Photochromic article and method for producing the same

Abstract

To provide a photochromic article excellent in adhesion between a photochromic layer and a substrate.SOLUTION: A photochromic article comprises a substrate, a primer layer produced by curing a polymerizable composition for primer layer formation, and a photochromic layer produced by curing a (meth)acrylic polymerizable composition containing a photochromic compound, in this order. The polymerizable composition for primer layer formation contains a urethane (meth)acrylate containing an isocyanate group, and the content of the isocyanate group in the polymerizable composition for primer layer formation is 2.0 mass% or more where the total amount of the composition is 100 mass%.SELECTED DRAWING: None

Description

[Technical Field]

[0001] PHOTOCHROMIC ARTICLES AND METHODS FOR MANUFACTURING THEM FIELD OF THE INVENTION The present invention relates to photochromic articles and methods for making photochromic articles. [Background technology]

[0002] A photochromic compound is a compound that exhibits the property (photochromic property) of being colored when irradiated with light in a photoresponsive wavelength range and fading in the absence of light irradiation. For example, Patent Document 1 discloses a photochromic article in which a layer containing a photochromic compound (photochromic layer) is provided on a substrate. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent No. 6346183 specification Summary of the Invention [Problem to be solved by the invention]

[0004] The present inventors have conducted extensive research to improve the adhesion between the photochromic layer and the substrate, with the aim of improving the performance of photochromic articles.

[0005] An object of one aspect of the present invention is to provide a photochromic article having excellent adhesion between a photochromic layer and a substrate. [Means for solving the problem]

[0006] The above-mentioned Patent Document 1 (Japanese Patent No. 6346183) discloses that a primer layer between a substrate and a photochromic layer is formed from a photocurable composition containing a urethane (meth)acrylate. In response to this problem, the present inventors conducted extensive research and discovered that the adhesion between the substrate and the photochromic layer can be improved by forming a primer layer between the substrate and the photochromic layer from a polymerizable composition for forming a primer layer that contains an isocyanate group-containing urethane (meth)acrylate and has an isocyanate group content of 2.0 mass% or more.

[0007] That is, one aspect of the present invention is A substrate; a primer layer obtained by curing a polymerizable composition for forming a primer layer; a photochromic layer obtained by curing a (meth)acrylate polymerizable composition containing a photochromic compound; in that order, The polymerizable composition for forming a primer layer contains an isocyanate group-containing urethane (meth)acrylate, and a photochromic article, wherein the isocyanate group content of the polymerizable composition for forming a primer layer is 2.0% by mass or more, with the total amount of the composition being 100% by mass; Regarding. [Effects of the Invention]

[0008] According to one aspect of the present invention, a photochromic article having excellent adhesion between a substrate and a photochromic layer can be provided. Also, according to another aspect of the present invention, a method for producing a photochromic article is provided. [Brief explanation of the drawings]

[0009] [Figure 1] The results of evaluation of the effect of the urethane (meth)acrylate mixing ratio on photochromic performance are shown below. DETAILED DESCRIPTION OF THE INVENTION

[0010] [Photochromic products] A photochromic article according to one embodiment of the present invention has a substrate, a primer layer, and a photochromic layer in this order. In the present invention and this specification, the term "photochromic article" refers to an article containing a photochromic compound.

[0011] The photochromic article according to one embodiment of the present invention will be described in further detail below.

[0012] <Base material> In one embodiment, the photochromic article can be an optical article. Optical articles include various articles such as eyeglass lenses, goggle lenses, sun visor visors, and helmet shields. For example, the photochromic article can have a primer layer and a photochromic layer in this order on a substrate selected depending on the type of optical article. As an example of the substrate, a plastic lens substrate or a glass lens substrate can be used as an eyeglass lens substrate. The glass lens substrate can be, for example, a lens substrate made of inorganic glass. As the lens substrate, a plastic lens substrate is preferred from the viewpoints of being lightweight, less likely to break, and easy to handle. Examples of plastic lens substrates include styrene resins such as (meth)acrylic resins, polycarbonate resins, allyl resins, allyl carbonate resins such as diethylene glycol bisallyl carbonate resin (CR-39), vinyl resins, polyester resins, polyether resins, urethane resins obtained by reacting an isocyanate compound with a hydroxy compound such as diethylene glycol, thiourethane resins obtained by reacting an isocyanate compound with a polythiol compound, and cured products (commonly referred to as transparent resins) obtained by curing a curable composition containing a (thio)epoxy compound having one or more disulfide bonds in the molecule. The term "(meth)acrylic resin" includes acrylic resins and methacrylic resins. The term "(thio)epoxy compound" includes epoxy compounds and thioepoxy compounds. Lens substrates may be undyed (colorless lenses) or dyed (dyed lenses). The refractive index of the lens substrate may be, for example, approximately 1.50 to 1.75. Polycarbonate resins are typically used as lens substrates with a refractive index of 1.59. Allyl carbonate resins, such as diethylene glycol bisallyl carbonate resin (CR-39), are typically used as lens substrates with a refractive index of 1.50. Urea resins obtained by reacting isocyanate-terminated prepolymers with aromatic diamines are typically used as lens substrates with a refractive index of 1.53. Diallyl phthalate resins are typically used as lens substrates with a refractive index of 1.55.Urethane resins obtained by reacting an isocyanate compound with a hydroxy compound such as diethylene glycol are typically used as lens substrates with a refractive index of 1.60. Thiourethane resins obtained by reacting an isocyanate compound with a polythiol compound are typically used as substrates with a refractive index of 1.67. However, the refractive index of the lens substrate is not limited to the above range and may be within the above range or may deviate above or below the above range. In this invention and this specification, the refractive index refers to the refractive index for light with a wavelength of 500 nm. Furthermore, the lens substrate may be a lens with refractive power (so-called prescription lens) or a lens without refractive power (so-called non-prescription lens).

[0013] The spectacle lens can be any of various lenses, such as a single-vision lens, a multifocal lens, or a progressive-power lens. The type of lens is usually determined by the surface shapes of both sides of the lens substrate. The surface of the lens substrate may be convex, concave, or flat. In typical lens substrates and spectacle lenses, the object-side surface is convex and the eyeball-side surface is concave. However, the present invention is not limited to this. The photochromic layer can usually be provided on the object-side surface of the lens substrate, but it may also be provided on the eyeball-side surface.

[0014] <Primer layer> (polymerizable compound) The primer layer contained in the photochromic article is a cured layer obtained by curing a polymerizable composition for forming a primer layer. In the present invention and this specification, the term "polymerizable composition" refers to a composition containing a polymerizable compound. The polymerizable compound is a compound having a polymerizable group. A specific example of the polymerizable group is the (meth)acryloyl group described below.

[0015] The polymerizable composition for forming a primer layer contains an isocyanate group-containing urethane (meth)acrylate. Furthermore, the isocyanate group content of the polymerizable composition for forming a primer layer is 2.0% by mass or more, with the total amount of the composition being 100% by mass. These factors are presumed to contribute to improving the adhesion between the substrate and the photochromic layer by disposing a primer layer formed by curing the polymerizable composition for forming a primer layer between the substrate and the photochromic layer.

