JP2002116302A - Plastic lens - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a high-refractive-index hard coat film or a primer layer having a refractive index of 1.53 or more and a hard coat film having a refractive index of 1.53 or more on a surface of a base material, and further to a surface thereof. Provided is a plastic lens provided with an inorganic antireflection film containing at least one layer of TiO _2, with improved weather (light) resistance, and with less change in color tone and fading of a dyed lens. SOLUTION: When at least one of layers constituting an antireflection film contains TiO ₂ , it is possible to improve the weather resistance (light) of the primer layer and the color tone change / fading of the color lens.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate in which a high refractive index hard coat film or a primer layer and a high refractive index hard coat film are provided on the surface of a plastic lens and an inorganic antireflection film is provided on the surface. is there. More specifically, the use of an inorganic anti-reflection film provided on the surface of the hard coat film, which includes at least one layer containing TiO ₂ , improves the weather (light) resistance of the hard coat film and simultaneously discolors the color lens due to ultraviolet irradiation. And a plastic lens capable of reducing color change.

[0002]

2. Description of the Related Art In recent years, plastic lenses have been used in various fields. In particular, plastic lenses are now the mainstream of spectacle lenses 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 becoming higher in refractive index to make it thinner. As a technical proposal therefor, Japanese Patent Laid-Open No. 59-1
JP-A-33211 and JP-A-63-46213 propose a high-refractive-index resin material having a refractive index of 1.60 or more. Further, in Japanese Patent Application Laid-Open No. H9-111056, the refractive index is 1.67, and in Japanese Patent Application Laid-Open No. 11-258402.
Japanese Patent Application Publication No. JP-A-2005-26464 proposes a high refractive index resin material having a refractive index of 1.74. In particular, plastic lenses made of allyl carbonate-based resin, acrylate-based resin, methacrylate-based resin, and thiourethane-based resin material,
It has been widely used because of its excellent workability, heat resistance and impact resistance, and its thin and thin appearance.

However, on the other hand, plastic eyeglass lenses have 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 used. The silicon-based hard coat film contains a colloidal dispersion (sol) of a metal oxide and a silane coupling agent as an organic silicon compound as main components. The metal oxide sol mainly imparts scratch resistance and adhesion to the inorganic vapor-deposited film formed on the hard coat film surface, and the silane coupling agent mainly provides scratch resistance and metal inorganic oxide particles. , And adhesion to the lens substrate.

Heretofore, sols of fine particles of silicon dioxide have been exclusively used as metal oxide sols. The refractive index of the hard coat film was about 1.50. However, as described above, the refractive index of plastic lenses has been increasing in recent years, and the mainstream is lens materials having a refractive index of 1.67 or more. When a hard coat film using a sol of silicon dioxide fine particles is applied to such a high refractive index lens material, interference fringes (colors) occur 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, Japanese Patent Publication No. 61-54
No. 331 and JP-B-63-37142, a colloidal dispersion of silicon dioxide fine particles used in a silicon-based coating composition has a high refractive index A.
A coating technique has been disclosed which replaces with a colloidal dispersion of inorganic oxide fine particles of 1, Ti, Zr, Sn and Sb.

Japanese Patent Application Laid-Open No. Hei 1-301517 discloses a method for producing a composite sol of titanium dioxide and cerium dioxide.
And inorganic fine particles of composite inorganic oxide of Ce, JP-A-3-68901
Japanese Patent Application Laid-Open Publication No. H11-163,055 discloses a technique in which fine particles obtained by treating a composite inorganic oxide of Ti, Ce and Si with an organosilicon compound are used in a coating composition. Also, JP-A-10-3
In Japanese Patent Application Laid-Open Nos. 24846, 11-116843 and 11-310755, Sn, T
A technique using i, Zr composite inorganic oxide fine particles in a coating composition has been proposed.

As described above, the method of using inorganic oxide fine particles having a high refractive index is generally used to increase the refractive index of a hard coat film. Specifically, Al, Sn, Sb, T
a single particle of an oxide selected from a, Ce, La, Fe, Zn, W, Zr, In, and Ti, and / or one or a mixture of two or more selected from composite particles thereof (a metal oxide having a high refractive index) Is often used. 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 cope with the design of a hard coat film, which is expected to require a higher refractive index in the future. Further, when the target refractive index of the hard coat film is the same, the addition amount may be smaller than that of other metal oxide fine particles. As a result, the occurrence of film crack failure during the curing reaction due to a decrease in toughness due to an excessive amount of the metal oxide in the hard coat film is suppressed. Thus, it can be said that titanium oxide is extremely useful as a high refractive index metal oxide.

