JP2013134345A - Manufacturing method of dyed optical lens - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for stably manufacturing a dyed optical lens for a long period of time, the lens having a silicone-based functional film on a surface of a plastic lens, suppressing an uneven dyed condition and having high scratch resistance.SOLUTION: The method for manufacturing a dyed optical lens comprises dying an optical lens having a silicone-based functional film on a surface of a plastic lens; and the method includes a step of dyeing the optical lens by immersing the optical lens in a water dispersion, which includes a dye insoluble or substantially insoluble with water dispersed therein, contains a buffer solution component and has a pH of 6.6 to 7.5.

Description

  The present invention relates to a method for producing a dyeing optical lens, and more particularly to a method for producing a plastic dyeing optical lens having a silicone functional film on the surface.

In recent years, plastic lens base materials have been mainly used as materials for optical lenses, particularly spectacle lenses, instead of inorganic glass base materials.
For dyeing optical lenses made of plastic lens substrates, that is, plastic lenses, water-based dyeing methods, solvent dyeing methods, high-temperature dyeing methods, gas phase dyeing methods, and printing methods have been proposed. An aqueous dyeing method in which a plastic lens is immersed in a dispersed aqueous dyeing bath is generally widely used.

  However, the conventional aqueous dye bath has a problem that the reproducibility of dyeing is poor due to poor stability over time. As a means for solving such a problem, Japanese Patent Application Laid-Open No. 2002-6271 (Patent Document 1) describes a colored plastic lens for dyeing a plastic lens by immersing it in a dyeing bath in which a disperse dye is dispersed and dissolved. A method of manufacturing a colored plastic lens using a dyeing bath containing a naphthalenesulfonic acid formaldehyde condensate salt salt as a dyeing bath is disclosed, and the pH of the dyeing bath is set to 2 to 6. It is described that the dyeing bath can be stabilized by adjusting to 5.

  Patent Document 1 also describes that an aqueous dispersion of a disperse dye usually contains an anionic surfactant and thus exhibits weak alkalinity at pH 7 to 9 ([0015]).

JP 2002-6271 A

In the embodiment specifically disclosed in Patent Document 1, a colored plastic lens is manufactured using a plastic lens that does not have a silicone functional film.
However, when the plastic lens substrate has a silicone-based functional film such as a hard coat film, when dyeing is performed by the method described in Patent Document 1, uneven dyeing occurs in the obtained dyeing optical lens. It has been found that problems such as inferior property and lack of long-term stability of the dyeing solution occur.

  In order to solve the above-described problems, the present invention stably produces a dyeing optical lens having a silicone functional film on the surface of a plastic lens, suppressing dyeing unevenness, and having high scratch resistance. It aims to provide a method.

  As a result of intensive studies, the present inventors have found that the above problem can be solved by using an aqueous dye bath containing a buffer component and having a pH of 6.6 to 7.5, and completed the present invention. .

  The method for producing a dyeing optical lens according to the present invention is a method for producing a dyeing optical lens by dyeing an optical lens having a silicone functional film on the surface of a plastic lens, in which a water-insoluble or sparingly soluble dye is dispersed. And a step of immersing and dyeing the optical lens in an aqueous dispersion containing a buffer component and having a pH of 6.6 to 7.5.

Preferably, the buffer component includes hydrogen phosphate and dihydrogen phosphate.
Examples of the dye include at least one dye selected from azo dyes, anthraquinone dyes, quinophthalone dyes, and nitrodiphenylamine dyes.

The immersion of the optical lens in the aqueous dispersion is preferably performed at a temperature of 80 to 99 ° C. for 30 seconds to 120 minutes.
Examples of the silicone functional film include a hard coat film formed from a coating composition containing the following components (1) and (2);
Component (1): oxide fine particles of at least one metal element selected from titanium, iron, zinc, tungsten, tin, tantalum, zirconium, antimony, niobium, indium, cerium, silicon, aluminum, yttrium, lead and molybdenum And / or composite oxide fine particles,
Component (2): From the group consisting of an organosilicon compound represented by the general formula R ¹ _a R ² _b Si (OR ³ ) _{4- (a + b)} , a hydrolyzate thereof, and a partial condensate of the hydrolyzate At least one silicon-containing compound selected (wherein R ¹ is an alkyl group having 1 to 6 carbon atoms, an organic group having 2 to 8 carbon atoms containing a vinyl group, or an epoxy group containing 2 to 8 carbon atoms) An organic group, an organic group having 4 to 8 carbon atoms containing a methacryloxy group, an organic group having 1 to 5 carbon atoms containing a mercapto group, or an organic group having 1 to 5 carbon atoms containing an amino group, and R ² is An alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 to 3 carbon atoms, a cycloalkyl group having 3 carbon atoms, or a halogenated alkyl group having 1 to ³ carbon atoms, and R ³ is an alkyl group having 1 to ³ carbon atoms. An alkenyl group having 2 to 3 carbon atoms or a cycloalkyl group having 3 carbon atoms. , A is an integer of 0 or 1, b is 0, 1 or 2 integer.).

Examples of the silicone-based functional film include a laminated film obtained by laminating the hard coat film and an antireflection film formed from a coating composition containing the following components (3) and (4) in order from the plastic lens side. Be
Component (3): hollow silica fine particles having an average particle diameter of 40 to 100 nm,
Component (4): selected from the group consisting of at least one organosilicon compound selected from the group consisting of the following components (A), (B) and (C), a hydrolyzate thereof and a partial condensate of the hydrolyzate At least one silicon-containing compound:
Component (A): Organosilicon compound represented by the general formula R ¹ R ² _a Si (OR ³ ) _3-a (wherein R ¹ is a carbon containing a hydrocarbon group having 1 to 6 carbon atoms and a vinyl group. An organic group having 2 to 8 carbon atoms, an organic group having 2 to 8 carbon atoms containing an epoxy group, an organic group having 4 to 8 carbon atoms containing a methacryloxy group, an organic group having 1 to 5 carbon atoms containing a mercapto group, or an organic group of 1 to 5 carbon atoms containing an amino group, R ² is a hydrocarbon group having 1 to 4 carbon atoms, R ³ is 1 to 8 carbon atoms hydrocarbon group, having 2 to 8 carbon atoms An alkoxyalkyl group or an acyl group having 2 to 8 carbon atoms, a represents 0 or 1);
Component (B): an organic silicon compound represented by the general formula [(R ⁴ ) _b Si (OR ⁵ ) _{3 -b} ] ₂ R ⁶ (wherein R ⁴ is an alkyl group having 1 to 5 carbon atoms, R ⁵ is an alkyl group having 1 to 4 carbon atoms or an acyl group having 2 to 4 carbon atoms, R ⁶ is a methylene group or an alkylene group having 2 to 20 carbon atoms, and b represents 0 or 1.);
Component (C): an organosilicon compound represented by the general formula Si (OR ⁷ ) ₄ (wherein R ⁷ is a hydrocarbon group having 1 to 8 carbon atoms, an alkoxyalkyl group having 2 to 8 carbon atoms, or 2 carbon atoms) ˜8 acyl groups).

