JPH1010301A - Photochromic plastic lens and method of manufacturing the same - Google Patents

Abstract

(57) [Problem] To easily manufacture a photochromic plastic lens. SOLUTION: In the present invention, a step of attaching a photochromic substance to the surface of a plastic lens substrate by a vacuum deposition method, and heating the plastic lens substrate to which the photochromic substance has adhered to form the inside of the plastic lens substrate surface A photochromic plastic lens is manufactured through the step of infiltrating the photochromic material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photochromic plastic lens and a method for manufacturing the same.

[0002]

2. Description of the Related Art In recent years, plastic lenses have been widely used as optical lenses, especially for spectacles, because of their characteristics such as being easy to mold, light and hard to break, and being easily colored by dyeing. Have been. Recently, studies have been made on spectacle lenses having photochromic performance. However, conventional lenses using plastic lenses are more problematic in terms of functions related to photochromic performance such as coloring density, coloring speed, fading speed, and durability of dimming performance than those using inorganic glass lenses. It was inferior.

Conventionally, the following method has been considered as a method for imparting photochromic performance to a plastic lens. A method in which a photochromic compound (hereinafter referred to as a photochromic substance) is mixed with a powder or a granular material to be a plastic lens substrate and then melt-kneaded. The photochromic substance is dispersed and dissolved in a monomer of a liquid plastic material to be a plastic lens substrate. A method of dispersing a photochromic substance in a suitable solvent and then impregnating the cured plastic lens substrate with the photochromic substance in a solution containing a suitable polymer and / or monomer and, if necessary, a solvent. After dispersing and dissolving in, inorganic glass, coating on the surface of various substrates such as plastics, a method of drying and / or curing, applying a photochromic substance to a plastic lens substrate after dispersing in a suitable solvent,
Then, a method of heating and infiltrating the photochromic substance into the plastic lens substrate is used.

[0004]

However, the above-mentioned conventional method is not a suitable method for producing a plastic lens for correcting eyesight. The reason is as follows. The photochromic plastic lens formed by the above method is cured in a state where the photochromic substance is uniformly dispersed in the lens. Generally, in a spectacle lens, since the thicknesses of the central portion and the outer peripheral portion are different, a density gradient always occurs in proportion to the thickness of the base material, and a lens having a uniform density cannot be obtained.

In the above-mentioned method, a solvent or a solvent for dispersing the photochromic substance is used, but there is a restriction that a solvent or a solvent of a type that does not attack the surface of the plastic lens substrate must be selected. Further, in the above method, types of polymers, monomers, and photochromic substances that can be coated on the surface of the plastic lens substrate are limited. In addition, a coating liquid must be prepared in advance for each color to be colored, and there is a disadvantage that productivity is extremely deteriorated.

[0006] Further, in the above-mentioned method, there is a limitation that the types of the photochromic substance and the solvent are limited, and the method must be one that does not attack the plastic lens substrate. In the manufacture of non-photochromic plastic lenses such as dyed lenses, the lens substrate is heated, the sublimable dye is heated and evaporated on the heated lens surface by resistance heating, and the sublimable dye is blown in a vacuum to heat the heated lens surface. There is known a method of adhering and infiltrating to the surface. However, in such a method for producing a dyed lens, there is a problem that the probability of adhesion of the dye is low, and most of the dye adheres to the peripheral portion in the bell jar. Furthermore, in this method, a sublimable dye is adhered to the surface of the plastic lens substrate in a vacuum, and this is heated in a vacuum to penetrate the inside of the substrate.
In addition, there is a disadvantage that it is not suitable for producing a colored lens having a high density.

Further, according to the conventional method for manufacturing a photochromic plastic lens, only a photochromic lens in which the entire surface of the lens substrate discolors and discolors can be obtained. Furthermore, it has been difficult to obtain a photochromic plastic lens of two or more colors, especially three or more colors by the conventional manufacturing method. Furthermore, photochromic plastic lenses are often used outdoors due to their performance, and lenses must be manufactured that can withstand various environments. In particular, when a permeation region of the photochromic substance exists inside the surface of the plastic lens substrate, it is necessary to further improve durability such as scratch resistance, impact resistance, adhesion, and stain resistance.
Further, it is necessary to improve the photochromic performance such as the light control speed, which is a characteristic of the photochromic plastic lens. Furthermore, photochromic plastic lenses having these various properties must be easily and inexpensively manufactured.

Accordingly, an object of the present invention is to solve the above problems and to manufacture a photochromic plastic lens having high durability and high photochromic performance at low cost and high productivity.

[0009]

In order to solve the above-mentioned problems, the present invention provides a plastic lens substrate having a photochromic substance adhered to the surface of a plastic lens substrate by a vacuum evaporation method, and then having the photochromic substance adhered to the surface. Is heated to make the photochromic substance permeate the substrate surface. A photochromic plastic lens formed by such a method has a region in which a photochromic substance has penetrated into the surface of a substrate.

Therefore, the present invention firstly provides a "step of adhering a photochromic substance to the surface of a plastic lens substrate by a vacuum deposition method, and heating the plastic lens substrate to which the photochromic substance is adhered by heating the surface of the plastic lens substrate. A method for producing a photochromic plastic lens (Claim 1), characterized by comprising a step of infiltrating the photochromic substance into the inside of a plastic lens. Injecting the monomer into a mold, irradiating the monomer injected into the mold with ultraviolet light and curing to form a plastic lens substrate, and photochromic on the surface of the plastic lens substrate by vacuum evaporation. Adhering the substance and the photochromic A method of manufacturing a photochromic plastic lens (claim 2), comprising a step of heating the plastic lens substrate to which the substance is attached and infiltrating the photochromic substance into the inside of the plastic lens substrate surface. . In addition, `` a step of injecting a monomer containing a polymerization initiator that initiates polymerization by irradiation with ultraviolet light and a polymerization initiator that initiates polymerization by heat, and irradiating and heating the monomer with ultraviolet light, A step of polymerizing and curing the monomer to form a plastic lens substrate, a step of attaching a photochromic substance to the surface of the plastic lens substrate by a vacuum deposition method, and heating the plastic lens substrate to which the photochromic substance is attached. A method for producing a photochromic plastic lens, comprising a step of permeating the photochromic substance into the inside of the surface of the plastic lens substrate. Further, `` the plastic lens substrate has a permeation region in which the photochromic material has penetrated inside the plastic lens substrate surface by heating the photochromic material attached to the surface of the plastic lens substrate by a vacuum deposition method. To provide a photochromic plastic lens (Claim 4). A step of attaching the photochromic material to the surface of the plastic lens substrate by a vacuum deposition method while controlling the amount of attachment so that a gradient occurs in the amount of attachment of the photochromic material when the photochromic plastic lens is viewed from the front; Heating the plastic lens substrate to which the photochromic substance adheres, and infiltrating the photochromic substance in an amount proportional to the amount of the photochromic substance adhered to the inside of the plastic lens substrate surface. A method for producing a photochromic plastic lens (Claim 5) "is provided. Also, a step of attaching a photochromic substance to the surface of the plastic lens substrate by a vacuum deposition method, and controlling the amount of heating so that a gradient occurs in the amount of heating with respect to the surface of the plastic lens substrate to which the photochromic substance is attached A method for producing a photochromic plastic lens, characterized by comprising a step of heating and causing the photochromic substance to penetrate into the inside of the surface of the plastic lens substrate in an amount proportional to the heating amount (claim 6). " . Further, `` a permeation region in which the photochromic material has permeated exists inside the surface of the plastic lens substrate by heating the photochromic material adhered to the surface of the plastic lens substrate by a vacuum deposition method, and the permeation region is the permeation region. A photochromic plastic lens (Claim 7) having a gradient of a permeation amount of a photochromic substance is provided. Also, a step of attaching a first photochromic substance to a part (area A) of a surface of a plastic lens substrate by a vacuum deposition method, and applying a second photochromic substance having a color different from the first photochromic substance to the area. A step of blocking the adhesion to A and adhering the second photochromic substance to a region other than the region A by a vacuum deposition method, and heating the plastic lens substrate to which the first and second photochromic substances adhere. , The first
And a step of permeating a second photochromic substance into the surface of the plastic lens substrate (claim 8). " The photochromic is characterized in that there is a permeation region in which the different photochromic material is permeated by heating different photochromic materials attached to different regions inside the plastic lens substrate surface by a vacuum deposition method. Plastic lens (Claim 8) "is provided. The photochromic is characterized in that there is a permeation region in which the different photochromic material is permeated by heating different photochromic materials attached to different regions inside the plastic lens substrate surface by a vacuum deposition method. Plastic lens (Claim 9) is provided. A step of attaching a photochromic substance to the surface of the plastic lens substrate by a vacuum deposition method, and heating the plastic lens substrate to which the photochromic substance is attached so as to penetrate the photochromic substance into the inside of the plastic lens substrate surface. 11. A method for manufacturing a photochromic plastic lens, comprising: a step of forming a hard coat layer by a CVD method on the plastic lens substrate in which the photochromic substance has penetrated into the surface of the substrate. )"I will provide a. In addition, "the plastic lens substrate in which a permeation area where the photochromic material has penetrated exists inside the surface of the plastic lens substrate by heating the photochromic material adhered to the surface of the plastic lens substrate by a vacuum deposition method. A photochromic plastic lens (Claim 11) having a hard coat layer formed on a material by a CVD method. Also, a step of attaching a photochromic substance to the surface of the plastic lens substrate by a vacuum deposition method, and heating the plastic lens substrate to which the photochromic substance is attached to infiltrate the photochromic substance into the inside of the plastic lens substrate surface Forming a modified layer having a refractive index changing in a thickness direction by a CVD method on the plastic lens substrate into which the photochromic substance has penetrated into the surface of the substrate; and CV on top
A method for producing a photochromic plastic lens, which comprises a step of forming a hard coat layer by Method D (Claim 12). Also, a step of attaching a photochromic substance to the surface of the plastic lens substrate by a vacuum deposition method, and heating the plastic lens substrate to which the photochromic substance is attached to infiltrate the photochromic substance into the inside of the plastic lens substrate surface And a modified layer having a refractive index changing in a thickness direction formed by a CVD method on the plastic lens substrate in which the photochromic substance has penetrated into the inside of the substrate surface, wherein the modified layer CV on top
A photochromic plastic lens (Claim 13) having a hard coat layer formed by the method D is provided. "The hard coat layer is made of Si
Using a mixed gas of an organic compound gas and oxygen gas containing
14. The method according to claim 10, wherein the film is formed by a chemical vapor deposition method using plasma.
The method for producing the photochromic plastic lens and the photochromic plastic lens according to claim 1
4) ”. Further, "the modified layer is formed by a vapor phase growth method using plasma using at least one of an organic compound gas containing Si and an organic compound gas containing Ti. The method for producing the photochromic plastic lens and the photochromic plastic lens according to claim 1
5) ”. The present invention also provides "a photochromic plastic lens and a method for manufacturing a photochromic plastic lens according to claims 12 and 13, wherein the thickness of the hard coat layer is relatively thicker than that of the modified layer." . Further, "the refractive index of the hard coat layer is substantially constant.
0, 11, 12, 13, and 14 and a method for producing a photochromic plastic lens (Claim 17). " Also, a step of attaching a photochromic substance to the surface of the plastic lens substrate by a vacuum deposition method, and heating the plastic lens substrate to which the photochromic substance is attached to infiltrate the photochromic substance into the inside of the plastic lens substrate surface Forming a primer layer by applying a compound mainly composed of a urethane-based resin or a crosslinked polyvinyl acetal resin onto the plastic lens substrate on which the photochromic substance has penetrated the inside of the substrate surface. A method for producing a photochromic plastic lens (claim 18). " In addition, "the plastic lens substrate in which a permeation area where the photochromic substance has permeated exists inside the surface of the plastic lens substrate by heating the photochromic substance adhered to the surface of the plastic lens substrate by a vacuum deposition method. A photochromic plastic lens (Claim 19) having a primer layer made of a urethane resin or a crosslinked polyvinyl acetal resin on a material. In addition, "the urethane-based resin contains active hydrogen selected from alkylene glycols, polyalkylene glycols, poly (alkylene adipates), poly-ε-caprolactone, polybutadiene glycols, poly- (alkylene carbonate) s and silicone polyols. 20. A resin obtained from a urethane solution of a compound and a polyisocyanate.
The method for producing the photochromic plastic lens and the photochromic plastic lens according to claim 2
0) ”. 20. The method of claim 18, wherein the polyvinyl acetal resin contains a compound represented by the following as a main component.

