JPH08295846A - Coating composition and laminate - Google Patents

Abstract

PURPOSE: To obtain a coating composition comprising complex fine particles composed of a metal oxide, a silane compound and an epoxy (meth)acrylate as main components, capable of making the surface highly hard, excellent in durability, adhesion, etc., forming a reflection preventing film. CONSTITUTION: This coating composition comprises (A) fine particles composed of at least one or more metal oxides selected from Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr, In and Ti having 1-100 millimicron particle diameter and/or complex fine particles composed of Si and two or more metal oxides selected from the metal element group, (B) a compound containing at least one or more polymerizable reactive groups (e.g. vinyl, allyl or acrylic groups), (C) an epoxy (meth)acrylate containing both a glycidyl group and a (meth)acryloyl group in one molecule as main components and preferably (D) silica fine particles having 1-100 millimicron particle diameter and/or an organosilicon compound hydrolyzate and/or its particle condensate.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention has a refractive index of 1.52.
A transparent film that has the same refractive index as the base material on the surface of the above synthetic resin lens, and has excellent durability and dyeability such as abrasion resistance, chemical resistance, warm water resistance, heat resistance, and weather resistance. Further, the present invention relates to a coating composition characterized in that an antireflection film (hereinafter referred to as an inorganic vapor deposition film) made of an inorganic substance can be provided on the coating film.

[0002]

2. Description of the Related Art Synthetic resin lenses, particularly diethylene glycol bis (allyl carbonate) resin lenses, are superior to glass lenses in safety, easy processability, fashionability, etc.
It has rapidly spread due to the development of hard coat technology and hard coat + antireflection technology. However, the refractive index of diethylene glycol bis (allyl carbonate) resin is 1.
Since it is 50, which is lower than that of the glass lens, the myopic lens has a drawback that the outer peripheral portion is thicker than the glass lens. Therefore, in the field of synthetic resin spectacle lenses,
Technological developments aimed at reducing the thickness using high-refractive index resin materials are being actively conducted. As technical proposals therefor, 1.60 in JP-A-59-133211, JP-A-63-46213, JP-A-2-270859 and the like.
Further, a high refractive index resin material having a refractive index higher than that has been proposed.

On the other hand, the plastic spectacle lens has a drawback that it is easily scratched. Therefore, a method of providing a silicon type hard coat film on the surface of the plastic lens is generally used. However, when the same method is applied to a high-refractive-index resin lens having a refractive index of 1.52 or more, interference fringes are generated due to the difference in the refractive index between the resin lens and the coating film, which causes poor appearance. As a technical proposal for solving this problem, a colloidal dispersion of silicon dioxide fine particles used in a silicon-based coating composition as disclosed in JP-B-61-54331 and JP-B-63-37142 has a high refractive index. Al, Ti, Zr, S having a ratio
A coating technique of replacing with a colloidal dispersion of n, Sb inorganic oxide fine particles is disclosed. Further, JP-A-1-301517 discloses a method for producing a composite sol of titanium dioxide and cerium dioxide, and JP-A-2-264902 discloses a composite inorganic oxide fine particle of Ti and Ce, and JP-A-3201. Japanese Patent No. 68901 discloses a technique in which fine particles obtained by treating a composite inorganic oxide of Ti, Ce and Si with an organic silicon compound are used in a coating composition.

[0004]

However, the above-mentioned composition for high refractive index coating has sufficient dyeability and various durability of the coating film itself, and various durability when the inorganic vapor deposition film is provided on the surface of the coating film. There is no product that satisfies both sex.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to solve these problems and found that metal oxide fine particles, a silane compound having a polymerizable reactive group,
Epoxy (meth) acrylate [(meth) acrylate having both a glycidyl group and a (meth) acryloyl group represents a methacrylate and an acrylate. ] A coating film obtained by heat-curing a composition containing as a main component or a combination of photo-curing and heat-curing, is excellent in transparency, and has dyeability and various durability, and an inorganic vapor deposition film is provided on the surface of the film. It was found that excellent performance was obtained in all the various durability at the time.

