JP2002121482A - Composition for transparent antistatic coating and cured product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an organosilane-based coating capable of forming a coating film which is excellent in coating film appearance, adhesion, weather resistance, and the like, and has high hardness, especially excellent colorless transparency and antistaticity. SOLUTION: This composition for transparent antistatic coatings, characterized by comprising (a) at least one compound selected from an organosilane represented by the general formula: (R1)nSi(OR2)4-n, the hydrolyzate of the organosilane and the condensate of the organosilane, (c) a high molecular cationic antistatic, and, if necessary, (b1) a silyl group-containing polymer or (b2) a silyl group-containing fluoropolymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition for a transparent antistatic coating material and a cured product thereof. The present invention relates to a coating material composition and a cured product thereof.

[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 performance required for an organosilane-based coating material to some extent, a composition containing a partial condensate of an organosilane, a dispersion of colloidal silica and a silicone-modified acrylic resin (Japanese Patent Application Laid-Open No. 60-1985). No. 135465), a composition comprising 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 Japanese Patent No. 65904 and U.S. Pat. No. 4,904,721 have the disadvantage that gloss is reduced by prolonged irradiation with ultraviolet light.
In addition, 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 is increased.

Furthermore, 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 have insufficient antistatic properties, and even if a general antistatic agent is blended in order to improve the antistatic properties,
It easily bleeds out and the antistatic effect tends to decrease over time. Further, in the conventional organosilane-based coating material, a material having both antistatic properties and transparency has not been found at present.

[0008]

SUMMARY OF THE INVENTION The present invention relates to adhesion, alkali resistance, organic chemical resistance, weather resistance, moisture resistance, and (temperature) resistance.
An object of the present invention is to provide a composition for a transparent antistatic coating material capable of forming a coating film having improved antistatic properties and transparency without lowering aqueous properties.

[0009]

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 50 carbon atoms;^TwoIs the same
One or different, an alkyl group having 1 to 5 carbon atoms, 1 carbon atom
And 6 represents an acyl group or a phenyl group;
An organosilane represented by the formula:
Group of hydrolysates of orchids and condensates of said organosilanes
At least one member selected from the group consisting of:
A transparent band characterized by containing a thione-based antistatic agent
Composition for antistatic coating material (hereinafter referred to as “composition (I)
U). Further, the present invention provides (II) the above (a)
(B1) bonding to a hydrolyzable group and / or a hydroxyl group
Polymer containing a silyl group having a silicon atom
(Hereinafter also referred to as “silyl group-containing polymer”), and (c)
Characterized by containing a polymeric cationic antistatic agent
Composition for transparent antistatic coating material (hereinafter referred to as “composition (I
I) "). Further, the present invention provides (III)
Component (a), (b2) a hydrolyzable group and / or
Having a silyl group having a silicon atom bonded to a hydroxyl group
Fluorine-containing acrylic polymer and / or hydrolysis
Having a silicon atom bonded to a functional group and / or a hydroxyl group
-Containing vinyl ether polymerization containing silyl group
(Hereinafter referred to collectively as “silyl group-containing fluorine-based polymer”
And (c) a polymeric cationic band.
A transparent antistatic coating characterized by containing an antistatic agent.
G composition (hereinafter also referred to as “composition (III)”
(I) to composition (III) are collectively referred to as "composition of the present invention".
Also referred to). Here, as the component (b2),
Is a structural unit represented by the following general formula (2) (hereinafter referred to as “(b
-1) 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-2) constituent unit”)Wherein Rf is an alkyl group containing a fluorine atom or
A oxyalkyl group;^Three~ R^FiveIs the general formula (2)
It is synonymous and, within the same meaning, R of the 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
(Silyl group-containing fluoropolymer) is preferred. Of the present invention
(C) Polymeric cationic antistatic agent used in the composition
Is a comb-shaped polymer with cationic groups incorporated into the backbone polymer.
Mers are preferred. Next, the present invention provides the above transparent antistatic core.
Characterized by having a coating film obtained from the composition for a coating material.
The cured product.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The composition of the present invention comprises the above component (a), component (a) to (b1), or
Since it contains the components (a) to (b2) and (c) a polymeric cationic antistatic agent as main components, it has excellent antistatic properties and transparency, and also has high hardness and excellent long-term durability. It has the property that antistatic performance lasts semipermanently.

Composition (I) The composition (I) contains (a) an organosilane or a hydrolytic condensate thereof, and (c) a high molecular weight cationic antistatic agent.

