JPH01217402A - Plastic lens provided with reflection reducing film - Google Patents

Abstract

PURPOSE:To obtain a plastic lens contg. no crack, having high adhesion, and being able to eliminate ripple from spectral reflection factor by providing an intermediate film consisting of an org. material having a film thickness and a refractive index satisfying specified conditions to between a plastic lens substrate and a hardened film. CONSTITUTION:An intermediate film having a thickness (t) and consisting of an org. material having a refractive index Ni which satisfies formula I and II is provided to between a plastic lens substrate and a hardened film. In formulas I and II, Nf is a refractive index of a hardened film consisting primarily of silicone resin; Ns is a refractive index of a plastic lens substrate; lambda is 450-600nm. An org. material having a refractive index Ni is coated on a plastic lens substrate as an intermediate film until the thickness attains (t). Suitable org. materials cited primarily are those selected from silicone resin, epoxy resin, urethane resin, melamine resin, and acrylic resin. One or >=two kinds of said material may be useful. Thus, a plastic lens having high scratch resistance, adhesion, and dyeability is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a synthetic resin lens with an anti-reflection film, in which a cured film and an anti-reflection film are formed on the surface of a synthetic resin lens substrate having a relatively high refractive index.

"Prior Art and its Problems" Glass lenses have excellent optical precision and scratch resistance, but have the disadvantage of being heavy and easily broken. For this reason, in recent years, synthetic resin lenses have come to be used particularly as materials for eyeglasses and the like.

Synthetic resin lenses have the advantages of being lightweight, hard to break, dyeable, and highly fashionable, and lenses made of polymethyl methacrylate, polydiethylene glycol bisallyl carbonate, etc. have already been used.

However, the above synthetic resin has a refractive index of about 1.49.
When molded into a lens, it becomes thicker than inorganic glass, and especially in negative strength number lenses, the edge thickness becomes extremely thick.

For this reason, attempts have been made to employ lenses made of synthetic resins having a higher refractive index.

By the way, synthetic resin lenses are generally more susceptible to scratches than inorganic glass lenses, so a hardened film may be formed on the surface of the lens.Also, a hardened film may be formed on the surface of the lens to prevent reflections on the lens surface and improve light transmittance. For this purpose, an antireflection film may be further formed on the cured film.

Therefore, a relatively high refractive index, e.g. 1.57 to 1.65
A lens substrate is created by molding a synthetic resin having a refractive index of Furthermore, when an antireflection film is formed thereon, ripples occur in the spectral reflectance characteristics, and these ripples shift due to subtle changes in the thickness and refractive index of the cured film whose main component is silicone resin. However, it is difficult to strictly control the thickness of cured film coatings whose main component is silicone resin, and slight variations from product to product or from part to part of the same product are unavoidable. As a result, the position of the ripples shifts depending on the product, resulting in variations in reflected color, and even in a single product, color unevenness occurs due to non-uniform film thickness, which is unfavorable in terms of appearance.

In JP-A-61-56302, the refractive index Ni
An interlayer film having a multilayer structure of an inorganic material having a lower refractive index Ni and an inorganic material having a higher refractive index Ni than the refractive index Ni is provided. However, synthetic resin lens substrates also
Since the cured film is also organic, in this inorganic intermediate film,
Cracks are likely to occur due to differences in expansion coefficients, and adhesion is also poor.Furthermore, since it is hard, it tends to have poor plasticity.

``Object of the Invention'' In view of the above-mentioned problems of conventional synthetic resin lenses, the object of the present invention is to form a lens substrate using a synthetic resin having a relatively high refractive index, and to apply a cured film and an anti-reflection film on the lens substrate. It is an object of the present invention to provide a synthetic resin lens with an antireflection film that does not cause cracks when formed, has good adhesion, and can eliminate ripples in spectral reflectance characteristics.

"Structure of the Invention" The synthetic resin lens with an antireflection film according to the present invention has a cured film mainly composed of silicone resin and an antireflection film on the surface of a synthetic resin lens substrate with a refractive index in the range of 57 to 1.65. In the synthetic resin lens with an antireflection film formed thereon, a film made of an organic substance having a refractive index Ni satisfying the following formulas (1) and (2) is disposed between the synthetic resin lens substrate and the cured film. It is characterized by a thick intermediate film.

