JP3220906B2 - Composition for coating - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antireflection coating thin film (hereinafter referred to as an inorganic vapor-deposited film) made of an inorganic substance having excellent transparency, dyeing properties and inorganic substance, which is applied to the surface of a substrate such as a transparent plastic material and cured. (Hereinafter referred to as "coating composition").

[0002]

2. Description of the Related Art Acrylic, methacrylic, vinyl, polycarbonate and allylic transparent plastic materials among the currently used plastic materials are more impact-resistant, lighter and more workable than glass. Because of their excellent properties such as colorability, they are used in a large amount in place of inorganic glass as optical materials such as lenses and transmission glass. However, they have the disadvantage that they are inferior in scratch resistance and chemical resistance as compared with inorganic glass. Diethylene glycol bisallyl carbonate resin (hereinafter referred to as CR-39) is a resin having relatively excellent scratch resistance, but this resin is not practically sufficient. As means for improving these disadvantages of plastic materials, for example, Japanese Patent Publication No. 57-2735 discloses a thermosetting paint composed of colloidal silica and epoxy-containing alkoxysilane.
In addition, JP-B-57-43168, JP-B-56-34033,
No. 55-29102, JP-A-57-67666 and the like disclose a thermosetting paint containing epoxy group-containing alkoxysilane and tetraalkoxysilane as main components.
7-15608, 57-57578, 57-209
68 and JP-A-57-128755 each disclose a photopolymerizable paint, and are each intended to improve chemical resistance and scratch resistance.

On the other hand, Japanese Patent Publication No. 57-50 discloses a thermosetting paint and a photocurable paint having the same performance.
JP-A-0984 proposes that heat energy consumption is low and adhesion to a plastic substrate is excellent.

Further, Japanese Patent Application Laid-Open Nos. 59-204669 and 60
No. 137,939 discloses a method of increasing the affinity with a polyfunctional acrylate using hydrophobic colloidal silica.

[0005]

However, the above-mentioned thermosetting paint has sufficient adhesion to CR-39, but has an adhesion to specific plastics such as polycarbonate, polymethyl methacrylate and polystyrene. Insufficient. In addition, there has not been obtained a dye that sufficiently satisfies both the dyeability and the adhesion to the inorganic vapor-deposited film.

Further, the photocurable paint has poor dyeing properties and poor adhesion to an inorganic vapor-deposited film.
In the method disclosed in JP-A-0984 / 1985, although the hardness and durability of the coating film are improved, the improvement of the dyeability and the adhesion to the inorganic vapor-deposited film, which are the objects of the present invention, cannot be obtained.

[0007]

The present inventors have made intensive studies to solve these problems, and found that silica fine particles, silane compounds having a polymerizable reactive group, glycidyl groups and (meth) acryloyl Epoxy (meth) acrylate having a group at the same time [(meth) acrylate represents methacrylate and acrylate. It has been found that a coating film obtained by heat-curing a composition containing the above-mentioned component as a main component has excellent transparency and excellent performance in both dyeability and adhesion to an inorganic vapor-deposited film.

That is, the present invention relates to a thermosetting coating composition containing at least the following components (A), (B) and (C) as main components.

(A), silica fine particles having a particle diameter of 1 to 100 millimicrons, 20 to 60% by weight (B), a silane compound having at least one or more polymerizable reactive group, 30 to 70% by weight (C), An epoxy (meth) acrylate having both a glycidyl group and a (meth) acryloyl group in one molecule,
2 to 25 % by weight Effective examples of the silica fine particles having a particle diameter of 1 to 100 mm of the component (A) used in the present invention include silica sol and silica fine particles. The silica sol is obtained by dispersing a high molecular weight silicic acid colloidally in a dispersion medium such as water, an alcohol or other organic solvent. The powdery silica fine particles are powders obtained by hydrophobizing the surface of colloidal silica, and all of them are commercially available. For the purpose of this invention, those having an average particle size of 1 to 100 millimicrons are used, but preferably those having a diameter of 5 to 30 millimicrons. If the particle diameter is less than 1 millimicron, fine silica particles do not exist stably, and constant quality cannot be obtained. Also 100
If it is more than millimicrons, there arises a problem that the coating film becomes cloudy.

