JP2002194285A - Hard coat film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hard coat film having excellent adhesion, weatherability, stain resistance, and abrasion resistance. SOLUTION: The hard coat film has a coating film composed of a coating composition (I) for undercoating comprising (a) at least one kind selected from the group consisting of an organosilane to be represented by the formula: (R1)nSi(OR2)4-n, a hydrolyzate of the organosilane, and a condensate of the organosilane and (b) a polymer containing a silyl group having a silicon atom bonded to a hydrolyzable group and/or a hydroxyl group on a plastic film and, further on the coating film, a coating film composed of a coating composition (II) for topcoating comprising the component (a).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to an organosilane coating agent having a low water contact angle from the initial stage of film formation, which is fixed on an organic substrate to ensure long-term adhesion, adhesion, weather resistance, stain resistance, and the like. It relates to a hard coat film having excellent wear resistance.

[0002]

2. Description of the Related Art The technical development of organosilane-based coating agents has been promoted as maintenance-free coating agents having excellent weather (light) resistance and stain resistance. The performance requirements for such organosilane-based coating agents 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 agent that is excellent in water-based properties, insulation resistance, abrasion resistance, stain resistance, and the like, and that can form a coating film with high hardness.

[0003] In particular, it has been recognized that the surface of a coating film is preferably made hydrophilic in order to improve the stain resistance. However, this is a treatment performed for the purpose of improving the stain recovery property (cleanability). The effect of the anti-staining property can be obtained only when the anti-staining property exceeds the adhesion amount of the contaminants. On the other hand, according to the method for imparting water repellency and oil repellency to the coating film, the adhesion to the coating film can be reduced regardless of whether the contaminant is hydrophilic or lipophilic. Conventionally, water and oil repellency is imparted to a coating film by adding an oil or a surfactant, but it is difficult to maintain stain resistance for a long time by such a method.

On the other hand, as a coating composition which satisfies the required performance of an organosilane-based coating agent to some extent, a composition comprising a partial condensate of an organosilane, a dispersion of colloidal silica and a silicone-modified acrylic resin (Japanese Patent 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 US Pat. No. 65,904 and US Pat. No. 4,904,721 have the disadvantage that gloss is reduced by prolonged irradiation with ultraviolet light.
Further, the composition described in JP-A-64-1769 has a problem that storage stability is not sufficient and gelation is likely to occur in a short period of time when the solid content concentration is increased.

Further, the applicant of the present application has already disclosed a hydrolyzate of organosilane and / or a partial condensate thereof, a vinyl resin having a hydrolyzable and / or silyl group having a silicon atom bonded to a hydroxyl group, and a metal chelate. A coating composition containing a compound and β-diketones and / or β-ketoesters
345877). This composition is:
Although excellent in the balance of the above-mentioned coating film performance required for the organosilane-based coating agent, it may take six months or more before the self-cleaning property is exhibited (the water contact angle is reduced). On the other hand, as a coating agent having a low water contact angle to some extent from the initial stage of film formation and exhibiting self-cleaning properties from the initial stage of film formation, there is an all-inorganic coating material based on tetrafunctional alkoxysilane. By reducing the organic group content in the coating film, the water contact angle can be increased to 5 from the beginning of film formation.
Although it is characterized by being less than 0 °, there is a problem that it is not possible to secure adhesion to an organic base material because it is an inorganic coating material.

[0007]

SUMMARY OF THE INVENTION According to the present invention, an organosilane-based coating agent having a low water contact angle is fixed on an organic substrate from the initial stage of film formation, ensuring long-term adhesion, adhesion, weather resistance, and contamination resistance. It relates to a hard coat film having excellent properties and abrasion resistance.

[0008]

According to the present invention, an undercoating coating composition (I) is provided on a plastic film.
The present invention relates to a hard coat film having a coating film composed of the following, and further having a coating film composed of the following coating composition (II) for overcoat. Undercoat coating composition (I) (a) the following general formula _{^{(1) (R 1) n}} Si (OR 2) 4-n ····· (1) ( In the formula, R ^1, there are two to Sometimes the same or different, and represents a monovalent organic group having 1 to 8 carbon atoms; R ² is the same or different and represents an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 6 carbon atoms; It is an integer of 0 to 2.)
And at least one selected from the group consisting of an organosilane represented by the formula: a hydrolyzate of the organosilane and a condensate of the organosilane; and (b) a hydrolyzable group and / or
Or an undercoating coating composition comprising a polymer containing a silyl group having a silicon atom bonded to a hydroxyl group. During overcoated coating composition (II) (a) the following general formula _{^{(1) (R 1) n}} Si (OR 2) 4-n ····· (1) ( wherein, R ¹ is present two to Sometimes the same or different, and represents a monovalent organic group having 1 to 8 carbon atoms; R ² is the same or different and represents an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 6 carbon atoms; It is an integer of 0 to 2.)
A coating composition for overcoating, comprising: an organosilane represented by the formula: or a hydrolyzate of the organosilane and a condensate of the organosilane. Here, the component (a) constituting the undercoating coating composition (I) of the present invention is selected from the group consisting of an organosilane having n = 0, a hydrolyzate of the organosilane, and a condensate of the organosilane. It is preferable that at least one of them (hereinafter, also referred to as “component (a1)”) be contained as an essential component, or the component (a1) be used. The component (a) constituting the undercoat coating composition (I) of the present invention includes (a) ′ a trifunctional and / or bifunctional trifunctional compound having an SiO bond and a weight average molecular weight of 300 to 100,000. Those containing an organosiloxane oligomer (hereinafter, also referred to as “component (a) ′ component”) are preferred. Further, as the component (a) constituting the undercoating coating composition (I) of the present invention, those composed of the components (a1) and (a) ′ are also preferable. The undercoating coating composition (I) of the present invention may further contain (c) silica and / or alumina. The undercoating coating composition (I) of the present invention may further contain (d) semiconductor fine particles having an ultraviolet absorbing ability. Further, as the component (a) constituting the topcoating coating composition (II) of the present invention, a component containing the component (a1) at 50% by weight or more is preferable. Furthermore, the coating composition for topcoat of the present invention
As the component constituting (II), the above (c) silica and / or alumina may be further blended. Further, as the component (a) constituting the topcoating coating composition (II) of the present invention, a component containing the component (a1) in an amount of 50% by weight or more and containing the component (c) is preferable. further,
The coating composition for overcoating (II) of the present invention preferably comprises a component (a1) and a component (c).

