JP2001279178A - Coating composition and cured product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an organosilane based coating material having excellent storage stability and, simultaneously, excellent external appearance of coating films, adhesion, weatherability, and the like, and having high hardness and ultraviolet absorption capacity as well and capable of preventing the deterioration of an organic substrate and a base. SOLUTION: The coating composition comprises (I) (a) at least one kind selected from the group consisting of an organosilane represented by the formula: (R1)nSi(OR2)4-n, a hydrolyzate of the organosilane, and a condensate of the oragnosilane, and (c) fine particles and/or a sol of a metal oxide containing titanium oxide whose surface has been coated with silica; the coating composition comprises (II) the component (a), (b1) a polymer containing a silyl group whose silicon atom is bonded to a hydrolyzable group and/or a hydroxyl group, and the component (c); or the coating composition comprises (III) the component (a), (b2) a silyl group-containing fluorine based polymer, and the component (c).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a coating composition and a cured product. More specifically, an organosilane-based UV-absorbing coating composition having UV-absorbing ability at a specific wavelength and containing fine particles and sol of titanium oxide whose surface is coated with silica, and UV absorption obtained therefrom The present invention relates to a cured product.

[0002]

2. Description of the Related Art Optical devices such as cathode ray tubes, liquid crystal display elements, and plasma display panels have the problem that liquid crystals and organic films are deteriorated due to leakage of ultraviolet rays. Also, it is necessary to cut off ultraviolet rays on the surface of fluorescent lamps, window glass of automobiles, eyeglass lenses, solar cells, and the like. The required performance of the UV-absorbing coating film used for these is that visible light is sufficiently transmitted even when ultraviolet rays are cut,
It is excellent in transparency, good in adhesion to a substrate, not degraded in ultraviolet absorption for a long time, and excellent in weather resistance of a coating film itself. In addition, for optical device applications, excellent insulation is an important required performance in order not to lower the voltage holding ratio of the element. Conventionally, paints and plastic films containing UV absorbers composed of inorganic fine particles and organic UV absorbers such as benzophenone and benzotriazole have been used. No membrane was obtained. In particular, paints and plastic films containing titanium oxide have an excellent ultraviolet absorbing ability, but have a problem of poor durability due to the photocatalytic action of titanium oxide.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems. In other words, it is excellent in storage stability, when it is used as a coating film, it has high hardness, weather resistance, light resistance, excellent transparency, has long-term durability adhesion, and has an ultraviolet absorption ability semipermanently persistent, insulating property, An object of the present invention is to provide a coating material having a high refractive index and capable of forming a film at a low temperature or a normal temperature, and a cured product obtained therefrom.

[0004]

The present invention provides (I) (a)
The following general formula (1) (R¹)_nSi (OR^Two)_4-n・ ・ ・ ・ ・ (1) (where R¹Are the same or different when there are two
Represents a monovalent organic group having 1 to 8 carbon atoms;^TwoAre the same
Or differently, an alkyl group having 1 to 5 carbon atoms, 1 to 5 carbon atoms
6 represents an acyl group or a phenyl group, and n represents an integer of 0 to 2.
An organosilane represented by the formula:
The group consisting of hydrolysates of silanes and condensates of the organosilanes
At least one member selected from the group consisting of
And (c) silica coated on its surface with silica.
Metal oxide fine particles and / or
(Hereinafter also referred to as “component (c)”).
Coating composition (hereinafter referred to as "composition (I)")
Also referred to). Further, the present invention relates to (II)
Component (b1) linked to a hydrolyzable group and / or a hydroxyl group.
Polymer containing silyl group having combined silicon atom
(Hereinafter also referred to as “silyl group-containing polymer”), and
(C) a cord containing the component (c).
Composition (hereinafter also referred to as “composition (II)”).
I do. Further, the present invention provides (III) the component (a), (b)
2) A structural unit represented by the following general formula (2) (hereinafter referred to as “(b
-2) Structural unit ")(Where R^Three~ R^FiveIs C_mY_{2m + 1}, M = an integer from 0 to 5,
Y is independently selected from F, H and Cl
You. ) And / or a structure represented by the following general formula (3)
Unit (hereinafter also referred to as “(b-3) constituent unit”)[In the formula, Rf represents an alkyl group containing a fluorine atom or an alkyl group.
A oxyalkyl group;^Three~ R^FiveIs the general formula (2)
It is synonymous and, within the same meaning, R in general formula (2) ^Three~ R
^FiveAnd may be different. ] And hydrolyzable
Having a silicon atom bonded to a group and / or a hydroxyl group
At least one selected from the group of polymers containing a silyl group
(Hereinafter also referred to as “silyl group-containing fluoropolymer”),
(C) It contains the component (c).
Coating composition (hereinafter also referred to as “composition (III)”)
U). Next, the present invention relates to the above compositions (I) to
Characterized by having a coating film obtained from any of (III)
And a cured product.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The coating composition [(I) to (III)] of the present invention comprises the above-mentioned component (a) as a binder,
Since the components (a) to (b1) or components (a) to (b2) and the component (c), which is a specific metal oxide having an ultraviolet absorbing ability, are the main components, particularly, It has the characteristics of excellent adhesion, high hardness, excellent long-term durability, semi-permanent UV absorption, and excellent insulation. That is, the present inventors, by coating the surface of the titanium oxide-containing metal oxide with silica,
By dispersing a UV absorber that has no photocatalytic activity and can have a high UV absorption capacity into an organosiloxane-based material that has long-term durability, it has excellent storage stability and can be used as a coating film. High hardness, excellent weather resistance, light resistance, transparency, long-term durability, semi-permanent UV absorption, insulation, high refractive index, low temperature or room temperature It has been found that a coating material that can be formed into a film can be obtained. The details will be described below.

Composition (I) The composition (I) comprises (a) an organosilane or a hydrolytic condensate thereof, and (c) a titanium oxide having an ultraviolet absorbing ability and coated on its surface with silica. The main component is fine particles and / or sol containing metal oxide.

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 organosilane (1) contains 2 to 4 O
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) Acryloxy group, ureido group, ammonium base, Si- (RO) _n- (R'O) _m- R "(where 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 those having a value of n + m of 2 to 30.
And a group represented by the following formula: Among them, Si- (RO) _n- (R'O) _m-
A group represented by R ″ is preferable. Si— (RO) _n —
The group represented by (R′O) _m -R ″ is a polyoxyalkylene group such as a polyoxyethylene group, a polyoxypropylene group, and a poly (oxyethylene / oxypropylene) group. By having such a terminal functional group, a hydrolysis condensate of the component (a) and a cocondensate of the component (a) and the component (b1) described below become hydrophilic,
Since the portion of the polyoxyalkylene group is easily adsorbed to the component (c), the dispersion stability of the component (c) is improved. When two R ¹ are present in the general formula (1), they may be the same or different from each other.

