WO2019216283A1 - 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 article

The present invention relates to a novel optical article having two types of chromic properties, electrochromic properties and photochromic properties.

In recent years, mainly in the United States, photochromic sunglasses in which photochromic properties are imparted to sunglasses having antiglare properties and electrochromic sunglasses in which electrochromic properties are imparted are rapidly gaining popularity.
Photochromic sunglasses can adjust the antiglare property by changing the transmittance of the lens according to the ambient brightness (amount of ultraviolet rays). Moreover, since the transmittance | permeability of a lens changes by applying a voltage, electrochromic sunglasses can adjust anti-glare property according to a user's desire.

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

However, the photochromic lens produced by these methods has a problem that the color density is lowered when the temperature is high. In particular, in summer, it is desired that the color density is increased because the ultraviolet intensity is strong, but there is a problem that the color density is lowered due to high temperature.
In addition, the electrochromic lens can change the coloring state by applying a voltage, but it is necessary to apply a voltage frequently in order to maintain the coloring state for a long time. There was a need to do.

International Publication No. 2014/136804 JP 2007-138186 A International Publication No. 2004/050775 JP 2012-052091 A JP-A-53-033161 Japanese Patent No. 6171737 Japanese Patent Laid-Open No. 01-209423

In order to solve the above problems, a spectacle lens having a photochromic layer using a spiropyran compound and an electrochromic element has been proposed (see Patent Document 7).
However, according to the study by the present inventors, even the method described in Patent Document 7 has room for improvement from the viewpoint of sufficient color density at a high temperature required in recent years.
Accordingly, an object of the present invention is to provide an optical article having two types of chromic characteristics, electrochromic characteristics and photochromic characteristics, which exhibits excellent color density even at high temperatures.

In order to solve the above problems, the present inventors have intensively studied the composition of a photochromic compound and a resin in which the photochromic compound is dispersed. As a result, it has been found that by using a chromene compound as a photochromic compound, the optical article exhibits excellent photochromic properties, that is, sufficient color density even at high temperatures. Moreover, when the structure which has the said photochromic characteristic was combined with an electrochromic layer, it discovered that it could use suitably, and came to complete this invention.

That is, the optical article according to the present invention is an optical article provided with an electrochromic layer having electrochromic characteristics and a photochromic layer having photochromic characteristics, and the photochromic layer is an optical article containing a chromene compound.

According to the present invention, it is possible to provide an optical article having two types of chromic characteristics, electrochromic characteristics and photochromic characteristics, which exhibits excellent color density even at high temperatures.

It is sectional drawing which shows the one aspect | mode of the optical article which concerns on this embodiment.

<Optical article>
The optical article according to the present embodiment has two types of chromic characteristics, electrochromic characteristics and photochromic characteristics.

One aspect of the optical article according to this embodiment is shown in FIG. An optical article 1 shown in FIG. 1 includes a photochromic layer 2 that exhibits photochromic characteristics, an electrochromic laminate 3 that includes an electrochromic layer that exhibits electrochromic characteristics, and an optical substrate 4.
When the optical article 1 is used as an optical lens, the side on which the photochromic layer 2 is formed is configured as a light incident side on which light such as sunlight enters, and the side on which the electrochromic laminate 3 is formed is similarly configured. It is preferable to configure as the light exit side.
FIG. 1 is a schematic diagram, and the shape of the optical article according to the present embodiment is not limited to this example. Hereinafter, the configuration of the optical article according to the present embodiment will be described in detail.

<Electrochromic layer>
In the optical article according to the present embodiment, as the electrochromic layer having electrochromic characteristics, a known electrochromic layer having a property that the color tone of a substance is reversibly changed by an electrochemical oxidation-reduction reaction caused by voltage application, in particular, Can be used without restrictions.
The electrochromic layer is formed on the electrode layer to form an electrochromic element as an electrochemical cell. Further, the electrochromic element is laminated on at least one optical sheet and used as an electrochromic laminate. This will be described in detail below.

<Electrochromic laminate>
The electrochromic laminate is a laminate in which electrochromic elements are laminated on at least one optical sheet. Preferably, it is a laminate in which an electrochromic element is disposed between two opposing optical sheets.

[Optical sheet]
As the optical sheet, a resin-made sheet having optical transparency is preferably used. Examples of the material of the optical sheet include polycarbonate resin, polyester resin, cellulose resin, polyamide resin, (meth) acrylic resin, urethane resin, urethane (urea) resin, epoxy resin, polyimide resin, polyolefin resin, and polyvinyl alcohol resin. Can be mentioned. Among these, polycarbonate resin, polyamide resin, cellulose resin (such as triacetyl cellulose), and polyvinyl alcohol resin are particularly preferable because of good adhesion.

The film thickness of the optical sheet is preferably 20 to 1000 μm, and more preferably 50 to 500 μm from the viewpoint of processability of the resulting electrochromic laminate.
In addition, the surface (both sides) of the optical sheet is subjected to physical surface treatment such as chemical treatment using a chemical solution such as an alkali solution or an acid solution, polishing treatment, corona discharge treatment, plasma discharge treatment, UV ozone treatment. It may be broken. A plurality of these processes may be combined.

A coating layer such as an adhesive layer or a hard coat layer may be formed on the surface (both sides) of the optical sheet.
Examples of the material for forming the adhesive layer or the coating layer are not particularly limited. For example, moisture-curable polyurethane, polyisocyanate-polyester two-component coating liquid, polyisocyanate-polyether two-component coating Liquid, polyisocyanate-polyacrylic two-component coating solution, polyisocyanate-polyurethane elastomer two-component coating solution, epoxy-based coating solution, epoxy-polyurethane two-component coating solution, acrylic coating solution, polyester And a coating solution using a polyurethane-based one-component coating solution, a water-dispersible polyurethane-based coating solution, a vinyl acetate-based coating solution, and a silane coupling agent.

[Electrochromic device]
In the electrochromic element, an electrochromic layer is formed on an electrode layer, and an electrochemical cell is formed using the electrode layer as a working electrode. Preferably, a laminate in which electrode layer / electrochromic layer / electrolyte layer or ion conductive layer / electrode layer is laminated, or electrode layer / reduction colored electrochromic layer / electrolyte layer or ion conductive layer / reversible electrolytic oxidation layer / A laminated body in which electrode layers are laminated.

[Electrochromic layer]
As the electrochromic layer, a structure in which electrochromic material is supported on conductive or semiconductive fine particles can be used. For example, a structure can be used in which the fine particles are attached to the electrode surface and an organic electrochromic compound having a polar group such as phosphonic acid, carboxyl group, or silanol group is adsorbed on the fine particle surface.
For example, when using an electrochromic element having a five-layer structure of electrode layer / reduction colored electrochromic layer / electrolyte layer or ion conductive layer / reversible electrolytic oxidation layer / electrode layer, the reduced electrochromic layer includes Tungsten oxide or molybdenum oxide is preferably used, and an oxide or hydroxide such as iridium, nickel, chromium, vanadium, ruthenium, or rhodium is preferably used for the reversible electrolytic oxidation layer.

(Electrochromic material)
The electrochromic layer includes an electrochromic material. The electrochromic material may be either an inorganic electrochromic compound or an organic electrochromic compound. Moreover, you may use the well-known conductive polymer which shows electrochromism.

Examples of the inorganic electrochromic compound include tungsten oxide, molybdenum oxide, iridium oxide, titanium oxide, vanadium oxide, indium oxide, nickel oxide, Prussian blue, Prussian blue, and similar compounds.
Examples of organic electrochromic compounds include viologen compounds, dipyridine compounds, rare earth phthalocyanine compounds, styryl compounds, tetrathiafulvalene compounds, azobenzene compounds, anthraquinone compounds, diarylethene compounds, dihydroprene compounds, styryl. Spiropyran compounds, spirooxazine compounds, spirothiopyran compounds, thioindigo compounds, terephthalic acid compounds, triphenylmethane compounds, triphenylamine compounds, naphthopyran compounds, pyrazoline compounds, phenazine compounds, phenylenediamine compounds Phenoxazine compounds, phenothiazine compounds, phthalocyanine compounds, fluoran compounds, fulgide compounds, benzopyran compounds, Tarosen based compounds.
Examples of the conductive polymer include polypyrrole, polythiophene, poly (3-phenylthiophene), poly (4,4′-di (2-thienyl) biphenyl), polyisothianaphthene, polyaniline, or derivatives thereof. Can be mentioned.

