JPH0619556B2 - Photosensitive material for heat development - Google Patents

Description

The present invention relates to a heat-developable photosensitive material having a photosensitive layer containing a silver halide, a reducing agent, a polymerizable compound and a color image-forming substance on a support (hereinafter, A photosensitive material for heat development is abbreviated as a photosensitive material.

BACKGROUND OF THE INVENTION A light-sensitive material having a photosensitive layer containing a silver halide, a reducing agent and a polymerizable compound on a support forms a latent image of silver halide and polymerizes the polymerizable compound by the action of the reducing agent. The image forming method can be used.

As an example of the image forming method, Japanese Patent Publication No. 45-11149.
No. 47-20741, No. 49-10697, JP-A Nos. 57-138632 and 58-169143. In these methods, when the exposed silver halide is developed with a developing solution, the reducing agent is oxidized and at the same time, a coexisting polymerizable compound (eg,
Vinyl compound) initiates polymerization to form an image-like polymer compound. Therefore, the above method requires a developing treatment using a liquid, and the treatment requires a relatively long time.

The present inventors attempted to improve the above method and invented a method capable of forming a polymer compound by a dry treatment, and the present invention has been applied for a patent (Japanese Patent Application No. 59-1913).
53). This method uses a photosensitive silver salt (silver halide),
A recording material (photosensitive material) having a photosensitive layer composed of a reducing agent, a crosslinkable compound (polymerizable compound) and a binder supported on a support is imagewise exposed to form a latent image, and then heated to form a photosensitive material. A polymer compound is formed in the portion where the latent image of silver salt is formed.

The above image forming method is a method of polymerizing the polymerizable compound in the portion where the latent image of silver halide is formed. The present inventors have further invented a method capable of polymerizing a polymerizable compound in a portion where a latent image of silver halide is not formed, and this invention has already been applied for a patent (Japanese Patent Application No. 60-
210657). In this method, heating causes a reducing agent to act on a portion where a latent image of silver halide is formed to suppress the polymerization of a polymerizable compound, and at the same time, promotes the polymerization of other portions.

As one aspect of the image forming method as described above, a photosensitive material having a photosensitive layer containing a silver halide, a reducing agent, a polymerizable compound, and a color image forming substance on a support is simultaneously exposed imagewise, Alternatively, after imagewise exposure, development processing is performed to polymerize and cure the polymerizable compound, thereby immobilizing the color image forming substance in the cured portion, and then receiving the photosensitive material in which the color image forming substance in the cured portion is immobilized. There is a method in which the color image forming substance in the uncured portion is transferred to the image receiving material by applying pressure in the state of being superposed on the material (Japanese Patent Application No. 60-121284).
issue). According to this method, a clear image can be obtained on the image receiving material, but it is necessary to use an image receiving material capable of transferring a color image forming substance in addition to the photosensitive material.

[Summary of the Invention] The present inventor has conducted extensive studies for the purpose of providing an excellent photosensitive material that can be used in an image forming method.

An object of the present invention is to provide a light-sensitive material capable of obtaining a color image by simple processing.

The present invention includes a silver halide, a reducing agent, a polymerizable compound, and two kinds of substances that cause a color reaction in a contact state, and one of the substances that cause the color reaction and the silver halide, a reducing agent and Having a photosensitive layer on a support in which a polymerizable compound is housed together in a photosensitive microcapsule, and the other substance out of the above-mentioned color-forming reaction is present outside the photosensitive microcapsule. A photosensitive material for heat development is provided.

[Effects of the Invention] The light-sensitive material of the present invention uses two kinds of substances that cause a color reaction in a contact state, one of these substances is housed in a microcapsule, and the other substance is present outside the microcapsule. It is characterized by

The above-mentioned light-sensitive material is subjected to development treatment simultaneously with or after imagewise exposure to polymerize and cure the polymerizable compound, and then microcapsules containing the uncured polymerizable compound using a means such as pressure. By rupturing, and by causing two or more compounds that cause the above-mentioned color forming reaction to be in contact with each other to develop color,
A color image can be obtained on the light-sensitive material.

That is, by using the light-sensitive material of the present invention, a color image can be obtained on the light-sensitive material by a simple process without using an image receiving material.

[Detailed Description of the Invention] There are no particular restrictions on the two types of substances that cause a color reaction in the contact state used in the light-sensitive material of the present invention, and various substances can be used. Further, the system of the color reaction, acid-base reaction between two or more components, redox reaction,
Various systems that develop a color by a coupling reaction, a chelate forming reaction and the like are included. For example, pressure-sensitive copying paper (pages 29 to 58) and azography (87) described in "Introduction to Special Paper Chemistry" by Hiroyuki Moriga (published in 1975).
~ 95), thermosensitive coloring due to chemical changes (118-120)
Page) and other well-known color development systems, or a seminar by Kinki Chemical Industry Association "Latest dye chemistry-Attractive utilization as a functional dye and new development-" Proceedings 26-32, (19
The coloring system described in June 19, 80) can be used. Specifically, a color-developing system composed of a colorant having a partial structure such as lactone, lactam, and spiropyran used for pressure-sensitive paper and an acidic substance (developing agent) such as acid clay or phenol; an aromatic diazonium salt or Diazotate, diazosulfonates and naphthols,
Systems utilizing azo coupling reactions of anilines and active methylenes; reactions of hexamethylenetetramine with ferric ions and gallic acid, reactions of phenolphthalein-complexones with alkaline earth metal ions, etc. Chelate forming reaction; a redox reaction such as a reaction between ferric stearate and pyrogallol or a reaction between silver behenate and 4-methoxy-1-naphthol can be used.

Also, as another example of the system in which the color is similarly developed by the reaction between two or more components, there is a system in which this reaction proceeds by heating. When this system is used, it is necessary to rupture the microcapsules by pressing or the like and heat the light-sensitive material at the same time as or immediately after the components are mixed.