[0016] In the present invention and this specification, "urethane (meth)acrylate" refers to a (meth)acrylate having a urethane bond. Urethane (meth)acrylates usually have a structure containing a "(meth)acryloyl group" at the end and / or side chain of the polyurethane skeleton. The present inventors speculate that the inclusion of a urethane (meth)acrylate having a urethane bond, which is a highly polar moiety, in the polymerizable composition for forming a primer layer can contribute to improving the wettability of the polymerizable composition for forming a photochromic layer to the primer layer. From this perspective, it is preferable that the primer layer and the photochromic layer are adjacent to each other in the photochromic article. Here, "adjacent" means that they are in direct contact without any other layer in between.

[0017] In the present invention and this specification, the term "(meth)acrylate" is used to encompass both acrylate and methacrylate. An "acrylate" is a compound having one or more acryloyl groups in one molecule. A "methacrylate" is a compound having one or more methacryloyl groups in one molecule. The functionality of a (meth)acrylate is the number of groups selected from the group consisting of acryloyl groups and methacryloyl groups contained in one molecule. In the present invention and this specification, a "methacrylate" refers to a compound containing only methacryloyl groups as (meth)acryloyl groups, and a compound containing both acryloyl and methacryloyl groups as (meth)acryloyl groups is called an acrylate. The acryloyl group may be contained in the form of an acryloyloxy group, and the methacryloyl group may be contained in the form of a methacryloyloxy group. The term "(meth)acryloyl group" is used to encompass both acryloyl and methacryloyl groups, and the term "(meth)acryloyloxy group" is used to encompass both acryloyloxy and methacryloyloxy groups. Unless otherwise specified, the groups described herein may be substituted or unsubstituted. When a group has a substituent, examples of the substituent include an alkyl group (e.g., an alkyl group having 1 to 6 carbon atoms), a hydroxyl group, an alkoxy group (e.g., an alkoxy group having 1 to 6 carbon atoms), a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom), a cyano group, an amino group, a nitro group, an acyl group, and a carboxy group. The term "carbon number" in a substituted group refers to the carbon number of the portion excluding the substituent.

[0018] The functionality of the isocyanate group-containing urethane (meth)acrylate contained in the polymerizable composition for forming a primer layer (the number of groups selected from the group consisting of acryloyl groups and methacryloyl groups contained in one molecule) is 1 or more, and can be, for example, in the range of 1 to 4. The isocyanate group content of the isocyanate group-containing urethane (meth)acrylate can be, for example, 1.0 mass% or more, 3 mass% or more, or 5 mass% or more, and can be, for example, 20.0 mass% or less, 18.0 mass% or less, 16.0 mass% or less, or 14.0 mass% or less. Due to the nature of synthesis, the isocyanate group-containing urethane (meth)acrylate does not contain a hydroxy group in its molecule. The absence of a hydroxy group in its molecule is preferable from the viewpoint of the storage stability of the polymerizable composition for forming a primer layer. The isocyanate group-containing urethane (meth)acrylate can be synthesized by a known method or is commercially available. Examples of commercially available products include EBECRYL 4141, 4250, 4510, 4396, and 4397 manufactured by Daicel Allnex Co., Ltd.

[0019] The polymerizable composition for forming a primer layer contains at least one isocyanate group-containing urethane (meth)acrylate as a polymerizable compound. In one embodiment, the polymerizable composition for forming a primer layer may contain only an isocyanate group-containing urethane (meth)acrylate as a polymerizable compound, or in another embodiment, may contain one or more other polymerizable compounds. Examples of such other polymerizable compounds include urethane (meth)acrylates that do not contain isocyanate groups. The functionality of the urethane (meth)acrylates that do not contain isocyanate groups (the number of groups selected from the group consisting of acryloyl groups and methacryloyl groups contained in one molecule) is 1 or more, for example, in the range of 1 to 4. From the viewpoint of storage stability of the polymerizable composition for forming a primer layer, it is preferable that the urethane (meth)acrylates that do not contain isocyanate groups do not contain hydroxy groups in the molecule. Urethane (meth)acrylates that do not contain isocyanate groups can be synthesized by known methods or are commercially available. Examples of commercially available products include KRM9276 (monofunctional), KRM9335 (bifunctional), and EBECRYL230 (bifunctional) manufactured by Daicel-Allnex Co., Ltd., and UA-224L (bifunctional) manufactured by Kyoeisha Chemical Co., Ltd.

[0020] The polymerizable composition for forming a primer layer may contain, for example, 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more of the isocyanate group-containing urethane (meth)acrylate, based on 100% by mass of the total of the isocyanate group-containing urethane (meth)acrylate and the urethane (meth)acrylate not containing an isocyanate group. From the viewpoint of improving adhesion between the substrate and the photochromic layer, it is preferable that the polymerizable composition for forming a primer layer contains a large amount of the isocyanate group-containing urethane (meth)acrylate. Furthermore, from the viewpoint of various performances of the photochromic article, the polymerizable composition for forming a primer layer preferably contains 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less of the isocyanate group-containing urethane (meth)acrylate, based on 100% by mass of the total of the isocyanate group-containing urethane (meth)acrylate and the urethane (meth)acrylate not containing an isocyanate group.

[0021] (optional ingredient) The polymerizable composition for forming the primer layer contains at least an isocyanate group-containing urethane (meth)acrylate, and may contain other polymerizable compounds such as an isocyanate group-free urethane (meth)acrylate, and may further contain one or more other components. Examples of such components include a polymerization initiator and a catalyst. These components may be used in any amount, and known compounds or commercially available products may be used as these components.

[0022] For example, as the polymerization initiator, a known polymerization initiator capable of functioning as a polymerization initiator for (meth)acrylate can be used, a radical polymerization initiator is preferred, and it is more preferred that the polymerization initiator contains only a radical polymerization initiator. Furthermore, as the polymerization initiator, a photopolymerization initiator or a thermal polymerization initiator can be used, and a photopolymerization initiator is preferred from the viewpoint of progressing the polymerization reaction in a short 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-octadione-2-(benzoyl)oxime; bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)phenylphosphine oxide, and the like. phosphine oxides 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-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 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 benzil dimethyl ketal; acridine compounds such as 9-phenylacridine and 1,7-bis(9,9'-acridinylheptane); N-phenylglycine, coumarin, and the like. In the 2,4,5-triarylimidazole dimer, the substituents on the aryl groups of the two triarylimidazole moieties may be the same to give a symmetrical compound, or may be different to give an asymmetrical compound. Furthermore, a thioxanthone compound may be combined with a tertiary amine, such as the combination of diethylthioxanthone and dimethylaminobenzoic acid. Among these, α-hydroxyketones and phosphine oxides are preferred from the viewpoints of curability, transparency, and heat resistance.

[0023] Examples of the catalyst include organotin compounds such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, dimethyltin dichloride, monomethyltin trichloride, trimethyltin chloride, tributyltin chloride, tributyltin fluoride, dimethyltin dibromide, etc. The organotin compounds can exhibit catalytic action on isocyanate groups.

[0024] The polymerizable composition for forming a primer layer may or may not contain a solvent. When a solvent is contained, any solvent can be used in any amount as long as it does not inhibit the progress of the polymerization reaction of the polymerizable compound. In the present invention and this specification, with regard to the content, the "total amount of the composition" refers to the total amount of all components excluding the solvent in a composition containing a solvent.

[0025] The polymerizable composition for forming a primer layer may further contain any amount of known additives that are typically added to compositions for forming a primer layer. Known compounds or commercially available products may be used as additives. The polymerizable composition for forming a primer layer may contain a total of 80.0% by mass or more, 85.0% by mass or more, 90.0% by mass or more, or 95.0% by mass or more of the isocyanate group-containing urethane (meth)acrylate and the isocyanate group-free isocyanate, based on 100% by mass of the total amount of the composition (excluding the polymerization initiator). Furthermore, the total content of the isocyanate group-containing urethane (meth)acrylate and the isocyanate group-free isocyanate, based on 100% by mass of the total amount of the composition (excluding the polymerization initiator), may be, for example, 100% by mass, 100% by mass or less, less than 100% by mass, or 99.0% by mass or less.