At least the fraction (a) of the structural unit having an acetal group in the general formula (the fraction is the ratio of the specific structural unit to the total number of structural units in the polymer) is 10 to 9
0, a polymer (A) in which the fraction (b) of the number of structural units having an OH group is 10 to 90 and a + b ≦ 100;
General formula (II)

[0012]

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(II) (wherein, R ² and R ³ are substituted or unsubstituted hydrocarbon groups having 1 to 8 carbon atoms, X ¹ is a hydrolyzate group, and d and e are 0 A hydrolyzable organosilane compound or a hydrolyzate thereof represented by the formula (III):

[0014]

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(III) (wherein, R ⁴ is an organic group having 2 to 8 carbon atoms;
R ⁵ and R ⁶ are a substituted or unsubstituted hydrocarbon group having 1 to 8 carbon atoms; X ² is a hydrolyzate group;
A hydrolyzable organosilane compound or a hydrolyzate thereof represented by the formula (IV):

[0016]

Embedded image (IV) (wherein, R ⁷ is a substituted or unsubstituted carbon atom of 1)
Or glyoxal represented by the general formula (V):

[0017]

Embedded image (V) (wherein, R ⁸ represents a substituted or unsubstituted carbon atom of 1)
And R ⁹ is a saturated hydrocarbon group having 1 to 4 carbon atoms), and at least one crosslinking agent selected from the group consisting of: C) A primer composition comprising an organic solvent and water, wherein the content of the component (A) is 1 to 30% by weight, and the content of the crosslinking agent (B) is 0.01 to 3% by weight.
0% by weight (claim 21). "

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The photochromic substances related to the present invention include chromene-based, spirooxazine-based, spironaphthoxazine-based, spiropyran-based, naphthopyran-based, fulgide-based, fulgimide-based, and viologen generally used for photochromic plastic lenses. System, triarylmethane system, diarylethene system, and diazo system.

For example, a photochromic substance that can be used in the present invention has a coloring mechanism represented by the following formula:

[0020]

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Spiropyran-based and spirooxazine-based substances represented by Actual photochromic substances include derivatives into which various substituents are introduced, and derivatives having slightly different skeleton structures. For example, the following formula illustrates various types of spirooxazine derivatives.

[0022]

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Also, the following equation

[0024]

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[0025]

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The flugimide-based substances and chromene-based substances represented by Next formula

[0027]

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Various naphthopyran derivatives represented by the following formulas are also exemplified as the photochromic substance that can be used in the present invention. The vacuum deposition of these photochromic substances is usually performed by setting the degree of vacuum evacuation to 5 × 10 ⁻⁵ torr or less and heating the photochromic substance in a crucible by heating with a heater. In the present invention, the heating temperature of the photochromic material is 100 to 200 degrees. As the vacuum deposition method, a conventionally known method or an appropriate method related to improvement thereof can be adopted. For example, the photochromic substance is resistance-heated in a vacuum, and the scattered photochromic substance adheres to the surface of the plastic lens substrate located above the photochromic substance. The plastic lens substrate to which the photochromic substance is adhered by the vacuum deposition method is subjected to a heat treatment. As a result, the photochromic substance permeates the surface of the plastic lens substrate, and a plastic lens having desired photochromic performance is manufactured.

The above-mentioned heat treatment of the plastic lens substrate having the photochromic substance adhered to the surface may be performed in the atmosphere or in an inert gas atmosphere under atmospheric pressure, which is also a practically important feature of the present invention. is there. Of course, if desired, reduced pressure conditions may be employed. It is not preferable to perform this heating together with the vacuum deposition of the photochromic substance on the surface of the plastic lens substrate. The heating of the plastic lens substrate to which the photochromic substance adheres after vapor deposition is about 0.5 to
Do for a few hours. Note that heating can be performed using an electromagnetic wave or a heat medium such as hot air, water, or oil as appropriate.

According to the present invention, as compared with the method of kneading a photochromic substance into a monomer, the amount of the photochromic substance used is about 1/10 to 1/20, and the cost is considerably reduced. In addition, in a method in which a photochromic substance is preliminarily mixed with a monomer serving as a plastic lens substrate, a large number of lenses of the same color are produced.
Although the production of photochromic lenses of ~ 2 colors was the limit, since the present invention is a batch process, by weighing the photochromic substance that matches the color for each batch,
It becomes possible to produce photochromic lenses of various colors.

Further, in the present invention, since no solvent is used, there is no problem of solvent selectivity or a problem in the production process involved in the treatment of the solvent, unlike the conventional method using solvent dispersion. Furthermore, since the dye is adhered to the substrate and the plastic substrate is not heated as in the method of manufacturing a colored lens by the vacuum deposition method using the sublimable dye described above, the dye is applied to the peripheral portion inside the vacuum bell jar. There are no problems such as adhesion, a long process, and difficulty in adjusting the concentration, and a photochromic plastic lens that can be uniformly colored with high reproducibility, low cost, and high productivity can be obtained.

In consideration of the photochromic properties such as the permeability of the photochromic substance and the light control speed, it is desirable to use a material having a volume that allows the photochromic substance to easily enter the inside of the lens substrate from the surface and move freely. . Therefore, it is also effective to coat a resin film on which the photochromic substance easily penetrates on the substrate surface. The resin film through which the photochromic substance can penetrate is preferably a thermoplastic resin, a thermosetting resin, a UV-curable resin, or the like. Specific examples of the material include resins such as polyamide resin, phenol resin, butyral resin, melamine resin, polyvinyl alcohol, cellulose resin, alkyd, acryl, epoxy resin, urethane resin, polyester resin, and silicone resin. These resins can be used alone or as a mixture or copolymer of several types. These resins function as a primer layer for improving impact resistance and adhesion.
The thickness of the resin film is preferably about 0.5 to 2 μm. When the resin film is formed on the surface of the plastic lens substrate, it is preferable to appropriately select the combination of the type of the photochromic substance to be used and the substrate material and the film thickness.

The plastic lens substrate used in the present invention may be of various types including conventionally known ones, for example, polymethyl methacrylate and its copolymer, acrylonitrile-styrene copolymer, polycarbonate, cellulose acetate, and poly (vinyl acetate). Plastic lens molded articles made of vinyl chloride, polyethylene terephthalate, epoxy resin, unsaturated polyester resin, polyurethane resin, diethylene glycol bisallyl carbonate polymer and the like are exemplified.

It is also possible to use an ultraviolet-curing resin or a resin having both ultraviolet-curing and thermosetting properties. The cured product made of an ultraviolet-curable resin has a larger photochromic performance because the intermolecular voids after curing are larger than the cured product made of the thermosetting resin, so that the photochromic substance easily penetrates and changes its structure more easily. become.

As the ultraviolet-curable resin used in the present invention, the following ultraviolet-curable resins polymerized by irradiation with ultraviolet light are used. However, a combination of ultraviolet curing and thermal curing may be used as described above. In this case, a polymerization initiator that initiates polymerization by ultraviolet light and a polymerization initiator that initiates polymerization by heat are added to the monomer. The ultraviolet polymerization reaction system requires a photopolymerization radical initiator that generates radicals by irradiation with ultraviolet light, and a monomer, oligomer, or prepolymer that undergoes radical polymerization. In addition, a sensitizer, a storage stabilizer, a polymerization inhibitor, You may mix | blend a polymer, a coloring material, etc. according to the objective. In addition, a cationic photopolymerization system is appropriately used.

The photo-radical initiator is not particularly limited and known ones can be used. Representative examples thereof include biacetyl, acetophenone, benzophenone, Michler's ketone, benzyl, benzoin, benzoin isobutyl ether, Benzyldimethyl ketal, tetramethylthiuram sulfide, azobisisobutylnitrile, 1-hydroxycyclohexylphenone, methyl ketone peroxide, acetylacetone peroxide, t-butyl peroxide, cumene hydroperoxide, α, α′-bis (t-butyl Peroxyisopropyl) benzene, t-butylperoxyisopropylcarbonate, benzoyl peroxide, di (t-butylperoxy) isophthalate, t-
Butyl peroxybenzoate, 3,3 ', 4,4'-
And tetra (t-butylperoxycarbonyl) benzophenone.

A radically polymerizable oligomer is used to efficiently cure the photoradical species, and a polymerizable monomer is appropriately added for the purpose of adjusting the viscosity. There are various types of photopolymerized oligomers, but there are unsaturated polyester / styrene type, epoxy / Lewis acid type, polyene / thiol type and acrylate. An acrylic group is frequently used as a polymerizable unit other than the unsaturated polyester. Acrylic oligomers are broadly classified into polyester acrylate, polyurethane acrylate, epoxy acrylate, polyether acrylate, oligo acrylate, alkyd acrylate, and polyol acrylate according to their basic structure. Is possible. The important thing in this is
Polyester, epoxy, urethane, and polyol acrylates. Main photopolymerizable monomers include monofunctional: lauryl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 1,6-hexanediol monoacrylate, dicyclopentadiene acrylate, and the like. . Bifunctional: 1,3 butanediol diacrylate, 1,4 butanediol diacrylate, 1,6 hexanediol diacrylate, diethylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, polyethylene glycol 400 diacrylate And hydroxypivalic acid ester neopentyl glycol diacrylate. Furthermore, trifunctional or more: trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate.

