JP2577670B2 - Coating composition for optical plastic molded products - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a coating composition for optical plastic molded articles.

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 the correspondence between metal oxides and chemical formulas in the present specification is shown.

[0004] The titanium oxide ... Ti0 _2, iron oxide ... Fe ₂ O
_3. Silicon oxide: SiO _{2 In} the following description, the blending units and composition ratios are based on weight unless otherwise specified. Also, “mμ” indicating the particle size is
It is “nm” in SI units.

[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. 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).

[0008]

However, when the coating composition is applied to an optical plastic molded article having a high refractive index (refractive index of 1.6 or more), the refractive index of the coating film is around 1.50. Therefore, it has been found that optical interference occurs and the optical function of the molded article is hindered.

[0009] Further, a problem easily occurs in the adhesion of the coating film due to light deterioration of the optical plastic molded product itself.

[0010] In view of the above, the present invention provides an optical plastic molded article having a high refractive index without impairing the optical function of the main body and sufficiently protecting the plastic molded article itself from light deterioration and the like. An object of the present invention is to provide a coating composition for an optical plastic molded article to be obtained.

[0011]

The present invention solves the above-mentioned problems by the following constitutions.

A coating composition for an optical plastic molded article comprising the following essential components in the following composition: (A) a hydrolyzate of a silane compound: 1 part, (B) iron oxide on titanium oxide, iron oxide on titanium oxide / Titanium oxide = 0.005 to 0.1
5 having a weight composition of 5 and a particle size of 1 to 1
Titanium oxide-based composite fine particles having a particle diameter of 00 μm: 0.2 to 5
Parts, (C) unsaturated or saturated polyhydric carboxylic acids or their anhydrides: 0.02 to 0.5 parts, (D) thermosetting catalysts: 0.01 to 0.2 parts,

[0013]

[Detailed Description of Means] Hydrolyzate of silane compound: (1) As the above-mentioned hydrolyzate, an epoxy group-containing silane compound represented by the following general formula is an essential component .

[0014] 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, an alkoxyalkyl group, or an acyl group having 1 to 4 carbon atoms. Also, a = 1, b = 0, 1, or 2. Specific examples of the silane compound are described 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 preferable to use a tetraalkoxysilane represented by the following general formula in combination.

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

"Tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetramethylmethoxysilanetetraethylethoxysilane, tetrapropylpropoxysilane, tetrabutylbutoxysilane." (3) Epoxy group represented by the general formula Silane compounds are abrasion resistant, dyeable, impact resistant, transparent, hot water resistant,
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. A silane compound represented by a tetraalkoxysilane is less likely to impart hot water resistance and plasticity to a coating film than an epoxy group-containing silane compound. 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. The composition ratio of both silane compounds in this case is the former, 1 part,
The latter is desirably 0.1 to 2 parts.

(4) The hydrolysis of the silane compound is performed with an acidic aqueous solution such as pure water with an alkoxy group or a dilute aqueous hydrochloric acid 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) The titanium oxide-based composite fine particles are obtained by integrally binding iron oxide to titanium oxide, and the compounding amount thereof is based on 1 part of the hydrolyzate of the silane compound. 0.2 to 5 parts (preferably 0.5 to 3 parts).

If the content of the titanium oxide-based composite fine particles is less than 0.2 part, it is not expected to impart a near-ultraviolet ray blocking effect to the coating film, and if it exceeds 5 parts, the coating film will be whitened and the coating film will not be scratched. Problems, such as a decrease in performance, are likely to occur.

The particle diameter of the composite particles is 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 between titanium oxide and iron oxide is as follows:
There are a chemically bonded complex oxide type, a solid solution type in which iron oxide is uniformly dissolved in titanium oxide, and the like.

The titanium oxide-based composite fine particles can suppress the optical activity without impairing the high refractive index characteristics 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 iron oxide / titanium oxide: 0.005 to 0.15 (preferably 0.01 to 0.7). If it is less than 0.005, 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. 0.15
When the value exceeds, the coating film is colored based on iron oxide, and the use as a coating film for optical plastic molded products is greatly restricted.

It is to be noted that, in addition to iron oxide, binding of silicon oxide to the titanium oxide-based composite fine particles increases the compatibility with the silane compound in preparing a coating composition. In addition, light resistance is improved.

Suitable composition ratios of the titanium oxide-based composite fine particles are as follows: iron oxide / titanium oxide = 0.005 to 1.0 (preferably 0.01 to 0.7), silicon oxide / (titanium oxide + oxide Iron) = 0.03-0.7 (preferably 0.05-
0.5). If the composition ratio of silicon oxide is less than 0.03 , the effect of increasing the miscibility with the silane compound cannot be expected, and therefore, the working life of the paint cannot be extended. Conversely, if it exceeds 0.7, the effect of improving the refractive index of the titanium oxide coating film is hindered, and it is difficult to cope with high refraction.

