TW202003787A - Electrochromic photochromic optical article - Google Patents

Abstract

Provided is an optical article having two types of chromic characteristics including electrochromic characteristics and photochromic characteristics. Through the present invention, it is possible to provide an optical article having two types of chromic characteristics including electrochromic characteristics and photochromic characteristics, wherein, through use of a chromene compound as a photochromic compound, the optical article exhibits excellent photochromic characteristics, and when electrochromic characteristics are combined therewith, the optical article exhibits adequate coloring density even at high temperature.

Description

Electrochromic photochromic optical items

The present invention relates to an optical article having two types of color-changing properties, electrochromic properties and photochromic properties.

In recent years, focusing on the United States, photochromic sunglasses with anti-glare properties and photochromic properties, and electrochromic with anti-glare properties and electrochromic properties Sunglasses are gaining popularity rapidly. The penetration rate of the lenses of photochromic sunglasses changes according to the surrounding brightness (the amount of ultraviolet rays), and the anti-glare property can be adjusted. In addition, the application of voltage to the electrochromic sunglasses will change the penetration rate of the lens, so the anti-glare property can be adjusted according to the user's expectation.

As a method of manufacturing a photochromic lens, for example, a method of molding a photochromic polymerizable composition prepared by blending a photochromic compound in a polymerizable composition into a lens shape; using a photochromic polymerizable composition As an adhesive (adhesive), a method of joining a pair of lenses, etc. (for example, refer to Patent Documents 1 to 4). On the other hand, as the electrochromic lens, a lens using various electrochromic elements is known (see Patent Document 5 and Patent Document 6).

However, the photochromic lenses manufactured by these methods have the following problems to be solved: when the temperature is high, the color density will be reduced. In particular, since the intensity of ultraviolet rays is strong in summer, it is desired to increase the color development density, but there is a problem that the color development density may be reduced due to high temperature. In addition, although the electrochromic lens can change the coloring state by applying a voltage, in order to maintain the coloring state for a long time, it is necessary to repeatedly apply the voltage multiple times. As a result, battery exchange and charging must be frequently performed. [Prior Technical Literature] (Patent Literature)

Patent Literature 1: International Publication No. 2014/136804 Patent Document 2: Japanese Patent Laid-Open No. 2007-138186 Patent Literature 3: International Publication No. 2004/050775 Patent Document 4: Japanese Patent Application Publication No. 2012-052091 Patent Literature 5: Japanese Patent Laid-Open No. 53-033161 Patent Document 6: Japanese Patent No. 6171637 Patent Document 7: Japanese Patent Laid-Open No. 01-209423

[Problems to be solved by the invention] In order to solve the above-mentioned problems to be solved, a spectacle lens having: a photochromic layer using a spiropyran compound; and an electrochromic element (refer to Patent Document 7). However, according to the research of the present inventors, even the method described in Patent Document 7, there is still room for improvement from the viewpoint of sufficient color development density at high temperatures required in recent years. Therefore, an object of the present invention is to provide an optical article having two types of color-changing properties, electrochromic properties and photochromic properties, which exhibits sufficient color density even at high temperatures. [Technical means to solve the problem]

In order to solve the above-mentioned problems to be solved, the present inventors are devoted to the study of the composition of the photochromic compound and the resin that disperses the photochromic compound. As a result, it was found that by using a chromene compound as a photochromic compound, the optical article exhibits excellent photochromic properties, that is, it exhibits a sufficient color density even at a high temperature. In addition, it has been found that, when combined with the electrochromic layer, the above-mentioned configuration having photochromic properties can be suitably used, and the present invention has been completed.

In other words, the optical article of the present invention includes: an electrochromic layer having electrochromic properties; and a photochromic layer having photochromic properties; and the photochromic layer includes a benzopiperan compound. [effect]

According to the present invention, it is possible to provide an optical article having two types of color-changing characteristics, electrochromic characteristics and photochromic characteristics, which exhibits a sufficient color density even at a high temperature.

>Optical items> The optical article of this embodiment has two types of color-changing characteristics, electrochromic characteristics and photochromic characteristics.

An aspect of the optical article of this embodiment is shown in Fig. 1. The optical article 1 shown in FIG. 1 includes: a photochromic layer 2 that exhibits photochromic properties; an electrochromic laminate 3 including an electrochromic layer that exhibits electrochromic properties; and, an optical base material 4. When the optical article 1 is used as an optical lens, it is preferable that the side on which the photochromic layer 2 is formed be the incident side where light such as sunlight enters, and the same is configured on the side where the electrochromic is formed The side of the laminated body 3 is made the light emitting side. In addition, FIG. 1 is a schematic view, and the shape of the optical article of this embodiment is not limited to this example. The structure of the optical article of this embodiment will be described in detail below.

>Electrochromic layer> In the optical article of the present embodiment, as the electrochromic layer having electrochromic properties, a conventional electrochromic layer can be used without particular limitations, and it has the following properties: the color tone of a substance is performed by applying voltage The electrochemical redox reaction changes reversibly. In addition, the above-mentioned electrochromic layer is formed on the electrode layer to form an electrochromic element as an electrochemical cell. Furthermore, the electrochromic element is laminated on at least one optical sheet to be used as an electrochromic laminate. The details are described below.

>Electrochromic laminate> The electrochromic laminate is a laminate formed by laminating electrochromic elements on at least one optical sheet. Preferably, the electrochromic element is disposed between two opposing optical sheets.

[Optical Sheet] As the optical sheet, a resin-made sheet having translucency can be suitably used. Examples of the material of the optical sheet include polycarbonate resin, polyester resin, cellulose resin, polyamide resin, (meth)acrylic resin, urethane resin, and urethane (urea) resin. , Epoxy resin, polyimide resin, polyolefin resin, polyvinyl alcohol resin, etc. Among them, polycarbonate resins, polyamide resins, cellulose resins (such as triethyl cellulose), and polyvinyl alcohol resins are particularly preferred because of their good adhesion.

The film thickness of the optical sheet is preferably 20 to 1000 μm, and preferably 50 to 500 μm from the viewpoint of processability of the obtained electrochromic laminate. In addition, the surface (both sides) of the optical sheet can be subjected to the following treatments: chemical treatment using chemical solutions such as alkaline solutions and acidic solutions; physical treatment such as grinding treatment, corona discharge treatment, plasma discharge treatment, UV ozone treatment, etc. Sexual surface treatment. Moreover, these processes can combine a plurality of kinds.

In addition, a coating layer such as an adhesive layer (adhesive layer) or a hard coat layer can be formed on the surface (both sides) of the optical sheet. Examples of the material for forming the adhesive layer or the coating film layer are not particularly limited, and examples thereof include moisture-curable polyurethane, polyisocyanate-polyester-based two-component coating liquid, and polyisocyanate-polyether-based diisocyanate. Liquid type coating liquid, polyisocyanate-polyacrylic two-component type coating liquid, polyisocyanate-polyurethane elastic system two-component type coating liquid, epoxy type coating liquid, epoxy-polyurethane type two-component type Coating liquid, acrylic coating liquid, polyester coating liquid, polyurethane urea one-component coating liquid, water-dispersible polyurethane coating liquid, vinyl acetate coating liquid, silane coupling agent Coating liquid, etc.

[Electrochromic element] The electrochromic element is formed by forming an electrochromic layer on an electrode layer and using the above electrode layer as a working electrode to form an electrochemical cell. Preferably: a laminate having an electrode layer/electrochromic layer/electrolyte layer or ion conductive layer/electrode layer; or an electrode layer/reduced color electrochromic layer/electrolyte layer or ion conductive layer/reversible Laminated body of electrolytic oxide layer/electrode layer.

[Electrochromic layer] As the electrochromic layer, it is possible to use a structure in which the electrochromic material is supported on conductive or semiconductor fine particles. For example, a structure can be used in which the above-mentioned fine particles are attached to the surface of the electrode, and phosphonic acid or an organic electrochromic compound having a polar group such as a carboxyl group or a silanol group is adsorbed on the surface of the above-mentioned fine particles. For example: when using a 5-layer structure electrochromic element that becomes an electrode layer/reduced color electrochromic layer/electrolyte layer or ion conductive layer/reversible electrolytic oxidation layer/electrode layer, the reduced electrochromic layer Preferably, tungsten oxide or molybdenum oxide is used, and the reversible electrolytic oxide layer preferably uses oxides or hydroxides of iridium, nickel, chromium, vanadium, ruthenium, rhodium, and the like.

(Electrochromic material) The electrochromic layer contains electrochromic materials. The electrochromic material may be any one of inorganic electrochromic compounds and organic electrochromic compounds. In addition, conventional conductive polymers that exhibit electrochromism can be used.

Examples of inorganic electrochromic compounds include tungsten oxide, molybdenum oxide, iridium oxide, titanium oxide, vanadium oxide, indium oxide, nickel oxide, Prussian blue, and Prussian blue-like compounds. Examples of organic electrochromic compounds include viologen compounds, dipyridine compounds, rare earth phthalocyanine compounds, styrene compounds, tetrathiafulvalene compounds, and azobenzene compounds. Compounds, anthraquinone compounds, diarylvinyl compounds, dihydropyrene compounds, styrylspiperan compounds, spirooxazine compounds, spirothiopyran compounds, thioindigo compounds Compounds, terephthalic acid compounds, triphenylmethane compounds, triphenylamine compounds, naphthopyran compounds, pyrazoline compounds, phenazine compounds, phenylenediamine compounds, Phenoxazine-based compounds, phenothiazine-based compounds, phthalocyanine-based compounds, fluoran-based compounds, fluoran-based compounds, fulgide-based compounds, benzopiperan-based compounds, Metallocene compounds, etc. Examples of conductive polymers include polypyrrole, polythiophene, poly(3-phenylthiophene), poly(4,4′-bis(2-thienyl)biphenyl), and polyisothianaphthene ), polyaniline, or derivatives thereof.