[0026] (Isocyanate Group Content of Polymerizable Composition for Forming Primer Layer) The isocyanate group content of the polymerizable composition for forming a primer layer is 2.0% by mass or more, more preferably 2.1% by mass or more, and even more preferably 2.2% by mass or more, based on 100% by mass of the total amount of the composition. The inventors believe that the reason that the adhesion between the substrate and the photochromic layer can be improved by disposing a primer layer formed from the polymerizable composition for forming a primer layer between the substrate and the photochromic layer is because the polymerizable composition for forming a primer layer contains an isocyanate group-containing urethane (meth)acrylate and the isocyanate group content in the composition is 2.0% by mass or more. The inventors believe that the isocyanate group can contribute to maintaining high adhesion between the substrate and the photochromic layer even in a high-temperature, high-humidity environment. The isocyanate group content of the polymerizable composition for forming a primer layer may be, for example, 5.0% by mass or less, 4.0% by mass or less, or 3.0% by mass or less. However, since a high isocyanate group content of the polymerizable composition for forming a primer layer is preferable from the viewpoint of improving adhesion between the substrate and the photochromic layer, the upper limit of the isocyanate group content of the polymerizable composition for forming a primer layer is not limited to the values ​​exemplified here. For example, in the polymerizable composition for forming a primer layer, when the only component containing an isocyanate group is an isocyanate group-containing urethane (meth)acrylate, the isocyanate group content of the polymerizable composition for forming a primer layer relative to the total amount of the composition (100 mass%) can be calculated, for example, by the following formula: Isocyanate group content of the polymerizable composition for forming a primer layer relative to the total amount of the composition (100 mass%) = Y × X / T In the above formula, the isocyanate group content of the isocyanate group-containing urethane (meth)acrylate is "X" mass %, the amount of isocyanate group-containing urethane (meth)acrylate in the polymerizable composition for forming a primer layer is "Y" g (grams), and the total amount of the composition is "T" g (grams).

[0027] The composition for forming a primer layer can be prepared by mixing the various components described above simultaneously or sequentially in any order.

[0028] By applying the primer layer-forming polymerizable composition to a substrate and subjecting the applied composition to a curing treatment, a primer layer can be formed on the substrate as a cured layer formed by curing the primer layer-forming polymerizable composition. The primer layer-forming polymerizable composition can be applied directly to the substrate surface, or can be applied to the surface of a layer provided on the substrate. That is, in the photochromic article, the substrate and the primer layer are adjacent to each other in one embodiment, and in another embodiment, the primer layer is located on the substrate via one or more other layers. Examples of other layers include known layers such as a hard coat layer. Known coating methods such as spin coating and dip coating can be used as the coating method, with spin coating being preferred from the viewpoint of coating uniformity. The substrate surface can optionally be subjected to one or more known pretreatments such as alkali treatment and UV ozone treatment to clean the substrate surface. The curing treatment can be light irradiation and / or heat treatment, with light irradiation being preferred from the viewpoint of progressing the curing reaction in a short period of time. The conditions for the curing treatment may be determined depending on the types of components contained in the polymerizable composition for forming a primer layer and the composition of the polymerizable composition for forming a primer layer.

[0029] The thickness of the primer layer can be, for example, 3 μm or more, and preferably 5 μm or more, and the thickness of the primer layer can be, for example, 15 μm or less, and preferably 10 μm or less.

[0030] <Photochromic layer> <<Polymerizable compounds>> The photochromic article has a photochromic layer on the primer layer. The photochromic layer included in the photochromic article is a cured layer obtained by curing a (meth)acrylate-based polymerizable composition. In the present invention and this specification, "(meth)acrylate-based polymerizable composition" refers to a polymerizable composition containing (meth)acrylate. The polymerizable composition for forming the primer layer also contains the urethane (meth)acrylate described above, and therefore can be called a (meth)acrylate-based polymerizable composition. The inventors speculate that the fact that both the primer layer and the photochromic layer are cured layers obtained by curing a (meth)acrylate-based polymerizable composition can also contribute to improving the adhesion between the substrate and the photochromic layer.

[0031] A (meth)acrylate-based polymerizable composition, which is one embodiment of the polymerizable composition for forming a photochromic layer, will be described below. However, the following embodiment is merely an example, and the present invention is not limited to this example.

[0032] In one embodiment, the polymerizable composition for forming a photochromic layer can be a (meth)acrylate-based polymerizable composition containing one or more polymerizable compounds selected from the group consisting of the following component A, the following component B, and the following component C.

[0033] (Component A) Component A is a polyfunctional (meth)acrylate containing a polyalkylene glycol moiety and having a molecular weight of 500 or more. In the present invention and this specification, the term "polyalkylene glycol moiety" refers to a polyfunctional (meth)acrylate having a molecular weight of 500 or more and having a molecular weight of 500 or more. [ka] In formula 2, R represents an alkylene group, and n represents the number of repetitions of the alkoxy group represented by RO and is 2 or more. * represents the bonding position where the partial structure represented by formula 2 is bonded to an adjacent atom. The number of carbon atoms in the alkylene group represented by R can be 1 or more or 2 or more, and can be, for example, 5 or less or 4 or less. Specific examples of the alkylene group represented by R include an ethylene group, a propylene group, and a tetramethylene group. n is 2 or more and can be, for example, 30 or less, 25 or less, or 20 or less. In one embodiment, component A can have the above partial structure in which R represents an ethylene group, i.e., a polyethylene glycol moiety. In another embodiment, component A can have an upper substructure in which R represents a propylene group, i.e., a polypropylene glycol moiety.

[0034] The molecular weight of component A is 500 or more. In the present invention and this specification, the molecular weight of the multimer is determined by the structural formula determined by structural analysis of the compound or the theoretical molecular weight calculated from the raw material charging ratio during production. The molecular weight of component A is 500 or more, preferably 510 or more, more preferably 520 or more, preferably 550 or more, more preferably 570 or more, even more preferably 600 or more, even more preferably 630 or more, and even more preferably 650 or more. From the viewpoint of increasing the hardness of the photochromic layer, the molecular weight of component A is preferably, for example, 2000 or less, 1500 or less, 1200 or less, 1000 or less, or 800 or less.

[0035] Component A is a polyfunctional (meth)acrylate, and may be, for example, a difunctional, trifunctional, tetrafunctional, or pentafunctional (meth)acrylate, and is preferably a difunctional or trifunctional (meth)acrylate. Component A may contain only acryloyl groups, only methacryloyl groups, or both acryloyl and methacryloyl groups as (meth)acryloyl groups. That is, Component A may be an acrylate or methacrylate.

[0036] In one embodiment, component A can be an acyclic polyfunctional (meth)acrylate. In the present invention and this specification, "acyclic" means not containing a cyclic structure. In contrast, "cyclic" means containing a cyclic structure. An acyclic polyfunctional (meth)acrylate refers to a bifunctional or higher functional (meth)acrylate that does not contain a cyclic structure. A specific example of such component A is a polyalkylene glycol di(meth)acrylate represented by the following formula 3.