Examples of the sensitizer include amines, ureas, sulfur compounds, nitriles, phosphorus compounds, other nitrogen compounds and chlorine compounds. Examples of the storage stabilizer include quaternary ammonium chloride, diethylhydroxyamine, cyclic amide, nitrile compound, substituted urea, benzothiazole, hydroquinone, hydroquinone monomethyl ether, and organic acids such as lactic acid, oxalic acid, and benzoic acid.

According to the present invention, since the amount of the photochromic substance permeated into the inside of the base material can be easily controlled, the color density can be variously changed. In the present invention, the lens substrate to which the photochromic substance is attached is heated after the photochromic substance is attached to the lens substrate surface, and the photochromic substance is penetrated into the inside of the substrate surface. The amount of permeation into the inside can be easily controlled. For example, in a heating step of the lens substrate after the photochromic substance is uniformly adhered to the entire surface of the lens substrate by a vacuum evaporation method, when the photochromic substance is penetrated into the surface of the substrate by heating, the surface of the lens substrate By controlling the thermal gradient, that is, the amount of heating of the surface of the lens substrate, the photochromic substance can be penetrated in a gradation.

Further, by controlling the heating time, the amount of permeation of the photochromic substance can be controlled, and the photochromic substance can be permeated in a gradation. In other words, the photochromic material permeates relatively more in the region where the heating time is long, and the photochromic material permeates relatively little in the region where the heating time is small, so that the photochromic material can be permeated in a gradation.

As a heating source, infrared rays, electromagnetic waves, hot air,
A heating medium such as heating water or heating oil is used, but is not limited thereto. It is also possible to manufacture a gradation-like photochromic plastic lens by controlling the amount of the photochromic substance attached. As a method of controlling the amount of adhesion, a lens base material is installed on the upper part in the chamber of the vacuum evaporation apparatus,
Alternatively, a shield plate is provided at the upper portion near the evaporation source, and the plate is gradually moved using a drive mechanism such as a motor. Thus, the amount of the photochromic substance adhered to the lens substrate surface is controlled, and the photochromic substance adheres in a gradation. By heating this plastic lens substrate, the photochromic substance penetrates into the lens substrate surface.However, since the plastic lens substrate to be heated has a gradient in the amount of photochromic substance attached, In addition, a gradient occurs in the amount of permeation into the substrate surface in proportion to the amount of the photochromic substance attached. As described above, according to the present invention, a photochromic plastic lens having a concentration gradient can be easily obtained.

In order to improve the scratch resistance, it is effective to form a hard coat layer. As the hard coat layer, a liquid polymer (hard coat solution) containing an organosilicon compound as a main component can be applied to the surface of the photochromic plastic lens. In particular, an organosilicon compound represented by the following general formula or a hydrolyzate thereof is preferable.

General formula: R ¹ _a R ² _b Si (OR ³ ) _{4- (a + b)} (wherein, R ¹ is a C 4-14 carbon atom having a functional group or an unsaturated double bond) R ² has 1 to 1 carbon atoms
6 is a hydrocarbon group or a halogenated hydrocarbon group, R ³ is an alkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group or an acyl group, a and b are each 0 or 1,
And a + b is 1 or 2. Regarding the compounds of the above general formula, when R ¹ has an epoxy group as a functional group, for example, the following compounds are used.

Since these have an epoxy group, they are also called epoxysilanes. Specific examples of the epoxy silane include, for example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane,
γ-glycidoxypropyltrimethoxyethoxysilane, γ-glycidoxypropyltriacetoxysilane,
γ-glycidoxypropylmethyldimethoxysilane, γ
-Glycidoxypropylmethyldiethoxysilane, β-
(3,4-epoxycyclohexyl) ethyltriethoxysilane and the like.

Examples of compounds of the above general formula other than those in which R ¹ has an epoxy group as a functional group (including those in which a = 0) include, for example, the following compounds.
Methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, γ-methacryloxypropyltrimethoxysilane, aminomethyltrimethoxysilane, 3-
Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, phenyltrimethoxysilane,
Various trialkoxysilanes such as phenyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, trisiloxysilane or trialkoxyalkoxysilane compounds.

The above-exemplified compounds of the above general formula are as follows:
In each case, there are three OR ³ groups bonded to the Si atom (a +
b = 1) This is an example of trifunctionality, but there are two OR ³ groups (b
= 2) Bifunctional equivalents can of course also be used. Examples of bifunctional equivalent compounds include dimethyldimethoxysilane, diphenyldimethoxysilane,
Examples include methylphenyldimethoxysilane, methylvinyldimethoxysilane, dimethyldiethoxysilane, and the like.

The compounds of the above general formula may be used alone or in combination of two or more according to the purpose. In particular, when a bifunctional compound is used, 3
It is preferable to use together with a functional compound. When they are used together, 2> a + b> 1 on average. Further, a + b = 0
It is also possible to use a compound corresponding to the above four functional groups in combination. Examples of tetrafunctional equivalent compounds include methyl silicate, ethyl silicate, isopropyl silicate,
n-propyl silicate, n-butyl silicate, t-
Butyl silicate, sec-butyl silicate and the like.

The compound of the above general formula may be used as it is, but is preferably used as a hydrolyzate for the purpose of increasing the reaction rate and lowering the curing temperature. When two or more compounds having the same functional number are used in combination of two or four functional compounds, or two or more compounds having different functional numbers are used in combination, they may be used together after hydrolysis, Co-hydrolysis may be carried out in combination before. The hydrolysis releases the HOR ³ allyl, and the compound of the general formula becomes the corresponding silanol. Silanol rapidly undergoes dehydration condensation to become an oligomer. Therefore, after hydrolysis, the reaction may be left (cured) for 1 to 24 hours so that this reaction proceeds sufficiently.

When these compositions are used, it is possible to add a sol to improve the hardness, prevent the occurrence of interference fringes, and further impart antistatic properties. In addition, various solvents such as water, lower alcohol, acetone, ether, ketone, and ester can be used in order to improve the flowability at the time of coating and improve the smoothness of the cured film.

The hard coat layer can contain a particulate inorganic oxide. By mixing the inorganic oxide, it is possible to adjust the refractive index and the hardness. As the sol, for example, zinc oxide, silicon oxide,
Fine particles of aluminum oxide, titanium oxide, zirconium oxide, tin oxide, beryllium oxide, antimony oxide, tungsten oxide, cerium oxide, tin oxide, and tungsten oxide can be used. In addition, these fine particles can be used not only alone but also in a mixed or composite state of two or more kinds as necessary.
For example, a modified state in which tin oxide fine particles are used as cores and coated with fine particles of a composite form of tungsten oxide and tin oxide can be used. Such a modified state does not aggregate in a solvent and forms a good dispersion state.
Such fine particles in a denatured state are disclosed in JP-A-3-217.
It is known as described in detail in US Pat.

In particular, titanium oxide, antimony oxide,
Tungsten oxide, cerium oxide, zirconium oxide,
When tin oxide is used, the refractive index of the composition can be increased. As a dispersion medium of the fine particles, water, alcohol, or another organic solvent is used, and it is preferable to add an organic amine or another stabilizer.

The particle diameter of the fine particles is preferably 1 to 200 mμ, particularly preferably 5 to 100 mμ. If it is smaller than this, the production is difficult, the stability of the fine particles themselves is poor, and the effect is small. If it is larger than this, the stability of the coating composition, the transparency and the smoothness of the coating film, etc. will be reduced. Such sols are partially available as commercial products. In addition to the above components, various additives may be used in combination as needed. By using the additive, for example, it is possible to improve the adhesion to the substrate (molded product) on the side to be coated or to improve the stability of the coating composition.

Examples of additives include a pH adjuster, a viscosity adjuster, a leveling agent, a matting agent, a stabilizer, an ultraviolet absorber, an antioxidant and the like. Various surfactants can be used in combination with the coating composition for the purpose of improving the flow at the time of application, improving the smoothness of the coating film, and reducing the friction coefficient of the coating film surface. Particularly, a block or graft copolymer of dimethylsiloxane and alkylene oxide, and a fluorine-based surfactant are effective.

As the coating method, a usual coating method such as brush coating, dipping, roll coating, spray coating, and flow coating can be used. At this time, the application conditions are determined mainly by the properties of the vehicle. In order to accelerate the reaction and cure at a low temperature, the following curing catalyst can be used.

The curing catalyst is obtained by polymerizing the vehicle component to obtain 3
In order to reduce the time required to form a coating film having a three-dimensional network structure, it is used as necessary (however, one that impairs the stability of the coating composition is not preferred). Is used. (1) Amines: monoethanolamine, diethanolamine, isopropanolamine, ethylenediamine,
Isopropylamine, diisopropylamine, morpholine, triethanolamine, diaminopropane, aminoethylethanolamine, dicyandiamide, triethylenediamine, 2-ethyl-4-methylimidazole.

(2) Various metal complex compounds: General formula: AlX _n Y _3-n (where X is OL (L is a lower alkyl group), and Y is general formula M ¹ COCH ₂ OM ² (M ¹ , M ² is a lower alkyl group) and M ¹ COCH ₂ COOM ² , and n is 0, 1 or 2).

Particularly useful chelate compounds include aluminum acetylacetonate, aluminum bisethylacetoacetate monoacetylacetonate, and aluminum-di-n from the viewpoints of solubility, stability, and catalyst curing.
-Butoxide-monoethylacetoacetate, aluminum-di-iso-propoxide-monomethylacetoacetate and the like.

In addition, chromium acetylacetonate, titanyl acetylacetonate, cobalt acetylacetonate, iron (III) acetylacetonate, manganese acetylacetonate, nickel acetylacetonate, E
DTA, and complex compounds of Al, Fe, Zn, Zr, and Ti. (3) Metal alkoxide: aluminum triethoxide, aluminum tri-n-propoxide, aluminum tri-n-butoxide, tetraethoxytitanium, tetra-n
-Butoxytitanium, tetra-i-propoxytitanium.

