JP2008058350A - Spectacle lens - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a spectacle lens which is made colorless and transparent by using a technique capable of effectively canceling the yellowing caused upon manufacturing of spectacle lens. <P>SOLUTION: In the spectacle lens, an organic antireflection layer is formed by applying coating liquid containing: an organic silicon compound (C) represented by the formula: R<SP>2</SP><SB>r</SB>R<SP>3</SP><SB>q</SB>SiX<SP>1</SP><SB>4-q-r</SB>(R<SP>2</SP>is organic group having a polymerizable reactive group, R<SP>3</SP>is hydrocarbon group of number of carbon 1 to 6, X<SP>1</SP>is hydrolytic group, q is 0 or 1 and r is 0 or 1); a fluorine-containing silane compound (D) represented by the formula: X<SB>m</SB>R<SP>1</SP><SB>3-m</SB>Si-Y-SiR<SP>1</SP><SB>3-m</SB>X<SB>m</SB>(R<SP>1</SP>is monovalent hydrocarbon group of number of carbon 1 to 6, Y is bivalent organic group containing one or more fluorine atoms, X is hydrolytic group and m is integer of 1 to 3); silica type fine particles (E) of the average particle size of 1 to 150 nm; and a coloring agent (F) which has no absorption of light of wavelength range of 400 to 500 nm. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

The present invention relates to a spectacle lens excellent in colorless and transparent appearance in which yellowing due to heating at the time of manufacture is canceled.

Plastic lenses are lighter than glass lenses, have excellent moldability, processability, dyeability and the like, and are hard to break and have high safety, and thus occupy most of them in the field of spectacle lenses. In recent years, high refractive index materials such as thiourethane resins and episulfide resins have been developed in order to meet further demands for reduction in thickness and weight. On the other hand, since a plastic lens is easily damaged compared with a glass lens, a hard coat layer is generally formed on the surface of the plastic lens to improve the surface hardness. Further, for the purpose of preventing surface reflection, it is common to form an antireflection layer by depositing an inorganic substance on the upper surface of the hard coat layer. Furthermore,
In order to mainly improve the adhesion between the high refractive index material constituting the lens and the hard coat layer, a primer layer is often interposed between the lens substrate and the hard coat layer.

Further, as disclosed in Patent Document 8, as a reflection preventing layer formed on a hard coating layer having a high refractive index, a coating liquid containing silica fine particles having internal cavities is applied to refract the hard coating layer. Having a refractive index 0.10 or more lower than the refractive index, and 50 nm to 150 nm
A technique for forming a single-layer antireflection layer composed of an organic thin film having a thickness of 5 mm by a wet method has been developed. Since this organic antireflection layer is thin and porous and easily penetrates water, an antireflection layer made of an organic silicon compound containing fluorine is further provided on the antireflection layer for the purpose of improving the surface water and oil repellency. Often forms a dirty layer.

As the lens material has a higher refractive index, the yellowing of the lens substrate tends to become noticeable. In addition, a primer layer, a hard coat layer, an organic antireflection layer, and an antifouling layer are formed in this order on the lens substrate, and heating is required for each film formation. Yellowing may occur in the membrane. Yellowing of yellowing deteriorates the appearance of the spectacle lens and reduces the commercial value.

For example, as shown in Patent Document 1, a blue colorant (blueing agent) is added to a polymerizable composition of a lens, and polymerized and cured to mix the lens base material with the lens base material. The method of canceling by doing is known. Moreover, as shown in Patent Document 2, for example, a technique is known in which a blueing agent is blended in a hard coat layer to cancel yellowing of yellowing to make the lens colorless and transparent.

JP-A-5-194616 JP-A-5-100103 JP 11-322930 A Japanese Patent Publication No. 4-58489 JP-A-5-148340 JP 2001-342252 A Japanese Patent Laid-Open No. 9-258003 JP 2003-222703 A

However, as described above, as the number of layers formed on the lens substrate increases, the degree of yellowing becomes stronger, and further development of technology for canceling yellowing is expected. .
The present invention has been made in view of the above circumstances, and an object thereof is to provide a colorless and transparent spectacle lens using a technique capable of effectively canceling yellowing of yellowing that occurs during the production of a spectacle lens. To do.

In order to achieve the above object, the present invention first has an organic antireflection layer formed from a coating liquid for forming an antireflection layer containing a colorant that does not absorb light in the wavelength region of 400 to 500 nm. An eyeglass lens is provided.

In this spectacle lens, so-called bluing agent is blended in the organic antireflection layer formed from the coating liquid, so that all yellowing of the lens substrate and the layer formed on it is counteracted. It becomes. When a blueing agent is blended in the organic antireflection layer, yellowing can be effectively canceled with a relatively small blending amount.

The present invention secondly provides the spectacle lens according to the first spectacle lens, wherein the colorant contains an anthraquinone dye.
Anthraquinone dyes often exhibit a blue color, are oleophilic and have good compatibility with the binder component, and are therefore suitable as a bluing agent for use in an organic antireflection layer.

