JP2001011379A - Coating composition for primer coat - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a coating composition for primer coat comprising a specific organosilane component, silica and/or alumina, excellent in storage stability and appearance of coating film, adhesiveness, weather resistance, etc., having high hardness and capable of preventing deterioration of base or substrate and improving adhesiveness between the substrate and top coat layer. SOLUTION: This coating composition for primer coat comprises (1) (a1) at least one kind of compound selected from an organosilane represented by the formula (R1)nSi(OR2)1-n [R1 are same or different when two R1 are present and each represents 1-8C monovalent organic groups; R2 are same or different and each represents a 1-5C alkyl group or a 1-6C acyl group; (n) is an integer of 0-2], a hydrolyzate of the above organosilane and a condensation product of the above organosilane and (b) colloidal silica and/or colloidal alumina or (2) the above (a1) component and (a2) a polymer containing a silyl group having silicon atom bonded to a hydrolyzable group and/or hydroxyl group and (b) colloidal silica and/or colloidal alumina.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating composition suitable for undercoating a paint.

[0002]

2. Description of the Related Art An organosilane coating material is a coating material having excellent weather (light) resistance, stain resistance, etc., and also has heat resistance, alkali resistance, organic chemical resistance, moisture resistance, water resistance, and insulation resistance. Excellent in wear resistance, abrasion resistance and scratch resistance. In recent years, there has been a great demand for coating materials having long-term durability, and among them, those for the purpose of protecting a base or a substrate have been increasing. By the way, the organosilane-based coating material has excellent weather resistance as described above. In other words, it is stable because it does not absorb ultraviolet light. However, on the other hand, the transmission of the ultraviolet rays may deteriorate the base and the substrate, and may cause peeling or cracking. In recent years, many coating compositions containing a photocatalytic component and coating compositions having water repellency and oil repellency have been proposed. However, when these coating compositions are directly applied to a substrate, the coating composition is not applied to the substrate. The adhesion to the film may be insufficient. Further, for example, an overcoating composition containing water (for example, containing 1% by weight or more of water of the composition) using a water dispersion sol or the like of a photocatalyst is directly coated on a substrate or on a conventional undercoating material. When applied to the film, repelling may occur or the appearance of the coating film may be poor.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of these problems, and contains a specific organosilane component and colloidal silica and / or colloidal alumina to improve storage stability. Excellent and coating appearance,
Excellent adhesion, weather resistance, etc., high hardness, can prevent deterioration of the base and substrate, improve the adhesion between the base material and the overcoat layer, and further overcoat with a water-containing coating material An object of the present invention is to provide an undercoating coating composition that can obtain a coating film having a good appearance without causing repelling even when applied as a base material.

[0004]

Means for Solving the Problems The present invention, (a1) represented by the following general formula _{^{(1) (R 1) n}} Si (OR 2) 4-n ····· (1) ( wherein, R ¹ is When two are present, they are the same or different and represent a monovalent organic group having 1 to 8 carbon atoms, and R ² is the same or different and is an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 6 carbon atoms. And n is an integer of 0 to 2.)
And at least one selected from the group consisting of an organosilane represented by the formula (1), a hydrolyzate of the organosilane and a condensate of the organosilane, and (b) colloidal silica and / or colloidal alumina. (Hereinafter, also referred to as “composition (I)”). Further, the present invention is (a1) represented by the following general formula _{^{(1) (R 1) n}} Si (OR 2) 4-n ····· (1) ( In the formula, R ^1, when present two in Same or different, represents 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 It is an integer of 2.)
(A2) a silyl having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group, which is selected from the group consisting of an organosilane represented by the formula: A polymer containing groups, and (b) colloidal silica and / or colloidal alumina,
Undercoat coating composition (hereinafter referred to as "composition (II)")
(Also called).

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Composition (I) The composition (I) contains the above components (a1) and (b) as main components. Component (a1): Component (a1) is an organosilane represented by the above general formula (1) (hereinafter referred to as “organosilane (1)”).
At least one selected from a hydrolyzate of organosilane (1) and a condensate of organosilane (1), and functions as a binder in the composition of the present invention. . That is, the component (a1) may be only one of these three types, or may be any two types.
It may be a mixture of species or a mixture containing all three types.

Here, the hydrolyzate of the above-mentioned organosilane (1) contains two to four O-silanes contained in the organosilane (1).
It is not necessary that all of the R ² groups be hydrolyzed. For example, the R ² group may be hydrolyzed only by one, may be hydrolyzed by two or more, or may be a mixture thereof. Further, the condensate of the organosilane (1) is a product in which a silanol group of a hydrolyzate of the organosilane (1) is condensed to form a Si—O—Si bond. It is not necessary that all are condensed, but only some of silanol groups are condensed
The concept includes a mixture of different degrees of condensation.

In the general formula (1), R ¹ has 1 to ¹ carbon atoms.
Examples of the monovalent organic group of 8 include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group,
i-butyl group, sec-butyl group, t-butyl group, n-
Alkyl groups such as hexyl group, n-heptyl group, n-octyl group and 2-ethylhexyl group; acyl groups such as acetyl group, propionyl group, butyryl group, valeryl group, benzoyl group, trioil group and caproyl group; vinyl group;
In addition to allyl group, cyclohexyl group, phenyl group, epoxy group, glycidyl group, (meth) acryloxy group, ureido group, amide group, fluoroacetamide group, isocyanate group, and the like, and substituted derivatives of these groups. it can.

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) An acryloxy group, a ureido group, an ammonium base and the like can be mentioned. However, the carbon number of R ¹ composed of these substituted derivatives is 8 or less including the carbon atom in the substituent. When two R ¹ are present in the general formula (1), they may be the same or different from each other.

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

Specific examples of the organosilane (1) include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane and tetra-n-butoxysilane. Class: methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane,
Ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyl Trimethoxysilane, n-
Hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3 -Chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3,
3,3-trifluoropropyltrimethoxysilane,
3,3,3-trifluoropropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane Methoxysilane, 2-hydroxypropyltriethoxysilane, 3-
Hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3- Glycidoxypropyltrimethoxysilane,
3-glycidoxypropyltriethoxysilane, 2-
(3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxy Trialkoxysilanes such as silane, 3-ureidopropyltrimethoxysilane and 3-ureidopropyltriethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n
-Propyldimethoxysilane, di-n-propyldiethoxysilane, di-i-propyldimethoxysilane, di-
i-propyldiethoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n
-Pentyldimethoxysilane, di-n-pentyldiethoxysilane, di-n-hexyldimethoxysilane, di-
n-hexyldiethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxysilane, di-n-octyldimethoxysilane, di-n-octyldiethoxysilane, di-n-cyclohexyldimethoxysilane, di-n-octyldiethoxysilane Examples thereof include dialkoxysilanes such as -n-cyclohexyldiethoxysilane, diphenyldimethoxysilane, and diphenyldiethoxysilane, as well as methyltriacetyloxysilane and dimethyldiacetyloxysilane.

Of these, trialkoxysilanes,
Dialkoxysilanes are preferable, and trialkoxysilanes are preferably methyltrimethoxysilane and methyltriethoxysilane. Further, dialkoxysilanes are preferably dimethyldimethoxysilane and dimethyldiethoxysilane.

In the present invention, as the organosilane (1), particularly, only trialkoxysilane, or
A combination of 40 to 95 mol% of trialkoxysilane and 60 to 5 mol% of dialkoxysilane is preferred. By using dialkoxysilane in combination with trialkoxysilane, the resulting coating film can be softened and the alkali resistance can be improved.

The organosilane (1) is used as it is or as a hydrolyzate and / or condensate. When the organosilane (1) is used as a hydrolyzate and / or condensate, it can be hydrolyzed and condensed in advance and used as the component (a1).
As will be described later, when the organosilane (1) is mixed with the remaining components to prepare a composition, an appropriate amount of water is added to hydrolyze and condense the organosilane (1) to obtain (a1 ) Component. The amount of water used for hydrolysis and condensation of the organosilane (1) is as follows:
Usually, from 0.3 to 1 mol of the organosilane (1).
It is about 3 mol, preferably about 0.4 to 2 mol. (A
1) When the component is used as a condensate, the condensate has a weight average molecular weight in terms of polystyrene (hereinafter referred to as “Mw”).
Is preferably from 800 to 100,000, and more preferably from 1,000 to 50,000.

