JPH09227833A - Coating composition and plastic part made by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating compsn. which causes no interference fringe on the surface of a plastic part, has good weather resistance, and is free from an uneven reflected color by compounding a specified organosilicon compd. or a hydrolyzate thereof with composite fine particles of tin oxide and zinc stannate. SOLUTION: The organosilicon compd. user is one represented by the formula: R<1> a R<2> b Si(OR<3> )4 -(a+b) (R<1> represents a 4-14C org. group having a functional group or an unsatd. double bond; R<2> is a 1-20C hydrocarbon group of a halogenated hydrocarbon group; R<3> represents a 1-4C alkyl, alkoxyalkyl, or acyl; a is 0 or 1; b is 0 to 2; and a+b is 0, 1 or 2) (e.g. γ-glycidoxypropyltrimethoxysilane). The composite fine particle compriser tin oxide constituting the nucleus and zinc stannate coating the nucleus. The fine particles are used on the form of a colloidal soln. thereof dispersed in water, an org. solvent, or a mixture of water with an prg. solvent (particle diameter: 1 to 300nm). The thickness of the coating layer (after drying) is pref. 0.05 to 30μm.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating composition for a plastic molding and a plastic optical component.

[0002]

2. Description of the Related Art Generally, plastic parts are lightweight and
It has useful features such as easy workability and impact resistance, but on the other hand, its hardness is insufficient and it is easily scratched, it is easily attacked by solvent, it adsorbs dust by charging, and its heat resistance is insufficient. It also has drawbacks such as Conventionally, various plastic base materials have been developed in order to eliminate the drawbacks of plastic parts, but by simply devising the components of the plastic parts, it is possible to obtain the ones that can sufficiently overcome the conventional defects. It wasn't done.

Therefore, a coating composition for improving the performance of a plastic part has been proposed by forming a layer having a specific property on the surface of the plastic part so as to make up for the drawbacks of the plastic part, and a lot of them have been proposed. Protective coating compositions have been proposed. Among them,
As a coating composition which is close to an inorganic type and gives a hard coating film, "a coating composition containing an organic silicon compound or a hydrolyzate thereof as a main component" (JP-A-52-11261).
Etc. are also proposed.

The coating layer formed by the above coating composition significantly improves the performance of plastic parts, but is insufficient in terms of scratch resistance (damage). Recently, in order to solve this problem, a coating composition containing silica fine particles dispersed in a colloidal state in a coating composition to improve the scratch resistance of the coating layer formed (Japanese Patent Laid-Open No. 53- No. 111336) has been proposed.

Also, in order to increase the refractive index of the coating layer, a coating composition using titanium oxide fine particles instead of silica fine particles (JP-A-63-275).
No. 682) and a coating composition using antimony oxide fine particles (Japanese Patent Application Laid-Open No. 62-151801) and a coating composition using composite fine particles of tin oxide and tungsten oxide (Japanese Patent Publication No. 6-102776). There is.

These are coating compositions comprising an organosilicon compound represented by the following general formula or a hydrolyzate thereof (hereinafter referred to as component (a)) and titanium oxide fine particles or antimony oxide fine particles. General formula; R ¹ _a R ² _b Si (OR ³ ) _{4- (a + b)} (wherein, R ¹ is a functional group or an organic group having an unsaturated double bond and having 4 to 14 carbon atoms) , R ² has 1 to ² carbon atoms
A hydrocarbon group of 0 or a halogenated hydrocarbon, R ³ is an alkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group or an acyl group, a is 0 or 1, b is 0 to 2; And a + b is 0 or 1 or 2. )

[0007]

However, when a coating layer is formed on the surface of a plastic part with a coating composition containing silica fine particles, interference fringes are generated on the surface of the plastic part, and the appearance of the plastic part is deteriorated. Problem has occurred. The titanium oxide fine particles can be stably present in the solvent alone,
Although it has a high refractive index, it is preferable, but when used as a component of a coating composition, it is difficult to stably exist with the component (a).

Further, when the coating layer is formed from the coating composition containing the component (a) and the titanium oxide fine particles, a problem occurs in the water resistance of the coating layer. The antimony oxide fine particles can be stably present in the solvent alone, and have a relatively high refractive index.
Further, when used as a component of a coating composition, it can stably exist with the component (a), but the coating layer formed by the coating composition containing the component (a) and antimony oxide sol is ,
There was a problem that the refractive index was not high enough.

The composite fine particles of tin oxide and tungsten oxide can be stably present in the solvent alone and have a relatively high refractive index. Furthermore, when used as a component of the coating composition, Although the component a) can exist stably, it has a problem in the weather resistance of the coating layer. Further, an antireflection film may be formed on the surface of the optical plastic component after forming a coating layer according to the purpose. The antireflection film may cause a reflection color on the surface of the plastic part, but this reflection color has a problem that color unevenness occurs due to the influence of the coating layer.

