JPH0980206A - Plastic lens - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a plastic lens excellent in impact resistance by providing a primer layer composed of a crosslinked polyvinyl acetal resin between the surface of a plastic lens base material and a hard coat layer. SOLUTION: The hard coat layers are provided on the both surfaces of the plastic lens base material. And the primer layer composed of the crosslinked polyvinyl acetal resin is provided between at least one surface of the plastic lens base material and the hard coat layer. The primer layer is formed by applying a primer composition prepared by dissolving a polyvinyl acetal of the main component, a hydrolyzable organosilane compound or the hydrolyzed condensation product, an organic metal alkoxide compound and a curing catalyst on the surface of a plastic lens and heat treating. An inorganic oxide fine particle is preferably incorporated by dispersing in the primer composition.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plastic lens having good adhesion of a coating film and excellent impact resistance, scratch resistance, chemical resistance, weather resistance and antireflection property.

[0002]

2. Description of the Related Art Plastic lenses are lightweight, shock-resistant,
It has advantages such as easy workability and dyeability, and has rapidly spread in recent years in the field of optical materials, particularly spectacle lenses. But,
Generally, plastic lenses have the drawback of being very vulnerable. Therefore, a silicon-based hard coat film is usually provided on the surface of the lens for the purpose of improving the surface hardness. In addition, for the purpose of suppressing the surface reflection which is a cause of image flicker (a decrease in light reflectance and an improvement in light transmittance and a decrease in contrast due to image superposition (flare) or double imaging (ghost)), By providing an antireflection film formed by depositing an inorganic substance on the surface of the hard coat film, high added value is given to the plastic lens.

However, a plastic lens provided with both a hard coat film and an antireflection film has flexibility, that is, shock absorption, as compared with a plastic lens provided with no film or a plastic lens provided with only a hard coat film. Has a drawback that the impact resistance is significantly reduced. In the United States, safety standards have been set for medical devices and pharmaceuticals including eyeglasses.
There is a safety standard called nistration (hereinafter referred to as "FDA"). According to FDA standards, a diameter of 5/8 inch (1
6.3mm), drop an iron ball weighing 0.56 ounces (15.9g),
It is required that the debris does not scatter. Still,
In the case of a plus lens, the center thickness is thick enough so
Although it passes the DA standard, the minus lens may not pass the FDA standard because the center thickness is thin.
In particular, a recent tendency is that the center thickness of the minus lens tends to be thin as a problem in appearance, and this is a big problem in terms of impact resistance.

[0004]

Some methods have already been proposed for passing the impact resistance test of the US FDA standard for plastic lenses having surface treatment such as hard coat and antireflection coat. There is. As a first method, the impact resistance is improved by increasing the center thickness of the minus lens.

However, this increases the edge thickness of the lens, which impairs the appearance and also increases the weight of the lens, which is not preferable in practice. Further, depending on the material of the plastic lens, it may not be possible to provide a lens that passes the impact resistance test of the FDA standard only by increasing the center thickness. As a second method, a plastic lens material having an impact strength sufficient to pass the impact resistance test of the US FDA standard even if the impact resistance is lowered by providing both a hard coat film and an antireflection film. Has been made quite a bit. For example, JP-A-61-170701, JP-A-1-244401, and JP-A-2-36
216, JP-A-4-159309, JP-A-4-161414, JP-A-4-126710, JP-A-5-5011, and JP-A-4-14231.
5, JP-A-4-161410, JP-A-4-161410
161411, Japanese Patent Laid-Open No. 4-202308,
Japanese Patent Application Laid-Open No. 4-202309.

However, neither of the proposals has an FD in which neither the hard coat film nor the antireflection film is applied.
It passed the A standard and the minimum center thickness of the lens was 1.
At present, a plastic lens material having a thickness as thick as 5 mm or 2 mm and exhibiting a practically sufficient impact resistance has not been proposed yet. A third method is to provide a primer layer made of a resin composition between the plastic lens substrate and the hard coat film.

Originally, the primer layer was proposed as a method for improving the adhesion between the plastic lens substrate and the hard coat film, and like the surface modification method such as saponification and plasma treatment, the primer layer has a good adhesion property. Improvement was the main objective. As a prior art of the primer layer proposed for this purpose, a method using an epoxy compound (Japanese Patent Laid-Open No. 60-214)
No. 301), a method containing an acrylic and / or methacrylic compound and an aromatic vinyl compound as main components (JP-A-60-214302), and a primer composition comprising an acrylic polyol and a polyfunctional organic isocyanate compound. Method (Japanese Patent Laid-Open No. 61-114203). In each case, the improvement of the adhesion, which is the main purpose, was achieved, and the characteristics such as chemical resistance were obtained, but the impact resistance was not improved.

