JP2010033021A - Plastic lens and method for manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To suppress a change of an interference color and also to suppress generation of cracks, when a hard coat layer having high refractive index is provided together with a primer layer in a plastic lens. <P>SOLUTION: The primer layer and the hard coat layer are formed in this order on a surface of a lens base material made of a plastics. The hard coat layer includes a metal oxide and a composition formed by mixing a material represented by a general formula (1): (R<SP>1</SP>)<SB>n</SB>Si(OR<SP>2</SP>)<SB>4-n</SB>and a material represented by general formula (2): (R<SP>3</SP>)<SB>n</SB>Si(OR<SP>4</SP>)<SB>4-n</SB>. The thickness of the hard coat layer is twice or more that of the primer layer. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a plastic lens for spectacles, in particular, a plastic lens having a high refractive index and a plastic lens suitable for application to a manufacturing method thereof, and a manufacturing method thereof.

  In recent years, plastic lenses having a high refractive index have been developed as plastic lenses for spectacles in order to achieve a reduction in thickness. Plastic lenses are advantageous in that they are lighter and easier to process than glass lenses and are relatively resistant to impacts, but they are inferior in scratch resistance and weather resistance due to their low hardness. For this reason, when providing as a spectacle lens especially, it is common to give the cured film called a hard coat. In the case of a spectacle lens, an antireflection film is formed on the surface, but if there is a difference in refractive index between the hard coat and an interference fringe is generated, the hard coat material is also required to have a high refractive index.

  As a hard coat material that achieves such a high refractive index, a hard coat material containing a metal oxide and an organic silicon compound, a so-called silane coupling material, has been proposed. For example, the following Patent Document 1 discloses a coating composition comprising an organosilicon compound or a hydrolyzate thereof and a composite oxide sol composed of titanium oxide, tin oxide and zirconium oxide. Improvements in hardness, wear resistance and the like are achieved.

  In addition, when an antireflection film is formed on a hard coat having a high refractive index, there is a drawback that impact resistance is lowered. In order to solve this problem, in Patent Document 2 below, a primer layer is provided between the lens surface and the hard coat layer, and the material is appropriately selected, thereby improving the high refractive index and impact resistance. A technique for achieving both of these has been proposed.

JP 2002-129102 A JP 09-136978 A

  When a hard coat material containing a metal oxide and an organosilicon compound as described in Patent Document 1 is used, a hard coat having a high refractive index and excellent scratch resistance can be obtained. However, if the thickness of the hard coat is simply increased in order to improve the scratch resistance, cracks may occur. In addition, when a primer layer as described in Patent Document 2 is provided in combination, the interference color may change. Particularly when applied to a plastic lens for spectacles, the interference color is preferably in a specific color range, and if the interference color varies, there is a problem that the product cannot be produced and the yield is reduced. .

  In view of the above problems, an object of the present invention is to improve scratch resistance when a hard coat layer that achieves a relatively high refractive index is provided on a plastic lens via a primer layer.

In order to solve the above problems, the present invention has a primer layer, a hard coat layer, and an antireflection film formed in this order on the surface of a lens substrate made of plastic.
The hard coat layer comprises a metal oxide and the following general formula (1)
(R ¹ ) _n Si (OR ² ) _4-n (1)
(In the formula, R ¹ is a monovalent hydrocarbon group having 1 to 20 carbon atoms having an amino group, R ² is an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, or 7 to 10 carbon atoms. aralkyl group, or an acyl group having 2 to 10 carbon atoms, n is an integer of 1 or 2, a plurality of R ¹ if R ¹ is more may be the same with or different from each other, a plurality of oR ² may be the same or different, and a material represented by the following general formula (2)
(R ³ ) _n Si (OR ⁴ ) _4-n (2)
(In the formula, R ³ is a monovalent hydrocarbon group having 1 to 20 carbon atoms having an isocyanate group, R ⁴ is an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, or 7 to 10 carbon atoms. aralkyl group, or an acyl group having 2 to 10 carbon atoms, n is an integer of 1 or 2, may be when there are a plurality of R ³ may have different plural R ³ is identical to each other, a plurality of oR ⁴ may be the same as or different from each other.), And a composition obtained by mixing the materials. And the thickness of a hard-coat layer is comprised as 2 times or more with respect to the thickness of a primer layer.

