JPH07168002A - Coating composition and plastic substrate - Google Patents

Abstract

(57) [Abstract] [Purpose] To provide a composition which forms a hard coating film having good physical properties and having no interference fringes as a plastic lens and having uniform anti-color, and a plastic substrate coated with the composition. . [Structure] (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 an organic group having 1 to 6 carbon atoms or a halogenated organic group. 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. ) A coating composition comprising an organosilicon compound represented by the formula (1) or a hydrolyzate thereof, and (b) a sol of a composite colloid of titanium oxide and zirconium oxide.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a coating composition for plastic moldings and a plastic substrate coated with this composition.

[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 enough to devise the components of the plastic base material to improve the conventional plastic lens base materials. No solution to the drawbacks has been obtained.

Therefore, a coating composition for improving the performance of a plastic substrate has been proposed by disposing 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. 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. 52-1261) is proposed as a coating composition which is close to an inorganic type and gives a hard coating film. .

However, although the coating layer formed by the above coating composition considerably improves the performance of the plastic substrate, it has a drawback of low scratch resistance (easiness of scratching). For this reason, 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 of the coating layer (JP-A-53-53). No. 111336) has been proposed.

A coating composition using titanium oxide instead of silica sol (JP-A-63-27)
5682) has also been proposed. This is a coating composition containing an organosilicon compound represented by the following general formula or a hydrolyzate thereof (hereinafter referred to as component (a)) and titanium oxide (component (b)).

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

[0007]

However, when a coating layer is formed on the surface of a plastic substrate by the above-mentioned coating composition containing silica sol,
Interference fringes are generated on the surface of the plastic base material, which causes a problem that the appearance of the plastic base material is deteriorated. Further, the titanium oxide sol is also preferable because it can exist as a sol by itself and has a high refractive index, but when it is used as a composition component of a coating composition, it is stable with the component (a). There was the problem of not being able to exist.

Further, when the coating layer is formed from the coating composition containing the component (a) and the titanium oxide sol, problems occur in the water resistance and weather resistance of the coating layer. Moreover, 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 has been made in view of the above circumstances, and solves the problems of the conventional coating composition and the plastic substrate coated with the conventional coating composition.
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 an object of the present invention to provide a new coating composition which does not cause color unevenness due to a reflection color caused by forming an antireflection film on a coating layer, and a plastic substrate to which the new coating composition is applied.

[0010]

In order to solve the above problems, the invention according to claim 1 of the present application provides (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, R ² is an organic group having 1 to 6 carbon atoms or a halogenated organic group, and 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 hydrolyzate thereof, and (b) a sol of a composite colloid of titanium oxide and zirconium oxide.

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 ] ₂ Na _e A metal complex compound (wherein M is 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: (a) a general formula; R ¹ _a R ² _b Si (OR ³ ) _{4- (a + b)} (wherein R is ¹ is a functional group or an organic group having an unsaturated double bond and having 4 to 14 carbon atoms, R ² is an organic group having 1 to 6 carbon atoms or a halogenated organic group, and R ³ is an organic group having 1 to 4 carbon atoms. 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 1 or 2. And a hydrolyzate thereof, and (b) a sol of a composite colloid of titanium oxide and zirconium oxide, a plastic substrate provided with a coating layer.

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 _e (wherein M is Zn,
Mn, Mg, Fe, Cu, Co, Ca, Bi and Al, and c is 1 or 2. ) Further comprises a plastic substrate.

[0014]

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)) and titanium oxide and zirconium oxide. Sol (hereinafter (b)
Component)), a sufficient refractive index is obtained even when a coating layer is formed on the surface of a plastic substrate, no interference fringes are generated, and the coating layer is not formed on the coating layer. It is possible to obtain a coating composition that does not cause color unevenness due to the reflected color caused by forming the antireflection film.

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 an organic group having 1 to 6 carbon atoms or a halogenated organic group, 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 1 or 2. ) Furthermore, a coating composition with improved defects such as scratch resistance, surface hardness, flexibility, transparency, antistatic property, dyeability, heat resistance, water resistance, chemical resistance, etc. Obtainable.

This is because the coating composition of the present invention contains the component (b), which is a sol of a composite colloid of titanium oxide and zirconium oxide, and therefore supplements the drawbacks when titanium oxide is used alone. This is because the desirable properties can be brought out. The sol of the composite colloid of the present invention is, for example, a colloidal solution in which fine particles of titanium oxide and zirconium oxide are dispersed in water or an organic solvent or a mixed solution of water and an organic solvent, and a suitable alkali, preferably The one that is stabilized by adding an organic amine is used.

