JP2003292896A - Coating composition and laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coating composition which meets both of sufficient dyeability and durability of the coated film as such and the durability when an anti-reflection film composed of an inorganic substance is provided on the surface of the coated film. <P>SOLUTION: The coating composition comprises a metal oxide, a silane compound, and an epoxy(meth)acrylate as the major components and enables both of sufficient dyeability and durability of the coated film as such and the durability when the anti-reflection film composed of an inorganic substance is provided on the surface of the coated film. <P>COPYRIGHT: (C)2004,JPO

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 Recently, plastic lenses have come to be used in various fields. In particular, in the case of eyeglass lenses, plastic lenses are now the mainstream because they are lighter, safer, and have more color variations than conventional glass lenses. Further, in recent years, the plastic lens material has been rapidly made to have a high refractive index with a reduction in thickness. As a technical proposal therefor, JP-A-59-1
A high refractive index resin material having a refractive index of 1.60 or more is proposed in Japanese Patent No. 33211, Japanese Patent Laid-Open No. 63-46213, and the like. Further, in JP-A-9-110956, the refractive index is 1.67, and JP-A-11-258402.
In the publication, a high refractive index resin material having a refractive index of 1.74 is proposed. In particular, plastic lenses made of allyl carbonate-based resins, acrylate-based resins, methacrylate-based resins, and thiourethane-based resin materials are widely used because of their excellent workability, heat resistance, and impact resistance, and their thin lens thickness and good appearance. It has come to be used. On the other hand, however, the plastic spectacle lens has a drawback that the surface is easily scratched. Therefore, a method of providing a silicon-based hard coat film on the surface of the plastic lens is generally performed. This silicon-based hard coat film contains a colloidal dispersion (sol) of metal oxide and a silane coupling agent which is an organic silicon compound as main components. The metal oxide sol mainly imparts scratch resistance and adhesion to the inorganic vapor deposition film formed on the surface of the hard coat film, and the silane coupling agent is mainly scratch resistance and metal inorganic oxide particles. Adhesiveness with the binding agent and the lens substrate is imparted. Conventionally, a sol of silicon dioxide fine particles has been exclusively used as a metal oxide sol. The refractive index of the hard coat film was about 1.50. However, as described above, in recent years, the refractive index of the plastic lens has been increased, and the mainstream thereof is a lens material having a refractive index of 1.67 or more. When a hard coat film using a sol of fine particles of silicon dioxide is applied to such a high refractive index lens material, interference fringes (color) are generated due to a difference in refractive index between the resin lens and the hard coat film, which is not preferable in 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 is proposed. A coating technique of replacing with a colloidal dispersion of fine particles of an inorganic oxide having a refractive index of Al, Ti, Zr, Sn, and Sb is disclosed. JP-A-1-301517 discloses a method for producing a composite sol of titanium dioxide and cerium dioxide, and JP-A-2-264902.
Japanese Unexamined Patent Publication No. 3-68901 discloses a technique of using fine particles of a composite inorganic oxide of Ti and Ce in a coating composition, and fine particles of a composite inorganic oxide of Ti, Ce, and Si treated with an organic silicon compound. There is. Also,
JP-A-10-324846 and JP-A-11-116
In Japanese Patent Laid-Open No. 843 and Japanese Patent Laid-Open No. 11-310755, there is proposed a technique of using composite inorganic oxide fine particles of Sn, Ti and Zr in a coating composition. As described above, the method of using the inorganic oxide fine particles having a high refractive index is generally used to increase the refractive index of the hard coat film. Specifically, Al, Sn, Sb, Ta, Ce, La, F
Single fine particles of oxides selected from e, Zn, W, Zr, In and Ti and / or one kind or a mixture of two or more kinds selected from composite fine particles thereof (referred to as high refractive index metal oxide) is used. Often. Among them, the oxide of Ti, that is, titanium oxide, has a higher refractive index than other metal oxides and therefore has many advantages. First, since it has a high refractive index, it can be applied to the design of a hard coat film which is expected to require a higher refractive index setting in the future. Further, when the target refractive index of the hard coat film is the same, the addition amount is smaller than that of other metal oxide fine particles. As a result, the occurrence of film crack defects during the curing reaction due to the decrease in toughness due to the excessive addition of the metal oxide in the hard coat film can be suppressed. Thus, it can be said that titanium oxide is extremely useful as a high refractive index metal oxide. However, when titanium oxide is used as a metal oxide for a hard coat film, the following problems have been pointed out in JP-A-11-310755. That is, titanium oxide is light (ultraviolet)
It is active when it receives energy, and has the property of decomposing organic substances by its strong oxidative decomposition power (hereinafter referred to as photoactivity). As a result, when the hard coat film is of a dyeable type, the dye molecule impregnated in the hard coat film is decomposed by the photoactivity of titanium oxide. In particular,
There is a problem that the color change (fading) of the color lens becomes extremely large due to long-term use. Although such a color change is somewhat different depending on the structure of the dye molecule, most of the dyes currently commonly used cannot be used. At present, there are two types of anatase-rutile crystal forms of titanium oxide that are industrially used, and it has been found that the rutile-type crystal structure is more stable than the anatase-type one in terms of photoactivity. There is. In the publication, the above problem is improved by selectively using titanium oxide having a rutile type crystal structure. An object of the present invention is to provide a plastic lens having excellent weather resistance (light) resistance and having little color change of a dyed lens even when titanium oxide having an anatase type crystal structure is used as a coating composition. .