Examples of the alkyl group having 1 to 5 carbon atoms for R ² include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group and a 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 such an 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, preferred compositions are trialkoxysilanes and dialkoxysilanes, and the organosilane with n = 0 in the general formula (1) is 0 to 80%, preferably 0 to 70%. 5 to 100%, preferably 10 to 100%, of an organosilane having n = 1,
0 to 80%, preferably 0 to 80%, of the organosilane of n = 2
70%. In particular, trialkoxysilane (n = 1)
Only, or a combination of 40 to 95 mol% of trialkoxysilane and 60 to 5 mol% of dialkoxysilane (n = 2) is preferable. By using dialkoxysilane in combination with trialkoxysilane, the resulting coating film can be softened and the alkali resistance can be improved. In addition, trialkoxysilanes are preferably methyltrimethoxysilane and methyltriethoxysilane, and dialkoxysilanes are more preferably dimethyldimethoxysilane and dimethyldiethoxysilane.

The organosilane (1) is used as it is or as a hydrolyzate and / or condensate. In particular, when the organosilane (1) is used as it is, the weight average molecular weight in terms of polystyrene (hereinafter referred to as “Mw”) 300
It is preferred to use a mixture or co-condensation of condensates of up to 100,000. In this case, a preferable mixing ratio is 5 to 95% by weight, preferably 10 to 90% by weight, and 5 to 95% by weight, preferably 10 to 90% by weight of the organosilane (1). When the organosilane (1) is used as a hydrolyzate and / or condensate,
Although it can be used as the component (a) after being hydrolyzed and condensed in advance, as described later, when the organosilane (1) is mixed with the remaining components to prepare a composition,
By adding an appropriate amount of water, the organosilane (1)
May be hydrolyzed and condensed to obtain the component (a). The amount of water used for the hydrolysis / condensation of the organosilane (1) is usually about 0.3 to 3 mol, preferably about 0.4 to 2 mol, per 1 mol of the organosilane (1). is there. The hydrolysis / condensation reaction at this time is performed at a temperature of 30 to 8
0 ° C, preferably 40 to 70 ° C, reaction time 0.5 to 10
Time, preferably about 1 to 7 hours. In the condensate of the organosilane (1), the ratio of O to Si in the SiO bond is usually in the range of 0.5 to 2, and a single condensate is one (bifunctional oligomer);
1.5 (trifunctional oligomer) and 2 (tetrafunctional oligomer), among which Si
(Oligomer) in which the ratio of O to 1.5 is 1.5
Is preferred. The condensate can be obtained by a hydrolysis / condensation reaction of the organosilane (1) or by a condensation reaction of chlorosilane. Further, in the above condensate, the terminal functional group of the siloxane may be a hydroxyl group, a halogen atom or an organic group having 1 to 15 carbon atoms, or may be a partially hydrolyzed / condensed one.

Examples of the halogen atom include fluorine and chlorine. Further, as the organic group having 1 to 15 carbon atoms, for example, a methyl group, an ethyl group, an n-propyl group, i
-Propyl group, n-butyl group, i-butyl group, sec-
Butyl group, t-butyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group,
Alkyl groups such as undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl, heptadecyl, octadecyl and 2-ethylhexyl; acyls such as acetyl, propionyl, butyryl, valeryl, benzoyl and trioil; Groups; alkoxyl groups such as methoxy, ethoxy, propoxy and butoxy groups; alkoxysilyl groups such as methoxysilyl, ethoxysilyl, propoxysilyl and butoxysilyl groups; vinyl, allyl, acetoxyl, acetoxysilyl Groups, a cyclohexyl group, a phenyl group, a glycidyl group, a (meth) acryloxy group, a ureido group, an amide group, a fluoracetamide group, an isocyanate group, and the like, and substituted derivatives of these groups.

The substituent in the above substituted derivative is
For example, 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, a ureido group, an ammonium base, a ketoester group, etc. Can be mentioned. (A)
When the component is used as a hydrolytic condensate, the Mw of the hydrolytic condensate is usually from 300 to 100,000,
Preferably 600 to 50,000, more preferably,
1,000 to 50,000.

The commercially available 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 Co., 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 Unica 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.

Component (c): The component (c) in the composition of the present invention comprises fine particles and / or sol of a metal oxide containing titanium oxide whose surface is coated with silica, and has an ultraviolet absorbing ability. . In the composition of the present invention, the ultraviolet absorbing ability of the component (c) makes it possible to obtain the ultraviolet absorbing ability of the coating film without substantially impairing the coating film performance, and to prevent the deterioration of organic substances due to ultraviolet light. Can be.

The component (c) is, for example, titanium dioxide (T
iO_Two) With silicon oxide (SiO_Two)
And / or sol, as the structure of titanium dioxide
Is anatase type, rutile type, amorphous type, etc.
Is mentioned. As the above metal oxide, titanium oxide
Besides zirconium oxide (ZrO _Two), Tin oxide
(SnO_Two), Cerium oxide (CeO)_Two) And other gold
15% by weight or less, preferably 10% by weight or less of metal oxide
The degree may be included. Used in the composition of the present invention
The component (c) is, for example, silica-encapsulated titanium.
Is a colloid or sol. The composition of component (c) is
In the metal oxide, the content of Ti, in terms of metal oxide, is usually
10 to 70% by weight, preferably 25 to 60% by weight, Si
The content is usually 90 to 10% by weight, preferably 20 to 5% by weight.
0% by weight (however, Ti + Si = 100% by weight)
You. If the Ti content is less than 10% by weight, sufficient ultraviolet absorption
Performance is not obtained, on the other hand, if it exceeds 70% by weight, titanic acid
Organic compounds such as liquid crystals are decomposed by the organic resolution of
May be

The component (c) may be in the form of a powder composed 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 nonpolar 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 fine particles. The average particle size of these fine particles is preferably as small as possible from the viewpoint of ultraviolet absorbing ability, and is preferably 0.5 μm.
m, particularly preferably 0.1 μm or less. (C)
By atomizing the components, ultraviolet rays of 300 nm or less
An ultraviolet absorber that can absorb 0% or more and can be used semi-permanently without deterioration can be obtained. Also,
Since the uniform dispersibility is good, it is possible to obtain a coating composition having excellent transparency and storage stability. For the purpose of improving the dispersibility and storage stability and preventing photocatalytic activity, these fine particles and sols are preferably added with a surfactant, a dispersant, a coupling agent, or the like, or those subjected to a surface treatment with these are also preferably used. Can be When the component (c) is an aqueous sol or a solvent sol, the solid content concentration is 60%.
% By weight or less, more preferably 50% by weight or less.

