JPH09241263A - Photosensitive composition and element using the same and photochromic compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive composition, comprising a new compound represented by a specific formula, having high color developing properties at high temperatures and useful for various dimming, displaying, coloring and recording applications. SOLUTION: This photosensitive composition contains a compound of the formula [X and Y are each an atomic group required to form a (substituted) aromatic hydrocarbon ring or an unsaturated heterocyclic ring; D is N or H; E is O or S; R1 to R3 , G and J are each H or a substituent group; R4 is H or a substituent group] therein. The compound is preferably emulsified and dispersed in a hydrophilic polymer and is preferably obtained by reacting, e.g. methyleneindoline derivative (e.g. 1,3,3-trimethyl-2methyleneindoline) with an o-hydroxynitroso aromatic ring (e.g. 1-nitroso-3-phenylcarbamoyl-2-naphthol).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive composition using a photochromic compound, which is useful for dimming, displaying, coloring and recording, and an element having photochromic properties and a novel photochromic compound 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 the books such as H. Bouas Laurent, Elsevier, New York 1989). Many applications have been filed because indolinospyro compounds (particularly indino spiro oxazine compounds) are far superior to other compounds in color development, decolorization speed, and high color density. It was Examples thereof include JP-A-1-106888 and US Pat. No. 4,931,219. However, these indolinospiro compounds have a major drawback that they have a low color developability at high temperatures (40 ° to 50 ° C).

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to overcome the above-mentioned deficiencies and to provide a photochromic photosensitive composition having high color developability at high temperature, an element in which the photosensitive composition is supported on a substrate, and a novel photochromic composition. To provide a compound.

[0004]

The objects of the present invention have been achieved by the following method. (1) A photosensitive composition comprising a photochromic compound (1) represented by the following general formula (1).

[0005]

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In the formula, X and Y represent an atomic group necessary for forming an aromatic hydrocarbon ring which may have a substituent or an unsaturated heterocyclic ring, D represents a nitrogen atom or CH, and E
Represents an oxygen atom or a sulfur atom, and R ₁ , R ₂ , R ₃ ,
G and J represent a hydrogen atom or a substituent. Provided that at least one of G and J represents a substituent having -NH an (R ₄₎ or -OH therein. R ₁ and R ₂ may together form a ring. R ₄ represents a hydrogen atom or a substituent. (2) The photosensitive composition as described in (1) above, wherein the photochromic compound (1) is emulsified and dispersed in a hydrophilic polymer. (3) An element in which the photosensitive composition according to the above (1) or (2) is carried on a substrate. (4) A photochromic compound represented by the following general formula (2).

[0007]

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Where X₁And Y₁Has a substituent
To form good aromatic hydrocarbon rings or unsaturated heterocycles
Represents the necessary atomic group, R_Five, R₆, G₁And J₁Is
Represents a hydrogen atom or a substituent. However, G₁And J₁of
At least one is -NH (R ₇) Having substituents therein
Represents R_FiveAnd R₆May form a ring together
Yes. R₇Represents a hydrogen atom or a substituent.

[0009]

The above general formulas (1) and (2) will be further described. Examples of the ring formed by X, Y, X ₁ and Y ₁ include the following.

[0010]

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[0011] ring on which may be substituted as a substituent an alkyl group (preferably C ₁ -C _10), halogen atom, an optionally substituted alkoxy group (preferably C ₁ ~
C _10), a nitro group, a cyano group, an ester group (preferably a C ₂ -C _10), a sulfamoyl group (preferably a C ₁ -C
_10), sulfonylamino group (C ₁ -C _10), a carbamoyl group (preferably a C ₂ -C _10), acyl groups (preferably C ₁ -C _10), acylamino groups (preferably C ₁ -C
₁₀ ), a sulfonyl group (preferably C _{1 to} C ₁₀ ), an optionally substituted amino group (preferably C _{0 to} C ₁₀ ), a carboxyl group, a sulfo group, a perfluoroalkyl group (preferably C _{1 to} C _10). ), A thioalkyl group (preferably C ₁
To C ₁₀ ) and aryl groups (preferably C _{6 to} C ₁₅ ). Among the rings formed by X and X ₁ , preferred is K-1 or K-2, and among the rings formed by Y and Y ₁ , preferred is K-2.

