JPH01257903A - High-refractive index plastic lens - Google Patents

Abstract

PURPOSE:To obtain the high-refractive index plastic lens having excellent transparency and color tone by providing a hard coating film contg. a coloring agent having a complementary color relation with the color tone of a plastic lens a polymer or copolymer having >=1.50 refractive index on the surface of the above-mentioned lens. CONSTITUTION:An org. hard coating liquid is prepd. by adding the coloring agent having the complementary color relation with the color tone of the plastic lens to an org. hard coating liquid and mixing and dissolving the same. The coloring agent may be any coloring agents if the agents have compatibility with the org. hard coating liquid. The amt. of the coloring agent to be added is in a 1-10,000ppm range of the solid content of the org. hard coating liquid. The formation of the hard coating film is formed by, for example, the method of immersing the plastic lens in the org. hard coating liquid dissolved with the coloring agent, then spinning the lens for 3-10s and curing the coating by heating or UV irradiation. The hard coating film which is uniform in the film thickness and is free from unequal colors over the entire surface is then formed. The coloration of the high-refractive index plastic lens is thereby decreased and the lens having the excellent color tone is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a high refractive index plastic lens with excellent transparency and color tone.

[Prior Art] In recent years, plastic lenses have been rapidly replacing glass lenses. This is because plastic lenses are lighter, have better impact resistance, and are easier to work with than conventional glass lenses.They are also easier to dye, making them more fashionable in eyeglass lenses. There is also the point that it can be enhanced.

Generally, the material used for plastic lenses is diethylene glycol bis, for example.

It is a transparent plastic made of a homopolymer or copolymer of (allyl carbonate), methyl methacrylate, styrene, polycarbonate, vinyl chloride, etc. In particular, thermosetting diethylene glycol bis(allyl carbonate) polymer is considered the most suitable for vision correction lenses because it is lightweight, has excellent impact resistance, transparency, and is easy to process. .

Widely used.

However, diethylene glycol bis(allyl carbonate) polymer has a refractive index of about 1.50, while conventional glass lenses (crown glass) have a refractive index of 1.52.
The refractive index is lower than that of about 3, and for this reason, concave lenses have the disadvantage that the peripheral thickness of the lens is larger than that of glass lenses, and this problem becomes especially noticeable when the power of the lens is large. be.

Therefore, various high refractive index resins for plastic lenses have been proposed to solve these problems. In general, in order to obtain a resin with a high refractive index, it is said that it is effective to include an aromatic ring as a monomer, (1) to have a halogen element other than fluorine, and (2) to have a metal salt.

By the way, regarding (2) above, there is a drawback that the original lightweight characteristic of plastic lenses is lost, and for this reason, in (2) above, for example, aromatic vinyl I'+t r
'; It is common practice to use a nuclear halogen-substituted aromatic vinyl monomer or a combination of (1) and (2). For example, JP-A-53-7787 discloses a high refractive index plastic lens made of a copolymer of diethylene glycol bis(allyl carbonate) and diallyl isophthalate; Publication No. 58-18602, Japanese Unexamined Patent Publication No. 60-51706
High refractive index plastic lenses made of bromine-substituted aromatic vinyl polymers have been proposed in Japanese Patent Application Laid-Open No. 61-64716.

It is well known that compounds having conjugated double bonds, represented by aromatic rings, are sensitive to heat or light, and in fact, when polymerizing compounds containing aromatic rings, polymerization Coloration progresses depending on the type and amount of peroxide used as an initiator, and heating conditions. Furthermore, there is a problem in that if the obtained lens molded body is left under ultraviolet light such as when exposed outdoors, the coloring will further increase. On the other hand, organic compounds containing halogens also have the problem of coloring due to the release of halogens when exposed to heat or light such as ultraviolet rays. Such a decrease in color tone due to heat or light, that is, coloration, tends to be further accelerated when an aromatic ring and an organic halogen compound coexist.