Among the color-developing systems described above, it is preferable to use the so-called color-developing / developing agent system. As the color former in the color former / developing agent system, (1) triarylmethane-based, (2) diphenylmethane-based, (3)
There are xanthene compounds, (4) thiazine compounds, (5) spiropyran compounds, and the like.
Examples thereof include those described in Japanese Patent No. 27253. Of these, the (1) triarylmethane-based and (3) xanthene-based colorants have less fog,
Many are preferable in terms of providing high color density. Specific examples of the color former include crystal violet lactone, 3-diethylamino-6-chloro-7- (β-
Ethoxyethylamino) fluorane, 3-diethylamino-6-methyl-7-anilinofluorane, 3-triethylamino-6-methyl-7-anilinofluorane, 3
-Cyclohexylmethylamino-6-methyl-7-anilinofluorane, 3-diethylamino-7-o-chloroanilinofluorane and the like can be mentioned. These color formers may be used alone or in combination.

As the developer of the system using the above-mentioned color former, a phenolic compound, an organic acid or a metal salt thereof,
There are oxybenzoic acid ester and acid clay.

Specific examples of the phenol compound include 4,4′-isopropylidene-diphenol (bisphenol A),
p-tert-butylphenol, 2,4-dinitrophenol, 3,4-dichlorophenol, 4,4'-methylene-bis (2,6-di-tert-butylphenol), p
-Phenylphenol, 1,1-bis (4-hydroxyphenyl) -2-ethylhexane, 2,2-bis (4-
Hydroxyphenyl) butane, 2,2′-methylenebis (4-tert-butylphenol), 2,2′-methylenebis (α-phenyl-p-cresol) thiodiphenol, 4,4′-thiobis (6-tert-butyl) In addition to -m-cresol) sulfonyldiphenol, p-tert-butylphenol-formalin condensate, p-phenylphenol formalin condensate and the like can be mentioned.

Specific examples of the organic acid or a metal salt thereof include phthalic acid, phthalic anhydride, maleic acid, benzoic acid, gallic acid,
o-toluic acid, p-toluic acid, salicylic acid, 3-te
rt-Butylsalicylic acid, 3,5-di-tert-butylsalicylic acid, 5-α-methylbenzylsalicylic acid, 3,5-
(Α-methylbenzyl) salicylic acid, 3-tert-octylsalicylic acid and zinc, lead, aluminum salts, magnesium salts, nickel salts thereof and the like can be mentioned. Among these, salicylic acid derivatives and zinc salts thereof,
The aluminum salt and the aluminum salt are excellent in terms of color developing ability, fastness of a color image, storability of a light-sensitive material and the like.

Examples of the oxybenzoic acid ester include ethyl p-oxybenzoate, butyl p-oxybenzoate, heptyl p-oxybenzoate, benzyl p-oxybenzoate and the like.

Among the above-described color developers, there are those that participate in the color development reaction after melting at a certain temperature or higher. When such a developer is used, it is added as a eutectic with a heat-fusible substance having a low melting point, or a low-melting compound is added in a state of being fused to the surface of the developer particles. Preferably.

Specific examples of the low melting point compound include higher fatty acid amides such as stearic acid amide, erucic acid amide, palmitic acid amide, ethylene bisstearamide; waxes such as higher fatty acid esters; phenyl benzoic acid derivatives; aromatic ethers. Derivatives: urea derivatives and the like can be mentioned.

Color formers / developers other than the above (1) to (5) include phenolphthalein, fluorescein,
2 ', 4', 5 ', 7'-tetrabromo-3,4,5,5
There is a system using 6-tetrachlorofluorescein, tetrabromophenolphthalein, eosin, aurincresol red, 2-naphtholphenolphthalein, etc. as a color former.

As the developer of the system using the above-mentioned color former, inorganic and organic ammonium salts, organic amines, amides, urea and thiourea and their derivatives, thiazoles,
Pyrroles, pyrimidines, piperazines, guanidines, indoles, imidazoles, imidazolines,
There are nitrogen-containing compounds such as triazoles, morpholines, piperidines, amidines, formazines and pyridines. Specific examples of these include ammonium acetate,
Tricyclohexylamine, tribenzylamine, octadecylbenzylamine, stearylamine, allylurea, thiourea, methylthiourea, allylthiourea, ethylenethiourea, 2-benzylimidazole, 4-phenylimidazole, 2-phenyl-4-methyl-imidazole, 2-undecyl-imidazoline, 2,4,5-trifuryl-2-imidazoline, 1,2-diphenyl-
4,4-dimethyl-2-imidazole, 2-phenyl-2
-Imidazoline, 1,2,3-triphenylguanidine, 1,2-ditolylguanidine, 1,2-dicyclohexylguanidine, 1,2-dicyclohexyl-3-phenylguanidine, 1,2,3-tricyclohexylguanidine, guanine Gintrichloroacetate, N, N'-
Dibenzylpiperazine, 4,4'-dithiomorpholine,
Examples thereof include morpholinium trichloroacetate, 2-amino-benzothiazole and 2-benzoylhydrazino-benzothiazole.

In the light-sensitive material of the present invention, one of the substances that cause the color-forming reaction as described above is contained in the microcapsule, and the other substance of the substance that causes the color-forming reaction is present outside the microcapsule.

When a color-developing / developing system is used as the color-developing system, it is general that the substance contained in the microcapsules is used as the color-developing agent and the substance existing outside the microcapsules is used as the color-developing agent. is there.

When the developer is contained in microcapsules,
An oil-absorbing white pigment may be used in combination with a developer to diffuse and fix the encapsulated material.

Further, a plurality of color developing systems as described above may be used. In this case, by combining with at least three kinds of silver halide emulsions having different sensitivities in different spectral regions (the silver halide emulsion will be described later), each microcapsule can be used so as to correspond to each emulsion. A full-color image can be easily formed.

In the light-sensitive material of the present invention, when a color-developing / developing system is used as the color-developing system, the color-developing agent is preferably used in the range of 0.5 to 50% by weight based on the polymerizable compound. It is more preferable to use it in the range of% by weight. The developer is preferably used in the range of 0.3 to 80% by weight based on the color former.

Hereinafter, the silver halide, the reducing agent, the polymerizable compound, the microcapsule, and the support which compose the light-sensitive material of the present invention will be sequentially described.