R₁, R_Two, R_Three, R_Five, R₆, J, J₁
The substituent represented by is an optionally substituted alkyl group.
Group (preferably C₁~ C_Ten). Alkyl
As a substituent of the group, a halogen atom, an alkoxy group (preferred
More preferably C₁~ C_Ten), Nitro group, cyano group, ester
A group (preferably C_Two~ C_Ten), Sulfamoyl group (preferred
Or C₁~ C_Ten), A sulfonylamino group (preferably
Is C₁~ C_Ten), A carbamoyl group (preferably C_Two~ C
_Ten), An acyl group (preferably C ₁~ C_Ten), Acylami
Group (preferably C₁~ C_Ten), Sulfonyl groups (preferred
Kuha C₁~ C_Ten), Optionally substituted amino group (preferably
Kuha C₀~ C_Ten), Carboxyl group, sulfo group, per
Fluoroalkyl group (preferably C₁~ C_Ten), Thioa
Rukyi group (preferably C₁~ C_Ten), Aryl groups (preferred
Or C₆~ C_Fifteen).

The substituents represented by R ₄ and R ₇ include
An optionally substituted alkyl group (preferably C _1-
C _10), aryl groups (preferably C ₆ ~C _15), a Hajime Tamaki (preferably include C ₃ ~C _15). G, G ₁
During the -NH (R ₄₎ or -OH is directly ring binding or G, alpha from a position where G ₁ is bound to the ring, it is preferably located in the β or gamma. -NH (R ₄₎ is -CONH (R
It is preferably present in G, G ₁ in the form of ₄ ). The novel compound represented by the general formula (2) is particularly preferable because it has high color developability at high temperatures. The compound represented by the general formula (1) or (2) is a general synthetic method of reacting a methyleneindoline derivative with an orthohydroxynitroso aromatic ring (or heterocycle) (for example, Photochromism, Molecule and S).
ystems, p.506-507, Ed. by H. Durr, H. Bouas Laur
ent, Elsevier, New York 1989) and the like. Specific examples of the compound represented by formula (1) or (2) are shown below.

[0014]

[Chemical 6]

[0015]

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[0016]

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[0017]

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The photosensitive composition comprising a compound having a specific skeleton and having photochromic properties and an organic solvent and an additive which are optionally used in combination is carried on a transparent substrate as follows. There are things. (1) A laminated body in which a liquid phase in which a photochromic compound and an additive which is optionally used together are dissolved in an organic solvent is directly sandwiched between transparent films or glass. (2) A liquid phase in which a photochromic compound and an additive used in combination as required are dissolved in an organic solvent, emulsified and dispersed in a hydrophilic polymer, and applied on a substrate.

(3) A photochromic compound and additives, which are optionally used in combination, are dissolved in a hydrophobic polymer together with an organic solvent, and melt-molded or coated on a substrate by various methods. (4) A coated material in which a liquid phase in which a photochromic compound and an additive which is optionally used together are dissolved in an organic solvent is microencapsulated and is carried on a substrate together with a binder. (5) A photochromic compound, and a liquid phase in which an additive to be optionally used together is dissolved in an organic solvent is microencapsulated using a synthetic polymer resin wall, and is carried on a substrate together with a binder. 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-
Diethylcaprylic acid amide, N, N-dimethylpalmitic acid amide,

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. When emulsifying and dispersing, polyvinyl butyral,
Polymers such as polyvinyl acetal may be used in place of or in combination with the high boiling organic solvent.

In the present invention, in order to dissolve the photochromic compound, 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. 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 for 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.

