JPH1147688A - Resin molded parts - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a resin molding parts excellent in weatherability, stain resistance, antibacterial property, antifungal property, etc., and high in surface hardness by forming a coating film containing polyorganosiloxane and inorg. particulates having a photocatalytic function on a surface. SOLUTION: The coating film containing the polyorganosiloxane and the inorg. particulates having the photocatalytic function is provided on the surface in order to increase the antifoulancy antibacterial property, antifungal property, etc., of the surface of the resin molding parts. And the coated film is formed by using a composition containing a hydrolyzed matter and/or its partial condensate of an organosilane expressed by formula (R<1> )n Si(OR<2> )4-n (R<1> is hydrogen atom or univalent org. group, R<2> is alkyl, acyl or phenyl group, (n) is an integer of 1 or 2), the inorg. particulates having the photocatalytic function and water and/or an org. solvent. The hydrolyzed matter and/or its partial condensate of the organosilane expressed by the formula operates as a binder by condensing making a three-dimensional structure.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a resin molded product,
More specifically, the present invention relates to a resin molded article having a coating film formed from an organosilane-based composition containing an inorganic fine particle component having photocatalytic ability on the surface.

[0002]

2. Description of the Related Art Conventionally, a resin molded product has been subjected to various treatments in order to enhance the surface's antifouling property, antibacterial property, antifungal property and the like. However, with the conventional surface treatment method, it was difficult to obtain a coating layer having excellent weather resistance, stain resistance, antibacterial property, antifungal property and the like and high hardness. In particular, in order to improve the stain resistance, it has been recognized that the surface of the coating film should be made hydrophilic. For example, a method of adding a hydrophilic substance or a water-soluble substance has been proposed. Thus, it has been 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.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems in the prior art, and has excellent weather resistance, stain resistance, antibacterial property, antifungal property and the like, and a resin having a high surface hardness. It is to provide a molded article.

[0004]

According to the present invention, there is provided a resin molded article characterized in that a coating containing (A) a polyorganosiloxane and (B) inorganic fine particles having photocatalytic activity is present on the surface. To provide. Hereinafter, the present invention will be described in detail, and the objects, advantages and effects of the present invention will become apparent.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The coating film present on the surface of the resin molded article of the present invention can be preferably formed from the following composition. [1] (A1) The following general formula (1): (R ¹ ) _n Si (OR ² ) _4-n . . . (1) (wherein, R ¹ represents a hydrogen atom or a monovalent organic group, R ²
Represents an alkyl group, an acyl group or a phenyl group, and n is an integer of 1 or 2. A) a composition containing a hydrolyzate of an organosilane represented by the formula (1), and / or a partial condensate thereof, (B) inorganic fine particles having photocatalytic activity, and (C1) water and / or an organic solvent (hereinafter referred to as “first Composition "). [2] (A2) The following general formula (2): (R ³ ) _m Si (OR ⁴ ) _4-m . . . (2) (wherein, R ³ represents an organic group, R ⁴ represents an alkyl group or an acyl group, and m is an integer of 0 to 2), and hydrolysis of the organosilane. At least one component selected from a product and a partial condensate of the organosilane, (B) inorganic fine particles having photocatalytic activity, and (C2) a silyl group having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group. A composition containing a polymer in a polymer molecular chain (hereinafter, referred to as a “second composition”).

Hereinafter, each component constituting the first composition and the second composition will be sequentially described. Component (A1) The component (A1) in the first composition is represented by the general formula (1).
(Hereinafter referred to as “organosilane (1)”) and / or a partial condensate thereof. When forming a coating film from the first composition, condensation / three-dimensional To become the main binder. In the general formula (1), as the R ¹ organic group, an organic group having 1 to 8 carbon atoms is preferable. For example, a methyl group, an ethyl group, an n-
Alkyl groups such as propyl group, i-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, vinyl group, allyl group, acyl group Groups, a glycidyl group, a (meth) acryloxy group, a ureido group, an amide group, a fluoroacetamide group, an isocyanate group and the like, and substituted derivatives of these groups. 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 ureido group, and an ammonium base. Here, R consisting of these substituted derivatives
¹ of carbon number, 1 to 8, including the carbon atoms 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 of R ² has 1 carbon atom.
5 to 5 are preferable, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, and an n-pentyl group. Examples of the acyl group having 1 to 6 carbon atoms include an acetyl group, a propionyl group, a butyryl group, a valeryl group, and a caproyl group. 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) in which n in the general formula (1) is 1 include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxy. Silane, n-propyltriethoxysilane, i-
Propyltrimethoxysilane, i-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-pentyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, Phenyltrimethoxysilane, phenyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl)-
3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3
4-epoxycyclohexyl) ethyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, vinyl Triacetoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-hydroxypropyltriethoxysilane Silane, 3-hydroxypropyl trimethoxysilane, 3-hydroxypropyl triethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyl triethoxysilane, 3-
In addition to trialkoxysilanes such as isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, and 3-ureidopropyltriethoxysilane,
Methyltriacetyloxysilane, methyltriphenoxysilane and the like can be mentioned.

[0009] Of these organosilanes, trialkoxysilanes are preferable, and methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane and ethyltriethoxysilane are more preferable. The organosilane (1) in which n of the general formula (1) is 1 can be used alone or in combination of two or more.

Specific examples of the organosilane (1) in which n in the general formula (1) is 2 include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, and di-n-propyl. Dimethoxysilane, di-n-propyldiethoxysilane, di-i-propyldimethoxysilane, di-i-propyldiethoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, n-pentyl
Methyldimethoxysilane, n-pentylmethyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, di-n-pentyldimethoxysilane, di-
n-pentyldiethoxysilane, di-n-hexyldimethoxysilane, di-n-hexyldiethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxysilane, di-n-octyldimethoxysilane,
In addition to dialkoxysilanes such as di-n-octyldiethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, diphenyldimethoxysilane, and diphenyldiethoxysilane, dimethyldiacetyloxysilane, dimethyldiphenoxysilane, and the like can be given. . In the general formula (1), n is 2
Can be used alone or in combination of two or more.

Further, in the general formula (1), the organosilane (1) wherein n is 1 and the organosilane (1) wherein n is 2
May be used alone or in combination.

The first composition contains the component (A1), that is, a hydrolyzate of the organosilane (1) represented by the general formula (1) and / or a partial condensate thereof. ) In which n is 0 (hereinafter, referred to as an organosilane)
"Other organosilanes". )) And / or a partial condensate thereof. Specific examples of other organosilanes include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetraacetyloxysilane, tetraphenoxysilane, and the like. be able to. These other organosilanes can be used alone or in combination of two or more. The amount of the other organosilane is usually from 0 to 2 based on 100 parts by weight of the component (A1).
00 parts by weight, preferably 0 to 100 parts by weight.

