JPH0731397B2 - Photosensitive material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a self-coloring type light-sensitive material containing a silver halide, a reducing agent, a polymerizable compound and a color image-forming substance in the same light-sensitive layer.

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 utilizes a latent image of silver halide to polymerize the polymerizable compound by the action of the reducing agent. The image forming method can be used.

Examples of the image forming method include, for example, Japanese Patent Publication No. 45-11149.
No. 47-20741, No. 49-10697, JP-A-57-138632
No. 58-169143 and the like. In these methods, when the exposed silver halide is developed using a developing solution, the reducing agent is oxidized and at the same time, the coexisting polymerizable compound (eg, vinyl compound) initiates the polymerization, resulting in high image quality. It is a method of forming a molecular compound. Therefore, the above method requires a developing treatment using a liquid, and the treatment requires a relatively long time.

As an improvement of the above method, JP-A-61-69062 discloses a method capable of forming a polymer compound by a dry treatment. In this method, a recording material (photosensitive material) having a photosensitive layer composed of a photosensitive silver salt (silver halide), 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 by heating, a polymer compound is formed on a portion of the photosensitive silver salt where the latent image is formed.

The above-mentioned image forming method is a method of polymerizing the polymerizable compound in the portion where the latent image of silver halide is formed, but the method of polymerizing the polymerizable compound in the portion where the latent image of silver halide is not formed is already available. A patent application has been filed (Japanese Patent Laid-Open No. 61-260
No. 241). This method is a method in which a reducing agent acts on a portion on which a latent image of silver halide is formed by heating to suppress the polymerization of a polymerizable compound, and at the same time, promotes the polymerization of other portions.

As a light-sensitive material capable of easily obtaining a desired color image by using the above-mentioned image forming method, the present applicant has proposed on a support that a silver halide, a reducing agent, a polymerizable compound and a color image are formed. A patent application has already been filed for a photosensitive material having a photosensitive layer containing a substance and having a constitution in which a polymerizable compound and a color image-forming substance are contained in the same microcapsule (JP-A-61-275742). This light-sensitive material is advantageous when a substance that employs a so-called two-component coloring system, which develops color by utilizing a reaction between two components, is used as a color image forming substance. That is, by microencapsulating one of the color image forming substances (component), it can be easily separated from the other substance (component). In particular, by mixing both the components in the same photosensitive layer. It is also possible to have a structure (self-coloring type light-sensitive material) coexisting with the above, and it is possible to more easily perform color image formation.
The present applicant has already filed a patent application for the self-coloring type light-sensitive material (Japanese Patent Application No. 61-53881).

Further, as another aspect of the image forming method, an image obtained on a light-sensitive material (an image composed of an unpolymerized polymerizable compound)
After transferring the image onto the image receiving material, a patent application has been filed for a method of curing the image by subjecting the image to a separate fixing process (light irradiation or heating) (Japanese Patent Application No. 61-3025 and 6).
1-55502 specification). By these methods, the storability of images and the like are enhanced.

SUMMARY OF THE INVENTION An object of the present invention is to provide a light-sensitive material capable of easily fixing an image.

Another object of the present invention is to provide a light-sensitive material having the above-mentioned fixing function and improved image storability.

That is, the present invention includes a support and a support provided on the support.
In a photosensitive material having a photosensitive layer containing silver halide, a reducing agent, a polymerizable compound, and two kinds of substances that cause a color forming reaction by contacting each other, one of the substances causing the color forming reaction and the polymerizable compound. And are contained in microcapsules, and on the outside of the microcapsules, a curing agent capable of polymerizing and curing the polymerizable compound without requiring external energy application is included. It is in the photosensitive material.

[Advantages of the Invention] The photosensitive material of the present invention contains a curing agent capable of curing an image without externally applying energy to the photosensitive layer. The polymerizable compound) is easily fixed without performing a separate fixing process. That is, in the photosensitive layer of the present invention, since a compound capable of easily polymerizing and curing with an unpolymerized polymerizable compound is present outside the microcapsules containing the polymerizable compound, it is destroyed after exposure and development. The unpolymerized polymerizable compound that oozes out from the capsules is easily polymerized and hardened with the curing agent. Therefore, the fixing can be performed without separately performing the fixing process (light irradiation or heating). still,
It is considered that this polymerization reaction (curing) is mainly due to a Michael addition reaction between the curing agent and the polymerizable compound. The color image formed in this manner prevents blurring of the image thereafter, fading of the light or blurring of the image,
A clear color image is maintained for a long time.