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-mentioned organosilane (1) contains 2-4 O-organosilanes (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. 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 such that the value of n + m is 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, the cocondensate of the component (a) and the component (b1) or the component (b2) in the compositions (II) to (III) described later becomes hydrophilic. )), When two R ¹ are present, 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-hydroxypropyltriethoxysilane 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- 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, more preferably a combination of 30 to 95 mol% of trialkoxysilane and 70 to 5 mol% of an organopolysiloxane having Mw of 3,000 to 15,000. 3-
(Meth) acryloyloxypropyl group, 3-glycidoxypropyl group, or 2- (3,4-epoxycyclohexyl) group-containing trialkoxysilane and methyltrialkoxysilane are used to form a coating film. In addition to softening, adhesion to an organic material or the like can be imparted, and compatibility with an organic compound can be improved. Further, by using a dialkoxysilane and a trialkoxysilane in combination, or by using a trialkoxysilane and an organopolysiloxane in combination, the resulting coating film can be softened and the alkali resistance can be improved.

The organosilane (1) is used as it is or as a hydrolyzate and / or condensate. When the organosilane (1) is used as a hydrolyzate and / or condensate, it can be hydrolyzed and condensed in advance and used as the component (a), but 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 from 0.3 to 3 based on 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 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.

(C) Polymeric cationic antistatic agent; The (c) polymeric cationic antistatic agent used in the composition (I) imparts an antistatic property to the obtained composition while being transparent. In addition, it has an effect of improving the adhesiveness to various substrates. (C) Since the polymeric cationic antistatic agent itself has a high molecular weight, it does not bleed out from the coating film, the antistatic property is maintained semipermanently, and the inorganic metal oxide antistatic agent is used. Agent [for example,
ITO (In-doped SnO ₂ ) or ATO (Sb-doped S
nO ₂ ) fine particles, ZnSb ₂ O ₅ fine particles or sol], the coating film is colorless and transparent without coloring the coating film. (C) The high molecular weight cationic antistatic agent is defined as a comb polymer in which a cationic group is incorporated into a skeletal polymer. Specific examples of the (c) polymer cationic antistatic agent include an antistatic agent C-SQ-M8S manufactured by Mitsubishi Chemical Corporation.

The amount of the component (c) used in the composition (I) is usually 1 to 40% by weight in terms of solid content in the component (a) (in terms of a completely hydrolyzed condensate) to the component (c). , Preferably 10 to 30% by weight. If the amount is less than 1% by weight, the antistatic property is not sufficient, while if it exceeds 40% by weight, the surface hardness of the coating film is remarkably reduced. The amount of the component (c) used in the composition (II) described below is calculated on a solids basis with respect to the total amount of the component (a) (completely hydrolyzed and condensed) and the total amount of the components (b1) and (c). % By weight of component (c)
And the amount of the component (c) used in the composition (III) described below is the amount of the component (a) (complete hydrolyzed condensate),
It is a weight percentage of the component (c) in terms of solid content based on the total amount of the component (b2) and the component (c). The amount of the component (c) used in the composition (II) or the composition (III) is as follows:
All are the same as the mixing amount range in the composition (I).

The composition (I) of the present invention contains the above 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 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. As described above, water is also used for the hydrolysis and condensation of the component (a) and the components (b1) and (b2) described below.

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), (b1) a polymer containing a silyl group, and (c) a high-molecular cationic antistatic agent as main components. Here, the components (a) and (c) in the composition (II) and the water and the organic solvent used are the same as the component (a), the component (c) and the water and the organic solvent in the composition (I). Since these are the same, the description thereof will be omitted, and (b1) a silyl group-containing polymer will be described below.

(B1) a silyl group-containing polymer; a composition (I
The component (b1) in I) has a silyl group having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group (hereinafter also referred to as a “specific silyl group”), and preferably has a specific silyl group as a polymer molecule. It is a polymer having a chain terminal and / or a side chain. Such a component (b1) is that when a coating film obtained from the composition (II) is cured, a hydrolyzable group and / or a 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 (b1) is usually 0.1 to 6 in the component (b1).
0 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 constituting the specific silyl group (b-3) represented by the general formula (4). 3) A monomer obtained by polymerizing a monomer, and if necessary, (b-4) another monomer copolymerizable with these monomers (hereinafter referred to as “(b-4) 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- 5) also referred to as “silane compound”).

