Method for manufacturing photochromic articles

Abstract

To provide a method for manufacturing photochromic articles that can produce photochromic articles with excellent adhesion of the photochromic layer. [Solution] A method for producing a photochromic article, comprising: applying a polymerizable composition for forming a primer layer directly onto a substrate or via another layer; curing the applied polymerizable composition for forming a primer layer by light irradiation to form a primer layer; applying a polymerizable composition for forming a photochromic layer containing a photochromic compound directly onto the formed primer layer; and curing the applied polymerizable composition for forming a photochromic layer by light irradiation to form a photochromic layer, wherein one of the polymerizable composition for forming a primer layer and the other polymerizable composition for forming a photochromic layer contains a hydroxyl group-containing polymerizable compound, and the other contains an isocyanate group-containing polymerizable compound.

Description

Technical Field

[0001] The present invention relates to a method for producing a photochromic article.

Background Art

[0002] A photochromic compound is a compound having the property (photochromic property) of being colored under irradiation with light in a wavelength region having photoresponsiveness and fading under non-irradiation. For example, Patent Document 1 discloses a photochromic article in which a layer containing a photochromic compound (photochromic layer) is provided on a base material.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] Desired performance for a photochromic article includes that the photochromic layer is less likely to peel off from the base material (that is, excellent in adhesion).

[0005] An aspect of the present invention aims to provide a method for producing a photochromic article that can produce a photochromic article having a photochromic layer with excellent adhesion.

Means for Solving the Problems

[0006] As a means for enhancing the adhesion of the photochromic layer, providing a primer layer for improving adhesion between the photochromic layer and the base material can be mentioned. In this regard, the previously mentioned Patent Document 1 (Japanese Patent No. 6346183 Specification) discloses, as a method for producing a photochromic article, a method of applying a photocurable primer composition onto a base material, then applying a composition for forming a photochromic layer, and performing photocuring. However, through further investigation, the inventors considered that the photochromic compound contained in the photochromic layer-forming composition may change color in response to the light irradiated for curing, potentially causing insufficient irradiation of the curing light in the region near the interface between the photochromic layer and the primer layer. When such a phenomenon occurs, it is thought that the adhesion between the photochromic layer and the primer layer decreases. As a result of further diligent research, the inventors have newly discovered that by including a hydroxyl group-containing polymerizable compound in one of the photochromic layer-forming composition and a primer layer-forming composition, and an isocyanate group-containing polymerizable compound in the other, it is possible to improve the adhesion between the photochromic layer and the primer layer. In this regard, the inventors surmise that the urethane bond formed by the reaction between the hydroxyl group and the isocyanate group contributes to strengthening the bond between the photochromic layer and the primer layer. The urethane reaction between the hydroxyl group and the isocyanate group is a reaction that can proceed even at room temperature. Therefore, the inventors believe that the reduction in adhesion caused by insufficient photocuring near the interface between the photochromic layer and the primer layer due to the reduced amount of light irradiation caused by the coloring of the photochromic compound can be compensated for by the formation of the above-mentioned urethane bond. However, the present invention is not limited to the surmise described herein.

[0007] That is, one aspect of the present invention is as follows. [1] Applying a polymerizable composition for primer layer formation directly onto a substrate or via another layer, The polymerizable composition for forming a primer layer is cured by light irradiation to form a primer layer. Applying a polymerizable composition for forming a photochromic layer containing a photochromic compound directly onto the formed primer layer, and A photochromic layer is formed by curing a coated polymerizable composition for photochromic layer formation by light irradiation. Includes, A method for producing a photochromic article, wherein one of the polymerizable composition for forming a primer layer and the polymerizable composition for forming a photochromic layer contains a hydroxyl group-containing polymerizable compound, and the other contains an isocyanate group-containing polymerizable compound. [2] The method for producing a photochromic article according to [1], wherein the hydroxyl group-containing polymerizable compound and the isocyanate group-containing polymerizable compound are (meth)acrylates. [3] The method for producing a photochromic article according to [1] or [2], wherein the isocyanate group-containing polymerizable compound is an isocyanate group-containing urethane (meth)acrylate. [4] The above hydroxyl group-containing polymerizable compound has one to three hydroxyl groups in one molecule, a method for producing a photochromic article according to any one of [1] to [3]. [5] Applying a polymerizable composition for forming a protective layer directly onto the photochromic layer or via another layer, and A protective layer is formed by curing a polymerizable composition applied to form a protective layer by light irradiation. A method for producing a photochromic article according to any one of [1] to [4], further comprising: Manufacturing method. [6] The above hydroxyl group-containing polymerizable compound is a (meth)acrylate, The above isocyanate group-containing polymerizable compound is an isocyanate group-containing urethane (meth)acrylate. The above hydroxyl group-containing polymerizable compound has one to three hydroxyl groups in one molecule, and Applying a polymerizable composition for forming a protective layer directly onto the above photochromic layer or via another layer, and A protective layer is formed by curing a polymerizable composition applied to form a protective layer by light irradiation. A method for producing a photochromic article according to any one of [1] to [5], further comprising: [7] The method for manufacturing a photochromic article according to any one of claims 1 to 6, wherein the photochromic article is an eyeglass lens. [8] The method for manufacturing a photochromic article according to any one of [1] to [6], wherein the photochromic article is a lens for goggles, a visor portion of a sun visor, or a shield component of a helmet. [Effects of the Invention]