[0037] [ka]

[0038] In formula 3, R 1 and R 2 each independently represents a hydrogen atom or a methyl group, R represents an alkylene group, and n represents the number of repetitions of the alkoxy group represented by RO and is 2 or more. R and n are as described above for the partial structure represented by formula 2. The polyalkylene glycol di(meth)acrylate represented by formula 3 may contain only acryloyl groups, only methacryloyl groups, or both acryloyl and methacryloyl groups as (meth)acryloyl groups. Specific examples of the polyalkylene glycol di(meth)acrylate represented by formula 3 include polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and polytetramethylene glycol di(meth)acrylate.

[0039] Specific examples of component A include tri(meth)acrylates represented by the following formula 4. The tri(meth)acrylates represented by formula 4 may contain only acryloyl groups, only methacryloyl groups, or both acryloyl and methacryloyl groups as (meth)acryloyl groups.

[0040] [ka]

[0041] In formula 4, R 40 , R 41 , R 44 , R 45 , R 47 and R 48 each independently represents an alkylene group, R 43 represents an alkyl group, and R 42 , R 46 and R 49 each independently represents a hydrogen atom or a methyl group; 41 n2 represents the number of repeating alkoxy groups represented by the formula: 45 n3 represents the number of repeating alkoxy groups represented by the formula: 48 The number of repetitions of the alkoxy group represented by the formula (I) is 2 or more.

[0042] Equation 4 will be explained in more detail below.

[0043] R in Equation 4 41 , R 45 and R 48 In Formula 4, n1, n2, and n3 are as described above for n in Formula 2. In Formula 4, R 41 , R 45 and R 48 may be the same, or two or three may be different. The same applies to n1, n2, and n3.

[0044] R 42 , R 46 and R 49 each independently represents a hydrogen atom or a methyl group. The tri(meth)acrylate represented by formula 4 may contain only acryloyl groups, only methacryloyl groups, or both acryloyl groups and methacryloyl groups as (meth)acryloyl groups.

[0045] R 43The number of carbon atoms in the alkyl group represented by R can be 1 or more, or 2 or more, and can be, for example, 5 or less, or 4 or less. 43 The alkyl group represented by R can be a straight chain alkyl group or a branched alkyl group. 43 Specific examples of the alkyl group represented by the formula include a methyl group and an ethyl group.

[0046] R 40 , R 44 and R 47 each independently represents an alkylene group. The number of carbon atoms in such an alkylene group can be 1 or more or 2 or more, and can be, for example, 5 or less or 4 or less. Specific examples thereof include an ethylene group, a propylene group, and a tetramethylene group.

[0047] Specific examples of the tri(meth)acrylate represented by formula 4 include trimethylolpropane polyoxyethylene ether tri(meth)acrylate.

[0048] Monofunctional (meth)acrylate From the viewpoint of increasing the (meth)acryloyl group content of a polymerizable composition containing a (meth)acrylate, a (meth)acrylate having a high ratio of (meth)acryloyl groups in the molecule is preferred. From this viewpoint, a low-molecular-weight monofunctional (meth)acrylate is preferred, and a monofunctional (meth)acrylate having a molecular weight of 150 or less is more preferred. The monofunctional (meth)acrylate having a molecular weight of 150 or less may be a cyclic monofunctional (meth)acrylate or an acyclic monofunctional (meth)acrylate. A specific example of a cyclic monofunctional (meth)acrylate having a molecular weight of 150 or less is glycidyl (meth)acrylate. A specific example of an acyclic monofunctional (meth)acrylate having a molecular weight of 150 or less is n-butyl (meth)acrylate. The molecular weight of a monofunctional (meth)acrylate having a molecular weight of 150 or less may be, for example, 100 or more, but is not limited thereto.

[0049] Multifunctional (meth)acrylate As described above, from the viewpoint of increasing the (meth)acryloyl group content of a polymerizable composition containing a (meth)acrylate, a (meth)acrylate with a high ratio of (meth)acryloyl groups in the molecule is preferred. From this viewpoint, a polyfunctional (meth)acrylate having a molecular weight smaller than that of Component A is also preferred. As such a polyfunctional (meth)acrylate, a polyfunctional (meth)acrylate having a higher functionality than the polyfunctional (meth)acrylate used as Component A is also preferred. The molecular weight of such a polyfunctional (meth)acrylate is preferably less than 500, 400 or less, 300 or less, or 200 or less. The molecular weight can be, for example, 100 or more, but is not limited thereto. Furthermore, such a polyfunctional (meth)acrylate can be, for example, a polyfunctional (meth)acrylate having 10 or more functionalities (e.g., 10 to 15 functionalities). Specific examples include poly[(3-methacryloyloxypropyl)silsesquioxane] derivatives described in the Examples section below.

[0050] Examples of (meth)acrylates that can be contained in the (meth)acrylate-based polymerizable composition, which is the polymerizable composition for forming a photochromic layer, include a monofunctional (meth)acrylate represented by the following formula 1 (hereinafter also referred to as "component B") and a bifunctional (meth)acrylate represented by the following formula 5 (hereinafter also referred to as "component C"). In one embodiment, the (meth)acrylate-based polymerizable composition can be a polymerizable composition containing one or more (meth)acrylates selected from the group consisting of a monofunctional (meth)acrylate represented by the following formula 1 and a bifunctional (meth)acrylate represented by the following formula 5. In another embodiment, the (meth)acrylate-based polymerizable composition can be a polymerizable composition that does not contain one or more (meth)acrylates selected from the group consisting of a monofunctional (meth)acrylate represented by the following formula 1 and a bifunctional (meth)acrylate represented by the following formula 5. In one embodiment, the (meth)acrylate-based polymerizable composition can also contain component B as a monofunctional (meth)acrylate having a molecular weight of 150 or less.

[0051] (Component B) Component B is a monofunctional (meth)acrylate represented by the following formula 1.

[0052] [ka]

[0053] Formula 1 will be explained in more detail below.

[0054] In formula 1, R 10 represents a hydrogen atom or a methyl group. The monofunctional (meth)acrylate represented by formula 1 may be an acrylate or a methacrylate.

[0055] R 11 represents a linear alkyl group having 3 or more carbon atoms or a branched alkyl group having 3 or more carbon atoms. 11 The number of carbon atoms in the linear or branched alkyl group represented by the formula (I) is 3 or more, preferably 4 or more, more preferably 5 or more, and further preferably 6 or more, 7 or more, 8 or more, 9 or more, 10 or more, and 11 or more in that order. On the other hand, from the viewpoint of the solubility of the photochromic compound in the composition, the number of carbon atoms is preferably 15 or less, more preferably 14 or less, and further preferably 13 or less, and 12 or less in that order.

[0056] The molecular weight of the monofunctional (meth)acrylate represented by Formula 1 can be, for example, 100 or more, or, for example, 300 or less. However, it is not limited to the above range. As described above, in one embodiment, the monofunctional (meth)acrylate represented by Formula 1 can be a monofunctional (meth)acrylate having a molecular weight of 150 or less. Specific examples of the monofunctional (meth)acrylate represented by Formula 1 include n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, and n-lauryl (meth)acrylate.

[0057] (Component C) Component C is represented by the following formula 5: [ka] It is a (meth)acrylate represented by the formula:

[0058] In formula 5, R 3 and R 4 each independently represents a hydrogen atom or a methyl group, and m represents an integer of 1 or greater. m is 1 or greater and can be, for example, 10 or less, 9 or less, 8 or less, 7 or less, or 6 or less.