That is, the present invention provides a coating composition comprising at least the following components (A), (B) and (C) as main components, and an inorganic substance on the surface of a coating comprising the coating composition. The present invention relates to a laminated body having an antireflection film made of

(A). A with a particle size of 1 to 100 millimicrons
l, Sn, Sb, Ta, Ce, La, Fe, Zn, W,
Fine particles composed of one or more metal oxides selected from Zr, In and Ti and / or Si, Al, Sn, Sb,
Ta, Ce, La, Fe, Zn, W, Zr, In, Ti
Composite fine particles composed of two or more kinds of metal oxides selected from

(B). A silane compound having at least one polymerizable reactive group.

(C). Epoxy (meth) having both glycidyl group and (meth) acryloyl group in one molecule
Acrylate.

Particle size 1 to 1 of the component (A) used in the present invention
00 millimicron Al, Sn, Sb, Ta, Ce, L
1 selected from a, Fe, Zn, W, Zr, In and Ti
Fine particles composed of one or more kinds of metal oxides and / or S
i, Al, Sn, Sb, Ta, Ce, La, Fe, Z
Specific examples of the composite fine particles composed of two or more kinds of metal oxides selected from n, W, Zr, In and Ti include:
_{SiO 2, Al 2 O 3,} SnO 2, Sb 2 O 5, Ta 2 O 5,
CeO ₂ , La ₂ O ₃ , Fe ₂ O ₃ , ZnO, WO ₃ , Zr
Inorganic oxide fine particles of O ₂ , In ₂ O ₃ and TiO ₂ are colloidally dispersed in a dispersion medium such as water, alcohol or other organic solvent. Alternatively, the composite fine particles composed of two or more kinds of these inorganic oxides are colloidally dispersed in water, alcohol or other organic solvent. Further, in order to enhance dispersion stability in the coating liquid, it is also possible to use those obtained by treating the surface of these fine particles with an organic silicon compound or an amine compound. Examples of the organosilicon compound used at this time include monofunctional silane, difunctional silane, trifunctional silane, and tetrafunctional silane. In the treatment, the hydrolyzable group may be untreated or may be hydrolyzed. Further, after the treatment, it is preferable that the hydrolyzable group reacts with the -OH group of the fine particles, but there is no problem in stability even if it remains partially. The amine compounds include ammonium or alkylamines such as ethylamine, triethylamine, isopropylamine and n-propylamine, aralkylamines such as benzylamine, alicyclic amines such as piperidine, alkanolamines such as monoethanolamine and triethanolamine. There is. It is necessary to add these organosilicon compound and amine compound within the range of about 1 to 15% based on the weight of the fine particles. All have a particle size of about 1 to 300 m
μ is preferred, and the type of application and the amount used in the coating composition of the present invention are determined by the desired coating performance.

The amount used is preferably 20 to 60% by weight of the total composition. That is, if it is less than 20% by weight, the adhesiveness to the inorganic vapor deposition film becomes insufficient, or the scratch resistance of the coating film becomes insufficient. If it exceeds 60% by weight, cracks occur in the coating film. In addition, the dyeability is also insufficient.

Subsequently, the component (B) is a silane compound having a polymerizable reactive group such as vinyl group, allyl group, acryl group, methacryl group, epoxy group, mercapto group, cyano group, isocyano group and amino group. Specific examples thereof include vinyltrialkoxysilane, vinyltrichlorosilane, vinyltri (β-methoxy-ethoxy) silane, allyltrialkoxysilane, acryloxypropyltrialkoxysilane, methacryloxypropyltrialkoxysilane and methacryloxypropyl. Dialkoxymethylsilane, γ-glycidoxypropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) -ethyltrialkoxysilane, mercaptopropyltrialkoxysilane, γ-aminopropyltrialkoxysilane 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. Further, it is more effective to use either after hydrolyzing or to perform acid treatment on the film after curing.