[Electrolyte layer; electrochromic device]
The electrolyte layer is a solid electrolyte layer, and a film obtained by mixing an electrolyte with a photocurable resin or a thermosetting resin can be used. As the electrolyte, a liquid electrolyte such as an ionic liquid, or a solid electrolyte dissolved in a solvent can be used.
Examples of liquid electrolytes such as ionic liquids include imidazole derivatives, pyridinium derivatives, and aliphatic quaternary ammonium compounds such as tetraalkylammonium as the cation component, BF ₄ ⁻ , CF ₃ SO ₃ ⁻ , and PF as the anion component. _An ionic liquid composed of a combination of ₄ ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , B (CN ₄ ) ^{− and the} like can be used.
As the solid electrolyte, for example, inorganic ion salts such as alkali metal salts and alkaline earth metal salts, quaternary ammonium salts, acids and supporting salts of alkalis can be used. _{Specifically, 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) 2 , etc. Is mentioned.

As the photocurable resin or thermosetting resin for forming the electrolyte layer, known 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 easily controlling the thickness of the obtained electrolyte layer, for example, oxides such as silicon, aluminum, titanium, zinc, and tin can be added to the electrolyte layer.

[Ion conductive layer; electrochromic device]
As the ion conductive layer, for example, an ion conductive material such as silicon oxide, tantalum oxide, titanium oxide, aluminum oxide, niobium oxide, zirconium oxide, hafnium oxide, lanthanum oxide, and magnesium fluoride is used. And it can be set as an ion conductive layer by setting it as the film | membrane which mixed the ion conductive substance concerning said photocurable resin or thermosetting resin.

[Electrode layer; electrochromic device]
As the material for the electrode layer, a transparent conductive oxide material is preferably used. Examples thereof include indium oxide doped with tin, tin oxide doped with fluorine, and tin oxide doped with antimony. Among these, an inorganic material containing any one of indium oxide, tin oxide, and zinc oxide formed by vacuum film formation is preferable. And the film | membrane which consists of this inorganic material should just be used as an electrode layer.
Indium oxide, tin oxide, and zinc oxide are materials that can be easily formed by a sputtering method, and are materials that can provide good transparency and electrical conductivity. Among these, InSnO, GaZnO, SnO, In ₂ O ₃ , ZnO, and InZnO are particularly preferable.
Further, a conductive metal thin film containing gold, silver, copper, aluminum having transparency, a carbon film such as carbon nanotube, graphene, and the like, and a network electrode such as conductive metal, conductive carbon, conductive oxide, or These composite layers can also be used.
Note that the material for forming these electrode layers can be used by stacking two or more layers.

[Method of manufacturing electrochromic element and laminate]
The method for producing the electrochromic element is not particularly limited, and an electrochromic layer, an electrolyte layer or an ion conductive layer, an electrode layer, and the like may be laminated by a known method. For example, an electrochromic element can be manufactured by laminating an electrochromic layer on an electrode layer by a method such as vacuum deposition, sputtering, CVD, sol-gel, chemical deposition, or electrolytic deposition.
Moreover, an electrochromic laminated body can be manufactured by sticking an optical sheet on at least one side, preferably both sides, of the electrochromic element obtained by the above method. The method for attaching the optical sheet and the electrochromic element is not particularly limited, and a known method is used.

<Electrochromic optical substrate>
An electrochromic optical base material is comprised by joining the electrochromic laminated body which has an optical sheet on both sides of an electrochromic element on an optical base material.
As the optical substrate, a resin selected from polyester resins, polyamide resins, allyl resins, (meth) acrylic resins, urethane resins, urethane urea resins, thiourethane resins, thioepoxy resins, and polycarbonate resins is preferably used. Moreover, the optical sheet on one side of the electrochromic laminate can be formed thick and regarded as an optical substrate.
Moreover, when using the optical article which concerns on this embodiment as an optical lens, the said optical base material is processed into a lens-like spherical shape, and is used.

[Joint Method of Electrochromic Laminate and Optical Substrate]
The method for joining the optical substrate and the electrochromic laminate is not particularly limited, and for example, the following method is used.
When the resin forming the optical base material is a thermoplastic resin, there is a method in which the electrochromic laminate is disposed in a mold and the thermoplastic resin forming the optical base material is injection-molded on the back surface thereof.
Moreover, the following method is mentioned when resin which forms an optical base material is a thermosetting resin. That is, a mold having a space for filling a thermosetting resin monomer serving as an optical substrate is produced by one electrochromic laminate and one glass plate. Next, a method of filling the space with a monomer for thermosetting resin, thermosetting and / or photocuring, and releasing the glass plate can be mentioned. Or an electrochromic laminated body is arrange | positioned through space between two glass plates, and a mold is formed. Next, a method of filling the space with a monomer for a thermosetting resin, thermosetting and / or photocuring, and releasing the two glass plates is exemplified.

It should be noted that the electrochromic laminate and the optical substrate may be in a form in which they are not directly joined. For example, when the optical article in the present embodiment is used in an optical lens application such as a spectacle lens, the photochromic layer / electrochromic laminate or the electrochromic laminate / photochromic is sequentially formed from the incident side of light such as sunlight. It may be formed in the order of the layers. Therefore, the aspect of the order of the electrochromic laminated body / photochromic layer / optical base material with which the said optical base material was joined with the photochromic layer may be sufficient. However, in consideration of moldability, function, etc. of the obtained optical article, an aspect of the optical article in which each layer is formed in the order of photochromic layer / electrochromic laminate / optical substrate in order from the light incident side of light such as sunlight. It is preferable to take

[Processing method of electrochromic laminate]
When the optical article according to the present embodiment is used as an optical lens, the electrochromic laminate is subjected to thermal bending before being integrated with the optical base material processed into a lens-like spherical shape, thereby forming a lens-like shape. It can also be processed into a spherical shape (processed sheet is manufactured). In addition, you may die-cut to a desired shape before performing a heat bending process. Examples of the hot bending method include hot press processing, pressure processing, and vacuum suction processing. Moreover, pressurization and vacuum suction can be used in combination.

<Photochromic layer>
In the optical article according to the present embodiment, the photochromic property is exhibited by using a chromene compound as the photochromic compound. Thereby, in the optical article which laminated | stacked the layer which has a photochromic characteristic, and the layer which has an electrochromic characteristic, the outstanding effect, ie, the outstanding coloring density under high temperature, is exhibited.
As the photochromic layer having photochromic characteristics, it is preferable to use a synthetic resin (layer) containing a chromene compound as a photochromic compound.

[Photochromic compound]
As the photochromic compound, a chromene compound is used from the viewpoint of improving photochromic properties (high durability, high color density, etc.) in the optical article. In addition, the chromene compound is easy to adjust various color tones, and is excellent in terms of easy adjustment to a desired color tone when combined with electrochromic properties. As a demand for color development in recent years, for example, in addition to general-purpose gray and brown, neutral gray, brown with strong reddishness, and further demands for colors such as green, purple, and violet can be cited.
In addition, if the chromene compound is contained as a photochromic compound, photochromic compounds other than chromene compounds, such as a spirooxazine compound and a fulgide compound, may be contained. However, it is preferable that only a chromene compound is included.

(Chromene compound)
The chromene compound is not particularly limited, and a known chromene compound is used. For example, Japanese Patent No. 3471107, Japanese Patent Application Laid-Open No. 08-157467, Japanese Patent Application Laid-Open No. 08-176139, Japanese Patent Application Laid-Open No. 08-295690, Japanese Patent Application Laid-Open No. 09-124645, Japanese Patent Application Laid-Open No. 09-218301, Japanese Patent No. 3982770, Japanese Patent Application Laid-Open No. 11-279171, Japanese Patent Application Laid-Open No. 11-286484, Japanese Patent Application Laid-Open No. 11-322739, Japanese Patent No. 4301621, Japanese Patent Application Laid-Open No. 2000-219686, JP 2000-219687, JP 2000-229972, JP 2000-229993, JP 2000-229974, JP 2000-229975, JP 2000-229976, 2000- No. 256347, Japanese Patent No. 4256985 Japanese Patent No. 4157225, Japanese Patent Laid-Open No. 2000-344761, Japanese Patent No. 4157227, Japanese Patent No. 3801386, Japanese Patent Laid-Open No. 2001-011067, Japanese Patent No. 4118458, Japanese Patent Laid-Open No. 2001-031670, Japanese Patent No. 4157239, Japanese Patent No. 4157245, Japanese Patent No. 3522189, International Publication No. 00/71544, Japanese Patent No. 41588881, JP 2003-277381 A, JP 2005-289812 A, Japanese Patent No. 4195615, Japanese Patent No. 4369754, Japanese Patent No. 4424962, Japanese Patent No. 42494981, Japanese Patent No. 4666323, Japanese Patent No. 5 Japanese Patent No. 52355, Japanese Patent Application Laid-Open No. 2008-074832, Japanese Patent Application Laid-Open No. 2009-057300, Japanese Patent Application Laid-Open No. 2009-067676, Japanese Patent Application Laid-Open No. 2009-066754, Japanese Patent Application No. 2009-120536, Japanese Patent No. 5444195 Gazette, Japanese Patent No. 5606441, Japanese Patent No. 5865541, Japanese Patent No. 6031035, Japanese Patent No. 3029460, Japanese Patent No. 4550281, Japanese Patent No. 4105436, Examples include chromene compounds described in US Pat. No. 5,658,501.