In the present invention, the silver halide is not particularly limited,
A silver halide known in the photographic art can be used. Any of silver chloride, silver bromide, silver iodide or silver chlorobromide, silver chloroiodide, silver iodobromide and silver chloroiodobromide can be used in the light-sensitive material of the present invention. The halogen composition of the silver halide grains may be uniform or non-uniform on the surface and inside. In the present invention, the average grain size of the silver halide grains is preferably 0.001 μm to 10 μm, and particularly preferably 0.001 μm to 5 μm. Two or more kinds of silver halides having different crystal habit, halogen composition, grain size, grain size distribution and the like can be used in combination. The amount of the silver halide contained in the photosensitive layer is preferably as small as possible in order to prevent silver from being formed from the silver halide remaining after image formation to cause turbidity in the image. Specifically, 1 mg to 1 g in terms of silver including an organic silver salt which is an optional component described later.
/ M ² is preferable and 1 mg to 100 m
The range of g / m ² is more preferable.

The reducing agent that can be used in the light-sensitive material of the present invention has a function of reducing silver halide and / or a function of accelerating (or suppressing) the polymerization of the polymerizable compound. There are various kinds of substances as the reducing agent having the above function.
Examples of the reducing agent include hydroquinones, catechols, p
-Aminophenols, p-phenylenediamines, 3
-Pyrazolidones, 3-aminopyrazoles, 4-amino-5-pyrazolones, 5-aminouracils, 4,5
-Dihydroxy-6-aminopyrimidines, reductones, aminoreductones, o- or p-sulfonamidophenols, o- or p-sulfonamidonaphthols, 2-sulfonamidoindanones, 4-sulfonamido-5- Examples include pyrazolones, 3-sulfonamidoindoles, sulfonamide pyrazolobenzimidazoles, sulfonamide pyrazolotriazoles, α-sulfonamido ketones, and hydrazines. By adjusting the type and amount of the reducing agent, it is possible to polymerize the polymerizable compound in the portion where the latent image of silver halide is formed or the portion where the latent image is not formed. In a system in which a polymerizable compound in a portion where a latent image of silver halide is not formed is polymerized, 1
It is particularly preferred to use -phenyl-3-pyrazolidones.

Regarding various reducing agents having the above functions, Japanese Patent Application Nos. 60-22980, 60-29894 and 60-
68874, 60-226084, 60-22
No. 7527 and No. 60-227528. Regarding the above reducing agents, see T. James
Author "The Theory of the Photographic Process" 4th edition, pages 291-334 (1977), Research Disclosure Vol. 170, June 1978, 170.
No. 29 (pages 9 to 15) and Vol.176, 1978.
No. 17643 (pages 22 to 31) of December, 2012 also describes. Also in the light-sensitive material of the present invention, the reducing agents (including those described as a developing agent or a hydrazine derivative) described in the above specifications and references can be effectively used. Therefore, the “reducing agent” in the present specification includes the reducing agents described in the above respective specifications and documents.

These reducing agents may be used alone or as a mixture of two or more reducing agents as described in the above specification. When two or more reducing agents are used in combination, the reducing agents may interact with each other by first promoting the reduction of silver halide (and / or organic silver salt) by so-called superadditivity. In addition, the polymerization of the polymerizable compound is caused via the redox reaction with the other reducing agent in which the oxidant of the first reducing agent generated by the reduction of silver halide (and / or organic silver salt) coexists ( Or
It may be possible to suppress the polymerization of the polymerizable compound).
However, in actual use, it is difficult to specify which of the above actions because the above reactions can occur simultaneously.

Specific examples of the reducing agent include pentadecylhydroquinone, 5-t-butylcatechol, p- (N, N-diethylamino) phenol, 1-phenyl-4-methyl-
4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-heptadecylcarbonyloxymethyl-3-pyrazolidone, 2-phenylsulfonylamino-4-hexadecyloxy-5-t-octylphenol, 2-phenyl Sulfonylamino-4-t-butyl-5-hexadecyloxyphenol, 2- (N-butylcarbamoyl) -4-phenylsulfonylaminonaphthol, 2- (N-methyl-N-octadecylcarbamoyl) -4-sulfonylaminonaphthol , 1-acetyl-2-phenylhydrazine, 1-acetyl-2-
{(P or o) -aminophenyl} hydrazine, 1-
Formyl-2-{(p or o) -aminophenyl} hydrazine, 1-acetyl-2-{(p or o) -methoxyphenyl} hydrazine, 1-lauroyl-2-{(p
Or o) -aminophenyl} hydrazine, 1-trityl-2- (2,6-dichloro-4-cyanophenyl) hydrazine, 1-trityl, 2-phenylhydrazine, 1
-Phenyl-2- (2,4,6-trichlorophenyl)
Hydrazine, 1- {2- (2,5-di-t-pentylphenoxy) butyroyl} -2-{(p or o) -aminophenyl} hydrazine, 1- {2- (2,5-di-t
-Pentylphenoxy) butyroyl} -2-{(p or o) -aminophenyl} hydramine pentadecyl fluorocaprylate, 3-indazolinone, 1- (3,
5-dichlorobenzoyl) -2-phenylhydrazine,
1-Trityl-2-[{2-N-butyl-N-octylsulfamoyl) -4-methanesulfonyl} phenyl]
Hydrazine, 1- {4- (2,5-di-t-pentylphenoxy) butyroyl} -2-{(p or o) -methoxyphenyl} hydrazine, 1- (methoxycarbonylbenzohydryl) -2-phenylhydrazine , 1-formyl-2- [4- {2- (2,4-di-t-pentylphenoxy) butylamido} phenyl] hydrazine, 1-
Acetyl-2- [4- {2- (2,4-di-t-pentylphenoxy) butyramide} phenyl] hydrazine,
1-trityl-2-[{2,6-dichloro-4- (N,
N-di-2-ethylhexyl) carbamoyl} phenyl] hydrazine, 1- (methoxycarbonylbenzohydryl) -2- (2,4-dichlorophenyl) hydrazine, and 1-trityl-2-[{2- (N-ethyl) −
N-octylsulfamoyl) -4-methanesulfonyl} phenyl] hydrazine and the like can be mentioned.

