JPH08239627A - Coating composition for optical plastic molding - Google Patents

Abstract

PURPOSE: To obtain a coating compsn. which can sufficiently protect an optical plastic molding from light degradation, esp. ultraviolet degradation. without detriment to the optical functions of the molding even when the molding has a high refractive index. CONSTITUTION: This compsn. contains. as the essential components. 1 pt.wt. hydrolyzed silane compd., 0.2-5 pts.wt. fine composite titanium oxide particles having particle sizes of 1-100nm and formed by integrally bonding 0.1-40wt.% (based on titanium oxide) zirconium oxide to titanium oxide, 0.02-0.5 pt.wt. unsatd. or satd. polycarboxylic acid or its anhydride, and 0.01-0.2 pt.wt. thermosetting catalyst.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a coating composition for optical plastic moldings.

Here, the optical plastic molded product means a plastic molded product used for spectacle lenses, camera lenses, and other optical components.

Next, a list of correspondence between metal oxides and chemical formulas in the present specification is shown.

[0004] Titanium oxide ... Ti0 _2, zirconium oxide ... ZrO _2, a silicon oxide ... SiO ₂ Incidentally, the blending unit and the composition ratio in the following description, the weight unless otherwise specified. Further, “mμ” indicating the particle size is “nm” in SI unit
That is.

[0005]

2. Description of the Related Art Optical plastic molded articles are expected to be used in various fields because of their properties such as light weight, excellent workability and impact resistance. However, there is a certain limit due to poor scratch resistance, light resistance, heat resistance and the like. The hardness, scratch resistance, and light resistance tend to decrease as the refractive index increases.

In order to solve these problems, it is common practice to apply a hard coat to an optical plastic molded product.

As a coating composition for a hard coat, the present inventors have previously made a coating composition for a dyeable optical plastic molded article comprising an epoxy group-containing silane compound, a carboxylic acid, and a curing agent. And partially put into practical use (see Japanese Patent Publication No. 57-42665).

However, when the coating composition is applied to an optical plastic molded product having a high refractive index (refractive index of 1.6 or more), since the refractive index of the coating film is around 1.50, there is no optical interference. It was found that the optical function of the molded product was hindered.

In order to deal with this, the present inventors have
Optical coating composition for optical plastic moldings with high refractive index (refractive index of 1.6 or more) --- epoxy group-containing silane compound, titanium oxide-based composite fine particles = silicon oxide / titanium oxide are generally bonded Of fine particles, carboxylic acids, and a curing agent were proposed (Japanese Patent Laid-Open No. 5-1258).
No.

The coating composition is applied to an article to be coated (plastic molded article) and cured to suppress optical interference between the optical plastic molded article and the coating film (does not impair the optical function). It has the effect of improving the light resistance of plastic molded products.

[0011]

However, the titanium oxide-based composite fine particles suppress the yellowing of the coating film itself in a long-term use (accelerated weathering test) by suppressing the optical activity of titanium oxide. It was possible, but it turned out that it was still insufficient. That is, it was found in the ultraviolet resistance test that problems such as deterioration of the coating film were likely to occur.

In view of the above, the present invention suppresses the light interference of the coating film (without impairing the optical function) even in the case of an optical plastic molded article having a high refractive index, and the ultraviolet light of the coating film. An object of the present invention is to provide a coating composition for an optical plastic molded product, which can suppress deterioration and sufficiently protect the plastic molded product itself from photodegradation and the like.

[0013]

The present invention is to solve the above-mentioned problems by the following constitution.

(1) The coating composition for an optical plastic molded article according to claim 1 is characterized by containing the following essential components in the following composition.

(A) Hydrolyzate of silane compound ... 1 part,
(B) Titanium oxide-based composite fine particles in which zirconium oxide is integrally bonded to titanium oxide in a weight composition of zirconium oxide / titanium oxide = 0.001 to 0.400 and the particle size is 1 to 100 mμ. 2 to 5 parts, (C) unsaturated or saturated polycarboxylic acid or acid anhydride thereof ...
0.02 to 0.5 part, (D) thermosetting catalyst ... 0.01 to
0.2 part.