The organosilane (1) and other optionally used organosilane can be used as the component (A1) by previously hydrolyzing and partially condensing it.
As described below, when an organosilane (1) is combined with the remaining components to prepare a composition, an appropriate amount of water ((C
It is preferable that the organosilane (1) is hydrolyzed and partially condensed by adding the component (1) to obtain the component (A1). When the component (A1) is used as a partial condensate, the polycondensed weight average molecular weight (hereinafter, referred to as “Mw”) of the partial condensate is usually 8.0 or less.
00 to 10,000, preferably 1,000 to 50,000
00 range. The Mw of the component (A1) composed of the partial condensate is appropriately selected depending on the film formability of the composition, or the hardness and flexibility of the coating film. In addition, commercially available products of the component (A1) include silicone resin manufactured by Dow Corning Toray Co., Ltd.
There are a silicone resin manufactured by Toshiba Silicone Co., Ltd. and a silicon oligomer manufactured by Nippon Unica Co., Ltd., and these may be used. In the first composition, the component (A1) can be used alone or in combination of two or more.

Component (A2) The component (A2) in the second composition is represented by the general formula (2)
(Hereinafter referred to as "organosilane (2)"), a hydrolyzate of organosilane (2) and a partial condensate of organosilane (2), When forming a coating film from the composition, it is condensed and three-dimensionalized, and becomes a main binder of the coating film.

In the general formula (2), the organic group for R ³ is preferably an organic group having 1 to 8 carbon atoms, for example, methyl, ethyl, n-propyl, i-propyl, n-propyl.
Butyl group, i-butyl group, sec-butyl group, t-butyl group, n-hexyl group, n-heptyl group, n-octyl group, alkyl group such as 2-ethylhexyl group, vinyl group, allyl group, cyclohexyl Groups, a phenyl group, an acyl group, a glycidyl group, a (meth) acryloxy group, a ureide group, an amide group, a fluoroacetamide group, an isocyanate group, and the like, and substituted derivatives of these groups. Examples of the substituent in the substituted derivative of R ³ 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, and a (meth) acryloxy group. Groups, ureido groups, ammonium bases and the like. Here, the carbon number of R ³ composed of these substituted derivatives is 1 to 8 including the carbon atom in the substituent. When a plurality of R ³ are present in the general formula (2), they may be the same or different from each other.

R ⁴ is preferably an alkyl group having 1 to 5 carbon atoms and an acyl group having 1 to 6 carbon atoms, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl. Group, sec-butyl group, t-butyl group, n-pentyl group, etc.
Examples of the acyl group 6 include an acetyl group, a propionyl group, a butyryl group, a valeryl group, and a caproyl group. A plurality of R ^{4 in} general formula (2)
May be the same or different from each other.

Specific examples of such an organosilane (2) include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane and tetra-n-butoxysilane. Classes: methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, 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, 2-
Hydroxypropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanate Natopropyltriethoxysilane,
3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4
-Epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) attacryloxypropyltriethoxysilane, 3 Trialkoxysilanes such as 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-pentyldimethoxysila , Di -n- pentyl distearate silane, di -n- hexyl dimethoxysilane, di -n- hexyl diethoxy silane, di -n- heptyl dimethoxysilane, di -n- heptyl diethoxy silane, di -n-
Octyldimethoxysilane, di-n-octyldiethoxysilane, di-n-cyclohexyldimethoxysilane,
Dialkoxysilanes such as di-n-cyclohexyldiethoxysilane, diphenyldimethoxysilane and diphenyldiethoxysilane; monoalkoxysilanes such as trimethylmethoxysilane and trimethylethoxysilane; methyltriacetyloxysilane and dimethyldiacetyloxysilane And trimethylacetyloxysilane. Of these, trialkoxysilanes and dialkoxysilanes are preferred, and trialkoxysilanes are preferably methyltrimethoxysilane and methyltriethoxysilane, and dialkoxysilanes are dimethyldimethoxysilane and
Dimethyldiethoxysilane is preferred.

In the present invention, the organosilane (2) is particularly preferably a trialkoxysilane alone or a combination of at least 80 mol% of a trialkoxysilane and less than 20 mol% of a dialkoxysilane. By using dialkoxysilane in combination with trialkoxysilane, the resulting coating film can be softened and alkali resistance can be improved.

The organosilane (2) is used as it is or as a hydrolyzate or partial condensate. When the organosilane (2) is used as a hydrolyzate and / or a partial condensate, it can be hydrolyzed and partially condensed in advance and used as the component (A2). ) Is mixed with the remaining components to prepare the composition, it is preferable to add an appropriate amount of water to hydrolyze and partially condense the organosilane (2) to obtain the component (A2). When the component (A2) is used as a partial condensate, the M
w is preferably from 800 to 100,000, and more preferably from 1,000 to 50,000. Also, (A
2) Commercially available components include MKC silicate manufactured by Mitsubishi Chemical Corporation, silicate manufactured by Tama Chemical Co., Ltd., silicone resin manufactured by Dow Corning Toray Co., Ltd., and Toshiba Silicone Co., Ltd.
And silicone oligomers manufactured by Nippon Yunika Co., Ltd., and these may be used. In the second composition, the component (A2) can be used alone or in combination of two or more.

Component (B) The component (B) in the first composition and the second composition is inorganic fine particles having photocatalytic activity. Here, the inorganic fine particles having photocatalytic ability refer to inorganic fine particles that exhibit an oxidation-reduction action by light irradiation. Due to the presence of the component (B), the surface of the coating film becomes hydrophilic, and a coating film having excellent stain resistance is obtained. As inorganic fine particles having photocatalytic ability, for example, TiO ₂ , TiO ₃ , SrTiO ₃ , FeTi
O ₃ , WO ₃ , SnO ₂ , Bi ₂ O ₃ , In ₂ O ₃ , ZnO,
Fe ₂ O ₃ , RuO ₂ , CdO, CdS, CdSe, Ga
P, GaAs, CdFeO ₃ , MoS ₂ , LaRhO _{3 and the} like can be mentioned, and TiO ₂ and ZnO are preferable. Particularly preferred is anatase TiO ₂ . Since the first composition and the second composition utilize the photocatalytic ability of the fine particles by external light irradiation, the fine particles are not subjected to a surface treatment that hinders photoactivity. Use is preferred.

Due to the photocatalytic activity of the component (B) contained in the first composition and the second composition, the surface of the coating film becomes hydrophilic in a short time even with weak light, and as a result, the performance of other coating films is reduced. The stain resistance of the coating film can be significantly improved without substantially impairing it.