In the light-sensitive material of the present invention, the reducing agent is preferably used in the range of 0.1 to 1500 mol% with respect to 1 mol of silver (including the above-described silver halide and an organic silver salt which is an optional component). .

The polymerizable compound that can be used in the light-sensitive material of the present invention is not particularly limited, and known polymerizable compounds can be used.
However, as a method of using the light-sensitive material, when a heat development process is scheduled, a high boiling point (for example,
It is preferable to use a compound having a boiling point of 80 ° C. or higher). Further, the photosensitive material of the present invention is intended to cure the microcapsules by polymerizing the polymerizable compound,
The polymerizable compound is preferably a crosslinkable compound having a plurality of polymerizable functional groups in the molecule.

The polymerizable compound used in the light-sensitive material is generally a compound having addition polymerization or ring-opening polymerization. The compound having an addition-polymerizable group includes a compound having an ethylenically unsaturated group, and the compound having a ring-opening polymerizable group includes a compound having an epoxy group. A compound having an ethylenically unsaturated group is particularly preferable.

The compound having an ethylenically unsaturated group that can be used in the light-sensitive material of the present invention includes acrylic acid and salts thereof,
Acrylic acid esters, acrylamides, methacrylic acid and its salts, methacrylic acid esters, methacrylamides, maleic anhydride, maleic acid esters, itaconic acid esters, styrenes, vinyl ethers,
Examples include vinyl esters, N-vinyl heterocycles, allyl ethers, allyl esters and their derivatives.

Specific examples of the polymerizable compound that can be used in the present invention include acrylic acid esters such as n-butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate, furfuryl acrylate, ethoxyethoxyethyl acrylate, dicyclohexyloxy. Ethyl acrylate, nonylphenyloxyethyl acrylate, hexanediol diacrylate, butanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentaacrylate,
Examples thereof include dipentaerythritol hexaacrylate, polyoxyethylenated bisphenol A diacrylate, hydroxypolyether polyacrylate, polyester acrylate and polyurethane acrylate.

Other specific examples of methacrylic acid esters include methyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, butanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, and pentaerythritol tetramethacrylate. Methacrylate and dimethacrylate of polyoxyalkylenated bisphenol A and the like can be mentioned.

The polymerizable compounds may be used alone or in combination of two or more. It should be noted that a substance in which a polymerizable functional group such as a vinyl group or a vinylidene group is introduced into the chemical structure of the above-mentioned substance that causes a color reaction or a reducing agent can also be used as the polymerizable compound of the present invention. Needless to say, the use of a substance that also functions as a substance that causes a color-forming reaction as described above and a polymerizable compound, or a substance that also serves as a reducing agent and a polymerizable compound, is included in the embodiments of the present invention.

In the light-sensitive material of the present invention, the polymerizable compound is preferably used in the range of 0.05 to 1200% by weight based on silver halide. A more preferable range of use is 5 to 950% by weight.

The polymerizable compounds that can be used in the light-sensitive material are described in the application specifications for a series of light-sensitive materials described above and below.

In the light-sensitive material of the present invention, among the components contained in the light-sensitive layer, at least one of the above-mentioned substances that cause a color-forming reaction and a polymerizable compound are contained in microcapsules. The microcapsules further contain silver halide and a reducing agent. However, at least one of the substances that cause a color reaction is present outside the microcapsules. In the present specification, the “substance contained in the microcapsule” means the substance existing in the core substance and / or the wall material forming the microcapsule. Various known techniques can be applied to the microcapsules without particular limitation. An example of a light-sensitive material using microcapsules and an image forming method using the same is described in Japanese Patent Application No. 60-117089.

As an example of the above-mentioned known technique, US Pat.
US Pat. No. 3,287,154 and British Patent No. 990443, and Japanese Patent Publication Nos. 38-19574 and 42. −
U.S. Pat. No. 3,418,250 and U.S. Pat. No. 3,603,603;
No. 04, a method by precipitation of the polymer described in US Pat. No. 4,967,691; isocyanates described in US Pat. No. 3,796,669.
Method using polyol wall material; US Pat. No. 39145.
A method using the isocyanate wall material described in No. 11; US Pat. Nos. 4,001,140 and 4,087,376.
Urea-formaldehyde-based or urea formaldehyde-resorcinol-based wall forming materials described in U.S. Pat.
Method using a wall forming material such as melamine-formaldehyde resin and hydroxypropyl cellulose described in Japanese Patent No. 25455; JP-B-36-9168 and JP-A-51-51168.
-9079 in sit by polymerization of monomers
u method; British Patent Nos. 927807 and 96507
No. 4, polymerization dispersion cooling method; US Pat. No. 311
1407 and British Patent No. 930422, the Sblading method and the like can be mentioned. The method of microencapsulation is not limited to the above, but a method of forming a polymer film as a microcapsule wall after emulsifying the core substance is particularly preferable.

The light-sensitive material of the present invention comprises a support and a light-sensitive layer containing the components described above. The support is not particularly limited, but as a method of using the light-sensitive material of the present invention, when heat development processing is planned, it is preferable to use a material that can withstand this processing temperature. Materials that can be used for the support include glass, paper,
Fine paper, coated paper, cast coated paper, synthetic paper, metal and its analogs, polyester, acetyl cellulose,
Examples thereof include films such as cellulose ester, polyvinyl acetal, polystyrene, polycarbonate, polyethylene terephthalate, and paper laminated with a resin material or a polymer such as polyethylene.

Optional components that can be contained in the photosensitive layer of the photosensitive material include sensitizing dyes, organic silver salts, various image forming accelerators (eg, bases or base breakers, oils, surfactants, antifoggants, thermal solvents). Etc.), thermal polymerization inhibitor, thermal polymerization initiator, development terminator, fluorescent whitening agent, anti-fading agent, halation or irradiation prevention dye, matting agent,
Anti-smudge agents, plasticizers, water release agents, binders, etc.

