JP2002294157A - Coating composition and cured product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organosilane-based coating material excellent in coating film appearance, adhesion, weather resistance, etc., high in hardness and particularly excellent in hydrophilicity. SOLUTION: (a) General formula (R ¹ ) _n Si (OR ² ) _4-n
, At least one selected from the group consisting of a hydrolyzate of the organosilane and a condensate of the organosilane, (c) a polymer-type hydrophilizing material, and if necessary, (b) A) a silyl group-containing polymer;

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating composition and a cured product thereof, and more particularly, to a hydrophilic organosilanol-based composition having a high hardness and excellent coating film appearance, adhesion, transparency and weather resistance. Related to coating materials.

[0002]

2. Description of the Related Art The technical development of organosilane-based coating materials has been promoted as maintenance-free coating materials having excellent weather (light) resistance and stain resistance. The performance requirements for such organosilane-based coating materials are becoming more and more severe. In recent years, coating film appearance, adhesion, weather resistance, heat resistance, alkali resistance, organic chemical resistance, moisture resistance, (temperature) resistance There is a need for a coating material that is excellent in water-based properties, insulation resistance, abrasion resistance, stain resistance, and the like, and that can form a coating film having high hardness.

In particular, it has been recognized that in order to improve the stain resistance, it is advisable to make the coating film surface hydrophilic, and for example, a method of adding a hydrophilic substance or a water-soluble substance has been proposed. However, in such a method, it is difficult to maintain the hydrophilicity of the coating film surface at a sufficient level for a long period of time because the hydrophilic substance and the water-soluble substance gradually deteriorate with light or are washed away with water. is there.

On the other hand, as a coating composition which satisfies the required performance of an organosilane-based coating material to some extent, a composition comprising a partial condensate of an organosilane, a dispersion of colloidal silica, and a silicone-modified acrylic resin (Japanese Patent Laid-Open No. 60-1985). JP-A-135465), a composition containing a condensate of an organosilane, a chelate compound of zirconium alkoxide and a vinyl resin having a hydrolyzable silyl group (JP-A-64-1769), a condensate of an organosilane, colloid A composition comprising alumina and a hydrolyzable silyl group-containing vinyl resin (US Pat. No. 4,904,721) has been proposed.

However, Japanese Patent Application Laid-Open No. Sho 60-1354 discloses
Coatings obtained from the compositions described in US Pat. No. 65,904 and US Pat. No. 4,904,721 have the disadvantage that gloss is reduced by prolonged irradiation with ultraviolet light.
Further, the composition described in JP-A-64-1769 has a problem that storage stability is not sufficient and gelation is likely to occur in a short period of time when the solid content concentration is increased.

Further, the applicant of the present application has already disclosed a hydrolyzate of organosilane and / or a partial condensate thereof, a vinyl resin having a hydrolyzable and / or silyl group having a silicon atom bonded to a hydroxyl group, and a metal chelate. A coating composition containing a compound and β-diketones and / or β-ketoesters
345877). This composition is:
Although excellent in the balance of the above-mentioned coating film performance required for the organosilane-based coating material, improvement in these performances is required, and particularly improvement in stain resistance is strongly demanded.

[0007] All of the above organosilane-based coating materials are not sufficiently hydrophilic, and even if a general hydrophilizing agent is blended in order to improve the hydrophilicity, they easily bleed out, and even over time. The effect of hydrophilicity tends to decrease. Further, in the conventional organosilane-based coating materials, at present, no material having a coating film appearance, adhesion, transparency, weather resistance, and hydrophilicity has been found.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a hydrophilic organosilanol-based coating material which has high hardness and is excellent in coating film appearance, adhesion, transparency and weather resistance.

[0009]

The present invention provides (I) (a)
The following general formula (1) (R ¹ ) _n Si (OR ² ) _4-n ... (1) (wherein, when two R ^{1 s} are present, they are the same or different and have 1 to 50 carbon atoms) Wherein R ² is the same or different and has 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms,
And n is an integer of 0 to 2), at least one selected from the group consisting of an organosilane, a hydrolyzate of the organosilane, and a condensate of the organosilane. Seed (hereinafter, also referred to as “component (a)”), and (c) a coating composition (hereinafter, also referred to as “composition (I)”) containing a polymer-type hydrophilizing material. The present invention relates to (II) a component (a) according to claim 1, and (b) a polymer containing 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 coating composition comprising a (c) polymer-type hydrophilicity-imparting material (hereinafter also referred to as “composition (II)”; composition (I) ~ Composition (II) collectively Relates also referred) and composition "of the present invention. Here, as the above-mentioned (c) polymer type hydrophilic material, a comb polymer having a hydrophilic group is preferable. Next, the present invention relates to a cured product obtained by forming a coating film obtained from the coating composition on a substrate. Here, as the base material, a ceramic base material, concrete, metal, glass, plastic molded body, plastic film, paper or fiber structure is preferable.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The composition of the present invention comprises the above component (a) or a component (a) to (b) as a binder,
(C) Since it is mainly composed of a polymer-type hydrophilizing material, it has excellent hydrophilicity, high hardness, excellent coating film appearance, adhesion, transparency, and weather resistance, and particularly semipermanent hydrophilicity. It has the property of lasting.

Composition (I) The composition (I) contains (a) an organosilane or a hydrolytic condensate thereof, and (c) a polymer-type hydrophilizing material as main components.

Component (a): Component (a) is an organosilane represented by the above general formula (1) (hereinafter referred to as "organosilane (1)"), a hydrolyzate of organosilane (1), and an organosilane. At least one selected from condensates of silane (1). That is, the component (a) may be only one of these three types, a mixture of any two types, or a mixture containing all three types. The hydrolyzate and the condensate are collectively referred to as
Hereinafter, it is also referred to as a hydrolysis condensate.

