Photochromic articles and eyeglasses

Abstract

To provide a photochromic article excellent in weather resistance.SOLUTION: A photochromic article comprises a polycarbonate substrate, a cured layer obtained by curing a polymerizable composition, and a photochromic layer containing a photochromic compound, in that order, and further comprises an intermediate layer adjacent to the polycarbonate substrate and the cured layer between the polycarbonate substrate and the cured layer. The cured layer and the intermediate layer contain inorganic oxide particles. The total content of the inorganic oxide particles contained in the cured layer and the inorganic oxide particles contained in the intermediate layer is more than 40.0 mass% based on the total mass of the cured layer and the intermediate layer.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to photochromic articles and glasses.

Background Art

[0002] A photochromic compound is a compound having the property (photochromism) of coloring under irradiation with light in a wavelength range having photoreactivity and fading under non-irradiation. For example, Patent Document 1 discloses a photochromic article provided with a layer containing a photochromic compound (photochromic layer) on a substrate.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] Desirable properties of the photochromic article as described above include excellent weather resistance.

[0005] One aspect of the present invention aims to provide a photochromic article having excellent weather resistance.

Means for Solving the Problems

[0006] One aspect of the present invention is a polycarbonate substrate, a cured layer obtained by curing a polymerizable composition, a photochromic layer containing a photochromic compound, having them in this order, further having an intermediate layer adjacent to the polycarbonate substrate and the cured layer between the polycarbonate substrate and the cured layer, the cured layer and the intermediate layer contain inorganic oxide particles, and A photochromic article having a total content of inorganic oxide particles in the hardened layer and inorganic oxide particles in the intermediate layer exceeding 40.0% by mass, relative to the total mass of the hardened layer and the intermediate layer. Regarding.

[0007] Patent Document 1 (Japanese Patent Publication No. 2010-33069), mentioned above, lists a polycarbonate substrate as the base material (see Claim 3 of Japanese Patent Publication No. 2010-33069, etc.). In conducting repeated studies on the weather resistance of photochromic articles, the inventors have newly discovered that photochromic articles having a polycarbonate substrate are prone to deterioration in weather resistance. Regarding this point, the inventors surmise that the plasticizer contained in polycarbonate, a thermoplastic resin, migrates from the polycarbonate substrate to the photochromic layer, causing alteration of the photochromic compound in the photochromic layer, which is the cause of the above-mentioned deterioration in weather resistance. In contrast, the above-mentioned photochromic article has an intermediate layer and a cured layer between the polycarbonate substrate and the photochromic layer, the intermediate layer containing inorganic oxide particles in the total content within the above range. This is thought to suppress the migration of components that may cause deterioration of the photochromic compound from the polycarbonate substrate to the photochromic layer. As a result, the inventors surmise that the above-mentioned photochromic article, although containing a polycarbonate substrate, can exhibit excellent weather resistance. However, the surmise described herein is not intended to limit the present invention. [Effects of the Invention]

[0008] According to one aspect of the present invention, a photochromic article with excellent weather resistance can be provided. [Modes for carrying out the invention]

[0009] [Photochromic articles] In the present invention and this specification, "photochromic article" means an article containing a photochromic compound. A photochromic article according to one aspect of the present invention described above will be described in more detail below.

[0010] <Polycarbonate base material> The substrate included in the above-mentioned photochromic article is a polycarbonate substrate. In the present invention and this specification, "polycarbonate substrate" means a substrate in which the resin constituting the substrate is polycarbonate. The polycarbonate substrate contains polycarbonate and may contain one or more additives that are normally contained in a polycarbonate substrate in any amount. The polycarbonate substrate may be undyed or dyed. For example, if the photochromic article is an eyeglass lens, the refractive index of the lens substrate may be, for example, about 1.50 to 1.75. However, the refractive index of the lens substrate is not limited to the above range, and may be within the above range or outside of it. In the present invention and this specification, refractive index means the refractive index for light with a wavelength of 500 nm. Furthermore, the lens substrate may be a lens with refractive power (so-called prescription lens) or a lens without refractive power (so-called non-prescription lens).