Due to these problems, it is difficult to obtain a multifunctional optical component adaptable to various usage environments and usage conditions. The present invention solves the problems of such conventional coating compositions and plastic parts, and when a coating layer is formed on the surface of the plastic part, a sufficient refractive index is obtained and interference fringes are generated. It is an object of the present invention to provide a coating composition and a plastic part which have good weather resistance and do not cause color unevenness due to a reflection color generated by forming an antireflection film on the coating layer.

Further, it is possible to improve scratch resistance, surface hardness, flexibility, transparency, antistatic property, dyeability, heat resistance, water resistance, chemical resistance, etc. of plastic parts, which have been problems in the past. An object of the present invention is to provide a coating composition which can be obtained and a plastic part having improved scratch resistance, surface hardness, flexibility, transparency, antistatic property, dyeability, heat resistance, water resistance, chemical resistance and the like.

[0012]

DISCLOSURE OF THE INVENTION The present inventors have studied fine particles used together with an organosilicon compound which is a component of a coating composition, which has been conventionally proposed. The present inventors, by using the novel fine particles never before,
Each problem can be solved, and by providing an antireflection film, a water repellent film, an oil repellent film, and a primer layer, it becomes possible to obtain a multifunctional optical component.

Therefore, the first aspect of the present invention is "(a) general formula; R
¹ _a R ² _b Si (OR ³ ) _{4- (a + b)} (wherein, R ¹ is a functional group or an organic group having an unsaturated double bond and having 4 to 14 carbon atoms, and R ² is It is a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon, R ³ is an alkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group or an acyl group, and a is 0.
Or 1, b is 0 to 2, and a + b is 0 or 1 or 2. And a hydrolyzate thereof, and (b) composite fine particles of tin oxide and zinc stannate are mainly contained in the coating composition (claim 1) ". .

Secondly, "amines, various metal complex compounds, metal alkoxides, organic tin compounds, organic metal salts,
A coating composition (claim 2) according to claim 1, which contains at least one of a perchlorate, an organic acid or a compound thereof, a Lewis acid, and a metal halide. Is. Thirdly, “the metal complex compound is represented by the general formula; M [CH ₂ N (CH ₂ COO) ₂ ].
₂ Nac represents a metal complex compound (provided that in the formula, M
Is Zn, Mn, Mg, Fe, Cu, Co, Ca, B
i and Al, and c is 1 or 2. The coating composition according to claim 2 (claim 3) ”is provided.

Fourth, "(a) on the surface of the plastic substrate
General formula; R ¹ _a R ² _b Si (OR ³ ) _{4- (a + b)} (In the formula, R ¹ is a functional group or an unsaturated double bond having 4 carbon atoms.
To 14 organic groups, R ² is a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon, and R ³ is 1 to 1 carbon atoms.
4 is an alkyl group, an alkoxyalkyl group or an acyl group, a is 0 or 1, b is 0 to 2, and a
+ B is 0 or 1 or 2. (4) A plastic part characterized in that a coating layer mainly containing an organosilicon compound or a hydrolyzate thereof represented by (4) and (b) composite fine particles of tin oxide and zinc stannate is formed (claim 4). "I will provide a.

Fifthly, "in the plastic part of claim 4, amines, various metal complex compounds, metal alkoxides, organic tin compounds, organic metal salts,
A plastic part (claim 5) characterized by containing at least one or more of a perchlorate, an organic acid or a compound thereof, a Lewis acid and a metal halide.

Sixth, "Amines are contained in the coating layer,
Various metal complex compounds, metal alkoxides, organic tin compounds, organic metal salts, perchlorates, organic acids or their compounds,
At least one or more of a Lewis acid and a metal halide is contained, and a general formula: M [CH ₂ N (CH ₂ COO)
₂ ] ₂ Nac A metal complex compound (provided that in the formula,
M is Zn, Mn, Mg, Fe, Cu, Co, Ca, B
i and Al, and c is 1 or 2. ) Is contained, the plastic part according to claim 4 (claim 6) "is provided.

Seventhly, there is provided "a plastic part characterized in that the plastic base material according to claim 4 has a high refractive index of 1.54 or more (claim 7)".