As a method of blending the component (c) into the composition of the present invention, it may be added after the preparation of the composition comprising the above-mentioned component (a) and other additives described below, or The organosilane (1) constituting the component (a) may be hydrolyzed and condensed in the presence of the component (c) by adding the composition during the preparation of the composition (a). When the component (c) is added during the preparation of the composition, the semiconductor compound in the component (c) can be co-condensed with the component (a) or the like,
The dispersibility of the component (c) can be improved. Also,
When the component (c) is an aqueous sol, the component (c) is preferably added at the time of preparation of the composition, and the component (c) is added even when the viscosity of the system increases due to the incorporation of the component (e) described later. It is more preferable to add it during the preparation of the product.

The component (c) is prepared by adding hydrogen peroxide to a dispersion containing fine titanium dioxide particles and an organic stabilizer to prepare hydrous titanic acid, and then adding a silicon compound to oxidize silica. A method of obtaining titanium fine particles and a sol may be used. Examples of the method for producing the titanium dioxide fine particles include a method of hydrolyzing and polycondensing metal salts, metal alkoxides, metal alkyl alkoxides, acetylacetonato chelate compounds, and the like.

The amount of the component (c) used is usually 1 to 500 parts by weight as a solid based on 100 parts by weight of the total of the component (a) (in terms of a completely hydrolyzed condensate of the organosilane (1)). Preferably it is 0.5 to 300 parts by weight. In the composition of the present invention, if the amount of the component (c) is too small,
The effect of the present invention is hardly exhibited due to insufficient ultraviolet absorbing ability. On the other hand, when the amount is too large, the film forming property of the obtained coating composition is poor, and cracking or peeling may occur. In addition, the completely hydrolyzed condensate of organosilane (1)
It means that the R ² O— group of the organosilane (1) is hydrolyzed 100% to form a SiOH group, and further completely condensed to form a siloxane structure.

The composition (I) of the present invention contains the above-mentioned components (a) and (c) as essential components, and optionally contains optional components as 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. Further, as described above, water is used as the component (a) and the components (b1) to
It is also used for hydrolysis and condensation of the component (b2).

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 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) comprises the component (a), (b1) a polymer containing a silyl group having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group, and c) The component is the main component. That is, the composition (II) is a coating composition comprising a hybrid polyorganosiloxane obtained by co-condensing the component (a) and the polymer (b1) containing a silyl group with the component (c) having an ultraviolet absorbing ability. . Here, the component (a) and the component (c) in the composition (II), the water and the organic solvent used are the same as the component (a) in the composition (I).
Since it is the same as the component, the component (c), water and the organic solvent,
These descriptions are omitted, and the (b1) silyl group-containing polymer will be described in detail below.

(B1) Silyl group-containing polymer: The component (b1) in the present invention has a silyl group having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group (hereinafter also referred to as "specific silyl group"). Preferably, the polymer has a specific silyl group at the terminal and / or side chain of the polymer molecular chain. When such a component (b1) hardens a coating film obtained from the coating composition of the present invention, the hydrolyzable group and / or hydroxyl group in the silyl group is
By co-condensing with the component (a), excellent coating performance can be obtained. The content of the specific silyl group in the component (b1) is usually 0.1% in the component (b1).
６０60 mol%, preferably 0.5 to 50 mol%.

The specific silyl group preferably has the following general formula (4) (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 ⁶ 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 (b1) contains a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group, which constitutes the specific silyl group (b-4) represented by the general formula (4). 4) A monomer obtained by polymerizing a monomer, and if necessary, (b-5) another monomer copolymerizable with these monomers (hereinafter referred to as “(b-5) monomer ) May also be obtained by polymerization. The component (b1) is a polymer obtained by polymerizing the monomer (b-4), and a silane compound having a functional group capable of reacting with the hydrolyzable group or hydroxyl group (hereinafter referred to as “(b- And 6) a silane compound).

Here, the monomer (b-4) 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-4) include the following general formula (4) ′ [Wherein X, R ^6, i has the same meaning as X, R ^6, i respectively in the general formula (4), R ⁷ represents an organic group having a polymerizable double bond] is represented by (Hereinafter also referred to as "unsaturated silane compound").

Specific examples of the unsaturated silane compound include CH ₂ ＝ CHSi (CH ₃ ) (OCH ₃ ) ₂ and CH ₂ ＝
CHSi (OCH ₃ ) ₃ , CH ₂ ＣＨCHSi (CH ₃ ) Cl
₂ , CH ₂ ＣＨCHSiCl ₃ , CH ₂ ＣＨCHCOO (C
H ₂ ) ₂ Si (CH ₃ ) (OCH ₃ ) ₂ , CH ₂ ＣＨCHCOO
(CH ₂ ) ₂ Si (OCH ₃ ) ₃ , CH ₂ ＣＨCHCOO (C
_{H 2) 3 Si (CH 3} ) (OCH 3) 2, CH 2 = CHCOO
(CH ₂ ) ₃ Si (OCH ₃ ) ₃ , CH ₂ ＣＨCHCOO (C
H ₂ ) ₂ Si (CH ₃ ) Cl ₂ , CH ₂ ＣＨCHCOO (CH
₂ ) ₂ SiCl ₃ , CH ₂ ＣＨCHCOO (CH ₂ ) ₃ Si
(CH ₃ ) Cl ₂ , CH ₂ ＣＨCHCOO (CH ₂ ) ₃ SiC
l 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 , CH ₂ ＣC (CH ₃ ) COO (CH ₂ )
₃ Si (CH ₃ ) (OCH ₃ ) ₂ , CH ₂ ＣC (CH ₃ ) CO
O (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , CH ₂ ＣC (CH ₃ ) C
OO (CH ₂ ) ₂ Si (CH ₃ ) Cl ₂ , CH ₂ ＣC (CH
₃ ) COO (CH ₂ ) ₂ SiCl ₃ , CH ₂ ＣC (CH ₃ ) C
OO (CH ₂ ) ₃ Si (CH ₃ ) Cl ₂ , CH ₂ ＣC (CH
₃ ) COO (CH ₂ ) ₃ SiCl ₃ ,

[0033]

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And the like. These unsaturated silane compounds (b) can be used alone or in combination of two or more.

