating a compound having a specific isocyanurate group and / or isocyanate group into a coating composition. ,
By applying this composition to a substrate, curability and adhesion are improved, and transparency, weather resistance, stain resistance, heat resistance, and
For storage stability that can form a coating member with a coating film that exhibits water resistance, seawater resistance, organic chemical resistance, acid resistance, alkali resistance, corrosion resistance, abrasion resistance, weather resistance, and moisture resistance. An object is to provide an excellent coating composition, as well as a coating member.

[0005]

The present invention includes (a) the following general formula (1) R ¹ _m M (OR ² ) _n (1) (wherein, M is a metal atom, R ¹ Are the same or different, and are an organic group having 1 to 8 carbon atoms, R ² are the same or different, and have 1 to 5 carbon atoms.
Is an alkyl group or an acyl group having 1 to 6 carbon atoms or a phenyl group, m and n are each an integer of 0 or more, and m + n is a valence of M) (hereinafter, referred to as “metal alcoholate”). (Also referred to as “metal alcoholate (1)”), a hydrolyzate of the metal alcoholate, a condensate of the metal alcoholate, a chelate compound of the metal alcoholate, a hydrolyzate of the metal chelate compound, and a metal chelate compound. At least one selected from the group consisting of a condensate, a metal acylate, a hydrolyzate of the metal acylate, and a condensate of the metal acylate, and (b) a silicon atom and an isocyanate bonded to a hydrolyzable group and / or a hydroxyl group. The present invention relates to a coating composition containing a compound having a nurate group and / or an isocyanate group. The composition of the present invention may further contain (c) a (co) polymer having a hydroxyl group and / or a hydrolyzable group.
The component (c) is preferably a polyvinyl alcohol resin and / or an acrylic silicon resin. The composition of the present invention further comprises (d) a compound containing a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group, a primary and / or secondary amino group, and / or an epoxy group. You may contain the compound which consists of. Next, the present invention provides the above coating composition on a substrate.
The present invention relates to a coating member having a coating film formed by applying more than one layer. The base material is preferably a member whose surface is composed of an inorganic compound.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.

Component (a): The component (a) used in the present invention is a metal alcoholate, a hydrolyzate of the metal alcoholate, or a condensate of the metal alcoholate represented by the general formula (1). A chelate compound of the metal alcoholate (hereinafter also referred to as “metal chelate compound”), a hydrolyzate of the metal chelate compound, a condensate of the metal chelate compound, a metal acylate, a hydrolyzate of the metal acylate,
And at least one selected from the group of condensates of the metal acylates. That is, the component (a) is
Only one of the species may be used, or a mixture of any two or more types may be used. Further, the metal chelate compound is a metal alcoholate and at least one compound selected from β-diketones, β-ketoesters, hydroxycarboxylic acids, hydroxycarboxylic acid salts, hydroxycarboxylic acid esters, keto alcohols and amino alcohols. It is obtained by a reaction with (hereinafter also referred to as “chelating agent”). Among these chelating agents, it is preferable to use β-diketones or β-ketoesters,
Specific examples thereof include acetylacetone, methyl acetoacetate, ethyl acetoacetate, acetoacetate-n-propyl, acetoacetate-i-propyl, acetoacetate-n-butyl, acetoacetate-sec-butyl, acetoacetate-t-. Butyl, 2,4-hexane-dione, 2,4-heptane-
Dione, 3,5-heptane-dione, 2,4-octane-dione, 2,4-nonane-dione, 5-methylhexane-dione and the like can be mentioned.

In the hydrolyzate of the metal alcoholate, the hydrolyzate of the metal chelate compound, and the hydrolyzate of the metal acylate, all OR ² groups contained in the metal alcoholate are hydrolyzed. There is no need, and for example, only one may be hydrolyzed, two or more may be hydrolyzed, or a mixture thereof. In addition, the condensate of the metal alcoholate, the condensate of the metal chelate compound, and the condensate of the metal acylate are M-O of the hydrolyzate of the metal alcoholate, the metal chelate compound, and the metal acylate.
Although the H groups are condensed to form an M-O-M bond, in the present invention, it is not necessary that all the M-OH groups are condensed, and a small part of the M-OH groups is condensed. Those having different degrees of condensation, M-OR group and MO
The concept also includes a mixture of condensates in which H groups are mixed.

When a condensate is used as the component (a), the metal alcoholate, the metal chelate compound, and the metal acylate may be previously hydrolyzed and condensed, or may be commercially available. You may use the condensate which exists. Further, the condensate of the metal alcoholate may be used as it is, or may be used as a condensate of the metal chelate compound by reacting with the above chelating agent. Commercially available products of the condensates of the metal alcoholates include A-10, B-2, B-4 and B manufactured by Nippon Soda Co., Ltd.
-7, B-10, etc.

As the metal atom represented by M in the general formula (1), silane, zirconium, titanium and aluminum can be mentioned as preferable ones, and titanium and silane are particularly preferable. The monovalent organic group having 1 to 8 carbon atoms of R ¹ differs depending on whether the compound represented by the general formula (1) is a metal alcoholate or a metal acylate. In the case of metal alcoholate, for example, methyl group, ethyl group, n-
Alkyl such as propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group Group: Acyl group such as acetyl group, propionyl group, butyryl group, valeryl group, benzoyl group, trioyl group; vinyl group, allyl group, cyclohexyl group, phenyl group, glycidyl group, (meth) acryloxy group, ureido group, amide In addition to groups, fluoroacetamido groups, isocyanate groups, etc., substituted derivatives of these groups can be mentioned. Examples of the substituent in the substituted derivative of R ¹ include a halogen atom, a substituted or unsubstituted amino group, a hydroxyl group, a mercapto group, an isocyanate group, a glycidoxy group, a 3,4-epoxycyclohexyl group, a (meth) acryloxy group, Ureido group,
Ammonium base etc. can be mentioned. However,
The carbon number of R ¹ including these substituted derivatives is 8 or less including the carbon atoms in the substituent. When it is a metal acylate, the monovalent organic group having 1 to 8 carbon atoms represented by R ¹ is an acetoxyl group, a propionyloxyl group, a butyryloxyl group, a valeryloxyl group, a benzoyloxyl group or a trioyloxyl group. And an acyloxyl group such as When two R ¹ 's are present in the general formula (1), they may be the same or different.

The alkyl group having 1 to 5 carbon atoms represented by R ² includes, for example, methyl group, ethyl group, n-propyl group,
i-propyl group, n-butyl group, sec-butyl group, t
-Butyl group, n-pentyl group and the like,
Examples of the acyl group having 1 to 6 carbon atoms include an acetyl group,
Examples thereof include a propionyl group, a butyryl group, a valeryl group and a caproyl group. A plurality of R ^{2 s} in the general formula (1) may be the same or different from each other.

Of these components (a), specific examples of metal alcoholates and chelate compounds of metal alcoholates include (a) tetramethoxysilane, tetraethoxysilane, methylsilicate, ethylsilicate, methyltrimethoxysilane, Methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane,
n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-
Propyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, γ-gly Sidoxypropyltrimethoxysilane, γ
-Glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, 3,4-epoxycyclohexylethyl Trimethoxysilane, 3,4-epoxycyclohexylethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, ureidopropyltrimethoxysilane, mercaptopropyltrimethoxysilane, ether-modified alkyl Trimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n- B pills dimethoxysilane, di -n
-Alkoxysilanes such as propyldiethoxysilane, di-i-propyldimethoxysilane, di-i-propyldiethoxysilane, divinyldimethoxysilane, divinyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane; tetraacetoxysilane, Organosilanes such as acyloxysilanes such as methyltriacetoxysilane, ethyltriacetoxysilane, dimethyldiacetoxysilane and diethyldiacetoxysilane, (b) tetra-n-butoxyzirconium, tri-n-butoxyethylacetoacetate zirconium Di-n-butoxy bis (ethylacetoacetate) zirconium, n-butoxy tris (ethylacetoacetate) zirconium, tetrakis (n-propylacetoacetate) G) zirconium, tetrakis (acetyl acetoacetate) zirconium, zirconium compounds such as tetrakis (ethylacetoacetate) zirconium;

(C) Tetra-i-propoxytitanium, tetra-n-butoxytitanium, tetra-t-butoxytitanium, di-i-propoxy.bis (ethylacetoacetate) titanium, di-i-propoxy.
Bis (acetylacetate) titanium, di-i-propoxy bis (acetylacetonato) titanium, di-n-butoxy bis (triethanolaminato) titanium, dihydroxybislactatertotitanium, dihydroxytitanium lactate, tetrakis (2 −
Titanium compounds such as ethylhexyloxy) titanium;

(D) tri-i-propoxy aluminum, di-i-propoxy ethyl acetoacetate aluminum, di-i-propoxy acetylacetonato aluminum, i-propoxy bis (ethyl acetoacetate) aluminum, i-propoxy Aluminum compounds such as bis (acetylacetonato) aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonato) aluminum, monoacetylacetonatobis (ethylacetoacetate) aluminum; and the like.