The commercially available products of the component (a1) include MKC silicate manufactured by Mitsubishi Chemical Corporation, ethyl silicate manufactured by Colcoat, silicon resin manufactured by Dow Corning Toray, and silicon resin manufactured by Toshiba Silicone Co., Ltd. Resin, a silicone resin manufactured by Shin-Etsu Chemical Co., Ltd., Dow Corning
There are hydroxyl group-containing polydimethylsiloxane manufactured by Asia Co., Ltd., and silicon oligomer manufactured by Nippon Yunika Co., Ltd., and these may be used as they are or after being condensed. In the present invention, the component (a1) can be used alone or in combination of two or more.

Component (b) The component (b) in the present invention is silica and / or alumina, preferably silica fine particles and / or alumina fine particles dispersed in water or an organic solvent. ,
Alumina sol and the like are included. The average particle diameter of these fine particles is preferably 500 μm or less, more preferably 200 μm or less.

As the component (b), silica includes, for example, Snowtex, isopropanol silica gel, methanol gel (manufactured by Nissan Chemical Industries, Ltd.);
Cataloid, Oscar [catalyzed by Kasei Kogyo Co., Ltd.]; Lu
dox (manufactured by DuPont, USA); Nalcoag (manufactured by Nalco Chemical Company, USA). Also,
Examples of the alumina include alumina sol-100, alumina sol-200, and alumina sol-520 manufactured by Nissan Chemical Industries, Ltd., and aluminum oxide C manufactured by Degussa West Germany. In the composition of the present invention,
The component (b) can be used alone or in combination of two or more. The amount of the component (b) used in the composition (I) is (R ¹ ) _n SiO 2 in the component (a1).
_{(4-n) / 2} [R ¹ and n are the same as in the above formula (1). Hereinafter, the same applies to 100 parts by weight of the structural unit represented by
Usually, 5 to 500 parts by weight, preferably 10
To 400 parts by weight, more preferably 15 to 300 parts by weight. If the amount is less than 5 parts by weight, repelling may occur when the overcoat layer is applied, and further, adhesion to the substrate or the overcoat layer may not be ensured. On the other hand, 50
If the amount exceeds 0 parts by weight, the resulting coating composition may be inferior in film-forming properties, causing cracking or peeling.

The composition (I) of the present invention contains the above-mentioned components (a1) and (b) as essential components, and optionally contains optional components described below. Water and / or organic solvents are used to mix and adjust the total solids concentration of the composition. Other roles of the water and / or organic solvent include making it applicable to various coating methods and further improving the dispersion stability and storage stability of the composition.

The organic solvent is not particularly limited as long as the above components can be uniformly mixed.
For example, alcohols, aromatic hydrocarbons, ethers, ketones, esters and the like can be mentioned.
Among these organic solvents, specific examples of alcohols include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol,
sec-butyl alcohol, t-butyl alcohol, n
-Hexyl alcohol, n-octyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monobutyl ether,
Examples include ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene monomethyl ether acetate, and diacetone alcohol.

Specific examples of aromatic hydrocarbons include benzene, toluene and xylene, specific examples of ethers include tetrahydrofuran and dioxane, and specific examples of ketones include acetone, methyl ethyl ketone, and the like. Specific examples of esters such as methyl isobutyl ketone and diisobutyl ketone include ethyl acetate, propyl acetate, butyl acetate, and propylene carbonate. These organic solvents can be used alone or in combination of two or more.

Composition (II) The composition (II) is a composition obtained by blending the component (a2) with the components (a1) and (b).

Component (a2): Component (a2) is a compound having a silyl group having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group (hereinafter referred to as “specific silyl group”), preferably at the terminal of the polymer molecular chain. And / or a polymer having a side chain. In the composition (II), the component (a2) provides excellent coating by curing the coating film by co-condensing the hydrolyzable group and / or hydroxyl group in the silyl group with the component (a1). It is a component that provides membrane performance. The content of the specific silyl group in the component (a2) is usually 0.001 relative to the polymer before introduction of the specific silyl group.
It is 1 to 20% by weight, preferably 0.01 to 15% by weight. Preferred specific silyl groups are groups represented by the following general formula (2).

[0022] (Wherein, X represents a hydrolyzable group such as a halogen atom, an alkoxyl group, an acetoxy group, a phenoxy group, a thioalkoxyl group, an amino group or a hydroxyl group, and R ³ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or Carbon number 1-10
Wherein i is an integer of 1 to 3. )

The component (a2) can be produced, for example, by the following methods (a) and (b). (A) A hydrosilane compound corresponding to the above general formula (2) (hereinafter referred to as “hydrosilane compound (A)”) is referred to as a vinyl polymer having a carbon-carbon double bond (hereinafter referred to as “unsaturated vinyl polymer”). )).

(B) The following general formula (3) Wherein, X, R ^3, i has the same meaning as X, R ^3, i, respectively, in formula (2), R ⁴ represents an organic group having a polymerizable double bond. ] (Hereinafter referred to as "unsaturated silane compound (II)") and another vinyl monomer.

Examples of the hydrosilane compound (a) used in the above method (a) include halogenated silanes such as methyldichlorosilane, trichlorosilane and phenyldichlorosilane; methyldimethoxysilane, methyldiethoxysilane And alkoxysilanes such as phenyldimethoxysilane, trimethoxysilane and triethoxysilane; acyloxysilanes such as methyldiacetoxysilane, phenyldiacetoxysilane and triacetoxysilane; methyldiaminooxysilane, triaminoxysilane, dimethyl Examples include aminoxysilanes such as aminoxysilane. These hydrosilane compounds (a) can be used alone or in combination of two or more.

The unsaturated vinyl polymer used in the above method (A) is not particularly limited as long as it is other than a polymer having a hydroxyl group, and examples thereof include the following (A-1) and (A)
It can be produced by the method 2) or a combination thereof. (A-1) After (co) polymerizing a vinyl monomer having a functional group (hereinafter referred to as "functional group (α)"), the functional group (α) in the (co) polymer is replaced with the functional group (α). By reacting a functional group capable of reacting with the group (α) (hereinafter referred to as “functional group (β)”) with an unsaturated compound having a carbon-carbon double bond, carbon- A method for producing an unsaturated vinyl polymer having a carbon double bond.

(A-2) A radical polymerization initiator having a functional group (α) (for example, 4,4-azobis-4-cyanovaleric acid or the like) is used, or a radical polymerization initiator and a chain transfer agent are used. A vinyl monomer is (co) polymerized using a compound having a functional group (α) on both sides (eg, 4,4-azobis-4-cyanovaleric acid and dithioglycolic acid) to obtain a polymer. After synthesizing a (co) polymer having a functional group (α) derived from a radical polymerization initiator or a chain transfer agent at one or both ends of the molecular chain, the functional group (α) in the (co) polymer is synthesized. Is reacted with an unsaturated compound having a functional group (β) and a carbon-carbon double bond to obtain an unsaturated vinyl polymer having a carbon-carbon double bond at one or both ends of the polymer molecular chain. A method of manufacturing coalescence.

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

Examples of the vinyl monomer having a functional group (α) include unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid; maleic anhydride, itaconic anhydride Unsaturated carboxylic anhydrides such as acids; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
Hydroxyl-containing vinyl monomers such as 3-hydroxypropyl (meth) acrylate, N-methylol (meth) acrylamide, and 2-hydroxyethyl vinyl ether; 2
Amino-containing vinyl monomers such as -aminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 3-aminopropyl (meth) acrylate, and 2-aminoethyl vinyl ether; 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-
Vinyl monomers containing an amine imide such as 2'-phenoxypropyl) amine (meth) acrylimide; vinyl monomers containing an epoxy group such as glycidyl (meth) acrylate and allyl glycidyl ether; These vinyl monomers having a functional group (α) can be used alone or in combination of two or more.