[Electrolyte layer, electrochromic element] The electrolyte layer is a solid electrolyte layer, and it is possible to use a film made by mixing an electrolyte in a photocurable resin or a thermosetting resin. As the electrolyte, a liquid electrolyte such as an ionic liquid or an electrolyte in which a solid electrolyte is dissolved in a solvent can be used. As a liquid electrolyte such as an ionic liquid, for example, an ionic liquid composed of a cationic component and an anionic component can be used; as a cationic component, for example, an aliphatic quaternary ammonium such as an imidazole derivative, a pyridinium salt derivative, and a tetraalkylammonium compounds and the like; as an anionic component, for example, ^{_{BF 4 -, CF 3 SO 3}} -, PF 4 -, (CF 3 SO 2) 2 N -, B (CN 4) - and the like. As the solid electrolyte, for example: inorganic ion salts such as alkali metal salts and alkaline earth metal salts; quaternary ammonium salts; acid and alkali supporting salts. Specifically, for example, LiClO ₄ , LiBF ₄ , LiAsF ₆ , LiPF ₆ , LiCF ₃ SO ₃ , LiCF ₃ COO, KCl, NaBF ₄ , NaSCN, KBF ₄ , Mg(ClO ₄ ) ₂ , Mg(BF ₄ ) _2nd class.

As the photocurable resin or thermosetting resin for forming the electrolyte layer, conventional acrylic resins, urethane resins, epoxy resins, vinyl chloride resins, olefin resins, melamine resins, phenol resins, and the like can be used. In addition, from the viewpoint of easy control of the thickness of the obtained electrolyte layer, oxides such as silicon, aluminum, titanium, zinc, tin, etc. can be added to the electrolyte layer.

[Ion conductive layer, electrochromic element] As the ion conductive layer, for example, ion conductive materials such as silicon oxide, tantalum oxide, titanium oxide, aluminum oxide, niobium oxide, zirconium oxide, hafnium oxide, lanthanum oxide, and magnesium fluoride are used. Furthermore, an ion conductive layer can be produced by mixing and forming an ion conductive substance blended with the photo-curable resin or thermosetting resin to form a film.

[Electrode layer, electrochromic element] As the material of the electrode layer, a transparent conductive oxide material can be suitably used. For example: indium oxide doped with tin, tin oxide doped with fluorine, tin oxide doped with antimony, etc. Among these, an inorganic material containing any one of indium oxide, tin oxide, and zinc oxide formed by vacuum film formation is preferable. Furthermore, it is only necessary to make a film composed of this inorganic material into an electrode layer. Indium oxide, tin oxide, and zinc oxide are materials that can be easily formed by sputtering, and are materials that can obtain good transparency and conductivity. Among these, InSnO, GaZnO, SnO, In ₂ O ₃ , ZnO, and InZnO are particularly preferred. In addition, conductive metal thin films containing gold, silver, copper, and aluminum with transparency; carbon films such as carbon nanotubes and graphene; and conductive metals, conductive carbon, and conductive oxides can also be used. Mesh electrode; or these composite layers. Furthermore, the material for forming these electrode layers can be used by stacking two or more layers.

[Manufacturing method of electrochromic element and laminate] The manufacturing method of the electrochromic element is not particularly limited, as long as the electrochromic layer, the electrolyte layer, the ion conductive layer, the electrode layer, etc. are laminated by a conventional method. The electrochromic element can be manufactured by, for example, the following methods: vacuum evaporation method, sputtering method, chemical vapor deposition (CVD) method, sol method, chemical precipitation method, electrolysis method, etc. The color-changing layer is laminated on the electrode layer. In addition, the electrochromic laminate can also be manufactured by pasting an optical sheet on at least one side, preferably both sides, of the electrochromic element obtained by the above method. The method of pasting the optical sheet and the electrochromic element is not particularly limited, and a conventional method can be used.

>Electrochromic optical substrate> The electrochromic optical base material is configured by bonding an electrochromic laminate having optical sheets on both sides of the electrochromic element to the optical base material. As the optical base material, it is preferably used from polyester resin, polyamide resin, allyl resin, (meth)acrylic resin, urethane resin, urethane resin, thiourethane resin, thio Selected resin among epoxy resin and polycarbonate resin. In addition, the optical sheet on one side of the electrochromic element can also be formed to be thick and regarded as an optical base material. In addition, when the optical article of this embodiment is used as an optical lens, the optical base material is processed into a lens-like spherical shape for use.

[Method of bonding electrochromic laminate and optical substrate] The bonding method of the optical base material and the electrochromic laminate is not particularly limited, and the following method can be used, for example. When the resin used to form the optical base material is a thermoplastic resin, for example, a method of arranging the electrochromic laminate in a mold and injection-molding the thermoplastic resin used to form the optical base material on the back surface thereof. In addition, when the resin used to form the optical base material is a thermosetting resin, the following method may be mentioned, for example. In other words, a plastic mold is produced by one electrochromic laminate and one glass plate, and the plastic mold has a space for filling a thermosetting resin that is an optical base material with a monomer. Then, for example, a method of filling the above-mentioned space with a monomer for thermosetting resin, and performing thermosetting and/or photosetting, and then releasing the glass plate. Alternatively, the electrochromic laminate is arranged between two glass plates with a space therebetween to form a mold. Then, for example, a method of filling the above-mentioned space with a monomer for thermosetting resin and performing thermosetting and/or photocuring, and then releasing the two glass plates.

Furthermore, the electrochromic laminate and the optical base material may also be in a state where the two are not directly joined. For example, when used in optical lens applications such as spectacle lenses, the optical article in this embodiment only needs to form a photochromic layer/electrochromic laminate or electrochromic layer in sequence from the incident side of light such as sunlight The laminate/photochromic layer may be sufficient. Therefore, the optical substrate may be bonded to the photochromic layer, and may be an electrochromic laminate/photochromic layer/optical substrate in this order. Among them, considering the formability and function of the obtained optical article, it is preferable to adopt an aspect of the optical article in which the following layers are sequentially formed from the incident side of light rays such as sunlight: photochromic layer /Electrochromic laminate/Optical substrate.

[Processing method of electrochromic laminate] When the optical article of this embodiment is used as an optical lens, the electrochromic laminate can also be processed into a lens by performing a thermal bending process before being integrated with an optical base material that has been processed into a lens-like spherical shape Spherical shape (manufacturing and processing sheet). In addition, the mold can be demolded into a desired shape before performing the hot bending process. Examples of the above-mentioned hot bending processing method include hot pressing processing, press processing, reduced pressure suction processing, and the like. In addition, pressure processing and reduced-pressure suction processing can also be used in combination.

>Photochromic layer> In the optical article of this embodiment, the photochromic property is achieved by using a benzopiperan compound as the photochromic compound. Thereby, in an optical article formed by laminating a layer having photochromic properties and a layer having electrochromic properties, an excellent effect, that is, an excellent color development density at a high temperature is exhibited. As the photochromic layer having photochromic properties, it is preferable to use a synthetic resin (layer) containing a benzopiperan compound as a photochromic compound.

[Photochromic Compound] From the viewpoint of improving the photochromic characteristics (high durability, high color rendering density, etc.) in the optical article, the photochromic compound is a benzopiperan compound. In addition, the benzopiperan compound is also excellent in that it is easy to adjust a colorful hue and when combined with an electrochromic property to a desired color rendering hue. In recent years, the requirements for color development hue include, for example, general gray, brown, neutral gray, brown with intense red, and hue such as green, purple, and blue-violet. In addition, as long as it contains a benzopiperan compound as a photochromic compound, it may contain a photochromic compound other than a benzopiperan compound such as a spermic anhydride compound. Among them, it is preferable to contain only the benzopiperan compound.

(Benzopran compound) The benzopiperan compound is not particularly limited, and conventional benzopiperan compounds can be used. For example, the benzopiperan compounds described in the following are mentioned: Japanese Patent No. 3471073, Japanese Patent Laid-Open No. 08-157467, Japanese Patent Laid-Open No. 08-176139, Japanese Patent Laid-Open No. 08-295690, Japan Japanese Patent Laid-Open No. 09-124645, Japanese Patent Laid-Open No. 09-218301, Japanese Patent No. 3982770, Japanese Patent Laid-Open No. 11-279171, Japanese Patent Laid-Open No. 11-286484, Japanese Patent Laid-Open No. 11-322739 Gazette, Japanese Patent No. 4301621, Japanese Patent Laid-Open No. 2000-219686, Japanese Patent Laid-Open No. 2000-219687, Japanese Patent Laid-Open No. 2000-229972, Japanese Patent Laid-Open No. 2000-229973, Japanese Patent Laid-Open 2000 -229974, JP 2000-229975, JP 2000-229976, JP 2000-256347, JP 4256985, JP 4157225, JP 4157225, JP JP 2000-344761, JP 4157227, JP 3801386, JP 2001-011067, JP 4118458, JP 2001-031670, Japan National Patent No. 4157239, Japanese Patent No. 4157245, Japanese Patent No. 3522189, International Publication No. 00/71544, Japanese Patent No. 4158881, Japanese Patent Laid-Open No. 2003-277381, Japan Japanese Patent Laid-Open No. 2005-289812, Japanese Patent No. 4195615, Japanese Patent No. 4369754, Japanese Patent No. 4244962, Japanese Patent No. 4244981, Japanese Patent No. 4663023, Japanese Patent No. 5052355, Japanese Unexamined Patent Publication No. 2008-074832, Japanese Unexamined Patent Publication No. 2009-057300, Japanese Unexamined Patent Publication No. 2009-067680, Japanese Unexamined Patent Publication No. 2009-067754, Japanese Unexamined Patent Publication No. 2009-120536 , Japanese Patent No. 5441895, Japanese Patent No. 5606441, Japanese Patent No. 5685541, Japanese Patent No. 6031035, Japanese Patent No. 3029460, Japanese Patent No. 4550281, Japan Chinese Patent No. 4105436, US Patent No. 5568501, etc.