Here, the hydrolyzate of the above organosilane (1) contains 2 to 4 O compounds 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. 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 all are condensed, but only some of the silanol groups are condensed,
This is a concept that 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 are also mentioned. 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) Acryloxy group, ureido group, ammonium base, Si- (RO) _n- (R'O) _m- R "(wherein R and R 'are the same or different and represent an alkyl group having 1 to 5 carbon atoms) , R ″ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and n and m are each an integer of 2 to 30 where n + m is an integer of 2 to 30).
Among them, a group represented by Si- (RO) _n- (R'O) _m- R "is preferable. Si- (RO) _n- (R'O) _m-
The group represented by R ″ is a polyoxyalkylene group such as a polyoxyethylene group, a polyoxypropylene group, and a poly (oxyethylene / oxypropylene) group.
By the component having such a terminal functional group,
The co-condensate of the component (a) and the component (b) in the composition (II) described later becomes hydrophilic. In the general formula (1), R ¹ is 2
When they exist, 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 and 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, tetra-n-butoxysilane and the like. 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, trialkoxysilane alone or
3- (meth) acryloyloxypropyl group, or 3
A combination of 5 to 60 mol% of a trialkoxysilane containing a glycidoxypropyl group or a 2- (3,4-epoxycyclohexyl) group and 95 to 40 mol% of a methyltrialkoxysilane, or 40 to 9 of a trialkoxysilane;
A combination of 5 mol% and 60 to 5 mol% of dialkoxysilane, and a combination of 30 to 95 mol% of trialkoxysilane and 70 to 5 mol% of organopolysiloxane having Mw of 3,000 to 15,000 are preferred. 3-
By using a (tri) acryloyloxypropyl group, a 3-glycidoxypropyl group or a 2- (3,4-epoxycyclohexyl) group-containing trialkoxysilane in combination with a methyltrialkoxysilane, In addition to softening, adhesion to an organic material or the like can be provided, and compatibility with an organic compound can be improved. Further, by using a combination of dialkoxysilane and trialkoxysilane or a combination of trialkoxysilane and organopolysiloxane, the resulting coating film can be softened and 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 (a). However, as described later, the organosilane (1) is When the composition is prepared by mixing with the remaining components, it is preferable that the organosilane (1) is hydrolyzed and condensed by adding an appropriate amount of water to obtain the component (a). The amount of water used for the hydrolysis / condensation of the organosilane (1) is usually 0.3 to 3 with respect to 1 mol of the organosilane (1).
Mol, preferably about 0.4 to 2 mol. The hydrolysis / condensation reaction at this time is performed at a temperature of 30 to 80 ° C, preferably 40 to 70 ° C, for a reaction time of 0.5 to 10 hours, preferably about 1 to 7 hours. When the component (a) is used as a hydrolysis-condensation product, the weight-average molecular weight in terms of polystyrene (hereinafter referred to as “Mw”) of the hydrolysis-condensation product is preferably from 800 to 100,000, more preferably from 1,100. 000 to 50,000.

The commercial products of the component (a) 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, silicone resin manufactured by Shin-Etsu Chemical Co., Ltd., hydroxyl group-containing polydimethylsiloxane manufactured by Dow Corning Asia Co., Ltd., and silicon oligomer manufactured by Nippon Yunika Co., Ltd. May be used. In the present invention, the component (a) may be used alone or
A mixture of more than one species can be used.

(C) High-molecular-weight hydrophilizing material: The (c) high-molecular-weight hydrophilizing material used in the composition (I) imparts hydrophilicity to the obtained composition and can be applied to various substrates. It has the function of improving the adhesiveness. (C) Since the polymer-type hydrophilizing material itself has a high molecular weight, it does not bleed out from the coating film, maintains the hydrophilic property semipermanently, has no haze of the coating film, and has high transparency. To maintain their sexuality. (C) The polymer type hydrophilic material is a comb polymer having a hydrophilic group such as a polyethylene glycol group or a hydroxyl group (a comb polymer containing a hydrophilic group). Here, the comb polymer is a branched polymer in which a large number of branches appear at equal intervals on a trunk.
It can be obtained by polymerization of a monomer having a long-chain alkyl group or homopolymerization of a macromonomer. Specific examples of the comb polymer having a hydrophilic group include a hydrophilic agent solution HP-S-7-11, HP-S-7-12 manufactured by Mitsubishi Chemical Corporation.

The amount of the component (c) used in the composition (I) is usually 0.5 to 40 in terms of solid content in the component (a) (in terms of a completely hydrolyzed condensate) to the component (c). %, Preferably 3 to 30% by weight. If it is less than 0.5% by weight, the hydrophilicity is not sufficient, while if it exceeds 40% by weight, the surface hardness of the coating film is significantly reduced. The amount of the component (c) used in the composition (II) described below is determined based on the amount of the component (a) (complete hydrolyzed condensate), the component (b),
It is the weight% of the component (c) in terms of the solid content based on the total amount of the components. The amount of the component (c) used in the composition (II) is the same as the mixing amount range in the composition (I).

The composition (I) of the present invention contains the above-mentioned components (a) and (c) as essential components, and optionally contains optional components described below. And water and / or an organic solvent is used to adjust the total solid content of the composition. Other roles of water and / or organic solvents include being adaptable to various coating methods and further improving the dispersion and storage stability of the composition. Water is also used for hydrolysis and condensation of the component (a) and the component (b) described below, as described above.

The organic solvent is not particularly limited as long as it can uniformly mix the above components.
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 thereof 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) contains the above-mentioned component (a), (b) a polymer having a silyl group, and (c) a polymer-type hydrophilizing material as main components. Here, the component (a) and the component (c) in the composition (II), the water and the organic solvent used are the same as those in the composition (I)
In the above, the components (a) and (c) are the same as the components, water, and the organic solvent.
(B) The silyl group-containing polymer will be described.