The component (B) comprises (i) a powder comprising fine particles,
(ii) Obtaining as three types of existing forms: aqueous sol in which fine particles are dispersed in water, and (iii) solvent sol in which fine particles are dispersed in a polar solvent such as isopropyl alcohol or a non-polar solvent such as toluene. Can be. For solvent-based sols,
Depending on the dispersibility of the fine particles, they may be further diluted with water or a solvent. The average particle diameter of the fine particles in these existing forms is preferably as small as possible from the viewpoint of photocatalytic ability, and is usually 1 μm or less, preferably 0.5 μm or less, particularly preferably 0.1 μm or less. When the component (B) is an aqueous sol or a solvent sol, the solid content concentration is preferably 50% by weight or less, more preferably 40% by weight or less.

The method of blending the component (B) into the composition includes (A ′) the component (A1) and the components (C1) to (C) described later.
A method comprising adding a component (B) after preparing a composition comprising the component (G) or a composition comprising the component (A2) and the components (C2) to (G) described below; I')
There is a method of adding the component (B) when preparing the composition of (1). When the component (B) is an aqueous sol, (b ′)
It is also preferable to add by the method of (b). Also, when the viscosity of the system increases due to the incorporation of the component (F) described later, (b ′)
It is preferred to add the component (B) at the time of preparing the composition (a) by the method described in (1). In the first composition and the second composition, the component (B) can be used alone or in combination of two or more.

The amount of the component (B) used in the first composition is the same as that of the organosilane (1) 10 in the component (A1).
The solid content is usually 1 to 500 parts by weight, preferably 5 to 400 parts by weight with respect to 0 parts by weight, and also in the second composition, 100 parts by weight of the organosilane (2) in the component (A2). To the solid content, usually 1 to 5
00 parts by weight, preferably 5 to 400 parts by weight.

Component (C1) The component (C1) of the first composition is water and / or an organic solvent. The first composition essentially includes the components (A1) and (B), and may optionally include components (D) to (C) described below.
(G) Contains components and the like. In preparing the first composition,
Water is usually added to cause the organosilane (1) and other organosilanes to undergo hydrolysis and partial condensation reactions or to disperse the particulate components. The amount of water used in the first composition is usually about 0.5 to 3 mol, preferably about 0.7 to 2 mol, per 1 mol of the total of the organosilane in the component (A1).

The second composition essentially contains the components (A2) and (B) and the component (C2) described below, and optionally contains the components (D) to (G) described below. is there. When preparing the second composition, the organosilane (2) or (C2) component is subjected to hydrolysis and partial condensation reaction,
Alternatively, it is preferable to add water to disperse the particulate component. The amount of water used in the second composition is (A
It is usually about 0.5 to 3 mol, preferably about 0.7 to 2 mol, per 1 mol of the organosilane (2) in 2).

The organic solvent in the first composition is not particularly limited as long as the above components can be uniformly mixed. Examples thereof include alcohols, aromatic hydrocarbons, ethers, ketones and esters. Or more. 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, and n-hexyl alcohol. -Octyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, and the like. Further, specific examples of aromatic hydrocarbons include benzene, toluene, xylene and the like, specific examples of ethers include tetrahydrofuran and dioxane, and specific examples of ketones.
Acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, etc., and specific examples of esters include ethyl acetate, propyl acetate, butyl acetate, propylene carbonate and the like. These solvents can be used alone or in combination of two or more.

The total solid content of the first and second compositions, which are coating compositions, is preferably 50% by weight or less, and is appropriately adjusted according to the purpose of use. For example, when forming a thin film on a substrate or impregnating the substrate, it is usually 2 to 30% by weight, and when used for forming a thick film, usually 10 to 50% by weight.
Preferably it is 20 to 45% by weight.

Component (C2) The component (C2) in the second composition is a polymer molecule comprising a silyl group having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group (hereinafter, referred to as “specific silyl group”). A polymer having a chain, for example, at a molecular terminal and / or a side chain. When such a component (C2) cures a coating film obtained from the second composition which is a coating composition, the hydrolyzable group and / or hydroxyl group in the silyl group is the same as the component (A2). It is a component that provides excellent coating performance by co-condensing with the component (B).
The content of the specific silyl group in the component (C2) is usually 0.001 to 20% by weight in terms of the amount of silicon atoms, based on the polymer before the introduction of the specific silyl group. The specific silyl group preferably has the following general formula (4)

[0030]

Embedded image

(Wherein, X represents a hydrolyzable group such as a halogen atom, an alkoxy group, an acyloxy group, an aminoxy group, a phenoxy group, a thioalkoxy group, an amino group or a hydroxyl group, R ⁸ is a hydrogen atom, a carbon atom of 1 Represents an alkyl group having 10 to 10 or an aralkyl group having 1 to 10 carbon atoms, i represents 1 to
It is an integer of 3. ). As the component (C2), for example, (A) a hydrosilane compound corresponding to the general formula (4) (hereinafter, referred to as “hydrosilane compound (A)”) is a vinyl polymer having a carbon-carbon double bond. (Hereinafter referred to as "unsaturated vinyl polymer") in which the carbon-carbon double bond is subjected to an addition reaction, (b) the following general formula (5)

[0032]

Embedded image

[0033] Table in (wherein, X, R ^8, i has the same meaning as X, R ^8, i, respectively, in the general formula (4), R ⁹ is an organic group having a polymerizable double bond.) Silane compound (hereinafter referred to as "unsaturated silane compound (b)")
And another vinyl-based monomer.

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

The unsaturated vinyl polymer used in the above method (a) is not particularly limited as long as it is not a polymer having a hydroxyl group. For example, the following (a-1) and (a)
It can be manufactured by the method 2) or a combination thereof. That is, (a-1) a functional group (hereinafter, referred to as “functional group (α)”).
After a (co) polymerization of a vinyl monomer having the above formula, the functional group (i) in the (co) polymer is replaced with a functional group capable of reacting with the functional group (α) (hereinafter referred to as “functional group (β ) ") And an unsaturated compound having a carbon-carbon double bond to produce an unsaturated vinyl polymer having a carbon-carbon double bond in a side chain of the polymer molecular chain. Can be. (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 functional group ( a) (for example, 4,4-azobis-4-cyanovaleric acid and dithioglycolic acid), and (co) polymerizing a vinyl monomer to form one end of the polymer molecular chain or After synthesizing a (co) polymer having a functional group (α) derived from a radical polymerization initiator or a chain transfer agent at both ends, a functional group (β) is added to the functional group (α) in the (co) polymer. ) Is reacted with an unsaturated compound having a carbon-carbon double bond to produce an unsaturated vinyl polymer having a carbon-carbon double bond at one or both ends of the polymer molecular chain. it can.

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, esterification reaction between carboxyl group and epoxy group, amidation reaction between carboxyl group and amino group, carboxylic acid anhydride A ring-opening amidation reaction between a substance 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, a combination of these reactions, and the like.