Here, the monomer (b-3) 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-3) 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 above unsaturated silane compound include CH ₂ ＣＨCHSi (CH ₃ ) (OCH ₃ ) ₂ , CH ₂ ＣＨCHSi (OCH ₃ ) ₃ , CH ₂ ＣＨCHSi (OC ₂ H ₅ ) ₃ , CH ₂ ＣＨCHSi (CH ₃ ) Cl ₂ , CH ₂ 3CHSiCl ₃ , CH ₂ ＣＨCHCOO (CH ₂ ) ₂ Si (CH ₃ ) (OCH ₃ ) ₂ , CH ₂ ＣＨCHCOO (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , CH ₂ ＣＨCHCOO (CH ₂ ) ₃ Si (CH ₃ ) (OCH ₃ ) ₂ , CH ₂ ＣＨCHCOO (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , CH ₂ ＣＨCHCOO (CH ₂ ) ₂ Si ( CH ₃ ) Cl ₂ , CH ₂ ＣＨCHCOO (CH ₂ ) ₂ SiCl ₃ , CH ₂ ＣＨCHCOO (CH ₂ ) ₃ Si (CH ₃ ) Cl ₂ , CH ₂ ＣＨCHCOO (CH ₂ ) ₃ SiCl ₃ , CH ₂ = _{C (CH 3) COO (CH} 2) 2 Si (CH 3) (OC _{3) 2, CH 2 = C} (CH 3) COO (CH 2) 2 Si (OCH 3) 3, CH 2 = C (CH 3) COO (CH 2) 3 Si (CH 3) (OCH 3) 2, CH ₂ ＣC (CH ₃ ) COO (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , CH ₂ ＣC (CH ₃ ) COO (CH ₂ ) ₂ Si (CH ₃ ) Cl ₂ , CH ₂ ＣC (CH ₃ ) COO (CH ₂ ) ₂ SiCl ₃ , CH ₂ ＣC (CH ₃ ) COO (CH ₂ ) ₃ Si (CH ₃ ) Cl ₂ , CH ₂ ＣC (CH ₃ ) COO (CH ₂ ) ₃ SiCl ₃ ,

[0033]

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

Examples of the monomer (b-4) which is another monomer copolymerizable with the monomer (b-3) include (a) methyl (meth) acrylate and ethyl (meth) acrylate.
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 1,4-dichlorostyrene, 2,6-dichlorostyrene and 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 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.

Examples of the (b-5) silane compound used in the above addition reaction include 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 at a time and polymerization is performed, a part of the monomer is polymerized, and then the remainder is continuously processed. Or a method in which the monomer is continuously added from the beginning of the polymerization. Further, a polymerization method in which these polymerization methods are combined may be employed. Preferred polymerization methods include solution polymerization. As the solvent used for the solution polymerization, a usual solvent can be used, and among them, ketones and alcohols are preferable. In this polymerization, known polymerization initiators, molecular weight regulators, chelating agents and inorganic electrolytes can be used.

The content of the structural unit (b-3) 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 composition tends to deteriorate. In addition,
The constituent unit (b-4) constituent unit composed of the monomer (b-4), which is another copolymerizable monomer, is usually 90 mol% or less, preferably in the component (b1). , 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 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 having a specific silyl group, vinylsilanes, carboxysilanes, glycidylsilanes and the like. The specific silyl group-containing polyester resin is, for example, produced by reacting a carboxyl group or a hydroxyl group contained in the polyester resin with an aminosilane having a specific silyl group, a carboxysilane, a glycidylsilane, or the like. Can be.

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, while if it exceeds 900 parts by weight, the weather resistance and light resistance of the coating film tend to decrease. . The term "completely hydrolyzed condensate" means that the R ² O— group of the organosilane (1) is hydrolyzed by 100% and SiOH
It is a group that becomes a group and is further completely condensed to form a siloxane structure.

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) comprises (a) an organosilane or a hydrolytic condensate thereof, (b2) a silyl group-containing fluoropolymer, and (c) a polymeric cationic antistatic agent. Main component. Here, component (a) and component (c) in composition (III),
The water and the organic solvent used are the same as the component (a) and the component (c) and the water and the organic solvent in the composition (I). The fluorine-containing polymer will be described in detail.