Among these chromene compounds, indeno [2,1-f] naphtho [1,2-b] represented by the following formula (I) from the viewpoint of photochromic properties such as color density, initial coloration, durability, and fading speed It is preferable to use one or more indenonaphthopyran compounds having a pyran skeleton.

（ここで、Ｒ^１は水素原子、炭素数が１～６個のアルコキシ基、Ｎ，Ｎ－ジメチルアミノ基、Ｎ，Ｎ－ジエチルアミノ基、Ｎ，Ｎ－ジフェニルアミノ基、モルホリノ基、２，６－ジメチルモルホリノ基、ピペリジノ基、２，６－ジメチルピペリジノ基から選ばれる基であり、Ｒ^２は水素原子、炭素数が１～６個のアルコキシ基、Ｎ，Ｎ－ジメチルアミノ基、Ｎ，Ｎ－ジエチルアミノ基、Ｎ，Ｎ－ジフェニルアミノ基、モルホリノ基、２，６－ジメチルモルホリノ基、ピペリジノ基、２，６－ジメチルピペリジノ基から選ばれる基であり、Ｒ^３はヒドロキシル基、アミノ基、メチル基、メトキシ基、４－メトキシフェニル基、２，４－ジメトキシフェニル基、４－（Ｎ，Ｎ－ジメチルアミノ）フェニル基、４－モルホリノフェニル基から選ばれる基であり、Ｒ^４はヒドロキシル基、アミノ基、メトキシ基、４－メトキシフェニル基、２，４－ジメトキシフェニル基、４－（Ｎ，Ｎ－ジメチルアミノ）フェニル基、４－モルホリノフェニル基、４－モルホリノフェニル基、２，４－ジメチルフェニルチオ基から選ばれる基であり、ここでＲ^３とＲ^４は－Ｓ－ＣＺ_２－Ｏ－基（Ｚ＝メチル基、エチル基、プロピル基、イソプロピル基）で結合していてもよく、Ｒ^５は水素原子、メチル基、メトキシ基、シアノ基、ハロアルキル基から選ばれる基であり、Ｒ^６は－（ＣＨ_２）_５－、－（ＣＨ_２）_９－、－Ｃ（ＣＨ_３）_２ＣＨ_２Ｃ（ＣＨ_３）_２－、－Ｃ（ＣＨ_３）_２ＣＨ_２ＣＨ_２Ｃ（ＣＨ_３）_２－、－ＣＣＨ_２Ｃ（Ｃ_２Ｈ_５）_２ＣＣＨ_２－、又は下記式（ＩＩＩ）から選ばれる基である。）

Among these indenonaphthopyran compounds, compounds having a molecular weight of 540 or more are more preferably used because they are excellent in color density and fading speed.
In addition to the above, it is more preferable to use an indenonaphthopyran compound having a structure represented by the following formula (II).

(Wherein R ¹ is a hydrogen atom, an alkoxy group having 1 to 6 carbon atoms, N, N-dimethylamino group, N, N-diethylamino group, N, N-diphenylamino group, morpholino group, 2,6 A group selected from a dimethylmorpholino group, a piperidino group, and a 2,6-dimethylpiperidino group, wherein R ² is a hydrogen atom, an alkoxy group having 1 to 6 carbon atoms, an N, N-dimethylamino group, an N , N-diethylamino group, N, N-diphenylamino group, morpholino group, 2,6-dimethylmorpholino group, piperidino group, 2,6-dimethylpiperidino group, R ³ is a hydroxyl group, Selected from amino group, methyl group, methoxy group, 4-methoxyphenyl group, 2,4-dimethoxyphenyl group, 4- (N, N-dimethylamino) phenyl group, 4-morpholinophenyl group That is a group, ^{R 4} is a hydroxyl group, an amino group, a methoxy group, a 4-methoxyphenyl group, 2,4-dimethoxyphenyl group, 4- (N, N-dimethylamino) phenyl group, 4-morpholinophenyl group, A group selected from a 4-morpholinophenyl group and a 2,4-dimethylphenylthio group, wherein R ³ and R ⁴ are —S—CZ ₂ —O— groups (Z = methyl group, ethyl group, propyl group, R ⁵ is a group selected from a hydrogen atom, a methyl group, a methoxy group, a cyano group, and a haloalkyl group, and R ⁶ is — (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 the following formula (I II).

In addition, as a chromene compound, a compound having a long chain group having a molecular weight of 300 or more as a substituent, among which a molecular chain such as a polysiloxane chain, a polyoxyalkylene chain, a polyester chain, or a polyester polyether chain is contained as a substituent. You may do. For example, Japanese Patent No. 4550281, Japanese Patent No. 4476930, Japanese Patent No. 4615564, Japanese Translation of PCT International Publication No. 2007-535592, International Publication No. 2005/105875, International Publication No. 2009/146509. Gazette, 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. Examples thereof include chromene compounds described in Japanese Patent No. 078086, International Publication No. 2019/013249, Japanese Patent Application No. 2018-079303 and Japanese Patent Application No. 2018-136374.
One kind of the chromene compounds exemplified above can be used, and a plurality of chromene compounds can be used in combination for color tone adjustment.

[Synthetic resin]
As the photochromic layer, a synthetic resin (layer) containing a chromene compound as a photochromic compound is preferably used. For example, it is preferable that a synthetic resin in which a chromene compound is dispersed is layered to form a photochromic layer.
As the synthetic resin, known synthetic resins such as polyester, cellulose, polyamide, polyimide, allyl, (meth) acryl, polyurethane (urea), polythiourethane, polyepoxy, polythioepoxy, polyolefin, and polycarbonate may be used. it can. From the viewpoint of photochromic properties, it is preferable to use (meth) acryl, polyurethane (urea), and polythiourethane, and it is more preferable to use polyurethane (urea) resin or crosslinkable (meth) acrylic resin.
The above “polyurethane (urea)” means both “polyurethane” and “polyurethane urea”.

[Polyurethane (urea) resin; synthetic resin]
In the present embodiment, when a polyurethane (urea) resin is used as the synthetic resin used for the photochromic layer, the following aspects are preferable.
As the polyurethane (urea) resin, a thermosetting polyurethane (urea) synthesized by a known method or a thermoplastic polyurethane (urea) can be used. Especially, it is preferable to be synthesized from (A1) polyisocyanate compound, (A2) polyol compound, (A3) chain extender, and (A4) reaction terminator described below.
Moreover, when forming a photochromic layer, it is preferable to set it as the polyurethane (urea) resin partially made high molecular weight from a viewpoint of photochromic characteristics and adhesiveness.

The polyurethane (urea) resin preferably has a number average molecular weight of 5,000 to 100,000, more preferably 8,000 to 50,000, as measured by gel permeation chromatography (GPC). More preferably, it is 10,000 to 40,000.
Further, it is preferable that the urea bonding portion is contained in an amount of 0.02 to 0.10 g per 1 g of polyurethane (urea) resin. Examples of such a polyurethane (urea) resin include, for example, JP 2012-167245 A, International Publication WO 2012/018070, JP 2012-207198 A, JP 2012-052091 A, and JP 2012-052091 A. And polyurethane (urea) resins described in JP-A-2016-147922 and the like.

((A1) polyisocyanate compound; polyurethane (urea) resin)
As the (A1) polyisocyanate compound, it is preferable to use an aliphatic polyisocyanate compound or an alicyclic polyisocyanate compound from the viewpoint of weather resistance. Specifically, aliphatic such as tetramethylene-1,4-diisocyanate, hexamethylene-1,6-diisocyanate, octamethylene-1,8-diisocyanate, 2,2,4-trimethylhexane-1,6-diisocyanate Polyisocyanate compounds, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, 2,4-methylcyclohexyl diisocyanate, 2,6-methylcyclohexyl diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 4,4'-methylenebis (cyclohexyl) Isocyanate) isomer mixture, hexahydrotoluene-2,4-diisocyanate, hexahydrotoluene-2,6-diisocyanate, hexahydrophenylene-1,3-diiso Examples thereof include alicyclic polyisocyanate compounds such as cyanate and hexahydrophenylene-1,4-diisocyanate, and it is more preferable to use isophorone diisocyanate and norbornene diisocyanate.

((A2) polyol compound; polyurethane (urea) resin)
(A2) As the polyol compound, polyol compounds such as polyether polyol, polycarbonate polyol, polycaprolactone polyol, and polyester polyol can be used. Of these, polycarbonate polyols and polycaprolactone polyols are preferably used from the viewpoints of heat resistance, adhesion, weather resistance, hydrolysis resistance, and the like. The number average molecular weight of the polyol compound is preferably 400 to 3000. Among them, the number average molecular weight is more preferably 400 to 2500 from the viewpoint of the heat resistance and photochromic properties (color density, fading speed, weather resistance, etc.) of the obtained polyurethane (urea) resin, particularly the weather resistance of the photochromic compound. 400 to 1500 is more preferable.