Thirdly, in the first or second spectacle lens according to the present invention, the antireflection layer-forming coating solution contains the following component (D), (D) general formula: X _m R ¹ _3-m Si-Y -SiR ¹ _3
-M X Fluorine-containing silane compound represented by _m (wherein, R ¹ is a monovalent hydrocarbon group having 1 to 6 carbon atoms, Y is a divalent organic group containing one or more fluorine atoms, and X is Hydrolyzable group, m is 1-3
Is an integer. A spectacle lens comprising:

The fluorine-containing silane compound blended to provide the organic antireflection layer with a low refractive index and water / oil repellency is the main cause of yellowing, and the organic antireflection layer is used to counteract the yellowing. It has been found that blending a bluing agent is effective.

Fourthly, the present invention provides the spectacle lens according to any one of the first to third spectacle lenses, wherein a content of the colorant in the antireflection layer forming coating liquid is 50 to 600 ppm. provide.

By setting the colorant content to 50 to 600 ppm, it becomes possible to effectively cancel the yellowing of the organic antireflection layer to make a transparent layer. Moreover, since the film thickness of the organic antireflection layer is about 1/20 of the thickness of the hard coat layer, it is necessary to add it about 10 times thicker than when the bluing agent is added to the hard coat layer. However, since the colorant content increases, it is possible to suppress a change in color (blueness) due to a change in the colorant content, and it becomes possible to produce a product stably in production.

Hereinafter, embodiments of the spectacle lens of the present invention will be described, but the present invention is not limited to the following embodiments.

The eyeglass lens of the present invention generally has a structure in which a primer layer, a hard coat layer, an organic antireflection layer, and an antifouling layer are formed in this order on a plastic lens substrate. A so-called bluing agent is blended in the prevention layer.

As the plastic lens base material, it is preferable to use a high refractive index material having a refractive index of 1.6 or more in order to achieve a refractive index difference of 0.10 or more with a low refractive index organic antireflection layer. Either a high refractive index material that can be used now or a high refractive index material that will be developed in the future may be used. As a high refractive index material that can be used at present, as an optical material excellent in the balance between a high refractive index and a high Abbe number, it has one or more disulfide bonds (SS) in the molecule and has an epoxy group and / or a thioepoxy. There is a compound having a group (Patent Document 3). Moreover, there is a plastic lens having a thiourethane structure obtained by a reaction between a poly (thio) isocyanate compound and a compound having an active hydrogen group such as a polythiol compound (Patent Documents 4 and 5). Moreover, there exists a compound which has a 2 or more mercapto group in a molecule | numerator (patent document 6).

When producing a plastic lens using these materials, casting polymerization is usually used. The side surface of two circular glass molds arranged opposite to each other is fixed with an adhesive tape or gasket, and a mold in which a gap between the glass molds is sealed is assembled. The composition can be filled and polymerized and cured by thermal energy or light energy to obtain a plastic lens substrate having a high refractive index.

The primer layer is interposed between the plastic lens base material made of a high refractive index material and the hard coat layer, improving the adhesion thereof, and improving the durability and durability of the lens. it can. As the primer layer, an aqueous acrylic-urethane resin or an aqueous polyester thermoplastic elastomer having excellent adhesion to both the plastic lens substrate and the hard coat layer made of a high refractive index material is preferable. The water-based acrylic-urethane resin is a copolymer of an acrylic polyol and a polyfunctional isocyanate compound, or a composite of an acrylic polyol and a water-based polyurethane resin, and is dispersed in water.

The acrylic polyol is a copolymerized acrylic resin of an acrylic monomer having a hydroxyl group, an acrylic monomer having the hydroxyl group, and a copolymerizable monomer such as an acrylate ester.
The water-based polyurethane resin is also called water-based urethane resin or water-dispersed polyurethane, and is obtained by dispersing a urethane resin obtained by a reaction between a polyfunctional isocyanate compound and a polyol as an emulsion.

As a polyester-based thermoplastic elastomer constituting the primer layer, JP-A-2000
Examples described in -144048 can be given. The polyester-based thermoplastic elastomer is a multi-block copolymer using polyester as a hard segment and polyether or polyester as a soft segment. The weight ratio of the hard segment (H) to the soft segment (S) is H / S = 30/70 to 90/10, preferably 40/60 to 80/20.

A method for forming a primer layer on a plastic lens substrate is, for example, an aqueous acrylic-
If necessary, metal oxide fine particles for adjusting the refractive index may be blended in an aqueous solution containing a urethane resin or a polyester-based thermoplastic elastomer, and diluted with a solvent if necessary to prepare a primer solution for use. As the solvent, solvents such as alcohols, esters, ketones, ethers and aromatics are used. The primer liquid can be applied by dipping, spin coating, spray coating, or roll coating. Thereafter, the primer layer can be formed by heating / drying at a temperature of 40 to 200 ° C. for several hours. The primer layer has a thickness of 0.05 to 5 μm, preferably 0.1 to 3 μm.

The hard coat layer is formed on the primer layer in order to improve the scratch resistance of the plastic lens. The hard coat layer comprises at least the following (A) component and (B) component (A) inorganic oxide fine particles having an average particle diameter of 1 to 200 nm,
(B) an organosilicon compound represented by the general formula: RSiX ₃ ;
(In the formula, R represents an organic group having 2 or more carbon atoms having a polymerizable reactive group, and X represents a hydrolyzable group.)
It is the coating film formed from the composition for coating containing this.