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 proportion of titanium oxide and zirconium oxide is 2 to 100 parts by weight, preferably 5 to 50 parts by weight of zirconium oxide based on 100 parts by weight of titanium oxide, in order to make use of the advantages while compensating for each defect. Parts are used. If the ratio is smaller than this, the stability of the composite colloid becomes insufficient when mixed with the component (a), and conversely,
If the ratio is higher than this, there is a problem in the refractive index of the coating composition.

That is, for example, 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 a hydrolyzate thereof and a titanium oxide sol, there is a problem in water resistance and weather resistance of the coating layer. . Further, for example, zirconium dioxide sol has a relatively high refractive index, but it is difficult to exist as a sol by itself. When used as a composition of a coating composition, it is difficult to stably exist with the component (a) which is an organosilicon compound or a hydrolyzate thereof. However, when it becomes a composite sol with titanium oxide, the poor weather resistance of titanium oxide can be eliminated. In the coating composition of the present invention, based on the above findings, titanium oxide and zirconium oxide are present in the coating composition as a sol of a composite colloid. For this reason, it is possible to compensate for the drawbacks when the titanium oxide sol or the zirconium oxide sol is used alone, and to bring out preferable properties.

Therefore, when a coating layer is formed from the coating composition of the present invention, it goes without saying that a plastic substrate having a preferable refractive index can be obtained.
It is possible to obtain a coating composition which is stable in the presence of the component (a) and has no problems such as water resistance and weather resistance. By the way, the component (a) in the coating composition of the present invention can be of a wide variety of types, but more preferably, an organosilicon compound such as a compound whose constitution is exemplified in the following formula is used. It is a kind and is preferably used after being hydrolyzed and then dehydrated and condensed to become 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.

[0023]

[Chemical 1]

(Wherein R ⁴ is an alkyl group having 1 to 4 groups, an alkoxyalkyl group, or an acyl group, R ⁵ is a hydrocarbon group having 1 to 6 carbon atoms, a halogenated hydrocarbon group, and R ⁶ is hydrogen or a methyl group. , M is 2 or 3, p is 1 to 6, and q is 0 to 2.)

[0025]

[Chemical 2]

(R ⁷ is an alkyl group having 1 to 4 groups, an alkoxyalkyl group, or an acyl group, R ⁶ is a hydrocarbon group having 1 to 4 carbon atoms or a halogenated hydrocarbon group, 1 is 2 or 3, and r is 1 It is possible to use only one kind of the organosilicon compound, but it is possible to form a coating film for various purposes if two or more kinds of the organosilicon compounds are mixed and used. In this case, different 3
The functional 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 also called epoxysilanes. 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 if 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. Further, as the tetrafunctional organosilicon compound, for example, methyl silicate, ethyl silicate,
Isopropyl silicate, n-propyl silicate, n
-Butyl silicate, t-butyl silicate, sec-
Butyl silicate etc. are mentioned.

Furthermore, when the above-mentioned organosilicon compound is hydrolyzed and a coating composition containing the hydrolyzed compound is prepared, the reaction rate during coating film processing is increased, the effective temperature is lowered, and the efficiency is improved. Coating film processing is possible.
Further, in the case of using two kinds of compounds having the same functional number in a surrounding combination among two to four functional compounds, or in the case of using two kinds of compounds having different functional numbers in combination, they may be used together after hydrolysis, Co-hydrolysis may be performed in combination before the decomposition. Upon hydrolysis, the alcohol that becomes HOR ³ is liberated and, for example, the compound of the above formula becomes a silanol corresponding to the following structure.

[0032]

[Chemical 3]

[0033]

[Chemical 4]

This silanol is rapidly dehydrated and condensed to become an oligomer, but preferably 1 after hydrolysis.
When left (cured) for about 24 hours, this reaction will proceed sufficiently. Further, in the coating composition according to the invention described in claim 2, in the general formula: M [CH ₂ N (CH
₂ COO) ₂ ] ₂ Na _e (where M is 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. Examples thereof include calcium ethylenediaminetetraacetate and bismuth ethylenediaminetetraacetate.

