JPH11119001A - Plastic lens - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a plastic lens having wear resistance sufficient for practical use by providing the one surface of the lens with a hard-coating film having excellent wear resistance and using this surface as a convex face. SOLUTION: The one surface of the plastic lens base material of the plastic lens formed by providing the one surface and another surface of the plastic lens base material with the hard-coating films consisting of respectively separate compsns. is provided with the hard-coating film having the wear resistance better than the wear resistance of the hard-coating film formed on the other surface. Further, the one surface is formed as the convex face side and the other surface as a concave face side. The hard-coating film which has the excellent wear resistance and is used for the one surface of the lens base material includes the compsn. contg. particulates consisting of the oxides of >=1 kind of the metals selected from Si, Sn, etc., and Ti of 1 to 100 millimicrons in grain size and/of composite particulates consisting of the oxides of >=2 kinds of the metals selected from Si, Al, etc., and Ti and components, such as curing catalysts.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plastic lens in which a hard coat film is provided on the surface of a plastic lens substrate.

[0002]

2. Description of the Related Art Among plastic lens materials, acrylic, methacrylic, vinyl, polycarbonate, urethane and allyl transparent plastic materials are more impact-resistant, lighter, more workable than glass. Because of excellent properties such as colorability, lenses, transparent glass, etc.
As an optical material, it is used in large quantities in place of inorganic glass. However, they have the disadvantage that they are inferior in wear resistance and chemical resistance as compared with inorganic glass. As means for improving these disadvantages of plastic materials, for example, Japanese Patent Publication No. 57-2735 discloses a non-dyeing type thermosetting paint composed of colloidal silica and an epoxy group-containing alkoxysilane, and Japanese Patent Publication No. 56-34033. No. 55-29102, etc., a non-dyeing type thermosetting paint containing epoxy group-containing alkoxysilane and tetraalkoxysilane as main components, and colloidal silica in JP-B 63-61981, etc. Dyeable type thermosetting paints containing a silanol partial condensate and a crosslinking agent as main components are disclosed in JP-A-59-231501, and colloidal silica, epoxy group-containing alkoxysilane and polyfunctional epoxy. Dyeable type thermosetting paints composed of compounds are also disclosed in JP-A-59-102964 and JP-A-58-2221.
In No. 60 public information etc., a thermosetting paint containing disilane as a main component,
In addition, Japanese Patent Publication No. 57-20968 and the like disclose photopolymerized paints, respectively, which improve chemical resistance and abrasion resistance, respectively. On the other hand, Japanese Patent Application Laid-Open No. Hei 3-145602 proposes a cured coating of a combination of heat curing and light curing.

[0003]

Some of the above-mentioned coating compositions satisfy various durability of the coating film and various durability when the inorganic vapor-deposited film is provided on the surface of the coating film. If one of the various characteristics is sufficient, the other characteristics may be reduced. For example, when the abrasion resistance is sufficient, the coatability of the coating film is reduced, the dyeing requires a long time, and the productivity in the lens dyeing process tends to be reduced. Further, if the coatability of the coating film is made sufficient, the abrasion resistance tends to decrease, and sufficient abrasion resistance as a hard-coated lens tends not to be obtained. An object of the present invention is to solve the above problems and to obtain a plastic lens satisfying both abrasion resistance and dyeability.

[0004]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and found that one surface and the other surface of a plastic lens substrate are each provided with a hard coat having a different composition. It has been found that by providing a coating, a plastic lens having excellent performance can be manufactured.

That is, the present invention relates to a plastic lens in which a hard coat film having a different composition is provided on one surface and the other surface of a plastic lens substrate.
It is characterized in that the wear resistance of the hard coat film provided on one surface of the plastic lens substrate is superior to the wear resistance of the hard coat film provided on the other surface. Further, the dyeability of the hard coat film provided on the other surface is superior to the dyeability of the hard coat film provided on the one surface. Further, it is a spectacle lens. Still further, the one surface is a convex surface and the other surface is a concave surface. Here, in the spectacle lens, the concave side refers to a surface located on the side of the face when wearing glasses,
The convex side refers to the opposite side.

In the present invention, a hard coat film having inferior wear resistance is used on the other surface of the plastic lens substrate, that is, on the concave side of the spectacle lens. Thus, practically sufficient abrasion resistance was obtained. This is because when using or carrying an eyeglass lens, the convex side is particularly likely to touch the object and is easily scratched, and the concave side is less likely to be in contact with the object than the convex surface and is less likely to be scratched. This is because if the hard coat film alone is excellent in wear resistance, practically sufficient wear resistance can be obtained even if the concave side hard coat film is not necessarily excellent in wear resistance. Further, in the present invention, a hard coat film having inferior dyeability is used on one surface of the plastic lens substrate, that is, on the convex side of the spectacle lens, but even if this lens is dyed, it is practically sufficient. Dyeability was obtained. This means that when a lens is dyed, if only the hard coat film on one side of the lens is excellent in dyeability, the hard coat film on the other side is not necessarily excellent in dyeability, but it is practically sufficient. This is because dyeability is obtained.