[0008] According to one aspect of the present invention, a method for manufacturing a photochromic article that can produce a photochromic article with excellent adhesion of the photochromic layer can be provided. [Modes for carrying out the invention]

[0009] A method for producing a photochromic article according to one aspect of the present invention includes: applying a polymerizable composition for forming a primer layer directly onto a substrate or via another layer; curing the applied polymerizable composition for forming a primer layer by light irradiation to form a primer layer; applying a polymerizable composition for forming a photochromic layer containing a photochromic compound directly onto the formed primer layer; and curing the applied polymerizable composition for forming a photochromic layer by light irradiation to form a photochromic layer. One of the polymerizable composition for forming a primer layer and the polymerizable composition for forming a photochromic layer contains a hydroxyl group-containing polymerizable compound, and the other contains an isocyanate group-containing polymerizable compound. In the present invention and this specification, "photochromic article" means an article containing a photochromic compound. In one aspect of the above production method, the polymerizable composition for forming a primer layer is a polymerizable composition containing an isocyanate group-containing polymerizable compound, and the polymerizable composition for forming a photochromic layer is a polymerizable composition containing a hydroxyl group-containing polymerizable compound. In another embodiment of the above manufacturing method, the polymerizable composition for forming the primer layer is a polymerizable composition containing a hydroxyl group-containing polymerizable compound, and the polymerizable composition for forming the photochromic layer is a polymerizable composition containing an isocyanate group-containing polymerizable compound.

[0010] A method for manufacturing a photochromic article according to one aspect of the present invention will be described in more detail below.

[0011] <substrate> The photochromic articles manufactured by the above manufacturing method can, in one form, be optical articles. Optical articles include various articles such as eyeglass lenses, goggle lenses, sun visor visors, and helmet shield components. For example, the photochromic articles manufactured by the above manufacturing method may have a primer layer and a photochromic layer in that order on a substrate selected according to the type of optical article. As an example of a substrate, a plastic lens substrate or a glass lens substrate can be used as an eyeglass lens substrate. A glass lens substrate may be, for example, a lens substrate made of inorganic glass. As a lens substrate, a plastic lens substrate is preferred from the viewpoint of being lightweight, less prone to breakage, and easy to handle. Examples of plastic lens substrates include (meth)acrylic resin, styrene resin, polycarbonate resin, allyl resin, allyl carbonate resin such as diethylene glycol bisallyl carbonate resin (CR-39), vinyl resin, polyester resin, polyether resin, urethane resin obtained by the reaction of an isocyanate compound with a hydroxyl compound such as diethylene glycol, thiourethane resin obtained by the reaction of an isocyanate compound with a polythiol compound, and cured products (generally called transparent resins) obtained by curing a curable composition containing a (thio)epoxy compound having one or more disulfide bonds in the molecule. The above "(meth)acrylic resin" includes acrylic resin and methacrylic resin. The above "(thio)epoxy compound" includes epoxy compound and thioepoxy compound. As the lens substrate, an undyed material (colorless lens) or a dyed material (dyed lens) may be used. The refractive index of the lens substrate can be, for example, about 1.50 to 1.76. Polycarbonate resin is usually used as a lens substrate with a refractive index of 1.59. For example, allyl carbonate resins such as allyl resin and diethylene glycol bisallyl carbonate resin (CR-39) are commonly used as lens substrates with a refractive index of 1.50. Urea resins obtained by the reaction of isocyanate-terminated prepolymers with aromatic diamines are commonly used as lens substrates with a refractive index of 1.53.Diallyl phthalate resin is usually used as a lens base material with a refractive index of 1.55. A urethane resin obtained by the reaction of an isocyanate compound and a hydroxy compound such as diethylene glycol is usually used as a lens base material with a refractive index of 1.60. A thiourethane resin obtained by reacting an isocyanate compound and a polythiol compound is usually used as a base material with a refractive index of 1.67. However, the refractive index of the lens base material is not limited to the above ranges, and may be within the above ranges or may deviate upward or downward from the above ranges. In the present invention and this specification, the refractive index refers to the refractive index for light with a wavelength of 500 nm. Further, the lens base material may be a lens having refractive power (a so-called prescription lens), or may be a lens having no refractive power (a so-called non-prescription lens).