[0003]

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.

[0004]

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 has made it possible to obtain excellent performance in all types of durability.

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

(A) S having a particle size of 1 to 100 mm
Composite fine particles (B) composed of metal oxide of i, Sb and Ti (B) Silane compound having at least one polymerizable reactive group (C) Simultaneously having a glycidyl group and a (meth) acryloyl group in one molecule Epoxy (meth) acrylate

Particle size of component (A) used in the present invention is 1 to 1
From 00 millimicron Si, Sb, Ti metal oxides
As a concrete example of the composite fine particles to be constituted, SiO 2₂，
Sb ₂O_Five, TiO₂Consisting of inorganic oxide fine particles
If the composite fine particles are water, alcohol, or other
It is a colloidal dispersion in an organic solvent. Furthermore
In order to improve dispersion stability in the coating solution,
The particle surface is treated with an organosilicon compound or an amine compound.
It is also possible to use an intelligent one. Used at this time
There is a monofunctional silane as the organosilicon compound.
Ia bifunctional silane, trifunctional silane, tetrafunctional silane
Etc. Treat with no hydrolyzable groups
Alternatively, it may be hydrolyzed. After processing
Is a state in which the hydrolyzable group reacts with the -OH group of the fine particles.
It is preferable, but there is no stability problem even if it remains partially
There is no. As the amine compound, ammonium or
Is ethylamine, triethylamine, isopropylamine
Alkylamines such as amine and n-propylamine, benzyl
Aralkylamines such as amines and alicyclic amines such as piperidine
Min, monoethanolamine, triethanolamine, etc.
There are alkanolamines. These organosilicon compounds
And the amount of amine compound added is from 1 to the weight of fine particles.
It is necessary to add within the range of about 15%. All are particles
The diameter is preferably about 1 to 300 mμ, and the coater of the present invention is used.
The coating type and amount used in the coating composition is the desired coating performance.
Determined by

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 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-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 between the epoxy compound and the monocarboxylic acid-containing (meth) acrylate is carried out by mixing the above and using a catalyst such as dimethylaminoethyl methacrylate as a catalyst.
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 preferable.

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.