Moreover, the method for producing a plastic lens according to the present invention includes a step of forming a primer layer on the surface of a lens substrate, and the following general formula (1):
(R ¹ ) _n Si (OR ² ) _4-n (1)
(In the formula, R ¹ is a monovalent hydrocarbon group having 1 to 20 carbon atoms having an amino group, R ² is an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, or 7 to 10 carbon atoms. aralkyl group, or an acyl group having 2 to 10 carbon atoms, n is an integer of 1 or 2, a plurality of R ¹ if R ¹ is more may be the same with or different from each other, a plurality of oR ² may be the same or different, and a material represented by the following general formula (2)
(R ³ ) _n Si (OR ⁴ ) _4-n (2)
(In the formula, R ³ is a monovalent hydrocarbon group having 1 to 20 carbon atoms having an isocyanate group, R ⁴ is an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, or 7 to 10 carbon atoms. aralkyl group, or an acyl group having 2 to 10 carbon atoms, n is an integer of 1 or 2, may be when there are a plurality of R ³ may have different plural R ³ is identical to each other, a plurality of oR ⁴ may be the same or different from each other), and a step of preparing a hard coat solution containing a composition comprising a mixture of a metal oxide and a metal oxide, A step of forming a film on the primer layer, a step of hardening the hard coat liquid to form a hard coat layer, and a hard coat so that the thickness after curing is more than twice the thickness of the primer layer Forming an antireflective coating on the layer. .

  As described above, in the present invention, when a primer layer and a hard coat layer are provided on a lens substrate made of plastic, the hard coat layer contains a metal oxide and the above general formulas (1) and (2). And a composition obtained by mixing the materials represented by In addition, the scratch resistance of the hard coat layer can be reliably improved by setting the thickness of the obtained hard coat layer to be twice or more the thickness of the primer layer.

  According to the present invention, when a hard coat layer that realizes a relatively high refractive index is provided on a plastic lens via a primer layer, the scratch resistance can be improved.

It is a flowchart which shows the process of the manufacturing method of the plastic lens which concerns on the embodiment of this invention. It is a flowchart which shows the process of the manufacturing method of the plastic lens which concerns on the embodiment of this invention. It is a photograph figure which shows the scratch test result of a plastic lens.

Examples of the best mode for carrying out the present invention will be described below, but the present invention is not limited to the following examples.
The plastic lens according to the present invention has a structure in which a hard coat layer is formed on a lens substrate made of plastic via a primer layer that improves adhesion and impact resistance, and at least an antireflection film is formed thereon. The

The following materials can be used as the lens substrate used in the plastic lens of the present invention. For example, methyl methacrylate homopolymer, copolymer having methyl methacrylate and one or more other monomers as monomer components, diethylene glycol bisallyl carbonate homopolymer, diethylene glycol bisallyl carbonate and one or more other monomers as monomer components Copolymer, sulfur-containing copolymer, halogen-containing copolymer, polycarbonate, polystyrene, polyvinyl chloride, unsaturated polyester, polyethylene terephthalate, polyurethane, polythiourethane, homopolymer of monomer having sulfide bond, sulfide and Copolymers containing one or more other monomers as monomer components, copolymers containing polysulfides and one or more other monomers as monomer components, polydisulfides and one or more other monomers as monomers A copolymer such as a component.
In particular, the present invention can be suitably applied when a lens is formed using a material having a relatively high refractive index having a refractive index of about 1.6 or more as the material of the lens substrate.

  In addition, as a material for the primer layer provided between the lens base material and the hard coat layer, the adhesion and impact resistance between the lens base material and the hard coat layer are improved, and the lens base material is a relatively high refractive index material. In the case of further configuration, any material that does not affect the optical characteristics may be used. For example, polyols, polyisocyanates, NCO group blocking agents of polyisocyanates, and materials containing metal oxides in addition to these can be used.

  Examples of the polyol include polycarbonate polyol (for example, “Nipporan 980 series (trade name)” manufactured by Nippon Polyurethane Industry Co., Ltd., “carbodiol (trade name)” manufactured by Toagosei Co., Ltd.), and polyether polyol (for example, (stock) ) "ADEKA Polyether (trade name)" manufactured by ADEKA, "ACTCOL PPG-Diol series (trade name)" manufactured by Mitsui Chemicals Polyurethane Co., Ltd.), acrylic polyol (for example, "Takelac (registered trademark)" ) ", DIC (formerly Dainippon Ink and Chemicals, Inc." Acridick (registered trademark) ", etc.), or polyester polyol (DIC Corporation" Polylite (registered trademark) ", Kuraray Co., Ltd.) Kuraray polyol series (trade name) ") and the like can be used.

  Polyisocyanates include polyisocyanate hexamethylene diisocyanate, 1,3,3-trimethylhexamethylene diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, hydrogenated xylylene diene. Polyisocyanates such as isocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, tetramethylxylylene diisocyanate or their modified products, isocyanurates, allophanates, burettes or carbodiimides, or trimers thereof An adduct body such as a body can be used.

  As a blocking agent for the NCO group of polyisocyanate, β-diketone and methyl ethyl ketoxime are preferable, but acetylacetone, 2,4-hexanedione, 3,5-heptanedione, acetoxime, methyl ethyl ketoxime, caprolactam, and the like can be used. .

  In addition, a metal oxide may be added to such a primer composition in order to increase the refractive index. Examples of the metal oxide include metal oxides composed of one or more metals selected from Si, Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr, In, and Ti, and further, A sol composed of the metal oxide fine particles can be used.

