JP4760456B2 - Plastic lens, plastic lens manufacturing method, colored plastic lens manufacturing method, and colored plastic lens - Google Patents

Description

The present invention relates to a plastic lens having a photosensitive layer, a method for producing a plastic lens, a method for producing a colored plastic lens , and a colored plastic lens .

  Conventionally, as a method for coloring plastic lenses, a so-called dip dyeing method is generally used in which various disperse dyes are dispersed in warm water together with a surfactant to prepare a dye solution, and the plastic lens is immersed in a heated dye solution. (For example, refer to Patent Document 1). In addition, a coloring method using a transfer method has been proposed as an alternative to this dip dyeing method (see, for example, Patent Document 2). In this coloring method, a colored sheet is printed using a coloring material in which a sublimable dye is dissolved or finely dispersed on a stretchable film, and a transfer sheet in which an adhesive layer is formed on the surface of the colored layer is manufactured in advance. Keep it. Next, after heating and pressurizing so that the printing side of the transfer sheet is in close contact with the surface of the plastic lens, the colored layer is transferred to the surface of the plastic lens by peeling off the transfer sheet. Thereafter, the sublimable dye in the transferred colored layer is sublimated and penetrated into the plastic lens, and finally the remaining colored layer and pressure-sensitive adhesive layer are removed.

JP-A-9-131565 JP 2000-9905 A

  However, in the dip dyeing method of Patent Document 1, there is a problem that the affinity of a dye to a plastic lens is low, dyeing is difficult depending on the type of substrate, and it takes a very long time to color at a high concentration. In addition, since a high-temperature solvent is used, there is a high work risk and there is also a problem of disposal of the dyeing solution. On the other hand, in the coloring method by the transfer method described in Patent Document 2, after the colored layer is transferred and the sublimable dye is sublimated and permeated, the remaining colored layer and pressure-sensitive adhesive layer are removed and washed using a solvent or the like. There is a need. Further, there is a problem that the pressure-sensitive adhesive layer prevents sublimation penetration of the sublimable dye. In addition, since the colorant layer is formed by screen printing, there is a problem in that it is not possible to respond quickly when toning is performed on the spot such as a custom color. Furthermore, there is also a problem that the plastic lens is deformed because the plastic lens is heated at a high temperature during sublimation.

An object of the present invention, the no problems as described problems, readily colorable nature plastic lens having a method of manufacturing a plastic lens, colored plastic lenses and colored plastic lens was colored the plastic lens It is to provide a manufacturing method.

Plastic lens of the present invention is a plastic lens having a protective layer on the substrate, between the substrate and the protective layer comprises a photosensitive layer capable color by the developing solution, the protective layer, the The developer is configured to be able to penetrate to the photosensitive layer.
According to the plastic lens of the present invention, there is a photosensitive layer that can be colored by a developer on the substrate, and the developer can easily reach the photosensitive layer through the permeable protective layer. It is possible to provide a plastic lens that can be colored (colored) by a simple method of developing by applying light. Conventionally, in order to perform the desired coloring on the plastic lens , a completely separate coloring process is required for each color. However, in the plastic lens of the present invention, the photosensitive layer is made of a predetermined color photosensitive material. Then, it becomes possible to realize colored plastic lenses of various shades in the same process only by controlling the wavelength, intensity, and time of the applied light. That is, it is possible to produce a variety of small lots of colored plastic lenses . Furthermore, by covering the protective layer, it is possible to protect the photosensitive layer that is easily damaged by external scratches or the like.

Further, in the present invention, the protective layer includes silica-based fine particles having an internal cavity,
R ¹ R ² _n SiX ¹ _3-n (wherein R ¹ is an organic group having a polymerizable reactive group, R ² is a hydrocarbon group having 1 to 6 carbon atoms, and X ¹ is a hydrolytic group. in it, n represents ing and an organic silicon compound represented by a 0 or 1.).