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;
Unsaturated carboxylic anhydrides such as maleic anhydride and itaconic anhydride; 2-hydroxyethyl (meth) acrylate;
Hydroxyl-containing vinyl monomers such as 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, N-methylol (meth) acrylamide, and 2-hydroxyethyl vinyl ether; 2-aminoethyl (meth) acrylate; 2-aminopropyl (meth) acrylate, 3-aminopropyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-diethylaminoethyl (meth) acrylate,
2-dimethylaminopropyl (meth) acrylate, 3
-Dimethylaminopropyl (meth) acrylate, 2-
Amino group-containing vinyl monomers such as aminoethyl vinyl ether, N, N-dimethylamino (meth) acrylamide, N, N-diethylamino (meth) acrylamide;
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-
Amine-containing vinyl monomers such as (2'-hydroxy-2'-phenoxypropyl) amine (meth) acrylimide and epoxy-containing vinyl monomers such as glycidyl (meth) acrylate and allyl glycidyl ether. Can be mentioned. These vinyl monomers having a functional group (α) can be used alone or in combination of two or more.

Other vinyl monomers to be copolymerized with a vinyl monomer having a functional group (α) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate,
N-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylic acid Cyclohexyl,
(Meth) acrylamide, crotonamide, maleic diamide, fumaric diamide, itaconic diamide, α
-Ethylacrylamide, N-butoxymethyl (meth)
Examples include acrylamide, (meth) acrylonitrile, styrene, α-methylstyrene, vinyl chloride, vinyl acetate, and vinyl propionate. These other vinyl monomers 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.

Specific examples of the unsaturated silane compound ( _II ) used in the method ( _II ) include CH ₂ ＣＨCH (CH ₃ ) Si (OCH ₃ ) ₂ and CH ₂ ＣＨCHSi (OCH _3). ) ₃ , CH ₂ ＣＨCH (CH ₃ ) SiCl ₂ , CH ₂ ＣＨCHSiCl
₃ , CH ₂ ＣＨCHCOO (CH ₂ ) ₃ Si (OCH ₃ ) ₂ , CH ₂ ＣＨCHCOO (CH ₂ ) ₃ Si (CH ₃ ) (OCHR
_{3) 3, CH 2 = CHCOO} (CH 2) 3 Si (CH 3) Cl 2, CH 2 = CHCOO (CH 2) 3 SiCl 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 (CH ₃ )
(OCH ₃ ) ₂ , CH ₂ ＣC (CH ₃ ) COO (CH ₂ ) ₃ SiCl ₂ , CH ₂ ＣC (CH ₃ ) COO (CH ₂ ) ₃ SiCl ₃ ,

[0041]

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[0042]

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[0043]

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[0044]

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And the like. These unsaturated silane compounds (b) can be used alone or in combination of two or more. Further, as other vinyl monomers to be copolymerized with the unsaturated silane compound (b),
For example, at least one kind of the vinyl monomer having the functional group (α) and other vinyl monomers exemplified in the method (a-1) can be used.

Preferred examples of the component (C2) obtained as described above are more specifically shown by the following general formula (6).

[0047]

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(Wherein, R ¹⁰ represents a hydrogen atom or a methyl group, and R ¹¹ represents a methyl group, an ethyl group, an n-propyl group, i
- propyl, n- butyl group, i- butyl, n- pentyl group, an alkyl group having 1 to 6 carbon atoms such as n- hexyl, R ¹² has the same meaning as R ^10, R ¹³ is methylene Group,
1 to 1 carbon atoms such as ethylene group, propylene group and butylene group
And R ¹⁴ has the same meaning as R ¹¹ ,
/(J+k)=0.01 to 0.4, preferably 0.02
０．２0.2. ))-Containing (meth) acrylate copolymer containing a trialkoxysilyl group.

Other specific examples of the component (C2) 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 epoxy resin, a bisphenol F epoxy resin, a hydrogenated bisphenol A epoxy resin, an aliphatic polyglycidyl ether, and an aliphatic polyglycidyl ester. And aminosilanes having a specific silyl group, vinylsilanes, carboxysilanes, glycidylsilanes and the like. Further, the specific silyl group-containing polyester resin is, for example, produced by reacting a carboxyl group or a hydroxyl group contained in the polyester resin with an aminosilane having a specific silyl group, a carboxysilane, a glycidylsilane, or the like. Can be. Further, the specific silyl group-containing fluororesin includes, for example, aminosilanes, carboxysilanes, glycidylsilanes and the like having a specific silyl group in a carboxyl group or a hydroxyl group contained in a (co) polymer such as ethylene fluoride. Can be produced by reacting

The polystyrene-equivalent number average molecular weight (hereinafter referred to as “Mn”) of the component (C2) is preferably 2,0.
00 to 100,000, more preferably 4,000 to
50,000. In the second composition, the component (C2) can be used alone or in combination of two or more. The amount of the component (C2) used in the second composition is the same as the amount of the organosilane (I) 100 in the component (A2).
The amount is usually 2 to 900 parts by weight, preferably 10 to 400 parts by weight, more preferably 20 to 200 parts by weight based on parts by weight. In this case, if the amount of the component (C2) is less than 2 parts by weight, the alkali resistance of the resulting coating film tends to decrease, while if it exceeds 900 parts by weight, the weather resistance of the coating film tends to decrease. .

Further, the following components (D) to (G) can be added to the first composition and the second composition. Component (D) In the first composition, the component (D) promotes the hydrolysis / condensation reaction of the component (A1), and in the second composition, the component (A2), the component (C2), and the like. And a catalyst that promotes the hydrolysis / condensation reaction of In the first composition and the second composition, by using the component (D), the curing speed of the obtained coating film is increased, and the polysiloxane resin formed by the polycondensation reaction of the organosilane component used is used. Mn is increased, and a coating film excellent in strength, long-term durability and the like can be obtained, and the coating film can be made thicker and the coating operation can be easily performed. Such components (D) include acidic compounds, alkaline compounds, organometallic compounds and / or
Alternatively, a partial hydrolyzate thereof (hereinafter, an organometallic compound and / or a partial hydrolyzate thereof is collectively referred to as “organometallic compound or the like”) is preferable.

Among the components (D), acidic compounds include:
For example, acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, alkyltitanic acid, p-toluenesulfonic acid, phthalic acid and the like can be mentioned, and acetic acid is preferable. Examples of the alkaline compound include sodium hydroxide, potassium hydroxide and the like, and preferably sodium hydroxide. Examples of the organometallic compound include, for example, the following general formula: M (OR ¹⁵ ) p (R ¹⁶ COCHCOR ¹⁷ ) q (where M represents zirconium, titanium or aluminum, and R ¹⁵ and R ¹⁶ are each independently An ethyl group,
n-propyl group, i-propyl group, n-butyl group, se
1 carbon atom such as c-butyl group, t-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group, phenyl group, etc.
A monovalent hydrocarbon group to 6, R ¹⁷ is, R ¹⁵ and R
^In addition to monovalent hydrocarbon groups having 1 to 6 carbon atoms similar to ¹⁶ , methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, sec-butoxy, t-butoxy, It represents an alkoxyl group having 1 to 16 carbon atoms such as a lauryloxy group and a stearyloxy group, p and q are integers of 0 to 4, and (p + q) = (valence of M). ) Or partial hydrolysates of these compounds.