(4) Organic metal salts: sodium acetate, zinc naphthenate, cobalt naphthenate, zinc octylate, tin octylate. (5) Perchlorates: magnesium perchlorate and ammonium perchlorate. (6) Organic acids or anhydrides: malonic acid, succinic acid, tartaric acid, adipic acid, azelaic acid, maleic acid, O-phthalic acid, terephthalic acid, fumaric acid, itaconic acid, oxaloacetic acid, succinic anhydride, maleic anhydride Acids, itaconic anhydride, 1,2-dimethylmaleic anhydride, phthalic anhydride, hexahydrophthalic anhydride, naphthalic anhydride.

(7) Lewis acid: ferric chloride, aluminum chloride. (8) Metal halide: stannous chloride, stannic chloride,
Tin bromide, zinc chloride, zinc bromide, titanium tetrachloride, titanium bromide, thallium bromide, germanium chloride, hafnium chloride, lead chloride, lead bromide.

The above catalysts are used alone or in combination of two or more. In particular, an aluminum chelate compound is one of the preferred catalysts. As a method of applying the coating film, there are a dipping method, a spray coating method, a roll coating method, a spin coating method, a brush coating and the like. In the photochromic plastic lens of the present invention formed as described above, the thickness of the coating film (for example, the hard coat layer) is about 2 μm with respect to the lens thickness of several mm.

In addition to the wet method, a hard coat layer can be formed by a dry CVD method. When the hard coat layer is formed by the CVD method, it is preferable to form the hard coat layer after forming the modified layer on the substrate surface, but it is also possible to form only the hard coat layer. The modified layer in the present invention is a layer which is formed on the surface of the substrate and whose refractive index gradually changes in the thickness direction from the substrate side. And the composition ratio of the substance in the modified layer is gradually changing. It has also been confirmed that the impact resistance is improved by providing a modified layer. This was because the internal stress of the hard coat layer was high because the thickness of the conventional hard coat layer was 3 μm or more, but the hard coat layer was provided between the base material and the hard coat layer. This is because the internal stress remaining in the layer can be reduced. Therefore, since the internal stress can be reduced, there is also an effect that cracks caused by hot water resistance and heat resistance can be avoided.

The organic compounds containing Si used in the production of the modified layer and the hard coat layer include tetraethoxysilane, dimethoxysilane, methylmethoxysilane, tetramethoxysilane, ethyltrimethoxysilane, diethoxydimethylsilane, methyltriethoxysilane. Silane or the like is preferably used. Further, as an organic compound containing Ti,
Tetramethoxytitanium, tetraethoxytitanium, tetraisopropoxytitanium, tetra-n-propoxytitanium, tetra-n-butoxytitanium, tetraisobutoxytitanium, tetra-sec-butoxytitanium, tetra-t
-Butoxytitanium, tetradiethylaminotitanium and the like are preferably used.

These organic compounds of Si and Ti are
One type may be used alone, or two or more types may be used in combination. The thickness of the hard coat layer is greater than 0.4 μm,
Preferably, it is thinner than 5 μm. In addition, the thickness of the denatured layer is more than 100 nm and preferably less than 900 nm.

In the chemical vapor deposition method, which is a CVD method, a raw material gas is discharged by applying thermal energy and electric energy to promote a reaction in a non-thermal equilibrium state in a plasma atmosphere to deposit a thin film on a substrate. Is the way. Commonly used types include a parallel plate electrode type, a capacitive coupling electrode type, and an inductive coupling type. In particular, in the present invention, it is preferable to form by a plasma enhanced CVD method in which an electric field and a magnetic field are applied in parallel to the main plane of the base.
If the hard coat layer is formed by such a dry method,
A photochromic plastic lens having excellent scratch resistance can be easily produced at low cost only by the dry method, and no waste liquid is discharged unlike the wet method, so that environmental destruction does not occur. In addition, CV is applied on a photochromic plastic lens having the above-mentioned gradation or a multicolor photochromic plastic lens.
It goes without saying that a hard coat layer can be formed by the method D. This hard coat layer can also be formed on a resin film formed on the surface of the base material. Further, it is preferable to form a single-layer or multilayer antireflection film made of an inorganic oxide on the hard coat layer by a vacuum evaporation method, a CVD method, or a sputtering method.

Further, a drainage-preventing layer is formed by a dipping method, a vacuum deposition method, a CVD method, or a sputtering method using an organic substance-containing cured product made of an organic polysiloxane polymer or a polymer obtained by polymerizing a perfluoroalkyl group-containing compound. In this case, a photochromic plastic lens having an effect of preventing drainage and having improved durability against water can be obtained. For the drainage preventing layer, an alkoxysilane-based compound having a siloxane bond, an aminosilane-based compound having a silazane bond, or a compound having a siloxazan bond having both of them is preferably used.

It is also possible to form a primer layer on the surface of the photochromic plastic lens. By forming the primer layer, it is possible to improve the adhesion between the hard coat layer formed thereon and the substrate, and it is also possible to improve the impact resistance. This makes it possible to manufacture a photochromic plastic lens that has excellent durability against impact and can withstand various use environments.

Materials used for the primer layer include:
A urethane-based material can be preferably used. The composition of the primer layer comprising a urethane-based material comprises an active hydrogen-containing compound and a polyisocyanate. Here, the active hydrogen-containing compound includes alkylene glycols such as ethylene glycol, 1,2-propylene glycol, 1,3-butanediol, 1,6 hexanediol, neopentyl glycol, dipropylene glycol and diethylene glycol; polypropylene glycol Polyalkylene glycols such as poly (ethylene glycol), polyethylene glycol and polytetramethylene glycol; polyalkylene adipates such as poly (diethylene adipate), poly (tetramethylene adipate), poly (hexamethylene adipate) and poly (neopenthylene adipate); poly -Ε-caprolactone; poly (1,4-butanediene) glycol, poly (1,2-butanediene)
Examples thereof include polybutadiene glycols such as glycol; poly (alkylene carbonate) s such as poly (hexamethylene carbonate); and silicone polyols. Other known active hydrogen-containing compounds can also be used.

Examples of the polyisocyanate include tolylene diisocyanate, xylylene diisocyanate,
4,4'-diphenylmethane diisocyanate, 1,5
-Naphthalenediisocyanate, 3,3'-dimethyl-
4,4 ′ diphenyl diisocyanate, aromatic diisocyanate; 1,6 hexamethylene diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, trimethylhexamethylene diisocyanate, etc. Aliphatic diisocyanates are exemplified. Further, as the polyisocyanate, a block type polyisocyanate can be used.

A mixture of an active hydrogen-containing compound and a polyisocyanate may be used, or a polymer may be used. Such a urethane-based material may be a solution made of a urethane-based material or a material in which particles made of a urethane-based material are dispersed in a solvent such as water. Further, it is also possible to form the primer layer from a material made of crosslinked polyvinyl acetal, in addition to a urethane-based material. The primer layer made of polyvinyl acetal dissolves polyvinyl acetal as a main component, a hydrolyzable organosilane compound or a hydrolysis condensate thereof, an aluminum or titanium alkoxide compound or an aluminum or titanium alkoxide diketonate compound, and a curing catalyst. It can be formed by applying the primer composition thus obtained to the surface of a plastic lens and subjecting it to heat treatment.

The primer composition composed of polyvinyl acetal applied to the present invention comprises at least a fraction (a) of a structural unit having an acetal group in the general formula (the fraction means the total amount of a specific structural unit in a polymer). A polymer (A) in which the ratio (b) of the number of the structural units having an OH group is 10 to 90, and a + b ≦ 100; Formula (II)

[0072]

Embedded image

(II) (wherein, R ² and R ³ are a substituted or unsubstituted hydrocarbon group having 1 to 8 carbon atoms, X ¹ is a hydrolyzate group, and d and e are 0 A hydrolyzable organosilane compound or a hydrolyzate thereof represented by the general formula (III):

[0074]

Embedded image

(III) (wherein, R ⁴ is an organic group having 2 to 8 carbon atoms;
R ⁵ and R ⁶ are a substituted or unsubstituted hydrocarbon group having 1 to 8 carbon atoms; X ² is a hydrolyzate group;
A hydrolyzable organosilane compound or a hydrolyzate thereof represented by the formula (IV):

[0076]

Embedded image (IV) (wherein, R ⁷ is a substituted or unsubstituted carbon atom of 1)
Or glyoxal represented by the general formula (V):

[0077]

Embedded image (V) (wherein, R ⁸ represents a substituted or unsubstituted carbon atom of 1)
And R ⁹ is a saturated hydrocarbon group having 1 to 4 carbon atoms), and at least one crosslinking agent selected from the group consisting of: C) A primer composition comprising an organic solvent and water, wherein the content of the component (A) is 1 to 30% by weight, and the content of the crosslinking agent (B) is 0.01 to 3% by weight.
0% by weight.

The hydrolyzable group in the organosilane compound is hydrolyzed to generate a silanol group, which reacts with the organometallic alkoxide compound. Then, a hydroxyl group in the polyvinyl acetal is further dehydrated and condensed by the action of the catalyst and heat, and cross-linking is performed between or within the molecules. The molecule participating in the crosslinking is a hydrolyzate of an organosilane compound or a condensate thereof. The organosilane compound may be added as it is, or a compound that has been hydrolyzed in advance may be added. Further, one kind of organosilane compound may be used alone, or two or more kinds of organosilane compounds may be used in combination.

Examples of the organosilane compound include halosilane compounds in which the hydrolyzable group is a halogen atom, alkoxysilane compounds in which the hydrolyzable group is an alkoxy group, carboxysilane compounds in which the hydrolyzable group is a carboxy group, and hydrolyzable compounds. Ketoxime silane compounds having a ketoxime group can be used, but alkoxy silane compounds are preferred.

Specific examples of the hydrolyzable organosilane compound represented by the general formula (II) include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, phenylmethyldimethoxysilane, 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-aminopropyl Ropirtrimethoxysilane, 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. A dialdehyde compound of general formula (IV) or an acetal compound of dialdehyde of general formula (V) is also used as a crosslinking agent. The dialdehyde compound and the acetal compound of dialdehyde may be used alone, or two or more compounds may be mixed.

Specific examples of the dialdehyde compound represented by the general formula (IV) include glutaraldehyde, hexanedial, 2-hydroxyhexanedial and the like. Further, as the dialdehyde acetal compound represented by the general formula (V), malonaldehyde tetramethyl acetal, malonaldehyde tetraethyl acetal, glutaraldehyde tetramethyl acetal, or the like can be used.
The addition amount of the dialdehyde compound or acetal compound in the primer composition is preferably 0.01 to 30% by weight.

As the organometallic alkoxide compound, an alkoxide or alkoxide diketonate compound of aluminum or titanium 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 reacts with hydroxyl groups in the polyvinyl acetal by the action of a catalyst and heat. The organometallic alkoxide compound has a function as a catalyst for promoting a dehydration condensation reaction between a silanol group in the organosilane compound generated by hydrolysis and a hydroxyl group in the polyvinyl acetal, and as a crosslinking agent for hydrolytic condensation with the organosilane compound. It is thought that there is an effect of.

