JP2006201424A - Plastic lens and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To improve weather resistance of a lens on which an antireflection layer is produced of an organic thin film. <P>SOLUTION: A hard coating layer to be a base layer of the antireflection layer of the organic thin film is formed of a 1st coating composition containing particulates consisting of one or more kinds of metal oxides chosen from an element group composed of Si, Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr and In instead of Ti and/or multiple oxide particulates consisting of two or more kinds of metal oxides chosen from the element group. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a plastic lens having an organic thin film antireflection layer and a method for producing the same.

  Glasses lenses use plastics as the base material (fabric) in addition to glass. Plastic lenses are lighter than glass lenses, have better moldability, processability and dyeability, and are more resistant to breakage and higher safety. There are many merits such as. However, plastic lenses are soft and very vulnerable. For this reason, a hard coat layer having a high hardness is formed on the surface of the plastic lens to improve the scratch resistance.

  Furthermore, since the eyeglass lens requires a lens having a high refractive index, when using a plastic lens substrate having a high refractive index, the hard coat layer formed thereon is also prevented from generating interference fringes. The same high refractive index is required.

Patent Document 1 discloses a method for producing a sol containing composite fine particles of cerium oxide and titanium oxide as a plastic surface coating agent. Patent Documents 2 and 3 disclose a method in which metal oxide fine particles such as high refractive index titanium dioxide, silicon, zirconium and / or aluminum oxide are used for the hard coat layer.
JP-A-1-301517 JP-A-2-264902 JP-A-8-48940

As the antireflection layer formed on the hard coat layer, as disclosed in Patent Document 3, a multilayer film made of an inorganic material such as SiO ₂ is used. On the other hand, the development of an antireflection layer made of an organic material (organic thin film) is underway. Since the antireflection layer of the organic thin film can be manufactured by a wet method, a vacuum process is unnecessary, and the apparatus for film formation can be reduced in size and simplified. In addition, organic materials have a thermal expansion coefficient close to that of plastic substrates, and plastic lenses have the advantage of being able to suppress the occurrence of cracks in high-temperature environments by adopting an organic antireflection layer. Is allowed.

However, it has been found that when an antireflection layer composed of an organic thin film is formed on the hard coat layer as shown in Patent Documents 1 to 3, the weather resistance deteriorates. As disclosed in Patent Documents 1 to 3, in order to realize a hard coat layer having a high refractive index, it is preferable to form a layer containing titanium. In contrast, titanium, in particular, anatase-type titanium that has been used conventionally, is activated when it receives light (ultraviolet light) energy, and has high characteristics (photoactivity) due to strong oxidative degradation power. The organic hard coat layer has high adhesion to the organic antireflection film, but both are organic and easily decomposed by the strong photoactivity of titanium. However, conventional antireflection layers made of inorganic materials such as SiO ₂ , ZrO ₂ , and TiO ₂ form a multilayer film of 5 to 7 layers, and each layer is dense so that it has excellent UV-cutting performance and water permeation. The nature is also low. For this reason, it is considered that the photoactivity of titanium has hardly been a problem.

  On the other hand, since the organic antireflection layer can be formed as a single layer or a thin film of about three layers on the hard coat layer, the antireflection layer is very thin. Further, the organic reflective layer is inferior in density to the inorganic antireflection layer. Therefore, compared with inorganic antireflection layers, organic antireflection layers have inferior UV-cut performance, and also have high water permeability, which promotes the photoactivity of titanium contained in the hard coat layer. It is thought that it becomes. For this reason, when the hard coat layer or the like is deteriorated even when being used for a long time, the antireflection layer composed of the organic thin film is deteriorated and peeled off. On the other hand, a thin antireflection layer made of an organic thin film leads to an improvement in adhesion to the hard coat layer in combination with a close thermal expansion coefficient. Therefore, increasing the film thickness of the organic antireflection film abandons the merit of the organic antireflection film. Furthermore, since the organic antireflection film contains silica-based fine particles, it has high water permeability, thereby ensuring antifogging properties, ensuring dyeability, and adding various functions. It is being considered. Therefore, increasing the film thickness to improve the ultraviolet ray blocking performance or reducing the water permeability also leads to abandoning the merit of the organic antireflection film.

  Accordingly, the present invention provides a plastic lens excellent in weather resistance and a method for producing the same without losing the original merit of the antireflection layer of an organic thin film such as being thin and having a thermal expansion coefficient close to that of a hard coat layer. It is aimed.

Accordingly, the present invention provides a plastic lens having a plastic lens substrate, a hard coat layer formed on the plastic lens substrate, and an antireflection layer formed on the hard coat layer. It is a coating film formed from the first coating composition containing at least the following components (A) and (B), and the antireflective layer has a refractive index lower than the refractive index of the hard coat layer. The difference in rate is 0.10 or more, and it can be constituted by an organic thin film having a film thickness of 50 nm to 150 nm.
(A) Fine particles composed of one or more metal oxides selected from the group consisting of Si, Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr, and In having an average particle diameter of 1 nm to 200 nm, and Composite oxide fine particles composed of two or more metal oxides selected from the element group.
(B) An organosilicon compound represented by the general formula: R ¹ SiX ¹ ₃ . In the formula, R ¹ represents an organic group having 3 or more carbon atoms having a polymerizable reactive group, and X ¹ represents a hydrolyzable group.