[0007]

However, when titanium oxide is used as a metal oxide for a hard coat film, the following problem arises.
No. 55 pointed out. That is, titanium oxide is activated when it receives light (ultraviolet) energy, and has the property of decomposing organic substances by strong oxidative decomposition power (hereinafter, referred to as photoactivity). As a result, when the hard coat film is of a type that can be dyed, the dye molecules impregnated in the hard coat film are decomposed by the photoactivity of titanium oxide.
Specifically, 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 slightly different depending on the structure of the dye molecule, most of the dyes generally used at present cannot be used. At present, there are two crystalline forms of titanium oxide used industrially, anatase and rutile, and it has been found that the rutile-type crystal structure is more stable in photoactivity than the anatase-type one. I have. In this 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 (light) resistance and a small change in color of a dyed lens even when titanium oxide having an anatase type crystal structure is used as a coating composition. .

[0008]

In order to achieve the above object, according to the present invention, a plastic lens substrate having the following components (A) and (B) as main components and having a refractive index of 1.5 is provided.
Three or more hard coat films are provided, and a multi-layer inorganic antireflection film comprising at least one layer containing TiO ₂ is provided on the surface thereof. The effect of the present invention is great in a lens obtained by dyeing the hard coat film with a disperse dye or a sublimation dye. Further, a primer layer made of polyurethane and / or polyester resin is provided on the surface of the plastic lens substrate before the hard coat film is provided.

Since TiO ₂ has excellent ultraviolet absorbing ability, by using it as a component of the antireflection film, it is possible to suppress the amount of ultraviolet light transmitted from the outside of the lens to the hard coat film. As a result of suppressing the amount of ultraviolet irradiation to the hard coat layer, it is possible to suppress the generation of photoactivity caused by absorbing ultraviolet light of titanium oxide, which is a component of the sol contained in the hard coat film. This has made it possible to improve the weather resistance (light) of the hard coat film and to improve the color tone change and fading of the color lens dyed with the hard coat.

(A) S having a particle size of 1 to 100 millimicrons
fine particles of at least one metal oxide selected from i, Sn, Sb, Ce, Zr, Ti and / or Si, A
1, Sn, Sb, Ta, Ce, La, Fe, Zn, W,
Composite fine particles composed of two or more metal oxides selected from Zr, In, and Ti

(B) A silane compound having at least one or more polymerizable reactive groups As a hard coat component, one of the following components (C), (D) and (E) is added to the above components (A) and (B). It is also useful to add more than one seed.

(C) Disilane compound The disilane compound can be synthesized by various known methods. For example, it can be obtained by performing an addition reaction between diallyl carbonate and trichlorosilane or the like, followed by alkoxylation. Alternatively, the compound can be obtained by adding a trichlorosilane or the like to a compound having an addable substituent at both ends and further containing an epoxy group or an epoxidizable functional group therein, followed by alkoxylation. It is more effective to use either of these disilane compounds after hydrolysis or to perform an acid treatment on the cured film.

(D) Polyfunctional epoxy compound The polyfunctional epoxy compound is widely used for paints, adhesives, casting, and the like. For example, a polyolefin epoxy resin synthesized by a peroxide method Alicyclic epoxy resins such as cyclopentadiene oxide, cyclohexene oxide or polyglycidyl ester obtained from hexahydrophthalic acid and epichlorohydrin; polyphenols such as bisphenol A, catechol and resorcinol; (poly) ethylene glycol; (poly) propylene Glycol, neopentyl glycol,
Polyglycidyl ether obtained from polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, diglycerol and sorbitol and epichlorohydrin, epoxidized vegetable oil, epoxy novolak obtained from novolak-type phenolic resin and epichlorohydrin, obtained from phenolphthalein and epichlorohydrin Epoxy resin obtained, a copolymer of glycidyl methacrylate and methyl methacrylate acrylic monomer or styrene, and an epoxy acrylate obtained by a glycidyl group ring-opening reaction between the above epoxy compound and a monocarboxylic acid-containing (meth) acrylic acid. Can be Specific examples of the polyfunctional epoxy compound include 1,
6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, nonaethylene glycol diglycidyl ether, propylene glycol diglycidyl ether,
Dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, tetrapropylene glycol diglycidyl ether, nonapropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, diglycidyl ether of neopentyl glycol hydroxyhivalic acid ester, trimethylolpropane Diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, diglycerol diglycidyl ether,
Diglycerol triglycidyl ether, diglycerol tetraglycidyl ether, pentaerythritol diglycidyl ether, pentaerythritol triglycidyl ether, pentaerythritol tetraglycidyl ether, dipentaerythritol tetraglycidyl ether, sorbitol tetraglycidyl ether, tris (2-hydroxyethyl) isocyan Aliphatic epoxy compounds such as diglycidyl ether of nurate, triglycidyl ether of tris (2-hydroxyethyl) isocyanurate, and alicyclic compounds such as isophoronediol diglycidyl ether and bis-2,2-hydroxycyclohexylpropane diglycidyl ether. Epoxy compound, resorcinol diglycidyl ether, bisphenol A diglycidyl ether, Scan phenol F diglycidyl ether, bisphenol S diglycidyl ether, orthophthalic acid diglycidyl ester, phenol novolak polyglycidyl ether, aromatic epoxy compounds such as cresol novolac polyglycidyl ether.

