JP2001150599A - Laminated body and coating composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a laminated body (a paint film) which is excellent in adhesion to a base material or the like, excellent in transparency, weather resistance, polution resistance, heat resistance, water resistance, corrosion resistance in sea water, organic chemicals-proof, acid resistance, alkali resistance, corrosion resistance, wear resistance, weather resistance, moisture resistance or the like, and high in hardeness. SOLUTION: A laminated body is obtained wherein at least one layer of paint films containing the constituent (I) and at least one layer of paint films containing the constituent (II) are provided, or at least one layer of paint films containing both the constituents (I) and (II) are provided. (I) Constituent; a polymer containing (a) at least one kind selected from a group of organosilane represented by (R1)n Si(OR2)4-n [however, excepting the following constituent (II)], hydrolyzate of the organosilane and a condensate of the organosilane, and (b) a silyl group having a silicon atom bonded with a hydrolyzate group and/or a hydroxyl group. (II) Constituent; a compound provided wherein a silicon atom combined with hydrolyzate and/or hydrozyl group, and class 1 and/or class 2 amine are contained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate and a coating composition for forming the laminate, and more particularly, to a material having excellent storage stability, such as stainless steel, aluminum, ceramics, plastics, inorganic ceramic substrates, and fabrics. The present invention relates to a laminate (coating film) having excellent performance formed on the surface of a laminate, and a coating composition suitable for forming the laminate.

[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 need for a coating composition that is excellent in weather resistance, moisture resistance, adhesion, and the like and that can form a coating film having high hardness. As a coating composition which satisfies a part of such requirements, a composition comprising a dispersion of a partially condensate of an organosilane and colloidal silica and a silicone-modified acrylic resin (JP-A-60-135465); A composition comprising a condensate, a chelate compound of a zirconium alkoxide and a hydrolyzable silyl group-containing vinyl resin (JP-A-64-1769);
A composition comprising a condensate of an organosilane and colloidal alumina and a hydrolyzable silyl group-containing vinyl resin (US Pat. No. 4,904,721), or a hydrolyzate of an organosilane and a metal chelate compound; A composition comprising a hydrolyzable or partially condensable silyl group-containing vinyl resin has been proposed.

[0003] However, Japanese Patent Application Laid-Open No.
Even when a coating film is formed using the coating composition described in Japanese Patent No. 65904 and U.S. Pat. No. 4,904,721, the gloss of the coating film is reduced by long-term ultraviolet irradiation. Further, the composition described in JP-A-64-1769 is obtained by adding a condensate of an organosilane, a chelate compound of a zirconium alkoxide and a hydrolyzable silyl group-containing vinyl resin to a hydrophilic organic solvent. However, storage stability is not sufficient, and if 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, high-temperature or long-time heat treatment is required, and there is a problem in practicality. When this heat treatment is performed at low temperature for a short time, the resulting coating film (laminate) generally has poor adhesion to the base material and the undercoat layer, or tends to have insufficient hardness. . In particular, when foreign matter such as moisture adheres to the coating film immediately after the formation of the coating film, there is a problem that the adhesion between the overcoat layer and the undercoat layer is significantly impaired.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned conventional technical problems, and has a curability and an adhesive property by containing a specific aminosilane compound in a laminate (coating film). Immediately develops transparency, weather resistance, stain resistance, heat resistance, water resistance, seawater resistance, organic chemical resistance, acid resistance, alkali resistance, corrosion resistance, abrasion resistance, weather resistance, and moisture resistance An object of the present invention is to provide a laminate (coating film) to be formed and a coating composition having excellent storage stability capable of forming the laminate.

[0005]

According to the present invention, there is provided one or more coating films containing the following component (I) and one or more coating films containing the following component (II), or The present invention relates to a laminate having at least one coating film containing both the components (I) and (II). (I) component; (a) the following general formula (1) (R ¹ ) _n Si (OR ² ) _4-n (1) (wherein, when two R ¹ are present, they are the same. Or differently, a monovalent organic group having 1 to 8 carbon atoms, R ² is the same or different and represents an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 6 carbon atoms, and n is 0 to 2 At least one selected from the group consisting of an organosilane represented by the following formula (excluding the component (II) below), a hydrolyzate of the organosilane and a condensate of the organosilane (hereinafter referred to as "( a) component) and (b) a vinyl polymer containing a silyl group having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group (hereinafter referred to as "(b) a silyl group-containing vinyl polymer"). Also called). Component (II): a compound containing a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group and a primary and / or secondary amino group (hereinafter also referred to as “(II) aminosilane compound”). Here, it is preferable that the laminate has one or more coating films containing the above-mentioned components (I) and (II) as a top-coating film. In addition, the laminate may be used as an undercoating film as the component (II), the component (III), the component (a), the component (b), an alkyd resin, an aminoalkyd resin, an epoxy resin, a polyester resin, and an acrylic resin. ,
A resin having at least one coating film containing at least one selected from the group consisting of a urethane resin, a fluorine resin and an acrylic silicone resin is preferable. Next, the present invention provides an overcoating coating composition (hereinafter, referred to as “overcoating composition”) comprising an aqueous dispersion obtained by dispersing the following components (I) and (II) in an aqueous medium. Composition "). (I) component; (a) the following general formula (1) (R ¹ ) _n Si (OR ² ) _4-n (1) (wherein, when two R ¹ are present, they are the same. Or differently, a monovalent organic group having 1 to 8 carbon atoms, R ² is the same or different and represents an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 6 carbon atoms, and n is 0 to 2 (Excluding the following component (II)), at least one selected from the group consisting of a hydrolyzate of the organosilane and a condensate of the organosilane, and (b A) a polymer containing a silyl group having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group. Component (II): a compound comprising a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group, and a primary and / or secondary amino group. Next, the present invention provides an undercoating coating composition (hereinafter referred to as "undercoating") comprising an aqueous dispersion in which the following components (II) and (III) are dispersed in an aqueous medium. The composition is also referred to as “composition for use”). Component (II): a compound comprising a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group, and a primary and / or secondary amino group. (III) component; at least one selected from the group consisting of the above component (a), the above component (b), an alkyd resin, an amino alkyd resin, an epoxy resin, a polyester resin, an acrylic resin, a urethane resin, a fluororesin, and an acrylic silicone resin. seed.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in the order of the components (I) to (III), the coating composition for top coating, the coating composition for undercoating, the substrate, and the laminate which constitute the laminate of the present invention. explain.

Component (I) The component (I) contains the above component (a) and (b) a vinyl polymer having a silyl group. Here, "containing (a) component and (b) a silyl group-containing vinyl polymer" means that these two components are present separately from each other, or that both components are chemically bonded to each other. It means that they are bonded, but it is preferable that they are chemically bonded. In addition,
In the component (I), when the component (a) and the component (b) are chemically bonded to form a polymer, such a polymer is hereinafter also referred to as a “specific polymer”.

Component (a): Component (a) is an organosilane represented by the above general formula (1) (hereinafter also referred to as "organosilane (1)" [excluding the following (II) aminosilane compound]), It is a hydrolyzate of the organosilane and / or a condensate thereof (hereinafter, “hydrolyzate and / or condensate thereof” is also referred to as “hydrolysis condensate”).
In the general formula (1), examples of the organic group having 1 to 8 carbon atoms for R ¹ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, and s.
ec-butyl group, t-butyl group, n-pentyl group, n-
Alkyl groups such as hexyl group, n-heptyl group and n-octyl group; acyl groups such as acetyl group, propionyl group and butyryl group; γ-chloropropyl group, γ-bromopropyl group, 3,3,3-trifluoro Propyl group, γ-glycidoxypropyl group, γ- (meth) acryloxypropyl group, γ-mercaptopropyl group, 2- (3,4-epoxycyclohexyl) ethyl group, vinyl group, phenyl group and the like. Examples of the alkyl group having 1 to 5 carbon atoms for R ² include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, and a t-group. -Butyl group, n-pentyl group and the like, and examples of the acyl group having 1 to 6 carbon atoms include an acetyl group, a propionyl group and a butyryl group.