Among these benzopiperan compounds, from the viewpoint of photochromic properties such as color development concentration, initial coloration, durability, and fading speed, it is preferable to use one or more types having the following formula (I) Indeno[2,1-f]naphtho[1,2-b]indenonaphthopyran compound of indan skeleton.

此處，R¹ 為從氫原子、碳數1～6個的烷氧基、N,N-二甲基胺基、N,N-二乙基胺基、N-嗎啉基(morpholino)、2,6-二甲基(N-嗎啉基)、N-哌啶基(piperidino)、2,6-二甲基(N-哌啶基)之中選出的基，R² 為從氫原子、碳數1～6個的烷氧基、N,N-二甲基胺基、N,N-二乙基胺基、N,N-二苯基胺基、N-嗎啉基、2,6-二甲基(N-嗎啉基)、N-哌啶基、2,6-二甲基(N-哌啶基)之中選出的基，R³ 為從羥基、胺基、甲基、甲氧基、4-甲氧基苯基、2,4-二甲氧基苯基、4-(N,N-二甲基胺基)苯基、4-(N-嗎啉基)苯基之中選出的基，R⁴ 為從羥基、胺基、甲氧基、4-甲氧基苯基、2,4-二甲氧基苯基、4-(N,N-二甲基胺基)苯基、4-(N-嗎啉基)苯基、4-(N-嗎啉基)苯基、2,4-二甲基苯硫基之中選出的基，此處，R³ 與R⁴ 可以－S－CZ₂ －O－基(Z＝甲基、乙基、丙基、異丙基)來鍵結在一起，R⁵ 為從氫原子、甲基、甲氧基、氰基、鹵烷基之中選出的基，R⁶ 為從－(CH₂ )₅ －、－(CH₂ )₉ －、－C(CH₃ )₂ CH₂ C(CH₃ )₂ －、－C(CH₃ )₂ CH₂ CH₂ C(CH₃ )₂ －、－CCH₂ C(C₂ H₅ )₂ CCH₂ －、或由下述式(III)之中選出的基。

Among these indenonaphthopyran compounds, compounds with a molecular weight of 540 or more are more preferably used because of their excellent color development density and discoloration rate. Furthermore, it is even more preferable to use an indenonaphthopyran compound having a structure represented by the following formula (II) in addition to the above.

Here, R ¹ is a hydrogen atom, an alkoxy group having 1 to 6 carbon atoms, N,N-dimethylamino group, N,N-diethylamino group, N-morpholino, 2,6-dimethyl (N-morpholinyl), N-piperidinyl (piperidino), 2,6-dimethyl (N-piperidinyl) selected group, R ² is from a hydrogen atom , Alkoxy having 1 to 6 carbons, N,N-dimethylamino, N,N-diethylamino, N,N-diphenylamino, N-morpholinyl, 2, 6-dimethyl (N-morpholinyl), N-piperidinyl, 2,6-dimethyl (N-piperidinyl) selected group, R ³ is selected from hydroxyl, amine, methyl , Methoxy, 4-methoxyphenyl, 2,4-dimethoxyphenyl, 4-(N,N-dimethylamino)phenyl, 4-(N-morpholinyl)benzene The selected group among the groups, R ⁴ is selected from the group consisting of hydroxyl, amine, methoxy, 4-methoxyphenyl, 2,4-dimethoxyphenyl, 4-(N,N-dimethylamine Group) phenyl, 4-(N-morpholinyl) phenyl, 4-(N-morpholinyl) phenyl, 2,4-dimethylphenylthio group, here, R ³ It can be bonded with R ^{4 by} -S-CZ ₂ -O- group (Z=methyl, ethyl, propyl, isopropyl), R ⁵ is selected from hydrogen atom, methyl, methoxy, cyanide Group selected from the group consisting of radicals and haloalkyl groups, R ⁶ is selected from -(CH ₂ ) ₅ -, -(CH ₂ ) ₉ -, -C(CH ₃ ) ₂ CH ₂ C(CH ₃ ) ₂ -, -C (CH ₃ ) ₂ CH ₂ CH ₂ C(CH ₃ ) ₂ -, -CCH ₂ C(C ₂ H ₅ ) ₂ CCH ₂ -, or a group selected from the following formula (III).

In addition, the benzopiperan compound may be a compound having a long-chain group with a molecular weight of 300 or more as a substituent, and may contain a polysiloxane chain, a polyoxyalkylene chain, a polyester chain, a polyester poly Molecular chains such as ether chains serve as substituents. Examples include the benzopiperan compounds described in the following: Japanese Patent No. 4550281, Japanese Patent No. 4476930, Japanese Patent No. 4615564, Japanese Patent Publication No. 2007-535592, International Publication No. 2005/105875, International Publication No. 2009/146509, International Publication No. 2010/020770, Japanese Patent No. 5813095, International Publication No. 2012/149599, International Publication No. 2012/162725, Japanese Patent No. 5920939, International Publication No. 2013/078086, International Publication No. 2019/013249, Japanese Patent Application No. 2018-079303, Japanese Patent Application No. 2018-136374, etc. One of the benzopiperan compounds exemplified above can be used, and in order to adjust the color tone, a plurality of benzopiperan compounds can also be used in combination.

[Synthetic resin] As the photochromic layer, it is preferable to use a synthetic resin (layer) containing a benzopiperan compound as a photochromic compound. Preferably, for example, a synthetic resin obtained by dispersing a benzopiperan compound is layered to produce a photochromic layer. As a synthetic resin, polyester, cellulose, polyamide, polyimide, allyl, (meth)acrylic, polyurethane (urea), polythiourethane, polyepoxy, polysulfide can be used It replaces conventional synthetic resins such as epoxy, polyolefin, and polycarbonate. From the viewpoint of photochromic properties, it is preferable to use (meth)acrylic acid, polyurethane (urea), and polythiourethane, and among them, it is more preferable to use polyurethane (urea) resin or crosslinkability (methyl ) Acrylic resin. In addition, the above-mentioned "polyurethane (urea)" means both "polyurethane" and "polyurethane urea".

[Polyurethane (urea) resin, synthetic resin] In this embodiment, when a polyurethane (urea) resin is used as the synthetic resin used in the photochromic layer, it is preferably set as follows. As the polyurethane (urea) resin, a thermosetting polyurethane (urea) or a thermoplastic polyurethane (urea) synthesized by a conventional method can be used. Among them, it is preferable to synthesize from the (A1) polyisocyanate compound, (A2) polyol compound, (A3) chain extender, and (A4) reaction stopper described below. In addition, when forming the photochromic layer, from the viewpoint of photochromic characteristics and adhesiveness, it is preferable to produce a part of a polyurethane (urea) resin whose molecular weight is quantified.

The polyurethane resin (urea) resin preferably has a number average molecular weight measured by gel permeation chromatography (GPC) of 5,000 to 100,000, more preferably a number measured by gel permeation chromatography (GPC) The average molecular weight is 8,000 to 50,000, and more preferably, the number average molecular weight measured by gel permeation chromatography (GPC) is 10,000 to 40,000. In addition, it is preferable that the polyurethane (urea) resin contains 0.02 to 0.10 g of the urea bond portion per 1 g. Examples of such polyurethane (urea) resins include those described below: Japanese Patent Laid-Open No. 2012-167245, International Publication WO2012/018070 Brochure, Japanese Patent Laid-Open No. 2012-207198, Japan JP 2012-052091, JP 2012-052091, JP 2016-147922, etc.

((A1) Polyisocyanate compound, polyurethane (urea) resin) From the viewpoint of weather resistance, as the (A1) polyisocyanate compound, an aliphatic polyisocyanate compound or an alicyclic polyisocyanate compound is preferably used. Specific examples include tetramethylene-1,4-diisocyanate, hexamethylene-1,6-diisocyanate, octamethylene-1,8-diisocyanate, and 2,2,4-triisocyanate. Aliphatic polyisocyanate compounds such as methylhexane-1,6-diisocyanate; cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, 2,4-methylcyclohexanedi Isocyanate, 2,6-methylcyclohexane diisocyanate, isophorone diisocyanate, norbornene diisocyanate, isomer mixture of 4,4'-methylenebis (cyclohexane isocyanate), hexahydrotoluene -2,4-diisocyanate, hexahydrotoluene-2,6-diisocyanate, hexahydrobenzene-1,3-diisocyanate, hexahydrobenzene-1,4-diisocyanate and other alicyclic polyisocyanate compounds, preferably Isophorone diisocyanate and norbornene diisocyanate are used.

((A2) Polyol compound, polyurethane (urea) resin) As the polyol compound (A2), polyol compounds such as polyether polyol, polycarbonate polyol, polycaprolactone polyol, and polyester polyol can be used. Among these, polycarbonate polyol and polycaprolactone polyol are preferably used from the viewpoints of heat resistance, adhesion, weather resistance, and hydrolysis resistance. The number average molecular weight of the polyol compound is preferably 400-3000. Among them, from the viewpoint of heat resistance, photochromic layer characteristics (color development concentration, fading speed, weather resistance, etc.) of the obtained polyurethane (urea) resin, especially the weather resistance of the photochromic compound, the number average molecular weight It is preferably 400-2500, more preferably 400-1500.

((A3) Chain extender, polyurethane (urea) resin) The (A3) chain extender is a compound having a functional group capable of reacting with two or more isocyanate groups in the molecule. From the viewpoint of heat resistance and photochromic properties of the obtained polyurethane (urea) resin Look, compounds with molecular weights of 50 to 300 are preferred. Examples of such (A3) chain extenders include: amino group-containing compounds such as diamine compounds and triamine compounds: hydroxyl group-containing compounds such as diol compounds and triol compounds; and amino alcohol compounds and amino carboxylic acid compounds , Aminothiol compounds, etc.

