JPH0973149A - Photosensitive composition and element using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photochromic photosensitive compsn. in which there is little change in the hue and a rate of developing or erasing colors is fast containing photochromic compds. having different max. absorption spectrum in a colored state, by specifying the structure, the max absorption spectrum in a colored state and the time from a colored state to a decolored state of each compd. SOLUTION: This photosensitive compsn. contains a photochromic compd. (1) having the max. absorption spectrum in the range from 356nm to 530nm and a photochromic comps. (2) having the max. absorption spectrum in the range from 560nm to 750nm in a colored state. The substantial time from the colored state to a decoloed state of each compd. (1), (2) is within 3min. Or the photosensitive compsn. contains a photochromic conpd.(1) having a structure expressed by formula and a photochrompoc compd. (2) having the max. absorption spectrum in a colored state in the range from 560nm to 750nm. In formula, R1 -R14 are hydrogen atoms or substituents.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive composition useful for various light control, display, coloring and recording using a photochromic compound and an element having photochromic properties using the same.

[0002]

2. Description of the Related Art In recent years, photochromic compounds have attracted attention as optical recording, display or light control materials.
hotochromism, Molecule and Systems (Ed. by H. Durr,
Various compounds have been developed as described in books such as H. Bouas-Laurent, Elsevier, New York 1989). When using photochromic compounds for display or light control materials, gray, amber, brown,
Although a color tone such as green is preferred, when a conventionally known compound is used alone, a desired color tone cannot be obtained,
Therefore, attempts have been made so far to mix and use a compound that develops yellow to orange and a compound that develops purple to blue. For example, JP-A-4-39382 and JP-A-6-
No. 5,105,19 is cited. When two color compounds are mixed and used, it is important that both color development and color erasing are performed to the same extent. The conventionally known mixed system has a drawback in that the color development and decolorization (particularly decolorization) of a compound that develops yellow to orange is slower than that of a compound that develops purple to blue.

[0003]

DISCLOSURE OF THE INVENTION The object of the present invention is to overcome the above-mentioned deficiencies, to provide a photochromic photosensitive composition having a small change in hue and a high rate of coloring and decoloring, and a photosensitive composition thereof on a substrate. To provide a carried element.

[0004]

The objects of the present invention have been achieved by the following method. (1) The maximum value of the light absorption spectrum is 350 in the colored state.
A photosensitive composition having a photochromic compound (1) in the range of nm to 530 nm and a photochromic compound (2) in the range of 560 nm to 750 nm, wherein each of compound (1) and compound (2) is A photosensitive composition, wherein the time from the substantially colored state to the decoloring is within 3 minutes. (2) A photosensitizer comprising a photochromic compound (1) represented by the following general formula (1) and a photochromic compound (2) having a maximum light absorption spectrum within a range of 560 nm to 750 nm in a colored state. Sex composition.

[0005]

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In the formula, R _{1 to} R ₁₄ each represent a hydrogen atom or a substituent. (3) A photochromic compound (1) represented by the following general formula (2), and a photochromic compound (2) having a maximum light absorption spectrum within a range of 560 nm to 750 nm in a colored state and an organic zinc salt. A characteristic photosensitive composition.

[0007]

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In the formula, R _{15 to} R ₂₂ each represent a hydrogen atom or a substituent, and R ₂₃ and R ₂₄ each represent an aryl group or a heterocyclic group. (4) The photosensitive composition as described in (1) or (2) above, which further contains an organic zinc salt. (5) The photosensitive composition as described in (2) above, wherein the photochromic compound is emulsified and dispersed in a hydrophilic polymer. (6) An element in which the photosensitive composition according to (1), (2), (3), (4) or (5) is carried on a substrate.

The above item 1 will be further described. It is preferable that the time for each of the compound (1) and the compound (2) to substantially decolor is within 1 minute. Further, the ratio of substantial decoloring time of the compound (1) and the compound (2) is preferably 0.5 to 1.5, and particularly preferably 0.8 to 1.2.