(B2) a silyl group-containing fluoropolymer; the component (b2) in the present invention is a fluorine-containing acrylic polymer having a silyl group having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group, and / or Or a fluorine-containing vinyl ether polymer containing a silyl group having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group. The component (b2) is preferably (b)
-1) a silyl group having a structural unit and / or a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group having the structural unit (b-2) (hereinafter also referred to as “specific silyl group”). Preferably, it is a fluoropolymer having a specific silyl group at the terminal and / or side chain of the polymer molecular chain. Such a component (b2) causes the hydrolyzable group and / or hydroxyl group in the silyl group of the above-mentioned component (a) when the coating film obtained from the composition of the present invention is cured.
By co-condensing with the components, excellent coating performance can be obtained. The content of the specific silyl group in the component (b2) is usually from 0.1 to 60 mol%, preferably from 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-1) a monomer that constitutes the structural unit (hereinafter, also referred to as “(b-1) monomer”) and / or (b) represented by the general formula (3). -2) a monomer that constitutes a structural unit (hereinafter, “(b-2) monomer”
(B-3) represented by the above general formula (4).
It is obtained by polymerizing a monomer (b-3) containing a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group constituting a specific silyl group, and if necessary, (b-4)
Other monomers copolymerizable with these monomers (hereinafter referred to as “(b
-4) also referred to as “monomer”). The monomer (b-4) may be a monomer having a fluorine atom which is not included in the monomers (b-1) and (b-2).

The component (b2) is the same as the component (b-1)
A polymer obtained by polymerizing a monomer and / or a monomer (b-2), or a polymer obtained by further adding a monomer (b-4) to these monomers, if necessary. And a silane compound having a functional group capable of reacting with the above-mentioned hydrolyzable group or hydroxyl group (hereinafter also referred to as “(b-5) silane compound”) to the carbon-carbon double bond of the polymer obtained as described above. May be obtained.

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

As the monomer (b-1), for example,
One polymerizable unsaturated double bond and at least one
Compounds having a fluorine atom can be given. (B
-1) 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
Any fluoroethylenes; CF_ThreeCF = CF_Two, CF_Three
CF = CHF, CF_ThreeCH = CF_Two, CF_ThreeCF = CH
_Two, CF_ThreeCF = CHF, CHF_TwoCF = CHF, CF
_ThreeCH = CH_Two, CH_ThreeCF = CF_Two, CH_ThreeCH = C
F_Two, CH_ThreeCF = CH_Two, CF_TwoClCF = CF_Two,
CF_ThreeCCl = CF_Two, CF_ThreeCF = CFCl, CF_Two
ClCCl = CF_Two, CF_TwoClCF = CFCl, CF
_TwoCCl = CCIF, CF_TwoCCl = CCl_Two, CCl
_ThreeCF = CF_Two, CF_TwoClCCl = CCl_Two, CFC
l_TwoCCl = CCl_Two, CF_ThreeCF = CHCl, CCl
F_TwoCF = CHCl, CF_ThreeCCl = CHCl, CHF
_TwoCCl = CCl_Two, CF_TwoClCH = CCl_Two, CF
_TwoClCCl = CHCl, CCl_ThreeCF = CHCl etc.
(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-1) containing these fluorine atoms
The monomers may be used alone or in combination of two or more.

The monomer (b-2) 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-2), for example,
Compounds having one polymerizable unsaturated double bond, ether bond and at least one fluorine atom can be mentioned. (B-2) 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-2) monomers containing a fluorine atom may be used alone or in combination of two or more.

When the monomer (b-1) and the monomer (b-2) are used in combination, hexafluoropropylene is combined with perfluoroalkyl perfluorovinyl ether or perfluoroalkoxyalkyl perfluorovinyl ether. It is preferable to use it.

The (b-3) monomer, (b-4) monomer and (b-5) silane compound are as described above. Further, the polymerization method for producing the component (b2) is also the same as the above-mentioned component (b1).