N5 = (NfXNi)l/2 ・・・・・・■
λ t=-XNi ...■ [However, Nt is the refractive index of the cured film mainly composed of silicone resin, Ni is the refractive index of the synthetic resin lens substrate, and λ is 450~
It is 600 nm. ] In the present invention, the refractive index is 1.
A synthetic resin lens substrate having a diameter in the range of 57 to 1.65 is used.

Such a substrate is made of, for example, a urethane resin that is an addition polymer of aliphatic thiol and aromatic isocyanate. Examples of the aliphatic thiol include pentaerythritol tetrakis (3-mercaptopropionate), and examples of the aromatic isocyanate include m-xylylene diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, and the like. For example, an addition polymer obtained by mixing pentaerythritol tetrakis (3-mercaptopropionate) and m-xylylene diisocyanate in a molar ratio of 1=2 has a refractive index of 1.60, Suitable for use in the present invention.

In the synthetic resin lens of the present invention, an organic material having a refractive index of Ni is first applied as an intermediate film to a thickness of t on the substrate as described above. This organic substance is
Organic substances mainly selected from the group consisting of silicone resins, epoxy resins, urethane resins, melamine resins, and acrylic resins can be used, and one or more of these can be used.

Examples of silicone resins include 3-acryloxypropyldimethylbis(trimethylsiloxy)silane, 3-acryloxypropyldimethylbis(trimethylsiloxy)silane,
Acryloxypropyltrimethoxysilane, 3-acryloxypropyltris(trimethylsiloxy)silane,
benzyldimethylsilane, benzyltrimethylsilane,
■, 3-bis((p-acryloxymethyl)phenethyl]tetramethyldisiloxane, 1,3-bis(carboxypropyl)tetramethyldisiloxane, p-bis(dimethylsilyl)benzene, 1,3-bis(trimethyl) siloxy)-1,3-dimethyldisiloxane, bis(trimethylsilyl)adipate, 1゜4-bis(trimethylsilyl)butadiine, bis(trimethylsilyl)methane, 2-(3-cyclohexenyl)ethyltrimethoxysilane, diallyldimethylsilane , diethylsilane, dimethylethoxysilane, 1,2-dimethyltetraphenyldisilane, diphenylmethylethoxysilane, diphenylsilanediol, ethyltriethoxysilane, hexaethylcyclotrisiloxane, hexamethyldisiloxane, isobutyltrimethoxysilane, 3- Methacryloxypropyltrimethoxysilane, methylphenyldiacetoxysilane, methyltris(2=methoxyethoxy)silane, phenethyltrimethoxysilane, phenyltris(trimethylsiloxy)silane, phenyltriethoxysilane, phenyltrimethoxysilane, n-propyl Trimethoxysilane, styrylethyltrimethoxysilane, tetrakis(trimethylsiloxy)titanium, tetrakis(trimethylsiloxy)zirconium, vinyltriacetoxysilane, (2-(3,4-epoxy-4-methylcyclohexyl)propylcomethyljethoxysilane) , (3-glycidoxypropyl)bis(trimethylsiloxy)methylsilane, 3-glycidoxypropyldimethylethoxysilane, (3-glycidoxypropyl)methyljethoxysilane, 3-glycidoxypropylpentamethyldisilane Siloxane, T-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyljethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane , β-(3,4-epoxycyclohexyl)ethyldimethylethoxysilane, and the like.

The above hydrolysis may be carried out by adding and stirring a weakly acidic aqueous solution containing an inorganic acid such as hydrochloric acid, sulfuric acid, or nitric acid, or an organic acid such as formic acid or acetic acid. However, depending on the compound, the hydrolysis may not proceed well because it is not soluble in water, or the reaction rate may be too fast and the compound may solidify, so it is necessary to dissolve the compound in an appropriate solvent beforehand. You can. Examples of solvents include lower alcohols such as methanol, ethanol, propatool, and butanol, lower carboxylic acids such as acetic acid and methyl acetate, or their alkyl esters, ethers such as cellosolve, ketones such as acetone, and carbonized halides such as methylene chloride. Hydrogens, aromatic hydrocarbons such as benzene, toluene, etc. can be used.

The hydrolyzate thus obtained can also be used after being diluted with the above-mentioned solvent at the time of coating.