The amount of the component (B) used is 30 to 30% of the total composition.
It is preferably 70% by weight. That is, if it is less than 30% by weight, the adhesion with the inorganic vapor deposition film tends to be insufficient. On the other hand, if it exceeds 70% by weight, it causes cracks 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) is an epoxy compound having two or more glycidyl groups in one molecule. It is obtained by a glycidyl group ring-opening reaction with (meth) 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, neopentyl glycol hydroxyhyvalinate diglycidyl ether, trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, diglycerol diglycidyl ether, di 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 Jigishi Ethers, triglycidyl ethers of tris (2-hydroxyethyl) isocyanurate, etc., aliphatic epoxy compounds, isophoronediol diglycidyl ether, alicyclic epoxy compounds such as bis-2,2-hydroxycyclohexylpropane diglycidyl ether, resorcin Examples thereof include aromatic epoxy compounds such as diglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, orthophthalic acid diglycidyl ester, phenol novolac polyglycidyl ether, and cresol novolac polyglycidyl ether.

In the present invention, since the epoxy (meth) acrylate which is 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 preferable. As the monocarboxylic acid-containing compound to be reacted with these epoxy compounds, in addition to acrylic acid and methacrylic acid, reaction of glycidyl (meth) acrylate or hydroxyethyl (meth) acrylate with an acid anhydride such as 0-phthalic anhydride There are monocarboxylic acid-containing (meth) acrylate compounds obtained by

The reaction of the epoxy compound with the monocarboxylic acid-containing (meth) acrylate is carried out by mixing the above and using a catalyst such as dimethylaminoethyl methacrylate 3
Add a quaternary amine compound or a quaternary amine salt such as benzyltrimethylammonium chloride to 60 ° C to 110 ° C.
It is obtained by heating to.

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 can be obtained, for example, by reacting 1 mol of glycerol triglycidyl ether with 1.5 mol of acrylic acid.

The amount of component (C) used is 2 to 3 of the total composition.
It is necessary to be 0% by weight. That is, if it is less than 2% by weight, the dyeability becomes insufficient. On the other hand, if it exceeds 30% by weight, the adhesion to the inorganic vapor deposition film tends to be insufficient,
Not preferred.

It is also possible to contain the component (D) in order to adjust the refractive index of the coating or further improve the durability of the coating.

Silica sol and silica fine particles are effective examples of the silica fine particles having a particle diameter of 1 to 100 mm as the component (D). Silica sol is a dispersion medium such as water, alcohol or other organic solvent in which high molecular weight silicic acid anhydride is colloidally dispersed. The powdery silica fine particles are powders obtained by subjecting the surface of colloidal silica to a hydrophobic treatment, and all of them are commercially available. For purposes of this invention, an average particle size of 1 to 1
00 millimicrons are used, but preferably 5
A diameter of -30 mm is used. If the particle size is 1 millimicron or less, the fine particle silica does not exist stably, and uniform quality cannot be obtained. On the other hand, when it is 100 milliminclone or more, there arises a problem that the coating film becomes cloudy.

The tetrafunctional silane compound represented by the general formula of Si (OR ⁴ ) ₄ is tetramethoxysilane,
Tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetraacetoxysilane, tetraallyloxysilane, tetrakis (2-methoxyethoxy) silane, tetrakis (2-ethylbutoxy) silane, tetrakis ( 2-ethylhexyloxy) silane and the like can be mentioned. These may be used alone or in combination of two or more. Further, it is preferable to hydrolyze these in the absence of solvent or in an organic solvent such as alcohol in the presence of acid.

The coating composition thus obtained can be used by diluting it with a solvent, if necessary. As the solvent, solvents such as alcohols, esters, ketones, ethers and aromatics are used.

In addition to the above components, the coating composition of the present invention may contain a small amount of a surfactant, an antistatic agent, an ultraviolet absorber, an antioxidant, a disperse dye / oil soluble dye /
It is also possible to add a fluorescent dye / pigment, a photochromic compound, a light-resistant heat-resistant stabilizer such as a hindered amine / hindered phenol system, etc. to improve the coatability of the coating solution and the film performance after curing.

