Photochromic article and method for manufacturing photochromic article

Abstract

The present invention provides a photochromic article having, in the following order, a base material, an undercoat layer obtained by curing a polymerizable composition for forming an undercoat layer, and a photochromic layer obtained by curing a (meth) acrylic acid ester-based polymerizable composition containing a photochromic compound, the polymerizable composition for forming the undercoat layer contains a urethane (meth) acrylate containing an isocyanate group, and the isocyanate group content of the composition is 2.0 mass% or more when the total amount of the polymerizable composition for forming the undercoat layer is taken as 100 mass%.

Description

Technical Field

[0001] The invention relates to a photochromic article and a method for manufacturing the photochromic article. Background Art

[0002] A photochromic compound is a compound having the property (photochromic property) of being colored when irradiated with light in a wavelength range having photoresponse and fading when not irradiated. For example, Patent Document 1 discloses a photochromic article in which a layer (photochromic layer) containing a photochromic compound is provided on a substrate.

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent No. 6346183 Summary of the invention

[0006] Problems to be solved by the invention

[0007] The present inventors have repeatedly conducted studies to improve the adhesion between a photochromic layer and a substrate in order to improve the performance of a photochromic article.

[0008] An object of one embodiment of the present invention is to provide a photochromic article having excellent adhesion between a photochromic layer and a substrate.

[0009] Solutions to the problem

[0010] Patent Document 1 (Japanese Patent No. 6346183) described above discloses a technique for forming a primer layer between a substrate and a photochromic layer from a photocurable composition containing urethane (meth)acrylate.

[0011] In this regard, the present inventors have repeatedly conducted in-depth studies and have newly discovered that by forming a primer layer between a substrate and a photochromic layer from a primer layer-forming polymerizable composition comprising an isocyanate group-containing urethane (meth) acrylate and having an isocyanate group content of 2.0% by mass or more, the adhesion between the substrate and the photochromic layer can be improved.

[0012] That is, one embodiment of the present invention relates to a photochromic article, which sequentially comprises:

[0013] Base material,

[0014] A primer layer formed by curing a primer layer-forming polymerizable composition, and

[0015] A photochromic layer formed by curing a (meth)acrylate polymerizable composition containing a photochromic compound,

[0016] The polymerizable composition for forming a primer layer comprises an isocyanate group-containing urethane (meth)acrylate.

[0017] Furthermore, the isocyanate group content of the polymerizable composition for forming a primer layer is 2.0% by mass or more, assuming that the total amount of the composition is 100% by mass.

[0018] Effects of the Invention

[0019] According to one embodiment of the present invention, a photochromic article having excellent adhesion between a substrate and a photochromic layer can be provided. In addition, according to one embodiment of the present invention, a method for producing a photochromic article can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 Evaluation results related to the influence of the urethane (meth)acrylate mixing ratio on the photochromic performance are shown. DETAILED DESCRIPTION

[0021] [Photochromic items]

[0022] A photochromic article according to one embodiment of the present invention comprises a substrate, a primer layer, and a photochromic layer in this order. In the present invention and this specification, a "photochromic article" refers to an article containing a photochromic compound.

[0023] Hereinafter, the photochromic article according to one embodiment of the present invention will be described in more detail.

[0024] <Base material>

[0025] In one embodiment, the photochromic article may be an optical article. Optical articles include various articles such as eyeglass lenses, goggles lenses, the brim (brim) portion of a sun hat, and a shielding member of a helmet. For example, the photochromic article may have a primer layer and a photochromic layer in sequence 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 may be used as an eyeglass lens substrate. The 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, not easy to break, and easy to handle. As plastic lens substrates, there can be mentioned: (meth) acrylic resins, styrene resins, polycarbonate resins, allyl resins, allyl carbonate resins such as diethylene glycol bisallyl carbonate resin (CR-39), vinyl resins, polyester resins, polyether resins, carbamate resins obtained by reacting isocyanate compounds with hydroxy compounds such as diethylene glycol, thiocarbamate resins obtained by reacting isocyanate compounds with polythiol compounds, and cured products (generally 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 above-mentioned "(meth) acrylic resin" includes acrylic resins and methacrylic resins. The above-mentioned "(thio) epoxy compound" includes epoxy compounds and thioepoxy compounds. As lens substrates, undyed substrates (colorless lenses) can be used, and dyed substrates (dyed lenses) can also be used. The refractive index of the lens substrate can be, for example, about 1.50 to 1.75. Polycarbonate resin is generally used as a lens substrate with a refractive index of 1.59. Allyl carbonate resins such as allyl resin and diethylene glycol bisallyl carbonate resin (CR-39) are generally used as lens substrates with a refractive index of 1.50. Urea-formaldehyde resins obtained by the reaction of isocyanate-terminated prepolymers with aromatic diamines are generally used as lens substrates with a refractive index of 1.53. Diallyl phthalate resins are generally used as lens substrates with a refractive index of 1.55. Urethane resins obtained by the reaction of isocyanate compounds with hydroxyl compounds such as diethylene glycol are generally used as lens substrates with a refractive index of 1.60. Thiourethane resins obtained by reacting isocyanate compounds with polythiol compounds are generally 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 deviate above or below the above range. In the present invention and this specification, the refractive index refers to the refractive index relative to light with a wavelength of 500nm. The lens substrate may be a lens having refractive power (so-called prescription lens) or a lens having no refractive power (so-called non-prescription lens).

[0026] The spectacle lenses may be various lenses such as single-focus lenses, multi-focus lenses, and progressive refractive lenses. The type of lens is usually determined by the surface shapes of the two sides of the lens substrate. In addition, the surface of the lens substrate may be any of a convex surface, a concave surface, and a flat surface. For common lens substrates 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 may usually be disposed on the object-side surface of the lens substrate, but may also be disposed on the eyeball-side surface.

[0027] <Base coating>

[0028] (Polymerizable compound)

[0029] The primer layer contained in the above-mentioned photochromic article is a cured layer formed by curing the polymerizable composition for primer formation. In the present invention and this specification, "polymerizable composition" refers to a composition containing a polymerizable compound. A polymerizable compound refers to a compound having a polymerizable group. As a specific example of the polymerizable group, a (meth)acryloyl group described later can be cited.

[0030] The polymerizable composition for forming the primer layer contains a urethane (meth) acrylate containing an isocyanate group. In addition, the total amount of the composition is set to 100% by mass, and the isocyanate group content of the polymerizable composition for forming the primer layer is 2.0% by mass or more. It can be inferred that these requirements help to achieve the improvement of the adhesion between the substrate and the photochromic layer by arranging the primer layer formed by curing the polymerizable composition for forming the primer layer between the substrate and the photochromic layer.

[0031] In the present invention and this specification, "urethane (meth) acrylate" refers to a (meth) acrylate having a urethane bond. Urethane (meth) acrylate generally has a structure containing a "(meth) acryloyl group" at the end and / or side chain of a polyurethane skeleton. The present inventors infer that the polymerizable composition for forming the above-mentioned primer layer contains a urethane (meth) acrylate having a urethane bond as a high polarity portion, which can help to improve the wettability of the polymerizable composition for forming the photochromic layer to the primer layer. From this point of view, it is preferred that in the above-mentioned photochromic article, the primer layer is adjacent to the photochromic layer. Here, "adjacent" means directly connected together without other layers in between.