Further, the light-sensitive material of the present invention is a light-sensitive material constituted by using the above-mentioned photopolymerization initiator or thermal polymerization initiator as a method for imparting a fixing function (Japanese Patent Application Nos. 61-3025 and 61-5550).
It can be configured in a relatively stable state against light or heat, as compared with (see No. 2 specification). Therefore, the storability of the light-sensitive material itself is not impaired even when the fixing function is imparted, and it can withstand long-term storage.

DETAILED DESCRIPTION OF THE INVENTION The light-sensitive material of the present invention comprises a support and a support provided thereon.
It comprises a silver halide, a reducing agent, a polymerizable compound and a photosensitive layer containing two kinds of substances which cause a color forming reaction by coming into contact with each other. The compound is present outside the microcapsule containing the compound.

A curing agent, which is a characteristic component of the present invention, capable of polymerizing and curing a polymerizable compound (polymerizable monomer) without the need for externally applying energy is a compound (a compound capable of reacting with a polymerizable compound ( Any compound can be used without particular limitation as long as it includes a compound which reacts in the presence of a catalyst. Therefore, as the curing agent used in the present invention, it is preferable to select a compound having good reactivity in correspondence with the polymerizable compound contained in the photosensitive material. As the polymerizable compound, as described in each of the above-mentioned publications, it is common to use a compound having at least two ethylenically unsaturated bonds in its structure (as a preferable example, Such as acrylic acid ester or acrylic acid amide). From such a viewpoint, the curing agent according to the present invention preferably has at least two or more nucleophilic groups in the same molecule, and
It is preferable that the compound has less steric hindrance and is highly nucleophilic. Preferred examples of such a nucleophilic group include:
The imino group, amino group and sulfinic acid group are typical.

Further, specific examples of compounds containing them include ethylenediamine, propylenediamine, and 1,3-diamino-2-
Hydroxypropane, 1,3-trimethylene diamine, N,
N'-dimethylethylenediamine, 1,4-diaminobutane, hexamethylenediamine, diethylenetriamine,
Triethylenetetramine, a compound represented by the following formula, Polyethyleneimine, polyallylamine, poly -L- lysine, poly -L- ornithine, compounds represented by the following formula, may be mentioned _{NaO 2 S-CH 2 CH =} CHCH 2 SO 2 Na , and sodium poly vinylbenzene sulfinic acid . These compounds may be used alone or in combination of several kinds. Among the above, especially polyethyleneimine,
Preference is given to 1,3-diamino-2-hydroxypropane and sodium polyvinylbenzenesulfinate. Although the above reaction is presumed to be carried out by the Michael addition reaction as described above, it is preferable that the reaction system of this reaction has low basicity. In particular, in the present invention, a color image forming substance is used. It is preferable that the reaction system is acidic because it contains the above.

The curing agent varies depending on the kind or amount of the polymerizable compound in the photosensitive layer, but is 0.1 to 200 with respect to the polymerizable compound.
It is preferably contained in the range of mol%,
It is preferably contained in the range of 1 to 50 mol%.

Hereinafter, the silver halide constituting the light-sensitive material, a reducing agent, a polymerizable compound, a substance which causes a color reaction by contact,
The support will be described in sequence.

Photosensitive materials include silver chloride, silver bromide,
Any grain of silver iodide or silver chlorobromide, silver chloroiodide, silver iodobromide, and silver chloroiodobromide can be used.

The halogen composition of the silver halide grains may be uniform or non-uniform on the surface and inside. Regarding silver halide grains having a multiple structure having different compositions on the surface and inside, JP-A-57-154232, JP-A-58-108533, and JP-A-59-48755
No. 59-52237, US Pat. No. 4433048, and European Patent No. 100984. Further, as in the light-sensitive material described in Japanese Patent Application No. 61-25576, silver halide grains having a high silver iodide ratio in the shell portion may be used.

There is also no particular limitation on the crystal habit of the silver halide grains. For example, tabular grains having an aspect ratio of 3 or more as in the light-sensitive material described in Japanese Patent Application No. 61-55509 may be used.

The silver halide grains described above are Japanese Patent Application No. 61-21458.
As in the light-sensitive material described in No. 0, it is preferable to use silver halide grains having a relatively low fog value.

Two or more kinds of silver halide grains having different halogen compositions, crystal habits, grain sizes and the like can be used in combination with the silver halide used in the light-sensitive material.

The grain size distribution of silver halide grains is not particularly limited. For example, monodisperse silver halide grains having a substantially uniform grain size distribution may be used, as in the light-sensitive material described in Japanese Patent Application No. 61-55508.

