OPTICAL ARTICLE AND MANUFACTURING PROCESS FOR OPTICAL ARTICLES

Description

[Technical Field]

[0001] The present invention relates to an optical article.[Background Art]

[0002] A photochromic compound is a compound having a property of coloring upon irradiation with light in a wavelength range where the photochromic compound has optical responsivity and fading in the absence of irradiation (photochromic properties). Hereinafter, an article containing a photochromic compound will be referred to as a photochromic article. For example, WO 2003 / 011967 discloses an optical article having a layer containing a photochromic compound (photochromic layer) provided on a substrate.

[0003] EP-A-3 795 602, which is prior art under Article 54(3) EPC, discloses an optical article comprising a substrate, a primer layer and a photochromic layer, wherein the primer layer is made from a polymerizable composition containing polyisocyanate, a hydroxy group-containing compound and a polymerizable selected from (meth)acrylates and vinyl ethers and having a viscosity of ≤ 100 cP.[Summary of Invention][Technical Problem]

[0004] With the intention of improving the performance of an optical article having a photochromic layer, the present inventors repeated studies to enhance the optical homogeneity.

[0005] That is, an object of one aspect of the present invention is to provide an optical article having a photochromic layer and having excellent optical properties.[Solution to Problem]

[0006] In one aspect, the present invention provides an optical article (also referred to as "the present optical article" hereinafter) comprising in this order: a substrate; a primer layer generated by curing a polymerizable composition (1) containing polyisocyanate as component (A), hydroxy group-containing compound as component (B); and a polymerizable compound having a viscosity of ≤ 100 cP, measured with a vibration-type viscometer at 25°C, and being selected from (meth)acrylates and vinyl ethers as component (C), wherein the content of component (C) is ≥ 30.0 mass%, based on the total of components (A), (B) and (C); and a photochromic layer containing a photochromic compound.

[0007] Preferred embodiments of the invention are as defined in the appended dependent claims and / or in the following detailed description.

[0008] In the optical article having the photochromic layer on the substrate, the primer layer is preferably provided between the substrate and the photochromic layer in order to improve the adhesive property between the substrate and the photochromic layer. Therefore, as a result of studying the primer layer provided between the substrate and the photochromic layer, the present inventors clarified that the deterioration of the optical properties attributed to the primer layer may occur. Therefore, as a result of further repeating intensive studies, the present inventors newly found that, when the polymerizable composition for forming the primer layer (also referred to as ("present composition (1)" hereinafter) contains not only the components A and B but also the component C, the generation of an optical defect attributed to the primer layer can be suppressed, which makes it possible to provide an optical article having excellent optical properties.[Advantageous Effects of Invention]

[0009] According to one aspect of the present invention, it is possible to provide an optical article having a photochromic layer and having excellent optical properties.[Description of Embodiments][Optical Article]

[0010] Hereinafter, the present optical article will be described in greater detail.

[0011] The optical article has a substrate, a primer layer and a photochromic layer in this order.<Substrate>

[0012] The optical article may have the photochromic layer on a substrate selected depending on the type of the optical article through the primer layer. As an example of the substrate, a spectacle lens substrate may be a plastic lens substrate or a glass lens substrate. The glass lens substrate may be, for example, a lens substrate made of inorganic glass. In terms of being lightweight, difficult to break and easy to handle, the lens substrate is preferably a plastic lens substrate. The plastic lens substrate may be, for example, a styrene resin (e.g. a (meth)acrylic resin), a polycarbonate resin, an allyl resin, an allyl carbonate resin (e.g. a di(ethylene glycol) bis(allyl carbonate) resin (CR-39)), a vinyl resin, a polyester resin, a polyether resin, a urethane resin generated by the reaction of an isocyanate compound and a hydroxy compound (e.g. diethylene glycol), a thiourethane resin generated by the reaction of an isocyanate compound and a polythiol compound, or a cured material (normally called a transparent resin) generated by curing a curable composition containing a (thio)epoxy compound having at least one disulfide bond in one molecule. The lens substrate may not be colored (colorless lens) or may be colored (colored lens). The refractive index of the lens substrate may be, for example, 1.60-1.75. However, the refractive index of the lens substrate is not limited to the above range and may be within the above range or may be above or below the above range. Herein, the refractive index refers to a refractive index with respect to light having a 500 nm wavelength. Further, the lens substrate may be a lens having index (prescription lens) or may be a lens having no index (flat lens).