Specific examples of the organometallic compound include tetra-n-butoxyzirconium and tri-n-butoxy.
Ethyl acetoacetate zirconium, di-n-butoxybis (ethyl acetoacetate) zirconium, n
-Butoxytris (ethylacetoacetate) zirconium, tetrakis (n-propylacetoacetate)
Organic zirconium compounds such as zirconium, tetrakis (acetylacetoacetate) zirconium and tetrakis (ethylacetoacetate) zirconium; tetra-i-propoxytitanium, di-i-propoxybis (ethylacetoacetate) titanium, di-i-propoxy. Organotitanium compounds such as bis (acetylacetate) titanium and di-i-propoxybis (acetylacetone) titanium; tri-i-propoxyaluminum, di-i-propoxyethylacetoacetatealuminum, di-i-propoxyacetylacetoacetate Aluminum nato, i-propoxybis (ethylacetoacetate) aluminum, i-propoxybis (acetylacetonato) aluminum, tris (ethylacetoacetate) Aluminum, tris (acetylacetonate) aluminum, organic aluminum compounds such as mono-acetylacetonate · bis (ethylacetoacetate) aluminum and can be given a partial hydrolysis products of these compounds. Of these,
n-butoxyethylacetoacetate zirconium,
Di-i-propoxybis (acetylacetonato) titanium, di-i-propoxyethylacetoacetate aluminum, tris (ethylacetoacetate) aluminum, or partial hydrolysates of these compounds are preferred. The component (D) can be used alone or in combination of two or more.

The amount of the component (D) used in the first composition and the second composition is as follows except for the organometallic compound and the like.
100 total organosilanes in component (A1)
It is usually 0 to 100 parts by weight, preferably 0.01 to 80 parts by weight, more preferably 0.1 to 50 parts by weight based on 100 parts by weight of the organosilane in the component (A2) or the total of 100 parts by weight. , Organometallic compounds, etc., the total of organosilanes in the component (A1) is 1
Usually, 0 to 100 parts by weight or 100 parts by weight of the total amount of the organosilane in the component (A2) is used.
Parts by weight, preferably 0.1 to 80 parts by weight, more preferably 0.5 to 50 parts by weight. In this case, when the use amount of the component (D) exceeds 100 parts by weight, the storage stability of the composition tends to decrease, and the coating film tends to crack.

Component (E) The component (E) has the following general formula: R ¹⁸ COCH ₂ COR ¹⁹ (wherein, R ¹⁸ and R ¹⁹ have the same meanings as R ¹⁶ and R ¹⁷ in each of the general formulas in the metal chelate compound). ), At least one selected from the group consisting of β-diketones and β-ketoesters, carboxylic acid compounds, dihydroxy compounds, amine compounds, and oxyaldehyde compounds. Such (E)
The components are preferably used in combination when an organometallic compound or the like among the components (D) is used. The component (E) functions as a stabilizer for the first and second compositions. That is, by coordinating the component (E) to a metal atom of the organometallic compound or the like, the condensation reaction of the component (A1), the component (A2), the component (C2) or the like by the organometallic compound or the like is promoted. It is considered that by appropriately controlling the action, the action of further improving the storage stability of the obtained composition is achieved. Specific examples of the component (E) include acetylacetone, methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, and acetoacetate-i.
-Propyl, acetoacetic acid-n-butyl, acetoacetic acid-s
ec-butyl, t-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, malon Acid, oxalic acid, phthalic acid, glycolic acid, salicylic acid, aminoacetic acid, iminoacetic acid, ethylenediaminetetraacetic acid, glycol, catechol, ethylenediamine,
Examples thereof include 2,2-bipyridine, 1,10-phenanthroline, diethylenetriamine, 2-ethanolamine, dimethylglyoxime, dithizone, methionine, and salicylaldehyde. Of these, acetylacetone, ethyl acetoacetate and 2-ethanolamine are preferred. The component (E) can be used alone or in combination of two or more. First composition and second composition
The amount of the component (E) used in the composition is usually based on 1 mol of the organometallic compound in the organometallic compound or the like.
It is 2 mol or more, preferably 3 to 20 mol.

Component (F) The component (F) is inorganic fine particles other than the component (B), and is blended according to the desired properties of the coating film. Specific examples of the inorganic fine particles of the component (F) include SiO ₂ , Al ₂ O ₃ ,
_{Al (OH) 3, Sb 2} O 5, Si 3 N 4, Sn-In 2 O 3,
_{Sb-In 2 O 3, MgF} , CeF 3, TiO 2, ZnO,
CeO ₂ , SiO ₂ , Al ₂ O ₃ , 3Al ₂ O ₃ .2Si
O ₂ , BeO, SiC, AlN, Al ₂ O ₃ , Fe, Fe _{2
O 3, Co, Co-FeOX} , CrO 2, Fe 4 N, Ba
Ferrite, SmCO ₅ , YCO ₅ , CeCO ₅ , PrC
O ₅ , Sm ₂ CO ₁₇ , Nd ₂ Fe ₁₄ B, ZrO ₂ , Al
₄ O ₃ , AlN, SiC, BeO and the like can be mentioned.

The component (F) comprises (i) a powder comprising fine particles;
(ii) a water-based sol or colloid in which fine particles are dispersed in water; and (iii) a solvent-based sol or colloid in which fine particles are dispersed in a polar solvent such as isopropyl alcohol or a nonpolar solvent such as toluene. In the case of a solvent-based sol or colloid, it may be further diluted with water or a solvent depending on the dispersibility of the fine particles. When the component (F) is an aqueous sol or colloid and a solvent sol or colloid, the solid concentration is preferably 40% by weight or less. The component (F) can be used alone or in combination of two or more. As a method of blending the component (F) into the first or second composition, the component (F) may be added after the preparation of the composition, or may be added during the preparation of the composition, and the component (F) is added to the first or second composition. In the composition, it may be hydrolyzed and co-partially condensed together with the component (A1) and the component (B), and in the second composition, the component (A2), the component (B), It may be hydrolyzed together with the component (C2) and the like and co-partially condensed. The amount of the component (F) used in the first composition and the second composition is 100 parts by weight of the total of the organosilane in the component (A1) or 100 parts by weight of the total of the organosilane in the component (A2). Solid content, usually from 0 to 50
0 parts by weight, preferably 0.1 to 400 parts by weight.