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Coating composition for undercoat
(I) The composition (I) contains the above components (a) and (b) as main components. Component (a): Component (a) includes an organosilane represented by the above general formula (1) (hereinafter referred to as “organosilane (1)”), a hydrolyzate of organosilane (1), and organosilane (1). At least one selected from the condensates of
It is a seed and acts as a binder in the compositions of the present invention. 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.

Here, the hydrolyzate of the organosilane (1) contains 2 to 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 are also mentioned. it can.

Examples of the substituent in the substituted derivative of R ¹ include a halogen atom, a substituted or unsubstituted amino group, a hydroxyl group, a mercapto group, an isocyanate group, a glycidoxy group, a 3,4-epoxycyclohexyl group, a (meth) An acryloxy group, a ureido group, an ammonium base and the like can be mentioned. However, the carbon number of R ¹ composed of these substituted derivatives is 8 or less including the carbon atom in the substituent. When two R ¹ are present in the general formula (1), they may be the same or different from each other.

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

Specific examples of the organosilane (1) include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane 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. Among these, tetraalkoxysilanes having n = 0 "component (a1)" are preferable, and tetramethoxysilane and tetraethoxysilane are more preferable. In the present invention, the component (a) can be used alone or in combination of two or more.

The organosilane (1) is used as it is or as a hydrolyzate and / or condensate. When a tetraalkoxysilane is used as the component (a) as a hydrolyzate and / or condensate, it can be hydrolyzed and condensed in advance and used as the component (a). When component (a) is mixed with the remaining components to prepare a composition, it is preferable to add an appropriate amount of water to hydrolyze and condense to obtain component (a).

Commercially available condensates (oligomers) of tetraalkoxysilanes include methyl silicate oligomer manufactured by Mitsubishi Chemical Corporation and ethyl silicate manufactured by Colcoat. These may be used as the component (a) or as a part of the component (a).

Component (a) ': The component (a) constituting the undercoat coating composition (I) of the present invention may contain the component (a)'. The component (a) ′ has an SiO bond and a weight average molecular weight of 300 to 1
It is a 00000 tri- and / or bi-functional siloxane oligomer, which may be used alone or as a mixture of two or more. The method for producing the component (a) ′ is not particularly limited, but is preferably a condensate of chlorosilane or a condensate of alkoxysilane. When a trialkoxysilane or a dialkoxysilane is used as the component (a), it may be used as the component (a) ′ which has been previously hydrolyzed and condensed before being mixed with other components described later. preferable. When the trialkoxysilanes or dialkoxysilanes are present in the undercoating coating composition without forming a condensate, they may migrate to the overcoating coating composition (II). In the case of migration, the water contact angle on the overcoating coating composition (II) becomes 50 ° or more, and the antifouling property cannot be exhibited from the initial stage of film formation.

In the siloxane oligomer, the terminal functional group of the siloxane is a hydroxyl group, a halogen atom, an organic group having 1 to 15 carbon atoms or an oxyalkylene group, preferably an alkoxyl group. These groups may be partially hydrolyzed and condensed. Examples of the halogen atom include fluorine and chlorine. Examples of the organic group having 1 to 15 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and an n-
Butyl, i-butyl, sec-butyl, t-butyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl, tridecyl Alkyl groups such as a group, tetradecyl group, hexadecyl group, heptadecyl group, octadecyl group and 2-ethylhexyl group; acyl groups such as acetyl group, propionyl group, butyryl group, valeryl group, benzoyl group and trioil group; methoxy group and ethoxy group , An alkoxyl group such as a propoxy group and a butoxy group; an alkoxysilyl group such as a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group and a butoxysilyl group; a vinyl group, an allyl group, an acetoxyl group, an acetoxysilyl group, a cyclohexyl group, and a phenyl group , Glycidyl group, (meth) acryloxy group, urea De group, amide group, fluoro acetamide group, isocyanate group; polyoxyethylene group, polyoxypropylene group, poly (oxyethylene /
In addition to polyoxyalkylene groups such as an (oxypropylene) group, substituted derivatives of these groups and the like can be mentioned.

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.

The weight average molecular weight of the component (a) ′ (hereinafter, referred to as
"Mw") is from 300 to 100,000, particularly preferably from 500 to 50,000. If it is less than 300, it shifts to the top coat, the water contact angle in the top coat becomes 50 ° or more, and the antifouling property may not be exhibited from the initial stage of film formation. The component (a) ′ includes Mw
May be used in combination. For example, an oligomer having Mw of 300 to 2,800 and an oligomer having Mw of
= 3,000 to 50,000 oligomers.

(A) The commercially available products of the component include silicone resin manufactured by Dow Corning Toray Co., Ltd., and Toshiba Silicone Co., Ltd.
Silicon resin manufactured by Shin-Etsu Chemical Co., Ltd., hydroxyl-containing polydimethylsiloxane manufactured by Dow Corning Asia Co., Ltd., and silicon oligomer manufactured by Nippon Unica Co., Ltd.
Alternatively, they may be used after condensation. In the present invention,
The component (a) ′ can be used alone or in combination of two or more.

The proportion of the component (a) ′ in the component (a) is 0 to 95% by weight, preferably 0 to 90% by weight. 95% by weight of the component (a) 'in the component (a)
If the ratio exceeds the above, the compatibility with the component (b) described below may be deteriorated, and the stability as a coating agent may be poor.

In the composition of the present invention, (a) ′
The components are usually co-hydrolyzed and condensed with the component (a). In this case, the amount of hydrolysis / condensation water of the organosilane (1) or (a) ′ siloxane oligomer used is usually
It is about 0.2 to 3 mol, preferably about 0.3 to 2 mol. The hydrolysis / condensation reaction at this time, that is, the reaction at the time of preparing the composition of the present invention, is performed at a temperature of 30 to 80 ° C, preferably 40 to 70 ° C, and a reaction time of 0.5 to 10 hours, preferably 1 to 7 hours. It is about.

In the composition (I) of the present invention,
Usually, water and / or an organic solvent is used in combination.

Water and / or an organic solvent; the composition (I) of the present invention essentially comprises the above-mentioned component (a) and the following component (b), and optionally the components (c) to (g) described below. Usually, water is added to prepare the composition, in order to cause hydrolysis / condensation reaction of the organosilane (1) or to disperse a particulate component described later. The amount of water used in the present invention is generally 0.2 to 3 mol, preferably about 0.3 to ² mol, per 1 mol of OR ² in the organosilane (1) in the component (a). .

The organic solvent is mainly composed of (a)
Ingredients, components (b) to (c), components (d) to (g), and the like, are uniformly mixed to adjust the total solid content of the composition, and at the same time, to be applicable to various coating methods, and It is used to further improve the dispersion stability and storage stability of the composition.

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,
Ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene monomethyl ether acetate,
Diacetone alcohol and the like can be mentioned.