[0013] The spectacle lens can be various lenses including a mono-focal lens, a multi-focal lens and a progressive index lens. The type of the lens is determined by the surface shape of both sides of the lens substrate. Further, the surface of the lens substrate may be any one of a convex surface, a concave surface and a flat surface. In general lens substrates and spectacle lenses, the surface on the object side is a convex surface, and the surface on the eyeball side is a concave surface. However, the present invention is not limited to this. The photochromic layer can be, generally, located on the object-side surface of the lens substrate, but may also be located on the eyeball-side surface.<Primer Layer>

[0014] The primer layer is a cured layer generated by curing the present composition (1) containing component A, component B and component C. Herein, a polymerizable composition refers to a composition containing a polymerizable compound. The polymerizable compound is a compound having a property of a polymerizable group.(Component A)

[0015] The component A is a polyisocyanate. The polyisocyanate is a compound having two or more isocyanate groups in one molecule. The number of the isocyanate groups contained in one molecule of the polyisocyanate is 2 or more and preferably 3 or more. Further, the number of the isocyanate groups contained in one molecule of the polyisocyanate may be, for example, 6 or less, 5 or less or 4 or less. The molecular weight of the polyisocyanate may be, for example, 100-500, but is not limited to this range. Specific examples of the polyisocyanate include aromatic diisocyanates such as xylylene diisocyanate, phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate and naphthalene diisocyanate, aliphatic or alicyclic diisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,3-bisisocyanatomethylcyclohexane, and tetramethylxylylene diisocyanate. Further, the specific examples also include allophanate bodies, adduct bodies, biuret bodies, and isocyanurate bodies of the polyisocyanates exemplified above. Examples of the commercially available products of the polyisocyanate include CORONATE HX, CORONATE HXR, CORONATE HXLV, CORONATE HK, CORONATE 2715, CORONATE HL, CORONATE L, CORONATE 2037, HDI, TDI, MDI (manufactured by Tosoh Corporation), TAKENATE 500, TAKENATE 600, DURANATE 24A-100, TPA-100, TKA-100, P301-75E, TAKENATE D-110N, D-120N, D-127N, D-140N, D-160N, D15N, D-170N, D-170HN, D-172N, D-177N, D-178N, and D-101E (manufactured by Mitsui Chemicals, Inc.).(Component B)

[0016] The component B is a hydroxy group-containing polymerizable composition. The number of the hydroxy groups contained in one molecule of component B is 1 or more and preferably 2 or more, and is preferably 4 or less and more preferably 3 or less. A urethane bond can be formed by reacting the isocyanate group in component A and the hydroxy group in component B. The present inventors presume that this urethan bond contributes to the fact that the primer layer is capable of functioning as a layer for improving the adhesive property.

[0017] The component B is a polymerizable compound and may have one or more polymerizable groups and preferably has two or more polymerizable groups in one molecule. In one form, the component B may be a (meth)acrylate. Herein, "(meth)acrylate" is used to encompass acrylate and methacrylate. "Acrylate" is a compound having one or more acryloyl groups in one molecule. "Methacrylate" is a compound having one or more methacryloyl groups in one molecule. For (meth)acrylates, the number of functional groups is the number of groups selected from acryloyl and methacryloyl contained in one molecule. Herein, "methacrylate" refers to a substance containing only methacryloyl as the (meth)acryloyl group, and a substance containing both methacryloyl and acryloyl as the (meth)acryloyl group will be referred to as an acrylate. The acryloyl group may be contained in a form of acryloyloxy, and the methacryloyl group may be contained in a form of methacryloyloxy. "(Meth)acryloyl group" in the following description is used to encompass both acryloyl and methacryloyl, and "(meth)acryloyloxy group" is used to encompass both acryloyloxy and methacryloyloxy. Further, unless particularly otherwise described, groups to be described below may have a substituent or may have no substituent. In a case where a certain group has a substituent, the substituent may be, for example, alkyl (for example, C 1-6 -alkyl), hydroxyl, alkoxy (for example, C 1-6 -alkoxy), halogen (for example, F, Cl or Br), cyano, amino, nitro, acyl, or carboxy . Further, for groups having a substituent, "the number of carbon atoms" means the number of carbon atoms in a portion containing no substituent.