Further, in applying the coating composition of the present invention, the surface of the substrate is previously treated with an alkali, an acid, a surfactant, an inorganic or organic substance for the purpose of improving the adhesion between the substrate lens and the coating. It is effective to carry out polishing treatment with fine particles, primer treatment or plasma treatment.

As a coating / curing method, a coating solution is applied by a dipping method, a spinner method, a spray method or a flow method, and then dried by heating at a temperature of 40 to 200 ° C. for several hours to form a film. be able to. In particular, for a base material having a heat distortion temperature of less than 100 ° C., a spinner method that does not require fixing the lens base material with a jig is suitable.

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

Preferred curing catalysts are perchloric acid, ammonium perchlorate, perchloric acid such as magnesium perchlorate, Cu (II), Zn (II), Co (II), Ni (I).
I), Be (II), Ce (III), Ta (III), Ti
(III), Mn (III), La (III), Cr (III
), V (III), Co (III), Fe (III), Al
Examples thereof include acetylacetonate having a central metal atom of (III), Ce (IV), Zr (IV), V (IV) and the like, amino acids such as amine and glycine, Lewis acids, and organic acid metal salts. Among these, the most preferable curing catalysts include magnesium perchlorate, Al (III) and Fe (III) acetylacetonate. The addition amount is preferably within the range of 0.01 to 5.0% of the solid content concentration.

The thickness of the cured coating is 0.05
It is preferably ˜30 μ. That is, 0.05μ
If it is less than 30 μm, the basic performance does not appear, and if it exceeds 30 μ,
The surface smoothness is impaired and optical distortion occurs, which is not preferable.

As the coating method, a dipping method or a spray method is used.
Method, roll coat method, spin coat method, flow coat method and the like.

Examples of the film forming method for forming the antireflection film made of an inorganic material in the present invention include a vacuum vapor deposition method, an ion plating method and a sputtering method.
In the vacuum vapor deposition method, an ion beam assist method in which an ion beam is simultaneously irradiated during vapor deposition may be used. As the film structure, either a single-layer antireflection film or a multilayer antireflection film may be used.

Specific examples of the inorganic material used include Si
O ₂ , SiO, ZrO ₂ , TiO ₂ , TiO, Ti ₂ O ₃ ,
Ti ₂ O ₅ , Al ₂ O ₃ , Ta ₂ O ₅ , CeO ₂ , MgO, Y ₂
O ₃ , SnO ₂ , MgF ₂ , WO _{3 and the} like can be mentioned. These inorganic substances may be used alone or as a mixture of two or more.

When forming the antireflection film, it is desirable to perform surface treatment of the hard coat film. Specific examples of the surface treatment include acid treatment, alkali treatment, ultraviolet irradiation treatment, plasma treatment by high frequency discharge in an argon or oxygen atmosphere, and ion beam irradiation treatment of argon, oxygen or nitrogen.

Hereinafter, the present invention will be described in more detail with reference to Examples.

[0036]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail by way of examples, but the present invention is not limited thereto.

Example 1 (1) Synthesis of Epoxy Acrylate In a 1 liter flask equipped with a thermometer and a reflux condenser, trimethylolpropane triglycidyl ether (manufactured by Nagase Kasei Kogyo KK; trade name "Denacol EX-321") ) 5
80 g, acrylic acid 112 g, dimethylaminoethyl methacrylate 3 g, hydroquinone methyl ether 0.
Add 4 g and 173 g of butyl cellosolve and stir for 2 hours at 70 ° C., 2 hours at 80 ° C., then 90
The reaction is carried out for 6 hours at a temperature of epoxy acrylate (EA-
1) was obtained. The obtained epoxy acrylate is APH
A150 and oxidation were 0.05.