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.

The composition (I) is preferably prepared by adding an appropriate amount of water to the organosilane (1) to hydrolyze and condense the organosilane (1). As described above, a hydrolyzate and / or condensate of the organosilane (1) can be used as the component (a).

Component (b): Component (b) is preferably a silyl group having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group (hereinafter referred to as a “specific silyl group”), and preferably a terminal of a polymer molecular chain. And / or a polymer having a side chain. In the composition (I), the component (b) provides excellent coating by curing the coating film by co-condensing the hydrolyzable group and / or hydroxyl group in the silyl group with the component (a). It is a component that provides membrane performance. The content of the specific silyl group in the component (b) is usually 0.001 to 20% by weight, preferably 0.01% by weight, based on the amount of the silicon atom, relative to the polymer before the introduction of the specific silyl group. ~ 1
5% by weight. Preferred specific silyl groups are groups represented by the following general formula (2).

[0031] (Wherein, X represents a hydrolyzable group such as a halogen atom, an alkoxyl group, an acetoxy group, a phenoxy group, a thioalkoxyl group, an amino group or a hydroxyl group, and R ³ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or Carbon number 1-10
Wherein i is an integer of 1 to 3. )

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

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

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

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

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

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

Examples of the vinyl monomer having a functional group (α) include unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid; maleic anhydride, itaconic anhydride Unsaturated carboxylic anhydrides such as acids; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
Hydroxyl-containing vinyl monomers such as 3-hydroxypropyl (meth) acrylate, N-methylol (meth) acrylamide, and 2-hydroxyethyl vinyl ether; 2
Amino-containing vinyl monomers such as -aminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 3-aminopropyl (meth) acrylate, and 2-aminoethyl vinyl ether; 1,1,1-trimethylamine ( (Meth) acrylimide, 1-methyl-1-
Ethylamine (meth) acrylimide, 1,1-dimethyl-1- (2-hydroxypropyl) amine (meth) acrylimide, 1,1-dimethyl-1- (2′-phenyl-2′-hydroxyethyl) amine ( (Meth) acrylimide, 1,1-dimethyl-1- (2'-hydroxy-
Examples thereof include vinyl monomers containing an amine imide such as 2'-phenoxypropyl) amine (meth) acrylimide; vinyl monomers containing an epoxy group such as glycidyl (meth) acrylate and allyl glycidyl ether. These vinyl monomers having a functional group (α) can be used alone or in combination of two or more.

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

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

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

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

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

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

In addition, the unsaturated method used in the above method (b)
Specific examples of the sum silane compound (b) include CH_Two= CH
Si (CH_Three) (OCH_Three)_Two, CH_Two= CHSi (OCH_Three)
_Three, CH_Three= CHSi (CH_Three) Cl_Two, CH_Two= CHSi
Cl_Three, CH_Two= CHCOO (CH_Two)_TwoSi (CH_Three)
(OCH_Three)_Two, CH_Two= CHCOO (CH_Two)_TwoSi (OC
H_Three)_Three, CH_Two= CHCOO (CH_Two)_ThreeSi (CH_Three) (O
CH_Three)_Two, CH_Two= CHCOO (CH_Two)_ThreeSi (OC
H_Three)_Three, CH_Two= CHCOO (CH_Two)_TwoSi (CH_Three) C
l_Two , CH_Two= CHCOO (CH_Two)_TwoSiCl_Three, CH_Two
= CHCOO (CH_Two)_ThreeSi (CH_Three) Cl_Two, CH_Two=
CHCOO (CH_Two)_ThreeSiCl_Three, CH_Two= C (CH_Three)
COO (CH_Two)_TwoSi (CH_Three) (OCH_Three)_Two, CH_Two=
C (CH_Three) COO (CH_Two)_TwoSi (OCH_Three)_Three, CH_Two
= C (CH_Three) COO (CH_Two)_ThreeSi (CH_Three) (OC
H_Three)_Two, CH_Two= C (CH_Three) COO (CH_Two)_ThreeSi (O
CH_Three)_Three, CH_Two= C (CH_Three) COO (CH_Two)_TwoSi
(CH_Three) Cl_Two, CH_Two= C (CH_Three) COO (CH_Two)_Two
SiCl_Three, CH_Two= C (CH_Three) COO (CH_Two)_ThreeS
i (CH _Three) Cl_Two, CH_Two= C (CH_Three) COO (CH
_Two)_ThreeSiCl_Three,

[0046]

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

Other examples of the component (b) include a specific silyl group-containing epoxy resin, a specific silyl group-containing polyester resin, and a specific silyl group-containing fluororesin. The specific silyl group-containing epoxy resin 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. To
It can be produced by reacting aminosilanes, vinylsilanes, carboxysilanes, glycidylsilanes, etc. having a specific silyl group. Further, the specific silyl group-containing polyester resin, for example, a carboxyl group or a hydroxyl group contained in the polyester resin,
It can be produced by reacting aminosilanes, carboxysilanes, glycidylsilanes, etc. having a specific silyl group. Further, the specific silyl group-containing fluororesin includes, for example, aminosilanes and carboxysilanes having a specific silyl group in a carboxyl group or a hydroxyl group contained in a (co) polymer such as ethylene fluoride;
It can be produced by reacting glycidylsilanes and the like.

The polystyrene-equivalent number average molecular weight (hereinafter referred to as “Mn”) of the component (b) is preferably from 2,000 to
100,000, more preferably 3,000 to 50,
000. The amount of the component (b) used in the composition (I) is determined by the amount of the completely hydrolyzed condensate of the organosilane (1)
0 to 100 parts by weight, usually 10 to 900 parts by weight, preferably 50 to 700 parts by weight, more preferably 100 parts by weight.
５００500 parts by weight. In this case, if the amount of the component (b) is less than 10 parts by weight, the adhesion to the plastic substrate may not be ensured. On the other hand, if it exceeds 900 parts by weight, the long-term weather resistance of the coating film tends to decrease. is there. In addition, the completely hydrolyzed condensate of the organosilane (1)
It means that the R ² O— group of the organosilane (1) is hydrolyzed by 100% to form a SiOH group and further completely condensed to form a siloxane structure.

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

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

Component (c) The undercoat coating composition (I) of the present invention may contain (c) silica and / or alumina. The component (c) is 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 (c) serves to improve the adhesion to the top coating agent in the composition (I) of the present invention.