It is necessary that the amount used is 20 to 60% by weight of the total composition. That is, if it is less than 20% by weight, the adhesion to the inorganic vapor-deposited film is insufficient, or the scratch resistance of the coating film is insufficient. On the other hand, if it exceeds 60% by weight, cracks occur in the coating film. In addition, the dyeability becomes insufficient.

The component (B) is a silane compound having a polymerizable reactive group such as a vinyl group, an allyl group, an acryl group, a methacryl group, an epoxy group, a mercapto group, a cyano group, an isocyano group, and an amino group. Specific examples thereof include vinyltrialkoxysilane, vinyltrichlorosilane, vinyltri (β-methoxy-ethoxy) silane, allyltrialkoxysilane, acryloxypropyltrialkoxysilane, methacryloxypropyltrialkoxysilane, and methacryloxypropyl. Dialkoxymethylsilane, γ-glycidoxypropyl trialkoxysilane, β- (3,4-epoxycyclohexyl) -ethyl trialkoxysilane, mercaptopropyl trialkoxysilane, γ-aminopropyl trialkoxysilane N-beta is (aminoethyl)-.gamma.-aminopropyl methyl dialkoxysilane, and the like.

The component (B) may be used as a mixture of two or more kinds. In addition, it is more effective to use either of the methods after hydrolysis and the use of an acid treatment on the cured film.

The amount of the component (B) used is 30 to 30% of the total composition.
It needs to be 70% by weight. That is, if it is less than 30% by weight, the adhesion to the inorganic vapor-deposited film tends to be insufficient. On the other hand, if it exceeds 70% by weight, cracks may occur in the cured film, which is not preferable.

Subsequently, the epoxy (meth) acrylate having a glycidyl group and a (meth) acryloyl group in one molecule of the component (C) refers to an epoxy compound having two or more glycidyl groups in one molecule. ) It is obtained by a glycidyl group ring-opening reaction with acrylic acid. Specific examples of the epoxy compound having two or more glycidyl groups in one molecule include 1,6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, and tetraethylene. Glycol diglycidyl ether, nonaethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, tetrapropylene glycol diglycidyl ether, nonapropylene glycol diglycidyl ether,
Neopentyl glycol diglycidyl ether, diglycidyl ether of neopentyl glycol hydroxyhivalate, trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, diglycerol diglycidyl ether, diglycol Glycerol triglycidyl ether, diglycerol tetraglycidyl ether, pentaerythritol diglycidyl ether, pentaerythritol triglycidyl ether, pentaerythritol tetraglycidyl ether, dipentaerythritol tetraglycidyl ether, sorbitol tetraglycidyl ether, tris (2-hydroxyethyl) isocyanurate Diglish Aliphatic epoxy compounds such as triglycidyl ether of tris (2-hydroxyethyl) isocyanurate, alicyclic epoxy compounds such as isophoronediol diglycidyl ether, bis-2,2-hydroxycyclohexylpropane diglycidyl ether, resorcinol Examples thereof include aromatic epoxy compounds such as diglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, diglycidyl orthophthalate, phenol novolak polyglycidyl ether, and cresol novolak polyglycidyl ether.

In the present invention, since the epoxy (meth) acrylate as the component (C) is used as a dyeing component, among the above, 1,6-hexanediol diglycidyl ether, diethylene glycol diglycidyl ether,
Aliphatic epoxy compounds such as trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, and triglycidyl ether of tris (2-hydroxyethyl) isocyanurate are particularly preferred. Examples of the monocarboxylic acid-containing compound to be reacted with these epoxy compounds include acrylic acid and methacrylic acid, as well as reaction of glycidyl (meth) acrylate or hydroxyethyl (meth) acrylate with an acid anhydride such as 0-phthalic anhydride. There is a monocarboxylic acid-containing (meth) acrylate compound obtained by the above method.