[0018] In a case where component B is a (meth)acrylate, the number of functional groups in the (meth)acrylate is 1 or more (that is, monofunctional or higher) and preferably 2 or more, and further is preferably 3 or less. As the (meth)acryloyl group, component B may contain only acryloyl, may contain only methacryloyl or may contain acryloyl and methacryloyl. In one form, component B preferably contains only acryloyl as the (meth)acryloyl group. The molecular weight of component B may be, for example, 300-400, but is not limited to this range. Specific examples of component B include 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1,4-cyclohexanedimethanol monoacrylate, 2-hydroxy-1-acryloxy-3-methodoroxypropane, 2-hydroxy 1-3 dimethacryloxypropane, pentaerythritol tetraacrylate, 2-hydroxy-3-phenoxypropyl acrylate, monoacryloxyethyl hexahydrophthalate, 2-acryloyloxyethyl phthalate, and 2-(acryloyloxy) ethyl 2-hydroxyethyl phthalate. Further, in one form, component B may have an amide group. Specific examples of component B having an amide group include N-(2-hydroxyethyl)acrylamide. Further, component B may have an epoxy ester structure in one form. The epoxy ester structure is a structure generated by a rection between an epoxy group and a carboxy group and can be represented by "-CH(OH)-CH 2 -O-C(=O)-". Examples of the commercially available products of component B having the epoxy ester structure include EPOXY ESTER 40EM (manufactured by Kyoeisha Chemical Co., Ltd.), EPOXY ESTER 70PA (manufactured by Kyoeisha Chemical Co., Ltd.), EPOXY ESTER 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), EPOXY ESTER 200PA (manufactured by Kyoeisha Chemical Co., Ltd.), EPOXY ESTER 3002M (N) (manufactured by Kyoeisha Chemical Co., Ltd.), EPOXY ESTER 3002A (N) (manufactured by Kyoeisha Chemical Co., Ltd.), EPOXY ESTER 3000MK (manufactured by Kyoeisha Chemical Co., Ltd.), and EPOXY ESTER 3000A (manufactured by Kyoeisha Chemical Co., Ltd.).(Component C)

[0019] The component C is a polymerizable compound having a viscosity of 100 cP (centipoise) or less and being selected from (meth)acrylates and vinyl ethers. The present inventors presume that the fact that a polymerizable compound having a low viscosity as described above is contained contributes to suppression of the generation of an optical defect in the primer layer formed of the polymerizable composition for forming the primer layer containing the components A and B. Herein, "viscosity" is a value measured with a vibration-type viscometer in the atmosphere of a temperature of 25°C. The viscosity of component C is 100 cP or less, preferably 70 cP or less and more preferably 50 cP or less, and further may be, for example, 5 cP or more or 10 cP or more. The (meth)acrylate, which is one form of component C, may be mono to tri-functional and is preferably mono or bifunctional. Further, the (meth)acrylate, which is one form of component C, may contain, for example, an aryl group (for example, phenyl), or an amide group. Herein, "vinyl ether" is a compound having one or more vinyl groups and one or more ether bonds in one molecule and preferably has two or more vinyl groups and more preferably has 2-4 vinyl groups in one molecule. Further, the number of the ether bonds contained in the vinyl ether is preferably 2-4 in one molecule. The molecular weight of component C may be, for example, 150-250, but is not limited to this range. Specific examples of component C may include 2-phenoxyethyl (meth)acrylate, acrylamide, methoxy polyethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, stearyl (meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, phenoxyethyl (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tricyclodecanedimethanol di(meth)acrylate, ethoxylated polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, dodecyl (meta)acrylate, tridecyl (meth)acrylate, diethylene glycol butyl ether (meth)acrylate, cyclohexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, benzyl (meth)acrylate, 2-phenoxyethyl methacrylate, isobornyl (meth)acrylate, 2-(dimethylamino)ethyl (meth)acrylate, 2-(diethylamino)ethyl (meth)acrylate, glycidyl (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meta)acrylate, polyethylene glycol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, hexanediol di(meth)acrylate, nonamethylene glycol di(meth)acrylate, isoamyl (meth)acrylate, ethylene glycol monovinyl ether, tetramethylene glycol monovinyl ether, diethylene glycol monovinyl ether, 2-ethylhexyl vinyl ether, 2-propenoic acid, 2-[2-(ethenyloxy)ethoxy]ethyl ester, and 2-(2-ethenoxyethoxy)ethyl 2-methylprop-2-enoate.

[0020] In the polymerizable composition for forming the primer layer, when the total of the components A, B and C is regarded as 100 mass%, the content rate of component C is 30.0 mass% or more and preferably 40.0 mass% or more, and may be, for example, 90.0 mass% or less, 80.0 mass% or less or 70.0 mass% or less. The present composition (1) may contain only one component C in one form or may contain two or more components C in another form. In a case where two or more components C are contained, the content rate of component C is the total content rate of the two or more components C. This is also true for the content rates of other components. In one form, component C is preferably, among the components A, B and C, a component having the largest fraction in the present composition (1).

[0021] In the present composition (1), when the total of the components A, B and C is regarded as 100 mass%, the content rate of component A is preferably 70.0 mass% or less, more preferably 60.0 mass% or less and still more preferably 50.0 mass% or less, and may be, for example, 10.0 mass% or more, 20.0 mass% or more or 30.0 mass% or more.