Examples of the disperser include a high-speed stirring disperser having a large shearing force and a disperser which gives high-strength ultrasonic energy. 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 emulsified 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 with other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and 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, besides lime-processed gelatin, acid-processed gelatin may be used, 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. Regarding the amount of the hydrophilic polymer used, the dispersant and the binder may be separate polymers, or the single polymer may be used together. The preferred amount used is about 0.01 to 200 parts by weight with respect to the photochromic compound (parts by weight),
Particularly, it is about 0.1 to 10 parts by weight. Further, in order to stabilize the composition containing the photochromic compound of the present invention, it is preferable to use a high molecular 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 used in a microencapsulated form, conventional encapsulation methods are 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.

Two or more kinds of the photochromic compounds of the present invention may be used. It may also be used in combination with a photochromic compound having another skeleton. Since most of the photochromic compounds of the present invention mainly develop blue to cyan, when used in combination with a photochromic compound which develops yellow to orange and / or red to magenta, they are colored in preferable colors such as gray, green and brown. A photosensitive composition is obtained. In particular, it is preferably used in combination with a compound represented by the following general formula (3).

[0032]

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Where R₁₂, R₁₃, R₁₄, R_FifteenIs that
Hydrogen atom or the above X, X₁, Y or Y₁Formed by
Selected from the substituents on the ring. Moreover, these are
Cyclize with each other at the contact position and consist of 5-8 membered non-metal atoms.
May form a saturated or unsaturated ring. Especially when condensed
Preferred is an aromatic ring which may be present. For example, cyclo
Xene, cyclopentene, azulene, benzene, naphtha
Len, pyridine, pyrimidine, quinoline, imidazo
Le, furan, thiophene, benzimidazole, naphtho
Thiophene, naphthopyran, pyrene, anthracene, na
A cyclic structure such as futoquinoline may be mentioned as an example.
R₁₆And R₁₇Are each an alkyl group (preferably C
₁~ C_Fifteen), Aryl groups (benzene, naphthalene, pyre)
, Anthracene, etc.), heterocyclic groups (pyridine, quino
Phosphorus, imidazole, furan, thiophene, benzimi
Dazol, naphthothiophene, naphthopyran, naphtho
Norin) and the like. These are R ₁₂, R₁₃,
R₁₄, R_FifteenDepending on the substituents described in (including cyclic structure)
It may be exchanged. R₁₆And R₁₇Combine with each other to form a ring
May be. R₁₆And R₁₇Is bound to an oxygen atom,
By a bond via a ton group, a methylene group, or a single bond.
Specific examples of the compound represented by the general formula (3) are shown below.
You.

[0034]

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[0035]

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[0036]

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The photochromic photosensitive composition of the present invention contains various additives such as organic zinc salts (particularly zinc salts of oil-soluble salicylic acid derivatives, such as zinc 3,5-di-α-methylbenzylsalicylate, and 3 , 5-di-α, α-dimethylbenzylsalicylate zinc, etc. Other specific examples are described in Japanese Patent Application No. 7-254884), photopolymerization initiators, photocurable compounds, vinyl monomers, and Ni. Singlet oxygen quencher, nitroxyl radical compound, etc., UV absorber, triplet quencher, radical scavenger, antioxidant, viscosity reducing agent, decolorization accelerator, color development accelerator, stabilizer, HALS Various materials selected from an oxidizing agent, a reducing agent, etc. can be contained in appropriate amounts according to the purpose. The photochromic compound 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 Synthesis of C-1 1,3,3-trimethyl-2-methylene indoline 3.
5 g (0.02 mol), 1-nitroso-3-phenylcarbamoyl-2-naphthol 5.8 g (0.02 mol)
Then, 1000 ml of ethanol was refluxed under a nitrogen stream for 3 hours. After the solvent was distilled off from the reaction mixture, the residue was purified by silica gel chromatography using chloroform as a developing solvent to obtain 6.6 g of the target C-1 (yield 74%).