The silicone-based functional film is formed in order from the refractive index of the hard coat film formed from the hard coat film and a coating composition containing the following components (5) and (4) in order from the plastic lens side. A laminated film formed by laminating a mirror coat film having a refractive index of 02 or higher;
Component (5): oxide fine particles and / or composites of at least one metal element selected from the group consisting of titanium, iron, zinc, tin, tungsten, tantalum, zirconium, antimony, niobium, indium, cerium, silicon and aluminum Oxide fine particle Component (4): Consists of at least one organic silicon compound selected from the group consisting of the following components (A), (B) and (C), a hydrolyzate thereof, and a partial condensate of the hydrolyzate. At least one silicon-containing compound selected from the group:
Component (A): Organosilicon compound represented by the general formula R ¹ R ² _a Si (OR ³ ) _3-a (wherein R ¹ is a carbon containing a hydrocarbon group having 1 to 6 carbon atoms and a vinyl group. An organic group having 2 to 8 carbon atoms, an organic group having 2 to 8 carbon atoms containing an epoxy group, an organic group having 4 to 8 carbon atoms containing a methacryloxy group, an organic group having 1 to 5 carbon atoms containing a mercapto group, or an organic group of 1 to 5 carbon atoms containing an amino group, R ² is a hydrocarbon group having 1 to 4 carbon atoms, R ³ is 1 to 8 carbon atoms hydrocarbon group, having 2 to 8 carbon atoms An alkoxyalkyl group or an acyl group having 2 to 8 carbon atoms, a represents 0 or 1);
Component (B): an organic silicon compound represented by the general formula [(R ⁴ ) _b Si (OR ⁵ ) _{3 -b} ] ₂ R ⁶ (wherein R ⁴ is an alkyl group having 1 to 5 carbon atoms, R ⁵ is an alkyl group having 1 to 4 carbon atoms or an acyl group having 2 to 4 carbon atoms, R ⁶ is a methylene group or an alkylene group having 2 to 20 carbon atoms, and b represents 0 or 1.);
Component (C): an organosilicon compound represented by the general formula Si (OR ⁷ ) ₄ (wherein R ⁷ is a hydrocarbon group having 1 to 8 carbon atoms, an alkoxyalkyl group having 2 to 8 carbon atoms, or 2 carbon atoms) ˜8 acyl groups).

  The optical lens may have a primer film between the plastic lens and the hard coat film.

  According to the method for manufacturing a dyeing optical lens according to the present invention, a dyeing optical lens with suppressed dyeing unevenness and high scratch resistance can be stably manufactured over a long period of time.

Hereinafter, the method for manufacturing a dyeing optical lens and the dyeing optical lens according to the present invention will be described in more detail.
[Method for producing dye optical lens]
1. Optical Lens In the manufacturing method according to the present invention, an optical lens having a silicone functional film on the surface of a plastic lens is dyed.

<Plastic lens>
A conventionally known plastic lens can be used as the plastic lens. Examples of the material include aliphatic allyl resins, acrylic resins, aromatic allyl resins, polycarbonate resins, polythiourethane resins, and polythioepoxy resins.
Refractive index of the plastic lens (n _e) is usually 1.49 to 1.76, preferably 1.49 to 1.67.

<Silicone-based functional membrane>
The optical lens has a silicone functional film on the surface of the plastic lens.
As the silicone-based functional film, a hard coat film, a laminated film in which the hard coat film and the antireflection film are laminated in order from the plastic lens side, and a hard coat film and a mirror coat film are laminated in order from the plastic lens side. The laminated film etc. which are formed are mentioned.

The silicone functional film may be formed directly on the surface of the plastic lens, or may be formed via another film (layer) such as a primer film.
Further, a top coat layer may be provided on the surface of the silicone functional film opposite to the plastic lens side.

(Hard coat film)
As the hard coat film, a conventionally known hard coat film including metal oxide fine particles and a silicone-based matrix provided on the surface of a plastic lens can be employed. Examples thereof include the following components (1) and ( 2) and a hard coat film formed from a coating composition (hereinafter also referred to as “coating composition (H)”).

  Component (1): at least one metal element selected from titanium, iron, zinc, tungsten, tin, tantalum, zirconium, antimony, niobium, indium, cerium, silicon, aluminum, yttrium, lead and molybdenum (here, Then, antimony and silicon are also classified as metal elements.) Oxide fine particles and / or composite oxide fine particles.

Component (2): an organosilicon compound represented by the general formula R ¹ _a R ² _b Si (OR ³ ) _{4- (a + b)} , a hydrolyzate thereof (including a partial hydrolyzate), and the hydrolysis At least one silicon-containing compound selected from the group consisting of partial condensates of the product (wherein R ¹ is an alkyl group having 1 to 6 carbon atoms, an organic group having 2 to 8 carbon atoms containing a vinyl group, an epoxy group) C 2-8 organic group containing C 1, C 4 C 8 organic group containing methacryloxy group, C 1 C 5 organic group containing mercapto group or C 1 C containing amino group R ² is an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 to 3 carbon atoms (eg, allyl group), a cycloalkyl group having 3 carbon atoms, or an alkyl halide having 1 to 3 carbon atoms. a group, R ³ is an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 to 3 carbon atoms The other is cycloalkyl group having 3 carbon atoms. Further, a is an integer of 0 or 1, b is an integer of 0, 1 or 2.).

  The component (1) may have a core-shell structure in which the surface of the core particle made of the metal element oxide or composite oxide is coated with the metal element composite oxide or the like. Examples of such metal oxide fine particles include core-shell composite oxide fine particles formed by coating the surface of a composite oxide fine particle containing titanium, tin and silicon with a composite oxide containing zirconium and silicon.

  The said component (1) can be manufactured by a well-known method, for example, the method described in the patent 2783417 gazette, the patent 3031571 gazette, the patent 3203142 gazette, etc.

  The component (1) preferably has a particle surface treated with an organosilicon compound or amines (surface treatment). This surface treatment can be performed by a known method, for example, a method described in JP-A-2009-258400 ([0018] to [0025]).

  As the organosilicon compound used for this surface treatment (hereinafter also referred to as “organosilicon compound (1)”), a conventionally known silane coupling agent having a hydrolyzable group can be used. The component (A) and the component (C) that may be used as 4) are preferred.

  This surface treatment may be performed before hydrolyzing the hydrolyzable group of the organosilicon compound (1), or may be performed after partial hydrolysis or hydrolysis. Further, at the stage where this surface treatment operation is completed, it is preferable that all of the hydrolyzable groups are in a state of reacting with —OH groups present on the surface of the metal oxide fine particles. The part may remain unreacted. When performing this surface treatment, it is desirable to use metal oxide fine particles having —OH groups on the surface as the metal oxide fine particles.

  Examples of amine compounds used for the surface treatment of the oxide fine particles and / or composite oxide fine particles include ammonia; alkylamines such as ethylamine, triethylamine, isopropylamine, and n-propylamine; aralkylamines such as benzylamine. Alicyclic amines such as piperidine; alkanolamines such as monoethanolamine and triethanolamine; quaternary ammonium salts such as tetramethylammonium salt and tetramethylammonium hydroxide or quaternary ammonium hydroxides. These amine compounds may be used alone or in combination of two or more.

The average particle diameter of the component (1), that is, the oxide fine particles and / or the composite oxide fine particles is preferably in the range of 2 to 100 nm, more preferably 3 to 80 nm. The value of the average particle diameter is a value measured by the laser Doppler method, more specifically, adjusted to pH 9.0 by adding ammonia-containing distilled water to the water sol of the oxide particles and / or composite oxide fine particles. Then, it is a value when this is put into a quartz cell having a length of 1 cm, a width of 1 cm, and a height of 5 cm and measured using NICOMP ^™ 380 manufactured by Particle Sizing Systems Inc. The same applies to the average particle sizes of components (3) and (5) described later.

When the average particle diameter is within the above range, a dyeing optical lens having excellent scratch resistance can be produced.
As an example of the organosilicon compound represented by the general formula R ¹ _a R ² _b Si (OR ³ ) _{4- (a + b)} in the component (2) (hereinafter also referred to as “organosilicon compound (2)”). Is a specific example of the component (A) described later. Among these, methyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and β- (3,4-epoxycyclohexyl) -ethyltrimethoxysilane are preferable. These compounds may be used alone or in combination of two or more.