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION A coating composition according to claim 1 of the present invention is mainly composed of an organosilicon compound represented by the following general formula or a hydrolyzate (a component) thereof and composite fine particles of tin oxide and zinc stannate. Because it contains,
When a coating layer is formed on the surface of plastic parts, a sufficient refractive index is obtained, interference fringes do not occur, and
It is possible to obtain a coating composition that has good weather resistance and does not cause color unevenness due to the reflection color that is caused by forming an antireflection film on the coating layer. General formula;
R ¹ _a R ² _b Si (OR ³ ) _{4- (a + b)} (wherein, R ¹ is a functional group or an organic group having an unsaturated double bond and having 4 to 14 carbon atoms, and R ² Is a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon, R ³ is an alkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group or an acyl group, a is 0 or 1, and b is 0. Is 2 and a + b is 0 or 1 or 2.) This is because the coating composition of the present invention contains composite fine particles of tin oxide and zinc stannate. This is because it can exist in a more stable state and can bring out preferable properties, as compared with the case of using composite fine particles of tungsten oxide. In the composite fine particles of tin oxide and zinc stannate, the core is tin oxide, and the periphery thereof is covered with zinc stannate. Zinc stannate is in a mixed state of tin and zinc, or in a composite state in which both are combined. Alternatively, both the mixed state and the complex state may coexist. It may include both a composite state in which tin and zinc stannate are combined and a state in which both are adsorbed.

The fine particles of the present invention are preferably used in the form of a colloidal solution dispersed in water or an organic solvent, or a mixed liquid of water and an organic solvent, to which a suitable alkali, preferably an organic amine is added. Use a stabilized product. The fine particles are generally present in a state in which about 5 particles are aggregated. The average particle size in the aggregated state is 1 to 3.
Within a range of 00 nm, but preferably 5 to 200 n
Those in the range of m are used. The particle size of one particle is about 5
20 nm. When the diameter of the fine particles is smaller than the above range, the stability of the colloidal solution itself is poor, the effect of scratch resistance is small, and the production is difficult. On the contrary, when the diameter of the fine particles is larger than the above range, the stability of the coating composition, the transparency and smoothness of the coating film are deteriorated.

By the way, the component (a) in the coating composition of the present invention is an organic silicon compound, and specific examples thereof include methyl silicate, ethyl silicate, isopropyl silicate, n-propyl silicate, n-butyl silicate, t-butyl silicate, sec-butyl silicate, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (βmethoxyethoxy)
Silane, vinyldimethylethoxysilane, allyltriethoxysilane, allyltrimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltri Methoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyldimethylethoxysilane, γ-methacryloxypropyldimethylmethoxysilane, γ-methacryloxypropyltrismethoxyethoxysilane, Glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α
-Glycidoxyethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β -Glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane,
γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltrimethoxyethoxysilane Silane, γ-glycidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltrimethoxysilane, β-glycidoxybutyltriethoxysilane Silane, γ-
Glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ-glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexyl) methyltrimethoxysilane , (3,4-epoxycyclohexyl) methyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β
-(3,4-Epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl)
Ethyltripropoxysilane, β- (3,4-epoxycyclohexyl) ethyltributoxysilane, β-
(3,4-epoxycyclohexyl) ethyltrimethoxyethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriphenoxysilane, γ- (3,4-epoxycyclohexyl) propyltrimethoxysilane,
γ- (3,4-epoxycyclohexyl) propyltriethoxysilane, δ- (3,4-epoxycyclohexyl) butyltrimethoxysilane, δ- (3,4-epoxycyclohexyl) butyltriethoxysilane, glycidoxymethylmethyl Dimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyl Diethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylmethyldiethoxysilane,
γ-glycidoxypropylmethyldimethoxysilane, γ
-Glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldimethoxyethoxysilane, γ-
Glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylethyldipropoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ- Glycidoxypropylvinyldiethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, mercaptomethyldimethylethoxysilane, mercaptomethylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, N-β (amino Ethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, γ Aminopropyltrimethoxysilane, .gamma.-aminopropyltriethoxysilane,
N-phenyl-γ-aminopropyltrimethoxysilane, δ-aminobutyldimethylmethoxysilane, δ-aminobutyltriethoxysilane, γ-aminopropyldimethylethoxysilane, γ-aminopropylmethyldiethoxysilane, t-butyldiphenylmethoxy Silane,
n-butylmethyldichlorosilane, n-butyltrichlorosilane, t-butyltrichlorosilane, n-butyltrimethoxysilane, di-n-propyldichlorosilane,
n-decyltrimethoxysilane, n-docosylmethyldichlorosilane, n-docosyltrichlorosilane, n-dodecyltrichlorosilane, n-dodecyltriethoxysilane, n-eicosyltrichlorosilane, n-heptylmethyldichlorosilane, n -Heptyltrichlorosilane, n-hexadecyldichlorosilane, n-hexadecyltrichlorosilane, n-hexadecyltriethoxysilane, hexa-5-enyldimethylchlorosilane, hexa-5-enyltrichlorosilane, hexyldichlorosilane, n-hexyl Dimethoxysilane, n-hexylmethyldichlorosilane, n-hexyltrichlorosilane,
n-hexyltrimethoxysilane, isobutyldichlorosilane, isobutyltrichlorosilane, isobutyltrimethoxysilane, methyldodecyldichlorosilane, methyldodecyldiethoxysilane, methyl-n-octadecyldichlorosilane, methyl-n-octadecyldiethoxysilane, methyl- n-octyldichlorosilane, methyltri-n-decylciolane, n-octadecyltrichlorosilane, n-octadecyltriethoxysilane, n
-Octadecyltrimethoxysilane, n-octyldimethylchlorosilane, n-octyltrichlorosilane, n
-Octyltriethoxysilane, n-propyltrimethoxysilane, n-acontylchlorosilane, tri-n
-Hexylchlorosilane, triisobutylsilane, n-
Undecyl trichlorosilane etc. are mentioned.