These metal complex compounds may be used alone or in a mixture of two kinds. Furthermore, in the plastic substrate to be mowed according to the invention of claim 3, a layer of the coating composition according to claim 1 is formed on the surface of the plastic substrate, and interference fringes are formed on the surface of the plastic substrate. It does not occur, so it looks good. 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. Moreover, in the plastic substrate according to the invention of claim 4, in the plastic substrate of claim 3, the coating composition formed on the surface of the plastic substrate has the general formula: M [CH ₂ N (CH ₂ COO)]. ₂ ]
₂ Na _e 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 metal complex compound is obtained by polymerizing the component (a),
Since a coating film having a three-dimensional network structure is formed, it is possible to obtain a plastic substrate on which a very hard coating layer is efficiently formed.

Further, in the present invention, amines and various metal complex compounds are added, if necessary, in order to shorten the time for polymerizing the component (a) to form a coating film having a three-dimensional network structure. , A metal alkoxide, an organic metal salt, a perchlorate, an organic acid or an anhydride thereof, a Lewis acid, a metal halide or the like curing catalyst (however, a composition which impairs the stability of the coating composition is not preferable) You may use together with.

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

Further, various metal complex compounds have the general formula Al
X _n Y _3-n (wherein, X is OL (L is a lower alkyl group), Y is a general formula M ¹ COCH ₂ COM ² (M ¹ , M ²
Is a lower alkyl group) and a ligand derived from M ¹ COCHCOM 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,
Examples include chromium acetylacetonate, titanyl acetylacetonate, cobalt acetylacetonate, iron (III) acetylacetonate, manganese acetylacetonate, nickel acetylacetonate, indium acetylacetonate, and the like.

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, 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 catalysts 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, a conventionally known solvent may be used in order to make the coating composition liquid 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 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, glycidyl methacrylate and methyl methacrylate copolymer, polyol, Fiber resin, melamine resin, etc. are mentioned.

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 n _e
= 1.54 or more It is used as a scratch-preventing film of a "spectacle lens" molded from a resin having a medium to high refractive index. further,
Not only the plastic substrate, but also inorganic glass, wood, metal articles, etc. may be used.

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 50 ° C to 200 ° C, preferably 80 ° C to 140 ° C.

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. are used.

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

[0052]

The present invention will be described in more detail with reference to the following examples. Of course, the present invention is not limited to the following examples. 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 further 1 hour and 30 minutes 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 0.01N 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 ethylenediaminetetraacetic acid aluminum acetate was added as a curing catalyst, and the resulting solution was sufficiently mixed and dissolved to prepare the preliminary composition C. And (4) Preparation of Preliminary Composition D To 261 parts by weight of the above-mentioned hydrolyzate y, 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 weighed and injected into a glass container based on Table 1, and 200 parts by weight of a commercially available composite sol of titanium dioxide and zirconium dioxide was added,
0.45 parts by weight of a silicone-based surfactant was added, and the mixture was sufficiently stirred and mixed to obtain a coating composition (I).

The sol of the composite colloid of titanium dioxide and zirconium dioxide is a methanol-dispersed sol having a solid content of 20%, and the average particle size of the composite colloid is 10 n.
m to 15 nm, and the ratio of titanium dioxide to zirconium dioxide in this composite colloid is 100 parts by weight / 20.
Parts by weight (TiO ₂ / ZrO ₂ ) are used. Similarly, the pre-compositions C and D were metered into a glass container based on Table 1, and 200 parts by weight of the commercially available titanium dioxide / zirconium dioxide composite colloid sol was added.
0.45 part by weight of a silicone-based surfactant was added and mixed sufficiently to obtain a coating composition (II). (6) to a commercially available polyurethane lens coating having a refractive index of n _e = 1.67, the coating composition of the above-described (I) (II) were each coated by a dip method (pulling rate 10 cm / min), 100 ° C.
The coating film was cured by heating for 2 hours to form a coating layer. (7) Evaluation: The polyurethane-based lens forming the coating layer obtained in (6) above was subjected to the test described below to evaluate the performance of the coating layer. <Abrasion resistance test> The surface of the coating layer is steel wool #
It was rubbed with 0000 to check the scratch resistance, and evaluated according to the following criteria.

◎ …… No scratches even if rubbed very strongly. ○ …… No scratches even when strongly rubbed. △ …… Scratches a little when strongly rubbed. × …… Scratches even if weakly rubbed. For reference, the evaluation of the polyurethane lens not having the coating layer formed was x. <Appearance> An antireflection film, which is generally used as a coating layer, was formed by a vacuum vapor deposition method, and the unevenness of the reflection color was visually inspected, and evaluated according to the following criteria.