[0012] The spectacle lens can be various lenses such as a monofocal lens, a multifocal lens, and a progressive-power lens. The type of lens is usually determined by the surface shapes of both sides of the lens base material. Further, the surface of the lens base material may be any of a convex surface, a concave surface, and a flat surface. In ordinary lens base materials and spectacle lenses, the object-side surface is a convex surface, and the eyeball-side surface is a concave surface. However, the present invention is not limited thereto. The photochromic layer can usually be provided on the object-side surface of the lens base material, but may be provided on the eyeball-side surface.

[0013] <Polymerizable Compound> In the present invention and this specification, the term "polymerizable composition" refers to a composition containing a polymerizable compound. A "polymerizable compound" is a compound having a polymerizable group. Specific examples of the polymerizable group include the (meth)acryloyl group described later. The "polymerizable group" in the present invention and this specification does not include a hydroxy group (OH) and an isocyanate group (NCO).

[0014] In the above production method, one of the polymerizable composition for forming a primer layer and the polymerizable composition for forming a photochromic layer contains a hydroxy group-containing polymerizable compound, and the other contains an isocyanate group-containing polymerizable compound. The present inventor's speculation that this enhances the interlayer adhesion between the photochromic layer and the primer layer is as described earlier. Hereinafter, the hydroxy group-containing polymerizable compound and the isocyanate group-containing polymerizable compound will be described in order.

[0015] (Hydroxy group-containing polymerizable compound) The hydroxy group-containing polymerizable compound has at least one hydroxy group (OH) in one molecule. The number of hydroxy groups contained in one molecule of the hydroxy group-containing polymerizable compound is 1 or more. The number of hydroxy groups contained in one molecule of the hydroxy group-containing polymerizable compound can be, for example, 4 or less, or 3 or less. However, more hydroxy groups may be contained in one molecule of the hydroxy group-containing polymerizable compound.

[0016] The hydroxy group-containing polymerizable compound can have one or more polymerizable groups in one molecule, and may have two or more. The number of polymerizable groups contained in one molecule of the hydroxy group-containing polymerizable compound can be, for example, 4 or less, 3 or less, or 2 or less. However, more polymerizable groups may be contained in one molecule of the hydroxy group-containing polymerizable compound.

[0017] The polymerizable group contained in a hydroxyl group-containing polymerizable compound can, in one form, be a (meth)acryloyl group. That is, in one form, a hydroxyl group-containing polymerizable compound can be a (meth)acrylate. In this invention and specification, "(meth)acrylate" is used to encompass both 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)acrylate, the functional number is the number of groups selected from the group consisting of acryloyl groups and methacryloyl groups contained in one molecule. In this invention and specification, "methacrylate" refers to a compound containing only a methacryloyl group as the (meth)acryloyl group, while a compound containing both an acryloyl group and a methacryloyl group as the (meth)acryloyl group is called an acrylate. The acryloyl group may be included in the form of an acryloyloxy group, and the methacryloyl group may be included in the form of a methacryloyloxy group. "(meth)acryloyl group" is used to encompass both the acryloyl group and the methacryloyl group, and "(meth)acryloyloxy group" is used to encompass both the acryloyloxy group and the methacryloyloxy group. Unless otherwise specified, the groups described may or may not have substituents. If a group has substituents, examples of substituents include alkyl groups (e.g., alkyl groups with 1 to 6 carbon atoms), hydroxyl groups, alkoxy groups (e.g., alkoxy groups with 1 to 6 carbon atoms), halogen atoms (e.g., fluorine atoms, chlorine atoms, bromine atoms), cyano groups, amino groups, nitro groups, acyl groups, carboxyl groups, etc. Furthermore, for groups with substituents, "number of carbon atoms" refers to the number of carbon atoms in the part that does not contain substituents.

[0018] One form of hydroxyl group-containing (meth)acrylate is the hydroxyl group-containing (meth)acrylate represented by the following formula 1.

[0019] [ka]

[0020] In Equation 1, R 1 R represents a hydrogen atom or a methyl group. 1 When R is a hydrogen atom, the compound represented by formula 1 is an acrylate. 1 When R is a methyl group, the compound represented by formula 1 is a methacrylate. 2 represents a hydrogen atom or a hydroxyl group. n is an integer greater than or equal to 1, for example, an integer between 1 and 4. Examples of commercially available hydroxyl group-containing (meth)acrylates represented by formula 1 include Bremmer GLM manufactured by NOF Corporation and HEMA (2-hydroxyethyl methacrylate) manufactured by Tokyo Chemical Industries Ltd.

[0021] Another form of hydroxyl group-containing (meth)acrylate is a (meth)acrylate having one or more epoxy ester structures in a single molecule. The "epoxy ester structure" is a structure produced by the reaction of an epoxy group and a carboxyl group, and can be represented as "-CH(OH)-CH2-OC(=O)-". When a hydroxyl group-containing (meth)acrylate is a (meth)acrylate having an epoxy ester structure, the hydroxyl group is at least included in the epoxy ester structure. The hydroxyl group may or may not be included in the parts other than the epoxy ester structure.