By the way, R ¹ in the organosilicon compound as the component (a) preferably has an epoxy group as a functional group from the viewpoints of adhesion, flexibility, scratch resistance and the like.
These are called epoxy silanes. For example, in the case of silicon compounds, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ
-Glycidoxypropyldimethoxyethoxysilane, γ
-Glycidoxypropyltriacetoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,
4-epoxycyclohexyl) ethyltriethoxysilane and the like.

Further, the structure of the component (a) in the coating composition of the present invention is preferably a trifunctional organosilicon compound in which three OR ³ groups are bonded to Si atoms from the viewpoint of scratch resistance. Of course, a bifunctional organosilicon compound having two OR ³ groups bonded to Si atoms and a tetrafunctional organosilicon compound having four OR ³ groups bonded to four Si atoms can also be used.

These organic silicon compounds may be used alone, but if two or more kinds are mixed and used, it is possible to obtain a coating layer for various purposes. In this case, the different trifunctional organosilicon compounds may be mixed and used, or the bifunctional and trifunctional organosilicon compounds may be mixed and used. still,
When the bifunctional organosilicon compound is used as the component (a), it is preferably mixed with the trifunctional organosilicon compound.

Further, if the organosilicon compound is hydrolyzed and a coating composition containing the hydrolyzed compound is prepared, the reaction rate at the time of processing the coating layer is increased, and the curing temperature is lowered. Can be used for coating film processing. In addition, when two or more compounds having the same functional number are used in combination among two to four functional compounds, or when two or more compounds having different functional numbers are used in combination, they may be used together after hydrolysis, or Co-hydrolysis may be performed in combination before the decomposition.

This hydrolyzate rapidly undergoes dehydration condensation to become an oligomer, but 1 to 100 hours after hydrolysis,
When left (cured) for 3 to 50 hours, this reaction can proceed sufficiently. In the coating composition according to the invention of claim 2, amines, various metal complex compounds, metal alkoxides, organic tin compounds, organic metal salts, perchlorates, organic acids or their compounds, Lewis acids, It contains at least one or more of metal halides, and this serves as a curing catalyst to accelerate the polymerization of the component (a) which is an organosilicon compound or a hydrolyzate thereof,
Since the coating layer having a three-dimensional network structure is formed, the target coating layer can be efficiently formed at low temperature and in a short time.

Examples of the amines include monoethanolamine, diethanolamine, isopropanolamine, ethylenediamine, isopropylamine, diisopropylamine, morpholine, triethanolamine, diaminopropane, aminoethylethanolamine, disialamide, triethylenediamine, 2-ethyleneamine. Ethyl-4-methylimidazole and the like can be mentioned.

Further, various metal complex compounds have the general formula: M
XnY3-n (where M is Zn, Mn, Mg,
Metals such as Fe, Cu, Co, Ca, Bi and Al, X is OL (L is a lower alkyl group), Y is a general formula M1COCH
2COM2 (M1 and M2 are lower alkyl groups), and M1
At least one selected from ligands derived from COCH2COM2, and n is 0, 1 or 2. }, The aluminum chelate compound is preferable from the viewpoint of scratch resistance.

For example, aluminum acetylacetonate, aluminum bisethylacetoacetate, monoacetylacetonate, aluminum-di-n-butoxide-monoethylacetoacetate, aluminum-di-
iso-propoxide-monomethylacetoacetate,
Chromium acetylacetonate, titanyl acetylacetonate, cobalt acetylacetonate, iron (III) acetylacetonate, manganese acetylacetonate,
Examples thereof include nickel acetylacetonate and indium acetylacetonate.

Further, examples of metal alkoxides include aluminum triethoxide, aluminum tri-n-propoxide, aluminum tri-n-butoxide, tetraethoxytitanium, tetra-n-butoxytitanium, tetra-i-propoxytitanium and the like. Can be mentioned. Further, as the organic tin compound, dimethyltin diacetate, diethyltin diacetate, dibutyltin diacetate, dimethyltin dilaurate, dibutyltin dilaurate,
Dimethyltin dimarkabutide, diethyltin dimarkabutide, dibutyltin dimarkabutide, dioctyltin dimarkabutide, dimethyltin thiocarboxylate, diethyltin thiocarboxylate, dibutyltin thiocarboxylate, dioxyltin thiocarboxylate, dimethyl Examples include tindimaleate, dimethyltindimaleate, dibutyltindimaleate, dimethyltin dichloride, diethyltin dichloride, dibutyltin dichloride and the like.