  The hard coat layer preferably has a refractive index of about ± 0.03 with respect to the refractive index of the plastic lens substrate having a high refractive index in order to suppress interference fringes. Therefore, the hard coat layer needs to have a high refractive index. In the present invention, the first coating composition, which is a component of the coating solution for forming the hard coat layer, is replaced with a component (A ) To increase the refractive index. These metal oxides do not have intense photoactivity like titanium and are stable even when exposed to ultraviolet rays. Therefore, by forming with the first coating composition, the weather resistance of the hard coat layer itself can be improved even in an environment where the hard coat layer is exposed to ultraviolet rays. For this reason, even if an antireflection layer is formed on the hard coat layer by an organic thin film, the hard coat layer can be prevented from being deteriorated, and has sufficient weather resistance and water resistance, that is, durability in a humid environment, Furthermore, the merit of the combination of the organic hard coat layer and the organic antireflection layer, that is, the thermal expansion coefficient is close, so there is no peeling and high heat resistance (high temperature durability), and the antireflection layer is thin and water-permeable. Because of this, it is possible to provide plastic lenses with the advantage of being dyeable.

  As described above, the average particle size of the component (A) composite oxide fine particles is preferably in the range of 1 nm to 200 nm, and more preferably in the range of 5 nm to 30 nm.

  Furthermore, in the present invention, the first coating composition that forms the hard coat layer is further provided with an organosilicon compound or a surface of the composite oxide fine particles of the component (A) in order to enhance dispersion stability. It is also possible to use those treated with an amine compound.

  Examples of the organosilicon compound used in this case include monofunctional silane, bifunctional silane, trifunctional silane, and tetrafunctional silane. In the treatment, the hydrolyzable group may be untreated or hydrolyzed. In addition, after the treatment, it is preferable that the hydrolyzable group reacts with the —OH group of the fine particles, but there is no problem in stability even if a part of the hydrolyzable group remains.

  Amine compounds include alkylamines such as ammonium or ethylamine, triethylamine, isopropylamine and n-propylamine, aralkylamines such as benzylamine, alicyclic amines such as piperidine, alkanols such as monoethanolamine and triethanolamine. There is an amine.

  The addition amount of these organosilicon compound and amine compound is preferably within a range of about 1 to 15% with respect to the weight of the inorganic oxide fine particles.

  The compounding amount of the composite oxide fine particles (A) is desirably in the range of 5 to 80% by weight, particularly 10 to 50% by weight, based on the solid content in the first coating composition. If the amount is too small, the wear resistance of the coating film may be insufficient. Moreover, when there are too many compounding quantities, a crack will arise in a coating film and dyeing | staining property may become inadequate.

The (B) component organosilicon compound functions as a binder for the hard coat layer. The (B) component formula R ¹ is an organic group having 3 or more carbon atoms having a polymerizable reactive group, and is an allyl group. , An acrylic group, a methacryl group, a 1-methylvinyl group, an epoxy group, a mercapto group, a cyano group, an isocyano group, and an amino group.

X ¹ is a hydrolyzable functional group, and specific examples thereof include alkoxy groups such as methoxy group, ethoxy group and methoxyethoxy group, halogen groups such as chloro group and bromo group, or acyloxy groups. Etc. The number of hydrolyzable groups is 3, and it is necessary to be able to form a three-dimensional crosslinked structure. When the number of hydrolyzable groups is 2 or less, the abrasion resistance of the coating film is insufficient.

  Specific examples of the organosilicon compound of component (B) include allyltrialkoxysilane, acryloxypropyltrialkoxysilane, methacryloxypropyltrialkoxysilane, γ-glycidoxypropyltrialkoxysilane, β- (3,4- Epoxycyclohexyl) -ethyltrialkoxysilane, mercaptopropyltrialkoxysilane, γ-aminopropyltrialkoxysilane and the like.

  Two or more organic silicon compounds as component (B) may be mixed and used. In addition, it is more effective to use the organosilicon compound as the component (B) after hydrolysis.

  In addition, it is preferable that the film thickness of a hard-coat layer is 0.05 micrometer-30 micrometers. If the thickness is less than 0.05 μm, the basic performance cannot be realized, and if it exceeds 30 μm, the smoothness of the surface may be impaired or optical distortion may occur.

  Moreover, the organic thin film used as an antireflection layer has a film thickness in the range of 50 nm to 150 nm, and a sufficient antireflection effect cannot be obtained if the film is too thick or too thin. Since the refractive index of the antireflection layer functions as an antireflection layer, the refractive index difference from the underlying hard coat layer is 0.10 or more, preferably 0.15 or more, more preferably 0.20 or more. is there. More preferably, it is the range of 1.30-1.45.

  As an organic thin film constituting the antireflection layer, silicone-based, acrylic-based, epoxy-based, urethane-based, melamine-based resins, or raw material monomers thereof are used alone or in combination with two or more other resins and raw material monomers. An antireflection layer can be formed by film formation. In addition, when considering various properties such as heat resistance, chemical resistance, and scratch resistance as a plastic lens, it is preferable to use a low refractive index layer containing a silicone resin. In order to improve or adjust the refractive index, it is more preferable to add a particulate inorganic substance. 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.

A preferred example of the organic thin film of the antireflection layer is a coating film formed from the second coating composition containing the following components (C) and (D).
(C) An organosilicon compound represented by the general formula: R ² _r R ³ _q SiX ² _4-q-r . In the formula, R ² is an organic group having a polymerizable reactive group, R ³ is a hydrocarbon group having 1 to 6 carbon atoms, X ² is a hydrolyzable group, q is 0 or 1, and r is 0 Or it is 1.
(D) Silica-based fine particles. The organosilicon compound of component (C) functions as a binder for the organic thin film, and the silica-based fine particles of component (D) are components for adjusting the refractive index.

R ^{2 of the} organosilicon compound of component (C) is an organic group having a polymerizable reactive group, for example, vinyl group, allyl group, acrylic group, methacryl group, epoxy group, mercapto group, cyano group, amino group, etc. Is mentioned.