[0032] In addition, in the present invention and this specification, "(meth)acrylate" is used to include acrylate and methacrylate. "Acrylate" refers to a compound having one or more acryloyl groups in one molecule. "Methacrylate" refers to a compound having one or more methacryloyl groups in one molecule. With respect to (meth)acrylate, the functional number is the number of groups selected from acryloyl and methacryloyl contained in one molecule. In the present invention and this specification, "methacrylate" refers to a compound containing only methacryloyl as a (meth)acryloyl group, and a compound containing both acryloyl and methacryloyl as a (meth)acryloyl group is referred to as acrylate. Acryloyl can be included in the form of acryloyloxy, and methacryloyl can be included in the form of methacryloyloxy. "(Meth)acryloyl" is used to include acryloyl and methacryloyl, and "(meth)acryloyloxy" is used to include acryloyloxy and methacryloyloxy. In addition, unless otherwise specified, the group described may have a substituent or may be unsubstituted. When a certain 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, a carboxyl group, etc. In addition, regarding a group having a substituent, the "number of carbon atoms" refers to the number of carbon atoms of the portion not including the substituent.

[0033] The functionality of the isocyanate-containing urethane (meth) acrylate contained in the polymerizable composition for forming the primer layer (the number of groups selected from acryloyl and methacryloyl contained in one molecule) is 1 or more, for example, it can be in the range of 1 to 4. In addition, the isocyanate group content of the isocyanate-containing urethane (meth) acrylate can be, for example, 1.0% by mass or more, 3% by mass or more, or 5% by mass or more, and can 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. In addition, based on the principle of synthesis, the isocyanate-containing urethane (meth) acrylate does not contain a hydroxyl group in the molecule. From the viewpoint of the storage stability of the polymerizable composition for forming the primer layer, it is preferred that the molecule does not contain a hydroxyl group. The isocyanate-containing urethane (meth) acrylate can be synthesized by a known method or obtained as a commercially available product. As a commercially available product, EBECRYL 4141, 4250, 4510, 4396, 4397 etc. manufactured by DAICEL-ALLNEX are mentioned, for example.

[0034] The polymerizable composition for forming the primer layer contains at least one or more isocyanate-containing urethane (meth) acrylates as polymerizable compounds. The polymerizable composition for forming the primer layer may contain only isocyanate-containing urethane (meth) acrylates as polymerizable compounds in one embodiment, and may contain one or more other polymerizable compounds in another embodiment. As the other polymerizable compounds, urethane (meth) acrylates that do not contain isocyanate groups can be cited. The functional number of the urethane (meth) acrylate that does not contain isocyanate groups (the number of groups selected from acryloyl and methacryloyl groups contained in one molecule) is 1 or more, for example, it can be in the range of 1 to 4. From the viewpoint of the storage stability of the polymerizable composition for forming the primer layer, it is preferred that the urethane (meth) acrylate that does not contain isocyanate groups does not contain hydroxyl groups in the molecule. The urethane (meth) acrylate that does not contain isocyanate groups can be synthesized by a known method, or it can be obtained as a commercially available product. Examples of commercially available products include KRM9276 (monofunctional), KRM9335 (bifunctional), and EBECRYL 230 (bifunctional) manufactured by Daicel-Allnex Co., Ltd., and UA-224L (bifunctional) manufactured by Kyoeisha Chemical Co., Ltd.

[0035] In the polymerizable composition for forming the above-mentioned primer layer, the total amount of carbamate (meth) acrylate containing isocyanate group and carbamate (meth) acrylate not containing isocyanate group is set to 100 mass%, and carbamate (meth) acrylate containing isocyanate group can be included, for example, 5 mass% or more, preferably 10 mass% or more, more preferably 15 mass% or more, and further preferably 20 mass% or more. From the viewpoint of improving the adhesion of the substrate and the photochromic layer, it is preferred that the amount of carbamate (meth) acrylate containing isocyanate group contained in the polymerizable composition for forming the above-mentioned primer layer is large. In addition, from the viewpoint of various performances of the above-mentioned photochromic article, the total amount of carbamate (meth) acrylate containing isocyanate group and carbamate (meth) acrylate not containing isocyanate group is set to 100 mass%, and the polymerizable composition for forming the above-mentioned primer layer preferably includes carbamate (meth) acrylate containing isocyanate group 50 mass% or less, more preferably 40 mass% or less, and further preferably 30 mass% or less.

[0036] (Optional ingredient)

[0037] The polymerizable composition for forming the above-mentioned primer layer comprises at least a carbamate (meth) acrylate containing an isocyanate group, may comprise other polymerizable compounds such as a carbamate (meth) acrylate not containing an isocyanate group, and may further comprise one or more components. As such components, polymerization initiators, catalysts, etc. may be cited. These components may be used in any amount, and in addition, as these components, known compounds may be used, or commercially available products may be used.

[0038] For example, as a polymerization initiator, a known polymerization initiator that can function as a polymerization initiator for (meth) acrylate can be used, preferably a free radical polymerization initiator, and more preferably only a free radical polymerization initiator is included as a polymerization initiator. In addition, as a polymerization initiator, a photopolymerization initiator or a thermal polymerization initiator can be used. From the perspective of allowing the polymerization reaction to proceed in a short time, a photopolymerization initiator is preferably used. As a photoradical polymerization initiator, for example: benzoin acetals such as 2,2-dimethoxy-1,2-diphenylethane-1-one; α-hydroxyketones such as 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propane-1-one; 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butane-1-one, 1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1 -ketone and other α-amino ketones; oxime esters such as 1-[(4-phenylthio)phenyl]-1,2-octanedione-2-(benzoyl)oxime; phosphine oxides such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide; 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylphosphine oxide 2,4,5-triarylimidazole dimers such as phenylimidazole 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; 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3- Quinone compounds such as benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthrenequinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone; benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether; benzoin compounds such as benzoin, methylbenzoin, ethylbenzoin; benzyl compounds such as benzyl dimethyl ketal; acridine compounds such as 9-phenylacridine, 1,7-bis(9,9'-acridinylheptane); N-phenylglycine, coumarin, etc. In addition, in the 2,4,5-triarylimidazole dimer, the substituents of the aryl groups at the two triarylimidazole sites may be the same to obtain a symmetrical compound, or different to obtain an asymmetrical compound. In addition, a thioxanthone compound and a tertiary amine may be combined, like the combination of diethylthioxanthone and dimethylaminobenzoic acid.Among these, α-hydroxyketone and phosphine oxide are preferred from the viewpoint of curability, transparency and heat resistance.

[0039] Examples of the catalyst include organic tin compounds such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, dimethyltin dichloride, monomethyltin trichloride, trimethyltin chloride, tributyltin chloride, tributyltin chloride, tributyltin fluoride, and dimethyltin dibromide. Organic tin compounds can act as catalysts for isocyanate groups.

[0040] The polymerizable composition for forming the primer layer may contain a solvent or may not contain a solvent. When a solvent is contained, any solvent that does not hinder the polymerization reaction of the polymerizable compound may be used, and any amount of the solvent may be used. In the present invention and this specification, regarding the content rate, the "total amount of the composition" refers to the total amount of all components other than the solvent in the composition containing the solvent.