In particular, when composed of a material formed by mixing a urethane resin and a rutile type titania sol, it has excellent adhesion and a relatively high refractive index, and the rutile crystalline TiO ₂ has a reduced weather resistance because its photoactivity is suppressed. Has the advantage of being suppressed.
Furthermore, when it comprises from the material formed by mixing a zirconia sol, there exists an advantage that the fall of a weather resistance can be suppressed more.

  Solvents include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, Propylene glycol monobutyl ether acetate, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether Le can be used diethylene glycol dibutyl ether, glycols such as propylene glycol dimethyl ether or propylene glycol diethyl ether.

  As other leveling agents, a copolymer of polyoxyalkylene and polydimethylsiloxane or a copolymer of polyoxyalkylene and fluorocarbon can be used.

  As a method for forming the primer layer, the primer layer can be formed by coating by dipping, spin coating, spraying, or the like, and then curing by heating or light irradiation.

And as a hard-coat liquid which comprises a hard-coat layer, the composition formed by mixing the material represented by the said General formula (1), (2) shall be included.
In the general formula (1), R ¹ is a monovalent hydrocarbon group having 1 to 20 carbon atoms having an amino group, such as a γ-aminopropyl group or N-β (aminoethyl) -γ-aminopropyl group. N-phenyl-γ-aminopropyl group and the like.

In general formula (1), ^{R 2} is an alkyl group, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, or an acyl group having 2 to 10 carbon atoms having 1 to 8 carbon atoms.
The alkyl group having 1 to 8 carbon atoms of R ² may be linear, branched or cyclic, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl. Group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, cyclopentyl group, cyclohexyl group and the like. Examples of the aryl group include a phenyl group and a tolyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group. Examples of the acyl group include an acetyl group.

In formula (1), n represents an integer of 1 or 2, a plurality of R ¹ if R ¹ is more may be the same with or different from each other, a plurality of OR ² are also identical to each other May be different.

  Specific examples of the organosilicon compound represented by the general formula (1) include γ-aminopropyltrimethoxysilane, γ-aminopropyldimethoxymethylsilane, γ-aminopropyltriethoxysilane, γ-aminopropyldiethoxymethylsilane, N-β (aminoethyl) γ-aminopropyldimethoxymethylsilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-β (amino Ethyl) γ-aminopropyldiethoxymethylsilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyldimethoxymethylsilane, N-phenyl-γ-aminopropyltriethoxysilane, N-phenyl -Γ-aminopropyldiethoxymethyl Amino-based silane coupling agent such as emissions and the like.

  Among these, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyldimethoxymethylsilane, and γ-aminopropyldiethoxymethylsilane are preferable, γ-aminopropyltrimethoxysilane, and γ-amino. More preferred are propyltriethoxysilane and γ-aminopropyltrialkoxysilane.

In the general formula (2), R ³ is a monovalent C1-C20 hydrocarbon group having an isocyanate group, for example, an isocyanate methyl group, an α-isocyanatoethyl group, a β-isocyanatoethyl group, an α-isocyanate. A propyl group, a β-isocyanatopropyl group, a γ-isocyanatopropyl group and the like can be mentioned.

In General Formula (2), R ⁴ is an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, or an acyl group having 2 to 10 carbon atoms. Examples of each group include the same examples as R ² described above.
In general formula (2), n represents an integer of 1 or 2, may be when there are a plurality of R ³ may have different plural R ³ is identical to each other, a plurality of OR ⁴ is also identical to each other May be different.

  Examples of the compound represented by the general formula (2) include γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyldimethoxymethylsilane, γ-isocyanatopropyltriethoxysilane, and γ-isocyanatopropyldiethoxymethylsilane. And γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, and γ-isocyanatopropyltrialkoxysilane are preferable.

  Further, in addition to the material obtained by mixing the materials represented by the above general formulas (1) and (2), as the organosilicon compound, an organosilicon compound represented by the following general formula (3); At least one selected from the organosilicon compounds represented by formula (4) and their hydrolysates can be used.

(R ⁵ ) _n Si (OR ⁶ ) _4-n (3)

In the general formula (3), R ⁵ is a monovalent hydrocarbon group having 3 to 20 carbon atoms having a functional group (epoxy group, acrylic group, vinyl group, methacryl group, styryl group, ureido group, mercapto group). For example, γ-glycidoxypropyl group, β-epoxycyclohexylethyl group, γ-acryloxypropyl group, vinyl group, γ-methacryloxypropyl group, p-styryl group, γ-ureidopropyl group, γ-mercaptopropyl group Etc.

In General Formula (3), R ⁶ is an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, or an acyl group having 2 to 10 carbon atoms.
As the material of R ^6, the same material as R ² can be used.