Component (G) The component (G) comprises a curing accelerator other than the component (D). By using such a component (G), it is possible to increase the curing speed of a coating film formed from the first composition and the second composition, which are coating compositions, and to cure at a relatively low temperature. Can be done. As the component (G), for example, alkali metal salts such as naphthenic acid, octylic acid, nitrous acid, sulfurous acid, aluminate, and carbonic acid; ethylenediamine, hexanediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, piperidine, piperazine, Metaphenylenediamine, ethanolamine, triethylamine, 3-aminopropyltriethoxysilane, 3- (2-aminoethyl) -aminopropyltrimethoxysilane, 3- (2-
Aminoethyl) - aminopropyl methyl dimethoxy silane, 3-Ani and Reno trimethoxysilane, amine compounds various modified amines used as curing agents for epoxy _{resin; (C 4 H 9) 2} Sn (OCOC
_{11 H 23) 2, (C} 4 H 9) 2 Sn (OCOCH = CHCOO
CH ₃ ) ₂ , (C ₄ H ₉ ) ₂ Sn (OCOCH = CHCO
O (C ₄ H ₉ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (OCOC
_{11 H 23) 2, (C} 8 H 17) 2 Sn (OCOCH = CHCO
OCH ₃ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (OCOCH ＝ CHC)
OO (C ₄ H ₉ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (OCOCH =
Carboxylic acid type organotin compounds such as CHCOOC ₈ H ₁₇ ) ₂ and Sn (OCOC ₈ H ₁₇ ) ₂ ; (C ₄ H ₉ ) ₂ Sn (SCH ₂
COOC ₈ H ₁₇ ) ₂ , (C ₄ H ₉ ) ₂ Sn (SCH ₂ CH ₂ C)
OOC 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,}

[0059]

Embedded image Mercaptide-type organotin compounds such as

(C ₄ H ₉ ) ₂ Sn = S, (C ₈ H ₁₇ ) ₂ Sn = S,

[0061]

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A sulfide type organotin compound such as (C)
Organic tin oxides such as ₄ H ₉ ) ₂ SnO and (C ₈ H ₁₇ ) ₂ SnO, and reaction formation between these organic tin oxides and ester compounds such as ethyl silicate, dimethyl maleate, diethyl maleate and dioctyl phthalate Objects and the like. The component (G) can be used alone or in combination of two or more. In the first composition, the amount of the component (G) is usually 0 to 100 parts by weight, preferably 0.1 to 80 parts by weight, based on 100 parts by weight of the organosilane (I) in the component (A1). Parts, more preferably 0.5 to 50 parts by weight, and in the second composition, it is usually 0 to 1 part by weight based on 100 parts by weight of the organosilane (2) in the component (A2).
00 parts by weight, preferably 0.1 to 80 parts by weight, more preferably 0.5 to 50 parts by weight.

Further, the first composition or the second composition includes:
A filler may be separately added and dispersed for coloring, thickening, and the like of the obtained coating film. As such a filler, for example, water-insoluble organic pigments and inorganic pigments, other than pigments, particulate, fibrous or scaly ceramics,
Examples thereof include metals and alloys, and oxides, hydroxides, carbides, nitrides, and sulfides of these metals. Specific examples of the filler include iron, copper, aluminum, nickel, silver, zinc, ferrite, carbon black, stainless steel, silicon dioxide, titanium oxide (such as rutile type), aluminum oxide, chromium oxide, manganese oxide, and oxide. Iron, zirconium oxide, cobalt oxide, synthetic mullite, 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, shale green, green earth, manganese green, pigment green, ultramarine blue, 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, loess, 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, bunchesone white, lead phthalate, manganese white, lead sulfate, graphite, bone black, diamond black, thermatomic black, vegetable black, potassium titanate whisker, molybdenum disulfide, etc. be able to. The amount of these fillers used is usually 300 parts by weight or less based on 100 parts by weight of the total solids of the composition.

The first composition and the second composition (hereinafter, also referred to as “coating composition”) may contain, if desired, known dehydrating agents such as methyl orthoformate, methyl orthoacetate, and tetraethoxysilane. Other additives such as a surfactant, a silane coupling agent, a titanium coupling agent, a dye, a dispersant, a thickener, and a leveling agent can also be blended.

In preparing the first composition, (D)
When the organometallic compound or the like in the components and the component (E) are not used, the method of mixing the components is not particularly limited,
When the organometallic compound or the like and the component (E) are used, preferably, a mixture obtained by removing the component (E) from the components (A1) to (E) is added, and the component (E) is added thereto. The following methods are specifically adopted. (A1) an organosilane (1) constituting a component,
A method in which a predetermined amount of water is added to a mixture composed of the component (B), the required amount of the organic solvent and the component (D) to perform a hydrolysis / partial condensation reaction, and then the component (E) is added. (A1) an organosilane (1) constituting a component,
(B) a mixture of the component and the required amount of the organic solvent,
A method in which a predetermined amount of water is added to perform a hydrolysis / partial condensation reaction, and then the component (D) is added and mixed, followed by a partial condensation reaction, and then adding the component (E). Also, the first
The coating composition of the composition can also be prepared by a method of adding the component (B) after performing the above-mentioned method or the method using each component except for the component (B) in some cases. In the first composition, components other than the components (A1) to (E) can be added at an appropriate stage for adjusting the composition.

In preparing the second composition,
In the case where the organometallic compound or the like in the component (D) is not used and the component (E) is not used, the method of mixing each component is not particularly limited. After obtaining a mixture excluding the component (E) among the components (A2) to (E), a method of adding the component (E) thereto, specifically, the following methods (1) to (4) are adopted.
(A2) an organosilane (2) constituting a component,
A predetermined amount of water is added to a mixture composed of the component (B), the component (C2), the component (D) and a required amount of an organic solvent to perform a hydrolysis / partial condensation reaction, and then the component (E) is added. Method. (A2) an organosilane (2) constituting a component,
(B) a mixture of the component and the required amount of the organic solvent,
A predetermined amount of water is added to perform a hydrolysis / partial condensation reaction, and then the components (C2) and (D) are added and mixed,
A method of further performing a partial condensation reaction and then adding the component (E). (A2) an organosilane (2) constituting a component,
A predetermined amount of water is added to a mixture composed of the component (B), the component (D), and a required amount of an organic solvent to perform a hydrolysis / partial condensation reaction, and then the component (C2) is added and mixed to further perform partial condensation. After the reaction, a method of adding the component (E). Further, the second composition can be also prepared by a method of adding the component (B) after performing the above-mentioned method or the method using each component except for the component (B) in some cases. In the second composition, components other than the components (A2) to (E) can be added at an appropriate stage of adjusting the composition.