Examples of other vinyl monomers copolymerizable with the vinyl monomer having a functional group (α) include (a) styrene, α-methylstyrene, 4-methylstyrene, and 2-methylstyrene. Styrene, 3-methylstyrene, 4-
Methoxystyrene, 2-hydroxymethylstyrene, 4
-Ethylstyrene, 4-ethoxystyrene, 3,4-dimethylstyrene, 3,4-diethylstyrene, 2-chlorostyrene, 3-chlorostyrene, 4-chloro-3-methylstyrene, 4-t-butylstyrene, Aromatic vinyl monomers such as 2,4-dichlorostyrene, 2,6-dichlorostyrene, 1-vinylnaphthalene;

(B) Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, amyl (meth) acrylate,
(meth) acrylate compounds such as i-amyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, and cyclohexyl methacrylate;

(C) divinylbenzene, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, Dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (meth) Polyfunctional monomers such as acrylates and pentaerythritol tetra (meth) acrylate;

(D) (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth)
Acrylamide, N, N'-methylenebisacrylamide, diacetone acrylamide, maleic amide,
Acid amide compounds such as maleimide; (e) vinyl compounds such as vinyl chloride, vinylidene chloride and fatty acid vinyl ester; (f) 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1 , 3-butadiene, 2-
Neopentyl-1,3-butadiene, 2-chloro-1,
Substituted linear conjugated pentadienes substituted with substituents such as 3-butadiene, 2-cyano-1,3-butadiene, isoprene, an alkyl group, a halogen atom, and a cyano group; linear and side-chain conjugated hexadienes; An aliphatic conjugated diene;

(G) vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; fluorine atom-containing monomers such as (thi) trifluoroethyl (meth) acrylate and pentadecafluorooctyl (meth) acrylate; (Meth) acryloyloxy-2,2,6
6-tetramethylpiperidine, 4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine,
4- (meth) acryloyloxy-1,2,2,6,6
-Piperidine monomers such as pentamethylpiperidine; and dicaprolactone. These can be used alone or in combination of two or more.

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

Specific examples of the unsaturated silane compound ( _II ) used in the above method ( _II ) include CH ₂ ＣＨCHSi (CH ₃ ) (OCH ₃ ) ₂ and CH ₂ ＣＨCHSi (OCH ₃ ). ₃ , CH ₃ ＣＨCHSi (CH ₃ ) Cl ₂ , CH ₂ ＣＨCHSi
Cl ₃ , CH ₂ ＣＨCHCOO (CH ₂ ) ₂ Si (CH ₃ ) (OC
H ₃ ) ₂ , CH ₂ ＣＨCHCOO (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , CH ₂ ＣＨCHCOO (CH ₂ ) ₃ Si (CH ₃ ) (OC
_{H 3) 2, CH 2 =} CHCOO (CH 2) 3 Si (OCH 3) 3, CH 2 = CHCOO (CH 2) 2 Si (CH 3) C
l ₂ , CH ₂ ＣＨCHCOO (CH ₂ ) ₂ SiCl ₃ , CH ₂ ＣＨCHCOO (CH ₂ ) ₃ Si (CH ₃ ) C
l ₂ , CH ₂ ＣＨCHCOO (CH ₂ ) ₃ SiCl ₃ , CH ₂ ＣC (CH ₃ ) COO (CH ₂ ) ₂ Si (C
H ₃ ) (OCH ₃ ) ₂ , CH ₂ ＣC (CH ₃ ) COO (CH ₂ ) ₂ Si (OCH
₃ ) ₃ , CH ₂ ＣC (CH ₃ ) COO (CH ₂ ) ₃ Si (C
H ₃ ) (OCH ₃ ) ₂ , CH ₂ ＣC (CH ₃ ) COO (CH ₂ ) ₃ Si (OCH
₃ ) ₃ , CH ₂ ＣC (CH ₃ ) COO (CH ₂ ) ₂ Si (C
_{H 3) Cl 2, CH 2} = C (CH 3) COO (CH 2) 2 SiCl 3, CH 2 = C (CH 3) COO (CH 2) 3 Si (C
H ₃ ) Cl ₂ , CH ₂ ＣC (CH ₃ ) COO (CH ₂ ) ₃ SiCl ₃ ,

[0037]

Embedded image

Embedded image

Embedded image

Embedded image

The following can be mentioned. These can be used alone or in combination of two or more. Examples of other vinyl monomers to be copolymerized with the unsaturated silane compound (b) include, for example, vinyl monomers having a functional group (α) exemplified for the method (a-1) and other vinyl monomers. At least one vinyl monomer.

Other examples of the component (a2) include a specific silyl group-containing epoxy resin, a specific silyl group-containing polyester resin, and a specific silyl group-containing fluororesin. The specific silyl group-containing epoxy resin,
For example, aminosilanes having a specific silyl group as an epoxy group in epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, aliphatic polyglycidyl ether and aliphatic polyglycidyl ester , Vinyl silanes, carboxy silanes, glycidyl silanes and the like. The specific silyl group-containing polyester resin is, for example, produced by reacting a carboxyl group or a hydroxyl group contained in the polyester resin with an aminosilane having a specific silyl group, a carboxysilane, a glycidylsilane, or the like. Can be. Further, the specific silyl group-containing fluororesin includes, for example, aminosilanes, carboxysilanes, and glycidylsilanes having a specific silyl group in a carboxyl group or a hydroxyl group contained in a (co) polymer such as ethylene fluoride. Can be produced by reacting

The number average molecular weight in terms of polystyrene of the component (a2) (hereinafter referred to as “Mn”) is preferably 2,000.
~ 100,000, more preferably 4,000 ~ 5
It is 0000. The amount of the component (a2) used in the composition (II) is determined by the amount of (R ¹ ) _n SiO in the component (a1).
It is usually 2 to 900 parts by weight, preferably 10 to 400 parts by weight, more preferably 20 to 300 parts by weight, based on 100 parts by weight of the structural unit represented by _{(4-n) / 2} .
If the amount of the component (a2) is less than 2 parts by weight, the resulting coating film may have poor alkali resistance.
If it exceeds 900 parts by weight, the long-term weather resistance of the coating film tends to decrease.

As the polymerization method for producing the component (a2), for example, a method in which a monomer is added at a time and polymerization is performed, a part of the monomer is polymerized, and then the remainder is continuously processed. Or a method in which the monomer is continuously added from the beginning of the polymerization. Further, a polymerization method in which these polymerization methods are combined may be employed. Preferred polymerization methods include solution polymerization. As the solvent used for the solution polymerization, a usual solvent can be used, and among them, ketones and alcohols are preferable. In this polymerization, known polymerization initiators, molecular weight regulators, chelating agents and inorganic electrolytes can be used.

In the present invention, the component (a2) can be used alone or as a mixture of two or more kinds obtained as described above. In the composition (II), the component (a2) is preferably co-condensed with the component (a1) in the presence of water and / or an organic solvent.

In the composition (II), the types of the component (a1) and the component (b) are the same as those of the composition (I), and will not be described. Composition of component (b) (II)
Is the amount of (R ¹ ) _n SiO in the component (a1).
_{Based on} 100 parts by weight of the total amount of the structural unit represented by _{(4-n) / 2} and the component (a2) (in terms of solids), the solid content is usually 5 to 500 parts by weight, preferably 10 to 500 parts by weight. It is 400 parts by weight, more preferably 15 to 300 parts by weight. 5
If the amount is less than parts by weight, repelling may occur when the overcoat layer is applied, and further, adhesion to the substrate or the overcoat layer may not be ensured. On the other hand, when the amount exceeds 500 parts by weight, the film forming property of the obtained coating material is inferior, and cracking or peeling may occur.

The composition (II) of the present invention essentially comprises the above-mentioned components (a1), (a2) and (b), and optionally contains optional components described later. Water and / or an organic solvent is used in order to uniformly mix the components and adjust the total solid concentration of the composition. Specific examples of the organic solvent include the organic solvents exemplified as those used in the composition (I).