Specific examples of the silica fine particles as the component (D) include silica sol and silica fine particles. 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 the purpose of the present invention, those having an average particle diameter of 1 to 100 mm are used, but those having a diameter of 5 to 30 mm are preferably 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 ₁ ) 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 optionally 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. The present invention also exerts a great effect when a primer layer made of a polyurethane resin and / or a polyester resin is formed before applying the hard coat film to the surface of the plastic lens substrate.

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

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.

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

The thickness of the cured film 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.

Further, 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 by way of examples.

[0033]

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 Chemtex Co., Ltd.); trade name "Denacol EX-32"
1 ”) 580 g, acrylic acid 112 g, dimethylaminoethyl methacrylate 3 g, hydroquinone methyl ether 0.4 g, and butyl cellosolve 173 g are added and stirred at 70 ° C. for 2 hours, 80 ° C. for 2 hours, and then 90 ° C. for 6 hours. The reaction was carried out for a time to obtain an epoxy acrylate (EA-1). The obtained epoxy acrylate had APHA of 150 and oxidation of 0.05.

(2) Preparation of hard coat solution 1000 g of methanol, 592.7 of 1,4-dioxane
g, methyl cellosolve-dispersed titanium dioxide antimony pentoxide-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 (Catalysts & Chemicals Industry Co., Ltd.)
221.6 g (manufactured by trade name "OSCAL 1132", solid content concentration 30% by weight) was mixed, and then 523.1 g of γ-glycidoxypropyltrimethoxysilane was mixed. To this mixed solution, 144 g of 0.05N hydrochloric acid aqueous solution was added dropwise with stirring, and the mixture was further stirred for 4 hours and aged overnight. After adding 518.6 g of EA-1 to this liquid, 11.7 g of magnesium perchlorate, 1.5 g of a silicon-based surfactant (manufactured by Nippon Unicar Co., Ltd., trade name "L-7001") and a hindered amine-based photostabilization. An agent (manufactured by 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 hard coat solution.

(3) Coating and curing The hard coat solution thus obtained is dipped in an alkali-treated eyeglass lens having a refractive index of 1.60 (lens material for Seiko Super Lucious, manufactured by Seiko Epson Corp.). Method was applied. Lifting speed is 2
It was 3 cm / min. After coating, it was air dried at 80 ° C. for 20 minutes and then baked at 110 ° C. 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 Each of the lenses obtained in Example-1 was processed by the following method.
Forming antireflection coating thin film made of inorganic material
It was (1) Formation of antireflection thin film The lens obtained by the above method was plasma treated (argon
After performing plasma 400W x 60 seconds),
In order of concern, SiO₂, ZrO₂, SiO ₂, Zr
O₂, SiO₂ The anti-reflection multilayer film consisting of 5 layers of
By wearing method (manufactured by Vacuum Instrument Co., Ltd .; BMC-1000)
Formed. The optical thickness of each layer is₂
Layer, next ZrO₂And SiO₂Equivalent film layer and the following ZrO
₂Layer, top layer of SiO₂ So that each layer is λ / 4
Formed. 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 multicoat lenses) were respectively tested as follows. Tests were conducted by the method described, and the results are shown in Table 1. (A) Abrasion resistance: Bonster # 0000 steel wool (manufactured by Nippon Steel Wool Co., Ltd.) was applied with a load of 1 kg, and the surface was rubbed for 10 reciprocations, and the degree of damage was visually evaluated in the following stages. . A: No scratches in the range of 1 cm * 3 cm B: 1 to 10 scratches in the above range C: 10 to 100 scratches in the above range D: Innumerable scratches , Smooth surface remains E: No smooth surface due to scratches on the surface (b) Water resistance / chemical resistance: 48 in water, alcohol, kerosene
Immersion for a period of time was evaluated as good if the surface condition was not changed. (C) Acid / detergent resistance: Immersed in 0.1N hydrochloric acid and 1% Mama lemon (manufactured by Lion Oil and Fat Co., Ltd.) aqueous solution for 12 hours,
Those with no change in surface condition were considered 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 JIS D-020.
A cross-cut tape test was performed according to 2.
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. next,
After strongly pressing cellophane adhesive tape (trade name "Cellotape (registered trademark)" manufactured by Nichiban Co., Ltd.) on it, it was pulled by 90 degrees from the surface and peeled off, and then adhered with the remaining squares of the coating film. It was used as a sex index. (E) Weather resistance: A sample having no change in surface condition after being exposed to a sunshine weather meter with a xenon lamp for 400 hours was regarded as good. (F) Heat resistance (cooling cycle property): 1 in hot air at 70 ° C
The surface condition was examined after storage for a period of time. Further at -5 ℃ 15
The cycle of 15 minutes at 60 ° C. for 5 minutes 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 carried out on those tested in (a) to (f) without peeling. Good things. (H) Dyeability (only for hard coat lens): 2 g of Seiko Plax Diamond Coat dye Amber D was dispersed in 1 liter of pure water at 92 ° C. to prepare a dyeing 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 In a 1-liter flask equipped with a thermometer and a reflux condenser, glycerol diglycidyl ether (manufactured by Nagase Chemtex Co., Ltd .; trade name "Denacol EX-313") 580
g, acrylic acid 144 g, benzyltrimethylammonium chloride 3 g, hydroquinone methyl ether 0.
4 g of butyl cellosolve and 181 g of butyl cellosolve were added, and the mixture was stirred and reacted at 70 ° C. for 2 hours and at 80 ° C. for 6 hours to obtain an epoxy acrylate (EA-2). The obtained epoxy acrylate had APHA of 150 and oxidation of 0.05.