Examples of the monomer (b-5), which is another monomer copolymerizable with the monomer (b-4), include (a) methyl (meth) acrylate and 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,
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; (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 Other than fluorine-containing (meth) acrylates such as (meth) acrylate; and dicaprolactone. These can be used alone or in combination of two or more.

The (b-6) 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 (b1), 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 remaining part is continuously polymerized. 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 structural unit (b-4) is such that the content of the specific silyl group is usually 0.1 to 6 in the component (b1).
The amount is 0 mol%, preferably 0.5 to 50 mol%. If it is less than 0.1 mol%, the effect of co-condensation with the component (a) cannot be obtained. On the other hand, if it exceeds 60 mol%, the storage stability of the obtained coating composition tends to be poor. In addition, it is another copolymerizable monomer (b-5).
The structural unit composed of a monomer [(b-5) structural unit] is
In the component (b1), the content is usually about 90 mol% or less, preferably about 80 mol% or less.

Other examples of the component (b1) 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 epoxy resin, a bisphenol F epoxy resin, a hydrogenated bisphenol A epoxy resin, an aliphatic polyglycidyl ether, or an aliphatic polyglycidyl ester. And aminosilanes, vinylsilanes, carboxysilanes, glycidylsilanes and the like 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 (b1) is preferably 2,0
00 to 100,000, more preferably 4,000 to
50,000. The amount of the component (b1) used in the composition (II) is generally 2 to 900 parts by weight, preferably 10 to 10 parts by weight, assuming that the component (a) is 100 parts by weight in terms of its completely hydrolyzed condensate. 800 parts by weight, more preferably 20 to 700 parts by weight. In this case, (b1)
If the amount of the component is less than 2 parts by weight, the resulting coating film may have poor alkali resistance, whereas if it exceeds 900 parts by weight, the weather resistance and light resistance of the coating film tend to decrease. .

In the present invention, the component (b1) can be used alone or as a mixture of two or more kinds obtained as described above. In the composition (II),
The component (b1) is preferably co-condensed with the component (a) in the presence of water and / or an organic solvent.

Composition (III) Composition (III) is composed of (a) an organosilane or a hydrolytic condensate thereof, (b2) a silyl group-containing fluoropolymer, and (c) a titanium coated on its surface with silica. The main component is fine particles and / or a sol of a metal oxide containing an oxide. That is, the composition (III) comprises the component (a) and the component (b2)
A coating composition comprising a hybrid type fluorine-containing polyorganosiloxane obtained by co-condensing a silyl group-containing fluorine-containing polymer with a component (c) having an ultraviolet absorbing ability. Here, the component (a) in the composition (III) and the component (c)
The components, water and organic solvent used are the same as component (a), component (c) and water and organic solvent in the composition (I), and therefore, the description thereof is omitted, and the following (b2)
The silyl group-containing fluoropolymer will be described in detail.

(B2) a silyl group-containing fluoropolymer; the component (b2) in the present invention has the structural unit (b-1) and / or the structural unit (b-2), and
A silyl group having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group (hereinafter also referred to as “specific silyl group”)
And is preferably a fluoropolymer having a specific silyl group at the terminal and / or side chain of the polymer molecular chain.
When such a component (b2) cures a coating film obtained from the coating composition of the present invention, the hydrolyzable group and / or hydroxyl group in the silyl group co-condenses with the component (a). Thereby, excellent coating film performance can be obtained. The content of the specific silyl group in the component (b2) is usually 0.1 to 60 mol%, preferably 0.5 to 50 mol% in the component (b2).

The specific silyl group is preferably represented by the above general formula (4). The component (b2) is represented by the above general formula (2)
(B-2) a monomer that constitutes the structural unit (hereinafter, also referred to as “(b-2) monomer”) and / or (b) represented by the general formula (3). -3) a monomer that constitutes a structural unit (hereinafter, “(b-3) monomer”
(B-4) represented by the above general formula (4).
It is obtained by polymerizing a monomer (b-4) containing a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group constituting a specific silyl group, and if necessary, (b-5)
Other monomers copolymerizable with these monomers (hereinafter referred to as “(b
-5) also referred to as “monomer”). The (b-5) monomer may be a monomer having a fluorine atom, which is not included in the (b-2) monomer and the (b-3) monomer.

The component (b2) is the same as the component (b-2)
A polymer obtained by polymerizing a monomer and / or a monomer (b-3), or a polymer obtained by further adding a monomer (b-5) to these monomers, if necessary. And a silane compound having a functional group capable of reacting with the above hydrolyzable group or hydroxyl group [(b-6) silane compound] may be added to the carbon-carbon double bond of the polymer obtained as described above. .

Here, the monomer (b-2) is represented by the following general formula (2) '. (Wherein, R ^{3 to} R ⁵ are C _m Y _{2m + 1} , and m is an integer of 0 to 5,
Y is independently selected from F, H and Cl. )

As the monomer (b-2), for example,
One polymerizable unsaturated double bond and at least one
Compounds having a fluorine atom can be given. (B-2) Specific examples of the monomer include (a) CF_Two= CF_Two, CHF = CF_Two, CH_Two= CF
_Two, CH_Two= CHF, CCIF = CF_Two, CHCl = C
F_Two, CCl_Two= CF_Two, CCIF = CCLF, CHF
= CCl_Two, CH_Two= CCIF, CCl_Two= CCLF
Which fluoroethylenes; CF_ThreeCF = CF_Two, CF_ThreeCF = CHF, CF_ThreeCH
= CF_Two, CF_ThreeCF = CH_Two, CF_ThreeCF = CHF,
CHF_TwoCF = CHF, CF_ThreeCH = CH_Two, CH_ThreeC
F = CF_Two, CH_ThreeCH = CF_Two, CH_ThreeCF = C
H_Two, CF_TwoClCF = CF_Two, CF_ThreeCCl = C
F_Two, CF_ThreeCF = CFCl, CF_TwoClCCl = CF
_Two, CF_TwoClCF = CFCl, CF_TwoCCl = CCl
F, CF_TwoCCl = CCl_Two, CCl_ThreeCF = CF_Two,
CF_TwoClCCl = CCl_Two, CFCl_TwoCCl = CC
l_Two, CF_ThreeCF = CHCl, CCIF_TwoCF = CHC
1, CF_ThreeCCl = CHCl, CHF_TwoCCl = CCl
_Two, CF_TwoClCH = CCl_Two, CF_TwoClCCl = C
HCl, CCl_ThreeFluoropropane such as CF = CHCl
(B) CF_ThreeCF_TwoCF = CF_Two, CF_ThreeCF = CFC
F_Three, CF_ThreeCH = CFCF_Three, CF_Two= CFCF_TwoC
HF_Two, CF_ThreeCF_TwoCF = CH_Two, CF_TwoCH = CH
CF_Three, CF_Two= CFCF_TwoCH_Three, CF_Two= CFCH
_TwoCH_Three, CF _ThreeCH_TwoCH = CH_Two, CF_ThreeCH = C
HCH_Three, CF_Two= CHCH_TwoCH_Three, CH_ThreeCF_TwoC
H = CH_Two, CFH_TwoCH = CHCFH_Two, CH_ThreeCF
_TwoCH = CH_Two, CH_Two= CFCH_TwoCH_Three, CF
_Three(CF_Two)_TwoCF = CF_Two, CF_Three(CF_Two)_TwoCF
= CF_TwoSuch as fluoroolefins having 4 or more carbon atoms
And so on.