  When preparing the coating composition (H), the organosilicon compound (2) is preferably partially hydrolyzed or hydrolyzed in the absence of a solvent or in a polar organic solvent such as alcohol in the presence of an acid and water. Or after further partially condensing the hydrolyzate (including the partial hydrolyzate) thus obtained, the mixture is mixed with the component (1). The organosilicon compound (2) is mixed with the component (1) or a dispersion thereof (dispersed sol or colloidal solution of the component (1)) and then partially hydrolyzed or hydrolyzed or partially condensed. May be.

The weight W ₁ of the component (1) contained in the coating composition (H) and the weight converted to SiO _{2 of} the component (2) (that is, the weight when silicon contained in the component (2) is converted to SiO _2. ) The ratio to W ₂ (W ₁ : W ₂ ) is preferably 10:90 to 70:30, more preferably 20:80 to 60:40. When the weight ratio is in this range, a hard coat film having excellent scratch resistance and high adhesion to a plastic lens is formed.

  In addition to the components (1) and (2), the coating composition (H) includes a curing catalyst, a surfactant (which may be included in a conventional coating composition for forming a silicone-based hard coat film). Leveling agents), ultraviolet absorbers, solvents and the like may be further included.

  Examples of the curing catalyst include trimellitic acid, trimellitic anhydride, itaconic acid, pyromellitic acid, pyromellitic anhydride and other organic carboxylic acids, nitrogen-containing organic compounds such as methylimidazole and dicyandiamide, metal alkoxides such as titanium alkoxide and zircoalkoxide, acetylacetone Examples thereof include metal complexes such as aluminum and acetylacetone iron, and alkali metal organic carboxylates such as sodium acetate and potassium acetate.

  Examples of the surfactant as a leveling agent include silicone surfactants such as polyoxyalkylene dimethylpolysiloxane, fluorine surfactants such as perfluoroalkylcarboxylates, and perfluoroalkylethylene oxide adducts. Of these, silicone surfactants are preferred.

Examples of the ultraviolet absorber include benzophenone ultraviolet absorbers, benzotriazole ultraviolet absorbers, hindered amine light stabilizers, and the like.
Examples of the solvent include water such as distilled water and pure water, alcohols such as methanol, ethanol and propanol, ethers such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether and propylene glycol monoethyl ether, methyl ethyl ketone, diacetone alcohol and the like. Ketones, esters such as ethyl acetate and butyl acetate, and cellsolves such as ethyl cellosolve and butyl cellosolve. Among these, lower alcohols such as methanol, water, and propylene glycol monomethyl ether are preferable. These solvents may be used alone or in combination of two or more.

  The hard coat film can be formed by forming a hard coat film-forming coating (for example, the coating composition (H)) on the surface of a plastic lens and curing (thermosetting) it. Conventionally known techniques can be applied as a coating method and a coating film curing method. You may perform the thermosetting of a coating film, for example at 80-130 degreeC over 0.5 to 5 hours.

  The thickness of the hard coat film is preferably 1.0 to 6.0 μm, more preferably 1.5 to 4.0 μm. A hard coat film having a thickness in this range is excellent in scratch resistance.

(Antireflection film)
As the antireflection film, a conventionally known antireflection film including inorganic oxide fine particles and a silicone-based matrix provided on the surface of a plastic lens can be employed, and includes, for example, the following components (3) and (4): Examples thereof include an antireflection film formed from a coating composition (hereinafter also referred to as “coating composition (AR)”).

Component (3): Hollow silica fine particles having an average particle size of 40 to 100 nm Component (4): At least one organosilicon compound selected from the group consisting of the following components (A), (B) and (C), and hydrolysis thereof At least one silicon-containing compound selected from the group consisting of products (including partial hydrolysates) and partial condensates of the hydrolysates:
Component (A): Organosilicon compound represented by the general formula R ¹ R ² _a Si (OR ³ ) _3-a (wherein R ¹ is a carbon containing a hydrocarbon group having 1 to 6 carbon atoms and a vinyl group. An organic group having 2 to 8 carbon atoms, an organic group having 2 to 8 carbon atoms containing an epoxy group, an organic group having 4 to 8 carbon atoms containing a methacryloxy group, an organic group having 1 to 5 carbon atoms containing a mercapto group, or an organic group of 1 to 5 carbon atoms containing an amino group, R ² is a hydrocarbon group having 1 to 4 carbon atoms, R ³ is 1 to 8 carbon atoms hydrocarbon group, having 2 to 8 carbon atoms An alkoxyalkyl group or an acyl group having 2 to 8 carbon atoms, a represents 0 or 1);
Component (B): an organic silicon compound represented by the general formula [(R ⁴ ) _b Si (OR ⁵ ) _{3 -b} ] ₂ R ⁶ (wherein R ⁴ is an alkyl group having 1 to 5 carbon atoms, R ⁵ is an alkyl group having 1 to 4 carbon atoms or an acyl group having 2 to 4 carbon atoms, R ⁶ is a methylene group or an alkylene group having 2 to 20 carbon atoms, and b represents 0 or 1.);
Component (C): an organosilicon compound represented by the general formula Si (OR ⁷ ) ₄ (wherein R ⁷ is a hydrocarbon group having 1 to 8 carbon atoms, an alkoxyalkyl group having 2 to 8 carbon atoms, or 2 carbon atoms) ˜8 acyl groups).

  The hollow silica fine particles as the component (3) have an average particle size of 40 to 100 nm, preferably 50 to 90 nm. When the average particle diameter is less than 40 nm, it may be difficult to obtain an antireflection film having a uniform film thickness depending on the coating method or processing method employed. The design of the prevention film may be difficult.

  The hollow silica fine particles are fine particles having a cavity inside an outer shell (shell part) made of a silica-based inorganic oxide, and the “cavity” is a spherical shape or irregular shape (non-spherical shape) formed inside the particle. The state in which a gaseous substance such as air is contained in the void portion.

  The refractive index of the hollow silica-based fine particles varies depending on the porosity (ratio occupied by cavities in the particles), but is generally in the range of 1.15 to 1.35, and the component ( When using a high refractive index as 1), it is preferable to use a low refractive index as the hollow silica-based fine particles.

  In addition, the outer shell (shell part) made of the silica-based inorganic oxide is composed of a silica-based composite oxide containing silicon and an element other than silicon, such as —O—Si—O—Al—O—Si—O—. You may be comprised with the complex oxide which has a structure. Here, examples of the element other than silicon include aluminum, boron, titanium, zirconium, tin, cerium, phosphorus, antimony, molybdenum, zinc, tungsten, and the like. From the viewpoint of forming an antireflection film, it is preferable to select from those that do not increase the refractive index of the hollow silica-based fine particles or give photocatalytic activity.

  Further, the hollow silica-based fine particles may be those in which a coating layer made of a silica component is provided on the surface thereof using an organosilicon compound having a hydrolyzing group or a silicic acid solution. The organosilicon compound is not particularly limited, and examples thereof include alkoxysilanes such as tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane.

  The hollow silica-based fine particles are described in conventionally known production methods such as JP 2001-233611 A, JP 2004-203683 A, JP 2006-21938 A, and International Publication WO 2006/9132. It can be manufactured based on the method. Furthermore, the hollow organic / inorganic hybrid fine particles described in JP-A-2009-242475 are produced, and the surface is obtained by a surface treatment (silica-based component coating) with a silane coupling agent or the like. Also good.

  Examples of the component (A) in the component (4) include methyltrimethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, α-glycidoxymethyltrimethoxysilane, α-glycidoxy Ethyltrimethoxysilane, β-glycidoxyethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxy Propylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) -ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) -ethyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyl Triethoxysilane, N-β ( Minoechiru)-.gamma.-aminopropylmethyldi methoxide xylan, N-beta (aminoethyl)-.gamma.-aminopropyl methyl diethyl Toki xylan and the like. Among these, methyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and β- (3,4-epoxycyclohexyl) -ethyltrimethoxysilane are preferable. These compounds may be used alone or in combination of two or more.