In general formula (3), n represents an integer of 1 or 2, may be the case where R ⁵ have multiple or different plural R ⁵ is identical to each other, a plurality of OR ⁶ is the same as or different from each other It may be.

  Specific examples of the organosilicon compound represented by the general formula (3) include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyldimethoxymethylsilane, γ-glycidoxypropyltriethoxysilane, and γ-glycol. Sidoxypropyldiethoxymethylsilane, β-epoxycyclohexylethyltrimethoxysilane, β-epoxycyclohexylethyldimethoxymethylsilane, β-epoxycyclohexylethyltriethoxysilane, β-epoxycyclohexylethyldiethoxymethylsilane, γ-acryloxypropyl Trimethoxysilane, γ-acryloxypropyldimethoxymethylsilane, γ-acryloxypropyltriethoxysilane, γ-acryloxypropyldiethoxymethylsilane, vinyltrimethoxysilane, vinyl Methoxymethylsilane, vinyltriethoxysilane, vinyldiethoxymethylsilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyldimethoxymethylsilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyldiethoxymethyl Silane, p-styryltrimethoxysilane, p-styryldimethoxymethylsilane, p-styryltriethoxysilane, p-styryldiethoxymethylsilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyldimethoxymethylsilane, γ-ureido Propyltriethoxysilane, γ-ureidopropyldiethoxymethylsilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyldimethoxymethylsilane, γ-merca DOO triethoxysilane, .gamma.-mercaptopropyl diethoxy methylsilane, and the like.

In the general formula (4), R ⁷ and R ⁸ are each an alkyl group having 1 to 4 carbon atoms or an acyl group having 2 to 4 carbon atoms, which may be the same or different, and R ⁹ and R ¹⁰ are These are monovalent hydrocarbon groups having 1 to 5 carbon atoms, each having or not having a functional group, and may be the same or different.
Examples of the alkyl group of R ⁷ and R ⁸ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Examples of the acyl group having 2 to 4 carbon atoms include an acetyl group.

Examples of the hydrocarbon group for R ⁹ and R ¹⁰ include an alkyl group having 1 to 5 carbon atoms and an alkenyl group having 2 to 5 carbon atoms. These may be either linear or branched, and examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group. Group, pentyl group, and the like. Examples of the alkenyl group include vinyl group, allyl group, and butenyl group.
Examples of the functional group of the hydrocarbon group include a halogen atom, a glycidoxy group, an epoxy group, an amino group, a mercapto group, a cyano group, and a (meth) acryloyloxy group.

In General formula (4), Y is a C2-C20 bivalent hydrocarbon group, and a C2-C10 alkylene group and an alkylidene group are preferable, for example, a methylene group, ethylene group, a propylene group, butylene Group, ethylidene group, propylidene group and the like.
In the general formula (4), a and b each represent an integer of 0 or 1, and a plurality of ORs ⁷ may be the same or different, and a plurality of ORs ⁸ may be the same or different. Good.

  Specific examples of the organosilicon compound represented by the general formula (4) include bis (triethoxysilyl) ethane, bis (trimethoxysilyl) ethane, bis (triethoxysilyl) methane, bis (trimethoxysilyl) hexane, bis (Triethoxysilyl) octane is exemplified, and bis (triethoxysilyl) ethane and bis (trimethoxysilyl) ethane are preferable.

  Among the above materials, the organosilicon compound used in the hard coat liquid in the present invention preferably includes at least one selected from the group consisting of epoxy-based, acrylic-based, vinyl-based, and methacrylic-based silane coupling agents. .

  Furthermore, as a solvent for the organosilicon compound, methanol, ethanol, isopropanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol propyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol Desirable to use monobutyl ether, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, diacetone alcohol, tetrahydrofuran, methyl ethyl ketone, methyl isobutyl ketone, toluene, ethyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc. Arbitrariness.

In the present invention, the metal oxide contained in the hard coat layer may be one or more oxides or composite oxides of metals such as Al, Ti, Sb, Zr, Si, Ce, Fe, In, and Sn. Can be mentioned. In particular, when TiO ₂ , ZrO ₂ , CeO ₂ , ZnO ₂ , SnO ₂ , ITO (indium-tin composite oxide) is used, the refractive index of the entire hard coat layer containing these can be made relatively high. It is suitable when a lens substrate having a high refractive index is used.

  Further, as a solvent for dispersing this metal oxide, alcohols such as methanol, ethanol, isopropanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol propyl ether, ethylene glycol monomethyl ether, ethylene Known raw materials such as glycol ethers such as glycol monoethyl ether and ethylene glycol monobutyl ether, glycols such as ethylene glycol, diethylene glycol, triethylene glycol and propylene glycol, and ketones such as methyl ethyl ketone and methyl isobutyl ketone can be used. .