Preferred among these metal alcoholates and chelate compounds of metal alcoholates are methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane and tri-n-butoxyethylacetoacetate. Zirconium, di-i-propoxy bis (acetylacetonato) titanium, tri-i-propoxy. (Acetylacetonato) titanium, di-n-butoxy.
Bis (triethanolaminato) titanium, dihydroxy bislactetatotitanium, di-i-propoxy ethylacetoacetate aluminum and tris (ethylacetoacetate) aluminum can be mentioned, and particularly preferred compounds are di-i-propoxy.
Bis (acetylacetonato) titanium, tri-i-
Titanium compounds such as propoxy. (Acetylacetonato) titanium, di-n-butoxybis (triethanolaminato) titanium, and dihydroxybislactatertotitanium.

Specific examples of the metal acylate include:
Dihydroxy titanium dibutyrate, di-i-propoxy titanium diacetate, di-i-propoxy titanium dipropionate, di-i-propoxy titanium dimaloneate, di-i-propoxy titanium dibenzoylate, di -N-butoxy zirconium diacetate, di-i-propylaluminum monomaloniate and the like can be mentioned, and particularly preferable compounds are titanium compounds such as dihydroxy titanium dibutyrate and di-i-propoxy titanium diacetate. is there. These (a) components may be used alone or in combination of two or more.

As the component (a), the viscosity of the coating liquid does not change with time and is easy to handle. It is preferable to use a hydrolyzed product. By performing such a hydrolysis treatment before mixing with other components, a mixture of unhydrolyzed (a) component, partially hydrolyzed (a) component, and partially condensed (a) component Therefore, a rapid increase in viscosity due to a shock or the like that occurs when the composition is mixed with other components during preparation of the composition and a temporal increase in viscosity are suppressed. In this case, the amount of water _{^{used, R 1 m M (OR 2}} ) n 1 mole of 0.1 to 1,000 moles, preferably 0.5 to 50
It is 0 mol. In the case of a mixed solvent, the mixing ratio of water and the hydrophilic organic solvent is water / hydrophilic organic solvent = 10 to 90 /
90-10 (weight ratio), preferably 20-80 / 80-
20 and more preferably 30 to 70/70 to 30.

Specific examples of the hydrophilic organic solvent include methanol, ethanol, n-propanol and i-
Propanol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, diacetone alcohol, ethylene glycol, diethylene glycol, triethylene glycol and other saturated aliphatic monohydric alcohols or dihydric alcohols having 1 to 8 carbon atoms; ethylene Saturated aliphatic ether compounds having 1 to 8 carbon atoms such as glycol monobutyl ether and ethylene glycol monoethyl ether acetate; 1 to 8 carbon atoms such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate and ethylene glycol monobutyl ether acetate Ester compounds of saturated aliphatic dihydric alcohols; sulfur-containing compounds such as dimethyl sulfoxide; lactic acid, methyl lactate, ethyl lactate, salicylic acid, salicyl In addition to hydrophilic organic solvents such as hydroxycarboxylic acid or hydroxycarboxylic acid ester such as methyl, for example, ethers such as tetrahydrofuran and dioxane, ketones such as acetone, methyl ethyl ketone, cyclohexanone and isophorone, esters such as ethyl acetate and butyl acetate. In addition to the group, methyl cellosolve, ethyl cellosolve, butyl cellosolve, dimethyl sulfoxide and the like can be mentioned. Of these, preferred are methanol, ethanol,
Examples thereof include saturated aliphatic monohydric alcohols having 1 to 8 carbon atoms such as n-propanol, i-propanol, n-butyl alcohol, sec-butyl alcohol and tert-butyl alcohol. These water and / or hydrophilic organic solvent are more preferably used as a mixture of water and a hydrophilic organic solvent.

In the above, the reaction conditions for hydrolysis and / or (co) condensation are a temperature of 5 to 100 ° C.
It is preferably 20 to 90 ° C., and the time is 0.005 to 20 hours, preferably 0.1 to 10 hours. As the one hydrolyzed with the above mixed solvent, particularly preferred are di-i-propoxy bis (acetylacetonato) titanium, tri-i-propoxy. (Acetylacetonato) titanium, and di-n-butoxy bis. (Triethanolaminato) Titanium compounds such as titanium and dihydroxy bislactate titanium are hydrolyzed with the above mixed solvent. Further, the condensate of the metal alcoholate (1) is one in which the hydroxyl groups of the hydrolyzate of the metal alcoholate (1) are condensed to form an MOM bond, but in the present invention, the hydroxyl group is It is not necessary to condense all of them, and it is a concept including a compound in which a small amount of hydroxyl groups are condensed, a mixture of compounds having different degrees of condensation, and the like. The hydrolysis-condensation product of the metal alcoholate (1) has a polystyrene-reduced weight average molecular weight (hereinafter, also referred to as “Mw”) of preferably 100 to 100,000, more preferably 1,000 to 50,000.

Component (b): The component (b) is a compound having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group and an isocyanurate group and / or an isocyanate group. By using the component (b), the adhesiveness between the base material and the coating film, especially the adhesiveness even when wet, is not significantly reduced. Specific examples of the component (b) used in the present invention include (trimethoxysilylpropyl) isocyanurate, (triethoxysilylpropyl) isocyanurate, (triisopropoxysilylpropyl) isocyanurate, and 1,3-bis (tri). Methoxysilylpropyl) isocyanurate, 1,3-bis (triethoxysilylpropyl) isocyanurate, 1,3-bis (triisopropoxysilylpropyl) isocyanurate,
1,5-bis (trimethoxysilylpropyl) isocyanurate, 1,5-bis (triethoxysilylpropyl) isocyanurate, 1,5-bis (triisopropoxysilylpropyl) isocyanurate, 1,3,5-
Isocyanurate group-containing compounds such as tris (trimethoxysilylpropyl) isocyanurate, 1,3,5-tris (triethoxysilylpropyl) isocyanurate, 1,3,5-tris (triisopropoxysilylpropyl) isocyanurate, Examples thereof include isocyanate group-containing compounds such as γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, and γ-isocyanatopropyltriisopropoxysilane. Of these, preferred are 1,3,5-tris (trimethoxysilylpropyl) isocyanurate and 1,3,5-tris (triethoxysilylpropyl) isocyanurate.
These compounds having an isocyanurate group and / or an isocyanate group can be used alone or in combination of two or more.

The amount of the above-mentioned component (b) used is the same as that of the component (a) [calculated as a complete hydrolyzed condensate of the metal alcoholate (1)].
It is usually 0.1 to 1,000 parts by weight, preferably 0.5 to 500 parts by weight, based on 100 parts by weight. In this case, if the amount of component (b) used is less than 0.1 parts by weight,
Adhesion may decrease, while if it exceeds 1,000 parts by weight, the weather resistance of the coating film tends to decrease. The complete hydrolyzed condensate of the metal alcoholate (1) means that the R ² O-group of the metal alcoholate (1) is 100% hydrolyzed to an M-OH group, and further completely condensed to M.
-O-M structure.

(C) (Co) polymer having hydroxyl group and / or hydrolyzable group; (c) As (co) polymer having hydroxyl group and / or hydrolyzable group, for example, hydroxyl group and / or hydrolyzable group Examples thereof include (co) polymers obtained by polymerizing a monomer having a decomposable group, and (co) polymers obtained by saponifying an ester group-containing (co) polymer. The (co) polymer has a hydroxyl group and / or a hydrolyzable group, but may also have a reactive functional group such as a carboxyl group, a thiol group, an epoxy group, an amino group and a sulfin group. Good. Contains (c) a hydroxyl group and / or a hydrolyzable group (co)
As the polymer, specifically, polyvinyl alcohol resin, acrylic resin, acrylic silicon resin, epoxy resin, polyester resin, alkyd resin, aminoalkyd resin, urethane resin, polystyrene resin,
And so on. Among these, polyvinyl alcohol resins and acrylic silicone resins are preferable, and acrylic silicone resins are particularly preferable. As the acrylic silicone resin, a silyl group (hereinafter also referred to as "specific silyl group") whose main chain is composed of a vinyl polymer and which has a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group at the terminal or side chain is used. A silyl group-containing vinyl polymer having at least one, preferably two or more, and more preferably at least one, preferably two or more hydrophilic functional groups in one molecule of the polymer can be mentioned. The silyl group-containing vinyl polymer contains a hydroxyl group and / or a hydrolyzable group.
It is preferably a polymer having at least one reactive functional group such as a thiol group, an epoxy group, an amino group and a sulfine group. Many of the specific silyl groups are represented by the following general formula (2).