According to the present invention, since the protective layer is configured to include silica-based fine particles (porous silica) having internal cavities, the penetration of the developer becomes extremely easy, and the time required for development can be further shortened. .
Further, the organosilicon compound represented by the above formula is a so-called silane coupling agent, and specific examples of the polymerizable reactive group of R ¹ include a vinyl group and an allyl group. Specific examples of R ² include a methyl group and an ethyl group. X ¹ is a hydrolyzable functional group, and examples thereof include a methoxy group and an ethoxy group. Since the organosilicon compound is such a specific silane coupling agent, a stronger protective layer can be formed after application to the substrate. This silane coupling agent is preferably hydrolyzed by a conventional method.

In the present invention, it is preferable that the protective layer further has antireflection properties.
According to the present invention, since the protective layer also serves as the antireflection layer, it is possible to provide a plastic lens having antireflection characteristics.
In particular, when silica-based fine particles having an internal cavity are present in the protective layer, a gas or a solvent having a refractive index lower than that of silica can be included. Therefore, the silica-based fine particles having internal cavities have a lower refractive index than the silica-based fine particles having no internal cavities, resulting in a lower refractive index of the antireflection layer. Therefore, by reducing the refractive index of the antireflection layer, the difference in refractive index with the substrate can be increased, and the antireflection function can be improved.

The present invention relates to a method for producing a plastic lens having a protective layer on a substrate , wherein a photosensitive layer capable of color development by a developer is formed on the surface of the substrate by applying a silver halide emulsifier. And a protective layer forming step of forming a protective layer that allows the developer to penetrate to the photosensitive layer on the photosensitive layer , wherein the protective layer includes silica-based fine particles having an internal cavity, R ¹ R ² _n SiX ¹ _3-n (wherein R ¹ is an organic group having a polymerizable reactive group, R ² is a hydrocarbon group having 1 to 6 carbon atoms, and X ¹ is a hydrolytic group. There, n represents characterized Rukoto such and an organic silicon compound represented by a 0 or 1.).
According to the method for producing a plastic lens of the present invention, it is possible to easily produce a plastic lens that can be easily colored (colored) simply by exposure and development in a subsequent process.

The method for producing a colored plastic lens according to the present invention includes a photosensitive step of irradiating the plastic lens with light to expose the photosensitive layer, and a coloring step of coloring the photosensitive layer with the developer. .
According to the method for producing a colored plastic lens of the present invention, color development (coloring) can be easily performed by simply exposing and developing, and a complicated coloring process is not required. Further, in the present invention, since the photosensitive layer can be easily colored (colored) simply by immersing the plastic lens in the developer, the waste liquid compared to the conventional method of immersing the plastic lens in a predetermined colored solution. The load on the environment is also low.

The colored plastic lens of the present invention is manufactured by the above-described method for manufacturing a colored plastic lens .
According to the colored plastic lens of the present invention, it is possible to apply light having a predetermined wavelength to the above-described plastic lens to cause it to be colored in an arbitrary color, so that various color variations can be provided. In particular, it is suitable as a spectacle lens and has excellent function. Further, such as color vision correcting eyeglass lenses, Ru suitable der even coloring spectacle lenses which gave various transmitted light wavelength pattern.

Hereinafter, an embodiment of the present invention will be described. In the present embodiment, it will be exemplified a plastic spectacle lens as a colored plastic lens of the present invention. In this embodiment, even a plastic lens before coloring is simply referred to as a plastic spectacle lens.

[1. (Configuration of plastic spectacle lens)
In the plastic spectacle lens of this embodiment, a photosensitive layer that can be colored by a developer is formed on a transparent substrate, and a porous antireflection layer through which the developer can penetrate is formed on the photosensitive layer. ing.
(1-1. Substrate)
The plastic as the material of the substrate is not particularly limited, but it is preferable to use a material having a refractive index of 1.6 or more.
For example, a polythiourethane plastic produced by reacting a compound having an isocyanate group or isothiocyanate group with a compound having a mercapto group, or a raw material monomer containing a compound having an episulfide group is produced by polymerization and curing. Episulfide plastics can be used as the substrate material.