R ^{3 of the} organosilicon compound of component (C) is a hydrocarbon group having 1 to 6 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a butyl group, a vinyl group, and a phenyl group.

(C) X ² of the organosilicon compound of the component is a hydrolyzable functional group, and specific examples include a methoxy group, an ethoxy group, an alkoxy group such as methoxyethoxy group, chloro group, a halogen group such as bromo group And an acyloxy group.

  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) -ethyltrialkoxysilane, mercaptopropyltrialkoxysilane, γ-aminopropyltrialkoxysilane, N-β (aminoethyl) -γ-aminopropylmethyl dialkoxysilane, tetraalkoxysilane and the like can be mentioned.

  Examples of the silica-based fine particles of component (D) include silica sol in which fine particles of silica having an average particle diameter of 1 nm to 100 nm are colloidally dispersed in a dispersion medium such as water, alcohol-based or other organic solvents.

  Furthermore, it is desirable that the silica-based fine particles of component (D) have an internal cavity (gap). By using silica-based fine particles having internal cavities, the refractive index of the antireflection layer can be lowered, and the difference in refractive index with the hard coat layer can be increased to increase the antireflection effect. 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.

  In addition to the above components (C) and (D), the second coating composition for forming the antireflection layer includes polyurethane resin, epoxy resin, melamine resin, polyolefin resin, urethane acrylate. It is possible to add various resins such as resins and epoxy acrylate resins, and various monomers such as methacrylates, acrylates, epoxies, vinyls and the like as raw materials for these resins. Among them, it is preferable to add various fluorine-containing polymers or various fluorine-containing monomers in order to reduce the refractive index. The fluorine-containing polymer at this time is preferably a polymer obtained by polymerizing a fluorine-containing vinyl monomer, and preferably has a functional group copolymerizable with other components.

  Furthermore, the second coating composition for the antireflection layer can be used by diluting in a solvent, if necessary. As the solvent, solvents such as water, alcohols, esters, ketones, ethers and aromatics are used.

  In addition to these components, the second coating composition (coating solution for the antireflection layer) containing the organosilicon compound (C) and the silica-based fine particles (D) is necessary. A small amount of curing catalyst, surfactant, antistatic agent, ultraviolet absorber, antioxidant, light stabilizer such as hindered amine / hindert phenol, disperse dye / oil soluble dye / fluorescent dye / pigment, etc. Can be added to improve the applicability of the coating solution and improve the film performance after curing.

  Moreover, it is desirable that the first coating composition further contains a polyfunctional epoxy compound as the component (E). The polyfunctional epoxy compound can improve the adhesion of the hard coat layer to the plastic substrate and improve the water resistance of the hard coat layer. Furthermore, the antireflection layer composed of an inorganic vapor deposition film functions as a protective film for the hard coat layer, whereas the antireflection layer composed of an organic thin film like the lens of the present invention is extremely thin, When silica-based fine particles having cavities are used, water resistance is required for the hard coat layer in order to pass water, and it is useful to contain a polyfunctional epoxy compound.

  Specific examples of the (E) component polyfunctional epoxy compound include 1,6-hexanediol glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, Nonaethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, tetrapropylene glycol diglycidyl ether, nonapropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, neopentyl Diglycidyl ether of glycol hydroxyhybalic acid ester, trimethylo Propane glycidyl ether, trimerol propane triglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, diglycerol diglycidyl ether, diglycerol triglycidyl ether, diglycerol tetraglycidyl ether, pentaerythritol triglycidyl ether, pentaerythritol tetra Aliphatic epoxy compounds such as glycidyl ether, dipentaerythritol tetraglycidyl ether, sorbitol tetraglycidyl ether, triglycidyl ether of tris (2-hydroxyethyl) isocyanate, isophoronediol diglycidyl ether, bis-2,2-hydroxycyclohexylpropane Alicyclic epoxy compounds such as diglycidyl ether Examples include aromatic epoxy compounds such as resorcin diglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, orthophthalic acid diglycidyl ether, phenol novolac polyglycidyl ether, and cresol novolac polyglycidyl ether. .

  Among these, 1,6-hexanediol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, trimerolpropane triglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, tris (2-hydroxyethyl) Aliphatic epoxy compounds such as triglycidyl ether of isocyanate are particularly preferred.

Furthermore, the first coating composition preferably contains the following component (F).
(F) An organosilicon compound represented by the general formula: R ⁴ _n SiX ³ _4-n . In the formula, R ⁴ represents a hydrocarbon group having 1 to 3 carbon atoms, X ³ represents a hydrolyzable group, and n represents 0 or 1.

  This organosilicon compound of component (F) is effective in further improving durability, particularly scratch resistance. The amount of the organosilicon compound (F) used is preferably 2 to 15% by weight of the total solid content composition. That is, if it is less than 2% by weight, there is no effect of addition, and if it exceeds 15% by weight, the coating film tends to be clouded or cracked, which is not preferable. These compounds may be used alone or in combination of two or more. Moreover, it is more effective to use the organosilicon compound of component (F) after hydrolysis.

R ^{4 of the} organosilicon compound of component (F) is a hydrocarbon group having 1 to 3 carbon atoms, and specific examples include vinyl group, allyl group, acrylic group, methacryl group, 1-methylvinyl group, epoxy group. , Mercapto group, cyano group, isocyano group, amino group, methyl group, ethyl group, propyl group and the like.

(F) X ³ of the organosilicon compound of the component is a hydrolyzable functional group, and specific examples include a methoxy group, an ethoxy group, an alkoxy group such as methoxyethoxy group or chloro group, such as bromo group A halogen group, an acyloxy group, etc. are mentioned.

  Specific examples of the organosilicon compound of component (F) include tetraalkoxysilane, vinyltrialkoxysilane, methyltrialkoxysilane, and allyltrialkoxysilane.