[0041] The polymerizable composition for forming the above-mentioned primer layer can further include a known additive that can be generally added to the composition for forming the primer layer in any amount. As an additive, a known compound can be used, or a commercially available product can be used. The total amount of the composition (wherein, except the polymerization initiator) is set to 100 mass %, and the polymerizable composition for forming the above-mentioned primer layer can include a total of 80.0 mass %, 85.0 mass %, 90.0 mass % or more than 95.0 mass % of the isocyanate-containing carbamate (meth) acrylate and isocyanate-free carbamate (meth) acrylate. In addition, in the polymerizable composition for forming the above-mentioned primer layer, the total amount of the composition (wherein, except the polymerization initiator) is set to 100 mass %, and the total content of the isocyanate-containing carbamate (meth) acrylate and isocyanate-free carbamate (meth) acrylate can be, for example, 100 mass %, 100 mass % or less, less than 100 mass % or 99.0 mass % or less.

[0042] (Isocyanate Group Content of Primer Layer-Forming Polymerizable Composition)

[0043] The total amount of the polymerizable composition for forming the primer layer is set to 100 mass%, and the isocyanate group content of the composition is 2.0 mass% or more, more preferably 2.1 mass% or more, and further preferably 2.2 mass% or more. The inventors infer that the reason why the adhesion between the substrate and the photochromic layer can be improved by arranging the primer layer formed by the polymerizable composition for forming the primer layer between the substrate and the photochromic layer is that the polymerizable composition for forming the primer layer contains a urethane (meth) acrylate containing an isocyanate group, and the isocyanate group content in the composition is 2.0 mass% or more. Regarding the isocyanate group, the inventors believe that it can help maintain the high adhesion between the substrate and the photochromic layer even in a high temperature and high humidity environment.

[0044] In addition, the isocyanate group content of the polymerizable composition for forming the 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, it should be noted that from the viewpoint of improving the adhesion between the substrate and the photochromic layer, the isocyanate group content of the polymerizable composition for forming the primer layer is preferably high, and therefore, the upper limit of the isocyanate group content of the polymerizable composition for forming the primer layer is not limited to the value exemplified here.

[0045] For example, in the above-mentioned polymerizable composition for forming a primer layer, when the component containing an isocyanate group is only an isocyanate group-containing urethane (meth) acrylate, the isocyanate group content relative to 100% by mass of the total composition of the above-mentioned polymerizable composition for forming a primer layer can be calculated, for example, by the following formula.

[0046] Isocyanate group content relative to 100% by mass of the total amount of the polymerizable composition for forming a primer layer = Y × X / T

[0047] In the above formula, the isocyanate group content of the isocyanate group-containing urethane (meth)acrylate is set to "X" mass %, the amount of the isocyanate group-containing urethane (meth)acrylate in the polymerizable composition for forming a primer layer is set to "Y" g (gram), and the total amount of the composition is set to "T" g (gram).

[0048] The above-described undercoat layer-forming composition can be prepared by mixing the various components described above simultaneously or sequentially in any order.

[0049] By applying the polymerizable composition for forming the primer layer on the substrate and curing the applied composition, a cured layer, i.e., a primer layer, formed by curing the polymerizable composition for forming the primer layer can be formed on the substrate. The polymerizable composition for forming the primer layer can be directly applied to the surface of the substrate, or it 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 in one embodiment, and in another embodiment, the primer layer is located on the substrate with one or more other layers separated. As other layers, well-known layers such as hard coatings can be exemplified. As a coating method, well-known coating methods such as spin coating and dip coating can be used. From the perspective of uniformity of coating, spin coating is preferred. In order to clean the surface of the substrate, one or more well-known pretreatments such as alkali treatment and UV ozone treatment can be arbitrarily applied to the surface of the substrate. The curing treatment can be light irradiation and / or heat treatment. From the perspective of allowing the curing reaction to proceed in a short time, light irradiation is preferred. The curing treatment conditions may be determined according to the types of various components contained in the polymerizable composition for forming a primer layer and the composition of the polymerizable composition for forming a primer layer.

[0050] The thickness of the primer layer may be, for example, 3 μm or more, preferably 5 μm or more, and the thickness of the primer layer may be, for example, 15 μm or less, preferably 10 μm or less.

[0051] <Photochromic layer>

[0052] <<Polymerizable compounds>>

[0053] The above-mentioned photochromic article has a photochromic layer on the above-mentioned primer layer. The photochromic layer contained in the above-mentioned photochromic article is a cured layer formed by curing a (meth)acrylate polymerizable composition. In the present invention and this specification, "(meth)acrylate polymerizable composition" refers to a polymerizable composition containing (meth)acrylate. The polymerizable composition for forming the above-mentioned primer layer also contains the urethane (meth)acrylate described above, and therefore, it can be called a (meth)acrylate polymerizable composition. The inventors infer that the primer layer and the photochromic layer are both cured layers formed by curing a (meth)acrylate polymerizable composition, which can also help improve the adhesion between the substrate and the photochromic layer.

[0054] Hereinafter, a (meth)acrylate polymerizable composition as one embodiment of the polymerizable composition for forming a photochromic layer will be described. However, the following embodiments are merely examples, and the present invention is not limited to such examples.

[0055] In one embodiment, the photochromic layer-forming polymerizable composition may be a (meth)acrylate-based polymerizable composition containing one or more polymerizable compounds selected from the following Component A, Component B, and Component C.

[0056] (ingredient A)

[0057] Component A is a polyfunctional (meth)acrylate having a molecular weight of 500 or more and containing a polyalkylene glycol moiety. In the present invention and this specification, the "polyalkylene glycol moiety" refers to a partial structure represented by Formula 2 below.

[0058] [Chemical formula 1]

[0059] (Formula 2)

[0060]

[0061] In Formula 2, R represents an alkylene group, and n represents the number of repetitions of the alkoxy group represented by RO, which is greater than or equal to 2. * represents the bonding position of the partial structure represented by Formula 2 to the adjacent atom. The number of carbon atoms of the alkylene group represented by R may be greater than or equal to 1 or greater than or equal to 2, and, for example, may be less than or equal to 5 or less than or equal to 4. Specific examples of the alkylene group represented by R include ethylene, propylene, tetramethylene, and the like. n is greater than or equal to 2, and, for example, may be less than or equal to 30, less than or equal to 25, or less than or equal to 20. In one embodiment, component A may have the above-mentioned partial structure in which R represents an ethylene group, i.e., a polyethylene glycol portion. In addition, in one embodiment, component A may have the above-mentioned partial structure in which R represents a propylene group, i.e., a polypropylene glycol portion.

[0062] The molecular weight of component A is 500 or more. In the present invention and this specification, the molecular weight of the polymer is determined by the structural formula determined by the structural analysis of the compound or the theoretical molecular weight calculated by the raw material feed ratio during production. The molecular weight of component A is 500 or more, preferably 510 or more, more preferably 520 or more, more preferably 550 or more, more preferably 570 or more, further preferably 600 or more, further preferably 630 or more, and further 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.

[0063] Component A may be a multifunctional (meth)acrylate, such as a bifunctional, trifunctional, tetrafunctional or pentafunctional (meth)acrylate, preferably a bifunctional or trifunctional (meth)acrylate. In component A, as a (meth)acryloyl group, only an acryloyl group may be included, only a methacryloyl group may be included, or both an acryloyl group and a methacryloyl group may be included. That is, component A may be an acrylate or a methacrylate.

[0064] In one embodiment, component A can be a non-cyclic multifunctional (meth)acrylate. In the present invention and this specification, "non-cyclic" means not containing a cyclic structure. In this regard, "cyclic" means containing a cyclic structure. Non-cyclic multifunctional (meth)acrylate refers to a (meth)acrylate with more than two functions that does not contain a cyclic structure. As a specific example of such component A, polyalkylene glycol di(meth)acrylate represented by the following formula 3 can be cited.