(2) The coating composition for an optical plastic molded article according to claim 1 is the same as in claim 1, wherein the component (B) is "titanium oxide contains zirconium oxide and silicon oxide, zirconium oxide / titanium oxide = 0. 001 to 0.400, silicon oxide / titanium oxide = 0.073 to 1.133 in a weight composition ratio, which are integrally bonded and have a particle size of 1 to 100 m.
μ titanium oxide-based composite fine particles ”.

[0017]

[Detailed description of means]

A. Hydrolyzate of silane compound: (1) The silane compound is not particularly limited,
It is desirable to use an epoxy group-containing silane compound represented by the following general formula as an essential component.

General formula: R _a ¹ R _b ² Si (OR ³ ) _{4- (a + b)} (wherein R ¹ is an organic group containing an epoxy group having 2 to 8 carbon atoms,
R ² is a hydrocarbon group having 1 to 3 carbon atoms, a halogen hydrocarbon group, an aryl group, and R ³ is an alkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group, or an acyl group. Also, a = 1, b = 0, 1 or 2. ) Specific examples of the silane compound are shown below.

[Glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, glycidoxymethyltripropoxysilane, glycidoxymethyltributoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycid Xyethyltriethoxysilane, α-glycidoxyethyltripropoxysilane, α
-Glycidoxyethyltributoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, β-glycidoxyethyltripropoxysilane, β-glycidoxyethyltributoxysilane, α -Glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, α
-Glycidoxypropyltripropoxysilane, α-glycidoxypropyltributoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, β-glycidoxypropyltripropoxysilane, β -Glycidoxypropyltributoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltributoxysilane, α
-Glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, α-glycidoxybutyltripropoxysilane, α-glycidoxybutyltributoxysilane, β-glycidoxybutyltrimethoxysilane, β -Glycidoxybutyltriethoxysilane, β-glycidoxybutyltripropoxysilane, β
-Glycidoxybutyltributoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltripropoxysilane, γ-glycidoxybutyltributoxysilane, Sidoxymethylmethyldiethoxysilane,
Glycidoxymethylmethyldiethoxysilane, glycidoxymethylmethyldipropoxysilane, glycidoxymethylmethyldibutoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, α- Glycidoxyethylmethyldipropoxysilane, α-glycidoxyethylmethyldibutoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyldiethoxysilane, α-glycidoxypropylethyldimethoxysilane Α-glycidoxypropylethyldiethoxysilane, β-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldipropoxysilane, γ-glycidoxypropylethyldibutoxysilane. (2) As a silane compound other than the above, it is desirable to use a tetraalkoxysilane represented by the following general formula in combination.

General formula Si (OR ¹ ) ₄ (In the formula, R ¹ is an alkyl group or an alkoxyalkyl group.) Specific examples of the tetraalkoxysilane are shown below.

"Tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetramethoxymethylsilane tetraethoxyethylsilane, tetrapropoxypropylsilane, tetrabutoxybutylsilane." (3) Epoxy group represented by the general formula The contained silane compound has abrasion resistance, dyeability, impact resistance, transparency, hot water resistance,
Plasticity and the like are imparted to the coating film (hard coat), and tetraalkoxysilane represented by the general formula imparts abrasion resistance to the coating film. The silane compound represented by tetraalkoxysilane is less likely to impart hot water resistance and plasticity to the coating film than the silane compound containing an epoxy group. For this reason, the coating composition of the present invention uses the epoxy group-containing silane compound alone or in combination as the silane compound. In this case, the composition ratio of both silane compounds is 1 part with respect to the former.
The latter is desirably 0.1 to 2 parts.

(4) Hydrolysis of the silane compound is carried out with pure water containing an alkoxy group or an acidic aqueous solution such as a dilute hydrochloric acid aqueous solution. It is also possible to carry out hydrolysis after mixing the silane compound and the solvent.

As the solvent, lower alcohols,
Examples include ketones, ethers, and toluene, xylene and monofunctional epoxies. Further, when the reaction of the initial condensate is advanced in a short time according to the purpose, 50
Reflux at ８０80 ° C. for 5-8 h. If performed at room temperature, leave for 24 to 84 h.