The inorganic fine particles of component (A) are Si, Al, Sn, Sb, Ta, Ce, La, Fe, Zn
, W, Zr, In, Ti, one or more kinds of oxide fine particles or composite fine particles selected from metals. In particular, the surface of the core particle of a composite oxide having a rutile type crystal structure composed of titanium oxide and tin oxide or titanium oxide, tin oxide and silicon oxide is oxidized on the surface of the composite oxide of silicon oxide and zirconium oxide, and oxidized with silicon oxide. Inorganic oxide fine particles having an average particle diameter of 1 to 200 nm including those coated with a composite oxide of aluminum or a composite oxide of silicon oxide, zirconium oxide and aluminum oxide can be suitably used. The inorganic oxide fine particles containing rutile titanium oxide have a high refractive index and are chemically stable.
The type and blending amount of the inorganic oxide fine particles are determined by the target hardness, refractive index, etc., but the blending amount is 5 to 80% by weight, particularly 10 to 50% by weight of the solid content in the hard coat composition. It is desirable to be in the range of% by weight. Similarly, fine inorganic oxide particles can be used for adjusting the refractive index of the primer layer.

The organosilicon compound as component (B) is a binder component for the hard coat layer. In the formula, R is an organic group having a polymerizable reactive group, and examples of the polymerizable reactive group include a vinyl group,
Examples include allyl group, acrylic group, methacryl group, epoxy group, mercapto group, cyano group, isocyano group, amino group and the like. X 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, and acyloxy groups. .

Examples of the organosilicon compound of component (B) include vinyltrialkoxysilane, vinyltrichlorosilane, vinyltri (β-methoxy-ethoxy) silane, allyltrialkoxysilane, acryloxypropyltrialkoxysilane, and methacryloxypropyltrialkoxysilane. , Methacryloxypropyl dialkoxymethylsilane, γ-glycidoxypropyltrialkoxysilane, β- (3,4-epoxycyclohexyl)-
Examples include ethyltrialkoxysilane, mercaptopropyltrialkoxysilane, γ-aminopropyltrialkoxysilane, and N-β (aminoethyl) -γ-aminopropylmethyl dialkoxysilane. The component (B) may be used as a mixture of two or more. It is more effective to use after hydrolysis.

The coating composition for forming the hard coat layer is blended with a curing catalyst, if necessary,
It can be used after diluted in a solvent. As the solvent, solvents such as alcohols, esters, ketones, ethers and aromatics are used.

In addition, as a coating / curing method for the coating composition, a coating composition is applied by dipping, spin coating, spray coating, roll coating, or flow coating, and then a temperature of 40 to 200 ° C. A hard coat film is formed by heating and drying for several hours. In addition, it is preferable that the film thickness of a hard-coat layer is 0.05-30 micrometers. If the film thickness is less than 0.05 μm, the basic performance may not be realized. On the other hand, if the film thickness exceeds 30 μm, the smoothness of the surface may be impaired or optical distortion may occur.

As the antireflection layer formed on the hard coat layer, in the spectacle lens of the present invention, 50 nm to 150 nm having a refractive index lower by 0.10 or more than the refractive index of the hard coat layer.
And a colorant (so-called bluing agent) that has the least absorption of light in the wavelength range of 400 to 500 nm and has no absorption of light.

The organic thin film constituting the antireflection layer is not limited as long as it has the above-mentioned refractive index and has the above-mentioned film thickness, but is not limited to silicone-based, acrylic-based, epoxy-based, urethane-based, melamine-based resins or the like. A material formed by using raw material monomers alone or in combination with two or more of other resins and raw material monomers is preferable. Heat resistance, chemical resistance, scratch resistance as a plastic lens,
In consideration of various characteristics such as, it is preferable to use a low refractive index layer containing a silicone resin. In this case, a fine inorganic material is added to improve the surface hardness and adjust the refractive index. More preferably. Examples of the fine inorganic particles include colloidally dispersed sols, and specific examples include silica sol, magnesium fluoride sol, calcium fluoride sol, and the like.

In particular, an organic thin film formed by a wet method using a coating liquid for forming an antireflection layer containing the following components (C) to (F) can be preferably used.
(C) an organosilicon compound represented by the general formula: R ² _r R ³ _q SiX ¹ _4-qr ,
(Wherein R ² is an organic group having a polymerizable reactive group, R ³ is a hydrocarbon group having 1 to 6 carbon atoms, X
¹ is a hydrolyzable group, q is 0 or 1, and r is 0 or 1. )
(D) the general _{^{formula: X m R 1 3-m}} Si-Y-SiR 1 3-m X fluorine-containing silane compound represented by _m,
(In the formula, R ¹ is a monovalent hydrocarbon group having 1 to 6 carbon atoms, Y is a divalent organic group containing one or more fluorine atoms, X is a hydrolyzable group, and m is an integer of 1 to 3) .)
(E) silica-based fine particles having an average particle diameter of 1 to 150 nm,
(F) A colorant having the least absorption of light in the wavelength region of 400 to 500 nm or no light absorption.