Specific examples of the organometallic alkoxide compound include aluminum trimethoxide, aluminum triethoxide, aluminum tripropoxide, aluminum tributoxide, titanium tetramethoxide, titanium tetraethoxide, titanium tetrapropoxide, and titanium. Tetrabutoxide, aluminum dipropoxide acetylacetonate, aluminum dipropoxide ethyl acetoacetate, aluminum dibutoxide acetylacetonate, aluminum dibutoxide ethyl acetoacetate, titanium dimethoxide bis (acetylacetonate), titanium diethoxide bis (acetyl) Acetonate), titanium dipropoxide bis (acetylacetonate), titanium dibutoxide bis (acetyl Cetyl acetonate), titanium dipropoxide Sid bis (ethylacetoacetate), titanium dibutoxide bis (ethylacetoacetate)
And so on. Of these, titanium alkoxide is particularly preferred.

The addition amount of the organometallic alkoxide compound in the primer composition is from 0.01 to 10% by weight, preferably from 0.1 to 3% by weight, and preferably not more than 50% by mole of the organosilane compound. The amount of the organometallic alkoxide compound is 50 times the amount of the organosilane compound.
If it exceeds mol%, the impact resistance is reduced.

The curing catalyst is not particularly limited as long as it promotes the dehydration condensation between the hydrolysis condensate 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. Absent. Specifically, organic tin compounds such as dibutyltin dilaurate, dibutyltin dioctate, dibutyltin diacetate, propylamine, butylamine,
Dipropylamine, dibutylamine, triethanolamine, tetramethylguanidine, methylimidazole,
Organic amines such as dicyandiamide, and organic metal complexes such as aluminum acetylacetonate and iron acetylacetonate can be used. Of these, organotin compounds are particularly preferred. These may be used alone or as a mixture 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% by weight.
１1% by weight. As the organic solvent in the primer composition, hydrocarbons, halogenated hydrocarbons, alcohols, ketones, esters, ethers and other known solvents, polyvinyl acetal well dissolved, and inorganic oxide fine particles Those that disperse well 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 hydrolysis of the organosilane compound. If the amount of water is too large, the smoothness of the primer-coated surface is lost, and if the amount of water is too small, the usable time of the primer solution is shortened. The primer composition further enhances the film performance by various leveling agents for the purpose of improving coatability or ultraviolet absorbers and antioxidants for the purpose of improving weather resistance, as well as dyes and pigments, photochromic dyes and photochromic pigments, and the like. A known additive for adding a function can be used in combination.

The method of applying the primer composition on the plastic optical component in the present invention is not particularly limited as long as it is a known method such as a spin coating method and a dipping method.
In addition, it is preferable that the surface of the plastic optical component be subjected to a pretreatment such as an alkali treatment, a plasma treatment, or an ultraviolet treatment as necessary. The cured film thickness of the primer layer is 0.1 to 5 μm, preferably 0.2 to 3 μm. If the thickness of the primer layer is less than 0.1 μm, the impact resistance is not sufficiently improved, and if it is more than 5 μm, there is no problem in terms of the impact resistance, but the heat resistance and surface accuracy are reduced.

Further, it is possible to mix the particulate inorganic oxide as mixed in the hard coat layer as described above in the primer solution. By mixing the fine particles, effects such as adjustment of refractive index and improvement of hardness can be provided. As these fine particles, commercially available fine particles dispersed in water or an organic solvent can be used as they are.

The average particle size of the finely divided inorganic oxide or the composite of these fine particles is from 1 to 300 nm, preferably from 1 to 50 nm. If the average particle diameter exceeds 300 nm, fogging of the lens occurs due to light scattering. The addition amount of the fine particles in the primer composition is 0.1 to
Although it is 30% by weight, the type and amount of the inorganic oxide fine particles are adjusted so that the refractive index of the cured primer layer matches or very close to the refractive index of the plastic lens.

In the case of a high refractive index plastic lens substrate having a refractive index of 1.60 or more, a high refractive index of titanium oxide, zirconium oxide, iron oxide, antimony oxide, oxide It is preferable to add 1 to 5 parts by weight of fine particles of tin, cerium oxide, tungsten oxide, or the like, or a composite thereof, or a mixture thereof. These inorganic fine particles can be added to a primer layer made of a urethane-based material.

The thickness of the primer layer is 0.01 to 30 μm.
m is preferred. Particularly preferably, 1 to 20 μm
It is. As a method of applying the resin to be the primer layer,
The method may be appropriately selected from known methods such as a spinner method, a dipping method, and a spray method, and may be formed by a dry method such as a CVD method or a vacuum evaporation method.

The primer layer can be formed on a photochromic lens having the above-mentioned gradation or a multicolored photochromic plastic lens. Can be manufactured. Further, it is also possible to form a primer layer on a resin film formed on a plastic lens substrate as described above.

On the primer layer, a hard coat layer made of the above-mentioned organic silicon compound and formed by a conventional wet method or a hard coat layer formed by a CVD method can also be formed. This makes it possible to produce a photochromic plastic lens that is excellent in fashionability and more excellent in durability such as scratch resistance and impact resistance.

Further, a compound of the following general formula may be added.

[0098]

Embedded image

(Wherein, R ¹ is a hydrogen atom or a saturated hydrocarbon base material having 1 to 20 carbon atoms, a is a fraction of a structural unit having an acetal group, 10 to 90, b is O
A polyvinyl acetal which is a fraction of a structural unit having an H group and is 0 to 10;

[0100]

Example 1 An ultraviolet curable acrylic resin was used as a substrate. The method of forming the substrate is as follows. First, a liquid curable acrylic resin is injected into a glass matrix having a lens-shaped space. A metal halide lamp having an irradiation output of 120 W is installed at a position of about 25 cm above and below the matrix into which the resin has been injected, and the mold is irradiated with ultraviolet rays for 2 minutes. At this time, the ambient temperature of the ultraviolet irradiation chamber was controlled at about 100 ° C. After the completion of the ultraviolet irradiation, the substrate was annealed at 110 ° C. for 2 hours in a hot-air circulation oven to remove distortion.

A spirooxazine-based material was used as a photochromic material, and these were sufficiently mixed and put into an evaporation source. The degree of vacuum was reduced to 5 × 10 ⁻⁵ Torr by a pump, and then the evaporation source was heated to scatter the photochromic substance and adhere to the surface of the lens substrate. The lens substrate having the photochromic substance adhered to its surface was colorless and transparent, and a slight interference color was observed. This lens substrate was heated in a hot air oven at 120 ° C. for 1 hour to allow the photochromic substance attached to the surface of the lens substrate to permeate and diffuse into the surface of the plastic lens substrate. The photochromic substance remaining on the surface without penetrating into the inside of the surface of the lens substrate is
Washed off with a washing machine.

Next, a hard coat layer made of an organic silicon-based material was formed by a dipping method for scratch resistance and antireflection, and then heated at 110 ° C. for 4 hours to be cured. Furthermore, SiO ₂ , Al ₂ O ₃ , Ti
An inorganic multilayer thin film made of O ₂ was formed by a vacuum evaporation method. The photochromic plastic lens thus produced had no initial coloring and was colored brown without unevenness under sunlight.

[0103]

Example 2 The same material and method as in Example 1 were used as the substrate.
The formed plastic lens substrate was used. This
Polyester resin on the surface of glass substrate by dipping method
And heated in a hot air oven at 100 ° C for 1 hour.
To form a resin film. Next, the same photo as in Example 1
Resin film made of chromic substance by vacuum evaporation under the same conditions
Was attached to the surface. This lens base material is
After heating for 10 minutes, the photochromic attached to the surface of the resin film
The mic substance was permeated and diffused inside the surface of the resin film. This
Wash the lens with a washing machine for extra photochromic material
Was removed. Further, an organic silicon-based material is
Harden by heating at 110 ° C for 4 hours.
Layer was formed. On top of that, SiO_Two, Al_TwoO_Three, T
iO _TwoFormed by vacuum evaporation of inorganic multilayer thin film consisting of
Was. The photochromic lens made in this way has an initial coloring
Colored evenly brown under sunlight
Was.

[0104]

Example 3 A plastic lens substrate formed by the same material and method as in Example 1 was used as a substrate, and a chromene-based and spirooxazine-based photochromic substance was adhered to the convex surface by a vacuum evaporation method. . These substances were sufficiently mixed according to a previously determined blending ratio so as to develop a brown color, and about 0.01 g of the mixture was weighed and placed in an evaporation source. The lens substrate was set 10 cm above the evaporation source. The film thickness was controlled to 700 ° by a crystal oscillation type film forming controller (CRTM-5000, manufactured by Japan Vacuum Technology Co., Ltd.) and a vapor deposition sensor (CRTS-4, manufactured by Japan Vacuum Technology Co., Ltd.). Use a pump to reduce the degree of vacuum to 5 × 10
^-5 Torr, the evaporation source is heated to scatter the photochromic substance, and the photochromic substance is attached to the surface of the lens substrate.

In the present embodiment, when the photochromic substance is attached to the surface of the lens substrate, the scattering of the vapor deposition material is partially blocked by a position-controllable shielding plate, and the shielding plate is moved by gradually moving the shielding plate. Change the area.
At first, about half of the surface of the lens substrate is shielded, and the photochromic substance is installed so as not to adhere to the shielded area. After that, the shielding plate is moved so that the shielding region gradually narrows. By gradually moving the shielding plate, the photochromic substance comes to adhere to the surface of the lens substrate such that a gradient occurs in the amount of the photochromic substance attached. The lens substrate to which the photochromic substance adhered was colorless and transparent, and a slight interference color was observed, and interference fringes were observed in a gradation portion. In this state, the entire surface of the lens substrate to which the photochromic substance was attached was heated in a hot air oven at 120 ° C. for 1 hour. By this heating, a photochromic substance in an amount proportional to the amount of adhesion permeates and diffuses into the surface of the lens substrate. Thereby, a photochromic plastic lens having a concentration gradient is obtained.

The lens was washed with a washing machine to remove excess photochromic substances. Further, for the purpose of abrasion resistance and antireflection, an organic silicon-based hard coat was applied by dipping and heated at 110 ° C. for 4 hours to be cured. An inorganic multilayer thin film made of SiO ₂ , Al ₂ O _3, and TiO ₂ was formed thereon by vacuum evaporation. The photochromic lens thus produced had no initial coloring, and was colored brown in a gradation under sunlight.