  In addition, the hard coat solution contains various organic solvents and surfactants for the purpose of improving the wettability at the time of application to the curing catalyst and the lens base material in order to promote the reaction, and improving the smoothness. You can also. Furthermore, ultraviolet absorbers, antioxidants, light stabilizers and the like can be added as long as they do not affect the physical properties of the hard coat layer.

  The curing catalyst is not particularly limited, but amines such as allylamine and ethylamine, and various acids and bases including Lewis acid and Lewis base, such as organic carboxylic acid, chromic acid, hypochlorous acid, boric acid, perchloric acid. , Bromic acid, selenious acid, thiosulfuric acid, orthosilicic acid, thiocyanic acid, nitrous acid, some citric acid, salts or metal salts such as carbonic acid, metal alkoxides or metal chelate compounds having aluminum, zirconium, titanium, etc. .

  Among these, a particularly preferable curing catalyst is an aluminum chelate that is an aluminum catalyst. Examples of aluminum chelates include ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), alkyl acetoacetate aluminum diisopropylate, aluminum monoacetylacetonate bis (ethylacetoacetate), aluminum tris (acetylacetonate) , Aluminum = monoisopropoxymonooroxyethyl acetoacetate and the like. When such an aluminum catalyst, particularly an aluminum chelate, is used, since it has a pH adjusting function, for example, when a plurality of materials containing a metal oxide are mixed, aggregation caused by different pH values can be suppressed. Become.

  The hard coat solution prepared in this manner is formed on the lens substrate by dipping, spin coating, spraying, etc., and then cured by heating, light irradiation, etc., and the hard coat layer is formed on the lens substrate. It is formed.

  As the antireflection film provided on the hard coat layer, either an inorganic material or an organic material can be used. When the lens base material is a high refractive index material, any material that does not affect the optical characteristics thereof may be used. . When it is made of an inorganic material, it can be formed by a vacuum deposition method or the like, and when it is made of an organic material, it can be formed by being applied by a dipping method, a spin coating method or the like, and then cured by heating, light irradiation or the like.

  Next, a method for manufacturing a plastic lens according to an embodiment of the present invention will be described with reference to FIG. As shown in FIG. 1, first, a lens substrate is prepared (step S1). Next, a primer layer made of the above-described material is formed on the lens substrate (step S2). Furthermore, a composition obtained by mixing the materials represented by the above general formulas (1) and (2), and if necessary, another organic silicon compound, and further a hard coat solution containing a metal oxide is prepared ( Step S3). Details of the step of preparing the hard coat solution will be described later. Then, the hard coat liquid prepared on the primer layer is formed with a predetermined thickness, that is, a thickness at which the thickness of the hard coat layer after curing is 2 to 10 times the thickness of the primer layer. Film and cure (step S4). The film forming method may be any of dipping method, spin coating method, spray method and the like, and the curing method is performed by heating, light irradiation or the like. Next, an antireflection film is formed on the hard coat layer to complete a plastic lens (step S5).

  Next, the process of preparing a hard coat liquid will be described with reference to FIG. As shown in FIG. 2, first, a solvent is prepared (step S11). Next, the material represented by the general formula (1) is added to this solvent (step S12). Further, a material represented by the general formula (2) is added (step S13). Furthermore, when using another organosilicon compound, for example, the material represented by the above general formula (3) or (4), although not shown, a step of adding these materials is added after step S13. A composition obtained by mixing the materials represented by the general formulas (1) and (2) is completed in a state where the chemical reaction of the materials mixed with the solvent is completed by stirring or the like (step S14). In addition, this composition is a composition which consists of a urea bond, and has a function which improves adhesiveness with a primer layer.

  Next, as a material containing a metal oxide, for example, a sol-like material in which a metal oxide such as particles is dispersed in a solvent is prepared in another container (step S15). Distilled water is added to this material as necessary (step S16). By adding water, changes in pH concentration can be mitigated when the material containing the metal oxide is not neutral.

  Thereafter, a catalyst for promoting curing or the like is added (step S17). And when mixing 2 or more types of metal oxides, for example, after adding a catalyst, the material containing another metal oxide is further added (step S18). When one type of metal oxide is used, this step S18 is omitted. As the material containing the second metal oxide, for example, a sol material in which a metal oxide such as particles is dispersed in a solvent can be used.

  When materials containing two or more kinds of metal oxides are mixed, there is a possibility that the materials containing the respective metal oxides to be mixed may aggregate when they are mixed due to, for example, different pH values. In such a case, a catalyst may be added in advance before adding the material containing the second metal oxide as in the example shown in FIG. This is because such agglomeration can be suppressed or avoided when a material having an action of adjusting the pH value, such as the above-described aluminum chelate, is used as the catalyst. Of course, other pH adjusting materials may be added. In addition to such a catalyst, other pH adjusting materials may be added before or after the catalyst is added.