[0023]

(In the formula, X is a halogen atom, an alkoxy group, an acyloxy group, a phenoxy group, a thioalkoxy group,
Hydrolyzable groups such as amino groups and acetoxy groups or hydroxyl groups, R ³ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aralkyl group having 1 to 10 carbon atoms, and p is an integer of 1 to 3. )

One or more kinds of the specific silyl group can be present in the silyl group-containing vinyl polymer. Further, examples of the hydrophilic functional group in the vinyl polymer containing a silyl group include a carboxyl group, a carboxylic acid anhydride group, a hydroxyl group, an amino group, an amide group, an amineimide group, and a glycidyl group. One or more kinds of these hydrophilic functional groups can be present in the silyl group vinyl polymer, but for example, any two or more kinds of carboxyl group, hydroxyl group, amide group, amineimide group or glycidyl group coexist. It is preferable.

The silyl group-containing vinyl polymer is, for example,
(A) A vinyl polymer having a carbon-carbon double bond and preferably a hydrophilic functional group (hereinafter referred to as "functional unsaturated polymer").
(Also referred to as the) carbon-carbon double bond, a method of adding a hydrosilane compound having a specific silyl group,
(B) It can be produced by a method of copolymerizing a vinyl-based monomer having a hydrolyzable silyl group or the like and preferably a vinyl-based monomer having a hydrophilic functional group.

The functional unsaturated polymer used in the above method (a) can be produced, for example, as follows. That is, (a-1) a vinyl-based monomer having a hydrophilic functional group is optionally (co) polymerized with another vinyl-based monomer to synthesize a precursor (co) polymer,
A suitable functional group (hereinafter also referred to as “complementary functional group (α)”) in the precursor (co) polymer is capable of reacting with a complementary functional group (α) (hereinafter referred to as “complementary functional group ( β) ”)
By reacting with an unsaturated compound having a carbon-carbon double bond, a functional unsaturated polymer having a carbon-carbon double bond in the side chain of the polymer molecular chain can be produced. Further, (a-2) a radical polymerization initiator having a complementary functional group (α) (for example, 4,4-azobis-4-cyanovaleric acid) is used, or a radical polymerization initiator and a chain transfer agent are used. When a compound having a complementary functional group (α) on both sides (eg, 4,4-azobis-4-cyanovaleric acid and dithioglycolic acid) is used and a vinyl-based monomer having a hydrophilic functional group is used, By (co) polymerization with other vinyl-based monomers by means of a precursor having a complementary functional group (α) derived from a radical polymerization initiator or a chain transfer agent at one or both ends of the polymer molecular chain (copolymer). ) After synthesizing the polymer, the complementary functional group (α) in the precursor (co) polymer is
By reacting an unsaturated compound having a complementary functional group (β) and a carbon-carbon double bond, a functional unsaturated polymer having a carbon-carbon double bond at one end or both ends of the polymer molecular chain. Coalescence can be produced. Further, (i-3) the functional unsaturated polymer can also be produced by a combination of the above (a-1) and (a-2). Examples of the reaction between the complementary functional group (α) and the complementary functional group (β) in the methods (a-1) and (a-2) include an esterification reaction between a carboxyl group and a hydroxyl group, a carboxylic acid anhydride. Ring-opening esterification reaction between a compound group and a hydroxyl group, esterification reaction between a carboxyl group and an epoxy group, amidation reaction between a carboxyl group and an amino group, ring-opening amidation reaction between a carboxylic acid anhydride group and an amino group, Examples thereof include a ring-opening addition reaction between an epoxy group and an amino group, and a urethanization reaction between a hydroxyl group and an isocyanate group.

Examples of the vinyl-based monomer having the hydrophilic functional group include (meth) acrylic acid, crotonic acid,
Unsaturation with carboxyl groups such as cinnamic acid, maleic acid, fumaric acid, itaconic acid, monomethyl maleate, monoethyl maleate, monomethyl itaconate, monoethyl itaconate, and mono-2- (meth) acryloyloxyethyl hexahydrophthalate Compounds: unsaturated carboxylic acid anhydrides such as maleic anhydride and itaconic anhydride; 2-hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl ( (Meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-
Hydroxyamyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, neopentyl glycol mono (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 3-amino -2
-Hydroxypropyl (meth) acrylate, glycerin mono- or di- (meth) acrylate, trimethylolpropane mono- or di- (meth) acrylate, pentaerythritol mono- or di- (meth)
Acrylate, N-methylol (meth) acrylamide, N, N-dimethylol (meth) acrylamide, 2
-Hydroxy group-containing vinyl monomers such as hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ether, 3-hydroxypropyl 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 vinyl monomers such as aminoethyl vinyl ether, N, N-dimethylamino (meth) acrylamide, N, N-diethylamino (meth) acrylamide; acrylamide, diacetone acrylamide, maleic acid diamide, fumaric acid diamide, itacone Amide group-containing vinyl monomers such as acid diamide, α-ethylacrylamide, N-butoxymethyl (meth) acrylamide; 1,1,1-trimethylamine (meth) acrylimide, 1-methyl-1-ethylamine (meth) Acrylic imide, 1,1-dimethyl-1- (2-hydroxypropyl) amine (meth) acrylimide, 1,1-dimethyl-1- (2′-phenyl-2′-hydroxyethyl) amine (meth) acrylimide , 1,1-dimethyl-1- (2'-hydroxy Amine-group-containing vinyl monomers such as -2'-phenoxypropyl) amine (meth) acrylimide; glycidyl group-containing vinyl monomers such as allyl glycidyl ether, glycidyl (meth) acrylate, and methylglycidyl (meth) acrylate And epoxy group-containing vinyl monomers such as epoxidized cyclohexyl (meth) acrylate; vinyl ester monomers such as vinyl acetate, vinyl propionate and vinyl versatate. These vinyl monomers can be used alone or in admixture of two or more.

Among the above-mentioned vinyl monomers having a hydrophilic functional group, (meth) acrylic acid is particularly preferable in the group of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, and as a vinyl monomer containing a hydroxyl group. Is particularly preferably 2-hydroxyethyl (meth) acrylate, and particularly 1,1-dimethyl-1- (2-hydroxypropyl) in the group of amino group-containing vinyl monomers and amineimide group-containing vinyl monomers. Amine (meth) acrylimide, 1,1-
Dimethyl-1- (2'-phenyl-2'-hydroxyethyl) amine (meth) acrylimide, 1,1-dimethyl-1- (2'-hydroxy-2'-phenoxypropyl) amine (meth) acrylimide, etc. The (meth) acrylic acid amide imide having a hydroxyl group of is preferable.

Other vinyl-based monomers copolymerized with the vinyl-based monomer having a hydrophilic functional group include, for example, methyl (meth) acrylate, ethyl (meth) acrylate,
(Meth) acrylic acid-n-propyl, (meth) acrylic acid-i-propyl, (meth) acrylic acid-n-butyl,
(Meth) acrylic acid esters such as t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and cyclohexyl (meth) acrylate; (meth) acrolein, crotonaldehyde, formylstyrene,
Formyl-α-methylstyrene, diacetone acrylamide, (meth) acrylamide pivalin aldehyde, 3
-(Meth) acrylamidomethyl-anisaldehyde,
β- (meth) acryloxy-α, α-dimethylpropanal [that is, β- (meth) acryloxypivalinaldehyde], β- (meth) acryloxy-α, α-diethylpropanal, β- (meth) acryloxy- α, α
-Dipropylpropanal, β- (meth) acryloxy-α-methyl-α-butylpropanal, β- (meth)
Acryloxy-α, α, β-trimethylpropanal,
Diacetone (meth) acrylamide, vinyl alkyl ketones having 4 to 7 carbon atoms (for example, vinyl methyl ketone, vinyl ethyl ketone, vinyl-n-propyl ketone, vinyl-i-propyl ketone, vinyl-n-).
Butyl ketone, vinyl-i-butyl ketone, vinyl-t
-Butyl ketone, etc.), vinyl phenyl ketone, vinyl benzyl ketone, divinyl ketone, diacetone (meth)
Acrylate, acetonitrile (meth) acrylate,
2-hydroxypropyl (meth) acrylate-acetyl acetate, 3-hydroxypropyl (meth) acrylate-acetyl acetate, 2-hydroxybutyl (meth) acrylate-acetyl acetate, 3-hydroxybutyl (meth) acrylate-acetyl acetate, 4- Vinyl-based monomers having a carbonyl group such as hydroxybutyl (meth) acrylate-acetylacetate and butanediol-1,4- (meth) acrylate-acetylacetate; 4- (meth) acryloyloxy-2,2,6 , 6, -Tetramethylpiperidine, 4
-(Meth) acryloylamino-2,2,6,6, -tetramethylpiperidine, 4- (meth) acryloyloxy-1,2,2,6,6, -pentamethylpiperidine,
4- (meth) acryloylamino-1,2,2,6
An ultraviolet-stable piperidine-based unsaturated monomer such as 6, -pentamethylpiperidine; (meth) acrylonitrile, styrene, α-methylstyrene, vinyl chloride, vinyl acetate, vinyl propionate and the like can be mentioned. These vinyl monomers can be used alone or in admixture of two or more. Complementary satiety group (β) and carbon-
Examples of the unsaturated compound having a carbon double bond include, for example, unsaturated carboxylic acids among the vinyl-based monomers having the hydrophilic functional group, unsaturated carboxylic acid anhydrides, hydroxyl-containing vinyl-based monomers or In addition to the amino group-containing vinyl monomer, for example, an epoxy group-containing unsaturated compound such as glycidyl (meth) acrylate and allyl glycidyl ether, and reacting the hydroxyl group-containing vinyl monomer and the diisocyanate compound in equimolar amounts The isocyanate group-containing unsaturated compound and the like obtained by.