In the present invention, the resin constituting the resin molded product includes acrylic resin, phenol resin, epoxy resin, polyester such as polyethylene terephthalate and polyethylene naphthalate, polycarbonate, polyethylene, polypropylene, and the like. ABS resin (acrylonitrile-butadiene-styrene copolymer resin), polyvinyl alcohol, polyurethane, polyimide and the like can be mentioned. In addition, resin molded products include injection molding, extrusion molding,
Blow molding, all those molded by ordinary molding methods such as cast molding can be targets for forming a coating film from the composition on the surface thereof, and in particular, films and sheets are suitable targets. . When applying the first composition and the second composition to a molded article, a brush, a roll coater, a flow coater, a centrifugal coater, an ultrasonic coater, or the like is used. Coating, dipping, flow coating, spraying, screen process, electrodeposition, vapor deposition, etc.
A coating film having a thickness of about 2 to 80 μm can be formed by coating about 2 to 3 times by about 40 μm. Then, dry at room temperature, or at a temperature of about 30 to 200 ° C for 10 to 6
By heating and drying for about 0 minutes, a coating film can be formed on the surface of various resin molded products. These resin molded products may be subjected to a surface treatment in advance for the purpose of improving adhesion and patterning. For example, blasting,
Examples include surface treatments such as chemical treatment, degreasing, flame treatment, oxidation treatment, steam treatment, corona discharge treatment, ultraviolet irradiation treatment, plasma treatment, and ion treatment.

Before applying the first composition and the second composition, it is preferable to apply a primer to the surface of the resin molded article. The type of the primer is not particularly limited, and may be any as long as it has an action of improving the adhesion between the resin molded product and the coating composition. The type of the material of the resin molded product and the purpose of use of the resin molded product Select according to. The primer is
Can be used alone or in combination of two or more,
Further, an enamel containing a coloring component such as a pigment or a clear containing the coloring component may be used. Examples of the type of primer include alkyd resin, amino alkyd resin, epoxy resin, polyester, acrylic resin, urethane resin, fluororesin, acrylic silicone resin, acrylic emulsion, epoxy emulsion, polyurethane emulsion, polyester emulsion, acrylic silicone emulsion, Fluorine emulsion and the like can be mentioned. In addition, these primers can be provided with various functional groups when adhesion between the substrate and the coating film under severe conditions is required. Examples of such a functional group include a hydroxyl group, a carboxyl group, a carbonyl group, an amide group, an amine group, a glycidyl group, an alkoxysilyl group, an ether bond, an ester bond and the like. In the case of molded articles of ABS resin and polyester resin, an alkoxysilyl group-containing acrylic resin as a primer,
Epoxy resins are preferred.

Examples of the form in which the first composition and the second composition (composition for coating) are applied to the surface of a resin molded product are as follows. (A) Resin molded product surface / coating composition (clear, enamel) (b) Resin molded product surface / coating composition (enamel) / coating composition (clear) (c) Resin molded product surface / other Paint / coating composition (clear, enamel) Here, clear is a coating composition containing no coloring component, and enamel is a coating composition containing a coloring component. Examples of the other paint include a fluorine-based paint, an acrylic silicone paint, and a paint having a composition obtained by removing the component (B) from the first composition and the second composition. In the above cases (a) to (d), a primer layer can be provided in advance on the surface of the resin molded product as required, as described above. Further, a layer not containing the inorganic fine particles (B) having photocatalytic ability can be provided below the coating composition layer. Further, in the present invention, the step of applying the first composition or the second composition can be performed either in the state of the material constituting the resin molded article or after the completion of the assembly of the resin molded article. The resin molded article of the present invention can be suitably used for furniture, toilet / bath articles, daily necessities, kitchen equipment, household electric appliances, toys and the like.

[0070]

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 by weight unless otherwise specified. Various measurements and evaluations in Examples and Comparative Examples were performed by the following methods. (1) Mw and Mn Measured by gel permeation chromatography (GPC) under the following conditions. Sample: Prepared by dissolving 1 g of a partial condensate of organosilane 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 (Waters, USA) (model 150-C ALC / G
PC) Column: SHOdex manufactured by Showa Denko KK
A-80M (length 50 cm) Measurement temperature: 40 ° C. Flow rate: 1 cc / min (2) Hardness Based on pencil hardness according to JIS K5400.

(3) Weather Resistance According to JIS K5400, an irradiation test was carried out for 3,000 hours with a sunshine weather meter, and the appearance (crack, peeling, etc.) of the coating film was visually observed. Further, the gloss of the coating film before and after the test was measured and evaluated according to the following criteria. Gloss retention of 90% or more: ○ Gloss retention of 50% to less than 90%: Δ Gloss retention of less than 50%: × (4) Hydrophilicity After irradiating the coating film with a 40 W fluorescent lamp for 5 hours, water Was measured for the contact angle (unit: degree). (5) Stain resistance Carbon black / kerosene = 1/2 (weight ratio) on the coating film
Was left at room temperature for 24 hours, washed with water using a sponge, the state of contamination of the coating film was observed, and evaluated according to the following criteria. ：: No contamination △: Slightly contaminated X: Severe contamination (5) Antibacterial activity The antibacterial activity against Escherichia coli was evaluated according to AATCC100-1981. It was diluted with sterile physiological saline (0.1% triton X-100 added) so that the number of viable bacteria per ml became about 10 6, and this was used as a bacterial solution. A resin composition molded article having a size of about 3 cm × 3 cm was inoculated with 0.5 ml of the bacterial solution, and the viable cell count was measured immediately after the inoculation and after standing at 35 ° C. for 6 hours. That is, the number of viable cells in the liquid obtained by shaking the molded article in 100 ml of SCDLP broth medium for 1 minute was measured by a pour plate method using SCDLP agar medium. The antibacterial activity was represented by the rate of decrease in the number of viable bacteria. (6) Antifungal test According to JIS-Z2911, antifungal property against black mold was evaluated. After spores were formed on the agar medium, the spores were
% Dioctyl sodium sulfosuccinate in sterile water to give a spore suspension. After autoclaving the agar medium,
An agar plate was prepared by dispensing 25 ml each into a petri dish and coagulating. A resin composition molded article was placed on this agar plate, and 1 ml of a spore suspension was evenly sprayed thereon.
After culturing for 14 days, the growth state of the bacteria formed on the surface of the molded article was examined, and the effect of mold resistance was determined in the following three stages. : No hyphal growth was observed at the contacted part of the molded article. : The area of the hyphal growth part observed in the part under the contact of the molded article does not exceed 1/3 of the total area. : The area of the hyphal growth area observed in the contacted part of the molded product exceeds 1/3 of the total area.

Synthesis Example 1 In a reactor equipped with a reflux condenser and a stirrer, 100 parts of methyltrimethoxysilane and 100 parts of an aqueous sol of titanium oxide [anatase type titanium oxide content 40% (average particle size 10 n
m), water 40%, alcohol 20%], 75 parts (solution) of a silica-based solvent sol, and 200 parts of i-propyl alcohol are mixed and allowed to react under stirring at 60 ° C. for 4 hours, and then to room temperature. The mixture was cooled, and 20 parts of 3-aminopropyltrimethoxysilane was added thereto to prepare a transparent coating composition (Ia) having a solid content of 20%.