As a method for reducing the coloring of high refractive index plastic lenses, for example, Japanese Patent Laid-Open No. 61-83212 discloses that an inorganic pigment or optical brightener is added as a bluing agent to the plastic lens material in advance and then polymerized. how to make
Another method has been proposed in which a plastic lens molded body is dyed with a disperse dye and blued. However, in the method of adding an inorganic pigment or optical brightener as a bluing agent into the plastic lens material in advance and polymerizing it, these bluing agents cause light scattering in the molded lens, reducing transparency. There are drawbacks to doing so. Also,
In the method of dyeing and bluing a plastic lens molded body with a disperse dye, it is very difficult to obtain a lens with excellent transparency and color tone, which is desired as a final product. In other words, commonly used disperse dyes for polyester fibers have poor heat resistance, and may undergo sublimation, redox decomposition, etc. due to heating in the antireflection film forming process, which is a post-process of the plastic lens molding process. The anti-reflection film formation process is accompanied by pre-treatments such as cleaning with water, various detergents and organic solvents, ultrasonic treatment, heat drying, etc., and vacuum deposition treatment, causing significant discoloration or fading.

Further, Japanese Patent Application Laid-open No. 5Z-S+6OT describes a method of adding and polymerizing a dye having a color complementary to the color tone of the lens. However, this method has the disadvantage that the dye reacts with peroxide, which is a polymerization initiator, at the same time as the polymerization reaction, resulting in significant discoloration or fading, making it extremely difficult to obtain lenses with excellent color tone as desired as final products. It is difficult to

[Problems to be Solved by the Invention] The present invention has been made to solve the above-mentioned blinding point in reducing the coloring of high refractive index plastic lenses that the prior art had, and its purpose is to , does not cause a decrease in transparency, discoloration or fading of dyes during the plastic lens molding process and subsequent processes,
The object of the present invention is to provide a high refractive index plastic lens with excellent transparency and color tone desired as a final product.

[Means for Solving the Problems] That is, the present invention provides a method in which a coloring agent having a color tone complementary to the color tone of the lens is applied to the surface of a plastic lens made of a polymer or copolymer having a refractive index nd of 1.50 or more. A transparent high refractive index plastic lens is characterized in that it is provided with a hard coat film containing the same, and a reflective anti-city film made of an inorganic compound is provided on the hard coat film of the plastic lens. The present invention provides a transparent high refractive index plastic lens.

In the transparent high refractive index plastic lens of the present invention,
'fl Fi as a raw material for the polymer or copolymer
1 body is not particularly limited, but is particularly effective when the clear body III contains an aromatic ring;
j; A more favorable effect is exhibited when one body contains an aromatic ring and a halogen element other than fluorine.

Thus, a plastic lens made of a polymer or copolymer having a refractive index nd of 1.50 or more can be obtained.
Examples of the radically polymerizable polyfunctional '1iHt body containing an aromatic ring in the Fit body include the following.

Bisallyl nisder prephthalate, bisallyl isophthalate, triallyl trimellitate, bis(aryloxycarbonylmethyl) prephthalate, 5,5'-dimethylbiphenyl-3,3'-dicarboxylic acid allyl ester, 1 .9-dimethoxynaphthalene-3,7-dicarboxylic acid allyl ester, 1. Dodime, polyvalent allyl esters such as tyldiphenylmethane-3,3'-dicarboxylic acid allyl ester, 1.3-
Pencene bisallyl carbonate, 1.4-naphthalene bisallyl carbonate, 1.5-naphthalene bisallyl carbonate, 1.6-naphthalene bisallyl carbonate, 1.7-naphthalene bisallyl carbonate,
2.6-Naphthalene bisallyl carbonate, 2.7-
Naphthalene bisallyl carbonate, 4,4'-diphenylpropane bisallyl carbonate, 4,4'-diphenylsulfone bisallyl carbonate, 1,3-bis(hydroxyethoxy)penzene bisallyl carbonate, 1,4-bis(hydroxyethoxy) ) Pencene bisallyl carbonate, 1,5-bis(hydroxyethoxy)naphthalenebisallyl carbonate, 1,6-bis(hydroxyethoxy)naphthalenebisallyl carbonate, 1,7-bis(hydroxyethoxy)naphthalenebisallyl carbonate, 2 .6-bis(hydroxyethoxy)naphthalene bisallyl carbonate, 2.7-
Bis(hydroxyethoxy)naphthalenebisallyl carbonate, 4.4'-bis(hydroxyethoxy)
Diphenylpropane bisallyl carbonate.