Epoxy resins that can be used to form the interlayer film include bisphenol A type, bisphenol F type, bisphenol S type, hydrogenated bisphenol A type, bisphenol A alkylene oxide adduct type, phenol-novolank type, or 0-talesol-novolak type. It is possible to use epoxy resins of the type, such as p-oxybenzoic acid glycidyl ester ether, dimer acid diglycidyl ester, 0-phthalic acid diglycidyl ester,
Terephthalic acid diglycidyl ester, hexahydrophthalic acid glycidyl ester, methyltetrahydrophthalic acid diglycidyl ester, 1゜6-hexanethiol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, ethylene glycol diglycidyl ether , polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, dibromoneopentyl glycol diglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether , sorbitol polyglycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, phenyl(EO)S glycidyl ether, p-tart-butylphenyl glycidyl ether, dibromophenyl glycidyl ether or lauryl alcohol (EOLs glycidyl ether) It is possible to use one type or a mixture of two or more of these polymers.

In addition, as the urethane resin, 2.4-1-lylene diisocyanate, (65/35)) lylene diisocyanate, (80/20)) lylene diisocyanate, 4.4
゛-Diphenylmethane diisocyanate, dianisidine diisocyanate, hexamethylene diisocyanate,
m-xylylene diisocyanate, transvinylene diisocyanate, 4.4',4''-trimethyl-3,3
'.

Isocyanate compounds such as 3°°-triisocyanate, 2,4.6-)liphenyl cyanurate, 2.6-diitsyanate methyl caproate, toluene diisocyanate, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, Hydroxy compounds such as trimethylolpropane, hexanetriol, glycerin, trimethylolethane, pentaerythritol, these hydroxy compounds and phthalic acid,
Polyurethane resins obtained from polyesters and polyethers produced from organic acids such as adipic acid, trimerized lyluic acid, and maleic acid can be used.

The melamine resin used to form the interlayer film is
General formula: [In the formula, R+, Rz, R3, R4, R6 and R6 each independently represent a hydrogen atom or -CH20R, (in the formula, R7 is an alkyl group having 1 to 8 carbon atoms)] Examples include melamine resins obtained by condensation polymerization of melamine compounds.

Furthermore, acrylic resins include acrylic acid or methyl acrylate, ethyl acrylate, propyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, tridecyl acrylate, stearyl acrylate, Tetrahydrofurfuryl acrylate, cyclohexyl acrylate, benzyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-butoxyethyl acrylate, acrylic 2-phenoxyethyl acid, 2-ethoxyethoxyethyl acrylate, octafluoropentyl acrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, Trimethylolpropane triacrylate, propoxylated TMP)
One or more acrylic esters or methacrylic acid, such as lyacrylate, pentaerythritol triacrylate, trisacryloxyethyl phosphate, epoxy acrylate, polyester acrylate, urethane acrylate, or methacrylic esters corresponding to the above acrylic esters, by a known method. An acrylic resin obtained by polymerization can be used.

In the present invention, a material having a refractive index Ni calculated from the following formula is selected as the interlayer film from among the above-mentioned various organic materials.

Ni= (NiXNi)I/2...■[
However, Ni indicates the refractive index of the cured film mainly composed of silicone resin, and Ni indicates the refractive index of the synthetic resin lens substrate. ] For example, if the refractive index Ni of the substrate is 1.60 and the refractive index Ni of the cured film is 1.48, then Ni#1.54=(1,60
x 1.48ν/2.

For example, the refraction l of the hydrolyzate of β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane is 1.52
The refractive index of bisphenol A-epichlorohydrin type epoxy resin is 1.57.

Therefore, hydrolyzate of β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane is particularly suitable for its stability of refractive index and good adhesion to synthetic resin lens substrates and cured films mainly composed of organic silicone. and bisphenol A
- A combination with an epichlorohydrin type epoxy resin is suitable as an interlayer film.

When forming an intermediate film on a synthetic resin lens substrate, in addition to one or more of the above-mentioned organic substances, a refractive index adjusting agent, such as a titanium alkoxide (generally hydrolyzed) such as tetra-n-butoxytitanium, is used. (used in the above formula), a solvent, a surfactant, a curing agent, etc., and apply the mixture to a film thickness calculated from the above formula (2).