As a primer layer for improving impact resistance, a method using a polyurethane resin has been proposed. JP-A-63-14001, JP-A-63-8
The method disclosed in Japanese Patent No. 7223 is a method in which a polyurethane resin solution is applied to a plastic lens and then the solvent is volatilized to obtain a polyurethane resin layer. The obtained polyurethane layer is a so-called thermoplastic resin having no crosslinked structure. Of the film. When the lens is dipped in a hard coat solution to form a hard coat film on a plastic lens having this polyurethane layer, the polyurethane of the primer layer dissolves in the solvent of the hard coat solution and is eluted into the hard coat solution to form the hard coat solution. Often pollutes. In addition, the primer layer is often opaque because it is corroded by the solvent and loses its transparency. Further, JP-A-61-114203 discloses that a primer composition comprising an acrylic polyol and a polyfunctional organic isocyanate compound is applied and cured to form a polyurethane layer having a crosslinked structure. However, since an isocyanate compound capable of reacting with active hydrogen at room temperature is used, the reaction between the hydroxyl group of the polyol and the isocyanate group proceeds even during storage of the primer solution, so that the usable time of the primer solution cannot be extended for a long time.

Japanese Unexamined Patent Publication Nos. 3-109502 and 4
JP-A-366801 and JP-A-5-25299 disclose a method of suppressing the reaction with a polyol at a low temperature by using a block-type isocyanate to improve the usable time of a primer solution. However, in order to cure the primer solution after coating it on the lens, it is necessary to first remove the blocking agent, which requires a high temperature exceeding 120 ° C. By this,
There is a restriction that this method itself cannot be applied to a plastic substrate whose softening temperature is not so high, and there is a problem that the color tone of a plastic lens dyed with an organic dye is significantly changed.

The present invention has been made in view of such conventional problems, and in a plastic lens having a hard coat film or a hard coat film and an antireflection film,
An object of the present invention is to provide a plastic lens excellent in impact resistance in which a primer layer curable by heat treatment at a relatively low temperature and a short time is provided between the plastic lens substrate and the hard coat film. .

[0011]

As a result of intensive studies to solve the above problems, in a plastic lens having hard coat layers on both surfaces of a plastic lens substrate, at least one of the plastic lens bases is provided. A plastic lens having a primer layer made of a cross-linked polyvinyl acetal resin between the surface of the material and the hard coat layer has excellent impact resistance,
It has been found that it has characteristics that sufficiently pass the standard.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a primer layer made of a crosslinked polyvinyl acetal is formed by using a polyvinyl acetal as a main component, a hydrolyzable organosilane compound or a hydrolyzed condensate thereof, an alkoxide of aluminum or titanium. It is possible to apply a compound or a primer composition in which an alkoxide diketonate compound of aluminum or titanium and a curing catalyst are dissolved to the surface of a plastic lens and heat-treat it.

Further, a polyvinyl acetal containing inorganic oxide fine particles dispersed therein and cross-linked by applying a primer composition in which the inorganic oxide fine particles are dispersed in the above primer composition to the surface of a plastic lens and subjecting to heat treatment. A primer layer made of resin can be formed. It is the main component of the primer composition of the present invention and has the general formula (I)

[0014]

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The polyvinyl acetal represented by can be one in which the alkyl group in the acetal part has 0 to 20 carbon atoms, preferably 0 to 10 carbon atoms, and particularly preferably the alkyl group has 3 carbon atoms. It is polyvinyl butyral. A polyvinyl acetal having an acetalization degree of 10 to 90% can be used, and a polyvinyl acetal having an acetalization degree of 20 to 80% is preferable.

When the degree of acetalization is less than 10%, the impact strength is not sufficiently improved, and polyvinyl acetal having a degree of acetalization of 90% or more is difficult to synthesize. A decrease in adhesion is expected. The polymerization degree of polyvinyl acetal is preferably 5,000 or less, more preferably 10 or less.
It is from 0 to 3,000. If the degree of polymerization is too high, it will be difficult to dissolve in a solvent, and it will be difficult to synthesize a polyvinyl acetal having an optimum degree of acetalization. Conversely, if the degree of polymerization is too low, the impact strength will not be sufficiently improved.

Incidentally, the acetyl group in the polyvinyl acetal of the general formula (I) is not an essential component in the present invention, but since the polyvinyl alcohol, which is a raw material of the polyvinyl acetal, is synthesized by the hydrolysis of polyvinyl acetate, a small amount thereof is used. It remains. The addition amount of polyvinyl acetal in the primer composition is 1 to 20% by weight, preferably 1 to 10% by weight. If the amount of polyvinyl acetal added is too large, the viscosity of the primer composition will be too high, making it difficult to apply to plastic optical parts, and the primer coating layer will be too thick and the uniformity of the coated surface will be lost. On the other hand, when the amount of polyvinyl acetal added is too small, the primer coating layer becomes too thin and the impact strength is insufficiently improved.