An inorganic film formed by a dry process such as vapor deposition or sputtering has low heat resistance due to a large difference in thermal expansion coefficient from the hard coat layer of the underlying organic film, whereas an organic film formed by such a wet process. The antireflection layer composed of a thin film has a small difference in thermal expansion coefficient from the hard coat layer, so that it is difficult for cracks to occur due to heating, and is excellent in heat resistance. Further, since it can be formed by a wet method, a vacuum apparatus or a large-sized facility is not necessary, and it can be easily manufactured.

The organosilicon compound as component (C) constitutes a binder component of the antireflection layer composed of an organic thin film. Examples of the organic group having a polymerizable reactive group represented by R ² in the general formula include a vinyl group, an allyl group, an acrylic group, a methacryl group, an epoxy group, a mercapto group, a cyano group, and an amino group. Specific examples of the hydrocarbon group having 1 to 6 carbon atoms of R ³ include a methyl group,
Examples include an ethyl group, a butyl group, a vinyl group, and a phenyl group. Specific examples of the hydrolyzable functional group for X ¹ include alkoxy groups such as methoxy group, ethoxy group, and methoxyethoxy group, halogen groups such as chloro group and bromo group, and acyloxy groups.

Specific examples of the organosilicon compound of component (C) include vinyltrialkoxysilane, vinyltrichlorosilane, vinyltri (β-methoxy-ethoxy) silane, allyltrialkoxysilane, acryloxypropyltrialkoxysilane, methacryloxypropyltrialkoxy. Silane, methacryloxypropyl dialkoxymethylsilane, γ-glycidoxypropyltrialkoxysilane, β- (3,4-epoxycyclohexyl)-
Examples include ethyltrialkoxysilane, mercaptopropyltrialkoxysilane, γ-aminopropyltrialkoxysilane, N-β (aminoethyl) -γ-aminopropylmethyl dialkoxysilane, tetraalkoxysilane, and the like.

Further, the fluorine-containing silane compound as the component (D) constitutes a binder component together with the component (C) and has a function of imparting a low refractive index and water / oil repellency to the organic antireflection layer. In the above formula,
Y is a divalent organic group having one or more fluorine atoms, and the number of fluorine atoms is preferably 4
To 50, particularly preferably 4 to 24. In particular, in order to develop various functions such as antireflection, antifouling, and water repellency, it is preferable to contain a large amount of fluorine atoms.
If the amount is too large, the crosslink density is lowered, and sufficient scratch resistance may not be obtained. Accordingly, Y preferably has the following structure.
_{-CH 2 CH 2 (CF 2)} n CH 2 CH 2 -,
_{-C 2 H 4 -CF (CF 3} ) - (CF 2) n -CF (CF 3) -C 2 H 4 -
N in the above structure preferably satisfies a value of 2 to 20, more preferably 2 to 2.
12, particularly preferably 4-10. If it is less than this, various functions such as antireflection properties, antifouling properties, water repellency, and chemical resistance may not be obtained sufficiently, and if it is too much, the crosslinking density is lowered and sufficient scratch resistance is obtained. May not be obtained.

R ¹ represents a monovalent hydrocarbon group having 1 to 6 carbon atoms, specifically, a methyl group, an ethyl group,
Examples thereof include alkyl groups such as propyl group, butyl group, hexyl group and cyclohexyl group, and phenyl group. A methyl group is preferred for obtaining good scratch resistance. m is an integer of 1 to 3, preferably 2 or 3, and m =
3 is preferred.

X represents a hydrolyzable group. Specific examples include halogen atoms such as Cl, ORX (RX
Is an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an alkenoxy group such as an isopropenoxy group, an acetoxy group Examples thereof include acyloxy groups such as ketoxime groups such as methyl ethyl ketoxime groups and alkoxyalkoxy groups such as methoxyethoxy groups. Among these, an alkoxy group is preferable, and a silane compound having a methoxy group or an ethoxy group is particularly preferable because it is easy to handle and the reaction during hydrolysis is easily controlled.

Specific examples of such a fluorine-containing silane compound as component (D) include the following.

The fluorine-containing silane compound as the component (D) is contained in the range of 60 to 99% by weight, preferably in the range of 60 to 90% by weight, based on the total amount of the resin component in the coating liquid for forming the antireflection layer. Is desirable.

Examples of the silica-based fine particles of component (E) include silica sol in which silica-based fine particles having an average particle diameter of 1 to 150 nm are colloidally dispersed in a dispersion medium such as water, alcohol-based or other organic solvents. In order to reduce the refractive index, for example, it is preferable to use a silica sol made of silica-based fine particles in which cavities or voids are formed. By including a gas or solvent having a refractive index lower than that of silica in the internal cavities of the silica-based fine particles, the refractive index is lower than that of silica-based fine particles having no cavities, and a low refractive index of the coating is achieved.

Silica-based fine particles having internal cavities are produced by the method described in JP-A No. 2001-233611. In the present invention, the average particle diameter is in the range of 20 to 150 nm and the refractive index is 1. It is desirable to use those in the range of .16 to 1.39. Here, when the average particle size of the particles is less than 20 nm, the void ratio inside the particles becomes small and a desired low refractive index cannot be obtained. When the average particle size exceeds 150 nm, the haze of the organic thin film increases. This is not preferable.