(2) Preparation of Hard Coat Liquid 395 g of butyl cellosolve, methanol-dispersed titanium dioxide antimony pentaoxide-silicon dioxide composite fine particle sol (manufactured by Catalysts & Chemicals Industry Co., Ltd., solid content concentration 20 wt%) 40
After mixing 9.6 g, 124.5 g of γ-glycidoxypropyltrimethoxysilane was mixed. 35 g of a 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 liquid, 2.0 g of aluminum (III) acetylacetonate, 0.3 g of a silicon-based surfactant (manufactured by Nippon Unicar Co., Ltd .; trade name "FZ-2110") and phenol-based oxidation 0.7 g of an inhibitor (manufactured by Kawaguchi Chemical Industry Co., Ltd., trade name "ANTAGE CRYSTAL") was added, and the mixture was stirred for 4 hours and aged overnight to give a hard coat solution.

(3) Coating and curing The thus obtained hard coat liquid had a refractive index of 1.
A 67-spectacle lens (lens material for Seiko Super Sovereign manufactured by Seiko Epson Corporation) was applied by the spinner method.

The coating conditions are as follows. Rotation speed 500 rpm for 10 seconds (coating liquid is applied 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, 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 The lens obtained by the above method was plasma treated (argon
After performing plasma 400W x 60 seconds),
ZrO₂, SiO₂, ZrO ₂, Si
O₂The anti-reflection multilayer film consisting of 4 layers of
BMC-1000) manufactured by Koki Kogyo Co., Ltd.
It was. The optical thickness of each layer depends on the initial ZrO ₂And SiO₂of
Equivalent membrane layer and the following ZrO₂Layer, top layer of SiO₂Layer
It was formed so that each had a λ / 4. The design wavelength λ is
It was set to 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 liter flask equipped with a thermometer and a reflux condenser, 1,6
-Hexanediol diglycidyl ether (manufactured by Nagase Chemtex Co., Ltd.); trade name "Denacol EX-21"
2 ") 600 g, methacrylic acid 189 g, dimethylaminoethyl methacrylate 3 g, hydroquinone methyl ether 0.4 g, and butyl cellosolve 338 g are added and stirred with stirring at 70 ° C for 2 hours, 80 ° C for 2 hours, and then 90 ° C for 6 hours. The reaction was performed to obtain epoxy methacrylate (EA-3). The obtained epoxy methacrylate had an APHA of 180 and an oxidation of 0.05.