In the light-sensitive material, the average grain size of silver halide grains is preferably 0.001 to 5 μm, and more preferably 0.001 to 2 μm.

The amount of silver halide contained in the photosensitive layer is 0.1 mg to 10 g / m ^{2 in} terms of silver including an organic silver salt which is an optional component described later.
It is preferable to set it as the range. Further, in terms of silver equivalent of silver halide alone, it is preferably 1 g / m ² or less, and particularly preferably 1 mg to 500 mg / m ² .

The reducing agent that can be used in the light-sensitive material 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-pyrazolones, 3-sulfonamidoindoles,
Examples include sulfonamide pyrazolobenzimidazoles, sulfonamide pyrazolotriazoles, α-sulfonamide 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 addition,
In the system in which the polymerizable compound in the portion where the latent image of silver halide is not formed is polymerized, it is particularly preferable to use 1-phenyl-3-pyrazolidones as the reducing agent.

Regarding various reducing agents having the above functions, see
61-183640, 61-188535, 61-228441, and Japanese Patent Applications 60-210657, 60-226084, 60
-227527, 60-227528 and 61-42746 (including those described as a developer or a hydrazine derivative). Regarding the reducing agent, see T. James
Author "The Theory of the photographic Process" 4th edition, 291-334 (1977), Research Disclosure Vol.170, June 1978, No. 17029 (9-15),
And Vol. 176, December 1978, No. 17643 (22-31
Page). Further, as in the light-sensitive material described in Japanese Patent Application No. 61-55505, a reducing agent precursor capable of releasing the reducing agent under heating conditions or in contact with a base is used instead of the reducing agent. Good. The reducing agent and the reducing agent precursor described in the above-mentioned respective specifications and references can be effectively used for the light-sensitive material in the present specification. Therefore, the “reducing agent” in the present specification includes the reducing agents and reducing agent precursors described in the above-mentioned publications, specifications and literatures. These reducing agents may be used alone, or as described in each of the above specifications, two or more reducing agents may be mixed and used. 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. To cause polymerization of the polymerizable compound via an oxidation-reduction reaction with another reducing agent in which the oxidant of the first reducing agent generated by reduction of silver halide (and / or organic silver salt) coexists (Or suppressing the polymerization) is considered. 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
-Phenylsulfonylamino-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- (2,2 5-di-t-pentylphenoxy)
Butyroyl} -2-{(p or o) -aminophenyl} hydrazine, 1- {2- (2,5-di-t-pentylphenoxy) butyroyl} -2-{(p or o) -aminophenyl} hydrazine -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)
Butylamido} phenyl] hydrazine, 1-trityl-
2-[{2,6-dichloro-4- (N, N-di-2-ethylhexyl) carbamoyl} phenyl] hydrazine, 1-
(Methoxycarbonylbenzohydryl) -2- (2,4-
Dichlorophenyl) hydrazine, 1-trityl-2-
[{2- (N-ethyl-N-octylsulfamoyl)
-4-Methanesulfonyl} phenyl] hydrazine, 1-
Benzoyl-2-tritylhydrazine, 1- (4-butoxybenzoyl) -2-tritylhydrazine, 1- (2,
4-dimethoxybenzoyl) -2-tritylhydrazine, 1- (4-dibutylcarbamoylbenzoyl) -2
-Tritylhydrazine, and 1- (1-naphthoyl)
-2-Trityl hydrazine etc. can be mentioned.

In the light-sensitive material, 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 photosensitive material is not particularly limited, and known polymerizable compounds can be used. As a method of using the light-sensitive material, when a heat development process is planned, a high boiling point (for example, a boiling point of 80 ° C.) that is hard to volatilize during heating is used.
It is preferable to use the above compounds). Further, in the embodiment in which the photosensitive layer contains a color image forming substance as an optional component described later, the color image forming substance is immobilized by polymerizing and curing the polymerizable compound. A crosslinkable compound having a polymerizable functional group is preferable. Further, as will be described later, when a transfer image is formed using an image receiving material, it is preferable to use a highly viscous substance as the polymerizable compound, as in the photosensitive material described in Japanese Patent Application No. 61-150079. preferable.

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.

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.

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

Specific examples of the polymerizable compound that can be used in the light-sensitive material 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 hexaacrylate,
Examples thereof include 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. The light-sensitive material containing two or more polymerizable compounds in combination is described in Japanese Patent Application No. 61-55504.
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 reducing agent or the substance which causes a coloring reaction described later can also be used as the polymerizable compound.