In the present invention, the above-described intermediate film is formed on the surface of the synthetic resin lens substrate, and a cured film is formed thereon. The main component of this cured film is a silicone resin, preferably a hydrolyzate of an epoxy group-containing alkoxysilane.

The cured film is preferably a coating composition comprising a hydrolyzate of an epoxy group-containing alkoxysilane, colloidal silica, colloidal antimony sol, a solvent, a curing agent, and a surfactant, which is cured with heat or ultraviolet rays.

In this case, the thickness of the cured film is preferably 1 to 10 μm in order to obtain sufficient scratch resistance.

In addition, as the epoxy group-containing alkoxysilane, (2
-(3,4-epoxy-4-methylcyclohexyl)propylcomethyljethoxysilane, (3-glycidoxypropyl)bis(trimethylsiloxy)methylsilane,
3-glycidoxypropyldimethylethoxysilane, (
3-glycidoxypropyl) methyljethoxysilane,
3-glycidoxypropylpentamethyldisiloxane,
T-glycidoxypropyltrimethoxysilane, T-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyljethoxysilane, β-(3,
4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyldimethylethoxysilane, etc. can be used. One or more of these epoxy group-containing alkoxysilanes can also be used.

In order to improve scratch resistance, adhesion and dyeability, T
-glycidoxypropyltrimethoxysilane, T-glycidoxypropylmethyldimethoxysilane, β-(3,
Preferred are 4-epoxycyclohexyl)ethyltrimethoxysilane and the like.

When forming a cured film, a hydrolyzate obtained by hydrolyzing the above-mentioned epoxy group-containing alkoxysilane by the method described for the silicone resin used for forming the interlayer film is used.

Further, colloidal silica and colloidal antimony are used as cured film components in order to further improve the surface hardness of the lens and improve antistatic properties. Colloidal silica is dispersed in water, lower alcohols such as methanol, ethanol, propatool, butanol, ethers such as cellosolve, or ethylene glycol, and the particle size is 10%.
It is used as a colorless and transparent solution with a SiO□ content of 20 to 31% by weight. In addition, colloidal antimony is dispersed in the above-mentioned solvent, and the particle size is about 10 to 50 mμ, and the content of 5b20° is 20
Used as a milky white solution of ~31% by weight.

The coating composition for forming the intermediate film or cured film in the present invention can be cured by simply heating the composition or irradiating it with ultraviolet rays, but it is also possible to accelerate curing (shorten curing time), cure at low temperature, etc. Various curing agents can also be used in combination for the purpose of making it possible.

Examples of the curing agent include ketones, various salts such as carboxylic acid salts, epoxy resins, and metal chelate compounds. In particular, epoxy resins such as Bunacol EX3'13 and Bunacol EX146 (manufactured by Nagashio Sangyo ■, trade name) are suitable in terms of dyeability and scratch resistance, and metal chelate compounds are suitable for stability and scratch resistance. Aluminum acetylacetonate is suitable in terms of adhesion and adhesion. One or two of these may also be used.

In addition, various surfactants such as silicone-based and fluorine-based surfactants can be used for the purpose of improving fluidity during coating and improving the smoothness of the coating film, and silicone-based surfactants are particularly suitable.

As the solvent, lower alcohols such as methanol, ethanol, propatool and butanol, lower carboxylic acids such as acetic acid and methyl acetate or their alkyl esters, ethers such as cellosolve, ketones such as acetone, etc. can be used.

Depending on the application method and other conditions, the above substances may be
It can be used as a species or as a mixture of two or more kinds.

Further, in the resin lens of the present invention, an antireflection film is formed on the above-mentioned cured film. As the anti-reflection film, for example, S
i Oz, A l z Oz, Y2O3, 'y'bzo
It can be formed by coating an inorganic material selected from the group consisting of Z, T a 20 s, Z r O2 and SiO. The formation of such an anti-reflection film is
This can be carried out by a known method such as a vacuum plating method or an ion assist method. Note that this antireflection film may be formed by laminating a plurality of layers having different refractive indexes.

The thus obtained synthetic resin lens of the present invention has no ripples in its spectral properties, and has very little variation in reflected color between products and color unevenness in a single product.

"Examples" Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.