Specific examples of such organosilane (1) include 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-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyl Triethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane, 3,4-epoxycyclohexylethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, ureidopropyltrimethoxy Silane, mercaptopropyltrimethoxysilane, ether-modified alkyltrimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxy Silane, diethyl diethoxy silane, di -n- propyl dimethoxysilane, di -n-
Alkoxysilanes such as propyldiethoxysilane, di-i-propyldimethoxysilane, di-i-propyldiethoxysilane, divinyldimethoxysilane, divinyldiethoxysilane, diphenyldimethoxysilane, and diphenyldiethoxysilane; tetraacetoxysilane;
Methyltriacetoxysilane, ethyltriacetoxysilane, dimethyldiacetoxysilane, acyloxysilanes such as diethyldiacetoxysilane and the like, preferably methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane is there.

These organosilanes (1) can be used alone or in combination of two or more. In the present invention, the organosilane (1) is used as it is or as a hydrolyzate and / or condensate.
Here, the hydrolyzate of the organosilane (1) does not need to have all of the OR ² groups contained in the organosilane (1) hydrolyzed, and only one hydrolyzate is hydrolyzed. May be hydrolyzed, or a mixture thereof. The condensate of the organosilane (1) is formed by condensing a silanol group of a hydrolyzate of the organosilane (1) to form a Si—O—Si bond. It is not necessary that they are all condensed, and the concept encompasses those in which a small portion of silanol groups are condensed, and mixtures of those having different degrees of condensation. In this case, when producing the component (I), the organosilane (1) and the silyl group-containing vinyl polymer (b) described later are formed while forming a polyorganosiloxane chain by a polycondensation reaction of the organosilane (1). And a polyorganosiloxane chain can be chemically bonded with the silyl group-containing vinyl polymer. The polystyrene-equivalent weight average molecular weight (hereinafter also referred to as “Mw”) of the hydrolyzed condensate of organosilane (1) is preferably from 500 to 100,000, more preferably from 1,000 to 50,000.

(B) a silyl group-containing vinyl polymer;
(B) The silyl group-containing vinyl polymer includes a silyl group having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group at a terminal or a side chain (hereinafter referred to as a “specific silyl group”). ") In one molecule of the polymer, more preferably at least one, and more preferably two or more hydrophilic functional groups. Also, (h) described later.
When a coating composition having a component is obtained, at least one reactive functional group such as a carboxyl group, a thiol group, a hydroxyl group, an epoxy group, an amino group, or a sulfine group is used.
And preferably two or more polymers. Many of the specific silyl groups are represented by the following general formula (2)
It is represented by

[0012]

(Wherein X is a halogen atom, an alkoxy group, an acyloxy group, a phenoxy group, a thioalkoxy group,
A hydrolyzable group such as an amino group or an acetoxy group or a hydroxyl group, 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 m is an integer of 1 to 3. )

[0014] One or more of the above-mentioned specific silyl groups may be present in the silyl group-containing vinyl polymer. Examples of the hydrophilic functional group in the silyl group-containing vinyl polymer include a carboxyl group, a carboxylic anhydride group, a hydroxyl group, an amino group, an amide group, an amine imide group, and a glycidyl group. One or more of these hydrophilic functional groups can be present in the silyl group vinyl polymer. For example, any two or more of a carboxyl group, a hydroxyl group, an amide group, an amine imide group and a glycidyl group coexist. Is preferred.

The (b) 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”). (B) adding a hydrosilane compound having a specific silyl group to the carbon-carbon double bond, and It can be produced by a method of copolymerizing with a vinyl monomer having the same.

The functional unsaturated polymer used in the above method (a) can be produced, for example, as follows. That is, after (a-1) a vinyl monomer having a hydrophilic functional group is (co) polymerized with another vinyl monomer in some cases 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 replaced with a functional group capable of reacting with the complementary functional group (α) (hereinafter “complementary functional group (α)”). β) ”)
And a unsaturated compound having a carbon-carbon double bond, a functional unsaturated polymer having a carbon-carbon double bond in a 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 or the like) is used, or a radical polymerization initiator and a chain transfer agent are used. When a compound having a complementary functional group (α) (for example, 4,4-azobis-4-cyanovaleric acid and dithioglycolic acid) is used, and a vinyl monomer having a hydrophilic functional group is used, (Polymerization) with other vinyl-based monomers by polymerization to form 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. ) After the synthesis of the polymer, the complementary functional group (α) in the precursor (co) polymer is
By reacting an unsaturated compound having a complementary functional group (β) with a carbon-carbon double bond, a functional unsaturated polymer having a carbon-carbon double bond at one end or both ends of a polymer molecular chain. Coalescence can be manufactured. Further, (A-3) a 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, and a carboxylic 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 anhydride group and an amino group, Examples include a ring-opening addition reaction between an epoxy group and an amino group, and a urethanation reaction between a hydroxyl group and an isocyanate group.

Examples of the vinyl monomer having a hydrophilic functional group include (meth) acrylic acid, crotonic acid,
Carboxyl group-containing unsaturated such as cinnamic acid, maleic acid, fumaric acid, itaconic acid, monomethyl maleate, monoethyl maleate, monomethyl itaconate, monoethyl itaconate, mono-2- (meth) acryloyloxyethyl hexahydrophthalate Compounds; unsaturated carboxylic 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
Hydroxyl-containing vinyl monomers such as -hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ether, and 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-containing vinyl monomers such as aminoethyl vinyl ether, N, N-dimethylamino (meth) acrylamide, N, N-diethylamino (meth) acrylamide; acrylamide, diacetone acrylamide, maleic diamide, fumaric diamide, itacone Amide group-containing vinyl monomers such as acid diamide, α-ethylacrylamide and N-butoxymethyl (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- (2'-hydroxy Amine-containing vinyl monomers such as -2'-phenoxypropyl) amine (meth) acrylimide; glycidyl-containing vinyl monomers such as allyl glycidyl ether, glycidyl (meth) acrylate and methyl glycidyl (meth) acrylate An epoxy group-containing vinyl monomer such as epoxidized cyclohexyl (meth) acrylate; and a vinyl ester monomer such as vinyl acetate, vinyl propionate, and vinyl versatate. These vinyl monomers can be used alone or in combination of two or more.

Among the above-mentioned vinyl monomers having a hydrophilic functional group, in the group of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, (meth) acrylic acid is particularly preferred. Is particularly preferably 2-hydroxyethyl (meth) acrylate, and in the group of the vinyl monomer containing an amino group and the vinyl monomer containing an amine imide, 1,1-dimethyl-1- (2-hydroxypropyl) is particularly preferable. 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 (Meth) acrylic amide imide having a hydroxyl group of

Other vinyl monomers to be copolymerized with a vinyl monomer having a hydrophilic functional group include, for example, methyl (meth) acrylate, ethyl (meth) acrylate,
N-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate,
(Meth) acrylates 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 pivalinaldehyde, 3
-(Meth) acrylamidomethyl-anisaldehyde,
β- (meth) acryloxy-α, α-dimethylpropanal [ie, 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), 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 monomers having a carbonyl group, such as hydroxybutyl (meth) acrylate-acetyl acetate and butanediol-1,4- (meth) acrylate-acetyl acetate; 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
UV-stable piperidine unsaturated monomers such as 6, -pentamethylpiperidine; (meth) acrylonitrile, styrene, α-methylstyrene, vinyl chloride, vinyl acetate, vinyl propionate and the like. These vinyl monomers can be used alone or in combination of two or more. Complementary unsaturated group (β) and carbon-
Examples of the unsaturated compound having a carbon double bond include unsaturated carboxylic acids, unsaturated carboxylic anhydrides, and hydroxyl group-containing vinyl monomers among the above-mentioned vinyl monomers having a hydrophilic functional group. In addition to an amino group-containing vinyl monomer, for example, an epoxy group-containing unsaturated compound such as glycidyl (meth) acrylate and allyl glycidyl ether, and the above-mentioned hydroxyl group-containing vinyl monomer and a diisocyanate compound are reacted in equimolar amounts. And an isocyanate group-containing unsaturated compound.