4. Polyvalent allyl carbonates such as 4'-bis(hydroxyethoxy)diphenylsulfone bisallyl carbonate, 1.4-diacryloxybenzene, 1.4-dimethacryloxybenzene, 1.4-diacryloxyethoxybenzene, 1.4-dimethacryloxyethoxybenzene, 1.6-diacryloxinaphthalene, 1.5-dimethacryloxinaphthalene, 1.5-bis(β-acryloxyethoxy)naphthalene, 1.5-bis(methacryloxythoxy)naphthalene (oxyethoxy)naphthalene, 2.2'-bisacryloxybiphenyl, 2.2''-bismethacryloxybiphenyl, 2.2'-bis(β-acryloxyethoxy)
Biphenyl, 2.2'-bis(β-methacryloxyethoxy)biphenyl, 2.2-bis(4-acryloxyphenyl)propane, 2.2-bis(4-methacryloxyphenyl)propane, 2.2-bis (4-acryloxyethoxyphenyl)propane, 2,2-bis(4-
methacryloxyethoxy)phenylpropane, 2.2-
Bis(4-acryloxypolyethoxyphenyl)propane, 2.2-bis(4-methacryloxypolyethoxyphenyl)propane, 2.2'-bis(4-acryloxyethoxyphenyl)sulfone, 2.2'-bis (methacryloxyphenyl)sulfone, 2,2'-bis(3-
Acryloyl-2-hydroxypropoxy)biphenyl, 2.2'-bis(3-methacryloyl-2-hydroxypropoxy)biphenyl, 2.2'-bis(3-
Polyvalent (meth)acrylates such as acryloyl-2-hydroxypropoxyphenyl)propane and 2,2'-bis(3-methacryloyl-2-hydroxypropoxyphenyl)propane, and polyvalent vinyl compounds such as divinylbenzene and divinylnaphthalene. be.

In addition, those in which the aromatic ring in these compounds is substituted with a nuclear halogen are radically polymerizable polyfunctional 1ira containing the above-mentioned aromatic ring and containing a halogen element other than fluorine.
It can be mentioned as a body.

These monomer compounds can be used not only alone, but also in combination of two or more.

(particularly preferred among the mer compounds are divinylbenzene, 2,2-bis(4-methacryloxyethoxy-3,5'-dibromophenyl)propane,
2.2-(4-acryloxyethoxy-3,5-dibromophenyl)propane, diallyl phthalate, diallyl isophthalate, 2.2-bis(4-methacryloxyethoxy-3,5-dibromophenyl) sulfone, 2. 2
-bis(4-acryloxyethoxy-3,5-dibromophenyl)sulfone, tetrabromophthalic acid diallyl ester, tetrabromoterephthalic acid diallyl ester, and the like.

Furthermore, as a monomer compound that can be used as a raw material for a plastic lens made of a polymer or copolymer having a refractive index nd of 1.50 or more, in addition to a functional group capable of radical polymerization in the molecule, -011 , -NCO, -C0
In the case of compounds containing functional groups such as -Nl+, epoxy groups, monomer compounds obtained by intermolecular bonds mediated by the functional groups may be used alone or mixed with the various monomers mentioned above. It can also be used as

As such a monomer compound, bisphenol A is an addition compound obtained by reacting 2 moles of 1-vinyl-4-hydroxybenzene with 1 mole of hexamethylene diisocyanate.
The addition compound, 2 moles of methacrylic acid, is reacted with 2 moles of monoacrylate and 1 mole of xylylene diisocyanate to form 2,2-bis(4-glycidoxyphenyl).
Addition compound reacted with 1 mole of propane; Addition compound reacted with 1 mole of 4-hydroxyphenyl methacrylate and 1 mole of glycidyl methacrylate; Addition compound reacted with 2 moles of vinyl acetic acid and 1 mole of xylylene diamine. etc. can be used.

In the present invention, a monofunctional monomer capable of radical polymerization may be added in addition to the polyfunctional monomer, depending on the degree of dual characteristics desired for the eyeglass lens.