The general formulas (1) and (2) will be further described. Examples of the substituent represented by R ₁ and R ₂ include a halogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, and an optionally substituted alkoxy group. Preferred among R ₁ and R ₂ is a hydrogen atom. Examples of the substituent represented by R _{3 to} R ₁₄ include an acyl group, an acylamino group, an ester group, an acyloxy group, a carbamoyl group, a sulfamoyl group, a sulfonylamino group, a sulfonyl group, an optionally substituted amino group, a carboxyl group, and a sulfo group. Group, a cyano group, a perfluoroalkyl group, a thioalkyl group, a nitro group, or a group having the same meaning as R ₁ . R _{9 to} R ₁₄ may be cyclized to each other at adjacent positions to form a saturated ring (for example, a cyclohexane ring) or an unsaturated ring (for example, a benzene ring) composed of a 5- to 8-membered non-metal atom. It is preferable that R _{9 to} R ₁₄ do not form a ring. Particularly preferred R _{9 to} R ₁₄ are a hydrogen atom, an alkoxy group, an alkyl group or a halogen atom. R ₁₅ and R ₁₆ have the same meaning as R _{1 in} formula (1), and R _{17 to} R ₂₂ have the same meaning as R _{3 in} formula (1). Examples of the aryl group and heterocyclic group of R ₂₃ and R ₂₄ are benzene, naphthalene, pyridine, quinoline, imidazole,
Furan, thiophene, benzimidazole, naphthothiophene, naphthopyran, pyrene, anthracene, naphthoquinoline and the like can be mentioned. These may be substituted by the substituent described as R ₃ .

Examples of the photochromic compound having a maximum light absorption spectrum within the range of 560 nm to 750 nm in the colored state include indolinospiroxazine-based compounds, indolinospiropyran-based compounds and indolinospirothiopyran-based compounds. These specific examples are shown in Tokuhyo 6-510.
No. 519, Japanese Examined Patent Publication No. 45-28892, Chemical Society of Japan No. 5
0 Spring Annual Conference Proceedings I, 259 (1985). Among them, the preferable one is the following general formula (3).
It is a compound represented by these. Among these, particularly preferred are the compounds represented by the following general formula (4).

[0012]

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In the formula, R ₂₅ represents an optionally substituted alkyl group. R _{26 to} R ₃₁ represent a hydrogen atom or a group having the same meaning as R _{3 in} formula (1). R _{26 to} R ₃₁ may be cyclized to each other at adjacent positions to form a saturated or unsaturated ring composed of a 5- to 8-membered non-metal atom. In this case, preferred rings include a benzene ring and a pyridine ring. X
Represents CR ₃₂ R ₃₃ (R ₃₂ and R ₃₃ represent an optionally substituted alkyl group), S or O. Y represents S or O. Z represents CH, CR ₃₄ (R ₃₄ may be substituted, and represents an alkyl group) or N. R ₃₅ ~ R ₃₇
Is an optionally substituted alkyl group (preferably C _1- ).
It represents a C ₈ alkyl group). R _{38 to} R ₄₂ have the same meaning as R ₂₆ . Preferred among R _{38 to} R ₄₂ is a hydrogen atom.

Specific examples of the compound represented by the general formula (1) or (2) are shown below.

[0015]

[Chemical 6]

[0016]

[Chemical 7]

[0017]

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Specific examples of the compound represented by formula (3) or (4) are shown below.

[0019]

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[0020]

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The compound represented by the general formula (3) or (4) is 0.1 to 10 parts by weight, preferably 0.3 to 4 with respect to 1 part by weight of the compound represented by the general formula (1) or (2). Used in a mixing ratio of parts by weight. The compound represented by the general formula (1) or (2) and the compound represented by the general formula (3) or (4) may be used alone or in combination of two or more kinds. When an organic zinc salt is used in combination with the photochromic compound of the present invention, color development is promoted. Preferred among the organic zinc salts are those having a carboxylic acid group,
Particularly preferred are zinc salts of salicylic acid derivatives (particularly oil-soluble salts). It does not matter whether they are low molecular weight or high molecular weight.

It is preferable to use an organic zinc salt in order to increase the coloring density of the photosensitive composition of the present invention. As the organic zinc salt, a zinc salt of an oil-soluble salicylic acid derivative is preferable.
The substituents of the zinc salt of the oil-soluble salicylic acid derivative will be described below. Examples of the substituent include an alkyl group (methyl group, ethyl group, isopyryl group, butyl group, hexyl group,
Lauryl group, cyclohexyl group, methylbenzyl group, dimethylbenzyl group, α, α-dimethylbenzyl group, naphthoxybutyl group, dicyclopentadienyl group), aryl group (phenyl group, dimethylphenyl group), substituted carbamoyl group, substituted sulfamoyl group Group, acyl group (acetyl group, benzoyl group, toluenesulfonyl group), chloro atom, alkoxy group (ethoxy group, phenoxyethoxy group, methoxyphenoxyethoxy group, chloropropoxyethoxy group, benzyloxypropoxy group, naphthoxyethoxy group), It is selected from an aryloxy group (phenoxy group, naphthoxy group, p-methoxyphenoxy group), a substituted ureido group, a substituted urethane group, a carboxyl group, a sulfo group and the like. Also included are zinc salts of derivatives of xylylene dihalides, xylylene glycols, etc., such as substituted benzyl groups, reacted with salicylic acid. The substitution position of these substituents is selected from the 3,5,6-position and the like. From the viewpoint of availability of raw materials, it is convenient to substitute the 3-position or / and 5-position with an alkyl group, aralkyl group or aryl group having about 2 to 18 carbon atoms. Those substituted at the 6-position with alkyl are also preferable in terms of performance. From the viewpoint of solubility, the total number of carbon atoms is preferably 12 or more and about 60 or less. An oil-soluble zinc salt of salicylic acid having two α-methyl-substituted benzyl groups at the 3-position and the 5-position is easy to synthesize and is particularly preferable in terms of safety and handling of the composition.