Examples of the component (c) include silica such as Snowtex, isopropanol silica gel, and methanol gel (manufactured by Nissan Chemical Industries, Ltd.);
Cataloid, Oscar (manufactured by Catalyst Chemical Industry 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 (I) of the present invention, the component (c) can be used alone or in combination of two or more. The amount of the component (c) used in the composition (I) is 10% in terms of a complete hydrolysis-condensation product of the component (a).
The amount is usually 5 to 500 parts by weight, preferably 10 to 400 parts by weight, more preferably 20 to 300 parts by weight with respect to 0 parts by weight. If the amount is less than 5 parts by weight, the adhesion to the overcoat layer may not be secured. On the other hand, when it exceeds 500 parts by weight, the film forming property of the obtained coating agent is inferior, and cracking or peeling may occur.

Component (d) The undercoating coating composition (I) of the present invention may contain (d) semiconductor fine particles having an ultraviolet absorbing ability. Examples of the semiconductor having an ultraviolet absorbing ability include rutile crystal TiO ₂ , Z
nO, CeO _{2 and the} like can be mentioned.
nO and CeO ₂ . In the composition (I) of the present invention, due to the ultraviolet absorbing ability of the component (d), the ultraviolet absorbing property of the coating film can be obtained without substantially impairing the performance of the coating film. Deterioration can be prevented. There are three types of the component (d): powder composed of fine particles, aqueous sol in which fine particles are dispersed in water, and solvent sol in which fine particles are dispersed in a polar solvent such as isopropyl alcohol or a nonpolar solvent such as toluene. There is. In the case of a solvent-based sol, it may be further diluted with water or a solvent depending on the dispersibility of the semiconductor fine particles. The average particle diameter of the semiconductor fine particles in these existing forms is preferably as small as possible from the viewpoint of ultraviolet absorbing ability, usually 1 μm or less, preferably 0.5 μm or less, particularly preferably 0.2 μm or less.
μm or less. By making the component (d) finely divided, it is possible to obtain an ultraviolet absorber that has the same ultraviolet absorbing power as an organic ultraviolet absorber and can be used semi-permanently without deterioration. In addition, because the uniform dispersibility is good, transparency,
A coating agent excellent in storage stability and the like can be obtained. These fine particles and sol are used for the purpose of improving dispersibility and storage stability and preventing photocatalytic activity, for example, a surfactant,
Those to which a dispersing agent, a coupling agent, or the like has been added, or which has been subjected to a surface treatment with this, are also preferably used. When the component (d) is an aqueous sol or a solvent sol, the solid content concentration is preferably 60% by weight or less, more preferably 5% by weight or less.
0% by weight or less.

As a method of blending the component (d) into the composition (I) of the present invention, it may be added after the preparation of the other components, or may be added during the preparation of the composition of the present invention. )
In the presence of the component, the organosilane constituting the component (a) and the component (b) can be hydrolyzed and partially condensed. When the component (d) is added during the preparation of the composition (I), the semiconductor compound in the component (d) can be co-condensed with the component (a) or the component (b), and the dispersibility of the component (d) Can be improved.

Commercially available products of component (d) include Ishihara Sangyo Co., Ltd.
TAIPAKE TTO manufactured by Sumitomo Osaka Cement Co., Ltd.
W-143, ZW-513C, ZS-300, ZS-3
03, ZnO-100, ZnO-200, Z-NOVE manufactured by Mitsui Mining & Smelting Co., Ltd., Neidral manufactured by Taki Chemical Co., Ltd., CERIGUAR manufactured by Nippon Inorganic Chemical Industry Co., Ltd.
D, Hi-Cera Super K29 and the like. In the composition (I) of the present invention, the component (d) can be used alone or in combination of two or more. The amount of the component (d) used in the composition (I) is a solid content based on 100 parts by weight of a completely hydrolyzed condensate of the component (a).
Usually, it is 1 to 500 parts by weight, preferably 5 to 300 parts by weight. If the amount is less than 1 part by weight, the ultraviolet absorbing ability may be insufficient. On the other hand, if the amount exceeds 500 parts by weight, the film forming property of the obtained coating agent may be poor, and cracking or peeling may occur.

The overcoating coating composition (II) The composition (II) is a topcoating coating composition containing the component (a) and, if necessary, the component (c). In the composition (II), the component (a) functions as a binder, and in particular, by using the component (a) where n = 0 in the general formula (1), the contact angle with water in the overcoat layer. Can be adjusted to 50 ° or less, and it is easy to apply, and as a result, the obtained coating film of the present invention can have an antifouling function.
Further, in the composition (II) of the present invention, the component (c) has effects of reducing volume shrinkage, improving crack resistance, and reducing a contact angle with water.

In the composition (II), the types of the components (a) and (c) are the same as those of the composition (I). In particular, the component (a) in the composition (II) is
As in the case of the composition (I), the component (a1) is contained as an essential component, the component (a1), the component (a) ′, or the component (a1) and ( a) Those comprising the 'component are preferred. As described above, as the component (a) in the overcoating coating composition (II), an organosilane represented by the general formula (1), wherein n is 0, a hydrolyzate of the organosilane, and the organosilane It is preferable that at least one selected from the group of condensates of the above is contained in an amount of 50% by weight or more in terms of complete condensate. Organosilanes in which n is 0 are tetraalkoxysilanes such as tetramethoxysilane and tetraethoxysilane, and when hydrolyzed and condensed, become silica, so that the resulting coating film has high hardness and high weather resistance. In addition, since it is rich in hydrophilic groups such as silanol groups, it is easily wetted with water, and the contact angle with water in the overcoat layer can be made 50 ° or less, and the antifouling property is further improved.
The amount of the component (c) used in the composition (II) is generally 500 parts by weight or less, preferably 5 to 500 parts by weight, based on 100 parts by weight of the component (a) in terms of complete hydrolysis and condensation.
Parts by weight, more preferably 10 to 400 parts by weight, particularly preferably 20 to 300 parts by weight. If the amount is less than 5 parts by weight, the adhesion to the substrate or the overcoat layer and the crack resistance may not be ensured in some cases. On the other hand, when it exceeds 500 parts by weight, the film forming property of the obtained coating agent is inferior, and cracking or peeling may occur.

Composition (I) and composition (II) of the present invention
Can be further blended with the following components (e) to (g), respectively. Hereinafter, regarding these components,
explain.

Component (e): Component (e) is a catalyst for promoting the hydrolysis / condensation reaction of components (a) and (b). By using the component (e), the curing speed of the obtained coating film is increased, and the molecular weight of the polysiloxane resin generated by the polycondensation reaction of the organosilane component used is increased, 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 (e) 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 organic acids such as acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, maleic anhydride, and methylmalonic acid. Adipic acid, sebacic acid, gallic acid, butyric acid, melitic acid, arachidonic acid, mykimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linoleic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid,
Malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid and the like can be mentioned. Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid. Examples of the alkaline compound include sodium hydroxide and potassium hydroxide, and preferably sodium hydroxide. Further, 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 (4) (hereinafter referred to as “organometallic compound (4)”), a compound having 1 to 1 carbon atoms bonded to the same tin atom. Examples thereof include organometallic compounds of tetravalent tin having 1 to 2 alkyl groups of 10 (hereinafter, referred to as “organotin compounds”), and partially hydrolyzed products of these compounds.