[0065] [Chemical formula 2]

[0066] (Formula 3)

[0067]

[0068] 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, which is 2 or more. R and n are as described above for the partial structure represented by Formula 2. In the polyalkylene glycol di(meth)acrylate represented by Formula 3, as a (meth)acryloyl group, only an acryloyl group may be included, only a methacryloyl group may be included, or both an acryloyl group and a methacryloyl group may be included. Specific examples of the polyalkylene glycol di(meth)acrylate represented by Formula 3 include polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, and the like.

[0069] 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 groups as the (meth)acryloyl groups.

[0070] [Chemical formula 3]

[0071] (Formula 4)

[0072]

[0073] 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, R 42 , R 46 and R 49 Each independently represents a hydrogen atom or a methyl group. n1 represents OR 41The number of repetitions of the alkoxy group is 2 or more. n2 represents OR 45 The number of repetitions of the alkoxy group is 2 or more. n3 represents OR 48 The number of repetitions of the alkoxy group shown is 2 or more.

[0074] Hereinafter, Formula 4 will be described in more detail.

[0075] Regarding R in Formula 4 41 , R 45 and R 48 , as described above for R in Formula 2. n1, n2, and n3 in Formula 4 are as described above for n in Formula 2. In Formula 4, R 41 , R 45 and R 48 The same may be true for n1, n2, and n3.

[0076] R 42 , R 46 and R 49 Each independently represents a hydrogen atom or a methyl group. As the (meth)acryloyl group, the tri(meth)acrylate represented by Formula 4 may include only an acryloyl group, only a methacryloyl group, or both an acryloyl group and a methacryloyl group.

[0077] R 43 The number of carbon atoms in the alkyl group represented by may be 1 or more or 2 or more, and may be 5 or less or 4 or less, for example. 43 The alkyl group represented by may be a straight chain alkyl group or a branched alkyl group. 43 Specific examples of the alkyl group represented by include a methyl group, an ethyl group, and the like.

[0078] R 40 , R 44 and R 47 Each independently represents an alkylene group. The number of carbon atoms of such an alkylene group may be 1 or more or 2 or more, and may be, for example, 5 or less or 4 or less. Specific examples thereof include ethylene, propylene, tetramethylene, and the like.

[0079] Specific examples of the tri(meth)acrylate represented by Formula 4 include trimethylolpropane polyoxyethylene ether tri(meth)acrylate and the like.

[0080] Monofunctional (meth)acrylate

[0081] From the viewpoint of increasing the (meth)acryloyl content of the polymerizable composition containing (meth)acrylate, (meth)acrylates having a high proportion of (meth)acryloyl groups in the molecule are preferred. From this point of view, low molecular weight monofunctional (meth)acrylates are preferred, and monofunctional (meth)acrylates having a molecular weight of 150 or less are more preferred. Monofunctional (meth)acrylates having a molecular weight of 150 or less may be cyclic monofunctional (meth)acrylates or non-cyclic monofunctional (meth)acrylates. Specific examples of cyclic monofunctional (meth)acrylates having a molecular weight of 150 or less include glycidyl (meth)acrylate, etc. Specific examples of non-cyclic monofunctional (meth)acrylates having a molecular weight of 150 or less include n-butyl (meth)acrylate, etc. The molecular weight of monofunctional (meth)acrylates having a molecular weight of 150 or less may be, for example, 100 or more, but are not limited thereto.

[0082] Multifunctional (meth)acrylate

[0083] As described above, from the viewpoint of increasing the (meth)acryloyl content of the polymerizable composition containing (meth)acrylate, a (meth)acrylate having a high proportion of (meth)acryloyl in the molecule is preferred. From this point of view, a multifunctional (meth)acrylate having a molecular weight smaller than that of component A is also preferred. As such a multifunctional (meth)acrylate, a multifunctional (meth)acrylate having a functional number greater than that of the multifunctional (meth)acrylate used as component A is also preferred. The molecular weight of the above-mentioned multifunctional (meth)acrylate is preferably less than 500, less than 400, less than 300 or less than 200. Its molecular weight may be, for example, more than 100, but is not limited thereto. In addition, such a multifunctional (meth)acrylate may be, for example, a multifunctional (meth)acrylate having more than 10 functions (for example, more than 10 functions and less than 15 functions). As a specific example, poly[(3-methacryloxypropyl)silsesquioxane] derivatives described in the embodiment column described later may be cited.

[0084] As the (meth)acrylate that can be included in the polymerizable composition for forming a photochromic layer, i.e., the (meth)acrylate polymerizable composition, there can also be mentioned a monofunctional (meth)acrylate represented by the following formula 1 (hereinafter, also described as "component B") and a bifunctional (meth)acrylate represented by the following formula 5 (hereinafter, also described as "component C"). In one embodiment, the above-mentioned (meth)acrylate polymerizable composition can be a polymerizable composition containing one or more (meth)acrylates selected from the monofunctional (meth)acrylate represented by the following formula 1 and the bifunctional (meth)acrylate represented by the following formula 5. In another embodiment, the above-mentioned (meth)acrylate polymerizable composition can be a polymerizable composition that does not contain one or more (meth)acrylates selected from the monofunctional (meth)acrylate represented by the following formula 1 and the bifunctional (meth)acrylate represented by the following formula 5. In one embodiment, the above-mentioned (meth)acrylate polymerizable composition can also contain component B as a monofunctional (meth)acrylate having a molecular weight of 150 or less.

[0085] (ingredient B)

[0086] Component B is a monofunctional (meth)acrylate represented by Formula 1 below.

[0087] [Chemical formula 4]

[0088] (Formula 1)

[0089]

[0090] Hereinafter, Formula 1 will be described in more detail.

[0091] 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.

[0092] 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 is 3 or more, preferably 4 or more, more preferably 5 or more, and more preferably in the order of 6 or more, 7 or more, 8 or more, 9 or more, 10 or more, and 11 or more. On the other hand, from the viewpoint of the solubility of the photochromic compound in the above composition, the number of carbon atoms is preferably 15 or less, more preferably 14 or less, and more preferably 13 or less, and 12 or less.

[0093] The molecular weight of the monofunctional (meth)acrylate represented by Formula 1 may be, for example, 100 or more, and may be, 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 may 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.

[0094] (Ingredient C)

[0095] Component C is a (meth)acrylate represented by Formula 5 below.

[0096] [Chemical formula 5]

[0097] (Formula 5)

[0098]

[0099] In formula 5, R 3 and R 4 Each independently represents a hydrogen atom or a methyl group, and m represents an integer greater than 1. m is greater than 1, and may be, for example, less than 10, less than 9, less than 8, less than 7, or less than 6.

[0100] The molecular weight of component C may be, for example, 400 or less, and from the viewpoint of further improving the color depth of the photochromic layer, it is preferably 350 or less, more preferably 300 or less, and even more preferably 250 or less. In addition, the molecular weight of component C may be, for example, 100 or more, 150 or more, or 200 or more.

[0101] As the (meth)acryloyl group, component C may contain only an acryloyl group, only a methacryloyl group, or both an acryloyl group and a methacryloyl group. 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.