As the compound having an isocyanate group or an isothiocyanate group as a main component of the polythiourethane plastic, a known compound can be used without any limitation.
Specific examples of the compound having an isocyanate group include ethylene diisocyanate, trimethylene diisocyanate, 2,4,4-trimethylhexane diisocyanate, hexamethylene diisocyanate, m-xylylene diisocyanate and the like. It is done.
Moreover, a well-known thing can be used also as a compound which has a mercapto group. For example, 1,2-ethanedithiol, 1,6-hexanedithiol, aliphatic polythiol such as 1,1-cyclohexanedithiol, 1,2-dimercaptobenzene, 1,2,3-tris (mercaptomethyl) benzene, etc. Aromatic polythiols are mentioned. In addition to the mercapto group, polythiol containing a sulfur atom is more preferably used to increase the refractive index of the plastic lens. Specific examples thereof include 1,2-bis (mercaptomethylthio) benzene, 1, Examples include 2,3-tris (mercaptoethylthio) benzene and 1,2-bis ((2-mercaptoethyl) thio) -3-mercaptopropane.

(1-2. Hard coat layer)
A hard coat layer is formed on the substrate as necessary. Moreover, you may form a primer layer before forming a hard-coat layer. The hard coat layer preferably comprises, for example, the following component (A) and component (B).
(A) General formula: Organosilicon compound represented by R ³ SiX ² ₃ (wherein R ³ is an organic group having a polymerizable reactive group, and X ² represents a hydrolyzable group)
(B) Inorganic oxide particles containing titanium oxide having a rutile crystal structure

The component (A) serves as a binder for the hard coat layer.
In the chemical formula of the component (A), R ³ is an organic group having a polymerizable reactive group, and has 1 to 6 carbon atoms. Examples of the polymerizable reactive group include a vinyl group, an allyl group, an acrylic group, a methacryl group, a 1-methylvinyl group, an epoxy group, a mercapto group, a cyano group, an isocyano group, and an amino group.
X ² is a hydrolyzable functional group, and examples thereof include alkoxy groups such as methoxy group, ethoxy group, and methoxyethoxy group, halogen groups such as chloro group and bromo group, and acyloxy groups.

The layer thickness of the hard coat layer is preferably 0.05 to 30 μm. If it is less than 0.05 μm, the basic function of the hard coat layer for protecting the substrate cannot be exhibited, and if it exceeds 30 μm, the smoothness of the surface of the hard coat layer is impaired.
When a primer layer or a hard coat layer is formed on the substrate, a known method may be used. For example, a dipping method (dipping method), a spin coating method, or a roll coating method can be used.

(1-3. Photosensitive layer)
On the above-described substrate, a photosensitive layer capable of color development by a developer is formed between the antireflection layer described later. However, the substrate means that a primer layer and a hard coat layer are also laminated on the substrate.
Here, specifically, the photosensitive layer is a layer formed by coating a silver halide emulsion, and those widely used as color photosensitive materials for color photography can be suitably used (for example, special features). (See Kaihei 7-301894 and JP-A 2004-157340).
Examples of the silver halide used in the silver halide emulsion layer include arbitrary silver halides such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide and silver chloroiodide.
The silver halide grains preferably used are silver halide grains mainly composed of silver chloride containing at least 80 mol% of silver chloride, more preferably 90 mol% or more, particularly preferably 95 mol% or more. The silver bromide content is preferably 5 mol% or less, and the silver iodide content is preferably 0.5 mol% or less. More preferred is silver chlorobromide having a silver bromide content of 0.1 to 2 mol%.

  The silver halide grains may be used alone or in combination with other silver halide grains having different compositions. Further, it may be used by mixing with silver halide grains having a silver chloride content of 80 mol% or less. Further, in the silver halide emulsion layer containing silver halide grains having a silver chloride content of 80 mol% or more, the silver chloride content is 95 mol% in the total silver halide grains contained in the emulsion layer. The ratio of the above silver halide grains is 60% by mass or more, preferably 80% by mass or more.

A known method can be used for reduction sensitization of the silver halide emulsion. For example, a method of adding various reducing agents may be used, or a method of aging under conditions where the silver ion concentration is high or a method of aging under conditions of high pH may be used. The silver halide emulsion can be used in combination with reduction sensitization and sensitization using a gold compound and sensitization using a chalcogen sensitizer. As the chalcogen sensitizer, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer and the like can be used, and a sulfur sensitizer is preferable. Examples of the sulfur sensitizer include thiosulfate, allyl thiocarbamide, thiourea, allyl isothiocyanate, cystine, p-toluene thiosulfonate, rhodanine and the like. As the gold sensitizer, various gold complexes such as chloroauric acid, gold sulfide and gold thiosulfate can be added. Examples of the ligand compound used include dimethyl rhodanine, thiocyanic acid, mercaptotetrazole, mercaptotriazole and the like.
For silver halide emulsions, known antifoggants and stabilizers are used for the purpose of preventing fogging that occurs during the preparation process of color light-sensitive materials, reducing performance fluctuations during storage, and preventing fogging that occurs during development. Can be used.