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

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

(B) Tetra-i-propoxytitanium, di-i-propoxybis (ethylacetoacetate) titanium, di-i-propoxybis (acetylacetate) titanium, di-i-propoxybis (acetylacetate) (Nato) organic titanium compounds such as titanium; (c) tri-i-propoxyaluminum, di-i-propoxyethyl 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.

Among these organometallic compounds (4) and partial hydrolysates thereof, tri-n-butoxyethylacetoacetate zirconium, di-i-propoxybis (acetylacetonato) titam, di-i-propoxy -Ethyl acetoacetate aluminum, tris (ethyl acetoacetate) aluminum, or partially hydrolyzed products 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 (OCOC
H = CHCOOCH ₃ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (OCO
CH = CHCOOC ₄ H ₉ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (O
COCH = CHCOOC ₈ H ₁₇ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn
(OCOCH = CHCOOC ₁₆ H ₃₃ ) ₂ , (C ₈ H ₁₇ )
₂ Sn (OCOCH = CHCOOC ₁₇ H ₃₅ ) ₂ , (C _{8
H 17) 2 Sn (OCOCH =} CHCOOC 18 H 37) 2,
(C ₈ H ₁₇ ) ₂ Sn (OCOCH = CHCOOC ₂₀ H ₄₁ )
₂ ,

[0069] (C ₄ H ₉ ) Sn (OCOC ₁₁ H ₂₃ ) ₃ , (C ₄ H ₉ ) S
carboxylic acid type organotin compounds such as n (OCONa) ₃ ;

(C ₄ H ₉ ) ₂ Sn (SCH ₂ COOC)
₈ H ₁₇ ) ₂ , (C ₄ H ₉ ) ₂ Sn (SCH ₂ CH ₂ COOC _{8
H 17) 2, (C 8} H 17) 2 Sn (SCH 2 COOC
₈ H ₁₇ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (SCH ₂ CH ₂ COOC
₈ H ₁₇ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (SCH ₂ COOC ₁₂ H
₂₅ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (SCH ₂ CH ₂ COOC _{12
H 25) 2, (C 4} H 9) Sn (SCOCH = CHCOO
C ₈ H ₁₇ ) ₃ , (C ₈ H ₁₇ ) Sn (SCOCH = CHC
OOC ₈ H ₁₇ ) ₃ ,

[0071] 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 Sn
Cl ₂ , (C ₈ H ₁₇ ) ₂ SnCl ₂ , (C ₄ H ₉ ) ₂ Sn
Organic tin oxides such as O, (C ₈ H ₁₇ ) ₂ SnO,
Reaction products of these organic tin oxides with ester compounds such as silicate, dimethyl maleate, diethyl maleate and dioctyl phthalate. Among the above components (e), acidic compounds, alkaline compounds, amine compounds, organic zirconium compounds,
Organic titanium compounds and organic aluminum compounds are particularly preferred. When these compounds are used as a curing catalyst for the undercoating coating composition of the present invention, there is no transfer of a hydrophobic component to the overcoat layer, and the water contact angle in the overcoat layer is 50.
゜ It becomes below.

The component (e) 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 (e) may be blended when preparing the composition of the present invention, or may be blended with the composition at the stage of forming a coating film. And the formation of the coating film. When the amount of the component (e) used is other than the organometallic compound, the amount of the component (a) is based on 100 parts by weight of the solid content of the completely hydrolyzed condensate of the organosilane (1) and the component (b). Usually, 0 to 100 parts by weight, preferably 0.01 to 80 parts by weight, more preferably 0.1 to 50 parts by weight,
In the case of an organometallic compound or the like, usually 0 to 100 parts by weight of the solid content of the completely hydrolyzed condensate of the organosilane (1) in the component (a) and the component (b).
100 parts by weight, preferably 0.1 to 80 parts by weight, more preferably 0.2 to 50 parts by weight. in this case,
If the amount of the component (e) exceeds 100 parts by weight, the storage stability of the composition tends to decrease, and the coating film tends to crack.

Component (f): Component (f) is represented by the following general formula (5): R ⁶ COCH2COR ⁷ (5) wherein R ⁶ and R ⁷ are each of the above-mentioned groups in organometallic compound (4) Which has the same meaning as R ⁶ and R ^{7 in the} general formulas, respectively
Β-diketones and β-ketoesters represented by
It is at least one selected from the group consisting of carboxylic acid compounds, dihydroxy compounds, amine compounds, and oxyaldehyde compounds. Such a component (f) is particularly preferably used together when an organometallic compound or the like is used as the component (e).

The component (f) acts as a stability improver for the composition. That is, the component (f) coordinates with a metal atom such as the above-mentioned organometallic compound to promote the (co) condensation reaction of the component (a) [and the component (b)] with the organometallic compound. It is presumed that by appropriately controlling the composition, the composition has an effect of further improving the storage stability of the obtained composition.

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

Component (g): Component (g) is composed of a powder and / or sol or colloid of an inorganic compound other than the components (c) and (d), and is blended according to the desired properties of the coating film. You. When the component (g) is in the form of a sol or a colloid, its average particle size is usually 0.005 to 10
It is about 0 μm.

Specific examples of the compound constituting the component (g) include AlGaAs, Al (OH) ₃ , Sb ₂ O ₅ , and Si ₃ N.
_{4, Sn-In 2 O 3} , Sb-In 2 O 3, MgF, Ce
_{F 3, BeO, SiC, AlN} , Fe, Co, Co-F
_{eO x, CrO 2, Fe 4} N, BaTiO 3, BaO-A
l ₂ O ₃ —SiO ₂ , Ba ferrite, SmCO ₅ , YCO
₅ , CeCO ₅ , PrCO ₅ , Sm ₂ CO ₁₇ , Nd ₂ Fe ₁₄
B, _{Al 4} O ₃ , α-Si, SiN ₄ , CoO, Sb-Sn
O ₂ , Sb ₂ O ₅ , MnO ₂ , MnB, Co ₃ O ₄ , Co
₃ B, LiTaO ₃ , MgO, MgAl ₂ O ₄ , BeAl ₂
O ₄ , ZrSiO ₄ , ZnSb, PbTe, GeSi, F
eSi ₂ , CrSi ₂ , CoSi ₂ , MnSi _1.73 , Mg ₂
Si, β-B, BaC, BP, TiB ₂ , ZrB ₂ , Hf
B ₂ , Ru ₂ Si ₃ , TiO ₃ , PbTiO ₃ , Al ₂ TiO
_{5, Zn 2 SiO 4, Zr} 2 SiO 4, 2MgO 2 -Al
_{2 O 3 -5SiO 2, Nb 2} O 5, Li 2 O-Al 2 O 3 -4S
iO _2, Mg ferrite, Ni ferrite, Ni-Zn
Ferrite, Li ferrite, Sr ferrite, and the like can be given. These components (g) can be used alone or in combination of two or more.