[0102] In the above-mentioned (meth) acrylate polymerizable composition, the total amount of the polymerizable compound contained in the composition is set to 100% by mass, and the content of component A is preferably 50% by mass or more, more preferably 55% by mass or more, and further preferably 60% by mass or more. In one embodiment, among the multiple polymerizable compounds contained in the composition, component A may be the component that occupies the largest proportion. In addition, the total amount of the polymerizable compound contained in the composition is set to 100% by mass, and the content of component A may be 90% by mass or less, 85% by mass or less, or 80% by mass or less. In one embodiment, the above-mentioned composition may contain only one component A, and in another embodiment, it may contain two or more components A. In the case of containing two or more components A, the content of the above-mentioned component A is the total content of two or more. This is also the same for the content related to other components in the present invention and this specification.

[0103] The (meth)acrylate polymerizable composition may contain the above-mentioned various (meth)acrylates in an amount such that the (meth)acryloyl content in the composition reaches 3.50 mmol / g or more. For example, when the total amount of the polymerizable compounds contained in the composition is 100% by mass, the (meth)acrylate polymerizable composition preferably contains 5% by mass or more of a monofunctional (meth)acrylate having a molecular weight of 150 or less, more preferably 10% by mass or more, and more preferably 15% by mass or more. In addition, when the total amount of the polymerizable compounds contained in the composition is 100% by mass, 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.

[0104] From the viewpoint of improving the weather resistance of the photochromic layer, the (meth)acryloyl content of the (meth)acrylic acid ester polymerizable composition is preferably 3.50 mmol / g or more, more preferably 3.55 mmol / g or more, further preferably 3.60 mmol / g or more, further preferably 3.65 mmol / g or more, further more preferably 3.70 mmol / g or more, and further preferably 3.75 mmol / g or more. The (meth)acryloyl content of the (meth)acrylic acid ester polymerizable composition may be, for example, 5.00 mmol / g or less, 4.50 mmol / g or less, or 4.00 mmol / g or less, or may be higher than the values ​​exemplified here.

[0105] The "(meth)acryloyl content" of the polymerizable composition containing a (meth)acrylate is a value calculated as follows.

[0106] The total amount of the (meth)acrylate contained in the polymerizable composition was defined as "1" on a mass basis, and the content rate of each (meth)acrylate was calculated.

[0107] For each (meth)acrylate, “(meth)acryloyl content×the above content ratio” was determined. The total of the values ​​calculated in this way for all (meth)acrylates contained in the polymerizable composition was defined as the (meth)acryloyl content of the polymerizable composition.

[0108] As an example, the photochromic compound contained in the photochromic layer is irradiated by light such as sunlight, and the structure changes through the excited state. The structure after the structural change after the light exposure can be called a "colored body". In contrast, the structure before the light exposure can be called a "colorless body". It should be noted that, with respect to the colorless body, "colorless" is not only limited to being completely colorless, but also includes the case where the color is lighter than the colored body. After the structure changes to the colored body by light exposure and coloring occurs, the faster the speed of the structural change from the colored body to the colorless body, the faster the fading speed. It can be considered that in the photochromic layer, in the matrix formed by the polymerization reaction of the polymerizable compound, the easier the photochromic compound is to undergo molecular motion, the faster the speed of the above structural change. From the viewpoint of accelerating such a speed, it can be considered that a soft matrix is ​​preferred. With respect to the above aspects, it can be inferred that component A can help to make the matrix soft. In detail, it can be considered that the molecular weight of component A is 500 or more and component A has a polyalkylene glycol portion, which is the reason why a soft matrix can be formed by component A.

[0109] In addition, it is believed that the (meth)acryloyl content of 3.50 mmol / g or more in the (meth)acrylate polymerizable composition contributes to the formation of a rigid polymer network between molecules in a matrix formed from such a composition. It is inferred that the diffusion of active species that may reduce weather resistance can be suppressed in a matrix having a rigid polymer network, which is the reason why a photochromic layer having excellent weather resistance can be formed from the (meth)acrylate polymerizable composition.

[0110] The total amount of the (meth) acrylate polymerizable composition is set to 100% by mass, and the content of the polymerizable compound in the composition (when a plurality of polymerizable compounds are included, the total content thereof) can be, for example, 80% by mass or more, 85% by mass or more, or 90% by mass or more. In addition, the total amount of the (meth) acrylate polymerizable composition is set to 100% by mass, and the content of the polymerizable compound in the 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. The (meth) acrylate polymerizable composition may contain a solvent 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 hinder the polymerization reaction of the polymerizable composition.

[0111] <<Photochromic compounds>>

[0112] The composition contains the polymerizable compound and a photochromic compound. As the photochromic compound contained in the composition, a known compound showing photochromic properties can be used. The photochromic compound can show photochromic properties to ultraviolet rays. For example, as the photochromic compound, fulgimide compounds, spiro The invention relates to a compound having a known skeleton showing photochromic properties, such as an oxazine compound, a chromene compound, an indeno-fused naphthopyran compound, etc. The photochromic compound can be used alone or in combination of two or more. The total amount of the composition is set to 100 mass %, and the content of the photochromic compound in the composition can be set to about 0.1 to 15 mass %, but is not limited to this range.

[0113] <<Other ingredients>>

[0114] In addition to the polymerizable compound and the photochromic compound, the polymerizable composition for forming a photochromic layer may also contain one or more of various additives that can be generally contained in the polymerizable composition at any content rate. As additives that can be contained in the polymerizable composition for forming a photochromic layer, for example, a polymerization initiator for causing the polymerization reaction to proceed can be cited. Regarding the polymerization initiator, reference can be made to the above description. The total amount of the composition is set to 100% by mass, and the content of the polymerization initiator can be, for example, in the range of 0.1 to 5.0% by mass.

[0115] The polymerizable composition for forming a photochromic layer may further contain any known additives that can be generally added to a composition containing a photochromic compound, for example, surfactants, antioxidants, free radical scavengers, light stabilizers, ultraviolet absorbers, anti-coloring agents, antistatic agents, fluorescent dyes, dyes, pigments, fragrances, plasticizers, silane coupling agents, etc. As these additives, known compounds may be used.

[0116] The polymerizable composition for forming a photochromic layer can be prepared by mixing the various components described above simultaneously or sequentially in any order.

[0117] The photochromic layer can be formed by coating a polymerizable composition for forming a photochromic layer on the primer layer and curing the coated composition. For the coating method, reference can be made to the above description. The curing treatment can be light irradiation and / or heat treatment. From the perspective of allowing the curing reaction to proceed in a short time, light irradiation is preferred. The curing treatment conditions are determined based on the types of various components (polymerizable compounds, polymerization initiators, etc. described above) contained in the polymerizable composition for forming a photochromic layer and the composition of the above composition. The thickness of the photochromic layer formed in this way is, for example, preferably in the range of 5 to 80 μm, and more preferably in the range of 20 to 60 μm.

[0118] The photochromic article having the above-mentioned photochromic layer may further have one or more functional layers in addition to the above-mentioned various layers, or may not have a functional layer. As the functional layer, a protective layer, a hard coating layer, an anti-reflection layer, a water-repellent or hydrophilic antifouling layer, an anti-fog layer, etc. for improving durability can be cited as layers known as functional layers of optical articles. For example, with respect to the protective layer, reference can be made to paragraphs 0009 to 0021, 0026 of Japanese Patent Gazette No. 2021-107909 and the records of the embodiments of the Gazette.

[0119] The photochromic article may be an optical article, and one form of the optical article is a spectacle lens. In addition, as one form of the optical article, a lens for goggles, a brim (brim) portion of a sun hat, a shielding member of a helmet, etc. may also be cited. By coating a polymerizable composition for forming a photochromic layer on a substrate for these optical articles via a primer layer and curing the coated composition to form a photochromic layer, an optical article having an anti-glare function may be obtained.