  Examples of the component (B) include methylene bismethyldimethoxysilane, ethylene bisethyldimethoxysilane, propylene bisethyldimethoxysilane, butylene bismethyldiethoxysilane, methylene bistriethoxysilane, ethylene bistrimethoxysilane, propylene bistrimethoxysilane, Examples include butylene bistrimethoxysilane and hexylene bistrimethoxysilane. Among these, hexylene bistrimethoxysilane etc. are mentioned. Among these, butylene bistrimethoxysilane and hexylene bistrimethoxysilane are preferable. These compounds may be used alone or in combination of two or more.

  Examples of the component (C) include tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane and the like. Among these, tetramethoxysilane and tetraethoxysilane are preferable. These compounds may be used alone or in combination of two or more.

  When preparing the coating composition (AR), preferably, the organosilicon compound selected from the components (A), (B) and (C) is used without a solvent or in a polar organic solvent such as alcohol. After partial hydrolysis or hydrolysis in the presence of acid and water, or after further partial condensation of the hydrolyzate thus obtained (including partial hydrolyzate), mixed with the component (3) To do. In addition, after mixing the organosilicon compound selected from the components (A), (B) and (C) with the component (3) or a dispersion thereof (dispersed sol or colloidal liquid of the component (3), etc.) , Partial hydrolysis or hydrolysis, or partial condensation.

The ratio (W ₄ : W ₄ ) between the weight W ₃ of the component (3) contained in the coating composition (AR) and the SiO ₂ equivalent weight W ₄ of the component ( ₄ ) is preferably 10:90 to It is 70:30, More preferably, it is 20: 80-60: 40. When the weight ratio is within this range, an antireflection film having a low refractive index, excellent scratch resistance, and high adhesion to the hard coat film is formed.

  In addition to the components (3) and (4), the coating composition (AR) is a curing catalyst that may be included in a conventional coating composition for forming a silicone-based antireflection film or hard coat film, Components such as surfactants (leveling agents), ultraviolet absorbers, solvents, and the like, specifically, components similar to those mentioned in the description of the coating composition (H) described above may be included. .

  The antireflection film is formed by forming a coating film of an antireflection film (for example, the coating composition (AR)) on the surface of the hard coat film and curing (thermosetting) the coating film. it can. Conventionally known techniques can be applied as a coating method and a curing method of the paint. You may perform the thermosetting of a coating film, for example at 80-130 degreeC over 0.5 to 3 hours.

  In addition, the coating film for forming the antireflection film is formed on the surface of the coating film for forming the hard coat film, which is hardened (precured) to the extent that the paint for forming the hard coat layer is not completely sticky, These two coating films may be heated and cured together to form a hard coat film and an antireflection film.

  The thickness of the cured coating film thus obtained, that is, the antireflection film, is preferably in the range of 80 to 130 nm, more preferably 90 to 120 nm. An antireflection film having a thickness in this range is excellent in scratch resistance and can reduce surface reflection.

(Mirror coat film)
As the mirror coat film, a conventionally known mirror coat film including metal oxide fine particles and a silicone matrix provided on the surface of a plastic lens can be employed. Examples thereof include the following component (5) and the above-described component. A mirror coat film formed from a coating composition containing the component (4) (hereinafter also referred to as “coating composition (M)”) and having a refractive index higher by 0.02 or more than the refractive index of the hard coat film. Can be mentioned.

  Component (5): oxide fine particles and / or composites of at least one metal element selected from the group consisting of titanium, iron, zinc, tin, tungsten, tantalum, zirconium, antimony, niobium, indium, cerium, silicon and aluminum Fine oxide particles (in this case, antimony and silicon are also classified as metal elements).

The details of the component (5) are as described in the description of the component (1) except that the choices of metal elements are different.
Further, the average particle size of the component (5), that is, the oxide fine particles and / or the composite oxide fine particles is preferably in the range of 2 to 100 nm, more preferably 3 to 80 nm, similarly to the component (1). .

As the component (5), fine particles having a refractive index higher than that of the component (1) used in the hard coat film are desirable.
The details of the component (4) are as described in the description of the antireflection film.

  When preparing the coating composition (M), the organosilicon compound selected from the components (A), (B) and (C) used for the component (4) is preferably used in the absence of a solvent or alcohol. After partial hydrolysis or hydrolysis in the presence of acid and water in a polar organic solvent such as, or after further partial condensation of the hydrolyzate thus obtained (including partial hydrolyzate) , Mixed with the component (5). Also, after mixing the organosilicon compound selected from the components (A), (B) and (C) with the component (5) or a dispersion thereof (dispersed sol or colloidal liquid of the component (5), etc.) , Partial hydrolysis or hydrolysis, or partial condensation.

The ratio (W ₅ : W ₄ ) between the weight W ₅ of the component (5) contained in the coating composition (M) and the SiO ₂ equivalent weight W ₄ of the component ( ₄ ) is preferably 10:90 to 70:30, more preferably 15:85 to 60:40. When the weight ratio is within this range, a mirror coat film having a high refractive index, excellent scratch resistance, and high adhesion to the hard coat film is formed.

  In addition to the components (5) and (4), the coating composition (M) includes a curing catalyst that may be included in a conventional coating composition for forming a silicone-based antireflection film or hard coat film, Components such as surfactants (leveling agents), ultraviolet absorbers, solvents, and the like, specifically, components similar to those mentioned in the description of the coating composition (H) described above may be included. .

  The mirror coat film is formed by forming a coating film for forming a mirror coat film (for example, the coating composition (M)) on the surface of the hard coat film, and curing (thermosetting) it. it can. Conventionally known techniques can be applied as a coating method and a curing method of the paint. You may perform the thermosetting of a coating film, for example at 80-130 degreeC over 0.5 to 3 hours.

  In addition, the coating film for forming the mirror coat film is formed on the surface of the coating film for forming the hard coat film which is hardened (preliminarily cured) to the extent that the paint for forming the hard coat layer is not completely sticky, These two coating films may be heated and cured together to form a hard coat film and a mirror coat film.

  The film thickness of the cured coating film thus obtained, that is, the film thickness of the mirror coat film (particularly the film thickness at the center of the optical lens) is preferably in the range of 150 to 550 nm, more preferably 200 to 500 nm. A mirror coat film having a thickness in this range is excellent in scratch resistance and can realize a desired constant color (reflective color).

The optical film thickness of the mirror coat film is appropriately set according to the desired color (that is, the reflection color of the mirror coat layer).
The refractive index (n _e ) of the mirror coat film is 0.02 or more, preferably 0.03 or more higher than the refractive index of the hard coat film in order to function as a mirror. Such a refractive index relationship can be achieved by appropriately adjusting the type, combination, amount, and the like of the component (1) and the component (5).

<Other layers>
The optical lens may have a primer film for imparting impact resistance to the optical lens between the plastic lens and the silicone functional film.

As the primer film, a conventionally known primer film that may be provided between a plastic lens and a silicone-based hard coat film can be employed.
Examples of the coating composition for forming the primer film (hereinafter also referred to as “coating composition (P)”) include a thermosetting polyurethane resin formed from a block type polyisocyanate and a polyol, and an aqueous emulsion type polyurethane. Examples thereof include compositions containing a resin, an acrylic resin, an epoxy resin, a melamine resin, and the like.

  The coating composition (P) may contain fine metal oxide particles (the metal oxide may be a metal double oxide) in order to adjust the refractive index of the primer film. Examples of the metal oxide fine particles include the component (1) and the component (5).

  Furthermore, the surface of the silicone functional film (the surface opposite to the plastic lens side) may be treated with a fluorosilane compound. The fluorosilane compound is not particularly limited as long as it imparts lubricity to the surface of the optical lens, and is a compound represented by the following general formula or “OPTOOL DSX” manufactured by Daikin Industries, Ltd. And the like are preferable.