[0011] Eyeglass lenses can be various types of lenses, such as single-vision lenses, multi-vision lenses, and progressive lenses. The type of lens is determined by the surface shape of both sides of the lens substrate. The surface of the lens substrate may be convex, concave, or flat. In typical lens substrates and eyeglass lenses, the object-side surface is convex, and the eye-side surface is concave. However, the present invention is not limited to this. The photochromic layer can usually be provided on the object-side surface of the lens substrate, but it may also be provided on the eye-side surface.

[0012] <Total content of inorganic oxide particles> The above photochromic article comprises, in this order, a cured layer obtained by curing a polymerizable composition and a photochromic layer containing a photochromic compound. Furthermore, the above photochromic article has an intermediate layer adjacent to the polycarbonate substrate and the cured layer between the polycarbonate substrate and the cured layer. In the present invention and this specification, "adjacent" means in direct contact without other layers in between. In the above photochromic article, the cured layer and the intermediate layer each contain inorganic oxide particles, and the total content of inorganic oxide particles in the cured layer and the intermediate layer is greater than 40.0% by mass relative to the total mass of these layers (i.e., with the total mass being 100% by mass). As previously described, this is thought to contribute to suppressing the deterioration of the weather resistance of the photochromic article containing the polycarbonate substrate. In this regard, the inventors surmise that having a total content of inorganic oxide particles greater than 40.0% by mass contributes to making the laminated structure of the intermediate layer and the cured layer denser. The inventors believe that this helps to suppress the migration of components from the polycarbonate substrate to the photochromic layer. From the viewpoint of further suppressing the deterioration of weather resistance, the total content is preferably 41.0% by mass or more, more preferably 42.0% by mass or more, and even more preferably 43.0% by mass or more. Furthermore, the total content can be, for example, 60.0% by mass or less, 55.0% by mass or less, or 50.0% by mass or less. However, since a higher total content is preferable from the viewpoint of suppressing the deterioration of weather resistance, the total content can exceed the values ​​exemplified herein.

[0013] <Inorganic oxide particles> Examples of inorganic oxide particles include metal oxide particles such as tungsten oxide (WO3), zinc oxide (ZnO), silicon oxide (SiO2), aluminum oxide (Al2O3), titanium oxide (TiO2), zirconium oxide (ZrO2), tin oxide (SnO2), beryllium oxide (BeO), and antimony oxide (Sb2O5). In this invention and specification, "metal" also includes metalloids. Although the composition formulas of oxides with stoichiometric composition are shown in parentheses above, the oxides constituting the inorganic oxide particles are not limited to oxides with stoichiometric composition. The intermediate layer and the hardened layer may contain only one type of inorganic oxide particle, or two or more types of inorganic oxide particles in any mixing ratio. From the viewpoint of dispersibility in the intermediate layer and the hardened layer, the inorganic oxide particles are preferably colloidal particles.

[0014] <Middle class> In the above-described photochromic article, the intermediate layer is a layer adjacent to the polycarbonate substrate and the cured layer. That is, the intermediate layer is a layer that is in direct contact with the polycarbonate substrate and also in direct contact with the cured layer. Such an intermediate layer can, for example, serve as a so-called primer layer to improve the adhesion between the polycarbonate substrate and the cured layer.

[0015] The above-mentioned intermediate layer contains inorganic oxide particles. The inorganic oxide particle content of the above-mentioned intermediate layer is preferably more than 40.0% by mass, preferably 41.0% by mass or more, more preferably 42.0% by mass or more, and even more preferably 43.0% by mass or more, based on the total mass of the above-mentioned intermediate layer as 100% by mass. Furthermore, the above total content can be, for example, 60.0% by mass or less, 55.0% by mass or less, or 50.0% by mass or less. However, since a higher content is preferable from the viewpoint of suppressing deterioration of weather resistance, the above content can exceed the values ​​exemplified herein.

[0016] The intermediate layer can be a layer containing at least a resin. From the viewpoint of improving the adhesion between the polycarbonate substrate and the cured layer, an aqueous resin is preferable as the resin. In the present invention and this specification, "aqueous resin" refers to a resin having the property of solidifying when a composition (aqueous resin composition) containing this resin and an aqueous solvent dries. An aqueous resin layer is a layer containing an aqueous resin, and the aqueous resin layer can be formed by drying and solidifying the aqueous resin composition. Also, "aqueous solvent" refers to a solvent containing at least water.