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 and triethoxysilane; methyldiacetoxysilane;
Acyloxysilanes such as phenyldiacetoxysilane and triacetoxysilane; aminoxysilanes such as dimethylaminoxysilane, methyldiaminooxysilane and triaminoxysilane; phenoxysilanes such as methyldiphenoxysilane and triphenoxysilane ;
Thioalkoxysilanes such as methyldi (thiomethoxy) silane and tri (thiomethoxy) silane; and aminosilanes such as methyldiaminosilane and triaminosilane. These hydrosilane compounds can be used alone or in combination of two or more.
Next, the vinyl monomer having a specific silyl group used in the method (b) is represented by the following general formula (3).

[0021] [Wherein, X, R ³ and m have the same meanings as in formula (2), respectively, and R ⁴ represents an organic group having a polymerizable carbon-carbon double bond. ]

Specific examples of such a vinyl monomer having a specific silyl group include CH ₂ ＣＨCHSi (CH ₃ )
(OCH ₃ ) ₂ , CH ₂ ＣＨCHSi (OCH ₃ ) ₃ , C
H ₂ ＣＨCHSi (CH ₃ ) Cl ₂ , CH ₂ ＣＨCHSiC
l ₃ , CH ₂ ＣＨCHCOO (CH ₂ ) ₂ Si (CH ₃ )
(OCH ₃ ) ₂ , CH ₂ ＣＨCHCOO (CH ₂ ) ₂ Si
(OCH ₃ ) ₃ , CH ₂ ＣＨCHCOO (CH ₂ ) ₃ Si
(CH ₃ ) (OCH ₃ ) ₂ , CH ₂ ＣＨCHCOO (CH
₂ ) ₃ Si (OCH ₃ ) ₃ , CH ₂ ＣＨCHCOO (CH
₂ ) ₂ Si (CH ₃ ) Cl ₂ , CH ₂ ＣＨCHCOO (C
H ₂ ) ₂ SiCl ₃ , CH ₂ ＣＨCHCOO (CH ₂ ) ₃
Si (CH ₃ ) Cl ₂ , CH ₂ ＣＨCHCOO (CH ₂ )
₃ SiCl ₃ , CH ₂ ＣC (CH ₃ ) COO (CH ₂ )
₂ Si (CH ₃ ) (OCH ₃ ) ₂ , CH ₂ ＣC (C
H ₃ ) COO (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , CH ₂
ＣC (CH ₃ ) COO (CH ₂ ) ₃ Si (CH ₃ ) (O
CH ₃ ) ₂ , CH ₂ ＣC (CH ₃ ) COO (CH ₂ ) ₃
Si (OCH ₃ ) ₃ , CH ₂ ＣC (CH ₃ ) COO (C
H ₂ ) ₂ Si (CH ₃ ) Cl ₂ , CH ₂ ＣC (CH ₃ )
COO (CH ₂ ) ₂ SiCl ₃ , CH ₂ ＣC (CH ₃ )
COO (CH ₂ ) ₃ Si (CH ₃ ) Cl ₂ , CH ₂ ＣC
(CH ₃ ) COO (CH ₂ ) ₃ SiCl ₃ ,

[0023]

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And the like. These vinyl monomers having a specific silyl group can be used alone or in combination of two or more. Examples of the vinyl monomer having a hydrophilic functional group used in the method (b) include, for example, the same vinyl monomer having a hydrophilic functional group exemplified in the method (a) above. One or more can be used. Further, in the method (b), one or more other vinyl monomers exemplified for the method (a) may be copolymerized.

The polystyrene-equivalent number average molecular weight (hereinafter also referred to as “Mn”) of the silyl group-containing vinyl polymer (b) obtained as described above is preferably from 2,000 to 2,000.
100,000, more preferably 4,000 to 50,
000. In the present invention, the silyl group-containing vinyl polymer (b) may be used alone or in combination of two or more.

The amount of the silyl group-containing vinyl polymer (b) used in the component (I) is usually 2 parts by weight based on 100 parts by weight of the organosilane (1) (complete hydrolyzed condensate).
９００900 parts by weight, preferably 10-400 parts by weight, more preferably 20-200 parts by weight. In this case, if the amount of the silyl group-containing vinyl polymer used is less than 2 parts by weight, the alkali resistance of the coating film formed from the aqueous dispersion tends to decrease. Tends to decrease in weather resistance. The completely hydrolyzed condensate of organosilane (1) is defined as a product in which the R ² O— group of organosilane (1) is hydrolyzed 100% to form a SiOH group, and further completely condensed to form a siloxane structure. Say.

The component (I) is preferably a component in which the component (a) and the (b) vinyl polymer containing a silyl group, preferably a specific polymer composed of both, are dispersed in an aqueous medium. . In this case, the specific polymer is, for example, dispersed in the form of particles or an aqueous sol, and the average particle diameter of the specific polymer in the form of a particle is usually 0.001 to 100 μm, preferably 0.001 to 10 μm. It is. The aqueous medium in the aqueous dispersion essentially consists of water, but may contain an organic solvent such as an alcohol up to about several weight% in some cases.

In the above aqueous dispersion, the particularly preferable content of the vinyl monomer having a hydrophilic functional group in the silyl group-containing vinyl polymer (b) varies depending on the type of the vinyl monomer. That is, the total content of the unsaturated carboxylic acid and / or the unsaturated carboxylic anhydride is particularly preferably 0.5 to 10% by weight, and the content of the hydroxyl group-containing vinyl monomer is particularly preferably 5 to 30%.
% By weight, and the total content of the amino group-containing vinyl monomer and / or the amine imide group-containing vinyl monomer is particularly preferably 0.03% by weight.
5 to 3% by weight is preferred. In the present invention, by setting the content of the vinyl monomer having a hydrophilic functional group in the above range, the storage stability of the obtained aqueous dispersion becomes particularly excellent. Further, in the present invention, it is preferable to use any two or more of the above-mentioned vinyl monomers in combination, and in particular, to use one or more of the above-mentioned and each of the above-mentioned vinyl monomers in combination. It is preferred to use.

The aqueous dispersion used in the present invention is preferably prepared by mixing (c) an organosilane (1) and (b) a silyl group-containing vinyl polymer in the presence of (c) an organometallic compound and water described below. After hydrolysis and / or condensation in an organic solvent, the reaction solution is dispersed in an aqueous medium, and then the organic solvent is removed. In the above method (c), the amount of water present at the time of hydrolysis and / or condensation depends on the amount of the organosilane (1) 1
It is usually about 0.5 to 3.0 mol, preferably about 0.7 to 2.0 mol, per mol. When the reaction product is dispersed in the aqueous medium in the method (c), an emulsifier, a pH adjuster, and the like can be used. Examples of the emulsifier include anionic surfactants such as alkyl sulfates, alkylaryl sulfates, alkyl phosphates, and fatty acid salts; and cationic surfactants such as alkyl amine salts and alkyl quaternary amine salts. Nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, and block type polyethers; amphoteric surfactants such as carboxylic acid type (eg, amino acid type, betaine type) and sulfonic acid type; Any of these can be used. These emulsifiers can be used alone or in combination of two or more. As the organic solvent used in the method (c), for example, alcohols, aromatic hydrocarbons, ethers, ketones, esters and the like are suitable. Some of these organic solvents can be removed before dispersing the reaction solution in an aqueous medium. Regarding the reaction conditions at the time of hydrolysis and / or condensation in the above method (c), the temperature is usually 20 to 70 ° C, and the reaction time is usually 1 to 8 hours.