Composition (I) and composition (II) of the present invention
Has, as an optional component, each of the following (c)
~ (F) component can be blended. Hereinafter, these components will be described.

Component (c) The component (c) is a catalyst for promoting the hydrolysis / condensation reaction of the component (a1) and the component (a2). By using the component (c), the curing speed of the obtained coating film is increased, and the molecular weight of the polysiloxane resin produced by the polycondensation reaction of the organosilane component used is increased, so that strength, long-term durability, etc. In addition, it is possible to obtain an excellent coating film, and it is easy to increase the thickness of the coating film and to perform a coating operation.

The component (c) includes an acidic compound, an alkaline compound, a metal salt, an amine compound, an organometallic compound and / or a partial hydrolyzate thereof (hereinafter referred to as an organometallic compound and / or a partial hydrolyzate thereof). Are collectively referred to as “organometallic compound or the like”). Examples of the acidic compound include acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, alkyltitanic acid, p-toluenesulfonic acid, and phthalic acid, and acetic acid is preferred. Examples of the alkaline compound include sodium hydroxide and potassium hydroxide, and preferably sodium hydroxide. Examples of the metal salt include alkali metal salts such as naphthenic acid, octylic acid, nitrous acid, sulfurous acid, aluminate, and carbonic acid.

Examples of the amine compound include ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, piperidine, piperazine, m-phenylenediamine, p-phenylenediamine, ethanolamine, triethylamine, and the like. -Aminopropyl-trimethoxysilane, 3-aminopropyl-triethoxysilane, 3- (2-aminoethyl) -aminopropyl-trimethoxysilane, 3- (2-aminoethyl) -aminopropyl-triethoxysilane, 3 -(2-aminoethyl) -aminopropylmethyldimethoxysilane, 3
-Anilinopropyltrimethoxysilane, alkylamine salts, quaternary ammonium salts, and various modified amines used as a curing agent for epoxy resins. Preferred are 3-aminopropyltrimethoxysilane. , 3-aminopropyl-triethoxysilane and 3- (2-aminoethyl) -aminopropyl-trimethoxysilane.

Examples of the organometallic compound and the like include a compound represented by the following general formula (4) (hereinafter referred to as “organometallic compound (4)”) and a compound having 1 to 1 carbon atoms bonded to the same tin atom. Examples thereof include organometallic compounds of tetravalent tin having 1 to 2 alkyl groups of 10 (hereinafter referred to as "organotin compounds"), and partially hydrolyzed products of these compounds.

[0050] [In the formula, M represents zirconium, titanium or aluminum, and R ⁵ and R ⁶ are the same or different and are an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, a t-butyl group. -Butyl group, n-pentyl group, n-hexyl group, cyclohexyl group, a monovalent hydrocarbon group having 1 to 6 carbon atoms such as a phenyl group, R ⁷ represents
In addition to the same monovalent hydrocarbon group having 1 to 6 carbon atoms as R ⁵ and R ⁶ , methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, sec-butoxy, t -Represents an alkoxyl group having 1 to 16 carbon atoms such as a butoxy group, a lauryloxy group and a stearyloxy group, r and s are integers of 0 to 4, and (r + s) = (valence of M). ]

Specific examples of the organometallic compound (4) include (a) tetra-n-butoxyzirconium and tri-n-
Butoxy ethyl acetoacetate zirconium, di-
n-butoxybis (ethylacetoacetate) zirconium, n-butoxytris (ethylacetoacetate) zirconium, tetrakis (n-propylacetoacetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, etc. An organic zirconium compound;

(B) Tetra-i-propoxytitanium, di-i-propoxybis (ethylacetoacetate) titanium, di-i-propoxybis (acetylacetate) titanium, di-i-propoxybis (acetylacetone) Organic titanium compounds such as titanium; (c) tri-i-propoxyaluminum, di-i-propoxyethyl acetoacetate aluminum,
aluminum i-propoxy acetylacetonate,
i-propoxybis (ethylacetoacetate) aluminum, i-propoxybis (acetylacetonate) aluminum, tris (ethylacetoacetate)
Organic aluminum compounds such as aluminum, tris (acetylacetonate) aluminum, and monoacetylacetonatobis (ethylacetoacetate) aluminum; and the like.

Among these organometallic compounds (4) and partial hydrolysates thereof, tri-n-butoxyethylacetoacetate zirconium, di-i-propoxybis (acetylacetonato) titanium, di-i-propoxy・ Ethyl acetoacetate aluminum, tris (ethyl acetoacetate) aluminum, or
Partial hydrolysates of these compounds are preferred.

Specific examples of the organotin compound include (C ₄ H ₉ ) ₂ Sn (OCOC ₁₁ H ₂₃ ) ₂ and (C ₄ H ₉ ) ₂ Sn (OCOCH = CHCOOCH ₃ ).
₂ , (C ₄ H ₉ ) ₂ Sn (OCOCH = CHCOOC)
_{4 H 9) 2, (C} 8 H 17) 2 Sn (OCOC 8 H 17) 2, (C 8 H 17) 2 Sn (OCOC 11 H 23) 2, (C 8 H 17) 2 Sn (OCOCH = CHCOOCH ₃ )
₂ , (C ₈ H ₁₇ ) ₂ Sn (OCOCH = CHCOOC)
_{4 H 9) 2, (C} 8 H 17) 2 Sn (OCOCH = CHCOOC
_{8 H 17) 2, (C} 8 H 17) 2 Sn (OCOCH = CHCOOC
_{16 H 33) 2, (C} 8 H 17) 2 Sn (OCOCH = CHCOOC
_{17 H 35) 2, (C} 8 H 17) 2 Sn (OCOCH = CHCOOC
_{18 H 37) 2, (C} 8 H 17) 2 Sn (OCOCH = CHCOOC
₂₀ H _{41) 2,}

[0055] Carboxylic acid type organotin compounds such as (C ₄ H ₉ ) Sn (OCOC ₁₁ H ₂₃ ) ₃ and (C ₄ H ₉ ) Sn (OCONa) ₃ ;

(C ₄ H ₉ ) ₂ Sn (SCH ₂ COOC ₈ H ₁₇ ) ₂ , (C ₄ H ₉ ) ₂ Sn (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)
₂ , (C ₄ H ₉ ) Sn (SCOCH = CHCOOC ₈ H ₁₇ )
₃ , (C ₈ H ₁₇ ) Sn (SCOCH = CHCOOC ₈ H ₁₇ )
₃ ,

[0057] Mercaptide-type organotin compounds such as;

(C ₄ H ₉ ) ₂ Sn = S, (C ₈ H ₁₇ ) ₂
Sn = S, Sulfide type organotin compounds such as;

(C ₄ H ₉ ) SnCl ₃ , (C ₄ H ₉ ) ₂ SnCl ₂ , (C ₈ H ₁₇ ) ₂ SnCl ₂ , (C ₄ H ₉ ) ₂ S
organic tin oxides such as nO and (C ₈ H ₁₇ ) ₂ SnO, and reaction products of these organic tin oxides with ester compounds such as silicate, dimethyl maleate, diethyl maleate and dioctyl phthalate. Can be.

The component (c) can be used alone or as a mixture of two or more kinds, and can also be used as a mixture with a zinc compound or another reaction retarder.

The component (c) may be blended when preparing the composition, or may be blended with the composition at the stage of forming a coating film. May be blended at both stages. The amount of the component (c) used is
In the case other than an organometallic compound or the like, the total amount of the structural unit represented by (R ¹ ) _n SiO _{(4-n) / 2} in the component (a1) and the specific silyl group in the component (a2) is 100 parts by weight. In general, 0 to 100 parts by weight, preferably,
0.01 to 80 parts by weight, more preferably 0.1 to 5 parts by weight
0 parts by weight, and in the case of an organometallic compound or the like, the above (a)
1 to 100 parts by weight based on 100 parts by weight of the total amount of the structural unit represented by (R ¹ ) _n SiO _{(4-n) / 2} in the component and the specific silyl group in the component (a2). Department,
Preferably, 0.1 to 80 parts by weight, more preferably,
It is 0.5 to 50 parts by weight. In this case, when the amount of the component (c) exceeds 100 parts by weight, the storage stability of the composition tends to decrease, and the coating film tends to crack.