Examples of the hydrosilane compound having a specific silyl group used in the method (a) include halogenated silanes such as methyldichlorosilane, phenyldichlorosilane and trichlorosilane; methyldimethoxysilane, methyl Alkoxysilanes such as diethoxysilane, phenyldimethoxysilane, trimethoxysilane, triethoxysilane; methyldiacetoxysilane,
Acyloxysilanes such as phenyldiacetoxysilane and triacetoxysilane; aminoxysilanes such as dimethylaminoxysilane, methyldiaminoxysilane and triaminoxysilane; phenoxysilanes such as methyldiphenoxysilane and triphenoxysilane ;
Examples thereof include thioalkoxysilanes such as methyldi (thiomethoxy) silane and tri (thiomethoxy) silane; aminosilanes such as methyldiaminosilane and triaminosilane. These hydrosilane compounds may be used alone or in combination of two or more.
Next, the vinyl-based monomer having a specific silyl group used in the above method (b) is represented by the following general formula (3).

[0032] [In the formula, X, R ³ and p each have the same meaning as in formula (2), and R ⁴ represents an organic group having a polymerizable carbon-carbon double bond. ]

Specific examples of the vinyl type monomer having such a specific silyl group include CH ₂ ═CHSi (CH ₃ ).
_{(OCH 3) 2, CH 2} = CHSi (OCH 3) 3, CH 2 = C
_{HSi (CH 3) Cl 2,} CH 2 = CHSiCl 3, CH 2 =
_{CHCOO (CH 2) 2 Si (} CH 3) (OCH 3) 2, CH 2
_{= CHCOO (CH 2) 2 Si} (OCH 3) 3, CH 2 = CH
_{COO (CH 2) 3 Si (} CH 3) (OCH 3) 2, CH 2 = C
_{HCOO (CH 2) 3 Si (} OCH 3) 3, CH 2 = CHCO
_{O (CH 2) 2 Si (} CH 3) Cl 2, CH 2 = CHCOO
_{(CH 2) 2 SiCl 3,} CH 2 = CHCOO (CH 2) 3 Si
_{(CH 3) Cl 2, CH} 2 = CHCOO (CH 2) 3 SiC
_{l 3, CH 2 = C (} CH 3) COO (CH 2) 2 Si (CH 3)
_{(OCH 3) 2, CH 2} = C (CH 3) COO (CH 2) 2 Si
_{(OCH 3) 3, CH 2} = C (CH 3) COO (CH 2) 3 Si
(CH ₃ ) (OCH ₃ ) ₂ , CH ₂ ═C (CH ₃ ) COO (CH
₂ ) ₃ Si (OCH ₃ ) ₃ , CH ₂ ═C (CH ₃ ) COO (C
_{H 2) 2 Si (CH 3} ) Cl 2, CH 2 = C (CH 3) COO
_{(CH 2) 2 SiCl 3,} CH 2 = C (CH 3) COO (C
_{H 2) 3 Si (CH 3} ) Cl 2, CH 2 = C (CH 3) COO
(CH ₂ ) ₃ SiCl ₃ ,

[0034]

[Chemical 1]

[Chemical 2]

[Chemical 3]

[Chemical 4]

And the like. These vinyl monomers having a specific silyl group can be used alone or in admixture of two or more. The vinyl-based monomer having a hydrophilic functional group used in the method (b) is, for example, the same as the vinyl-based monomer having a hydrophilic functional group exemplified in the method (a) above. One or more types can be used. Further, in the method (b), one or more kinds of the other vinyl-based monomers exemplified in the method (a) can be copolymerized.

The polystyrene-converted number average molecular weight (hereinafter also referred to as "Mn") of the silyl group-containing vinyl polymer obtained as described above is preferably 2,000 to 10.
10,000, more preferably 4,000 to 50,000
It is 0. In the present invention, the silyl group-containing vinyl polymer may be used alone or in combination of two or more.

The polyvinyl alcohol resin as the component (c) used in the present invention includes at least one selected from the group consisting of polyvinyl alcohol and ethylene / vinyl alcohol copolymers. Among the above polyvinyl alcohol resins, polyvinyl alcohol is generally obtained by saponifying polyvinyl acetate. The polyvinyl alcohol may be a partially saponified polyvinyl alcohol having an acetic acid group remaining of several tens%, a fully saponified polyvinyl alcohol having no acetic acid group remaining, or a modified polyvinyl alcohol having an OH group modified, It is not limited. Specific examples of the polyvinyl alcohol include:
Kuraray Co., Ltd. RS polymer RS-110 (saponification degree = 99%, degree of polymerization = 1,000), Kuraray Poval LM-20SO manufactured by the same company (saponification degree = 40%, degree of polymerization = 2,) 000), Goshenol NM-14 manufactured by Nippon Synthetic Chemical Industry Co., Ltd. (degree of saponification = 99%, degree of polymerization = 1,40)
0) and the like. Further, among the above polyvinyl alcohol-based resins, ethylene-vinyl alcohol copolymer is a saponified product of a copolymer of ethylene and vinyl acetate,
That is, it is obtained by saponifying an ethylene-vinyl acetate random copolymer, and from a partially saponified product in which several tens mol% of acetic acid groups remain, only several mol% of acetic acid groups remain or acetic acid The group is not particularly limited, including a completely saponified product in which no group remains. The content of repeating units derived from ethylene in the ethylene / vinyl alcohol copolymer (hereinafter, also referred to as "ethylene content") is usually 0 to 50 mol%, preferably 20 to 45 mol%. Specific examples of the ethylene / vinyl alcohol copolymer include Eval EP-F101 manufactured by Kuraray Co., Ltd.
(Ethylene content: 32 mol%), Nippon Synthetic Chemical Industry Co., Ltd., Soarnol D2908, D2935 (Ethylene content: 29 mol%), D2630 (Ethylene amount: 26)
%), A4412 (ethylene content 44%) and the like.

The above polyvinyl alcohol resin has a melt flow index of 210 ° C. and a load of 21.168.
Under N condition, 1 to 50 g / 10 minutes, preferably 5 to 45
g / 10 minutes. Melt flow index is 1g /
If it is less than 10 minutes, the gas barrier properties may be deteriorated. On the other hand, if it exceeds 50 g / 10 minutes, the water resistance and solvent resistance may decrease, which is not preferable. These polyvinyl alcohol-based resins may be used alone,
Alternatively, two or more kinds may be mixed and used.

When the coating film obtained from the composition of the present invention is cured, the hydroxyl group and / or the hydrolyzable group present in the repeating unit derived from the above (c) is converted into the above (a).
By co-condensing with the component, the component (b), and at least one selected from the inorganic compounds on the surface of the base material described below, it is possible to obtain a coating member having excellent coating performance, particularly excellent adhesion under high humidity. . Further, the component (c) can also be cured with (f) a curing accelerator, (g) a polyfunctional hydrazine derivative, (h) an oxazoline derivative, etc. described later.

The amount of the component (c) used is usually 0 to 100,000 parts by weight, preferably 100 parts by weight, based on 100 parts by weight of the component (a) (calculated as a complete hydrolyzed condensate of the metal alcoholate (1)). 10 to 50,000 parts by weight, more preferably 2
It is 0 to 10,000 parts by weight. In this case, 100,0
If it exceeds 00 parts by weight, the adhesiveness of the coating film tends to decrease.