In the above method (c), when (b) the silyl group-containing vinyl polymer has an acidic group such as a carboxyl group or a carboxylic anhydride group, hydrolysis and / or
Alternatively, it is preferable to dissociate the carboxyl group by adding at least one basic compound after the condensation. Thereby, the emulsification dispersibility of the specific polymer can be improved.

Examples of the basic compound include amines such as ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethanolamine, diethanolamine, and dimethylaminoethanol; and alkali metal hydroxides such as sodium hydroxide and sodium hydroxide. Examples of the acidic compound include inorganic acids such as hydrochloric acid, phosphoric acid, sulfuric acid, and nitric acid; formic acid, acetic acid, propionic acid,
Organic acids such as lactic acid, oxalic acid, citric acid, adipic acid, (meth) acrylic acid, maleic acid, fumaric acid, and itaconic acid. The pH value after emulsification and dispersion is usually 6 to
10, preferably 6.5 to 9.

Component (II) The component (II) is an aminosilane compound containing a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group, and a primary and / or secondary amino group. By using the component (II), the adhesiveness and curability between the substrate and the coating film are improved. This (II) aminosilane compound is incorporated into the top coating composition or the undercoat coating composition of the present invention, and contributes to improving the adhesiveness to a substrate and other coating films. Alternatively, by providing a layer in which an aminosilane compound is applied and cured between the overcoat layer and the undercoat layer, the adhesion between the overcoat layer and the undercoat layer is improved.

As such an aminosilane compound (II), for example, a compound represented by the following general formula (4) can be mentioned. (Wherein, X represents a group containing one or more monovalent or divalent amino groups and an alkyl group and / or a phenyl group, and R ¹ is the same or different when two are present,
Represents a monovalent organic group having 1 to 8 carbon atoms, wherein R ² is the same or different and has an alkyl group having 1 to 5 carbon atoms or 1 to 5 carbon atoms
6 represents an acyl group, a is an integer of 1 or 2,
Is an integer of 0 to 2, c is an integer of 1 to 3, provided that a + b + c = 4. )

Specific examples of such (II) aminosilane compounds include aminopropyltrimethoxysilane, aminopropyltriethoxysilane, aminopropylmethyldimethoxysilane, aminopropylmethyldiethoxysilane, 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-aminopropyl Triethoxysilane, 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] Phenethyltrimethoxysilane, N-[(3-trimethoxysilyl) propyl] diethylenetriamine, N-[(3-trimethoxysilyl)
Propyl] triethylenetetramine, N-3-trimethoxysilylpropyl-m-phenylenediamine and the like.

Component (III) As the component (III), besides the above-mentioned component (a) and the above-mentioned (b) silyl group-containing vinyl polymer, alkyd resins and aminoalkyd resins which are usually used as primers,
Solvent-based resins such as epoxy resin, polyester, acrylic resin, urethane resin, fluorine resin, and acrylic silicone resin can also be used, but among them, acrylic silicone resin emulsion, acrylic resin emulsion, epoxy resin emulsion, polyurethane emulsion,
An aqueous emulsion such as a polyester emulsion can be mentioned as a particularly preferred one. These are 1
Species can be used alone or in combination of two or more. Further, it can be cured with (F) a curing accelerator described later, (g) a polyfunctional hydrazine derivative, (h) an oxazoline derivative, or the like.

Topcoat Coating Composition The topcoat coating composition of the present invention is an aqueous dispersion obtained by dispersing a specific polymer containing the above components (I) and (II) in an aqueous medium. It contains. The mixing ratio of the component (I) and the component (II) in the overcoating composition of the present invention is such that the amount of the aminosilane compound (II) used is 100 wt. Parts, usually 0.1 to 50
Parts by weight, preferably 0.5 to 40 parts by weight. If the amount is less than 0.1 part by weight, the adhesion of the obtained coating film to other coating films such as a base material and an undercoat layer is poor. Sexual decline occurs.

The total solid content of the overcoating composition of the present invention is appropriately adjusted depending on the purpose of use. When no pigment is contained, the total solid content is preferably 50% by weight or less.
When a pigment is contained, it is preferably at most 60% by weight.
For example, when the purpose is to impregnate the base material for forming a thin film, it is usually 5 to 30% by weight, and when it is used for the purpose of thick film and coloring, it is usually 20 to 60% by weight, preferably, , 30 to 50% by weight. If the total solid content of the overcoating coating composition exceeds 60% by weight, storage stability may be reduced.

The overcoating composition of the present invention may contain the following components (c) to (h). Also,
In the laminate of the present invention, when the overcoat layer is a coating film obtained from a solvent-based coating composition having the component (I), the solvent-based coating composition includes the following (c) to (f): Components can be blended.

(C) an organometallic compound; (c) the organometallic compound promotes a hydrolysis and / or condensation reaction between the component (a) and the (b) silyl group-containing vinyl polymer,
It is considered that the compound promotes the formation of a co-condensate of both components. Examples of (c) the organometallic compound (C) include the general formula Zr (OR ⁵ ) _p (R ⁶ COCHCOR ⁷ ) _q , Ti (OR ⁵ ) _r (R ⁶ COCHCOR ⁷ ) _s , or Al ( OR ⁵ ) _t (R ⁶ COCHCOR ⁷ ) _u or a partial hydrolyzate of these compounds.

(C) R ⁵ and R ⁶ in the organometallic compound are each independently a monovalent hydrocarbon 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-pentyl group, n-hexyl group, cyclohexyl group, phenyl group, etc., and R ⁷ has the same carbon number as R ⁵ and R ^6. To 6 monovalent hydrocarbon groups, and alkoxy groups having 1 to 16 carbon atoms, specifically, methoxy, ethoxy, n-propoxy, i-propoxy, n-
Butoxy, sec-butoxy, t-butoxy, lauryloxy, stearyloxy and the like. P, q, r and s are numbers from 0 to 4, and t and u are 0
(P + q), (r + s) and (t +
u) is the valence of zirconium, titanium and aluminum, respectively.

Specific examples of the organometallic compound (c) include zirconium tri-n-butoxyethylacetoacetate, zirconium di-n-butoxybis (ethylacetoacetate), and zirconium n-butoxytris (ethyl). Zirconium compounds such as acetoacetate) zirconium, tetrakis (n-propylacetoacetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium and tetrabutoxyzirconium;
Di-i-propoxy bis (ethyl acetoacetate)
Titanium compounds such as titanium, di-i-propoxy bis (acetyl acetate) titanium, di-i-propoxy bis (acetylacetone) titanium, tetraisopropyl titanate, tetra-n-butyl titanate, and tetrastyryl titanate; di-i- Propoxy
Aluminum ethyl acetoacetate, aluminum di-i-propoxy acetylacetonate, aluminum i-propoxy bis (ethyl acetoacetate),
i-propoxybis (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonate) aluminum, monoacetylacetonatebis (ethylacetoacetate) aluminum, aluminum-i-propionate, monosec- Aluminum compounds such as butoxyaluminum diisopropylate, aluminum-sec-butylate and aluminum ethylate are exemplified. Among these compounds, tri-n-butoxyethylacetoacetate zirconium, di-i-propoxybis (acetylacetonato) titanium, di-i-
Propoxy ethyl acetoacetate aluminum and tris (ethyl acetoacetate) aluminum are preferred. These (c) organometallic compounds may be used alone or
A mixture of more than one species can be used. (C) The organometallic compound is preferably used after being dissolved in an organic solvent. As the organic solvent in this case, for example, alcohols, aromatic hydrocarbons, ethers, ketones, esters and the like are suitable.

The amount of the organometallic compound (c) used in the present invention is preferably 0.01 to 50 parts by weight based on 100 parts by weight of the organosilane (1) (in terms of a completely hydrolyzed condensate).
Parts by weight, more preferably 0.1 to 50 parts by weight.
In this case, if the amount of the (c) organometallic compound exceeds 50 parts by weight, the storage stability of the aqueous dispersion may be reduced, or cracks may be easily generated in the coating film.