The reaction between the epoxy compound and the monocarboxylic acid-containing (meth) acrylate is carried out by mixing the above components and using a catalyst such as dimethylaminoethyl methacrylate as a catalyst.
A quaternary amine salt such as a quaternary amine compound or benzyltrimethylammonium chloride;
Obtained by heating.

In the present invention, in order to make the coating film tough, it is more preferable to use an epoxy (meth) acrylate having both a glycidyl group and a (meth) acryloyl group in one molecule.

This compound is obtained, for example, by reacting 1 mol of glycerol triglycidyl ether with 1.5 mol of acrylic acid.

Component (C) is used in an amount of 2 to 2 parts of the total composition.
It needs to be 5 % by weight. That is, if it is less than 2% by weight, the dyeability becomes insufficient. On the other hand, if it exceeds 25 % by weight, the adhesion to the inorganic vapor-deposited film tends to be insufficient,
Not preferred.

The coating composition thus obtained can be used after being diluted with a solvent, if necessary. As the solvent, solvents such as alcohols, esters, ketones, ethers, and aromatics are used. It is also useful to add a silicone surfactant, a nonionic surfactant, a thixotropic agent, a silicone oil, an ultraviolet absorber, an antistatic agent or the like as a slip agent for improving defects on the coated surface.

It is also useful to add a curing catalyst for silanol or epoxy compound.

The most preferred catalyst is magnesium perchlorate. Other examples include metal acetylacetonates such as aluminum acetyl acetate, amino acids such as amine and glycine, Lewis acids, metal salts of organic acids, and perchloric acid. Ammonium and the like. The addition amount is desirably within the range of 0.01 to 5.0% of the solid concentration.

The thickness of the cured film in the present invention is as follows:
It is preferably 0.05 to 30 μm. That is,
If it is less than 0.05 μm, the basic performance is not obtained, and if it exceeds 30 μm, the surface smoothness is impaired and optical distortion occurs, which is not preferable.

The coating method includes a dipping method, a spray method, a roll coating method, a spin coating method, a flow coating method and the like.

The coating composition applied in this manner is thermally cured after being applied to the substrate. In order to perform heat curing, a method of performing a condensation reaction in warm air at 80 ° C to 200 ° C is preferable. Especially in the case of a substrate having poor heat resistance,
A temperature between 80C and 130C is more desirable. An antireflection film described below can be provided on a plastic substrate having a cured film obtained in this manner. That is, SiO, SiO ₂ , Si ₃ N ₄ , TiO ₂ , ZrO ₂ , A
By laminating a single-layer or multilayer thin film made of an inorganic derivative of l ₂ O ₃ or MgF ₂ , reflection at the interface with the atmosphere can be suppressed low. Other than these materials, for example, Sb ₂ O ₃ , Sb ₂ O ₅ , CaF ₂ , Ce
O ₂ , CeF ₃ , Na ₃ AlF ₃ , La ₂ O ₃ , LaF ₃ , P
bF ₃ , NdF ₃ , Pr ₆ O ₁₁ , ThO ₂ , ThF ₂ , Zn
There are materials such as S, Ti ₂ O ₃ , Ta ₂ O ₅ , Y ₂ O ₃ , and MgO.

The thickness of the antireflection film used here is λ ₀
/ 4 single-layer structure of (λ ₀ = 450~650nm) _{or,, λ 0/4-λ} 0/2-λ 0/4 or, λ _{0/4-λ 0}
/ 4-λ _0/4 multilayer films of different three-layer structure refractive index or a useful made of anti-reflection film by the multilayer film is replaced by some equivalent layer, its refractive index, for example, a single-layer in the case of the air, the anti-reflection film, a substrate (or a cured coating layer) of each refractive index of, when _{n 0, n 1, n 2} , n 1
= (N ₀ · n ₂ ) ^1/2 is the one with the least reflection. In the case of a multi-layer film, an effect superior to that of a single-layer film can be exhibited by combining materials having different refractive indexes as partially shown in the examples. When the antireflection film is formed by vacuum deposition, the adhesion may be improved by subjecting the lens to a surface treatment with a gas plasma such as oxygen or argon in advance. Hereinafter, the present invention will be described in more detail with reference to examples.