As the crosslinking agent, a compound represented by the general formula (II)

[0019]

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Or general formula (III)

[0021]

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An organometallic alkoxide compound of the organosilane compound (1) is used. The hydrolyzable group in the organosilane compound is hydrolyzed to form a silanol group, which has the general formula (IV)

[0023]

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Reacts with organometallic alkoxide compounds.
Then, by the action of the catalyst and heat, a dehydration condensation reaction occurs with the hydroxyl group in the polyvinyl acetal, and crosslinking is carried out intermolecularly or intramolecularly. The molecule that participates in crosslinking is a hydrolyzate of an organosilane compound or a condensate thereof. The organosilane compound may be added as it is, or may be previously hydrolyzed. Also,
One type of organosilane compound may be used alone, or two or more types of organosilane compound may be mixed and used.

As the organosilane compound, halosilane compounds whose hydrolyzable group is a halogen atom, alkoxysilane compounds whose hydrolyzable group is an alkoxy group, carboxysilane compounds whose hydrolyzable group is a carboxy group, or hydrolyzed A ketoxime silane compound whose group is a ketoxime group can be used, but an alkoxysilane compound is preferable.

Specific examples of the hydrolyzable organosilane compound represented by the general formula (II) include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, phenylmethyldimethoxysilane and phenylmethyl. Diethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-
Chloropropylmethyldiethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane , Γ-aminopropylmethyldiethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxy Silane, methyltripropoxysilane,
Methyltributoxysilane, methyltris (2-methoxyethoxy) silane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane,
Ethyltributoxysilane, ethyltris (2-methoxyethoxy) silane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, vinyltrimethoxysilane, vinyl Triethoxysilane, vinyltris (2-methoxyethoxy) silane, phenyltrimethoxysilane, phenyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxy Silane, 3,3,3-trifluoropropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-aminop Ropyltrimethoxysilane, γ
-Aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, N-β-aminoethyl) -γ-aminopropyltrimethoxysilane , N
-Β-aminoethyl) -γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane,
(3,4-epoxycyclohexylmethyl) trimethoxysilane, (3,4-epoxycyclohexylmethyl)
Triethoxysilane, β- (3,4-epoxycyclohexylethyl) trimethoxysilane, β- (3,4-epoxycyclohexylethyl) triethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, And so on.

Specific examples of the hydrolyzable organosilane compound represented by the general formula (III) include 1,1
-Bis (trimethoxysilyl) ethane, 1,1-bis (triethoxysilyl) ethane, 1,2-bis (trimethoxysilyl) ethane, 1,2-bis (triethoxysilyl) ethane, 1,3-bis (Trimethoxysilyl) propane, 1,3-bis (triethoxysilyl) propane, 2,2-bis (trimethoxysilyl) propane,
2,2-bis (triethoxysilyl) propane, and the like.

The addition amount of the organosilane compound in the primer composition is 0.01 to 10% by weight, preferably 0.1 to 5% by weight. As the organometallic alkoxide compound of the general formula (IV), an aluminum or titanium alkoxide or alkoxide diketonate compound is used. These may be used alone or as a mixture of two or more compounds. The organometallic alkoxide compound easily reacts with the organosilane compound or its hydrolytic condensate, and the product thereof reacts with the hydroxyl group in the polyvinyl acetal by the action of catalyst and heat. The organometallic alkoxide compound acts as a catalyst that accelerates the dehydration condensation reaction between the silanol group in the organosilane compound generated by hydrolysis and the hydroxyl group in the polyvinyl acetal, and as a crosslinking agent that hydrolytically condenses with the organosilane compound. Is considered to have the effect of.

Specific examples of the organometallic alkoxide compound represented by the general formula (IV) include aluminum trimethoxide, aluminum triethoxide, aluminum tripropoxide, aluminum tributoxide, titanium tetramethoxide and titanium tetraethoxy. , Titanium tetrapropoxide, titanium tetrabutoxide, aluminum dipropoxide acetylacetonate, aluminum dipropoxide ethyl acetoacetate, aluminum dibutoxide acetylacetonate, aluminum dibutoxide ethyl acetoacetate, titanium dimethoxide bis (acetylacetonate) , Titanium diethoxide bis (acetylacetonate), titanium dipropoxide bis (acetylacetonate), titani Arm dibutoxide bis (acetyl acetonate), titanium dipropoxide Sid bis (ethylacetoacetate), etc. titanium dibutoxide bis (ethylacetoacetate) and the like. Among these, titanium alkoxide is particularly preferable.

The amount of the organic metal alkoxide compound added to the primer composition is 0.01 to 10% by weight, preferably 0.1 to 3% by weight, but 50 mol% or less of the organosilane compound is preferable. The amount of the organometallic alkoxide compound added is 50 times the amount of the organosilane compound added.
If it exceeds mol%, the impact resistance decreases.

The inorganic oxide fine particles are Al ₂ O ₃ and Ti.
O ₂ , ZrO ₂ , Fe ₂ O ₃ , Sb ₂ O ₅ , BeO, ZnO,
Metal oxide fine particles such as SnO ₂ , CeO ₂ , SiO ₂ and WO ₃ or their composites, which may be used alone or by mixing two or more kinds of metal oxide fine particles or their composites. It can also be used. As these inorganic oxide fine particles, a commercially available sol dispersed in water or an organic solvent can be used as it is.