[0017] The aqueous solvent contained in the aqueous resin composition is, for example, water, a mixed solvent of water and a polar solvent, etc., and preferably water. Also, from the viewpoints of liquid stability and film-forming property, the solid content concentration of the aqueous resin composition is preferably 1 to 62% by mass, and more preferably 5 to 38% by mass. When forming the intermediate layer from the aqueous resin composition, the aqueous resin composition contains an aqueous resin and inorganic oxide particles, and further, if necessary, can also contain additives such as an antioxidant, a dispersant, and a plasticizer. Also, inorganic oxide particles can be added to a commercially available aqueous resin composition and, if necessary, diluted with a solvent such as water, alcohol, or propylene glycol monomethyl ether and used.

[0018] Examples of the aqueous resin include an aqueous polyurethane resin, an aqueous acrylic resin, and an aqueous epoxy resin. Regarding the aqueous resin composition and its preparation method, for example, reference can be made to paragraphs 0009 to 0013 of Japanese Patent No. 3588375, paragraphs 0012 to 0021 of JP-A-8-34897, paragraphs 0010 to 0033 of JP-A-11-92653, paragraphs 0010 to 0033 of JP-A-11-92655, etc.

[0019] By directly applying the aqueous resin composition described above onto the surface of a polycarbonate substrate and drying it, an aqueous resin layer can be formed as an intermediate layer adjacent to the polycarbonate substrate. As the coating method, known coating methods such as dip coating method, spin coating method, etc. can be used. The coating conditions may be appropriately set so as to form an intermediate layer with a desired thickness. The above points are the same for the coating of the polymerizable composition described below.

[0020] The thickness of the above intermediate layer, regardless of whether it is an aqueous resin layer or not, can be, for example, 0.050 μm or more or 0.060 μm or more, and can also be, for example, 0.500 μm or less, 0.300 μm or less or 0.100 μm or less. Before applying the aqueous resin composition, one or more known surface treatments such as chemical treatment with acids, alkalis, various organic solvents, etc., physical treatment with plasma, ultraviolet rays, ozone, etc., and detergent treatment using various detergents can also be performed on the surface of the polycarbonate substrate which is the coated surface.

[0021] After applying the aqueous resin composition, by drying this composition, an aqueous resin layer can be formed as an intermediate layer. The above drying can be carried out, for example, by placing the polycarbonate substrate coated with the aqueous resin composition in an atmosphere of room temperature to 100 °C for 5 minutes to 24 hours. Note that "room temperature" refers to the ambient temperature without temperature control such as heating or cooling, and generally, it is about 15 - 25 °C, but it can vary depending on the weather and season, and thus is not limited to the above range.

[0022] <Curing layer> The above photochromic article has the above-mentioned cured layer as a layer adjacent to the above-mentioned intermediate layer. The above-mentioned cured layer contains inorganic oxide particles. The inorganic oxide particle content of the above-mentioned cured layer is preferably more than 40.0% by mass, preferably 41.0% by mass or more, more preferably 42.0% by mass or more, and even more preferably 43.0% by mass or more, based on the total mass of the above-mentioned cured layer as 100% by mass. Furthermore, the above total content can be, for example, 60.0% by mass or less, 55.0% by mass or less, or 50.0% by mass or less. However, since a higher content is preferable from the viewpoint of suppressing deterioration of weather resistance, the above content can also exceed the values ​​exemplified herein.

[0023] The above-mentioned cured layer is a layer obtained by curing a polymerizable composition. In the present invention and this specification, "polymerizable composition" refers to a composition containing a polymerizable compound, and "polymerizable compound" refers to a compound having a polymerizable group. The polymerizable composition hardens as polymerization of the polymerizable compound proceeds, thereby forming a cured layer. Such a cured layer can function, for example, as a so-called hard coat layer. As such a cured layer, an organosilicon-based cured layer is preferred.