The total content of the constituent units (b-1) and (b-2) 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 them, the content of the (b-1) structural unit is preferably 0.5 to
70 mol%. The content of the structural unit (b-2) is preferably 0.5 to 70 mol% in the component (b2). Further, the content of the structural unit (b-3) 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 composition tends to deteriorate. In addition, the structural unit [(b-4) structural unit] composed of the monomer (b-4), which is another copolymerizable monomer, is (b)
2) In the component, usually 90 mol% or less, preferably 8 mol% or less.
It is about 0 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 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 completely hydrolyzed condensate. , 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) used 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-3) and the component (b)
-4) copolymerizing with a monomer, or (b-4)
It can be obtained by subjecting the polymer obtained by polymerizing the monomer to an addition reaction with the above-mentioned (b-5) silane compound.
The content of the component (b ′) is usually 5 parts by weight when the component (a) is converted to a complete hydrolyzed condensate to 100 parts by weight.
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, but the compositions (I) + (II) and (II) + (II
I), composition (I) + (III), composition (I) + (II) +
It goes without saying that (III) can be used in combination. Further, the composition of the present invention [Composition (I) to
(III)] may further contain the following components (d) to (g) 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. In addition, 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. Organic zirconium compounds;

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

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 an organometallic compound or the like, the composition of the present invention [(a)
Component (complete hydrolyzed condensate equivalent) and component (c),
Component (a) (in terms of complete hydrolysis condensate), component (b1) and component (c), or component (a) (in terms of complete hydrolysis condensate), total amount of component (b2) and component (c) The same applies to the following).
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 the same as those in the organometallic compound (5). Having the same meanings as R ⁹ and R ^{10 in} general formula (5)], a carboxylic acid compound, a dihydroxy compound, an amine compound, and an oxyaldehyde compound represented by the formula: At least one of them. 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 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) 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, 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.

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 Industry Co., Ltd., and alumina sol manufactured by Catalyst Chemical Industry Co., Ltd.
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, and 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_TwoEach metal oxide 3)
It may be a mixture of seeds, a solid solution, or
From three metals consisting of tan, zirconium and tin
Metal oxides formed by oxidizing different alloys or solid solutions
They may be combined, and are not particularly limited. in this way,
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. 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 which can absorb ultraviolet rays of 300 nm or less by 80% or more and can be used semi-permanently 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 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 (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.

The method for blending the component (g) into the composition of the present invention is as follows.
(C) component; in the case of the composition (II), the above (a), (b)
1) and (c) components; in the case of the composition (III),
It may be added after the preparation of the composition comprising the components (b2) and (c) and other additives described later, or may be added during the preparation of the composition of the present invention, and may be added in the presence of the component (g). , (A) component organosilane (1) and (b)
The components 1) to (b2) can be hydrolyzed and condensed. When the component (g) is added during the preparation of the composition,
The semiconductor compound in the component (g) is replaced by the component (a) or the component (b1)
It can be co-condensed with the component (b2), and the dispersibility of the component (g) can be improved. When the component (g) is an aqueous sol, the component (g) is preferably added at the time of preparing the composition. Also, when the viscosity of the system increases due to the incorporation of the component (e), the component (g) It is preferable to add it during the preparation of the composition.

[0092] Examples of the commercially available 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 amount of the component (g) is too small, the ultraviolet absorbing ability becomes insufficient. 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 for coloring, thickening, and the like of 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, or 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,
Celluloses such as hydroxypropylcellulose and hydroxypropylmethylcellulose; castor oil derivatives; thickeners such as ferrosilicate; ammonium carbonate;
Inorganic blowing 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 organic foaming agents, as well as other surfactants, silane coupling agents, titanium coupling agents, dyes, and other additives.

The composition of the present invention contains, for example, 360
In order to increase the ability to absorb UV 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, and 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 can 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 Co., Ltd .; Emulgen and Homogenol of Kao Corporation. Can be mentioned.

By adding such a leveling agent, the finished appearance of the coating film is improved, and the coating film can be uniformly applied as a thin film. 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 at the time of 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.

Suitable substrates 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 articles 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. Depending on the use, 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 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, 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 comprising only the component (a) or the component (a) and the component (b1) of the present invention. 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 of applying the composition of the present invention to a substrate, a brush, a roll coater, a flow coater, a spin coater, an ultrasonic coater, a (micro) gravure coater, etc. 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 dry film having a 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, weather resistance, etc., high in hardness, and particularly excellent in colorless transparency and antistatic properties. 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 product) obtained by the composition of the present invention is excellent in colorless transparency,
In particular, the antistatic property can be maintained semipermanently.
Further, if the component (g) is blended, ultraviolet rays having a specific wavelength of 90 to 350 nm, particularly 200 to 320 nm, are added to 70
It can cut about 100%, and is excellent in ultraviolet absorption. Since the composition of the present invention is excellent in colorless transparency and antistatic properties, various kinds of transparent antistatic properties such as a transparent antistatic layer of various optical use films and a transparent antistatic layer of a polarizing plate (film) for LCD are required. Used for applications.