[0027]

The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1 (1) Synthesis of Epoxy Acrylate In a flask equipped with a thermometer and a reflux condenser, trimethylolpropane triglycidyl ether (manufactured by Nagase Kasei Kogyo Co., Ltd .; trade name "Denacol EX-321") )) 5
80 g, acrylic acid 112 g, dimethylaminoethyl methacrylate 3 g, hydroquinone mer ether 0.4
g and 173 g of butyl cellosolve, and while stirring, 2 hours at 70 ° C., 2 hours at 80 ° C., and then 90 ° C.
And reacted for 6 hours with epoxy acrylate (EA-1)
I got The obtained epoxy acrylate is APHA1
50 and oxidation 0.05.

(2) Preparation of Coating Solution After mixing 156.6 g of methyl cellosolve and 205.3 g of methanol-dispersed colloidal silica (trade name “Oscar 1132” manufactured by Catalyst Chemical Industry Co., Ltd., solid content concentration 30 wt%), γ- Glycidoxypropyltrimethoxysilane 6
7.3 g were mixed. To this mixture, 18.5 g of a 0.05N aqueous hydrochloric acid solution was added dropwise with stirring, and the mixture was further stirred for 4 hours and then aged for 24 hours. After adding 51.0 g of EA-1 to this solution, 1.5 g of magnesium perchlorate and a silicon-based surfactant (trade name “L-700” manufactured by Nippon Unicar Co., Ltd.)
1 ") 0.1 g and a hindered phenolic antioxidant (trade name" IRGANO "manufactured by Nippon Ciba Geigy Co., Ltd.)
X1010 "), and the mixture was stirred for 4 hours and then aged all day long to obtain a coating solution.

(3) Coating and Curing The thus obtained coating liquid was applied to an alkali-treated CR-39 spectacle lens by an immersion method.
The lifting speed was 20 cm / min. 80 after application
After air drying at 20 ° C for 20 minutes, baking was performed at 130 ° C for 120 minutes. The thickness of the cured film thus obtained is about 2
The micron was excellent in both appearance and dyeability.

Example 2 An anti-reflection coating thin film made of an inorganic substance was formed on each of the lenses obtained in Example 1 by the following method.

(1) Formation of anti-reflection thin film The obtained lens is subjected to plasma treatment (argon plasma 40).
(0 W × 60 seconds), and an anti-reflection multilayer film composed of five layers of SiO ₂ , ZrO ₂ , SiO ₂ , ZrO ₂ , and SiO ₂ is sequentially deposited from the substrate to the atmosphere by a vacuum deposition method (Vacuum Instruments Co., Ltd. ); BMC-1000).
The film thickness is the thickness of the lowermost layer of SiO ₂ , and the thickness of the next layer of ZrO ₂ and SiO _2.
2, the total thickness of ZrO _{2, and} the thickness of the uppermost layer of SiO ₂ were all λ / 4. The design wavelength λ was 520 nm.

(2) Test and Evaluation Results The lens obtained in Example 1 (hereinafter referred to as a hard-coated lens) and the lens obtained in Example 2 (hereinafter referred to as a hard multi-coated lens) are each described below. , And the results are shown in Table 1.

(A) Abrasion resistance: The surface was rubbed for 10 reciprocations under a load of 1 kg with 0000 steel wool, and the degree of damage was visually evaluated in the following stages.

A: There is no damage in the area of 1 cm * 3 cm.

B: 1 to 10 scratches are made within the above range.

C: 10 to 100 scratches are made within the above range.

D: Although there are countless scratches, a smooth surface remains.

E: Due to scratches on the surface, no smooth surface remains.

(B) Water and chemical resistance: water, alcohol,
It was immersed in kerosene for 48 hours, and those having no change in the surface state were evaluated as good.