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

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

As a method of blending the component (g) into the composition, the component (g) may be added after the preparation of the composition, or may be added during the preparation of the composition, and the component (g) may be added to the composition (a). Co-hydrolysis with component (b) or the above condensate
It may be condensed.

The amount of the component (g) used is usually a solid content based on 100 parts by weight of the solid content of the completely hydrolyzed condensate of the organosilane (1) in the component (a) and the component (b). , 0 to 500 parts by weight, preferably 0.1 to
400 parts by weight.

Other additives: The composition used in the present invention may further contain, for coloring and thickening the obtained coating film,
A filler can be separately added and dispersed. Such fillers include, for example, water-insoluble organic pigments and inorganic pigments, other than pigments, particulate, fibrous or flaky ceramics, metals or alloys, and oxides and hydroxides of these metals. , Carbides, nitrides, sulfides and the like.

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

The composition of the present invention may further contain, if desired, a known dehydrating agent such as methyl orthoformate, methyl orthoacetate and tetraethoxysilane; polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene. Fatty acid ester, polycarboxylic acid type polymer surfactant, polycarboxylate, polyphosphate, polyacrylate, polyamide ester salt,
Dispersants such as polyethylene glycol; methyl cellulose, ethyl cellulose, hydroxyethyl cellulose,
Hydroxypropylcellulose, celluloses such as hydroxypropylmethylcellulose, castor oil derivatives, thickeners such as ferrosilicate; ammonium carbonate,
Inorganic foaming agents such as ammonium bicarbonate, ammonium nitrite, sodium borohydride and calcium azide; azo compounds such as azobisisobutyronitrile; hydrazine compounds such as diphenylsulfone-3,3'-disulfohydrazine; semicarbazide compounds , A triazole compound, an N-nitroso compound, and other additives, as well as other additives such as a surfactant, a silane coupling agent, a titanium coupling agent, and a dye. The undercoat coating composition (I) of the present invention
For the purpose of improving the weather resistance and the durable adhesion, an organic ultraviolet absorber, an ultraviolet stabilizer and the like may be used in combination with the component (d). 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 blended to further improve the coating property of the composition of the present invention. Among such leveling agents, as a fluorine-based leveling agent (trade name; the same applies hereinafter), for example, BM1000 of BM-CHEMIE,
BM1100; Efka 772 and Efka 777 of Efka Chemicals; Floren series of Kyoeisha Chemical Co., Ltd .; FC series of Sumitomo 3M Co., Ltd .; Fluonal TF series of Toho Chemical Co., Ltd. As a leveling agent, for example,
BYK series of Big Chemie; Schmegman (Ss
hmegmann) Shmego series; Efka Chemicals Efka 30, Efka 31, Efka
4, Efka 35, Efka 36, Efka 39, Efka 8
3, Efka 86, Efka 88 and the like,
As ether-based or ester-based leveling agents,
Examples thereof include Carfinol manufactured by Nissin Chemical Industry Co., Ltd .; and Emulgen and Homogenol manufactured by Kao Corporation.

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

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

The composition used in the present invention may be blended with another resin. In particular, the undercoating coating composition (I) may be blended with another resin depending on the base material. Other resins include acryl-urethane resin, epoxy resin, polyester, acrylic resin, fluorine resin, acrylic resin emulsion, epoxy resin emulsion, polyurethane emulsion, polyester emulsion and the like.

Further, a coating composition for overcoating (II)
In the above, water and / or an organic solvent can be separately blended. In this case, the blending amount of water and / or the organic solvent is the same as that of the composition (I).

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

The total solid content of the composition (I) and the composition (II) used in the present invention is preferably 50% by weight.
The following 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 2% by weight.
0 to 45% by weight. If the total solid content of the composition exceeds 50% by weight, storage stability tends to decrease. In particular, the undercoating coating composition (I) of the present invention preferably has a total solid content concentration of 1 to 30% by weight,
It is appropriately adjusted according to the type of the base material, the coating method, the coating film thickness, and the like.

[0096] The structure of the hard coat film of a hard coat film present invention, for example, substrate (plastic film) / subbing coating composition of the present invention (I) / topcoat coating composition of the present invention (II), Alternatively, there may be mentioned a substrate / primer / the composition for undercoating (I) / the coating composition for overcoating (II). The undercoating coating composition (I) and the overcoating composition (I) of the present invention
When applying I) to a substrate, any of the compositions can be applied using a brush, a roll coater, a bar coater, a (micro) gravure coater, a flow coater, a centrifugal coater, an ultrasonic coater, or a dip coater. ,
Examples include flow coating, spraying, screen processes, electrodeposition, vapor deposition, and the like.

The coating compositions (I) to (I) of the present invention
In the case of I), the dry film thickness is 0.05
When applied twice, a coating film having a thickness of about 0.1 to 40 μm can be formed. Thereafter, the coating film can be formed by drying at normal temperature or by heating and drying at a temperature of about 30 to 200 ° C., usually for about 1 to 60 minutes.

In the case of the undercoating coating composition (I), the composition (I) is used, and as a dry film thickness, about 0.05 to 20 μm in a single coating and 0.1 in a double coating.
A coating film having a thickness of about 40 μm can be formed. Thereafter, the undercoat layer can be formed by drying at room temperature or by heating at a temperature of about 30 to 200 ° C., usually for about 1 to 60 minutes to dry. The total film thickness of the undercoat and the top coat is a dry film thickness, and is usually
It is about 0.1 to 80 μm, preferably about 0.2 to 60 μm.

The undercoat layer and the overcoat layer in the present invention can be photocured by adding a known photoacid generator and irradiating ultraviolet rays.

Further, when a primer is used according to the application, the type of the primer is not particularly limited, as long as it has an action of improving the adhesion between the substrate and the composition. Select according to the purpose of use. The primers can be used alone or in combination of two or more, and may contain coloring components such as pigments and dyes.