The average particle size of the inorganic oxide fine particles or the composite of these inorganic oxides is 1 to 300 nm, preferably 1 to 50 nm. When the average particle size exceeds 300 nm, the lens is clouded due to light scattering. The amount of the inorganic oxide fine particles added to the primer composition is 0.1 to 30% by weight as a solid content concentration, so that the refractive index of the primer cured film matches or is extremely close to the refractive index of the plastic lens. The type and amount of the inorganic oxide fine particles are adjusted.

In the case of a high refractive index plastic lens substrate having a refractive index of 1.60 or more, 1 part by weight of polyvinyl acetal has a high refractive index of TiO ₂ , ZrO ₂ , and F.
_{e 2 O 3, Sb 2 O} 5, SnO 2, CeO 2, WO 3 inorganic oxide fine particles or their complexes to add 1 to 5 parts by weight preferred, such as. The curing catalyst is not particularly limited as long as it accelerates the dehydration condensation reaction between the hydrolysis condensation product of the organosilane compound and the organometallic alkoxide compound and the hydroxyl group in the polyvinyl acetal, and the dehydration condensation reaction between the silanol groups.

Specifically, dibutyltin dilaurate,
Organic tin compounds such as dibutyltin dioctate and dibutyltin diacetate, organic amines such as propylamine, butylamine, dipropylamine, dibutylamine, triethanolamine, tetramethylguanidine, methylimidazole, dicyandiamide, aluminum acetylacetonate, iron An organometallic complex such as acetylacetonate can be used. Of these, organotin compounds are particularly preferable. These may be used alone or in combination of two or more kinds of catalysts.

The amount of the curing catalyst added to the primer composition is 0.002 to 1% by weight, preferably 0.005.
~ 1% by weight. As the organic solvent in the primer composition, hydrocarbons, halogenated hydrocarbons, alcohols, ketones, esters, ethers and other known solvents, well dissolves polyvinyl acetal, and inorganic oxide fine particles Well-dispersed ones can be used. Particularly preferred are methanol, ethanol, propanol, butanol, hexanol, methyl cellosolve and ethyl cellosolve, but these may be used alone or as a mixture of two or more organic solvents.

Water in the primer composition is added in an amount of 0.1 to 20% by weight as a component necessary for the hydrolysis of the organosilane compound. If the amount of water added is too large, the smoothness of the primer-coated surface is lost, and if the amount of water added is too small, the usable time of the primer solution becomes shorter. The primer composition in the present invention is further various leveling agents for the purpose of improving coating properties or ultraviolet absorbers and antioxidants for the purpose of improving weather resistance, further dyes and pigments, photochromic dyes and photochromic pigments, and other films. Known additives for enhancing performance or adding functions can be used in combination.

The method of applying the primer composition of the present invention onto a plastic optical component is not particularly limited as long as it is a known method such as a spin coating method or a dipping method.
Moreover, it is preferable that the surface of the plastic optical component is subjected to a pretreatment such as an alkali treatment, a plasma treatment, or an ultraviolet treatment, if necessary. The film thickness of the primer layer is 0.1 to 5 μm, preferably 0.2 to 3 μm after the heat curing.
m. If the thickness of the primer layer is thinner than 0.1 μm, the impact resistance is not sufficiently improved, and if it is thicker than 5 μm, there is no problem in impact resistance, but heat resistance and surface accuracy are deteriorated.

The material and molding method of the plastic optical component are not particularly limited. To cure the primer coat film applied to the surface of the plastic optical component, 50 to 50
It may be heated at 120 ° C., preferably 70 to 110 ° C. for 1 to 60 minutes. Hydrolyzed organosilane compound in the primer composition applied by heat treatment and the hydrolysis-condensation product of the organotitanate compound and the hydroxyl group contained in the polyvinyl acetal are dehydrated and condensed, and the polyvinyl acetal molecule is cross-linked, The water generated by the condensation reaction and the organic solvent and water previously contained in the primer composition evaporate. In this way, a three-dimensionally crosslinked polyvinyl acetal primer layer is formed on the surface of the plastic optical component.

For a plastic lens provided with a cured primer film, a hard coat can be formed by a known method for the purpose of improving its surface hardness. As a method for forming the hard coat film, a wet method in which a hydrolyzate of organoalkoxysilane, inorganic oxide fine particles, and a hard coat solution in which a metal complex catalyst is dissolved are applied by dipping or spin coating and then heat-cured, plasma A known method such as a dry method such as CVD can be used.

Specific examples of the organoalkoxysilane used in the wet method include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, Examples thereof include methyltrimethoxysilane, methyltriethoxysilane, and 1,2-bis (trimethoxysilyl) ethane. These alkoxysilane hydrolyzates are prepared by hydrolyzing the above-mentioned organoalkoxysilane compounds alone or in combination of two or more with an acidic aqueous solution such as hydrochloric acid.