[0120] [Glasses]

[0121] One embodiment of the present invention relates to a pair of glasses, which includes a spectacle lens as one embodiment of the above-mentioned photochromic article. The details of the spectacle lens included in the glasses are as described above. The glasses include the spectacle lens, for example, when outdoors, the photochromic compound included in the photochromic layer is irradiated with sunlight to be colored (coloring), thereby exerting an anti-glare effect like sunglasses, and when returning to the room, the photochromic compound fades and the transmittance is restored. The structure of the glasses, the frame, etc. can be applied to the known technology.

[0122] [Method for producing photochromic article]

[0123] One embodiment of the present invention relates to a method for manufacturing a photochromic article, the method comprising:

[0124] Applying the above-described polymerizable composition for forming a primer layer on a substrate;

[0125] The applied polymerizable composition for forming a primer layer is subjected to a curing treatment by irradiation with light to form a primer layer;

[0126] coating a (meth)acrylate polymerizable composition containing a photochromic compound on the formed primer layer; and

[0127] The applied (meth)acrylate polymerizable composition containing a photochromic compound is cured by irradiation with light to form a photochromic layer.

[0128] According to the above production method, a photochromic article having excellent adhesion between the substrate and the photochromic layer can be produced. For details of the above production method, reference can be made to the above description.

[0129] Example

[0130] Hereinafter, the present invention will be further described by way of examples, but the present invention is not limited to the embodiments shown in the examples.

[0131] <Base material>

[0132] The various substrates described below are plastic lens substrates described below. All substrates have a convex surface on the object side and a concave surface on the eyeball side. Substrate 4 (refractive index 1.59) is a substrate with hard coatings on both sides, and the primer layer formation described below is performed on the hard coating surface by coating with a polymerizable composition.

[0133] Substrate 1: Refractive index 1.50 (diethylene glycol bisallyl carbonate resin (CR-39))

[0134] Substrate 2: Refractive index 1.53 (urea-formaldehyde resin)

[0135] Substrate 3: Refractive index 1.55 (diallyl phthalate resin)

[0136] Substrate 4: Refractive index 1.59 (polycarbonate resin)

[0137] Substrate 5: Refractive index 1.60 (urethane resin)

[0138] Substrate 6: Refractive index 1.67 (thiocarbamate resin)

[0139] [Example 1]

[0140] <Production of eyeglass lenses (photochromic articles)>

[0141] The plastic lens substrate was immersed in a 10 mass % sodium hydroxide aqueous solution (liquid temperature 60° C.) for 5 minutes, then washed with pure water and dried. Then, a primer layer was formed on the convex surface (object side surface) of the plastic lens substrate. In detail, KRM 9276 manufactured by DAICEL-ALLNEX was used as the urethane acrylate not containing an isocyanate group, and EBECRYL 4141 manufactured by DAICEL-ALLNEX (isocyanate group content: 12.0 mass %) was used as the urethane acrylate containing an isocyanate group, and the above two urethane acrylates (total 20 g, KRM 9276:EBECRYL 4141 (mass ratio) = 8:2) were mixed. In the mixture thus obtained, 0.02% by mass of an organic tin 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 B.V.)) and 0.25% by mass of a leveling agent (LE-605 manufactured by Kyoeisha Chemical Co., Ltd.) were mixed relative to 100% by mass of the total amount of the mixture, and the mixture was stirred thoroughly. Then, degassing was performed by stirring the degassing device by rotation and revolution. The total amount of the composition was set to 100% by mass, and the isocyanate group content of the polymerizable composition for forming a primer layer thus obtained was 2.4% by mass.

[0142] The polymerizable composition for forming a primer layer was applied to the convex surface of the plastic lens substrate by spin coating in an environment of temperature 25°C and relative humidity 50%, and then the composition for forming a primer layer 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 cure the composition, thereby forming a primer layer. The thickness of the formed primer layer was 6 μm.

[0143] A polymerizable composition for forming a photochromic layer ((meth)acryloyl content: 3.61 mmol / g) prepared as described below was applied to the above-mentioned primer layer by spin coating. The spin coating was performed by the method described in Japanese Patent Publication No. 2005-218994. Then, the polymerizable composition for forming a photochromic layer applied to the primer layer was irradiated with ultraviolet rays (wavelength 405 nm) in a nitrogen atmosphere (oxygen concentration 500 ppm or less), and the composition was cured to form a photochromic layer. The thickness of the formed photochromic layer was 40 μm.

[0144] On the photochromic layer formed in this way, a protective layer was formed by the method described in Example 1 of Japanese Patent Application Laid-Open No. 2021-107909. The thickness of the formed protective layer was 15 μm.

[0145] In this manner, an eyeglass lens having a substrate, a primer layer, and a photochromic layer in this order, and further having a protective layer on the photochromic layer, was produced.

[0146] (Preparation of polymerizable composition for forming photochromic layer)

[0147] The components shown in Table 1 were mixed in the amounts shown in Table 1 in a plastic container.

[0148] The thus obtained mixture of polymerizable compounds was mixed with a photochromic compound (an indeno-fused naphthopyran compound represented by the structural formula described in the specification of U.S. Patent No. 5,645,767), a photoradical polymerization initiator (bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (Omnirad819 manufactured by IGM Resin BV)), an antioxidant (bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][ethylenebis(oxyethylene)]ester), and a light stabilizer (bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate), and stirred thoroughly. Then, degassing was performed using a rotation-revolution stirring degassing device. In this way, a polymerizable composition for forming a photochromic layer was prepared. The contents of the above components when the total amount of the composition is 100 mass % are as follows: 94.9 mass % of the mixture of the above polymerizable compounds, 3 mass % of the photochromic compound, 0.3 mass % of the photoradical polymerization initiator, 0.9 mass % of the antioxidant, and 0.9 mass % of the photostabilizer.

[0149] [Table 1]

[0150]

[0151] [Comparative Example 1]

[0152] A spectacle lens was produced in the same manner as described in Example 1 except that the total amount of 20 g of urethane acrylate was changed to urethane acrylate not containing an isocyanate group (KRM 9276 manufactured by DAICEL-ALLNEX).

[0153] [Comparative Example 2]

[0154] The spectacle lenses were prepared as described in Example 1 except that the mixing ratio of the urethane acrylate not containing an isocyanate group (KRM 9276 manufactured by DAICEL-ALLNEX) and the urethane acrylate containing an isocyanate group (EBECRYL 4141 manufactured by DAICEL-ALLNEX) was changed to KRM 9276:EBECRYL 4141 (mass ratio) = 9:1. In the polymerizable composition for forming a primer layer prepared in Comparative Example 2, the isocyanate group content was 1.2% by mass, with the total amount of the composition being 100% by mass.

[0155] [Example 2]

[0156] EBECRYL 4396 (isocyanate group content: 7.5% by mass) manufactured by DAICEL-ALLNEX was used as the isocyanate group-containing urethane acrylate, and the mixing ratio of the isocyanate group-free urethane acrylate (KRM 9276 manufactured by DAICEL-ALLNEX) to the isocyanate group-containing urethane acrylate was changed to KRM9276:EBECRYL 4396 (mass ratio) = 7:3. Spectacle lenses were prepared as described in Example 1. In the primer layer-forming polymerizable composition prepared in Example 2, the isocyanate group content was 2.2% by mass, with the total amount of the composition being 100% by mass.