[0059] The molecular weight of component C can be, for example, 400 or less, and from the viewpoint of further increasing the color density of the photochromic layer, it is preferably 350 or less, more preferably 300 or less, and even more preferably 250 or less. The molecular weight of component C can be, for example, 100 or more, 150 or more, or 200 or more.

[0060] Component C may contain only acryloyl groups, only methacryloyl groups, or both acryloyl and methacryloyl groups as (meth)acryloyl groups. Specific examples of component C include 1,9-nonanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and 1,10-decanediol di(meth)acrylate.

[0061] In the (meth)acrylate-based polymerizable composition, the content of component A is preferably 50% by mass or more, more preferably 55% by mass or more, and even more preferably 60% by mass or more, based on 100% by mass of the total amount of polymerizable compounds contained in the composition. In one embodiment, component A may be the component that accounts for the largest proportion of the multiple polymerizable compounds contained in the composition. Furthermore, the content of component A may be 90% by mass or less, 85% by mass or less, or 80% by mass or less, based on 100% by mass of the total amount of polymerizable compounds contained in the composition. In one embodiment, the composition may contain only one type of component A, or in another embodiment, two or more types. When two or more types of component A are contained, the content of component A mentioned above is the total content of the two or more types. This also applies to the contents of other components in the present invention and this specification.

[0062] The (meth)acrylate polymerizable composition may contain the various (meth)acrylates in an amount such that the (meth)acryloyl group content of the composition is 3.50 mmol / g or more. For example, the (meth)acrylate polymerizable composition preferably contains 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more of a monofunctional (meth)acrylate having a molecular weight of 150 or less, based on 100% by mass of the total amount of polymerizable compounds contained in the composition. Furthermore, the content of the monofunctional (meth)acrylate having a molecular weight of 150 or less is preferably 30% by mass or less, more preferably 25% by mass or less, based on 100% by mass of the total amount of polymerizable compounds contained in the composition.

[0063] From the viewpoint of improving the weather resistance of the photolayer, the (meth)acryloyl group content of the (meth)acrylate polymerizable composition is preferably 3.50 mmol / g or more, more preferably 3.55 mmol / g or more, even more preferably 3.60 mmol / g or more, even more preferably 3.65 mmol / g or more, even more preferably 3.70 mmol / g or more, and even more preferably 3.75 mmol / g or more. The (meth)acryloyl group content of the (meth)acrylate polymerizable composition can be, for example, 5.00 mmol / g or less, 4.50 mmol / g or less, or 4.00 mmol / g or less, or may exceed the values ​​exemplified here.

[0064] The "(meth)acryloyl group content" of a polymerizable composition containing a (meth)acrylate is calculated as follows. The content of each (meth)acrylate is calculated by taking the total amount of (meth)acrylate contained in the polymerizable composition as "1" on a mass basis. For each (meth)acrylate, the "(meth)acryloyl group content x the above content" is calculated. The sum of the values ​​thus calculated for all (meth)acrylates contained in the polymerizable composition is taken as the (meth)acryloyl group content of the polymerizable composition.

[0065] For example, the photochromic compound contained in the photochromic layer undergoes a structural change upon irradiation with light such as sunlight, passing through an excited state. The structure after structural change upon irradiation with light can be called a "colored form." In contrast, the structure before irradiation with light can be called a "colorless form." Note that "colorless" in the colorless form does not necessarily mean completely colorless, but also encompasses a state in which the color is lighter than the colored form. After structural change to a colored form upon irradiation with light, the faster the rate of structural change from the colored form to the colorless form, the faster the fading rate. In the photochromic layer, the easier the molecular movement of the photochromic compound in the matrix formed by the polymerization reaction of the polymerizable compound is thought to be the faster the rate of the structural change. From the perspective of accelerating this rate, a flexible matrix is ​​considered desirable. In relation to the above points, it is believed that Component A contributes to making the matrix flexible. Specifically, the molecular weight of Component A is 500 or more, and Component A contains a polyalkylene glycol moiety, which are thought to be the reasons why Component A can form a flexible matrix. Furthermore, the (meth)acryloyl group content of 3.50 mmol / g or more in the (meth)acrylate polymerizable composition is thought to contribute to the formation of a rigid polymer network between molecules in a matrix formed from such a composition. In a matrix having a rigid polymer network, the diffusion of active species that can cause a decrease in weather resistance can be suppressed, which is presumably the reason why the (meth)acrylate polymerizable composition can form a photochromic layer with excellent weather resistance.

[0066] The content of the polymerizable compound in the (meth)acrylate polymerizable composition (when multiple polymerizable compounds are included, the total content of these compounds) can be, for example, 80% by mass or more, 85% by mass or more, or 90% by mass or more, based on 100% by mass of the total amount of the composition. The content of the polymerizable compound in the (meth)acrylate polymerizable composition can be, for example, 99% by mass or less, 95% by mass or less, 90% by mass or less, or 85% by mass or less, based on 100% by mass of the total amount of the composition. The (meth)acrylate polymerizable composition may or may not contain a solvent. When a solvent is included, any solvent can be used in any amount as long as it does not inhibit the polymerization reaction of the polymerizable composition.

[0067] <<Photochromic compounds>> The composition contains a photochromic compound in addition to the polymerizable compound. The photochromic compound contained in the composition can be a known compound exhibiting photochromic properties. The photochromic compound can exhibit photochromic properties, for example, when exposed to ultraviolet light. Examples of photochromic compounds include compounds having a known skeleton exhibiting photochromic properties, such as fulgimide compounds, spirooxazine compounds, chromene compounds, and indeno-fused naphthopyran compounds. The photochromic compounds can be used alone or in combination of two or more. The content of the photochromic compound in the composition can be, for example, about 0.1 to 15% by mass, with the total amount of the composition being 100% by mass, but is not limited to this range.

[0068] <<Other Ingredients>> In addition to the polymerizable compound and the photochromic compound, the photochromic layer-forming polymerizable composition may contain one or more of the various additives that are typically contained in polymerizable compositions, at any content. Examples of additives that may be contained in the photochromic layer-forming polymerizable composition include a polymerization initiator for promoting the polymerization reaction. The above description of the polymerization initiator can be referenced. The content of the polymerization initiator may be, for example, in the range of 0.1 to 5.0% by mass, with the total amount of the composition being 100% by mass.

[0069] The polymerizable composition for forming a photochromic layer may further contain any amount of known additives that are typically added to compositions containing a photochromic compound, such as surfactants, antioxidants, radical scavengers, light stabilizers, ultraviolet absorbers, color inhibitors, antistatic agents, fluorescent dyes, dyes, pigments, fragrances, plasticizers, and silane coupling agents. Known compounds may be used as these additives.

[0070] The polymerizable composition for forming a photochromic layer can be prepared by mixing the various components described above simultaneously or sequentially in any order.

[0071] The photochromic layer can be formed by applying a photochromic layer-forming polymerizable composition onto the primer layer and curing the applied composition. The above description can be referenced for the coating method. The curing treatment can be light irradiation and / or heat treatment, with light irradiation being preferred from the viewpoint of progressing the curing reaction in a short time. The curing treatment conditions can be determined depending on the types of various components (such as the polymerizable compound and polymerization initiator described above) contained in the photochromic layer-forming polymerizable composition and the composition of the composition. The thickness of the photochromic layer thus formed is preferably in the range of 5 to 80 μm, and more preferably in the range of 20 to 60 μm.