(B) Silyl group-containing polymer; composition (II)
(B) is a polymer having a silyl group having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group at a terminal or a side chain (hereinafter, also referred to as “specific silyl group”). The component (b) is such that when a coating film obtained from the composition (II) is cured, the hydrolyzable group and / or hydroxyl group in the silyl group is co-condensed with the component (a). Thereby, excellent coating film performance can be obtained. The content of the specific silyl group in the component (b) is usually from 0.1 to 60 mol%, preferably from 0.5 to 50 mol%, in the component (b).

The specific silyl group preferably has the following general formula (2) (Wherein, X represents a hydrolyzable group such as a halogen atom, an alkoxy group, an acetoxy group, a phenoxy group, a thioalkoxy 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 And represents an aralkyl group having 1 to 10 carbon atoms, and i is an integer of 1 to 3).

The component (b) is a monomer (b-1) containing a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group, which constitutes the specific silyl group represented by the general formula (2). And, if necessary, (b-
2) It may be obtained by further polymerizing other monomers copolymerizable with these monomers (hereinafter, also referred to as “(b-2) monomer”). In addition, the component (b) is obtained by polymerizing the monomer (b-2) into a silane compound having a functional group capable of reacting with a hydrolyzable group or a hydroxyl group (hereinafter referred to as “(b- 3) also referred to as “silane compound”).

Here, the monomer (b-1) is a monomer containing a polymerizable unsaturated double bond and a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group in one molecule. is there. Examples of the monomer (b-1) include the following general formula (2) ′ [Wherein X, R ³ and i in the formula are the same as X, R ³ and i in the general formula (2), respectively, and R ⁴ represents an organic group having a polymerizable double bond]. A silane compound (hereinafter also referred to as “unsaturated silane compound”) and the like can be given.

Specific examples of the above unsaturated silane compounds include CH ₂ ＝ CHSi (CH ₃ ) (OCH ₃ ) ₂ and CH ₂ ＝
CHSi (OCH ₃ ) ₃ , CH ₂ ＣＨCHSi (OC ₂ H ₅ )
₃ , CH ₂ ＣＨCHSi (CH ₃ ) Cl ₂ , CH ₂ ＣＨCHSi
Cl ₃ , CH ₂ ＣＨCHCOO (CH ₂ ) ₂ Si (CH ₃ ) (O
CH ₃ ) ₂ , CH ₂ ＣＨCHCOO (CH ₂ ) ₂ Si (OC
_{H 3) 3, CH 2 =} CHCOO (CH 2) 3 Si (CH 3)
(OCH ₃ ) ₂ , CH ₂ ＣＨCHCOO (CH ₂ ) ₃ Si (O
CH ₃ ) ₃ , CH ₂ ＣＨCHCOO (CH ₂ ) ₂ Si (CH ₃ )
Cl ₂ , CH ₂ ＣＨCHCOO (CH ₂ ) ₂ SiCl ₃ , C
H 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 (CH ₃ ) COO (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , C
H 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 (CH ₂ ) ₂ S
i (CH ₃ ) Cl ₂ , CH ₂ ＣC (CH ₃ ) COO (CH ₂ )
₂ SiCl ₃ , CH ₂ ＣC (CH ₃ ) COO (CH ₂ ) ₃ S
i (CH ₃ ) Cl ₂ , CH ₂ ＣC (CH ₃ ) COO (CH ₂ )
₃ SiCl ₃ ,

[0033]

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And the like. These are 1
Species can be used alone or in combination of two or more.

The (b-2) monomer which is another monomer copolymerizable with the (b-1) monomer includes, for example, (a) methyl (meth) acrylate, ethyl (meth)
Acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, amyl (meth) acrylate, i-amyl (meth) acrylate, hexyl (meth) acrylate, 2
Alkyl (meth) acrylates having 4 to 12 carbon atoms, such as -ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, and cyclohexyl methacrylate; (ii) styrene, α-methylstyrene, 4-methylstyrene, -Methylstyrene, 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;

(C) Hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyamyl (meth) acrylate, hydroxyhexyl (meth) acrylate, etc. Hydroxyalkyl (meth) acrylate; epoxy compounds such as allyl glycidyl ether, glycidyl (meth) acrylate, and methyl glycidyl (meth) acrylate;

(D) 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;

(E) (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; (f) vinyl compounds such as vinyl chloride, vinylidene chloride and fatty acid vinyl ester; (g) 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1 , 3-butadiene, 2-
Neopentyl-1,3-butadiene, 2-chloro-1,
3-butadiene, 2-cyano-1,3-butadiene, isoprene, substituted straight-chain conjugated pentadienes substituted with a substituent such as an alkyl group, a halogen atom, a cyano group, straight-chain and side-chain conjugated hexadienes, etc. (H) (meth) acrylic acid, fumaric acid, itaconic acid, monoalkylitaconic acid, maleic acid, crotonic acid, 2-
Ethylenically unsaturated carboxylic acids such as (meth) acryloyloxyethyl hexahydrophthalic acid;

(Ii) vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; (nu) 4- (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;

(V) Vinyl glycidyl ether, 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl Vinyl ethers such as vinyl ether;

(ヲ) Allyl ethers such as allyl glycidyl ether, 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether and glycerol monoallyl ether; (v) methyl vinyl ether, ethyl vinyl ether;
n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, n-
Alkyl vinyl ethers or cycloalkyl vinyl ethers such as octyl vinyl ether, n-dodecyl vinyl ether, 2-ethylhexyl vinyl ether and cyclohexyl vinyl ether;

(F) 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, 2- (perfluorobutyl) ethyl (meth) acrylate , 2- (perfluorohexyl) ethyl (meth) acrylate, 2-
(Perfluorooctyl) ethyl (meth) acrylate, 2- (perfluorodecyl) ethyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, 1H, 1H, 2H, 2H-heptadecafluorodecyl In addition to fluorine-containing (meth) acrylates such as (meth) acrylate; and dicaprolactone. These can be used alone or in combination of two or more.