Such monomers include styrene, monochlorostyrene, dichlorostyrene, monobromostyrene, dipromostyrene, phenyl acrylate, phenyl methacrylate, monochlorophenyl acrylate, monochlorophenyl methacrylate, dichlorophenylacrylate,
Dichlorophenyl methacrylate, trichlorophenyl acrylate, trichlorophenyl methacrylate, monobromophenyl acrylate, monobromophenyl methacrylate, dibromophenyl acrylate, dibromophenyl methacrylate, tribromophenyl acrylate, tribromophenyl methacrylate, pentabromophenyl methacrylate, pentabromophenyl methacrylate, Monochlorophenoxyethyl acrylate, monochlorophenoxyethyl methacrylate, dichlorophenoxyethyl acrylate, dichlorophenoxyethyl methacrylate, trichlorophenoxyethyl acrylate, trichlorophenoxyethyl methacrylate, monobromophenoxyethyl acrylate, monobromophenoxydiethyl methacrylate, dibromophenoxyethyl acrylate, dibromophenoxyethyl Methacrylate, tribromophenoxyethyl acrylate, tribromophenoxyethyl methacrylate, pentaprodried phenoxyethyl acrylate, pentabromophenoxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, bromobenzyl acrylate, dibromobenzyl acrylate, α-naphthyl acrylate, α-naphthyl methacrylate , β−
naphthyl acrylate, β-naphthyl methacrylate,
Examples include ethyl acrylate, ethyl methacrylate, tribromopentyl acrylate, tribromopentyl methacrylate, 2,3-dibromopropyl acrylate, phenyl acrylic carbonate, benzyl allyl carbonate, allyl benzoate, allyl naphthalene carboxylate, and halogen-substituted products thereof. It will be done.

Plastic lenses are mainly molded by cast polymerization, which is a well-known radical polymerization method.

Photopolymerization methods are used. That is, the monomer alone,
Alternatively, after mixing the above-mentioned various 1i +, 1, a polymerization initiator, such as diisopropyl peroxydicarbonate, similystyl peroxydicarbonate, tert-butyl peroxyvivalate, lauroyl peroxide, tert-butyl peroxyiso butyrate,
Tert-butyl peroxyisopropyl carbonate, di-tert-butyl peroxide, benzoyl peroxide, azodiisobutyronitrile, azobister-octane, etc. are mixed in an amount of 1000 parts by weight and about 0.01 to 10 parts by weight of the rtt form. The resulting mixture is poured into a mold prepared in advance and heated gradually to complete polymerization. At this time, the polymerization is stopped midway, and the prepolymer is taken out of the mold.
It is also possible to complete the polymerization using the prepolymer and the polymerization initiator again. Polymerization temperature and polymerization time vary depending on the type of monomers used, composition ratio, and selection of polymerization initiator, so they cannot be uniformly limited, but are generally 40 to 1
It is preferable to complete the polymerization at 50° C. over 1 to 100 hours.

Furthermore, a photopolymerization method can also be used for molding the plastic lens of the present invention. That is, after using the monomer Li1 alone or mixing the various monomers mentioned above, a photosensitizer such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzophenone, 2-hydroxy-2-
Methyl-propiophenone, benzyl dimethyl ketal, benzoin isopropyl ether, acetophenone,
Dimethoxyacetophenone, 1-chloroanthraquinone, 1,4-naphthoquinone, etc., per 100 parts by weight of monomer, 0. The mixture is mixed with 10 parts by weight and polymerized by irradiation with an ultraviolet lamp, a mercury lamp, or the like. In this case, it is also possible to use partial polymerization initiation cutting.

In manufacturing the high refractive index plastic lens with excellent color tone according to the present invention, in addition to the above-mentioned essential ingredients, additives such as antistatic agent 1, anticoloring agent, surface smoothing agent, ultraviolet absorber, and antioxidant are also added. This makes it possible to improve practicality. For example, antistatic agents include nonionic surfactants and quaternary ammonium salts; anticoloring agents include triphenylphosphine, triphenylantimony, and triphenyl arsenic; and surface smoothing agents include silicone compounds. , fluorine-based surfactants, organic surfactants, etc. As ultraviolet absorbers, 2-(hydroxy-5-methylphenyl)benzotriazole, 2-(
hydroxy-5-tert-butylphenyl)benzotriazole, 2-(3',5''-ditertiary-butyl-2-hydroxyphenyl)-benzotriazole,
As the antioxidant, hindered phenol, hindered amine, etc., such as 2-hydroxy-4-n-octoxybenzophenone, can be added.