The silica-based fine particles having internal cavities as described above are suriria and recum, manufactured by Catalyst Kasei Kogyo Co., Ltd., which are dispersed sols 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. Etc.

The colorant having the least absorption of light in the wavelength range of 400 to 500 nm of the component (F) or no light absorption is an additive called a bluing agent. 400-500n white light
Light in the wavelength region of m is absorbed, and light having a wavelength of 500 nm or more is reflected and incident on the eye, so that the human eye looks yellow. If white light reflects light in a wavelength range of 400 to 500 nm and light in a wavelength range of about 500 nm or more is absorbed, it looks blue. Blue and yellow have a complementary relationship, and by adding a bluing agent, the yellowness of the spectacle lens can be compensated by blue color and canceled to form a colorless and transparent lens.

Yellowing occurs in any of the lens substrate, the hard coat layer, and the organic antireflection layer. As the lens material has a higher refractive index, the yellowing of the lens substrate tends to become noticeable. In addition, slight yellowing may occur in the hard coat layer. In the organic antireflection layer, yellowing is noticeably generated by blending the fluorine-containing silane compound as the component (D). The reason is unknown.

In the spectacle lens of the present invention, it has been found that the yellowing of the entire spectacle lens can be canceled by blending at least the organic antireflection layer with a bluing agent. Of course, a blueing agent may be added to the organic antireflection layer, and a blueing agent may be added to one or more of the plastic lens substrate, the primer layer, and the hard coat layer.

As the bluing agent, a blue pigment or dye that is used as a coloring agent that has the least absorption of light in the wavelength region of 400 to 500 nm or no light absorption can be used. Above all,
From the viewpoint of compatibility with the binder component, it is preferable to use a disperse dye or an oil-soluble dye. The disperse dye is used for the purpose of dyeing a dye atomized in micron units in an aqueous dispersant in an aqueous medium in the presence of various dyeing assistants. Oil-soluble dyes are used for dyeing by dissolving in organic solvents. As a preferred dye, an anthraquinone dye that develops a blue color can be exemplified. Anthraquinone dyes are classified as both disperse dyes and oil-soluble dyes. In general dyes, the polymerizable monomers of the components (C) and (D) may be decomposed when radically polymerized, but anthraquinone dyes are not decomposed during radical polymerization and are stable. It is recognized that Moreover, the anthraquinone dye has good compatibility with the cured product of the polymerizable monomer of the component (C) and the component (D). As a specific example of the anthraquinone dye, it is preferable to use a blue colorant that is commercially available as a plastic colorant. As a commercial item, the brand name dialresin made from Mitsubishi Chemical Corporation, the brand name Sumiplast made from Sumitomo Chemical Co., Ltd. can be illustrated, for example. In some cases, the lens becomes green due to yellowing and blue of the bluing agent. In this case, it is preferable to add a red colorant to cancel the green color.

Such a composition for forming an antireflection layer can be used as a coating liquid after being diluted with a solvent, if necessary. As the solvent, solvents such as water, alcohols, esters, ketones, ethers and aromatics are used.

The blending amount of the bluing agent in the antireflection layer forming coating liquid is preferably 50 to 600 ppm, preferably 100 to 500 ppm, depending on the degree of yellowing.
The thickness of the organic antireflection layer is about 100 nm, which is about 1/20 of the thickness of the hard coat layer of about 2 μm. Therefore, it is necessary to mix | blend deeper than the case where a blueing agent is mix | blended with a hard-coat layer. However, when blending a blueing agent in a coating composition for forming a hard coat layer, the range of 10 to 60 ppm is generally used, so that yellow is more efficient than when a blueing agent is blended in a hard coat layer. It can be said that the effect of canceling the change appears. In addition, the blending amount and the lens yellowing canceling effect tend to be proportional. If a bluing agent is added to the hard coat layer, the proportional relationship may not be established.

A coating liquid for forming an antireflection layer containing an organosilicon compound as component (C), a fluorine-containing silane compound as component (D), silica-based fine particles as component (E), and a bluing agent as component (F) In addition to these components, if necessary, a small amount of a curing catalyst, a surfactant, an antistatic agent, an ultraviolet absorber, an antioxidant, a light stabilizer such as hindered amine / hindered phenol,
Fluorescent dyes and pigments can be added to improve the coating property of the coating liquid and improve the film performance after curing.

Specifically, as a method for forming a low-refractive index antireflection layer by a wet method, a dipping method,
Known methods such as a spinner method, a spray method, and a flow method can be used. In consideration of forming a thin film with a thickness of 50 nm to 150 nm on a curved surface like a plastic lens among various film forming methods, a dipping method or a spinner method is preferable.

When forming the low refractive index layer on the hard coat layer, it is preferable to pre-treat the hard coat layer surface. Specific examples of this pretreatment include surface polishing, UV-ozone cleaning,
A method of hydrophilizing the hard coat surface (contact angle θ 60 ° or less) such as plasma treatment is effective.