(B-2) containing these fluorine atoms
The monomers may be used alone or in combination of two or more.

The monomer (b-3) is represented by the following general formula (3) '. [In the formula, Rf represents an alkyl group or an alkoxyalkyl group containing a fluorine atom, and R ^{3 to} R ⁵ have the same meaning as in the general formula (2) ′, and within the same meaning, the general formula (2) ′ It may be different from R ^{3 to} R ⁵ . ]

As the monomer (b-3), for example,
Compounds having one polymerizable unsaturated double bond, ether bond and at least one fluorine atom can be mentioned. (B-3) Specific examples of the monomer include (a) CH ₂ ＣＨCH—O—Rf (Rf represents an alkyl group or an alkoxyalkyl group containing a fluorine atom) (fluoroalkyl) Vinyl ether or (fluoroalkoxyalkyl) vinyl ethers; (ii) perfluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether), perfluoro (propyl vinyl ether), perfluoro (butyl vinyl ether), perfluoro (isobutyl vinyl ether)
(C) perfluoro (alkoxyalkyl vinyl ethers) such as perfluoro (propoxypropyl vinyl ether); and the like. These (b-3) monomers containing a fluorine atom may be used alone or in combination of two or more.

When the monomers (b-2) and (b-3) are used in combination, hexafluoropropylene and perfluoroalkyl perfluorovinyl ether or perfluoroalkoxyalkyl perfluorovinyl ether are used in combination. It is preferable to use it.

The (b-4) monomer, (b-5) monomer and (b-6) silane compound are as described in the component (b1). Further, the polymerization method for producing the component (b2) is also the same as the component (b1).

The total content of the constituent units (b-2) and (b-3) constituting the component (b2) is usually 0.5 to 80 mol%, preferably 0.5 to 80 mol%, in the component (b2). Is 1 to
70 mol%. If the amount is less than 0.5 mol%, it may be difficult to obtain a well-balanced coating film having water repellency and oil repellency, as well as excellent transparency and adhesion. On the other hand, if it exceeds 80 mol%, the resulting coating film may have poor adhesion to the substrate. Among these, the content of the (b-2) structural unit is preferably 0.5 to
70 mol%. Further, the content of the (b-3) structural unit in the component (b2) is preferably 0.5 to 70 mol%. Further, the content of the structural unit (b-4) is usually such that the content of the specific silyl group is 0.1% in the component (b2).
The amount is 1 to 60 mol%, preferably 0.5 to 50 mol%. If it is less than 0.1 mol%, the effect of co-condensation with the component (a) cannot be obtained. On the other hand, if it exceeds 60 mol%, the storage stability of the obtained coating composition tends to be poor. The constituent unit (b-5) constituent unit composed of the monomer (b-5), which is another copolymerizable monomer, is usually 90 mol% or less in the component (b2). Preferably, it is about 80 mol% or less.

The Mw of the component (b2) is preferably 1,
000-50,000, more preferably 5,000
~ 30,000. In the present invention, the component (b2) can be used alone or as a mixture of two or more kinds obtained as described above.

The amount of the component (b2) used in the composition (III) is usually 2 to 900 parts by weight, preferably 100 parts by weight, when the component (a) is 100 parts by weight in terms of its complete hydrolysis and condensation product. , 10 to 800 parts by weight, more preferably, 2
0 to 700 parts by weight. In this case, if the amount of the component (b2) is less than 2 parts by weight, the resulting coating film tends to have reduced alkali resistance and crack resistance. On the other hand, 900
If the amount exceeds the weight part, the weather resistance and light resistance of the coating film tend to decrease.

In the composition (III), a vinyl copolymer containing no specific fluorine atom and containing a specific silyl group (hereinafter also referred to as “component (b ′)”) may be used in combination with component (b2). ) May be used as long as the effects of the present invention are not impaired. The component (b ′) is composed of the monomer (b-4) and the (b)
-5) copolymerizing with a monomer, or (b-5)
It can be obtained by subjecting the polymer obtained by polymerizing the monomer to an addition reaction with the above-mentioned (b-6) silane compound.
The content of the component (b ′) is usually 5 parts by weight when the component (a) is converted to 100 parts by weight in terms of its complete hydrolysis condensate.
Not more than 00 parts by weight.

In the composition (III), the above (b)
It is preferable that the component 2) is co-condensed with the component (a) in the presence of water and / or an organic solvent. The method of adding the component (c) in the composition (III) is the same as that of the composition (I).

In the composition of the present invention, the compositions (I) to (III) can be used alone, however, the compositions (I) to (III) can be used in combination. Needless to say. The compositions (compositions (I) to (III)) of the present invention may further contain the following components (d) to (f) as optional components. Hereinafter, these components will be described.

Component (d): Component (d) is a catalyst that promotes the hydrolysis / condensation reaction of the organosilane (1) and the component (b1) or (b2) constituting the component (a). By using the component (d), 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 (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 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 include a compound represented by the following general formula (5) (hereinafter referred to as “organometallic compound (5)”), 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.