In addition, the performance evaluation of the coating film was performed by the following method.

Performance evaluation a) The transparency of the coating film, presence or absence of coating unevenness, etc. were observed by visual inspection.

(1) Interference fringes After the cured film is cured, the lens is placed under a mercury fluorescent lamp, and the degree of interference fringes caused by reflection is observed with the naked eye, and evaluation is performed according to the following criteria.

A: There are almost no interference fringes.

B: There are some interference fringes.

C: Interference fringes are present throughout.

c) Rub the surface of the cured film with scratch-resistant steel wool #OOOO, examine the state of the scratches, and evaluate according to the following criteria.

A: There are almost no scratches on the coating surface.

B: The surface of the coating film is slightly scratched.

C: The surface of the coating film is deeply scratched.

2) Adhesion Use a knife, etc. to make 11 parallel lines on the surface of the coating film at intervals of 1 mm across the fir, making 100 squares.

A cellophane adhesive tape is strongly attached on top of the tape, rapidly peeled off in a 90 degree direction, and the number of pieces remaining out of 100 pieces is determined and evaluated as follows (number of times of peeling: 3 times).

Good: 95/100 or more Bad: 94/100 or less E) Weather resistance Sunshine Weather Meter (manufactured by Suga Test Instruments)
Evaluate the surface condition after 00 hours of exposure.

f) Dyeability Using a disperse dye solution containing a mixture of red, yellow, and blue dyes, 8
The product with the cured film was dyed at 5°C for 10 minutes, and the total light transmittance was checked and the value was recorded.

Tests were conducted in the following Examples, focusing on the above performance evaluation items, and the results are shown in Table 1.

Example 1 (a) Preparation of coating solution for interlayer film 0.05N H was added to 28.5 g of β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane with stirring.
A mixed solution of 5 g of C425 and 4.5 g of ethanol was slowly added dropwise, and the mixture was stirred day and night to obtain a hydrolyzate.

Next, 4.5 g of n-butyl alcohol was mixed with 13.5 g of Epikote 827 (trade name of epoxy resin manufactured by Shell Chemical Company), and heated and stirred at 40 to 60°C for 2 hours until the liquid temperature reached 25°C. 18.2 g of methyl ethyl ketone, 34 g of isopropyl alcohol
5.3 g, ethyl acetate 18.2 g, silicone surfactant 0.05 g and aluminum acetylacetonate 0.5 g were added, stirred for 2 hours, and further 38.5 g of the above hydrolyzate was added. After stirring for 3 hours, the mixture was aged at room temperature day and night to obtain a coating solution for an interlayer film.

(b) Preparation of coating solution for cured film T-glycidoxypropylmethyljethoxysilane 21
．． 5g, r-glycidoxypropyltrimethoxysilane 60.5g, β-(3,4-epoxycyclohexyl)
Mix 18g of ethyltrimethoxysilane and mix with stirring.
．． 22.5 g of 05N HCf was slowly added dropwise, and the mixture was stirred day and night to obtain a hydrolyzate.

Next, colloidal silica dispersed in isopropyl alcohol (
(manufactured by Catalyst Kasei) 223.5 g, isopropyl alcohol 52.3 g, n-butyl alcohol 22.2 g, ethyl acetate 21.2 g, methyl ethyl ketone 21.2 g,
1.5 g of silicone surfactant, 0.75 g of aluminum acetylacetonate and Bunacol EX-14
6 (trade name of epoxy resin manufactured by Nagashio Sangyo ■) was mixed and stirred for 2 hours, and 122.5 g of the above hydrolyzate was obtained.
was added, stirred for 6 hours, and then aged at room temperature overnight.
A coating liquid for a cured film was obtained.

(c) Coating and curing Pentaerythrintetrakis (3-mercaptopropionate) and m-xylylene diisocyanate in 1:
A polyurethane resin lens substrate with a refractive index of 1.60 obtained by addition polymerization at a molar ratio of 2:2 is treated with a 3% sodium hydroxide solution, washed, dried, immersed in an interlayer coating solution, and pulled up. Dip coating was performed at a speed of 80 mm/min. After lifting, harden at 100°C for 40 minutes,
An interlayer film with a good appearance was obtained. The refractive index at that time is 1.54
7 (λ-51Qnrn).