[0022] In the present composition (1), when the total of the components A, B and C is regarded as 100 mass%, the content rate of component A is preferably 3.0 mass% or more, more preferably 5.0 mass% or more and still more preferably 7.0 mass% or more, and the content rate of the component B may be, for example, 30.0 mass% or less or 20.0 mass% or less.

[0023] The present composition (1) may further contain a polymerization initiator. When the total of the components A, B and C is regarded as 100 mass%, the present composition (1) may contain the polymerization initiator in a content rate, for example, of 0.01-3.0 mass%.

[0024] As the polymerization initiator, known polymerization initiators can be used, a radical polymerization initiator is preferable, and only a radical polymerization initiator is more preferably contained as the polymerization initiator. Further, as the polymerization initiator, a photopolymerization initiator or a thermopolymerization initiator can be used, and a photopolymerization initiator is preferable from the viewpoint of progressing a polymerization reaction within a short period of time. Examples of the photoradical polymerization initiator include benzoin ketals such as 2,2-dimethoxy-1,2-diphenylethan-1-one; α-hydroxyketones such as 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one and 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one; α-aminoketones such as 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one and 1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one; oxime esters such as 1-[(4-phenylthio)phenyl]-1,2-octadion-2-(benzoyl) oxime; phosphine oxides such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; 2,4,5-triarylimidazole dimers such as 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer and 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer; benzophenone compounds such as benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone, N,N'-tetraethyl-4,4'-diaminobenzophenone and 4-methoxy-4'-dimethylaminobenzophenone; quinone compounds such as 2-ethyl anthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenyl anthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone and 2,3-dimethylanthraquinone; benzoin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin phenyl ether; benzoin compounds such as benzoin, methylbenzoin and ethylbenzoin; benzyl compounds such as benzyl dimethyl ketal; acridine compounds such as 9-phenylacridine and 1,7-bis(9,9'-acridinylheptane): N-phenylglycine, and coumarin. Further, in the 2,4,5-triarylimidazole dimer, as substituents for the aryl groups in two triarylimidazole portions, identical and symmetric compounds may be imparted or different and asymmetric compound may be imparted. Further, a thioxanthone compound and a tertiary amine may be combined, such as a combination of diethylthioxanthone and dimethylaminobenzoic acid. Among these, α-hydroxyketones and phosphine oxides are preferable from the viewpoint of curing properties, transparency and heat resistance.

[0025] The present composition (1) may or may not contain a solvent. In a case where a solvent is contained, as a usable solvent, any solvent can be used in any amount as long as the progress of the polymerization reaction of the polymerizable composition is not impaired. In a case where the solvent is contained, when the total of the components A, B and C is regarded as 100 mass%, the content rate of the solvent is preferably 10.0 mass% or less, more preferably 5.0 mass% or less and still more preferably 3.0 mass% or less.

[0026] The present composition (1) may further contain a known additive that may be generally added to compositions for forming a primer layer in any amount. As the additive, a known compound can be used. When the total amount of the present composition (1) (here, the polymerization initiator is excluded) is regarded as 100 mass%, the composition may contain the components A, B and C in a total of 80.0 mass% or more, 85.0 mass% or more, 90.0 mass% or more or 95.0 mass% or more, and further may be, for example, 100 mass%, 100 mass% or less, less than 100 mass%, 99.0 mass% or less or 98.0 mass% or less. Herein, regarding the content rate, for a composition containing a solvent, "the total amount of the composition" refers to the total amount of all components excluding the solvent.

[0027] The composition (1) for forming the primer layer can be prepared by mixing the above-described various components at the same time or sequentially in any order.

[0028] The present composition (1) is applied to the substrate, and a curing treatment is performed on the applied composition, whereby a primer layer, which is a cured layer generated by curing the present composition (1), can be formed on the substrate. As an application method, a known application method such as a spin coating method or a dipping method can be adopted, and a spin coating method is preferable from the viewpoint of the uniformity of the application. In order for e.g. the cleaning of the surface of the substrate, one or more of any known pretreatments such as an alkali treatment and a UV ozone treatment can be performed on the surface of the substrate before the application. The curing treatment may be light irradiation and / or a heating treatment and is preferably light irradiation from the viewpoint of progressing a curing reaction within a short period of time. The conditions for the curing treatment may be determined depending on the types of various components contained in the present composition (1) or the composition of the present composition (1). After the curing treatment, an annealing treatment (heating treatment) can also be performed as necessary. The annealing treatment can be performed in, for example, a heat treatment furnace at an atmospheric temperature of 90-130°C.