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

Further, on the surface of a coating film formed from the composition (II) of the present invention, for example, US Pat.
A clear layer composed of a siloxane resin-based coating such as a stable dispersion of colloidal silica and a siloxane resin described in US Pat. No. 7,027,073 and US Pat. .

Substrates (Plastic Films): Substrates to which the composition of the present invention can be applied include, as plastic films, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene
Polyesters such as 2,6-naphthalate (PEN);
Polyamides such as nylon 6, nylon 6,6; polyolefins such as polyethylene (PE) and polypropylene (PP); polyacryls such as polycarbonate (PC) and polymethyl methacrylate (PMMA); Tetrafluoroethylene (PT
FE), ethylene tetrafluoroethylene (ETFE)
And the like.

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. For example, blast treatment, chemical treatment, degreasing, flame treatment, oxidation treatment, steam treatment, corona discharge treatment, ultraviolet irradiation treatment, plasma treatment, ion treatment and the like can be mentioned.

According to the hard coat film of the present invention,
An undercoat layer comprising a polyorganosiloxane-based component (a);
Since it is composed of a coating film composed of the composition (I) with the component (b) which is a silyl group-containing vinyl polymer, it has excellent adhesion and followability to a plastic film and an overcoat layer as a substrate. In addition, by blending (c) silica and / or alumina into the undercoating coating composition of the present invention, the adhesion to the overcoat layer can be improved. Further, when the component (d) is blended in the undercoat layer, the plastic film as the base material can be protected from ultraviolet rays because of excellent ultraviolet absorbing ability. In addition, since the overcoat layer is composed of a coating film composed of the composition (II), it has excellent adhesion to the undercoat layer containing the same component (a), and has excellent weather resistance and chemical resistance.
It has high hardness and is easily applied to water due to a hydrophilic group such as a silanol group present in the component (a), and can be easily washed away with water even if dirt adheres, so that it has excellent antifouling properties. Therefore, according to the hard coat film of the present invention, antifouling properties can be imparted to road signs, marking films, windows and the like.

[0106]

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

(1) Mw Measured by gel permeation chromatography (GPC) under the following conditions. Sample: Prepared by dissolving 1 g of an organosilane condensate or 0.1 g of a silyl group-containing vinyl resin in 100 cc of tetrahydrofuran using tetrahydrofuran as a solvent. 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: 1 cc / min

(2) Transparency The visible light transmittance of the test piece was measured and evaluated according to the following criteria. ◎: transmittance of 85% or more ；: transmittance of 75% or more and less than 85% △: transmittance of 60% or more and less than 75% ×: transmittance of less than 60% (3) Water contact angle Immediately after film formation The water contact angle of the test piece was measured. (4) Organic Chemical Resistance 2 cc of isopropyl alcohol was dropped on the coating film, wiped off with a cloth one minute later, and then visually inspected for the state of the coating film. (5) Adhesion grid test according to JIS K5400
), The tape peeling test was performed three times, and evaluated by the average number of the adhered pieces.

(6) Weather Resistance According to JIS K5400, an irradiation test was carried out for 1,500 hours using a sunshine weather meter, and the appearance (crack, peeling, etc.) of the coating film was visually observed. (7) Long-term adhesion After the weather resistance test of (8), a tape peeling test was performed three times, and the presence or absence of peeling was evaluated according to the following criteria. ：: No peeling △: 1 to 2 peels ×: Peel all 3 times

Reference Example 1 [Synthesis of Component (b)] In a reactor equipped with a reflux condenser and a stirrer, 55 parts of methyl methacrylate, 5 parts of 2-ethylhexyl acrylate,
5 parts of cyclohexyl methacrylate, 10 parts of γ-methacryloxypropyltrimethoxysilane, 20 parts of glycidyl methacrylate, 4- (meth) acryloyloxy-
After adding and mixing 5 parts of 2,2,6,6-tetramethylpiperidine, 75 parts of i-butyl alcohol, 50 parts of methyl ethyl ketone and 25 parts of methanol, the mixture was heated to 80 ° C. while stirring, and azobis A solution of 3 parts of isovaleronitrile dissolved in 8 parts of xylene was added dropwise over 30 minutes, and the mixture was reacted at 80 ° C. for 5 hours. Thereafter, 36 parts of methyl ethyl ketone was added and stirred to obtain a polymer solution having a solid content of about 35% and an Mw of 12,000 (hereinafter referred to as “(b-1)”).

Preparation Example 1 [Preparation of Undercoating Coating Composition] In a reactor equipped with a stirrer and a reflux condenser, 26 parts of tetramethoxysilane was used as the component (a), and 35% solid content was used as the component (b). b-1) 69 parts were added, mixed, and stirred.
The temperature was raised to 0 ° C. (E) 1.5 parts of di-i-propoxyethyl acetoacetate aluminum as a component
After adding what was dissolved in 2 parts of propyl alcohol,
6 parts of water was added for 30 minutes and reacted at 60 ° C. for 4 hours. Then, acetylacetone 1.
After adding 2 parts and stirring for 1 hour, it cooled to room temperature. Then, 239 parts of methyl isobutyl ketone was added as a post-diluting solvent under stirring to obtain an undercoating composition I-1 having a solid content of about 10%. Table 1 shows the prepared components.

Preparation Examples 2 to 5 (Preparation of Undercoat Coating Composition) The same procedures as in Preparation Example 1 were carried out except that the respective components were listed in Table 1,
Undercoat coating compositions (I-2 to I-5) were obtained. Further, i-propyl alcohol-dispersed colloidal silica (solid concentration 10%) is used as the component (c), and methyl isobutyl ketone-dispersed CeO ₂ (solid content 10%) or i-propyl alcohol-dispersed CeO is used as the component (d). _{When 2} (solid content: 10%) was added, the solution was cooled to room temperature, and added after dilution with a diluting solvent shown in Table 1 so as to have a solid content of about 10%. Table 1 shows the prepared components.

[0113]

[Table 1]

Preparation Example 6 [Preparation of Coating Composition for Overcoat] To a reactor equipped with a reflux condenser and a stirrer, 145 parts of tetramethoxysilane and 406 parts of propylene glycol monopropyl ether were added, and the mixture was thoroughly stirred. The temperature was raised to 60 ° C. Next, with stirring, a solution prepared by dissolving 2.4 parts of maleic anhydride in 69 parts of water was added over 1 hour. Then, after reacting at 60 ° C. for 4 hours, it was cooled to room temperature,
An overcoating coating composition (II-1) was obtained. Table 2 shows the results.