Component (d) The component (d) is represented by the following general formula (5): R ⁶ COCH ₂ COR ⁷ (5) wherein R ⁶ and R ⁷ are the same as defined above in the organometallic compound (4). Which is the same as R ⁶ and R ^{7 in} each of the general formulas], is selected from the group consisting of β-diketones and β-ketoesters, carboxylic acid compounds, dihydroxy compounds, amine compounds, and oxyaldehyde compounds At least one type. Such a component (d) is particularly preferably used together when an organometallic compound or the like is used as the component (c).

The component (d) functions as a stability improver for the composition. That is, the component (d) coordinates to a metal atom of the above-mentioned organometallic compound or the like, and appropriately controls the action of the organometallic compound or the like to promote the co-condensation reaction of the above-mentioned component (a) and component (a2). By doing
It is presumed that they act to further improve the storage stability of the obtained composition.

Specific examples of component (d) include acetylacetone, methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, i-propyl acetoacetate, n-butyl acetoacetate, and sec-butyl acetoacetate. Tert-butyl acetoacetate, hexane-2,4-dione, heptane-2,4-dione, heptane-3,5-dione,
Octane-2,4-dione, nonane-2,4-dione,
5-methylhexane-2,4-dione, malonic acid, oxalic acid, phthalic acid, glycolic acid, salicylic acid, aminoacetic acid, iminoacetic acid, ethylenediaminetetraacetic acid, glycol, catechol, ethylenediamine, 2,2-bipyridine, 1,10 -Phenanthroline, diethylenetriamine, 2-ethanolamine, dimethylglyoxime, dithizone, methionine, salicylaldehyde and the like. Of these, acetylacetone and ethyl acetoacetate are preferred. The component (d) can be used alone or in combination of two or more.

The amount of the component (d) is usually 2 to 1 mol of the organometallic compound in the organometallic compound or the like.
Mol or more, preferably 3 to 20 mol. in this case,
If the amount of the component (d) is less than 2 mol, the effect of improving the storage stability of the obtained composition tends to be insufficient.

Component (e) The component (e) is composed of semiconductor fine particles having an ultraviolet absorbing ability. The semiconductors having ultraviolet absorbing ability, for example, TiO _2, ZnO rutile crystal, and the like can be illustrated CeO _2, preferably ZnO and CeO _2. In the composition of the present invention, due to the ultraviolet absorbing ability of the component (e), the ultraviolet absorbing property of the coating film can be obtained without substantially impairing the coating film performance, and the deterioration of the base or the substrate due to the ultraviolet rays can be prevented. can do. The component (e) can be present in three forms: a powder composed of fine particles, an aqueous sol in which fine particles are dispersed in water, and a solvent sol in which fine particles are dispersed in a polar solvent such as isopropyl alcohol or a nonpolar solvent such as toluene. There is. In the case of a solvent-based sol, it may be further diluted with water or a solvent depending on the dispersibility of the semiconductor fine particles. The average particle diameter of the semiconductor fine particles in these existing forms is preferably smaller from the viewpoint of ultraviolet absorbing ability, and is usually 1 μm or less, preferably 0.5 μm or less,
Particularly preferably, it is 0.1 μm or less. By making the component (e) finely divided, it is possible to obtain an ultraviolet absorbing agent which has the same ultraviolet absorbing ability as an organic ultraviolet absorbing agent and can be used semi-permanently without deterioration. In addition, since the uniform dispersibility is good, a coating composition having excellent transparency, storage stability, and the like can be obtained. For the purpose of improving the dispersibility and storage stability and preventing the photocatalytic activity, these fine particles and sols are preferably added with a surfactant, a dispersant, a coupling agent, or the like, and are preferably subjected to a surface treatment. Used. When the component (e) is an aqueous sol or a solvent sol, the solid content concentration is preferably 60% by weight or less, more preferably 50% by weight or less.

As a method of blending the component (e) into the composition of the present invention, the component (e) may be added after the preparation of the other component, or may be added during the preparation of the composition of the present invention. In the presence, the organosilane or the like constituting the component (a1) can be hydrolyzed and condensed. When the component (e) is added during the preparation of the composition, the semiconductor compound in the component (e) can be co-condensed with the component (a) and the like.
The dispersibility of the components can be improved. (E)
When the component is an aqueous sol, it is preferable to add the component during the preparation of the composition. Also, when the viscosity in the system increases due to the incorporation of the component (f) described later, the component (e) is prepared. It is preferable to add it at times.

The commercially available products of component (e) include Ishihara Sangyo Co., Ltd.
TAIPAKE TTO manufactured by Sumitomo Osaka Cement Co., Ltd.
W-143, ZW-513C, ZS-300, ZS-3
03, ZnO-100, ZnO-200, Z-NOVE manufactured by Mitsui Mining & Smelting Co., Ltd., Neidral manufactured by Taki Chemical Co., Ltd., CERIGUAR manufactured by Nippon Inorganic Chemical Industry Co., Ltd.
D, Hi-Cera Super K29 and the like. In the composition of the present invention, the component (e) can be used alone or in combination of two or more. The amount of the component (e) used in the composition of the present invention may be a solid content based on 100 parts by weight of the structural unit represented by (R ¹ ) _n SiO _{(4-n) / 2} in the component (a1). Usually, it is 150 parts by weight or less, preferably 5 to 100 parts by weight. If the amount exceeds 150 parts by weight, the resulting coating material may be inferior in film-forming properties and may be cracked or peeled off, which is not preferred.

Component (f) The component (f) comprises a powder and / or a sol or a colloid of an inorganic compound other than the components (b) and (e), and is blended according to the desired properties of the coating film. . When the component (f) is in the form of a sol or colloid, the average particle size is usually about 0.005 to 100 μm.

Specific examples of the compound constituting the component (f)
Are AlGaAs, Al (OH)_Three, Sb_TwoO_Five, Si
_ThreeN_Four, Sn-In_TwoO_Three, Sb-In_TwoO_Three, Mg
F, CeF_Three, BeO, SiC, AlN, Fe, Co,
Co-FeOx, CrO_Two, Fe _FourN, BaTiO_Three,
BaO-Al_TwoO_Three-SiO_Two, Ba ferrite, Sm
CO_Five, YCO_Five, CeCO_Five, PrCO_Five, Sm_TwoC
O₁₇, Nd_TwoFe₁₄B, Al_FourO_Three, Α-Si, SiN
_Four, CoO, Sb-SnO_Two, Sb_TwoO_Five, MnO _Two,
MnB, Co_ThreeO_Four, Co_ThreeB, LiTaO_Three, Mg
O, MgAl_TwoO_Four, BeAl_TwoO_Four, ZrSiO_Four,
ZnSb, PbTe, GeSi, FeSi_Two, CrSi
_Two, CoSi_Two, MnSi_1.73, Mg_TwoSi, β-B,
BaC, BP, TiB_Two, ZrB_Two, HfB_Two, Ru_Two
Si_Three, TiO_Three, PbTiO_Three, Al _TwoTiO_Five, Z
n_TwoSiO_Four, Zr_TwoSiO_Four, 2MgO_Two-Al_TwoO
_Three-5SiO_Two, Nb_TwoO_Five, Li_TwoO-Al_TwoO_Three−
4SiO_Two, Mg ferrite, Ni ferrite, Ni-
Zn ferrite, Li ferrite, Sr ferrite, etc.
Can be mentioned. These components (f) are used alone.
Alternatively, two or more kinds can be used as a mixture.

The component (f) may be in the form of a powder, an aqueous sol or colloid dispersed in water, a polar solvent such as isopropyl alcohol, or a solvent sol or colloid dispersed in a nonpolar solvent such as toluene. There is. In the case of a solvent-based sol or colloid, depending on the dispersibility of the semiconductor, it may be used after being diluted with water or a solvent, or may be used after surface treatment to improve the dispersibility.