As the coupler used in the color light-sensitive material, there can be used a compound capable of forming a coupling product having a spectral absorption maximum wavelength in a wavelength region longer than 340 nm by a coupling reaction with an oxidized form of a color developing agent. In particular, a yellow coupler having a spectral absorption maximum wavelength in the wavelength range of 350 to 500 nm, a magenta coupler having a spectral absorption maximum wavelength in the wavelength range of 500 to 600 nm, and a cyan coupler having a spectral absorption maximum wavelength in the wavelength range of 600 to 750 nm are preferable.
As a yellow coupler that can be preferably used in the present invention, a coupler represented by the general formula [Y-1] described in the upper right column of page 3 of JP-A-4-114154 can be exemplified. Can include couplers represented by general formulas (M-I) and (M-II) described on page 12 of the publication. Examples of cyan couplers include couplers represented by general formulas (CI) and (C-II) described on page 17 of the publication.

The photosensitive layer preferably has a layer containing a silver halide emulsion spectrally sensitized in a specific region of a wavelength region of 400 to 900 nm in combination with such a yellow coupler, magenta coupler, and cyan coupler. The silver halide emulsion contains one or more sensitizing dyes in combination.
As the sensitizing dye, any known compound can be used. As the blue-sensitive sensitizing dye, BS-1 described in JP-A-3-251840, page 28, upper right column to lower left column. ~ 8 can be preferably used alone or in combination. As the green photosensitive sensitizing dye, GS-1 to GS-5 described in page 28, lower right column are preferably used, and as the red photosensitive sensitizing dye, page 29, upper left column to upper right column. The described RS-1 to 8 are preferably used.

In color light-sensitive materials, gelatin is preferably used as a binder. However, other gelatin derivatives, gelatin and other polymer graft polymers, proteins other than gelatin, sugar derivatives, cellulose derivatives, single or common are used as necessary. Hydrophilic colloids such as synthetic hydrophilic polymer materials such as polymers can also be used.
Such a photosensitive layer can be easily formed by applying a silver halide emulsion (color photosensitive material) to a plastic spectacle lens substrate by a dipping method or a roll coating method. For example, the first layer (red-sensitive layer), the second layer (intermediate layer), the third layer (green-sensitive layer), the fourth layer (intermediate layer), and the fifth layer (blue-sensitive layer) on the substrate. A photosensitive layer capable of developing any color can be formed by applying the coating.

(1-4. Protective layer (antireflection layer))
The antireflection layer is composed of a single organic layer on the photosensitive layer, and has a thickness of about 50 to 150 nm. The refractive index of the antireflection layer is preferably 0.10 or more lower than the photosensitive layer, more preferably 0.15 or more, and particularly preferably 0.20 or more.
Here, the antireflection layer includes silica-based fine particles (porous silica) having an internal cavity,
R ¹ R ² _n SiX ¹ _3-n (wherein R ¹ is an organic group having a polymerizable reactive group, R ² is a hydrocarbon group having 1 to 6 carbon atoms, and X ¹ is a hydrolytic group. And n is 0 or 1.) and an organic silicon compound.

  If the silica-based fine particles have internal cavities, they can include gases and solvents having a refractive index lower than that of silica itself. Therefore, the silica-based fine particles having internal cavities have a lower refractive index than the silica-based fine particles having no internal cavities, resulting in a lower refractive index of the antireflection layer. That is, by reducing the refractive index of the antireflection layer, the difference in refractive index with the hard coat layer is increased, and the antireflection function can be improved.