The (b-3) silane compound used in the above addition reaction includes halogenated silanes such as methyldichlorosilane, trichlorosilane and phenyldichlorosilane; methyldiethoxysilane, methyldimethoxysilane and phenyldimethoxysilane. Alkoxysilanes such as silane, trimethoxysilane and triethoxysilane; acyloxysilanes such as methyldiacetoxysilane, phenyldiacetoxysilane and triacetoxysilane;
Examples include aminoxysilanes such as methyldiaminoxysilane, triaminoxysilane, and dimethylaminoxysilane. These can be used alone or in combination of two or more.

As the polymerization method for producing the component (b), for example, a method in which a monomer is added in a lump and polymerization is performed, a part of the monomer is polymerized, and then the remainder is continuously processed Or a method of adding the monomer intermittently, or a method of continuously adding the monomer 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.

The content of the specific silyl group in the component (b) is generally 0.1 to 60 mol%, preferably 0.5 to 60 mol%.
The amount is 50 mol%. If less than 0.1 mol%,
The effect of co-condensation with the component (a) cannot be obtained. On the other hand, 60
When the amount exceeds mol%, the storage stability of the obtained composition tends to deteriorate. The structural unit [(b-2) structural unit] composed of the monomer (b-2), which is another copolymerizable monomer, is usually 90 mol% or less in the component (b). Preferably, it is about 80 mol% or less.

Other examples of the component (b) include a specific silyl group-containing epoxy resin and a specific silyl group-containing polyester resin. The specific silyl group-containing epoxy resin is, for example, an epoxy group in an epoxy resin such as a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a hydrogenated bisphenol A type epoxy resin, an aliphatic polyglycidyl ether, and an aliphatic polyglycidyl ester. And aminosilanes, vinylsilanes, carboxysilanes, glycidylsilanes, etc. having a specific silyl group. 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.

The Mw of the component (b) is preferably 2,000
0-100,000, more preferably 4,000-5
000. The amount of the component (b) used in the composition (II) is usually 2 to 900% by weight, preferably 10 to 80% by weight, based on the component (a) (in terms of a completely hydrolyzed condensate).
0% by weight. In this case, if the amount of the component (b) is less than 2% by weight, the resulting coating film may have poor alkali resistance, whereas if it exceeds 900% by weight, the weather resistance and light resistance of the coating film may be poor. Tends to decrease. In addition, the complete hydrolysis condensate refers to R ² O— of the organosilane (1).
A group in which a group is hydrolyzed by 100% to form a SiOH group and further completely condensed to form a siloxane structure.

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

In the composition of the present invention, the compositions (I) to (II) can be used alone, but the compositions (I) and (II) are used in combination. It goes without saying that it can be done. The compositions (compositions (I) to (II)) of the present invention may further contain, as optional components, the following components (d) to (g). Hereinafter, these components will be described.

Component (d): The component (d) is a catalyst that promotes the hydrolysis / condensation reaction of the organosilane (1) constituting the component (a) and the component (b). By using the component (d), the curing speed of the obtained coating film is increased, and the molecular weight of the polysiloxane resin generated by the polycondensation reaction of the organosilane component used is increased,
A coating film with excellent strength and long-term durability can be obtained,
In addition, the thickness of the coating film and the painting work are also facilitated.

The component (d) 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 compounds 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 (3) (hereinafter referred to as “organometallic compound (3)”) 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.

M (OR^Five)_r(R⁶COCHCOR⁷)_s... (3) [where M is zirconium, titanium or aluminum
And R^FiveAnd R⁶Are the same or different and are ethyl
Group, n-propyl group, i-propyl group, n-butyl group,
sec-butyl group, t-butyl group, n-pentyl group, n
-Charcoal such as hexyl, cyclohexyl, phenyl, etc.
A monovalent hydrocarbon group having a prime number of 1 to 6, ⁷Is R^FiveAnd
And R⁶And other monovalent hydrocarbon groups having 1 to 6 carbon atoms.
Or methoxy, ethoxy, n-propoxy, i-
Propoxy group, n-butoxy group, sec-butoxy group,
t-butoxy group, lauryloxy group, stearyloxy
Represents an alkoxyl group having 1 to 16 carbon atoms such as a group,
And s are integers from 0 to 4, and (r + s) = (valence of M)
It is. ]

Specific examples of the organometallic compound (3) 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-propoxy aluminum, di-i-propoxy ethyl acetoacetate aluminum, di-
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.

Of these organometallic compounds (3) 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.

Further, specific examples of the organotin compound include:
(C ₄ H ₉ ) ₂ Sn (OCOC ₁₁ H ₂₃ ) ₂ , (C ₄ H ₉ ) ₂ S
n (OCOCH = CHCOOCH ₃ ) ₂ , (C ₄ H ₉ ) ₂ S
n (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 = CHCO
OCH ₃ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (OCOCH = CHCO
OC ₄ H ₉ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (OCOCH = CHC
OOC ₈ H ₁₇ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (OCOCH = CH
COOC ₁₆ H ₃₃ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (OCOCH =
CHCOOC ₁₇ H ₃₅ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (OCOC
H = CHCOOC ₁₈ H ₃₇ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (OC
OCH = CHCOOC ₂₀ H ₄₁ ) ₂ ,

[0059] (C ₄ H ₉ ) Sn (OCOC ₁₁ H ₂₃ ) ₃ , (C ₄ H ₉ ) Sn
Carboxylic acid type organotin compounds such as (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,

[0061] 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 Sn
Organic tin oxides such as O, (C ₈ H ₁₇ ) ₂ SnO,
Reaction products of these organic tin oxides with ester compounds such as silicate, dimethyl maleate, diethyl maleate and dioctyl phthalate.