[0107]

[Embodiment 4] In the present embodiment, the first embodiment was used as a substrate.
Using the same lens substrate as described above, a gradation photochromic plastic lens was manufactured by the method shown in FIG. As shown in FIG. 1, the lens substrate 4 to which the photochromic substance 3 is attached is placed substantially horizontally with the concave (or convex) surface facing upward, and the far-infrared ray source 1 is placed about 10 cm above the lens substrate 4. Lens substrate 4 and far infrared ray source 1
Between them, a shielding plate 2 which shuts off heating and is movable in the horizontal direction is provided.

At the time of the first heating, the shielding plate 2 is set so that about one third of the surface of the lens substrate 4 is hidden. When the lens substrate 4 is heated in this state, about one third of the unshielded area on the surface of the lens substrate 4 is heated, and the remaining shielded area is not heated. The shielding plate 2 is gradually moved in a direction indicated by an arrow by a driving means (not shown) such as a motor. Then, the shielding plate 2 is moved by a motor (not shown) so that the entire surface is heated from about one third of the surface of the lens substrate 4 over time. This moving program is created in advance according to a desired pattern.

As a result, the area that has been shielded on the surface of the lens substrate 4 is also gradually heated.
Such movement of the shielding plate 2 causes a gradient in the amount of heating of the surface of the lens substrate 4. The photochromic substance 3 permeates into the surface of the lens substrate 4 in proportion to the gradient of the heating amount. Therefore, a gradient also occurs in the amount of the permeated photochromic substance inside the surface of the lens substrate 4, and a gradation-like photochromic plastic lens can be obtained.

Thereafter, the photochromic substance remaining on the surface of the lens substrate 4 without permeating into the surface of the lens substrate 4 was washed away with a washing machine. Then, in order to further improve the scratch resistance and the antireflection, an organic silicon-based hard coat was applied by dipping and heated at 110 ° C. for 4 hours to be cured. Further thereon, a multilayer antireflection film made of SiO ₂ , Al ₂ O _3, and TiO ₂ was formed by a vacuum deposition method. The photochromic lens manufactured in this manner had no initial coloring and was colored brown in a gradation under sunlight.

[0111]

Embodiment 5 In this embodiment, the same lens base as that of Embodiment 1 was used as a plastic lens base. As shown in FIG. 2, the lens 24 to which the photochromic substance 23 is attached is installed with the concave (or convex) surface facing upward, and the lens substrate 24 is a far-infrared source provided approximately 10 cm above the lens substrate 24. Heated at 21. Lens substrate 24
Is set on the moving means 25 during heating. Lens 2
A shielding plate 22 is fixedly installed between the four substrates and the far-infrared ray source 21. As shown in FIG. 2, the shielding plate 22 has a shape that is obliquely cut when viewed from above.

First, the lens substrate 24 is installed in a state where about half of the surface of the lens substrate 24 is shielded by the shielding plate 22. Heat for about 10 minutes in this state. Thereafter, the lens substrate 24 is gradually moved in the direction of the arrow by the moving means 25. As described above, in the initial stage of heating, half the region of the photochromic substance 23 on the surface of the lens substrate 24 is heated without being shielded by the shielding plate 22 as described above. Then, as the lens moves in the direction of the arrow, the portion that blocks the lens gradually changes, and the blocking region gradually increases. As a result, when the heating of the lens is completed, a gradient occurs in the amount of the photochromic substance 23 to be heated. A gradient also occurs in the amount of the photochromic substance 23 penetrating into the inside of the surface of the lens substrate 24 in proportion to the amount to be heated, and a gradation-like photochromic plastic lens is obtained.

Thereafter, the lens substrate 24 is washed with a washing machine,
Excess photochromic material remaining on the surface of the lens substrate 24 without permeating was removed. Then, an organic silicon-based hard coat was applied by dipping for abrasion resistance and anti-reflection, and was cured by heating at 110 ° C. for 4 hours. An inorganic multilayer thin film made of SiO ₂ , Al ₂ O _3, and TiO ₂ was formed thereon by vacuum evaporation. The photochromic lens thus produced had no initial coloring, and was colored brown in a gradation under sunlight.

[0114]

[Embodiment 6] In this embodiment, the base material of Embodiment 1 was used.
The same lens substrate 33 was used. FIG. 3 is a schematic view of an apparatus for manufacturing a photochromic plastic lens according to the present embodiment. As shown in FIG. 3, a lens substrate 33 having a photochromic substance 32 adhered to its surface was placed obliquely on a lens substrate installation table 34, and heated by a far-infrared lamp 31 from above.

As can be seen from FIG. 3, the distance between the far-infrared lamp 31 and the photochromic substance 32 attached to the surface of the lens substrate 33 changes because the lens substrate 33 is installed obliquely. This change causes a difference in the amount of heating of the lens substrate 33 between a portion near the far infrared lamp 31 and a portion far from the far infrared lamp 31. The difference in temperature of the lens substrate 33 due to the difference in the amount of heating includes the region of the lens substrate 33 where the amount of heating is the largest (the portion closest to the far-infrared lamp 31) and the portion where the temperature is the lowest (the far-infrared lamp 31). The farthest part) was about 60 degrees.

As described above, the amount of heating of the surface of the lens substrate 33 has a gradient. As in the case of the fifth embodiment, the amount of permeation and diffusion of the photochromic substance into the surface of the lens substrate 34 changes in proportion to the amount of heating,
A gradation-like photochromic plastic lens was produced. Thereafter, the lens was similarly washed with a washing machine to remove excess photochromic substances.

Then, an organic silicon-based hard coat was applied by dipping for abrasion resistance and antireflection, and the coating was cured by heating at 110 ° C. for 4 hours. An inorganic multilayer thin film made of SiO ₂ , Al ₂ O _3, and TiO ₂ was formed thereon by vacuum evaporation. The photochromic lens thus produced had no initial coloring, and was colored brown in a gradation under sunlight.

[0118]

Embodiment 7 This embodiment will be described with reference to FIG. FIG.
FIG. 3 is a schematic view showing steps of a method for manufacturing a multicolor photochromic plastic lens in this example. In this embodiment, a photochromic plastic lens is manufactured in which the upper region and the lower region have the same color when the lens substrate is viewed from the front, and the intermediate region is coated with a photochromic material of a different color.

The lens substrate 41 is made of the same material as in the first embodiment.
Formed by the method. First, as shown in FIG.
1 is installed substantially horizontally, a first shielding plate 42 that can move in the direction of the arrow is installed below the convex surface, and an evaporation source (not shown) made of a photochromic substance is further installed below the first shielding plate 42.
Is installed. In this state, as a photochromic substance,
Using chromene-based and spirooxazine-based substances,
These substances were sufficiently mixed in accordance with a previously determined mixing ratio so as to develop a brown color, and about 0.01 g thereof was weighed and placed in an evaporation source. The lens substrate 41 was set about 10 cm above the evaporation source. In addition, a crystal oscillation type film forming controller (manufactured by Japan Vacuum Engineering Co., Ltd .: CRTM)
-5000) and a vapor deposition sensor (manufactured by Japan Vacuum Engineering Co., Ltd .:
The film thickness was controlled to 700 ° by CRTS-4). The degree of vacuum was set to 5 × 10 ⁻⁵ Torr by a pump. Thereafter, the evaporation source was heated to scatter the photochromic substance. A part of the scattered photochromic substance is shielded by the first shielding plate 42, and the photochromic substance adheres only to the surface of the substrate in the region A.

Next, using a material different from the photochromic substance attached to the region A, the photochromic material is attached only to the region B on the surface of the lens substrate 41. FIG.
As shown in (b), the regions other than the B region of the lens substrate 41 are shielded from scattering of the photochromic material by the shielding plates 42 and 43, and the photochromic material adheres only to the B region.

Further, as shown in FIG. 4C, similarly to FIG. 4A, the shielding plate 43 is moved so that the photochromic substance adheres only to the C region on the surface of the lens substrate 41. The lens substrate 4 to which the photochromic substance is attached as described above.
1 is heated in a hot air oven at 120 ° C. for 1 hour,
The photochromic substance attached to the surface of the lens substrate 41 was permeated and diffused inside the surface of the plastic lens substrate 41. Thereafter, the lens was washed with a washing machine to remove the photochromic substance remaining on the surface of the lens substrate 41.

Further, for the purpose of scratch resistance and anti-reflection, an organic silicon-based hard coat was applied by dipping, and was cured by heating at 110 ° C. for 4 hours.
An inorganic multilayer thin film made of SiO ₂ , Al ₂ O _3, and TiO ₂ was formed thereon by vacuum evaporation. The photochromic lens made in this way is a multicolored photochromic plastic lens that, when viewed from the front, sees the top and bottom of the lens in the same color under the sunlight and a different color near the center. was gotten.

[0123]

Embodiment 8 A hard coat layer formed by a CVD method is formed on the photochromic plastic lens of this embodiment. In this embodiment, a lens substrate was formed by using the same material and method as in the first embodiment. A photochromic substance was attached to the convex surface by a vacuum evaporation method. Chromene-based and spirooxazine-based materials were used as photochromic materials. These substances are thoroughly mixed in accordance with a previously determined compounding ratio so as to develop a brown color, and about 0.01 g thereof is weighed and placed in an evaporation source. The lens was set 10 cm above the evaporation source. In addition, a crystal oscillation type deposition controller (Nihon Vacuum Technology Co., Ltd.)
The photochromic substance was adhered to the surface of the lens substrate using a CRTM-5000 (manufactured by Japan Vacuum Engineering Co., Ltd.) and CRTS-4 (manufactured by Japan Vacuum Engineering Co., Ltd.). The thickness of the photochromic substance to be deposited was controlled at 700 °. Using a pump, the vacuum chamber was evacuated to 5 × 10 ⁻⁵ Torr,
The evaporation source was heated to cause the photochromic substance to adhere to the surface of the lens substrate. The deposited lens was colorless and transparent, and a slight interference color was observed. The lens was heated in a hot air oven at 120 ° C. for 1 hour to allow the photochromic substance attached to the surface to penetrate and diffuse into the plastic lens surface. The lens was washed with a washing machine to remove excess photochromic material remaining on the surface of the substrate.

To improve the scratch resistance, a coating was formed on the photochromic plastic lens formed by the above method. An evaporation apparatus for forming a film is configured to use a PECVD apparatus manufactured by Balzers and a vacuum evaporation apparatus to heat an evaporation source by an electron beam. In this example, a modified layer was formed on the surface of a photochromic plastic lens substrate by a CVD method, and a hard coat layer was formed thereon.