For example, zinc 3,5-dibutylsalicylate, 3,
Zinc 5-diamylsalicylate, Zinc 3,5-dibutyl-6-methylsalicylate, Zinc 3-amyl-6-methylsalicylate, 3-
Benzyl-5-benzoylsalicylate zinc, 3,5-diα-methylbenzylsalicylate Zn, zinc 5-laurylsalicylate, 3,5-diα, zinc α-dimethylbenzylsalicylate,
Zinc 5-lauryl-3-methylsalicylate, 5-lauryl-3-
Zinc acetamide salicylate, 5- (p-butylphenoxy)-
Zinc α-butylacetamidosalicylate and zinc 5-phenylureidosalicylate are preferred. These are used in an amount of 0.001 to 500 parts by weight, preferably 0.1 to 10 parts by weight, relative to 1 part by weight of the compound represented by the general formula (1) or (2).

A photosensitive composition comprising a compound having a photochromic property having a specific skeleton of the present invention, a zinc salt of a salicylic acid derivative having a specific property which is optionally used in combination, and an organic solvent which is optionally used in combination is provided. The following may be mentioned as a form of being carried on a transparent substrate. (1) A composition comprising a photochromic compound, and a laminate in which a liquid phase in which a zinc salt of an oil-soluble salicylic acid derivative which is optionally used together is dissolved in an organic solvent is directly sandwiched between transparent films or glass. (2) Photochromic compound having a specific skeleton, a liquid phase in which a zinc salt of an oil-soluble salicylic acid derivative, which is optionally used in combination, is dissolved in an organic solvent, emulsified and dispersed in a hydrophilic polymer, and laminated on a substrate. body. (3) A photochromic compound having a specific skeleton, and a zinc salt of an oil-soluble salicylic acid derivative which is optionally used in combination are dissolved in a hydrophobic polymer together with a high-boiling organic solvent,
A laminate formed by melt molding or coating on a substrate by various methods.

(4) Spiropyran compound having a specific skeleton,
A coated material in which a liquid phase, in which a zinc salt of an oil-soluble salicylic acid derivative, which is optionally used together, is dissolved in an organic solvent having a specific boiling point, is microencapsulated and is carried on a substrate together with a binder. (5) A liquid phase in which a foot chromic compound having a specific skeleton and a zinc salt of an oil-soluble salicylic acid derivative which is optionally used together are dissolved in an organic solvent having a specific boiling point is microencapsulated using a synthetic polymer resin wall and a binder A laminated body supported on a substrate together with. In each of the above methods, the aspects (2) and (4) are preferable from the viewpoints of the speed of color development and decolorization of the footchromic compound, safety in production, simplicity, and the like.

The photosensitive composition of the present invention is used by dissolving it in an organic solvent or by emulsifying and dispersing it. The high boiling point organic solvent which is dissolved when emulsifying and dispersing is practically insoluble in water,
It is preferable that the boiling point is 190 ° C. or higher and 300 ° C. or lower. Examples of this type of organic substance include carboxylic acid esters, phosphoric acid esters, carboxylic acid amides, ethers, phenols, anilines, acetals, ketals, alcohols, substituted hydrocarbons and surface-inactive substances. It can be selected from among hydrophobic organic polymers and the like. Specific examples thereof include dibutyl phthalate, diisooctyl phthalate, dicyclohexyl phthalate, dimethoxyethyl phthalate, di-n-butyl adipate, diisooctyl azelate, tributyl citrate, butyl laurate, dibutyl sebacate, phosphorus. Tricyclohexyl acid,
Tributyl phosphate, triisooctyl phosphate, N, N-
Diethyl caprylic acid amide, N, N-dimethylpalmitic acid amide, tetrahydrofurfuryl alcohol, α,
α-dimethoxytoluene, 1,3-dimethyl-2-imidazolidinone, 18-crown 6-ether, N, N-
Dimethylglycine methyl ester ethyl orthoacetate,