Examples of the organic metal salt include sodium acetate, zinc naphthenate, cobalt naphthenate, tin octylate, and examples of the perchlorate include magnesium perchlorate and ammonium perchlorate. . Furthermore, examples of organic acids or their anhydrides include malonic acid, succinic acid, tartaric acid, adipic acid, azelaic acid, maleic acid, O-phthalic acid, terephthalic acid, fumaric acid, itaconic acid, oxaloacetic acid, maleic anhydride, Examples thereof include succinic anhydride, itaconic anhydride, 1,2-dimethylmaleic anhydride, phthalic anhydride, hexahydrophthalic anhydride, and naphthalic anhydride.

Examples of Lewis acids include ferric chloride and aluminum chloride, and examples of metal halides include stannous chloride, stannic chloride, tin bromide, zinc chloride and bromide. Zinc, titanium bromide, titanium tetrachloride,
Examples include thallium bromide, germanium chloride, hafnium chloride, lead chloride, and lead bromide. By the way, the above curing catalysts may be used alone or in combination of two or more depending on the purpose. Also, among these curing catalysts,
When the component (a) has an epoxy group, it can also serve as a catalyst for the ring-opening polymerization. For example, an aluminum chelate compound is one of the preferred catalysts.

Further, in the coating composition according to the invention as defined in claim 3, the general formula; M [CH ₂ N (C
H ₂ COO) ₂ ] ₂ Nac Metal complex compound (wherein M is Zn, Mn, Mg, Fe, Cu, C
o, Ca, Bi and Al, and c is 1 or 2. )
This metal complex compound is a very hard coating layer because the component (a), which is an organosilicon compound or a hydrolyzate thereof, is polymerized at a low temperature to form a coating film having a three-dimensional network structure. Can be formed efficiently.

Specific examples of the above metal complex compounds include iron ethylenediaminetetraacetate, aluminum ethylenediaminetetraacetate, zinc ethylenediaminetetraacetate, manganese ethylenediaminetetraacetate, magnesium ethylenediaminetetraacetate, copper ethylenediaminetetraacetate, cobalt ethylenediaminetetraacetate and ethylenediamine. Examples thereof include calcium tetraacetate and bismuth ethylenediamine tetraacetate.

These metal complex compounds may be used alone or in combination of two or more. Further, these metal complex compounds may be used in combination with the curing catalyst shown in claim 2. Furthermore, in the plastic part according to the invention described in claim 4, since a layer of the coating composition according to claim 1 is formed on the surface of the plastic part, interference fringes do not occur on the surface of the plastic part. It looks good. further,
Even if the antireflection film is formed on the coating layer of the plastic part, the reflected color does not occur, so that the plastic part in which the color unevenness due to the influence of the reflected color does not occur can be obtained.

In addition, scratch resistance, which is a conventional problem,
It is possible to obtain a plastic part having excellent surface hardness, flexibility, transparency, antistatic property, dyeability, heat resistance, water resistance, chemical resistance and the like. Further, in the plastic parts according to the invention described in claim 5 and claim 6,
In the plastic part, the coating composition formed on the surface thereof contains a curing catalyst, and this curing catalyst polymerizes the component (a) to form a coating film having a three-dimensional network structure. It is possible to obtain a plastic part in which a desired coating layer is efficiently formed.

Further, in the present invention, a conventionally known solvent may be used in order to adjust the solid content of the coating composition or to reduce the viscosity. For example, water, lower alcohol, acetone, ether, ketone, ester and the like can be mentioned. In addition to the components mentioned above,
Various additives may be used in combination according to various purposes. For example, a pH adjusting agent, a viscosity adjusting agent, a leveling agent, a matting agent, a dye, a pigment, a stabilizer, a UV absorber, an antioxidant and the like can be mentioned.

Furthermore, an epoxy resin or other organic polymer may be used in combination for the purpose of improving the dyeability and flexibility of the coating layer. For example, polyolefin epoxy, cyclopentadiene oxide, cyclohexene oxide, alicyclic epoxy resin such as polyglycidyl ester, polyglycidyl ether, epoxidized vegetable oil, epoxy novolac, copolymer of glycidyl methacrylate and methyl methacrylate, polyol, fiber resin , Melamine resin and the like.