As the inorganic oxide fine particles, a commercially available inorganic oxide fine particle sol dispersed in water or an organic solvent is used. Specific compounds include ZnO, SiO ₂ , Al ₂
O ₃ , TiO ₂ , ZrO ₂ , SnO ₂ , BeO, Fe ₂ O ₃ ,
Examples of the sol include fine particle inorganic oxides such as Sb ₂ O ₅ , WO ₃ , and CeO ₂ , or a complex of these inorganic oxides. In addition, BaTiO ₃ , SrTiO ₃ , BaZrO ₃ ,
Compound oxide fine particles such as CoFe ₂ O ₄ , NiFe ₂ O ₄ , and MnFe ₂ O ₄ , and (Ba, Sr) TiO ₃ and Sr (T
It is also possible to use fine particles of solid solution oxide such as i, Zr) O ₃ and (Mn, Zn) Fe ₂ O ₄ . These oxide fine particles can be used alone or in combination of two or more.

As the metal complex catalyst, acetylacetone metal salt, ethylenediaminetetraacetic acid metal salt and the like are used. Further, a hard coat liquid is prepared by adding a surfactant, a colorant, a solvent and the like, if necessary. The film thickness of the hard coat layer is 1 μm or more, preferably 2 to 3 μm.

Further, a vapor-deposited film of an inorganic compound having an antireflection property can be formed on the surface provided with the hard coat by a known method. As the antireflection film, a single-layer or multi-layer structure film based on optical theory is adopted. Methods such as vacuum deposition, sputtering, ion plating, and CVD are generally used for forming the antireflection film. Specific materials used include SiO, SiO ₂ , Al ₂ O ₃ ,
Y ₂ O ₃ , Yb ₂ O ₃ , CeO ₂ , ZrO ₂ , Ta ₂ O ₃ , Ti
Inorganic dielectrics such as O ₂ and MgF ₂ can be mentioned.

Further, if necessary, an organic compound having a hydrophobic group such as an alkyl group, a phenyl group or a polyfluoroalkyl group on its side chain is provided on the antireflection film for the purpose of preventing stains on the antireflection film and preventing water stain. It is also possible to form an ultrathin film of a silicon compound or a fluorine-containing hydrocarbon compound. The reason why the impact resistance of the plastic optical component provided with the cured coating of the primer composition in the present invention is remarkably improved is not necessarily clear, but it is considered as follows.
That is, since the cured film of the primer composition of the present invention has a high degree of elasticity and a high degree of flexibility, it is considered to play a role in absorbing the energy of a plastic optical component when it receives some impact. To be Further, since the cured film of the primer composition in the present invention is three-dimensionally crosslinked, polyvinyl acetal and other substances are dissolved in the hard coat liquid even when performing a hard coat by a wet method, and the hard coat liquid is contaminated. There is nothing to do. Furthermore, since the polyvinyl acetal, which is the main component of the primer composition in the present invention, has an appropriate hydroxyl group, it is possible to three-dimensionally crosslink, and at the same time, the primer layer and the plastic optical component, and the primer layer and the hard coat film are sufficient. It is considered that the adhesiveness is achieved.

[0045]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited thereto. [A] Preparation of Primer Composition (1) Preparation of Primer Composition (A-1) A reaction vessel equipped with a rotor was charged with 2.2 parts by weight of methyltrimethoxysilane and 19.8 parts by weight of methanol,
0.9 parts by weight of 0.001N hydrochloric acid was added, and the mixture was stirred for 1 hour to carry out hydrolysis.

Titanium tetra n- was added to the above hydrolyzate.
A solution prepared by dissolving 2.2 parts by weight of butoxide in 19.8 parts by weight of n-propanol was added and stirred for 30 minutes to obtain a hydrolyzed condensate of organoalkoxysilane / organotitanate. Nissan Kagaku Co., Ltd.
Manufactured SnO ₂ / WO ₃ composite fine particle dispersed methanol sol (HI
S-30M, average particle diameter 25 nm, solid content concentration 30%)
133.3 parts by weight, 2.0 parts by weight of dibutyltin dilaurate as a curing catalyst, Fluorosurfactant FC430 manufactured by Sumitomo 3M Ltd. as a leveling agent
1.3 parts by weight are sequentially added. Further, a solution prepared by dissolving 40 parts by weight of polyvinyl butyral resin SREC BM-2 (average degree of polymerization: 800, butyralization degree: 68%) manufactured by Sekisui Chemical Co., Ltd. in 360 parts by weight of methanol, and 70.2 parts by weight of methanol and n -Add 328.3 parts by weight of propanol and 20 parts by weight of pure water and stir for 1 hour. Then 3
The mixture was filtered through a μm membrane filter to prepare a primer composition. (2) Preparation of primer compositions (A-2) to (A-20) Tables 1 to 4 were prepared in the same manner as in the primer composition (A-1).
A primer composition was prepared with the formulation shown in. The inorganic oxide fine particle dispersed sol, polyvinyl butyral resin and surfactant used are shown below.