[0028] (3) A method of manufacturing the upper hexane titanium-based fine particles, for example, carried out by the method described in JP-A-2-178219 JP.

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

In the case of the combination of titanium oxide / iron oxide / silicon oxide, a hydrated iron oxide sol and a hydrated titanium oxide sol are prepared, peptized with an acid, dissolved by adding hydrogen peroxide, and further dissolved in silica. Add the acid dispersion and hydrolyze at high temperature. The silicic acid dispersion is, for example, an alkali silicic acid.
It is prepared by dealkalizing an aqueous acid solution.

The hydrolyzate is a dispersion of fine particles.
is there. This fine particle dispersion is prepared by ion exchange, reverse osmosis,
It is desirable to purify by ultrafiltration and vacuum evaporation.
No.

(4) The titanium oxide-based composite fine particles are desirably used after surface modification with a silane coupling agent. 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 is a treatment for improving the dispersibility of the composite fine particles by blocking the hydroxyl groups remaining in the titanium oxide, iron 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." 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 compounding 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 hydrolysis of the silane compound. For this reason,
A carboxyl group is introduced into 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 cocatalytic action to promote the catalytic action of a thermosetting catalyst described below.

When the compounding amount of the polycarboxylic acid 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 described 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 anhydride, chlormaleic acid , Helic acid (chlorendic acid), trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride. "Among these, maleic acid, itaconic acid,
Trimellitic acid and trimellitic anhydride are preferred.

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 compounding amount of the thermosetting catalyst is 0.01 to 0.2 parts (preferably, 1 part by weight of the above silane compound).
0.02 to 0.15 parts). If less than 0.01 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 parts, the thermosetting catalyst itself tends to bloom and impair the appearance of the coating film.

(2) As the thermosetting catalyst, for example,
An imidazole compound represented by the following general formula can be used.

[0044]

Embedded image

(Provided that 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, and R ³ is hydrogen or a carbon atom having 1 to ³ carbon atoms. ~ 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 described 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. In these, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2, in which the substituent R ¹ is a cyanoalkyl group.
4-dimethylimidazole, 1-cyanoethyl-2-propylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenyl-4,
5-dicyanomethylimidazole is preferred.

As other thermosetting catalysts of the above-mentioned imidazole catalysts, dicyanamide, metal salts of acetylacetone represented by the following general formula, Reinecke salts and the like can be mentioned.

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) It is desirable that the coating composition of the present invention contains various additives in order to improve the performance of the coating film.

For example, as an additive for improving adhesion and dyeing property with an object to be coated (optical plastic molded article), polyolefin epoxy resin, polyglycidyl ester resin, epichlorohydrin and bisphenol A
Glycidyl methacrylate, acrylic copolymer, etc.

As an ultraviolet absorbing material for preventing ultraviolet rays from reaching an object to be coated, benzophenone-based
There are benzotriazole-based and phenol-based ultraviolet absorbers.

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

(2) As a coating method, a commonly used method such as brush coating, roll coating, spraying, spinning, and dipping can be used. At this time, the dry coating thickness is 0.5
It is applied so as to have a thickness of 〜20 μm (preferably 1 to 7 μm).

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

The coating composition of the present invention is cured by heat treatment. Depending on the characteristics of the object to be coated, 60 to 1
A temperature range of 50 ° C gives good results, especially 80-1
00 ° C is desirable. In addition, it is preferable that the heating is applied for 2 to 3 hours or more to give a good result.

(3) The plastic material of the coated object (optical plastic molded product) to which the coating composition of the present invention can be applied is polymethyl methacrylate, polycarbonate, or the like.
Examples include polystyrene, polyester, polyurethane, polythiourethane, aliphatic allyl carbonate, aromatic allyl carbonate, and the like.

[0057]

According to the present invention, a coating composition for an optical plastic molded article is applied to an object to be coated (plastic molded article) and cured by the above-mentioned composition, thereby obtaining an optical plastic having a high refractive index. Even if it is a molded product, it does not impair the optical function of the plastic molded product, and
The plastic molded product can be sufficiently protected from light deterioration and the like.

That is, in the present invention, a coating composition for an optical plastic molded article is a polyvalent resin having a good reactivity with an organosilicon compound serving as a skeleton and special titanium oxide-based composite fine particles, as compared with a conventional coating composition of the same kind. Weather resistance, impact resistance, adhesion to metal deposited film, transparency, heat resistance, hot water resistance, dyeability, abrasion resistance, chemical resistance, plasticity, depending on the combination of carboxylic acid and its anhydride and curing agent Is applied to the coating film to provide a coating film corresponding to the refractive index of the optical plastic molded product.