(C) Acid / detergent resistance: 12% in 0.1N hydrochloric acid and 1% mama lemon (manufactured by Lion Oil & Fat Co., Ltd.) aqueous solution
It was immersed for a period of time, and those having no change in the surface state were evaluated as good.

(D) Adhesion: The adhesion between the substrate and the hard coat film and between the hard coat film and the multi-coat film is determined by JI
A cross cut tape test was performed according to SD-0202. That is, cuts are made at 1 mm intervals on the base material surface using a knife, and 100 squares of 1 square mm are formed. Next, a cellophane adhesive tape (Nichiban Co., Ltd., product name "Cellotape") was strongly pressed onto the tape, and then it was suddenly pulled 90 degrees from the surface and peeled off. The index was used.

(E) Weather resistance: A sample having no change in surface state after being exposed to a sunshine weather meter using a xenon lamp for 400 hours was evaluated as good.

(F) Heat resistance (cooling cycle property): 70 ° C.
After storing in warm air for 1 hour, the surface condition was examined. Further-
A cycle at 5 ° C. for 15 minutes and at 60 ° C. for 15 minutes was repeated five times, and those having no change in the surface state were evaluated as good.

(G) Durability: It is considered that durability is essentially an adhesive connection, and the cross-cut tape test described above was performed on the test pieces (a) to (f), and the coating film was obtained. Those without peeling were regarded as good.

(H) Dyeing property (hard coat lens only): 1 g of pure water at 92 ° C. was dispersed with 2 g of Aiko D, a dye for Seiko Plux diamond coating, to prepare a dyeing solution. This dyeing solution was immersed in the dyeing solution for 5 minutes for dyeing, and a dye having no unevenness in dyeing and having a total light transmittance of 30% or more between before and after dyeing was evaluated as good.

Example 3 (1) Synthesis of Epoxy Acrylate Glycerol diglycidyl ether (Nagase Chemical Industries, Ltd.) was placed in 11 flasks equipped with a thermometer and a reflux condenser.
580 g, acrylic acid 144 g, benzyltrimethylammonium chloride 3 g, hydroquinone methyl ether 0.4 g,
While adding 181 g of butyl cellosolve and stirring,
The reaction was carried out at 70 ° C. for 2 hours and at 80 ° C. for 6 hours to obtain an epoxy acrylate (EA-2). The obtained epoxy acrylate was APHA150 and oxidation 0.05.

(2) Preparation of Coating Liquid 194.5 g of butyl cellosolve, colloidal silica dispersed with isopropyl alcohol (trade name “Oscar 1432”, manufactured by Catalyst Chemical Industry Co., Ltd., solid content concentration 30 wt%) 16
After mixing 0.8 g, 73.0 g of γ-glycidoxypropyltrimethoxysilane was mixed. 20.1 g of a 0.05N hydrochloric acid aqueous solution was added dropwise to the mixture with stirring, and the mixture was stirred for 4 hours and then aged for 24 hours. EA-
2. Magnesium perchlorate after adding 50.15 g of 2.
0 g, a silicon-based surfactant (manufactured by Nippon Unicar Co., Ltd .;
0.1 g of a trade name “FZ-2110” and 0.7 g of a phenolic antioxidant (trade name “Antage Crystal” manufactured by Kawaguchi Chemical Industry Co., Ltd.) are added, stirred for 4 hours, aged for 24 hours, and then ripened all day long. And

(3) Coating and Curing The coating liquid thus obtained was applied to an alkali-treated CR-39 spectacle lens by a spinner method.

The coating conditions are as follows.

Rotation speed: 500 rpm for 10 seconds (coating liquid is applied during this time) Rotation speed: 2,000 rpm for 1 second Rotation speed: 500 rpm for 5 seconds After coating, air-dry at 80 ° C. for 20 minutes, then at 130 ° C. for 120 minutes
Baking was performed for minutes. The cured film thus obtained had a thickness of about 2.3 microns, and was excellent in both appearance and dyeability.