The hard coat film containing a coloring agent having a complementary color relationship with the color tone of the lens, which is provided on the surface of the plastic lens in the present invention, is prepared by applying an organic hard coat liquid in which the colorant is dissolved to the lens surface and curing it. This results in the formation of a hardened film. The coloring agent to be dissolved in the organic hard coating liquid may be any coloring agent as long as it is compatible with the organic hard coating liquid.5 For example, dyes, organic pigments, etc. may be used. In some cases, better effects can be obtained not only when the lens is molded, but also when the lens is left under heating or under ultraviolet light, such as when exposed outdoors. The coloring agent is preferably a water-insoluble disperse dye or an oil-soluble dye in view of its transparency, brightness, brightness of one tone, coloring power, heat resistance, and other properties. There are commercially available disperse dyes for polyester and acetate, and disperse dyes for polyester include Diani
x series (Mitsubishi Chemical Corporation), Dispers
al series (IC1 product), Foron series (Sandoz Co., Ltd.), Niyalon PolyyesLer
Series (Nippon Kayakusha Life), Miketon Po
1yester series (Mitsui Toatsu Dye Co., Ltd.), S
amaron series (1 item of hexton), Sumi
Examples include the karon series (manufactured by Sumitomo Chemical Industry Co., Ltd.). In addition, to illustrate the acedate river disperse dye, Di
acelliLon series (Mitsubishi Kasei Co., Ltd.), Niyalon Fast series (Kuchihon Kayaku Co., Ltd.),
Examples include the MikeLon Fast series (Mitsui Toatsu Dye Co., Ltd.).

Furthermore, examples of oil-soluble dyes include AizenSpil
on series (Odogaya Chemical Co., Ltd.), Fat: Leeds (Hoechst Co., Ltd.), Valifas L series (Orient Chemical Co., Ltd.), Oil series (Shirad Chemical Co., Ltd.), Kayaset series ([1Ponka Pharmaceutical Co., Ltd.]) , ^1sol Fast series (Dai 11 Ink Kagaku Kogyo Co., Ltd.), 1risol FasL series (Bayer Co., Ltd.), Kano asol series (Ciba Geigy Co., Ltd.), 01eosol series ([11 Oka Kagaku Co., Ltd.]).

Waxoline series (Imperial Chemical
Industries, Ltd.), etc.

A variety of machine 0 hard coating liquids have been proposed, including melamine, acrylic, polysiloxane, urethane, and fluororesin types, and there are many commercially available products, but none of them can dissolve colorants. Any system may be used if there is one. -Generally, the components of commercially available hard coating agents are not disclosed. The typical melamine type is etherified melamine-alkyd resin.
There are known products that consist of a prepolymer and a curing agent made of a combination of nitrified cotton, etc., and there are also commercially available products, and others that are presumed to be made of modified melamine, fine particle silica, polyhydric alcohol as the main components, and an organic solvent. There is also. There are two types of acrylics: heat-curing types and UV-curing types. UV-curing types are made of polyfunctional acrylics such as methacryloyl groups and acryloyl groups, such as trimedylolbroban (meth)acrylate and pentaerythritol tetra(meth)acrylate. Examples of suitable commercially available products include "Fuji Hard" (trade name: Fujikura Kasei Co., Ltd.) and "Unidix" (trade name: Futnin Nippon Ink Co., Ltd.). The polysiloxane type is composed of a partially hydrolyzed condensate of alkoxysilane and an organic solvent, and forms a film having an organosiloxane structure that is easily crosslinked by heat curing. Examples of alkoxysilane include methyltrialkoxysilane, ethyltrialkoxysilane, etc.
A material containing a functional compound as the main component is preferable because it has a high coating strength, and commercially available hard coating agents include "
P-85J, rX-12-2319C'', 'X-12
-2321A” (Shin-Etsu Chemical Co., Ltd.), “Tosguard” (
Toshiba Silicone Co., Ltd.), and others, which can be exemplified as suitable examples. However, such commercially available products are mainly composed of a hydrolyzed condensate of one or more alkoxysilanes, and a zero-organic solvent solution in which a catalyst, an organosilica sol, a silane coupling agent, an epoxy compound, etc. are appropriately combined. However, its composition and blending ratio have not been disclosed.

Organic hard coat liquid with dissolved colorant.

It is prepared by adding a colorant having a complementary color tone to the color tone of the plastic lens to an organic hard coat liquid, and mixing and dissolving the colorant. When selecting the color tone of the blue agent, normally if the plastic lens has a yellow tone, a blue-violet colorant is selected, but it is also possible to combine red and blue colorants to create the desired complementary color relationship. It can also be prepared and used as a mixed colorant. The amount of the coloring agent added is appropriately determined as an amount suitable for eliminating the coloring of the Plus Deck lens. In this case, the change in color tone can be easily confirmed by visual observation.
By measuring the x and y values of a CIE (Commission Internationale de l'Eclairage) colorimeter using a color computer, slight changes in color tone can be ascertained, making it easy to adjust the amount of colorant added. Generally, the amount of colorant added is 0.000000000000000000000000000000,0000,000,0000,0000,000,000,000,000,0000,000, based on the solid content of the organic hard coating liquid. I~+00000pp
n+, preferably 1 to +0000 ppn+
within the range of If it is less than 1 ppm, curing is insufficient to improve the color tone, and if it exceeds 10,000 pprn, the color of the colorant becomes predominant, resulting in a noticeable decrease in transmitted light, and the function as an eyeglass lens is deteriorated.