[0024] An organosilicon-based cured layer is a cured layer obtained by curing a polymerizable composition containing an organosilicon compound. Examples of organosilicon compounds include organosilicon compounds that can generate silanol groups by polymerization treatment, and organopolysiloxanes having reactive groups such as halogen atoms and amino groups that condense with silanol groups. Other examples of organosilicon compounds include silane coupling agents having polymerizable groups such as epoxy groups, vinyl groups, allyl groups, (meth)acryloyl groups, and (meth)acryloyloxy groups, and hydrolyzable groups such as alkoxy groups. For details of polymerizable compositions containing organosilicon compounds, known technologies relating to organosilicon-based cured layers that can function as hard coat layers can be applied.

[0025] The above-mentioned cured layer can be formed by curing a polymerizable composition containing inorganic oxide particles, polymerizable compounds, etc. Specifically, the polymerizable composition can be cured by directly applying the polymerizable composition to the surface of the intermediate layer and performing light irradiation and / or heat treatment depending on the type of components contained in the composition, thereby promoting a polymerization reaction. In this way, the above-mentioned cured layer can be formed as a layer adjacent to the intermediate layer.

[0026] The thickness of the hardened layer can be, for example, 1.0 μm or more, or 2.0 μm or more, and can also be, for example, 10.0 μm or less, 8.0 μm or less, or 5.0 μm or less.

[0027] <Photochromic layer> (Photochromic compounds) As the photochromic compound, any known compound exhibiting photochromic properties can be used. The photochromic compound can, for example, exhibit photochromic properties in response to ultraviolet light. Examples of photochromic compounds include compounds with known photochromic skeletons such as flugimide compounds, spirooxazine compounds, chromene compounds, and indeno-condensed naphthopyran compounds. The photochromic compound can be used alone or in mixtures of two or more. The content of the photochromic compound can be, for example, about 0.1 to 15% by mass, based on 100% by mass of the total mass of the photochromic layer, but is not limited to this range.

[0028] (Components for forming a photochromic layer) The photochromic layer can be a cured layer obtained by curing a polymerizable composition containing one or more photochromic compounds. Regarding the various components, such as polymerizable compounds, included in the polymerizable composition for forming the photochromic layer, prior art relating to photochromic articles can be applied. In one embodiment, the photochromic layer can be a cured layer obtained by curing a polymerizable composition containing (meth)acrylate as the polymerizable compound. 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. In this invention and specification, "methacrylate" refers to a compound containing only methacryloyl groups as (meth)acryloyl groups, while a compound containing both acryloyl and methacryloyl groups as (meth)acryloyl groups is called 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. For groups with substituents, "number of carbon atoms" refers to the number of carbon atoms in the part that does not have substituents. For polymerizable compositions containing (meth)acrylate, see, for example, paragraphs 0010 to 0022 and the examples described in Japanese Patent Application Publication No. 2020-164692.

[0029] The polymerizable composition for forming a photochromic layer can be applied directly to the surface of the cured layer, or to the surface of another layer formed on top of the cured layer. Such other layers include, for example, a primer layer for improving adhesion. Such primer layers are known. The polymerizable composition applied directly to the cured layer or via another layer can be cured by subjecting it to light irradiation and / or heat treatment, depending on the type of components contained in the composition, to advance the polymerization reaction. In this way, a photochromic layer can be formed on the cured layer. The thickness of the photochromic layer can be, for example, 5 μm or more, 10 μm or more, or 20 μm or more, and can also be, for example, 80 μm or less, or 60 μm or less.

[0030] The above-mentioned photochromic article 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, anti-fogging layers, and primer layers for improving adhesion.

[0031] For example, the protective layer may be a cured layer obtained by curing a polymerizable composition containing (meth)acrylate. For details on such a protective layer, please refer to paragraphs 0009 to 0021, 0026 and the examples described in Japanese Patent Application Publication No. 2021-107909. The thickness of the protective layer is preferably 10 μm or more, more preferably 15 μm or more, even more preferably 20 μm or more, and even more preferably 25 μm or more. Furthermore, the thickness of the protective layer is preferably 45 μm or less, and more preferably 40 μm or less. The protective layer can contribute to improving the durability of the photochromic article. It can also protect the photochromic layer and suppress the occurrence of scratches on the photochromic layer until further processing (e.g., formation of another layer on the protective layer) is performed.