(4) Test and Evaluation Results The lenses thus obtained were tested in the same manner as in Example 1, and the results are shown in Table 1.

(Example 4) (1) Formation of antireflection thin film The lens obtained in Example 3 was used in the same manner as in Example 2,
An anti-reflection coating thin film made of an inorganic substance was formed.

(2) Test and Evaluation Results The lenses thus obtained were tested in the same manner as in Example 2, and the results are shown in Table 1.

Example 5 (1) Synthesis of Epoxy Methacrylate 1,6 flasks were equipped with a thermometer and a reflux condenser.
-Hexanediol diglycidyl ether (manufactured by Nagase Kasei Kogyo Co., Ltd .; trade name "Denacol EX-212") 6
Of methacrylic acid, 189 g of methacrylic acid, 3 g of dimethylaminoethyl methacrylate, 0.4 g of hydroquinone methyl ether and 338 g of butyl cellosolve. The mixture was stirred at 70 ° C. for 2 hours, at 80 ° C. for 2 hours, and then stirred for 9 hours.
After reacting at 0 ° C. for 6 hours, epoxy methacrylate (EA
-3) was obtained. The obtained epoxy methacrylate has A
PHA180, oxidation 0.05.

(2) Preparation of coating liquid 130.0 g of isopropyl cellosolve and 74.3 g of pure water
And 172.9 g of methylcellosolve-dispersed colloidal silica (trade name “Oscar 1832”, solid content concentration: 30 wt%, manufactured by Catalyst Chemical Industry Co., Ltd.), 61.2 g of γ-methacryloxypropyltrimethoxysilane and γ-glycol Sidoxypropyltrimethoxysilane 14.6
g were mixed. This mixture is added to a 0.05N aqueous hydrochloric acid solution 2
0.0 g was added dropwise with stirring. After further stirring for 5 hours, the mixture was aged for one day. 26.7 g of EA-3, 0.5 g of magnesium perchlorate and a silicon surfactant (manufactured by Nippon Unicar Co., Ltd .; trade name "L-7604") were added to this solution.
0.1 g was added, and the mixture was stirred for 4 hours and then aged for 24 hours to obtain a coating solution.

(3) Coating and Curing The coating liquid obtained as described above is used with Seiko Highroad S
A dough lens for MX (manufactured by Seiko Epson Corporation) was applied by a spinner method. The coating conditions are
This was performed in the same manner as in Example 3.

After air-drying at 80 ° C. for 15 minutes after application,
The firing was performed at 0 ° C. for 4 hours. The thickness of the cured film thus obtained was about 2.1 microns, and both the appearance and the dyeability were excellent.

(4) Formation of Antireflection Thin Film The hard coat lens thus obtained was used in Example 2.
An anti-reflection coating thin film made of an inorganic substance was formed in the same manner as described above.

(5) Test and Evaluation Results The lenses thus obtained were tested in the same manner as in Example 2, and the results are shown in Table 1. The dyeability was evaluated in the state of a hard coat lens.

Example 6 (1) Synthesis of Epoxy Methacrylate Tripropylene glycol diglycidyl ether (manufactured by Nagase Kasei Kogyo Co., Ltd .; trade name "Denacol EX-921") was placed in 11 flasks equipped with a thermometer and a reflux condenser. )) 6
15 g, 129 g of methacrylic acid, 3 g of benzyltrimethylammonium chloride, 0.4 g of hydroquinone methyl ether, and 319 g of butyl cellosolve were stirred and reacted at 70 ° C. for 2 hours, at 80 ° C. for 2 hours, and then at 90 ° C. for 6 hours. Epoxy methacrylate (E
A-4) was obtained. The obtained epoxy methacrylate is
APHA200, oxidation was 0.05.