(2) Preparation of coating liquid 1000 g of methanol, 1,4-dioxane 592.7
g, methyl cellosolve-dispersed titanium dioxide ferrosoferric oxide-silicon dioxide composite fine particle sol (manufactured by Catalysts & Chemicals Industry Co., Ltd., solid content concentration 20% by weight) 1988. 7g, methanol-dispersed colloidal silica (manufactured by Catalysts & Chemicals Industry Co., Ltd.) , Brand name "Oscar 1132", solid content concentration 30% by weight) 221.6
After mixing g, 523.1 g of γ-glycidoxypropyltrimethoxysilane was mixed. 0.0 to this mixture
144 g of 5N hydrochloric acid aqueous solution was added dropwise with stirring, and the mixture was further stirred for 4 hours and aged overnight. Add EA-1 to this solution 5
After adding 18.6 g, magnesium perchlorate 11.7
g, silicon-based surfactant (Nippon Unicar Co., Ltd., trade name "L-7001") 1.5 g, and hindered amine light stabilizer (Sankyo Co., Ltd., trade name [Sanol LS-
770 ") 5.3 g was added, and the mixture was stirred for 4 hours and aged overnight to give a coating liquid.

(3) Coating and curing With the coating liquid thus obtained, an eyeglass lens having a refractive index of 1.60 and treated with an alkali (Seiko Epson Corp.)
The lens material for Seiko High Road SMX manufactured by Seiko Co., Ltd.) was applied by the dipping method. Lifting speed is 23 cm / mi
It was set to n. After coating, air-dry at 80 ℃ for 20 minutes and then 110 ℃
And baked for 180 minutes. The cured film thus obtained had a thickness of about 2 μm and was excellent in both appearance and dyeability.

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

(1) Formation of Antireflection Thin Film After the lens obtained by the above method was subjected to plasma treatment (argon plasma 400 W × 60 seconds), SiO ₂ , ZrO ₂ and SiO were sequentially turned from the substrate to the atmosphere. ₂ , Zr
An antireflection multilayer film consisting of five layers of O ₂ and SiO ₂ was formed by a vacuum vapor deposition method (manufactured by Vacuum Instrument Co., Ltd .; BMC-1000). Optical film thickness of each layer, the first SiO ₂
Layer, the next equivalent ZrO ₂ and SiO ₂ film layer and the next ZrO 2
_{The two} layers and the uppermost SiO ₂ layer were formed to have λ / 4, respectively. The design wavelength λ was 520 nm.

The reflection interference color of the obtained multilayer film was green and the total light transmittance was 98%.

(2) Test and Evaluation Results The lenses obtained in Example 1 (hereinafter referred to as hard coat lenses) and the lenses obtained in Example 2 (hereinafter referred to as hard multi coat lenses) were respectively tested as follows. Tests were conducted by the method described, and the results are shown in Table 1.

(A) Abrasion resistance: 1 kg of Bonster # 0000 steel wool (manufactured by Nippon Steel Wool Co., Ltd.)
Then, the surface was rubbed for 10 reciprocations, and the degree of damage was visually evaluated in the following stages.

A: There is no scratch in the area of 1 cm * 3 cm. B: 1 to 10 scratches are formed within the above range. C: 10 to 100 scratches are formed within the above range. D: Countless scratches are attached, but a smooth surface remains. E: No smooth surface remained due to scratches on the surface.

(B) Water resistance / chemical resistance: water, alcohol,
It was soaked in kerosene for 48 hours, and those having no change in surface condition were regarded as good.

(C) Acid resistance / detergent resistance: 12 in 0.1N hydrochloric acid and 1% Mama lemon (manufactured by Lion Oil & Fat Co., Ltd.) aqueous solution
Immersion for a period of time was evaluated as good if the surface condition was not changed.

(D) Adhesion: The adhesion between the substrate and the hard coat film and between the hard coat film and the multi coat film is JI.
A cross-cut tape test was performed according to SD-0202. That is, cuts are made at intervals of 1 mm on the surface of the substrate using a knife to form 100 squares of 1 mm 2. Then, after strongly pressing the cellophane adhesive tape (trade name "Cellotape" manufactured by Nichiban Co., Ltd.) on top of it, it was pulled by 90 degrees from the surface and peeled off rapidly. It was used as an index.

(E) Weather resistance: The one having no change in surface condition after being exposed to a sunshine weather meter by a xenon lamp for 400 hours was regarded as good.