Component (d) The component (d) is a silane compound containing a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group and a primary and / or secondary amino group or an epoxy group.
By using the component (d), the adhesiveness and curability between the base material and the coating film are further improved.

As such a silane compound (d),
For example, the compound represented by the following general formula (4) may be mentioned. (In the formula, Y represents a group containing one or more monovalent or divalent amino groups and an alkyl group and / or a phenyl group, and R ⁵ is the same or different when two are present,
A monovalent organic group having 1 to 8 carbon atoms is shown, and R ⁶ is the same or different and is an alkyl group having 1 to 5 carbon atoms or 1 to 5 carbon atoms.
6 represents an acyl group, q is an integer of 1 or 2, and r
Is an integer of 0 to 2 and s is an integer of 1 to 3, provided that q + r + s = 4. )

Specific examples of the (d) silane compound include aminopropyltrimethoxysilane, aminopropyltriethoxysilane, aminopropylmethyldimethoxysilane, aminopropylmethyldiethoxysilane and N-phenyl-γ-aminopropyl. Trimethoxysilane, N-butyl-γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane, N -Β (aminoethyl) -γ-aminopropyltriethoxysilane, N
-(6-aminohexyl) -γ-aminopropyltrimethoxysilane, N- (6-aminohexyl) -γ-aminopropylmethyldimethoxysilane, N- (6-aminohexyl) -γ-aminopropyltriethoxysilane,
N- [styryl (aminomethyl)]-γ-aminopropyltrimethoxysilane, N- [styryl (aminomethyl)]-γ-aminopropylmethyldimethoxysilane,
N- [styryl (aminomethyl)]-γ-aminopropyltriethoxysilane, N- [N-β (aminoethyl)
Aminoethyl] -γ-aminopropyltrimethoxysilane, N- [N-β (aminoethyl) aminoethyl] -γ
-Aminopropylmethyldimethoxysilane, N- [N-
β (aminoethyl) aminoethyl] -γ-aminopropyltriethoxysilane, N- [N- (benzylmethyl)
Aminoethyl] -γ-aminopropyltrimethoxysilane, N- [N- (benzylmethyl) aminoethyl] -γ
-Aminopropylmethyldimethoxysilane, N [N-
(Benzylmethyl) aminoethyl] -γ-aminopropyltriethoxysilane, N- [N- (benzyl) aminoethyl] -γ-aminopropyltrimethoxysilane, N
-[N- (benzyl) aminoethyl] -γ-aminopropylmethyldimethoxysilane, N- [N- (benzyl)
Aminoethyl] -γ-aminopropyltriethoxysilane, N-phenylaminopropyltrimethoxysilane,
N-phenylaminopropylmethyldimethoxysilane,
N-phenylaminopropyltriethoxysilane, N-
Phenylaminomethyltrimethoxysilane, N-phenylaminomethylmethyldimethoxysilane, N-phenylaminomethyltriethoxysilane, bis (trimethoxysilylpropyl) amine, P- [N- (2-aminoethyl) aminomethyl] phenethyltri Methoxysilane, N
Amino group-containing silane compounds such as-[(3-trimethoxysilyl) propyl] diethylenetriamine, N-[(3-trimethoxysilyl) propyl] triethylenetetramine, N-3-trimethoxysilylpropyl-m-phenylenediamine Β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β
-(3,4-Epoxycyclohexyl) ethyltriisopropoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriisopropoxysilane, γ-glycid Examples thereof include epoxy group-containing silane compounds such as xypropylmethyldimethoxysilane and γ-glycidoxypropylmethyldiethoxysilane. Of these, particularly preferred are aminopropyltrimethoxysilane, aminopropyltriethoxysilane, N-β- (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane. Silane, and N-β (aminoethyl) γ-aminopropyltriethoxysilane, γ
-Glycyloxypropyltrimethoxysilane and γ-
Glycyloxypropyltriethoxysilane, and the like. The amount of these silane compounds used is the amount of the component (a) [calculated as the complete hydrolysis condensate of the metal alcoholate (1)] 10
It is usually 0 to 1,000 parts by weight, preferably 0.1 to 100 parts by weight, based on 0 parts by weight. In this case, if the amount of the component (b) used exceeds 1,000 parts by weight, the weather resistance of the coating film tends to decrease.

(E) Filler: The coating composition of the present invention has various properties such as coloring, thickening of the obtained cured product, prevention of ultraviolet ray transmission to the substrate, corrosion resistance, and heat resistance. In addition, a filler can be added and dispersed.

It is added to further increase the hardness of the cured product.
As a filling material (hereinafter also referred to as "filling material (e1)")
Is an inorganic compound particle and / or sol or co
Lloyd is mentioned. Specific examples of the above-mentioned inorganic compound
Is SiO₂, Al₂O₃, Al (OH)₃, Sb ₂O_Five, S
i₃N_Four, Sn-In₂O₃, Sb-In₂O₃, MgF, C
eF₃, CeO₂3 Al₂O₃・ 2SiO₂, BeO, S
iC, AlN, Fe, Fe₂O₃, Co, Co-Fe
O_X, CrO₂, Fe_FourN, Ba ferrite, SmCO_Five,
YCO_Five, CeCO_Five, PrCO_Five, Sm₂CO₁₇, ZrO
₂, Nd₂Fe₁₄B, Al_FourO₃Can be mentioned
It These inorganic compounds may be used alone or in combination of two or more.
Can be used together.

The existing form before the filler (e1) is mixed with the coating composition is a particulate powder or a sol or colloid in which fine particles are dispersed in a solvent. Filler (e
The solid content concentration of 1) is preferably 40% by weight or less. Among the fillers (e1), the colloidal silica is, for example, Snowtex, methanol silica sol, isopropanol silica sol [above, manufactured by Nissan Chemical Industry Co., Ltd.]; ; L
Udex (manufactured by DuPont, USA); Syton (manufactured by Monsanto, USA); Nalcoag (manufactured by Nalco Chemical, USA) and the like, and the colloidal alumina is
For example, alumina sol-100, alumina sol-20
0, Aluminasol-520 [above, Nissan Chemical Industries, Ltd.
Manufactured], alumina clear sol, alumina sol 10, alumina sol 132 [above, Kawaken Fine Chemicals Co., Ltd.
It is commercially available under the trade name such as "made".

As a method of blending the filler (e1),
It may be added to the coating composition of the present invention, or may be added during the preparation of the composition, and in the presence of the component (e1), the component (a), the component (b), the component (c), or the component (d).
The components and the like can be hydrolyzed and condensed. The amount of the filler (e1) used in the present invention is usually 0 to 500 parts by weight, preferably 0.1 parts by weight based on 100 parts by weight of the metal alcoholate (1) constituting the component (a). ~
It is 400 parts by weight.

On the other hand, examples of the filler (hereinafter, also referred to as "filler (e2)") for exhibiting coloring, design or thickening of the coating film, and further enhancing corrosion resistance, weather resistance, etc. Metals and alloys; compounds such as metal oxides, hydroxides, carbides, nitrides and sulfides; water-insoluble pigments such as organic pigments and inorganic pigments. These components are used in the form of particles, fibers, whiskers or scales. Specific examples of the filler (e2) include iron, nickel, aluminum, zinc, copper, silver, carbon black, graphite, stainless steel, ferric oxide, ferrite, cobalt oxide, manganese oxide, chromium oxide,
Zirconium oxide for pigments, titanium oxide (rutile type) for pigments, zirconium oxide, silicon dioxide, lead suboxide, aluminum oxide, zinc oxide, cuprous oxide, ferric hydroxide, aluminum hydroxide, slaked lime, barium carbonate, carbonic acid Calcium, magnesium carbonate, lead sulfate, basic lead sulfate, barium sulfate, gypsum, molybdenum disulfide, lead sulfide, copper sulfide, lead silicate, calcium leadate, copper borate, potassium titanate,
Silicon Carbide, Silicon Nitride, Boron Nitride, Lead Phthalate, Synthetic Mullite, Clay, Diatomaceous Earth, Talc, Bentonite, Mica, Green Earth, Cobalt Green, Manganese Green, Viridian, Guinea Green, Cobalt Chrome Green, Sure Green, Green Earth, Chrome green, zinc green, pigment green, ultramarine blue, rock ultramarine, dark blue, cobalt blue, cerulean blue, molybdenum blue, cobalt purple, mars purple, manganese purple, pigment violet, zinc yellow, chrome yellow, cadmium yellow, strontium yellow, titanium yellow , Lisage, pigment yellow,
Loess, cadmium red, selenium red, chrome vermillion,
Examples thereof include red iron oxide, lead zinc white, bunchson white, manganese white, bone black, diamond black, thermatomic black, and vegetable black. These fillers (e
2) can be used alone or in admixture of two or more.