Butyl- (m-pentadecyl) phenyl ether, ethyl- (2,4-di-t-butyl) phenyl ether, 2,5-diamylphenol, 2-n-butoxy-5-tert-octylaniline, Chlorinated paraffin, poly (methyl methacrylate), poly (ethyl methacrylate), poly (ethyl acrylate), poly (cyclohexyl methacrylate), poly (N-tert-butylacrylamide), poly (N-tert-octylacrylamide), ditolylethane, Examples include isopropyl naphthalene, xylyl phenyl ethane, ditolyl ether, butyl anisole, pentaerythritol dimethyl acetal, benzyl morpholine and oligobutylene oxide.

In the present invention, a low boiling organic solvent (having a boiling point of 130 ° C. or lower) may be used in addition to the above high boiling organic substance in order to dissolve the photochromic compound. Examples of those organic solvents include propylene carbonate, methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, ethyl propionate, butyl alcohol, methyl ethyl ketone, pentanone, cyclohexanone, dimethylformamide, dimethyl sulfoxide, and the like. To be The total amount of the high-boiling and low-boiling organic solvents is preferably 0.1 to 100 times the weight of the photochromic compound to be dispersed. Further, in emulsifying and dispersing the photochromic compound of the present invention, as described in International Patent Publication WO93 / 3420, after increasing the amount of the surfactant and finely dispersing it, a method of removing excess surfactant by washing with water is also available. It is valid. The co-solvent or surfactant can be removed by a known method, for example, US Pat. Nos. 2322027 and 28011.
No. 71, No. 2946360, No. 3396027, No. 4233397 and the like.

As a method of dispersing the composition containing the photochromic compound of the present invention, specifically, a photochromic compound kept in a solution state by any of the following methods is used:
It can be prepared by mixing with water or an aqueous solution of a hydrophilic polymer. If necessary, in order to further reduce the size of the dispersion particles from the micron level to the submicron level, the following disperser may be used.

As the disperser, there are a high-speed stirring type disperser having a large shearing force, a disperser giving high-strength ultrasonic energy, and the like. Specifically, there are a colloid mill, a homogenizer, a capillary type emulsifying device, a liquid siren, an electromagnetic distortion type ultrasonic generator, and an emulsifying device having a Paulman whistle. Preferred high speed agitation dispersers for use in the present invention are dissolvers, polytrons, homomixers, homoblenders, kedimills, jet agitators and the like.
Of these, a disperser of the type in which the essential part of the dispersing action rotates at high speed in the liquid. As the high-speed stirring type disperser, a dissolver or a high-speed impeller disperser may be used. As described in Japanese Patent Application Laid-Open No. 55-129136, it is also a preferable example to mount an impeller in which sawtooth blades are alternately bent in the vertical direction on a shaft that rotates at high speed.

In preparing the emulsion dispersion of the photochromic compound, various processes can be followed. When the photochromic compound is dissolved in an organic solvent, it is dissolved in one or two or more arbitrary multi-component mixtures selected from the above high boiling point organic substances or low boiling point organic solvents, and then the presence of a hydrophilic polymer. Below, a method of emulsifying and dispersing in water or an aqueous solution of a hydrophilic polymer is general. The method for mixing the oily liquid containing the photochromic compound and the aqueous liquid may be a so-called forward mixing method in which the oily liquid is added to the aqueous liquid with stirring, or a reverse mixing method which is the reverse of the method.

In the present invention, the composition of the photochromic compound can be stably dispersed either in water or in the hydrophilic polymer aqueous solution, but it is preferably dispersed in the hydrophilic polymer aqueous solution. When dispersing in water, it is preferable to add an aqueous solution of a hydrophilic polymer at the time of application after dispersion. Gelatin is advantageously used as the hydrophilic polymer, but other hydrophilic polymers can also be used. For example, a gelatin derivative,
Graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sodium alginate,
Sugar derivatives such as starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetals, polyvinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Molecular substances can be used.