A specific method for forming the antireflection layer can be performed by the following procedure. First, the organosilicon compound of component (C) and the fluorine-containing silane compound of component (D) are diluted with an organic solvent, and hydrolyzed by adding water, thin hydrochloric acid, acetic acid or the like as necessary. Further, a product in which the silica-based fine particles of the component (E) are colloidally dispersed in an organic solvent at a fraction of 5 to 50% by weight is added. Thereafter, a blueing agent as component (F) and, if necessary, a surfactant, an ultraviolet absorber, an antioxidant and the like are added and sufficiently stirred and used as a coating liquid. At this time, the concentration of the coating solution diluted with respect to the solid content after curing is preferably 0.5 as the solid content concentration.
-15% by weight, more preferably 1-10% by weight. When the solid content concentration exceeds 15% by weight, it is difficult to obtain a predetermined film thickness even if the pulling speed is reduced by the dipping method or the rotation speed is increased by the spinner method. It becomes thicker than necessary. If the solid content concentration is less than 0.5% by weight, the film thickness becomes thinner than necessary even if the pulling speed is increased by the dipping method or the rotation speed is decreased by the spinner method. It is difficult to obtain the film thickness. Also, if you make the speed too fast or make the speed too slow,
The uneven coating on the lens tends to be large, and even when a surfactant or the like is added, the corresponding partition cannot be made.

The antireflection layer can be obtained by applying the coating liquid to the plastic lens and then curing it with heat or ultraviolet rays, but it is preferable to cure it by heat treatment. In this case, the heating temperature is appropriately determined in consideration of the composition of the coating solution, the heat resistance of the plastic lens substrate, and the like, but is preferably 50 ° C to 200 ° C, more preferably 80 ° C to 140 ° C.

The film thickness of the obtained antireflection layer needs to be in the range of 50 nm to 150 nm. If it is too thick or too thin than this range, a sufficient antireflection effect cannot be obtained. Further, the refractive index of the antireflection layer has a refractive index difference of 0.10 with respect to the underlying hard coat layer in order to function as an antireflection layer.
Above, preferably 0.15 or more, more preferably 0.20 or more. The specific refractive index is preferably in the range of 1.28 to 1.45.

For the formation of the antifouling layer, for example, a fluorine-containing silane compound represented by the following general formula (1) proposed in Patent Document 7 is preferably used.

R _f in the general formula (1) is a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms, preferably CF ₃ —, C ₂ F ₅ —, C ₃ F ₇ —. X ² is iodine or hydrogen, Y ¹ is hydrogen or a lower alkyl group, and Z is fluorine or a trifluoromethyl group.
R ⁵ is a hydrolyzable group, for example, halogen, —OR ⁷ , —OCOR ⁷ , —OC (R
_{^{7) = C (R 8)}} 2, -ON = C (R 7) 2, -ON = CR 9 are preferred. More preferably, _chlorine, -OCH 3, is _-OC 2 _{H 5.} Here, R ⁷ is an aliphatic hydrocarbon group or an aromatic hydrocarbon group, R ⁸ is hydrogen or a lower aliphatic hydrocarbon group, and R ⁹ is a C 3-6 divalent aliphatic hydrocarbon group. R ⁶ is hydrogen or an inert monovalent organic group, and is preferably a monovalent hydrocarbon group having 1 to 4 carbon atoms. a, b, c and d are integers of 0 to 200, preferably 1 to 50, and e is 0 or 1. k and n are integers of 0 to 2, preferably 0. t is an integer greater than or equal to 1, Preferably it is an integer of 1-10. Moreover, although molecular weight is 5 * 10 < ² > -1 * 10 < ⁵ >, Preferably it is 5 * 10 < ² > -1 * 10 < ⁴ >.
It is.

上記式中、ｕは１〜５０の整数を表す。 Moreover, what is shown by following General formula (2) is mentioned as a thing of the preferable structure of the fluorine-containing silane compound shown by the said General formula (1).

In said formula, u represents the integer of 1-50.

In order to form the antifouling layer on the spectacle lens using the fluorine-containing silane compound, a method of dissolving in an organic solvent and applying to the spectacle lens surface can be employed. As a coating method, a dipping method, a spin coat method, a spray method, a flow method, a doctor blade method, a roll coat coating, a gravure coat coating, a curtain flow coating, or the like is used. As an organic solvent,
Examples include perfluorohexane, perfluoromethylcyclohexane, perfluoro-1,3-dimethylcyclohexane and the like.

The concentration when diluted with an organic solvent is preferably in the range of 0.03 to 1 wt%. If the concentration is too low, it may be difficult to form a sufficiently thick antifouling layer and a sufficient antifouling effect may not be obtained. On the other hand, if the concentration is too high, the antifouling layer may become too thick. There is a risk of increasing the burden of rinsing work to eliminate post-coating unevenness.

As a method for applying the fluorine-containing silane compound, a vacuum vapor deposition method in which the fluorine-containing silane compound is evaporated in a vacuum chamber and adhered to the spectacle lens surface may be employed. In the vacuum deposition method, the raw material compound can be used at a high concentration or without a diluting solvent.

The film thickness of the antifouling layer is not particularly limited, but is 0.001 to 0.5 μm, preferably 0.00.
1 to 0.03 μm. If the film thickness of the antifouling layer is too thin, the antifouling effect is poor, and if it is too thick, the surface becomes sticky, which is not preferable. Further, when the antifouling layer is provided on the surface of the antireflection layer, if the antifouling layer is thicker than 0.03 μm, the antireflection effect is lowered, which is not preferable.