The component (d) 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 (d) 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 (d) used is
In the case other than an organometallic compound or the like, the composition of the present invention [(a)
Component (complete hydrolyzed condensate) and component (c), or component (a) (complete hydrolyzed condensate),
The total amount of the component (b) and the component (c), the same applies hereinafter] 10
0 to 100 parts by weight, preferably 0.01 to 80 parts by weight, more preferably 0.1 to 100 parts by weight, based on 0 parts by weight.
５０50 parts by weight.

Component (e): The component (e) is represented by the following general formula (4): R ⁶ COCH ₂ COR ⁷ (4) wherein R ⁶ and R ⁷ are the same as those in the organometallic compound (3). It is synonymous with R ⁶ and R ^{7 in} general formula (3), respectively.
Β-diketones and β-ketoesters represented by
It is at least one selected from the group consisting of carboxylic acid compounds, dihydroxy compounds, amine compounds, and oxyaldehyde compounds. Such a component (e) is particularly preferably used together when an organometallic compound or the like is used as the component (d).

The component (e) functions as a stability improver for the composition. That is, the component (e) coordinates to a metal atom such as the above-mentioned organometallic compound, and the action of accelerating the condensation reaction of the above-mentioned component (a) or (b) by the organometallic compound is appropriately controlled. Is presumed to act to further improve the storage stability of the obtained composition.

Specific examples of the component (e) 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 (e) can be used alone or in combination of two or more.

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

Component (f) The component (f) in the present invention is silica, alumina or zirconia, preferably silica fine particles, alumina fine particles or zirconia fine particles dispersed in water or an organic solvent. , Silica sol, alumina sol, zirconia sol and the like. The average particle diameter of these fine particles is preferably 500
μm or less, more preferably 200 μm or less. The component (f) serves to improve the hardness of the cured coating film, improve the flexibility, and increase the critical thickness in the composition of the present invention.

Examples of the component (f) include silica such as Snowtex, isopropanol silica gel, and 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, for example, alumina sol-100, alumina sol-200, and alumina sol-520 manufactured by Nissan Chemical Industries, Ltd., and alumina sol manufactured by Catalyst Chemicals, Inc.
Alumina Cresol, manufactured by Kawaken Fine Chemical Co., Ltd.
And aluminum oxide C manufactured by Degussa West Germany. Furthermore, examples of the zirconia sol include zirconia sol manufactured by Nissan Chemical Industries, Ltd. In the composition of the present invention, the component (f) can be used alone or in combination of two or more. The amount of the component (f) used in the composition is the composition (solid content conversion) 1 of the present invention.
The amount is usually 5 to 500 parts by weight, preferably 10 to 400 parts by weight, more preferably 15 to 300 parts by weight, based on 00 parts by weight.

Component (g): Component (g) is an inorganic oxide fine particle and / or sol having an ultraviolet absorbing ability such as cerium oxide and zinc oxide, and further includes titanium oxide, zirconium oxide and tin oxide. And / or a sol of a composite metal oxide containing a substance. In the composition of the present invention, the ultraviolet absorbing ability of the component (g) enables the ultraviolet absorbing ability of the coating film to be obtained without substantially impairing the coating film performance, and prevents the deterioration of organic substances due to ultraviolet light. Can be.

The component (g) is, for example, cerium oxide.
Examples of ceramics and zinc oxide manufactured by Taki Kagaku Co., Ltd.
ZS-303 manufactured by Sumitomo Osaka Cement Co., Ltd.
I can do it. As the Ti-Zr-Sn composite oxide, diacid
Titanium chloride (TiO_Two), Zirconium oxide (ZrO)_Two)
And tin oxide (SnO)_Two3) each metal oxide
Mixture or solid solution, or
Metal, zirconium and tin.
Of metal oxides formed by oxidizing alloys or solid solutions
It may be a body and is not particularly limited. Thus, the book
The component (g) used in the composition of the present invention includes, for example,
For example, a ternary solid solution of Ti-Zr-Sn-based metal oxide (roller
Id). The composition of the component (g) is Ti, Zr or
And the total metal content of Sn, the Ti content is usually 10 to 70
%, Preferably 15 to 60% by weight (however, Ti +
(Zr + Sn = 100% by weight). Ti content is 10 layers
If the amount is less than%, sufficient ultraviolet absorbing ability cannot be obtained, while
If the content exceeds 70% by weight, the organic oxide decomposability of titanium oxide
Organic compounds such as liquid crystal may be decomposed. Also,
The Zr content and the Sn content are each 1 to 89% by weight.
You. In addition, as a metal oxide having ultraviolet absorption ability
Is, for example, ZnO, CeO _TwoEtc.
The form of the presence of these metal oxides is the same as above.
You. Further, these metal oxides constitute the component (g).
And a complex with the above metal oxide. this
The commercial products include Taipaque TT manufactured by Ishihara Sangyo Co., Ltd.
O, ZW-143, ZW- manufactured by Sumitomo Osaka Cement Co., Ltd.
513C, ZS-300, ZS-303, ZnO-10
0, ZnO-200, Z-NO manufactured by Mitsui Kinzoku Mining Co., Ltd.
UVE, Nidral, manufactured by Taki Kagaku Co., Ltd.
CERIGARD, manufactured by Gaku Kogyo Co., Ltd.
-K29 and the like.