Examples of sensitizing dyes that can be used in the light-sensitive material are described in Japanese Patent Application No. 60-139746, and examples of organic silver salts are described in Japanese Patent Application No. 60-141799. . The image forming method using a base or a base breaker and a photosensitive material are described in Japanese Patent Application No. 60-227528, and the image forming method and a photosensitive material using a thermal polymerization initiator are described in Japanese Patent Application No. Each of them is described in the specification of 60-223347. Further, regarding a light-sensitive material using an antifoggant, Japanese Patent Application Nos. 60-294337 and 60-2943.
38, 60-294339 and 60-294.
No. 341, and a light-sensitive material using a polyethylene glycol derivative as a heat solvent is described in Japanese Patent Application No. 60-294340. Examples of other components and their use modes are also described in the specification of the application relating to the series of light-sensitive materials described above, and research.
Disclosure Magazine Vol.170, 1st June 1978
7029 (pages 9 to 15).

The sensitizing dye that can be used in the light-sensitive material of the present invention is
There is no particular limitation, and a silver halide sensitizing dye known in the photographic art can be used. The sensitizing dyes include methine dyes, cyanine dyes, merocyanine dyes, complex cyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. These sensitizing dyes may be used alone or in combination. In particular, for the purpose of supersensitization, it is common to use a combination of sensitizing dyes. Further, together with the sensitizing dye, a dye which does not have a spectral sensitizing effect itself, or a substance which does not substantially absorb visible light but exhibits supersensitization may be used together. The addition amount of the sensitizing dye is generally about 10 ^{-8 to} 10 ^-2 mol per mol of silver halide.

In the light-sensitive material of the present invention, the use of an organic silver salt is particularly effective when heat development processing is planned as a method of using the light-sensitive material. That is, when heated to a temperature of 80 ° C. or higher, the organic silver salt is considered to participate in the redox reaction using the latent image of silver halide as a catalyst. in this case,
It is preferable that the silver halide and the organic silver salt are in contact with or in close proximity to each other. As the organic compound that constitutes the organic silver salt, an aliphatic or aromatic carboxylic acid,
Examples thereof include a thiocarbonyl group-containing compound having a mercapto group or α-hydrogen, and an imino group-containing compound. Among them, benzotriazole is particularly preferable. The organic silver salt is generally a silver halide 1
It is used in an amount of 0.01 to 10 mol, preferably 0.01 to 1 mol, per mol. The same effect can be obtained by adding an organic compound (for example, benzotriazole) constituting the organic silver salt to the photosensitive layer instead of the organic silver salt.

Various image forming accelerators can be used in the light-sensitive material of the present invention. The image forming accelerator includes a silver halide (and / or an organic silver salt) and a reducing agent for promoting the redox reaction of the redox agent, and the transfer of the color image forming substance from the light-sensitive material to the image receiving material or the image receiving layer. There are functions such as promotion. The image forming accelerator is a base or a base precursor, an oil, a surfactant, an antifoggant, from the viewpoint of physicochemical functions.
It is classified as a hot solvent. However, these substance groups generally have a composite function, and usually have some of the above-mentioned accelerating effects together. Therefore, the above classification is convenient, and in fact, one compound often has a plurality of functions.

Examples of the image forming accelerator include bases, base breakers, oils, surfactants, antifoggants, and hot solvents.

Examples of preferred bases include alkali metal or alkaline earth metal hydroxides, secondary or tertiary phosphates, borates, carbonates, metaborates as inorganic bases; ammonium hydroxides; quaternary Alkyl ammonium hydroxide;
Other metal hydroxides and the like can be mentioned. As organic bases, aliphatic amines (trialkylamines, hydroxylamines, aliphatic polyamines); aromatic amines (N-alkyl-substituted aromatic amines) , N-hydroxylalkyl-substituted aromatic amines and bis [p- (dialkylamino) phenyl] methanes), heterocyclic amines, amidines, cyclic amidines, guanidines, cyclic guanidines, quinolinates, and the like. Especially pKa
Is preferably 7 or more.

As a base breaker, a salt of an organic acid and a base that is decarboxylated by heating, a compound that releases amines by a reaction such as intramolecular nucleophilic substitution reaction, Rossen rearrangement, Beckmann rearrangement, etc., causes a reaction to generate a base by heating. Compounds that release and generate a base by electrolysis are preferably used. Specific examples of the base breaker include guanidine trichloroacetic acid, piperidine trichloroacetic acid, morpholine trichloroacetic acid, p-triidine trichloroacetic acid, 2-picoline trichloroacetic acid, phenylsulfonylacetic acid guanidine, 4-chlorophenylsulfonylacetic acid guanidine, and 4-methyl. -Sulfonylphenyl sulfonylacetate guanidine, 4-acetylaminophenylpropiolic acid guanidine and the like can be mentioned.

In the light-sensitive material of the present invention, the base or base breaker can be used in a wide range of amount. It is appropriate to use a base or a base breaker in an amount of 50% by weight or less in terms of weight of the coating film of the photosensitive layer, and more preferably 0.
A range of 01% to 40% by weight is useful. In the present invention, the base and / or base breaker may be used alone or as a mixture of two or more kinds.

As the oil, a high boiling point organic solvent used as a solvent for emulsifying and dispersing a hydrophobic compound can be used.

Examples of the surfactant include pyridinium salts, ammonium salts, phosphonium salts described in JP-A-59-74547 and polyalkylene oxides described in JP-A-59-57231.

As the antifoggant, compounds having a 5-membered or 6-membered nitrogen-containing complex reduction structure (including compounds having a cyclic amide structure), thiourea derivatives, thioether compounds, thiol derivatives, etc., which are known in conventional photographic techniques, etc. Can be mentioned.

As the hot solvent, a compound which can be a solvent for the reducing agent, a compound which is a substance having a high dielectric constant and is known to accelerate the physical development of the silver salt, and the like are useful. As a useful thermal solvent,
Polyethylene glycols described in U.S. Pat. No. 3,347,675, derivatives of polyethylene oxide such as oleic acid ester, beeswax, monostearin and -SO.
High dielectric constant compounds having _2- and / or -CO- groups, polar substances described in U.S. Pat. No. 3,667,959, 1,10-decane described in Research Disclosure, December 1976, pages 26-28. Diol, methyl anisate, biphenyl suberate and the like are preferably used.