Synthetic Examples 2 and 3 The same procedures as in Synthetic Example 1 were carried out except that the formulation was as shown in Table 1, and the transparent coating compositions (Ib) and (1-b) each having a solid content of 20% were prepared. c) was prepared.

Synthesis Examples 4 to 6 In Synthesis Examples 1 to 3, 50 parts by weight of a pigment [titanium oxide for paint (rutile type)] was further added, and the amount of i-propyl alcohol added was 400 parts (Synthesis Example 4). ),
A colored coating having a solid content of about 20% was prepared in the same manner as in Synthesis Examples 1 to 3, except that the reaction was carried out with 325 parts (Synthesis Example 6) and the addition amount of i-butyl alcohol being 400 parts (Synthesis Example 5). Compositions (Ia '), (Ib') and (I-
c ′) was prepared.

Synthesis Example 7 A reactor equipped with a stirrer and a reflux condenser was charged with 100 parts of methyltrimethoxysilane and 50 parts of dimethyldimethoxysilane.
Parts, 200 parts of an aqueous sol of titanium oxide (anatase type titanium oxide content 40% (average particle size 10 nm), water 10%, alcohol 50%), Kanekazemurak (trade name, manufactured by Kanegafuchi Chemical Industry Co., Ltd.) Ingredients: silicone modified acrylic resin,
(50% solids concentration), 20 parts of di-i-propoxyethyl acetoacetate aluminum and 200 parts of i-propyl alcohol were mixed and reacted at 60 ° C. for 4 hours with stirring. Then, the mixture was cooled to room temperature, and 20 parts of acetylacetone was added thereto to obtain a transparent composition (II-a) having a solid content of about 30%.

Synthesis Example 8 A solid content of about 30% was obtained in the same manner as in Synthesis Example 7 except that the formulation was as shown in Table 1 and the reaction time was 3 hours.
Was prepared as a transparent coating composition (II-b).

Synthesis Examples 9 and 10 In Synthesis Examples 7 and 8, the reaction was carried out by further adding 100 parts by weight of a pigment [titanium oxide for coating (rutile type)] and adding 600 parts of i-propyl alcohol. Other than that, in the same manner as in Synthesis Examples 7 and 8, respectively, the colored coating compositions (II-a ′) and (I-a ′) having a solid content of about 30% were used.
Ib ′) was prepared.

Synthesis Example 11 The formulation was as shown in Table 1 (without using anatase type titanium oxide), and the reaction was carried out in the same manner as in Synthesis Example 1.
Transparent coating composition having a solid content of 20% (III-
a) was prepared.

Synthesis Example 12 Synthesis Example 11 was the same as Synthesis Example 11, except that 50 parts by weight of a pigment (titanium oxide for coating (rutile type)) was further added, and the addition amount of i-propyl alcohol was 290 parts. In the same manner as in Example 11, a colored coating composition (III-a ′) having a solid content of about 30% was prepared.

Examples 1-4, Comparative Example 1 A coating film was formed on the surface of an acrylic resin plate (polymethyl acrylate) according to the coating specifications shown in Table 2. When the primer is epoxy, the amount of coating is 10 g in terms of solid content.
/ M ^2, and dried at 100 ° C. for 10 minutes to form a primer layer. In the case of an acrylic resin, the coating amount is 10 g / m ^{2 in} terms of solid content, and dried at 80 ° C. for 10 minutes. Was formed. The intermediate coat on the primer layer was prepared by coating the coating composition shown in Table 2 with a solid content of 10 g.
/ M ² and heated at 80 ° C. for 10 minutes to form. The top coat on the middle coat layer was formed by applying the coating composition shown in Table 2 at a solid content of 10 g / m ² and heating at 80 ° C. for 10 minutes. Table 2 shows the evaluation results of the coating films.

Examples 11 to 15 and Comparative Example 2 A coating film was formed on the surface of a polycarbonate plate according to the coating specifications shown in Table 3. The amounts of the primer, the intermediate coating layer and the overcoat layer and the forming method were the same as in Example 1.
Table 3 shows the evaluation results of the coating films.

Examples 21 to 25 and Comparative Example 3 A coating film was formed on the surface of an ABS resin plate according to the coating specifications shown in Table 4. The amounts of the primer, the intermediate coating layer and the overcoat layer and the forming method were the same as in Example 1. Table 4 shows the evaluation results of the coating films.

Examples 31 to 35, Comparative Example 4 A coating film was formed on the surface of a polyethylene terephthalate film according to the coating specifications shown in Table 5. The coating amounts and forming methods of the primer, the middle coat layer and the top coat layer were determined in Example 1.
The same was done. Table 5 shows the evaluation results of the coating films.

The epoxy primer and acrylic primer used in the above Examples and Comparative Examples are as follows. Epoxy-based primer: Eponics AK (manufactured by Dainippon Paint Co., Ltd.) Acrylic-based primer: Kanekazemurak (manufactured by Kaneka Chemical Industry Co., Ltd.) Polyester-based primer: Pesresin S series (manufactured by Takamatsu Yushi Co., Ltd.) : 100 parts of Kaneka Zemlak (manufactured by Kaneka Chemical Industry Co., Ltd.) and 30 parts of pigment [titanium oxide for coating (rutile type)] added and dispersed

[0085]

[Table 1]

[0086]

[Table 2]

[0087]

[Table 3]

[0088]

[Table 4]

[0089]

[Table 5]

[0090]

The resin molded article of the present invention is excellent in weather resistance, stain resistance, mold resistance, antibacterial property, etc. since a specific coating film is formed on the surface. Moreover, the surface of the resin molded product of the present invention has high hardness.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08K 3/00 C08K 3/00 C09D 183/04 C09D 183/04

Claims (2)

[Claims] 1. A coating film comprising (A) a polyorganosiloxane and (B) inorganic fine particles having photocatalytic activity,
A resin molded product characterized by being present on the surface. 2. The resin molded article according to claim 1, wherein the coating film is formed from any one of the following compositions [1] and [2]. [1] (A1) The following general formula (1): (R ¹ ) _n Si (OR ² ) _4-n . . . (1) (wherein, R ¹ represents a hydrogen atom or a monovalent organic group, R ²
Represents an alkyl group, an acyl group or a phenyl group, and n is an integer of 1 or 2. A composition comprising a hydrolyzate of an organosilane represented by the formula (1) and / or a partial condensate thereof, (B) inorganic fine particles having photocatalytic activity, and (C1) water and / or an organic solvent. [2] (A2) The following general formula (2): (R ³ ) _m Si (OR ⁴ ) _4-m . . . (2) (wherein, R ³ represents an organic group, R ⁴ represents an alkyl group or an acyl group, and m is an integer of 0 to 2), and hydrolysis of the organosilane. At least one component selected from a product and a partial condensate of the organosilane, (B) inorganic fine particles having photocatalytic activity, and (C2) a silyl group having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group. A composition containing a polymer in a polymer molecular chain.