Furthermore, after cooling, it was immersed in a coating solution for a cured film and dip coated at a pulling speed of 150 mm/min.

After pulling up, heat curing was performed at 120°C for 2 hours to obtain a cured film with good appearance.

Table 1 shows the results of the performance evaluation test of the obtained resin lens.

Example 2 (a) Preparation of coating solution for interlayer film T-glycidoxypropylmethyldimethoxysilane6.
5g, r-glycidoxypropyltrimethoxysilane 1
8.2 g and 5.3 g of β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane were mixed, and a mixed solution of 6.8 g of 0.05 N HCf and 5.6 g of ethanol was slowly added dropwise while stirring. - A hydrolyzed product was obtained by stirring day and night.

Next, in the same manner as in Example 1 (a), Epikote 827
, various solvents, surfactants and curing agents are mixed.

The mixture was stirred and aged at room temperature day and night to obtain a coating solution for an interlayer film.

(b) Coating and curing In the same manner as in Example 1, using the above coating solution for interlayer film,
Dip coat at a pulling speed of 0 M/min,
Heat curing was performed at 0'C for 40 minutes to obtain an intermediate film with good appearance. The refractive index at that time is 1.540 (λ=510
nm).

Further, the cured film coating liquid used in Example 1 was dip coated at a pulling speed of 150 mm/min, and heat curing was performed at 120° C. for 2 hours to obtain a good cured film.

Table 1 shows the results of the performance evaluation test for the obtained resin lenses.

Example 3 (a) Coating liquid for interlayer film Example 1 Hydrolyzate of β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane prepared in (a) 38.5 g Ni, Buna: 1-JL/ EX-313 (manufactured by Nagashio Sangyo ■) 11.2g and methyl ethyl ketone 22.7
A mixed solution of g and 15.5 g of isopropyl alcohol was added, and in addition, 15.5 g of ethyl acetate, 3.5 g of t-phthyl alcohol, 20.8 g of ethyl cellosolve,
Isopropyl alcohol 198.3g, surfactant 0.
06 g, hardener aluminum acetylacetonate 0
．． 5 g was added, stirred for 3 hours, and aged at room temperature day and night to obtain an interlayer film coating solution.

(b) Coating and curing The same transparent lens substrate used in Example 1 was treated with alkali, washed, dried, immersed in the above interlayer coating solution, dip coated at a pulling rate of 70+++n/min, and pulled up. Thereafter, heat curing was performed at 110'C for 40 minutes to obtain an intermediate film with good appearance.

The refractive index at that time was 1.542 (λ=510 nm).

After cooling, the coating liquid for a cured film was further dip-coated in the same manner as in Example 1, and heat-cured to obtain a good cured film.

Table 1 shows the results of the performance evaluation test for the obtained resin lenses.

Example 4 (a) Preparation of coating solution for interlayer film r-glycidoxypropylmethyldimethoxysilane5.
6g, γ-glycidoxypropyltrimethoxysilane 2
2.6 g and 3.0 g of isopropyl alcohol were mixed, and while stirring, 2 g of 0.05N HC426 was slowly added dropwise, followed by stirring day and night to obtain a hydrolyzed product.

Next, 3.4 g of tetra-n-butoxy titanium (manufactured by Nippon Soda, trade name B 7), Atron NTi (manufactured by Nippon Soda, brand name B 7),
Product name of titanium alkoxide) 22.4 g, methyl ethyl ketone 24.5 g, ethyl acetate 24.5 g, ethyl cellosolve 40.3 g, t-butyl alcohol 35
．． 2 g of isopropyl alcohol, 345.2 g of isopropyl alcohol, 0.05 g of surfactant and 0.5 g of hardening agent aluminum acetylacetonate were mixed, and after stirring for 2 hours, 40.4 g of the hydrolyzate was added and stirred for 3 hours. , - Aged day and night at room temperature to obtain a coating solution for an interlayer film.

(b) Coating and curing Using the coating solution for interlayer film prepared in (a) above, Example 3
Coating and curing were carried out according to the following. The refractive index at that time is 1
．． 545 (λ=510 nm). Next, Example 1
The coating solution for a cured film was dip coated in the same manner as above, and cured by heating to obtain a good cured film.

Table 1 shows the results of the performance evaluation test for the obtained resin lenses.