[0022] For example, polyfunctional (meth)acrylates having two epoxy ester structures in one molecule include the bifunctional (meth)acrylate represented by formula 2 below and the bifunctional (meth)acrylate represented by formula 3 below.

[0023] [ka]

[0024] In equations 2 and 3, Z 1 , Z 2 and Z 3 Each of these independently represents a hydrogen atom or a methyl group. In Equation 3, Z4 n represents a hydrogen atom, a methyl group, or a hydroxyl group. In formula 2, n1 and in formula 3, n2 each independently represent an integer between 1 and 3. In formulas 2 and 3, the ester group (-C(=O)O-) contained in the (meth)acryloyloxy group constitutes part of the epoxy ester structure. Examples of commercially available bifunctional (meth)acrylates represented by formula 2 or 3 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.), and the like.

[0025] Another form of (meth)acrylate having two epoxy ester structures in one molecule is the (meth)acrylate generally called bisphenol A type epoxy (meth)acrylate or bisphenol A type epoxy resin. Such (meth)acrylate has the following bisphenol A structure, for example, one of the following bisphenol A structures in one molecule. Specific examples of commercially available products include 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.), epoxy ester 3000A (manufactured by Kyoeisha Chemical Co., Ltd.), etc.

[0026] [ka]

[0027] (Isocyanate group-containing polymerizable compound) An isocyanate group-containing polymerizable compound has at least one isocyanate group (NCO) in one molecule, and may have two or more. The isocyanate group content of the isocyanate group-containing polymerizable compound can be, for example, 1.0% by mass or more, 3% by mass or more, or 5% by mass or more, and can also be, for example, 20.0% by mass, 18.0% by mass or less, 16.0% by mass or less, or 14.0% by mass or less.

[0028] An isocyanate group-containing polymerizable compound may have one or more polymerizable groups in one molecule, and may have two or more. The number of polymerizable groups in one molecule of a hydroxyl group-containing polymerizable compound may be, for example, four or less, three or less, or two or less. However, a larger number of polymerizable groups may be contained in one molecule of an isocyanate group-containing polymerizable compound.

[0029] The polymerizable group contained in an isocyanate group-containing polymerizable compound can, in one form, be a (meth)acryloyl group. That is, in one form, an isocyanate group-containing polymerizable compound can be a (meth)acrylate. For example, an isocyanate group-containing (meth)acrylate is an isocyanate group-containing urethane (meth)acrylate. "Urethane (meth)acrylate" refers to a (meth)acrylate having a urethane bond. Urethane (meth)acrylate usually has a structure in which a "(meth)acryloyl group" is included at the terminal and / or side chain of the polyurethane backbone. Urethane (meth)acrylate containing an isocyanate group can be synthesized by known methods and is also available commercially. Examples of commercially available products include EBECRYL 4141, 4250, 4510, 4396, and 4397 from Daicel Ornex.

[0030] The polymerizable composition for forming a primer layer and the polymerizable composition for forming a photochromic layer used in the above manufacturing method each contain a hydroxyl group-containing polymerizable compound and an isocyanate group-containing polymerizable compound. From the viewpoint of improving the adhesion between the photochromic layer and the primer layer, the content of the hydroxyl group-containing polymerizable compound in the polymerizable composition containing the hydroxyl group-containing polymerizable compound is preferably 1.0% by mass or more, more preferably 1.5% by mass or more, and even more preferably 2.0% by mass or more, based on 100% by mass of the total amount of polymerizable compounds contained in the composition. The content of the hydroxyl group-containing polymerizable compound in the polymerizable composition containing the hydroxyl group-containing polymerizable compound can be, for example, 7.0% by mass or less, 6.5% by mass or less, 6.0% by mass or less, 5.5% by mass or less, or 5.0% by mass or less, based on 100% by mass of the total amount of polymerizable compounds contained in the composition.

[0031] In a polymerizable composition containing an isocyanate group-containing polymerizable compound, the content of the isocyanate group-containing polymerizable compound is preferably 2.0% by mass or more, more preferably 2.5% by mass or more, and even more preferably 3.0% by mass or more, 3.5% by mass or more, and 4.0% by mass or more, in that order, based on 100% by mass of the total amount of polymerizable compounds contained in the composition. The content of the isocyanate group-containing polymerizable compound in a polymerizable composition containing an isocyanate group-containing polymerizable compound can be, for example, 10.0% by mass or less, 9.5% by mass or less, 9.0% by mass or less, 8.5% by mass or less, 8.0% by mass or less, 7.5% by mass or less, 7.0% by mass or less, 6.5% by mass or less, or 6.0% by mass or less, based on 100% by mass of the total amount of polymerizable compounds contained in the composition.