B. Titanium oxide-based composite fine particles: (1) Titanium oxide-based composite fine particles are those in which zirconium oxide is integrally bonded to titanium oxide, or those in which zirconium oxide and silicon oxide are integrally bonded to titanium oxide. The blending amount is 0.2 to 5 parts (preferably 0.5 to 3 parts) with respect to 1 part of the hydrolyzate of the silane compound.

If the amount of the titanium oxide-based composite fine particles is less than 0.2 part, it cannot be expected that the coating film has a near-UV blocking effect, and if it exceeds 5 parts, the coating film is whitened and the coating film is scratch resistant. Problems such as deterioration of the property are likely to occur.

The particle size of the composite part particles is from 1 to 100.
mμ (preferably 2 to 60 μm). If it is less than 1 μm, it cannot be expected to improve the scratch resistance and the refractive index of the coating film, and
If it exceeds 00 μm, the problem of coating whitening is likely to occur.

(2) The bonding mode of titanium oxide with zirconium oxide and silicon oxide is a chemically bonded complex oxide type, zirconium oxide, a solid solution type in which silicon oxide is uniformly dissolved in titanium oxide, etc. There is.

The titanium oxide-based composite fine particles can suppress the optical activity without impairing the characteristics of high refractive index as compared with the conventional fine particles of titanium oxide alone. Therefore, it is possible to reduce the deterioration effect of both the coating film and the object to be coated (optical plastic molded product) due to near ultraviolet rays.

The suitable composition ratio of the titanium oxide-based composite fine particles is zirconium oxide / titanium oxide = 0.001 to 0.40.
It is set to 0 (desirably 0.05 to 0.20). 0.00
When it is less than 1, the optical activity of titanium oxide can hardly be suppressed. For this reason, deterioration of the optical plastic molded article substrate and the coating film itself are promoted, and yellowing poor adhesion is likely to occur.
If it exceeds 0.400, the refractive index of the coating film will decrease, causing optical interference with high-refraction (refractive index of 1.6 or more) optical plastic molded products, and used as a coating film for optical plastic molded products. Is significantly limited.

It is to be noted that, in addition to zirconium oxide, silicon oxide is bound to the titanium oxide-based composite fine particles to increase the compatibility with the silane compound when preparing a coating composition. At the same time, the light resistance is also improved.

In this case, the suitable composition ratio of the titanium oxide composite fine particles is zirconium oxide / titanium oxide = 0.001.
˜0.400 (preferably 0.05 to 0.20), and silicon oxide / titanium oxide = 0.073 to 1.133 (preferably 0.15 to 0.70). If the composition ratio of silicon oxide is less than 0.073, the effect of increasing the miscibility with the silane compound cannot be expected, and therefore the extension of the pot life of the paint cannot be expected. On the other hand, when it exceeds 1.133, the effect of improving the refractive index of the titanium oxide coating film is hindered, and it becomes difficult to cope with high refraction.

(3) The method for producing the titanium oxide-based composite fine particles is carried out, for example, by a method similar to the method described in JP-A-2-178219.

In the case of the combination of zirconium oxide / titanium oxide, a hydrated titanium oxide sol and a hydrated zirconium oxide sol are prepared by a conventional method, peptized with an acid, and then hydrogen peroxide is added and dissolved. Hydrolyze at high temperature.

In the case of the combination of titanium oxide / zirconium oxide / silicon oxide, a hydrated zirconium oxide sol and a hydrated titanium oxide sol are prepared, peptized with an acid, and then hydrogen peroxide is added to dissolve the sol. Add an aqueous acid solution and hydrolyze at high temperature. The silicic acid dispersion is prepared, for example, by dealkalizing an alkaline silicic acid aqueous solution.

The hydrolyzate is a dispersion of fine particles. It is desirable that this fine particle dispersion liquid be subjected to a purification treatment by an ion exchange method, a reverse osmosis method, an ultrafiltration method, or a vacuum evaporation method.

(4) The titanium oxide composite fine particles are preferably surface-modified with a silane coupling agent before use. By modifying the surface of the titanium oxide-based composite fine particles in this way, the miscibility with the silane compound is further improved, and the physical properties of the coating film are favorably affected, such as the improvement of scratch resistance.