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

(G) Durability: Considering that durability is essentially an adhesive connection, the above-mentioned cross-cut tape test was performed on the coat films subjected to the tests (a) to (f). Those without peeling were considered good.

(H) Dyeability (hard coat lens only): 2 g of Seiko Plax Diamond Coat dye Amber D was dispersed in 1 liter of pure water at 92 ° C. to prepare a dye solution.

Dyeing was carried out by immersing in this dyeing solution for 5 minutes, and there was no dyeing unevenness and the total light transmittance was 30% or more before and after dyeing.

Example-3 (1) Synthesis of Epoxy Acrylate A glycerol diglycidyl ether (Nagase Kasei Co., Ltd.) was placed in a 1 liter flask equipped with a thermometer and a reflux condenser.
Made; trade name "Denacol EX-313") 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,
Epoxy acrylate (EA-2) was obtained by reacting at 70 ° C for 2 hours and at 80 ° C for 6 hours. The obtained epoxy acrylate had APHA of 150 and oxidation of 0.05.

(2) Preparation of coating liquid butyl cellosolve 395 g, methyl cellosolve dispersion cerium dioxide-titanium dioxide-silicon dioxide composite fine particle sol (manufactured by Catalysts & Chemicals Co., Ltd., trade name "Optlake 18")
32 "solid content concentration 20 wt%) 409.6 g, and then γ-glycidoxypropyltrimethoxysilane 12
4.5g was mixed. 35 g of 0.05N hydrochloric acid aqueous solution was added dropwise to this mixed solution with stirring, and the mixture was stirred for 4 hours and aged overnight. After adding 35 g of EA-2 to this solution, 2.0 g of aluminum acetylacetonate and a silicon-based surfactant (manufactured by Nippon Unicar Co., Ltd .; trade name “FZ-2”).
110 ") and 0.3 g of a phenolic antioxidant (Kawaguchi Chemical Co., Ltd., trade name" ANTAGE CRYSTAL ") were added, and the mixture was stirred for 4 hours and aged overnight to give a coating solution.

(3) Coating and curing The coating liquid thus obtained was applied to a spectacle lens having a refractive index of 1.66 (lens material for Seiko Super Sovereign manufactured by Seiko Epson Corp.) by a spinner method. It was

The coating conditions are as follows.

Rotation speed: 500 rpm for 10 seconds (application of the coating liquid during this time) Rotation speed: 2000 rpm for 1 second Rotation speed: 500 rpm for 5 seconds After coating, air-dry at 80 ° C. for 20 minutes, and then at 130 ° C. for 120 seconds.
Baking was performed for a minute. The thickness of the cured film thus obtained was about 2.3 μm and was excellent in both appearance and dyeability.

(4) Test and Evaluation Results The lens thus obtained was 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 After subjecting the lens obtained by the above method to plasma treatment (argon plasma 400 W × 60 seconds), ZrO ₂ , SiO ₂ , ZrO ₂ , Si
An antireflection multilayer film consisting of four layers of O ₂ was formed by a vacuum evaporation method (manufactured by Vacuum Instrument Co., Ltd .; BMC-1000). The optical film thickness of each layer was formed so that the equivalent film layer of the first ZrO ₂ and SiO ₂ , the next ZrO ₂ layer, and the uppermost SiO ₂ layer were each λ / 4. The design wavelength λ was 520 nm.

The reflection interference color of the obtained multilayer film was green, and the total light transmittance was 98%.

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

Example-5 (1) Synthesis of Epoxy Methacrylate In a 1 l flask equipped with a thermometer and a reflux condenser, 1,6
-Hexanediol diglycidyl ether (manufactured by Nagase Kasei Co., Ltd .; trade name "Denacol EX-212") 6
00 g, 189 g of methacrylic acid, 3 g of dimethylaminoethyl methacrylate, 0.4 g of hydroquinone methyl ether, and 338 g of butyl cellosolve were added with stirring and at 70 ° C. for 2 hours, 80 ° C. for 2 hours, and then 9
Epoxy methacrylate (EA
-3) was obtained. The obtained epoxy methacrylate is A
The PHA was 180 and the oxidation was 0.05.