B) Inorganic oxide fine particle dispersion sol HIS-30M Nissan Chemical Co., Ltd. SnO ₂ / WO ₃ composite fine particle methanol dispersion sol, average particle diameter 25 nm, solid content concentration 30% HIS-30MN Nissan Chemical Co., Ltd. SnO ₂ / WO ₃ composite fine particle methanol dispersion sol, average particle diameter 30 nm, solid content concentration 30% AMT-130S Nissan Chemical Co., Ltd. Sb ₂ O ₅ fine particle methanol dispersion sol, average particle diameter 15 to 20 nm, solid content concentration 30 % B) Polyvinyl butyral resin S-REC BM-1 Sekisui Chemical Co., Ltd., average degree of polymerization 6
00, butyralization degree 65% S-REC BM-2 manufactured by Sekisui Chemical Co., Ltd., average degree of polymerization 8
00, butyralization degree 68% S-REC BM-5 manufactured by Sekisui Chemical Co., Ltd., average degree of polymerization 8
50, butyralization degree 65% S-REC BH-S manufactured by Sekisui Chemical Co., Ltd., average degree of polymerization 1,000, butyralization degree 70% C) Surfactant Florard FC430 Sumitomo 3M Co., Ltd. fluorine-based surfactant SH30PA Toray Silicone surfactant manufactured by Dow Corning Co., Ltd. L7001 Silicone surfactant manufactured by Nippon Unicar Co., Ltd. [B] Preparation of hard coat liquid (1) Silicon high refractive index hard coat liquid (B-1)
Preparation of γ-glycidoxypropyltrimethoxysilane (180 parts by weight) was charged into a reaction vessel equipped with a rotor, and the mixture was vigorously stirred with a magnetic stirrer at 0.01%.
40 parts by weight of a normal hydrochloric acid aqueous solution was added at once and hydrolysis was continued for 1 hour to obtain a partially condensed hydrolyzate.

The above hydrolyzate was added to S manufactured by Nissan Kagaku Co., Ltd.
nO ₂ / WO ₃ composite fine particle dispersed methanol sol (HIS-
30M), 630 parts by weight, ethylenediaminetetraacetic acid aluminum 4 parts by weight as a curing catalyst, and Toray Dow Corning Co., Ltd. silicon-based surfactant SH30PA as a leveling agent 0.45 parts by weight, and sufficiently stirred and mixed. Then, it was filtered with a 3 μm membrane filter to prepare a hard coat liquid. (2) Preparation of Silicon-Based High Refractive Index Hard Coat Liquid (B-2) In the procedure for preparing the hard coat liquid (B-1), SnO ₂ / WO ₃ composite fine particle-dispersed methanol sol (HIS- manufactured by Nissan Chemical Industries, Ltd.) was used. 30M) instead of Nissan Chemical Co., Ltd. Sn
O ₂ / WO ₃ composite fine particle dispersed methanol sol (HIS-3
0 MN) was used to prepare a hard coat solution by the same procedure. (3) Preparation of Silicon-Based High Refractive Index Hard Coat Liquid (B-3) In a reaction vessel equipped with a rotor, 210 parts by weight of γ-glycidoxypropyltrimethoxysilane was charged and vigorously stirred using a magnetic stirrer. 0.01 with stirring
40 parts by weight of a normal hydrochloric acid aqueous solution was added at once and hydrolysis was continued for 1 hour to obtain a partially condensed hydrolyzate.

Nissan Chemical Co., Ltd. S
b ₂ 0 ₅ fine particle dispersion methanol sol (AMT-130S)
600 parts by weight, aluminum acetylacetonate 4 parts by weight as a curing catalyst, and silicon surfactant L7001 manufactured by Nippon Unicar Co., Ltd. as a leveling agent.
5 parts by weight was added, and the mixture was sufficiently stirred and mixed, and then filtered through a 3 µ membrane filter to prepare a hard coat solution. [C] Preparation and Performance Evaluation of Plastic Lens Having Composite Film [Example 1] (1-1) Application and Curing of Primer Composition -4.00 Diopter, Center Thickness 1.0 mm, Refractive Index Thermosetting urethane resin plastic lens NLIV made of 1.66 of 10% N at 60 ° C as pretreatment
It was immersed in an aOH aqueous solution for 5 minutes, washed with warm water and dried. The primer composition (A-1) was applied to both surfaces of this plastic lens by the dipping method (withdrawing speed 5 mm / sec), and heat-treated at 90 ° C. for 30 minutes to cure the primer. (1-2) Application and Curing of Silicon-based High Refractive Index Hard Coat Liquid On both sides of the plastic lens having the primer layer obtained in (1-1), the silicon-based high refractive index hard coat liquid (B-1) is applied. Dipping method (Pulling speed 5mm /
Second). The coated lens was heated at 100 ° C. for 4 hours to cure the hard coat layer. (1-3) Formation of Antireflection Film SiO ₂ / Zr is formed on both surfaces of the plastic lens having the primer layer and the hard coat layer obtained in (1-2).
An O ₂ -based five-layer antireflection film was formed by a vacuum deposition method. (1-4) Performance Evaluation of Plastic Lens Having Composite Film The plastic lens having the composite film obtained in (1-3) was subjected to the following tests to evaluate the performance.
The evaluation results are shown in Table 5. 1) Adhesion of film The crosshatch tape test was carried out by the following method in order to evaluate the adhesion of the film. Make a 1 mm square grid (100 squares) on the surface of the coating layer with a cutter knife, and then strongly adhere a cellophane adhesive tape (trade name "Cellotape" manufactured by Nichiban Co., Ltd.). Was repeated ten times.