[0029] The thickness of the primer layer may be, for example, 3 µm or more and is preferably 5 µm or more, and further may be, for example, 15 µm or less and is preferably 10 µm or less.<Photochromic Layer>(Polymerizable Compound)

[0030] The optical article has a photochromic layer on the primer layer. In one form, the photochromic layer may be a cured layer generated by curing a (meth)acrylate-based polymerizable composition. Herein, "(meth)acrylate-based polymerizable composition" refers to a polymerizable composition containing a (meth)acrylate. In a case where the present composition (1) is a (meth)acrylate-based polymerizable composition, the present inventors presume that the fact that the composition for forming the photochromic layer is also a (meth)acrylate-based polymerizable composition is preferable from the viewpoint of further improving the adhesive property between the primer layer and the photochromic layer.

[0031] Hereinafter, a (meth)acrylate-based polymerizable composition, which is one form of a polymerizable composition for forming the photochromic layer, will be described. Here, the following form is merely an example, and the present invention is not limited only to such an example.

[0032] The polymerizable composition for forming the photochromic layer (also referred to as "present composition (2)" hereinafter) may contain the component C in one form.

[0033] Further, in one form, the present composition (2) may contain the following component D.

[0034] The component D is an acyclic methacrylate having a molecular weight of 500 or more. Herein, "acyclic" means that no cyclic structures are included. In contrast, "cyclic" means that a cyclic structure is included. The acyclic methacrylate refers to a mono- or higher functional methacrylate including no cyclic structures.

[0035] The component D may be a mono- or higher functional methacrylate and is preferably a bi- or trifunctional methacrylate and more preferably a bifunctional methacrylate. The component D may be polyalkylene glycol dimethacrylate, and can be represented by formula (1):

[0036] Wherein R is alkylene, n indicates the number of times of repetition of an alkoxy group represented by RO and is 2 or more. Examples of the alkylene group R include ethylene, propylene, and tetramethylene. n is 2 or more and may be, for example, 30 or less, 25 or less or 20 or less. Specific examples of the polyalkylene glycol dimethacrylate may include polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, an polytetramethylene glycol dimethacrylate.

[0037] The molecular weight of the component D is 500 or more. Herein, as the molecular weights of polymers, a structural formula determined by a structural analysis of a compound or a theoretical molecular weight calculated from the ratio of raw materials prepared at the time of producing the compound is adopted. The molecular weight of the component D is 500 or more, preferably 510 or more, more preferably 520 or more, preferably 550 or more, more preferably 570 or more, still more preferably 600 or more, far still more preferably 630 or more and even far still more preferably 650 or more. From the viewpoint of increasing the degree of curing of the photochromic layer, the molecular weight of the component D is preferably, for example, 2000 or less, 1500 or less, 1200 or less, 1000 or less or 800 or less.

[0038] Further, in one form, the present composition (2) may contain the following component E.

[0039] The component E is a (meth)acrylate having a molecular weight of 400 or less of formula (2): wherein R 1< and R 2< each independently are H or methyl, and m is an integer of 1 or more, and may be, for example, 10 or less, 9 or less, 8 or less, 7 or less or 6 or less.

[0040] The molecular weight of the component E is 400 or less, preferably 350 or less, more preferably 300 or less and still more preferably 250 or less from the viewpoint of further increasing the color optical density of the photochromic layer. Further, the molecular weight of the component E may be, for example, 100 or more, 150 or more or 200 or more.

[0041] As a (meth)acryloyl group, the component E may contain only acryloyl, may contain only methacryloyl or may contain acryloyl and methacryloyl. In one form, the component B preferably contains only acryloyl as the (meth)acryloyl group. Specific examples of the component E may include 1,9-nonanediol diacrylate, 1,6-hexanediol diacrylate, and 1,10-decanediol diacrylate.

[0042] The composition may contain, as the polymerizable compound, only the components D and E in one form or may contain, in addition to the components D and E, one or more different polymerizable compounds in another form. Hereinafter, the different polymerizable compounds that may be contained in the composition will be exemplified.

[0043] The present composition (2) may also contain a component F exemplified below in one form. The component F is a preferable component since the component F is capable of contributing to improvement in the performance, such as application suitability, of the composition without significantly affecting the coloring property of the photochromic layer formed of the composition upon light irradiation and the visible light transmission property in the absence of irradiation.