The method of forming the hard coat film containing the blue agent on the surface of the plastic lens is not particularly limited. First, as a method for applying an organic hard coat liquid in which a colorant is dissolved to the surface of a plastic lens, a commonly used method such as a dipping method, a spray method, a spinning method, or a combination thereof is used. To illustrate one of the preferred coating methods in the present invention, after immersing a plastic lens in a core hard coat solution in which a blue agent is dissolved,
00 rpm, more preferably 1300-3500
2 to 40 strokes at a rotation speed of rpm, more preferably 3 to 1
One example is a method of spinning within a rotation time range of 0 seconds. The organic hard coat liquid that dissolves the colorant applied to the surface of the plastic lens is cured by heating or UV irradiation, creating a colored hard coat film with a uniform thickness, no uneven color over the entire surface, and no variation in tone or density. The conditions for curing by heating the organic hard coat liquid in which the colorant is dissolved to form 0 differ depending on the main components and composition of the hard coat liquid used, and cannot be unconditionally determined.
A heating time of 40 to 120 minutes at a temperature of 00 to 150°C is sufficient. In addition, curing of an organic hard coat liquid in which a coloring agent is dissolved by ultraviolet irradiation is 5, for example, a high-pressure mercury lamp (output 8
Irradiation for 1-10 seconds at 0 W/cm) is sufficient.

The thickness of the dark blue hard coat film formed by various coating methods is preferably 0.3 to 30 μm, and more preferably 1 μm.
It is preferable that it is 10 micrometers.

In the present invention, the hard coat liquid in which the colorant is dissolved is
Depending on its composition, it may have poor adhesion to the surface of a plastic lens; in such cases, a primer may be applied and a coat film made of an organic hard coat liquid containing a colorant dissolved therein may be formed on the cured pre-coat film. .

The coating method, curing conditions, etc. are not particularly limited, similar to the method of forming a hard coat film using an organic hard coat liquid in which a colorant is dissolved. Brimers are generally made of acrylic polymers, but there are commercially available products whose components appear to be modified acrylic polymers, such as rCR-A and CR.
-BJ (Shin-Etsu Chemical Co., Ltd.) is preferably used. The curing conditions for the above-mentioned commercially available pre-coat agent containing a modified acrylic polymer as a main component are sufficient at a temperature of 80-100''c and a heating time of 10-40 minutes.

A plastic lens on which a hard coat film is formed using the 0 machine hard coat liquid in which the colorant is dissolved does not contain aromatic rings or halogen elements, such as diethylene glycol bis(allyl carbonate), as its polymer or copolymer. Of course, it can also be applied favorably to the case where monomers are used.

The present invention includes a transparent high refractive index plastic lens having an anti-reflection coating on the crotch of a hard coat containing a colorant. The antireflection film can be formed on the colored head coat film by a conventional vacuum evaporation method, ion blasting method, sputtering method, CVD method, plasma processing method, or the like. The anti-reflection film is a multi-layered film made of metal oxide and is usually formed by vacuum evaporation. Metal oxides used in such antireflection films include SiO□ and Sin.

AIJs, 5bzOs, 5bxOs, CON2.
LazOs, Ti0a, T! J4°ZrL and the like are generally known. The multilayer anti-reflection coating has a high refractive index,
It is known that when a thin film with an arbitrary refractive index is formed using two materials with low refractive index, the dispersion becomes smaller as the number of layers increases, but in the present invention, the number of layers is particularly limited. It is determined by the desired performance.

Generally, when forming an antireflection film on a plus deck lens, it is considered undesirable to heat the lens itself to a high temperature. Below, 60-100℃
Even if the antireflection film is formed under relatively low temperature conditions such as the above, the adhesion with the colored hard coat film is good, and a dense and hard antireflection film is formed.

Depending on the selection of conditions when forming the antireflection film on the colored hard coat film, the lens may become colored.