In this manner, a hard coat film having excellent abrasion resistance but not necessarily excellent in dyeability is provided on one surface of a plastic lens substrate, and the other surface has excellent wear resistance but abrasion resistance. By providing a hard coat film, which is not always excellent, and making one surface a convex surface, it is possible to produce a plastic lens excellent in both abrasion resistance and dyeability.

The following are examples of the hard coat film having excellent abrasion resistance used on one surface of the lens substrate in the present invention. A hard coat composition containing at least the following components (A), (B) and (C).

(A) S having a particle size of 1 to 100 millimicrons
1 selected from i, Sn, Sb, Ce, Zr and Ti
Fine particles comprising an oxide of one or more metals and / or S
i, Al, Sn, Sb, Ta, Ce, La, Fe, Z
Composite fine particles composed of oxides of two or more metals selected from n, W, Zr, In and Ti.

(B) General formula

[0011]

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An organosilicon compound represented by the formula (wherein R ¹
Is an organic group having a polymerizable reactive group, R ² is a hydrocarbon group having 1 to 6 carbon atoms, X is a hydrolyzable group, and n is 0 or 1.)

(C) Curing catalyst.

The details will be described below. The component (A) is a fine particle composed of an oxide of at least one metal selected from the group consisting of Si, Sn, Sb, Ce, Zr and Ti having a particle size of 1 to 100 μm and / or Si, Al, Sn, Sb, Ta, C
e, La, composite fine particles composed of oxides of two or more metals selected from Fe, Zn, W, Zr, In and Ti. Specific examples thereof include SiO ₂ , SnO ₂ , and S
It is obtained by dispersing inorganic oxide fine particles of bO ₂ , CeO ₂ , ZrO ₂ or TiO _{2 in} a colloidal form in a dispersion medium, for example, water, an alcohol or another organic solvent. Or Si, Al, Sb, Ta, Ce, La, F
Composite fine particles composed of two or more oxides of e, Zn, W, Zr, In or Ti are colloidally dispersed in water, an alcohol-based or other organic solvent. Further, it is also possible to use those obtained by treating the surfaces of these fine particles with an organosilicon compound or an amine compound in order to enhance the dispersion stability in the hard coat liquid. As the organosilicon compound used at this time, there are monofunctional silane, difunctional silane, trifunctional silane, tetrafunctional silane and the like. Regarding 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. As the amine compound, ammonium or ethylamine, triethylamine,
There are alkylamines such as isopropylamine and n-propylamine, aralkylamines such as benzylamine, alicyclic amines such as piperidine, and alkanolamines such as monoethanolamine and triethanolamine. It is necessary to add these organosilicon compounds and amine compounds in the range of about 1 to 15% based on the weight of the fine particles. These fine particles used in the present invention have a particle size of about 1
１００100 mμ is used, preferably 5 to 3
0 mμ is preferred. The kind and amount of application to the hard coat composition used in the present invention are determined by the target film performance, but the amount used is 10 to 6 of the solid content.
It is desirably 0% by weight. That is, if it is less than 10% by weight, the adhesion to the inorganic vapor deposition film becomes insufficient. Also, 6
If the amount exceeds 0% by weight, cracks occur in the coating film. Here, in the present invention, the term "% by weight based on the solid content" means the% by weight based on the hard coat film obtained by applying the hard coat composition to the lens substrate and curing the composition.

Component (B) is an organosilicon compound of the above general formula, wherein R ¹ is a polymerizable reactive group such as vinyl, allyl, axyl, methacryl, epoxy, mercapto, cyano, isocyano. And an organic group having an amino group and the like. R ² is a hydrocarbon group having 1 to 6 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a butyl group, a vinyl group, and a phenyl group.
X is a hydrolyzable functional group, and specific examples include a methoxy group, an ethoxy group, an alkoxy group such as a methoxyethoxy group, a chloro group, a halogen group such as a bromo group,
Acyloxy groups and the like. Specific examples of the organosilicon compound include vinyltrialkoxysilane, vinyltrichlorosilane, vinyltri (β-methoxy-ethoxy) silane, allyltrialkoxysilane, acryloxypropyltrialkoxysilane, methacryloxypropyltrialkoxysilane, methacryloxypropyl Dialkoxymethylsilane, γ-glycidoxypropyl trialkoxysilane, β- (3,4-epoxycyclohexyl) -ethyl trialkoxysilane, mercaptopropyl trialkoxysilane, γ-aminopropyl trialkoxysilane, N-β (amino Ethyl)-
γ-aminopropylmethyldialkoxysilane and the like. The component (B) may be used as a mixture of two or more kinds. It is preferable to use it after hydrolysis. The use amount of the component (B) is desirably 20% to 60% by weight of the solid content. That is, if it is less than 20% by weight, the adhesion to the inorganic vapor deposition film tends to be insufficient.
On the other hand, if it exceeds 60%, it is not preferable because it causes cracks in the cured film.

The component (C) is added as a curing catalyst for the silanol or epoxy compound of the component (B). Preferred are perchloric acids, ammonium perchlorates, perchloric acids such as magnesium perchlorate, and Cu (II). ), Zn (II), Co
(II), Ni (II), Be (II), Ce (III), Ta (III), Ti
(III), Mn (III), La (III), Cr (III), V (III), C
o (III), Fe (III), Al (III), Ce (IV), Zr
Examples thereof include amino acids such as acetylacetonate, amine, and glycine having a central metal atom of (IV), V (IV) or the like, Lewis acids, metal salts of organic acids, and the like. Among them, in the composition of the present invention, magnesium perchlorate, Al (II
I) and acetylacetonate of Fe (III) are more preferable. The addition amount is preferably in the range of 0.01 to 5.0% of the solid content.

The hard coat film composed of these components and used on one surface of the lens substrate has excellent wear resistance. However, the dyeability is not always excellent as compared with the hard coat film used on the other surface of the lens substrate described later.

Next, the following are examples of the hard coat film having excellent dyeability used on the other side of the lens substrate in the present invention. A hard coat composition comprising at least the components (A), (B) and (C) and the components (D) described below.

(D) a polyfunctional epoxy compound.

The details will be described below. The polyfunctional epoxy compound (D) is widely used for paints, adhesives, casting, and the like. For example, a polyolefin-based epoxy resin synthesized by a peroxide method, cyclopentanediene oxide, cyclohexene oxide or Alicyclic epoxy resins such as polyglycidyl esters obtained from hexahydrophthalic acid and epichlorohydrin, polyhydric phenols such as bisphenol A, catechol and resorcinol, or (poly) ethylene glycol, (poly) propylene glycol, neopentyl glycol, glycerin , Trimethylolpropane, pentaerythritol,
Diglycerol, polyglycidyl ether obtained from polyhydric alcohols such as sorbitol and epichlorohydrin, epoxidized vegetable oil, epoxy novolak obtained from novolak-type phenolic resin and epichlorohydrin,
Epoxy resin obtained from phenolphthalein and epichlorohydrin, copolymers of glycidyl methacrylate and methyl methacrylate, acrylic monomers or styrene, and glycidyl group ring-opening reaction of the above epoxy compounds with monocarboxylic acid-containing (meth) acrylic acid And the like. 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, diglycidyl ether of tris (2-hydroxyethyl) isocyanurate, triglycidyl ether of tris (2-hydroxyethyl) isocyanurate, Aliphatic epoxy compounds such as Alicyclic epoxy compounds such as didiol diglycidyl ether, bis-2, 2-hydroxycyclohexylpropane diglycidyl ether, resorcin diglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, orthophthalic acid Aromatic epoxy compounds such as diglycidyl ester, phenol novolak polyglycidyl ether, and cresol novolak polyglycidyl ether can be used. In the present invention, the component (D) is used as one component of a hard coat film having excellent dyeability that is used on the other side of the lens substrate. That is, the component (D) is used to enhance the dyeability of the hard coat film. 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-hydroxyethyl Aliphatic epoxy compounds such as triglycidyl ether of isocyanurate) are particularly preferred. The amount of the component (D) used is 1% of the solid content.
Desirably, it is 0 to 50% by weight. That is, if the amount is less than 10% by weight, the dyeability of the hard coat film is insufficient. On the other hand, if it exceeds 50% by weight, the adhesion to the inorganic vapor-deposited film tends to be insufficient, which is not preferable.

The hard coat film made of these components and provided on the other surface of the lens substrate has excellent dyeability. However, the abrasion resistance is not always superior to the hard coat film provided on one surface of the lens substrate.

The hard coat composition used on one side and the hard coat composition used on the other side of the lens substrate described above can be diluted with a solvent, if necessary. Examples of the solvent include solvents such as alcohols, esters, ketones, ethers, and aromatics. In addition to the components described above, if necessary, a small amount of a surfactant, an antistatic agent, a UV absorber, an antioxidant, a disperse dye, an oil-soluble dye, a fluorescent dye, a pigment, a photochromic compound, a hindered amine. The coatability of the hard coat composition and the film performance after curing can be improved by adding a light and heat resistant stabilizer such as a hindered phenol compound. In particular, it is possible to impart excellent weather resistance to the hard coat film by adding one or two or more selected from UV light stabilizers, antioxidants, light- and heat-resistant stabilizers such as hindered amines and hindered phenols. It is possible. Further, in order to improve the durability of the hard coat film, it is also effective to add a tetrafunctional silane compound represented by the general formula Si (OR) ₄ . Specific examples include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane,
Tetrabutoxysilane, tetraphenoxysilane, tetraacetoxysilane, tetraallyloxysilane, tetrakis (2-methoxyethoxy) silane, tetrakis (2
-Ethylbutoxy) silane, tetrakis (2-ethylhexyloxy) silane and the like. These may be used alone or as a mixture of two or more. Further, it is preferable to use them after hydrolysis in the absence of a solvent or in an organic solvent such as an alcohol in the presence of an acid.

In the present invention, a plastic film is formed on the surface of a plastic lens substrate by using the above-mentioned hard coat composition to produce a target plastic lens. As a method of providing a coating, a method of applying a hard coat composition to a plastic lens substrate and then curing the same is used. As a coating method, a method such as a spin coating method, a spray method, a roll coating method, and a flow coating method, which can apply the hard coat composition to only one surface of the lens, is adopted. At this time, first, the first hard coat composition may be applied to one surface and cured, and then the next hard coat composition may be applied and cured to the other surface, or both surfaces of the lens substrate may be cured. May be simultaneously applied with different hard coat compositions and cured at once. As a curing method,
A thermosetting method, a curing method using an active energy ray such as UV or the like can be used. The thickness of the cured film is 0.05 to
It is preferably 30 μm. That is, when the thickness is less than 0.05 μm, the performance of the basic film is not obtained. If it exceeds 30 μm, it is not preferable because the smoothness of the surface is impaired and optical distortion occurs. In addition, in order to improve the adhesion between the plastic lens substrate and the hard coat film, the surface of the substrate is previously subjected to an alkali treatment, an acid treatment, a surfactant treatment, a polishing treatment with inorganic or organic fine particles, and a blast treatment. It is effective.

On the surface of the hard coat lens thus obtained, an antireflection film made of an inorganic substance can be provided. Examples of a method for forming the antireflection film include a vacuum deposition method, an ion plating method, and a sputtering method. In the vacuum evaporation method, an ion beam assist method in which an ion beam is simultaneously irradiated during the evaporation may be used. As the film configuration, either a single-layer antireflection film or a multilayer antireflection film may be used. Specific examples of the inorganic substance used include SiO ₂ , SiO,
ZrO ₂ , TiO ₂ , TiO, Ti ₂ O ₃ , Ti
₂ O ₅ , Al ₂ O ₃ , Ta ₂ O ₅ , CeO ₂ , MgO,
Y ₂ O ₃ , SnO ₂ , MgF ₂ , WO _{3 and the} like can be mentioned. These inorganic substances may be used alone or as a mixture of two or more. When forming the antireflection film, it is desirable to perform a surface treatment on the hard coat film.
Specific examples of the surface treatment include an acid treatment, an alkali treatment, an ultraviolet irradiation treatment, a plasma treatment by a high-frequency discharge in an argon or oxygen atmosphere, and an ion beam irradiation treatment with argon, oxygen or nitrogen.

[0025]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in more detail by way of examples, but the present invention is not limited thereto. (Example-1) (1) Preparation of hard coat composition used on one side of lens substrate 2.73 kg of methyl cellosolve, silicon-based surfactant (trade name "L7604" manufactured by Nippon Unicar Co., Ltd.) 3 .0
g, 1.9 kg of γ-glycidoxypropyltrimethoxysilane. To this is added 0.05N hydrochloric acid 52
2.9 g was added and stirred for 1 hour to hydrolyze γ-glycidoxypropyltrimethoxysilane. Isopropyl alcohol-dispersed colloidal silica (trade name "Oscar 1432", manufactured by Kasei Kagaku Kogyo Co., Ltd .; solid content concentration: 30)
4.84 kg, 2.9 g of magnesium perchlorate
And 50 g of a phenolic antioxidant (trade name "Antage Crystal" manufactured by Kawaguchi Chemical Industry Co., Ltd.)
After stirring for an hour, the mixture was stored at 0 ° C. for 24 hours and aged.
Use after returning to room temperature.

(2) Preparation of Hard Coat Composition Used on the Other Surface of Lens Substrate 4.82 kg of methyl cellosolve, silicone surfactant (trade name "L7604" manufactured by Nippon Unicar Co., Ltd.) 3.0
g, γ-glycidoxypropyltrimethoxysilane 7
60 g were mixed. 210 g of 0.05N hydrochloric acid
Was added and stirred for 1 hour to hydrolyze γ-glycidoxypropyltrimethoxysilane. After storing at 0 ° C. for 12 hours and aging, the temperature is returned to room temperature, and isopropyl alcohol-dispersed colloidal silica (trade name “Oscar 1432”)
(Catalyst Kasei Kogyo Co., Ltd .; solid content concentration 30% by weight) 3.1
4 kg, magnesium perchlorate 46.6 g, glycerol diglycidyl ether (trade name “Denacol EX31
3) 1.02 kg of Nagase Kasei Kogyo Co., Ltd.) and 50 g of a phenolic antioxidant (trade name "ANTAGE CRYSTAL" manufactured by Kawaguchi Chemical Co., Ltd.) were added, stirred for 1 hour, and again at 0 ° C. for 24 hours. Stored for a while and aged. After returning to room temperature,
use.

(3) Application and Curing of Hard Coat An eyeglass lens fabric (trade name “Seiko Plux Fabric” manufactured by Seiko Epson Corporation; refractive index: 1.5) was applied by spin coating. First, the lens was subjected to an alkali treatment. Next, one surface of the lens material was polished with a sponge soaked in pure water to remove dust, washed with pure water and then with isopropyl alcohol, and dried to make the surface of one surface clean. While rotating the lens cloth with one side up at a rotation speed of 800 rpm,
2 cm ^{3 of the} hard coat composition used on one surface of the lens prepared in (1) was dropped. After the dropping, the lens was rotated at a rotation speed of 2000 rpm for 0.5 seconds. The lens was dried in an oven at 135 ° C. for 30 minutes and then cooled to room temperature. Next, the other surface of the lens was cleaned in the same procedure as the one surface. The hard coat composition used for the other surface of the lens prepared in (2) was applied to the other surface of the lens by the same method as described above, and the lens was dried in an oven at 135 ° C. for 3 hours. The thus obtained hard coat film on the lens surface had a thickness of 2 μm on both sides and had a good appearance.

(4) Test and Evaluation The obtained lens was tested by the following method, and the results are shown in Table 1.

(A) Portable test of lens abrasion resistance A lens prepared so that one side of the lens is on the convex side is framed in a spectacle frame such that the concave side is on the side facing the face. Was actually used for one month, and the degree of damage on the lens surface was visually evaluated in the following stages. However, two left and right lenses were evaluated, and the evaluation result is an average per one lens.

A: Both surfaces of the lens are not damaged at all. B: A total of 1 to 10 scratches are present on both surfaces of the lens. C: A total of 10 to 50 scratches are present on both surfaces of the lens. D: Both surfaces of the lens have a total of 50 to 100 scratches. E: A total of 100 or more scratches are present on both surfaces of the lens.

(B) Abrasion test of lens abrasion resistance A 1 kg load was applied with Bonstar # 0000 steel wool (manufactured by Nippon Steel Wool Co., Ltd.), and one side and the other side of the lens were rubbed for 10 reciprocations. The degree of damage was visually evaluated in the following stages.

A: There is no scratch in the area of 1 cm × 3 cm. B: 1 to 10 scratches are made in the above range. C: 10 to 100 scratches are made in the above range. D: Countless scratches are present in the above range, but a smooth surface remains. E: Countless scratches are present in the above range, and no smooth surface remains.

(C) Dyeing test 2 g of Seiko Plux Diamond Coating Dye Gray D was dispersed in 1000 cm ³ of pure water at 92 ° C. to prepare a dyeing solution. The lens was immersed in this dyeing solution for 5 minutes for dyeing, and a sample having a total light transmittance of 30% or more before and after dyeing and having no uneven dyeing was evaluated as good.

(D) Water / Chemical Resistance Test A sample which was immersed in water, alcohol, or kerosene for 48 hours and whose surface condition did not change was evaluated as good.

(E) Acid / detergent resistance test 0.1N hydrochloric acid and 1% mama lemon (Lion Oil & Fat Co., Ltd.)
Manufactured) and immersed in an aqueous solution for 12 hours.

(F) Adhesion test The adhesion between the lens substrate and the hard coat film was measured according to JISD.
This was carried out by a cross cut tape test according to 0202. That is, cuts are made at intervals of 1 mm on the base material surface using a knife, and 100 squares of 1 mm ² are formed.
Next, after strongly pressing a cellophane adhesive tape (trade name “Cellotape” manufactured by Nichiban Co., Ltd.) on the surface, it is suddenly pulled away from the surface in the direction of 90 °, and adhered with the squares with the remaining hard coat film. Sex index.

(G) Weather Resistance Test A sample having no change in surface condition after being exposed to a sunshine weather meter using a xenon lamp for 400 hours was evaluated as good.

(H) Heat Resistance (Cooling Cycle Property) Test After storage in hot air at 70 ° C. for 1 hour, the surface condition was examined. Further, the cycle at -5 ° C. for 15 minutes and at 60 ° C. for 15 minutes was repeated 5 times, and those having no change in the surface state were evaluated as good.

(I) Durability test The durability is considered to be essentially a continuity of the adhesion, and the results of the above tests (g) and (h) were subjected to the adhesion test of the above (f). The hard coat film without peeling was evaluated as good.

(Embodiment-2) An antireflection film made of an inorganic substance was applied to a lens obtained by the same method as in the steps (1), (2) and (3) of the above-mentioned embodiment-1 by the following method. Formed.

(5) Formation of anti-reflection film Plasma treatment (400 W × 6 argon plasma) was applied to the lens.
0 second), and sequentially from the lens surface to the atmosphere, SiO ₂ , ZrO ₂ , SiO ₂ , ZrO ₂ , SiO
_An anti-reflection multilayer film consisting of five layers ₂ was deposited on a vapor deposition machine ("BMC-
1000 "manufactured by Vacuum Instruments Co., Ltd.) by a vacuum evaporation method. The optical thickness of each layer is
₂ layers, next equivalent thin film of ZrO ₂ and SiO ₂ and next Zr
The O ₂ layer and the uppermost SiO ₂ layer were each formed to have a wavelength of λ / 4. The design wavelength λ was 520 nm. The reflection interference color of the obtained multilayer film was green, and the total light transmittance was 98%.

The obtained lens was tested in the same manner as in Example-1 (4). However, the (c) staining test was performed before the above (5) formation of the antireflection film. The results are shown in Table 1.

Example 3 (1) Preparation of Hard Coat Composition Used on One Side of Lens Substrate 2.79 kg of butyl cellosolve, a silicon-based surfactant (trade name “FZ-2110”, Nihon Unicar Co., Ltd.) )
3.0 g, γ-glycidoxypropyltriethoxysilane 1.13 kg, and methacryloxypropyltrimethoxysilane 789.5 g were mixed. 0.05N
Was added and stirred for 1 hour to hydrolyze γ-glycidoxypropyltriethoxysilane and methacryloxypropyltrimethoxysilane. Methanol-dispersed colloidal silica (trade name “Oscar 113
2 "Catalyst Chemical Industry Co., Ltd .; solid content concentration 30 wt%)
4.78 kg, iron (III) acetylacetonate 2.9
g, phenolic antioxidant (trade name “ANTAGE W4
00 "(manufactured by Kawaguchi Chemical Industry Co., Ltd.), and the mixture was further stirred for 1 hour, then stored at 0 ° C. for 24 hours and aged. Use after returning to room temperature.

(2) Preparation of Hard Coat Composition Used on the Other Surface of Lens Substrate 5.0 kg of butyl cellosolve, silicon surfactant (trade name "FZ-2110" manufactured by Nippon Unicar Co., Ltd.)
3.0 g, γ-glycidoxypropyltriethoxysilane 444.8 g, and methacryloxypropyltrimethoxysilane 292 g were mixed. To this, 198 g of 0.05N hydrochloric acid was added and stirred for 1 hour to hydrolyze γ-glycidoxypropyltriethoxysilane and methacryloxypropyltrimethoxysilane. 12 at 0 ° C
After storage for a period of time and aging, the temperature was returned to room temperature, and 2.97 kg of methanol-dispersed colloidal silica (trade name “Oscar 1132” manufactured by Catalyst Chemical Industry Co., Ltd .; solid content concentration 30% by weight);
6.3 g of iron (III) acetylacetonate, 1,6-hexanediol diglycidyl ether (trade name "Denacol EX212" manufactured by Nagase Kasei Kogyo Co., Ltd.) 1.08 k
g, phenolic antioxidant (trade name “ANTAGE W4
00 "(manufactured by Kawaguchi Chemical Industry Co., Ltd.), stirred for 1 hour, stored again at 0 ° C. for 24 hours and aged. Use after returning to room temperature.

(3) Coating and curing of hard coat Eyeglass lens fabric (trade name “Seiko Plux IIGX”)
Fabric for Seiko Epson Corporation; refractive index 1.56)
Was applied by a spray method. First, the lens was subjected to an alkali treatment. Next, one surface of the lens material was polished with a sponge soaked in pure water to remove dust, washed with pure water and then with isopropyl alcohol, and dried to make the surface of one surface clean. Spray (trade name "Iwata Weider 61" manufactured by Iwata Coating Machine Co., Ltd .; Nozzle diameter 1)
mm) with a spray pressure of 3 kg / cm ² and a liquid discharge amount of 100 ml / min, on one surface of the lens cloth (1).
The hard coat composition to be used was applied to one surface of the lens prepared in the above step. Put this lens in a 135 ° C oven for 30 minutes.
After drying for a minute, the mixture was cooled to room temperature. Next, the other surface of the lens was cleaned in the same procedure as the one surface. After applying the hard coat composition used for the other surface of the lens prepared in (2) to the other surface of the lens in the same manner as described above, the lens was dried in an oven at 135 ° C. for 3 hours. The hard coat film on the surface of the spectacle lens obtained in this way had a thickness of 3 μm on both sides and had a good appearance. The obtained lens was evaluated in the same manner as in Example 1, (4). The results are shown in Table 1.

(Embodiment-4) A lens obtained by the same method as in the steps (1), (2) and (3) of the above-mentioned embodiment-3 is added to a lens similar to the above-mentioned embodiment-2 (5). In the process, an antireflection film made of an inorganic substance was formed. The obtained lens was tested in the same manner as in Example-1 (4). However, the (c) staining test was performed before the above (5) formation of the antireflection film. The results are shown in Table 1.

Example 5 (1) Preparation of Hard Coat Composition Used on One Side of Lens Substrate 2.23 kg of isopropyl cellosolve, a silicon-based surfactant (trade name “L-7001” Nippon Unicar ( stock)
2.7 g, γ-glycidoxypropyltrimethoxysilane 1.67 kg, tetramethoxysilane 193.
4 g were mixed. 566.9 g of 0.05N hydrochloric acid
And stirred for 1 hour to hydrolyze γ-glycidoxypropyltrimethoxysilane and tetramethoxysilane. Methyl cellosolve-dispersed cerium dioxide-titanium dioxide-silicon dioxide composite fine particle sol (trade name "Optreak 1820" manufactured by Catalyst Chemical Industry Co., Ltd .; solid content concentration 2)
5.26 kg, 3.9 g of manganese (III) acetylacetonate, 20 g of a hindered amine light stabilizer (trade name "Sanol LS-770" manufactured by Sankyo Co., Ltd.),
Phenolic antioxidants (trade name "Seanox 226"
M "(produced by Cipro Kasei Co., Ltd.), and the mixture was further stirred for 1 hour, then stored at 0 ° C for 24 hours and aged. Use after returning to room temperature.

(2) Preparation of Hard Coat Composition Used on the Other Surface of Lens Substrate 4.18 kg of isopropyl cellosolve, silicon-based surfactant (trade name “L-7001” Nippon Unicar Co., Ltd.)
2.7 g), 501 g of γ-glycidoxypropyltrimethoxysilane, and 96.8 g of tetramethoxysilane. 192.7 g of 0.05N hydrochloric acid was added thereto and stirred for 1 hour to hydrolyze γ-glycidoxypropyltrimethoxysilane and tetramethoxysilane. After storage at 0 ° C. for 12 hours and aging, the temperature is returned to room temperature, and methylcellosolve-dispersed cerium dioxide-titanium dioxide-silicon dioxide composite fine particle sol (trade name “Optreak 18
20 "(manufactured by Catalyst Chemical Industry Co., Ltd .; solid content concentration: 20% by weight)
3.92 kg, glycerol triglycidyl ether (trade name “Denacol EX-314” Nagase Kasei Co., Ltd.)
1.1 kg, 5.9 g of manganese (III) acetylacetonate, 20 g of a hindered amine light stabilizer (trade name "Sanol LS-770" manufactured by Sankyo Co., Ltd.), and a phenolic antioxidant (trade name "Seanox") 20 g of "226M" (produced by Cipro Kasei Co., Ltd.) was added, stirred for 1 hour, and again stored at 0 ° C. for 24 hours to ripen. Use after returning to room temperature.

(3) Coating and curing of hard coat Eyeglass lens fabric (trade name “Seiko Super Sovereign Fabric” manufactured by Seiko Epson Corporation; refractive index 1.66)
Was applied by a spray method. First, the lens was subjected to an alkali treatment. Next, one surface of the lens material was polished with a sponge soaked in pure water to remove dust, washed with pure water and then with isopropyl alcohol, and dried to make the surface of one surface clean. Spray (trade name "Iwata Weider 61" manufactured by Iwata Coating Machine Co., Ltd .; Nozzle diameter 1)
mm) with a spray pressure of 3 kg / cm ² and a liquid discharge amount of 100 ml / min, on one surface of the lens cloth (1).
The hard coat composition to be used was applied to one surface of the lens prepared in the above step. Put this lens in a 135 ° C oven for 30 minutes.
After drying for a minute, the mixture was cooled to room temperature. Next, the other surface of the lens was cleaned in the same procedure as the one surface. After the hard coat composition used for the other surface of the lens prepared in (2) was applied to the other surface of the lens in the same manner as described above, the lens was dried in an oven at 135 ° C. for 3 hours. The hard coat film on the surface of the spectacle lens obtained in this way had a thickness of 3 μm on both sides and had a good appearance. The obtained lens was evaluated in the same manner as in Example 1, (4). The results are shown in Table 1.

(Embodiment 6) An antireflection film made of an inorganic substance was applied to a lens obtained by the same method as in the steps (1), (2) and (3) of the above-mentioned embodiment 5 by the following method. Formed.

(5) Formation of Anti-Reflection Film After the lens is subjected to ion beam irradiation treatment with oxygen gas (acceleration voltage: 500 V × 60 seconds), SiO ₂ , ZrO ₂ , SiO ₂ are sequentially applied from the lens surface to the atmosphere. , Ti
An antireflection multilayer film composed of five layers of O ₂ and SiO ₂ was formed by a vacuum deposition method using a vapor deposition machine (“BMC-1000” manufactured by Vacuum Instruments Co., Ltd.). At that time, the fourth layer of TiO
₂ was formed by ion beam assisted deposition. The optical film thickness of each layer is such that the first SiO ₂ layer, the next equivalent thin film of ZrO ₂ and SiO ₂ are λ / 4, the TiO ₂ layer is λ / 2, and the uppermost SiO ₂ layer is λ / 4. Formed. In addition,
The design wavelength λ was 520 nm. The reflection interference color of the obtained multilayer film was green, and the total light transmittance was 99%.

The obtained lens was tested in the same manner as in Example-1 (4). However, the (c) staining test was performed before the above (5) formation of the antireflection film. The results are shown in Table 1.

Comparative Example 1 In Example 1, (3)
The hard coat composition to be used for one surface of the lens was applied to one surface of the lens by the application and curing of the hard coat, and the lens was cured. Next, on the other side, the same hard coat composition as used on one side was applied and cured. The obtained lens was tested in the same manner as in Example-1 (4). The results are shown in Table 1.

Comparative Example 2 In Example 1, (3)
By applying and curing the hard coat described above, the same hard coat composition as used on the other side was applied to one side of the lens and cured. Next, the other side was coated with the hard coat composition used for the other side and cured. The obtained lens was tested in the same manner as in Example-1 (4). The results are shown in Table 1.

(Comparative Example 3) In Example 1, (3)
In the application and curing of the hard coat, the same hardening process as when the hard coat composition was applied was applied without coating the hard coat composition on one surface of the lens. Next, the other side was coated with the hard coat composition used for the other side and cured. The obtained lens was tested in the same manner as in Example-1 (4). The results are shown in Table 1.

Comparative Example 4 In Example 1, (3)
The hard coat composition to be used for one surface of the lens was applied to one surface of the lens by the application and curing of the hard coat, and the lens was cured. Next, the same hardening process as when the hard coat composition was applied was applied to the other surface without applying the hard coat composition at all. The obtained lens was tested in the same manner as in Example-1 (4). The results are shown in Table 1.

(Evaluation results)

[0058]

[Table 1]

In Examples 1 to 6, (a) the lens abrasion resistance was not always at a satisfactory level as a result of the abrasion test of the lens abrasion resistance. The result of the portable test is A, showing practically sufficient lens abrasion resistance, and (c) the result of the dyeability test is good, showing practically sufficient dyeability, and (d-i)
The results of the various lens quality tests were all good. On the other hand, in Comparative Examples 1 to 4, none of the results of (a) the portable test of the lens abrasion resistance and (c) the results of the dyeability test were good.

[0060]

According to the present invention, a hard-coated film having excellent wear resistance is provided on one surface of the lens, and this surface is used as a convex surface to obtain a practically sufficient wear-resistant plastic lens. be able to. By providing a hard coat film having excellent dyeability on the other surface of the lens substrate, a plastic lens having practically sufficient dyeability can be obtained. Furthermore, by providing a hard coat film having excellent wear resistance on one surface of the lens and providing a hard coat film having excellent dyeability on the other surface, and using one surface as a convex surface for a spectacle lens, A plastic lens having both sufficient abrasion resistance and practically sufficient dyeability can be obtained. Further, the plastic lens of the present invention can be dyed in a short time, has high productivity in the dyeing process, and has a sufficient adhesion when a hard coat film and an inorganic vapor-deposited film are provided on the film. Also has various durability.

Plastic lenses having such excellent abrasion resistance, dyeability, coating adhesion and various durability are commercially available as spectacle lenses, camera lenses, light beam focusing lenses, and light diffusing lenses. Alternatively, it can be widely applied for industrial use. Particularly when used as a spectacle lens, the effect obtained is enormous. Further, the effects of the present invention can be applied to transparent glasses such as watch glass and cover glass for displays, and transparent plastics for optical use such as cover glasses.

Claims (4)

[Claims] 1. A plastic lens in which a hard coat film having a different composition is provided on one surface and the other surface of a plastic lens substrate, wherein the hard coat film provided on one surface of the plastic lens substrate is provided. A plastic lens, wherein the wear resistance is superior to the wear resistance of a hard coat film provided on the other surface. 2. The dyeable property of the hard coat film provided on the other surface is better than the dyeability of the hard coat film provided on the one surface. The plastic lens described. 3. The plastic lens according to claim 1, wherein the plastic lens is an eyeglass lens. 4. The plastic lens according to claim 3, wherein said one surface is a convex surface and said other surface is a concave surface.