[0070] [Wherein M represents zirconium, titanium or aluminum, and R ⁸ and R ⁹ 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 ¹⁰ is
In addition to the same monovalent hydrocarbon groups having 1 to 6 carbon atoms as R ⁸ and R ⁹ , 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 (5) 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 (5) 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 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 = CHC
OOCH ₃ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (OCOCH = C
HCOOC ₄ H ₉ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (OCOC
H = CHCOOC ₈ H ₁₇ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (O
COCH = CHCOOC ₁₆ H ₃₃ ) ₂ , (C ₈ H ₁₇ ) ₂ S
n (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 = CHC
OOC ₂₀ H ₄₁ ) ₂ ,

[0075] (C ₄ H ₉ ) Sn (OCOC ₁₁ H ₂₃ ) ₃ , (C ₄ H ₉ )
Carboxylic acid type organotin compounds such as 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 COO
C 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 CO
OC ₈ H ₁₇ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (SCH ₂ COO)
C ₁₂ H ₂₅ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (SCH ₂ CH ₂ C)
OOC ₁₂ H ₂₅ ) ₂ , (C ₄ H ₉ ) Sn (SCOCH = C
HCOOC ₈ H ₁₇ ) ₃ , (C ₈ H ₁₇ ) Sn (SCOCH)
ＣＨCHCOOC ₈ H ₁₇ ) ₃ ,

[0077] 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 (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 the coating film. May be blended at both stages. The amount of the component (d) used is
In the case other than the organometallic compound or the like, the component (a) is usually added in an amount of 0 to 1 with respect to 100 parts by weight of the complete hydrolysis condensate.
00 parts by weight, preferably 0.01 to 80 parts by weight, more preferably 0.1 to 50 parts by weight.

Component (e): Component (e) is represented by the following general formula (6): R ⁹ COCH 2 COR ¹⁰ (6) [wherein R ⁹ and R ¹⁰ are general Having the same meanings as R ⁹ and R ^{10 in the} formula (5)], a carboxylic acid compound, a dihydroxy compound, an amine compound, and an oxyaldehyde compound. At least one kind. 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 an agent for improving the stability of the composition. That is, the component (e) coordinates to a metal atom such as the above-mentioned organometallic compound and the component (a), the component (b1) or the component (b)
2) It is presumed that by appropriately controlling the action of accelerating the condensation reaction of the components, the action of further improving the storage stability of the obtained composition is achieved.

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 component (e) used is usually 2 moles per mole of the organometallic compound in the organometallic compound or 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 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. The component (f) serves to improve the flexibility of the cured coating film and increase the critical film thickness in the composition of the present invention.

As the component (f), 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 (f) can be used alone or in combination of two or more. The amount of the component (f) used in the composition is 1 when the component (a) is converted into its completely hydrolyzed condensate.
When the amount is 00 parts by weight, it is usually 5 to 500 in terms of solid content.
Parts by weight, preferably 10 to 400 parts by weight, more preferably 15 to 300 parts by weight.

Other additives; Also, the composition of the present invention includes:
A filler may be separately added and dispersed for coloring and thickening 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, or 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.

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 (c) may be blended. Examples of the metal oxide having the ultraviolet absorbing ability include ZnO, CeO _{2, and the} like, and the existence form of these metal oxides is the same as the component (c) of the present invention. Further, these metal oxides may form a complex with the metal oxide constituting the component (c). These commercial products include Taipaque TTO manufactured by Ishihara Sangyo Co., Ltd., and ZW manufactured by Sumitomo Osaka Cement Co., Ltd.
-143, ZW-513C, ZS-300, ZS-30
3, ZnO-100, ZnO-200, Z-NOUVE 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. Also,
In the coating 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. As organic UV absorbers,
Salicylic acids, benzophenones, benzotriazoles, cyanoacrylates, triazines and the like can be mentioned. Examples of the ultraviolet stabilizer include piperidine.

Further, a leveling agent can be added to the 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 (BM-CH)
EMIE) BM1000, BM1100; Efka Chemicals Efka 772, Efka 777; Kyoeisha Chemical Co., Ltd. Floren series; Sumitomo 3M Ltd.
FC series; Fluoral TF series of Toho Chemical Co., Ltd., and the like. Examples of silicone-based leveling agents include BYK series of BYK Chemie; Ss of SHMegmann;
hmego series; Efka 3 of Efka Chemicals
0, Efka 31, Efka 34, Efka 35, Efka 3
6, Efka 39, Efka 83, Efka 86, Efka 88
Examples of the ether-based or ester-based leveling agent include Nissin Chemical Industry Co., Ltd.
Carfinol; Kao Corporation's emulgen, homogenol and the like.

By incorporating 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.

The leveling agent may be compounded at the time of preparing the composition, may be added to the composition at the stage of forming the coating film, or may be prepared 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 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 obtained by removing the component (e) from the components (a) to (f), 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 depending on 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 coating composition of the present invention preferably has a total solid content of 1 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 concentration may be adjusted by reducing or supplementing the water and / or organic solvent.

Suitable substrates for using the composition of the present invention include, for use in optical devices, glasses such as float glass and soda glass; plastics such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone and polycarbonate. Can be used. The substrate is not limited to these, and metals such as iron, aluminum and stainless steel; inorganic ceramic materials such as cement, concrete, ALC, flexible board, mortar, slate, gypsum, ceramics and brick; phenolic resin, epoxy resin, acrylic Plastic molded products such as resin, polyester, polyethylene, polypropylene and ABS resin (acrylonitrile-butadiene-styrene resin); plastic films such as polyethylene, polypropylene, polyvinyl alcohol, polyurethane and polyimide;
Wood, paper and the like can be mentioned. 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.

The coating composition of the present invention may optionally use a primer. 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 in combination of two or more.

Examples of the type of primer include alkyd resin, amino alkyd 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 having the component (a) of the present invention and a hydrolyzable silyl group-containing vinyl resin. 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,
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 with a single coating and a coating thickness of about 0.02 to 40 μm with a double coating. . The film thickness can be adjusted according to the application. Then, dry at room temperature or 30 to 3
By heating and drying at a temperature of about 00 ° C. for usually about 0.5 to 60 minutes, a coating film (cured body) can be formed.

According to the coating composition of the present invention, in addition to being excellent in storage stability, being excellent in coating appearance, adhesion, weather resistance, etc., it is also excellent in electrical insulation, having high hardness, and having an ultraviolet absorbing ability. It is possible to prevent deterioration of the organic base and the substrate. The cured film (cured product) obtained by the composition of the present invention has an ultraviolet absorbing ability semipermanently persistent, and
UV rays having a specific wavelength of 0 to 350 nm, particularly 200 to 320 nm, can be cut by about 70 to 100% in total, and are excellent in UV absorbing ability. Since the coating composition of the present invention is also excellent in electrical insulation, a liquid crystal protective film of a liquid crystal display device or a projection television, an ultraviolet cut film formed on the surface of a back plate of a plasma display panel, an ultraviolet cut film of a cathode ray tube inner surface, and light emission. Diode (LED) sealing material, EPROM window coating material, etc.
It is suitably used for electronic materials. In addition, it can be suitably used as an ultraviolet cut coating material for a window glass of an automobile, an eyeglass lens, a solar cell, and the like.