[0032] The hard coat layer can be provided, for example, directly on the surface of the protective layer, or on the protective layer via another layer (e.g., a primer layer). By providing a hard coat layer in addition to the protective layer, the durability of the photochromic article can be further enhanced. An example of a hard coat layer is an organosilicon-based cured layer. Organosilicon-based cured layers are generally preferred because they have excellent impact resistance. Furthermore, if an anti-reflective layer is provided, for example, the organosilicon-based cured layer is also preferred because it generally has excellent adhesion to the anti-reflective layer. For details on the hard coat layer, refer to paragraphs 0030 to 0032 and the examples described in Japanese Patent Application Publication No. 2021-107909. The thickness of the hard coat layer can be, for example, in the range of 1.0 to 10.0 μm, preferably in the range of 1.0 to 8.0 μm, and more preferably in the range of 1.0 to 5.0 μm. In one embodiment, the hard coat layer can be a thinner layer than the protective layer.

[0033] The above-mentioned photochromic articles can be optical articles, and one form of an optical article is an eyeglass lens. Other forms of optical articles include lenses for goggles, the visor portion of a sun visor, and the shield component of a helmet. By forming a photochromic layer on a substrate for these optical articles via the above-mentioned various layers, an optical article with anti-glare functionality can be obtained.

[0034] [glasses] One aspect of the present invention relates to eyeglasses equipped with spectacle lenses, which are a form of the above-described photochromic article. Details of the spectacle lenses included in these eyeglasses are as previously described. By being equipped with such spectacle lenses, these eyeglasses can, for example, exhibit an anti-glare effect like sunglasses outdoors, as the photochromic compound contained in the photochromic layer changes color when exposed to sunlight, and can restore transparency when returning indoors as the photochromic compound fades. Regarding the structure of the frames and other components of these eyeglasses, known technologies can be applied. [Examples]

[0035] 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.

[0036] [Example 1] <Preparation of an aqueous resin composition for forming an intermediate layer> A water-based resin composition for intermediate layer formation was prepared using a commercially available aqueous urethane (HA50C, manufactured by Nikka Chemical Co., Ltd.) and a commercially available inorganic oxide particle (colloidal particle) dispersion (HZ407MH, manufactured by Nissan Chemical Corporation) as follows. The above-mentioned HA50C from Nikka Chemical Co., Ltd. is an aqueous urethane resin composition (aqueous solution) containing water as a solvent. The above-mentioned HZ407MH from Nissan Chemical Corporation is a dispersion of inorganic oxide particles (colloidal particles) containing tin oxide, zirconium oxide, antimony oxide, silicon oxide, and tungsten oxide, and in addition to the inorganic oxide particles, it contains water, methanol, and diisobutylamine (inorganic oxide particle concentration: 40% by mass). In a glass container equipped with a magnetic stirrer, 23 parts by mass of water, 72 parts by mass of ethanol, 1.5 parts by mass of HZ407MH, 3.5 parts by mass of HA50C, and 0.05 parts by mass of a silicone-based surfactant were added and thoroughly mixed. After stirring at room temperature for 24 hours, the mixture was filtered to prepare a polymerizable composition for forming an intermediate layer. In the above-mentioned aqueous resin composition for forming the intermediate layer, the inorganic oxide particle content is 46.2% by mass, with the total amount of components excluding the solvent (i.e., solid content) being 100% by mass. Therefore, the inorganic oxide particle content of the intermediate layer formed from the above-mentioned aqueous resin composition for forming the intermediate layer is 46.2% by mass.

[0037] <Preparation of polymerizable composition for hardened layer formation> Using a commercially available silane coupling agent (KBM-403, γ-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Silicone Co., Ltd.) and a commercially available inorganic oxide particle (colloidal particle) dispersion (SL-50A, manufactured by JGC Catalysts & Chemicals Co., Ltd.), an aqueous resin composition for intermediate layer formation was prepared as follows. In a glass container equipped with a magnetic stirrer, 16 parts by mass of KBM-403, 20 parts by mass of methanol, and 43 parts by mass of SL-50A (solids content 30% by mass) were added and thoroughly mixed, and stirred at room temperature for 24 hours. Next, 14 parts by mass of propylene glycol monomethyl ether, 5 parts by mass of diacetone alcohol, 0.6 parts by mass of aluminum acetylacetonate as a curing agent, and 0.1 parts by mass of a silicone-based surfactant were added, and after thorough stirring, the mixture was filtered to prepare a polymerizable composition for forming a cured layer. In the polymerizable composition for forming a hardened layer described above, the inorganic oxide particle content is 44.1% by mass, with the total amount of components excluding the solvent (i.e., solid content) being 100% by mass. Therefore, the inorganic oxide particle content of the hardened layer formed from the polymerizable composition for forming a hardened layer is 44.1% by mass.