Thereafter, a material including a composition obtained by mixing the materials represented by the general formulas (1) and (2) is mixed with the metal oxide (step S19).
Furthermore, an additive such as a leveling agent for increasing the film smoothness and keeping the film thickness constant is added as necessary (step S20). When such an additive is unnecessary, step S20 can be omitted.
Through the above steps, the operation for preparing the hard coat liquid as the material of the hard coat layer is completed.

  In addition, in the flowchart shown in FIG. 2, the process of preparing the composition formed by mixing the materials represented by the general formulas (1) and (2) is shown as an example, but a material containing a metal oxide is used. The step of preparing may be performed first or at the same time.

  Next, as an example, a plastic lens was manufactured by changing the film thicknesses of the primer layer and the hard coat layer, and the film hardness on the surface, the presence or absence of cracks, and the interference color were evaluated. The film thickness of the hard coat layer was controlled by changing the mixing ratio of the materials of the hard coat liquid to be prepared and changing the ratio of the active ingredient that does not volatilize in the liquid. These examples will be described below.

In the following examples, as a material of a general hard coat layer provided on a lens substrate having a high refractive index, two kinds of metal oxides of TiO ₂ and ZrO ₂ and the general formulas (1) and (2) are used. A hard coat liquid containing a composition obtained by mixing the materials and another organosilicon compound was used.

  First, at room temperature, DAA (diacetone alcohol) was prepared as a solvent for an organosilicon compound in a first container. First, as a first organosilicon compound, γ-APS (γ-aminopropyltrimethoxysilane, manufactured by Momentive Performance Materials Japan G.K., trade name A-1110) was added, and stirring was started. . Thereafter, γ-IPS (γ-isocyanatopropyltrimethoxysilane, manufactured by Momentive Performance Materials Japan LLC, trade name Y-5187) was added dropwise as another organosilicon compound, and stirring was continued. After stirring for several hours to complete the reaction of these materials, γ-GPS (γ-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM403) is used as another organosilicon compound. The mixture was added and stirring was continued until the reaction was completed, thereby completing a material including a composition obtained by mixing the materials represented by the general formulas (1) and (2).

Next, a material containing particulate ZrO ₂ was prepared as a material containing a metal oxide in a second container under an atmosphere of 5 ° C. As this material, a sol-like material (ZrO ₂ sol) in which 40% by weight of a trade name HZ-407MH manufactured by Nissan Chemical Industries, Ltd. was dispersed in methanol was used.
Distilled water was added to the second container, and DIBA (diisobutylamine) was further added. DIBA has a function of adjusting pH.
Further, aluminum trisacetylacetonate (manufactured by Kawaken Fine Chemical Co., Ltd., trade name: Aluminum Chelate A (W)) was added as a curing catalyst.

When the above-described material containing ZrO ₂ is used, the pH is about 7, but by adding distilled water, DIBA and an aluminum catalyst, the pH becomes about 8-11.

Next, a material containing particulate TiO ₂ was added as a material containing another metal oxide. In this example, a relatively light activity is small and light resistance good rutile crystal TiO ₂ (e.g., catalyst Chemical Industry Co., Ltd. trade name: Optolake 2120Z) as a material containing TiO _2, PGM (propylene glycol monomethyl ether) A sol-like material dispersed in 20% by weight was used. In the case of using PGM, since the viscosity of PGM is relatively high, it is possible to form the hard coat layer with a large film thickness, and there is an advantage that the film thickness can be easily controlled.

The rutile crystalline TiO ₂ sol has a pH of about 3.5 to 4.5, but since the dispersion stability is good up to a weak alkali, it can be added to a solution having a pH of about 8 to 11 as described above. As a result of adding the rutile crystalline TiO ₂ sol, a material containing a metal oxide is obtained as a solution having a pH of about 6. If the rutile crystal TiO ₂ sol is added without adding distilled water, DIBA, and an aluminum catalyst, the pH becomes about 4 to 5, and the ZrO ₂ sol aggregates. By adding an amine-based material such as water or DIBA, and further an aluminum-based catalyst to the step between the two metal oxide sols, the occurrence of such aggregation can be suppressed or avoided.

  In addition, when the ratio which mixes an aluminum-type catalyst is less than 0.3 wt%, the pH adjustment function and the function as a catalyst are not enough. Moreover, when it mixes exceeding 1.8 wt%, reaction will be accelerated | stimulated excessively. Accordingly, in this case, the mixing ratio of the aluminum-based catalyst is desirably 0.3 wt% or more and 1.8 wt% or less.

  And the material containing the composition formed by mixing the materials represented by the general formulas (1) and (2) mixed in the first container is mixed with the material containing the metal oxide in the second container. Add and mix. Since the material mixed in the second container is a weakly acidic solution to which an appropriate amount of water is added, hydrolysis proceeds gradually by mixing the material containing the organic silicon compound mixed in the first container.