[0157] [Comparative Example 3]

[0158] The spectacle lenses were prepared as described in Example 2 except that the mixing ratio of the urethane acrylate not containing an isocyanate group (KRM 9276 manufactured by DAICEL-ALLNEX) and the urethane acrylate containing an isocyanate group (EBECRYL 4396 manufactured by DAICEL-ALLNEX) was changed to KRM 9276:EBECRYL 4396 (mass ratio) = 8:2. In the polymerizable composition for forming a primer layer prepared in Comparative Example 3, the isocyanate group content was 1.5% by mass, with the total amount of the composition being 100% by mass.

[0159] [Adhesion Evaluation]

[0160] In Examples and Comparative Examples, two eyeglass lenses were produced using the substrates shown in Table 2.

[0161] One of the two manufactured spectacle lenses was evaluated for initial adhesion, and the other was evaluated for adhesion under high temperature and high humidity.

[0162] The initial adhesion was evaluated by a cross-cut method in accordance with JIS K5600-5-6:1999.

[0163] Regarding the adhesion under high temperature and high humidity conditions, the eyeglass lenses were immersed in boiling hot water for 1 hour and then taken out of the hot water, and the adhesion was evaluated by the cross-section method in accordance with JIS K5600-5-6:1999.

[0164] The evaluation results based on the following evaluation criteria are shown in Table 2, and the number of remaining squares is shown in parentheses. For the eyeglass lenses where the squares peeled, the peeled parts were observed, and it was confirmed that the film peeled off on the substrate surface, that is, peeling occurred between the substrate and the primer layer.

[0165] From the results shown in Table 2, it can be confirmed that the spectacle lenses of Example 1 and Example 2 are superior to the spectacle lenses of Comparative Examples 1 to 3 in terms of adhesion between the substrate and the photochromic layer.

[0166] (Evaluation Criteria)

[0167] A: Relative to the total number of squares 100, the number of remaining squares is 100 (no peeling);

[0168] B: The number of remaining squares is greater than 96 and less than 99 relative to the total number of squares 100;

[0169] C: The number of remaining squares is greater than 90 and less than 95 relative to the total number of squares 100;

[0170] D: The number of remaining squares is 89 or less out of the total number of squares 100.

[0171]

[0172] Regarding Example 1, the above-mentioned adhesion evaluation was also performed on the spectacle lenses using substrates 3 to 6. As a result, in Example 1, the spectacle lenses using substrates 3 to 6 also confirmed that the evaluation results for both the initial adhesion and the adhesion under high temperature and high humidity were "A".

[0173] On the other hand, regarding Comparative Example 2, the evaluation result of the initial adhesion was confirmed to be "C" (number of remaining squares: 95) for the spectacle lens using substrate 4, and the evaluation result of the adhesion at high temperature and high humidity was confirmed to be "D" (number of remaining squares: 2) for the spectacle lens using substrate 5. Regarding Comparative Example 3, the evaluation results of the initial adhesion and the adhesion at high temperature and high humidity were confirmed to be "C" (number of remaining squares: 95) for the spectacle lens using substrate 6.

[0174] In addition, the adhesion at high temperature and high humidity of the spectacle lens using the substrate 4 was evaluated after immersing the lens in warm water at a temperature of 50° C. for 1 hour.

[0175] [Study on the influence of urethane (meth) acrylate mixing ratio on photochromic properties]

[0176] Figure 1 Evaluation results related to the influence of the urethane (meth)acrylate mixing ratio on the photochromic performance are shown. Figure 1 The evaluation results shown were obtained as follows.

[0177] In Example 1, in the primer-forming composition, the mixing ratio of the urethane acrylate not containing an isocyanate group (KRM 9276 manufactured by DAICEL-ALLNEX) and the urethane acrylate containing an isocyanate group (EBECRYL 4141 manufactured by DAICEL-ALLNEX) was set to KRM 9276:EBECRYL 4141 (mass ratio) = 8:2. Except for changing the mixing ratio, an eyeglass lens was produced by the method described in Example 1 using the substrate 1 as the substrate. For the produced eyeglass lenses, various performances were evaluated by the following methods (relative evaluation based on the difference with the reference lens (reference) not containing a primer). Figure 1 In the graph, the horizontal axis represents the content rate (unit: mass %) of the isocyanate group-containing urethane acrylate (EBECRYL 4141 manufactured by DAICEL-ALLNEX) relative to 100 mass % of the total urethane (meth)acrylate.

[0178] <Transmittance>

[0179] The light transmittance was determined by the following method based on JIS T7333:2005.

[0180] The transmittance of each eyeglass lens before the following color depth measurement was measured using a spectrophotometer manufactured by Otsuka Electronics. The relative evaluation results of the light transmittance (referred to as "initial transmittance") obtained from the measurement results in the wavelength range of 380nm to 780nm are shown in Figure 1 The larger the value of the initial transmittance obtained in this way is, the better the visible light transmittance under non-irradiation is.

[0181] <Color depth>

[0182] The light transmittance was determined by the following method based on JIS T7333:2005.

[0183] A xenon lamp was used as a light source to irradiate the convex surface of each eyeglass lens with light that had passed through an air mass filter for 15 minutes to color the photochromic layer. The irradiation light was performed in a manner such that the irradiance and the allowable difference in irradiance became the values ​​shown in Table 3 as specified in JIS T7333:2005. The transmittance during coloring was measured using a spectrophotometer manufactured by Otsuka Electronics. The relative evaluation results of the light transmittance (recorded as "transmittance during coloring") obtained from the measurement results within the wavelength range of 380nm to 780nm are shown in FIG. Figure 1 The smaller the value of the transmittance during coloring obtained in this way is, the higher the depth of coloring of the photochromic layer is.

[0184] [Table 3]

[0185] Wavelength range (nm) <![CDATA[Irradiance (W / m 2 )]]> <![CDATA[Permissible difference in irradiance (W / m 2 )]]> 300～340 ＜2.5 - 340～380 5.6 ±1.5 380～420 12 ±3.0 420~4 Lu 12 ±3.0 460～500 26 ±2.6

[0186] <Fading speed>

[0187] The convex surface of each eyeglass lens was irradiated with light for 15 minutes (900 seconds) through an air mass filter using a xenon lamp to color the photochromic compound in the photochromic layer. The transmittance during the coloring was measured using a spectrophotometer manufactured by Otsuka Electronics Co., Ltd. (measurement wavelength: 550 nm). The above-mentioned irradiation was performed in accordance with JIS T7333:2005 so that the irradiance and the allowable difference in irradiance reached the values ​​shown in Table 3 below. The transmittance measured in this way is referred to as "transmittance during coloring".

[0188] After the above-mentioned coloring transmittance measurement, the transmittance was measured 60 seconds after the light was stopped (hereinafter referred to as "fading 60s transmittance"). The fading speed (unit: % / second) was calculated according to the calculation formula of fading speed = [(fading 60s transmittance - coloring transmittance) / 60], and the relative evaluation results are shown in Figure 1 It can be considered that the larger the value of the fading speed obtained in this way is, the faster the fading speed is.

[0189] <Time to reach 70% transmittance>

[0190] After stopping the light used for the above-mentioned coloring transmittance measurement, the initial transmittance was set to 100%, and the time required for the transmittance of the lens to return to 70% (lens fading) was calculated. The time thus calculated was referred to as "70% transmittance reaching time", and the relative evaluation results were shown in Figure 1 It is considered that the smaller the value of the time to reach 70% transmittance obtained in this way is, the faster the fading speed is.