Example 2 Synthesis of C-3 1,3,3-triethyl-5-methyl-2-methyleneindoline 4.6 g (0.02 mol), 1-nitroso-3
-Isoamylcarbamoyl-2-naphthol 5.7 g
C-3 (7.2 g, yield 72%) was obtained from (0.02 mol) and 800 ml of ethanol in the same manner as in Example 1.

Example 3 Synthesis of C-8 4.0 g (0.02 mol) of 3,3-dimethyl-1-propyl-2-methyleneindoline, 4.6 g of 1-nitroso-3-acetylamino-2-naphthol In the same manner as in Example 1, 4.1 g (yield 50%) of C-8 was obtained from (0.02 mol) and 500 ml of ethanol.

Example 4 Synthesis of C-15 3,3-Dimethyl-1-isoamylcarbamoylmethyl-2-methyleneindoline 5.7 g (0.02 mol),
C-15 was obtained from 3.5 g (0.02 mol) of 1-nitroso-2-naphthol and 500 ml of ethanol in the same manner as in Example 1 (yield 54%).

Example 5 Synthesis of C-18 1-Butyl-2,3,3-trimethylbenz [e] indolium iodine salt 7.9 g (0.02 mol), 1-nitroso-3-phenylcarbamoyl- 2-naphthol 5.8 g (0.02 mol), triethylamine 2.0 g
(0.02 mol) and 1,000 ml of ethanol in the same manner as in Example 1 to give 6.3 g of C-18 (yield 58%).
Obtained.

Example 6 Synthesis of C-27 7.9 g (0.02 mol) of iodine salt of 1-butyl-2,3,3-trimethylbenz [e] indolium, 2-ethylcarbamoyl-4-methoxy- 4.5 g (0.02 mol) of 6-nitrosophenol, triethylamine 2.
3.2 g of C-27 (yield 35%) in the same manner as in Example 1 from 0 g (0.02 mol) and 500 ml of ethanol.
Obtained.

Example 7 [Emulsion of photochromic compound, photosensitive composition for coating]
Preparation of (1)] As a photochromic compound, C-1
0.1 g as a high boiling organic solvent, 0.2 g of isopropylated triphenyl phosphate, 0.4 g of ethyl acetate
Was dissolved in to obtain an oil phase (A). 1 of lime processed gelatin
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 the 0% aqueous solution. The oil phase and the aqueous phase were mixed and emulsified and dispersed for 5 minutes at 10,000 rpm with a mini homogenizer. To this emulsified dispersion, 3 cc of water and 2 g of 14% gelatin aqueous solution were added to prepare a photosensitive composition for coating (1).

[Preparation of Photochromic Photosensitive Material 101] The above-mentioned photosensitive 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. [Production of Photochromic Photosensitive Materials 102 to 109 and Comparative Materials (1) and (2)] The photosensitive material 101 was prepared in the same manner as the photosensitive material 101 except that the photochromic compound and the high boiling point solvent were changed as shown in Table 1. -10
9 and comparative materials (1) and (2) were prepared. Comparative material (1)
, The known photochromic compound used in (2) is H-
1 and H-2.

[0060]

Embedded image

[0061]

[Table 1]

[Coloring and Decoloring Test] Photosensitive materials 101 to 10
9 and comparative materials (1) and (2) at 40 ° C. with Remington's tanning tandem model TF-1, UV light 30
When irradiated for a second, a color developed from blue to cyan. Table 1 shows the results of measuring the concentration of λmax at that time using MCPD100 manufactured by Union Giken. When the irradiation was stopped, all of them disappeared immediately. As is clear from these results, the material containing the photochromic compound of the present invention has a higher color density than the comparative material containing the known photochromic compound.

Example 8 [Preparation of Photochromic Photosensitive Material 201] 0.1 g of photochromic compound C-1 and 2 g of ethylene / vinyl acetate copolymer were added to cyclohexane / ethyl acetate = 50/5.
It was dissolved in 20 ml of a mixed solvent of 0 and coated on a 100 μm polyethylene terephthalate film so as to have a dry film thickness of 7 μm, to prepare a photochromic photosensitive material 201. [Production of Photochromic Photosensitive Materials 202 to 209 and Comparative Materials (3) and (4)] Photosensitive Material 2 except that the photochromic compound is as shown in Table 2
In the same manner as in No. 01, photosensitive materials 202 to 209 and comparative materials (3) and (4) were prepared. Comparative materials (3) and (4)
As the above compound, H-1 and H-2 were used as described above.