(D) a β-keto compound; a component (d), for example, a general formula R ⁶ COCH ₂ COR ⁷ wherein R ⁶ and R ⁷ are each (c) an organic metal compound in the above general formula R ⁶ and R ⁷ have the same meanings as defined above] (hereinafter, these compounds are collectively referred to as “(d) β-keto compound”). It can be blended to further improve the storage stability of the resulting coating composition. When the coating composition for overcoating of the present invention contains the above-mentioned (c) organometallic compound, it is particularly preferable to further blend (d) a β-keto compound.

Specific examples of such a (d) β-keto compound include acetylacetone, methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, i-acetoacetate i
-Propyl, n-butyl acetoacetate, acetoacetate sec
-Butyl, t-butyl acetoacetate, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 2,4-nonanedione,
5-methyl-2,4-hexanedione. Of these, ethyl acetoacetate and acetylacetone are preferred, and acetylacetone is particularly preferred. The amount of the (d) β-keto compound used in the present invention is usually 2 mol or more, preferably 3 to 20 mol, per 1 mol of the (c) organometallic compound. In this case, when the amount of the (d) β-keto compound used is less than 2 mol, the effect of improving the storage stability of the resulting aqueous dispersion tends to decrease.

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

Added to further increase the hardness of the cured product
Filler (hereinafter also referred to as “filler (e1)”)
Are particles of inorganic compounds and / or sols or rollers
Id. Specific examples of the inorganic compound,
SiO_Two, Al_TwoO_Three, Al (OH)_Three, Sb_TwoO_Five,
Si_ThreeN_Four, Sn-In_TwoO_Three, Sb-In_TwoO_Three, M
gF, CeF_Three, CeO_Two, 3Al_TwoO_Three・ 2Si
O_Two, BeO, SiC, AlN, Fe, Fe_TwoO_Three, C
o, Co-FeO_X, CrO_Two, Fe_FourN, Ba Blow
Site, SmCO_Five, YCO_Five, CeCO_Five, PrC
O_Five, Sm_TwoCO₁₇, ZrO_Two, Nd _TwoFe₁₄B, Al
_FourO_ThreeAnd the like. These inorganic compounds
Can be used alone or as a mixture of two or more.
Wear.

Before the filler (e1) is blended with the coating composition, the filler may be in the form of a particulate powder, an aqueous sol or colloid in which fine particles are dispersed in water, or a polar solvent such as isopropyl alcohol or toluene. And sols or colloids in a solvent system dispersed in a nonpolar solvent. In the case of a solvent-based sol or colloid, it may be further diluted with water or a solvent depending on the dispersibility of the semiconductor fine particles. When the filler (e1) is an aqueous sol or colloid and a solvent sol or colloid, the solid content concentration is preferably 40% by weight or less. Filler (e
Among 1), colloidal silica includes, for example, snowtex, methanol silica sol, and isopropanol silica sol (all manufactured by Nissan Chemical Industries, Ltd.);
N, Oscar [all, manufactured by Catalyst Chemical Industry Co., Ltd.]; Lud
ex (Dupont, USA); Syton (Monsanto, USA); Nalcoag (Nalco Chemical, USA)
And the above-mentioned colloidal alumina is, for example, alumina sol-100, alumina sol-200, alumina sol-520 (all manufactured by Nissan Chemical Industries, Ltd.),
It is commercially available under trade names such as Alumina Clear Sol, Alumina Sol 10, and Alumina Sol 132 (all manufactured by Kawaken Fine Chemical Co., Ltd.).

As a method of blending the filler (e1),
It may be added after the preparation of the aqueous dispersion, or may be added during the preparation of the aqueous dispersion, and hydrolyze the organosilane (1), (b) the silyl group-containing vinyl polymer or the like in the presence of the component (e1). It can also be decomposed and condensed. The amount of the filler (e1) used in the present invention depends on the amount of the organosilane (1).
Usually, 0 to 500 parts by weight, preferably 0.1 to 100 parts by weight, based on 100 parts by weight (complete hydrolyzed condensate).
400 parts by weight.

On the other hand, as a filler (hereinafter also referred to as “filler (e2)”) for imparting coloring, design properties or thickening of the coating film and further enhancing corrosion resistance, weather resistance, etc., for example, And metal and alloys; compounds such as metal oxides, hydroxides, carbides, nitrides and sulfides; and 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 for pigments (rutile type), zirconium oxide, silicon dioxide, lead oxide, 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 plumbate, 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, biryan, Guinea green, cobalt chrome green, schule green, green earth, Chrome green, zinc green, pigment green, ultramarine, rock ultramarine, navy 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,
Ocher, cadmium red, selenium red, chrome vermillion,
Bengala, lead zinc white, bunchison white, manganese white, bone black, diamond black, thermatomic black, vegetable black and the like can be mentioned. These fillers (e
2) can be used alone or in combination of two or more.

The amount of the filler (e2) used in the present invention is 100% of the total solid content of the aqueous dispersion used in the present invention.
It is usually 300 parts by weight or less based on parts by weight. If the amount of the filler (e2) 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 overcoating composition of the present invention, depending on the curing conditions, a curing accelerator other than the above (c) organometallic compound (hereinafter referred to as “the curing accelerator”). (Also referred to as "(f) curing accelerator")
Can be used in combination, and is particularly effective when cured 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, aluminate, and carbonic acid; methanesulfonic acid and the like; ethylenediamine, hexanediamine, diethylenetriamine, triethylenetetramine, tetraethylene Amine compounds other than the component (II), such as pentamine, 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 = CHCOOC
H ₃ ) ₂ , (C ₄ H ₉ ) ₂ Sn (OCOCH = CHCO
O (C ₄ H ₉ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (OCOC ₁₁ H
₂₃ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (OCOCH = CHCOO
CH ₃ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (OCOCH = CHC
OO (C ₄ H ₉ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (OCOCH
= CHCOOC ₈ H ₁₇ ) ₂ , Sn (OCOC ₈ H ₁₇ )
Carboxylic acid type organotin compounds such as ₂ ; (C ₄ H ₉ ) ₂
Sn (SCH ₂ COOC ₈ H ₁₇ ) ₂ , (C ₄ H ₉ ) ₂ S
n (SCH 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 COOC 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
Sulfide type organotin compounds such as Sn = S; (C ₄ H
₉ ) ₂ SnO, organic tin oxides such as (C ₈ H ₁₇ ) ₂ SnO, and these organic tin oxides and alkyl silicates, dimethyl maleate, diethyl maleate,
Examples thereof include a reaction product with an ester compound such as dioctyl phthalate. These (f) curing accelerators can be used alone or in combination of two or more. Examples of the method of adding the (f) curing accelerator to the aqueous dispersion include (f) a method of diluting the curing accelerator with an alcohol solvent in advance, and (f) adding an emulsifier to the curing accelerator and then adding the emulsifier to water. And emulsified and dispersed. The amount of the curing accelerator (f) used in the present invention is usually 0 to 100 parts by weight, preferably 0.1 to 80 parts by weight, based on 100 parts by weight of the organosilane (1) (in terms of a completely hydrolyzed condensate). Parts, more preferably 0.5 to 50 parts by weight.

(G) polyfunctional hydrazine derivative; Further, the overcoating coating composition of the present invention comprises a polyfunctional hydrazine derivative having two or more hydrazino groups in a molecule (hereinafter referred to as “(g) polyfunctional hydrazine derivative”). Hydrazine derivative "). (G) The polyfunctional hydrazine derivative is preferably blended when (b) the silyl group-containing vinyl polymer contains a carbonyl group.
(G) The polyfunctional hydrazine derivative has a function of forming a network structure by reacting the hydrazino group with the carbonyl group in a drying process after the application of the aqueous dispersion, thereby crosslinking the coating film.

(G) Examples of the 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, and terephthalic acid. Dihydrazides having a total carbon number of 2 to 10, especially 4 to 6 carbon atoms, such as dihydrazide, maleic dihydrazide, fumaric acid dihydrazide, and itaconic acid dihydrazide; Hydrazides having three or more functions, such as tetrahydrazide and ethylenediaminetetraacetic acid; 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 water-soluble dihydrazines such as aliphatic dihydrazines having a total of 2 to 4 carbon atoms such as 3-dihydrazine.