Further, by improving the flow at the time of coating,
In order to improve the smoothness of the coating layer and reduce the friction coefficient on the surface of the coating layer, it is possible to use various kinds of surfactants together. Examples thereof include block or graft copolymers of dimethylcyclohexane and alkylene oxide, silicone-based surfactants, fluorine-based surfactants, and the like.

By the way, the coating composition of the present invention has particularly preferable properties as a coating film for an eyeglass lens molded from a resin having a medium to high refractive index of nd = 1.54 or more. It is not limited to lenses, but can also be used for other plastic parts. Further, it may be used for inorganic glass, wood, metal articles and the like.

Further, the coating means is preferably
A manufacturing method such as brush coating, dip coating, roll coating, spray coating, or flow coating is used. For example, after applying the coating composition of the present invention to a mold, a plastic part having a coating layer formed by casting polymerization of a raw material to be a plastic part may be obtained, or as another method, the surface of the plastic part of the present invention may be formed. After applying the coating composition, it may be brought into close contact with a mold to cure the coating film to obtain a plastic part having a coating layer formed thereon.

The thickness of the coating layer after drying is 0.05 μm to 30 μm, preferably 0.1 μm to 1
It is better to set it to 0 μm. The plastic part of the present invention is preferably one in which the coating composition is applied and then heated to cure the coating composition. The heating temperature is about 50 ° C to 200 ° C, preferably 80 ° C to 140 ° C.

The plastic substrate of the plastic part of the present invention is not particularly limited, but polymethylmethacrylate and its copolymer, acrylonitrile-styrene copolymer, polycarbonate, cellulose acetate, polyvinyl chloride, polyethylene terephthalate, Transparent plastic parts such as epoxy resin, unsaturated polyester resin, polyurethane resin, styrene resin, allyl resin, urethane-vinyl copolymer, urethane-acryl-styrene copolymer, and diethylene glycol bisallyl carbonate polymer are preferable.

As the form of the plastic part of the present invention, preferably, a lump, a cotton material, a film or the like is used. Furthermore, a single-layer or multi-layer antireflection film may be formed on the coating layer comprising the organosilicon compound of the present invention and fine particles. This can be formed by a vacuum vapor deposition method or sputtering. Then, a film such as a water repellent film or an oil repellent film may be formed on the antireflection film. It is also possible to provide a film having a film thickness of 0.0005 to 0.5 μm with a curable organic substance such as fluorine-containing polysiloxane. By forming a film of these antireflection film, water repellent film, oil repellent film, etc. on the coating layer of the present invention, it is possible to obtain an optical component further having an effect comparable to that of an optical component.

Further, if a resin such as urethane resin or polyvinyl acetal resin is applied on the base material and the coating of the present invention is formed thereon, scratch resistance, surface hardness,
It is possible to obtain an optical component having excellent impact resistance in addition to flexibility, transparency, antistatic property, dyeability, heat resistance, water resistance, chemical resistance, and particularly a spectacle lens having a medium or high refractive index.

[0046]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited thereto. (1) Preparation of preliminary composition A γ-glycidoxypropylmethyldiethoxysilane 24
While vigorously stirring 8 parts by weight, 36 parts by weight of a 0.05N hydrochloric acid aqueous solution was added at once, and the stirring was continued for 1 hour and a half to obtain a hydrolyzate x corresponding to the component (a).

As the solvent, 56.
After adding 6 parts by weight of ethanol and 53.4 parts by weight of ethylene glycol, 4.7 parts by weight of aluminum acetylacetonate was added as a curing catalyst, and the resulting solution was sufficiently mixed and dissolved to prepare the preliminary composition A. And (2) Preparation of preliminary composition B γ-glycidoxypropyltrimethoxysilane 212.
48.6 parts by weight of 0.01N hydrochloric acid aqueous solution was gradually added dropwise while keeping 4 parts by weight at 10 ° C. with vigorous stirring. Immediately after dripping, stop cooling, and
Hydrolyzate y corresponding to the component was obtained.

77. As a solvent for the above hydrolyzate y.
After adding 1 part by weight of ethanol and 37.7 parts by weight of ethylene glycol, 7.65 parts by weight of aluminum acetylacetonate as a curing catalyst was added, and the mixture was sufficiently mixed and dissolved to prepare a preliminary composition B. And (3) Preparation of Preliminary Composition C 284 parts by weight of the above-mentioned hydrolyzate was mixed with 56.
After adding 6 parts by weight of ethanol and 53.4 parts by weight of ethylene glycol, 4.0 parts by weight of ethylenediaminetetraaluminum acetate as a curing catalyst was added, and the resulting solution was sufficiently mixed and dissolved to prepare the preliminary composition C. And

(4) Preparation of Preparative Composition D 261 parts by weight of the above-mentioned hydrolyzate y was used as a solvent in 77.
After adding 1 part by weight of ethanol and 37.7 parts by weight of ethylene glycol, 6.0 parts by weight of ethylenediaminetetraaluminumacetate as a curing catalyst was added and sufficiently mixed and dissolved to prepare a preliminary composition D. And

(5) Preparation of coating composition Preliminary compositions A and B were placed in a glass container according to Table 1.
200 parts by weight of a commercially available composite colloidal solution of tin oxide and zinc stannate was added, 0.45 parts by weight of a silicone-based surfactant was added, and the mixture was sufficiently stirred to mix and coat. A composition (I) was obtained.