As the gelatin, acid-treated gelatin may be used in addition to lime-treated gelatin, and gelatin hydrolyzate and gelatin enzyme dispersion can also be used. Examples of the gelatin derivative include gelatin such as acid halide, acid anhydride, isocyanates, bromoacetic acid, alkane sultones, vinyl sulfonamides, maleimide compounds,
Those obtained by reacting various compounds such as polyalkylene oxides and epoxy compounds are used. Furthermore,
In order to stabilize the composition containing the photochromic compound of the present invention, it is preferable to use the polymer compound in combination with the hydrophilic polymer.

Modified PVA is particularly preferred. Among them, a random or block copolymer of vinyl alcohol and vinyl ester in which the terminal is modified with a hydrophobic group such as a decylthio group is conveniently used. These hydrophilic polymers can be used alone, or can be used as a mixture of two or more kinds with other hydrophilic polymers. The hydrophilic polymer is 350 nm, more preferably 320 n.
Polymers that do not have absorption in the longer wavelengths than m are useful.

When the composition of the present invention is microencapsulated and used, a usual encapsulation method is conveniently used. The present inventors have already summarized these as literatures, and the method described therein can be conveniently used. For example, organic materials for imaging, Bushin Publishing,
See Tokyo, 1993, Chapter 4. Above all, it is convenient to use a capsule made of a synthetic polymer having a polyurea / urethane as a wall material, which uses polyisocyanate, from the viewpoint of stability, color developability, handling suitability and the like of the photochromic compound. Examples of the organic solvent used in (1) and (4) of the method for supporting the above-mentioned photosensitive composition on a substrate include
Both the high-boiling point organic solvent and the low-boiling point organic solvent described in the method (2) can be used.

The method (3) for supporting the above-mentioned photosensitive composition on a substrate will be described. As the high boiling organic solvent used in this method, the high boiling organic solvent described in (2) above can be used. The compound known as a plasticizer has an advantage that it is easily available and easy to handle. Also,
Examples of the hydrophobic polymer include polyvinyl butyral resin, polyvinyl formal resin, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, vinyl chloride resin, polymethylmethacrylate, acrylic ester-methacrylic acid ester copolymer. Coal, polyester resin, vinyl acetate-vinyl chloride copolymer, polycarbonate resin, polystyrene, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, polysulfone, phenoxy resin, styrene-butadiene copolymer, silicon Resin etc. are mentioned.

The photochromic photosensitive composition of the present invention contains various additives such as a photopolymerization initiator, a photocurable compound, a vinyl monomer, a singlet oxygen quencher typified by Ni, and a nitroxyl radical compound. Etc., selected from UV absorbers, triplet quenchers, radical scavengers, antioxidants, viscosity reducers, decolorization accelerators, color development accelerators, stabilizers, HALS, oxidizing agents or reducing agents, etc. Various materials can be contained in appropriate amounts according to the purpose. The photochromic compound, the oil-soluble salicylic acid derivative and the organic solvent used in the present invention can be used as a mixture of two or more kinds. The photosensitive layer containing the photochromic compound of the present invention may be composed of two or more layers that develop different colors.

A polymer latex may be incorporated into these layers in order to improve the film quality and curling characteristics. Examples of the monomer constituting the polymer latex that can be used in the present invention include acrylic acid ester, methacrylic acid ester, crotonic acid ester, vinyl ester, maleic acid diester, fumaric acid diester, itaconic acid diester, and acrylamides. , Methacrylamides, vinyl ethers, styrenes and the like.

The glass transition point of the polymer composed of these monomers is preferably 40 ° C. or lower. It may be a homopolymer or a copolymer. Preferred are acrylic esters, copolymers of acrylic esters and methacrylic esters, and copolymers of acrylic esters and acrylic acid or methacrylic acid.

Radical polymerization of ethylene monomers is already well known. For example, the usage of the initiator is described in F.
A. Bovey "Emulsion Polymerization" Interscienc
e Publishers Inc. New York, 1955, pp. 59-93.

As the emulsifier, a compound having a surface activity is used, and preferably, soap, sulfonate, phosphate and sulfate, cationic compound, amphoteric compound, polymer protective colloid and the like can be mentioned. Examples and uses of these are found in Belgische Chemische Industrie Vol 28
16 to 20 (1963), etc.

In the present invention, a polymer latex having a glass transition point of 20 ° C. or lower is particularly preferable. Specific examples of the polymer latex are described below, but the present invention is not limited thereto. Polyethyl acrylate, polypropyl acrylate, polyethoxyethyl acrylate, propyl acrylate / styrene copolymer, ethyl acrylate / styrene copolymer, propyl acrylate / acrylic acid (95: 5) copolymer, polybutyl acrylate, polyphenoxyethyl Acrylate, polydiethylene glycol monoacrylate methyl ether, nonaethylene glycol methacrylate methyl ether polymer, propyl acrylate / methacrylic acid (95: 5)
There are copolymers, ethylhexyl acrylate / diacetone acrylamide copolymers, methyl acrylate / butyl methacrylate copolymers, hexyl methacrylate / methacrylic acid (9: 1) copolymers and the like.