[0032] A polymerizable composition containing a hydroxyl group-containing polymerizable compound may contain one or more polymerizable compounds other than the hydroxyl group-containing polymerizable compound. A polymerizable composition containing an isocyanate group-containing polymerizable compound may contain one or more polymerizable compounds other than the isocyanate group-containing polymerizable compound. Hereinafter, polymerizable compounds other than hydroxyl group-containing polymerizable compounds and polymerizable compounds other than isocyanate group-containing polymerizable compounds will be referred to as "other polymerizable compounds." Other polymerizable compounds are not particularly limited and can include various monofunctional and polyfunctional (2 or more functional) polymerizable compounds. The number of functions in a polymerizable compound is the number of polymerizable groups contained in the polymerizable compound. Other polymerizable compounds can be, for example, one or more monofunctional (meth)acrylates and polyfunctional (meth)acrylates with 2 or more functionalities.

[0033] The total content of polymerizable compounds in each polymerizable composition containing a hydroxyl group-containing polymerizable compound and a polymerizable composition containing an isocyanate group-containing polymerizable compound 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. Furthermore, the content of polymerizable compounds in the above compositions 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. In the present invention and this specification, with respect to content, "total amount of composition" means the total amount of all components excluding the solvent in the case of a composition containing a solvent. The above compositions may or may not contain a solvent. If a solvent is included, any solvent can be used in any amount, as long as it does not inhibit the progress of the polymerization reaction of the polymerizable composition.

[0034] <Photochromic compounds> The polymerizable composition for photochromic layer formation used in the above manufacturing method is a polymerizable composition containing a hydroxyl group-containing polymerizable compound or a polymerizable composition containing an isocyanate group-containing polymerizable compound. The polymerizable composition for photochromic layer formation contains a photochromic compound together with one or more polymerizable compounds. Known compounds that exhibit photochromic properties can be used as the photochromic compound included in the polymerizable composition for photochromic layer formation. The photochromic compound can exhibit photochromic properties, for example, to ultraviolet light. "Photochromic property" refers to the property of becoming colored under irradiation with light in a photoresponsive wavelength range and fading under non-irradiation conditions. In the present invention and this specification, the wavelength range of "ultraviolet light" is defined as the wavelength range of 200 nm to 440 nm. For example, examples of photochromic compounds include compounds having known skeletons that exhibit photochromic properties, such as azobenzenes, spiropyrans, spirooxazines, naphthopyrans, indenonaphthopyrans, phenantropyrans, hexaarylbisimidazoles, donor-acceptor Stenhaus adducts (DASAs), salicylideneanilines, dihydropyrenes, anthracene dimers, flugides, diarylethenes, phenoxynaphthacenones, and stilbenes. Preferred photochromic compounds include flugimide compounds, spirooxazine compounds, chromene compounds, and indeno-condensed naphthopyran compounds. In addition, one or more photochromic compounds selected from the group consisting of photochromic compounds represented by general formula A, photochromic compounds represented by general formula B, and photochromic compounds represented by general formula C, as described in WO2022 / 138966, can also be listed. Photochromic compounds can be used individually or in combination of two or more. The content of the photochromic compound in the above composition can be, for example, about 0.1 to 15% by mass, based on 100% by mass of the total amount of the composition, but is not limited to this range.

[0035] <Other ingredients> Polymerizable compositions containing a hydroxyl group-containing polymerizable compound and polymerizable compositions containing an isocyanate group-containing polymerizable compound may contain one or more of various additives that are commonly found in polymerizable compositions in any proportion. Examples of such additives include polymerization initiators for promoting polymerization reactions.

[0036] For example, known polymerization initiators can be used as polymerization initiators, radical polymerization initiators are preferred, and it is more preferable to include only radical polymerization initiators as polymerization initiators. Examples of photoradical polymerization initiators include benzoin ketals such as 2,2-dimethoxy-1,2-diphenylethane-1-one; α-hydroxyketones such as 1-hydroxycyclohexylphenyl 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, and bis(2,6-dimethoxybenzo Phosphine oxides such as 2-(o-chlorophenyl)-2,4,4-trimethylpentylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; 2,4,5-triarylimidazole dimers such as 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-phenantraquinone, 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 benzyldimethylketal; acridine compounds such as 9-phenylacridine and 1,7-bis(9,9'-acridinylheptane); N-phenylglycine, coumarin, etc. Furthermore, in the 2,4,5-triarylimidazole dimer, the substituents on the aryl groups of the two triarylimidazole moieties may be identical and symmetric, or they may be different and asymmetric. Also, 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 viewpoint of curability, transparency, and heat resistance. The content of the polymerization initiator can be, for example, in the range of 0.1 to 5% by mass, based on 100% by mass of the total amount of the composition.

[0037] Polymerizable compositions containing a hydroxyl group-containing polymerizable compound and polymerizable compositions containing an isocyanate group-containing polymerizable compound may further contain, in any amount, known additives that can be commonly added to polymerizable compositions, such as crosslinking agents, surfactants, leveling agents, antioxidants, radical scavengers, light stabilizers, UV absorbers, color inhibitors, antistatic agents, fluorescent dyes, dyes, pigments, fragrances, plasticizers, and silane coupling agents. Known compounds can be used as these additives.