The step of forming the modified layer will be described.
By heating the vessel containing methyltriethoxysilane connected to the vacuum chamber, methyltriethoxysilane is vaporized, and the methyltriethoxysilane gas is supplied at a flow rate of 10
Flow into the vacuum chamber at 0 SCCM. 0.7P vacuum chamber pressure
When it becomes a, a current of 5 A is passed through the electromagnet coil outside the vacuum chamber to apply a magnetic field between the electrodes, and at the same time, a high-frequency output of 2 KW is applied to the cathode for 3 minutes. Thereby, plasma is generated between the electrodes. Thereafter, the high-frequency output of the cathode was gradually increased at a rate of 40 W / min in a stepwise manner.
Control to reach 2.5 KW per minute. In this 12 minutes, a denatured layer in which the refractive index changes stepwise is formed.
The thickness of the modified layer was 200 nm.

Next, the step of forming a hard coat layer will be described. Continuing with the step of forming the denatured layer, oxygen gas was flowed at 50 SCCM into the vacuum chamber, and the pressure in the vacuum chamber was set at 0.
5 Pa, the flow rate of methyltriethoxysilane gas 1
80SCCM, high frequency output 2.5KW, electromagnet coil 5
A, A first hard coat layer is formed in 20 minutes. Thereafter, oxygen gas was flowed into the vacuum chamber at 100 SCCM, the pressure in the vacuum chamber was set to 0.8 Pa, the flow rate of methyltriethoxysilane gas was 180 SCCM, the high frequency output was 3 KW, and the electromagnetic coil was kept at 5 A. A second hard coat layer is formed on the coat layer. Finally, oxygen gas was flowed into the vacuum chamber at 200 SCCM, the pressure in the vacuum chamber was set to 1.0 Pa, the flow rate of methyltriethoxysilane gas was 180 SCCM, the high-frequency output was 3 KW, and the third hard coat layer was further kept while being kept at the electromagnetic coil 5A. Form. The thickness of the hard coat layer was 2 μm.

On the third hard coat layer, SiO ₂ , Al ₂ O
_{3, An} inorganic multilayer thin film made of TiO ₂ was formed by vacuum evaporation. The photochromic lens thus produced had no initial coloring and was colored brown without unevenness under sunlight.

[0128]

Embodiment 9 In this experimental example, a high refractive index plastic lens made of urethane resin was used as a plastic lens substrate. As in Example 1, a photochromic substance was attached to the convex surface of the lens substrate by a vacuum evaporation method. Chromene-based and spirooxazine-based materials were used as photochromic materials. These photochromic substances are sufficiently mixed according to a predetermined blending ratio so as to develop a brown color.
Weigh 01 g and place in evaporation source. The lens substrate was set 10 cm above the evaporation source. A crystal oscillation type film forming controller (manufactured by Japan Vacuum Engineering Co., Ltd .: CRTM-500)
0) and a deposition sensor (manufactured by Japan Vacuum Engineering Co., Ltd .: CRTS
-4), the film thickness was controlled to 700 °. 5 × 10 ^-5
After pumping air to Torr vacuum,
The photochromic substance was scattered by heating the evaporation source to attach the photochromic substance to the surface of the lens substrate. The deposited lens was colorless and transparent, and a slight interference color was observed.
This lens was heated in a hot air oven at 120 ° C. for 1 hour to allow the photochromic substance attached to the surface to permeate and diffuse into the surface of the plastic lens substrate. The lens was washed with a washing machine to remove excess photochromic material.

A primer layer, which is a coating for improving impact resistance, was formed on the surface of the photochromic plastic lens manufactured by the above method. Hereinafter, a method for forming the primer layer will be described. (1-1) Preparation of Primer Composition Block type polyisocyanate “Coronate 252”
9 "(Nippon Polyurethane Industry Co., Ltd.) 25 parts by weight, polyester polyol 18 parts by weight, ethyl cellosolve 100
Parts by weight, and then a commercially available composite sol of tin oxide and tungsten oxide (methanol-dispersed sol, average particle diameter of 1) was added thereto.
0 to 15 mμ, ratio of tin oxide to tungsten oxide 10
0 parts by weight / 40 parts by weight, solid content 30%) was 140 parts by weight (not solid content), and the silicone surfactant was 0.15 parts by weight.
The coating composition in the form of a solution was obtained by adding parts by weight and sufficiently stirring and mixing.

(1-2) Coating and Curing of Primer Composition A plasma treatment was performed for the purpose of enhancing the adhesion between the photochromic plastic lens substrate and the primer layer. Conditions are oxygen gas pressure about 0.2Tool, RF output 2
00W and a processing time of 30 seconds. Thereafter, the primer composition prepared in (1-1) is dipped on the concave surface of the high refractive index plastic lens (with a lifting speed of 180 mm / m).
in). This film thickness was about 2 μm. Thereafter, the high refractive index plastic lens coated with the primer composition was placed in a heating furnace and heat-treated at 130 ° C. for 60 minutes to cure the primer composition and form a primer layer. The refractive index of the cured primer layer was about 1.60.

Further, a lens having a primer layer formed thereon
The organic silicon compound for abrasion resistance and anti-reflection
Immersed in a hard coat solution consisting of
Heat at 10 ° C for 4 hours to cure and form hard coat layer
Done. On top of that, SiO_Two, Al _TwoO_3,, TiO_TwoInorganic
The layer film was formed by vacuum evaporation. Work in this way
The photochromic lens has no initial coloring and
Under the sun, it was colored even brown.

[0132]

Embodiment 10 The operation was performed under the same conditions as in Embodiment 9. (2-1) Preparation of Primer Composition In a reaction vessel equipped with a rotor, 2.2 parts by weight of methyltrimethoxysilane and 19.8 parts by weight of methanol were charged.
0.9 parts by weight of 0.001N hydrochloric acid was added, and the mixture was stirred for 1 hour to carry out hydrolysis.

The hydrolyzate was added to titanium tetra-n-
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 Chemical Co., Ltd.
Ltd. SnO ₂ / WO ₃ composite Biko dispersion methanol sol (HIS
-30 M, average particle size 25 nm, solid content concentration 30%) 1
33.3 parts by weight, 2.0 parts by weight of dibutyltin dilaurate as a curing catalyst, Fluorosurfactor FC430 manufactured by Sumitomo 3M Ltd. as a leveling agent
1.3 parts by weight are added sequentially. 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.

A) 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 size 15-20 nm, solid content concentration 30% B) Polyvinyl butyral resin ESREC BM-1 Sekisui Chemical Co., Ltd., average polymerization degree 600, butyralization degree 65% ESREC BM-2 Sekisui Chemical Co., Ltd., average polymerization degree 800, butyralization degree 68% ESREC BM- 5 Sekisui Chemical Co., Ltd., average degree of polymerization 850, butyralization degree 65% ESREC BH-S Sekisui Chemical Co., Ltd. , Average degree of polymerization 1,000, degree of butyralization 70% c) Surfactant Florado FC430 Fluorosurfactant SH30PA manufactured by Sumitomo 3M Limited Silicone surfactant L7001 manufactured by Toray Dow Corning Co., Ltd. Nippon Unicar Co., Ltd. ) Silicon-based surfactant In a reaction vessel equipped with a rotor, 180 parts by weight of γ-glycidoxypropyltrimethoxysilane was charged, and stirred vigorously using a magnetic stirrer.
40 parts by weight of a normal hydrochloric acid aqueous solution was added at a time, and hydrolysis was continued for 1 hour to obtain a partially condensed hydrolyzate.

The above hydrolyzate was added to Nissan Chemical Co., Ltd. S
nO ₂ / WO ₃ composite fine particle dispersed metal sol (HIS-3
OM), 630 parts by weight, a curing catalyst of 4 parts by weight of aluminum ethylenediaminetetraacetate, and a silicon-based surfactant S manufactured by Toray Dow Corning Co., Ltd. as a leveling agent.
After adding 0.45 parts by weight of H30PA and sufficiently stirring and mixing, the mixture was filtered through a 3 μm membrane filter to prepare a hard coat liquid.

(2-1) Application and Curing of Primer Composition A thermosetting urethane resin plastic lens for spectacles having a degree of -4.00 diopter, a center thickness of 1.0 mm and a refractive index of 1.66 was used. 10% NaOH at 60 ° C as pretreatment
It was immersed in an aqueous solution for 5 minutes, washed with warm water and dried. A primer composition was applied to both surfaces of the plastic lens by a dipping method (pulling speed: 5 mm / sec), and was heated at 90 ° C. for 30 minutes to cure the primer.

On both sides of a plastic lens having a primer layer and a hard coat layer, an SiO ₂ / ZrO ₂ system
The layer antireflection film was formed by a vacuum deposition method. The plastic lens having the composite film thus obtained was subjected to the following tests to evaluate the performance. 1) Adhesion of film In order to evaluate the adhesion of the film, a cross hatch tape test was performed by the following method. 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.

Thereafter, the number of grids on the surface of the coating layer which were not peeled off from the lens was examined, and the number of grids which were not peeled off was expressed as 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.

[0139]

As described above, according to the present invention, the photochromic substance is adhered to the surface of the plastic lens substrate by the vacuum evaporation method, and then the photochromic substance penetrates and diffuses into the surface of the lens substrate by heating. Photochromic plastic lenses can be manufactured with high productivity and low cost, and the manufactured lenses have stable photochromic performance.

Further, by manufacturing the plastic lens substrate from a material containing at least an ultraviolet-curable resin, the plastic lens substrate can be easily permeated and diffused into the surface of the lens substrate, and the production is further facilitated. In addition, when a lens substrate containing an ultraviolet curable resin is used, the structure of the photochromic material that has penetrated and diffused into the surface of the substrate is easily changed as compared with a lens substrate formed of a thermosetting resin, and the A photochromic plastic lens having a high light speed and excellent dimming performance can be obtained. In addition, since the structural change of the photochromic substance is sufficiently performed according to the light control, a lens that fully utilizes the performance of the photochromic substance to be used can be obtained. Furthermore, since the performance of the photochromic substance can be fully utilized, the amount of the photochromic substance used can be reduced, and a photochromic plastic lens can be obtained at a lower cost as compared with a case where the lens substrate is formed of a thermosetting resin. Can be Further, since the curing time of the ultraviolet curable resin is short, it can be manufactured at lower cost, and the productivity is also improved.

Further, it has become possible to easily produce a gradation-like photochromic plastic lens having uniform photochromic performance at low cost with good reproducibility. Further, a photochromic plastic lens having multicolor photochromic performance can be easily manufactured. Thereby, a photochromic plastic lens having an unprecedented multicolored color and excellent appearance can be obtained.

Further, a photochromic substance is adhered onto the lens substrate by a vacuum evaporation method, and the photochromic substance is permeated and diffused on the surface of the lens substrate by heating, thereby producing a photochromic plastic lens. Is formed by the CVD method,
The photochromic plastic lens can be manufactured only by the dry process, and the manufacturing process of the photochromic plastic lens with improved scratch resistance can be simplified and the cost can be reduced. Further, the scratch resistance of the lens in which the permeation region of the photochromic substance is formed inside the surface of the lens substrate can be further improved.