  In the method for producing a plastic lens having an organic thin film according to the present invention, a hard coat layer is formed on a plastic lens substrate by a first coating composition containing at least the following components (A) and (B). An antireflection layer for forming an organic thin film having a hard coat layer forming step, a refractive index lower than the refractive index of the hard coat layer by 0.10 or more, and a film thickness of 50 nm to 150 nm on the hard coat layer Forming step.

  (A) Fine particles composed of one or more metal oxides selected from the group consisting of Si, Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr, and In having an average particle diameter of 1 nm to 200 nm, and Composite oxide fine particles composed of two or more metal oxides selected from the element group.

(B) An organosilicon compound represented by the general formula: R ¹ SiX ¹ ₃ . In the formula, R ¹ represents an organic group having 3 or more carbon atoms having a polymerizable reactive group, and X ¹ represents a hydrolyzable group.

  In the antireflection layer forming step, it is preferable to form an organic thin film by a wet method. By adopting the wet method, a vacuum process necessary for forming the inorganic antireflection layer is unnecessary, and the apparatus for film formation can be reduced in size and simplified. Specifically, known methods such as a dipping method, a spinner method, a spray method, and a flow method can be used. In consideration of forming a thin film having 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.

  An inorganic film formed by a dry method such as vapor deposition or sputtering is formed by such a wet method, whereas the heat resistance is low due to a large difference in thermal expansion coefficient from the hard coat layer of the underlying organic coating. Since the antireflection layer has a small difference in coefficient of thermal expansion from the hard coat layer, cracking due to heating hardly occurs, and a lens having excellent heat resistance can be obtained.

  Moreover, when forming an antireflection layer on a hard-coat layer, it is preferable to pre-process the hard-coat layer surface. As a specific example of this pretreatment, a method of hydrophilizing the hard coat surface (contact angle θ is 60 ° or less) such as surface polishing, ultraviolet-ozone cleaning, plasma treatment, or the like is effective.

  In addition, a curing catalyst can be mix | blended with the 1st composition for coating which forms a hard-coat layer. However, it can be cured without a curing catalyst. Preferred curing catalysts include perchloric acids such as perchloric acid, ammonium perchlorate, and magnesium perchlorate, Cu (II), Zn (II), Co (II), Ni (II), Be (II), and Ce. (III), Ta (III), Ti (III), Mn (III), La (III), Cr (III), V (III), Co (III), Fe (III), Al (III), Ce Examples include amino acids such as acetylacetonate, amine, glycine, Lewis acid, organic acid metal salts and the like having (IV), Zr (IV), V (IV) and the like as a central metal atom. Among these, magnesium perchlorate, Al (III), and acetylacetonate of Fe (III) are more preferable in terms of curing conditions and pot life of the coating liquid. The addition amount is desirably within the range of 0.01 to 5.0% by weight of the solid content concentration.

  The first coating composition thus obtained can be diluted with a solvent and used as necessary. As the solvent, solvents such as alcohols, esters, ketones, ethers and aromatics are used.

  The first coating composition for forming the hard coat layer may contain a small amount of a metal chelate compound, a surfactant, an antistatic agent, an ultraviolet absorber, an antioxidant, a disperse dye, as necessary, in addition to the above components. Oil-resistant dyes, pigments, photochromic compounds, hindered amines, hindered phenol-based light and heat resistant stabilizers and the like can be added to improve the coating properties of the coating liquid, the curing speed, and the film performance after curing.

  Furthermore, when the first coating composition is applied to the substrate, the surface of the plastic lens substrate is previously subjected to alkali treatment, acid treatment, surfactant treatment for the purpose of improving the adhesion between the plastic lens substrate and the film. It is effective to perform peeling / polishing treatment with inorganic or organic fine particles, primer treatment or plasma treatment.

  In addition, as a method for forming a hard coat layer, that is, as a method for applying and curing the coating composition, the coating composition was applied by a dipping method, a spin coating method, a spray coating method, a roll coating method, or a flow coating method. Then, a film can be shape | molded by heat-drying for several hours at the temperature of 40-200 degreeC.

  Hereinafter, the present invention will be further described based on Examples and Comparative Examples in which a plastic lens for spectacles is manufactured using the present invention. The experimental results of the lenses obtained by the examples and comparative examples described below are shown together in FIG.

Example 1
(Hard coat layer)
A first coating composition (hereinafter, coating solution) HC1 for applying a hard coat layer on a plastic lens substrate was prepared as follows. First, to 710 parts of propylene glycol methyl ether, 1160 parts of methanol-dispersed methanol-dispersed tin dioxide-tungsten dioxide composite fine particle sol (manufactured by Nissan Chemical Industries, Ltd., solid content concentration 30 wt%) as component (A) was mixed, 313 parts of (B) component γ-glycidoxypropyltrimethoxysilane was mixed. To this solution, 129 parts of 0.1N hydrochloric acid aqueous solution was added dropwise with stirring, followed by stirring for 4 hours.

  And it was aged overnight. In this solution, 2.9 parts of Fe (III) acetylacetonate, 0.7 parts of silicone surfactant (manufactured by Nippon Unicar Co., Ltd., trade name L-7001), phenolic antioxidant (Kawaguchi Chemical Industry Co., Ltd.) ), Trade name Antage Crystal) After adding 3.1 parts, the mixture was stirred for 3 hours to obtain a coating solution HC1.

  This coating solution HC1 was applied to the lens substrate by a dipping method (pickup speed 25 cm / min) (hard coat layer forming step). As a lens base material, Seiko Epson KK-made Seiko Super Sovereign (SSV) lens fabric was used. The same lens substrate is used in the following examples and comparative examples. And after apply | coating to a lens base material, after air-drying for 30 minutes at 80 degreeC, baking for 90 minutes at 120 degreeC was performed, and the lens by which the hard-coat layer with a film thickness of 2.3 micrometers was formed on the lens base material is obtained. (Hard coat layer forming step).