Preparation Examples 7 to 11 [Preparation of Coating Composition for Overcoating] The same procedures as in Preparation Example 6 were carried out except that the respective components were listed in Table 2,
Coating compositions for overcoating (II-2 to II-6) were obtained. When i-propyl alcohol-dispersed colloidal silica (solid content: 10%) was added as the component (c), it was added after cooling to room temperature. Table 2 shows the results.

[0116]

[Table 2]

Examples 1 to 12 On a base material (plastic film) described in Tables 3 and 4, 100 parts of the undercoating coating composition obtained by the preparation example was added with di-i-propoxybis (acetylacetonate). G) 10 parts of an i-propyl alcohol solution of titam (solid content: 10%) was added, and the mixture was thoroughly stirred.
After coating and drying to a thickness of 0.1 μm, the coating composition for top coating of the present invention was applied and dried to a dry coating thickness of 0.1 μm to obtain test pieces. Various evaluations were performed using this test piece. The results are shown in Tables 3 and 4.

Comparative Example 1 An undercoating coating composition (I-2) 100 obtained in Preparation Example 2 was coated on an acrylic film having a thickness of 50 μm.
1 part of methyltrimethoxysilane was added to the mixture, and the mixture was stirred well. After stirring, dry film thickness 1
After coating and drying so as to have a thickness of 0.1 μm, the coating composition for overcoating (II-2) was applied so as to have a dry coating thickness of 0.1 μm and dried to obtain test pieces.

Comparative Example 2 On an acrylic film having a thickness of 50 μm, 100 parts of the undercoating coating composition (I-
To 3), 1 part of dimethyldimethoxysilane was added, and after stirring well, 10 parts of an i-propyl alcohol solution of di-i-propoxybis (acetylacetonate) titum (solid content: 10%) was added. The agitated product was applied to a dry film thickness of 1 μm and dried, and then the top coating composition (II-2) was applied to a dry film thickness of 0.1 μm and dried to obtain test pieces.

[0120]

[Table 3]

[0121]

[Table 4]

Examples 13 to 18 On the base material (plastic film) shown in Table 5, the undercoating coating composition 100 obtained by the preparation example was prepared.
In part, i-propyl alcohol solution of γ- (2-aminoethyl) aminopropyltrimethoxysilane (solid content: 10%)
After adding 10 parts and applying a well-stirred mixture to a dry film thickness of 1 μm and drying, the top coating composition of the present invention is coated to a dry film thickness of 0.1 μm.
It dried and was set as the test piece. Various evaluations were performed using this test piece. Table 5 shows the results.

[0123]

[Table 5]

1) PET film containing UV absorber, modified acrylic surface treated

[0125]

According to the hard coat film of the present invention, it has excellent adhesion, weather resistance, stain resistance and abrasion resistance, and can impart antifouling property to road signs, marking films, windows and the like.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 183/04 C09D 183/04 201/10 201/10 // C08L 101: 00 C08L 101: 00 (72) Inventor Yuichi Hashiguchi 2-11-24 Tsukiji, Chuo-ku, Tokyo F-term in JSR Co., Ltd. (reference) 4F006 AA18 AA22 AA35 AA36 AA38 AB39 BA02 DA04 4F100 AA19B AA19C AA19H AA20B AA20C AA20A AK52 AT52AAK52A CA07B CA07H CA23B CA23C CA23H CC01B CC01C GB07 GB32.

Claims (10)

[Claims] 1. A hard coat having a coating film comprising the following coating composition for undercoating (I) on a plastic film and further having a coating film comprising the following coating composition for overcoating (II) on the plastic film the film. Undercoat coating composition (I) (a) the following general formula _{^{(1) (R 1) n}} Si (OR 2) 4-n ····· (1) ( In the formula, R ^1, there are two to Sometimes the same or different, and represents a monovalent organic group having 1 to 8 carbon atoms; R ² is the same or different and represents an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 6 carbon atoms; It is an integer of 0 to 2.)
And at least one selected from the group consisting of an organosilane represented by the formula: a hydrolyzate of the organosilane and a condensate of the organosilane; and (b) a hydrolyzable group and / or
Or an undercoating coating composition comprising a polymer containing a silyl group having a silicon atom bonded to a hydroxyl group. During overcoated coating composition (II) (a) the following general formula _{^{(1) (R 1) n}} Si (OR 2) 4-n ····· (1) ( wherein, R ¹ is present two to Sometimes the same or different, and represents a monovalent organic group having 1 to 8 carbon atoms; R ² is the same or different and represents an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 6 carbon atoms; It is an integer of 0 to 2.)
A coating composition for overcoating, comprising: an organosilane represented by the formula: or a hydrolyzate of the organosilane and a condensate of the organosilane. The component (a) constituting the undercoating coating composition (I) is at least selected from the group consisting of an organosilane having n = 0, a hydrolyzate of the organosilane, and a condensate of the organosilane. The hard coat film according to claim 1, comprising one kind as an essential component. The component (a) constituting the undercoating coating composition (I) is at least one selected from the group consisting of an organosilane having n = 0, a hydrolyzate of the organosilane, and a condensate of the organosilane. The hard coat film according to claim 1, which is one kind. 4. The component (a) constituting the undercoating coating composition (I) has (a) ′ an SiO bond and a trifunctional and / or difunctional organo having a weight average molecular weight of 300 to 100,000. The hard coat film according to claim 1, comprising a siloxane oligomer. 5. The component (a) constituting the undercoating coating composition (I) is at least selected from the group consisting of an organosilane having n = 0, a hydrolyzate of the organosilane, and a condensate of the organosilane. 1 species, and (a) '
It has an SiO bond and has a weight average molecular weight of 300 to 100,0.
The hard coat film according to claim 1, comprising a trifunctional and / or bifunctional organosiloxane oligomer of No. 00. 6. The hard coat film according to any one of claims 1 to 5, wherein the undercoat coating composition (I) further contains (c) silica and / or alumina. 7. The hard coat film according to claim 1, wherein the undercoat coating composition (I) further comprises (d) semiconductor fine particles having an ultraviolet absorbing ability. 8. The component (a) constituting the topcoating coating composition (II), wherein at least one selected from the group consisting of an organosilane having n = 0, a hydrolyzate of the organosilane and a condensate of the organosilane. The hard coat film according to any one of claims 1 to 7, wherein the hard coat film contains 50% by weight or more of one type. 9. A coating composition for overcoating (II),
The hard coat film according to any one of claims 1 to 8, further comprising (c) silica and / or alumina. 10. Coating composition for overcoating (II)
Comprises at least one selected from the group consisting of an organosilane of n = 0, a hydrolyzate of the organosilane and a condensate of the organosilane, and (c) silica and / or alumina. Or the hard coat film according to item 1.