  Here, the silica-based fine particles having internal cavities can be produced by the method described in JP-A-2001-233611, but in the present invention, the average particle diameter is in the range of 20 to 150 nm. In addition, it is desirable to use one having a refractive index in the range of 1.16 to 1.39. When the average particle diameter of the particles is less than 20 nm, the porosity inside the particles becomes small, and a desired low refractive index cannot be obtained. On the other hand, if the average particle size exceeds 150 nm, the haze of the organic thin layer increases, which is not preferable. As the silica-based fine particles having internal cavities as described above, a dispersion sol containing hollow silica fine particles having an average particle diameter of 20 to 150 nm and a refractive index of 1.16 to 1.39 (manufactured by Catalyst Chemical Industry Co., Ltd., through rear and recumen). ) And the like.

In the organosilicon compound in the above formula, specific examples of the polymerizable reactive group of R ¹ include vinyl group, allyl group, acrylic group, methacryl group, epoxy group, mercapto group, cyano group, amino group and the like. . Specific examples of R ² include a methyl group, an ethyl group, a butyl group, a vinyl group, and a phenyl group. X ¹ is a hydrolyzable functional group, and specific examples thereof include alkoxy groups such as methoxy group, ethoxy group and methoxyethoxy group, halogen groups such as chloro group and bromo group, acyloxy groups and the like.

  Specific examples of such silane compounds include vinyltrialkoxysilane, vinyltrichlorosilane, vinyltri (β-methoxy-ethoxy) silane, allyltrialkoxysilane, acryloxypropyltrialkoxysilane, methacryloxypropyltrialkoxysilane, methacrylic Oxypropyl dialkoxymethylsilane, γ-glycidoxypropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) -ethyltrialkoxysilane, mercaptopropyltrialkoxysilane, γ-aminopropyltrialkoxysilane, N-β (Aminoethyl) -γ-aminopropylmethyl dialkoxysilane and the like. Two or more of the above-described silane compounds may be mixed and used.

In addition, it is preferable that the composition for forming an antireflection layer contains a surfactant because uneven coating hardly occurs during application to a substrate. As the surfactant, a silicone surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant can be used.
In addition, the composition for forming the antireflection layer includes resins such as polyurethane resins, epoxy resins, melamine resins, polyolefin resins, urethane acrylate resins, epoxy acrylate resins, and methacrylates and acrylates that are raw materials for these resins. It is possible to add various monomers such as epoxy, epoxy and vinyls.
In addition to these components, if necessary, curing catalysts, antistatic agents, ultraviolet absorbers, antioxidants, hindered amines, hindered phenols and other light stabilizers, disperse dyes, oil-soluble dyes, fluorescent dyes Further, pigments and the like may be added to improve light resistance and coatability.

In order to form the antireflection layer on the photosensitive layer, a coating composition is first prepared by the following procedure. The aforementioned silane compound is diluted with an organic solvent, and hydrolyzed by adding water or dilute hydrochloric acid, acetic acid or the like as necessary. Further, the silica-based fine particles dispersed in an organic solvent at a fraction of 5 to 50% by mass are added. Thereafter, if necessary, an ultraviolet absorber, an antioxidant and the like are added, and the mixture is sufficiently stirred and used as a coating solution. At this time, the concentration of the coating solution diluted with respect to the solid content after curing is preferably 1 to 15% by mass, and more preferably 1 to 10% by mass as the solid content concentration. When the solid content concentration exceeds 15% by mass, it is difficult to obtain a predetermined layer thickness, and the layer thickness becomes unnecessarily thick.
Next, the composition obtained by the above-described method is applied to the photosensitive layer by, for example, an immersion method, and then baked. The baking conditions may be about 120 ° C. for about 5 minutes, and there is little risk of degrading the gelatin of the photosensitive layer.

[2. (Coloring of plastic eyeglass lenses)
The plastic spectacle lens having the above-described configuration is colored as follows.
First, light of a predetermined color (wavelength) is irradiated for a predetermined time to a photosensitive plastic spectacle lens with an appropriate color light source to form a latent image on the photosensitive layer (photosensitive process).
Next, development is performed by immersing the exposed plastic spectacle lens in a developer (coloring step). As the developer and development conditions, those used for general photographic color films (negative, reversal) are applicable. For example, the developer and development conditions described in JP-A-7-301894 and JP-A-2004-157340 are preferably applicable. Below, this coloring process is demonstrated.