Further, at least a part of the hydrazino group of these water-soluble dihydrazines is converted to a carbonyl compound such as acetaldehyde, propionaldehyde, butyraldehyde, acetone, methyl ethyl ketone, diethyl ketone, methyl propyl ketone, methyl butyl ketone or diacetone alcohol. (Hereinafter also referred to as "blocked polyfunctional hydrazine derivative"), for example, dihydrazide monoacetone hydrazone adipate, dihydrazide diacetone hydrazone adipate and the like can also be used. By using such a blocked polyfunctional hydrazine derivative, the progress of the cross-linking reaction of the aqueous dispersion can be moderately suppressed, so that redispersibility, which is particularly important as a printing ink, can be further improved. Among these polyfunctional hydrazine derivatives, adipic dihydrazide, sebacic dihydrazide, isophthalic dihydrazide, adipic dihydrazide diacetone hydrazone and the like are preferable.
(G) Polyfunctional hydrazine derivatives can be used alone or in combination 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: 1:
0.5-1.5, more preferably 1: 0.7-1.2
Is in the range of In this case, if the amount of the hydrazino group is less than 0.1 equivalent relative to 1 equivalent of the carbonyl group, the solvent resistance and damage resistance of the coating film tend to decrease. Water resistance and transparency of the film tend to decrease. However, the equivalent ratio when the blocked polyfunctional hydrazine derivative is used as the polyfunctional hydrazine derivative is based on the equivalent ratio between the carbonyl group and the hydrazino group in the polyfunctional hydrazine derivative before blocking. . (G) The polyfunctional hydrazine derivative can be blended in an appropriate step of preparing the aqueous dispersion used in the present invention. In order to maintain
(G) It is desirable to blend the entire amount of the polyfunctional hydrazine derivative after the production of the component (I).

(H) oxazoline derivative; Further, the coating composition for overcoating of the present invention comprises an oxazoline derivative having one or more oxazoline groups (dihydrooxazolyl groups) in a molecule (hereinafter referred to as “(h) oxazoline derivative”). "). (H) The oxazoline derivative is a component (I) wherein the (b) silyl group-containing vinyl polymer is a carboxyl group, a thiol group,
Hydroxyl group, epoxy group, amino group, sulfine group (hereinafter, referred to as
These organic groups are preferably incorporated when they contain a “reactive functional group”, and particularly preferred when they contain a carboxyl group. The oxazoline derivative is
In the drying process after the application of the aqueous dispersion, the oxazoline group reacts with the functional group contained in the component (I) to form a network structure, and has an effect of crosslinking the coating film. (H) The oxazoline derivative is synthesized by an emulsion polymerization method or a suspension polymerization method of a copolymerizable oxazoline such as 2-isopropenyl-2-oxazoline and another vinyl resin having copolymerizability. A commercially available product is Epocross K- manufactured by Nippon Shokubai Chemical Industry Co., Ltd.
1000, K-1020E, K-1030E, K-20
10E, K-2020E, K-2030E, WS-50
0 and the like.

The amount of the oxazoline derivative (h) used in the present invention is such that the equivalent ratio of the reactive functional group to the oxazoline group in the component (I) is usually from 1: 0.1 to 5, preferably from 1: 0.1. 0.5 to 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 relative to 1 equivalent of the reactive functional group, the solvent resistance, damage resistance, and the like of the coating film tend to decrease, while the amount exceeds 5 equivalents. And the water resistance of the coating film,
Transparency tends to decrease. (H) The oxazoline derivative can be blended in an appropriate step of preparing the aqueous dispersion used in the present invention. However, in order to suppress the generation of coagulated product during the production of the component (I) and maintain the polymerization stability. Preferably, (h) the entire amount of the oxazoline derivative is blended after the production of the component (I).

Other Additives: The coating composition for top coating of the present invention may contain a resinous additive. Examples of the resinous additive include, for example, water-soluble polyester resins, water-soluble or water-dispersible epoxy resins, water-soluble or water-dispersible acrylic resins, and styrene-maleic acid copolymers which are usually used in water-based paints. Examples thereof include a carboxyl group-containing aromatic vinyl resin and a urethane resin. These resinous additives can be used alone or in combination 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 aqueous dispersion.

The overcoating composition of the present invention may contain an organic solvent for the purpose of improving film formability and wettability. Examples of the organic solvent include methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, i-butyl alcohol, n-amyl alcohol, and n
Alcohols such as 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,
Examples thereof include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-i-propyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and tributoxymethyl phosphate. These organic solvents can be used alone or in combination of two or more. The amount of the organic solvent used in the present invention is usually 50% by weight or less, preferably 20% by weight or less of the total aqueous dispersion.

Further, the coating composition for overcoating of the present invention may contain, 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 agent, an antioxidant, an antioxidant, an adhesive, an antifogging agent, and a flame retardant can be blended.

Undercoating Coating Composition The undercoating coating composition of the present invention serves as a primer for the overcoat layer in the laminate of the present invention, and contains (II) an aminosilane compound for improving adhesion. This is an aqueous dispersion in which the above component (III) is blended. In the undercoating coating composition of the present invention, (II) the amount of the aminosilane compound used is (III)
Usually, 0.1 to 50 parts by weight based on 100 parts by weight of the component [in terms of solid content, but when the component (III) is the component (a), in terms of the completely hydrolyzed condensate of the organosilane (1)] Parts, preferably 0.5 to 40 parts by weight. When the amount of the component (II) is less than 0.1 part by weight, the adhesion is poor, and when it exceeds 50 parts by weight, the storage stability is reduced.

The total solid content of the undercoating coating composition of the present invention is usually 50% by weight or less, preferably 20% by weight or less.
To 40% by weight, and is appropriately adjusted according to the purpose of use, the type of the substrate, the coating method, the coating film thickness, and the added components. If the total solid content of the undercoating coating composition exceeds 50% by weight, storage stability may decrease.

Substrates The substrates used for the laminate of the present invention include, for example, metals such as iron, aluminum and stainless steel; inorganic ceramics such as cement, concrete, ALC, flexible boards, mortar, slate, gypsum, ceramics and bricks System material: phenolic resin, epoxy resin, polyester, polycarbonate, polyethylene, polypropylene, AB
Plastic molded products such as S resin (acrylonitrile-butadiene-styrene resin); polyethylene, polypropylene, polyvinyl alcohol, polycarbonate,
Examples include plastic films such as polyethylene terephthalate, polyurethane, and polyimide, wood, paper, and glass. The composition of the present invention is also useful for repainting a deteriorated coating film.

These substrates may be subjected to a surface treatment in advance for the purpose of adjusting the base, improving the adhesion, filling the porous substrate, smoothing, and patterning. Examples of the surface treatment on the metal-based substrate include polishing, degreasing, plating, chromate treatment, flame treatment, and coupling treatment. Examples of the surface treatment on the plastic-based substrate include blasting, Chemical treatment,
Degreasing, flame treatment, oxidation treatment, steam treatment, corona discharge treatment, ultraviolet irradiation treatment, plasma treatment, ion treatment and the like can be mentioned. As the surface treatment for the inorganic ceramics-based substrate, for example, polishing, filling, patterning The surface treatment for the wood substrate, for example, polishing, filling, insect repellent treatment and the like,
As the surface treatment for the paper base material, for example,
Insect repellent treatment and the like can be mentioned, and as the surface treatment for the degraded coating film, for example, kelenium and the like can be mentioned.