The above component (g) may be present in the form of fine particles, an aqueous sol in which the fine particles are dispersed in water, or a solvent sol in which a polar solvent such as methyl alcohol or a non-polar solvent such as toluene is dispersed. . In the case of a solvent-based sol, it may be further diluted with water or a solvent depending on the dispersibility of the ternary fine particles. The average particle diameter of these ternary fine particles is preferably as small as possible from the viewpoint of ultraviolet absorbing ability, preferably 0.5 μm or less, particularly preferably 0.1 μm or less. By atomizing the above components, an ultraviolet absorber that can absorb ultraviolet rays of 300 nm or less by 80% or more and can be used semipermanently without deterioration can be obtained. In addition, because the uniform dispersibility is good, transparency,
An excellent coating composition such as storage stability 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 used by adding a surfactant, a dispersant, a coupling agent, or the like, or by performing a surface treatment with them. Can be
When the component (g) 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 (g) into the composition of the present invention, in the case of the composition (I), the above (a),
(C) component; in the case of the composition (II), the above (a),
It may be added after the preparation of the composition comprising the components (b) and (c) and other additives described below, or may be added during the preparation of the composition of the present invention, and in the presence of the component (g). ,
The organosilanes (1) and (b) constituting the component (a) can be hydrolyzed and condensed. When the component (g) is added during the preparation of the composition, the semiconductor compound in the component (g) can be co-condensed with the component (a) or the component (b), thereby improving the dispersibility of the component (g). be able to. When the component (g) is an aqueous sol, it is preferably added at the time of preparing the composition. Also, when the viscosity of the system increases due to the mixing of the component (e), the component (g) is preferably used.
More preferably, the components are added during the preparation of the composition.

The commercially available products of the component (g) include HIT-30M and HIT-32M manufactured by Nissan Chemical Industries, Ltd. In the composition of the present invention, the component (g) can be used alone or in combination of two or more.

The amount of the component (g) is usually 1 to 500 parts by weight, preferably 0.5 to 300 parts by weight, based on 100 parts by weight of the composition of the present invention (in terms of solids). It is. In the composition of the present invention, if the use amount of the component (g) is too small, the ultraviolet absorbing ability becomes insufficient, while if it is too large, the film formability of the obtained composition is inferior and cracking or peeling may occur. is there.

Other additives; Also, the composition of the present invention includes:
As long as the transparency is not impaired, a filler can be separately added and dispersed in order to color and thicken the obtained coating film.

The composition of the present invention may further contain, if desired, a known dehydrating agent such as methyl orthoformate, methyl orthoacetate, 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 surfactants, silane coupling agents, titanium coupling agents, and dyes.

The composition of the present invention contains, for example, 360
For the purpose of increasing the ability to absorb ultraviolet light below nm,
A metal oxide having an ultraviolet absorbing ability other than the component (g) may be blended. Further, in the composition of the present invention, an organic ultraviolet absorber, an ultraviolet stabilizer, or the like may be used for the purpose of improving weather resistance and durable adhesion. Examples of the organic ultraviolet absorber include salicylic acid, benzophenone, benzotriazole, cyanoacrylate, and triazine. Examples of the ultraviolet stabilizer include piperidine.

Further, a leveling agent may be added to the composition of the present invention in order to further improve the coating property of the composition. Among such leveling agents,
Examples of the fluorine-based leveling agent (trade name; the same applies hereinafter) include BM1000 and BM1100 manufactured by BM-CHEMIE; Efka 772 and 777 manufactured by Efka Chemicals; Floren series manufactured by Kyoeisha Chemical Co., Ltd. FC series of Sumitomo 3M Co., Ltd .; Fluornal TF series of Toho Chemical Co., Ltd .; and as a silicone-based leveling agent, for example, BYK series of Big Chemie Co .; and Shmego series of Shmegmann Co. ; Efka 30 and Efka 3 of Efka Chemicals
1, Efuka 34, Efka 35, Efka 36, Efka 3
9, Efka 83, Efka 86, Efka 88 and the like. Examples of the ether-based or ester-based leveling agent include Carfinol of Nissin Chemical Industry Co., Ltd .; Emulgen and Homogenol of Kao Corporation. Can be mentioned.

By blending 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.

Method for Preparing the Composition of the Present Invention: In preparing the composition of the present invention, when the components (d) and (e) are not used, the method of mixing the components is not particularly limited. When the component (d) and the component (e) are used, preferably, after obtaining a mixture excluding the component (e) among the components (a) to (g), the component (e) is added thereto. Is adopted.

The total solid content of the composition of the present invention is preferably 50% by weight or less, and is 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 it is 20 to 45% by weight. If the total solid content of the composition exceeds 50% by weight, storage stability tends to decrease. In particular, the composition of the present invention has a total solid content of 1%.
It is preferably from 30% by weight to 30% by weight, but is appropriately adjusted according to the type of the base material, the coating method, the coating film thickness and the like. In addition,
In the composition of the present invention, the total solid content may be adjusted by reducing or supplementing the water and / or organic solvent.

Substrates suitable for using the composition of the present invention include, for example, glass such as float glass and soda glass; polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, (tri or di) acetyl cellulose, A plastic film or a plastic molded body made of a plastic such as an acrylic resin or a thermoplastic norbornene resin can be used. Also, the substrate is not limited to these,
Metals such as iron, aluminum and stainless steel; cement,
Inorganic ceramic materials such as concrete, ALC, flexible board, mortar, slate, gypsum, ceramics, brick, etc .; phenolic resin, epoxy resin, acrylic resin, polyamide, polyethylene, polypropylene, A
Plastic molded products such as BS resin (acrylonitrile-butadiene-styrene resin) and polycarbonate; polyethylene, polypropylene, polyvinyl alcohol,
Examples thereof include plastic films such as polyurethane and polyimide, wood and paper, and fabrics (fibrous structures) such as nonwoven fabrics, woven fabrics and knitted fabrics. Depending on the application, 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.

A primer may be used in the composition of the present invention, if necessary. The type of primer is not particularly limited as long as it has an effect 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 in combination of two or more.

Examples of the type of the 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, Examples of the composition of the present invention include a composition obtained by removing the component (c) from the composition of the present invention, and a composition composed of only the component (a) or the component (a) and the component (b) of the present invention. In addition, these primers can be provided with various functional groups when the 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,
Examples include an amide group, an amine group, a glycidyl group, an alkoxysilyl group, an ether bond, and an ester bond. Further, an ultraviolet absorber, an ultraviolet stabilizer and the like may be blended in the primer.