_{F 3 C- (CF 2) C} - (R 8) -Si (OR 9) 3
(Wherein R ⁸ is an alkylene group having 1 to 4 carbon atoms, and R ⁹ is a hydrocarbon group having 1 to 8 carbon atoms, an alkoxyalkyl group having 2 to 8 carbon atoms, or an acyl group having 2 to 8 carbon atoms. And c represents an integer of 1 to 10.)

2. Dyeing step In the production method of the present invention, dyeing is performed by immersing the optical lens in an aqueous dispersion in which a dye that is insoluble or hardly soluble in water is dispersed and that includes a buffer component and has a pH of 6.6 to 7.5. The process (dyeing process) to do.

  The temperature of the aqueous dispersion during this immersion is preferably 80 to 99 ° C, more preferably 90 to 95 ° C. Moreover, what is necessary is just to set immersion time suitably according to the density | concentration of the dye in an aqueous dispersion, the desired color tone of a dyeing optical lens, etc., for example, 30 seconds-120 minutes may be sufficient.

The optical lens after the dyeing process may be subjected to a washing process, a drying process, and the like as in the prior art.
The degree of dyeing of the optical lens may be adjusted by subjecting the optical lens taken out of the aqueous solution to the dyeing process again.

<Water dispersion>
In this aqueous dispersion, a dye that is insoluble or hardly soluble in water is dispersed in water, and a buffer component is further added to adjust the pH to 6.6 to 7.5, more preferably 6.8 to 7. It can be prepared by adjusting to 2. In the preparation of the aqueous dispersion, the temperature of water is preferably 80 to 99 ° C.

(dye)
As the dye, a water-insoluble or sparingly soluble dye (dispersed dye) used in a conventional water-based dye bath for plastic lenses can be used. Specific examples include azo dyes, anthraquinone dyes, quinophthalone dyes, nitrodiphenylamine dyes, and commercially available products such as “Sumikaron” manufactured by Sumitomo Chemical Co., Ltd., Dystar Japan ( "Diaoelliton", "Dianix", "Samaron" manufactured by Nihon Kayaku Co., Ltd .; "Kayalon Polyester" manufactured by Nippon Kayaku; manufactured by Mitsui BASF Dye Co., Ltd. "Miketon Polyester".
The amount of the dye is preferably 1 to 10 parts by weight, more preferably 3 to 7 parts by weight with respect to 1000 parts by weight of water used in the aqueous dispersion.

(Buffer component)
The buffer solution component is a component other than the solvent (usually water) contained in the buffer solution (solution having a buffering action against the hydrogen ion concentration). In the present invention, the aqueous dispersion may be prepared by mixing each buffer solution component with other components, and a previously prepared buffer solution (that is, a solution containing the buffer solution component and the solvent) may be mixed with another buffer solution. The aqueous dispersion may be prepared by mixing with components.

The buffer component is not particularly limited as long as the pH of the aqueous dispersion can be adjusted to 6.6 to 7.5, and since it is highly safe, hydrogen phosphate (for example, dihydrogen phosphate) A combination of sodium, dipotassium hydrogen phosphate) and dihydrogen phosphate (for example, sodium dihydrogen phosphate, potassium dihydrogen phosphate) is preferred. As the hydrogen phosphate, a hydrogen phosphate containing a hydrate (H ₂ O), for example, disodium hydrogen phosphate dihydrate or sodium dihydrogen phosphate monohydrate is used. You can also. However, the mass ratio shown below needs to be calculated based on the value excluding the mass of this hydrate.

When disodium hydrogen phosphate and potassium dihydrogen phosphate are used, the mass ratio between the two is preferably disodium hydrogen phosphate: potassium dihydrogen phosphate = 3: 7 to 8: 2. When the weight ratio is within this range, an optical lens in which a change in color quality is suppressed can be manufactured.
The total amount of the buffer component is preferably 0.1 to 3 parts by weight, more preferably 0.5 to 2 parts by weight with respect to 1000 parts by weight of water used in the aqueous dispersion.

(Other additives)
The aqueous dispersion contains, in addition to the dye, buffer component and water, components contained in a conventional aqueous dye solution for plastic lenses, for example, a surfactant for dispersing the dye, a dispersion stabilizer, and the like. You may go out.

  Examples of the surfactant include hydrocarbon surfactants, and specifically, anionic interfaces such as alkylbenzene sulfonate, alkylnaphthalene sulfonate, alkyl sulfosuccinate, alkyl sulfate, and alkyl phosphate. Activators and nonionic surfactants such as polyoxyethyl alkyl ethers, alkyl amine ethers, polyoxyalkylene sorbitan fatty acid esters, and the like.

When the surfactant is used, the amount thereof is preferably 0.5 to 2 parts by weight with respect to 1000 parts by weight of water used in the aqueous dispersion.
Examples of the dispersion stabilizer include naphthalene sulfonic acid formaldehyde condensate salt. When naphthalene sulfonic acid formaldehyde condensate salt is used as the dispersion stabilizer, the amount is preferably 1 to 100 parts by weight, more preferably 3 to 50 parts by weight with respect to 1000 parts by weight of water used in the aqueous dispersion. Part.

[Dyeing optical lens]
The dyeing optical lens according to the present invention is manufactured by the above-described method for manufacturing a dyeing optical lens according to the present invention, and uneven dyeing is suppressed and scratch resistance is high.

Hereinafter, the present invention will be described more specifically based on examples and the like. However, the present invention is not limited to the scope described in the examples.
Preparation of coating composition for forming hard coat film [Preparation Example 1]
45 g of γ-glycidoxypropyltrimethoxysilane (Monthivetive Performance Materials Japan GK “TSL8350”) and γ-glycidoxypropylmethyldimethoxysilane (Montmentive Performance Materials Japan GK) 70 g of “TSL8355”) was mixed with 300 g of methanol (manufactured by China Essential Oil Co., Ltd.), and 50 g of 0.01N hydrochloric acid aqueous solution was dropped into this solution while stirring. The solution thus obtained was stirred overnight at room temperature to hydrolyze the silane compound to obtain a mixed solution.

  Next, 150 g of water-dispersed colloidal silica (“Cataloid SN” solid content concentration 20%, manufactured by JGC Catalysts & Chemicals Co., Ltd.) 150 g, tris (2,4-pentanedionato) iron (III) (Tokyo Chemical Industry ( 2.0 g, pyromellitic anhydride (manufactured by Kishida Chemical Co., Ltd.) 9.0 g, and 0.5 g of a silicone surfactant (“L-7001” manufactured by Toray Dow Corning Co., Ltd.) as a leveling agent. In addition, these were stirred overnight at room temperature to prepare a coating composition for forming a hard coat film (hereinafter referred to as “hard coat paint H1”).

[Preparation Example 2]
65 g of γ-glycidoxypropyltrimethoxysilane (manufactured by Monmentive Performance Materials Japan GK “TSL8350”) and γ-glycidoxypropylmethyldimethoxysilane (manufactured by Monmentive Performance Materials Japan GK) “TSL8355”) (65 g) was mixed with 300 g of methanol (manufactured by China Essential Oil Co., Ltd.), and further 30 g of 0.01N hydrochloric acid aqueous solution was added dropwise with stirring. The solution thus obtained was stirred overnight at room temperature to hydrolyze the silane compound to obtain a mixed solution.

  Next, 190 g of methanol dispersion “OPTRAIK 1120Z (S-95 / A8)” (manufactured by JGC Catalysts & Chemicals Co., Ltd.), pyromellitic anhydride (Kishida Chemical) 10 g, 1-methylimidazole (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), and 1.0 g of a silicone surfactant (“L-7604” manufactured by Toray Dow Corning Co., Ltd.) as a leveling agent These were stirred at room temperature all day and night to prepare a coating composition for forming a hard coat film (hereinafter referred to as “hard coat paint H2”).