The amount of the filler (e2) used in the present invention is usually 300 parts by weight or less based on 100 parts by weight of the total solid content of the coating composition used in the present invention. If the amount of the filler (e2) used exceeds 300 parts by weight, the adhesion of the coating film may decrease.

(F) Curing accelerator: In order to further increase the curing speed of the coating composition of the present invention, depending on the curing conditions, a curing accelerator other than the above (d) silane compound (hereinafter referred to as "(f)" (Also referred to as "curing accelerator") can be used in combination, and it is particularly effective when curing at a relatively low temperature. (F) Examples of the curing accelerator include alkali metal salts such as naphthenic acid, octylic acid, nitrous acid, sulfurous acid, aluminic acid and carbonic acid; methanesulfonic acid; ethylenediamine, hexanediamine, diethylenetriamine,
Triethylenetetramine, tetraethylenepentamine,
Amine-based compounds such as piperidine, piperazine, metaphenylenediamine, ethanolamine, triethylamine, and various modified amines used as curing agents for epoxy resins;

(C ₄ H ₉ ) ₂ Sn (OCOC ₁₁ H ₂₃ ) ₂ , (C
_{4 H 9) 2 Sn (OCOCH} = CHCOOCH 3) 2, (C 4 H
₉ ) ₂ Sn (OCOCH = CHCOO (C ₄ H ₉ ) ₂ , (C ₈ H
₁₇ ) ₂ Sn (OCOC ₁₁ H ₂₃ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (OC
_{OCH = CHCOOCH 3) 2, (} C 8 H 17) 2 Sn (OCO
_{CH = CHCOO (C 4 H 9} ) 2, (C 8 H 17) 2 Sn (OC
OCH = 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 (S
_{CH 2 CH 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 (SCH ₂ CH ₂ C
OOC ₈ H ₁₇ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (SCH ₂ COOC _{12
H 25) 2, (C 8} H 17) 2 Sn (SCH 2 CH 2 COOC 12 H
₂₅ ) Mercaptide-type organotin compounds such as ₂ ;

(C ₄ H ₉ ) ₂ Sn = S, (C ₈ H ₁₇ ) ₂ Sn =
Sulfide type organotin compounds such as S; (C ₄ H ₉ ) ₂ Sn
O, organotin oxides such as (C ₈ H ₁₇ ) ₂ SnO,
Examples thereof include reaction products of these organic tin oxides with ester compounds such as alkyl silicates, dimethyl maleate, diethyl maleate and dioctyl phthalate. These (f) curing accelerators can be used alone or in admixture of two or more. Examples of the method of adding the above-mentioned (f) curing accelerator to the composition of the present invention include a method of previously diluting the curing accelerator (f) with a solvent and adding it. (F) in the present invention
The amount of the curing accelerator used is usually 0 to 100 parts by weight, preferably 0.1 to 80 parts by weight, and more preferably 0.1 to 100 parts by weight of the component (a) (calculated as a complete hydrolysis-condensation product). 5 to 50 parts by weight.

(G) Polyfunctional hydrazine derivative; Furthermore, in the coating composition of the present invention, the polyfunctional hydrazine derivative having two or more hydrazino groups in the molecule (hereinafter referred to as "(g) polyfunctional hydrazine derivative" Also called)
May be contained. The polyfunctional hydrazine derivative (g) is preferably blended when the silyl group-containing vinyl polymer used as the component (c) contains a carbonyl group. The (g) polyfunctional hydrazine derivative has a function of reacting the hydrazino group with the carbonyl group to form a network structure and crosslinking the coating film in the drying process after the application of the aqueous dispersion.

Examples of the (g) polyfunctional hydrazine derivative include oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, phthalic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid. Dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, itaconic acid dihydrazide, etc. dicarboxylic acid dihydrazides having 2 to 10 carbon atoms, especially 4 to 6 carbon atoms; , Trifunctional or higher functional hydrazides such as ethylenediaminetetraacetic acid tetrahydrazide; ethylene-
1,2-dihydrazine, propylene-1,2-dihydrazine, propylene-1,3-dihydrazine, butylene-
1,2-dihydrazine, butylene-1,3-dihydrazine, butylene-1,4-dihydrazine, butylene-2,
And aliphatic dihydrazines having a total carbon number of 2 to 4, such as 3-dihydrazine.

Further, at least a part of the hydrazino groups of these dihydrazines are substituted with acetaldehyde, propionaldehyde, butyraldehyde, acetone, methyl ethyl ketone, diethyl ketone, methyl propyl ketone,
Compounds blocked by reacting with carbonyl compounds such as methyl butyl ketone and diacetone alcohol (hereinafter also referred to as “blocked polyfunctional hydrazine derivatives”), for example, adipic dihydrazide monoacetone hydrazone, adipic dihydrazide diacetone hydrazone, etc. Can also be used. By using such a blocked polyfunctional hydrazine derivative, the progress of the crosslinking reaction of the coating film can be appropriately suppressed,
Particularly, the redispersibility which is important as a printing ink can be further improved. Among these polyfunctional hydrazine derivatives, adipic acid dihydrazide, sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide diacetonehydrazone and the like are preferable. The polyfunctional hydrazine derivative (g) can be used alone or in admixture of two or more.

The amount of the polyfunctional hydrazine derivative (g) used in the present invention is such that the equivalent ratio of the carbonyl group to the hydrazino group is usually 1: 0.1 to 5, preferably 1 :.
0.5-1.5, more preferably 1: 0.7-1.2
The amount is in the range of. In this case, if the hydrazino group is less than 0.1 equivalent with respect to 1 equivalent of the carbonyl group, the solvent resistance and damage resistance of the coating film tend to be reduced, while if it exceeds 5 equivalents, the coating property is increased. The water resistance and transparency of the film tend to decrease. However, when the blocked polyfunctional hydrazine derivative is used as the polyfunctional hydrazine derivative, the above equivalence ratio is based on the equivalence ratio between the carbonyl group and the hydrazino group in the polyfunctional hydrazine derivative before blocking. . The (g) polyfunctional hydrazine derivative can be compounded in an appropriate step of preparing the coating composition of the present invention, but it suppresses the generation of coagulation during the production of the composition of the present invention, and improves the polymerization stability. In order to maintain, it is desirable to incorporate the total amount of (g) polyfunctional hydrazine derivative after the preparation of the composition of the present invention.

(H) Oxazoline derivative; Further, the coating composition of the present invention includes an oxazoline derivative having one or more oxazoline groups (dihydrooxazolyl groups) in the molecule (hereinafter referred to as "(h) oxazoline derivative"). It may be contained. (H) In the oxazoline derivative, the silyl group-containing vinyl polymer has a carboxyl group, a thiol group, a hydroxyl group, an epoxy group, an amino group, and a sulfin group (hereinafter, these organic groups are also referred to as “reactive functional groups”). When it contains, it is preferable to mix it, and especially when it contains a carboxyl group. The oxazoline derivative acts to crosslink the coating film by reacting the oxazoline group with the functional group contained in the component (c) in the drying process after the composition of the present invention is applied, to form a network structure. Is to have. The (h) oxazoline derivative is synthesized by a radical polymerization method of a copolymerizable oxazoline such as 2-isopropenyl-2-oxazoline and a vinyl resin having other copolymerizability. As a commercially available product, Epocros K manufactured by Nippon Shokubai Chemical Co., Ltd.
-1000, K-1020E, K-1030E, K-2
010E, K-2020E, K-2030E, WS-5
00 and the like.

The amount of the (h) oxazoline derivative used in the present invention is such that the equivalent ratio of the reactive functional group to the oxazoline group in the component (c) is usually 1: 0.1-5, preferably 1 :. 0.5-1.5, more preferably 1: 0.7
The amount is in the range of 1.2. In this case, if the oxazoline group is less than 0.1 equivalent with respect to 1 equivalent of the reactive functional group, the solvent resistance and damage resistance of the coating film tend to decrease, while it exceeds 5 equivalents. And the water resistance of the coating,
Transparency tends to decrease. The (h) oxazoline derivative can be blended in an appropriate step of preparing the coating composition used in the present invention, but in order to suppress the generation of coagulation during production and maintain the polymerization stability, (h) ) It is desirable to mix the entire amount of the oxazoline derivative after the preparation of the other components is completed.