Example 5 (a) Preparation of coating solution for interlayer film 13.6 g of β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and 13.6 g of phenyltriethoxysilane were mixed and mixed with 0.05N under stirring. H
A mixed solution of 2 g of Cl and 5.7 g of ethanol was slowly added dropwise, and the mixture was stirred day and night to obtain a hydrolyzate.

Separately, 13.5 g of Epicoat 827 (trade name of epoxy resin manufactured by Shell Chemical Company) was added in the same manner as in Example 1.
- Mix with 4.5 g of butyl alcohol and heat and stir. After cooling, 40.5 g of methyl ethyl ketone, 5 g of Atron NTi (trade name of titanium alkoxide manufactured by Nippon Soda)
．． 5 g of ethanol, 42.4 g of ethanol, 205.6 g of isopropyl alcohol, 59.8 g of ethyl cellosolve, 22.4 g of ethyl acetate, 0.03 g of surfactant, and 0.3 g of aluminum acetylacetonate). Further, 31.2 g of the above hydrolyzate was added, stirred for 3 hours, and aged at room temperature day and night to obtain an interlayer film coating solution.

(b) Coating and curing Using the coating solution for interlayer film prepared in (a) above, Example 1
Coating and curing were carried out according to the following. The refractive index at that time is 1
．． 544 (λ=510 nm). Next, the coating solution for a cured film was dip coated in the same manner as in Example 1, and cured by heating to obtain a good cured film.

Table 1 shows the results of the performance evaluation test for the obtained resin lenses.

Example 6 (a) 4.8 g of γ-glycidoxypropylmethyldimethoxysilane and APZ-6601 (trade name of a silicone primer made by Nippon Unicar) were mixed, and while stirring, 3.5 g of 0.0 IN HCl and 1 part of ethanol were added. .5g
A mixed solution was slowly added dropwise and stirred day and night to obtain a hydrolyzate.

Next, to this hydrolyzate, isopropyl alcohol 36
．． 5 g, 16.8 g of methyl ethyl ketone, 16.9 g of ethyl acetate, and 24.2 g of ethyl cellosolve, and further added 0.02 g of silicone surfactant.
g to 45.3 g of 1,4-dioxysan? The dissolved liquids were mixed, stirred, and aged at room temperature day and night to obtain a coating liquid for an interlayer film.

(b) Coating and curing Using the coating solution for interlayer film prepared in (a) above, Example 1
Coating and curing were carried out according to the following. The refractive index at that time is 1
．． 540 (λ=510 nm). Next, the coating solution for a cured film was dip coated in the same manner as in Example 1, and cured by heating to obtain a good cured film.

Table 1 shows the results of the performance evaluation test for the obtained resin lenses.

Example 7 (a) Preparation of coating solution for interlayer film 256.5 g of APZ-730 (trade name of silicone primer made by Nippon Unicar) was mixed with 5.2 g of γ-glycidoxypropylmethyldimethoxysilane, and the mixture was stirred. to 0
．． A mixed solution of 4.2 g of 0IN HCl and 2.3 g of ethanol was slowly added dropwise, and the mixture was stirred day and night to obtain a hydrolyzate.

Next, isopropyl alcohol-dispersed colloidal silica 1
83.2 g of antimony oxide sol (Nissan Chemical Industry ■)
Add a mixture of 89.3 g and 193.9 g of isopropyl alcohol, and further add 48.2 g of methyl ethyl ketone,
48.2 g of ethyl acetate, 185.4 g of ethyl cellosolve
g, 178.5 g of ethanol, 0.04 g of silicone surfactant and 0.75 g of hardening agent aluminum acetylacetonate were added, mixed and stirred for 2 hours, and 268.2 g of the above hydrolyzate was added. Stir for an hour, -
A coating solution for an interlayer film was obtained by aging at room temperature day and night.

(b) Coating and Curing According to Example 3, the interlayer coating solution prepared in (a) above was coated and cured. The refractive index at that time is 1.547
(λ=510 nm). Next, the coating solution for a cured film was dip coated in the same manner as in Example 1, and cured by heating to obtain a good cured film.

Table 1 shows the results of the performance evaluation test for the obtained resin lenses.