Preparation of coating for forming antireflection film [Preparation Example 3]
20 g of γ-glycidoxypropyltrimethoxysilane (“TSL8350” manufactured by Monmentive Performance Materials Japan Godo Kaisha) and 10 g of methanol (manufactured by China Essential Oil Co., Ltd.) were mixed and stirred while adding 0 to them. . 5 g of 1N hydrochloric acid was added dropwise. The solution thus obtained was stirred overnight at room temperature to hydrolyze the γ-glycidoxypropyltrimethoxysilane to obtain a mixed solution.

  Next, 50 g of an organic solvent dispersion “through rear” (manufactured by JGC Catalysts & Chemicals), 700 g of propylene glycol monomethyl ether, tris (2,4-pentanedionato) aluminum (III) ) (Manufactured by Tokyo Chemical Industry Co., Ltd.) 1.0 g, and 0.5 g of a silicone surfactant (“L-7001” manufactured by Toray Dow Corning Co., Ltd.) as a leveling agent are added and stirred at room temperature all day and night. Thus, a coating composition for forming an antireflection film (hereinafter referred to as “antireflection coating AR1”) was prepared.

  The hollow silica-based fine particle-containing dispersion “Thruria” is obtained by dispersing hollow silica-based fine particles having cavities inside and having an average particle diameter of 60 nm in isopropyl alcohol at a concentration of 20% by weight.

Preparation of coating composition for forming mirror coat film [Preparation Example 4]
While mixing 50 g of methanol with 17 g of γ-glycidoxypropyltrimethoxysilane (Montmentive Performance Materials Japan GK “TSL8350”) and 3 g of tetraethoxysilane (Kishida Chemical Co., Ltd.), stirring, In this solution, 10 g of 0.01N hydrochloric acid aqueous solution was added dropwise. Furthermore, this solution was stirred at room temperature for a whole day and night to hydrolyze the silane compound to obtain a hydrolyzed solution.

  Next, 60 g of methanol-dispersed titania-based composite metal oxide fine particles (“Optlake 1130Z (F-2 · A8)” solid content concentration: 30%) manufactured by Catalyst Chemical Industry Co., Ltd.), propylene glycol monomethyl ether ( 800 g of Dow Chemical Japan Co., Ltd., 1.0 g of Tris (2,4-pentanedionato) aluminum (III) (manufactured by Tokyo Chemical Industry Co., Ltd.), and a silicone surfactant (Toray 0.5 g of “L-7001” manufactured by Dow Corning Co., Ltd. was added and stirred for a whole day and night at room temperature to prepare a coating composition for forming a mirror coat film (hereinafter referred to as “mirror coating paint M1”).

Preparation of primer film-forming coating composition [Preparation Example 5]
200 g of a commercially available polyurethane emulsion “Superflex 130” (Daiichi Kogyo Seiyaku Co., Ltd.), 100 g of pure water, and 480 g of methanol (Chinese Essential Oil Co., Ltd.) are mixed and stirred at room temperature for 1 hour to mix. A liquid was obtained.

  Next, 1.0 g of a silicone surfactant (manufactured by Toray Dow Corning Co., Ltd., L-7604) as a leveling agent is added to this mixed solution, and the mixture is stirred overnight at room temperature to form a primer film-forming coating material. A composition (hereinafter referred to as “primer paint P1”) was prepared.

[Preparation Example 6]
130 g of commercially available polyurethane emulsion “Superflex 150” (Daiichi Kogyo Seiyaku Co., Ltd.), methanol dispersion containing core / shell type metal oxide fine particles “OPTRAIK 1120Z (S-7 · G)” (JGC Catalyst) 250 g of Kasei Chemical Co., Ltd.) and 480 g of methanol (Chinese Essential Oil Co., Ltd.) were mixed and stirred at room temperature for 1 hour to obtain a mixed solution.

  Next, 1.0 g of a silicone surfactant (manufactured by Toray Dow Corning Co., Ltd., L-7001) as a leveling agent was added to the mixed solution, and the mixture was stirred at room temperature all day and night. Thus, a primer film-forming coating composition (hereinafter referred to as “primer coating P2”) was prepared.

Preparation of paint for water repellent coating treatment (top coat layer forming paint) [Preparation Example 7]
Fluorine compound of chemical formula CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃ (AY43-158E, manufactured by Toray Dow Corning Co., Ltd.) and fluorine-containing organic solvent (Shin-Etsu Chemical Co., Ltd.) “FR-THINNER” (500 g) was mixed and stirred for 24 hours to prepare a coating composition for water-repellent coating treatment (hereinafter referred to as “water-repellent coating coating T1”).

Pretreatment of plastic lens substrate [Preparation Example 8]
From the commercially available products shown below, the plastic lens substrates of the number required for testing and evaluation in Examples and Comparative Examples were prepared.
(A) Plastic lens base material A having a refractive index of 1.50 (this lens base material is obtained by polymerizing a monomer having a product name “CR-39” manufactured by PPG Co., Ltd.)
(B) Plastic lens base material B having a refractive index of 1.60 (this lens base material is obtained by polymerizing a monomer having a product name “MR-8” manufactured by Mitsui Chemicals, Inc.)

  Subsequently, these plastic lens substrates were etched by being immersed in an aqueous potassium hydroxide solution (KOH concentration: 10% by weight) maintained at a temperature of 40 ° C. for 2 minutes. These lens substrates were taken out from the aqueous solution, washed with water, and then sufficiently dried.

Production of optical lens [Production Example 1]
The plastic lens base material A (refractive index: 1.50) obtained in Preparation Example 8 is immersed in the pot containing the primer coating P1 obtained in Preparation Example 5, and the plastic is further removed using a dipping method. The lens substrate B was pulled up at a speed of 100 mm / min, and the primer coating P1 was applied to the surface of the substrate.

  The plastic lens substrate A coated with the primer paint P1 is placed in a hot-air circulating furnace (ST-120, manufactured by Espec Co., Ltd.) in which hot air at 80 ° C. is circulated and supplied onto the plastic lens substrate A. The formed coating film was heated in a temperature atmosphere of 80 ° C. for 10 minutes to pre-cure the coating film.

  Next, the plastic lens substrate A having the coating film preliminarily cured as described above is immersed in the pot containing the hard coat paint H1 obtained in Preparation Example 1, and the plastic is further removed using a dipping method. The lens substrate A was pulled up at a speed of 120 mm / min, and the hard coat paint H1 was applied to the surface of the substrate.

  Hot air circulation in which hot air of 100 ° C. is circulated through a plastic lens substrate A having a laminated coating film in which the hard coat coating material H1 is applied on the coating film preliminarily cured by applying the primer coating material P1. In a furnace (Espec Co., Ltd., ST-120), the coating film formed on the plastic lens substrate A is heated at 100 ° C. for 10 minutes to pre-cure the coating film. After the heat treatment, heat treatment is performed for 1 hour in a hot-air circulating furnace (manufactured by ESPEC Co., Ltd., ST-120) maintained at a temperature of 100 ° C., and the surface has a laminated film composed of a primer film and a hard coat film. An optical lens (hereinafter referred to as “optical lens A-1”) was obtained.

[Production Example 2]
The plastic lens base material B (refractive index: 1.60) obtained in Preparation Example 8 is immersed in the pot containing the primer coating P2 obtained in Preparation Example 6, and the plastic is further removed using a dipping method. The lens substrate B was pulled up at a speed of 120 mm / min, and the primer coating P2 was applied to the surface of the substrate.

  The plastic lens base material B coated with the primer coating P2 is placed in a hot air circulation furnace (ST-120, manufactured by Espec Corp.) to which hot air of 80 ° C. is circulated and supplied onto the plastic lens base material B. The formed coating film was heated in a temperature atmosphere of 80 ° C. for 10 minutes to pre-cure the coating film.