  The plastic lens substrate may be either a high refractive index material that can be used at present or a high refractive index material that will be developed in the future. The refractive index of the material is preferably 1.60 or more. 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 are compounds having groups. In addition, 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. In addition, there are compounds having two or more mercapto groups in the molecule.

  Examples of the compound having one or more disulfide bonds (SS) in the molecule and having an epoxy group and / or a thioepoxy group include bis (2,3-epoxypropyl) disulfide and bis (2,3 -(Thiothiopropyl) disulfide (thio) epoxy compound having one disulfide bond in the molecule, bis (2,3-epithiopropyldithio) methane, bis (2,3-epithiopropyldithio) ethane, Bis (6,7-epithio-3,4-dithiaheptane) sulfide, 1,4-dithian-2,5-bis (2,3-epithiopropyldithiomethyl), 1,3-bis (2,3-epi Thiopropyldithiomethyl) benzene, 1,6-bis (2,3-epithiopropyldithiomethyl) -2- (2,3-epithiopropyldithioethyl) O) -4 Chiahekisan, 1,2,3-tris (2,3-a epithiopropyl dithio) in the molecule, such as propane having two or more disulfide bonds (thio) epoxy compounds. These 1 type can be used individually or in combination of 2 or more types.

  Examples of the compound having two or more iso (thio) cyanate groups in the molecule include aliphatic polyisocyanate compounds such as ethylene diisocyanate, trimethylene diisocyanate, 2,4,4-trimethylhexane diisocyanate, hexamethylene diisocyanate, An alicyclic polyisocyanate compound such as isophorone diisocyanate, an aromatic polyisocyanate compound such as xylylene diisocyanate, a sulfur-containing aliphatic polyisocyanate compound such as bis (isocyanate methyl) sulfide, and 2-isocyanate phenyl-4-isocyanate phenyl sulfide. Aromatic disulfide polyisocyanate compounds, aromatic disulfide polyisocyanate compounds such as bis (4-isocyanatophenyl) disulfide, 2,5 Sulfur-containing alicyclic polyisocyanate compounds such as diisocyanate tetrahydrothiophene, aromatic polyisothiocyanate compounds such as 1,2-diisothiocyanate benzene, aliphatic polyisothiocyanate compounds such as 1,2-diisothiocyanate ethane, thiobis ( Sulfur-containing aliphatic polyisothiocyanate compounds such as 3-isothiocyanate propane) can be exemplified.

  As polythiol having two or more thiol groups in one molecule that undergoes addition reaction with these epoxy group, thioepoxy group, and iso (thio) cyanate group, two polythiols in the molecule represented by the following general formula (G) The polythiol compound having the above mercapto group can be preferably used. The resin obtained using this polythiol compound is excellent in high refractive index, impact resistance, and heat resistance.

R ^5- (SCH ₂ SH) _t (G)
In the above formula (G), R ⁵ represents an organic residue except an aromatic ring. The organic residue is selected from linear or branched aliphatic, alicyclic, heterocyclic, or linear or branched aliphatic, alicyclic or heterocyclic having a sulfur atom in the chain. One or more of these may be mentioned. In the formula, t is an integer of 1 or more, and one or more, preferably two or more mercaptomethylthio groups are required in one molecule. Moreover, you may have mercapto groups other than a mercaptomethylthio group.

(Antireflection layer)
Next, a second coating composition (hereinafter referred to as a low flexion liquid) AR1 serving as a coating solution for the antireflection layer was prepared. First, 105.245 g of propylene glycol monomethyl ether (hereinafter referred to as PGME) and 42.370 g of tetramethoxysilane as component (C) were mixed, and then 24.104 g of 0.1N hydrochloric acid aqueous solution was added dropwise with stirring. Stir for hours. 0.112 g of a silicone-based surfactant (trade name: L7604, manufactured by Nihon Unicar Co., Ltd.) was mixed with this liquid and stirred, and then the component (D), isopropyl alcohol-dispersed hollow silica sol (manufactured by Catalyst Kasei Co., Ltd., solid content) 83.625 g (concentration 20 Wt%) and PGME 859.5544 g were mixed and sufficiently stirred to obtain a low-refractive liquid AR1 for an antireflection layer having a solid content concentration of 3.0%.

  This low refractive liquid AR1 was spin-coated on a lens with a hard coat layer by the following procedure to form an antireflection layer made of an organic thin film (antireflection layer forming step). First, while rotating the lens substrate at 500 rpm, the surface (convex surface) is coated with the low flexure AR1 for 5 seconds, and then the rotational speed is increased to 1800 rpm and maintained for 15 seconds. Thereafter, it is air-dried at 100 ° C. for 10 minutes. Next, while rotating the lens substrate at 800 rpm, the low flexure AR1 is applied to the back surface (concave surface) for 5 seconds, and then the rotation speed is increased to 1800 rpm and maintained for 15 seconds. Thereafter, baking was performed at 100 ° C. for 60 minutes to obtain a lens in which an antireflection layer having a film thickness of about 100 nm and a refractive index of 1.37 was formed on both surfaces of the lens (antireflection layer forming step).

(Example 2)
(Hard coat layer)
Different coating liquids HC2 for forming a hard coat layer were prepared. This coating liquid HC2 was mixed with 506 parts of butyl cellosolve and 583 parts of water-dispersed antimony pentoxide fine particle sol (manufactured by Nissan Chemical Industries, Ltd., solid content concentration 30 wt%) as component (A). 124 parts of certain γ-glycidoxypropyltrimethoxysilane and 37 parts of tetramethoxysilane as component (F) were mixed. To this solution, 55 parts of 0.1N hydrochloric acid aqueous solution was added dropwise with stirring, and the mixture was further stirred for 3 hours.