[0038] Polymerizable compositions containing hydroxyl group-containing polymerizable compounds and polymerizable compositions containing isocyanate group-containing polymerizable compounds can be prepared by mixing the various components described above simultaneously or sequentially in any order. From the viewpoint of improving the storage stability of the polymerizable compositions, polymerizable compositions containing hydroxyl group-containing polymerizable compounds preferably do not contain isocyanate group-containing polymerizable compounds, and polymerizable compositions containing isocyanate group-containing polymerizable compounds preferably do not contain hydroxyl group-containing polymerizable compounds.

[0039] <Formation of the primer layer> A polymerizable composition for forming a primer layer, which is a polymerizable composition containing a hydroxyl group-containing polymerizable compound or a polymerizable composition containing an isocyanate group-containing polymerizable compound, can be applied directly to a substrate or via another layer, and the applied polymerizable composition can be photocured to form a primer layer on the substrate, which is a cured layer of the polymerizable composition for forming a primer layer. The polymerizable composition for forming a primer layer can be applied directly to the surface of the substrate or to the surface of a layer provided on the substrate. That is, in a photochromic article produced by the above manufacturing method, the substrate and the primer layer are adjacent 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. For example, the hard coat layer can be formed on the substrate as a cured layer of the polymerizable composition.

[0040] As a method for applying the polymerizable composition for forming the primer layer, known application methods such as spin coating and dip coating can be used, and spin coating is preferred from the viewpoint of uniformity of application. One or more known pretreatments such as alkali treatment and UV ozone treatment can be optionally applied to the substrate surface for cleaning the substrate surface. The polymerizable composition for forming the primer layer is cured by light irradiation. Photocuring is preferred because the curing reaction can proceed in a short time. The light irradiation conditions should be determined according to the types of various components contained in the polymerizable composition for forming the primer layer and the composition of the polymerizable composition for forming the primer layer. Examples of light used for photocuring include ultraviolet light.

[0041] The thickness of the primer layer can be, for example, 3 μm or more, and preferably 5 μm or more. Alternatively, the thickness of the primer layer can be, for example, 15 μm or less, and preferably 10 μm or less.

[0042] <Formation of photochromic layer> A polymerizable composition for forming a photochromic layer, which is a polymerizable composition containing a hydroxyl group-containing polymerizable compound or a polymerizable composition containing an isocyanate group-containing polymerizable compound, can be directly applied onto a primer layer, and the applied polymerizable composition can be photocured to form a photochromic layer, which is a cured layer of the polymerizable composition for forming a photochromic layer, as a layer that is in direct contact (i.e., adjacent) to the primer layer. For details on applying the photochromic layer-forming composition and photocuring treatment, refer to the previous description regarding the application and photocuring treatment of the primer layer-forming composition. After applying the photochromic layer-forming composition onto the primer layer, a heat treatment may be performed before and / or after the photocuring treatment. The heat treatment can be performed, for example, in a heated atmosphere of about 50°C to 120°C. The heat treatment can be performed, for example, for about 30 minutes to 3 hours. The inventors believe that such a heat treatment can further advance the urethane reaction between the hydroxyl group and the isocyanate group. However, as mentioned earlier, the urethane reaction between the hydroxyl group and the isocyanate group can proceed even at room temperature, so the above heat treatment is not essential. The thickness of the formed photochromic layer is preferably in the range of 5 to 80 μm, and more preferably in the range of 20 to 60 μm.

[0043] A photochromic article having the above-described photochromic layer may or may not have one or more additional functional layers in addition to the various layers described above. Examples of functional layers include layers known as functional layers for optical articles, such as protective layers for improving durability, hard coat layers, anti-reflective layers, water-repellent or hydrophilic anti-fouling layers, and anti-fogging layers. For example, regarding protective layers, refer to paragraphs 0009 to 0021, 0026 and the examples described in Japanese Patent Application Publication No. 2021-107909. The protective layer can be formed as a cured layer by curing a polymerizable composition directly on the photochromic layer or via one or more other layers.

[0044] Photochromic articles manufactured by the above manufacturing method can be optical articles, and one form of optical article is an eyeglass lens. Other forms of optical articles include various optical articles with anti-glare functions, such as lenses for goggles, visors for sun visors, and shield components for helmets.

[0045] [glasses] One aspect of the present invention relates to eyeglasses equipped with spectacle lenses, which are a form of photochromic article manufactured by the above manufacturing method. Details of the spectacle lenses included in these eyeglasses are as previously described. By being equipped with such spectacle lenses, these eyeglasses can exhibit an anti-glare effect like sunglasses, for example, outdoors, when the photochromic compound contained in the photochromic layer is exposed to sunlight and changes color, and when returning indoors, the photochromic compound fades, restoring transparency. Regarding the frame and other components of these eyeglasses, known technologies can be applied. [Examples]

[0046] The present invention will be further described below with reference to examples. However, the present invention is not limited to the embodiments shown in the examples. Unless otherwise specified, the following steps and operations were carried out at room temperature (20-25°C).