Other Additives: The coating composition of the present invention may contain a resinous additive having no hydroxyl group and / or hydrolyzable group. Examples of the resinous additives include polyester resins, epoxy resins, acrylic resins, carboxyl group-containing aromatic vinyl resins such as styrene-maleic acid copolymers and urethane resins that are commonly used in paints. You can These resinous additives may be used alone or in admixture of two or more. The amount of the resinous additive used in the present invention is usually 50 parts by weight or less, preferably 30 parts by weight or less, based on 100 parts by weight of the total solid content of the composition of the present invention.

The coating composition of the present invention may contain an organic solvent for the purpose of improving film-forming property and wettability. Examples of the organic solvent include methyl alcohol, ethyl alcohol, n-propyl alcohol, i.
-Alcohols such as propyl alcohol, n-butyl alcohol, i-butyl alcohol, n-amyl alcohol, n-hexyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene Glycol mono-i-propyl ether,
Ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-i-
Examples thereof include propyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, tributoxymethyl phosphate and the like. These organic solvents may be used alone or in admixture of two or more.

Further, in the coating composition of the present invention, if necessary, a pigment, a thickener, a dispersant, a silane coupling agent, a titanium coupling agent, a leveling agent, a dye, a fungicide, a preservative, Other additives such as an anti-aging agent, an antioxidant, a pressure-sensitive adhesive, an antifogging agent, and a flame retardant can also be added.

Optional component: The coating composition of the present invention may further contain a nitrogen-containing compound, if necessary. Examples of the nitrogen-containing compound include N, N-dimethylacetamide, N, N-dimethylformamide, γ
-Byrolactone, N-methyl-2-pyrrolidone, hydrophilic nitrogen-containing organic solvents such as pyridine; thymine, glycine,
Nucleobases such as cytosine and guanine; hydrophilic nitrogen-containing polymers such as polyvinylpyrrolidone, polyacrylamide and polymethacrylamide, and copolymers obtained by copolymerizing these components. Among these, N,
N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, and polyvinylpyrrolidone are preferred. Further, by mixing the above-mentioned nitrogen-containing compound, in coating with a thin film, a more transparent and good coating film can be obtained, and a catalytic effect at the time of condensation with a functional group existing at the interface of the inorganic substrate is exhibited. To do. The proportion of the nitrogen-containing compound used is usually 70% by weight or less, preferably 50% by weight or less, based on the total amount of the solvent.

Substrates Examples of the substrates used for the coating member of the present invention include metals such as iron, aluminum, and stainless steel, cement, concrete, ALC, flexible boards, mortar, slate, gypsum, ceramics, inorganic ceramics such as bricks. Inorganic base materials such as base materials, polyolefin resins such as polyethylene and polypropylene, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polyamide resins, polycarbonate resins, polystyrene resins, polyvinyl alcohol, ethylene-vinyl acetate Organic resins such as polyvinyl alcohol resins such as saponified parts of polymers, polyacrylonitrile resins, polyvinyl chloride resins, polyvinyl acetal resins, polyvinyl butyral resins, fluorine resins, etc. A substrate (resin-based substrate) can be used.

Examples of the surface treatment for the inorganic base material include polishing, degreasing, plating treatment, chromate treatment, flame treatment and coupling treatment. Examples of the surface treatment for the plastic base material include: , Blast treatment, chemical treatment, degreasing, flame treatment, oxidation treatment, steam treatment, corona discharge treatment, ultraviolet irradiation treatment, plasma treatment, ion treatment, and the like. As the surface treatment for the inorganic ceramic base material, for example, , Polishing,
Examples of the surface treatment for the wooden base material include polishing, sealing, insect repellent treatment, and the like. Examples of the surface treatment for the paper base material include sealing. , Insect repellent treatment, and the like, and as the surface treatment for the deteriorated coating film,
For example, keren and the like can be mentioned.

As the method for forming the resin-based substrate, for example, one or more of the above resins are used,
A method in which the above resin is independently formed into a film using an inflation method, a T-die method, or another film forming method, or 2
A resin film is formed by a method of forming a multilayer coextrusion film by using two or more different resins, and further by a method of using two or more kinds of resins and mixing them before forming a film. It is possible to manufacture a sheet and further form a resin film or sheet formed by uniaxially or biaxially stretching using, for example, a tenter system or a tubular system. In the present invention, the thickness of the substrate film is preferably about 5 to 200 μm, more preferably about 10 to 50 μm. In the above, when forming the resin into a film, for example, the processability of the film, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness, releasability, flame retardancy, and antifungal properties. Characteristics, electrical characteristics,
Various plastic compounding agents and additives may be added for the purpose of improving and modifying the others. The amount of addition thereof can be arbitrarily added from a very small amount to several tens of% depending on the purpose. Further, in the above, as a general additive, for example, a lubricant, a crosslinking agent, an antioxidant, an ultraviolet absorber, a filler, a reinforcing agent, a reinforcing agent, an antistatic agent, a flame retardant, a flameproofing agent, a foaming agent, Antifungal agents, pigments, and the like can be used, and further, a modifying resin and the like can also be used.

In the present invention, the above-mentioned base material may be subjected to, for example, corona discharge treatment, ozone treatment, low-temperature plasma treatment using oxygen gas or nitrogen gas, if necessary,
Glow discharge treatment, oxidation treatment using chemicals, and other pretreatments can be optionally performed. The above surface pretreatment may be carried out in a separate step before forming a vapor deposition film of inorganic oxide, and, for example, in the case of surface treatment such as low temperature plasma treatment or glow discharge treatment, the above inorganic oxidation treatment is carried out. As a pretreatment for forming a vapor deposition film of a substance, the pretreatment can be performed by an in-line treatment, and in such a case, there is an advantage that the manufacturing cost can be reduced. The surface pretreatment is carried out as a method for improving the adhesion between the substrate film and the vapor deposition film of the inorganic oxide, but as a method for improving the above adhesion, other, for example, A primer coat agent layer, an undercoat agent layer, a vapor deposition anchor coat agent layer, or the like can be optionally formed in advance on the surface of the material film. As the coating agent layer for the above pretreatment, for example, a resin composition containing a polyester resin, a polyurethane resin, or the like as a main component of the vehicle can be used. Further, in the above, as a method for forming the coating agent layer, for example, a solvent type, an aqueous type, or an emulsion type coating agent is used, and a roll coating method, a gravure roll coating method, a kiss coating method, or another coating method is used. The coating can be performed as a post-process after the biaxial stretching treatment of the substrate film, or as an in-line treatment of the biaxial stretching treatment.

These base materials may be surface-treated in advance for the purpose of adjusting the base, improving the adhesion, sealing the porous base material, smoothing, patterning and the like. In the above, when the surface is composed of an inorganic compound, a hydroxyl group and / or a hydrolyzable group present on the inorganic compound form a chemical bond by co-condensing during the formation of a coating film, resulting in a stronger bond. It will be a mess and it is preferable.

Coating Member A coating member can be formed by forming one or more coating films containing the coating composition of the present invention and / or a cured coating film on the above-mentioned substrate. In the coating film of the present invention and / or the cured coating film, (b)
It contains a compound having a hydrolyzable and / or hydroxyl group-bonded silicon atom and an isocyanurate group and / or an isocyanate group, whereby the adhesion between the substrate and the coating layer is significantly improved. . In particular, the adhesiveness becomes excellent when wet with water.

In the above coating member, a coating composition for forming a coating film can be applied by a brush, roll coater, flow coater, centrifugal coater,
Using an ultrasonic coater, dip coating, spin coating, flow coating, spraying, screen process,
Examples include electrodeposition and vapor deposition.

The dry film thickness is 0.01 after one coating.
~ 20 μm, thickness is 0.02-40 μm by double coating
A coating film of a certain degree can be formed. Then, by drying at room temperature or by heating at a temperature of about 30 to 200 ° C. for about 1 to 60 minutes and drying, a coating film or a cured coating film can be formed on various substrates. it can.
The total film thickness of the coating member is a dry film thickness of usually 0.02 to 80 μm, preferably 0.05.
It is about 60 μm.

[0071]

The present invention will be described in more detail with reference to the following examples, but the invention is not limited to the following examples. In the examples, parts and% are based on weight unless otherwise specified. In addition, various measurements in the examples are as follows.