  Next, the plastic lens base material B having the coating film preliminarily cured as described above is immersed in the pot containing the hard coat paint H2 obtained in Preparation Example 2, and the plastic is further removed using a dipping method. The lens base material B was pulled up at a speed of 150 mm / min, and the hard coat paint H2 was applied to the surface of the base material.

  Hot air circulation in which hot air of 100 ° C. is circulated through a plastic lens substrate B having a laminated coating film in which the hard coat paint H2 is applied on the paint film preliminarily applied by applying the primer paint P2. Put in a furnace (Espec Co., Ltd., ST-120) and heat the coating film formed on the plastic lens substrate B for 10 minutes in a temperature atmosphere of 100 ° C. to pre-cure the coating film. After the heat treatment, heat treatment is performed for 1 hour in a hot-air circulating furnace (manufactured by ESPEC Co., Ltd., ST-120) maintained at a temperature of 100 ° C., and the surface has a laminated film composed of a primer film and a hard coat film. An optical lens (hereinafter referred to as “optical lens A-2”) was obtained.

[Production Example 3]
The plastic lens base material B (refractive index: 1.60) obtained in Preparation Example 8 is immersed in the pot containing the hard coat paint H2 obtained in Preparation Example 2, and the dipping method is used to further immerse the plastic lens base material B (refractive index: 1.60). The plastic lens base material B was pulled up at a speed of 150 mm / min, and the hard coat paint H2 was applied to the surface of the base material.

  The plastic lens base material B coated with the hard coat paint H2 is placed in a hot air circulating furnace (ST-120, manufactured by Espec Corp.) in which hot air of 100 ° C. is circulated and supplied. The coating film formed in (1) was heated in a temperature atmosphere of 100 ° C. for 10 minutes to pre-cure the coating film.

  Next, the plastic lens base material B having the coating film preliminarily cured as described above is immersed in the pot containing the antireflection coating AR1 obtained in Preparation Example 3, and the plastic is further removed using a dipping method. The lens base material B was pulled up at a speed of 60 mm / min, and the antireflection coating AR1 was applied to the surface of the base material.

  Hot air in which hot air at 100 ° C. is circulated and supplied to the plastic lens substrate B having a laminated coating film in which the antireflection coating AR1 is applied onto the coating film that has been pre-cured by applying the hard coating material H2. Pre-curing the coating film by placing it in a circulating furnace (Espec Co., Ltd., ST-120) and heating the coating film formed on the plastic lens substrate B at 100 ° C. for 10 minutes. Then, heat treatment is performed for 1 hour in a hot-air circulating furnace (manufactured by ESPEC Corp., ST-120) maintained at a temperature of 100 ° C., and a laminated film comprising a hard coat film and an antireflection film on the surface An optical lens having the following (hereinafter referred to as “optical lens A-3”) was obtained.

[Production Example 4]
The plastic lens substrate A obtained in Preparation Example 8 is immersed in the pot containing the hard coat paint H1 obtained in Preparation Example 1, and the plastic lens substrate A is further added to the 100 mm / mm by dipping method. The hard coat paint H1 was applied to the surface of the substrate by pulling up at a rate of minutes.

  The plastic lens substrate A having a laminated coating film coated with the hard coat paint H1 is placed in a hot air circulation furnace (ST-120, manufactured by Espec Corp.) in which hot air at 100 ° C. is circulated and supplied. The coating film formed on the plastic lens substrate A was heated in a temperature atmosphere of 100 ° C. for 10 minutes to pre-cure the coating film.

  Next, the plastic lens substrate A having the coating film preliminarily cured as described above is dipped in the pot containing the coating M1 for mirror coating obtained in Preparation Example 4, and the plastic is further removed using a dipping method. The lens substrate A was pulled up at a speed of 20 mm / min, and the mirror coating paint M1 was applied to the surface of the substrate.

  The plastic lens substrate A having the laminated coating film coated as described above is placed in a hot air circulation furnace (ST-120 manufactured by Espec Corp.) to which hot air of 100 ° C. is circulated and supplied. The coating film formed above was heated for 10 minutes in a temperature atmosphere of 100 ° C., and after pre-curing the coating film, a hot-air circulating furnace maintained at a temperature of 100 ° C. (manufactured by ESPEC Corporation, In ST-120), heat treatment was performed for 1 hour to obtain an optical lens (hereinafter referred to as “optical lens A-4”) having a laminated film composed of a primer film, a hard coat film, and a mirror coat film on the surface thereof.

[Production Example 5]
The optical lens A-4 obtained in Production Example 4 was etched using plasma. The treatment conditions were O ₂ gas flow rate: 40 cc / min, high-frequency output: 50 W, treatment time: 20 seconds, equipment used: Plasma reactor PR510A manufactured by Yamato Scientific Co., Ltd.

  Next, the plasma-etched plastic substrate with a mirror coat film is coated with a fluorosilane compound “OPTOOL DSX” (manufactured by Daikin Co., Ltd.) using hydrofluoroether “HFE-7200” (manufactured by Sumitomo 3M Co., Ltd.) with a solid content of 2 It was immersed in a solution prepared by diluting to a weight percent, pulled up at a rate of 100 mm / min, and allowed to stand at room temperature all day and night. Next, the surface was wiped off with a cloth with acetone to obtain a plastic substrate with a mirror coat film treated with a fluorosilane compound (hereinafter referred to as “optical lens A-5”).

Preparation of dyeing bath [Preparation Example 9]
To 1 liter of water heated to 90 ° C., 5.0 g of Dianix Blue AC-E (manufactured by Mitsubishi Kasei Hoechst), 10.0 g of sodium salt of naphthalenesulfonic acid formaldehyde condensate, disodium hydrogen phosphate (Kanto Chemical Co., Ltd.) )) 0.5 g, potassium dihydrogen phosphate (Kanto Chemical Co., Ltd.) 0.5 g was added, stirred well, and pH 7.0 aqueous dispersion (hereinafter referred to as “dye bath D-1”). .)

[Preparation Example 10]
To 1 liter of water heated to 90 ° C., 3.0 g of MLP Red 2 (manufactured by Mitsui Chemicals), 5.0 g of sodium salt of naphthalenesulfonic acid formaldehyde condensate, disodium hydrogen phosphate (manufactured by Kanto Chemical Co., Ltd.) ) 0.5 g and 0.8 g of potassium dihydrogen phosphate (manufactured by Kanto Chemical Co., Inc.) were added, stirred well, and an aqueous dispersion with pH 6.8 (hereinafter referred to as “dyeing bath D-2”). Got.

[Preparation Example 11]
The same operation as in Preparation Example 9 was performed except that disodium hydrogen phosphate and potassium dihydrogen phosphate were not added, and an aqueous dispersion having pH 7.1 (hereinafter referred to as “dyeing bath D-3”) was obtained. Obtained.

[Preparation Example 12]
The same operations as in Preparation Example 10 were performed except that disodium hydrogen phosphate and potassium dihydrogen phosphate were not added, and an aqueous dispersion having pH 7.2 (hereinafter referred to as “dyeing bath D-4”) was obtained. Obtained.

[Examples 1 and 2]
The dyeing baths D-1 and D-2 obtained in Preparation Examples 9 and 10 were kept at 92 ° C., and each of the optical lenses A-1 to A-5 obtained in Preparation Examples 1 to 5 was used. Soaked for 1 hour in a continuous dye bath. The dyeing unevenness of the dyed optical lens was visually confirmed. The laminated film after dyeing was subjected to a scratch resistance test with steel wool. The results are shown in Table 1 and Table 2, respectively.

[Evaluation method]
<Dyeability test>
The dyeing unevenness of the dyed optical lens was visually evaluated in the following three stages.
○: Dyed evenly.
Δ: Dyeing is slightly uneven.
X: Dyeing is uneven.