The color development process basically includes a color development process, a bleach-fixing process, and a water washing process.
(Color development process)
As the color developing agent used in the color development step, known compounds are used, but aromatic primary amines are preferable, and 3-methyl-4- (N-ethyl-N- (β-hydroxyethylamino) aniline is particularly preferable. 4-Amino-3-methyl-N-ethyl-N- (β-methanesulfonamidoethyl) aniline and 4-amino-3-methyl-N-ethyl-N-methoxyethylaniline are preferred.
The color developing agent is usually used in a developer concentration of 1 × 10 ⁻² to 2 × 10 ⁻¹ mol / L, and from the viewpoint of processing speed, 1.5 × 10 ⁻² to 2 × 10 ^−1. A range of mol / L is preferred.
The color developer can be used in any pH range, but is preferably pH 9.5 to 13.0, more preferably pH 9.8 to 12.0, from the viewpoint of processing speed. . Since the above-mentioned antireflection layer is resistant to an alkaline solution, there is no problem even at high pH.
The processing temperature for color development is preferably 25 to 70 ° C. The higher the temperature, the shorter the treatment is possible and the better, but the treatment at 25 to 50 ° C. is preferred in view of the stability of the treatment liquid. The color development time is preferably 50 to 120 seconds. When the time is shorter than 50 seconds, the maximum density becomes unstable, and when the time is longer than 140 seconds, fog is likely to occur.
The replenishment amount of the color developer is preferably 0.5 L or less per 1 m ² of the photosensitive layer, more preferably 50 to 400 mL.

(Bleaching and fixing process)
The bleaching agent used in the bleach-fixing solution is not limited, but is preferably a metal complex salt of an organic acid. The complex salt is obtained by coordination of an organic acid such as polycarboxylic acid, aminopolycarboxylic acid or oxalic acid to a metal ion such as iron, cobalt or copper.
Examples of the silver halide fixing agent contained in the bleach-fixing solution include compounds that react with silver halide to form a water-soluble complex salt as used in normal fixing processing, such as thiosulfate, thiocyanate, and thiourea. , Thioether and the like are preferable.
The pH of the bleach-fixing solution is 4.0 or higher, but is generally used in the range of 4.0 to 9.5, preferably 4.5 to 8.5. Most preferably, it is in the range of 5.0 to 8.5. The processing temperature for bleach-fixing is 80 ° C. or lower, preferably 55 ° C. or lower. The treatment time is preferably 120 seconds or less.

(Washing process)
In the development processing, a water washing step is carried out following the color development step and the bleach-fixing step described above, and it is preferable to add a chelating agent having a chelate stabilizing action against iron ions to the water washing solution. For example, organic carboxylic acid chelating agents, organic or inorganic phosphoric acid chelating agents, polyhydroxy compounds and the like can be mentioned.
The washing solution may contain an antifungal agent, which can prevent sulfidation and improve the storage stability of the color developing layer. Examples of antifungal agents include sorbic acid, benzoic acid compounds, phenol compounds, thiazole compounds, isoxazole compounds, sulfamide compounds, pyronone compounds, and the like.
Ion exchange water treated with an ion exchange resin may be used for the washing solution, and the pH of the washing water is in the range of 5.5 to 10.0. As an applicable pH adjuster, generally known alkalis and acids are used. The water washing treatment temperature is preferably 15 to 60 ° C, and more preferably 20 to 45 ° C. The amount of the washing solution is preferably 0.1 to 50 times, more preferably 0.5 to 30 times the amount of the pre-bath (usually bleach-fixing solution or fixing solution) brought in per unit area of the photosensitive layer.

In the above-described coloring process, a process may be added within a range not impairing the effects of the present invention, or a substantially equivalent process may be replaced. For example, the bleach-fixing process may be separated into a bleaching process and a fixing process, or a bleaching process may be placed before the bleach-fixing process. As the processing step used in this embodiment, it is preferable to provide a bleach-fixing step immediately after the color development step.
In addition, as a developing processing apparatus for the photosensitive layer (color photosensitive material) used in the present embodiment, a known apparatus for developing a photograph can be used.