Here, the surface modification means a treatment for improving the dispersibility of the composite fine particles by blocking the hydroxyl groups remaining in titanium oxide, zirconium oxide and silicon oxide with a silane coupling agent.

Examples of the silane coupling agent (surface modifier) include the following.

“Tetramethoxysilane, methyltrimethoxysilane, trimethylchlorosilane, vinyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane.” As the surface modification method, , Can be carried out in a conventional manner. For example, immersion is performed in an alcohol solution in which the above-mentioned organic silane compound is dissolved.

C. Polyhydric carboxylic acids: (1) The polyhydric carboxylic acids include both saturated and unsaturated, and also include their acid anhydrides. The blending amount is 0.02 to 0.5 with respect to 1 part of the hydrolyzate of the silane compound.
Parts (preferably 0.05 to 0.4 parts).

The polyvalent carboxylic acids condense the silanol groups after the hydrolysis of the silane compound. For this reason,
Introducing a carboxyl group on the side chain of polysiloxane,
The coating can be dyed, and a coating film having excellent heat resistance, hot water resistance, antistatic property, abrasion resistance and surface hardness can be obtained.
In addition, the polyvalent carboxylic acids have a co-catalyst action that promotes the catalytic action of the thermosetting catalyst described below.

The polycarboxylic acid content is 0.02.
If the amount is less than 0.5 part, improvement of hot water resistance, abrasion resistance and surface hardness of the coating film cannot be expected, and if the amount exceeds 0.5 part, the polyvalent carboxylic acid itself blooms and may impair the appearance when the coating film is formed. There is.

(2) Specific examples of polycarboxylic acids are shown below.

"Maleic acid, maleic anhydride, fumaric acid, fumaric anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, malic acid, malic anhydride, tetrahydrophthalic acid, nadic acid, chloromaleic acid , Het acid (chlorendic acid), trimellitic acid, trimellitic acid anhydride, pyromellitic acid, pyromellitic acid anhydride. "Among these, maleic acid, itaconic acid, trimellitic acid and trimellitic acid anhydride are desirable.

D. Thermosetting Catalyst: (1) The thermosetting catalyst acts as a catalyst for the epoxy group polymerization reaction and the silanol group condensation polymerization reaction in the silane compound and increases the degree of crosslinking of the coating film resin.

The amount of the thermosetting catalyst compounded is 0.01 to 0.2 part (preferably 0.02 to 0.15 part) per 1 part of the hydrolyzate of the silane compound. 0.0
If it is less than 1 part, it is difficult to impart sufficient hot water resistance, abrasion resistance and surface hardness to the coating film, and if it exceeds 0.2 part, the thermosetting catalyst itself is liable to bloom to impair the appearance of the coating film.

(2) Examples of the thermosetting catalyst include:
An imidazole compound represented by the following general formula can be used.

[0048]

Embedded image

(However, R ¹ is H or a cyanoalkyl group having 1 to 3 carbon atoms, R ² is hydrogen, a phenyl group or an alkyl group having 1 to 3 carbon atoms, R ³ is hydrogen, or 1 carbon atom ~ 3
R ⁴ represents hydrogen, a hydroxymethyl group, or an alkoxyalkyl group having 1 to 3 carbon atoms, an alkyl group, a cyanoalkyl group, an alkoxyalkyl group, and a hydroxymethyl group.

Specific examples of the imidazole compound are shown below.

"2-Methylimidazole, 2-ethylimidazole, 2-ethyl-4-ethylimidazole, 2
-Propylimidazole, 2-propyl-4-methylimidazole, 2-propyl-4-ethylimidazole,
2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-cyanomethyl-2-methylimidazole, 1-cyanoethyl-2,4-dimethylimidazole, 1-cyanoethyl-2-propylimidazole, 1
-Cyanoethyl-2-phenylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 1-cyanoethyl-2-phenyl-4,5-dicyanoethoxyimidazole. Among these, 1-cyanoethyl-2-methylimidazole in which the substituent R ¹ is a cyanoalkyl group, 1
-Cyanoethyl-2,4-dimethylimidazole, 1-
Cyanoethyl-2-propylimidazole, 1-cyanoethyl-2-phenylimidazole and 1-cyanoethyl-2-phenyl-4,5-dicyanomethylimidazole are preferable.