[0072] The photochromic article having the photochromic layer may or may not further have one or more functional layers in addition to the various layers described above. Examples of functional layers include protective layers for improving durability, hard coat layers, anti-reflection layers, water-repellent or hydrophilic antifouling layers, anti-fogging layers, and other layers known as functional layers for optical articles. For example, for the protective layer, see paragraphs 0009 to 0021, 0026 of JP 2021-107909 A and the descriptions in the Examples of the same publication.

[0073] The photochromic article can be an optical article, and one example of the optical article is a spectacle lens. Other examples of the optical article include a goggle lens, a sun visor visor, and a helmet shield. A photochromic-forming polymerizable composition is applied to a substrate for such an optical article via a primer layer, and the applied composition is cured to form a photochromic layer, thereby obtaining an optical article with antiglare properties.

[0074] [glasses] One aspect of the present invention relates to eyeglasses equipped with eyeglass lenses, which are one form of the photochromic article. Details of the eyeglass lenses included in the eyeglasses are as described above. By including such eyeglass lenses, the eyeglasses can, for example, exhibit anti-glare effects similar to sunglasses outdoors by coloring the photochromic compound contained in the photochromic layer when exposed to sunlight, and regain their transparency when returning indoors by fading the photochromic compound. Known technologies can be applied to the construction of the frames and other components of the eyeglasses.

[0075] [Method of manufacturing photochromic articles] One aspect of the present invention is applying the above-described polymerizable composition for forming a primer layer onto a substrate; subjecting the applied polymerizable composition for forming a primer layer to a curing treatment by light irradiation to form a primer layer; applying a (meth)acrylate polymerizable composition containing a photochromic compound onto the formed primer layer; The applied (meth)acrylate polymerizable composition containing the photochromic compound is subjected to a curing treatment by light irradiation to form a photochromic layer; a method for producing a photochromic article, comprising: Regarding.

[0076] According to the above-mentioned manufacturing method, a photochromic article having excellent adhesion between the substrate and the photochromic layer can be manufactured. For details of the above-mentioned manufacturing method, please refer to the above description. [Example]

[0077] The present invention will be further described below with reference to examples, although the present invention is not limited to the embodiments shown in the examples.

[0078] <Base material> The various substrates described below are plastic lens substrates as follows. Each substrate has a convex object-side surface and a concave eyeball-side surface. Substrate 4 (refractive index 1.59) is a substrate with hard coat layers on both sides, and the polymerizable composition for forming a primer layer described below was applied to the hard coat layer surface. Substrate 1: Refractive index 1.50 (diethylene glycol bisallyl carbonate resin (CR-39)) Base material 2: Refractive index 1.53 (urea resin) Base material 3: Refractive index 1.55 (diallyl phthalate resin) Base material 4: Refractive index 1.59 (polycarbonate resin) Base material 5: Refractive index 1.60 (urethane resin) Base material 6: Refractive index 1.67 (thiourethane resin)

[0079] [Example 1] <Production of eyeglass lenses (photochromic products)> A plastic lens substrate was immersed in a 10% by weight aqueous solution of sodium hydroxide (liquid temperature 60°C) for 5 minutes, then rinsed with pure water and dried. A primer layer was then formed on the convex surface (object-side surface) of the plastic lens substrate. Specifically, Daicel-Allnex Corporation's KRM 9276 was used as the isocyanate-free urethane acrylate, and Daicel-Allnex Corporation's EBECRYL 4141 (isocyanate group content: 12.0% by weight) was used as the isocyanate-containing urethane acrylate. These two urethane acrylates (20 g total, KRM 9276:EBECRYL 4141 (mass ratio) = 8:2) were mixed. The resulting mixture was mixed with 0.02% by mass of an organotin compound (dibutyltin dilaurate, manufactured by Tokyo Chemical Industry Co., Ltd.), 0.005% by mass of a photoradical polymerization initiator (bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (Omnirad 819, manufactured by IGM Resin BV)), and 0.25% by mass of a leveling agent (LE-605, manufactured by Kyoeisha Chemical Co., Ltd.), based on 100% by mass of the total mixture, and thoroughly stirred. The mixture was then degassed using a rotation-revolution type stirring and degassing device. The isocyanate group content of the resulting polymerizable composition for forming a primer layer was 2.4% by mass, based on 100% by mass of the total composition. The primer layer-forming polymerizable composition was applied to the convex surface of a plastic lens substrate by spin coating in an environment of 25°C and 50% relative humidity, and then the primer layer-forming composition applied to the plastic lens substrate was irradiated with ultraviolet light (wavelength 405 nm) in a nitrogen atmosphere (oxygen concentration 500 ppm or less) to harden the composition and form a primer layer. The formed primer layer had a thickness of 6 μm. A polymerizable composition for forming a photochromic layer ((meth)acryloyl group content: 3.61 mmol / g) prepared as follows was applied onto the primer layer by spin coating. The spin coating was performed according to the method described in JP 2005-218994 A. The polymerizable composition for forming a photochromic layer applied onto the primer layer was then irradiated with ultraviolet light (wavelength 405 nm) in a nitrogen atmosphere (oxygen concentration 500 ppm or less) to cure the composition and form a photochromic layer. The thickness of the formed photochromic layer was 40 μm. A protective layer was formed on the photochromic layer thus formed by the method described in Example 1 of JP-A-2021-107909. The thickness of the formed protective layer was 15 μm. In this way, a spectacle lens was produced which had the substrate, primer layer and photochromic layer in this order, and further had a protective layer on the photochromic layer.

[0080] (Preparation of Polymerizable Composition for Forming Photochromic Layer) The ingredients shown in Table 1 were mixed in the amounts shown in Table 1 in a plastic container. The resulting mixture of polymerizable compounds was mixed with a photochromic compound (an indeno-fused naphthopyran compound represented by the structural formula described in U.S. Pat. No. 5,645,767), a photoradical polymerization initiator (bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (Omnirad 819, manufactured by IGM Resin BV)), an antioxidant (bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][ethylenebis(oxyethylene)]), and a light stabilizer (bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate) and thoroughly stirred. The mixture was then degassed using a rotation-revolution type stirring and degassing device. Thus, a polymerizable composition for forming a photochromic layer was prepared. The contents of the above components, taking the total amount of the composition as 100% by mass, are 94.9% by mass for the mixture of polymerizable compounds, 3% by mass for the photochromic compound, 0.3% by mass for the photoradical polymerization initiator, 0.9% by mass for the antioxidant, and 0.9% by mass for the light stabilizer.

[0081] [Table 1]

[0082] [Comparative Example 1] Spectacle lenses were prepared as described in Example 1, except that the total amount of 20 g of urethane acrylate was urethane acrylate containing no isocyanate group (KRM 9276 manufactured by Daicel-Allnex Corporation).

[0083] Comparative Example 2 Spectacle lenses were produced as described in Example 1, except that the mixing ratio of the urethane acrylate containing no isocyanate group (KRM 9276 manufactured by Daicel-Allnex Corporation) to the urethane acrylate containing an isocyanate group (EBECRYL 4141 manufactured by Daicel-Allnex Corporation) was changed to KRM 9276:EBECRYL 4141 (mass ratio) = 9:1. The isocyanate group content of the polymerizable composition for forming a primer layer prepared in Comparative Example 2 was 1.2% by mass, with the total amount of the composition being 100% by mass.