((A3) chain extender; polyurethane (urea) resin)
(A3) The 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 resulting polyurethane (urea) resin, a molecular weight of 50 to 300 compounds are preferred. Such (A3) chain extenders include, for example, amino group-containing compounds such as diamine compounds and triamine compounds, hydroxyl group-containing compounds such as diol compounds and triol compounds, amino alcohol compounds, aminocarboxylic acid compounds, and aminothiols. Compounds and the like.

Examples of the amino group-containing compound include isophorone diamine, ethylene diamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,2-diaminobutane, 1,3-diaminobutane, 1,4-diaminobutane, 1, 5-diaminopentane, 1,6-diaminohexane, 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, norbornanediamine, hydrazine, dihydrazine adipate, phenylenediamine, 4,4′-diphenylmethanediamine, N, N′-diethylethylenediamine, N, N'-dimethylethylenediamine, N, N'-dipropylethylenedia Min, N, N′-dibutylethylenediamine, N-methylethylenediamine, N-ethylethylenediamine, bis (hexamethylene) triamine, 1,2,5-pentanetriamine and the like are preferably used.
Of these, isophoronediamine, bis- (4-aminocyclohexyl) methane, and norbornanediamine are more preferably used from the viewpoint of adhesion, heat resistance, photochromic properties, and ease of synthesis of polyurethane (urea) resin.

Examples of the hydroxyl group-containing compound include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, 1,5-dihydroxypentane, 1,6-dihydroxyhexane, 1,7-dihydroxyheptane, 1,8-dihydroxyoctane, 1,9-dihydroxynonane, 1,10-dihydroxydecane, 1,11-dihydroxyundecane, 1,12-dihydroxydodecane, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, di (trimethylolpropane), butane Triol, 1,2-methylglucoside, pentaerythritol, dipentaerythritol, tripentaerythritol and the like are preferably used.
Of these, ethylene glycol, propylene glycol, 1,4 butanediol, trimethylolpropane, and di (trimethylolpropane) are preferably used from the viewpoints of adhesion, heat resistance, and photochromic properties.

(Other components: Polyurethane (urea) resin)
The terminal of the polyurethane (urea) resin obtained from the above (A1) polyisocyanate compound, (A2) polyol compound, and (A3) chain extender may be an isocyanate group, or (A4) is not effective due to the reaction terminator. It may be activated.

(A4) The reaction terminator contains one substituent that can react with an isocyanate group. Moreover, the substituent and structure which can exhibit various functions may be included. (A4) As the reaction terminator, amine, alcohol, thiol, and carboxylic acid can be used. Examples thereof include normal butylamine, sec-butylamine, tert-butylamine, dibutylamine, diisopropylamine, methanol, ethanol, isopropanol, normal butanol, sec-butanol, tert-butanol, acetic acid and the like.
Further, by using a compound having an antioxidant function or a photostability function as the (A4) reaction terminator, these functions are introduced into the polyurethane (urea) resin, and at the same time, the terminal isocyanate group is inactivated. Can be activated.

(Ratio of each component in polyurethane (urea) resin)
(A1) polyisocyanate compound (hereinafter sometimes referred to as “(A1)”) constituting the polyurethane (urea) resin, and (A2) polyol compound (hereinafter referred to as “(A2)”). )) May be appropriately determined in consideration of the use of the polyurethane (urea) resin, etc., but from the viewpoint of the balance of the heat resistance and adhesive strength of the resulting polyurethane (urea) resin, the ratio is as follows: It is preferable to set the ratio to a high value. That is, when the total number of moles of isocyanate groups contained in (A1) is n1, and the total number of moles of hydroxyl groups contained in (A2) is n2, n1: n2 = 1.0: (0.2-0 .8), and more preferably n1: n2 = 1.0: (0.3 to 0.7).

In addition to (A1) and (A2), when (A3) a chain extender (hereinafter sometimes referred to as “(A3)”) is used as a component, (A1), (A2), The ratio of (A3) is preferably set to the following ratio from the viewpoint of the balance between the heat resistance and adhesive strength of the resulting polyurethane (urea) resin. That is, the total number of moles of isocyanate groups contained in (A1) is n1, the total number of hydroxyl groups contained in (A2) is n2, and the total number of active hydrogen groups contained in (A3) is n3. Sometimes, n1: n2: n3 = 1.0: (0.2 to 0.8) :( 0.2 to 0.8) is preferable, and n1: n2: n3 = 1.0: (0 .3 to 0.7): (0.3 to 0.7) is more preferable. Here, n1 to n3 can be obtained as the product of the number of moles of the compound used as each component and the number of each functional group present in one molecule of the compound.

When (A4) reaction terminator (hereinafter sometimes referred to as “(A4)”) is used and the terminal of the polyurethane (urea) resin is a non-reactive group, (A4) When the total number of moles of active hydrogen groups contained is n4, n1: n2: n3: n4 = 1.0: (0.2 to 0.8) :( 0.2 to 0.8) :( 0 0.01: 0.2), preferably n1: n2: n3: n4 = 1.0: (0.3-0.7) :( 0.3-0.7) :( 0.01-0 .18) is more preferable. In addition, when using (A4), it is preferable to satisfy the relationship of n2 = n1 + n3 + n4 = 1.0.

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

(Photochromic layer using polyurethane (urea) resin)
In this embodiment, when the polyurethane (urea) resin is used as a synthetic resin to form a photochromic layer in which a chromene compound is dispersed, the chromene compound is added in an amount of 0.1 to 100 parts by mass with respect to 100 parts by mass of the polyurethane (urea) resin. It is preferable that 20 mass parts is contained.

In addition, when forming the said photochromic layer using (A3) component which has a trifunctional or more active hydrogen group, since the crosslinked structure which does not melt | dissolve in a general organic solvent is formed, it is set as the following method. It is preferable. That is, the urethane (urea) prepolymer composed of the chromene compound, the component (A1), and the component (A2), and the component (A3) having a trifunctional or higher functional hydrogen group were mixed with an organic solvent. After applying the photochromic adhesive composition to a smooth substrate, the organic solvent is removed by drying, and the urethane (urea) prepolymer and the (A3) component having a trifunctional or higher functional hydrogen group are reacted to form a polyurethane. It is preferable to obtain a (urea) resin.

Further, when a polyurethane (urea) resin is used for forming a photochromic layer, the photochromic layer can be used as an adhesive layer. Therefore, it is preferable to laminate an optical sheet described later on at least one surface. In that case, in order to further stabilize the adhesion to the optical sheet, a polyisocyanate compound (I) described later (hereinafter sometimes referred to as “component (I)”) may be added to the photochromic layer. preferable. That is, the photochromic layer in this case is formed from a composition containing a polyurethane (urea) resin, a polyisocyanate compound (I), and a chromene compound.

The polyisocyanate compound (I) is not particularly limited, and the compounds listed as the (A1) polyisocyanate compound used in the polyurethane (urea) resin may be used, but the polyisocyanate compound (I1) described below, It is preferable to use (I2).

Examples of the polyisocyanate compound (I1) (hereinafter sometimes referred to as “component (I1)”) include isomer mixtures of 4,4′-methylenebis (cyclohexyl isocyanate), cyclobutane-1,3-diisocyanate, cyclohexane 1,3-diisocyanate, cyclohexane-1,4-diisocyanate, hexahydrotoluene-2,4-diisocyanate, hexahydrotoluene-2,6-diisocyanate, hexahydrophenylene-1,3-diisocyanate, hexahydrophenylene-1, Polyisocyanate compounds having at least two isocyanate groups in the molecule and having an isocyanate group bonded to a secondary carbon, such as 4-diisocyanate and isophorone diisocyanate trimer (isocyanurate compound) And the like.

The polyisocyanate compound (I2) (hereinafter sometimes referred to as “component (I2)”) includes hexamethylene diisocyanate, hexamethylene diisocyanate biuret compound, hexamethylene diisocyanate isocyanurate compound, and hexamethylene diisocyanate adduct compound. And polyisocyanate compounds other than the component (I1) having at least two isocyanate groups in the molecule and having 4 to 40 carbon atoms in the molecule.

(I1) component and (I2) component may be used independently and may use 2 or more types together. Among them, it is preferable to use a mixture of isomers of 4,4′-methylenebis (cyclohexyl isocyanate) as the component (I1), and from the biuret compound of hexamethylene diisocyanate and the isocyanurate compound of hexamethylene diisocyanate as the component (I2). It is preferable to use a polyisocyanate compound selected from the group consisting of

In the present embodiment, the blending ratio of the component (I) is 4.0 to 20 parts by mass with respect to 100 parts by mass of the polyurethane (urea) resin from the viewpoint of the adhesiveness and heat resistance of the obtained photochromic layer. Is preferred. When forming the photochromic layer using the component (I), 0.1 to 20 parts by mass of the chromene compound is used with respect to 100 parts by mass of the total amount of the polyurethane (urea) resin and the component (I). Is preferred. In addition, the said ratio is based on these total amounts, when using both (I1) component and (I2) component as (I) component.