(2) Preparation of hard coat solution 268.3 g of isopropyl cellosolve, 92.1 g of pure water
And methanol-dispersed titanium dioxide antimony pentaoxide-silicon dioxide composite fine particle sol (Catalyst Chemical Co., Ltd.)
Manufactured, solid concentration 25 wt%) 344.6 g, and then γ-methacryloxypropyltrimethoxysilane 5
4.8 g and γ-glycidoxypropyltrimethoxysilane 62.6 g and tetramethoxysilane 16.8
g were mixed. 0.05N hydrochloric acid aqueous solution 4
1.5 g was added dropwise with stirring. After stirring for further 5 hours, the mixture was aged overnight. 76.3 g of EA-3, 1.5 g of acetylacetone iron (III) salt, and a silicon-based surfactant (manufactured by Nippon Unicar Co., Ltd .; trade name "L-76" are added to this liquid.
04 "), 0.3 g was added, and the mixture was stirred for 4 hours and aged overnight to give a hard coating solution.

(3) Coating and curing The hard coat liquid thus obtained had a refractive index of 1.
58 polycarbonate injection-molded spectacle lenses were applied 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 method was used as a ZrO ₂ of Example-4 in which a mixture of ZrO ₂ and a Ti oxide (ZrO ₂ / Ti oxide =
The antireflection film was formed in the same manner except that the ratio was changed to 65/35 (weight ratio)).

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 Chemtex Co., Ltd .; trade name “Denacol EX-92”).
1 ") 615 g, 129 g of methacrylic acid, 3 g of benzyltrimethylammonium chloride, 0.4 g of hydroquinone methyl ether and 319 g of butyl cellosolve, with stirring, at 70 ° C. for 2 hours, at 80 ° C. for 2 hours, and then at 90 ° C. for 6 hours. The reaction was performed to obtain epoxy methacrylate (EA-4). The obtained epoxy methacrylate had an APHA of 200 and an oxidation of 0.05.

(2) Preparation of Hard Coat Liquid Methylcellosolve 915.6 g, water-dispersed titanium dioxide antimony pentaoxide-silicon dioxide fine particle sol (Catalyst Kasei Co., Ltd., solid content concentration 30 wt%) 1244.4 g
Were mixed, and then 211.7 g of γ-glycidoxypropylmethyldimethoxysilane and 211.7 g of γ-methacryloxypropyltrimethoxysilane were mixed. 93 g of a 0.05N hydrochloric acid aqueous solution was added dropwise to this mixed solution while stirring, and the mixture was stirred for 4 hours and aged overnight. E to this liquid
After adding 321 g of A-4, 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”) were added, and the mixture was stirred for 4 hours and aged overnight. The hard coat liquid was used.

(3) Coating and curing The thus obtained hard coat liquid had a refractive index of 1.
Application was carried out by a spray method using No. 56 spectacle lens (lens material for Seiko Plax IIGX manufactured by Seiko Epson Corp.).

The spraying was carried out using an Iwata Wider 61 (manufactured by Iwata Coating Machine Co., Ltd .; nozzle diameter 1 mm) at a spraying 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 with oxygen gas (accelerating voltage 500 V × 60 seconds), the substrate was moved to the atmosphere. In order of SiO ₂ , Zr
Reflection consisting of 5 layers of O ₂ , SiO ₂ , TiO ₂ and SiO _2.
Vacuum evaporation method (manufactured by Vacuum Instrument Co., Ltd .; BM
C-1000). At that time, T of the fourth layer
A film of iO ₂ was formed by ion beam assisted vapor deposition. The optical film thickness of each vapor-deposited layer is as follows: first SiO ₂ , second Z
The equivalent film layer of rO ₂ and SiO ₂ is λ / 4, and the 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.