As the above-mentioned amine group-containing compound, isophorone diamine, ethylene diamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,2-diaminobutane, 1,3-diaminobutane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminopentane, piperazine, N,N- Bis(2-aminoethyl)piperazine, bis(4-aminocyclohexyl)methane, bis(4-amino-3-butylcyclohexyl)methane, 1,2-, 1,3- and 1 ,4-diaminocyclohexane, norbornane diamine, hydrazine, adipic acid dihydrazine, phenylenediamine, 4,4'-diphenylmethanediamine, N,N'-diethylethanediamine Amine, N,N'-dimethylethylenediamine, N,N'-dipropylethylenediamine, N,N'-dibutylethylenediamine, N-methylethylenediamine, N-ethyl Ethylenediamine, bis(hexamethylene)triamine, 1,2,5-pentanetriamine, etc. Among them, from the viewpoint of adhesion, heat resistance, photochromic properties, and ease of synthesis of polyurethane (urea) resin, it is more preferable to use isophorone diamine and bis(4-aminocyclohexyl) methane , Norbornane diamine, etc.

The above hydroxyl-containing compound is preferably used: ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, 1,5-dihydroxypentane, 1,6-dihydroxyhexane, 1,7-di Hydroxyheptane, 1,8-dihydroxyoctane, 1,9-dihydroxynonane, 1,10-dihydroxydecane, 1,11-dihydroxyundecane, 1,12-dihydroxydodecane , Neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, bis (trimethylolpropane), butanetriol, 1,2-methylglucoside, pentaerythritol, dipentaerythritol, tripentaerythritol Wait. Among them, ethylene glycol, propylene glycol, 1,4-butanediol, trimethylolpropane, and bis(trimethylolpropane) are more preferred from the viewpoint of adhesion, heat resistance, and photochromic properties. ).

(Other ingredients, polyurethane (urea) resin) Polyurethane (urea) resin obtained from the above (A1) polyisocyanate compound, (A2) polyol compound and (A3) chain extender may have an isocyanate group at the end and may also be reacted by (A4) Stop agent to deactivate.

(A4) The reaction stopper contains one substituent capable of reacting with an isocyanate group. In addition, it may include substituents and structures capable of exerting various functions. As the (A4) reaction stopper, amine, alcohol, thiol, and carboxylic acid can be used. Examples thereof include n-butylamine, secondary butylamine, tertiary butylamine, dibutylamine, diisopropylamine, methanol, ethanol, isopropanol, n-butanol, secondary butanol, tertiary butanol, and acetic acid. In addition, by using a compound with antioxidant function and light stability function as the (A4) reaction stopper, it is possible to introduce these functions to the polyurethane (urea) resin and simultaneously deactivate the terminal isocyanate group Change.

(Proportion of each component in polyurethane (urea) resin) The ratio of (A1) polyisocyanate compound (hereinafter sometimes referred to as "(A1)") to (A2) polyol compound (hereinafter sometimes referred to as "(A2)") constituting the polyurethane (urea) resin, as long as It may be appropriately determined in consideration of the use of the polyurethane (urea) resin and the like. From the viewpoint of the balance between the heat resistance and adhesive strength of the obtained polyurethane (urea) resin, it is preferably set as follows proportion. In other words, when the total number of moles of isocyanate groups contained in (A1) is set to n1, and the total number of moles of hydroxyl groups contained in (A2) is set to n2, it is preferably set to n1:n2 = 1.0: (0.2 to 0.8), more preferably n1: n2 = 1.0: (0.3 to 0.7).

In addition, when (A3) chain extender (hereinafter sometimes referred to as "(A3)") is used as a constituent in addition to (A1) and (A2), the heat resistance of the obtained polyurethane (urea) resin From the viewpoint of the balance between adhesive strength and the like, the ratio of (A1), (A2), and (A3) is preferably set to the following ratio. In other words, the total number of moles of isocyanate groups contained in (A1) is set to n1, the total number of moles of hydroxyl groups contained in (A2) is set to n2, and the activity contained in (A3) When the total mole number of hydrogen groups is set to n3, it is preferably set to n1: n2: n3 = 1.0: (0.2 to 0.8): (0.2 to 0.8), and more preferably set to n1: n2: n3 = 1.0: (0.3 to 0.7): (0.3 to 0.7). Here, the aforementioned n1 to n3 can be obtained as a product of the number of moles of the compound used as each component and the number of the aforementioned functional groups present in one molecule of the aforementioned compound.

In addition, when using (A4) reaction stopper (hereinafter sometimes referred to as "(A4)") to set the terminal of the polyurethane (urea) resin as a non-reactive group, the active hydrogen group contained in (A4) When the total mole number is set to n4, it is preferably set to n1: n2: n3: n4 = 1.0: (0.2 to 0.8): (0.2 to 0.8): (0.01 to 0.2), more preferably set to n1: n2: n3: n4=1.0: (0.3 to 0.7): (0.3 to 0.7): (0.01 to 0.18). Furthermore, when (A4) is used, it is preferable to satisfy the relationship of n2=n1+n3+n4=1.0.

(Manufacturing method of polyurethane (urea) resin) The method for producing the polyurethane (urea) resin is not particularly limited, and conventional methods can be used. For example, the so-called one-shot method or the prepolymer method can be used. For example, the following method can be used: (A1) a polyisocyanate compound and (A2) a polyol compound are reacted, then (A3) a chain extender is reacted, and (A4) a reaction stopper is reacted as needed. In addition, conventional methods can be used for these reaction conditions and purification methods.

(Photochromic layer using polyurethane (urea) resin) In this embodiment, when the above-mentioned polyurethane (urea) resin is used as a synthetic resin to form the photochromic layer in which the benzopiperan compound is dispersed, it is preferable to contain benzopiperan relative to the polyurethane (urea) resin 0.1 to 20 parts by mass of the compound.

Furthermore, when the (A3) component having an active hydrogen group of 3 or more is used to form the above photochromic layer, since a cross-linked structure insoluble in a general organic solvent is formed, it is preferably set as follows method. In other words, it is preferable to combine an amine ester (urea) prepolymer composed of a benzopiperan compound, (A1) component and (A2) component, and an (A3) component having an active hydrogen group of more than 3 functions and an organic After mixing the solvent and coating the obtained photochromic adhesive composition into a smooth base material, the organic solvent is removed by drying, and the amine ester (urea) prepolymer and the trifunctional or more The (A3) component of the active hydrogen group reacts to obtain a polyurethane (urea) resin.

In addition, when a polyurethane (urea) resin is used to form the photochromic layer, since the photochromic layer can be used as an adhesive layer, it is preferable to laminate the optical sheet described later on at least one side. At this time, in order to make the adhesiveness with the above-mentioned optical sheet more stable, it is preferable to dispose a polyisocyanate compound (I) described later (hereinafter sometimes referred to as "(I) component") in the photochromic layer. In other words, at this time, the photochromic layer is formed of a composition including: polyurethane (urea) resin, polyisocyanate compound (I), and benzopiperan compound.

The polyisocyanate compound (I) is not particularly limited, although it is also possible to use a compound listed in the (A1) polyisocyanate compound used in the polyurethane (urea) resin, preferably the following polyisocyanate compound (I1) , (I2).

As the polyisocyanate compound (I1) (hereinafter sometimes referred to as "(I1) component"), for example, an isomer mixture of 4,4'-methylenebis (cyclohexane isocyanate), cyclobutane- 1,3-diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, hexahydrotoluene-2,4-diisocyanate, hexahydrotoluene-2,6-diisocyanate , Hexahydrobenzene-1,3-diisocyanate, hexahydrobenzene-1,4-diisocyanate, and isophorone diisocyanate trimer (isocyanurate compound), etc. have at least 2 isocyanates in the molecule A polyisocyanate compound having an acid group and having an isocyanate group bonded to a secondary carbon.

Examples of the polyisocyanate compound (I2) (hereinafter sometimes referred to as "(I2) component") include hexamethylene diisocyanate, a biuret compound of hexamethylene diisocyanate, and hexamethylene diisocyanate. Polyisocyanate compounds other than the component (I1) having at least 2 isocyanate groups in the molecule and having 4 to 40 carbon atoms in the molecule, such as an isocyanurate compound and an addition compound of hexamethylene diisocyanate.

The component (I1) and the component (I2) may be used alone or in combination of two or more. Among them, the component (I1) is preferably a mixture of isomers of 4,4'-methylenebis (cyclohexane isocyanate), and the component (I2) is preferably a compound from hexamethylene diisocyanate A polyisocyanate compound selected from the group consisting of urea compounds and isocyanurate compounds of hexamethylene diisocyanate.

In this embodiment, from the viewpoint of the adhesiveness and heat resistance of the obtained photochromic layer, the compounding ratio of the component (I) is preferably 4.0 to 20 parts by mass relative to 100 parts by mass of the polyurethane (urea) resin. . When the component (I) is used to form the photochromic layer, it is preferable to use 0.1-20 parts by mass of the benzopiperan compound relative to 100 parts by mass of the total amount of the polyurethane (urea) resin and the component (I). In addition, when both (I1) component and (I2) component are used as (I) component, the said ratio is based on this total amount.

When the blending amount of the component (I) satisfies the above range, the obtained adhesive layer will exert excellent effects. When the blending amount of the component (I) is less than the above range, a sufficient effect of improving the adhesiveness and heat resistance cannot be obtained. In addition, when the amount of the above-mentioned (I) component is more than the above range, there is a tendency that the adhesive layer becomes cloudy, the adhesiveness decreases, and the like. We believe that component (I) can interact with the urethane bond and/or urea bond of the polyurethane (urea) resin to quantify the polymer of the polyurethane (urea) resin.

