JPH06329988A - Coating composition and plastic substrate - Google Patents

Abstract

PURPOSE:To obtain a coating compsn. which gives a coating film having improved scratch resistance, surface hardness, flexibility, transparency, antistatic properties, etc., by incorporating a specific organosilicon compd. or its hydrolyzate and a composite colloidal sol comprising tatinium and antimony oxides into the compsn. CONSTITUTION:A coating compsn. contains an organosilicon compd. of formula I [wherein R<1> is a 4-14C org. group having a functional group or a double bond; R<2> is a 1-6C (halogenated) hydrocarbon group; R<3> is 1-4C alkyl, alkoxyalkyl, or acyl; and a is 0 or 1 and b is 0-2 provided a+b is 1 or 2] or its hydrolyzate, a composite colloidal sol comprising 100 pts.wt. titanium oxide and 2-100 pts.wt. antimony oxide, and, if necessary, a metal complex of formula II (wherein M is Zn, Mn, Mg, Fe, Cu, Co, Ca, Bi, or Al; and c is 1 or 2).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to coating compositions for plastic moldings and plastic substrates.

[0002]

2. Description of the Related Art Generally, a plastic substrate is lightweight and
It has fairly useful characteristics 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 due to charging, and it has poor heat resistance. It also has drawbacks such as being sufficient.

Although various plastic lens base materials have been developed in order to overcome such drawbacks of plastic lens base materials, it is sufficient to devise the components of the plastic base material. However, there has been no solution to the conventional drawbacks.

Therefore, there has been proposed a coating composition for improving the performance of a plastic substrate by forming a layer having a specific property on the surface of the plastic substrate so as to make up for the defects of the plastic substrate. Have been made and numerous protective coating compositions have been proposed.

Among them, a "coating composition containing an organic silicon compound or its hydrolyzate as a main component" (Japanese Patent Application Laid-Open No. 52-11261) is proposed as a coating composition which is close to an inorganic type and gives a hard coating film. ing.

The coating layer formed by the above coating composition considerably improves the performance of the plastic substrate, but has a drawback of low scratch resistance (easiness of scratching). Therefore, recently, in order to solve this difficulty, a silica sol dispersed in a colloidal form is contained in the above coating composition to improve the scratch resistance when a coating layer is formed. (Sho 53-111336) has been proposed.

A coating composition using titanium oxide instead of silica sol (Japanese Patent Laid-Open No. 63-27).
5682) and a coating composition using antimony oxide (JP-A-62-151801).

This is a coating composition comprising an organosilicon compound represented by the following general formula or a hydrolyzate thereof (hereinafter referred to as component (a)) and titanium oxide or antimony oxide (component (b)). It is what

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 is a group having 1 to 6 carbon atoms
Is a hydrocarbon group or a halogenated hydrocarbon, R ³ is an alkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group or an acyl group, a and b are each 0 or 1, and a + b is 1 or 2 Is. )

[0010]

However, when a coating layer is formed on the surface of a plastic substrate by using the above-mentioned coating composition containing silica sol, interference fringes are generated on the surface of the plastic substrate, and the appearance of the plastic substrate looks good. There was a problem of making things worse.

Further, in the above titanium oxide sol,
It is preferable because it can exist as a sol by itself and has a high refractive index, but when it is used as a composition of a coating composition, it cannot stably exist with the component (a).

Further, when the coating layer was formed from the coating composition containing the component (a) and the titanium oxide sol, there was a problem in the water resistance of the coating layer.

The above antimony oxide sol can exist as a sol by itself and has a relatively high refractive index. Furthermore, when it is used as a coating composition, it is stable with the component (a). Although it can exist, the coating layer formed from the coating composition containing the component (a) and antimony oxide sol has a problem that the refractive index is not sufficiently high.

Further, in general, an antireflection film is often formed on the surface of a plastic substrate after forming a coating layer according to the purpose. However, due to the presence of the antireflection film on the coating layer, a reflection color is generated on the surface of the plastic substrate, and the unevenness of the color occurs on the surface of the plastic substrate due to the reflection color. there were.

The present invention solves the problems of the conventional coating composition and the plastic substrate, and when a coating layer is formed on the surface of the plastic substrate, a sufficient refractive index can be obtained. No interference fringes occur,
Moreover, it is an object of the present invention to provide a coating composition and a plastic substrate which do not cause color unevenness due to a reflection color caused by forming an antireflection film on a coating layer.