The composite colloidal solution of tin oxide and zinc stannate is a methanol-dispersed colloidal solution having a solid content of 20%, and the average particle size of the colloid is about 50 nm. Similarly, first place the pre-compositions C and D in a glass container.
Based on the table, weigh and inject, further add 200 parts by weight of the above-mentioned commercially available composite colloidal solution of tin oxide and zinc stannate, add 0.45 parts by weight of a silicone-based surfactant, and stir thoroughly. And mixed to obtain a coating composition (II).

(6) Coating A commercially available polyurethane lens having a refractive index of nd = 1.67 was coated with each of the above coating compositions (I) and (II) by a dipping method (pulling speed: 10 cm / min). 100 ° C
The coating film was cured by heating for 2 hours to form a coating layer. (7) Evaluation The polyurethane lens forming the coating layer obtained in (6) above was used in the following test to evaluate the performance of the coating layer.

(A) Abrasion resistance test The surface of the coating layer was rubbed with steel wool # 0000 to examine the scratch resistance, and the evaluation was carried out according to the following criteria. ◎ ・ ・ ・ ・ No scratches even if rubbed very strongly. ○ ・ ・ ・ ・ No scratches even if rubbed strongly.

△ ・ ・ ・ ・ Scratch is slightly caused when strongly rubbed. × ・ ・ ・ ・ Scratches occur even if rubbed weakly. For reference, the evaluation of the polyurethane lens not having the coating layer formed was X. (B) Appearance A generally used antireflection film was formed on the coating layer by a vacuum vapor deposition method, and the unevenness of the reflection color was examined by visual observation, and evaluated according to the following criteria.

⊚ ··· No unevenness due to reflected color. ○ ・ ・ ・ ・ Some unevenness due to reflected color. X ...- There is significant unevenness due to the reflected color. (C) Weather resistance A UV long life fade meter (manufactured by Suga Test Instruments Co., Ltd.) was used to perform a weather resistance test for 300 hours, after which the degree of yellowing was measured and evaluated according to the following criteria. .

◎ ・ ・ ・ Yellowness after 300 hours is less than 2.0 ○ ・ ・ ・ ・ Yellowness after 300 hours is 2.0 or more and less than 2.5 × ・ ・ ・ Yellowness after 300 hours Degree of 2.5 or more (d) Dyeability 90 in a disperse dye bath in which red, yellow and blue are mixed.
It was immersed at 30 ° C. for 30 minutes, and the light transmittance was measured to examine the dyeability.

Table 1 shows the results of (a), (b), (c), and (d).

[0058]

[Table 1]

(E) Adhesiveness A 1 mm square substrate (10
After making a cellophane adhesive tape (product name “Cellotape” Nichiban Co., Ltd.) strongly, it was held with one end of the tape and peeled off vigorously in 90 directions. After that, the number of eyes of the substrate on the surface of the coating layer was peeled off, and the number of eyes of the peeled substrate was x, and x / 1
It was represented by 00. In this case, the smaller the x, the better the adhesion.

Further, in Comparative Example 1 in Table 1, instead of using a composite colloidal solution of tin oxide and zinc stannate, a commercially available silica colloidal solution (average particle size: 13 ± 1 nm, solid content: 20%) was used. Is a result of similarly evaluating a polyurethane-based lens having a coating layer formed by a coating composition prepared by using (1) which is a methanol-dispersed colloidal solution.

Further, in Comparative Example 2 in Table 1, instead of using the composite colloidal solution of tin oxide and zinc stannate, a commercially available antimony pentoxide colloidal solution (having an average particle size of 13
The results are obtained by similarly evaluating a polyurethane lens having a coating layer formed by a coating composition prepared by using a colloidal solution having a solid content of 20%.

[0062]

EFFECTS OF THE INVENTION The coating composition of the present invention, when applied to a plastic part, does not cause interference fringes on the surface of the plastic part, has good weather resistance, and has an antireflection film. Thus, it is possible to obtain a coating composition that forms a coating layer that does not cause uneven reflection color.

Furthermore, scratch resistance, which has been a conventional problem,
A coating composition for forming a coating layer having further improved surface hardness, abrasion resistance, transparency, heat resistance, water resistance, and antistatic property can be obtained. In addition, when a coating layer is formed by the coating composition of the present invention, the coating layer has a large elongation, and the risk of cracking on the surface of the coating layer is significantly reduced even when the base material is bent. A high surface reflectance can be obtained.