As a method for applying the composition of the present invention to a substrate, any of the compositions may be applied using a brush, a roll coater, a flow coater, a spin coater, an ultrasonic coater, a (micro) gravure coater, or the like. Examples include dip coating, flow coating, spraying, screen processes, electrodeposition, and vapor deposition. Further, the composition of the present invention can be applied by previously applying an undercoat to the substrate.

The coating composition of the present invention can form a coating film having a dry film thickness of about 0.01 to 20 μm in a single application and a thickness of about 0.02 to 40 μm in a double application. . The film thickness can be adjusted according to the application. Then, dry at room temperature, or 30 ~ 2
By heating and drying at a temperature of about 00 ° C. for about 0.5 to 60 minutes, a coating film (cured body) can be formed.

According to the coating composition of the present invention, the coating film is excellent in appearance, adhesion, transparency and weather resistance, and particularly excellent in hydrophilicity. Further, when the component (g) is added, it has an ultraviolet absorbing ability and can prevent deterioration of the organic base and the substrate. The cured film (cured body) obtained from the composition of the present invention can particularly maintain the hydrophilicity semipermanently. Also, if the component (g) is blended, 90 to 350 n
m, in particular, ultraviolet rays having a specific wavelength of 200 to 320 nm can be cut by about 70 to 100% in total, and are excellent in ultraviolet absorbing ability. The composition of the present invention is high in hardness, excellent in coating film appearance, adhesion, transparency, weather resistance, and particularly excellent in hydrophilicity, and is required to have properties such as antifouling property, antifogging property, and dripproofing property. Used for various applications. For example, the composition of the present invention may be used for paints for exterior building materials for prefabricated houses, paints for metal coatings such as structures such as buildings, tanks and bridges, paints for road side walls, road signs, signboards and other plastic molded articles and films. It can be suitably used for various uses such as a coating material, a coating material for a tunnel interior material, a window glass and a bathroom glass coating material.

[0092]

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

The weight average molecular weight was measured by gel permeation chromatography (GPC) under the following conditions. The sample was used as a tetrahydrofuran solvent, and the silyl group-containing vinyl resin was prepared by dissolving 0.1 gr in 100 cc of tetrahydrofuran. In addition, standard polystyrene manufactured by Pressure Chemical Co., USA was used. Equipment: High-speed GPC equipment (Model HLC manufactured by Tosoh Corporation)
8120 GPC) Column: HXL-H, manufactured by Tosoh Corporation, length 30 cm, 4 pieces, measurement temperature 40 ° C., flow rate 1 cc / min

The composition of the present invention was applied on a glass plate so as to have a dry film thickness of about 2 μm, and dried at 120 ° C. for 30 minutes to determine the adhesion, pencil hardness, hydrophilicity and transparency. It was measured. Adhesion was measured in accordance with JIS K5400, after a grid test using 25 squares of 2 mm square, a tape peeling test was performed, and the residual ratio of the squares was shown. The pencil hardness was based on the pencil hardness according to JIS K5400.
For the hydrophilicity, the water contact angle on the surface of the coating film was measured. Transparency is measured by a haze-gard manufactured by BYK-Gardner.
The haze was measured using plus.

Reference Example 1 (Preparation of Silyl Group-Containing Vinyl Resin B) In a reactor equipped with a reflux condenser and a stirrer, 60 parts of methyl methacrylate, 15 parts of n-butyl acrylate, 15 parts of 2-ethylhexyl acrylate, γ- Methacryloxypropyltrimethoxysilane 10 parts, isobutanol 1
After adding and mixing 00 parts and 30 parts of methyl ethyl ketone, the mixture was heated to 80 ° C. with stirring, and a solution obtained by dissolving 4 parts of azobisisovaleronitrile in 10 parts of isobutanol was added dropwise to the mixture over 30 minutes. The reaction was carried out at 80 ° C. for 5 hours to obtain a silyl group-containing vinyl resin B having a solid content of 42%. GP of this silyl group-containing vinyl resin B
The weight average molecular weight in terms of polystyrene by C is 20,000.
It was 0.

Example 1 (Preparation of hydrophilic coating material A and preparation of composition of the present invention) In the same reactor as in Reference Example 1, (a-1) 100 parts of methyltrimethoxysilane, (a-2) After adding and mixing 50 parts of γ-glycidoxypropyltrimethoxysilane, adding 26 parts of ion-exchanged water and reacting at 60 ° C. for 4 hours, (c) a comb polymer having a hydrophilic group [Mitsubishi Chemical ( Co., Ltd., HP-S-7-12, 30% concentration of methyl isobutyl ketone (MIBK) solution], 200 parts of isobutanol and 212 parts of methyl ethyl ketone, and then cooled to room temperature, and the solid content concentration was 15%. Was prepared. This hydrophilic resin solution was diluted with a mixed solution of i-butyl alcohol / methyl isobutyl ketone = 1/1 (weight ratio) to prepare a base polymer solution having a solid content concentration of 15%. To 100 parts of this polymer solution, as a curing agent, a TBZR chelate (TBZR / acetylacetone = 1/2 molar ratio mixed reactant, active ingredient concentration 2
0% i-propyl alcohol solution).
A composition for a hydrophilic coating was prepared. Next, on a glass plate, the composition was applied to a dry film thickness of about 2 μm, and dried at 120 ° C. for 30 minutes.
The adhesiveness, pencil hardness, hydrophilicity, and transparency were measured. Table 1 shows the evaluation results.