(2) Preparation of coating liquid 368.3 g of isopropyl cellosolve, 92.1 g of pure water
And methanol-dispersed tin dioxide-tungsten dioxide composite fine particle sol (manufactured by Nissan Chemical Industries, Ltd., solid content concentration 3)
07.2 wt%) 287.2 g, and then γ-methacryloxypropyltrimethoxysilane 54.8 g and γ-
62.6 g of glycidoxypropyltrimethoxysilane and 16.8 g of tetramethoxysilane were mixed. 41.5 g of 0.05N hydrochloric acid aqueous solution was added dropwise to this mixed solution while stirring. After stirring for further 5 hours, the mixture was aged overnight. 76.3 g of EA-3 and acetylacetone Fe were added to this liquid.
(III) 1.5 g of salt and 0.3 g of silicon-based surfactant (manufactured by Nippon Unicar Co., Ltd .; trade name "L-7604]"
Was added, and the mixture was stirred for 4 hours and aged overnight to give a coating liquid.

(3) Coating and curing The coating solution thus obtained was applied to a polycarbonate injection molded spectacle lens having a refractive index of 1.58 by the spinner method. The coating conditions were the same as in Example-3.

After coating, air-dry at 80 ° C. for 15 minutes, and then 13
Baking was performed at 0 ° C. for 2 hours. The thickness of the cured film thus obtained was about 2.1 μm and was excellent in both appearance and dyeability.

(4) Formation of Antireflection Thin Film The lens obtained by the above-mentioned method was used as a mixture of ZrO ₂ of Example-4 and a mixture of ZrO ₂ and Ti oxide (ZrO ₂ / Ti oxide = 65/35 (weight ratio). )) Was changed to form an antireflection film by the same method.

The reflection interference color of the obtained multilayer film was green and the total light transmittance was 98.5%.

(5) Test and Evaluation Results The lens thus obtained was 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 the hard coat lens.

Example-6 (1) Synthesis of Epoxy Methacrylate In a 1 liter flask equipped with a thermometer and a reflux condenser, tripropylene glycol diglycidyl ether (manufactured by Nagase Chemical Industry Co., Ltd .; trade name "Denacol EX-921"). ) 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 added and stirred, and reacted at 70 ° C. for 2 hours, 80 ° C. for 2 hours, and then 90 ° C. for 6 hours. Epoxy methacrylate (E
A-4) was obtained. The obtained epoxy methacrylate is
APHA 200, oxidation 0.05.

(2) Preparation of coating liquid Methyl cellosolve 915.6 g, water-dispersed antimony pentoxide fine particle sol (manufactured by Nissan Chemical Industries, Ltd., solid content concentration 30)
wt%) 1244.4 g, and then γ-glycidoxypropylmethyldimethoxysilane 211.7 g and γ-methacryloxypropyltrimethoxysilane 21
1.7 g were mixed. 93 g of 0.05N hydrochloric acid aqueous solution was added dropwise to this mixed solution with stirring, and the mixture was stirred for 4 hours and aged overnight. 321 g of EA-4 was added to this solution, and then 3.5 g of stannous chloride and 0.1 g of a silicon-based surfactant (manufactured by Big Chemie Co., Ltd .; trade name "BYK-300").
Was added, and the mixture was stirred for 4 hours and aged overnight to give a coating liquid.

(3) Coating and curing With the coating liquid thus obtained, a spectacle lens having a refractive index of 1.56 (manufactured by Seiko Epson Corporation, Seiko Plax)
IIGX lens cloth) Coating was performed by a spray method.

The spraying was carried out using an Iwata Wider 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 coating, air-dry at 80 ° C. for 10 minutes and then 130.
Firing was performed at 2 ° C. for 2 hours. The cured coating thus obtained had a thickness of about 4 μm and was excellent in both appearance and dyeability.