[0038] <Preparation of polymerizable composition 1 for primer layer formation> In a plastic container, 15 parts by mass of polyisocyanate (Colonate 2715, manufactured by Tosoh Corporation), 85 parts by mass of a mixture of acrylic ester and epoxy ester, 0.02 parts by mass of a photopolymerization initiator (bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide), and 0.05 parts by mass of a silicone-based surfactant were mixed, and then the mixture was stirred and defoamed using a rotation-and-revolving stirring and defoaming apparatus. In this way, polymerizable composition 1 for primer layer formation was prepared.

[0039] <Preparation of polymerizable composition for photochromic layer formation> In a plastic container, a (meth)acrylate mixture was prepared by mixing 85% by mass of polyethylene glycol dimethacrylate (acyclic bifunctional (meth)acrylate) and 15% by mass of tricyclodecanedimethanol dimethacrylate (alicyclic bifunctional (meth)acrylate) with a total of 100% by mass of (meth)acrylates. A (meth)acrylate mixture was then mixed with a photochromic compound (an indeno-condensed naphthopyran compound represented by the structural formula described in U.S. Patent No. 5,645,767), a photopolymerization initiator (bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide), a photostabilizer (bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate), and an antioxidant (bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][ethylenebis(oxyethylene)]), and then stirred and defoamed using a rotation-and-revolving stirring and defoaming apparatus. Using the above method, polymerizable compositions having the compositions shown in Table 1 below were prepared.

[0040] [Table 1]

[0041] <Preparation of polymerizable composition for forming a protective layer> In a plastic container, 95 parts by mass of tricyclodecanedimethanol diacrylate (a cyclic bifunctional (meth)acrylate), 4.7 parts by mass of a photopolymerization initiator (1-hydroxycyclohexylphenyl ketone), 0.3 parts by mass of an ultraviolet absorber (hydroxyphenyl triazine), and 0.1 parts by mass of a silicone-based surfactant were mixed, and then the mixture was stirred and defoamed using a rotation-and-revolving stirring and defoaming apparatus. In this way, a polymerizable composition for forming a protective layer was prepared.

[0042] <Preparation of polymerizable composition 2 for primer layer formation> In a glass container equipped with a magnetic stirrer, 67 parts by mass of water-based urethane resin (HUX232, manufactured by ADEKA), 4.2 parts by mass of water, 13 parts by mass of methanol, 13 parts by mass of propylene glycol monomethyl ether, and 0.4 parts by mass of a silicone-based surfactant were added and thoroughly mixed, and stirred at room temperature for 24 hours. Subsequently, the mixture was filtered to prepare polymerizable composition 2 for primer layer formation.

[0043] <Preparation of polymerizable composition for hard coat layer formation> In a glass container equipped with a magnetic stirrer, 16 parts by mass of γ-glycidoxypropyltrimethoxysilane, 20 parts by mass of methanol, and 43 parts by mass of aqueous-dispersed colloidal silica (30% solids) were added and thoroughly mixed, and stirred at room temperature for 24 hours. Next, 14 parts by mass of propylene glycol monomethyl ether, 5 parts by mass of diacetone alcohol, 0.6 parts by mass of aluminum acetylacetonate as a curing agent, and 0.1 parts by mass of a silicone-based surfactant were added, and after thorough stirring, the mixture was filtered to prepare a polymerizable composition for hard coat layer formation.