Further, a coating composition having improved coating layer scratch resistance, surface hardness, inflexibility, transparency, antistatic property, dyeability, heat resistance, water resistance, chemical resistance, etc. And to provide a plastic substrate.

[0017]

[Means for Solving the Problems] To achieve the above object,
The invention according to claim 1 of the present application is (a) a 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 organic group having an unsaturated double bond and having 4 to 14 carbon atoms, and R ² is 1 to 6 carbon atoms. Is a hydrocarbon group 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 1 or 2.), and a coating composition mainly containing an organosilicon compound represented by the formula (1) or a hydrolyzate thereof, and (b) a sol of a composite colloid of titanium oxide and antimony oxide. is there.

The invention according to claim 2 of the present application is the coating composition according to claim 1, wherein the general formula: M [CH
_{2 N (CH 2 COO) 2} ] metal complex compound represented by the ₂ Na _c (In the formula, M represents, Zn, Mn, Mg, Fe, C
u, Co, Ca, Bi and Al, and c is 1 or 2. ) Is further provided.

Further, the invention according to claim 3 of the present application is such that (a) the general formula; R ¹ _a R ² _b Si is formed on the surface of the plastic substrate.
(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 is a hydrocarbon group having 1 to 6 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 to 2 and a + b is 1 or 2. The present invention provides a plastic substrate comprising a coating layer mainly containing an organosilicon compound represented by the formula (4) or a hydrolyzate thereof, and (b) a sol of a composite colloid of titanium oxide and antimony oxide.

The invention according to claim 4 of the present application is the plastic substrate according to claim 3, wherein the coating layer has the general formula: M [CH ₂ N (CH ₂ COO) ₂ ] ₂ Na.
A metal complex compound represented by _c (wherein M is Zn,
Mn, Mg, Fe, Cu, Co, Ca, Bi and Al, and c is 1 or 2. ) Further comprises a plastic substrate.

[0021]

The coating composition according to claim 1 of the present invention is a composite colloid of an organosilicon compound represented by the following general formula or a hydrolyzate thereof (hereinafter referred to as component (a)), titanium oxide and antimony oxide. Sol (hereinafter referred to as component (b))
When a coating layer is formed on the surface of a plastic substrate, a sufficient refractive index is obtained, interference fringes do not occur, and
It is possible to obtain a coating composition that does not cause color unevenness due to a 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) R ² is a group having 1 to 6 carbon atoms
Is a hydrocarbon group 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 1 or 2. )

Further, the drawbacks of the conventional coating layer,
For example, a coating composition having improved scratch resistance, surface hardness, inflexibility, transparency, antistatic property, dyeability, heat resistance, water resistance, chemical resistance and the like can be obtained.

This is because the coating composition of the present invention is
Since it contains the component (b), which is a sol of a composite colloid of titanium oxide and antimony oxide, it is possible to compensate for the drawbacks of both titanium oxide and antimony oxide when they are used alone, and bring out desirable properties. This is because.

The sol of the composite colloid of the present invention is, for example, a colloid solution in which fine particles of titanium oxide and antimony oxide are dispersed in water or an organic solvent or a mixed solution of water and an organic solvent, and a suitable alkali is used. Preferably, an organic amine added and stabilized is used.

The component (b), which is a sol of the composite colloid of titanium oxide and antimony oxide in the coating composition of the present invention, is a state in which a large number of antimony oxides are coated around titanium oxide as a core. Use one.

The diameter of the composite colloid is 1 to 200 nm.
However, it is preferably in the range of 5 to 100 nm. If the diameter of the composite colloid is smaller than the above range, the stability of the sol itself is poor, the effect is small, and the production is difficult. On the contrary, when the diameter of the composite colloid is larger than the above range, the stability of the coating composition, the transparency of the coating film, the smoothness, etc. are deteriorated.

The proportions of titanium oxide and antimony oxide are 2 parts antimony oxide based on 100 parts by weight of titanium oxide in order to make up for each of the drawbacks and to further utilize the advantages.
˜100 parts by weight, preferably 5 to 30 parts by weight are used. If the ratio is smaller than this, the stability of the composite colloid becomes poor when mixed with the component (a), and conversely, if the ratio is larger than this, a problem occurs in the refractive index of the coating composition.

That is, for example, a titanium oxide sol is preferable because it can exist as a sol by itself and has a high refractive index, but when it is used as a composition of a coating composition, it is not preferable because of the essential properties of the substance. It could not exist stably with the component (a), which is the organosilicon compound or its hydrolyzate contained in the composition.