  After aging all day and night, 15 parts of glycerol polyglycidyl ether (manufactured by Nagase Kasei Kogyo Co., Ltd., trade name Denacol EX313) as component (E) and 2.1 parts of Al (III) acetylacetonate are added to this solution. , 0.5 parts of silicone surfactant (Nihon Unicar Co., Ltd., trade name L-7604), 1.8 parts of hindered amine light stabilizer (Sankyo Co., Ltd., trade name Sanol LS-770) are added. Thereafter, the mixture was stirred for 3 hours to obtain a coating liquid (coating liquid) HC2.

  This coating solution HC2 is applied to the lens substrate by dipping method (pickup speed 35 cm / min), air-dried at 80 ° C. for 30 minutes, and then baked at 120 ° C. for 90 minutes to hard coat with a film thickness of 2.2 μm. A lens having a layer formed thereon was obtained (hard coat layer forming step).

(Antireflection layer)
Next, different low flexures AR2 for the antireflection layer were prepared. First, 150.115 g of 1-propanol and 36.554 g of (C) component γ-glycidoxypropyltrimethoxysilane were mixed, and then 10.045 g of 0.1N aqueous hydrochloric acid solution was added dropwise with stirring, and then Stir for 3 hours. 0.215 g of a silicone-based surfactant (trade name L7001 manufactured by Nihon Unicar Co., Ltd.) was mixed in this liquid and stirred, and then the isopropyl alcohol-dispersed hollow silica sol (Catalyst Kasei Co., Ltd., solid content) as component (D) was stirred. A coating solution AR2 for an antireflection layer having a solid content concentration of 2.5% was obtained by mixing 194.0 g and a 1-propanol 1762.34 g, and stirring sufficiently.

  This low refractive liquid AR2 was spin coated on a lens with a hard coat layer by the following procedure to form an antireflection layer. First, while rotating the lens substrate at 500 rpm, the surface (convex surface) is coated with the low flexure AR2 for 5 seconds, and then the rotational speed is increased to 1500 rpm and maintained for 15 seconds. Thereafter, it is air-dried at 100 ° C. for 10 minutes. Next, while rotating the lens substrate at 500 rpm, the low flexure AR2 is applied to the back surface (concave surface) for 5 seconds, and then the rotation speed is increased to 1800 rpm and maintained for 15 seconds. Thereafter, baking was performed at 100 ° C. for 60 minutes to obtain a lens in which an antireflection layer having a film thickness of about 100 nm and a refractive index of 1.37 was formed on both surfaces of the lens (antireflection layer forming step).

(Example 3)
Different coating liquids HC3 for the hard coat layer were prepared. This coating liquid HC3 is composed of 510 parts of methanol, 617 parts of butyl cellosolve, and methanol-dispersed tin dioxide-zirconium dioxide-antimony pentoxide composite fine particle sol (Nissan Chemical Industry Co., Ltd., solid content concentration 30 wt%) 1498 which is component (A). After mixing the parts, 218 parts of (B) component γ-glycidoxypropyltrimethoxysilane and 101 parts of (F) component γ-glycidoxypropylmethyldimethoxysilane were mixed. To this solution, 101 parts of a 0.1N hydrochloric acid aqueous solution was added dropwise with stirring, and the mixture was further stirred for 2 hours.

  Then, after aging all day and night, 75 parts of 1,6-hexanediol diglycidyl ether (manufactured by Nagase Kasei Kogyo Co., Ltd., trade name Denacol EX-212) as component (E) is added to this liquid. 4.6 parts of acetylacetonate, 0.9 part of silicone surfactant (manufactured by Nippon Unicar Co., Ltd., trade name FZ-2110), phenolic antioxidant (manufactured by Kawaguchi Chemical Industry Co., Ltd., trade name ANTAGE) After adding 3.1 parts of crystal), the mixture was stirred for 3 hours to obtain a coating solution HC3.

  This coating solution HC3 is applied to the lens substrate by dipping (pickup speed 35 cm / min), air-dried at 80 ° C. for 30 minutes, and then baked at 125 ° C. for 100 minutes to form a hard coat layer having a thickness of 2.0 μm. A lens in which was formed was obtained (hard coat layer forming step).

(Antireflection layer)
Next, the antireflective layer anti-reflective liquid AR1 prepared in Example 1 was applied to the lens on which the hard coat layer was formed by the same method as in Example 1 to form an antireflective layer (antireflective layer). Forming step).

(Comparative Example 1)
(Hard coat layer)
Different coating liquids HC4 for the hard coat layer were prepared. This coating liquid HC4 is obtained by mixing 130 parts of propylene glycol methyl ether and 1740 parts of methanol-dispersed anatase type titanium dioxide-zirconium dioxide-silicon dioxide composite fine particle sol (manufactured by Catalyst Chemical Industry Co., Ltd., solid content concentration 20% by weight). , 313 parts of γ-glycidoxypropyltrimethoxysilane were mixed. To this solution, 129 parts of 0.1N hydrochloric acid aqueous solution was added dropwise with stirring, followed by stirring for 4 hours.

  After aging for a whole day and night, 2.9 parts of Fe (III) acetylacetonate, 0.7 part of silicone surfactant (manufactured by Nippon Unicar Co., Ltd., trade name L-7001), phenolic antioxidant (Kawaguchi Chemical) After adding 3.1 parts of Kogyo Co., Ltd., trade name Antage Crystal), the mixture was stirred for 3 hours to obtain a coating solution HC4.