[0044] <Eyeglass lens manufacturing> (Formation of the intermediate layer) A plastic lens substrate (polycarbonate substrate) 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, an intermediate layer was formed on both sides of the plastic lens substrate. Specifically, the above-mentioned aqueous resin composition for forming the intermediate layer (liquid temperature 15°C) was applied to both sides of the plastic lens substrate by dip coating in an environment of 23°C and 30% relative humidity, and then heated and cured in a heat treatment furnace at a furnace temperature of 90°C for 20 minutes, thereby forming an intermediate layer with a thickness of 0.085 μm on each side of the plastic lens substrate.

[0045] (Formation of a hardened layer) The polymerizable composition for forming the hardened layer was applied to the surface of the intermediate layer by a dip-coat method. Subsequently, a hardened layer with a thickness of 3.3 μm was formed by heating and curing in a heat treatment furnace at a furnace temperature of 100°C for 60 minutes.

[0046] (Formation of photochromic layer) A polymerizable composition 1 for primer layer formation was applied to the surface of the hardened layer by spin coating to form a coated layer. Ultraviolet light (wavelength 405 nm) was irradiated onto the surface of this coated layer in a nitrogen atmosphere (oxygen concentration 500 ppm or less) to cure the coated layer and form a primer layer 1. The thickness of the formed primer layer 1 was 7.5 μm. A polymerizable composition for photochromic layer formation was applied to the surface of the primer layer 1 by spin coating to form a coated layer. The spin coating was performed according to the method described in Japanese Patent Application Publication No. 2005-218994. Subsequently, the coated layer was irradiated with ultraviolet light (wavelength 405 nm) in a nitrogen atmosphere (oxygen concentration 500 ppm or less) to cure the coated layer and form a photochromic layer. The thickness of the formed photochromic layer was 40 μm.

[0047] (Formation of a protective layer) The polymerizable composition for forming the protective layer was applied to the surface of the photochromic layer by spin coating to form a coating layer. Ultraviolet light (wavelength 405 nm) was irradiated onto the surface of this coating layer in a nitrogen atmosphere (oxygen concentration 500 ppm or less) to cure the coating layer and form a protective layer. The thickness of the formed protective layer was 38 μm.

[0048] (Formation of the hard coat layer) The polymerizable composition 2 for primer layer formation was applied to the surface of the protective layer by a dip-coat method. Subsequently, a primer layer 2 with a thickness of 0.9 μm was formed by heating and curing in a heat treatment furnace at a furnace temperature of 90°C for 20 minutes. After the formation of the primer layer 2 described above, the polymerizable composition for hard coat layer formation described above was applied by dip coating. Subsequently, a hard coat layer (organosilicon-based cured layer) with a thickness of 3.2 μm was formed by heating and curing in a heat treatment furnace at a furnace temperature of 100°C for 60 minutes.

[0049] In the eyeglass lens thus produced, the total content of inorganic oxide particles contained in the hardened layer and the intermediate layer, relative to the total mass of the hardened layer and the intermediate layer, is 44.2% by mass.

[0050] [Comparative Example 1] Except for the fact that the intermediate layer forming composition was prepared without the addition of inorganic oxide particles, the thickness of the intermediate layer was set to 0.9 μm, and the thickness of the hardened layer adjacent to the intermediate layer was set to 3.2 μm, an eyeglass lens was manufactured by the method described for Example 1. In the eyeglass lens thus manufactured, the total content of inorganic oxide particles contained in the hardened layer and inorganic oxide particles contained in the intermediate layer (in Comparative Example 1, the intermediate layer did not contain inorganic oxide particles) relative to the total mass of the hardened layer and the intermediate layer was 34.4% by mass.

[0051] [Weather resistance evaluation] The weather resistance of each spectacle lens in Example 1 and Comparative Example 1 was evaluated using the weather resistance test method described in ISO 8980-3:2013. The weather resistance evaluation result was determined as the change in transmittance during color development (hereinafter referred to as ΔDarkness), and a smaller ΔDarkness value indicates superior weather resistance. As a result of the evaluation, when expressed as a relative value with Comparative Example 1's ΔDarkness set to 100%, the ΔDarkness of Example 1 was 92.8%. From this result, it can be confirmed that the spectacle lens of Example 1 has superior weather resistance compared to the spectacle lens of Comparative Example 1.