Furthermore, when a coating layer is formed from a coating composition containing a component (a) which is an organosilicon compound or its hydrolyzate and a titanium oxide sol, there is a problem in water resistance of the coating layer.

Further, for example, antimony pentoxide sol is
It can exist as a sol by itself, has a relatively high refractive index, and when used as a composition of a coating composition, also stably exists with an organosilicon compound or its hydrolyzate (a) component. However, the refractive index of the coating layer formed from the coating composition containing the component (a) and the antimony pentoxide sol was not sufficiently high.

In the coating composition of the present invention, since titanium oxide and antimony oxide are present in the coating composition as the sol of the composite colloid, the drawbacks of using titanium oxide sol or antimony oxide sol alone Can be supplemented to bring out desirable properties.

Therefore, when a coating layer is formed by the coating composition of the present invention, a plastic substrate having a preferable refractive index can be obtained, and of course, it is stable in the presence of the component (a) and has water resistance and the like. A coating composition without problems can be obtained.

By the way, the component (a) in the coating composition of the present invention is represented by the following formulas (1) and (2), and is a kind of organosilicon compound, which is hydrolyzed and then dehydrated and condensed. Becomes an oligomer.

Further, its constitution is preferably a trifunctional organosilicon compound in which three OR ³ groups are bonded to Si atoms. Of course, bifunctional organosilicon compounds in which two OR ³ groups are bonded to two Si atoms can also be used.

[0036]

[Chemical 1]

However, in the formula, R ⁴ is an alkyl group of 1 to 4, an alkoxyalkyl group or an acyl group, and R ⁵ is a carbon number of 1 to 6.
Hydrocarbon group, halogenated hydrocarbon group, R ⁶ is hydrogen or a methyl group, m is 2 or 3, p is 1 to 6, and q is 0 to 2.

[0038]

[Chemical 2]

In the formula, R ⁷ is an alkyl group of 1 to 4, an alkoxyalkyl group or an acyl group, and R ⁸ is a carbon number of 1 to 4
Hydrocarbon group or halogenated hydrocarbon group, 1 is 2 or 3, and r is 1 to 4.

The organosilicon compound may be used alone, but if two or more kinds are mixed and used, it is possible to form a coating film 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. When the bifunctional organosilicon compound is used as the component (a), it is preferably mixed with the trifunctional organosilicon compound.

By the way, R ¹ in the organosilicon compound as the component (a) preferably has an epoxy group as a functional group. These are called epoxy silanes. For example, in the trifunctional organosilicon compound, r-glycidoxypropyltrimethoxysilane, r-glycidoxypropyltriethoxysilane, r-glycidoxypropyldimethoxyethoxysilane, r -Glycidoxypropyltriacetoxysilane, r-glycidoxypropylmethyldimethoxysilane, r-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane and the like.

Further, the organosilicon compound as the component (a) preferably contains an epoxy group, but the organosilicon compound containing no epoxy group can also be used. For example, in the case of the trifunctional organosilicon compound, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyldimethoxyethoxysilane, γ-methacryloxypropyltrimethoxy. Silane, aminomethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, Examples include various trialkoxysilanes such as 3,3,3-trifluoropropyltrimethoxysilane, triacyloxysilane, and dialkoxyalkoxysilane compounds.

Examples of the bifunctional organosilicon compound include dimethyldimethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane, methylvinyldimethoxysilane, dimethyldiethoxysilane, and the like. When using an organosilicon compound, it is desirable to mix it with a trifunctional compound.

By the way, the tetrafunctional organosilicon compound can also be used in combination with another organosilicon compound having a different number of functions or / and a compound containing an epoxy group. Of course, it is also possible to use together with the above-mentioned organosilicon compound which does not contain an epoxy group but can be used.

Examples of the tetrafunctional organosilicon compound include, for example, methyl silicate, ethyl silicate,
Isopropyl silicate, n-propyl silicate, n
-Butyl silicate, t-butyl silicate, sec-
Butyl silicate etc. are mentioned.

Further, when the above-mentioned organosilicon compound is hydrolyzed and a coating composition containing the hydrolyzed compound is prepared, the reaction rate at the time of coating film processing is increased and the effective temperature is lowered. Can be used for coating film processing.