According to the embodiment as described above, the following effects can be obtained.
Since there is a photosensitive layer that can be colored by a developer on the substrate, and the developer can easily pass through a highly permeable antireflection layer containing porous porous silica and reach the photosensitive layer, It is possible to color the plastic spectacle lens by a simple method of developing by applying light.
If the photosensitive layer is made of a color photosensitive material, plastic eyeglass lenses colored in various colors can be easily provided. In other words, it is possible to easily obtain a target colored plastic spectacle lens simply by developing by applying light of a target color or its complementary color.
Since the composition for forming an antireflection layer according to this embodiment can be baked in a relatively short time, there is little possibility that the gelatin in the photosensitive layer is altered. In addition, since the antireflection layer is resistant to alkali, the degree of freedom in selecting a developing solution in the color development step is increased, and a desired color can be easily achieved.
In addition, because of the coloring of plastic spectacle lenses, there is little waste liquid and no burden on the environment because no dye is used and only a developer or a fixer is used.

The aspect described above shows one aspect of the present invention, and the present invention is not limited to the above-described embodiment, and is within the scope of achieving the object and effect of the present invention. Needless to say, modifications and improvements are included in the content of the present invention. Also, specific structure, shape and the like in the practice of the present invention, within the range that can achieve the objects and advantages of the present invention, the problem is not name the other structures and shapes and the like.
Further, the photosensitive material for forming the photosensitive layer is not a color photosensitive material that can be colored (colored) in an arbitrary color, but may be formulated such that only a specific color is developed. The photosensitive material may be a negative type as well as a reversal type, and these may be properly used.
Further, when exposing, an appropriate pattern may be generated without aiming at simple coloring.
In addition, the specific structure, shape, and the like in the implementation of the present invention may be other structures as long as the object of the present invention can be achieved.

Hereinafter, the present invention will be described more specifically based on examples.
(Example)
In this example, a plastic spectacle lens in which a photosensitive layer and an antireflection layer were formed on a substrate was manufactured and subjected to light exposure and development.
As the substrate, a substrate made of thiourethane plastic (manufactured by Seiko Epson Corporation; trade name Seiko Super Sovereign Fabric) and subjected to a hard coat treatment was used.

(Photosensitive layer forming process)
Preparation of a light-sensitive material-containing halogenated emulsion for forming a photosensitive layer was carried out in accordance with the method described in Example 1 of JP-A-7-301894.
Specifically, on the substrate, the first layer (red sensitive layer), the second layer (intermediate layer), the third layer (green sensitive layer), the fourth layer (intermediate layer) and the fifth layer (blue sensitive layer). ) A silver halide emulsion (coating solution) containing a photosensitive material for forming each of the above layers was prepared.
For the red photosensitive layer, a coating solution mainly comprising a red sensitive silver chlorobromide emulsion and a cyan coupler is prepared. For the green photosensitive layer, a green sensitive silver chlorobromide emulsion and a magenta coupler are mainly used. A coating solution was prepared, and for the blue-sensitive layer, a coating solution mainly comprising a blue-sensitive silver chlorobromide emulsion and a yellow coupler was prepared.
Next, after applying a predetermined amount of gelatin and a hardener on the substrate, the above-described silver halide emulsion for each layer was repeatedly coated and dried. Finally, a color photosensitive material as a photosensitive layer was formed on the substrate by these five layers.

(Antireflection layer (protective layer) formation process)
First, a composition for forming an antireflection layer was prepared as follows.
Add 5000 parts by weight of propylene glycol monomethyl ether and 100 parts by weight of γ-glycidoxypropyltrimethoxysilane to a stainless steel container, add 299 parts by weight of 0.01 mol / liter hydrochloric acid while stirring, and continue stirring all day and night. A silane hydrolyzate was obtained. In another container, 100 parts by weight of a silica-based fine particle sol having an internal cavity (manufactured by Catalyst Kasei Kogyo Co., Ltd.), 1 part by weight of a silicone surfactant (L-7001 by Nippon Unicar Co., Ltd.) and iron (III ) And 1 part by weight of acetylacetonate having a central metal atom was added and stirring was continued for a whole day and night, and then combined with the silane hydrolyzate and further stirred for a whole day and night. Thereafter, the mixture was filtered with a 3 μm filter to obtain a coating solution.
Next, the substrate (plastic eyeglass lens) on which the photosensitive layer has been formed in the above-described photosensitive layer forming step is immersed in a coating solution, and after 30 seconds, pulled up at a lifting speed of 10 cm / min, and further in an oven set at 120 ° C. An antireflection layer was formed by heating for 5 minutes. The thickness of this antireflection layer was 100 nm.
The above operation was performed in a dark room.