Examples of other thermosetting catalysts other than the above imidazole-based catalysts include dicyanamide, acetylacetone metal salts represented by the following general formula, and Reineck's salts.

General formula: M (CH ₂ COCH ₂ COCH
₃ ) _n (where M is Zn (II), Co (III), Fe (III
), Cr (III), Al (III); n is a number corresponding to the valence of M: 2 or 3) Preparation and application of coating composition: (1) The coating composition of the present invention preferably contains various additives in order to improve each performance of the coating film.

For example, as an additive for improving the adhesion and the dyeability to the article to be coated (optical plastic molded article), a polyolefin epoxy resin, a polyglycidyl ester resin, epichlorohydrin and bisphenol A are used.
Polycondensation products, glycidyl methacrylate, acrylic copolymers, and the like.

A benzophenone-based material is used as an ultraviolet absorber for preventing ultraviolet rays from reaching the object to be coated.
There are UV absorbers such as benzotriazole type and phenol type.

Further, as a leveling agent for improving the smoothness of the coating film, there are a silicone type surfactant and a fluorine type surfactant.

(2) As a coating method, a brush coating method, a roll coating method, a spray method, a spin method, a dipping method or the like which is usually used can be used. At this time, the dry coating film thickness is 0.5
It is applied so as to be ˜20 mμ (desirably 1 to 7 μm).

Examples of the pretreatment method for the object to be coated include degreasing cleaning with an acid-alkali detergent solvent, plasma processing, ultrasonic cleaning and the like.

The coating composition of the present invention is cured by heat treatment. 60 to 1 depending on the characteristics of the object to be coated
A temperature range of 50 ° C gives good results, especially 80-1
10 ° C is desirable. Further, it is preferable that the heating is performed for 2 to 3 hours or more.

(3) As the plastic material of the article to be coated (optical plastic molded article) to which the coating composition of the present invention can be applied, polymethylmetallate, polycarbonate,
Examples include polystyrene, polyester, polyurethane, polythiourethane, aliphatic allyl carbonate, aromatic allyl carbonate, and the like.

[0061]

The present invention provides a coating composition for an optical plastic molded article having a high refractive index by applying it to an article to be coated (plastic molded article) and curing it by the above constitution. It is possible to suppress the light interference between the molded product and the coating film (does not hinder the optical function), and to suppress the ultraviolet deterioration of the coating film, thereby sufficiently protecting the plastic molded product from the light deterioration and the like.

That is, the present invention provides a coating composition for an optical plastic molded article, which is more polyvalent than a conventional coating composition of the same kind, with good reactivity to an organosilicon compound as a skeleton and special titanium oxide-based composite fine particles. Weather resistance, UV resistance, impact resistance, adhesion to metal vapor deposition film, transparency, heat resistance, hot water resistance, dyeability, abrasion resistance, chemical resistance, depending on the combination of carboxylic acid and its anhydride and curing agent. It is possible to provide the coating film with properties and plasticity, and to provide a coating film corresponding to the refractive index of the optical plastic molded product.

[0063]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples. The present invention is not limited to the following examples.

A. The object to be coated and the curing agent used in each example are as follows.

(I) Articles to be coated in each Example Examples 1 to 3 Comparative Examples 1 to 3: Polycarbonate molded articles ("Lexan" manufactured by General Electric Co.) were used.

Examples 4-10, Comparative Examples 4-6, 7
9: Glasses cast by casting with a plastic composition (monomer composition: diallyl diphenate 90 parts, urethane acrylate 10 parts ("NKU-200AX" manufactured by Shin-Nakamura Kogyo Co., Ltd.), diisoproperperoxydicarbonate 4 parts) Lens (80mmφ, center thickness 2mm, frequency: -2.00
D) was used.

(Ii) Curing agent In each example, the following symbols are used.