When the blending amount of the component (I) satisfies the above range, the obtained adhesive layer exhibits an excellent effect. When the blending amount of the component (I) is less than the above range, sufficient adhesion and heat resistance improvement effects cannot be obtained. On the other hand, when the amount is larger than the above range, the adhesive layer tends to become cloudy, decrease in adhesiveness and the like.
It is considered that the component (I) can increase the molecular weight of the polyurethane (urea) resin by acting on the urethane bond part and / or the urea bond part of the polyurethane (urea) resin.

(Laminated body including photochromic layer using polyurethane (urea) resin)
In the present embodiment, a photochromic layer using a polyurethane (urea) resin as a synthetic resin is also used as an adhesive layer and can be bonded to other layers. Specifically, after the photochromic layer is formed on a substrate such as polyethylene terephthalate, polypropylene, etc., only the photochromic layer is peeled off from the substrate to form a photochromic adhesive layer, which is adhered to other layers such as an optical sheet, It can be set as a laminated body.

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 chromene compound (which may further contain the component (I)) is kneaded, and a uniform photochromic layer is produced by the above method. Next, a photochromic laminate in which the optical sheets are bonded via the adhesive layer can be manufactured by disposing the photochromic layer between the optical sheets and pressing the optical sheets together. In addition, when a composition containing a polyurethane (urea) resin containing an organic solvent and a chromene compound (which may further contain the component (I)) is used, the composition is once formed on the optical sheet. A laminated body can also be obtained by applying an object to form an application layer, removing the organic solvent from the application layer to form an adhesive layer, placing another optical sheet on the adhesive layer, and press-contacting.

(Optical sheet)
As the optical sheet bonded to the photochromic layer, an optical sheet equivalent to the optical sheet used in the above-described electrochromic laminate is suitably used. Among these, polycarbonate resin, polyamide resin, cellulose resin (such as triacetyl cellulose), and polyvinyl alcohol resin are more preferable because of good adhesiveness.
The surface (upper surface and lower surface) of the optical sheet is subjected to physical surface treatment such as chemical treatment using an alkaline solution or a chemical solution such as an acid solution, polishing treatment, corona discharge treatment, plasma discharge treatment, or UV ozone treatment. It may be broken.

Further, a coating layer (primer layer) may be formed on the surface (upper surface and lower surface) of the optical sheet. Examples of the coating layer include water-dispersible polymers such as water-dispersed polyurethane resins, water-dispersed polyester resins, water-dispersed acrylic resins, and water-dispersed polyurethane / acrylic resins; among the water-dispersible polymers, polymers having a carbonyl group Cross-linked product with hydrazide compound; cross-linked product of water-soluble polymer such as polyvinyl alcohol; polymerizable monomer having (meth) acrylic group and / or epoxy group, (meth) acrylic group, vinyl group, amino group, and mercapto group A composition of a hydrolyzable organosilicon compound having a group selected from: a silanol group or a polymerizable group selected from a group that can be hydrolyzed to form a silanol group, a (meth) acrylate group, an epoxy group, and a vinyl group Urethane urea resin composition having propenyl ether group-containing compound, polyene compound And ene / thiol-based composition comprising a thiol compound, the photocurable composition or the like comprising an oxetane compound or the like, resin, crosslinked, those formed from the composition is used.

Also, it is preferable to stack an optical sheet on at least one surface of the photochromic layer, and it is more preferable to stack an optical sheet on both surfaces. That is, a layer exhibiting photochromic properties (hereinafter sometimes referred to as “photochromic sheet”) is formed by bonding two optical sheets through a photochromic layer that is also used as the adhesive layer. Is preferred. In this case, the film thickness of the photochromic layer is preferably in the range of 5 to 100 μm, more preferably 10 to 60 μm, from the viewpoints of the color density of the chromene compound, weather resistance, adhesive strength, and the like.

The photochromic sheet may have another adhesive layer in order to further improve the adhesiveness with the optical sheet. That is, another optical layer made of polyurethane (urea) resin not containing a photochromic compound is laminated on both sides of the photochromic layer (the same as the “second adhesive layer” described later) is laminated, and two optical sheets The photochromic sheet | seat formed by adhere | attaching may be sufficient.
In addition, it is preferable to provide the said adhesive layer in both between two optical sheets and a photochromic layer.

(Joint method of photochromic layer and electrochromic laminate using polyurethane (urea) resin)
One of the optical sheets bonded to the photochromic layer may be an electrochromic laminate optical sheet or other optical sheet. In other words, when a polyurethane (urea) resin is used for the photochromic layer, the photochromic layer itself has adhesiveness, so the photochromic layer is formed on the optical sheet of the electrochromic laminate, and on the opposite side. Other optical sheets can be laminated.
That is, a single optical sheet interposed between the electrochromic element and the photochromic layer may be used, and a laminated body in which layers are formed in the order of optical sheet / photochromic layer / optical sheet / electrochromic element / optical sheet. .

(Second adhesive layer)
An adhesive layer that does not contain a chromene compound may exist between the photochromic layer and the electrochromic laminate. For example, an adhesive layer made of the above polyurethane (urea) resin not containing a chromene compound, an adhesive layer made of a composition containing the above polyurethane (urea) resin not containing a chromene compound, and the component (I), or a coating film to be described later There may be a layer (primer layer) (hereinafter sometimes referred to as “second adhesive layer”).

As the second adhesive layer, the resin described as the polyurethane (urea) resin can be used. Among them, the number of substituents n1, n2, and n3 in the components (A1), (A2), and (A3) is n1: n2: n3 = 1.00: (0.30-0.90) :( 0.10 It is preferable to use a polyurethane (urea) resin synthesized at a ratio of ˜0.70), and n1: n2: n3 = 1.00: (0.40 to 0.80) :( 0.20 to 0) .60) is more preferable. When the component (A4) is used, n1: n2: n3: n4 = 1.00: (0.30 to 0.89) :( 0.10 to 0.69) :( 0.01 to 0.20) is preferable, and n1: n2: n3: n4 = 1.00: (0.40 to 0.80): (0.15 to 0.58): (0.01 to 0.15) ) Is more preferable.
In addition, the primer layer mentioned later can also be used as a 2nd contact bonding layer.

The thickness of the second adhesive layer is not particularly limited, but is preferably 5 to 15 μm.

When the optical article according to this embodiment is used as an optical lens, the photochromic sheet is used after being bent into a spherical shape. In addition, when using the photochromic sheet integrally with the electrochromic optical substrate processed into a lens-like spherical shape, bending is performed before the integration, so that the same spherical shape as the electrochromic optical substrate is obtained. It is preferable to process.

Examples of the method of bending the photochromic sheet into a spherical shape include hot press processing, pressure processing, and vacuum suction processing.
The temperature at the time of bending may be appropriately determined depending on the type of the optical sheet used in the photochromic sheet, but it is preferably carried out at a temperature of more than 100 ° C. and 200 ° C.

As described above, it is preferable that a second adhesive layer is formed between the photochromic sheet and the electrochromic laminate (the surface of the optical sheet). Then, after joining the bent photochromic sheet and the electrochromic optical substrate, in order to further improve the adhesion between the electrochromic laminate and the second adhesive layer and between the second adhesive layer and the photochromic sheet, 60 to 120 Heat treatment is preferably performed in the temperature range of 0.5 ° C. for about 0.5 to 6 hours. Thereby, an optical article having good adhesion at all interfaces can be obtained.

[Crosslinkable (meth) acrylic resin; synthetic resin]
In this embodiment, when a crosslinkable (meth) acrylic resin is used as the synthetic resin used for the photochromic layer, the following aspects are preferable.
Here, the crosslinkable (meth) acrylic resin is a crosslinked (meth) acrylic resin obtained by polymerizing and curing a composition containing a monomer having a plurality of (meth) acrylic groups in the molecule, which will be described in detail below. Point to. “(Meth) acrylic resin” means both “acrylic resin” and “methacrylic resin”.

The crosslinkable (meth) acrylic resin is not particularly limited, but a polymerized and hardened compound containing a crosslinkable (meth) acrylic monomer, a polymerization initiator, and the like is used.