[0064]

[Table 2]

[Coloring and Decoloring Test] Photosensitive materials 201 to 20
9 and comparative materials (3) and (4) at 40 ° C. as in Example 7.
Table 2 shows the densities when the UV light was irradiated for 30 seconds. When the irradiation was stopped, all of them disappeared immediately. As is clear from these results, the material containing the photochromic compound of the present invention has a higher coloring density than the material containing the known photochromic compound, and the emulsion-coated material has a higher coloring density than the solvent-coated material (Table 1). And comparison of Table 2).

Example 9 [Preparation of Photochromic Photosensitive Material 301] 0.1 g of photochromic compound C-1 and 2 g of polyvinyl butyral (BLS manufactured by Denka) were dissolved in 20 ml of a mixed solvent of cyclohexane / ethyl acetate = 50/50, and 100 μm was prepared.
Dry film thickness 7 on m polyethylene terephthalate film
The photosensitive material 301 was manufactured by coating so as to have a thickness of μm. [Production of Photochromic Photosensitive Materials 302 to 307] In the photosensitive material 301, the photochromic compound C-1 is used.
To C-4, C-5, C-7, C-12, C-20, C-
Except that it is replaced with 34,
Photosensitive materials 302 to 307 were produced. When a color developing / decoloring test was conducted in the same manner as in Example 7, the light-sensitive materials 301 to 3
All 07 materials developed a high density of color and disappeared immediately when irradiation was stopped.

Example 10 [Preparation of Photochromic Photosensitive Materials 401 to 403] In the photosensitive material 301 of Example 9, polyvinyl butyral was used as polyester (Nisshinbo Byron 200), polyester (Nisshinbo Byron 590) or polyvinyl acetal (Sekisui Chemical Co., Ltd.). Sensitive Materials 401 to 4 in the same manner as Sensitive Material 301 except that it was replaced with S-REC KX)
03 was produced. When a color development and a color erasing test were conducted in the same manner as in Example 9, all the materials developed a high density, and the color was rapidly erased when the irradiation was stopped.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical display location // C07D 513/10 C07D 513/10 (72) Inventor Yasushi Ichijima 210 Nakanuma, Minamiashigara City, Kanagawa Fuji Photo inside film company

Claims (4)

[Claims] 1. A photosensitive composition comprising a photochromic compound (1) represented by the following general formula (1). Embedded image In the formula, X and Y represent an atomic group necessary for forming an aromatic hydrocarbon ring which may have a substituent or an unsaturated heterocycle, D represents a nitrogen atom or CH, and E is an oxygen atom. Or a sulfur atom, and R ₁ , R ₂ , R ₃ , G and J represent a hydrogen atom or a substituent. Provided that at least one of G and J represents a substituent having -NH an (R ₄₎ or -OH therein. R ₁ and R ₂ may together form a ring. R ₄ represents a hydrogen atom or a substituent. 2. The photosensitive composition according to claim 1, wherein the photochromic compound (1) is emulsified and dispersed in a hydrophilic polymer. 3. An element carrying the photosensitive composition according to claim 1 or 2 on a substrate. 4. A photochromic film represented by the following general formula (2):
Mick compound (2). Embedded imageWhere X₁And Y₁Is an aromatic carbon which may have a substituent
Atomic groups necessary to form a hydrogenated ring or unsaturated heterocycle
And R_Five, R₆, G₁And J₁Is a hydrogen atom or
Represents a substituent. However, G₁And J₁At least one of
-NH (R ₇) Represents a substituent having therein. R
_FiveAnd R₆May together form a ring. R₇Is hydrogen
Represents an atom or a substituent.