(Laminated body including photochromic layer using polyurethane (urea) resin) In this embodiment, a photochromic layer using polyurethane (urea) resin as a synthetic resin can also be used as an adhesive layer to adhere to other layers. Specifically, after forming a photochromic layer on a substrate such as polyethylene terephthalate, polypropylene, etc., only the photochromic layer can be peeled off the substrate to form a photochromic adhesive layer, and then the optical sheet After the other layers are bonded, a laminate is made.

As a method of obtaining such a laminate, for example, the following method is preferable. First, a composition containing a polyurethane (urea) resin and a benzopiperan compound (which may further contain (I) component) is kneaded, and a photochromic layer in a uniform state is produced by the above method. Then, the photochromic layer is disposed between the optical sheets, and the optical sheets are pressed against each other, whereby a photochromic laminate can be manufactured, which is formed by joining the optical sheets through the adhesive layer. In addition, when a composition containing an organic solvent-containing polyurethane (urea) resin and a benzopiperan compound (which may further contain (I) component) is used, the laminate can also be obtained by temporarily: The composition is coated on the optical sheet to form a coating layer, and the organic solvent is removed from the coating layer to form an adhesive layer, and then other optical sheets are arranged on the adhesive layer and pressed together.

(Optical sheet) As the optical sheet to be bonded to the photochromic layer, a sheet equivalent to the optical sheet used in the aforementioned electrochromic laminate can be suitably used. Among them, polycarbonate, polyamide resin, cellulose resin (triacetyl cellulose, etc.), and polyvinyl alcohol resin are preferred for the reason of good adhesion. The surface (upper surface and lower surface) of the above-mentioned optical sheet can be subjected to the following treatments: chemical treatment using chemical agents such as alkaline solution and acid solution; grinding treatment, corona discharge treatment, plasma discharge treatment, UV ozone Physical surface treatment such as treatment.

In addition, a coating film layer (primer layer) may be formed on the surface (upper surface and lower surface) of the optical sheet. As the coating film layer, a layer formed of, for example, the following resin, crosslinked body, or composition: water-dispersed polyurethane resin, water-dispersed polyester resin, water-dispersed acrylic resin, water-dispersed polyurethane-acrylic resin, or other water is used Dispersible polymer; cross-linked body of polymer with carbonyl group and hydrazine compound among the above water-dispersible polymers; cross-linked body of water-soluble polymer such as polyvinyl alcohol; with (meth)acrylic acid group Composition of polymerizable monomer and/or hydrolyzable organosilicon compound having a group selected from epoxy group, (meth)acryloyl group, vinyl group, amine group, mercapto group, etc.; having a silanol group Or a composition capable of being hydrolyzed to form a silanol group, a (meth)acrylic group, an epoxy group and a vinyl group, a polymerizable group of amine ester urea resin; including a compound containing an acryl ether group, many An ene/thiol-based composition of an ene compound and a thiol compound, a photo-curable composition containing an oxetane compound, etc.

In addition, it is preferable that the optical sheet is laminated on at least one side of the photochromic layer, and it is more preferable that the optical sheet is laminated on both sides of the photochromic layer. In other words, it is preferable to form a layer that exhibits photochromic properties by bonding two optical sheets through a photochromic layer that is also used as the above-mentioned adhesive layer (hereinafter sometimes referred to as "photochromic sheet" "). Furthermore, at this time, the film thickness of the photochromic layer is preferably set in the range of 5 to 100 μm from the viewpoint of the color development concentration, weather resistance, and adhesive strength of the benzopiperan compound, and more preferably Set to 10 to 60 μm.

In addition, in order to further improve the adhesiveness with the optical sheet, the above-mentioned photochromic sheet may have another adhesive layer. In other words, it can be a photochromic sheet in which another adhesive layer (using the same layer as the "second adhesive layer" described later) composed of a polyurethane resin (urea) resin that does not contain a photochromic compound is laminated on The two sides of the photochromic layer are formed by bonding two optical sheets. Furthermore, it is preferable that the above-mentioned adhesive layers are respectively provided between the two optical sheets and the photochromic layer.

(Method of bonding photochromic layer and electrochromic laminate using polyurethane (urea) resin) One of the optical sheets bonded to the photochromic layer may be an optical sheet of an electrochromic laminate, and may be other optical sheets. In other words, when polyurethane resin (urea) resin is used in the photochromic layer, the photochromic layer itself has adhesiveness, so that the photochromic layer can be formed on the optical sheet of the electrochromic laminate, and other The optical sheets are stacked on the opposite side. In other words, it is also possible to set one optical sheet interposed between the electrochromic element and the photochromic layer, and set it as a kind of laminate in which the optical sheet/photochromic layer/optical are formed in sequence Sheet/electrochromic element/optical sheet layer.

(Second adhesive layer) Between the photochromic layer and the electrochromic laminate, there may be an adhesive layer free of benzopiperan compound. There may be, for example, the following layers: an adhesive layer composed of the above-mentioned polyurethane (urea) resin containing no benzopiperan compound; or consisting of the above-mentioned polyurethane (urea) resin containing no benzopiperan compound and (I) The adhesive layer formed by the composition of the components; or a coating film layer (primer layer) described later (hereinafter sometimes referred to as "second adhesive layer").

As the second adhesive layer, the resin described in the above-mentioned polyurethane (urea) resin can be used. Among them, it is preferable to use the number of substituents n1, n2, and n3 in the components (A1), (A2), and (A3) as n1: n2: n3=1.00: (0.30 to 0.90): (0.10 to 0.70) Polyurethane (urea) resin synthesized in the ratio of, preferably using the above-mentioned number of substituents n1, n2, n3 in the components (A1), (A2), (A3) becomes n1: n2: n3 = 1.00: (0.40 ～0.80): Polyurethane (urea) resin synthesized in the ratio of (0.20～0.60). In addition, when the (A4) component is used, the ratio of n1: n2: n3: n4 = 1.00: (0.30 to 0.89): (0.10 to 0.69): (0.01 to 0.20) is preferable, so that it is n1: n2: n3: n4=1.00: (0.40 to 0.80): (0.15 to 0.58): (0.01 to 0.15) is preferred. Furthermore, a primer layer described later can also be used for the second adhesive layer.

In addition, the film thickness of the second adhesive layer is not particularly limited, but it is preferably 5 to 15 μm.

When the optical article of the present embodiment is used as an optical lens, the photochromic sheet is bent into a spherical shape and used. Furthermore, when the photochromic sheet and the electrochromic optical base material that have been processed into a lens-like spherical shape are used as a unit, it is preferable to perform a bending process to form the electrochromic unit before forming the unit The optical substrate has the same spherical shape.

As a method of bending the photochromic sheet into a spherical shape, for example, hot press processing, press processing, vacuum suction processing, etc. may be mentioned. The temperature during the bending process may be appropriately determined according to the type of optical sheet used in the photochromic sheet, and it is preferably performed at a temperature exceeding 100°C and 200°C or lower.

As described above, the second adhesive layer is preferably formed between the photochromic sheet and the electrochromic laminate (the surface of the optical sheet). Furthermore, after the bent photochromic sheet and the electrochromic optical substrate are joined, in order to further improve the electrochromic laminate and the second adhesive layer, and between the second adhesive layer and the photochromic sheet The adhesiveness between them is preferably heat-treated in a temperature range of 60 to 120°C for about 0.5 to 6 hours. Thereby, an optical article with good adhesion at all interfaces can be obtained.

[Crosslinkable (meth)acrylic resin, synthetic resin] In the present embodiment, when a crosslinkable (meth)acrylic resin is used as the synthetic resin used in the photochromic layer, it is preferably set as follows. Here, the cross-linkable (meth)acrylic resin refers to a cross-linked (meth)acrylic resin described in detail below, which contains a plurality of (meth)acrylic amides in the molecule The monomer-based composition is obtained by polymerization and hardening. Furthermore, "(meth)acrylic resin" means both "acrylic resin" and "methacrylic resin".

The crosslinkable (meth)acrylic resin is not particularly limited, and a resin can be used which is prepared by polymerizing and curing a crosslinkable (meth)acrylic monomer, a polymerization initiator, and the like.

The crosslinkable (meth)acrylic monomer is not particularly limited, and examples thereof include trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, and tetramethylolmethane trimethacrylate. , Tetramethylolmethane triacrylate, tetramethylolmethane tetramethacrylate, tetramethylolmethane tetraacrylate, trimethylolpropane triethylene glycol trimethacrylate, trimethylolpropane Triethylene glycol triacrylate, bis (trimethylolpropane) tetramethacrylate, bis (trimethylolpropane) tetraacrylate, dipentaerythritol hexaacrylate, bisphenol A dimethacrylate, 2 ,2-bis(4-methacryloyloxyethoxyphenyl)propane, average molecular weight 628 2,2-bis(4-methacryloyloxypolyethylene glycol phenyl)propane, average molecular weight 804 of 2,2-bis(4-methacryloyloxy polyethylene glycol phenyl) propane, average molecular weight of 776 of 2,2-bis(4-acryloyloxy polyethylene glycol phenyl) propane, Methoxy polyethylene glycol methacrylate with an average molecular weight of 468, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, pentaethylene glycol Dimethacrylate, pentapropylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, pentaethylene glycol diacrylate, tripropylene glycol dimethyl Acrylate, tetrapropylene glycol dimethacrylate, pentapropylene glycol dimethacrylate, polyethylene glycol dimethacrylate with an average molecular weight of 330, polyethylene glycol dimethacrylate with an average molecular weight of 536, average molecular weight 736 polytetraethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, tetrapropylene glycol dimethacrylate, polypropylene glycol dimethacrylate with an average molecular weight of 536, polyethylene glycol diacrylate with an average molecular weight of 258 Acrylic ester, polyethylene glycol diacrylate with average molecular weight 308, polyethylene glycol diacrylate with average molecular weight 508, polyethylene glycol diacrylate with average molecular weight 708, polycarbonate diol and (meth)acrylic acid The reaction products are polyfunctional amine esters such as polycarbonate di(meth)acrylate, amine ester oligomer tetraacrylate, amine ester oligomer hexamethacrylate, amine ester oligomer hexaacrylate ( Multifunctional polyester (meth)acrylates such as meth)acrylates and polyester oligomers hexaacrylate, which have (meth)acryloyl groups and have cage, ladder, and random structures are doubled Hemi-siloxane monomer, polyrotaxane compound having (meth)acryloyl group in the side chain, 2-isocyanatoethyl methacrylate, γ-methacryloxypropyl trimethoxy Silane, γ-methacryloxypropylmethyldimethoxysilane, glycidyl methacrylate, etc., contain (meth)acryloyl group and have two or more polymerizable groups crosslinkability ( Methacrylic monomer.