[0108]

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 hydrolyzed condensate of an organosilane or 1 g of a polymer using tetrahydrofuran as a solvent
Was prepared by dissolving in 100 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

The composition was applied on a glass plate having a surface hardness of 1.5 μm in a dry film thickness.
For the coating film dried at 20 ° C. for 20 minutes, JIS K54
The pencil hardness according to 00 was measured.

The composition was applied on a polyethylene terephthalate film having a haze value of 50 μm to a dry thickness of 1.5 μm, dried at 100 ° C. for 20 minutes, and then dried by BYK-Gardner.
Measured using an aze-gard plus.

The composition was applied on a polyethylene terephthalate film having a surface resistivity of 50 μm in thickness to a dry thickness of 1.5 μm and dried at 100 ° C. for 20 minutes.
The measurement was performed using a model HT-201.

Production Example 1 A reaction vessel equipped with a stirrer and a reflux condenser was charged with 15 parts of 3-methacryloyloxypropyltrimethoxysilane as a monomer and 4-methacryloyloxy-1,2,2,6,6-pentamethyl as a monomer. 5 parts of piperinodine, 65 parts of methyl methacrylate and 15 parts of 2-ethylhexyl methacrylate as monomers, and 80 parts of xylene and 20 parts of butyl acetate as solvents were added and mixed, and then heated to 80 ° C. with stirring, A solution prepared by dissolving 4 parts of azobisisovaleronitrile in 10 parts of xylene was added to 30 parts.
Dropped over minutes. Subsequently, the mixture was polymerized at 80 ° C. for further 5 hours to obtain a polymer solution having a solid content of 50%. The Mw of this polymer was 12,000.

Production Example 2 In a reaction vessel equipped with a stirrer and a reflux condenser, 66.3 parts of hexafluoropropylene as a monomer, 5.1 parts of vinyltrimethoxysilane as a monomer, 28.6 parts of ethyl vinyl ether as a monomer, and a solvent After adding and mixing 320 parts of methyl isobutyl ketone, the mixture was heated to 100 ° C. with stirring,
3 parts of an azo initiator containing a siloxane unit and 0.5 part of lauryl peroxide were added dropwise, and the mixture was further reacted at 100 ° C. for 5 hours to obtain a fluorine-containing vinyl ether polymer having a solid concentration of 24%. The Mw of this polymer is 2300
It was 0.

Synthesis Example 1 [Synthesis of Component (a)] In a reactor equipped with a reflux condenser and a stirrer, 100 parts of methyltrimethoxysilane, 50 parts of an organopolysiloxane [YR3370, manufactured by Toshiba Silicone Co., Ltd.], ethyl Add 1 part of acetoacetate aluminum diisopropylate (ALCH, manufactured by Kawaken Fine Chemical Co., Ltd.), 150 parts of i-propyl alcohol, and 20 parts of water, and add 60 ° C.
And reacted for 5 hours. Thereafter, 1.5 parts of acetylacetone was added, and the mixture was further reacted for 1 hour, and then cooled to room temperature. Thereafter, 177.5 parts of a mixed solution of methyl ethyl ketone / methyl isobutyl ketone = 1/1 (weight ratio) was added to obtain a hydrolyzed condensate solution having a solid content concentration of 20% and Mw of 8,000.

Synthesis Example 2 [Synthesis of Components (a) / (b1)] In a reaction vessel equipped with a stirrer and a reflux condenser, 70 parts of methyltrimethoxysilane and 30 parts of dimethyldimethoxysilane were used as organosilane (1). As the component (b1), 50 parts of the polymer obtained in Production Example 1 was used, and as the component (d), diisopropoxyethyl acetoacetate aluminum 5
, 13 parts of ion-exchanged water and 60 parts of i-propyl alcohol, and reacted at 60 ° C for 4 hours with stirring.
Next, 5 parts of acetylacetone was added as the component (e) to obtain a polymer solution having a solid content of 35% and an Mw of 15,000.

Synthesis Example 3 [Synthesis of Component (a) / (b2)] In a reactor equipped with a reflux condenser and a stirrer, 51 parts of methyltrimethoxysilane, 27 parts of dimethyldimethoxysilane,
82 parts of the fluorine-containing vinyl ether polymer obtained in Production Example 2 [solid content: 24%], i-propyl alcohol 62
, 62 parts of methyl ethyl ketone and 6 parts of an i-propyl alcohol solution having a concentration of 75% aluminum di-i-propoxyethyl acetoacetate.
After dropping 14 parts of water at 0 ° C over 90 minutes,
, And allowed to react for 5 hours. Then, 6 parts of acetylacetone was added, and the reaction was continued for another 1 hour. Obtained.