When two or more compounds having the same functional number are used in combination among compounds having 2 to 4 functional groups, or when two or more compounds having different functional numbers are used in combination, they may be used together after hydrolysis. However, co-hydrolysis may be performed in combination before hydrolysis. Upon hydrolysis, the alcohol HOR ³ is released, and the compounds of the formulas shown in Chemical formula 1 and Chemical formula 2
Or / and it becomes a silanol corresponding to the structure shown in Chemical formula 4.

[0048]

[Chemical 3]

[0049]

[Chemical 4]

This silanol rapidly undergoes dehydration condensation to become an oligomer, but preferably 1 after hydrolysis.
When left (cured) for about 24 hours, this reaction will proceed sufficiently.

In the coating composition according to the second aspect of the invention, the general formula; M [CH ₂ N (CH
₂ COO) ₂ ] ₂ Na _c (where M represents Zn, Mn, Mg, Fe, Cu, C)
o, Ca, Bi and Al, and c is 1 or 2. )
This metal complex compound polymerizes the organosilicon compound or its hydrolyzate (a) component to form a coating film having a three-dimensional network structure, so that a very hard coating layer can be efficiently formed. It can be formed well.

Specific examples of the above metal complex compounds include, for example, 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, in the plastic substrate according to the invention described in claim 3, a layer of the coating composition according to claim 1 is formed on the surface of the plastic substrate, and the surface of the plastic substrate is formed. Good appearance because no interference fringes occur. Furthermore, even if an antireflection film is formed on the coating layer of the plastic base material, a reflection color does not occur, and thus a plastic base material free from color unevenness due to the influence of the reflection color can be obtained.

In addition, scratch resistance, which is a conventional problem,
It is possible to obtain a plastic substrate having excellent surface hardness, flexibility, transparency, antistatic property, dyeability, heat resistance, water resistance, chemical resistance and the like.

Further, in the plastic substrate according to the invention of claim 4, the coating composition formed on the surface of the plastic substrate of claim 3,
A metal complex compound represented by the general formula: M [CH ₂ N (CH ₂ COO) ₂ ] ₂ Na _c (wherein, M is Zn, M
n, Mg, Fe, Cu, Co, Ca, Bi and Al, and c is 1 or 2. This metal complex compound polymerizes the component (a) to form a coating film having a three-dimensional network structure, so that a plastic substrate having a very hard coating layer formed efficiently can be obtained. be able to.

Further, in the present invention, when the component (a) is polymerized to form a coating film having a three-dimensional network structure,
In order to shorten the time, if necessary, amines, various metal complex compounds, metal alkoxides, organic metal rims, perchlorates, organic acids or their anhydrides, Lewis acids, curing catalysts of metal halides ( However, those which impair the stability of the coating composition are not preferred) may be used in combination with the coating composition.

For example, among amines, monoethanolamine, diethanolamine, isopropanolamine,
Examples thereof include ethylenediamine, isopropylamine, diisopropylamine, morpholine, triethanolamine, diaminopropane, aminoethylethanolamine, disialamide, triethylenediamine, 2-ethyl-4-methylimidazole and the like.

Further, various metal complex compounds have the general formula: A
1X _n Y _3-n (wherein, X is OL (L is a lower alkyl group), and Y is a general formula M ¹ COCH ₂ COM ² (M ¹ , M
² is a lower alkyl group) and at least one selected from ligands derived from M ¹ COCH ₂ COM ² and n is 0.
Or 1 or 2. } The aluminum chelate compound shown by these is used.

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 the metal alkoxide include aluminum triethoxide, aluminum tri-n-propoxide, aluminum tri-n-butoxide, tetraethoxytitanium, tetra-n-butoxytitanium, tetra-i-propoxytitanium and the like. Can be mentioned.

Examples of the organic metal salt include sodium acetate, zinc naphthenate, cobalt naphthenate and tin octylate, and examples of the perchlorate include magnesium perchlorate and ammonium perchlorate. .

Further, as an example of the organic acid or its anhydride,
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, succinic anhydride, itaconic anhydride, 1,2- Examples thereof include dimethyl maleic 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 thereof include thallium bromide, germanium chloride, hafnium chloride, lead chloride and lead bromide.

By the way, the above-mentioned curing catalyst may be used alone or in combination of two or more depending on the purpose. In addition to these curing catalysts, it is also possible to use those that also serve as ring-opening polymerization of the epoxy group of component (a). For example, an aluminum chelate compound is one of the preferred catalysts.