It is useful to provide a protective layer on these coating layers (outermost layer). As a material used for the protective layer, a hydrophilic polymer, a hydrophobic polymer, latex or the like can be used. As the hydrophilic polymer and latex, the hydrophilic polymer and polymer latex as the above-mentioned dispersion medium can be used. As the hydrophobic polymer, polyvinyl butyral resin, polyvinyl formal resin, ethylene-vinyl acetate copolymer,
Ethylene-acrylic acid copolymer, vinyl chloride resin, polymethylmethacrylate, acrylic acid ester-methacrylic acid ester copolymer, polyester resin, vinyl acetate-vinyl chloride copolymer, polycarbonate resin, styrene-maleic anhydride copolymer, Examples thereof include styrene-vinyltoluene copolymer, chlorosulfonated polyethylene, nitrocellulose, polyolefin and polyimide. In addition, organic substances such as silane coupling agents, ω
Cumulative films formed by the Langmuir-Projet method (LB method) such as tricosanoic acid, dioctadecyldimethylammonium chloride and methyl stearate can also be used. A metal vapor deposition film such as aluminum may also be used. The material used for the protective layer is preferably 350 nm, more preferably 320 nm, as described above.
Those having no absorption in longer waves are useful.

The thickness of the photosensitive layer containing the photochromic compound of the present invention depends on the purpose, but is preferably about 150 μm or less, particularly 20 μm or less, and may be laminated in 2 to 6 layers. The thickness of the coating film of the protective layer is 10 μm
The following is particularly desirable, 5 μm or less.

Hardeners used as needed are described in US Pat. No. 4,678,739, column 41, JP-A-59-11.
No. 6655, No. 62-245261, No. 61-189.
42 and the hardeners described in JP-A-62-234157 and the like. More specifically, aldehyde type hardener (formaldehyde etc.), aziridine type hardener, epoxy type hardener, vinyl sulfone type hardener (N, N'-ethylene-bis (vinylsulfonylacetamide)) Compounds such as ethane), N-methylol hardeners (dimethylol urea, etc.), polymer hardeners and the like. Among the above-mentioned hardeners, viewpoints of coatability (that is, stability of coating solution over time and reactivity with an adjacent layer during coating) and film quality (stability of raw sample and hardenability) Therefore, the epoxy hardener is particularly preferable. Specific examples of the epoxy hardener include JP-A-62-9194.
The hardeners described in No. 2 can be mentioned.

Uses of the composition or element of the present invention include printed matter, dyes, transfer agents, sunglasses, protective glasses,
Examples include optical recording materials, light control materials, light control filters, display materials, interior products, toys, light meters, clothes, cosmetics, writing instruments, etc., but they respond quickly to the intensity of sunlight, including UV light, It is particularly useful for applications such as light control filters for controlling the amount of color development or sunglasses. When it is used as a light control filter in a camera, it is particularly preferable to use it in a camera without a diaphragm and / or a shutter speed adjusting mechanism.

The photosensitive composition of the present invention can also be used in the form of a plastic lens. Injection-molded plastic lenses using dyes are already well known, and those techniques can be used without any problem. A method of copolymerizing a photochromic compound derived from diallyl ether or (meth) acrylate with methyl methacrylate or ethylene glycol diallyl ether, which is known as a monomer for plastic lenses, and molding this into a lens, or polymethyl methacrylate or polyethylene glycol. A method of mixing a photosensitive composition of the present invention with diallyl ether or the like in a specific combination and performing injection molding, and a method of immersing the composition of the photochromic compound in a molded product of a plastic lens are used.

It is sufficient that the plastic is transparent,
Polymethylmethacrylate, ethylene glycol diallyl ether polymer, triacetyl cellulose, polyethylene cyclohexane-1,4-dicarboxylate, PET
, PBT, or a mixture or laminate of these. For molding these, methods and processing conditions well known in the field of plastic lenses or sunglasses are used. For example, techniques such as using a dye together to provide a variety of density color tone, providing a protective layer to improve durability, providing an antireflection film, and using a stabilizer together are used. For example, as the protective layer, a polymer such as polyvinyl alcohol, a hardened material thereof, a polysiloxane crosslinked material, a metal vapor deposition film, or the like is one example.