The weight average molecular weight and the number average molecular weight in terms of Mw polystyrene were measured by the gel permeation chromatography (GPC) method under the following conditions. A sample was prepared by dissolving 1 g of organopolysiloxane in 100 cc of tetrahydrofuran using tetrahydrofuran as a solvent. The standard polystyrene used was standard polystyrene manufactured by Pressure Chemicals, Inc., USA. The silyl group-containing vinyl polymer was prepared by dissolving 0.1 g of tetrahydrofuran in 100 cc of tetrahydrofuran. Apparatus; Waters high-performance gel permeation chromatogram (Model 150-C ALC / GPC) manufactured by US Waters Co., Ltd .; Showa Denko KK, SHODEX A-80
M, length 50 cm Measurement temperature; 40 ° C Flow rate; 1 cc / min

Initial Adhesion A peeling test using a tape was carried out and evaluated as follows. ◯: Not peeled at all Δ: Partially peeled off ×: Whole peeled off Initial hardness Based on pencil hardness according to JIS K5400.

The initial water resistance test piece was immersed in pure water at room temperature for 5 minutes, and then JIS
Using the pencil hardness according to K5400, the load was changed with a pencil having a hardness of H to confirm the load at which the coating film scratches did not occur. ◯: Load of 500 g or more Δ: Load of 200 g or more and less than 500 g ×: Load of less than 200 g Chemical resistance 2 cc of isopropyl alcohol was dropped on the coating film, wiped off with a cloth after 5 minutes, and the state of the coating film was visually observed. ◯: No change Δ: Drop marks remain, but there is no change in gloss or adhesion X: Decrease in gloss or dissolution of coating film

Weather resistance According to JIS K5400, an irradiation test was carried out with a sunshine weather meter for 3,000 hours, and the appearance (cracks, peeling, etc.) of the coating film was visually observed. ⊚: Gloss retention is 90% or more ◯: Gloss retention is 80 to less than 90% Δ: Gloss retention is 50% or more and less than 80% ×: Gloss retention is less than 50% A water-resistant inorganic base material is used The test piece was immersed in warm water at 60 ° C. for 14 days, and then the state of the coating film was visually observed. ◯: No cracks △: Cracks observed under microscope ×: Cracks observed under visual observation

Reference Example 1 <Synthesis of silyl group-containing vinyl polymer> 40 parts of methyl methacrylate and 2-ethylhexyl methacrylate 2 were placed in a reactor equipped with a stirrer and a reflux condenser.
3 parts, 10 parts of 2-hydroxyethyl methacrylate,
γ-methacryloxypropyltrimethoxysilane 15
Part, 4- (meth) acryloyloxy-2,2,6
After 6 parts of 6, -tetramethylpiperidine, 6 parts of diacetone acrylamide, 1 part of 1,1,1-trimethylamine methacrylimide and 135 parts of i-propyl alcohol were added and mixed, the mixture was heated to 80 ° C. with stirring, A solution of 4 parts of azobisisovaleronylolyl dissolved in 15 parts of methyl ethyl ketone was added dropwise to this mixture over 30 minutes, and then the mixture was reacted at 80 ° C. for 5 hours to give a solid content concentration of 40%.
% Silyl group-containing vinyl polymer (hereinafter referred to as "(c-
1) ”).

Example 1 In a reactor equipped with a stirrer and a reflux condenser, 65 parts of methyltrimethoxysilane, 35 parts of dimethyldimethoxysilane,
50 parts of vinyl polymer (c-1) obtained in Reference Example 1 (solid content: 20 parts), tris (ethylacetoacetate)
5 parts of aluminum, 15 parts of ion-exchanged water, 15 parts of methyl ethyl ketone, and 25 parts of i-propyl alcohol were added, and the mixture was reacted at 60 ° C. for 5.5 hours. Next, this reaction product was cooled to room temperature to obtain a solution of the specific polymer having a solid content concentration of 40%. When the Mw of this specific polymer was measured, it was 20,000. 1,3,5-N-tris (trimethoxysilylpropyl) isocyanurate 2 was added to 100 parts of this specific polymer solution as a post-addition component.
Parts, and 1 part of N-β- (aminoethyl) γ-aminopropylmethyldimethoxysilane are added to the coating composition (a) of the present invention (hereinafter referred to as "composition (a)").
Got

Example 2 The coating composition (b) of the present invention was used in the same manner as in Example 1 except that N-tris (trimethoxysilylpropyl) isocyanurate was replaced by γ-isocyanatopropyltrimethoxysilane. (Hereinafter, referred to as “composition (b)”).

Examples 3 to 6 The composition (a) or the composition (b) was applied to various base materials so as to have a dry film thickness of 30 μm to obtain coating members. After that, it is dried at 80 ° C for 5 minutes, and then at room temperature for 1 minute.
The sample was left to stand for a day and evaluated for initial hardness, initial adhesion and initial water resistance. Furthermore, chemical resistance, weather resistance, and hot water resistance were evaluated. The results are shown in Table 1.

[0080]

[Table 1]

Example 7 To a reactor equipped with a reflux condenser and a stirrer, 100 parts of tetra-i-propoxytitanium and 70 parts of acetylacetone were added and stirred at 60 ° C for 30 minutes to obtain a titanium chelate compound. 2 parts of this reaction product, 16.8 parts of n-propyl alcohol, and 11.2 parts of water were mixed and the mixture was mixed at 55 ° C. for 4 hours.
The hydrolyzed solution was mixed at 40 ° C. and then stirred for 2 hours. This reaction mixture and an ethylene / vinyl alcohol copolymer [Soarnol D290 manufactured by Nippon Synthetic Chemical Industry Co., Ltd.]
8, saponification degree; 98% or more, ethylene content; 29 mol%, melt flow index; 8% / 10 minutes] 5%
Water / n-propyl alcohol (water / n-propyl alcohol weight ratio = 40/60) 100 parts, 1,3,5-N-
0.5 part of tris (trimethoxysilylpropyl) isocyanurate was mixed to obtain the coating composition (c) of the present invention (hereinafter, "composition (c)".

Example 8 According to Example 7, except that 0.5 part of γ-glycidoxypropyltrimethoxysilane was newly added, the coating composition (d) of the present invention (hereinafter, " Composition (d) ") was obtained.

Examples 9 to 12 The composition (c) or the composition (d) was applied to various base materials to give a dry film thickness of 0.5 μm to obtain coating members. Then, after drying at 120 ° C. for 1 minute, the initial adhesion evaluation and the initial water resistance evaluation were performed. Furthermore, chemical resistance, weather resistance, and hot water resistance were evaluated. The results are shown in Table 2.

[0084]

[Table 2]

[0085]

According to the present invention, by incorporating a specific isocyanurate group- and / or isocyanate group-containing silane compound into the coating film, the adhesion between the substrate and the coating film is excellent, and the transparency and weather resistance are excellent. Coating material with excellent hardness, high resistance, stain resistance, heat resistance, water resistance, seawater resistance, organic chemical resistance, acid resistance, alkali resistance, corrosion resistance, abrasion resistance, weather resistance, moisture resistance, etc. can get.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09D 183/04 C09D 183/04 183/08 183/08 // C08G 18/77 C08G 18/77 Z F term (Reference) 4J034 CE01 DM11 DP18 HA04 HB16 HC01 JA06 RA07 4J038 CC022 CE022 CF022 CG002 CG022 CG082 CG162 CG172 CH122 CH172 CH192 CH202 CL002 DB002 DD002 DG002 DG262 DG292 DL021 DL031 DL051 DL071 DL111 DM001 GA25 JA35 GA03 GA15 GA07 GA07 GA09 GA09 GA07 GA09 KA06 MA08 PC02 PC04 PC08

Claims (6)

[Claims] (A) The following general formula (1) R ¹ _m M (OR ² ) _n (1) (wherein, M is a metal atom, R ¹ is the same or different, and has 1 carbon atom). ~ 8 organic groups, R ² are the same or different, and have 1 to 5 carbon atoms.
An alkyl group, an acyl group having 1 to 6 carbon atoms or a phenyl group, m and n are each an integer of 0 or more, and m + n is a valence of M), a metal alcoholate or a metal thereof. Hydrolyzate of alcoholate, condensate of metal alcoholate, chelate compound of metal alcoholate, hydrolyzate of metal chelate compound, condensate of metal chelate compound, metal acylate, hydrolyzate of metal acylate And at least one selected from the group of condensates of the metal acylate, and (b) a compound having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group and an isocyanurate group and / or an isocyanate group. Coating composition. 2. The coating composition according to claim 1, further comprising (c) a (co) polymer having a hydroxyl group and / or a hydrolyzable group. 3. The coating composition according to claim 2, wherein the component (c) is a polyvinyl alcohol resin and / or an acrylic silicone resin. 4. Further comprising (d) a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group, a compound containing a primary and / or secondary amino group, and / or an epoxy group. A compound comprising
~ The coating composition according to any one of 3 to 3. 5. A coating member having a coating film formed by coating one or more layers of the coating composition according to any one of claims 1 to 4 on a substrate. 6. The coating member according to claim 5, wherein the surface of the base material is composed of an inorganic compound.