[0102]

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. In addition, various measurements and measurements in Examples and Comparative Examples
The evaluation was performed by the following method.

Mw was measured by gel permeation chromatography (GPC) under the following conditions. Sample: 1 g of a sample such as a hydrolyzed condensate of organosilane (1) was prepared using tetrahydrofuran as a solvent.
Prepared by dissolving in 00 cc of tetrahydrofuran. Standard polystyrene: Standard polystyrene manufactured by Pressure Chemical Co., USA was used. Apparatus; High-temperature high-speed gel permeation chromatogram (model 150-C ALC / GPC) manufactured by Waters, USA Column: SHODEX A-80M manufactured by Showa Denko KK
(Length 50cm) Measurement temperature; 40 ° C Flow rate; 1cc / min

Storage stability The composition to which the curing accelerator was not added was sealed in a polyethylene bottle at room temperature for 3 months, and the presence or absence of gelation was visually determined. For those that did not cause gelation, the viscosity was measured using a BM viscometer manufactured by Tokyo Keiki Co., Ltd.
Those with more than 20% were marked as changed (x).

[0105] was based on pencil hardness by the hardness JIS K5400. The integrated absorptivity at 300 nm or less was measured with an ultraviolet absorbing Hitachi self-recording spectrophotometer. Visible light transmittance Each composition was applied on quartz glass so as to have a dry film thickness of 10 μm, and then the visible light transmittance was measured and evaluated according to the following criteria. ◎: transmittance of 90% or more ；: transmittance of 80% or more and less than 90% Δ: transmittance of 70% or more and less than 80% ×: transmittance of less than 70% Each insulating composition was coated on quartz glass. The resultant was applied to a dry film thickness of 1 μm and baked at 200 ° C. for 30 minutes, and then the surface resistivity was measured using a high resistance meter manufactured by Hewlett-Packard Company.

Reference Example 1 [Synthesis of Component (b1)] 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, 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. After the solution dissolved in 10 parts was added dropwise over 30 minutes, the mixture was reacted at 80 ° C. for 5 hours to obtain a solid concentration of 40%.
% And a polymer solution having an Mw of 11,000 (hereinafter referred to as “(b1-
A) ”).

Reference Example 2 [Synthesis of Component (b1)] 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 mixture was reacted at 80 ° C. for 5 hours to obtain a polymer solution having a solid concentration of 40% and Mw of 13,000 (hereinafter referred to as “(b1-B)”).

Reference Example 3 [Synthesis of component (b1)] 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 prepared by dissolving 4 parts of azobisisovaleronitrile in 10 parts of xylene was added dropwise to the mixture over 30 minutes. Reaction for 40 hours, solid content concentration 40%, M
w is a polymer solution of 10,000 (hereinafter "(b1-C)"
).

Reference Example 4 [Synthesis of Component (b2)] After a stainless steel autoclave equipped with an electromagnetic stirrer was sufficiently replaced with nitrogen gas, 150 parts of methyl isobutyl ketone, 30 parts of ethyl vinyl ether and peroxide in the autoclave were added. Lauroyl (radical polymerization initiator) 2
After the solution in the autoclave was cooled to -50 ° C with dry ice-methanol, oxygen in the system was removed again with nitrogen gas. Next, 20 parts of hexafluoropropylene, 45 parts of perfluoro (methyl vinyl ether) and 5 parts of vinyltrimethoxysilane were added, and the temperature was raised. The temperature in the autoclave is 60
When the pressure in the autoclave reaches 5 ° C, the pressure is 5k.
gf / cm ² . The polymerization reaction was continued for 20 hours by stirring while maintaining the temperature of the reaction system at 60 ° C. When the pressure in the autoclave dropped to 1.5 kgf / cm ² , the reaction was stopped by cooling with water and the solid content was reduced. Concentration 4
0%, Mw 30,000 polymer solution (hereinafter referred to as “(b2
-A) ").

Reference Examples 5 to 6 [Synthesis of Component (b2)] A polymer solution (b2-) having a solid content of 40% was prepared in the same manner as in Reference Example 4 except that the monomer components shown in Table 1 were used. B) ~
(B2-C) was obtained.

[0111]

[Table 1]

Example 1 In a reactor equipped with a reflux condenser and a stirrer, as a component (a), 90 parts of methyltrimethoxysilane and X-40-9225 (manufactured by Shin-Etsu Chemical Co., Ltd.) Containing trifunctional oligomer, Mw = about 2,500.
After adding 10 parts of "(a-B)" and stirring, adding 20 parts of ion-exchanged water and 10 parts of di-i-propoxyethyl acetoacetate aluminum and reacting at 60 ° C for 2 hours, and then adding (c) ) As a component, a silica-coated titanium oxide (methanol dispersion, solid content concentration 30%, the same applies hereinafter) 1
00 parts and 200 parts of isobutyl alcohol were added and mixed to prepare a composition of the present invention having a solid content of 20%.
Next, the composition was placed on a quartz glass plate at 500 rpm for 20 minutes.
Spin coating was performed for 2 seconds, followed by drying by heating at 200 ° C. for 30 minutes to obtain test pieces for testing hardness, ultraviolet absorption, transparency, and insulation. Table 2 shows the evaluation results of the storage stability of the composition and various evaluation results of the test pieces. In Table 2, the Mw of the composition is the Mw of the composition obtained by removing the component (c) from the obtained composition by filtration.

Examples 2 to 8 and Comparative Example 1 Preparation of a composition having a solid content of 20% and preparation of each test piece were carried out in the same manner as in Example 1 except that the formulation was as shown in Tables 2 and 3. Was done. Table 2 shows the evaluation results of the storage stability of each composition and various evaluation results of each test piece.