[0052] The same polycarbonate substrate used in Example 1 and Comparative Example 1 was subjected to UV irradiation and heat treatment, and then analyzed by TOF-SIMS (Time-of-Flight Secondary Ion Mass Spectrometry). As a result of the analysis, isodecyl di(phenyl)phosphate was detected on the surface of the polycarbonate substrate. Isodecyl di(phenyl)phosphate is a compound used as a thermoplastic agent when injection molding polycarbonate substrates. Chemically, it has highly reactive phosphate and phenyl groups and is a highly reactive compound that is activated by UV irradiation to generate radicals. It is thought that this highly reactive compound bleeds out onto the polycarbonate substrate, migrates to the photochromic layer, and alters the photochromic compound in the photochromic layer, causing a decrease in the weather resistance of the photochromic article containing the polycarbonate substrate. In contrast, in Example 1, the reduction in weather resistance was suppressed by providing the above-mentioned intermediate layer and the above-mentioned cured layer between the polycarbonate substrate and the photochromic layer.

[0053] Finally, we will summarize each of the aforementioned aspects.

[0054] [1] Polycarbonate substrate and A cured layer obtained by curing a polymerizable composition, A photochromic layer containing a photochromic compound, It has them in this order, The above polycarbonate substrate and the above cured layer further have an intermediate layer adjacent to the polycarbonate substrate and the above cured layer. The above-mentioned cured layer and the above-mentioned intermediate layer contain inorganic oxide particles, A photochromic article in which the total content of inorganic oxide particles contained in the hardened layer and the intermediate layer exceeds 40.0% by mass, relative to the total mass of the hardened layer and the intermediate layer. [2] The photochromic article according to [1], wherein the inorganic oxide particle content of the hardened layer is greater than 40.0% by mass. [3] The photochromic article according to [1] or [2], wherein the inorganic oxide particle content of the intermediate layer is greater than 40.0% by mass. [4] The photochromic article according to any one of [1] to [3], wherein the intermediate layer is a water-based resin layer. [5] The inorganic oxide particle content of the above-mentioned hardened layer is more than 40.0% by mass, The inorganic oxide particle content of the above intermediate layer is more than 40.0% by mass, and The above-mentioned intermediate layer is a water-based resin layer, the photochromic article as described in [1]. [6] A photochromic article described in any of [1] to [5], which is an eyeglass lens. [7] A photochromic article described in any of [1] to [5], which is a lens for goggles. [8] The visor portion of a sun visor, a photochromic article as described in any of [1] to [5]. [9] A photochromic article according to any of [1] to [5], which is a shield component of a helmet. Eyeglasses equipped with the spectacle lenses described in

[10] [6].

[0055] The various embodiments and forms described herein can be combined in any combination of two or more.

[0056] 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]

[0057] This invention is useful in the technical fields of eyeglasses, goggles, sun visors, helmets, and the like.

Claims

1. Polycarbonate base material, A cured layer obtained by curing a polymerizable composition, A photochromic layer containing a photochromic compound, It has them in this order, The polycarbonate substrate and the cured layer further have an intermediate layer adjacent to the polycarbonate substrate and the cured layer. The cured layer and the intermediate layer contain inorganic oxide particles, A photochromic article in which the total content of inorganic oxide particles contained in the hardened layer and the inorganic oxide particles contained in the intermediate layer is greater than 40.0% by mass, relative to the total mass of the hardened layer and the intermediate layer.

2. The photochromic article according to claim 1, wherein the inorganic oxide particle content of the cured layer is more than 40.0% by mass.

3. The photochromic article according to claim 1, wherein the inorganic oxide particle content of the intermediate layer is more than 40.0% by mass.

4. The photochromic article according to claim 1, wherein the intermediate layer is a water-based resin layer.

5. The inorganic oxide particle content of the hardened layer is more than 40.0% by mass. The inorganic oxide particle content of the intermediate layer is more than 40.0% by mass, and The photochromic article according to claim 1, wherein the intermediate layer is a water-based resin layer.

6. A photochromic article according to any one of claims 1 to 5, which is an eyeglass lens.

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

8. A photochromic article according to any one of claims 1 to 5, which is the visor portion of a sun visor.

9. A photochromic article according to any one of claims 1 to 5, which is a shield member for a helmet.

10. Eyeglasses equipped with the eyeglass lenses described in claim 6.

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