As the substrate used in the present invention, various substrates can be selected according to the above-mentioned uses, but specifically,
Metal, ceramics, fibers, wood, synthetic resin, glass or various plastic films, plastic lenses, etc. can be used. A plastic product is preferable because it has processability, weight, strength, and transparency. For example, diethylene glycol bisallyl carbonate, methyl polymethacrylate, polyethylene terephthalate, polyethylene-2,6-naphthalate, polycarbonate, polyurethane, nylon, triacetyl cellulose, polyacrylate, polysulfone, polyether sulfone, polyolefin, polyimide, etc. Further, the laminated material with glass can be effectively used. A transparent substrate is particularly preferable when the photochromic compound is used as a light control material for glasses or cameras (especially films with high-sensitivity lenses).

The photosensitive layer and the protective layer of the present invention are formed by a vapor deposition method,
It can be formed as a thin layer on the substrate by any coating method such as curtain coating, blade coating, spin coating, dip coating, and extrusion coating. If necessary, two or more layers can be simultaneously coated by the method described in US Pat. Nos. 2,761,791 and 8,370,95.

The photosensitive composition carrying the photochromic compound of the present invention is stable and colorless when it is not irradiated with UV light, but develops color immediately when it is irradiated with light containing UV light. The same applies whether the light source is UV light or sunlight, room temperature or low temperature. Further, if irradiation is stopped, there is an advantage that the material becomes colorless immediately. These coloring and colorless processes are repeated stably and with good durability.

[0052]

EXAMPLES The present invention will be described in more detail based on examples. Example 1 Preparation of Emulsion of Photochromic Compound, Coating Composition (1) As a photochromic compound, Y-1 0.1 g, B
-1 0.1 g was dissolved in 0.2 g of isopropylated triphenyl phosphate and 0.4 g of ethyl acetate as a high boiling organic solvent to obtain an oil phase (A). An aqueous phase (B) was prepared by adding 0.2 cc of a 5% aqueous solution of dodecylbenzenesulfonic acid as a surfactant to 2 g of a 10% aqueous solution of lime-processed gelatin. The oil phase and the aqueous phase were mixed and emulsified and dispersed for 5 minutes at 10,000 rpm with a mini homogenizer. 3 cc of water and 2 g of 14% gelatin aqueous solution were added to this emulsified dispersion to prepare a photosensitive layer coating composition (1).

Preparation of Photochromic Photosensitive Material 101 The photosensitive layer coating composition (1) was applied onto a polyethylene terephthalate film having a thickness of 100 μm and a wet film thickness of 65 μm.
It was applied so as to have a thickness of m and dried at 40 ° C. Next, a gelatin protective layer was applied thereon by a rod coating method so as to have a dry film thickness of 1 μm, to prepare a photochromic photosensitive material 101. Preparation of Photochromic Compound Emulsion, Coating Composition (2) As a photochromic compound, Y-1 0.1 g, B
-1 0.1 g, as an oil-soluble salicylic acid derivative, 3,
Zinc 5-di-α-methylbenzyl salicylate 0.07 g
Was dissolved in 0.2 g of isopropylated triphenyl phosphate and 0.4 g of ethyl acetate to obtain an oil phase (C). After that, the same treatment as in the coating composition (1) was carried out to prepare a photosensitive layer coating composition (2).

Preparation of Photochromic Photosensitive Material 102 The coating composition (2) was processed in the same manner as the photosensitive material 101 to prepare a photosensitive material 102. Preparation of Photochromic Photosensitive Materials 103 to 107 The photosensitive material 103 is the same as the photosensitive material 102 except that the photochromic compound, the oil-soluble salicylic acid derivative, and the high-boiling organic solvent in the photosensitive material 102 are changed as shown in Table 1.
~ 107 were produced.

Preparation of Photochromic Photosensitive Material 108 Y-1 0.05 g and Y-1 instead of Y-1 0.1 g
-3 The photosensitive material 108 was prepared in the same manner as the photosensitive material 101 except that 0.05 g was used. Preparation of Photochromic Photosensitive Material 109 Y-1 0.05 g and Y-1 instead of Y-1 0.1 g
-3 A photosensitive material 109 was prepared in the same manner as the photosensitive material 102 except that 0.05 g was used. Production of Photochromic Photosensitive Materials 110 to 114 Instead of (Y-1, B-1), (Y-1, B-13),
(Y-21, B-13), (Y-22, B-14),
Photosensitive material 110 in the same manner as photosensitive material 101 except that (Y-21, B-15) and (Y-21, B-16) are used.
~ 114 were produced.