Among the above, 1,6-hexanediol diglycidyl ether, diethylene glycol diglycidyl ether, trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, tris (2- Aliphatic epoxy compounds such as triglycidyl ether of (hydroxyethyl) isocyanurate are particularly preferred.

(E) a glycidyl group and (meth)
Epoxy (meth) acrylate having both acryloyl group and epoxy (meth) acrylate having simultaneously glycidyl group and (meth) acryloyl group in one molecule,
It is obtained by a glycidyl group ring-opening reaction between an epoxy compound having two or more glycidyl groups in one molecule and (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 di Diglycidyl of glycidyl ether, neopentyl glycol hydroxyhivalic acid ester Ether, trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, diglycerol diglycidyl ether, diglycerol triglycidyl ether, diglycerol tetraglycidyl ether, pentaerythritol diglycidyl ether, Pentaerythritol triglycidyl ether, pentaerythritol tetraglycidyl ether,
Aliphatic epoxy compounds such as dipentaerythritol tetraglycidyl ether, sorbitol tetraglycidyl ether, diglycidyl ether of tris (2-hydroxyethyl) isocyanurate, triglycidyl ether of tris (2-hydroxyethyl) isocyanurate, etc., isophorone diol Glycidyl ether, bis-
Alicyclic epoxy compounds such as 2,2-hydroxycyclohexylpropane diglycidyl ether, resorcin diglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, diglycidyl orthophthalate, phenol novolak poly Aromatic epoxy compounds such as glycidyl ether and cresol novolak polyglycidyl ether are exemplified.

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 the hard coat film is applied to the surface of the plastic lens substrate.

The reason is that polyurethane resin and / or
Or the primer layer made of polyester resin plays a large role in improving the impact resistance of plastic lenses,
It is not a resin having excellent weather (light) resistance. In particular, the degree of weather resistance (light) of the primer layer containing metal oxide fine particles for improving the refractive index is poor. Therefore,
By providing a multilayer inorganic anti-reflection film composed of at least one layer containing TiO ₂ as the uppermost layer, it is possible to improve the weather resistance (light) of the primer layer and to improve the color when the primer layer is also colored when the hard coat is dyed. It is possible to improve the color tone change and fading of the lens.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION As a specific example of the component (A),
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 , ZrO
Inorganic oxide fine particles of ₂ , In ₂ O ₃ and TiO ₂ are colloidally dispersed in a dispersion medium such as water, alcohol or other organic solvent. Alternatively, composite fine particles composed of two or more of these inorganic oxides are colloidally dispersed in water, an alcohol-based or other organic solvent. Further, it is also possible to use those obtained by treating the surface of these fine particles with an organosilicon compound or an amine compound in order to enhance the dispersion stability in the coating liquid. As the organosilicon compound used at this time, there are monofunctional silane, difunctional silane, trifunctional silane, tetrafunctional silane and the like. In the treatment, the hydrolyzable group may be untreated or hydrolyzed. Further, after the treatment, a state in which the hydrolyzable group has reacted with the —OH group of the fine particles is preferable, but there is no problem in stability even when a part remains. Examples of the amine compound include ammonium or alkylamines such as ethylamine, triethylamine, isopropylamine and n-propylamine, aralkylamines such as benzylamine, alicyclic amines such as piperidine, and alkanolamines such as monoethanolamine and triethanolamine. There is. It is necessary to add the organosilicon compound and the amine compound within the range of about 1 to 15% based on the weight of the fine particles. In any case, the particle diameter is preferably about 1 to 300 mμ.