[0047] [Example 1] <Preparation of polymerizable composition for primer layer formation> 25 parts by mass of EBECRYL 4141 (isocyanate group content: 12.0% by mass), an isocyanate group-containing urethane acrylate manufactured by Daicel Ornex, and 75 parts by mass of KRM 9276 (isocyanate group-free urethane acrylate), also manufactured by Daicel Ornex, were weighed and mixed. To the resulting mixture, 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 (Omnirad819, manufactured by IGM Resin BV)), and 0.25% by mass of a leveling agent (LE-605, manufactured by Kyoeisha Chemical Co., Ltd.) were added per 100% by mass of the total mixture, and the mixture was thoroughly stirred. Subsequently, the mixture was degassed using a rotation-and-revolution type stirring and degassing apparatus.

[0048] <Formation of the primer layer> A plastic lens substrate (refractive index 1.50 (diethylene glycol bisallyl carbonate resin (CR-39))) was immersed in a 10% by mass sodium hydroxide aqueous solution (liquid temperature 60°C) for 5 minutes, then washed with pure water and dried. After that, a primer layer was formed on the convex surface (object-facing surface) of the plastic lens substrate as follows. The polymerizable composition for primer layer formation described above was applied to the convex surface of a plastic lens substrate by spin coating in an environment of 25°C and 50% relative humidity. Then, the primer layer formation composition applied to the plastic lens substrate was irradiated with ultraviolet light (wavelength: 405 nm) in a nitrogen atmosphere (oxygen concentration of 500 ppm or less) to cure the composition and form a primer layer. The thickness of the formed primer layer was 6 μm. Although the above-mentioned spectacle lens has a primer layer directly on the substrate, it is also possible to provide one or more other layers between the substrate and the primer layer.

[0049] <Preparation of polymerizable composition for photochromic layer formation> The polymerizable compounds shown in Table 1 were mixed in the amounts shown in Table 1 within a plastic container. The mixture of polymerizable compounds obtained in this way was mixed with the following photochromic compound (an indeno-condensed naphthopyran compound represented by the structural formula described in U.S. Patent No. 6,296,785), 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. Then, the mixture was degassed using a rotation-and-revolution type stirring and degassing apparatus. In this way, a polymerizable composition for photochromic layer formation was prepared. The content of each component, relative to the total amount of the composition (100% by mass), is as follows: the mixture of polymerizable compounds is 94.9% by mass, the photochromic compound is 3% by mass, the photoradical polymerization initiator is 0.3% by mass, the antioxidant is 0.9% by mass, and the photostabilizer is 0.9% by mass.

[0050] [ka]

[0051] [Table 1]

[0052] [ka]

[0053] [ka]

[0054] [ka]

[0055] [ka]

[0056] [ka]

[0057] [ka]

[0058] Among the various polymerizable compounds in Table 1, the hydroxyl group-containing (meth)acrylate is glycerol monomethacrylate. The other polymerizable compounds shown in Table 1 do not contain either a hydroxyl group or an isocyanate group.

[0059] <Formation of photochromic layer> The polymerizable composition for photochromic layer formation, prepared above, was applied to the surface of a primer layer formed on a plastic lens substrate by spin coating. The spin coating was performed according to the method described in Japanese Patent Application Publication No. 2005-218994. Subsequently, the applied polymerizable composition for photochromic layer formation was 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. The laminate thus prepared was placed in a heat treatment furnace at an ambient temperature of 90°C for 120 minutes and subjected to heat treatment.

[0060] <Formation of a protective layer> A protective layer was formed on the photochromic layer formed as described above using the method described in Example 1 of Japanese Patent Application Publication No. 2021-107909. The thickness of the formed protective layer was 15 μm. Thus, an eyeglass lens was fabricated having a substrate, a primer layer, and a photochromic layer in that order, and further having a protective layer on the photochromic layer.

[0061] [Example 2] Except for changing the polymerizable compound of the photochromic layer-forming composition as shown in Table 2 below, an eyeglass lens having a substrate, a primer layer, and a photochromic layer in that order, and further having a protective layer on the photochromic layer, was fabricated by the method described for Example 1.

[0062] [Table 2]

[0063] [Example 3] Except for changing the polymerizable compound of the photochromic layer-forming composition as shown in Table 3 below, an eyeglass lens having a substrate, a primer layer, and a photochromic layer in that order, and further having a protective layer on the photochromic layer, was fabricated by the method described for Example 1.

[0064] [Table 3]

[0065] Among the various polymerizable compounds in Table 3, the hydroxyl group-containing (meth)acrylate is 2-hydroxyethyl methacrylate. The other polymerizable compounds shown in Table 3 do not contain either a hydroxyl group or an isocyanate group. The structure of 2-hydroxyethyl methacrylate is as follows.