[0067] Configuration of the laminate of the laminated body present invention 1 containing the component (I)
One or more layers and one or more layers containing the component (II), or one or more layers containing both the components (I) and (II) It is. As a configuration of the laminate of the present invention, for example,
The following structures are mentioned. The components (I) and (III) in these laminates are preferably applied in the form of an aqueous dispersion. Base material / coating film obtained from undercoat composition of the present invention / coating film obtained from topcoating composition of the present invention Base material / coating film obtained from undercoating composition of the present invention /
Coating film containing component (I) and not containing component (II) Base material / Coating film containing component (III) and not containing component (II) / Coating film obtained from the topcoating composition of the present invention / Coating film containing component (III) but not component (II) / Coating film containing component (II) / Coating film containing component (I) and not containing component (II) In the laminate, the (II) aminosilane compound is always contained at the interface between the overcoat layer and the undercoat layer, whereby the adhesion between the overcoat layer and the undercoat layer is remarkably improved. Incidentally, (I) in the laminate of the present invention
The compounding amount of the component (I) is usually about 0.1 to 40% by weight, preferably about 0.1 to 30% by weight, in the whole laminate (in terms of solid content).

In the laminate of the present invention, as a method of applying the coating composition for forming each layer, a brush, a roll coater, a flow coater, a centrifugal coater, an ultrasonic coater, or the like, a dip coat, a flow coat,
Spraying, screen processes, electrodeposition, vapor deposition and the like can be mentioned.

In the case of undercoating, a dry film thickness of 1
The second coating can form a coating film having a thickness of about 0.05 to 20 μm and the second coating can have a thickness of about 0.1 to 40 μm. Then, dry at room temperature, or 30 ~ 20
By heating and drying at a temperature of about 0 ° C. for about 1 to 60 minutes, a coating film can be formed on various substrates. In the case of overcoating, the dry film thickness is 1
The second coating can form a coating film having a thickness of about 0.05 to 20 μm and the second coating can have a thickness of about 0.1 to 40 μm. Then, dry at room temperature, or 30 ~ 20
By heating and drying at a temperature of about 0 ° C. for about 1 to 60 minutes, a coating film can be formed on the undercoat layer. The total film thickness of the laminate of the present invention is a dry film thickness, usually 0.1 to 80 μm, preferably 0.2 to 80 μm.
It is about 60 μm.

[0070]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples, but it should not be construed that the invention is limited thereto. In the examples, parts and% are by weight unless otherwise specified. 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 a gel permeation chromatography (GPC) method under the following conditions. The sample was prepared by dissolving 1 g of organopolysiloxane in 100 cc of tetrahydrofuran using tetrahydrofuran as a solvent. In addition, standard polystyrene manufactured by Pressure Chemical Co., USA was used. Further, the silyl group-containing vinyl polymer was prepared by dissolving 0.1 g in 100 cc of tetrahydrofuran. Apparatus: Waters, USA, high-temperature high-speed gel permeation chromatogram (model 150-C ALC / GPC) Column; Showa Denko KK, SHOdex A-80
M, length 50 cm Measurement temperature; 40 ° C. Flow rate: 1 cc / min

A peeling test was carried out using an initial adhesive tape and evaluated as follows. ：: not peeled at all Δ: partially peeled ×: completely peeled Initial hardness Based on pencil hardness according to JIS K5400.

After the initial water resistance test piece was immersed in pure water at normal temperature for 5 minutes,
Using a pencil hardness of K5400, the load at which the coating film was not displaced was confirmed by changing the load with a pencil having a hardness of H. ：: load of 500 g or more △: load of 200 g or more and less than 500 g ×: load of less than 200 g 2 cc of isopropyl alcohol was dropped on the chemically resistant coating film, and after 5 minutes, wiped off with a cloth, and the state of the coating film was visually observed. ：: no change △: trace of dripping remains but no change in gloss and adhesion ×: decrease in gloss or dissolution of coating film

A weathering test was performed using a sunshine weather meter for 3,000 hours in accordance with JIS K5400, and the appearance (cracks, peeling, etc.) of the coating film was visually observed. ：: Gloss retention of 90% or more ：: Gloss retention of 80 to 90% or more Δ: Gloss retention of 50% or more and less than 80% ×: Gloss retention of less than 50% Test using a water-resistant inorganic base material After immersing the pieces in hot water at 60 ° C. for 14 days, the state of the coating film was visually observed. ：: no cracks △: cracks observed by microscopic observation ×: cracks observed by visual observation

Reference Example 1 <(b) Synthesis of silyl group-containing vinyl polymer> In a reactor equipped with a stirrer and a reflux condenser, 40 parts of methyl methacrylate, 2-ethylhexyl methacrylate 1
8 parts, acrylic acid 5 parts, 2-hydroxyethyl methacrylate 10 parts, γ-methacryloxypropyltrimethoxysilane 15 parts, 4- (meth) acryloyloxy-
5 parts of 2,2,6,6-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, followed by stirring with 80 parts. ° C
Azobisisovaleronirolyl 4
Was dissolved in 15 parts of methyl ethyl ketone over 30 minutes, and the mixture was reacted at 80 ° C. for 5 hours to obtain a silyl group-containing vinyl polymer having a solid content of 40% (hereinafter, referred to as “polymer”).
"(B-1)").

Reference Examples 2 and 3 <(b) Synthesis of Silyl Group-Containing Vinyl Polymer> Reference Example 1 was conducted except that the monomer compositions shown in Table 1 below were used.
In the same manner as in the above, a silyl group-containing vinyl polymer (b-2)
To (b-3) were obtained.

[0077]

[Table 1]

Example 1 In a reactor equipped with a stirrer and a reflux condenser, 65 parts of methyltrimethoxysilane, 35 parts of dimethyldimethoxysilane were used as organosilane (1), and a vinyl polymer (b) was used in Reference Example 1 as a vinyl polymer. 50 parts of the obtained vinyl polymer (b-1),
5 parts of tris (ethylacetoacetate) aluminum, 15 parts of ion-exchanged water and 40 parts of i-propyl alcohol were added as the organometallic compound (d), and 5.5 parts at 60 ° C.
Allowed to react for hours. Next, the reaction product was cooled to room temperature to obtain a solution of the specific polymer having a solid content of 40%.
When the Mw of this specific polymer was measured, it was found to be 20,000
Met. To 100 parts of the solution of the specific polymer, at a temperature of 30 ° C. or lower, an alkyl sulfate ester salt 1.
5 parts and 3 parts of 10% ammonia water were added, and then diluted with 50 parts of i-propyl alcohol, and the resulting solution was gradually added to 200 parts of ion-exchanged water over 2 hours to form an emulsion. Next, from this emulsion under reduced pressure,
I-Propyl alcohol and water were removed at a temperature of 50 ° C or lower, and the total solid content was adjusted to 35%. The pH value at this time was 7.5. As a post-addition component, 6 parts of a 10% aqueous solution of adipic dihydrazide and 1.0 part of N-β- (aminoethyl) γ-aminopropylmethyldimethoxysilane were added to this composition as a post-addition component. Hereinafter, referred to as “composition (a)”).

Examples 2 to 23 and Preparation Examples 4 to 6 <Preparation of Overcoating Composition> The overcoating coating composition of the present invention was prepared in the same manner as in Example 1 except that the compositions shown in Tables 2 to 6 below were used. Object (b) ~
(W) and coating compositions (x) to (z) for overcoating used in the laminate of the present invention were obtained. * 1 in the table)
To * 3) are as follows. * 1) Trifunctional methyl silicone oligomer Mw = 50
0 * 2) trifunctional methyl silicone oligomer Mw = 5
000 * 3) Nippon Shokubai Chemical Industry Co., Ltd., solid content concentration 40%

[0080]

[Table 2]

[0081]

[Table 3]

[0082]

[Table 4]

[0083]

[Table 5]

[0084]

[Table 6]

Examples 24 to 29 <Preparation of Undercoating Composition> The components shown in Table 7 below were stirred and mixed to prepare undercoating coating compositions (I) to (III) of the present invention and a laminate of the present invention. Undercoat coating compositions (IV) to (V)
I got.