IM-4: 2-Ethyl-4-methylimidazole IM-8: 2-Phenyl-4-methylimidazole IM-12: 1-Cyanoethyl-2-methylimidazole B.I. Each performance test of the coating film was performed as follows. The test results are shown in Table 1 (Examples 1 to 3 and Comparative Examples 1 to 3) and Table 2 (Examples 4 to 10 and Comparative Examples 4 to 8), respectively (i) Abrasion resistance test # 0000 steel wool The surface was rubbed with and judged as follows.

A There is almost no scratch.

B Slightly scratched.

C Many scratches are attached.

(Ii) Surface hardness test According to JISK-5400, a pencil scratch tester (load 1
kg) and the highest pencil hardness without scratching is indicated.

(Iii) Appearance Presence / absence of interference fringes A fluorescent lamp (3 wavelength type neutral white) [trade name; Lupica Ace 15W: Mitsubishi Electric Corp.] is placed in the blackened background and fluorescent lamp is illuminated on the surface of the object. It was judged by the presence or absence of a light interference color (rainbow pattern) formed on the surface of the object by reflection.

A No light interference color is observed.

B A slight light interference color is recognized.

C A light interference color is clearly recognized.

Presence or absence of fog The fluorescent light was transmitted through the object under the above conditions, and the presence or absence of the object was fogged.

(Iv) Adhesion test In accordance with JIS D-0202, 100 squares were prepared, and a peeling test was conducted 3 times with a cellophane adhesive tape, and the number of remaining squares is shown.

(V) Hot water resistance test Judgment was made by immersing in boiling water at 100 ° C. for 1 hour and judging from the appearance and the adhesion of the coating film.

(Vi) Weather resistance test An accelerated weather resistance test ("Sunshine Super Long Life Weather Meter" manufactured by Suga Test Co., Ltd.) was exposed for 400 hours, and the presence or absence of abnormality such as appearance was judged.

(Vii) UV Resistance Test Accelerated UV resistance tester (Suga Test Co., Ltd. "Super Xenon Accelerated Weathering Tester" exposed for 200 hours, abnormal appearance etc .: confirmation of yellowing, etc .: the coating film (Iv) Judgment was made based on the results of the adhesion test and the like.

(Viii) Dyeability test 0.4 parts of a dye ("Danix Brown 2B-FS" manufactured by Mitsubishi Kasei Co., Ltd.) and a surfactant (Nippon Senka Kogyo Co., Ltd.) were added to 100 parts of hot water at 90 ° C. ) "GNK-01")
After adding 0.4 part and stirring, the object is immersed for 5 minutes,
The extinction ratio at 550 nm was measured. The extinction ratio is measured by a luminous transmittance meter ("Core, SMS-" manufactured by UJIKODEN).
1)).

O Light attenuation rate of 30% or more B Light attenuation rate of 20% or more and less than 30% X Light attenuation rate of less than 20% C.I. Examples and comparative examples were performed as follows.

<Examples 1 to 3> (1) Preparation of hydrolyzate of silane compound 0.01 part of 125 parts of γ-glycidoxypropyltrimethoxysilane and 110 parts of tetraethoxysilane, and 0.01N HCl.
Add 54 parts of aqueous solution and stir at 60 rpm for 1 h
Stir. Thereafter, methyl alcohol 92 was used as a diluent.
Part, 200 parts of methyl ethyl ketone, and then 1
After stirring for h, it was left at room temperature for 24 hours. Hereinafter, this hydrolyzate is referred to as “HG-40”.

[0085] (2) Preparation HG-40 290 Titanium oxide based on parts composite fine particles "Optolake -1120Z (S-25)" of the coating composition Catalysts & Chemicals Industries Co., Ltd. _{(TiO 2 / ZrO 2 = 95.4} / 4 .6, SiO ₂ /
TiO ₂ = 34/66, particle size 15 mμ, solid content concentration 30
%, Dispersion solvent: methyl alcohol, surface modifier: tetraethoxysilane) 45 parts and stirred. Then, 12 parts of itaconic acid was added and dissolved by stirring at 120 rpm for 1 h, and 4 parts of each of the imidazole compounds shown in Table 1 as a curing agent were added and stirred for 2 h to obtain a coating composition.