  This coating solution HC4 is applied to the lens substrate by dipping (pickup speed 25 cm / min), air-dried at 80 ° C. for 30 minutes, and then baked at 120 ° C. for 90 minutes to form a hard coat layer having a thickness of 2.2 μm. Got the lens.

(Antireflection layer)
Next, the antireflective layer anti-reflective liquid AR1 prepared in Example 1 was applied to the lens on which the hard coat layer was formed by the same method as in Example 1 to form an antireflective layer.

(Comparative Example 2)
Furthermore, a different coating solution HC5 for the hard coat layer was prepared. This coating solution HC5 was mixed with 212 parts of butyl cellosolve and 878 parts of methyl cellosolve dispersed anatase type titanium dioxide-iron trioxide-silicon dioxide composite fine particle sol (catalyst chemical industry Co., Ltd., solid content concentration 20% by weight). After mixing 124 parts of γ-glycidoxypropyltrimethoxysilane and 37 parts of tetramethoxysilane, 55 parts of 0.1N hydrochloric acid aqueous solution was added dropwise with stirring, and the mixture was further stirred for 3 hours.

  After aging for a whole day and night, 15 parts of glycerol polyglycidyl ether (manufactured by Nagase Kasei Kogyo Co., Ltd., trade name Denacol EX313), 2.1 parts of Al (III) acetylacetonate, silicone surfactant (Nihon Unicar Co., Ltd.) Manufactured, trade name L-7604) 0.5 parts, hindered amine light stabilizer (manufactured by Sankyo Co., Ltd., trade name Sanol LS-770) 1.8 parts, and then stirred for 3 hours to obtain coating solution HC5 It was.

  This coating solution HC5 is applied to the lens substrate by dipping (pickup speed 25 cm / min), air-dried at 80 ° C. for 30 minutes, and then baked at 120 ° C. for 90 minutes to form a hard coat layer having a thickness of 2.1 μm Got the lens.

(Antireflection layer)
Next, the antireflective layer low flexure AR2 prepared in Example 2 was applied to the lens on which the hard coat layer was formed by the same method as in Example 2 to form an antireflective layer.

(Comparative Example 3)
Further, a different coating solution HC6 for the hard coat layer was prepared. This coating liquid HC6 was mixed with 171 parts of methanol, 207 parts of butyl cellosolve, 2246 parts of methyl cellosolve dispersed cerium dioxide-titanium dioxide-silicon dioxide composite fine particle sol (manufactured by Catalyst Chemical Industry Co., Ltd., solid content concentration 20%), After mixing 218 parts of γ-glycidoxypropyltrimethoxysilane and 101 parts of γ-glycidoxypropylmethyldimethoxysilane, 101 parts of 0.1N aqueous hydrochloric acid solution was added dropwise with stirring, and the mixture was further stirred for 2 hours.

  After aging for a whole day and night, 75 parts of 1,6-hexanediol diglycidyl ether (manufactured by Nagase Kasei Kogyo Co., Ltd., trade name Denacol EX-212), 4.6 parts of Fe (III) acetylacetonate, silicone surfactant 3 parts after adding 0.9 parts of an agent (made by Nippon Unicar Co., Ltd., trade name FZ-2110) and 3.1 parts of a phenolic antioxidant (made by Kawaguchi Chemical Industry Co., Ltd., trade name Antage Crystal) Stirring was performed to obtain a coating liquid HC6.

  This coating solution HC6 is applied to the lens substrate by dipping method (pulling speed 35 cm / min), air-dried at 80 ° C. for 30 minutes, and then baked at 125 ° C. for 100 minutes to form a hard coat layer having a thickness of 2.0 μm. A formed lens was obtained.

(Antireflection layer)
Next, the antireflective layer anti-reflective liquid AR1 prepared in Example 1 was applied to the lens on which the hard coat layer was formed by the same method as in Example 1 to form an antireflective layer.

(Evaluation of weather resistance and water resistance)
The lenses with antireflection layers obtained in Examples 1 to 3 and Comparative Examples 1 to 3 were subjected to tests and evaluations of weather resistance and water resistance, and the results are shown in FIG.

  In the weather resistance test, each lens manufactured in Examples 1 to 3 and Comparative Examples 1 to 3 was placed on a sunshine weather meter (WEL-SUN-HC manufactured by Suga Test Instruments Co., Ltd.) using a xenon lamp. Exposure for 80 hours.

  Thereafter, the degree of change in the surface condition of each lens was visually observed and ranked in four stages. “◎” indicates that no change is observed in the surface state, “◯” indicates that white turbidity is generated on the surface, “Δ” indicates that cracks are generated on the surface, and “×” "" Indicates that peeling occurs on the surface.

  In the water resistance test, each lens manufactured according to Examples 1 to 3 and Comparative Examples 1 to 3 was set to 60 ° C. and 100 RH% (manufactured by Davai Speck Co., Ltd .: PR- 1G) for 7 days.

  Thereafter, the adhesion of the lens substrate and the surface treatment layer (hard coat layer and antireflection layer) was evaluated by a cross-cut tape test according to JIS D-0202. First, cuts are made at intervals of 1 mm on the surface of the substrate using a knife to form 100 squares of 1 mm 2. Next, after strongly pressing cellophane tape (trade name cello tape (registered trademark), manufactured by Nichiban Co., Ltd.) onto the surface, the sheet is abruptly pulled away from the surface in the direction of 90 degrees, and the coat film remains. The squares were visually observed as an adhesion index and ranked in four stages. “◎” indicates the area where the squares of the coating film remain, 100%, “◯” indicates that the area where the squares of the coating film remain is 95% to less than 100%, and “Δ” indicates that the area of the coating film The area where the squares remain is 50% or more and less than 95%, and “x” indicates that the area where the squares of the coat film remain is less than 50%.