<Abrasion resistance test>
The surface of the laminated coating film formed on the sample substrate is manually rubbed with Bonstar Steel Wool # 0000 (manufactured by Nippon Steel Wool Co., Ltd.), and the degree of damage is visually determined and evaluated according to the following criteria.
A: There is almost no scratch.
B: Some scratches enter.
C: There are considerable scratches.
D: Scratches appear on almost the entire surface of the rubbed area.

[Comparative Examples 1 and 2]
The dyeing baths D-3 and D-4 obtained in Preparation Examples 11 and 12 were kept at 92 ° C., and each of the optical lenses A-1 to A-5 obtained in Preparation Examples 1 to 5 was used. The sample was immersed in the dyeing bath continuously for 1 hour, and dyeing unevenness of the dyed optical lens was visually confirmed. The laminated film after dyeing was subjected to a scratch resistance test with steel wool. The results are shown in Table 3 and Table 4, respectively.

Claims (8)

  A method for producing a dyed optical lens by dyeing an optical lens having a silicone functional film on the surface of a plastic lens, wherein a dye insoluble or sparingly soluble in water is dispersed, contains a buffer component, and has a pH of 6. A method for producing a dyeing optical lens, comprising the step of immersing and dyeing the optical lens in an aqueous dispersion of 6 to 7.5.   The method for producing a dyeing optical lens according to claim 1, wherein the buffer solution components are hydrogen phosphate and dihydrogen phosphate.   2. The method for producing a dyeing optical lens according to claim 1, wherein the dye is at least one selected from an azo dye, an anthraquinone dye, a quinophthalone dye, and a nitrodiphenylamine dye.   The dyeing optical lens according to any one of claims 1 to 3, wherein the immersion of the optical lens in the aqueous dispersion is performed for 30 seconds to 120 minutes under a temperature condition of 80 to 99 ° C. Production method. The dyeing optical lens according to any one of claims 1 to 4, wherein the silicone functional film is a hard coat film formed from a coating composition containing the following components (1) and (2): Production method.
Component (1): oxide fine particles of at least one metal element selected from titanium, iron, zinc, tungsten, tin, tantalum, zirconium, antimony, niobium, indium, cerium, silicon, aluminum, yttrium, lead and molybdenum And / or composite oxide fine particles Component (2): an organosilicon compound represented by the general formula R ¹ _a R ² _b Si (OR ³ ) _{4- (a + b)} , a hydrolyzate thereof, and a hydrolyzate of the hydrolyzate At least one silicon-containing compound selected from the group consisting of partial condensates (wherein R ¹ contains an alkyl group having 1 to 6 carbon atoms, an organic group having 2 to 8 carbon atoms containing a vinyl group, and an epoxy group) C2-C8 organic group, C4-C8 organic group containing methacryloxy group, C1-C5 organic group containing mercapto group or C1-C1 containing amino group 5 is an organic group, R ² is an alkyl group, an alkenyl group having 2 to 3 carbon atoms, a halogenated alkyl group having a cycloalkyl group, or 1 to 3 carbon atoms having 3 carbon atoms having 1 to 3 carbon atoms, R ³ is an alkyl group having 1 to ³ carbon atoms, an alkenyl group having 2 to 3 carbon atoms, or a cycloalkyl group having 3 carbon atoms, a is an integer of 0 or 1, b is an integer of 0, 1, or 2. is there.) The silicone-based functional film is a laminated film obtained by laminating the hard coat film and an antireflection film formed from a coating composition containing the following components (3) and (4) in order from the plastic lens side. The method for producing a dyeing optical lens according to claim 5.
Component (3): Hollow silica fine particles having an average particle size of 40 to 100 nm Component (4): At least one organosilicon compound selected from the group consisting of the following components (A), (B) and (C), and hydrolysis thereof And at least one silicon-containing compound selected from the group consisting of a partial condensate of the hydrolyzate:
Component (A): Organosilicon compound represented by the general formula R ¹ R ² _a Si (OR ³ ) _3-a (wherein R ¹ is a carbon containing a hydrocarbon group having 1 to 6 carbon atoms and a vinyl group. An organic group having 2 to 8 carbon atoms, an organic group having 2 to 8 carbon atoms containing an epoxy group, an organic group having 4 to 8 carbon atoms containing a methacryloxy group, an organic group having 1 to 5 carbon atoms containing a mercapto group, or an organic group of 1 to 5 carbon atoms containing an amino group, R ² is a hydrocarbon group having 1 to 4 carbon atoms, R ³ is 1 to 8 carbon atoms hydrocarbon group, having 2 to 8 carbon atoms An alkoxyalkyl group or an acyl group having 2 to 8 carbon atoms, a represents 0 or 1);
Component (B): an organic silicon compound represented by the general formula [(R ⁴ ) _b Si (OR ⁵ ) _{3 -b} ] ₂ R ⁶ (wherein R ⁴ is an alkyl group having 1 to 5 carbon atoms, R ⁵ is an alkyl group having 1 to 4 carbon atoms or an acyl group having 2 to 4 carbon atoms, R ⁶ is a methylene group or an alkylene group having 2 to 20 carbon atoms, and b represents 0 or 1.);
Component (C): an organosilicon compound represented by the general formula Si (OR ⁷ ) ₄ (wherein R ⁷ is a hydrocarbon group having 1 to 8 carbon atoms, an alkoxyalkyl group having 2 to 8 carbon atoms, or 2 carbon atoms) ˜8 acyl groups.) The silicone-based functional film is formed from the hard coat film and a coating composition containing the following components (5) and (4) in order from the plastic lens side. The refractive index of the hard coat film is 0.02 6. The method for producing a dyeing optical lens according to claim 5, wherein the dyeing optical lens is a laminated film obtained by laminating a mirror coat film having a high refractive index.
Component (5): oxide fine particles and / or composites of at least one metal element selected from the group consisting of titanium, iron, zinc, tin, tungsten, tantalum, zirconium, antimony, niobium, indium, cerium, silicon and aluminum Oxide fine particle Component (4): Consists of at least one organic silicon compound selected from the group consisting of the following components (A), (B) and (C), a hydrolyzate thereof, and a partial condensate of the hydrolyzate. At least one silicon-containing compound selected from the group:
Component (A): Organosilicon compound represented by the general formula R ¹ R ² _a Si (OR ³ ) _3-a (wherein R ¹ is a carbon containing a hydrocarbon group having 1 to 6 carbon atoms and a vinyl group. An organic group having 2 to 8 carbon atoms, an organic group having 2 to 8 carbon atoms containing an epoxy group, an organic group having 4 to 8 carbon atoms containing a methacryloxy group, an organic group having 1 to 5 carbon atoms containing a mercapto group, or an organic group of 1 to 5 carbon atoms containing an amino group, R ² is a hydrocarbon group having 1 to 4 carbon atoms, R ³ is 1 to 8 carbon atoms hydrocarbon group, having 2 to 8 carbon atoms An alkoxyalkyl group or an acyl group having 2 to 8 carbon atoms, a represents 0 or 1);
Component (B): an organic silicon compound represented by the general formula [(R ⁴ ) _b Si (OR ⁵ ) _{3 -b} ] ₂ R ⁶ (wherein R ⁴ is an alkyl group having 1 to 5 carbon atoms, R ⁵ is an alkyl group having 1 to 4 carbon atoms or an acyl group having 2 to 4 carbon atoms, R ⁶ is a methylene group or an alkylene group having 2 to 20 carbon atoms, and b represents 0 or 1.);
Component (C): an organosilicon compound represented by the general formula Si (OR ⁷ ) ₄ (wherein R ⁷ is a hydrocarbon group having 1 to 8 carbon atoms, an alkoxyalkyl group having 2 to 8 carbon atoms, or 2 carbon atoms) ˜8 acyl groups.)   The method for producing a dyeing optical lens according to claim 1, wherein the optical lens has a primer film between the plastic lens and the hard coat film.