When the component (f) is an aqueous sol or colloid, or a solvent sol or colloid, the solid content concentration is preferably 40% by weight or less.

As a method of blending the component (f) into the composition, the component (f) may be added after the preparation of the composition, or may be added during the preparation of the composition, and the component (f) may be added to the composition (a). It may be co-hydrolyzed / condensed with the component, the component (a2) or the above condensate.

The amount of the component (f) used is determined based on the structural unit represented by (R ¹ ) _n SiO _{(4-n) / 2} in the component (a1) and the component (a2) (in terms of solid content). The solid content is generally 0 to 500 parts by weight, preferably 0.1 to 400 parts by weight, based on 100 parts by weight in total.

Other Additives In the composition used in the present invention, a filler may be separately added and dispersed for the purpose of coloring the obtained coating film and increasing the thickness of the coating film. Such fillers include, for example, water-insoluble organic pigments and inorganic pigments, other than pigments, particulate, fibrous or flaky ceramics, metals or alloys, and oxides and hydroxides of these metals. , Carbides, nitrides, sulfides and the like.

Specific examples of the filler include iron, copper, aluminum, nickel, silver, zinc, ferrite, carbon black, stainless steel, silicon dioxide, chromium oxide, manganese oxide, iron oxide, synthetic mullite, and aluminum hydroxide. , Iron hydroxide, silicon carbide, silicon nitride, boron nitride, clay, diatomaceous earth, slaked lime, gypsum, talc, barium carbonate, calcium carbonate, magnesium carbonate, barium sulfate, bentonite, mica, zinc green, chrome green, cobalt green, Viridian, Guinea green, cobalt chrome green,
Scheele green, green earth, manganese green, pigment green,
Ultramarine, Navy Blue, Pigment Green, Rock Ultramarine, Cobalt Blue, Cerulean Blue, Copper Borate, Molybdenum Blue, Copper Sulfide, Cobalt Purple, Mars Purple, Manganese Purple, Pigment Violet, Lead Oxide, Calcium Lead Oxide, Zinc Yellow, Lead Sulfide , Chrome yellow, ocher, cadmium yellow, strontium yellow, titanium yellow, litharge, pigment yellow, cuprous oxide, cadmium red, selenium red, chrome vermillion, red iron, zinc white, antimony white, basic lead sulfate,
Titanium white, lithopone, lead silicate, zircon oxide, tungsten white, lead, zinc white, vanchison white, lead phthalate, manganese white, lead sulfate, graphite, bone black, diamond black, thermatomic black, vegetable black, titanium Potassium whisker, molybdenum disulfide and the like. These fillers can be used alone or in combination of two or more. The amount of the filler used is usually 300 parts by weight or less based on 100 parts by weight of the total solid content of the composition.

The composition of the present invention may further contain, if desired, a known dehydrating agent such as methyl orthoformate, methyl orthoacetate, and tetraethoxysilane; polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene. Fatty acid ester, polycarboxylic acid type polymer surfactant, polycarboxylate, polyphosphate, polyacrylate, polyamide ester salt,
Dispersants such as polyethylene glycol; methyl cellulose, ethyl cellulose, hydroxyethyl cellulose,
Hydroxypropylcellulose, celluloses such as hydroxypropylmethylcellulose, castor oil derivatives, thickeners such as ferrosilicate; ammonium carbonate,
Inorganic foaming agents such as ammonium bicarbonate, ammonium nitrite, sodium borohydride and calcium azide; azo compounds such as azobisisobutyronitrile; hydrazine compounds such as diphenylsulfone-3,3'-disulfohydrazine; semicarbazide compounds , A triazole compound, an N-nitroso compound, and other additives, as well as other additives such as a surfactant, a silane coupling agent, a titanium coupling agent, and a dye. Further, the undercoating coating composition of the present invention includes:
For the purpose of improving weather resistance and durable adhesion, an organic UV absorber, a UV stabilizer, or the like may be used. Organic UV absorbers include salicylic acid, benzophenone,
Benzotriazole-based, cyanoacrylate-based, triazine-based, and the like. Examples of the ultraviolet stabilizer include piperidine.

Further, a leveling agent can be added to the undercoating coating composition of the present invention in order to further improve the coating properties of the composition. Among such leveling agents, as a fluorine-based leveling agent (trade name; the same applies hereinafter), for example, BM Chemie (B
M-CHEMIE) BM1000, BM1100;
Efka 772 and Efka 777 of Fuka Chemicals; Floren series of Kyoeisha Chemical Co., Ltd .; FC series of Sumitomo 3M Co., Ltd .; Fluonal TF series of Toho Chemical Co., Ltd., and silicone-based leveling. Examples of the agent include B-Chemie B
YK series; Shmegmann
Shfme series of Efka Chemicals; Efka 30, Efka 31, Efka 34, Efka 35, Efka 36, Efka 39, Efka 83, Efka 86, Efka 88 of Efka Chemicals, and ether-based or ester-based leveling. Examples of the agent include Carfinol manufactured by Nissin Chemical Industry Co., Ltd .; Emulgen and Homogenol manufactured by Kao Corporation.

By adding such a leveling agent, the finished appearance of the coating film is improved, and the coating film can be uniformly applied. The amount of leveling agent used is
Preferably 0.01 to 5% by weight, based on the total composition,
More preferably, the content is 0.02 to 3% by weight.

As a method of blending the leveling agent, it may be blended when preparing the composition, or may be blended with the composition at the stage of forming the coating film. It may be blended at both stages of film formation.

The composition used in the present invention may be used by blending another resin. As other resins,
An acryl-urethane resin, an epoxy resin, a polyester, an acrylic resin, a fluorine resin, an acrylic resin emulsion, an epoxy resin emulsion, a polyurethane emulsion, a polyester emulsion and the like can be mentioned.

In preparing the composition of the present invention,
When the components (c) and (d) are not used, the method of mixing the components is not particularly limited, but the components (c) and (d)
When using the components, preferably (a) to (f)
After obtaining a mixture from which the component (d) has been removed, a method of adding the component (d) to the mixture is employed.

The total solid content of the composition (I) and the composition (II) used in the present invention is preferably 50% by weight.
The following are appropriately adjusted according to the purpose of use. For example, when it is intended to impregnate a thin film forming substrate, it is usually 1 to 30% by weight, and when it is used for forming a thick film, it is usually 10 to 50% by weight, preferably 2% by weight.
0 to 45% by weight. If the total solid content of the composition exceeds 50% by weight, storage stability tends to decrease. In particular, the undercoating coating composition of the present invention preferably has a total solid content of 1 to 30% by weight, but is appropriately adjusted depending on the type of the base material, the coating method, the coating film thickness, and the like.

Suitable substrates for using the undercoat coating composition of the present invention include, for example, metals such as iron, aluminum, and stainless steel; cement, concrete, and the like.
Inorganic ceramic materials such as ALC, flexible board, mortar, slate, gypsum, ceramics, bricks; plastic molded products such as phenolic resin, epoxy resin, polyester, polycarbonate, polyethylene, polypropylene, ABS resin (acrylonitrile-butadiene-styrene resin) A plastic film such as polyethylene, polypropylene, polyvinyl alcohol, polycarbonate, 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 inorganic ceramics-based substrates, for example, polishing, eye treatment Stop,
Patterning and the like can be mentioned. Examples of the surface treatment for the wood substrate include polishing, filling, and insect repellent treatment. Examples of the surface treatment for the paper substrate include the filling and insect repellent treatment. The surface treatment for the deteriorated coating film includes, for example, kerosene.

[0085] A primer may be used in the coating composition of the present invention, if necessary. You. For example, in the case of a metal-based substrate, if it is necessary to prevent rust, in addition to the undercoating coating composition of the present invention, a primer is used. In the case of an inorganic ceramic-based substrate, the characteristics (surface roughness, , Alkalinity, etc.), the primer may be used because the opacity of the coating film differs. In the case of repainting a deteriorated coating film, a primer is used when the old coating film is significantly deteriorated.
In the case of other substrates, for example, plastic, wood, paper, glass, etc., a primer may or may not be used depending on the application. The type of primer is not particularly limited as long as it has an action of improving the adhesion between the substrate and the composition, and is selected according to the type of the substrate and the purpose of use. The primers can be used alone or as a mixture of two or more, and may be an enamel containing a coloring component such as a pigment or a clear containing no coloring component.