Further, in the present invention, in order to make the coating composition liquid or to reduce the viscosity,
Conventionally known solvents may be used. For example,
Examples thereof include water, lower alcohols, acetone, ethers, ketones and esters.

In addition to the components described above, various additives may be used in combination for 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 of the coating layer. In the epoxy resin, 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-based resins, melamine resins and the like.

Further, by improving the flow at the time of coating,
In order to reduce the smoothness of the coating layer and the friction coefficient of the surface of the coating layer, it is possible to use various surfactants together. For example, a block or graft copolymer of dimethylcyclohexane and alkylene oxide, a fluorochemical surfactant, etc. may be mentioned.

By the way, the coating composition of the present invention is preferably used as an anti-scratch film for a "spectacle lens" molded from a resin having a medium to high refractive index of n _e = 1.54 or more. Further, it is not limited to the plastic base material, and 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, dipping, roll coating, spray coating, or flow coating is used. For example, after applying the coating composition of the present invention to a mold, to obtain a plastic substrate having a coating layer formed by casting polymerization of a raw material to be a plastic substrate, or as another method, on the surface of the plastic substrate. After applying the coating composition of the present invention,
It is also possible to obtain a plastic substrate having a coating layer formed by bringing the coating film into contact with the mold and curing the coating film.

The thickness of the coating layer after drying is 0.3 μm to 30 μm, preferably 0.5 μm to 10 μm.
It is better to set it to μm.

The plastic substrate of the present invention is preferably the one obtained by applying the coating composition and then heating it to cure the coating composition. The heating temperature is about 5
It is 0 ° C to 200 ° C, preferably 80 ° C to 140 ° C.
It is good to carry out at ℃.

By the way, the plastic substrate of the present invention is
Preferably, polymethylmethacrylate and its copolymer, acrylonitrile-styrene copolymer, polycarbonate, cellulose acetate, polyvinyl chloride, polyethylene terephthalate, epoxy resin, unsaturated polyester resin, polyurethane resin, polymer of CR-39, etc. To use.

As the form of the plastic substrate of the present invention, preferably, a lump, a cotton material, a film or the like is used.

[0076]

【Example】

(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).

The above hydrolyzate x was added with a solvent of 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 0.01 N hydrochloric acid aqueous solution was gradually added dropwise while stirring 4 parts by weight while maintaining the temperature at 10 ° C. Immediately after dripping, stop cooling, and
Hydrolyzate y corresponding to the component was obtained.

77. As a solvent to the above-mentioned 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 Preliminary Composition D 261 parts by weight of the above-mentioned hydrolyzate y was added with 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.
Weigh and inject, and then add 200 parts by weight of commercially available titanium dioxide and antimony pentoxide composite colloid sol,
0.45 part by weight of a silicone-based surfactant was added and mixed sufficiently with stirring to obtain a coating composition (I).

The sol of the composite colloid of titanium dioxide and antimony pentoxide is a methanol-dispersed sol having a solid content of 20%, and the average particle size of the composite colloid is 10 nm.
The ratio of titanium dioxide to antimony pentoxide of this composite colloid is 100 parts by weight / 20 parts by weight (TiO ₂ / Sb ₂ O ₅ ).

Similarly, the preparative compositions C and D were weighed and poured into a glass container according to Table 1, and 200 parts by weight of the commercially available sol of the composite colloid of titanium dioxide and antimony pentoxide was added. , 0.45 part by weight of a silicone-based surfactant was added, and the mixture was sufficiently stirred and mixed to obtain a coating composition (II).

(6) Coating A commercially available polyurethane lens having a refractive index of n _e = 1.67 was coated with each of the above coating compositions (I) and (II) by the 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 the above (6) 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 following criteria were evaluated. ◎ ・ ・ ・ ・ No scratches even if rubbed very strongly. ○ ・ ・ ・ ・ No scratches even if rubbed strongly. △ ・ ・ ・ ・ If scratched strongly, it will be slightly scratched. X ... ・ Scratches even if rubbed lightly. For reference, the evaluation of the polyurethane lens not having the coating layer formed was X.

(B) Appearance An antireflection film, which is generally used as a coating layer, was formed by a vacuum vapor deposition method, and the unevenness of reflected color was visually inspected, and evaluated according to the following criteria. ◎ ・ ・ ・ ・ There is no unevenness due to the reflected color. ○ ・ ・ ・ ・ Some unevenness due to reflected color. X ...- There is significant unevenness due to the reflected color.