(3) Pretreatment of coated object The coated object was immersed in a warm bath of 0.05% of alkali detergent (Shiraron HS manufactured by Hakusui Henkel Kogyo Co., Ltd.) at a temperature of 50 ° C. for 3 minutes and then pulled up. It was washed with water and oven dried.

(4) Formation of Coating Film Each coating composition was applied to each of the above-mentioned pretreated objects by a dipping method (pulling speed: 70 mm / min),
The coating was cured (condition: 100 ° C. × 2 h) to form a coating film on the PC surface.

Examples 4 to 6 (1) Preparation of hydrolyzate of silane compound 200 parts of γ-glycidoxypropyltrimethoxysilane, 35 parts of tetraethoxysilane and 92 of methyl alcohol
0.01 N and 54 parts of HCl were added to the parts, and the mixture was stirred with a stirrer at 60 rpm for 2 hours. Thereafter, 200 parts of isopropyl alcohol was added as a diluent, and the mixture was further stirred for 2 hours, and then left at room temperature for 24 hours. Hereinafter, this hydrolyzate is referred to as "HG-41".

[0089] (2) Preparation HG-41 290 Titanium oxide based on parts composite fine particles "Optolake -1120Z (S-7)" of the coating composition Catalysts & Chemicals Industries Co., Ltd. _{(TiO 2 / ZrO 2 = 98.6} / 1 .4, SiO ₂ /
TiO ₂ = 23/77, particle size 15 mμ, solid content concentration 30
%, Dispersion solvent: methyl alcohol, surface modifier: ethyl silicate) and after stirring, 12 parts of polyvalent carboxylic acids shown in Table 2 were added and dissolved. After that, 5 parts of aluminum acetylacetone was added, and a leveling agent (“Florard FC-430” manufactured by Sumitomo 3M)
0.5 part was added to obtain a coating composition.

(3) Pre-treatment of coating object Pre-treatment of coating object is a caustic soda aqueous solution (10% temperature 5
After immersing in (0 ° C.) for 10 minutes, washing with water for 5 minutes, further immersing in pure water for 3 minutes, and oven drying.

(4) Formation of coating film Each coating composition was applied to each of the above-mentioned pretreated objects by a dipping method (liquid lowering speed 90 mm / min) and cured (condition: 100 ° C. × 2 h). Then, a coating film was formed on the surface of the article to be coated.

<Example 7> HG ~ 40 290 parts of titanium oxide-based composite fine particles "Optlake-1120Z (S-
7) ”manufactured by Catalyst Kasei Kogyo Co., Ltd. (TiO ₂ / ZrO ₂ = 98.
6 / 1.4, SiO ₂ / TiO ₂ = 23/77, particle size:
15 mμ, solid content concentration 30%, dispersion solvent: methyl alcohol, surface modifier: γ-glycidoxyppropyltriethoxysilane) 90 parts were added and stirred, then 10 parts of trimellitic anhydride were added and dissolved, and then dicyandiamide 5 parts were added, and a leveling agent (manufactured by Nippon Yunika Kogyo KK
2 parts of ETL-77 ") was added to obtain a coating composition. The pretreatment of the coated object and the coating film formation were performed in the same manner as in Examples 4 to 6.

<Embodiment 8> The eyeglass lens prepared in Embodiment 7 was subjected to a vacuum deposition method from the lens surface side to SiO ₂ λ.
/ 4, ZrO ₂ λ / 4, SiO ₂ λ / 4, ZrO ₂ λ /
4, SiO ₂ λ / 4, ZrO ₂ λ / 4, SiO ₂ λ /
2. Vapor deposition was performed by an optical design consisting of (λ = 520 nm).

Example 9 Example 9 was repeated except that 10 parts of trimellitic anhydride in Example 7 was replaced with 12 parts of itaconic acid.

<Example 10> Glasses obtained in Example 9
The lens is made of SiO from the lens surface side by vacuum evaporation. ₂ λ
/ 4, TiO₂ λ / 4, SiO₂ + TiO₂ λ / 4, S
iO₂ For optical design consisting of λ / 8, (λ = 520 nm)
Vapor deposition was performed.