As the polymerization initiator, those conventionally used as photopolymerization initiators can be used. Examples include: benzophenone; 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1 -Phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1- [4-(methylthio)phenyl]-2-(N-morpholinyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-(N-morpholine Group) phenyl) butanone-1, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one and other acetophenone-based compounds; 1,2-diphenylethyl Α-dicarbonyl compounds such as diketone and methylphenyl glyoxylate; 2,6-dimethylbenzyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzyl) Phenylphosphine oxide, bis(2,6-dimethoxybenzyl)-2,4,4-trimethylpentylphosphine oxide, 2,4,6-trimethylbenzyl diphenyl Phosphine oxide, methyl 2,4,6-trimethylbenzyl diphenylphosphonate, 2,6-dichlorobenzyl diphenylphosphine oxide, 2,6-dimethoxybenzene Acetylphosphine oxide-based compounds such as methyldiphenylphosphine oxide; 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzoyloxime)], hydroxybenzene 2-[2-keto-2-phenylacetoxyethoxy]ethyl hydroxyacetate, 2-[2-hydroxyethoxy]ethyl hydroxyphenylacetate, etc.

(Photochromic layer using cross-linkable (meth)acrylic resin) The photochromic layer using a crosslinkable (meth)acrylic resin is not particularly limited, but it is preferable to prepare a crosslinkable (meth)acrylic monomer, a benzopiperan compound, a polymerization initiator, etc. It is made into a photochromic coating composition and polymerized and hardened. Furthermore, although it is also possible to mechanically mix a crosslinkable (meth)acrylic monomer with a benzopiperan compound to form a photochromic layer, the dispersion of the benzopiperan compound and the optical properties obtained From the viewpoint of the adhesion, productivity, photochromic properties, etc. of the article, the above method is preferred.

In the photochromic coating composition, the mixing ratio of the crosslinkable (meth)acrylic monomer and the polymerization initiator is not particularly limited, and it is 100 parts by mass in total with respect to the crosslinkable (meth)acrylic monomer. Preferably, the polymerization initiator is in the range of 0.001 to 10 parts by mass, and more preferably the polymerization initiator is in the range of 0.01 to 5 parts by mass.

In addition, in the photochromic coating composition, the mixing ratio of the benzopiperan compound is not particularly limited, and it is preferably 100 parts by mass relative to the total amount of the cross-linkable (meth)acrylic monomer and the polymerization initiator. The benzopiperan compound is in the range of 0.1 to 20 parts by mass, more preferably the benzopiperan compound is in the range of 0.5 to 10 parts by mass.

From the viewpoint of forming a uniform layer when performing spin coating described below, the viscosity of the photochromic coating composition is preferably set to a viscosity in the range of 50 to 1,000 cP at 25°C, more preferably The viscosity at 25°C is in the range of 100-500 cP.

From the viewpoint of photochromic properties, optical properties, solvent resistance, surface hardness, and adhesion of the photochromic layer, such photochromic coating compositions can also use, for example, the photochromic materials described below Color-changing coating composition: International Publication No. 03/011967, International Publication No. 04/050775, International Publication No. 05/014717, International Publication No. 2011/125956, Japan Patent No. 5991980 Gazette, International Publication No. 2013/008825, Japanese Patent Laid-Open No. 2013-072000, Japanese Patent Laid-Open No. 2015-025063, International Publication No. 2014/136919 Booklet, International Publication No. 2014/136804 Booklet , International Publication No. 2015/068798, International Publication No. 2016/013677, Japanese Patent Publication No. 2017-052869, Japanese Patent Publication No. 2017-19973, International Publication No. 2017/038957, etc.

The method of forming the photochromic layer using the cross-linkable (meth)acrylic resin is not particularly limited, and from the viewpoint of productivity, for example, spin coating can be used. When spin coating is used, the photochromic layer is preferably formed on the optical sheet of the electrochromic laminate. In this case, it is preferable to use an electrochromic laminate bonded to an optical substrate.

In addition, it is also possible to use the above-mentioned photochromic composition to form a photochromic layer by a so-called kneading method. In this case, the method of forming the photochromic layer is preferably a method of forming a mold and filling the photochromic composition therein in the same manner as the method of forming an optical substrate on the electrochromic laminate.

The thickness of the photochromic layer formed by any of the above methods is not particularly limited, and is preferably 5 to 100 μm.

(Primer layer, cross-linkable (meth)acrylic resin) In this embodiment, a cross-linkable (meth)acrylic resin is used as the photochromic layer of the synthetic resin. In order to improve the adhesion with other layers, for example, it is preferably used in the optical of the electrochromic laminate After forming a primer layer on the sheet, a photochromic layer is formed thereon.

The primer layer is not particularly limited, and conventional adhesive resins can be used. For example, moisture-curable polyurethane-based, polyisocyanate-polyester-based two-component type, polyisocyanate-polyether-based two-component type, polyisocyanate-polyacrylic-based two-component type, polyisocyanate-polyurethane elastic system can be used Adhesives such as two-component, epoxy-based, epoxy-polyurethane-based two-component, acrylic, polyester-based, polyurethane-urea-based one-component, water-dispersible polyurethane.

In addition, the primer layer is preferably composed of an urethane resin. Through the above, it is possible to maintain a high optical penetration rate and joint strength of the optical article finally obtained. The urethane resin is not particularly limited, and conventional urethane resins can be used. For example, the following moisture-curable urethane resin and/or its precursor, or water dispersion urethane resin emulsion. In addition, in the above, from the viewpoint of showing a stronger adhesion between the optical sheet of the electrochromic laminate and the photochromic layer, it is preferable to use a moisture-curable urethane resin and/or Its precursor.

(Moisture-curable urethane resin, primer layer) The moisture-curable urethane resin and/or its precursor (hereinafter sometimes only referred to as "moisture-curable urethane resin") refers to an isocyanate group-containing compound or a precursor that will become such a compound Compounds, or a combination of these compounds, will be cross-linked and hardened by: a part of a plurality of isocyanate groups present in the molecule react with, for example, moisture in the atmosphere to produce carbamic acid , Decarbonization produces amine, and the amine reacts with residual isocyanate groups to produce urea bonds. In addition, although urea bonds are generated as a result of the reaction between the water and the isocyanate, in the present embodiment, the primer layer may contain an urethane resin (urethane urea resin) containing such urea bonds.

The moisture-curable urethane resin is preferably formed by: a polyisocyanate compound, which is composed of an aromatic isocyanate compound; and/or a polyisocyanate oligomer compound, which is like an isocyanate group The compounding ratio is left to synthesize the aromatic isocyanate compound and the compound having active hydrogen. Based on the above, the primer layer can exhibit excellent adhesion even at lower temperatures. Furthermore, when a polyisocyanate oligomer compound is used, as the compound having active hydrogen, it is preferably used: polyalkylene glycols, polyols containing three or more hydroxyl groups, and polyalkylene adipate , Polyalkylene carbonates, polycaprolactones, polyester polyols, etc. The compounds having the above active hydrogen can be used alone or in combination of two or more.

The molecular weight of the moisture-curable urethane resin and/or its precursor is preferably set to be higher than the molecular weight generally used. As a method of increasing the molecular weight, it may be adjusted so that the number of remaining isocyanate groups is small when the polyisocyanate compound and the compound having active hydrogen are blended. In addition, as another method, for example, a method of bonding a plurality of isocyanate groups present in the molecules of the moisture-curable polyurethane resin and/or its precursor with a chain extender or the like may be mentioned. Here, examples of the chain extender include the above-mentioned compounds having active hydrogen, and diamine compounds such as ethylenediamine. Examples include: alkylene glycols such as 1,3-butanediol, 1,4-butanediol, propylene glycol, and 1,6-hexanediol; and polyalkylene glycols such as polypropylene glycol. From the viewpoint of easy control of the chain extension reaction, it is preferable to use the above-mentioned compound.

It can be diluted with organic solvents such as toluene, xylene, ethyl acetate, butyl acetate, etc., and the above-mentioned moisture-curable urethane resin can be diluted, and a leveling agent can be further formulated as needed to produce a primer. Coating composition.

(Water-dispersed urethane resin emulsion, primer layer) The so-called water-dispersible urethane resin emulsion means that the urethane resin is dispersed in water to form an emulsion. The urethane resin contained in the water-dispersible urethane resin emulsion is preferably obtained by reacting the active hydrogen group-containing component with a polyisocyanate compound. In addition, the active hydrogen group-containing component is preferably at least a polyol compound, an anionic active hydrogen group-containing compound, an active hydrogen group-containing acrylate compound, and/or an alkoxysilane group-containing polyamine compound.