Although it does not restrict | limit especially as a crosslinkable (meth) acryl monomer, For example, a trimethylol propane trimethacrylate, a trimethylol propane triacrylate, a tetramethylol methane trimethacrylate, a tetramethylol methane triacrylate, a tetramethylol methane tetramethacrylate, a tetramethylol methane Tetraacrylate, trimethylolpropane triethylene glycol trimethacrylate, trimethylolpropane triethylene glycol triacrylate, ditrimethylolpropane tetramethacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexaacrylate, bisphenol A dimethacrylate, 2,2-bis ( 4-Methacryloyloxyethoxypheny Propane, 2,2-bis (4-methacryloyloxypolyethylene glycol phenyl) propane having an average molecular weight of 628, 2,2-bis (4-methacryloyloxypolyethylene glycol phenyl) propane having an average molecular weight of 804, 2,2 having an average molecular weight of 776 -Bis (4-acryloyloxypolyethylene glycol phenyl) propane, methoxypolyethylene 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 Coal diacrylate, pentaethylene glycol diacrylate, tripropylene glycol diacrylate, tetrapropylene glycol diacrylate, pentapropylene glycol diacrylate, polyethylene glycol dimethacrylate having an average molecular weight of 330, polyethylene glycol dimethacrylate having an average molecular weight of 536, and an average molecular weight of 736 Polytetramethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, tetrapropylene glycol dimethacrylate, polypropylene glycol dimethacrylate having an average molecular weight of 536, polyethylene glycol diacrylate having an average molecular weight of 258, polyethylene glycol diacrylate having an average molecular weight of 308, and an average molecular weight of 508 Polyethylene glycol di Acrylate, polyethylene glycol diacrylate having an average molecular weight of 708, polycarbonate di (meth) acrylate which is a reaction product of polycarbonate diol and (meth) acrylic acid, urethane oligomer tetraacrylate, urethane oligomer hexamethacrylate, urethane oligomer hexaacrylate, etc. Silsesquioxane monomer having various structures such as polyfunctional polyester (meth) acrylate such as functional urethane (meth) acrylate and polyester oligomer hexaacrylate, (meth) acrylic group, cage shape, ladder shape and random , Polyrotaxane compounds having a (meth) acryl group in the side chain, 2-isocyanatoethyl methacrylate, γ-methacryloxypropyltrimethoxysilane, γ- Examples thereof include crosslinkable (meth) acrylic monomers containing (meth) acrylic groups and having two or more polymerizable groups, such as methacryloxypropylmethyldimethoxysilane and glycidyl methacrylate.

As the polymerization initiator, those known as photopolymerization initiators are used. For example, benzophenone; 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl 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-morpholinopropan-1-one Acetophenone compounds such as 2-benzyl-2dimethylamino-1- (4-morpholinophenyl) -butanone-1, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one; Α-dicarbonyl compounds such as 1,2-diphenylethanedione and methylphenylglycoxylate; Zoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, 2,4 Acylphosphine such as 6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine acid methyl ester, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide Finoxide compounds; 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)], oxy-phenyl-acetic acid 2- [2-oxo-2-phenyl-acetate And xyl-ethoxy] -ethyl ester, oxy-phenyl-acetic acid 2- [2-hydroxy-ethoxy] -ethyl ester, and the like.

(Photochromic layer using crosslinkable (meth) acrylic resin)
The photochromic layer using the crosslinkable (meth) acrylic resin is not particularly limited, but a crosslinkable (meth) acrylic monomer, a chromene compound, a polymerization initiator, etc. are blended to form a photochromic coat composition, and polymerization is performed. It is preferably formed by curing. In addition, although a crosslinkable (meth) acrylic resin and a chromene compound can be mechanically mixed to form a photochromic layer, the dispersibility of the chromene compound, the adhesion of the resulting optical article, the productivity, the photochromic properties, etc. From the viewpoint, the above method is preferable.

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

Further, the blending ratio of the chromene compound in the photochromic coating composition is not particularly limited, but 0.1 to 20 parts by mass of the chromene compound with respect to 100 parts by mass in total of the crosslinkable (meth) acrylic monomer and the polymerization initiator. The range is preferably set, and the range of 0.5 to 10 parts by mass of the chromene compound is more preferable.

The viscosity of the photochromic coating composition is preferably in the range of 50 to 1,000 cP, more preferably in the range of 100 to 500 cP, from the viewpoint of uniform layer formation in spin coating described later. preferable.

As such a photochromic coating composition, from the viewpoint of photochromic properties, optical properties, solvent resistance of the photochromic layer, surface hardness, and adhesion, for example, International Publication No. 03/011967, International Publication No. 04 / 050775 pamphlet, WO 05/014717 pamphlet, WO 2011/12595 pamphlet, Japanese Patent No. 5991980, WO 2013/008825, JP 2013-072000, JP 2015-025063. Gazette, international publication 2014/136919 pamphlet, international publication 2014/136804 pamphlet, international publication 2015/068798 pamphlet, international publication 2016/013677 pamphlet, JP-A-2 17-052869, JP-it can also be used photochromic coating compositions described in JP 2017-19973 and JP International Publication 2017/038957 pamphlet or the like.

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

Moreover, a photochromic layer can also be formed by a so-called kneading method using the photochromic composition. In this case, the method for forming the photochromic layer is preferably a method in which a mold is formed and the photochromic composition is filled therein in the same manner as the method for forming the optical substrate on the electrochromic laminate.

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

(Primer layer; crosslinkable (meth) acrylic resin)
In the present embodiment, a photochromic layer using a crosslinkable (meth) acrylic resin as a synthetic resin has a primer layer formed on an optical sheet of an electrochromic laminate, for example, in order to improve adhesion with other layers. A photochromic layer is preferably formed thereon.

The primer layer is not particularly limited, and a known adhesive resin is used. For example, moisture-curable polyurethane, polyisocyanate-polyester two-part, polyisocyanate-polyether two-part, polyisocyanate-polyacryl two-part, polyisocyanate-polyurethane elastomer two-part Adhesives such as epoxy-based, epoxy-polyurethane two-component, acrylic, polyester-based, polyurethane-urea one-component, and water-dispersible polyurethane are used.

The primer layer is preferably made of a urethane resin. As described above, the luminous transmittance and the bonding strength of the finally obtained optical article can be maintained high.
The urethane resin is not particularly limited, and a known urethane resin is used. For example, the moisture-curing urethane resin / precursor thereof described below or a water-dispersed urethane resin emulsion may be mentioned.
Of the above, it is preferable to use a moisture curable urethane resin / precursor thereof from the viewpoint of expressing stronger adhesion between the optical sheet of the electrochromic laminate and the photochromic layer.

(Moisture curable urethane resin; primer layer)
Moisture curable urethane resin and / or its precursor (hereinafter sometimes simply referred to as “moisture curable urethane resin”) is a part of a plurality of isocyanate groups present in the molecule, for example, moisture in the atmosphere. An isocyanate group-containing compound that undergoes cross-linking by reacting to produce carbamic acid and then decarboxylating to produce an amine and reacting the amine with the remaining isocyanate group to form a urea bond, or a precursor of such a compound Or a combination of these compounds.
In addition, although a urea bond produces | generates as a result of reaction of the said water | moisture content and isocyanate, the primer layer in this embodiment may contain the urethane resin (urethane urea resin) containing such a urea bond. .

The moisture curable urethane resin is a polyisocyanate synthesized from a polyisocyanate compound composed of an aromatic isocyanate compound and / or a compound having an active hydrogen and the aromatic isocyanate compound in such a ratio that the isocyanate group remains. It is preferably formed by an oligomer compound. As described above, the primer layer can exhibit excellent adhesion even at a relatively low temperature.
In the case of using a polyisocyanate oligomer compound, examples of the compound having active hydrogen include polyalkylene glycols, polyols containing three or more hydroxy groups, polyalkylene adipates, polyalkylene carbonates, polycaprolactones, Polyester polyols and the like are preferably used. The compounds having active hydrogen may 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 higher than that usually used. As a method for increasing the molecular weight, adjustment may be made so that the number of remaining isocyanate groups decreases when the polyisocyanate compound and the compound having active hydrogen are blended. Other methods include a method of bonding a plurality of isocyanate groups in the molecule of the moisture curable polyurethane resin and / or its precursor with a chain extender or the like. Here, examples of the chain extender include compounds having the above active hydrogen and diamine compounds such as ethylenediamine. Examples thereof include alkylene glycols such as 1,3-butanediol, 1,4-butanediol, propylene glycol and 1,6-hexanediol, and polyalkylene glycols such as polypropylene glycol. The above compound is preferably used from the viewpoint of easy control of the chain extension reaction.

The moisture curable urethane resin as described above can be diluted with an organic solvent such as toluene, xylene, ethyl acetate, butyl acetate, and a primer coating composition can be prepared by further blending a leveling agent as necessary.

(Water-dispersed urethane resin emulsion; primer layer)
A water-dispersed urethane resin emulsion is one in which a urethane resin is dispersed in water to form an emulsion.
The urethane resin contained in the water-dispersed urethane resin emulsion is preferably obtained by reacting an active hydrogen group-containing component with a polyisocyanate compound. Further, as the active hydrogen group-containing component, it is preferable to use at least a polyol compound, an anionic group active hydrogen group-containing compound, an active hydrogen group-containing acrylate compound, and / or an alkoxysilyl group-containing polyamine compound.