[0044] The component F is an acyclic tri- or higher functional (meth)acrylate. The component F is preferably a tri- to pentafunctional (meth)acrylate, more preferably a trifunctional or tetrafunctional (meth)acrylate and still more preferably a trifunctional (meth)acrylate. Specific examples of the component F may include pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, and tetramethylolmethane tri(meth)acrylate. The molecular weight of the component F may be, for example, 200-400, but is not limited to this range. As a (meth)acryloyl group, the component C may contain only acryloyl, may contain only methacryloyl or may contain acryloyl and methacryloyl. In one aspect, the acyclic tri- or higher functional (meth)acrylate preferably contains only methacryloyl as the (meth)acryloyl group, that is, methacrylate.

[0045] In one form, present composition (2) may contain, as the polymerizable compound, one or more different polymerizable compounds other than the above-described components. In the present composition (2), when the total amount of the polymerizable compounds contained in the composition is regarded as 100 mass%, the content rate of the component D is preferably 50.0 mass% or more, more preferably 55.0 mass% or more and still more preferably 60.0 mass% or more, and further may be 90.0 mass% or less, 85.0 mass% or less, 80.0 mass% or less or 75.0 mass% or less. In one form, the component D may be, among the plurality of polymerizable compounds contained in the composition, a component having the largest fraction..

[0046] According to the present inventors' studies, regarding the component E, a tendency for the color optical density when the photochromic layer has colored upon light irradiation to increase as the content rate of the component E increases is shown. On the other hand, according to the present inventors' studies, a tendency for the fading speed, which is one of indexes indicating optical responsivity, to become slower as the content rate of the component E increases is also shown. From the viewpoint of the color optical density, when the total amount of the polymerizable compounds contained in the composition is regarded as 100 mass%, the content rate of the component E is preferably 5.0 mass% or more, more preferably 10.0 mass% or more and more preferably 15.0 mass% or more, and further, from the viewpoint of the optical responsivity, is preferably 30.0 mass% or less and more preferably 25.0 mass% or less.

[0047] Regarding the component F, the content rate of the component F may be, with respect to the total amount of the polymerizable compounds contained in the present composition (2), 0 mass% and can be 0 mass% or more, more than 0 mass%, 1.0 mass% or more, 3.0 mass% or more, 5 mass% or more or 7 mass% or more, and may be20.0 mass% or less or 15.0 mass% or less.

[0048] Regarding the component C, the content rate of the component C may be, with respect to the total amount of the polymerizable compounds contained in the present composition (2), 0 mass% and can be 0 mass% or more, more than 0 mass%, 1.0 mass% or more, 3.0 mass% or more, 5 0 mass% or more or 7.0 mass% or more, and may be 20.0 mass% or less or 15.0 mass% or less.

[0049] When the total amount of the present composition (2) is regarded as 100 mass%, the content rate of the polymerizable compounds in the composition may be, for example, 80.0 mass% or more, 85.0 mass% or more or 90.0 mass% or more, and further may be, for example, 99.0 mass% or less, 95.0 mass% or less, 90.0 mass% or less or 85.0 mass% or less.(Photochromic Compound)

[0050] The present composition (2) contains a photochromic compound together with the polymerizable compounds. As the photochromic compound contained in the present composition (2), a known compound exhibiting photochromic properties can be used. The photochromic compound is capable of exhibiting photochromic properties to, for example, ultraviolet rays. Examples of the photochromic compound may include compounds having a known skeleton exhibiting photochromic properties such as a fulgimide compound, a spirooxazine compound, a chromene compound and an indeno-fused naphthopyran compound. The photochromic compound can be used singly or two or more photochromic compounds can also be used in a mixture form. When the total amount of the composition is regarded as 100 mass%, the content rate of the photochromic compound in the present composition (2) may be set to, for example, about 0.1 to 15.0 mass%, but is not limited to this range.(Other Components)

[0051] The present composition (2) may contain, in addition to the polymerizable compounds and the photochromic compound, one or more of various additives that can be generally contained in the polymerizable composition at any content rate. As the additives that can be generally contained in the present composition (2), for example, a polymerization initiator for progressing a polymerization reaction can be exemplified. Regarding the polymerization initiator, the above description can be referred to. When the total amount of the composition is regarded as 100 mass%, the content rate of the polymerization initiator may be, for example, within a range of 0.1 to 5.0 mass%.

[0052] To the present composition (2), it is possible to further add, at any amount, known additives that can be generally added to the composition containing the photochromic compound, for example, a surfactant, an antioxidant, a radical scavenger, a light stabilizer, an ultraviolet absorber, an anti-coloring agent, an antistatic agent, a fluorescent dye, a dye, a pigment, a perfume, a plasticizer, and a silane coupling agent. As these additives, known compounds can be used.

[0053] The present composition (2) can be prepared by mixing the above-described various components at the same time or sequentially in any order.