[0066] [ka]

[0067] [Example 4] Except for changing the polymerizable compound of the photochromic layer-forming composition as shown in Table 4 below, an eyeglass lens having a substrate, a primer layer, and a photochromic layer in that order, and further having a protective layer on the photochromic layer, was fabricated by the method described for Example 1.

[0068] [Table 4]

[0069] Among the various polymerizable compounds in Table 4, the hydroxyl group-containing (meth)acrylate is a glycerol polydiglycidyl ether-acrylic acid adduct. The other polymerizable compounds shown in Table 4 do not contain either a hydroxyl group or an isocyanate group. The structure of the glycerol polydiglycidyl ether-acrylic acid adduct is as follows.

[0070] [ka]

[0071] [Comparative Example 1] Except for not adding the above-mentioned glycerin monomethacrylate to the polymerizable composition for forming the photochromic layer, an eyeglass lens having a substrate, a primer layer, and a photochromic layer in that order, and further having a protective layer on the photochromic layer, was fabricated by the method described in Example 1.

[0072] [Comparative Example 2] Except for replacing the glycerin monomethacrylate in the polymerizable composition for photochromic layer formation with a non-curable polyol (polyethertriol) that does not have polymerizable groups, an eyeglass lens having a substrate, a primer layer, and a photochromic layer in that order, and further having a protective layer on the photochromic layer, was fabricated by the method described in Example 1.

[0073] [Adhesion evaluation] With the eyeglass lens held in place by a gripping device, high-pressure water at a water pressure of 7.5 MPa was sprayed from the nozzle of a Kärcher K3 Silent high-pressure washer toward the side of the eyeglass lens. The distance between the nozzle tip and the side of the eyeglass lens was approximately 3 cm. The presence or absence of delamination on the side surface of eyeglass lenses after high-pressure water spraying was confirmed using a Dektak Pro Stylus Profiler manufactured by Bruker Japan. The above evaluation was performed on multiple eyeglass lenses for each of Examples 1-4, Comparative Example 1, and Comparative Example 2. The evaluation results are shown in Table 5 below. In each eyeglass lens in which delamination was observed, measurements using a Bruker Japan Dektak Pro Stylus Profiler confirmed that delamination occurred between the photochromic layer and the primer layer.

[0074] [Table 5]

[0075] The results shown in Table 5 confirm that the spectacle lenses of Examples 1 to 4 exhibit excellent interlayer adhesion between the photochromic layer and the primer layer.

[0076] The various embodiments and forms described herein can be combined in any combination of two or more.

[0077] The embodiments disclosed herein should be considered in all respects to be illustrative and not restrictive. The scope of the present invention is indicated by the claims rather than by the foregoing description, and all modifications within the meaning and scope equivalent to the claims are intended to be included. [Industrial applicability]

[0078] This invention is useful in the technical fields of eyeglasses, goggles, sun visors, helmets, and the like.

Claims

1. Applying a polymerizable composition for primer layer formation directly onto a substrate or via another layer, The polymerizable composition for forming a primer layer is cured by light irradiation to form a primer layer. Applying a polymerizable composition for forming a photochromic layer containing a photochromic compound directly onto the formed primer layer, and A photochromic layer is formed by curing a coated polymerizable composition for photochromic layer formation by light irradiation. Includes, A method for producing a photochromic article, wherein one of the polymerizable composition for forming a primer layer and the polymerizable composition for forming a photochromic layer contains a hydroxyl group-containing polymerizable compound, and the other contains an isocyanate group-containing polymerizable compound.

2. The method for producing a photochromic article according to claim 1, wherein the hydroxyl group-containing polymerizable compound and the isocyanate group-containing polymerizable compound are (meth)acrylates.

3. The method for producing a photochromic article according to claim 1, wherein the isocyanate group-containing polymerizable compound is an isocyanate group-containing urethane (meth)acrylate.

4. The method for producing a photochromic article according to claim 1, wherein the hydroxyl group-containing polymerizable compound has one to three hydroxyl groups in one molecule.

5. Applying a polymerizable composition for forming a protective layer directly onto the photochromic layer or via another layer, and A protective layer is formed by curing a polymerizable composition applied to form a protective layer by light irradiation. A method for producing a photochromic article according to claim 1, further comprising: Manufacturing method.

6. The hydroxyl group-containing polymerizable compound is a (meth)acrylate, The isocyanate group-containing polymerizable compound is an isocyanate group-containing urethane (meth)acrylate. The hydroxyl group-containing polymerizable compound has one to three hydroxyl groups in one molecule, and Applying a polymerizable composition for forming a protective layer directly onto the photochromic layer or via another layer, and A protective layer is formed by curing a polymerizable composition applied to form a protective layer by light irradiation. A method for producing a photochromic article according to claim 1, further comprising:

7. The method for manufacturing a photochromic article according to any one of claims 1 to 6, wherein the photochromic article is an eyeglass lens.

8. The method for manufacturing a photochromic article according to any one of claims 1 to 6, wherein the photochromic article is a lens for goggles, a visor portion of a sun visor, or a shield member for a helmet.

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