As said polyol compound and polyisocyanate compound, the thing similar to what was mentioned as a raw material of moisture hardening type urethane resin can be used.
The anionic group-active hydrogen group-containing compound has, for example, one or more anionic groups such as a carboxyl group, a sulfonyl group, a phosphate group, a betaine structure-containing group (sulfobetaine, etc.), and an isocyanate group. It is a compound which can react, for example, has two or more active hydrogen groups, such as a hydroxyl group and an amino group. For example, as an anionic group active hydrogen group-containing compound having a carboxyl group, 2,2-dimethylolacetic acid, 2,2-dimethylollactic acid, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2, Examples thereof include dihydroxylcarboxylic acids such as 2-dimethylolbutyric acid and 2,2-dimethylolvaleric acid, and diaminocarboxylic acids such as lysine and arginine.

The active hydrogen group-containing acrylate compound is a (meth) acrylate compound having one or more hydroxyl groups in the molecule. For example, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 2,2-dihydroxymethylbutyl (meth) acrylate, polyhydroxyalkyl maleate, polyhydroxyalkyl fumarate, etc. Can be mentioned.

Examples of the alkoxysilyl group-containing polyamine compound include alkoxysilyl compounds having a primary amino group and a secondary amino group. For example, N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropyldimethoxysilane, γ- (2-aminoethyl) aminopropyldiethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyldimethoxysilane, γ- Examples thereof include aminopropyldiethoxysilane, N, N′-bis [α- (trimethoxysilyl) propyl] ethylenediamine, and the like.

The water-dispersed urethane resin can be synthesized by a one-shot method or a prepolymer method, but it is preferable to use a prepolymer method.
A chain extender may be used for the synthesis of the water-dispersed urethane resin. As the chain extender, other amines and hydrazines (other amines and hydrazines are included in the active hydrogen group-containing component) other than the alkoxysilyl group-containing polyamine compound can also be used in combination. For example, such other amines include ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,6-hexamethylenediamine, 1,4-cyclohexanediamine, and 3-isocyanatomethyl-3. , 5,5-trimethylcyclohexyl isocyanate (isophoronediamine), 4,4'-dicyclohexylmethanediamine, 2,5 (2,6) -bis (aminomethyl) bicyclo [2.2.1] heptane, 1,3- Examples thereof include diamines such as bis (aminomethyl) cyclohexane, and polyamines such as diethylenetriamine, triethylenetetramine, and tetraethylenepentamine.

The water-dispersed urethane resin obtained as described above can be dispersed in water to obtain a water-dispersed urethane resin emulsion. Examples of water-dispersed urethane resin emulsions include those described in Japanese Patent No. 5016266 and Japanese Patent No. 5084727.
Moreover, it is preferable to mix | blend water, a leveling agent, an organic solvent, etc. with respect to the said water-dispersed urethane resin emulsion as needed, and let it be a primer coat composition.

(Method for forming photochromic layer on primer layer; crosslinkable (meth) acrylic resin)
In this embodiment, after the primer layer is formed on the electrochromic optical substrate, a photochromic layer (using a crosslinkable (meth) acrylic resin) is formed on the primer layer.

Examples of the method for forming the primer layer include a method in which the primer coat composition is applied to the surface of the electrochromic optical substrate and then dried and cured.
The coating method is not particularly limited, and a known method is used. For example, a method of applying the composition or the like by a method such as spin coating, spray coating, dip coating, dip-spin coating or the like can be mentioned. Among these coating methods, it is preferable to employ spin coating because the film thickness can be easily controlled and a coating film having a good appearance can be obtained.

When applying the primer coat composition by spin coating, the viscosity at 25 ° C. of the primer coat composition is preferably in the range of 5 to 200 cP because it is easy to obtain a primer layer having a uniform thickness. A range of 10 to 100 cP is more preferable. The viscosity can be adjusted by changing the type and amount of the dispersion medium.
The thickness of the primer layer formed by the above method is preferably 1 to 20 μm.

When the primer coating composition contains water or an organic solvent, the primer layer can be formed by applying the primer coating composition on the electrochromic optical substrate by spin coating or the like and then drying it under appropriate conditions.

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

As a method of laminating a photochromic layer on the primer layer formed as described above, for example, a primer coat composition was applied on an electrochromic optical substrate and then dried at 10 to 40 ° C. for 5 to 30 minutes. Examples include a method in which a photochromic sheet is bonded on the primer layer and heated, and a method in which a photochromic coating composition is applied, placed in an inert gas such as nitrogen, and the photochromic layer is photocured by UV irradiation. These methods are preferably used from the viewpoint of adhesion between the primer layer and the photochromic sheet or the photochromic coat layer. Among these, from the viewpoint of productivity of the obtained optical article, a method by photocuring is more preferable.

Among the above-mentioned photocuring conditions, particularly, the ultraviolet (UV) intensity condition affects the properties of the resulting photochromic layer. This condition is influenced by the type and amount of the photopolymerization initiator and the type of the (meth) acrylic monomer, and thus cannot be generally limited. However, generally, UV light of 50 to 500 mW / cm ² is used at a wavelength of 365 nm. Is preferably irradiated with light for 0.5 to 5 minutes.

In the present embodiment, after the photochromic layer is laminated by photocuring by the above method, the adhesion between the electrochromic optical substrate and the primer layer and between the primer layer and the photochromic layer is further improved. Heat treatment is preferably performed at a temperature range of 120 ° C. for about 0.5 to 6 hours. Thereby, the electrochromic photochromic optical article with favorable adhesiveness in all the interfaces can be obtained.

[Other additives; Photochromic layer]
In this embodiment, a photochromic layer can be formed using the said polyurethane (urea) resin or a crosslinkable (meth) acrylic resin as a synthetic resin (layer) containing the chromene compound as a photochromic compound.
Further, the photochromic layer may contain other additives as other components as long as adhesion and other performances are not impaired. For example, additives such as surfactants, ultraviolet absorbers, infrared absorbers, ultraviolet stabilizers, antioxidants, anti-coloring agents, antistatic agents, fluorescent dyes, dyes, pigments, fragrances and other stabilizers are required. It may be included accordingly.

<Configuration of other optical articles>
According to the above method, an optical article having both photochromic characteristics and electrochromic characteristics can be formed.
As described above, when the optical article in the present embodiment is used for an optical lens application such as a spectacle lens, the photochromic layer / electrochromic laminate or the electrochromic layer is sequentially formed from the light incident side of sunlight or the like. What is necessary is just to be formed in order of a laminated body / photochromic layer. However, in consideration of moldability, function, etc. of the obtained optical article, an aspect of the optical article in which each layer is formed in the order of photochromic layer / electrochromic laminate / optical substrate in order from the light incident side of sunlight or the like It is preferable to take

The optical article according to the present embodiment has been post-processed by a known method such as a hard coat treatment, a water repellent treatment, an antifogging treatment, or an antireflection film on one side or both sides according to the application to be used. May be. Or the layer which has a polarizing function, or the film which has a polarizing function may be laminated | stacked as needed.

Hereinafter, the present invention will be described in detail using examples and comparative examples, but the present invention is not limited to the examples. In the examples and comparative examples, the above-described components, methods for evaluating photochromic characteristics and electrochromic characteristics, and the like are as follows.

(Electrochromic laminate and optical substrate; electrochromic lens substrate)
EC1; between two 0.3 mm thick polycarbonate sheets (optical sheets), a 50 nm thick ITO transparent electrode, a 700 mm thick iridium oxide and tin oxide mixture, an oxidation colored electrochromic layer, 5000 mm thick Ta An electrochromic laminate having a transparent ion conductive layer made of ₂ O _3, a reduced-color electrochromic layer made of WO _{3 having a} thickness of 5000 mm, and an ITO transparent electrode layer having a thickness of 50 nm was injected into a 2 mm thick polycarbonate resin (optical). The base material was joined to produce an electrochromic lens base material as an electrochromic optical base material.
The EC1 has an initial luminous transmittance of 85%, and is colored blue when a voltage of about 2.1 V is applied between the electrodes, and has a performance of reaching a luminous transmittance of 30%. In addition, after coloring, when a voltage of about −2.1 V is applied between the electrodes, the color disappears and the original luminous transmittance returns to 85%.