[0054] The photochromic layer can be formed by applying the present composition (2) onto the primer layer and performing a curing treatment on the applied composition. Regarding an application method, the above description can be referred to. The curing treatment may be light irradiation and / or a heating treatment and is preferably light irradiation from the viewpoint of progressing a curing reaction within a short period of time. The conditions for the curing treatment may be determined depending on the types of various components contained in the composition (e.g. the polymerizable compounds, and the polymerization initiator described above) or the composition of the composition. The thickness of the photochromic layer to be formed as described above is, for example, preferably 5-80 µm and more preferably 20-60 µm. The substrate and the primer layer are preferably adjacent to each other, and the primer layer and the photochromic layer are preferably adjacent to each other. Here, "adjacent" means that the components are in direct contact with each other without any layer therebetween.

[0055] The optical article having the photochromic layer may or may not further have, in addition to the above-described various layers, one or more functional layers. Examples of the functional layers may include known layers as functional layers for optical articles such as a protective layer, an antireflection layer, a water repellent or hydrophilic antifouling layer and an antifogging layer, which are intended to improve the durability of the optical article.

[0056] An aspect of the optical article is a spectacle lens. Further, as an aspect of the optical article, a goggle lens, a visor portion of a sun visor, and a shield member of a helmet can be exemplified. The above-described composition is applied onto a substrate for these optical articles, and a curing treatment is performed on the applied composition to form a photochromic layer, whereby an optical article having an anti-glare function can be obtained.[Spectacles]

[0057] Another aspect of the present invention relates to spectacles having the spectacle lenses, which are an aspect of the optical article. Details of the spectacle lenses of the spectacles are as described above. The spectacles have such spectacle lenses and are thus capable of, for example, outdoors, exhibiting an anti-glare effect like sunglasses due to the photochromic compound contained in the photochromic layer being irradiated with sunlight and coloring and capable of recovering the transmission property due to the photochromic compound fading when brought back indoors. Regarding the spectacles, a known technique may be applied to the configuration of a frame.[Examples]

[0058] Hereinafter, the present invention will be further described using examples. However, the present invention is not limited to embodiments described in the examples.[Spectacle Lens A]<Manufacturing of Spectacle Lens>

[0059] A plastic lens substrate (trade name EYAS manufactured by HOYA Corporation; central wall thickness 2.5 mm, radius 75 mm, S-4.00) was immersed in a 10 mass% sodium hydroxide aqueous solution (liquid temperature 60°C) for 5 minutes, then cleaned with pure water and dried. After that, a primer layer was formed on the convex surface (object-side surface) of this plastic lens substrate. In detail, a hydroxyl group-containing bifunctional acrylate (10 parts by mass (pbm)) having the following structure: which was a component B, was mixed with CORONATE 2715 (40 pbm) manufactured by Tosoh Corporation as a polyisocyanate, which was a component A, and 2-phenoxyethyl acrylate (viscosity: 13 cP) (50 pbm), which was a component C. With the mixture obtained as described above, a photoradical polymerization initiator (bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (Omnirad819 manufactured by IGM Resin B.V.)) was mixed in an amount of 0.02 mass% with respect to a total of 100 mass% of the mixture and sufficiently stirred. After that, the mixture was defoamed with a rotation-revolution type stirring and defoaming apparatus.

[0060] A polymerizable composition (1) for forming the primer layer obtained as described above was applied to the convex surface of the plastic lens substrate by a spin coating method at 25°C and a relative humidity of 50%, then, the composition for forming the primer layer applied to the plastic lens substrate was irradiated with ultraviolet rays (wavelength 405 nm) in a nitrogen atmosphere (oxygen concentration 500 ppm or less), and this composition was cured to form a primer layer. The thickness of the formed primer layer was 8 µm.

[0061] Next, an annealing treatment (heating treatment) was performed on a laminate of the primer layer and the substrate for 2 hours in a heating furnace at an atmospheric temperature of 90°C, and then a coating composition for forming a photochromic layer prepared as described below was applied onto the primer layer by the spin coating method. The spin coating was performed by a method described in JP-A-2005-218994. After that, the composition applied onto the plastic lens substrate was irradiated with ultraviolet rays (wavelength 405 nm) in a nitrogen atmosphere (oxygen concentration 500 ppm or less), and this composition was cured to form a photochromic layer. The thickness of the formed photochromic layer was 25 µm.

[0062] A spectacle lens A having the photochromic layer was manufactured.<Preparation of Polymerizable Composition for Forming Photochromic Layer>

[0063] In a plastic container, 61.2 pbm of polyethylene glycol dimethacrylate (in the formula 2, n = 14, R is ethylene, molecular weight 736), which was a component D, 18.0 pbm of 1,9-nonanediol diacrylate (in the formula 2, R 1< and R 2< are H, m = 9, molecular weight 268), which was a component E, 10.8 pbm of trimethylolpropane trimethacrylate (molecular weight 296), which was a component F, and 10.0 pbm of 2-phenoxyethyl acrylate (viscosity 13 cP), which was a component C, were mixed together.