(2) Preparation of Coating Solution 126.4 g of butyl cellosolve, colloidal silica dispersed with isopropyl alcohol (manufactured by Catalyst Chemical Industry Co., Ltd .; trade name “Oscar 1432”, solid content concentration 30 wt%) 20
After mixing 9.5 g, 46.5 g of γ-glycidoxypropylmethyldimethoxysilane and 69.8 g of γ-methacryloxypropyltrimethoxysilane were mixed.
26.4 g of a 0.05N aqueous hydrochloric acid solution was added dropwise to the mixture with stirring, and the mixture was stirred for 4 hours and then aged for 24 hours. After adding 20.2 g of EA-4 to this solution, 3.0 g of magnesium perchlorate and 0.1 g of a silicon-based surfactant (manufactured by Big Chemie Co., Ltd .; trade name "BYK-300") are added, followed by stirring for 4 hours. Thereafter, it was aged one day and night to obtain a coating solution.

(3) Coating and Curing The coating liquid obtained as described above was spray-formed onto an injection molded acrylic plate (manufactured by Mitsubishi Rayon Co., Ltd .; trade name "Acrypet VH" 100 mm * 100 mm * 3 mmt). Was applied.

The spraying was performed using Iwata Weider 61 (manufactured by Iwata Coating Machine Co., Ltd .; nozzle diameter 1 mm) at a spray pressure of 3 kg / square cm and a paint discharge rate of 100 ml / min.

After air-drying at 50 ° C. for 10 minutes after application, 80 ° C.
For 4 hours. The thickness of the cured film thus obtained was 4 microns, and both the appearance and the dyeability were excellent.

(4) Test and Evaluation Results The acrylic plate thus obtained was tested in the same manner as in Example 1, and the results are shown in Table 1.

Example 7 (1) Formation of Antireflection Thin Film The acrylic plate obtained in Example 6 was formed into an antireflection coated thin film made of an inorganic substance in the same manner as in Example 2.

(2) Test and Evaluation Results The acrylic plate thus obtained was tested in the same manner as in Example 2, and the results are shown in Table 1.

Comparative Example 1 In Example 1, EA-1 was used.
Was applied to the lens in the same manner except that no was added.

The lenses thus obtained were tested in the same manner, and the results are shown in Table 1.

Comparative Example 2 Butyl Cellosolve 111.7
g, 323.8 g of isopropyl alcohol-dispersed colloidal silica (trade name “Oscar 1432”, solid content concentration: 30 wt%, manufactured by Catalyst Chemical Industry Co., Ltd.), and then 25.5 g of γ-glycidoxypropyltrimethoxysilane. did. To this mixture was added dropwise 7.0 g of a 0.05N aqueous hydrochloric acid solution with stirring, and the mixture was stirred for 4 hours and then aged for 24 hours. After adding 31.0 g of EA-2 used in Example 3 to this solution, 0.8 g of magnesium perchlorate and a silicon-based surfactant (manufactured by Nippon Unicar Co., Ltd .; trade name “FZ-21”)
10 ") 0.1 g and a phenolic antioxidant (manufactured by Kawaguchi Chemical Industry Co., Ltd .; trade name" Antage Crystal ")
0.7 g was added, and the mixture was stirred for 4 hours and then aged all day and night to obtain a coating solution.

A lens was coated in the same manner as in Example 3 except that this coating solution was used.

The lens obtained in this manner was used in Example 1.
A test was conducted in the same manner as in Example 1 and the results are shown in Table 1.

(Comparative Example 3) An antireflection coated thin film made of an inorganic substance was formed on the lens obtained in Comparative Example 2 in the same manner as in Example 2.

The lens thus obtained is described in Example 2.
A test was conducted in the same manner as in Example 1 and the results are shown in Table 1.

Comparative Example 4 In Example 3, EA-2 was used.
Was applied to the lens in the same manner except that glycerol diglycidyl ether was added instead of.

The lens obtained in this manner was used in Example 1.
A test was conducted in the same manner as in Example 1 and the results are shown in Table 1.

Comparative Example 5 An antireflection film was formed on the lens obtained in Comparative Example 4 in the same manner as in Example 2.

The lens obtained in this manner was used in Example 2.
A test was conducted in the same manner as in Example 1 and the results are shown in Table 1.