In such cases, the color tone can be improved by adding in advance a complementary coloring agent to the monomer that provides the polymer or copolymer of the lens, depending on the degree of coloration of the lens.

A lens with improved color tone described here means that the absorption is uniform and small for each wavelength in the visible region, and there is no strong absorption at a specific wavelength, but depending on the degree of the desired lens color tone, It is also possible to make a complementary color effect manifest by adding a coloring agent complementary to the lens color tone in an amount that cancels out the lens color tone, thereby obtaining a bluish glass-like lens.

[Example] In the following Examples and Comparative Examples, the characteristics of the obtained plastic lenses were measured by the following test method.

(+) Refractive index Measured at 20° C. using an Atsube refractometer (manufactured by Atago Corporation).

(2) Luminous transmittance Measure the luminous transmittance using a luminous transmittance meter (format ^SC-Mode 1
304, manufactured by Asahi Bunko Co., Ltd.).

(3) Color tone The Yl value of the CIE color system was measured for the color tone of a test piece with a thickness of 2 mm using a color computer (type S12, Suga Test Instruments Co., Ltd.! J1).

Example 1 (1) Production of base lens A mixture consisting of 60 parts by weight of diallyl isophthalate, 30 parts by weight of diethylene glycol bis(allyl carbonate), 810 parts by weight of glycidyl methacrylate, and 2.2 parts by weight of diisopropyl peroxydicarbonate. A liquid was prepared. This mixed solution was injected into a mold assembled using two glass molds and a polyethylene gasket, and after sealing the injection port, it was heated from 30°C to 95°C for 18 hours. Processed. Thereafter, the lens cured by one polymerization was taken out from the mold and further heat-treated at 120°C for 1 hour to obtain a lens having a dioptric power of -5,00 and a refractive index of 1.537.

(2) Formation of a brimer film As a brimer film, commercially available acrylic resin coating materials rCR-A and CR-BJ (Shin-Etsu Chemical Co., Ltd.) are applied to the surface of the base lens using a spinner method at 1600 rpm+ for 5 seconds. After that, it was kept at a temperature of 80° C. for 30 minutes to be cured to form a film.

(3) Preparation of colored hard coat liquid and formation of the hard coat film Commercially available hard coat agent of polysiloxane r X-12-
2306J (Shin-Etsu Chemical Co., Ltd.) with oil-soluble dye R1
An organic hard coat liquid in which a dye was dissolved was prepared by dissolving risol Fast Blue BLN J (manufactured by Bayer AG) to a concentration of 50 ppm. This hard coat liquid was applied onto the lens surface brimer film obtained in (2) using a spinner method at 150 rpm for 5 seconds, and then held at a temperature of 120°C for 60 minutes to harden. A high refractive index plastic lens was obtained. The obtained lens is colorless and transparent and has a fade meter (type FAL-3,
A 100-hour weather resistance test was carried out using a test tube (manufactured by Suga Test Instruments Co., Ltd.), but the progress of coloring was slight and was sufficient for practical use. Further, the characteristics were measured using the test method described above, and the results are shown in Table 1.

Example 2 After cleaning the high refractive index plastic lens with the hard coat film formed in Example 1 using an ultrasonic cleaner,
Insert it into a vacuum evaporator, and mark the surface with Sin, and Z".
02 and ♀ at a vacuum level of 1 to 5 x 10-' Tor
r, the film thickness of the metal oxide is Sun at a temperature of 60~too℃.
0.45 μs, ZrL 0.032 μs.

5iOa O, OlOum, ZrL 0.086μm,
A five-layer anti-reflection film was formed by vacuum evaporation to a designed value of SiO, 0,089 μm. The obtained lens was colorless and transparent. This lens was subjected to the same weather resistance test as in Example 1, but the progress of coloring was slight and it was sufficient for practical use. Further, the characteristics were measured using the test method described above, and the results are shown in Table 1.

Example 3 In preparing a colored hard coat solution, a disperse dye [Niyalon
nPolyyesLer Blue EBL-EJ (Nippon Kayaku Co., Ltd.) was dissolved to a concentration of 50 pp16 to prepare a 4-pack organic hard coat solution in which the dye was dissolved. Next, this hard coat liquid was applied to the surface of the base lens obtained in the same manner as in Example 1 (1).
m, after applying by spinner method under the conditions of 4 seconds, 12
The resin was cured by being held at a temperature of 0° C. for 90 minutes to obtain a high refractive index plastic lens on which a hard coat film was formed.