1. Manufacture of spectacle lenses The plastic lens in the example is a primer layer on a plastic lens substrate,
A hard coat layer, an organic antireflection layer, and an antifouling layer were sequentially formed.
(1) Lens substrate A plastic lens substrate having a refractive index of 1.67 (product name “Seiko Super Sovereign (SSV)” manufactured by Seiko Epson Corporation) was used.
(2) Primer layer The primer layer was formed by applying a coating solution to a lens substrate. First, a commercially available water-based polyester “A-160
P "(Takamatsu Yushi Co., Ltd., solid concentration 25%) 77 g, methanol 220 g, propylene glycol monomethyl ether (PGME) 31.5 g, water 91.8 g, methanol-dispersed titanium dioxide-zirconium dioxide-silicon dioxide composite fine particle sol (Catalyst Chemical Industry Co., Ltd.)
Manufactured, solid concentration 20 wt%)) 78.8 g, silicone surfactant (Nihon Unicar Co., Ltd., trade name “L-7604”) 0.1 g was added and stirred for 2 hours. For the application, a dipping method (pickup speed: 20 cm / min) was used, and the applied base lens was heat-cured at 80 ° C. for 20 minutes. The primer layer thus formed has a film thickness of 0.5 μm and a refractive index of 1.67.
(3) Hard coat layer The following coating liquid was formed on the primer layer. First, butyl cellosolve 62.
5 g and 67.1 g of γ-glycidoxypropyltrimethoxysilane were mixed. To this mixed solution, 30.7 g of 0.1 N hydrochloric acid aqueous solution was added dropwise with stirring, and the mixture was further stirred for 4 hours and then aged overnight. In this liquid, 325 g of methanol-dispersed titanium dioxide-zirconium dioxide-silicon dioxide composite fine particle sol (manufactured by Catalyst Kasei Kogyo Co., Ltd., solid content concentration 20% by weight), glycerol diglycidyl ether (manufactured by Nagase ChemteX Corporation, trade name “ Denacor EX-313
)) After adding 12.5 g, iron (III) acetylacetonate 1.36 g, silicone surfactant (manufactured by Nippon Unicar Co., Ltd., trade name “L-7001”) 0.15 g, phenolic antioxidant 0.63 g (manufactured by Kawaguchi Chemical Industry Co., Ltd., trade name “ANTAGE CRYSTAL”) was added, and the mixture was stirred for 4 hours and then aged overnight. Application is a dipping method (pickup speed 35 cm / min)
Then, after heat-curing treatment at 80 ° C. for 30 minutes, heat-curing treatment at 125 ° C. for 180 minutes was further performed. The hard coat layer thus formed has a thickness of 2.0 μm and a refractive index of 1.67.

(4) Organic antireflection layer The following coating liquid was formed on the hard coat layer. In the stainless steel container, the following formula (
47.8 parts by weight (0.08 mol) of the fluorine-containing silane compound shown in A) and methanol 312.
4 parts by weight were added, and 4.7 parts by weight of γ-glycidoxypropyltrimethoxysilane (0.
02 mol) and 36 parts by weight of 0.1N (0.1 mol / L) hydrochloric acid aqueous solution were further added to obtain a mixed solution. This mixed solution was stirred in a thermostatic bath at 25 ° C. for 2 hours to obtain a composition having a solid content of 10% by weight.
_{(CH 3 O) 3 Si-} C 2 H 4 -C 6 F 12 -C 2 H 4 -Si (OCH 3) 3 (A)
This composition and a hollow silica-isopropanol dispersion sol (manufactured by Catalyst Kasei Kogyo Co., Ltd .; solid content concentration 20% by weight, average primary particle size 35 nm, outer shell thickness 8 nm) 30 so that propylene glycol monomethyl ether (P
GME) 935 parts and diluted, and further, an anthraquinone oil-soluble dye that is a colorant that does not absorb light in the wavelength range of 400 to 500 nm (trade name “Diaresin” manufactured by Mitsubishi Chemical Corporation).
Blue J ") was added in an amount of 0.045 g (the amount of blueing agent added to the coating composition was 90 ppm) to obtain a coating solution for forming an antireflection layer having a solid content of 3% by weight.
The application was performed by an immersion method, the pulling rate was 10 cm / min, and the liquid temperature was 25 ° C. After application, annealing was performed at 125 ° C. for 90 minutes. The thus formed organic antireflection layer had a thickness of about 91 nm and a refractive index of about 1.42.

(5) Antifouling layer Fluorosilane compound A having a molecular weight of 2500 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KY-13”)
0 ”) (hereinafter compound A1) and fluorine silane compound B having a molecular weight of 497.5 (trade name“ KP-801 ”manufactured by Shin-Etsu Chemical Co., Ltd.) (hereinafter compound B1), It was diluted with Sumitomo 3M Co., Ltd., trade name "Novec HFE-7200") to prepare a 3% solid content concentration solution. A porous ceramic pellet impregnated with 1 g and dried was set in a chamber as a deposition source. After drying this pellet, it is set in a vacuum vapor deposition machine, exhausted until the ultimate pressure is in the range of 1.0 to 4.0 × 10 ⁻² Pa, the plastic lens described above is introduced into the vacuum vapor deposition machine, and the pellet Was heated from 400 ° C. to 500 ° C. to evaporate the silane compound, and an antifouling layer was formed on the surface of the antireflection layer. After vapor deposition, the inside of the vapor deposition machine was gradually returned to atmospheric pressure, and the plastic lens was taken out. After this, 90 ° C
It was kept in a constant temperature and humidity chamber set to 90% RH for 2 hours. Further, the antifouling layer may be formed not only by the dry method but also by dipping. In the case of the wet type, the lens is immersed in a 0.3% solid concentration solution and held for 1 minute, then pulled up at 15 cm / min, and then put into a constant temperature and humidity chamber set at 90 ° C. and 90% RH. Hold for 5 hours.