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

The component (B) may be used as a mixture of two or more kinds. It is more effective to use either method after hydrolysis or use of an acid treatment on the cured film.

For the purpose of improving the impact resistance of the plastic lens substrate, a primer layer may be provided between the substrate and the hard coat film in some cases. Specific examples of the primer layer include a primer layer made of a polyurethane resin and / or a polyester resin.

The surface of the coated film thus obtained
On top, at least one layer is made of TiO _TwoConsisting of a layer containing
As a coating method for forming an inorganic antireflection film of a multilayer film
Are vacuum deposition, ion plating, sputtering
And the like. During vacuum deposition,
Beam assist to simultaneously irradiate the ion beam to the surface
Method may be used. Also, when forming an anti-reflection film,
It is desirable to perform surface treatment of the hard coat film.
No. Specific examples of this surface treatment include acid treatment and alkali treatment.
Reprocessing, UV irradiation, argon or oxygen atmosphere
Treatment by high frequency discharge in air, argon and oxygen
Or irradiation with ion beam such as nitrogen
It is.

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

<Example 1> The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

(1) Preparation of Primer Composition and Application and Curing Block type polyisocyanate “Coronate 252”
9 "(Nippon Polyurethane Industry Co., Ltd.), 1755 g of polyester polyol" Nipporan 1100 "(Nippon Polyurethane Industry Co., Ltd.), ethyl cellosolve 6
630 g, and then a commercially available metal oxide sol (manufactured by Catalyst Chemical Industry Co., Ltd .: product name: Optolake 1120)
Z, S-7 · G, solid content concentration: 20 wt%) 3510 g
And silicon-based surfactant (Nihon Unicar Co., Ltd.)
(Trade name: FZ-2104), and then sufficiently stirred and mixed. This primer composition was applied to a spectacle lens having a refractive index of 1.67 (a lens fabric for Seiko Super Sovereign manufactured by Seiko Epson Corporation) by an immersion method. The lifting speed was 20 cm / min. The coated base lens was heat-cured at 100 ° C. for 50 minutes to form a 1.2 μm-thick primer layer on the base material.

(2) Preparation and application of hard coat liquid
Cured butyl cellosolve 3111 g, methanol-dispersed titanium dioxide-zirconium dioxide-silicon dioxide composite fine particle sol (manufactured by Catalyst Chemical Industry Co., Ltd., product name: Optrake 11)
20Z, S-7 / A8, solid content concentration 20 wt%) 459
0 g, γ-glycidoxypropyltrimethoxysilane 2
83 g and 1130 g of γ-glycidoxypropylmethyldimethoxysilane were mixed. Add 0.05 to this mixture
275 g of an aqueous solution of N hydrochloric acid was added dropwise with stirring.
The mixture was aged for 24 hours after stirring for an hour. 587 g of glycerol diglycidyl ether (trade name “Denacol EX-313”, manufactured by Nagase Kasei Kogyo Co., Ltd.) and Fe (II)
I) 27 g of acetylacetonate, silicone surfactant (trade name "L-7001" manufactured by Nippon Unicar Co., Ltd.)
3g, phenolic antioxidant (Kawaguchi Chemical Co., Ltd.)
17.5 g of polyethylene glycol bis [3- {3-t-butyl-
5 (2H-benzotriazol-2-yl) -4-hydroxyphenyl} propionate] was added, and the mixture was stirred for 4 hours and aged all day long to obtain a coating solution.

The thus obtained coating solution was applied to the lens with primer obtained in the above (1) by an immersion method. The lifting speed was 20 cm / min. Air-dry at 95 ° C for 30 minutes after application, then 12 at 130 ° C.
Baking was performed for 0 minutes. The thickness of the cured film thus obtained was about 2 microns.

(3) Formation of antireflection film The lens obtained by the above method is subjected to plasma treatment (oxygen plating).
(400 W x 60 seconds) and then from the substrate to the atmosphere
In order, SiO_Two, TiO_Two, SiO_Two, Ti
O_Two, SiO_TwoVacuum deposition of antireflection multilayer film consisting of 5 layers
By the method (manufactured by SYNCHRON CORPORATION; CES-34)
became. The optical thickness of each layer is _TwoTo λ / 2
Then, the next TiO_TwoAnd SiO_TwoTo λ / 4 and the next TiO_TwoTo
At λ / 2, the uppermost layer SiO_TwoFormed so that layer becomes λ / 4
did. The design wavelength λ was 520 nm.