Finally, a leveling agent was added to improve the surface smoothness. In this example, a material obtained by diluting Toyo Dow Corning Co., Ltd., trade name Y7006 with PGM was used as a leveling agent. In addition, since the alcohol solvent which is a general material as a solvent has high volatility and the liquid viscosity is very low, it was difficult to make the film 3 μm or more, but by using PGM, it is 3 μm or more. It becomes possible to form in a desired film thickness including the film thickness.
The above materials were gradually hydrolyzed over an appropriate time (for example, 3 to 14 days, 8 days in this example) to prepare a hard coat solution.

The above materials were prepared by changing the composition as the mixing ratio shown in Table 1 below, and the film thickness after curing was adjusted. The weight ratio of the active ingredient ratio in composition 1 to composition 6 is as follows.
[Percentage of active ingredients that do not volatilize in hard coat solution, film thickness]
Composition 1: 15 wt%, 1 μm
Composition 2: 17 wt%, 1.5 μm
Composition 3: 20 wt%, 2 μm
Composition 4: 25 wt%, 3 μm
Composition 5: 30 wt%, 4 μm
Composition 6: 35 wt%, 5 μm
Composition 7: 40 wt%, 6 μm

  Further, as a material for the primer layer, a crystal coat (trade name, manufactured by SDC Technologies Asia Co., Ltd.) made of a urethane material and containing Ti was used. The thickness of the primer layer was also controlled by changing the solid content concentration of the material. The composition example and film thickness of the primer layer are shown in Table 2 below.

The primer materials of compositions 1 to 6 shown in Table 2 above were applied to the surface of a lens substrate made of thiourethane and an epithio resin (made by HOYA, trade name EYRY, refractive index 1.70) by a dipping method, A primer layer was formed by heat curing at 100 ° C. for 40 minutes. On this primer layer, the hard-coat liquid of the composition 1-6 shown in the above-mentioned Table 1 was apply | coated by the dipping method, and 75 degreeC and the thermosetting for 20 minutes were performed, and the hard-coat layer was formed. Then, in order to completely cure the formed primer layer and hard coat layer, thermal curing was performed at 110 ° C. for 1 hour. Furthermore, an antireflection film was formed by a vacuum vapor deposition method to produce a plastic lens in which the thicknesses of the primer layer and the hard coat layer were changed. In each example, the antireflection film was composed of a laminated film in which SiO ₂ and Ta ₂ O ₅ were alternately laminated.

The plastic lens of each example thus produced was evaluated for a scratch test, crack confirmation, and interference color confirmation.
First, as a scratch evaluation, steel wool (# 0000) was used, and a 20-reciprocal scratch test was performed at a load of 4 kg. The results and evaluation criteria are shown in Tables 3 and 4 below.

Of the results shown in Table 3, the hard coat layer thickness is 1.5 μm, 2 μm, and 5 μm, and the primer layer thickness is 1.5 μm, 1 μm, 0.75 μm, and 0.5 μm. A photograph of the surface of the plastic lens after the scratch test is shown in FIG.
From the results of the scratch test shown in Table 3, it can be seen that when the film thickness of the hard coat layer is 1 μm, the scratch resistance is low and not suitable for practical use. When the film thickness of the hard coat layer is 1.5 μm, as is apparent from FIG. 3, it can be seen that there are few scratches when the film thickness of the primer layer is 0.75 μm or less. Moreover, when the thickness of the hard coat layer is 2 μm, it can be said that good results can be obtained if the thickness of the primer layer is 1 μm or less.
From these facts, it can be said that good scratch resistance can be obtained when the thickness of the hard coat layer is twice or more the thickness of the primer layer.

  Moreover, the plastic lens after the thermosetting process which formed the primer layer and the hard-coat layer was confirmed visually, and generation | occurrence | production of the crack was evaluated. The results and evaluation criteria are shown in Table 5 and Table 6 below.

  From the results in Table 5, it can be seen that the occurrence of cracks occurs when the thickness of the hard coat layer is 6 μm. Therefore, it can be said that the film thickness of the hard coat layer is preferably less than 6 μm, and more preferably 5 μm or less.

  Further, the plastic lens after the formation of the antireflection film was visually confirmed and evaluated by confirming the interference color. The results and evaluation criteria are shown in Table 7 and Table 8 below.

  As shown in Table 7, no change in interference color was observed in all examples. Therefore, it can be said that the interference color does not change when the thickness of the primer layer is 0.1 μm or more and 2.0 μm or less and the thickness of the hard coat layer is 1 μm or more and 6 μm or less.

  Table 9 below shows the overall evaluation results obtained by integrating the results of Table 3, Table 5, and Table 7 above.

  From the results in Table 9, when a hard coat layer containing the material represented by the above general formulas (1) and (2) and a metal oxide is provided on the primer layer, the thickness is the thickness of the primer layer. It can be said that sufficient scratch resistance can be obtained when the amount is 2 times or more.