EC2: Oxidized colored electrochromic layer composed of a mixture of ITO transparent electrode of 50 nm thickness, 700 mm thickness of iridium oxide and tin oxide, between two 0.3 mm thickness polyamide sheets (optical sheets), 5000 mm thickness of Ta Both surfaces of an electrochromic laminate having a transparent ion conductive layer made of ₂ O _3, a reduced-colored electrochromic layer made of 5000 Å thick WO ₃ and an ITO transparent electrode layer having a thickness of 50 nm were subjected to corona etching. After the obtained electrochromic laminate is placed in two glass plates and a mold is assembled, the mold is filled with an allyl diglycol carbonate monomer composition containing IPP (diisopropyl peroxydicarbonate) as an initiator. Then, an electrochromic lens substrate having a total thickness of 3 mm was produced by thermal polymerization.
The EC2 has an initial luminous transmittance of 85%, and is colored blue when a voltage of about 2.1 V is applied between the electrodes, and has a performance of reaching a luminous transmittance of 30%. In addition, after coloring, when a voltage of about −2.1 V is applied between the electrodes, the color disappears and the original luminous transmittance returns to 85%.

EC3; 50 nm thick ITO transparent electrode, first electrochromic layer (containing triarylamine compound having monofunctional acrylate), electrolyte layer (1-ethyl) between two 0.3 mm thick polycarbonate sheets (optical sheets) -3-Methylimidazolium bis (trifluoromethylsulfonyl) imide), second electrochromic layer (titanium oxide particle film / electrochromic compound-containing layer of the following formula), and 50 nm thick ITO transparent electrode A 2 mm thick polycarbonate resin (optical base material) was joined to the body by injection molding to produce an electrochromic lens base material.
The EC3 has an initial luminous transmittance of 85%, and is colored blue-green when a voltage of about 2 V is applied between the electrodes, and has a performance of reaching a luminous transmittance of 30%. In addition, after coloring, when a voltage of about 2 V is applied between the electrodes, the color disappears and the original luminous transmittance returns to 85%.

(Primer coat composition)
PR1: Moisture curable primer (Product name: TR-SC-P, manufactured by Tokuyama Corporation)
PR2: Water-dispersed urethane emulsion (Product name: NJ-321A, manufactured by Tokuyama Corporation)

(Photochromic compound)
Chromene 1: Compound represented by the following formula

<Example 1>
(Method for forming primer layer on electrochromic lens substrate)
Using a spin coater (1H-DX2, manufactured by MIKASA) on the surface of the electrochromic lens substrate EC1, a water-dispersed urethane emulsion (product name: NJ-321A, manufactured by Tokuyama Corporation; PR2) is rotated at a rotational speed of 70 rpm. Second, followed by a 5 second coat at 800 rpm. Then, it dried for 10 minutes at room temperature (about 23 degreeC), and formed the primer layer. The thickness of the primer layer was about 7 μm.

(Photochromic coating composition)
γ-methacryloyloxypropyltrimethoxysilane 5 parts by mass, trimethylolpropane trimethacrylate 20 parts by mass, 2,2-bis (4-methacryloyloxyethoxyphenyl) propane 35 parts by mass, urethane oligomer hexaacrylate 10 parts by mass, average molecular weight 532 100 parts by mass of a polymerizable monomer consisting of 20 parts by mass of polyethylene glycol diacrylate and 10 parts by mass of glycidyl methacrylate, 3 parts by mass of chromene 1 and bis (1,2,2,6,6 as stabilizer) -Pentamethyl-4-piperidyl) sebacate, 0.3 parts by weight of CGI148 (1-hydroxycyclohexyl phenyl ketone) as a polymerization initiator, and CGI819 (bis (2,4,6-trimethylbenzoyl) -phenylphosphine fin Kisaido) were added 0.3 part by weight was sufficiently stirred, it was used as the photochromic coating composition is degassed.

(Production of electrochromic photochromic optical articles)
Next, 2.0 g of the photochromic coating composition was applied onto the electrochromic lens substrate on which the primer layer was formed by the above method, by spin coating so that the film thickness of the formed photochromic layer was 30 μm. Thereafter, UV light generated from an electrodeless lamp was irradiated in a nitrogen gas atmosphere for 80 seconds from a height of 200 mm above the workpiece (lens substrate). At this time, the UV intensity at 365 nm on the workpiece surface was 125 mW / cm ² , and the integrated light amount was 10 J. Then, it heated at 80 degreeC for further 1 hour, and produced the electrochromic photochromic optical article which has a photochromic layer in a 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 coat 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>
An optical article was produced under the following conditions.
(Synthesis of polyurethane-urea resin (U1))
A three-necked flask having a stirrer chip, a cooling tube, a thermometer, and a nitrogen gas introduction tube was charged with 9.0 g of polyether diol having a number average molecular weight of 400, 10.0 g of isophorone diisocyanate, and 80 ml of DMF at 120 ° C. in a nitrogen atmosphere. The mixture was allowed to react for 5 hours, then cooled to 25 ° C., 3.4 g of isophoronediamine as a chain extender was added dropwise, reacted at 25 ° C. for 1 hour, the solvent was distilled off under reduced pressure, and the polyurethane-urea resin (U1) was removed. Obtained. The molecular weight of the obtained polyurethane-urea resin was 150,000 in terms of polystyrene and 10,000 in terms of polyoxyethylene (molecular weight is a theoretical value).

(Preparation of photochromic composition)
Polyurethane-urea resin (U1) 5 g, photochromic compound (chromene 1) 0.25 g, isopropyl alcohol 20 g as an organic solvent, and bis (1,2,2,6,6-pentamethyl-4-piperidyl as a photo-oxidant ) 0.25 g of sebacate was added and dissolved by ultrasonic wave while stirring at 80 ° C. to obtain a photochromic composition.

(Preparation of photochromic laminate)
The photochromic composition is applied onto a fluororesin sheet having a smooth surface and dried at 80 ° C. for 1 hour. The obtained 30 μm-thick photochromic sheet is sandwiched between two 400 μm-thick polycarbonate sheets. A laminate having photochromic properties was obtained.

(Production of electrochromic photochromic optical articles)
A polyisocyanate-polyester two-component coating solution was applied to the surface of the electrochromic lens substrate EC1, and the photochromic laminate was bonded thereon 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 the photochromic layer was not formed on the electrochromic lens substrate EC1 and only the electrochromic lens substrate EC1 was used.

<Comparative example 2>
An optical article was produced under the same conditions as in Example 1 except that a polycarbonate lens having 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 spiropyran 1 represented by the following formula was used instead of chromene 1.

For the optical articles of Examples 1 to 6 and Comparative Examples 1 to 3, the luminous transmittance, antiglare property and visibility were evaluated by the following methods. The results are shown in Table 1.

[Evaluation method of luminous transmittance (when only the electrochromic layer is colored)]
Using the obtained electrochromic photochromic optical article as a sample, a voltage of about 2.1 V is applied between the electrodes of the lens to develop a color, and the luminous transmittance of the electrochromic photochromic optical article in a 23 ° C. or 35 ° C. environment Was measured.

[Evaluation method of luminous transmittance (when only the photochromic layer is colored)]
The obtained electrochromic photochromic optical article was used as a sample, and a xenon lamp L-2480 (300 W) SHL-100 manufactured by Hamamatsu Photonics Co., Ltd. was passed through an aeromass filter (manufactured by Corning) at 23 ° C. or 35 The color intensity was measured by irradiation 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 at ℃, and the luminous transmittance of the electrochromic photochromic optical article was measured.

[Evaluation method of luminous transmittance (when both electrochromic layer and photochromic layer are colored)]
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 a color, and a xenon lamp L-2480 (300W) SHL- manufactured by Hamamatsu Photonics Co., Ltd. 100 is irradiated through an aeromass filter (Corning) at 23 ° C. or 35 ° C. 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. The luminous transmittance of the electrochromic photochromic optical article was measured.

A spectrophotometer (instant multi-channel photo director MCPD1000) manufactured by Otsuka Electronics Co., Ltd. was used to measure the three types of luminous transmittance.

[Evaluation of anti-glare and visibility]
Using the electrochromic photochromic optical article produced by the above method and having 10 subjects wear the electrochromic optical article outdoors on a sunny day with a temperature of 30 to 36 ° C., antiglare and visibility Satisfaction was investigated. The numbers indicate the percentage of satisfied people (%).

As is apparent from Table 1, the optical articles of Examples 1 to 6 are excellent in luminous transmittance, antiglare property, and visibility at high temperatures. On the other hand, an optical article having only one of electrochromic properties or photochromic properties as shown in Comparative Example 1 or 2, or electrochromic photochromic using spiropyran as a photochromic compound as shown in Comparative Example 3 Optical articles have insufficient luminous transmittance, antiglare properties, and visibility at high temperatures.

1: (Electrochromic photochromic) Optical article 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,
The photochromic layer is an optical article containing a chromene compound. The optical article according to claim 1, wherein the photochromic layer is made of a urethane (urea) resin or a crosslinkable (meth) acrylic resin containing a chromene compound. The optical article according to claim 1 or 2, wherein the optical article is used as an optical lens, wherein the photochromic layer is disposed on a light incident side and the electrochromic layer is disposed on a light exit side.

Images