In the light-sensitive material, the polymerizable compound is preferably used in the range of 50 to 120,000 parts by weight with respect to 1 part by weight of silver halide. A more preferred range of use is 12 to 12000 parts by weight.

Examples of the substance that develops a color when contacted with another component include an acid-base reaction between two or more components, a 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 29-58) and azography (87-95) described in "Introduction to Special Paper Chemistry" by Hiroyuki Moriga (published in 1975).
Page), known color development systems such as thermosensitive color development due to chemical changes (pages 118-120), or a seminar by Kinki Chemical Industry Association "Latest dye chemistry-Attractive utilization and new development as functional dyes-" The coloring system and the like described on pages 26 to 32, (June 19, 1980) can be used. Specifically, lactones, lactams, which are used for pressure-sensitive paper,
A coloring system consisting of a color-forming agent having a partial structure such as spiropyran and an acidic substance (developing agent) such as acid clay or phenols; aromatic diazonium salts and diazotates, diazosulfonates and naphthols, anilines, active methylenes System utilizing azo coupling reaction such as; Chelate forming reaction such as reaction of hexamethylenetetramine with ferric ion and gallic acid or reaction of phenolphthalein-complexons with alkaline earth metal ion; stearic acid A redox reaction such as a reaction between ferric iron and pyrogallol or a reaction between silver behenate and 4-methoxy-1-naphthol can be used.

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-based compounds, (4) thiazine-based compounds, and (5) spiropyran-based compounds, and specific examples thereof are JP-A-55-272.
Those described in Japanese Patent No. 53, etc. can be mentioned. Among these, (1) triarylmethane type,
(3) Most of the xanthene-based color formers are preferable because they have less fog and give a 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- Examples thereof include o-chloroanilinofluorane. 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
In addition to -tert-butyl-m-cresol) sulfonyldiphenol, p-tert-butylphenol-formalin condensate, p-phenylphenolformalin condensate and the like can be mentioned.

Specific examples of the organic acid or the metal salt thereof include phthalic acid, phthalic anhydride, maleic acid, benzoic acid, gallic acid, o-toluic acid, p-toluic acid, salicylic acid, 3-
tert-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 their zinc salts and aluminum salts 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-meltable substance having a low melting point, or the low-melting compound is added in a state of being fused to the surface of the developer particles. It is preferable.

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.

Examples of the color former / developer system of the above (1) to (5) include phenolphthalein, fluorescein,
2 ', 4', 5 ', 7'-Tetrabromo-3,4,5,6-tetrachlorofluorescein, toterabromophenolphthalein, eosin, aurincresol red, 2-naphtholphenolphthalein, etc. There is a system used as.

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-imidazoline, 2-phenyl-2-imidazoline, 1,2,3-triphenyl Guanidine, 1,2-ditolylguanidine, 1,2-dicyclohexylguanidine, 1,2-
Dicyclohexyl-3-phenylguanidine, 1,2,3-
Tricyclohexylguanidine, guanidine trichloroacetate, N, N'-dibenzylpiperazine, 4,4'-dithiomorpholine, morpholinium trichloroacetate, 2-amino-benzothiazole, 2-benzoylhydrazino-
Examples thereof include 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 a microcapsule together with the polymerizable compound, and the other substance among the substances that cause the color-forming reaction is the micro-capsule. It exists outside the capsule.

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.

The color developer may be contained in the microcapsules. In this case, an oil-absorbing white pigment may be used in combination with the color developer to diffuse and immobilize the capsule inclusion.

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 a proportion of 0.5 to 20 parts by weight with respect to 100 parts by weight of the polymerizable compound. It is more preferable to use 7 parts by weight. When a developer is used, it is preferably used in a proportion of about 0.3 to 80 parts by weight with respect to 1 part by weight of the color developer.

Incidentally, the general description of the photographic material using a substance which causes a color reaction upon contact is also described in the above-mentioned JP-A-61-73145. Further, for a light-sensitive material using a leuco dye, Japanese Patent Application No. 61-53876, and for a light-sensitive material using a triazene compound, Japanese Patent Application No. 61-96339, a yellow-coloring leuco dye was used. The photosensitive materials are described in Japanese Patent Application Nos. 61-133091 and 61-133092, and the photosensitive materials using a cyan color-forming leuco dye are described in Japanese Patent Application No. 61-197963.

The “substance contained in the microcapsule” means the substance present in the core substance and / or the wall material forming the microcapsule.

Various known techniques can be used for the microcapsules without particular limitation, and details thereof will be described later.