[0064] With the mixture of the polymerizable compounds obtained as described above, a photochromic compound (indeno-fused naphthopyran compound of a structural formula shown in US 5,645,767), a photoradical polymerization initiator (bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (Omnirad819 manufactured by IGM Resin B.V.)), an antioxidant (bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate] [ethylenebis(oxyethylene)]) and a light stabilizer (bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate) were mixed and sufficiently stirred. After that, the mixture was defoamed with a rotation-revolution type stirring and defoaming apparatus. A polymerizable composition for forming a photochromic layer was prepared as described above. When the total amount of the composition was regarded as 100 mass%, the content rates of the above-described components are 94.90 mass% for the mixture of the polymerizable compounds, 3.00 mass% for the photochromic compound, 0.30 mass% for the photoradical polymerization initiator, 0.90 mass% for the antioxidant and 0.90 mass% for the light stabilizer. In the polymerizable composition for forming a photochromic layer prepared here, when the total amount of the polymerizable compounds was regarded as 100 mass%, the content rate of the component D is 61.2 mass%, the content rate of the component E is 18.0 mass%, the content rate of the component F is 10.8 mass% and the content rate of the component C is 10.0 mass%.[Spectacle Lens B]

[0065] In the preparation of a composition for forming a primer layer, a hydroxy group-containing bifunctional acrylate having the above-shown structure (27.5 pbm), which was a component B, CORONATE 2715 (25.0 pbm) manufactured by Tosoh Corporation as a polyisocyanate, which was a component A and propylene glycol monomethyl ether acetate (27.5 pbm), which was added instead of using a component C, were mixed together. A spectacle lens B was obtained in the same manner as in the manufacturing of the spectacle lens A except this point.[Evaluation of Optical Homogeneity]

[0066] The spectacle lenses A and B were observed with an optical microscope under irradiation with highly bright light emitted from a zircon lamp in a dark room. In the spectacle lens B, a plurality of optical defects of about several tens of micrometers was confirmed, but such optical defects were not shown in the spectacle lens A. That is, the spectacle lens A was superior to the spectacle lens B in terms of the optical homogeneity.<Evaluation of Adhesive Property>

[0067] For the spectacle lens A, the adhesive property was evaluated by a cross-cut method according to JIS K 5600-5-6: 1999. The evaluation result was "the number of remaining squares / the total number of squares" was "100 / 100", and it was confirmed that the spectacle lens A was excellent in terms of the adhesive property between the substrate and the photochromic layer.

[0068] As a result of immersing the spectacle lens A in warm water of 100°C for 30 minutes and then evaluating the adhesive property by the cross-cut method in the same manner as in the above-described method, "the number of remaining squares / the total number of squares" was "100 / 100".[Industrial Applicability]

[0069] The present invention is useful in the technical fields of e.g. spectacles, goggles, sun visors, and helmets.

Claims

1. An optical article comprising in this order: - a substrate; - a primer layer generated by curing a polymerizable composition (1) containing polyisocyanate as component (A), hydroxy group-containing compound as component (B); and a polymerizable compound having a viscosity of ≤ 100 cP, measured with a vibration-type viscometer at 25°C, and being selected from (meth)acrylates and vinyl ethers as component (C), wherein the content of component (C) is ≥ 30.0 mass%, based on the total of components (A), (B) and (C); and - a photochromic layer containing a photochromic compound.

2. The optical article of claim 1, wherein the content of component (C) in the polymerizable composition (1) is 30.0-90.0 mass%, based on the total of components (A), (B) and (C).

3. The optical article of claim 1 or 2, wherein, in the polymerizable composition (1), the component (C) is the component having the largest fraction among the components (A), (B) and (C).

4. The optical article of any of claims 1-3, wherein the number of OH groups contained in one molecule of component (B) is ≥ 2.

5. The optical article of any of claims 1-4, wherein component (B) is a hydroxy group-containing (meth)acrylate.

6. The optical article of claim 5, wherein component (B) is a bi- or higher functional (meth)acrylate.

7. The optical article of any of claims 1-6, which is a spectacle lens.

8. The optical article of any of claims 1-6, which is a goggle lens.

9. The optical article of any of claims 1-6, which is a visor portion of a sun visor.

10. The optical article of any of claims 1-6, which is a shield member of a helmet.

11. Spectacles comprising the spectacle lens of claim 7.