Further, by forming a primer layer on the lens substrate in which the photochromic substance has penetrated and diffused into the surface of the lens substrate, a photochromic plastic lens with improved impact resistance can be obtained. Further, by forming a hard coat layer on the primer layer, a photochromic plastic lens excellent in scratch resistance and impact resistance and easily manufactured can be obtained.

Since the photochromic plastic lens of the present invention has excellent appearance and high durability, it can provide a photochromic plastic lens applicable to spectacle wearers of various tastes in various environments.

[Brief description of the drawings]

FIG. 1 is a schematic view showing an apparatus for manufacturing a photochromic plastic lens having gradation according to an embodiment of the present invention.

FIG. 2 is a schematic view showing an apparatus for manufacturing a photochromic plastic lens having gradation according to an embodiment of the present invention.

FIG. 3 is a schematic view showing an apparatus for manufacturing a photochromic plastic lens having gradation according to an embodiment of the present invention.

FIG. 4 is a schematic view showing an apparatus for manufacturing a multicolor photochromic plastic lens according to an embodiment of the present invention.

[Description of Signs of Main Parts]

1, 21, 31 ... heating means 2, 22, 42, 43 ... shield plate 3, 23, 32 ... adhere to lens substrate Photochromic substance 4,24,33,41 ..... Lens substrate 25 ........ Means for moving lens substrate 34... ..... Mounting base for lens substrate

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical indication G02C 7/10 G02B 1/10 Z // B29K 33:04 (31) Claimed priority number 8-102875 (32) Priority date Hei 8 (1996) April 24 (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese Patent Application 8-105708 (32) Priority date Hei 8 (1996) ) April 25 (33) Priority claiming country Japan (JP)

Claims (21)

[Claims] 1. A step of depositing a photochromic substance on a surface of a plastic lens substrate by a vacuum deposition method, and heating the plastic lens substrate to which the photochromic substance has adhered to form the photochromic substance inside the plastic lens substrate surface. A method for producing a photochromic plastic lens, comprising a step of infiltrating a plastic lens. 2. A step of injecting a monomer containing a polymerization initiator which initiates polymerization by irradiation with ultraviolet rays into a mold, and irradiating the monomers injected into the mold with ultraviolet rays to cure the plastic lens. A step of forming a substrate, a step of attaching a photochromic substance to the surface of the plastic lens substrate by a vacuum deposition method, and heating the plastic lens substrate to which the photochromic substance is attached to the inside of the surface of the plastic lens substrate. And a step of infiltrating the photochromic substance into the photochromic plastic lens. 3. A step of injecting into a mold a monomer containing a polymerization initiator which initiates polymerization by irradiation with ultraviolet light and a polymerization initiator which starts polymerization by heat, and irradiating the monomer with ultraviolet light. A step of polymerizing and curing the monomer by heating to form a plastic lens substrate, a step of attaching a photochromic substance to the surface of the plastic lens substrate by a vacuum deposition method, and a step of attaching the photochromic substance to the plastic lens substrate And heating the photochromic material to the inside of the surface of the plastic lens substrate. 4. A permeation region in which the photochromic substance has penetrated exists inside the surface of the plastic lens substrate by heating the photochromic substance attached to the surface of the plastic lens substrate by a vacuum deposition method. A photochromic plastic lens characterized by the following. 5. The photochromic material is adhered to the surface of the plastic lens substrate by a vacuum deposition method while controlling the amount of the photochromic material adhered to the photochromic plastic lens so that a gradient occurs when the photochromic plastic lens is viewed from the front. And the step of heating the plastic lens substrate to which the photochromic substance adheres, and the step of infiltrating the photochromic substance in an amount proportional to the amount of the photochromic substance adhered to the inside of the plastic lens substrate surface. A method for producing a photochromic plastic lens. 6. A step of adhering a photochromic substance to the surface of the plastic lens substrate by a vacuum deposition method, and the step of heating the plastic lens substrate to which the photochromic substance is adhered so that a heating amount has a gradient with respect to the surface of the plastic lens substrate. A method for producing a photochromic plastic lens, comprising a step of heating while controlling an amount of the photochromic material and infiltrating the photochromic substance in an amount proportional to the amount of heating into the inside of the surface of the plastic lens substrate. 7. A permeation area in which the photochromic substance has permeated exists inside the surface of the plastic lens substrate by heating the photochromic substance attached to the surface of the plastic lens substrate by a vacuum deposition method,
A photochromic plastic lens, wherein the permeation region has a gradient of a permeation amount of the photochromic substance. 8. A step of attaching a first photochromic substance to a part (area A) of the surface of the plastic lens substrate by a vacuum deposition method, and a second photochromic substance having a color different from the first photochromic substance. Applying a second photochromic material to a region other than the region A by a vacuum deposition method while blocking the adhesion to the region A; and a plastic lens substrate having the first and second photochromic materials adhered thereto. And heating the first and second photochromic substances into the inside of the surface of the plastic lens substrate. 9. A permeation area in which the different photochromic substances are infiltrated by heating different photochromic substances attached to different areas inside the surface of the plastic lens substrate by a vacuum deposition method. Photochromic plastic lens. 10. A step of attaching a photochromic substance to the surface of a plastic lens substrate by a vacuum deposition method,
Heating the plastic lens substrate to which the photochromic substance is attached, and infiltrating the photochromic substance into the inside of the plastic lens substrate surface,
Forming a hard coat layer by a CVD method on the plastic lens substrate having the photochromic substance penetrated into the inside of the substrate surface. 11. The method according to claim 11, wherein the permeation area in which the photochromic substance is permeated exists inside the surface of the plastic lens substrate by heating the photochromic substance attached to the surface of the plastic lens substrate by a vacuum deposition method. A photochromic plastic lens having a hard coat layer formed on a plastic lens substrate by a CVD method. 12. A step of attaching a photochromic substance to a surface of a plastic lens substrate by a vacuum deposition method,
Heating the plastic lens substrate to which the photochromic substance is attached, and infiltrating the photochromic substance into the inside of the plastic lens substrate surface,
Forming a modified layer having a refractive index changing in a thickness direction by a CVD method on the plastic lens substrate having the photochromic substance permeated into the inside of the substrate surface; A method for producing a photochromic plastic lens, comprising a step of forming a hard coat layer by a method. 13. A step of attaching a photochromic substance to a surface of a plastic lens substrate by a vacuum deposition method,
Heating the plastic lens substrate to which the photochromic substance is attached, and infiltrating the photochromic substance into the inside of the plastic lens substrate surface,
A modified layer having a refractive index changing in a thickness direction formed by a CVD method on the plastic lens substrate in which the photochromic substance has penetrated into the inside of the substrate surface; A photochromic plastic lens having a hard coat layer formed by a method. 14. A method according to claim 10, wherein said hard coat layer is formed by a chemical vapor deposition method using plasma using a mixed gas of an organic compound gas containing Si and oxygen gas. , 11, 12, and 13 and the method for producing a photochromic plastic lens. 15. The method according to claim 1, wherein said modified layer is formed by a vapor phase growth method using plasma using at least one of an organic compound gas containing Si and an organic compound gas containing Ti. 14. The photochromic plastic lens according to 12 or 13, and a method for producing the photochromic plastic lens. 16. The hard coat layer according to claim 12, wherein the thickness of the hard coat layer is relatively thicker than that of the modified layer.
The method for producing the photochromic plastic lens and the photochromic plastic lens described above. 17. The method according to claim 10, wherein the refractive index of the hard coat layer is substantially constant.
15. The photochromic plastic lens according to items 3 and 14, and a method for producing the photochromic plastic lens. 18. A step of attaching a photochromic substance to a surface of a plastic lens substrate by a vacuum deposition method,
Heating the plastic lens substrate to which the photochromic substance is attached, and infiltrating the photochromic substance into the inside of the plastic lens substrate surface,
Forming a primer layer by applying a compound containing a urethane resin or a crosslinked polyvinyl acetal resin as a main component on the plastic lens substrate into which the photochromic substance has penetrated into the inside of the substrate surface. A method for producing a photochromic plastic lens. 19. The method according to claim 19, wherein the photochromic material attached to the surface of the plastic lens substrate is heated by a vacuum deposition method, so that a permeation region where the photochromic material has penetrated exists inside the surface of the plastic lens substrate. A photochromic plastic lens having a primer layer made of a urethane resin or a crosslinked polyvinyl acetal resin on a plastic lens substrate. 20. The urethane resin is selected from alkylene glycols, polyalkylene glycols, poly (alkylene adipates), poly-ε-caprolactone, polybutadiene glycols, poly- (alkylene carbonate) s and silicone polyols. 20. A resin obtained from a urethane solution of an active hydrogen-containing compound and a polyisocyanate.
The method for producing the photochromic plastic lens and the photochromic plastic lens described above. 21. The photochromic plastic lens and the method for producing a photochromic plastic lens according to claim 18, wherein the polyvinyl acetal resin comprises a compound represented by the following as a main component. At least the fraction (a) of the structural unit having an acetal group in the general formula (the fraction is the ratio of the specific structural unit to the total number of structural units in the polymer) is 10 to 90, and OH
A polymer (A) in which the fraction (b) of the number of structural units having a group is 10 to 90 and a + b ≦ 100, and (B) a polymer represented by the general formula (II): (II) (wherein, R ² and R ³ are a substituted or unsubstituted hydrocarbon group having 1 to 8 carbon atoms, X ¹ is a hydrolyzate group, and d and e are 0 to 3 A hydrolyzable organosilane compound or a hydrolyzate thereof represented by the general formula (III): (III) (wherein, R ⁴ is an organic group having 2 to 8 carbon atoms;
R ⁵ and R ⁶ are a substituted or unsubstituted hydrocarbon group having 1 to 8 carbon atoms; X ² is a hydrolyzate group;
Or an integer from 2 to 2), or a hydrolyzable organosilane compound represented by the formula (IV): (IV) (wherein, R ⁷ is a substituted or unsubstituted carbon atom of 1)
Or a glyoxal or a glyoxal represented by the general formula (V): (V) (wherein, R ⁸ represents a substituted or unsubstituted carbon atom of 1)
And R ⁹ is a saturated hydrocarbon group having 1 to 4 carbon atoms), and at least one crosslinking agent selected from dialdehyde acetal compounds represented by the formula: C) a primer composition comprising an organic solvent and water, wherein the content of the component (A) is 1 to 30% by weight;
The content of the crosslinking agent (B) is 0.01 to 30% by weight.