Comparative Example 1 Coating and curing were performed in the same manner as in Example 1, except that the interlayer film coating solution of Example 1 was not applied, and the cured film coating solution was directly applied to the substrate.

Comparative Example 2 An interlayer film coating solution prepared in the same manner as in Example 1 except that Epicoat 827 and n-butyl alcohol were not added to the interlayer film coating solution of Example 1 was applied, and after curing, Furthermore, a coating liquid for a cured film was applied and cured.

Comparative example 3 435g APZ-6601 (Japan Unicar).

(trade name of silicone primer), 26.6 g of methyl ethyl ketone, and 10.6 g of ethyl acetate. ．． 3g, ethyl cellosolve 40.5g and silicone surfactant 0.0
2 g was added to prepare an interlayer film coating solution.

After coating and curing, a coating liquid for a cured film was applied and cured in the same manner as in Example 6.

Example 8 The products provided with the cured films obtained in Examples 1 to 7 were washed with a washing machine, and Ybz (1+ was λ/4
(λ=510 nm), TazOs was evaporated at λ/4, and SiO□ was evaporated at λ/4, and the performance of the coating film was evaluated. The results are shown in Table 1.

Example 9 The products provided with the cured films obtained in Examples 1 to 7 were washed with a washing machine, and Af□03 was λ
/4(λ-510nm), Zr0z to λ/2.5iO
z was sequentially deposited at λ/4, and the performance of the coating film was evaluated. The results are shown in Table 1.

Comparative Example 4 The products provided with the cured films obtained in Comparative Examples 1 to 3 were washed with a washing machine, and the film composition of Example 8 was deposited using a vacuum evaporation method.The performance of the coating film was evaluated, and the results were It is shown in Table 1.

Table 1 "Effects of the Invention" The present invention achieves excellent performance in terms of scratch resistance, adhesion, and dyeability by providing a specific interlayer film on a synthetic resin lens substrate having a high refractive index. was completed. Furthermore, according to the present invention, interference fringes caused by ripples in spectral reflectance characteristics can be eliminated. In other words, even if the refractive index of the substrate or cured film changes, interference fringes etc. can be eliminated by adjusting the refractive index of the intermediate film.
Performance that is unsatisfactory with the substrate and cured film can be supplemented and improved by the intermediate film.

Therefore, the present invention has no ripples in its spectral characteristics, and
It is possible to provide extremely high-quality synthetic resin lenses that are free from variations in reflected color depending on the product and color unevenness in a single product.

Patent applicant: Asahi Optical Industry Co., Ltd.

Claims (1)

[Claims] 1. With an anti-reflection film in which a cured film mainly composed of silicone resin and an anti-reflection film are formed on the surface of a synthetic resin lens substrate with a refractive index in the range of 1.57 to 1.65. In the synthetic resin lens, there is a refractive index N_ that satisfies the following formulas (1) and (2) between the synthetic resin lens substrate and the cured film.
1. A synthetic resin lens with an anti-reflection film, characterized in that it is provided with an intermediate film having a thickness t and made of an organic substance having an anti-reflection film. N_i=(N_f×N_s)^1^/^2・・・・・・(
1) t=λ/4×Ni...(2) [However, N_f is the refractive index of the cured film whose main component is silicone resin, N_s is the refractive index of the synthetic resin lens substrate, and λ
is 450 to 600 nm. 2. The synthetic resin lens according to claim 1, wherein the organic substance forming the intermediate film is mainly at least one organic substance selected from the group consisting of silicone resin, epoxy resin, urethane resin, melamine resin, and acrylic resin. 3. The synthetic resin lens according to claim 1 or 2, wherein the synthetic resin lens substrate is made of a urethane resin which is an addition polymer of aliphatic thiol and aromatic isocyanate. 4. Claims 1 to 3 wherein the cured film is obtained by curing a coating composition comprising a hydrolyzate of an epoxy group-containing alkoxysilane, colloidal silica, colloidal antimony, a solvent, a curing agent, and a surfactant using heat or ultraviolet light. The synthetic resin lens according to any one of the above. 5. Anti-reflection film is SiO_2, Al_2O_3, Y_2
O_3, Yb_2O_3, Ta_2O_5, ZrO_2
The synthetic resin lens according to any one of claims 1 to 4, comprising an inorganic material selected from the group consisting of and SiO.