The obtained lens was colorless and transparent. Further, the characteristics were measured using the test method described above, and the results are shown in Table 1.

Example 4 Example 2 was applied on the hard coat film of the high refractive index plastic lens on which the hard coat film obtained in Example 3 was formed.
A vacuum evaporation process was performed in a vacuum evaporation machine in the same manner as above to form an antireflection film having a five-layer structure of metal oxide. The obtained lens was colorless and transparent. Further, the characteristics were measured using the test method described above, and the results are shown in Table 1.

Example 5 In preparing a colored organic hard coating liquid, an oil-soluble dye ``Rasol Violet RN J'' (Ciba) was added to a commercially available hard coating agent ``Fujihard IIT 50190'' (FujiQ Kaseisha Mei) consisting of a photocurable acrylic resin.・
A colored organic head coat solution in which a dye was dissolved was prepared by dissolving 50 ppm of Geigy Co., Ltd.). Next, this hard coat liquid was applied to the surface of the base lens obtained in the same manner as in Example 1-(1) at 1500 rp+m, 5
After applying with a spinner method under the conditions of seconds, apply using a high-pressure mercury lamp (
The resin was cured by irradiation with an output of 80 W/c+m for 3 seconds to obtain a high refractive index plastic lens on which a hard coat film was formed. The obtained lens was colorless and transparent. Further, the characteristics were measured using the test method described above, and the results are shown in Table 1.

Example 6 Example 2 was applied onto the hard coat film of a high refractive index plastic lens on which the hard coat film obtained in Example 5 was formed.
A vacuum evaporation process was performed in a vacuum evaporation machine in the same manner as above to form an antireflection film having a five-layer structure of metal oxide. The obtained lens was colorless and transparent. Further, the characteristics were measured using the test method described above, and the results are shown in Table 1.

Comparative Example 1 A high refractive index plastic lens on which a hard coat film was formed was prepared in the same manner as in Example 1, except that the oil-soluble dye was not dissolved in the hard coat liquid in the preparation of the colored organic hard coat liquid in Example 1. Obtained. Although the obtained lens was transparent, it was clearly colored pale yellow and could not be put to practical use in terms of appearance quality. Also.

The properties were measured using the test method described above, and the results are shown in Table 1.

Comparative Example 2 In preparing the colored organic hard coat liquid of Example 3, the procedure of Example 3 was performed except that the disperse dye was not dissolved in the hard coat liquid.
In the same manner as above, a high refractive index plastic lens on which a hard coat film was formed was obtained. Although the obtained lens was transparent, it was clearly colored pale yellow, and could not be put to practical use in terms of appearance quality. Further, the characteristics were measured using the test method described above, and the results are shown in Table 1.

Comparative Example 3 A high refractive index plastic lens on which a hard coat film was formed was prepared in the same manner as in Example 5, except that the oil-soluble dye was not dissolved in the hard coat liquid in the preparation of the colored organic hard coat liquid in Example 5. Obtained. Although the obtained lens was transparent, it was clearly colored pale yellow and could not be put to practical use due to its poor appearance. Further, the characteristics were measured using the test method described above, and the results are shown in Table 1.

Table 1 [Effects of the Invention] The high refractive index plastic lens of the present invention has an improved lens color tone by forming a hard coat film containing a specific colorant, and also has the characteristics required as a lens. It has the effect of being excellent.

In particular, in plastic lenses made of high refractive index polymers or copolymers, it is possible to use monomers containing halogen atoms and aromatic rings that are sensitive to heat and light and easily colored. This also has the effect of Naturally, in addition to lenses made of polymers or copolymers of monomers such as those mentioned above, lenses made of polymers or copolymers of diethylene glycol bis(allyl carbonate), which have been conventionally suitable, may also be used. It is applicable.

Claims (4)

[Claims] (1) On the surface of a plastic lens made of a polymer or copolymer with a refractive index nd of 1.50 or more, a hard coat film containing a coloring agent having a complementary color relationship with the color tone of the lens is provided. Features a transparent high refractive index plastic lens. (2) A high refractive index plastic lens according to claim (1), characterized in that an antireflection film made of an inorganic compound is provided on the hard coat film of the high refractive index plastic lens. (3) The high refractive index plastic lens according to claim (1) or (2), wherein the colorant is a dye. (4) The high refractive index plastic lens according to claim (1) or (2), wherein the hard coat film is a cured film of an organic hard coat liquid.