(4) Test and Evaluation Results Each of the lenses obtained by the above method was tested by the following method, and the results are shown in Table 1. (A) Abrasion resistance: A 1 Kg load was applied with Bonstar # 0000 steel wool (manufactured by Nippon Steel Wool Co., Ltd.), the surface was rubbed for 10 reciprocations, and the degree of damage was visually evaluated in the following stages. .

A: No damage at all 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 E: Smooth surface does not remain due to scratches on surface. (B) Adhesion: Adhesion between substrate and hard coat film or between hard coat film and multi-coat film Sex is JISD-020
According to No. 2, a cross-cut tape test was performed.
That is, cuts are made at 1 mm intervals on the base material surface using a knife, and 100 squares of 1 square mm are formed. next,
After strongly pressing a cellophane adhesive tape (trade name “Cellotape” manufactured by Nichiban Co., Ltd.) on the top, 9
After the film was suddenly pulled in the 0 degree direction and peeled off, the square where the coat film remained remained was used as an index of adhesion. (C) Weather resistance: A sample having no change in surface state after being exposed to a sunshine weather meter using a xenon lamp for 400 hours was evaluated as good. (D) Moisture resistance test: An adhesive test after standing for 10 days in an atmosphere of 50 ° C. × 99% RH showed no peeling and no change in surface condition. (E) Light resistance of stained lens: After exposing for 80 hours to a xenon long life fade meter (manufactured by Suga Test Co., Ltd .; FAL-25AX) using a xenon lamp, the degree of color change of the stained lens is visually divided into the following stages. Was evaluated. ◎: no change in both color tone and color density ；: color density decreased but little change in color tone △: change in both color tone and color density ×; almost no color

<Example 2> In Example 1, except that the dyeing was performed by the following method before the formation of the anti-reflection film, the same primer processing, hard coat processing and anti-reflection film processing were performed. .

(1) Dyeing process 2 g of the dye Amber D for Seiko Plux diamond coating was dispersed in 1 liter of pure water at 91 ° C. to prepare a dyeing solution. After the primer and the hard-coated lens obtained in (2) of Example-1 were immersed in the staining solution for 3 minutes to perform staining, annealing was performed at 100 ° C. for 1 hour.

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

Example 3 (1) Preparation, application and curing of hard coat liquid 1360 g of propylene glycol monomethyl ether,
Methanol-dispersed titanium dioxide-zirconium dioxide-silicon dioxide composite fine particle sol (trade name "Optreak 1120Z (S-7A8), solid content concentration 20% by weight", manufactured by Catalyst Chemical Industry Co., Ltd.) 6450 g and γ-glycidoxy 1700 g of propyltrimethoxysilane was mixed in. 500 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, aged for 24 hours, and then Fe (II).
I) 10 g of acetylacetonate, silicone surfactant (trade name "L-7001" manufactured by Nippon Unicar Co., Ltd.)
After adding 3 g and stirring for 4 hours, the mixture was aged for 24 hours to obtain a coating solution.

The coating liquid thus obtained was applied to a spectacle lens having a refractive index of 1.74 (lens cloth for Seiko Super Prestige, manufactured by Seiko Epson Corporation) by an immersion method. The lifting speed was 20 cm / min. After coating, air-dry at 80 ° C for 20 minutes, then 12 at 130 ° C.
Baking was performed for 0 minutes.

(2) Dyeing process A photosensitive resin plate PG250 manufactured by Toray Industries, Inc. was used as a plate material.
Using a film on which a gradation pattern was prepared in advance using a plate making machine PGP300 manufactured by Toray Industries, Inc., an underlay was created by an exposure method.

Next, the target color is set to Seiko Nouveau color.
Amber 20 is used by using appropriate amounts of the three primary colors of red, blue and yellow of the SUB series of thermal sublimation inks for screen printing of Toyo Ink Mfg. Co., Ltd. so that the plastic lens after coloring has the target hue. Toyo Ink Mfg. Co., Ltd. diluted solution C-002 solvent was added, the prepared coloring material was applied to the previously prepared plate, and the excess coloring material under the plate was removed to prepare a plate. Next, the coloring material of the plate was transferred to a transfer member made of silicon, and the coloring material was transferred to the convex side of the plastic lens obtained in (1). Thereafter, the plastic lens was placed in a heating device that emits infrared rays, and the sublimation dye was sublimated and permeated for 20 minutes under normal pressure while controlling the surface temperature of the plastic lens to 130 ° C.