(Comparative Example 1)
Blueing agent (Anthraquinone oil-soluble dye (Mitsubishi Chemical Corporation)
0.045 g of trade name “Diaresin Blue J”)) was added. The amount of the blueing agent added to the coating composition was 90 ppm.
(Comparative Example 2)
0.015 g of the bluing agent was added only to the hard coat layer. The amount of the blueing agent added to the coating composition was 30 ppm.
(Example)
As described above, 0.03 g of the bluing agent was added only to the organic antireflection layer. The amount of bluing agent added to the coating solution for forming the antireflection layer was 200 ppm.
(Comparative Example 3)
None of the bluing agents were added.

2. Evaluation of the obtained lenses The lenses obtained in the examples and comparative examples were evaluated as follows.
-Abrasion resistance A load of 1 kg was applied with Bonstar # 0000 steel wool (manufactured by Nippon Steel Wool Co., Ltd.), 10 reciprocating surfaces were rubbed, and the degree of scratching was visually evaluated in the following stages.
A: Scratches are hardly observed in the rubbed range.
B: 1 to 5 scratches were attached within the above range.
C: 5 to 10 scratches were in the above range.
・ Adhesion Sunshine weather meter with xenon lamp (Suga Test Co., Ltd .; WEL-
After exposure to SUN-HC) for 80 hours, a cross-cut tape test was conducted according to JIS D-0202. That is, using a knife, cuts are made on the substrate surface at intervals of 1 mm to form 100 squares of 1 mm square. Next, cellophane adhesive tape (Nichiban (
Co., Ltd .: product name “Selotape (registered trademark)”) was pressed strongly, and then suddenly pulled away from the surface in the direction of 90 °, and then the cells with the coat film remaining were visually observed as an adhesion index.
“◯”: 100 to 96 squares remain.
“Δ”: 95 to 90 squares remain.
“×”: Less than 90 squares remain.
・ B *
CIELAB color method (JISZ-87) for pre-coated and hard-coated lenses
The value of b ^* according to 30) was measured. The higher the value, the stronger the yellowness.
-Color tone and appearance Using a black background and a fluorescent lamp in a dark box, the color tone of the lens was confirmed visually. A colorless and transparent product, a product that was very close to colorless and transparent, was evaluated as “◯”, and a product that could not be said as colorless and transparent was evaluated as “C”.
3. Evaluation results

The evaluation results are summarized in the following table.

When a blueing agent is blended in the primer layer (Comparative Example 1), when a blueing agent is blended in the hard coat layer (Comparative Example 2), and when a blueing agent is blended in the organic antireflection layer (Example) In any case, the lens is colorless and transparent, and the effect of blending the blueing agent is seen as compared with the case where the blueing agent is not blended (Comparative Example 3).

However, the primer layer is a layer that is not completely cured, and the bluing agent may melt out. In addition, when a bluing agent is added to the hard coat layer, there is a phenomenon in which the yellowing cancellation effect is not so much even if the bluing agent is added so that it looks quite blue when viewed from the edge. The proportional relationship between quantity and effect may not be established.

On the other hand, when a bluing agent is added to the organic antireflection layer, the amount of bluing agent added and the yellowing canceling effect tend to be proportional. Moreover, when coloring a plastic lens base material, there is little influence on the color of a lens compared with the case where a blueing agent is mix | blended with a hard-coat layer. Moreover, there is an advantage that a relatively small amount of addition is sufficient.

  The spectacle lens of the present invention can be used as a technique for manufacturing a colorless and transparent spectacle lens.

Claims (4)

An eyeglass lens having an organic antireflection layer formed from a coating liquid for forming an antireflection layer containing a colorant that does not absorb light in the wavelength region of 400 to 500 nm. The spectacle lens according to claim 1,
The eyeglass lens, wherein the colorant contains an anthraquinone dye. The spectacle lens according to claim 1 or 2,
The coating liquid for forming the antireflection layer has the following component (D):
(D) the general ^{_{formula: X m R 1 3-m}} Si-Y-SiR 1 3-m fluorine-containing silane compound represented by _{X m} (In the formula, ^{R 1} is monovalent hydrocarbon having 1 to 6 carbon atoms A hydrogen group, Y is a divalent organic group containing one or more fluorine atoms, X is a hydrolyzable group, and m is an integer of 1 to 3.)
An eyeglass lens comprising: The spectacle lens according to any one of claims 1 to 3,
The content of the colorant in the antireflection layer forming coating solution is 50 to 600 ppm.
The spectacle lens characterized by being.