The thermal polymerization initiator that can be used in the light-sensitive material of the present invention is generally a compound that thermally decomposes under heating to generate a polymerization initiation species (particularly a radical), and is usually used as a radical polymerization initiator. is there. Regarding the thermal polymerization initiator, pages 6 to 18 of “Additional Polymerization / Ring-Opening Polymerization”, edited by Editorial Committee of Polymer Society for Polymer Science, 1983, Kyoritsu Publishing)
It is described in the page etc. Specific examples of the thermal polymerization initiator include azobisisobutyronitrile, 1,1′-azobis (1-cyclohexanecarbonitrile), dimethyl-
Azo compounds such as 2,2′-azobisisobutyrate, 2,2-azobis (2-methylbutyronitrile) and azobisdimethylvaleronitrile, benzoyl peroxide, di-t
-Organic peroxides such as peroxide, dicumyl peroxide, t-butylhydroperoxide, cumene hydroperoxide, inorganic peroxides such as hydrogen peroxide, potassium persulfate, ammonium persulfate, and p-toluenesulfinic acid Examples thereof include sodium. The thermal polymerization initiator is preferably used in the range of 0.1 to 120% by weight, more preferably 1 to 10% by weight, based on the polymerizable compound.

The development terminator that can be used in the light-sensitive material of the present invention is a compound or silver and a silver salt which, after proper development, rapidly neutralize the base or react with the base to lower the concentration of the base in the film and stop the development. It is a compound that interacts and suppresses development. Specific examples thereof include an acid breaker that releases an acid when heated, an electrophilic compound that causes a substitution reaction with a coexisting base when heated, a nitrogen-containing heterocyclic compound, and a mercapto compound. For example, Japanese Patent Application Sho 5
8-216928 and 59-48305, the oxime esters described in each specification, Japanese Patent Application No. 59-85834.
Examples thereof include compounds that release an acid by Rossen rearrangement, and electrophilic compounds that undergo a substitution reaction with a base upon heating include compounds described in Japanese Patent Application No. 59-85836.

As the anti-smudge agent that can be used in the light-sensitive material of the present invention, particulate matter that is solid at room temperature is preferable. Specific examples thereof include starch particles described in British Patent No. 12322347, polymer fine powder described in US Pat. No. 3,625,736, etc., and microcapsule particles containing no color former described in British Patent No. 12359991. , A fine cellulose powder described in US Pat. No. 2,711,375,
Talc, kaolin, bentonite, pyrophyllite, zinc oxide,
Examples thereof include inorganic particles such as titanium oxide and alumina. The average particle size of the particles is preferably in the range of 3 to 50 μm in volume average diameter, and 5 to 40 μm.
The range of m is more preferable. It is more effective that the particles are larger than the microcapsules described above.

The binder that can be used in the light-sensitive material of the present invention is
They can be contained in the photosensitive layer individually or in combination. It is preferable to mainly use a hydrophilic binder. As the hydrophilic binder, a transparent or translucent hydrophilic binder is typical, and examples thereof include natural substances such as gelatin, gelatin derivatives, cellulose derivatives, starch, and arabic gum, and polyvinyl alcohol, polyvinylpyrrolidone, acrylamide polymers and the like. Includes synthetic polymeric materials such as water soluble polyvinyl compounds. Other synthetic polymeric materials include dispersed vinyl compounds in the form of latices, which increase the dimensional stability of photographic materials in particular.

As the layer that can be optionally provided in the photosensitive material, a heating element layer, a protective layer, an antistatic layer, an anti-curl layer, a peeling layer,
Examples thereof include a matting agent layer.

For the photosensitive material using the heating element layer, Japanese Patent Application No.
-135568. In addition, examples of other auxiliary layers and usage modes thereof are also described in the specification of the above-mentioned series of photosensitive materials.

The light-sensitive material of the present invention can be manufactured as described below.

Although various methods can be used as a method for producing a light-sensitive material, a general production method is to prepare a coating solution by dissolving, emulsifying or dispersing the components of the photosensitive layer in an appropriate solvent, and applying the coating solution. Is applied to a support and dried to obtain a light-sensitive material.

Generally, the coating solution is prepared by preparing a liquid composition containing each component for each component, and then mixing each liquid composition. The liquid composition may be prepared for each component, or may be prepared to contain a plurality of components. A part of the components of the photosensitive layer may be added and used at the stage of preparing the liquid composition or the coating solution or after the preparation. Furthermore, as described below, a method of preparing a secondary composition by emulsifying an oily (or aqueous) composition containing one or more components in an aqueous (or oily) solvent can also be used. .

Hereinafter, a method for preparing a liquid composition and a coating liquid will be described with respect to main components contained in the photosensitive layer.

In the production of a light-sensitive material, silver halide is preferably prepared as a silver halide emulsifier. There are various methods known in the photographic art for preparing a halogenated emulsion, but there is no particular limitation regarding the production of the light-sensitive material of the present invention. The silver halide emulsion can be implemented by any of the acidic method, the neutral method and the ammonia method. The reaction mode of the soluble silver salt and the soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method, or a combination thereof. A back-mixing method in which grains are formed under conditions of excess silver ions and a controlled double-jet method in which pAg is kept constant can also be adopted. Further, the silver halide emulsion may be a surface latent image type in which a latent image is mainly formed on the surface of a grain, or an internal latent image type in which a latent image is formed inside the grain. A direct reversal emulsion in which an internal latent image type emulsion and a nucleating agent are combined can also be used.

In the preparation of a silver halide emulsion used for producing a light-sensitive material, it is preferable to use a hydrophilic colloid as a protective colloid. By preparing a silver halide emulsion using a hydrophilic colloid, the sensitivity of a light-sensitive material produced using this emulsion is improved. The silver halide emulsion contains ammonia and an organic thioether derivative as a silver halide solvent in the step of forming silver halide grains (Japanese Examined Patent Publication No.
No. 7-386) and sulfur-containing compounds (Japanese Patent Laid-Open No. Sho 5).
3-144319 gazette) etc. can be used. Further, in the process of grain formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt or the like may be allowed to coexist. Further, for the purpose of improving the high illuminance failure and the low illuminance failure, water-soluble iridium such as iridium chloride (III valence or IV valence), hexachloroiridium salt ammonium, or water-soluble rhodium salt such as rhodium chloride can be used.