[0191] according to Figure 1The results shown can be considered that, considering the various properties of photochromic articles, when the total of carbamate (meth) acrylate containing isocyanate groups and carbamate (meth) acrylate not containing isocyanate groups is set to 100% by mass, the polymerizable composition for the formation of the primer layer preferably includes carbamate (meth) acrylate containing isocyanate groups 50% by mass or less, more preferably includes 40% by mass or less, and further preferably includes 30% by mass or less. On the other hand, from the viewpoint of improving the adhesion of the substrate and the photochromic layer, it is preferred that the amount of carbamate (meth) acrylate containing isocyanate groups contained in the polymerizable composition for the formation of the primer layer is large. From this point of view, when the total of carbamate (meth) acrylate containing isocyanate groups and carbamate (meth) acrylate not containing isocyanate groups is set to 100% by mass, the polymerizable composition for the formation of the primer layer can include carbamate (meth) acrylate containing isocyanate groups, such as 5% by mass or more, preferably including 10% by mass or more, more preferably including 15% by mass or more, and further preferably including 20% ​​by mass or more.

[0192] Finally, summarize the above methods.

[0193] [1] A photochromic article, which comprises:

[0194] Base material,

[0195] A primer layer formed by curing a primer layer-forming polymerizable composition, and

[0196] A photochromic layer formed by curing a (meth)acrylate polymerizable composition containing a photochromic compound,

[0197] The polymerizable composition for forming a primer layer comprises an isocyanate group-containing urethane (meth)acrylate.

[0198] Furthermore, the isocyanate group content of the composition is 2.0% by mass or more, based on 100% by mass of the total amount of the polymerizable composition for forming a primer layer.

[0199] [2] The photochromic article according to [1], wherein

[0200] The above-mentioned polymerizable composition for forming a primer layer further contains urethane (meth)acrylate not containing an isocyanate group.

[0201] [3] The photochromic article according to [2], wherein

[0202] The primer layer-forming polymerizable composition contains 10% to 50% by mass of the isocyanate group-containing urethane (meth)acrylate, assuming that the total of the isocyanate group-containing urethane (meth)acrylate and the isocyanate group-free urethane (meth)acrylate is 100% by mass.

[0203] [4] The photochromic article according to any one of [1] to [3], which is a spectacle lens.

[0204] [5] The photochromic article according to any one of [1] to [3], which is a lens for goggles.

[0205] [6] The photochromic article according to any one of [1] to [3], which is a brim portion of a sun hat.

[0206] [7] The photochromic article according to any one of [1] to [3], which is a shielding member of a helmet.

[0207] [8] A pair of glasses comprising the glasses lens described in [4].

[0208] [9] A method for manufacturing a photochromic article, the method comprising:

[0209] applying a polymerizable composition for forming a primer layer on a substrate;

[0210] The applied polymerizable composition for forming a primer layer is subjected to a curing treatment by irradiation with light to form a primer layer;

[0211] coating a (meth)acrylate polymerizable composition containing a photochromic compound on the formed primer layer; and

[0212] The applied (meth)acrylate polymerizable composition containing a photochromic compound is cured by light irradiation to form a photochromic layer.

[0213] The polymerizable composition for forming a primer layer comprises an isocyanate group-containing (methyl)urethane acrylate.

[0214] Furthermore, the isocyanate group content of the composition is 2.0% by mass or more, based on 100% by mass of the total amount of the polymerizable composition for forming a primer layer.

[0215]

[10] The method for producing a photochromic article according to [9], wherein:

[0216] The above-mentioned polymerizable composition for forming a primer layer further contains urethane (meth)acrylate not containing an isocyanate group.

[0217]

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

[10] , wherein:

[0218] The primer layer-forming polymerizable composition contains 10% by mass to 50% by mass of the isocyanate group-containing urethane (meth)acrylate, assuming that the total amount of the isocyanate group-containing urethane (meth)acrylate and the isocyanate group-free urethane (meth)acrylate is 100% by mass.

[0219]

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

[11] , wherein:

[0220] The above-mentioned photochromic article is a spectacle lens.

[0221]

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

[11] , wherein:

[0222] The photochromic article is a lens for goggles.

[0223]

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

[11] , wherein:

[0224] The photochromic article is the brim of a sun hat.

[0225]

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

[11] , wherein

[0226] The photochromic article is a shielding member of a helmet.

[0227] The various modes and aspects described in this specification may be combined in any combination of two or more.

[0228] The embodiments disclosed herein are to be considered in all respects as illustrative and not restrictive. The scope of the present invention is indicated by the claims rather than the above description, and includes all modifications within the meaning and scope equivalent to the claims.

[0229] Industrial Applicability

[0230] The present invention is useful in the technical fields of glasses, goggles, sun hats, helmets, etc.

Claims

1. A photochromic article, which comprises: Base material, A primer layer formed by curing a primer layer-forming polymerizable composition, and A photochromic layer formed by curing a (meth)acrylate polymerizable composition containing a photochromic compound, The polymerizable composition for forming a primer layer comprises an isocyanate group-containing urethane (meth)acrylate, Furthermore, the isocyanate group content of the composition is 2.0% by mass or more, based on 100% by mass of the total amount of the polymerizable composition for forming a primer layer.

2. The photochromic article according to claim 1, wherein: The polymerizable composition for forming a primer layer further includes a urethane (meth)acrylate not containing an isocyanate group.

3. The photochromic article according to claim 2, wherein: The primer layer-forming polymerizable composition contains 10% by mass to 50% by mass of the isocyanate group-containing urethane (meth)acrylate, assuming that the total of the isocyanate group-containing urethane (meth)acrylate and the isocyanate group-free urethane (meth)acrylate is 100% by mass. 4 . The photochromic article according to claim 1 , which is a spectacle lens. 5 . The photochromic article according to claim 1 , which is a lens for goggles. 6 . The photochromic article according to claim 1 , which is a brim portion of a sun hat. 7 . The photochromic article according to claim 1 , which is a shielding member of a helmet.

8. Glasses comprising the spectacle lens according to claim 4.

9. A method for manufacturing a photochromic article, the method comprising: applying a polymerizable composition for forming a primer layer on a substrate; The applied polymerizable composition for forming a primer layer is subjected to a curing treatment by irradiation with light to form a primer layer; coating a (meth)acrylate polymerizable composition containing a photochromic compound on the formed primer layer; as well as The applied (meth)acrylate polymerizable composition containing the photochromic compound is cured by light irradiation to form a photochromic layer. The polymerizable composition for forming a primer layer comprises a (methyl)urethane acrylate containing an isocyanate group. Furthermore, the isocyanate group content of the composition is 2.0% by mass or more, based on 100% by mass of the total amount of the polymerizable composition for forming a primer layer.

10. The method for producing a photochromic article according to claim 9, wherein: The polymerizable composition for forming a primer layer further includes a urethane (meth)acrylate not containing an isocyanate group.

11. The method for producing a photochromic article according to claim 10, wherein: The primer layer-forming polymerizable composition contains 10% by mass to 50% by mass of the isocyanate group-containing urethane (meth)acrylate, assuming that the total amount of the isocyanate group-containing urethane (meth)acrylate and the isocyanate group-free urethane (meth)acrylate 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 the brim of a sun hat.

15. The method for producing a photochromic article according to any one of claims 9 to 11, wherein: The photochromic article is a shielding component of a helmet.

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