[Comparative Example] In order to see whether or not the titanium oxide-based composite fine particles in the examples are due to the improvement of the film performance of the coating film, titanium oxide-based composite fine particles (titanium oxide, iron oxide and silicon oxide). Was changed to titanium oxide fine particles or titanium oxide / silicon oxide composite fine particles, and the film performance was observed.

<Comparative Example A. 1-3> In Examples 1 to 3, titanium oxide-based composite fine particles-1 were used as titanium oxide fine particles "Sunvale 11-1530" manufactured by Catalysts & Chemicals Industries Co., Ltd. (TiO ₂ solid content concentration 30%, particle diameter 15 mμ, dispersion solvent. : Methyl alcohol, surface modifier: tetraethoxysilane).

<Comparative Example A. 4-7, 9> Examples 4-7,
In 9, the same procedure was performed except that the titanium oxide composite fine particles-2 and 3 were replaced with the same titanium oxide fine particles as in Comparative Examples 1 to 3.

<Comparative Example B. 1-3> In Examples 1 to 3, the titanium oxide-based composite fine particles-1 were replaced with titanium oxide / silicon oxide composite fine particles "Queen Titanic-1.
1-1 ”manufactured by Catalysts & Chemicals Industry Co., Ltd. (TiO ₂ / SiO ₂ = 70
/ 30, particle size: 15 mμ, solid content concentration 30%, dispersion solvent: methyl alcohol, surface modifier: tetraethoxysilane).

<Comparative Example B. 4-7, 9> Examples 4-7,
In Comparative Example B.9, the titanium oxide-based composite fine particles-2 were used. The same procedure was carried out except that the same titanium oxide & silicon oxide as in 1 to 3 was replaced by composite fine particles.

D. Tables 1 and 2 show the results of each test in the above Examples and Comparative Examples. It can be seen that each example is superior to each comparative example in most of the physical properties. The yellowing when the titanium oxide-based fine particles were contained was greenish.

[0102]

[Table 1]

[0103]

[Table 2]

Note * (1) Hot water resistance test not conducted. This is because the deposited film itself has no durability in a hot water test (100 ° C. × 1 h).

* (2) No dyeability test was conducted. The deposited film itself cannot be dyed.

Claims (4)

[Claims] 1. A coating composition for an optical plastic molded article, which comprises the following essential components in the following composition: (A) Hydrolyzate of silane compound ... 1 part by weight, (B) Zirconium oxide is integrally bonded to titanium oxide at a weight composition ratio of zirconium oxide / titanium oxide = 0.001 to 0.400, Titanium oxide-based composite fine particles having a particle size of 1 to 100 mμ: 0.2 to 5 parts by weight, (C) unsaturated or saturated polyvalent carboxylic acid or acid anhydride thereof: 0.02 to 0.5 part by weight , (D) Thermosetting catalyst ... 0.01 to 0.2 parts by weight. 2. A coating composition for an optical plastic molded article, which comprises the following essential components in the following composition: (A) Hydrolyzate of silane compound ... 1 part by weight, (B) Zirconium oxide and silicon oxide in titanium oxide,
Zirconium oxide / titanium oxide = 0.001 to 0.40
0, silicon oxide / titanium oxide = 0.073 to 1.133
The weight composition ratio of the particles is integrally combined, and the particle size is 1 to 1
Titanium oxide-based composite fine particles having a particle size of 00 m. Curable catalyst: 0.01 to 0.2 parts by weight. 3. The silane compound according to claim 1, wherein the silane compound is represented by the general formula: R _a ¹ R _b ² Si (OR ³ ) _{4- (a + b)} (wherein R ¹ has 2 to 8 carbon atoms ₎ . An organic group containing an epoxy group,
R ² is a hydrocarbon group having 1 to 3 carbon atoms, a halogenated hydrocarbon group, an aryl group, and R ³ is an alkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group, or an acyl group. Also, a = 1 and b = 0, 1 or 2. ] The coating composition for optical plastic molded articles characterized by being shown by these. 4. The coating composition for optical plastic moldings according to claim 1, wherein the titanium oxide-based composite fine particles are surface-modified with a silane coupling agent.