Soluble salts may be removed from the silver halide emulsion after formation of a precipitate or after physical ripening. In this case, it can be carried out according to the Nudel washing method or the precipitation method. The silver halide emulsion may be used without ripening, but it is usually chemically sensitized before use. In the emulsion for conventional type sensitizers, known sulfur sensitization method, reduction sensitization method, noble metal sensitization method, or the sensitization method using the sensitizing dye described in Japanese Patent Application No. 60-139746 mentioned above may be used alone or It can be used in combination. These chemical sensitizations can be carried out in the presence of a nitrogen-containing heterocyclic compound (see JP-A Nos. 58-126526 and 58-215644).

When the organic silver salt described in Japanese Patent Application No. 60-141799 is contained in the photosensitive layer, the organic silver salt emulsion can be prepared by a method similar to the method for preparing a silver halide emulsion. .

The polymerizable compound in the production of the photosensitive material is used as a solvent when preparing the composition of other components in the photosensitive layer, so that these components can be easily accommodated in the microcapsules together with the polymerizable compound. it can. That is, at least one of the above-mentioned substances that cause a color-forming reaction, or a silver halide (including a silver halide emulsion), a reducing agent, or any other component is dissolved or emulsified in a polymerizable compound. Dispersed and used in the production of a light-sensitive material. In addition, components such as wall materials necessary for microencapsulation may be added to the polymerizable compound.

A photosensitive composition in which silver halide is dispersed in a polymerizable compound can be prepared using a silver halide emulsion.
Further, in the preparation of the photosensitive composition, the silver halide can be used as a dry powder by freeze-drying or the like in addition to the preparation as a silver halide emulsion. The photosensitive composition containing these silver halides can be obtained by stirring with a homogenizer, blender, mixer or other commonly used stirrer.

In addition, in the polymerizable compound used for preparing the photosensitive composition, it is preferable to dissolve a copolymer composed of a hydrophilic repeating unit and a hydrophobic group repeating unit.
The photosensitive composition containing the above copolymer is described in Japanese Patent Application No. 60-261887.

Further, instead of using the above copolymer, microcapsules containing a silver halide emulsion as a core substance may be dispersed in a polymerizable compound to prepare a photosensitive composition. A photosensitive composition containing microcapsules containing the above silver halide emulsion as a core substance is described in Japanese Patent Application No. 61-5750.

Further, at least one of the substances that cause a color-forming reaction is a polymerizable compound (including those containing other constituents such as the above-mentioned photosensitive composition; hereinafter, it may be simply referred to as a polymerizable compound). It is possible to dissolve it directly in. Alternatively, by dissolving the above substance in a suitable solvent,
This solution can also be added to the polymerizable compound.

The polymerizable compound is emulsified in an aqueous solvent and used as an emulsion. Among the emulsions of the polymerizable compound, when the photosensitive composition containing silver halide as the polymerizable compound is not used, the emulsion and the silver halide emulsion, and optionally other composition such as an organic silver salt emulsion. Mix with. A reducing agent and other optional components may be added at the stage of this emulsion. Further, components such as wall materials necessary for microencapsulation may be added to this emulsion.

A microcapsule liquid can be obtained by performing the above-mentioned microencapsulation treatment on the above aqueous emulsion. At the stage of the microcapsule liquid, a substance existing outside the microcapsules among the substances that cause the above-mentioned color development reaction is added. Further, a reducing agent or some optional components can be added.

As described above, the coating liquid of the photosensitive material of the present invention can be prepared. The light-sensitive material of the present invention can be manufactured by coating the above-mentioned coating liquid on the support and drying it. The coating of the coating liquid on the support can be easily carried out according to known techniques.

The method of using the light-sensitive material of the present invention will be described below.

The light-sensitive material of the present invention is subjected to a developing treatment at the same time as the imagewise exposure or after the imagewise exposure before use.

Although various exposing means can be used as the exposing method, a latent image of silver halide is generally obtained by imagewise exposure of radiation including visible light. The type of light source and the amount of exposure are
Sensitive wavelength of silver halide (when dye sensitization is performed,
It can be selected according to the sensitized wavelength) and the sensitivity. The original image may be a monochrome image or a color image.

The photosensitive material of the present invention is subjected to a heat development treatment to polymerize the polymerizable compound. Since the heat development process is a dry process, it has advantages that the operation is simple and the process can be performed in a short time.

As the heating method, various conventionally known methods can be used. In addition, the above-mentioned Japanese Patent Application No. 60-13556.
Like the light-sensitive material described in No. 8, the light-sensitive material may be provided with a heating element layer and used as a heating means. The heating temperature is generally 80 ° C to 200 ° C, preferably 100 ° C to 160 ° C. The heating time is generally 1 second to 5 seconds.
Minutes, preferably 5 seconds to 1 minute.

The light-sensitive material of the present invention is subjected to the development processing as described above,
It is possible to polymerize the polymerizable compound in either a latent image-formed portion or a latent image-not-formed portion of silver halide. In the light-sensitive material of the present invention, the polymerizable compound in a portion where a latent image of silver halide is not formed is generally polymerized in the above-mentioned development processing, but as described above, it is described in Japanese Patent Application No. 60-210657. It is also possible to polymerize the polymerizable compound in the portion where the latent image of silver halide is not formed, by adjusting the type and amount of the reducing agent as in the light-sensitive material.

The above development treatment is carried out to polymerize the polymerizable compound in either the portion where the latent image of silver halide is formed or the portion where the latent image is not formed, thereby curing the microcapsules in this portion. Let A photographic material that has been subjected to a development treatment can form a color image on the photographic material by rupturing the uncured microcapsules and allowing two or more substances that cause a color-forming reaction to coexist and develop color. .

As a method of rupturing the above-mentioned microcapsules, there is generally a method of using a pressing means. Various conventionally known methods can be used for the pressing means.