After that, it was examined how many grids on the surface of the coating layer remained without being peeled off from the lens, and the number of grids that did not peel off was represented by X / X / 100. In this case, the larger the value of X, the better the adhesion. That is, the result of the cross hatch tape test is “1”.
"00/100" indicates that the film was not peeled at all. 2) Scratch resistance The surface of the antireflection film of the plastic lens having the composite film is rubbed with steel wool (# 0000) under a load of 600 g for 30 times, and the degree of scratching is evaluated as follows. It was evaluated by.

A: The scratched area is within 10%. B: The scratched area is more than 10% and less than 30%. C: The scratched area exceeds 30%. 3) Impact resistance The impact resistance of the plastic lens having the composite film was evaluated by a hard ball falling ball test. 20.0g of hard sphere 127c
The impact resistance of the lens is defined as the number of times before the plastic lens is cracked or cracked by letting it naturally fall from the height of m toward the center of the plastic lens, and the maximum is 5
Dropped up to times. 4) Heat resistance A plastic lens having a composite film was left in a constant temperature oven at 100 ° C for 10 minutes and then taken out in a normal temperature environment. At that time, the presence or absence of cracks, the thickness of the cracks and the change with time were as follows. It evaluated by various standards. Fine cracks can be confirmed to have cracks, but have disappeared after being left for 15 minutes. Medium-sized cracks are 15 after cracks have been confirmed.
It was assumed that it would not disappear even if left for a minute.

A: No cracks were generated in an environment of 100 ° C. for 10 minutes. B: Fine cracks were generated in an environment of 100 ° C. for 10 minutes. C: Medium-sized cracks were generated at 100 ° C. for 10 minutes. 5) Weather resistance The weather resistance of a plastic lens having a composite film is determined by an ultraviolet long life fade meter (manufactured by Suga Test Instruments Co., Ltd.).
Was used for a 300-hour weather resistance test, and the degree of yellowing of the lens was measured thereafter. The evaluation was performed according to the following criteria.

A: Yellowing degree after 300 hours is less than 2.0. B: Yellowing degree after 300 hours is 2.0 or more and less than 2.5. C: Yellowing degree after 300 hours is 2.5 or more. 6) Appearance Regarding the appearance of the plastic lens having the composite film, the transparency was visually observed by shining light of a fluorescent lamp in a dark room. The evaluation was performed according to the following criteria.

A: No cloudiness. B: Kumori stands out a little. C: Kumori is clearly visible. 7) Interference fringes The presence or absence of interference fringes in a plastic lens having a composite film depends on whether the light of the fluorescent lamp is reflected on the lens surface in a dark room.
The generation of a striped pattern due to light interference was visually observed. The evaluation was performed according to the following criteria.

A: No striped pattern is recognized. B: A slight striped pattern is recognized. C: A striped pattern is noticeable. [Example 2] to [Example 40] A plastic lens having a composite film was obtained in the same procedure as in [Example 1] using the primer solutions and hard coat solutions shown in Tables 5 to 7. The plastic lens substrate used was NLIV having a power of -4.00 diopter and a center thickness of 1.0 mm, or a power of -4.00 diopter and a center thickness of 1.0 mm,
NLEF and shown in Table 5 to Table 7. Each performance evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Tables 5 to 7.

Comparative Example 1 (1) Preparation of Primer Composition (C-1) 100 parts by weight of hexamethylene diisocyanate type unblocked polyisocyanate (trade name "Coronate HX" manufactured by Nippon Polyurethane Industry Co., Ltd.) , 167 parts by weight of a polyester type polyol (trade name “Nipporan 125” manufactured by Nippon Polyurethane Industry Co., Ltd.), 2 parts by weight of zinc octylate as a curing catalyst, 0.1 parts by weight of Florard FC430 as a leveling agent, and a solvent. 500 parts by weight of ethyl acetate and 250 parts by weight of methyl ethyl ketone were uniformly mixed. (2) Preparation of plastic lens having composite film and performance evaluation The same procedure as in [Example 1] except that the primer composition (C-1) was used and the curing condition of the primer was 60 ° C. for 30 minutes. A plastic lens having a composite film was prepared. The plastic lens substrate used was NLIV having a power of -4.00 diopter and a center thickness of 1.0 mm. Each performance evaluation was performed in the same manner as in Example 1. The results of each evaluation are shown in Table 7.