Examples of the type of primer include alkyd resin, aminoalkyd resin, epoxy resin, polyester, acrylic resin, urethane resin, fluororesin, acrylic silicone resin, acrylic resin emulsion, epoxy resin emulsion, polyurethane emulsion, polyester emulsion and the like. Can be mentioned. In addition, these primers can be provided with various functional groups when adhesion between the substrate and the coating film under severe conditions is required. Examples of such a functional group include a hydroxyl group, a carboxyl group, a carbonyl group, an amide group, an amine group, a glycidyl group, an alkoxysilyl group, an ether bond, an ester bond, and the like. further,
The primer may contain an ultraviolet absorber, an ultraviolet stabilizer, and the like.

As a method for applying the composition of the present invention to a substrate, a brush, a roll coater, a flow coater, a centrifugal coater, an ultrasonic coater,
Use a (micro) gravure coater, dip coat, flow coat, spray, screen process,
Electrodeposition, vapor deposition and the like can be mentioned. Further, the composition of the present invention can be applied by previously applying an undercoat to the substrate.

The undercoat coating composition of the present invention comprises:
As a dry film thickness, it is possible to form a coating film having a thickness of about 0.01 to 20 μm with a single coating and a thickness of about 0.02 to 40 μm with a double coating. Then, it is dried at room temperature, or at a temperature of about 30 to 200 ° C., usually for 0.5 to
By heating and drying for about 60 minutes, a coating film can be formed.

Topcoat Layer Various paints can be used as the topcoat layer of the undercoating coating composition of the present invention, and examples thereof include photocatalyst-containing paints, silicone-based paints, and fluorine-based paints. . As the composition used as the photocatalyst-containing paint, for example, the composition containing the component (a1) and the photocatalyst, the component (a1),
And a composition containing the component (a2) and a photocatalyst. These compositions preferably contain the above component (b), and may contain the above components (c) to (f). As the photocatalyst, titanium oxide fine particles, titanium oxide sol, and the like are preferably used.

Examples of the composition used as the silicone-based paint include a composition containing the component (a1) and a composition containing the components (a1) and (a2). These compositions may contain the components (b) to (f). Further, an aqueous dispersion obtained by dispersing a polymer obtained by condensing the component (a) and the component (a2) in an aqueous medium can be used as the coating composition.

As the composition used as the above-mentioned fluorine-based paint, for example, the above-mentioned component (a1) and (a3-
1) Structural unit represented by the following general formula (6) (Wherein, R ^{8 to} R ¹⁰ are C _m Y _{2m + 1} , m is an integer of 0 to 5,
Y is independently selected from F, H and Cl. ) And (a3-2) a structural unit represented by the following general formula (7)

Wherein Rf is a fluorine atom-containing alkyl
A group or an alkoxyalkyl group,⁸~ R^TenHaichi
Synonymous with general formula (6), and within the same meaning, general formula
R of (6) ⁸~ R^TenAnd may be different. Selected from
Having at least one structural unit, and
Having a silicon atom bonded to a group and / or a hydroxyl group
Examples include a composition containing a copolymer containing a silyl group.
It is. These compositions include the above components (b) to (f)
May be contained.

The above coating composition for top coat has a dry film thickness of about 0.01 to 20 μm in a single coat,
In the second coating, a coating film having a thickness of about 0.02 to 40 μm can be formed. Then, it is dried at normal temperature or at a temperature of about 30 to 200 ° C., usually for 0.5 to 6
By heating and drying for about 0 minutes, a coating film can be formed on various substrates. In addition, the total thickness of the undercoat layer and the overcoat layer is a dry film thickness, usually 0.04 to 80 μm.
m, preferably about 0.08 to 60 μm.

[0094]

EXAMPLES Hereinafter, embodiments of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these embodiments. Parts and% in Examples and Comparative Examples are based on weight unless otherwise specified. Various measurements and evaluations in Examples and Comparative Examples were performed by the following methods.

(1) Hardness Pencil hardness according to JIS K5400 was used. (2) Transparency After applying each composition on quartz glass so as to have a dry film thickness of 10 μm, the transmittance of visible light was measured and evaluated according to the following criteria. ◎: transmittance of 90% or more ；: transmittance of 80% or more and less than 90% △: transmittance of 70% or more and less than 80% ×: transmittance of less than 70% (3) Alkali resistance After dipping in a calcium hydroxide aqueous solution for 60 days, the state of the coating film was visually observed. (4) Resistance to Organic Chemicals 2 cc of isopropyl alcohol was dropped on the coating film, and after 5 minutes, wiped off with a cloth, and the state of the coating film was visually observed. (5) Moisture Resistance After the test piece was kept under an environment of a temperature of 50 ° C. and a humidity of 95% for 1,000 hours, the test piece was taken out and the state of the coating film was visually observed. (6) Adhesion grid test according to JIS K5400
), The tape peel test was performed three times, and the average was used. (7) Weather Resistance According to JIS K5400, an irradiation test was performed for 3,000 hours with a sunshine weather meter, and the appearance (crack, peeling, etc.) of the coating film was visually observed. (8) Water resistance After the test piece was immersed in tap water at room temperature for 60 days, the state of the coating film was visually observed. (9) Warm Water Resistance A test piece using an inorganic material was immersed in hot water at 60 ° C. for 14 days, and the state of the coating film was visually observed.

Reference Example 1 [Synthesis of component (a2)] In a reactor equipped with a reflux condenser and a stirrer, 70 parts of methyl methacrylate, 40 parts of n-butyl acrylate, 20 parts of γ-methacryloxypropyltrimethoxysilane, and acrylic 5 parts of acid, 2-hydroxyethyl methacrylate 13
Part, 1,1,1-trimethylamine methacrylimide 1
Part, 4- (meth) acryloyloxy-2,2,6,6
-1 part of tetramethylpiperidine, 150 parts of i-propyl alcohol, 50 parts of methyl ethyl ketone and 25 parts of methanol were added and mixed, followed by heating to 80 ° C with stirring, and 4 parts of azobisisovaleronitrile in xylene. The solution dissolved in 10 parts was added dropwise over 30 minutes, and then reacted at 80 ° C. for 5 hours to obtain a solid concentration of 40%.
(Hereinafter referred to as “(a2-1)”).

Reference Example 2 [Synthesis of Component (a2)] In a reactor equipped with a reflux condenser and a stirrer, 70 parts of methyl methacrylate, 40 parts of n-butyl acrylate, 20 parts of γ-methacryloxypropyltrimethoxysilane, glycidyl 18 parts of methacrylate, 1 part of 1,1,1-trimethylamine methacrylimide, 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine 1
And 150 parts of i-propyl alcohol, 50 parts of methyl ethyl ketone and 25 parts of methanol were added and mixed, and the mixture was heated to 80 ° C. with stirring, and 4 parts of azobisisovaleronitrile was dissolved in 10 parts of xylene in this mixture. After the solution was added dropwise over 30 minutes, the reaction was carried out at 80 ° C. for 5 hours to give a polymer solution having a solid content concentration of 40% (hereinafter “(a2
-2) ").

Reference Example 3 [Synthesis of Component (a2)] In a reactor equipped with a reflux condenser and a stirrer, 70 parts of methyl methacrylate, 30 parts of n-butyl acrylate, 20 parts of γ-methacryloxypropyltrimethoxysilane, 18 parts of acrylate, 10 parts of acrylamide,
1 part of 1,1,1-trimethylamine methacrylimide,
4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine 1 part, i-propyl alcohol 1
50 parts, methyl ethyl ketone 50 parts and methanol 2
After adding and mixing 5 parts, the mixture was heated to 80 ° C. while stirring, and a solution of 4 parts of azobisisovaleronitrile dissolved in 10 parts of xylene was added dropwise to the mixture over 30 minutes. The reaction was carried out for an hour to obtain a polymer solution having a solid content of 40% (hereinafter referred to as “(a2-3)”).