(Photosensitive process)
Three plastic spectacle lenses after the formation of the antireflection layer were prepared, and the photosensitive layer was exposed by irradiating red light, green light and blue light, respectively.

(Coloring process)
The plastic spectacle lens after exposure was developed and fixed according to the method described in Example 1 of JP-A-7-301894.
Specifically, the plastic spectacle lens after exposure was immersed in a developer, and the developer was permeated from the antireflection layer on the surface, and color development of the exposed photosensitive layer was performed. Thereafter, a predetermined fixing process was further performed.

(Comparative example)
In the comparative example, the antireflection layer was an inorganic antireflection layer containing an inorganic substance as a main component.
Other conditions are the same as those in the first embodiment.
(Antireflection layer (protective layer) formation process)
The plastic spectacle lens substrate on which the hard coat layer is formed in the hard coat layer forming step is put into a vapor deposition apparatus, heated to 85 ° C. while being evacuated, and subjected to ion gun treatment (carrier gas: oxygen, voltage: 400 eV, treatment time: 30). Second).
Next, after evacuation was continued to a vacuum degree of 5.0 × 10 ⁻⁵ mbar, a deposition raw material was deposited by an electron beam heating method, and SiO ₂ (0.25λ) / TiO ₂ (0.12λ ) / SiO ₂ (0.05λ) / TiO ₂ (0.25λ) / SiO ₂ (0.25λ) to form an inorganic antireflection layer. (Λ (design wavelength) = 550 nm)

(result)
In the examples, the three plastic spectacle lenses subjected to photosensitivity and development were vividly colored green, red and yellow, which are complementary colors of the irradiated light. Further, since the antireflection layer was baked in a short time, the gelatin of the photosensitive layer was not altered.
On the other hand, in the comparative example, the developer did not penetrate the antireflection layer, and the photosensitive layer could not be developed.

The present invention can be suitably used in the field of plastic lenses that may be colored, such as plastic eyeglass lenses.

Claims (6)

A plastic lens having a protective layer on a substrate,
Between the substrate and the protective layer, a photosensitive layer formed by applying a silver halide emulsifier and capable of color development with a developer,
The protective layer includes silica-based fine particles having internal cavities, and R ¹ R ² _n SiX ¹ _3-n (wherein R ¹ is an organic group having a polymerizable reactive group, and R ² has 1 to ² carbon atoms). 6 is a hydrocarbon group, X ¹ is a hydrolytic group, and n is 0 or 1.)
A plastic lens, wherein the developer is configured to be able to penetrate to the photosensitive layer. The plastic lens according to claim 1,
The plastic lens , wherein the protective layer further has antireflection characteristics. A method of manufacturing a plastic lens having a protective layer on a substrate,
A photosensitive layer forming step of forming a photosensitive layer capable of color development with a developer on the surface of the substrate by applying a silver halide emulsifier ;
A protective layer forming step of forming the protective layer on the photosensitive layer so that the developer can penetrate to the photosensitive layer ;
The protective layer includes silica-based fine particles having internal cavities, and R ¹ R ² _n SiX ¹ _3-n (wherein R ¹ is an organic group having a polymerizable reactive group, and R ² has 1 to ² carbon atoms). 6 is a hydrocarbon group, X ¹ is a hydrolyzable group, n is 0 or 1.) a method of manufacturing a plastic lens according to claim Rukoto such and an organic silicon compound represented by the. A method for producing a colored plastic lens having a protective layer on a substrate,
A photosensitive step of exposing the photosensitive layer by irradiating the plastic lens according to claim 1 or 2 with light;
A method for producing a colored plastic lens , comprising: a color developing step for coloring the photosensitive layer with the developer. Colored plastic lens characterized by being manufactured by the manufacturing method of the colored plastic lens according to claim 4. The colored plastic lens according to claim 5, wherein the colored plastic lens is a spectacle lens .