(3) Formation of antireflection film The obtained lens is subjected to ion beam irradiation treatment with oxygen gas.
(Acceleration voltage 500V × 60 seconds)
SiO toward the atmosphere_Two, ZrO_Two, SiO_Two, T
iO_Two, SiO_TwoVacuum evaporation of the antireflection multilayer film consisting of five layers
By the wearing method (manufactured by Vacuum Instruments Co., Ltd .; BMC-1000)
The formation was performed. At that time, the fourth layer of TiO _TwoThe ion bee
Film formation was carried out by vacuum assisted evaporation. Optical of each layer
The film thickness is the first SiO_Two, The next ZrO_TwoAnd SiO_TwoThe equivalent of
The film layer is λ / 4, TiO_TwoThe layer is λ / 2, the uppermost layer is SiO_Twolayer
Is λ / 4. The design wavelength λ is 52
It was set to 0 nm.

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

<Comparative Example 1> In Example 2, the formation of the antireflection film was performed in the order from the substrate toward the atmosphere.
O ₂ , ZrO ₂ , SiO ₂ , an anti-reflection multilayer film composed of five layers of ZrO ₂ , SiO ₂ is vacuum-deposited (Vacuum Instruments Co., Ltd.)
BMC-1000). The optical thickness of each layer is as follows: the first SiO ₂ layer, the next ZrO ₂ and SiO ₂
And the next ZrO ₂ layer and the uppermost SiO ₂ layer are λ
A lens was obtained in the same manner except that the lens was formed so as to be / 4.

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

<Comparative Example 2> In Example 3, the anti-reflection film was formed by performing ion beam irradiation treatment with an oxygen gas (acceleration voltage: 500 V × 60 seconds), and then forming SiO 2 in order from the substrate toward the atmosphere. ₂ , ZrO ₂ , SiO ₂ , Z
An antireflection multilayer film composed of five layers of rO ₂ and SiO ₂ was formed by a vacuum evaporation method (BMC-1000, manufactured by Vacuum Instruments Co., Ltd.). The optical thickness of each deposited layer is
O ₂ , the next equivalent film layer of ZrO ₂ and SiO ₂ is λ / 4, Zr
All the lenses were obtained in the same manner except that the O ₂ layer was formed so as to have λ / 2 and the uppermost SiO ₂ layer was formed so as to have λ / 4.
The lens thus obtained was tested in the same manner as in Example 1, and the results are shown in Table 1.

[0043]

[Table 1]

According to the present invention, even when titanium oxide having an anatase type crystal structure is used as a coating composition, the weather resistance (light) is improved and the color tone change and fading of the dyed lens are small. Plastic lenses can be provided.

Continued on the front page F term (reference) 2K009 AA08 AA15 BB11 CC03 CC09 CC12 CC34 CC35 CC42 DD02 DD03 DD04 DD06 DD07 DD08 EE00 EE04 4J038 DL031 DL051 DL081 DL091 DL111 GA01 GA02 GA07 GA09 GA13 HA216 HA446 KA08 KA17 PC08 NA11

Claims (6)

[Claims] 1. A plastic lens substrate, comprising a hard coat film having a refractive index of 1.53 or more provided on a surface thereof and an inorganic anti-reflection film containing at least one layer containing TiO ₂ provided on the surface. Plastic lens. 2. The plastic lens according to claim 1, wherein the hard coat according to claim 1 is dyed with a disperse dye or a sublimation dye. 3. The plastic lens according to claim 1, wherein the hard coat comprises a coating composition containing at least the following components (A) and (B). (A) Si, Sn, S having a particle size of 1 to 100 millimicrons
fine particles comprising at least one metal oxide selected from b, Ce, Zr, Ti and / or Si, Al, Sn, S
b, Ta, Ce, La, Fe, Zn, W, Zr, In,
Composite fine particles composed of two or more metal oxides selected from Ti (B) Silane compound having at least one or more polymerizable reactive groups 4. The component (A) is a composite fine particle composed of at least one metal oxide selected from Si, Sn, and Zr having a particle size of 1 to 100 millimicrons and a metal oxide of Ti. The plastic lens according to any one of claims 1 to 3, wherein: 5. The plastic lens according to claim 1, wherein a primer layer is provided before providing a hard coat on the surface of the plastic lens substrate. 6. A plastic lens, wherein a main component of the primer layer according to claim 5 is made of a polyurethane resin and / or a polyester resin.