Further, when the thickness of the hard coat layer is less than 6 μm, more preferably 5 μm or less, generation of cracks can be avoided.
When the total film thickness of the hard coat layer and the primer layer is 7 μm or less, the occurrence of cracks can be reliably suppressed.
Furthermore, when the film thickness of the hard coat layer is 1 μm, the scratch resistance is poor regardless of the film thickness of the primer layer. Therefore, when the thickness of the hard coat layer is 1.5 μm or more, and the thickness of the hard coat layer is more than twice the thickness of the primer layer as described above, the scratch resistance is surely improved. Can be achieved.
As described above, the change in the interference color can be suppressed in the entire range where the thickness of the primer layer is 0.1 μm to 2.0 μm and the thickness of the hard coat layer is 1 μm to 6 μm.

  As described above, according to the plastic lens and the manufacturing method thereof of the present invention, by selecting the material of the hard coat layer and appropriately selecting the thickness relationship between the primer layer and the hard coat layer, It is possible to improve the scratch resistance, suppress the occurrence of cracks, and suppress variations in interference colors.

  It should be noted that the present invention is not limited to the above-described examples, and it should be understood that various modifications and application examples are included without departing from the gist of the present invention described in the claims. Absent.

Claims (9)

A primer layer, a hard coat layer, and an antireflection film are formed in this order on the surface of a plastic lens substrate.
The hard coat layer comprises a metal oxide and the following general formula (1)
(R ¹ ) _n Si (OR ² ) _4-n (1)
(In the formula, R ¹ is a monovalent hydrocarbon group having 1 to 20 carbon atoms having an amino group, R ² is an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, or 7 to 10 carbon atoms. aralkyl group, or an acyl group having 2 to 10 carbon atoms, n is an integer of 1 or 2, a plurality of R ¹ if R ¹ is more may be the same with or different from each other, a plurality of oR ² may be the same or different, and a material represented by the following general formula (2)
(R ³ ) _n Si (OR ⁴ ) _4-n (2)
(In the formula, R ³ is a monovalent hydrocarbon group having 1 to 20 carbon atoms having an isocyanate group, R ⁴ is an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, or 7 to 10 carbon atoms. aralkyl group, or an acyl group having 2 to 10 carbon atoms, n is an integer of 1 or 2, may be when there are a plurality of R ³ may have different plural R ³ is identical to each other, a plurality of oR ⁴ may be the same or different from each other), and a composition formed by mixing a material represented by
A plastic lens in which the thickness of the hard coat layer is at least twice the thickness of the primer layer.   The plastic lens according to claim 1, wherein the total thickness of the hard coat layer and the primer layer is less than 7 µm.   The plastic lens according to claim 1 or 2, wherein a thickness of the hard coat layer is 1.5 µm or more.   The plastic lens according to claim 1, wherein the primer layer has a thickness of 0.1 μm or more. 5. The metal oxide contained in the hard coat layer is at least one of TiO ₂ , ZrO ₂ , CeO ₂ , ZnO ₂ , SnO ₂ , and ITO (indium-tin composite oxide). The plastic lens according to any one of the above. Forming a primer layer on the surface of the lens substrate;
The following general formula (1)
(R ¹ ) _n Si (OR ² ) _4-n (1)
(In the formula, R ¹ is a monovalent hydrocarbon group having 1 to 20 carbon atoms having an amino group, R ² is an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, or 7 to 10 carbon atoms. aralkyl group, or an acyl group having 2 to 10 carbon atoms, n is an integer of 1 or 2, a plurality of R ¹ if R ¹ is more may be the same with or different from each other, a plurality of oR ² may be the same or different, and a material represented by the following general formula (2)
(R ³ ) _n Si (OR ⁴ ) _4-n (2)
(In the formula, R ³ is a monovalent hydrocarbon group having 1 to 20 carbon atoms having an isocyanate group, R ⁴ is an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, or 7 to 10 carbon atoms. aralkyl group, or an acyl group having 2 to 10 carbon atoms, n is an integer of 1 or 2, may be when there are a plurality of R ³ may have different plural R ³ is identical to each other, a plurality of oR ⁴ may be the same or different from each other), and a step of preparing a hard coat liquid containing a composition comprising a mixture of a metal oxide and a metal oxide,
Depositing the hard coat liquid on the primer layer such that the thickness after curing thereof is twice or more the thickness of the primer layer;
Curing the hard coat liquid to form a hard coat layer;
Forming an antireflection film on the hard coat layer. A method for producing a plastic lens.   The method for producing a plastic lens according to claim 6, wherein in the step of forming the hard coat liquid, a composition comprising urea bonds is mixed.   The method for producing a plastic lens according to claim 6 or 7, wherein in the step of forming the hard coat liquid, rutile type titania sol and zirconia sol are mixed.   The method for producing a plastic lens according to any one of claims 6 to 8, wherein a urethane resin and a rutile-type titania-type sol are mixed with the material of the primer layer.