The light-sensitive material of the present invention is a black-and-white or color photographing and printing sensitive material, printing sensitive material, printing plate, X-ray sensitive material, medical sensitive material (for example, ultrasonic diagnostic machine CRT photographing sensitive material), computer graphic hard copy. There are many applications such as light-sensitive materials and light-sensitive materials for copying machines.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

[Example 1] Preparation of silver halide emulsion An aqueous solution containing 21 g of sodium chloride and 56 g of potassium bromide in a stirring gelatin aqueous solution (containing 20 g of gelatin and 3 g of sodium chloride in 1000 m of water and kept at 75 ° C). 600m and silver nitrate aqueous solution (water 600m
4) simultaneously dissolving 0.59 mol of silver nitrate)
Added at equal flow rate over 0 minutes. Thus, a monodisperse cubic silver chlorobromide emulsion (bromine 80 mol%) having an average grain size of 0.35 μm was prepared.

The above emulsion was washed with water and desalted, and then 5 mg of sodium thiosulfate and 4-hydroxy-6-methyl-1,3,3a,
20 mg of 7-tetrazaindene was added and chemical sensitization was performed at 60 ° C. The yield of emulsion was 600 g.

Preparation of benzotriazole silver emulsion 28 g of gelatin and 13.2 g of benzotriazole were added to 3 parts of water.
It was melted in 000m. This solution was stirred while maintaining it at 40 ° C., and a solution prepared by dissolving 17 g of silver nitrate in 100 m of water was added over 2 minutes. By adjusting the pH of the obtained emulsion, excess salt was precipitated and removed. Then adjust the pH to 6.30
And a benzotriazole silver emulsion was obtained. The yield of emulsion was 400 g.

Preparation of Photosensitive Composition 0.40 g of the following copolymer, 4.00 g of crystal violet lactone, and 2 g of Emalex NP-8 (manufactured by Nippon Emulsion Co., Ltd.) were dissolved in 100 g of trimethylolpropane triacrylate. Dissolution 1 above
0.002 g of the following Thiol derivative was dissolved in 8.00 g. 0.16 g of the following hydrazine derivative (reducing agent) and the following developing agent (reducing agent) were added to this solution.
A solution of 1.22 g dissolved in 1.80 g of methylene chloride was added. Furthermore, 3.50 g of the silver halide emulsion prepared as described above and 3.3 of the benzotriazole silver emulsion.
Add 5g and use homogenizer to 15,000 min.
By stirring for 5 minutes by rotation, a photosensitive composition was obtained.

(Copolymer) (Thiol derivative) (Hydrazine derivative) (Developer) Preparation of microcapsule solution 18.6% aqueous solution of Isoban (manufactured by Kuraray Co., Ltd.)
51 g and 48.56 g of a 2.89% aqueous solution of pectin were added, and the photosensitive composition was added to an aqueous solution whose pH was adjusted to 4.0 with 10% sulfuric acid, and a homogenizer was used at 7,000 rpm for 2 minutes. With stirring, the photosensitive composition was emulsified in an aqueous solvent.

Urea 40% aqueous solution 8.32 was added to 72.5 g of this aqueous emulsion.
g, resorcin 11.3% aqueous solution 2.82 g, formalin 37% aqueous solution 8.56 g, ammonium sulfate 8.76
% Aqueous solution 2.74 g was sequentially added, and heating was continued at 60 ° C. for 2 hours while stirring. Thereafter, the pH was adjusted to 7.0 using a 10% aqueous sodium hydroxide solution, and 3.62 g of a 30.9% aqueous sodium hydrogen sulfite solution was added to prepare a microcapsule solution.

Preparation of developer liquid To 125 g of water, 11 g of 40% sodium hexametaphosphate aqueous solution was added, and further 34 g of 3,5-di-α-methylbenzylbenzyl salicylate zinc and 82 g of 55% calcium carbonate slurry were mixed and coarsely dispersed with a mixer. did. The liquid was dispersed with a Dynamill disperser, and 6 g of 50% SBR latex and 55 g of 8% polyvinyl alcohol were added to 200 g of the obtained liquid and uniformly mixed to prepare a developer liquid.

Preparation of Photosensitive Material 5.0 g of the microcapsule solution prepared as described above and 5.0 g of the developer solution were mixed, and 1.0 g of an anionic surfactant 1% aqueous solution described below and guanidine trichloroacetate were mixed in the mixed solution. 10% (water / ethanol = 50/50 volume ratio)
Add 1.0 g of the solution and apply 3 onto the 100 μm thick polyethylene terephthalate using the # 40 coating rod.
It was coated so as to have a wet film thickness of 0 μm and dried at about 40 ° C. to prepare a light-sensitive material according to the present invention.

(Anionic surfactant) Evaluation of Photosensitive Material The photosensitive material obtained as described above was imagewise exposed for 1 second using a tungsten bulb of 500 lux, and then 12
Heated for 40 seconds on a hot plate heated to 5 ° C.
Next, when the light-sensitive material was passed through a pressure roller of 350 kg / cm ² , a blue positive color image was obtained on the light-sensitive material. The maximum density of the above image was 0.8 and the minimum density was 0.3.

Claims (5)

[Claims] 1. A silver halide, a reducing agent, a polymerizable compound, and two kinds of substances that cause a color reaction in a contact state, and one of the substances causing the color reaction and the silver halide and a reducing agent. And a polymerizable compound together in a state of being housed in a photosensitive microcapsule, and the other substance among the substances causing the color-forming reaction is present outside the photosensitive microcapsule on the support. A heat-developable photosensitive material having. 2. Of the two types of substances that cause the color-forming reaction,
2. The photothermographic material according to claim 1, wherein the substance contained in the photosensitive microcapsules is a color former, and the substance present outside the photosensitive microcapsules is a developer. 3. A photosensitive layer containing silver halide in the range of 1 mg to 1 g / m ^{2 in} terms of silver amount.
A heat-developable photosensitive material as described in the item. 4. The photothermographic material according to claim 1, wherein the photosensitive layer further contains an organic silver salt. 5. The photothermographic material according to claim 4, wherein the photosensitive layer contains silver halide and an organic silver salt in the range of 1 mg to 1 g / m ² .