A: No unevenness due to reflected color. ○: There is some unevenness due to the reflected color. ×: Significant unevenness due to reflected color. <Adhesiveness> A 1 mm square grid (100 squares) is made on the surface of the coating layer with a knife, and then cellophane adhesive tape (product name “Cellotape” manufactured by Nichiban Co., Ltd.) is strongly adhered, and one end of the tape is used to hold 90 It was peeled off vigorously in the ° direction. After that, check how many grids on the surface of the coating layer were peeled off, and let x be the number x of grids on the surface.
It was expressed as / 100. In this case, the smaller the x, the better the adhesion. <Dyeability> The dyeability was examined by immersing the lens in a disperse dye bath in which three colors of red, yellow and blue were mixed at 90 ° C. for 30 minutes and measuring the light transmittance.

The above evaluation results are shown in Table 1.

[0059]

[Table 1]

In Comparative Example 1 of Table 1, instead of using a sol of a composite colloid of titanium dioxide and zirconium dioxide, a commercially available silica sol (having an average particle size of 13 ± 1 nm) is used.
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.

Furthermore, in Comparative Example 2 in Table 1, instead of using a sol of a composite colloid of titanium dioxide and zirconium dioxide, commercially available zirconium dioxide (a sol having an average particle size of 13 nm and a solid content of 20%) is used. The results are obtained by similarly evaluating a polyurethane lens having a coating layer formed by the coating composition prepared by using (1).

[0062]

The coating composition of the present invention is applied to, for example, a plastic substrate to form a coating layer on which no interference fringes are generated on the surface of the plastic substrate and no unevenness due to reflected color is generated. A coating composition can be obtained. Furthermore, it is possible to obtain a coating composition that forms a coating layer having improved scratch resistance, surface hardness, abrasion resistance, transparency, heat resistance, water resistance, and antistatic property, which have been problems in the past.

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 that a crack is generated on the surface of the coating layer even if the base material 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 properties (low coefficient of friction) and good adhesion to antireflection films, metal vapor deposition films, etc. formed on the coating layer.

Further, 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 a small shrinkage upon curing. There is no problem such as curling when doing. In addition, the general formula: M [CH ₂ N (CH
_{By including} a metal complex compound represented by ₂ COO) ₂ ] ₂ Na _e , 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 provided. Obtainable.

Moreover, the plastic substrate of the present invention is
Since no interference fringes are generated on the surface, it looks good and increases the 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 the plastic base material in which the color unevenness due to the influence of the reflection color does not occur. The plastic substrate of the present invention has improved scratch resistance, surface hardness, abrasion resistance, transparency, heat resistance, water resistance, and antistatic property, and further, the reflectance of the plastic substrate surface is It is large and has good surface sliding characteristics (low friction coefficient), and has good adhesiveness to antireflection films, metal vapor deposition films and the like formed on the surface of plastic substrates.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tomoya Tsujiya Marunouchi 3-chome 3-3 Chiyoda-ku, Tokyo Nikon (72) Inventor Koji Watanabe 3-chome Marunouchi Chiyoda-ku Tokyo 2-3 shares Ceremony Company Nikon

Claims (4)

[Claims] 1. (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 an organic group having 1 to 6 carbon atoms or a halogen. Is an organic group, 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. ) An organosilicon compound represented by the formula (4) or a hydrolyzate thereof, and (b) a sol of a composite colloid of titanium oxide and zirconium oxide, which is a coating composition. 2. A general formula; M [CH ₂ N (CH ₂ COO)]
₂ ] ₂ Na _e A metal complex compound (wherein M is
Zn, Mn, Mg, Fe, Cu, Co, Ca, Bi, A
1 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; R¹ _aR² _bSi (OR³)_{4- (a + b)} (R¹Is a functional group or unsaturated double bond having 4 to 4 carbon atoms.
14 organic groups, R ²Is an organic group having 1 to 6 carbon atoms or
R is a halogenated organic group³Is an alky having 1 to 4 carbon atoms
Is an alkyl group, an alkoxyalkyl group or an acyl group, and a is
0 or 1, b is 0 to 2, and a + b is 1
Or 2. ) An organosilicon compound represented by
Of (b) titanium oxide and zirconium oxide composite colloid
A coating layer containing sol is provided.
A plastic base material characterized in that 4. The plastic substrate according to claim 3, wherein
The coating layer has a general formula: M [CH ₂ N (CH ₂ CO
O) ₂ ] ₂ Na _e A metal complex compound (in the formula, M
Is Zn, Mn, Mg, Fe, Cu, Co, Ca, B
i and Al, and c is 1 or 2. ) Is contained in the plastic base material.