Example 2 (Preparation of hydrophilic coating material A and preparation of composition of the present invention) In the same reactor as in Reference Example 1, (a-1) 20 parts of methyltrimethoxysilane, (a-2) 14 parts of γ-glycidoxypropyltrimethoxysilane, (b-1) 12 parts of the silyl group-containing vinyl resin B of Reference Example 1, 20% aluminum trisethylacetoacetate toluene solution [manufactured by Kawaken Fine Chemical Co., Ltd. ALCH-TR20] 1
After 3 parts and 16 parts of methyl ethyl ketone were added and mixed, 6 parts of ion-exchanged water was added and reacted at 60 ° C. for 3 hours. Then, 5 parts of acetylacetone and 1 part of methyl isobutyl ketone were added.
After adding 6 parts, (c) a comb polymer having a hydrophilic group [Mitsubishi Chemical Corporation], HP-S-7-12, concentration 30
% MIBK solution], and cooled to room temperature. Then, 35 parts of isobutanol and 35 parts of methyl ethyl ketone were added to prepare a hydrophilic coating material resin solution having a solid content of 15%.
Using this resin solution A, a coating composition was prepared and evaluated in the same manner as in Example 1. Table 1 shows the results.

Comparative Example 1 (Preparation of coating material C and preparation of coating composition) In the same reactor as in Reference Example 1, (a-1) 100 parts of methyltrimethoxysilane, (a-2) γ-gly After adding and mixing 50 parts of sidoxypropyltrimethoxysilane, adding 26 parts of ion-exchanged water and reacting at 60 ° C. for 4 hours, 191 parts of isobutanol and 19 parts of methyl ethyl ketone were added.
After adding 1 part, the mixture was cooled to room temperature to prepare a coating material resin solution C having a solid content concentration of 15%. Using this resin solution c, a coating composition was prepared and evaluated in the same manner as in Example 1. Table 1 shows the results.

Comparative Example 2 (Preparation of coating material d and preparation of coating composition) In the same reactor as in Reference Example 1, (a-1) 20 parts of methyltrimethoxysilane, (a-2) γ-gly 14 parts of siloxypropyltrimethoxysilane, (b-1) 12 parts of the silyl group-containing vinyl resin B of Reference Example 1, aluminum trisethylacetoacetate 20% concentration toluene solution [ALCH-TR20 manufactured by Kawaken Fine Chemical Co., Ltd. ] 1
After 3 parts and 16 parts of methyl ethyl ketone were added and mixed, 6 parts of ion-exchanged water was added and reacted at 60 ° C. for 3 hours. Then, 5 parts of acetylacetone and 1 part of methyl isobutyl ketone were added.
After adding 6 parts and cooling to room temperature, isobutanol 31
And 31 parts of methyl ethyl ketone, and the solid content
% Of a coating material resin solution D was prepared. Using this resin solution d, a coating composition was prepared and evaluated in the same manner as in Example 1. Table 1 shows the results.

Comparative Example 3 (Preparation of hydrophilic coating material E and preparation of coating composition) In the same reactor as in Reference Example 1, (a-1) 20 parts of methyltrimethoxysilane, (a-2) γ 14 parts of glycidoxypropyltrimethoxysilane, (b-1) 12 parts of silyl group-containing vinyl resin B of Reference Example 1, aluminum trisethylacetoacetate 20% concentration toluene solution [manufactured by Kawaken Fine Chemical Co., Ltd., ALCH -TR20] 1
After 3 parts and 16 parts of methyl ethyl ketone were added and mixed, 6 parts of ion-exchanged water was added and reacted at 60 ° C. for 3 hours. Then, 5 parts of acetylacetone and 1 part of methyl isobutyl ketone were added.
After adding 6 parts, (c) a hydrophilic group-containing comb-shaped polymer [HP-S-7-12, manufactured by Mitsubishi Chemical Corporation, concentration: 30%
After adding 170 parts of MIBK solution and cooling to room temperature, 120 parts of isobutanol and 120 parts of methyl ethyl ketone were added to prepare a hydrophilic coating material resin solution having a solid content concentration of 15%. Using this resin solution (4), a coating composition was prepared and evaluated in the same manner as in Example 1. Table 1 shows the results.

[0101]

[Table 1]

[0102]

The hydrophilic coating composition of the present invention, when formed into a coating film, has high hardness, excellent coating film appearance, adhesion, transparency, weather resistance, especially hydrophilicity, and can be used at low or normal temperature. It has an extremely high balance of properties as an organosiloxane-based coating material that can be formed into a film. The cured product of the present invention has high hardness and excellent coating film appearance, transparency, weather resistance, and hydrophilicity, so that it is used for various applications requiring performance such as antifouling property, antifogging property, and dripproofing property. . For example, the composition of the present invention may be used for paints for exterior building materials for prefabricated houses, paints for metal coatings such as structures such as buildings, tanks and bridges, paints for road side walls, road signs, signboards and other plastic molded articles and films. It can be suitably used for various uses such as a coating material, a coating material for a tunnel interior material, a window glass and a bathroom glass coating material.

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Claims (5)

[Claims] (I) (a) The following general formula (1) (R ¹ ) _n Si (OR ² ) _4-n (1) (wherein, R ¹ exists two times) the same or different when, represents a monovalent organic group having 1 to 50 carbon atoms, R ² are the same or different, an alkyl group having 1 to 5 carbon atoms, 1 to 4 carbon atoms
And n is an integer of 0 to 2), at least one selected from the group consisting of an organosilane, a hydrolyzate of the organosilane, and a condensate of the organosilane. A coating composition comprising: a seed; and (c) a polymer-type hydrophilizing material. (II) The component (a) according to claim 1, (b) a polymer containing a silyl group having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group at a terminal or a side chain, and (C) A coating composition comprising a polymer-type hydrophilizing material. 3. The coating composition according to claim 1, wherein (c) the polymer type hydrophilic material is a comb polymer having a hydrophilic group. 4. A cured product obtained by forming a coating film obtained from the coating composition according to claim 1 on a substrate. 5. The cured product according to claim 4, wherein the substrate is a ceramic substrate, concrete, metal, glass, plastic molded product, plastic film, paper or fiber structure.