(Comparative Example 6) Butyl cellosolve 180.1
g of isopropyl alcohol-dispersed colloidal silica (manufactured by Katsura Kasei Kogyo Co., Ltd .; trade name: “Oscar 1432”, solid content: 30 wt%), and then 29.1 g of γ-glycidoxypropylmethyldimethoxysilane.
And 46.5 g of γ-methacryloxypropyltrimethoxysilane were mixed. 17.3 g of a 0.05N aqueous hydrochloric acid solution was added dropwise to this mixed solution while stirring, and the mixture was stirred for 4 hours and then aged for 24 hours. After adding 96.1 g of EA-4 to this solution, 2.0 g of magnesium perchlorate and a silicon-based surfactant (manufactured by Big Chemie Co., Ltd .; trade name "BYK-3")
00 "), and the mixture was stirred for 4 hours and then aged all day and night to obtain a coating solution.

An acrylic plate was coated in the same manner as in Example 6 except that this coating solution was used.

The acrylic plate thus obtained was tested in the same manner as in Example 1, and the results are shown in Table 1.

(Comparative Example 7) An anti-reflection film was formed on the acrylic plate obtained in Comparative Example 6 in the same manner as in Example 2.

The acrylic plate thus obtained was tested in the same manner as in Example 1, and the results are shown in Table 1.

[0085]

[Table 1]

[0086]

As described above in detail, according to the present invention, good dyeing properties and adhesion to an antireflection film made of an inorganic substance can be obtained at the same time, and the surface can be hardened. In optical plastic materials such as acrylic resin, it was not put into practical use due to insufficient adhesion.
The effect of enabling antireflection processing with an inorganic substance is significant. That is, as a plastic lens material, various functions such as a styrene resin, a carbonate resin, an allyl resin, an allyl carbonate resin, a vinyl resin, a polyester resin, a polyether resin, a polymer of a new monomer or a comonomer, including (meth) acrylic resin. It can be applied to moistened resin.

A plastic material having both excellent scratch resistance, good dyeing properties, and durability with a good antireflection film made of an inorganic material can be used as a spectacle lens, a camera lens, a light beam condensing lens or a light diffusing lens. It can be widely applied for consumer or industrial use. Further, the effects of the present invention can be applied to transparent glasses such as watch glasses and cover glasses for displays and transparent plastics for optical use such as cover glasses, and the effects obtained are enormous.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Takao Mogami 3-5-3 Yamato, Suwa-shi, Nagano Seiko Epson Corporation (72) Inventor Hiroshi Fukushima 4-6-1, Sunadabashi, Higashi-ku, Nagoya-shi, Aichi Prefecture Mitsubishi Inside Rayon Co., Ltd. (72) Inventor Akira Motonaga 4-6-1, Sunadabashi, Higashi-ku, Nagoya City, Aichi Prefecture Inside Mitsubishi Rayon Co., Ltd. (72) Inventor Eriko Suda 4-6-1, Sunadabashi, Higashi-ku, Nagoya City, Aichi Prefecture Mitsubishi Rayon (56) References JP-A-4-1186 (JP, A) JP-A-3-14879 (JP, A) JP-A-11-1131021 (JP, A) JP-A 8-295846 (JP, A A) JP-A-11-138092 (JP, A) JP-A-7-252333 (JP, A) JP-A-5-179157 (JP, A) JP-A-3-140371 (JP, A) JP-A-6060 99103 (JP, A) (58 ) investigated the field (Int.Cl. ^7, DB name) C09D 4/02 G02B 1/10 CA (STN ) CAOLD (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] 1. A thermosetting coating composition comprising at least the following components (A), (B) and (C) as main components. (A). Silica fine particles with a particle size of 1 to 100 millimicrons,
20 to 60% by weight (B). A silane compound having at least one or more polymerizable reactive groups, 30 to 70% by weight (C). An epoxy (meth) acrylate having both a glycidyl group and a (meth) acryloyl group in one molecule,
2 to 25 % by weight