Comparative Example Preparation of Comparative Material (1) Comparative Example (1) was carried out in the same manner as in Photosensitive Material 101 except that C-1 (a compound described in JP-A-4-39382) was used instead of Y-1. Was produced.

[0057]

Embedded image

Preparation of Comparative Material (2) Comparative Example (2) was prepared in the same manner as in Photosensitive Material 101 except that C-2 (a compound described in JP-A-6-510519) was used instead of Y-1. It was made.

[0059]

[Chemical 12]

Coloring and Decoloring Test When the photosensitive material 101 was exposed to sunlight at 23 ° C. for 1 minute, it developed a substantially gray color. When the sunlight was cut off, the color disappeared in about 20 seconds. Substantially no change in hue was observed until the color disappeared. Photosensitive material 102-
114 and comparative materials (1) and (2) are also photosensitive materials 1
The same test as 01 was conducted. The results are shown in Table 2.
As is clear from these results, it is clear that the photosensitive composition of the present invention is excellent in that the color density is high, the decoloring is fast, and the hue hardly changes until the color is decolored.

[0061]

[Table 1]

[0062]

[Table 2]

Example 2 Preparation of Photochromic Photosensitive Material 201 Photochromic compounds Y-1 and B-1 were each added to 0.2.
g, 2 g of polyvinyl butyral are dissolved in 20 ml of a mixed solvent of cyclohexane / ethyl acetate = 50/50 to give 100
A photosensitive material 201 was prepared by coating on a μm polyethylene terephthalate film so as to have a dry film thickness of 7 μm.

The light-sensitive material 201 was changed to 2 as in Example 1.
After irradiating with UV light for 30 seconds at 5 ° C., the color density was measured, and the density having a gray hue was substantially 0.30.
showed that. When the irradiation was stopped, the color disappeared in about 30 seconds.
Substantially no change in hue was observed until the color disappeared.

Example 3 Preparation of Photochromic Photosensitive Material 301 Photochromic compounds Y-1 and B-1 were each added to 0.2.
g, 0.1 g of 3,5-di-α-methylbenzylsalicylate, and 2 g of ethylene-vinyl acetate copolymer were dissolved in 20 ml of a mixed solvent of cyclohexane / ethyl acetate = 50/50, and the solution was placed on a 100 μm polyethylene terephthalate film. Photosensitive material 3 is coated so that the dry film thickness is 7 μm.
01 was produced.

The light-sensitive material 301 was formed in the same manner as in Example 1
After irradiating with UV light at 30 ° C. for 30 seconds, the color density was measured, and it was found that the density having a substantially gray hue was 0.31.
showed that. When the irradiation was stopped, the color disappeared in about 35 seconds.
Substantially no change in hue was observed until the color disappeared. As is clear from these results, it is understood that the photosensitive composition of the present invention has a high color density, is fast in decoloring, and the hue is unlikely to change until decoloring.

[0067]

EFFECT OF THE INVENTION An element carrying a photosensitive composition in which a specific photochromic compound is used in combination has a high color density and is fast in decoloring and hardly changes in hue until decoloring.

Claims (6)

[Claims] 1. A photosensitive composition comprising a photochromic compound (1) having a maximum light absorption spectrum in the range of 350 nm to 530 nm in a colored state and a photochromic compound (2) having a maximum value of 560 nm to 750 nm. The photosensitive composition is characterized in that each of the compound (1) and the compound (2) takes 3 minutes or less from the substantially colored state to the decolored state. 2. A photochromic compound (1) represented by the following general formula (1) and a photochromic compound (2) having a maximum light absorption spectrum within a range of 560 nm to 750 nm in a colored state. A photosensitive composition to be used. Embedded image In the formula, R _{1 to} R ₁₄ each represent a hydrogen atom or a substituent. 3. A photochromic compound (1) represented by the following general formula (2), and a photochromic compound (2) having a maximum light absorption spectrum within a range of 560 nm to 750 nm in a colored state and an organic zinc salt. A photosensitive composition comprising: Embedded image In the formula, R _{15 to} R ₂₂ each represent a hydrogen atom or a substituent, and R ₂₃ and R ₂₄ each represent an aryl group or a heterocyclic group. 4. The photosensitive composition according to claim 1, further comprising an organic zinc salt. 5. The photosensitive composition according to claim 2, wherein the photochromic compound is emulsified and dispersed in a hydrophilic polymer. 6. An element carrying a photosensitive composition according to claim 1, 2, 3, 4 or 5 on a substrate.