In Tables 2 and 3, the details of component (a), component (c) and silica sol are as follows. a-A: tetrafunctional oligomer having a terminal alkoxysilyl group. Mw: 2,000 (MKC silicate MS51, manufactured by Mitsubishi Chemical Corporation) aB: Trifunctional oligomer having a terminal methoxysilyl group.
Mw: about 2,500 (manufactured by Shin-Etsu Chemical Co., Ltd., X-40-9)
225) aC: Terminal hydroxyl group-containing trifunctional oligomer. M
w; 8,000 (YR337 manufactured by Toshiba Silicone Co., Ltd.)
0) a-D: bifunctional oligomer having a terminal alkoxysilyl group / oxyalkylene group. Mw: 5,000 (manufactured by Nippon Yunika Co., Ltd., MAC2101) Silica sol: i-propyl alcohol dispersion, solid content concentration 30%

[0115]

[Table 2]

[0116]

[Table 3]

Example 9 In a reactor equipped with a stirrer and a reflux condenser, 70 parts of methyltrimethoxysilane and 30 parts of dimethyldimethoxysilane were obtained as the component (a), and the component (b1) was obtained in Reference Example 1 as the component (b). -A), 10 parts of aluminum di-i-propoxyethyl acetoacetate and 5 parts of isobutyl alcohol 5
Add 0 parts and stir, add 20 parts of ion-exchanged water and add 60 parts.
After reacting at 4 ° C. for 4 hours, acetylacetone was added and cooled. Thereafter, (c) 250 parts of silica-coated titanium oxide, 100 parts of isobutyl alcohol, and 150 parts of 2-isopropoxyethanol were added and mixed to prepare a composition of the present invention having a solid concentration of 20%. Next, the composition was applied to a quartz glass plate by spin coating at 500 rpm for 20 seconds, and dried by heating at 200 ° C. for 30 minutes.
Test pieces for hardness, ultraviolet absorption, transparency, and insulation test were obtained. Table 4 shows the evaluation results of the storage stability of the composition and various evaluation results of the test pieces. In Table 2, Mw of the composition refers to (c) from the composition obtained.
It is Mw of the component removed by filtration.

Examples 10 to 17 and Comparative Example 2 Preparation of a composition having a solid content of 20% and preparation of each test piece were carried out in the same manner as in Example 9 except that the formulation was as shown in Tables 4 and 5. Was performed. Table 4 to Table 4 show the storage stability evaluation results of each composition and various evaluation results of each test piece.
It is shown in FIG.

[0119]

[Table 4]

[0120]

[Table 5]

Example 18 In a reactor equipped with a stirrer and a reflux condenser, 70 parts of methyltrimethoxysilane and 30 parts of dimethyldimethoxysilane were obtained as the component (a), and the component (b2) obtained in Reference Example 4 was obtained as the component (b). -A), 10 parts of di-i-propoxyethyl acetoacetate aluminum and 50 parts of isobutyl alcohol are added and stirred.
After reacting for 7 hours, acetylacetone was added for cooling. Then, 250 parts of silica-coated titanium oxide, 100 parts of isobutyl alcohol,
-150 parts of isopropoxyethanol are added and mixed,
A composition of the present invention having a solid content of 20% was prepared. Next, the composition was applied to a quartz glass plate by spin coating at 500 rpm for 20 seconds, and dried by heating at 200 ° C. for 30 minutes to obtain test pieces for hardness, ultraviolet absorption, transparency, and insulation test. . Table 6 shows the evaluation results of the storage stability of the composition and various evaluation results of the test pieces. In addition,
In Table 6, the Mw of the composition is the Mw of the composition obtained by removing the component (c) from the obtained composition by filtration.

Examples 19 to 20 and Comparative Example 3 Example 18 was repeated except that the formulation was as shown in Table 6.
Preparation of a composition having a solid content concentration of 20% and preparation of each test piece were performed in the same manner as in the above. Table 6 shows the evaluation results of the storage stability of each composition and various evaluation results of each test piece.

[0123]

[Table 6]

[0124]

The coating composition of the present invention has excellent storage stability and, when formed into a coating film, has high hardness, excellent weather resistance, light resistance, transparency, long-term durability adhesion, and ultraviolet absorption. Noh lasts semi-permanently, has insulation, high refractive index,
As an organosiloxane-based coating material capable of forming a film at a low or normal temperature, it has a very high property balance. The cured product of the present invention is excellent in both ultraviolet absorbing ability and visible light transmittance, excellent in weather resistance, light resistance, transparency, has long-term durability adhesion, and is excellent in insulation, so that it is a cathode ray tube, a liquid crystal. In addition to display devices, ultraviolet shielding films for optical devices such as plasma display panels, coating materials for EPROM windows, liquid crystal protective films for projection televisions, etc.
It can be suitably used for various applications such as an ultraviolet cut coat material for a fluorescent lamp surface and an ultraviolet cut coat material for an automobile window.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Toshiki Sakagami 2-11-24 Tsukiji, Chuo-ku, Tokyo FSR in JSR Co., Ltd. (Reference) 4J035 BA02 BA03 CA01N CA022 CA161 EB02 GA02 LB01 4J038 DL031 GA01 GA03 GA07 GA09 GA11 GA12 GA15 HA216 HA446 KA15 KA20 LA06 MA07 MA10 NA01 NA03 NA11 NA12 NA19 NA21 NA23 NA25 PA19 PB09 PC03

Claims (4)

[Claims] (I) (a) The following general formula (1) (R ¹ ) _n Si (OR ² ) _4-n (1) (wherein, R ¹ exists two times) Sometimes the same or different, and represents 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,
6 represents an acyl group or a phenyl group, and n is an integer of 0 to 2), and at least one selected from the group consisting of an organosilane hydrolyzate and an organosilane condensate And (c) a fine particle and / or a sol of a metal oxide containing a titanium oxide whose surface is coated with silica. (II) The component (a) according to claim 1, (b1) a polymer containing a silyl group having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group, and (c) A coating composition comprising the component (c) according to 1 above. (III) The component (a) according to claim 1, (b2) a structural unit represented by the following general formula (2)(Where R^Three~ R^FiveIs C_mY_{2m + 1}, M = an integer from 0 to 5,
Y is independently selected from F, H and Cl
You. ) And / or a structure represented by the following general formula (3)
Unit[In the formula, Rf represents an alkyl group containing a fluorine atom or an alkyl group.
A oxyalkyl group;^Three~ R^FiveIs the general formula (2)
It is synonymous and, within the same meaning, R in general formula (2) ^Three~ R
^FiveAnd may be different. ] And hydrolyzable
Having a silicon atom bonded to a group and / or a hydroxyl group
At least one selected from the group of polymers containing a silyl group
A seed, and (c) a component (c) according to claim 1.
A coating composition comprising: 4. A cured product having a coating film obtained from the coating composition according to claim 1.