As the above-mentioned polyol compound and polyisocyanate compound, the same compounds as listed for the raw materials of the moisture-curable urethane resin can be used. The above-mentioned anionic active hydrogen group-containing compound is, for example, a compound having at least one anionic group such as a carboxyl group, a sulfonyl group, a phosphate group, a group containing a betaine structure (sulfobetaine, etc.), and has 2 More than one active hydrogen group such as a hydroxyl group and an amine group that can react with an isocyanate group. For example, as an anionic active hydrogen group-containing compound having a carboxyl group, for example, 2,2-dimethylolacetic acid, 2,2-dimethylollactic acid, 2,2-dimethylolpropionic acid, 2, Dihydroxycarboxylic acids such as 2-dimethylolbutyric acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolvaleric acid; and diaminocarboxylic acids such as lysine and arginine .

Examples of the active hydrogen group-containing acrylate compound include (meth)acrylate compounds having one or more hydroxyl groups in the molecule. Examples include: 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, 2,2-di(hydroxymethyl)butyl (meth)acrylate , Polyhydroxyalkyl maleate, polyhydroxyalkyl fumarate, etc.

Examples of the alkoxysilane group-containing polyamine compound include alkoxysilane group compounds having a primary amine group and a secondary amine group. Examples include: N-β(aminoethyl)-γ-aminopropylmethyldimethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethoxysilane, γ -(2-aminoethyl)aminopropyltriethoxysilane, γ-(2-aminoethyl)aminopropyldimethoxysilane, γ-(2-aminoethyl)amine Propylpropyldiethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyldimethoxysilane, γ-aminopropyl Diethoxysilane, N,N'-bis[α-(trimethoxysilyl)propyl]ethylenediamine, etc.

The water-dispersible urethane resin can be synthesized by a one-step method, a prepolymer method, and the like, and it is preferable to use a prepolymer method. In addition, a chain extender can be used when synthesizing the above-mentioned water-dispersed urethane resin. The chain extender can also use other amines and hydrazines other than the alkoxysilyl group-containing polyamine compound (other amines and hydrazines are included in the active hydrogen group-containing component). For example, examples of such other amines include ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,6-hexanediamine, and 1,4-cyclohexanediamine. , 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diamine), 4,4'-dicyclohexylmethane diamine, 2,5(2,6) -Diamines such as bis(aminomethyl)bicyclo[2.2.1]heptane, 1,3-bis(aminomethyl)cyclohexane; diethylenetriamine, triethylenetetramine, tetraethylene Polyamines such as ethylene pentaamine.

The water-dispersed urethane resin obtained by the above can be dispersed in water to prepare a water-dispersed urethane resin emulsion. Examples of the water-dispersible urethane resin emulsion include the emulsions described in the following: Japanese Patent No. 5016266 and Japanese Patent No. 5084727. In addition, it is preferable that the water-dispersible amine ester resin emulsion is mixed with water, a leveling agent, an organic solvent, etc. as necessary to prepare a primer coating composition.

(Method for forming photochromic layer on primer layer, crosslinkable (meth)acrylic resin) In this embodiment, after forming a primer layer on an electrochromic optical base material, a photochromic layer (using a cross-linkable (meth)acrylic resin) is formed on the primer layer.

As a method of forming the primer layer, for example, a method of applying a primer coating composition to the surface of the electrochromic optical base material, and then drying and hardening. The coating method is not particularly limited, and a conventional method can be used. For example, the method of applying a composition etc. by the method of spin coating, spray coating, dip coating, dip spin coating, etc. is mentioned. Among these coating methods, spin coating is preferred because of the ease of controlling the film thickness and the ability to obtain a coating film with good appearance.

When the primer coating composition is applied by spin coating, the viscosity of the primer coating composition at 25° C. is preferably 5 to 200 because of the ease of obtaining a primer layer with a uniform thickness. In the range of cP, it is more preferably in the range of 10 to 100 cP. The viscosity can be adjusted by changing the type and amount of dispersion medium. In addition, the film thickness of the primer layer formed by the above method is preferably 1 to 20 μm.

When the primer coating composition contains water and an organic solvent, the primer layer can be formed by applying the primer coating composition to the electrochromic optical substrate by the above spin coating or the like After the application, it is dried under appropriate conditions.

From the viewpoint of good optical properties and adhesion between the electrochromic optical substrate and the primer layer, and between the primer layer and the photochromic sheet or photochromic coating layer, the electrochromic The thickness of the primer layer formed on the optical substrate is preferably in the range of 1 to 20 μm, and more preferably in the range of 1 to 20 μm. The range of -10 μm, and more preferably, the film thickness of the primer layer formed after drying is in the range of 1-7 μm.

The method for laminating the photochromic layer on the primer layer formed above may be, for example, after applying the primer coating composition on the electrochromic optical substrate, and then drying at 10-40°C for 5-30 minutes , A method of joining the photochromic sheet to the obtained primer layer and heating; and applying the photochromic coating composition, setting it in an inert gas such as nitrogen, and illuminating the light by irradiating UV The method of photo-hardening the color changing layer. From the viewpoint of the adhesion between the primer layer and the photochromic sheet or photochromic coating layer, it is preferable to use these methods. Among them, from the viewpoint of productivity of the obtained optical article, a method of curing by light is preferable.

Among the above-mentioned photo-curing conditions, especially ultraviolet (UV) intensity conditions may affect the property state of the obtained photochromic layer. This condition is affected by the type and amount of the photopolymerization initiator and the type of (meth)acrylic monomer, so it cannot be defined in general. Generally speaking, it is preferable to use a wavelength of 365 nm and 50～ Conditions such as 500 mW/cm ² of UV light irradiation for 0.5 to 5 minutes.

In this embodiment, after the photochromic layer is laminated by photohardening in the above method, in order to further improve the density between the electrochromic optical base material and the primer layer, and between the primer layer and the photochromic layer It is preferable to heat-treat in a temperature range of 60 to 120°C for about 0.5 to 6 hours. This makes it possible to obtain an electrochromic photochromic optical article with good adhesion at all interfaces.

[Other additives, photochromic layer] In this embodiment, the above-mentioned polyurethane (urea) resin or cross-linkable (meth)acrylic resin can be used as a synthetic resin (layer) containing a benzopiperan compound as a photochromic compound to form a photoinduced Color changing layer. In addition, the photochromic layer may contain other additives as other components within a range that does not hinder adhesion and other properties. Various stabilizers such as surfactants, ultraviolet absorbers, infrared absorbers, ultraviolet stabilizers, antioxidants, anti-colorants, antistatic agents, fluorescent dyes, dyes, pigments, perfumes, and other additives may be included as needed.

>Composition of other optical items> An optical article having both photochromic characteristics and electrochromic characteristics can be formed according to the above method. Furthermore, as described above, when used in optical lens applications such as spectacle lenses, the optical article in this embodiment only needs to form a photochromic layer/electrochromic build-up layer in order from the incident side of light such as sunlight The body, or the electrochromic laminate/photochromic layer may be sufficient. However, considering the formability, function, etc. of the obtained optical article, it is preferable to adopt an aspect of the optical article in which the following layers are sequentially formed from the incident side of light rays such as sunlight: photochromic layer /Electrochromic laminate/Optical substrate.

The optical article of this embodiment can be post-processed by a conventional method such as hard coating treatment, water repellent treatment, anti-fogging treatment, and anti-reflection film, depending on the intended use. Alternatively, a layer having a polarizing function or a film having a polarizing function may be laminated as required. [Example]

Hereinafter, the present invention will be described in detail using Examples and Comparative Examples, but the present invention is not limited by the Examples and the like. In the examples and comparative examples, the above-mentioned components, the evaluation method of photochromic characteristics and electrochromic characteristics, etc. are as follows.

(Electrochromic laminate and optical substrate, electrochromic lens substrate) EC1: 2 mm thick polycarbonate resin (optical substrate) is joined to the electrochromic laminate by injection molding to produce electricity The electrochromic lens substrate is used as an electrochromic optical substrate. The electrochromic laminate has 50 nm thick indium tin oxide (ITO) between two 0.3 mm thick polycarbonate sheets (optical sheets) Transparent electrode, 700 Å thick oxide colored electrochromic layer composed of a mixture of iridium oxide and tin oxide, 5000 Å thick transparent ion conductive layer composed of Ta ₂ O ₃ , 5000 Å thick composed of WO ₃ The formed reduction color electrochromic layer and 50 nm thick ITO transparent electrode layer. The above EC1 has the following properties: the initial visual transmittance is 85%, and if a voltage of about 2.1 V is applied between the electrodes, it will be colored blue and the visual transmittance will reach 30%. In addition, it has the following properties: after coloring, if a voltage of about -2.1 V is applied between the electrodes, the color will be eliminated and the original visual transmittance will be restored to 85%.

EC2: Corona etching of both surfaces of the electrochromic laminate with 50 nm thick ITO transparent electrode, 700 between two 0.3 mm thick polyamide sheets (optical sheets) Å-thick oxidatively colored electrochromic layer composed of a mixture of iridium oxide and tin oxide, 5000 Å-thick transparent ion conductive layer composed of Ta ₂ O ₃ , and 5000 Å-thick reduction composed of WO ₃ Colored electrochromic layer and 50 nm thick ITO transparent electrode layer. After disposing the obtained electrochromic laminate in two glass plates and assembling a mold, allyl glycol carbonate monomer containing IPP (diisopropyl peroxydicarbonate) as an initiator After the composition is filled in the mold, thermal polymerization is carried out, thereby manufacturing an electrochromic lens substrate with a total thickness of 3 mm. The above EC2 has the following properties: the initial visual penetration rate is 85%, and if a voltage of about 2.1 V is applied between the electrodes, it will be colored blue and the visual penetration rate will reach 30%. In addition, it has the following properties: after coloring, if a voltage of about -2.1 V is applied between the electrodes, the color will be eliminated and the original visual transmittance will be restored to 85%.