[0084] [Example 2] Except for using EBECRYL 4396 (isocyanate group content: 7.5% by mass) manufactured by Daicel-Allnex Corporation as the isocyanate group-containing urethane acrylate and changing the mixing ratio of the isocyanate group-free urethane acrylate (KRM 9276 manufactured by Daicel-Allnex Corporation) to the isocyanate group-containing urethane acrylate to KRM 9276:EBECRYL 4396 (mass ratio) = 7:3, eyeglass lenses were produced as described for Example 1. The isocyanate group content of the polymerizable composition for forming a primer layer prepared in Example 2 was 2.2% by mass, with the total amount of the composition being 100% by mass.

[0085] Comparative Example 3 Spectacle lenses were produced as described for Example 2, except that the mixing ratio of the urethane acrylate not containing an isocyanate group (KRM 9276 manufactured by Daicel-Allnex Corporation) to the urethane acrylate containing an isocyanate group (EBECRYL 4396 manufactured by Daicel-Allnex Corporation) was changed to KRM 9276:EBECRYL 4396 (mass ratio) = 8:2. The isocyanate group content of the polymerizable composition for forming a primer layer prepared in Comparative Example 3 was 1.5% by mass, with the total amount of the composition being 100% by mass.

[0086] [Adhesion evaluation] In each of the examples and comparative examples, two eyeglass lenses were produced using the base materials shown in Table 2. One of the two eyeglass lenses produced was subjected to evaluation of initial adhesion, and the other was subjected to evaluation of adhesion under high temperature and high humidity conditions. The initial adhesion was evaluated by the cross-cut method in accordance with JIS K5600-5-6:1999. Regarding adhesion under high temperature and high humidity, the eyeglass lenses were immersed in boiling water for 1 hour, and then the adhesion of the eyeglass lenses taken out of the water was evaluated by the cross-cut method in accordance with JIS K5600-5-6:1999. Table 2 shows the evaluation results according to the following evaluation criteria, with the number of remaining squares shown in parentheses. For eyeglass lenses in which peeling of the squares occurred, the peeled areas were observed, and it was confirmed that peeling of the film had occurred on the surface of the substrate, i.e., peeling had occurred between the substrate and the primer layer. The results shown in Table 2 confirm that the eyeglass lenses of Examples 1 and 2 are superior to the eyeglass lenses of Comparative Examples 1 to 3 in terms of adhesion between the substrate and the photochromic layer. (Evaluation criteria) A: 100 remaining squares out of a total of 100 squares (no peeling) B: 96 to 99 remaining squares out of a total of 100 squares C: 90 to 95 remaining squares out of a total of 100 squares D: 89 or less remaining squares out of a total of 100 squares

[0087] [Table 2]

[0088] For Example 1, the above-mentioned adhesion evaluation was also carried out on the eyeglass lenses using substrates 3 to 6. As a result, it was confirmed that in Example 1, the eyeglass lenses using substrates 3 to 6 also received an evaluation result of "A" for both initial adhesion and adhesion under high temperature and high humidity conditions. On the other hand, for Comparative Example 2, the evaluation result for initial adhesion for the eyeglass lens using substrate 4 was "C" (number of remaining squares: 95), and the evaluation result for adhesion under high temperature and high humidity for the eyeglass lens using substrate 5 was "D" (number of remaining squares: 2). For Comparative Example 3, the evaluation results for both initial adhesion and adhesion under high temperature and high humidity for the eyeglass lens using substrate 6 were "C" (number of remaining squares: 95). For the eyeglass lenses using the substrate 4, the adhesion under high temperature and high humidity conditions was evaluated after immersion in warm water at a temperature of 50° C. for 1 hour.

[0089] [Investigation of the effect of urethane (meth)acrylate mixing ratio on photochromic performance] Figure 1 shows the evaluation results regarding the effect of the urethane (meth)acrylate mixing ratio on the photochromic performance. The evaluation results shown in Figure 1 were obtained as follows. In Example 1, the mixing ratio of an isocyanate group-free urethane acrylate (KRM 9276 manufactured by Daicel-Allnex Corporation) to an isocyanate group-containing urethane acrylate (EBECRYL 4141 manufactured by Daicel-Allnex Corporation) in the primer layer-forming composition was KRM 9276:EBECRYL 4141 (mass ratio) = 8:2. Except for this change in the mixing ratio, eyeglass lenses were fabricated using substrate 1 as the substrate in the same manner as in Example 1. Various performance characteristics of the fabricated eyeglass lenses were evaluated using the following methods (relative evaluation based on the difference from a reference lens (reference) that did not contain a primer layer). In Figure 1, the horizontal axis represents the content (unit: mass%) of the isocyanate group-containing urethane acrylate (EBECRYL 4141 manufactured by Daicel-Allnex Corporation) relative to 100 mass% of the total urethane (meth)acrylate.

[0090] <Transmittance> The luminous transmittance was determined by the following method in accordance with JIS T7333:2005. The transmittance of each spectacle lens was measured using a spectacle photometer manufactured by Otsuka Electronics before the following measurement of color density. The relative evaluation results of the luminous transmittance (referred to as "initial transmittance") obtained from the measurement results in the wavelength range of 380 nm to 780 nm are shown in Figure 1. The larger the value of the initial transmittance obtained in this way, the more excellent the visible light transmittance under non-irradiation.

[0091] <Coloring density> The luminous transmittance was determined by the following method in accordance with JIS T7333:2005. The photochromic layer was colored by irradiating the convex surface of each eyeglass lens with light from a xenon lamp through an aeromass filter for 15 minutes. The irradiance and irradiance tolerance, as specified in JIS T7333:2005, were measured to obtain the values ​​shown in Table 3. The transmittance after coloring was measured using an Otsuka Electronics spectrophotometer. Figure 1 shows the relative evaluation results of the luminous transmittance (hereinafter referred to as "transmittance after coloring") calculated from the measurement results in the wavelength range of 380 nm to 780 nm. The smaller the value of the transmittance after coloring calculated in this way, the more intensely the photochromic layer was colored.

[0092] [Table 3]

[0093] <Fading speed> The convex surface of each eyeglass lens was irradiated with light using a xenon lamp through an aeromass filter for 15 minutes (900 seconds) to color the photochromic compound in the photochromic layer. The transmittance (measurement wavelength: 550 nm) after coloring was measured using a spectrophotometer manufactured by Otsuka Electronics Co., Ltd. The light irradiation was carried out so that the irradiance and irradiance tolerance, as specified in JIS T7333:2005, were the values ​​shown in Table 3 below. The transmittance measured in this manner is referred to as the "transmittance after coloring." After measuring the transmittance in the colored state as described above, the transmittance was measured 60 seconds after the light irradiation was stopped (hereinafter referred to as "transmittance after 60 seconds of fading"). The fading rate (unit: % / second) was calculated using the formula: fading rate = [(transmittance after 60 seconds of fading - transmittance after coloring) / 60], and the relative evaluation results are shown in Figure 1. The higher the value of the fading rate calculated in this way, the faster the fading rate.

[0094] <Time to reach 70% transmittance> After stopping the light irradiation for measuring the transmittance when colored, the time required for the lens transmittance to recover to 70% (the lens faded) was calculated, with the initial transmittance set at 100%. The time calculated in this way was designated the "time to reach 70% transmittance," and the relative evaluation results are shown in Figure 1. The shorter the value of the time to reach 70% transmittance calculated in this way, the faster the fade rate.