Reference Example 4 [Synthesis of component (a3)] After a stainless steel autoclave equipped with an electromagnetic stirrer was sufficiently replaced with nitrogen gas, the autoclave was placed in the autoclave.
150 parts of methyl isobutyl ketone, 86 parts of ethyl vinyl ether and lauroyl peroxide (radical polymerization initiator)
After charging 1.5 parts and cooling the solution in the autoclave to -50 ° C with dry ice-methanol,
Oxygen in the system was removed again with nitrogen gas. Then
Hexafluoropropylene 2 parts, perfluoro (propyl vinyl ether) 2 parts, vinyltrimethoxysilane 1
0 parts were added and the temperature was raised. The pressure inside the autoclave when the temperature inside the autoclave reached 60 ° C. was 5 kgf / cm ² . When the temperature of the reaction system is 60
The polymerization reaction was continued for 20 hours by stirring while maintaining the temperature in the autoclave at 1.5 kgf.
/ Cm ² , the reaction was stopped by cooling with water, and the component (a3) having a solid content of 40% (hereinafter referred to as “(a3-1)”)
).

Reference Example 5 [Synthesis of component (a3)] A stainless steel autoclave equipped with an electromagnetic stirrer was
After sufficient replacement with elemental gas, the autoclave
150 parts of methyl isobutyl ketone and ethyl vinyl acetate
30 parts of ter and lauroyl peroxide (radical polymerization initiator)
1.5 parts and dry the solution in the autoclave
After cooling to -50 ° C with ice-methanol,
Oxygen in the system was removed again with nitrogen gas. Then
30 parts hexafluoropropylene, perfluoro (pro
30 parts of vinylvinyl ether)
10 parts were added, and the temperature was raised. In autoclave
In the autoclave when the temperature of
Pressure is 5kgf / cm ^TwoMet. The temperature of the reaction system
By stirring at a temperature of 60 ° C., the weight is reduced for 20 hours.
The reaction is continued and the pressure in the autoclave is 1.5k
gf / cm^TwoThe reaction was stopped by water cooling when the
(A3) component (hereinafter referred to as “(a3-
2) ").

Synthesis Examples 1 to 6 [Synthesis of Coating Composition] Into a reactor equipped with a reflux condenser and a stirrer, each component (except water and post-addition components) of the kind and number of parts shown in Table 1 was added. After stirring well, water was added dropwise under stirring with the number of copies shown in Table 1 and reacted at 60 ° C. for 4 hours. Next, the post-addition component was added, the mixture was cooled to room temperature, and a predetermined amount of i-propyl alcohol was added to obtain a composition having a solid concentration of 30%. To 100 parts of the obtained composition, 66 parts of i-propyl alcohol,
After 66 parts of butyl acetate and 67 parts of methyl ethyl ketone were added and mixed well, a solution of dioctyltin dimaleate ester in i-propyl alcohol (solid content: 15%) was added to 1 part.
0 parts were added and stirred well to obtain coating compositions (I-1) to (I-6) of the present invention.

[0102]

[Table 1]

In Table 1, * 1 and * 2 are as follows. * 1: i-propyl alcohol-dispersed silica sol (silica concentration 30%) * 2: water-dispersed alumina sol (alumina concentration 20%)

Examples 1 to 6 The coating compositions obtained in the synthesis examples and the comparative synthesis examples were applied to a quartz glass plate with a bar coater and dried to form a coating film having a thickness of 1 μm. , And transparency were evaluated. Table 2 shows the results.

[0105]

[Table 2]

Reference Examples 6 and 7 (Synthesis of Coating Composition Containing Photocatalyst for Overcoating) In a reactor equipped with a reflux condenser and a stirrer, each component (except for the post-addition component) of the kind and number of parts described in Table 3 was added. The mixture was stirred well and reacted at 60 ° C. for 4 hours. Next, the mixture was cooled to room temperature, and post-additional components were added to obtain a composition having a solid content of 20%. After 100 parts of i-propyl alcohol was added to 100 parts of the obtained composition and mixed well, 10% of an i-propyl alcohol solution (15% solid content) of a reactant composed of dibutyltin diacetate and a silicate oligomer was added.
And the mixture was stirred well to obtain photocatalyst-containing coating compositions (II-1) to (II-2).

Reference Examples 8 to 9 (Synthesis of Silicone Coating Composition for Top Coating) Into a reactor equipped with a stirrer and a reflux condenser, each component (except for the post-addition component) of the type and the number of parts described in Table 3 was added. The mixture was stirred well and reacted at 60 ° C. for 4 hours. Next, the mixture was cooled to room temperature, and post-added components were added to obtain a composition having a solid concentration of about 40%. After 300 parts of i-propyl alcohol was added to 100 parts of the obtained composition and mixed well, 10% of an i-propyl alcohol solution (15% solid content) of a reactant composed of dibutyltin diacetate and a silicate oligomer was added.
Parts and stirred well to obtain silicone-based coating compositions (II-3) to (II-4).

Reference Examples 10 to 11 (Synthesis of Fluorine Coating Composition for Overcoating) In a reactor equipped with a stirrer and a reflux condenser, each component (except for water and post-addition components) of the kind and number of parts described in Table 3 was added. Was added thereto, and the mixture was stirred. Then, water was added dropwise in the number of parts shown in Table 5, and the mixture was reacted at 60 ° C. for 5 hours with stirring. Next, the mixture was cooled to room temperature, and 10 parts of acetylacetone was added thereto to add a fluorine-containing coating composition (II-5) to (II-5) having a solid concentration of about 30%.
-6) was obtained.

[0109]

[Table 3]

* 5) Anatase type titanium oxide content: 20%
(Solid content: 20%) Examples 7 to 22, Comparative Examples 1 to 6 The undercoating coating composition having the composition described in Tables 4 to 7 having a dry film thickness of 1 was applied to the surface of a PET film having a thickness of 50 µm.
The coating composition for overcoating was then applied to a thickness of 0.2 μm and dried to obtain a cured product. Various evaluations were performed on the obtained cured product. The results are shown in Tables 4 to 7.

[0111]

[Table 4]

[0112]

[Table 5]

[0113]

[Table 6]

[0114]

[Table 7]

Examples 23 to 49 Each of the base materials shown in Tables 8 and 9 was coated with the undercoating coating composition shown in Tables 8 and 9 to a dry film thickness of 1 μm.
m, and then dried. Then, the coating composition for overcoating described in Tables 8 and 9 was dried to a dry film thickness of 0.1.
It was applied to a thickness of 2 μm and dried to obtain a cured product. The obtained cured product was evaluated for adhesion and weather resistance. The results are shown in Tables 8 and 9. In Examples using two types of undercoating coating compositions, the compositions were not mixed, and an undercoating layer having a thickness of 1 μm was provided on the substrate.

[0116]

[Table 8]

[0117]

[Table 9]

[0118]

The coating composition of the present invention can be used as an undercoat to form a substrate, a photocatalyst-containing coating,
It is possible to impart long-term adhesion and weather resistance to various paints such as silicone paints and fluorine paints.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Toshiki Sakagami 2-11-11 Tsukiji, Chuo-ku, Tokyo JSR Co., Ltd. F-term (reference) 4J038 DL021 DL031 GA03 HA216 HA446 JC32 PA07

Claims (2)

[Claims] (A1) 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 Is an integer.)
And at least one selected from the group consisting of an organosilane represented by the following formula, a hydrolyzate of the organosilane and a condensate of the organosilane, and (b) colloidal silica and / or colloidal alumina. A coating composition for undercoating, characterized by: 2. (a1) 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 Is an integer.)
At least one selected from the group consisting of an organosilane represented by the following formula, a hydrolyzate of the organosilane and a condensate of the organosilane; (a2) a silyl having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group; An undercoating coating composition comprising a group-containing polymer and (b) colloidal silica and / or colloidal alumina.