(C) Adhesion The surface of the coating layer was cut with a knife to form 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 base on the surface of the coating layer was peeled off, and the number of eyes of the peeled base was x, and x / 100
Expressed as In this case, the smaller the x, the better the adhesion.

(D) Dyeability The lens is put in a disperse dye bath in which three colors of 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. The results of (a), (b), (c) and (d) are shown in Table 1 above.

[0091]

[Table 1]

Further, in Comparative Example 1 in Table 1, instead of using a sol of a composite colloid of titanium dioxide and antimony pentoxide, a commercially available silica sol (average particle size: 13 ± 1 nm
And a polyurethane-based lens having a coating layer formed by a coating composition prepared by using a methanol-dispersed sol having a solid content of 20%) was similarly evaluated.

Further, in Comparative Example 2 in Table 1, instead of using a sol of a composite colloid of titanium dioxide and antimony pentoxide, a commercially available antimony pentoxide sol (average particle size: 13 nm, solid content: 20%) was used. Is a result of similarly evaluating a polyurethane lens having a coating layer formed by the coating composition prepared by using the sol).

[0094]

The coating composition of the present invention is applied to, for example, a plastic substrate to form a coating layer on the surface of which no interference fringes occur and no unevenness due to reflected color occurs. A coating composition can be obtained.

Furthermore, scratch resistance, which has been a problem in the past,
It is possible to obtain a coating composition that forms a coating layer having improved surface hardness, abrasion resistance, transparency, heat resistance, water resistance, and antistatic property.

Further, when a coating layer is formed by the coating composition of the present invention, a coating layer having a large elongation and a risk of cracks on the surface of the coating layer being significantly reduced even when the substrate is bent can be obtained. A coating layer having a large surface reflectance can be obtained.

In addition, the surface of the coating layer has good sliding characteristics (low coefficient of friction) and good adhesion to antireflection films, metal vapor deposition films and the like formed on the coating layer.

Further, the coating composition of the present invention comprises
In addition to being easy to apply and easy to use, the composition has a long pot life, and further, the shrinkage upon curing is small, and there is no problem such as curling when applied to a thin film-like substrate.

In addition, the general formula; M [CH ₂ N (CH ₂ CO
By incorporating a metal complex compound represented by O) ₂ ] ₂ Na _c , the curing time of the composition is shortened, and a coating composition capable of efficiently forming a coating layer having a three-dimensional network structure is obtained. be able to.

Further, the plastic base material 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 the antireflection film is formed on the coating layer of the plastic base material, the reflection color does not occur, so that it is possible to obtain a plastic base material that does not cause color unevenness due to the influence of the reflection color.

The plastic substrate of the present invention has scratch resistance,
It has improved surface hardness, abrasion resistance, transparency, heat resistance, water resistance, and antistatic properties. Furthermore, the reflectance of the plastic substrate surface is large, and the sliding property of the surface is good (friction coefficient is It is low), and the adhesiveness is good with an antireflection film, a metal vapor deposition film and the like formed on the surface of the plastic substrate.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kazuo Konishi 3 2-3 Marunouchi, Chiyoda-ku, Tokyo Inside Nikon (72) Inventor Toru Yatsushiro 3 2-3 Marunouchi, Chiyoda-ku, Tokyo Stock company Nikon

Claims (4)

[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 6 carbon atoms or 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, and b is 0 to
2 and a + b is 1 or 2. And a hydrolyzate thereof, and (b) a sol of a composite colloid of titanium oxide and antimony oxide. 2. The general formula; M [CH ₂ N (CH ₂ COO).
₂ ] ₂ Na _c A metal complex compound (provided that
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 1, further comprising: 3. On the surface of a plastic substrate, (a) a general formula; R ¹ _a R ² _b Si (OR ³ ) _{4- (a + b)} (wherein R is
¹ is a C 4-14 having a functional group or an unsaturated double bond
R ² is a hydrocarbon group having 1 to 6 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
Is 0 or 1, b is 0 to 2, and a + b is 1
Or 2. And a hydrolyzate thereof, and (b) a sol of a composite colloid of titanium oxide and antimony oxide, a coating layer formed mainly containing the sol. 4. The plastic substrate according to claim 3, wherein
The coating layer has a general formula: M [CH ₂ N (CH ₂
COO) ₂ ] ₂ Na _c (where M is Zn, Mn, Mg, Fe, Cu, C)
o, Ca, Bi and Al, and c is 1 or 2. )
A plastic base material containing: