JP2001201602A - Plastic lens - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a plastic lens excellent in various qualities as a high refractive index plastic lens obtained by curing a polymerizable composition containing a (thio)epoxy compound having one or more disulfide bonds in one molecule and to particularly ensure excellent appearance, shock resistance, adhesion and weather resistance. SOLUTION: A primer layer and a hard coat layer are successively disposed on the surface of a plastic lens substrate using a transparent resin obtained by curing a polymerizable composition containing a (thio)epoxy compound having one or more disulfide bonds in one molecule or an antireflection film is further disposed on the hard coat layer to obtain the objective plastic lens. The primer layer is formed from a polyurethane resin or further contains inorganic fine particles.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plastic lens, and more particularly, to a plastic lens requiring a high refractive index and high transparency, a primer layer, a hard coat layer and an inorganic antireflection film are laminated on the surface of the plastic lens. Plastic lenses with excellent quality (appearance, scratch resistance, heat resistance, moisture resistance, impact resistance, weather resistance, adhesion between transparent resin and surface treatment layer, durability, etc.) It is.

In the following description, a plastic lens for spectacles will be described as an example, but the present invention is not limited to this.

[0003]

2. Description of the Related Art Plastic lenses are widely used in the field of spectacle lenses because they are lighter in weight, have better moldability, workability, dyeability, are less likely to break, and have higher safety than glass lenses. However, since plastic lenses are soft and very easily damaged, a hard coat layer having high hardness is provided on the surface of the plastic lens to improve scratch resistance.
When the adhesion between the plastic lens substrate and the hard coat layer is insufficient, a primer layer is provided between the plastic lens and the hard coat layer to improve the adhesion. Further, an anti-reflection film in which an inorganic substance is vapor-deposited may be provided on the surface of the hard coat layer in order to prevent surface reflection. Due to such surface treatment of the plastic lens, the quality of the plastic lens is high.

[0004] However, a plastic lens which has been subjected to a surface treatment of a hard coat layer or an antireflection film has a drawback that the impact resistance is reduced as compared with a plastic lens which has not been subjected to any surface treatment. Particularly, in the case of a lens having a negative power with a small center thickness of the lens, the impact resistance is remarkably reduced and the lens is liable to be broken. If the center thickness is increased to improve this, the thickness (edge thickness) at the peripheral portion of the lens becomes extremely large, which is not preferable in appearance. In addition, the weight of the lens increases, and the feeling of use of the eyeglasses decreases, which is not preferable in practical use. In recent years, the development of plastic lens substrates with a high refractive index has progressed, and it is possible to reduce the center thickness and edge thickness of the lens.However, plastic lens substrates with a high refractive index have low impact resistance, It has the disadvantage of being easy.

To solve this problem, Japanese Patent Application Laid-Open No.
87223 and JP-A-63-141001 disclose a method in which a urethane resin primer layer comprising a specific polyalcohol and an isocyanate is provided between a lens substrate and a hard coat layer. Similarly, Japanese Patent Application Laid-Open No. 3-109502 discloses a method using a urethane resin primer layer comprising a polyalcohol and a blocked isocyanate. Originally, the primer layer is a layer for the purpose of improving the adhesion between the plastic lens substrate and the hard coat layer, but by selecting a specific resin for the primer layer, the impact resistance of the plastic lens can be improved. .

However, since the primer layer made of these resins has a refractive index of about 1.50, if the refractive index of the plastic lens material is high, interference fringes occur due to the difference in the refractive index, which is not preferable in appearance. For the purpose of improving this, a method of adding fine particles made of metal oxide to the primer layer to make the refractive index of the primer layer close to that of the plastic lens material (JP-A-6-337376)
Japanese Patent Application Laid-Open No. H11-279, although the generation of interference fringes can be suppressed, but when the amount of metal oxides increases, the primer layer tends to become cloudy, which is not only unfavorable in appearance, but also lowers adhesion and impact resistance. . Further, JP-A-11-1933
No. 55 discloses a method in which a primer composition of a thiourethane resin solution is used to make the refractive index close to the refractive index of a plastic lens material. However, a primer layer made of these resins is generally inferior in weather resistance and requires a long time. With the passage of time, the adhesion of the surface treatment layer decreases, the surface treatment layer peels off,
It is likely to be unfavorable in appearance. In recent years, high quality plastic lenses have been demanded. In addition to simply providing a hard coat layer and an anti-reflection film, various quality (appearance, scratch resistance, heat resistance, moisture resistance, impact resistance, weather resistance, There is a demand for the development of a plastic lens having excellent adhesion between the lens substrate and the surface treatment layer, durability, etc., particularly, a plastic lens having excellent impact resistance and high safety. In recent years, with the development of plastic lens substrates with high refractive index,
Corresponding plastic lens surface treatment techniques have become important.

[0007]

SUMMARY OF THE INVENTION On the surface of a plastic lens substrate using a transparent resin obtained by curing a polymerizable composition containing a (thio) epoxy compound having one or more disulfide bonds in the molecule. , Plastic lenses with a primer layer and a hard coat layer in order from the substrate side, or plastic lenses with an anti-reflective coating on the surface, have various quality (appearance, scratch resistance, heat resistance, moisture resistance, impact resistance) The purpose of the present invention is to provide a plastic lens having excellent heat resistance, weather resistance, adhesion between a lens substrate and a surface treatment layer, durability, and the like, in particular, a highly safe plastic lens having excellent impact resistance. Things.

[0008]

The present invention provides a plastic lens substrate using a transparent resin obtained by curing a polymerizable composition containing a (thio) epoxy compound having at least one disulfide bond in a molecule. In a plastic lens provided with a primer layer and a hard coat layer in order from the substrate side on the surface, or a plastic lens further provided with an antireflection film on the surface, use a primer layer in which the primer layer is formed from a polyurethane resin. It has been found that this purpose is achieved.

The plastic lens according to the first aspect of the present invention comprises a primer layer formed on a transparent resin obtained by curing a polymerizable composition containing a (thio) epoxy compound having one or more disulfide bonds in a molecule. A plastic lens provided with a hard coat layer formed on the primer layer, wherein the primer layer is formed of a polyurethane resin, which is a disadvantage of the transparent resin, which is easily broken. It is possible to provide a plastic lens which supplements the properties and has excellent impact resistance.

A plastic lens according to a second aspect of the present invention is the plastic lens according to the first aspect, wherein the primer layer further contains inorganic fine particles, whereby the refractive index of the primer layer is reduced by the refractive index of the transparent resin. The refractive index can be adjusted to be equal to or close to the refractive index, and it is possible to provide a plastic lens having an excellent appearance with no or reduced interference fringes.

According to a third aspect of the present invention, there is provided a plastic lens according to the first or second aspect, further comprising an anti-reflection film made of an inorganic substance on a surface of the hard coat layer, thereby forming an image by surface reflection. It is possible to provide a high-value-added plastic lens having a function of suppressing flicker.

[0012] In the plastic lens according to any one of claims 1 to 3, the polyurethane resin contained in the primer layer is a polyether polyol,
It is preferably a polyurethane resin obtained from an active hydrogen-containing compound selected from a modified polyether polyol, a polyester polyol, a polybutadiene polyol, a polyamine, an alkanolamine, and a polythiol, and a polyisocyanate (claim 4). These polyether polyols, modified polyether polyols, polyester polyols, polybutadiene polyols, polyamines, alkanolamines,
By using a polyurethane resin obtained from an active hydrogen-containing compound selected from polythiols and a polyisocyanate, it is possible to provide a plastic lens having excellent impact resistance, which compensates for the disadvantage of the transparent resin, that is, the property of being easily broken. It is. Further, the adhesion between the transparent resin and the primer layer, and the adhesion between the primer layer and the hard coat layer are increased, so that a plastic lens having excellent weather resistance can be provided.

In the plastic lens according to any one of the first to fourth aspects, the inorganic fine particles contained in the primer layer may be made of Si, Al, Sn, Sb, Ta, C
Fine particles or composite fine particles comprising a metal oxide of at least one metal selected from e, La, Fe, Zn, W, Zr, In, and Ti are preferable (claim 5). These Si, Al, Sn, Sb, Ta, Ce, La, Fe,
By using fine particles or composite fine particles made of a metal oxide of one or more metals selected from Zn, W, Zr, In, and Ti, the refractive index of the primer layer is equal to or close to the refractive index of the transparent resin. The refractive index can be adjusted, and a plastic lens having an excellent appearance with no or reduced interference fringes can be provided. Further, the adhesion between the transparent resin and the primer layer, and the adhesion between the primer layer and the hard coat layer are increased, so that a plastic lens having excellent weather resistance can be provided.

The plastic lens of the present invention has one
A primer layer formed on a transparent resin obtained by curing a polymerizable composition containing a (thio) epoxy compound having two or more disulfide bonds, and a hard coat layer formed on the primer layer were provided. In a plastic lens, the primer layer is formed of a polyurethane resin, wherein a polymerizable composition containing a (thio) epoxy compound having one or more disulfide bonds in a molecule is provided. As the transparent resin obtained by curing, for example, a resin obtained by carrying out the one disclosed in detail in JP-A-11-322930 can be used. A primer layer containing a polyurethane resin is formed on the transparent resin. The polyurethane resin contained in the formed primer layer is a resin formed from the reaction of a compound containing active hydrogen at both ends with polyisocyanate. Here, as the active hydrogen-containing compound, ethylene glycol, 1,2-propylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, dipropylene glycol, diethylene glycol Polyether polyols such as polypropylene glycol, polyethylene glycol, polytetramethylene glycol, urethane-modified polyether polyols, polyether ester copolymer polyols, terminally aminated polyether polyols, and polyether polyol-modified products such as silicon-modified polyether polyols, Ethylene adipate, diethylene adipate, tetramethylene adipate, hexamethylene adipate, butylene adipate, neopentylene adipate, ε- Ring-opened polymer of prolactone, polyester polyols such as polycarbonate diol, polybutadiene polyols such as 1,4-polybutadiene polyol and 1,2-polybutadiene polyol, 3,3′-dichloro-4,4′-diaminodiphenylmethane, Methylene dianiline sodium chloride complex, 1,2-bis (2-aminophenylthio) ethane, trimethylene glycol-di-
p-aminobenzoate, di (methylthio) -toluenediamine, diaminophenylcarboxylate, bis- (2
Polyamines such as -cyanoethylamino) ethane, N
Alkanolamines such as -methyldiethanolamine, 1,2-ethanedithiol, 1,4-butanedithiol, 1,6-hexanedithiol, 1,9-nonanedithiol, 1,10-decanedithiol, 1,2-benzenedithiol , Dithioerythritol, 2,3-dimercapto-1-propanol, 3,4-dimercaptotoluene, trimethylolpropane tristhiopropionate, bis (3-mercaptopropylthio) methane,
1,2-bis (3-mercaptopropylthio) ethane,
1,3-bis (3-mercaptopropylthio) propane, 1,2,3-bis (3-mercaptopropylthio)
Active hydrogen-containing compounds selected from polythiols such as propane, 2-mercaptoethanol, p-mercaptophenol, and 3-mercapto-1,2-propanediol, and other known active hydrogen-containing compounds can also be used. is there.

Examples of the polyisocyanate include toluene diisocyanate, diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-diphenylene diisocyanate, 1,5-naphthalene diisocyanate,
Trizine diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, p-phenylene diisocyanate, t-cyclohexane-1,4-diisocyanate, xylene diisocyanate, hydrogenated xylene diisocyanate, hydrogenated diphenylmethane diisocyanate, lysine diisocyanate, tetramethyl xylene diisocyanate, trimethyl hexane Diisocyanates such as methylene diisocyanate and 1,3-bis (isocyanatomethyl) cyclohexane, triphenylmethane triisocyanate, tris (isocyanatephenyl) thiophosphate, lysine ester triisocyanate, and 2-isocyanatoethyl-2,6-diisocyanatohexano Eate, 1,6,11-undecane triisocyanate, , 8-diisocyanate-4-isocyanate methyl octane, 1,3,6-hexamethylene triisocyanate, the triisocyanate such as bicycloheptane triisocyanate and the like. Furthermore, urethane modified products obtained from these diisocyanates and triisocyanates can be used. Examples of the urethane-modified product include an adduct, a uretdione (a dimer), an isocyanurate (a trimer), a carbodiimide, an allohanate-modified, a urea-modified polyisocyanate, a buret-modified polyisocyanate, and an isocyanate prepolymer (semi-prepolymer). Is raised. Furthermore, these polyisocyanates are acetylacetone, dimethylmalonate, diethylmalonate, 2,4-hexanedione,
Blocked isocyanates blocked with a blocking agent such as 3,5-heptanedione, acetoxime, methylethylketoxime, butanone oxime, caprolactam and the like can be mentioned.

The polyurethane resin can be produced by a known method, and various amines and metal compounds such as dibutyltin dilaurate can be used as a catalyst. As a method of forming a primer layer containing a polyurethane resin, a method of applying a solution of a polyurethane resin in which an active hydrogen-containing compound and a polyisocyanate have been reacted in advance on the transparent resin and heating and drying the same, A method in which a solution containing an isocyanate is applied on the transparent resin, reacted on the transparent resin, and dried by heating.

Further, a ply formed on the transparent resin
The mer layer preferably contains inorganic fine particles. Inorganic fine
Specific examples of particles include SiO_Two, Al_TwoO_Three, SnO_Two,
Sb _TwoO_Five, Ta_TwoO_Five, CeO_Two, La_TwoO_Three, Fe_TwoO_Three,
ZnO, WO_Three, ZrO_Two, In_TwoO_Three, TiO_TwoEtc. metal
Metal oxidation of oxide fine particles or two or more metals
The composite fine particles made of the product are dispersed in a dispersion medium such as water or alcohol.
Disperse colloidally in aqueous or other organic solvents
Items.

As a solvent for the primer composition used for forming the primer layer of the present invention, a conventionally known solvent can be used. Examples thereof include hydrocarbons, halogenated hydrocarbons, esters, alcohols, ketones, and ethers, which may be used alone or as a mixed solvent of two or more. Specifically, toluene, ethyl acetate, methyl ethyl ketone, tetrahydrofuran, methanol, diacetone alcohol,
Use of propylene glycol monoethyl ether or the like is possible. The components for forming the primer layer are diluted with these solvents to a concentration suitable for coating, and coated on the transparent resin. As a coating method, a conventionally known method such as a dipping method and a spin coating method can be used.
After coating by these methods, the primer layer is formed by heating and drying at an arbitrary range of 50 ° C. to 150 ° C. The thickness of the primer layer is 0.01 to 50 μm.
Is preferred. When the thickness is 0.01 μm or less, the effect of impact resistance is small, and when it is 50 μm or more, surface accuracy is reduced.
Further, the primer layer of the present invention can contain various conventionally known additives. It can contain various leveling agents for improving coatability, ultraviolet absorbers and antioxidants for improving weather resistance, and additives such as dyes and pigments.

The hard coat layer used in the present invention may be any layer which improves the scratch resistance which is an original function of the hard coat layer, and a conventionally known hard coat layer for a plastic lens can be used. As a conventionally known material, a hard coat layer using a melamine-based resin, a silicone-based resin, a urethane-based resin, an acrylic-based resin, or the like can be given, and a hard coat using a silicone-based resin is most preferable. As a specific example, a coating composition comprising metal oxide fine particles and a silane compound is applied and cured to form a hard coat layer. The coating composition may include components such as colloidal silica and polyfunctional epoxy compounds. Specific examples of the metal oxide fine particles include SiO ₂ , Al ₂ O ₃ , SnO ₂ , Sb ₂ O ₅ , and Ta.
₂ O ₅ , CeO ₂ , La ₂ O ₃ , Fe ₂ O ₃ , ZnO, WO ₃ ,
Fine particles of a metal oxide such as ZrO ₂ , In ₂ O ₃ , TiO ₂ , or composite fine particles of a metal oxide of two or more metals are colloidally dispersed in a dispersion medium such as water, an alcohol, or another organic solvent. Dispersed ones are mentioned. Specific examples of the silane compound include vinyl trialkoxy silane, vinyl trichlorosilane, vinyl tri (β-
Methoxy-ethoxy) silane, allyltrialkoxysilane, acryloxypropyltrialkoxysilane,
Methacryloxypropyl trialkoxysilane, methacryloxypropyl dialkoxymethylsilane, γ-
Glycidoxypropyl trialkoxysilane, β-
(3,4-epoxycyclohexyl) -ethyl trialkoxysilane, mercaptopropyl trialkoxysilane, γ-aminopropyl trialkoxysilane, N-β
(Aminoethyl) -γ-aminopropylmethyldialkoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetraacetoxysilane, tetraallyloxysilane, tetrakis ( 2-methoxyethoxy) silane, tetrakis (2-ethylbutoxy) silane, tetrakis (2
-Ethylhexyloxy) silane and the like. The colloidal silica is obtained by dispersing silica fine particles having a particle diameter of 1 to 100 mm in a solvent such as alcohol and water. 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. Further, the hard coat layer used in the present invention can contain various conventionally known additives. It can contain various leveling agents for improving coatability, ultraviolet absorbers and antioxidants for improving weather resistance, and additives such as dyes and pigments.

Examples of the method for forming an anti-reflection film made of an inorganic substance used in the present invention 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.
Further, as the layer configuration, either a single-layer antireflection film or a multilayer antireflection film may be used.

Specific examples of the inorganic substance used include Si
O ₂ , SiO, ZrO ₂ , TiO ₂ , TiO, Ti ₂ O ₃ ,
Ti ₂ O ₅ , Al ₂ O ₃ , Ta ₂ O ₅ , CeO ₂ , MgO, Y ₂
O ₃ , SnO ₂ , MgF ₂ , WO _{3 and the} like can be mentioned. These inorganic substances are used alone or as a mixture of two or more.

In forming the antireflection film, it is desirable to perform a surface treatment on the hard coat layer. 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. Hereinafter, the present invention will be described in more detail with reference to examples.

[0023]

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. The obtained lenses were tested and evaluated by the methods described below, and the results are shown in Table 1. (A) Appearance: White light turbidity and interference fringes were observed with transmitted light and reflected light using a fluorescent lamp in a dark box with a black background. (B) Abrasion resistance: A load of 1 kg was applied with Bonstar # 0000 steel wool (manufactured by Nippon Steel Wool Co., Ltd.), and the surface was rubbed for 10 reciprocations, and the degree of damage was visually evaluated. (C) Adhesion: The adhesion between the substrate and the hard coat layer and between the hard coat layer and the multi-coat layer was determined according to 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 squares remaining in the coating layer were used as adhesion indices. (D) 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. (E) Heat resistance (cooling cycle property): 1 in hot air at 70 ° C
After storage for a time, the surface condition was examined. Further 15 at -5 ° C
A cycle of 15 minutes at 60 ° C. for 15 minutes was repeated five times. (F) Moisture resistance test: A sample which was left in an atmosphere of 60 ° C. × 99% for 10 days and had no change in surface state was evaluated as good. (G) Durability: The durability is considered to be essentially an adhesive connection, and the test of (d) to (f) is performed, and the above-mentioned cross cut tape test is performed. Things were good. (H) Impact resistance test: A 16.3 g hard sphere was naturally dropped from a height of 127 cm to the center of the convex surface of the lens, and cracking of the lens was confirmed. The lenses used in this test all had a center thickness of 1.2 mm.

(Example 1) (1-I) Production of plastic lens substrate 50 g of bis (2,3-epithiopropyl) disulfide
And bis (2-mercaptoethyl) sulfide 1.5
g, 0.5 g of SEESORB 701 (Cipro Kasei Kogyo) as an ultraviolet absorber and sufficiently mixed.
0.05 g of dimethylcyclohexylamine was added and mixed, and the mixture was thoroughly stirred at room temperature, and then degassed for 10 minutes while stirring under reduced pressure of 5 mmHg. This raw material was poured into a mold held by an adhesive tape using two mirror-finished glass plates, and the temperature was raised from 30 ° C. to 130 ° C. over 22 hours to polymerize and cure. Thereafter, the lens was released from the mold, and heated at 130 ° C. for 2 hours to perform an annealing treatment.
The plastic lens manufactured in this way had a refractive index ne of 1.741, an Abbe number of 33, and a specific gravity of 1.48. (1-II) Preparation of primer composition and coating curing Commercially available polyurethane LQ3510 [manufactured by Sanyo Chemical Co., Ltd.
Solid concentration 30% (using polyalkylene adipate)]
Toluene / IPA (isopropyl alcohol) in 83g
(Mixing ratio 2/1) 417 g of a mixed solvent was added, and the solid content was 5
Dilute to%. Next, a silicon-based surfactant (L-700 manufactured by Nippon Unicar Co., Ltd.) was slowly added to this solution with stirring.
2) 0.3 g was added to obtain a primer composition. This primer composition is immersed on the plastic lens substrate obtained in the above (1-I) (with a pulling speed of 15 cm / m
in). The coated base lens was heat-cured at 100 ° C. for 30 minutes to form a 3.0 μm thick primer layer on the base material. (1-III) Preparation and Hardening of Hard Coat Composition 76.6 g of butyl cellosolve and cerium dioxide-titanium dioxide-silicon dioxide composite fine particle sol dispersed in methyl cellosolve (catalyst Chemical Industry Co., Ltd., trade name "Optrake 1832" (Partial concentration: 20 wt%) and 19 g of γ-glycidoxypropyltrimethoxysilane were mixed. 5.4 g of a 0.1N aqueous hydrochloric acid solution was added dropwise to the mixture with stirring, and the mixture was stirred for 4 hours and then aged for 24 hours. To this solution was added glycerol triglycidyl ether (trade name "Denacol EX-31", manufactured by Nagase Kasei Kogyo Co., Ltd.).
4 ") was added 15.4g _{of, Fe (C 5 H 7 O} 2) 3 to 0.4g and _{Mn (C 5 H 7 O 2} ) 2 0.22g, silicon surfactant (Nippon Unicar (strain ), Product name "FZ
-2110 "and 0.2 g of a phenolic antioxidant (trade name" Antage Crystal "manufactured by Kawaguchi Chemical Industry Co., Ltd.), stirred for 4 hours, and aged all day long to obtain a coating solution. This hard coat composition was treated with (1-I
On the primer layer of the plastic lens substrate having the primer layer obtained in I), dipping method (pulling speed 12 cm)
/ Min). The applied lens is heated and cured at 130 ° C. for 90 minutes to form a film having a thickness of 2.5 on the primer layer.
A μm hard coat layer was formed. The obtained plastic lens (with a primer layer and a hard coat layer) was excellent in appearance, impact resistance, adhesion of a coat film, and weather resistance.

(Example 2) After the plastic lens obtained in Example 1 was subjected to an ion beam irradiation treatment with oxygen gas (acceleration voltage 500 V × 60 seconds), SiO ₂ , ZrO ₂ were sequentially applied from the substrate to the atmosphere. ₂ , SiO ₂ , Ti
An antireflection multilayer film composed of five layers of O ₂ and SiO ₂ was formed by a vacuum evaporation method (BMC-1000, manufactured by Vacuum Instruments Co., Ltd.). At this time, a fourth layer of TiO ₂ was formed by ion beam assisted vapor deposition. The optical film thickness of each deposited layer is λ / 4 for the first SiO ₂ , the equivalent film layer of the next ZrO ₂ and SiO ₂ , λ / 2 for the TiO ₂ layer, and λ / 4 for the uppermost SiO ₂ layer. Formed in the same manner. The design wavelength λ is 520
nm. The reflection interference color of the obtained multilayer film was green, and the total light transmittance was 99%. The obtained plastic lens (with a primer layer, a hard coat layer, and an antireflection film) was excellent in appearance, impact resistance, adhesion of the coat film, and weather resistance.

Example 3 (3-I) Production of Plastic Lens Substrate A treatment was performed in the same manner as in Example 1 (1-I). (3-II) Preparation of composition for primer and coating and curing 140 g of commercially available aqueous emulsion polyurethane "Superflex 150" (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., solid content concentration 30%, non-yellowing type, ether-ester type) ,
280 g of pure water and 80 g of methanol were added, and the solid concentration was 8%.
Dilute to. This primer composition was prepared using the above (3-I)
Was applied by a dipping method (pulling speed: 10 cm / min) on the plastic lens substrate obtained in the above. The coated base lens was heat-cured at 100 ° C. for 10 minutes to form a 1.0 μm-thick primer layer on the base material. (3-III) Preparation of Hard Coat Composition and Coating and Curing Treatment was performed in the same manner as in Example 1 (1-III). The obtained plastic lens (with a primer layer and a hard coat layer) was excellent in appearance, impact resistance, adhesion of a coat film, and weather resistance.

Example 4 The plastic lens obtained in Example 3 was subjected to plasma treatment (400 W argon plasma).
X 60 seconds), and from the substrate to the atmosphere,
An antireflection multilayer film composed of four layers of ZrO ₂ , SiO ₂ , ZrO ₂ , and SiO ₂ is formed by a vacuum deposition method (manufactured by Vacuum Equipment Co., Ltd .:
BMC-1000) to form a film at a film forming temperature of 250 ° C. The optical film thickness of each layer is as follows: the first equivalent film layer of ZrO ₂ and SiO ₂ , the next ZrO ₂ layer, and the uppermost Si layer.
The O ₂ layers were formed so as to be λ / 4 each. The design wavelength λ was 520 nm. The reflection interference color of the obtained multilayer film was green, and the total light transmittance was 99.0%. The obtained plastic lens (with a primer layer, a hard coat layer, and an antireflection film) was excellent in appearance, impact resistance, adhesion of the coat film, and weather resistance.

Example 5 (5-I) Production of Plastic Lens Substrate A treatment was performed in the same manner as in Example 1 (1-I). (5-II) Preparation of primer composition and coating curing Hexamethylene diisocyanate (Wako Pure Chemical Industries, Ltd., reagent grade 1) 33.6 g as polyisocyanate
Was dissolved in 200 g of cyclohexanone, and a small amount of dibutyltin dilaurate was added as a catalyst while stirring at 40 ° C. Next, butanone oxime was added little by little, and butanone oxime was added little by little until the absorption of isocyanate disappeared by IR measurement. To this solution was added 1,10-decanedithiol (Wako Pure Chemical Industries, Ltd., first grade reagent).
2 g and 0.2 g of a silicon-based surfactant "L7604" (manufactured by Nippon Unicar Co., Ltd.) were mixed and sufficiently stirred to obtain a primer composition. This primer composition was applied to the plastic lens substrate obtained in the above (5-I) by a dipping method (pulling speed: 20 cm / min). The applied base lens was heat-cured at 120 ° C. for 50 minutes to form a 2.5 μm-thick primer layer on the base. (5-III) Preparation of Hard Coat Composition and Coating and Curing 44.2 g of butyl cellosolve and 28.7 g of γ-glycidoxypropyltrimethoxysilane were mixed, and 7.9 g of a 0.1N hydrochloric acid aqueous solution was stirred in the mixed solution. The mixture was added dropwise while stirring for 4 hours and then aged all day long. This solution was added to a commercially available metal oxide sol “OPTLAKE 1120Z (S-7,
G) "manufactured by Catalyst Kasei Co., Ltd .: ZrO ₂ / TiO ₂ = 0.0
2, SiO ₂ / TiO ₂ = 0.22, particle size: 10 nm, solid content concentration: 20% ”and stirred, and then glycerol triglycidyl ether (trade name“ Nagase Kasei Kogyo Co., Ltd., trade name ”) 7.5 g of Denacol EX-314 ”), and 0.4% of Fe (C ₅ H ₇ O ₂ ) ₃ .
g and Mn (C ₅ H ₇ O ₂ ) ₂ 0.22 g, a silicon-based surfactant (trade name “FZ-21” manufactured by Nippon Unicar Co., Ltd.)
10 "0.1 g and a phenolic antioxidant (trade name" ANTAGE CRYSTAL "manufactured by Kawaguchi Chemical Industry Co., Ltd.)
0.2 g was added, and the mixture was stirred for 4 hours and then aged all day and night to obtain a coating solution. This hard coat composition is immersed on the primer layer of the plastic lens substrate having the primer layer obtained in the above (5-II) by a dipping method (pulling speed: 25 cm / mi).
n). The applied lens was heat-cured at 130 ° C. for 90 minutes to form a 2.0 μm-thick hard coat layer on the primer layer. The obtained plastic lens (with a primer layer and a hard coat layer) was excellent in appearance, impact resistance, adhesion of a coat film, and weather resistance.

Example 6 The plastic lens obtained in Example 5 was treated in the same manner as in Example 4. The obtained plastic lens (with a primer layer, a hard coat layer, and an antireflection film) was excellent in appearance, impact resistance, adhesion of the coat film, and weather resistance.

Example 7 (7-1) Preparation of Plastic Lens Substrate Bis (2,3-epithiopropyl) disulfide 50 g
4,8 or 4,7 or 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 5 g of UV absorber, SEESORB7
After adding 0.5 g of C.01 (Cipro Kasei Kogyo) and mixing well, 0.05 g of N, N-dimethylcyclohexylamine was added.
Was added and mixed, and thereafter a plastic lens was produced in the same manner as in Example 1 (1-I). The plastic lens produced in this manner had a refractive index ne of 1.739, an Abbe number of 33, and a specific gravity of 1.47. (7-II) Preparation of Composition for Primer and Coating and Curing Commercially available aqueous emulsion polyurethane “Superflex 300” (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., solid content concentration 3)
0%, non-yellowing type, 140 g of ether / ester type, 280 g of pure water, aqueous sol of Fe ₂ O ₃ / TiO ₂ composite (F
(e ₂ O ₃ / TiO ₂ = 2/97, average particle size 30 nm, solid content concentration 10%) 90 g are mixed. This primer composition was applied on the plastic lens substrate obtained in the above (7-I) by a dipping method (pulling speed: 10 cm / min). The coated base lens was heat-cured at 100 ° C. for 30 minutes to form a 0.8 μm-thick primer layer on the base material. (7-III) Preparation of Hard Coat Composition and Coating and Hardening Treatment was performed in the same manner as in Example 5 (5-III). The obtained plastic lens (with a primer layer and a hard coat layer) was excellent in appearance, impact resistance, adhesion of a coat film, and weather resistance.

Example 8 The plastic lens obtained in Example 7 was treated in the same manner as in Example 2. The obtained plastic lens (with a primer layer, a hard coat layer, and an antireflection film) was excellent in appearance, impact resistance, adhesion of the coat film, and weather resistance.

Example 9 (9-1) Production of Plastic Lens Substrate A treatment was performed in the same manner as in Example 7 (7-I). (9-II) Preparation of Composition for Primer and Coating and Curing Block-Type Polyisocyanate “Coronate 252”
9 "(Nippon Polyurethane Industry Co., Ltd.), 32 g of polyester polyol" Nipporan 1100 "(Nippon Polyurethane Industry Co., Ltd.) and 170 g of ethyl cellosolve were mixed, and a commercially available metal oxide sol" OPTLAKE 1120Z (S -7, G) "manufactured by Catalyst Chemicals, Inc .: Zr
O ₂ / TiO ₂ = 0.02, SiO ₂ / TiO ₂ = 0.2
2. 90 g of particle size: 10 nm, solid content concentration: 20%, and 0.15 part by weight of a silicon-based surfactant are added and sufficiently stirred and mixed. This primer composition was subjected to the above (9-1)
Was applied by a dipping method (pulling speed: 20 cm / min) on the plastic lens substrate obtained in the above. 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. (9-III) Preparation of Hard Coat Composition and Coating and Hardening Treatment was performed in the same manner as in Example 5 (5-III). The obtained plastic lens (with a primer layer and a hard coat layer) was excellent in appearance, impact resistance, adhesion of a coat film, and weather resistance.

Example 10 The plastic lens obtained in Example 9 was treated in the same manner as in Example 4.
The obtained plastic lens (with a primer layer, a hard coat layer, and an antireflection film) was excellent in appearance, impact resistance, adhesion of the coat film, and weather resistance.

(Comparative Example 1)
Except that the treatment was carried out without forming the primer layer of -II), the same treatment as in Example 1 was carried out to produce a plastic lens.

Comparative Example 2 The lens obtained in Comparative Example 1 was treated in the same manner as in Example 4 to produce a plastic lens.

[0036]

[Table 1]

[0037]

As described in detail above, according to the present invention, a high refractive index plastic obtained by curing a polymerizable composition containing a (thio) epoxy compound having one or more disulfide bonds in a molecule. It is possible to provide plastic lenses excellent in various qualities (appearance, abrasion resistance, heat resistance, moisture resistance, impact resistance, weather resistance, adhesion between a transparent resin and a surface treatment layer, durability, etc.). It is possible.
Especially excellent appearance, impact resistance, adhesion and weather resistance were realized.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G02B 1/10 G02B 1/10 A G02C 7/02 Z F term (Reference) 2K009 AA07 AA15 BB23 CC03 CC09 CC35 CC42 DD02 DD03 DD06 4J002 CK031 CK041 CK051 DE096 DE106 DE116 DE126 DE136 DE146 DJ016 GH02 GP01 HA05 4J038 DG001 DG111 DG131 DG191 DG261 HA216 KA20 NA19 PA07 PB08 PC08

Claims (5)

[Claims] 1. A primer layer formed on a transparent resin obtained by curing a polymerizable composition containing a (thio) epoxy compound having at least one disulfide bond in a molecule, and a primer layer formed on the transparent resin. A plastic lens provided with a formed hard coat layer, wherein the primer layer is formed from a polyurethane resin. 2. The plastic lens according to claim 1, wherein said primer layer further contains inorganic fine particles. 3. The plastic lens according to claim 1, further comprising an antireflection film made of an inorganic substance on the surface of the hard coat layer. 4. The plastic lens according to claim 1, wherein the polyurethane resin contained in the primer layer is a polyether polyol, a modified polyether polyol, a polyester polyol, or a polybutadiene polyol. A plastic lens, which is a polyurethane resin obtained from an active hydrogen-containing compound selected from polyamines, alkanolamines and polythiols and a polyisocyanate. 5. The plastic lens according to claim 1, wherein the inorganic fine particles contained in the primer layer are made of Si, Al, Sn, Sb, Ta, Ce,
A plastic lens comprising fine particles or composite fine particles comprising a metal oxide of at least one metal selected from La, Fe, Zn, W, Zr, In, and Ti.