EC3: By injection molding, a 2 mm thick polycarbonate resin (optical substrate) is joined to an electrochromic laminate to produce an electrochromic lens substrate. The electrochromic laminate is made of two 0.3 mm thick Between polycarbonate sheets (optical sheets), a 50-nm-thick ITO transparent electrode, a first electrochromic layer (containing a triarylamine compound with a monofunctional acrylate), and an electrolyte layer (containing bis(trifluoromethanesulfonate) (A) Imine 1-ethyl-3-methylimidazolium salt), the second electrochromic layer (titanium oxide particle film/layer containing an electrochromic compound of the following formula), and 50 nm thick ITO transparent Electrode layer. The above EC3 has the following properties: the initial visual transmittance is 85%, and if a voltage of about 2 V is applied between the electrodes, it will be colored blue-green and the visual transmittance will reach 30%. In addition, it has the following properties: after coloring, if a voltage of about -2 V is applied between the electrodes, the color will disappear and return to the original visual transmittance of 85%.

(Primer coating composition) PR1: Moisture-curing primer (product name: TR-SC-P, manufactured by TOKUYAMA Co., Ltd.) PR2: Water-dispersed amine ester emulsion (product name: NJ-321A, manufactured by TOKUYAMA Co., Ltd.)

(Photochromic compound) Benzopiperan 1: compound represented by the following formula

>Example 1> (Method for forming primer layer on electrochromic lens substrate) On the surface of the electrochromic lens substrate EC1, a spin coater (1H-DX2, manufactured by MIKASA) was used to disperse the water-dispersed amine ester emulsion (product name: NJ-321A, manufactured by TOKUYAMA Co., Ltd.; PR2) , Coating at 70 rpm for 15 seconds, then coating at 800 rpm for 5 seconds. Then, it was dried at room temperature (about 23°C) for 10 minutes to form a primer layer. The thickness of the primer layer is about 7 μm.

(Photochromic coating composition) In 5 parts by mass of γ-methacryloxypropyltrimethoxysilane, 20 parts by mass of trimethylolpropane trimethacrylate, 2,2-bis(4-methacryloxyethoxy) Polymerization consisting of 35 parts by mass of phenylphenyl)propane, 10 parts by mass of amine oligomer hexaacrylate, 20 parts by mass of polyethylene glycol diacrylate having an average molecular weight of 532, and 10 parts by mass of glycidyl methacrylate To 100 parts by mass of the total monomer, 3 parts by mass of benzopiperan 1, bis sebacate (1,2,2,6,6-pentamethyl-4-piperidinyl ester) as a stabilizer 5 Parts by mass, 0.3 parts by mass of CGI148 (1-hydroxycyclohexylphenyl ketone) as a polymerization initiator, and 0.3 parts by mass of CGI819 (bis(2,4,6-trimethylbenzyl)phenylphosphine oxide) Stir well and thoroughly degas, then use as a photochromic coating composition.

(Preparation of electrochromic photochromic optical article) Then, the photochromic coating composition 2.0 g was applied by spin coating so that the thickness of the formed photochromic layer was 30 μm. On the electrochromic lens substrate with the primer layer formed by the above method. Then, in a nitrogen atmosphere, the UV light generated by the electrodeless lamp was irradiated from the height of 200 mm above the product (lens substrate) for 80 seconds. At this time, the UV intensity of 365 nm on the surface of the product was 125 mW/cm ² , and the cumulative light intensity was 10 J. Then, it was further heated at 80°C for 1 hour to produce an electrochromic photochromic optical article having a photochromic layer on the surface layer.

>Example 2> An electrochromic photochromic optical article was produced under the same conditions as in Example 1, except that EC2 was used as the electrochromic lens substrate and PR1 was used as the primer coating composition.

>Example 3> An electrochromic photochromic optical article was produced under the same conditions as in Example 1, except that EC3 was used as the electrochromic lens substrate.

>Example 4> The optical article was produced under the following conditions. (Synthesis of Polyurethane-Urea Resin (U1)) In a three-necked flask with a stirring bar, cooling tube, thermometer, and nitrogen introduction tube, feed 9.0 g of polyether polyol with a number average molecular weight of 400, 10.0 g of isophorone diisocyanate, and dimethylformamide (DMF) 80 mL, and react at 120°C for 5 hours in a nitrogen atmosphere, then cool to 25°C, and drop 3.4 g of a chain extender, ie, isophorone diamine, to react at 25°C 1 Hours, and the solvent was distilled off under reduced pressure to obtain polyurethane-urea resin (U1). The molecular weight of the obtained polyurethane-urea resin is 150,000 in terms of polystyrene and 10,000 in terms of polyoxyethylidene (the molecular weight is the theoretical value).

(Modulation of photochromic composition) Add 5 g of polyurethane-urea resin (U1), 0.25 g of photochromic compound (benzopiperan 1), 20 g of isopropyl alcohol as an organic solvent, and sebacic acid bis(1,2 , 2,6,6-pentamethyl-4-piperidinyl ester) 0.25 g, and dissolved by ultrasonic waves while stirring at 80° C. to obtain a photochromic composition.

(Manufacture of photochromic laminate) After applying the above photochromic composition to a sheet made of fluororesin with a smooth surface and drying it at 80°C for 1 hour, the obtained photochromic sheet with a thickness of 30 μm was sandwiched between 2 sheets of thickness Between 400 μm polycarbonate sheets, the target laminate with photochromic properties was obtained.

(Manufacture of electrochromic photochromic optical articles) A polyisocyanate-polyester-based two-component coating solution is applied to the surface of the electrochromic lens substrate EC1, and the photochromic laminate is attached to it to produce an electrochromic photochromic optical article .

>Example 5> An electrochromic photochromic optical article was produced under the same conditions as in Example 4 except that EC2 was used as the electrochromic lens substrate.

>Example 6> An electrochromic photochromic optical article was produced under the same conditions as in Example 4 except that EC3 was used as the electrochromic lens substrate.

>Comparative example 1> An optical article was produced under the same conditions as in Example 1 except that only the electrochromic lens substrate EC1 was used without forming a photochromic layer on the electrochromic lens substrate EC1.

>Comparative example 2> An optical article was produced under the same conditions as in Example 1, except that a polycarbonate lens with a thickness of 2 mm was used instead of the electrochromic lens substrate EC1.

>Comparative Example 3> An optical article was produced under the same conditions as in Example 1, except that spiropiperan 1 represented by the following formula was used instead of benzopiperan 1.

The optical articles of Examples 1 to 6 and Comparative Examples 1 to 3 described above were evaluated for visual transmittance, anti-glare property, and visibility by the following method. The results are shown in Table 1.

[Evaluation method of visual transmittance (only when the electrochromic layer has color development)] Using the obtained electrochromic photochromic optical article as a sample, a voltage of about 2.1 V was applied between the electrodes of the lens to develop color, and then the electrochromic photoluminescence in an environment of 23°C or 35°C was measured The visual penetration of color-changing optical items.

[Evaluation method of visual transmittance (only when the photochromic layer has color development)] The obtained electrochromic photochromic optical article was used as a sample at 23°C or 35 via an airomas filter (manufactured by CORNING). Xenon lamp L-2480 (300 W) SHL-100 manufactured by Hamamatsu Photonics Co., Ltd. was irradiated for 120 seconds at a beam intensity of 365 nm=2.4 mW/cm ² and 245 nm=24 μW/cm ^{2 on the} surface of the laminate After the color is developed, the visual permeability of the electrochromic photochromic optical article is measured.

[Evaluation method of visual transmittance (when both the electrochromic layer and the photochromic layer have color development)] Using the obtained electrochromic photochromic optical article as a sample, apply approximately between the electrodes of the lens A voltage of 2.1 V is used for color development, and the xenon lamp L-2480 (300 W) SHL-100 manufactured by Hamamatsu Photonics Co., Ltd. is placed at 23°C or 35°C via an airomas filter (manufactured by CORNING). The beam intensity of the surface was 365 nm=2.4 mW/cm ² and 245 nm=24 μW/cm ² to irradiate it for 120 seconds to develop color, and then the visual transmittance of the electrochromic photochromic optical article was measured.

The spectrophotometer (momentary multi-channel light indicator MCPD1000) manufactured by Otsuka Electronics Co., Ltd. was used to measure the three types of visual transmittance.

[Evaluation of Anti-glare and Recognition] Using the electrochromic photochromic optical article made by the above method, on a sunny day with a temperature of 30 to 36°C, 10 subjects are asked to wear the electrochromic photochromic optical article outdoors and investigate anti-glare Satisfaction of sex and identification. The number is the percentage (%) of people who are satisfied.

[Table 1]

As is clear from Table 1, the optical articles of Examples 1 to 6 are excellent in high-temperature visual transmittance, anti-glare property, and visibility. On the other hand, optical articles such as those shown in Comparative Examples 1 or 2 that have only either electrochromic or photochromic characteristics, or those shown in Comparative Example 3 use spiperane as The electrochromic photochromic optical article of the photochromic compound has insufficient visual transmittance, anti-glare property and recognizability at high temperature.

1‧‧‧ (Electrochromic Photochromic) Optical Items 2‧‧‧Photochromic layer 3‧‧‧Electrochromic laminate 4‧‧‧Optical substrate

FIG. 1 is a cross-sectional view showing an aspect of the optical article of this embodiment.

Domestic storage information (please note in order of storage institution, date, number) no

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1‧‧‧ (Electrochromic Photochromic) Optical Items

2‧‧‧Photochromic layer

3‧‧‧Electrochromic laminate

4‧‧‧Optical substrate

Claims (3)

An optical article comprising: an electrochromic layer having electrochromic properties; and, a photochromic layer having photochromic properties; Furthermore, the aforementioned photochromic layer contains a benzopiperan compound. The optical article according to claim 1, wherein the photochromic layer is composed of an amine (urea) resin containing a benzopiperan compound or a cross-linkable (meth)acrylic resin. The optical article according to claim 1 or 2, which is used as an optical lens, and wherein the photochromic layer is disposed on the light entrance side, and the electrochromic layer is disposed on the light exit side.

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