Example-8 (1) Preparation of Primer Liquid 212.0 g of methanol, commercially available aqueous emulsion polyurethane (manufactured by Nika Kagaku Co., Ltd., trade name "Neosticker 700", solid content concentration 37%) 103.0 g After mixing, methanol-dispersed titanium dioxide antimony pentaoxide-
Silicon dioxide composite fine particle sol (Catalyst Chemical Co., Ltd.,
185.0 g (solid content concentration 20 wt%) was mixed and well stirred to obtain a primer solution.

(2) Preparation of Hard Coat Liquid A hard coat liquid was prepared in the same manner as in Example-3.

(3) Coating and curing The obtained primer liquid was applied to a spectacle lens having a refractive index of 1.67 (lens material for Seiko Super Sovereign manufactured by Seiko Epson Corporation) by a spinner method.

The coating conditions are as follows. The rotation speed was 500 rpm for 10 seconds (the coating liquid was applied during this time) The rotation speed was 1000 rpm for 1 second The rotation speed was 500 rpm for 5 seconds, and the film was air-dried at 80 ° C. for 20 minutes.

The hard coat solution prepared in (2) was applied to the surface coated with the primer by the spinner method.

The coating conditions are as follows. Rotation speed 500 rpm for 10 seconds (coating liquid is applied 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, then at 130 ° C for 120 seconds
Baking was performed for a minute.

(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-9 (1) Formation of Antireflection Thin Film An antireflection film was formed on the lens obtained by the above method in the same manner as in Example-4.

(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 In Example-1, the lenses were applied in the same manner 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, methanol-dispersed titanium dioxide was used instead of methanol-dispersed titanium dioxide antimony pentaoxide-silicon dioxide composite fine particle sol (manufactured by Catalysts & Chemicals Industries Co., Ltd., solid content concentration 20 wt%). Zirconium dioxide-silicon dioxide composite fine particle sol (manufactured by Catalysts & Chemicals Industry Co., Ltd., trade name "Optlake 1120Z (S-7 / A8), solid content concentration 20% by weight") is all added by the same method. The coating was applied to the lens.

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 An antireflection film was formed on the lens obtained in Comparative Example-2 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.

[0080]

[Table 1]

[0081]

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,
In addition to (meth) acrylic resins, styrene resins, carbonate resins, allyl resins, allyl carbonate resins, vinyl resins, polyester resins, polyether resins, urethane resins and resins with various functions such as new monomers and polymers of 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. Furthermore, 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 front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G02B 1/11 G02B 1/10 AF term (reference) 2K009 CC03 CC09 CC24 CC33 CC42 DD03 DD04 DD07 4F100 AA17B AA20B AA21B AA21C AA29B AH06B AK25B AK52B AK53B AL01B AL05B AR00C AT00A BA03 BA07 BA10A BA10C CC00B DE01B GB90 JL00 JN06C 4J038 DL031 DL032 DL101 DL102 FA171 FA172 GA07 HA216 HA446 PB03 PB08

Claims (4)

[Claims] 1. A coating composition comprising at least the following components (A), (B) and (C) as main components. (A) Si, Sb, Ti with a particle size of 1 to 100 mm
(B) at least one silane compound having a polymerizable reactive group, and (E) an epoxy (meth) acryloyl group having at the same time a glycidyl group and a (meth) acryloyl group in one molecule - 2. A composition comprising the following component (D):
The coating composition according to claim 1. (D) Silica fine particles having a particle size of 1 to 100 millimicrons and
And / or the general formula Si (OR₁)_Four A hydrolyzate of an organosilicon compound represented by and / or
Is a partial condensate (where R ₁Is a hydrocarbon having 1 to 8 carbon atoms
Group represents 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. 4. A laminate, wherein at least one layer of the antireflection film made of the inorganic material according to claim 3 contains TiO ₂ .