[0095] 1, taking into consideration various performance characteristics of the photochromic article, it can be said that the polymerizable composition for forming a primer layer preferably contains 50% by mass or less of the isocyanate group-containing urethane (meth)acrylate, more preferably 40% by mass or less, and even more preferably 30% by mass or less, of the isocyanate group-containing urethane (meth)acrylate, where the total of the isocyanate group-containing urethane (meth)acrylate and the urethane (meth)acrylate not containing an isocyanate group is 100% by mass. On the other hand, from the viewpoint of improving adhesion between the substrate and the photochromic layer, it is preferable that the amount of the isocyanate group-containing urethane (meth)acrylate contained in the polymerizable composition for forming a primer layer is large. From this point of view, the polymerizable composition for forming a primer layer may contain, for example, 5% by mass or more of the isocyanate group-containing urethane (meth)acrylate, preferably 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more, of the isocyanate group-containing urethane (meth)acrylate, where the total of the isocyanate group-containing urethane (meth)acrylate and the urethane (meth)acrylate not containing an isocyanate group is 100% by mass.

[0096] Finally, the above-mentioned aspects will be summarized.

[0097] [1] A substrate, a primer layer obtained by curing a polymerizable composition for forming a primer layer; a photochromic layer obtained by curing a (meth)acrylate polymerizable composition containing a photochromic compound; in that order, The polymerizable composition for forming a primer layer contains an isocyanate group-containing urethane (meth)acrylate, and The photochromic article, wherein the polymerizable composition for forming a primer layer has an isocyanate group content of 2.0% by mass or more, with the total amount of the composition being 100% by mass. [2] The photochromic article according to [1], wherein the polymerizable composition for forming a primer layer further contains a urethane (meth)acrylate that does not contain an isocyanate group. [3] The photochromic article according to [2], wherein the polymerizable composition for forming a primer layer contains 10% by mass or more and 50% by mass or less of an isocyanate group-containing urethane (meth)acrylate, where the total of the isocyanate group-containing urethane (meth)acrylate and the urethane (meth)acrylate not containing an isocyanate group is 100% by mass. [4] The photochromic article according to any one of [1] to [3], which is a spectacle lens. [5] The photochromic article according to any one of [1] to [3], which is a lens for goggles. [6] The photochromic article according to any one of [1] to [3], which is a visor part of a sun visor. [7] The photochromic article according to any one of [1] to [3], which is a shielding material for a helmet. [8] Eyeglasses equipped with the eyeglass lenses described in [4]. [9] Applying a polymerizable composition for forming a primer layer onto a substrate; subjecting the applied polymerizable composition for forming a primer layer to a curing treatment by light irradiation to form a primer layer; applying a (meth)acrylate polymerizable composition containing a photochromic compound onto the formed primer layer; The applied (meth)acrylate polymerizable composition containing the photochromic compound is subjected to a curing treatment by light irradiation to form a photochromic layer; Including, The polymerizable composition for forming a primer layer contains an isocyanate group-containing (meth)urethane acrylate, and The method for producing a photochromic article, wherein the polymerizable composition for forming a primer layer has an isocyanate group content of 2.0% by mass or more, with the total amount of the composition being 100% by mass.

[10] The method for producing a photochromic article according to [9], wherein the polymerizable composition for forming a primer layer further contains a urethane (meth)acrylate that does not contain an isocyanate group.

[11] The method for producing a photochromic article according to

[10] , wherein the polymerizable composition for forming a primer layer contains 10% by mass or more and 50% by mass or less of an isocyanate group-containing urethane (meth)acrylate, where the total amount of the isocyanate group-containing urethane (meth)acrylate and the urethane (meth)acrylate not containing an isocyanate group is 100% by mass.

[12] The method for producing a photochromic article according to any one of [9] to

[11] , wherein the photochromic article is a spectacle lens.

[13] The method for producing a photochromic article according to any one of [9] to

[11] , wherein the photochromic article is a lens for goggles.

[14] The method for producing a photochromic article according to any one of [9] to

[11] , wherein the photochromic article is a visor portion of a sun visor.

[15] The method for producing a photochromic article according to any one of [9] to

[11] , wherein the photochromic article is a shielding material for a helmet.

[0098] Two or more of the various aspects and configurations described herein may be combined in any combination.

[0099] The embodiments disclosed herein should be considered to be illustrative in all respects and not restrictive. The scope of the present invention is defined by the claims, not by the above description, and is intended to include all modifications within the meaning and scope of the claims. [Industrial Applicability]

[0100] The present invention is useful in the technical fields of eyeglasses, goggles, sun visors, helmets, etc.

Claims

1. A substrate; a primer layer obtained by curing a polymerizable composition for forming a primer layer; a photochromic layer obtained by curing a (meth)acrylate polymerizable composition containing a photochromic compound; in that order, the polymerizable composition for forming a primer layer contains an isocyanate group-containing urethane (meth)acrylate; and The photochromic article, wherein the polymerizable composition for forming a primer layer has an isocyanate group content of 2.0% by mass or more, relative to 100% by mass of the total amount of the composition.

2. The photochromic article according to claim 1 , wherein the primer layer-forming polymerizable composition further comprises a urethane (meth)acrylate that does not contain an isocyanate group.

3. 3. The photochromic article according to claim 2, wherein the polymerizable composition for forming a primer layer contains 10% by mass or more and 50% by mass or less of the isocyanate group-containing urethane (meth)acrylate, where the total of the isocyanate group-containing urethane (meth)acrylate and the urethane (meth)acrylate not containing an isocyanate group is 100% by mass.

4. The photochromic article according to any one of claims 1 to 3, which is a spectacle lens.

5. The photochromic article according to any one of claims 1 to 3, which is a lens for goggles.

6. The photochromic article according to any one of claims 1 to 3, which is a visor portion of a sun visor.

7. The photochromic article according to any one of claims 1 to 3, which is a shield member of a helmet.

8. Eyeglasses comprising the eyeglass lens according to claim 4.

9. applying a polymerizable composition for forming a primer layer onto a substrate; subjecting the applied polymerizable composition for forming a primer layer to a curing treatment by light irradiation to form a primer layer; applying a (meth)acrylate-based polymerizable composition containing a photochromic compound onto the formed primer layer; The applied (meth)acrylate polymerizable composition containing the photochromic compound is subjected to a curing treatment by light irradiation to form a photochromic layer; Including, The polymerizable composition for forming a primer layer contains an isocyanate group-containing (meth)urethane acrylate, and The method for producing a photochromic article, wherein the polymerizable composition for forming a primer layer has an isocyanate group content of 2.0% by mass or more, relative to 100% by mass of the total amount of the composition.

10. The method for producing a photochromic article according to claim 9 , wherein the polymerizable composition for forming a primer layer further contains a urethane (meth)acrylate that does not contain an isocyanate group.

11. 11. The method for producing a photochromic article according to claim 10, wherein the polymerizable composition for forming a primer layer contains 10% by mass or more and 50% by mass or less of the isocyanate group-containing urethane (meth)acrylate, where the total amount of the isocyanate group-containing urethane (meth)acrylate and the urethane (meth)acrylate not containing an isocyanate group is 100% by mass.

12. The method for producing a photochromic article according to any one of claims 9 to 11, wherein the photochromic article is a spectacle lens.

13. The method for producing a photochromic article according to any one of claims 9 to 11, wherein the photochromic article is a lens for goggles.

14. The method for producing a photochromic article according to any one of claims 9 to 11, wherein the photochromic article is a visor portion of a sun visor.

15. The method for producing a photochromic article according to any one of claims 9 to 11, wherein the photochromic article is a shield member of a helmet.

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