[0086]

[Table 7]

* 1) JSR Corporation, solid content concentration 32% * 2) JSR Corporation, solid content concentration 32% * 3) Yuka Shell Epoxy Co., Ltd., solid content concentration 32%

Examples 30 to 60 According to the specifications of Tables 8 to 11, the undercoating composition was applied to an inorganic ceramic base material so as to have a dry film thickness of 30 μm. After providing a layer of an aminosilane compound having a thickness of 1 μm, the overcoating composition was dried to a thickness of 3 μm.
It was applied so as to have a thickness of 0 μm to obtain a laminate of the present invention. Then, after drying at 80 ° C. for 5 minutes, it was left at room temperature for 1 day, and the initial hardness, the initial adhesion evaluation, and the initial water resistance evaluation were performed. Further, chemical resistance, weather resistance and warm water resistance were evaluated. These results are also shown in Tables 8 to 11.

[0089]

[Table 8]

[0090]

[Table 9]

[0091]

[Table 10]

[0092]

[Table 11]

Examples 61 to 62 30 parts of a cross-linked polymethyl methacrylate resin having a particle size distribution of 30 to 100 μm was dispersed in 100 parts of the emulsion (solid content concentration: 35%) before mixing the post-addition component in Example 1, The mixture was stirred at 2,000 rpm to obtain an aqueous dispersion having a solid content of 50%. To this aqueous dispersion, 7.5% of the oxazoline derivative k-2020E (40% solution) was added.
And 1 part of N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane were added to obtain a topcoating composition (a2) of the present invention. Similarly, using the emulsion before mixing the post-addition components in Example 7, a topcoating composition (g2) of the present invention was obtained. Example 3 was obtained using the obtained compositions (a2) and (g2) and following the specifications in Table 12.
In the same manner as in Example No. 0, the laminate of the present invention was obtained and evaluated.
The evaluation results are also shown in Table 12.

Examples 63 to 64 100 parts of the emulsion (solid content: 35%) before mixing the post-additional components in Example 1 were mixed with Si having an average particle diameter of 50 μm.
30 parts of O ₂ particles were dispersed and stirred at 2000 rpm to obtain an aqueous dispersion having a solid content of 50%. To this aqueous dispersion, 7.5 parts of the oxazoline derivative k-2020E (40% solution) and 1 part of N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane were added, and the overcoating composition (a3) of the present invention was added. I got Similarly, using the emulsion before mixing the post-addition components in Example 7, a topcoating composition (g3) of the present invention was obtained. The resulting composition (a
Using 3) and (g3), a laminate of the present invention was obtained and evaluated in the same manner as in Example 30, except that the specifications in Table 12 were followed. The evaluation results are also shown in Table 12.

Examples 65 to 66 25 parts of pigment, 25 parts of isopropyl alcohol, 0.5 part of cellulosic thickener, 0.5 part of pigment dispersant were added to 100 parts of the emulsion (solid content concentration: 35%) before mixing the post-addition components in Example 1. A mill base consisting of 0.5 parts was mixed and stirred for 30 minutes in a sand mill. To this, 7.5 parts of the oxazoline derivative k-2020E (40% solution) and N-β
One part of (aminoethyl) γ-aminopropylmethyldimethoxysilane was added to obtain a topcoating composition (a4) of the present invention. Similarly, the emulsion (g4) for overcoating of the present invention was obtained using the emulsion before mixing the post-addition components in Example 7. Using the obtained compositions (a4) and (g4),
According to the specifications in Table 12, a laminate of the present invention was obtained and evaluated in the same manner as in Example 30, except that the overcoat layer was applied so that the dry film thickness became 50 μm. The evaluation results are also shown in Table 12.

[0096]

[Table 12]

[0097]

According to the present invention, by including a specific aminosilane compound in a laminate (coating film), the adhesion between the overcoat layer and the undercoat layer is excellent, and transparency, weather resistance, stain resistance, and heat resistance are improved. It is intended to obtain a laminated body (coating film) that is excellent in water resistance, seawater resistance, organic chemical resistance, acid resistance, alkali resistance, corrosion resistance, abrasion resistance, weather resistance, moisture resistance, etc. and has high hardness. Further, the coating composition forming this laminate has excellent storage stability.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Tamaki Ando 2--11-24 Tsukiji, Chuo-ku, Tokyo Inside JSR Co., Ltd. (72) Inventor Junsei Shimada 2-11-24 Tsukiji, Chuo-ku, Tokyo Inside JSR Co., Ltd. (72) Inventor Koji Shiho 2--11-2 Tsukiji, Chuo-ku, Tokyo F-term in JSR Co., Ltd. 4D075 CA13 CA18 CA32 CA34 CA38 CA40 CB06 DB04 DB07 DB14 DB20 DB31 EA06 EB16 EB19 EB19 EB22 EB32 EB33 EB35 EB38 EB43 4F100 AB01A AE00A AG00A AH03C AH03D AH03E AH06B AH06C AH06D AH06E AH08 AK01A AK02B AK02D AK02E AK17E AK25E AK25J AK41E AK51E AK52B AK52D AK52E AK52J AK53E AL01E AL08B AL08D AL08E AP00A AT00A BA02 BA03 BA07 BA10D BA13 CC00B CC00C CC00D CC00E GB90 JB01 JB02 JB07 JJ03 JK09 JK12 JL06 JL09 JL11 JM01D JM01E JM02B JM02C JM02D JM02E JN 01 4J002 BG004 CD004 CF014 CF284 CK004 CP02W CP03W CP09Y CP14X CP16X GH01 4J038 CL002 DL021 DL031 JC32 JC35 MA08 MA10 NA26 PB03

Claims (5)

[Claims] 1. It has one or more coating films containing the following component (I) and one or more coating films containing the following component (II), or has the following components (I) and (II): Characterized by having one or more coating films containing both of these. (I) component; (a) the following general formula (1) (R ¹ ) _n Si (OR ² ) _4-n (1) (wherein, when two R ¹ are present, they are the same. Or differently, a monovalent organic group having 1 to 8 carbon atoms, R ² is the same or different and represents an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 6 carbon atoms, and n is 0 to 2 (Excluding the following component (II)), at least one selected from the group consisting of a hydrolyzate of the organosilane and a condensate of the organosilane, and (b) A) a vinyl polymer containing a silyl group having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group. Component (II): a compound comprising a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group, and a primary and / or secondary amino group. 2. The laminate according to claim 1, wherein the laminate has one or more coatings containing the component (I) and the component (II). Laminate. 3. The undercoating film according to claim 1, wherein component (II) according to claim 1, component (a) according to claim 1, and component (b) according to claim 1 ) At least one selected from the group consisting of a component, an alkyd resin, an amino alkyd resin, an epoxy resin, a polyester resin, an acrylic resin, a urethane resin, a fluororesin, and an acrylic silicone resin.
2. The laminate according to claim 1, wherein the laminate has one or more coating films containing a seed. 4. A topcoat coating composition comprising an aqueous dispersion in which the following components (I) and (II) are dispersed in an aqueous medium. (I) component; (a) the following general formula (1) (R ¹ ) _n Si (OR ² ) _4-n (1) (wherein, when two R ¹ are present, they are the same. Or differently, a monovalent organic group having 1 to 8 carbon atoms, R ² is the same or different and represents an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 6 carbon atoms, and n is 0 to 2 (Excluding the following component (II)), at least one selected from the group consisting of a hydrolyzate of the organosilane and a condensate of the organosilane, and (b A) a polymer containing a silyl group having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group. Component (II): a compound comprising a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group, and a primary and / or secondary amino group. 5. An undercoating coating composition comprising an aqueous dispersion in which the following components (II) and (III) are dispersed in an aqueous medium. Component (II): a compound comprising a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group, and a primary and / or secondary amino group. Component (III): Component (a) according to claim 1, component (b) according to claim 1, alkyd resin, aminoalkyd resin, epoxy resin, polyester resin, acrylic resin, urethane resin, fluororesin and acrylic silicone resin At least one selected from the group of