(4) Test and Evaluation Results The lens 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 After subjecting the lens obtained in Example-6 to ion beam irradiation treatment (accelerating voltage 500 V × 60 seconds) with oxygen gas, the substrate was exposed to the atmosphere. In order of SiO ₂ , Zr
An antireflection multilayer film consisting of five layers of O ₂ , SiO ₂ , TiO ₂ , and SiO ₂ was formed by vacuum deposition (manufactured by Vacuum Instrument Co., Ltd .; BMC
-1000). At that time, Ti of the fourth layer
O ₂ was deposited by ion beam assisted vapor deposition.
The optical film thickness of each vapor-deposited layer is as follows: first SiO ₂ , second ZrO ₂
And SiO ₂ equivalent film layer is λ / 4, TiO ₂ layer is λ / 2,
The uppermost SiO ₂ layer was formed to have a λ / 4. The design wavelength λ was 520 nm.

The reflection interference color of the obtained multilayer film was green, and the total light transmittance was 99%.

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

Comparative Example-1 The lenses were applied in the same manner as in Example-1, except that EA-1 was not added.

The lens thus obtained was tested by the same method, and the results are shown in Table 1.

Comparative Example-2 In Example-3, instead of the methylcellosolve-dispersed cerium dioxide-titanium dioxide-silicon dioxide composite fine particle sol, water-dispersed colloidal silica (Catalyst Kasei Kogyo Co., Ltd.) was used.
Made, product name "Cataloid SN", solid content concentration 20
The coating was performed on the lens in the same manner as in Example-3, except that (% by weight) was used.

The lens thus obtained was used as an example-
A test was conducted in the same manner as in No. 1 and the results are shown in Table 1.

COMPARATIVE EXAMPLE 3 The lenses were applied in the same manner as in Example 3, except that glycerol diglycidyl ether was added instead of EA-2.

The lens thus obtained was used as an example-
A test was conducted in the same manner as in No. 1 and the results are shown in Table 1.

Comparative Example-4 An antireflection film was formed on the lens obtained in Comparative Example-3 by the same method as in Example-4.

The lens thus obtained was used as an example-
A test was conducted in the same manner as in 2, and the results are shown in Table 1.

[0087]

[Table 1]

[0088]

As described in detail above, according to the present invention, it is possible to increase the hardness of the surface, and at the same time obtain good dyeability and adhesion (durability) with an antireflection film made of an inorganic material. did it. That is, as a plastic lens material,
Resins with various functions such as (meth) acrylic resins, styrene resins, carbonate resins, allyl resins, allyl carbonate resins, vinyl resins, polyester resins, polyether resins, urethane resins and polymers of new monomers and comonomers. It can be applied.

A plastic material having excellent scratch resistance, good dyeability, and good adhesion (durability) with an antireflection film made of an inorganic material is a spectacle lens, a camera lens, a light beam condensing lens or a light beam. It can be widely applied as a diffusion lens for consumer use 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 applications such as cover glasses, and the obtained effects are great.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location C23C 14/08 C23C 14/08 NG02B 1/11 C09D 163/00 PJQ // C09D 163/00 PJQ G02B 1 / 10 A

Claims (3)

[Claims] 1. A coating composition comprising at least the following components (A), (B) and (C) as main components. (A). Al, Sn, S with a particle size of 1-100 mm
b, Ta, Ce, La, Fe, Zn, W, Zr, In,
Fine particles composed of one or more metal oxides selected from Ti and / or Si, Al, Sn, Sb, Ta, Ce,
Composite fine particles composed of two or more kinds of metal oxides selected from La, Fe, Zn, W, Zr, In and Ti (B). A silane compound having at least one polymerizable reactive group (C). Epoxy (meth) acrylate having simultaneously glycidyl group and (meth) acryloyl group in one molecule 2. The coating composition according to claim 1, further comprising the following component (D). (D) Silica fine particles having a particle size of 1 to 100 millimicrons and / or a hydrolyzate and / or partial condensate of an organosilicon compound represented by Si (OR ¹ ) ₄ in the general formula (wherein R ¹ is the number of carbon atoms). 1 to 8 represents a hydrocarbon group or an alkyl group) 3. A laminate comprising an antireflection film made of an inorganic substance provided on the surface of a coat film made of the coating composition according to claim 1.