[0059]

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) Materials to be Coated in Each Example Examples 1 to 3 Comparative Examples 1 to 3: Polycarbonate molded products (Lexan, manufactured by General Electric Co., Ltd.) were used.

Examples 4 to 10, Comparative Examples 4 to 6, 7
- 9: plastic compositions (monomer composition: diphenyl et phosphate diallyl 90 parts, 10 parts of urethane acrylate (Shin Nakamurakogyo Co. "NKU-200AX"), di-isopropyl peroxy dicarbonate 4 parts) casting in Lens for glasses (80mmφ, center thickness 2mm, frequency: -2.00
D) was used.

(Ii) Curing agent In each of the examples, the curing agent is indicated by the following symbols.

IM-4: 2-ethyl-4-methylimidazole IM-8: 2-phenyl-4-methylimidazole IM-12: 1-cyanoethyl-2-methylimidazole 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).

(I) Abrasion Resistance Test The surface was rubbed with # 0000 steel wool and judged as follows.

A: Almost no scratch.

B: Some scratches are made.

C Many scratches are made.

(Ii) Surface hardness test According to JIS K-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 neutral white) (trade name: Lupica Ace 15W: manufactured by Mitsubishi Electric Corporation) is placed on a black background and fluorescent light is applied to the surface of the object. Judgment was made based on the presence or absence of a light interference color (rainbow pattern) formed on the object surface by reflection.

A No light interference color is observed.

B: Light interference color is slightly observed.

C: Light interference color is clearly observed.

Regarding the presence or absence of fogging The fluorescent lamp light was transmitted through the object under the above conditions, and the determination was made based on the presence or absence of fogging of the object.

(Iv) Adhesion test In accordance with JISD-0202, 100 squares were prepared, and a peeling test was performed three times with a cellophane adhesive tape, and the number of remaining squares was indicated.

(V) Hot water test: Immersion in boiling water at 100 ° C. for 1 hour, and judgment was made based on the appearance and adhesion of the coating film.

(Vi) Weathering Resistance Test An accelerated weathering resistance test (“Sunshine Super Long Life Weather Meter” manufactured by Suga Test Co., Ltd.) was performed for 400 hours, and the presence or absence of abnormalities in appearance and the like was determined.

(Vii) Dyeability test In 100 parts of hot water at 90 ° C., 0.4 part of a dye (“Dyanix Brown 2B-FS” manufactured by Mitsubishi Kasei Kogyo Co., Ltd.) and a surfactant (Nippon Senka Kogyo Co., Ltd.) ) "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)).

Δ extinction ratio 30% or more △ extinction ratio 20% to less than 30% × extinction ratio less than 20% <Examples 1 to 3> (1) Preparation of hydrolyzate of silane compound γ-glycidoxy 0.01N HCl in 125 parts of propyltrimethoxysilane and 110 parts of tetraethoxysilane
54 parts of an aqueous solution was added, and the mixture was stirred at 60 rpm for 1 hour.
Stir. Thereafter, methyl alcohol 92 was used as a diluent.
And 200 parts of methyl ethyl ketone, and
After stirring for h, the mixture was left at room temperature for 24 h. Hereinafter, this hydrolyzate is referred to as “HG-40”.

(2) Preparation of Coating Composition 290 parts of HG-40 were mixed with titanium oxide-based composite fine particles “OPTLAKE-1130F” manufactured by Catalyst Chemicals, Inc. (TiO ₂ /
Fe ₂ O ₃ = 98/2, particle size 15 mμ, solid content concentration 30
%, Dispersion solvent: methyl alcohol, surface modifier: tetraethoxysilane) 45 parts and stirred. Thereafter, 12 parts of itaconic acid were added, and the mixture was stirred and dissolved at 120 rpm for 1 hour, and 4 parts of each of the imidazole compounds shown in Table 1 were added as a curing agent, followed by stirring for 2 hours to obtain a coating composition.

(3) Pretreatment of the object to be coated The object to be coated was immersed in a warm bath at a temperature of 50 ° C. for 3 minutes in a 0.05% alkaline detergent (“Shiralon HS” manufactured by Hakusui Henkel Industries Co., Ltd.) and then pulled up. Washed with water and oven dried.

(4) Formation of Coating Film Each coating composition was applied to each of the objects to be subjected to the above pretreatment 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 methyl alcohol 92
0.01N and 54 parts of HCl were added to the mixture, 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”.

(2) Preparation of Coating Composition 290 parts of HG-41 were mixed with titanium oxide-based composite fine particles “Optreak-1130F-1” manufactured by Catalyst Chemicals, Inc. (TiO 2).
₂ / Fe ₂ O ₃ = 95/5, SiO ₂ / (TiO ₂ + F
e ₂ O ₃ ) = 10/90, particle size 15 μm, solid content 3
(0%, dispersing solvent: methyl alcohol, surface modifier: vinyltriethoxysilane) 95 parts, and after stirring, 12 parts of each of the polyvalent carboxylic acids shown in Table 2 was added and dissolved. Then, 5 parts of zinc acetylacetone was added,
Leveling agent ("FLORADE FC-43" manufactured by Sumitomo 3M)
0 ") 0.5 part was added to obtain a coating composition.