In addition, the sliding property of the surface of the coating layer is good (the friction coefficient is low), and the adhesive property is good with the antireflection film, the metal vapor deposition film and the like formed on the coating layer. Furthermore, the coating composition of the present invention is not only easy to apply and easy to use, but also has a long pot life, and further, has a small shrinkage at the time of curing and curls particularly when applied to a thin film-like substrate. There is no such trouble.

Further, by including the curing catalyst according to the present invention, the curing time of the composition can be shortened and a coating composition capable of efficiently forming a coating layer having a three-dimensional network structure can be obtained. . Further, the plastic part of the present invention does not have interference fringes on the surface, so that it has a good appearance and a commercial value. Further, even if an antireflection film is formed on the coating layer of the plastic part, the reflected color does not occur, so that it is possible to obtain a plastic part in which color unevenness due to the influence of the reflected color does not occur.

Further, the plastic part of the present invention, by using the composite colloidal solution of tin oxide and zinc stannate, can obtain the weather resistance superior to that of the ordinary metal oxide colloidal solution. The plastic part of the present invention has improved scratch resistance, surface hardness, abrasion resistance, transparency, heat resistance, water resistance, antistatic property, and further has a large reflectance of the surface of the plastic part, It has good surface slip characteristics (low coefficient of friction) and good adhesion to antireflection films, metal deposition films, etc. formed on the surface of plastic parts.

Furthermore, in addition to scratch resistance, surface hardness, flexibility, transparency, antistatic property, dyeability, heat resistance, water resistance and chemical resistance, by providing an antireflection film or a primer layer,
It is possible to obtain a plastic part having antireflection properties, impact resistance, and adhesion between the base material and the coating layer. Therefore, it is possible to manufacture a multifunctional optical component that can cope with various environments and use conditions.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08J 7/04 C08J 7/04 M

Claims (7)

[Claims] 1. (a) General formula; R ¹ _a R ² _b Si (OR ³ ).
_{4- (a + b)} (wherein, R ¹ is a functional group or an organic group having an unsaturated double bond and having 4 to 14 carbon atoms, and R ² is a hydrocarbon group having 1 to 20 carbon atoms or It is a halogenated hydrocarbon, R ³ is an alkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group or an acyl group, a is 0 or 1, b is 0 to 2, and a + b is 0 or 1. Or 2.)
An organosilicon compound represented by or a hydrolyzate thereof,
And (b) a composite composition mainly containing tin oxide and zinc stannate composite particles. 2. Amines, various metal complex compounds, metal alkoxides, organic tin compounds, organic metal salts, perchlorates,
The coating composition according to claim 1, which contains at least one of an organic acid or a compound thereof, a Lewis acid, and a metal halide. 3. The various metal complex compounds represented by the general formula: M
A metal complex compound represented by [CH ₂ N (CH ₂ COO) ₂ ] ₂ Nac (wherein, M is Zn, Mn, Mg, F
e, Cu, Co, Ca, Bi and Al, and c is 1 or 2. ) Is contained.
A coating composition as described. 4. On the surface of a plastic substrate, (a) the general formula; R ¹ _a R ² _b Si (OR ³ ) _{4- (a + b)} (wherein R
¹ is a C 4-14 having a functional group or an unsaturated double bond
An organic group, R ² is a hydrocarbon group or halogenated hydrocarbon having 1 to 20 carbon atoms, R ³ is an alkyl group, an alkoxyalkyl group or an acyl group having 1 to 4 carbon atoms,
a is 0 or 1, b is 0 to 2, and a + b is 0 or 1 or 2. ) A plastic part having a coating layer formed mainly containing an organosilicon compound represented by the formula (1) or a hydrolyzate thereof, and (b) composite fine particles of tin oxide and zinc stannate. 5. The plastic part according to claim 4,
Amines, various metal complex compounds in the coating layer,
A plastic part containing at least one of a metal alkoxide, an organic tin compound, an organic metal salt, a perchlorate, an organic acid or a compound thereof, a Lewis acid and a metal halide. 6. The coating layer comprises at least one of amines, various metal complex compounds, metal alkoxides, organic tin compounds, organic metal salts, perchlorates, organic acids or their compounds, Lewis acids and metal halides. One or more, and a general formula; M [CH ₂ N (CH ₂ COO) ₂ ] ₂
A metal complex compound represented by Nac (however, in the formula, M is
Zn, Mn, Mg, Fe, Cu, Co, Ca, Bi, A
1 and c is 1 or 2. ) Is contained, The plastic part of Claim 4 characterized by the above-mentioned. 7. A plastic part characterized in that the plastic base material according to claim 4 has a high refractive index of 1.54 or more.