Example 1 The hydrolyzed condensate solution obtained in Synthesis Example 1 was converted to a solid content of 90%, and an antistatic agent C-SQ-M8S manufactured by Mitsubishi Chemical Corporation was used as a high molecular weight cationic antistatic agent. A 10% mixture 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 of 15%. To 100 parts of this polymer solution, 10 parts of a TBZR chelate (TBZR / acetylacetone = 1/2 molar ratio mixed reaction, i-propyl alcohol solution having an active ingredient concentration of 20%) as a curing agent was added, and a transparent antistatic coating material was added. A composition for use was prepared. Next, using this composition, a test piece for testing hardness, transparency (cloudiness value), and antistatic property (surface resistivity) was obtained. Table 1 shows the evaluation results.

Example 2 The polymer solution obtained in Synthesis Example 2 was converted to a solid content of 90%
Except for using, a coating material composition was prepared in the same manner as in Example 1. Next, a test piece was obtained in the same manner as in Example 1. Table 1 shows the evaluation results.

Examples 3-4, Comparative Examples 1-4 Preparation of compositions and preparation of test specimens were carried out in the same manner as in Example 1 except that the formulation was as shown in Tables 1-2. . The results are shown in Tables 1 and 2.

[0121]

[Table 1]

In Tables 1 and 2, * 1 and * 2 are as follows. Table 2 is the same. * 1) Mitsubishi Chemical Corporation, C-SQ-M8S (solid content 30%, i-propyl alcohol / methyl ethyl ketone = 1/1 weight ratio solution) * 2) TBZR (tetrabutoxyzirconium) / acetylacetone = 1 / 2 mole mixture reaction, active ingredient concentration =
Polymer solution containing 20% as a main agent (methanol / i-butyl alcohol / methyl isobutyl ketone = 1/3/3)
Weight ratio of mixed solvent, concentration 15%). Based on 100 parts of base polymer solution, add the above number of parts.

[0123]

[Table 2]

[0124]

The composition for a transparent antistatic coating material of the present invention, when formed into a coating film, has high hardness, excellent weather resistance and excellent long-term durability adhesion, and particularly excellent colorless transparency and antistatic properties. 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
Various applications such as various recording sheets such as OHP, optical film applications, and various display applications such as EL devices and display devices, because of its excellent transparency and antistatic properties, and excellent weather resistance and long-term durability adhesion. Can be suitably used.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J038 CP022 CP092 DL021 DL031 DL071 DL112 DL122 GA01 GA03 GA07 GA08 GA09 GA10 GA11 GA12 HA096 HA176 HA276 HA326 HA376 HA416 HA446 JB04 JC13 JC35 JC38 JC40 KA04 KA12 MA14 NA01 NA03 NA04 NA11 PB08 PB11

Claims (6)

[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 50 carbon atoms, and R ² is the same or different and is an alkyl group having 1 to 5 carbon atoms,
And n represents 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 composition for a transparent antistatic coating material comprising: a seed; and (c) a polymeric cationic antistatic agent. (II) The component (a) according to claim 1, (b)
1) For a transparent antistatic coating material comprising a polymer containing a silyl group having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group, and (c) a polymeric cationic antistatic agent Composition. (III) The component (a) according to claim 1, (b)
2) A fluorine-containing acrylic polymer having a silyl group having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group and / or containing a silyl group having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group. A composition for a transparent antistatic coating material, comprising: a fluorine-containing vinyl ether polymer; and (c) a polymeric cationic antistatic agent. 4. The component (b2) is represented by the following general formula (2).
Constituent units(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)
UnitWherein Rf is an alkyl group containing a fluorine atom or
A oxyalkyl group;^Three~ R^FiveIs the general formula (2)
It is synonymous and, within the same meaning, R of the 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
The composition for a transparent antistatic coating material according to claim 3, which is: 5. The polymer cationic antistatic agent (c),
The composition for a transparent antistatic coating material according to any one of claims 1 to 4, wherein the composition is a comb polymer in which a cationic group is incorporated in a skeletal polymer. 6. A cured product having a coating film obtained from the composition for a transparent antistatic coating material according to any one of claims 1 to 5.