(3) Pretreatment of the object to be coated The pretreatment of the object to be coated is performed by using an aqueous solution of caustic soda (10% temperature 5%).
(0 ° C.) for 10 minutes, washed with water for 5 minutes, further immersed in pure water for 3 minutes, and then oven-dried.

(4) Formation of Coating Film Each coating composition was applied to each of the objects to be subjected to the above pretreatment by a dipping method (dipping speed: 90 mm / min) and cured (condition: 100 ° C. × 2 hours). ) To form a coating film on the surface of the object to be coated.

<Example 7> 290 to 290 parts of titanium oxide-based composite fine particles "Optreak-1130F-2"
Manufactured by Catalyst Kasei Kogyo Co., Ltd. (TiO ₂ / Fe ₂ O ₃ = 98/2,
SiO ₂ / (TiO ₂ + Fe ₂ O ₃ ) = 10/90, particle size: 20 μm, solid content concentration: 30%, dispersion solvent: methyl alcohol, surface modifier: γ-glycidoxypropyl propyl triethoxysilane) 90 parts Is added and stirred, 10 parts of trimellitic anhydride is added and dissolved, and dicyandiamide 5 is added.
Part, and add a leveling agent (“SI
LWET L-77 ") was added to obtain a coating composition. The pretreatment of the object and the formation of the coating film were carried out in Example 4.
-6 were performed.

<Eighth Embodiment> The spectacle lens prepared in the seventh embodiment was applied to the SiO ₂ λ from the lens surface side by a vacuum evaporation method.
/ 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> The procedure of Example 7 was repeated, except that 10 parts of trimellitic anhydride in Example 7 was changed to 12 parts of itaconic acid.

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

[Comparative Example] Whether the titanium oxide-based composite fine particles in the examples are due to the improvement of the film performance of the coating film, or whether the titanium oxide-based composite fine particles (titanium oxide and iron oxide, or titanium oxide, iron oxide and silicon oxide) To titanium oxide fine particles to see the film performance.

<Comparative Examples 1 to 3> In Examples 1 to 3, titanium oxide-based composite fine particles-1 were replaced with titanium oxide fine particles "Sanver 11-1530" manufactured by Catalyst Chemicals, Inc. (T
iO ₂ solid concentration 30%, particle size 15 μm, dispersion solvent: methyl alcohol, surface modifier: tetraethoxysilane)
The procedure was the same except for changing to.

<Comparative Examples 4 to 7 and 9> In Examples 4 to 7 and 9, the titanium oxide-based composite fine particles-2.3 were used in Comparative Example 1.
The same operation was performed except that the titanium oxide fine particles were changed to the same as those of the titanium oxide fine particles.

[0094]

[Table 1]

[0095]

[Table 2]

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

* (2) No dyeability test was performed. Because the deposited film itself cannot be dyed.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location G11B 7/24 526 8721-5D G11B 7/24 526

Claims (3)

(57) [Claims] 1. A coating composition for optical plastic molded articles, comprising the following essential components in the following composition. (A) hydrolyzate of a silane compound: 1 part by weight; (B) iron oxide in titanium oxide; iron oxide / titanium oxide =
Complex oxide type with a weight composition ratio of 0.005 to 0.15
Alternatively, titanium oxide-based composite fine particles having a particle size of 1 to 100 μm which are integrally bonded in a solid solution type : 0.2
To 5 parts by weight, (C) unsaturated or saturated polycarboxylic acid or their anhydrides: 0.02 to 0.5 part by weight, (D) thermosetting catalyst for the silane compound : 0.0
1 to 0.2 parts by weight. However, the silane compound is one of the following:
The component consisting of the general formula is defined as an essential component. 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 halogenated hydrocarbon
A group, an aryl group, and R ³ are an alkyl group having 1 to 4 carbon atoms;
It is a alkoxyalkyl group or an acyl group. Also
a = 1, b = 0, 1, or 2. ) 2. A method according to claim 1 Come on optical plastic moldings for coating composition, wherein the titanium oxide-based composite fine particles, iron oxide and silicon oxide to titanium oxide composite oxide capacitor
They are integrally bonded in the form of ip or solid solution , and their weight composition ratio is iron oxide / titanium oxide = 0.
005 to 0.15, silicon oxide / (iron oxide + titanium oxide) = 0.03 to 0.70, a coating composition for an optical plastic molded product. 3. The coating composition for an optical plastic molded product according to claim 1, wherein said titanium oxide-based composite fine particles are surface-modified with a silane coupling agent. Paint composition.