  As summarized in FIG. 1, the surfaces of the lenses manufactured in Examples 1 to 3 were excellent in both weather resistance and water resistance, and a high-quality lens having an organic antireflection layer was obtained. I understand that.

  On the other hand, in the lenses manufactured in Comparative Examples 1 to 3, that is, in the lens in which the hard coat layer having the same conditions as the inorganic antireflection layer is formed and the organic antireflection layer is manufactured on the lens, Although no effect was observed, it was confirmed in the exposure test (weather resistance test) that peeling occurred on the surface of the lens, and it was found that a lens having sufficient weather resistance could not be produced.

  The coating liquids HC4 to 6 used for the lenses of Comparative Examples 1 to 3 each contain anatase-type titanium oxide, and the effect of photoactivity due to ultraviolet rays contained in the irradiation light of the xenon lamp appears. it is conceivable that. In other words, the hard coat layer contains titanium, which is active when exposed to energy and decomposes organic substances by strong oxidative degradation, so it is blocked by the antireflection layer of the organic thin film on the hard coat layer. It is considered that the hard coat layer was deteriorated by the photoactivity of titanium due to ultraviolet rays that could not be produced, and the weather resistance was lowered due to the deterioration.

  On the other hand, the coating liquids HC1 to HC3 used for the lenses of Examples 1 to 3 do not contain titanium. Since titanium is not included in the hard coat layer as the underlayer of the antireflection layer made of an organic thin film, it is considered that the influence of the irradiation light of the xenon lamp does not appear. Therefore, by forming a hard coat layer using a coating solution that does not contain titanium, and forming an antireflection layer with an organic thin film on the hard coat layer, the hard coat layer can be prevented from being deteriorated. It can be seen that since the adhesion between the hard coat layer and the antireflection layer can be improved, a lens with an antireflection layer having higher durability can be provided.

  It can also be seen that the lenses manufactured according to Examples 2 and 3 have higher water resistance than the lens manufactured according to Example 1. The coating liquids HC2 and HC3 used in Examples 2 and 3 contain a polyfunctional epoxy compound, and the durability of the hard coat layer in a high humidity environment, that is, the weather resistance is improved due to the factors. It is considered a thing. Therefore, it can be seen that when manufacturing a lens having an antireflection layer formed of the organic thin film as described above, it is desirable to form a hard coat layer with a coating liquid containing a polyfunctional epoxy compound.

  In the above description, the present invention has been described by an experimental example using a plastic lens substrate. However, the present invention can be applied even when a glass lens substrate is used. Further, the surface of the lens with an antireflection layer may be water-repellent treated with a fluorine-based silane compound to form a water-repellent layer, and a primer layer is provided between the plastic lens substrate and the hard coat layer. You may apply through.

It is a figure which shows evaluation of the lens of an Example and a comparative example.

Claims (6)

In a plastic lens having a plastic lens substrate, a hard coat layer formed on the plastic lens substrate, and an antireflection layer formed on the hard coat layer,
The hard coat layer is a coating film formed from a first coating composition containing at least the following component (A) and component (B):
The antireflection layer is a plastic lens having a refractive index lower than that of the hard coat layer, a difference in refractive index of 0.10 or more, and an organic thin film having a thickness of 50 nm to 150 nm.
(A) Fine particles composed of one or more metal oxides selected from the group consisting of Si, Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr, and In having an average particle diameter of 1 nm to 200 nm, and / Or composite oxide fine particles (B) composed of two or more kinds of metal oxides selected from the above element group, an organic silicon compound represented by the general formula: R ¹ SiX ¹ ₃ (wherein R ¹ is polymerizable) An organic group having 3 or more carbon atoms having a reactive group, and X ¹ represents a hydrolyzable group.) 2. The plastic lens according to claim 1, wherein the antireflection layer is a coating film formed from a second coating composition containing the following components (C) and (D).
(C) An organic silicon compound represented by the general formula: R ² _r R ³ _q SiX ² _4-qr (wherein R ² is an organic group having a polymerizable reactive group, and R ³ has 1 to 1 carbon atoms) 6 is a hydrocarbon group, X ² is a hydrolyzable group, q is 0 or 1, and r is 0 or 1.)
(D) Silica-based fine particles   3. The plastic lens according to claim 2, wherein the silica-based fine particles have an internal cavity. 4. The plastic lens according to claim 1, wherein the first coating composition further contains the following component (E): 5.
(E) Polyfunctional epoxy compound 5. The plastic lens according to claim 1, wherein the first coating composition further contains the following component (F).
(F) General formula: Organosilicon compound represented by R ⁴ _n SiX ³ _4-n (wherein R ⁴ represents a hydrocarbon group having 1 to 3 carbon atoms, X ³ represents a hydrolyzable group, n represents 0 or 1.) A hard coat layer forming step of forming a hard coat layer with a first coating composition containing at least the following component (A) and component (B) on a plastic lens substrate;
(A) Fine particles composed of one or more metal oxides selected from the group consisting of Si, Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr, and In having an average particle diameter of 1 nm to 200 nm, and / Or composite oxide fine particles (B) composed of two or more kinds of metal oxides selected from the above element group, an organic silicon compound represented by the general formula: R ¹ SiX ¹ ₃ (wherein R ¹ is polymerizable) An organic group having 3 or more carbon atoms having a reactive group, and X ¹ represents a hydrolyzable group.)
An antireflection layer forming step of forming an organic thin film having a refractive index lower by 0.10 or more than the refractive index of the hard coat layer and a film thickness of 50 nm to 150 nm on the hard coat layer; Manufacturing method of plastic lens.

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