Comparative Example 2 (1) Preparation of Primer Composition (C-2) Block type polyisocyanate (trade name "Coronate 2")
529 "manufactured by Nippon Polyurethane Industry Co., Ltd., 250 parts by weight, and polyester type polyol (trade name" Nipporan 1100 "manufactured by Nippon Polyurethane Industry Co., Ltd.) 180
Parts by weight, and 2 parts by weight of zinc octylate as a curing catalyst,
1.5 parts by weight of a silicon-based surfactant as a leveling agent, 1000 parts by weight of ethyl cellosolve as a solvent, and 1500 parts by weight of methanol were uniformly mixed. (2) Preparation of plastic lens having composite film and performance evaluation The same procedure as in [Example 1] except that the primer composition (C-2) was used and the curing condition of the primer was 130 ° C. for 60 minutes. Then, a plastic lens having a composite film was prepared. The plastic lens substrate used was NLEF having a power of -4.00 diopter and a center thickness of 1.0 mm. Each performance evaluation was performed in the same manner as in Example 1. The results of each evaluation are shown in Table 7.

[Comparative Example 3] A plastic lens having a hard coat layer and an antireflection coat layer was prepared by using an NLIV plastic lens having a power of -4.00 diopter and a center thickness of 1.0 mm, without forming a primer layer. Then
The same performance evaluation as in [Example 1] was performed. The evaluation results are shown in Table 7.

[Comparative Example 4] A plastic lens having a hard coat layer and an antireflection coat layer was prepared by using an NLEF plastic lens having a diopter of -4.00 diopter and a center thickness of 1.0 mm, without forming a primer layer. Then
The same performance evaluation as in [Example 1] was performed. The evaluation results are shown in Table 7.

[0060]

[Table 1]

[0061]

[Table 2]

[0062]

[Table 3]

[0063]

[Table 4]

[0064]

[Table 5]

[0065]

[Table 6]

[0066]

[Table 7]

[0067]

According to the present invention, a plastic lens having a hard coat film formed on the surface of a plastic lens substrate, or a hard coat film provided on the surface of a plastic lens substrate, and a single layer made of an inorganic substance on the surface thereof are provided. Of a plastic lens on which a layer or a multilayer antireflection film is formed,
By providing a primer layer made of cross-linked polyvinyl acetal between at least one plastic lens substrate and a hard coat film, it is possible to provide a plastic lens having excellent impact resistance and sufficiently passing the US FDA standard. Became possible.

Further, the primer layer of the present invention can be formed on a substrate at a relatively low temperature and in a short time, and it is a very useful characteristic in that there is almost no elution from the primer layer when forming a hard coat film. With.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Michiko Seki Marunouchi 3 2-3 3 Chiyoda-ku, Tokyo Nikon Co., Ltd. (72) Inventor Tomoya Oka 1956, Okano, Karasuyama-cho, Nasu-gun, Tochigi Prefecture Inside the ceremony company Nasu Nikon (72) Inventor Hisashi Ogasawara 1956 No. 3 Hirono, Karasuyama Town, Nasu District, Tochigi Prefecture

Claims (7)

[Claims] 1. A plastic lens in which a hard coat layer is provided on both surfaces of a plastic lens substrate, wherein a polyvinyl acetal resin cross-linked between at least one surface of the plastic lens substrate and the hard coat layer is used. A plastic lens, which is provided with a primer layer. 2. The plastic lens according to claim 1, further comprising dispersed inorganic oxide fine particles. 3. The plastic lens according to claim 1, wherein the primer layer is made of a polyvinyl acetal resin crosslinked with a hydrolyzable organosilane compound or a hydrolyzed condensate thereof and an organic metal alkoxide compound. 4. The plastic lens according to claim 1, wherein the organometallic alkoxide compound is an aluminum or titanium alkoxide compound or an aluminum or titanium alkoxide diketonate compound. 5. The plastic lens according to claim 1, wherein an antireflection film is provided on the hard coat layer. 6. The inorganic oxide fine particles are made of Al ₂ O ₃ and T.
iO ₂ , ZrO ₂ , Fe ₂ O ₃ , Sb ₂ O ₅ , BeO, Zn
O, an SnO _2, CeO _2, SiO _2, 1 kind or two or more inorganic oxides selected from among WO ₃ fine particles or complexes of these inorganic oxide fine particles, an average particle diameter of 1 to It is 300 nm, It is characterized by the above-mentioned.
The plastic lens according to 5 above. 7. The film thickness of the primer layer is 0.2-5.
7. The plastic lens according to claim 1, wherein the plastic lens has a thickness of μm.