In the light-sensitive material of the present invention, it is preferable that the above-mentioned microcapsules also contain the silver halide and the reducing agent.

The present applicant has already applied for a patent for a photosensitive material in which the above-mentioned polymerizable compound is dispersed in the photosensitive layer in the form of oil droplets, or a photosensitive material having various structures including this embodiment. (Japanese Patent Application Nos. 60-218603, 60-261888, 61-5751
And No. 61-25577 each specification). When silver halide is contained in oil droplets, the number of silver halide grains contained in oil droplets should be 5 or more as described in Japanese Patent Application No. 61-160592. Preferably.

Further, an example of a light-sensitive material in which oil droplets of a polymerizable compound are in a microcapsule state is described in JP-A-61-278441.

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

When the support is made of a porous material such as paper, the support used in the light-sensitive material described in Japanese Patent Application No. 61-52996 has a certain smoothness according to a prescribed method due to waviness. It is preferable to have When a paper support is used, a paper support having a low water absorption such as the light-sensitive material described in Japanese Patent Application No. 61-183050 and a light-sensitive material described in Japanese Patent Application No. 61-191273 are used. A paper support having a certain Beck smoothness, a paper support having a low shrinkage ratio such as the photosensitive material described in Japanese Patent Application No. 61-227766, and a photosensitive material described in Japanese Patent Application No. 61-227768. Paper support with low air permeability,
It is also possible to use a paper support having a pH value of 5 to 9 such as the light-sensitive material described in Japanese Patent Application No. 61-243552.

Hereinafter, various aspects of the light-sensitive material, optional components that can be contained in the light-sensitive layer, auxiliary layers that can be optionally provided in the light-sensitive material, and the like will be sequentially described.

In the light-sensitive material of the present invention, as described above, the polymerizable compound is contained in the light-sensitive layer in the form of microcapsules together with one of the substances that cause a color forming reaction.

The wall material forming the outer shell of the microcapsule is also not particularly limited. Regarding the photosensitive material using the microcapsules having an outer shell made of a polyamide resin and / or a polyester resin, Japanese Patent Application No. 61-53871 discloses microcapsules having an outer shell made of a polyurea resin and / or a polyurethane resin. Japanese Patent Application No. 61-53872 describes a light-sensitive material using the above, and Japanese Patent Application No. 61-53873 describes a light-sensitive material using a microcapsule having an outer shell made of an amino-aldehyde resin. Japanese Patent Application No. 61-53874 discloses a photosensitive material using microcapsules having an outer shell, and Japanese Patent Application No. 61-53875 discloses a photosensitive material using microcapsules having an epoxy resin outer shell. Japanese Patent Application No. 61-538 discloses a photosensitive material using microcapsules having a composite resin shell containing a polyamide resin and a polyurea resin. 77
Japanese Patent Application No. 61-53878 describes a photosensitive material using microcapsules having a composite resin shell containing a polyurethane resin and a polyester resin.

When aldehyde-based microcapsules are used, it is preferable that the amount of residual aldehyde is not more than a certain value as in the light-sensitive material described in Japanese Patent Application No. 61-176415.

When the silver halide is contained in the microcapsules, it is preferable that the silver halide be present in the wall material that constitutes the outer shell of the microcapsules. Japanese Patent Application No. 61-1 for photosensitive materials containing silver halide in the wall material of microcapsules.
It is described in the specification of 1556.

In addition, two or more microcapsules in which at least one of the components contained in the microcapsules such as silver halide, a reducing agent, a polymerizable compound, and one of the substances that cause a color reaction are different may be used in combination. Good. In particular, in the case of forming a full-color image, it is preferable to use together three or more types of microcapsules in which the color hue of the color image forming substance contained is different. The light-sensitive material containing two or more kinds of microcapsules in combination is described in Japanese Patent Application No. 61-42747.

The average particle size of the microcapsules is preferably 3 to 20 μm. The particle size distribution of the microcapsules is
As in the light-sensitive material described in Japanese Patent Application No. 61-150080, it is preferable that the light-sensitive material is uniformly distributed over a certain value. Also,
The film thickness of the microcapsules is preferably within a certain range with respect to the particle diameter, as in the light-sensitive material described in Japanese Patent Application No. 61-227767.

When accommodating silver halide in microcapsules, it is preferable that the average grain size of the silver halide grains described above is one-fifth or less, preferably one-tenth or less of the average size of microcapsules. Is more preferable.
By setting the average grain size of the silver halide grains to be one fifth or less of the average size of the microcapsules, a uniform and smooth image can be obtained.

Optional components that can be contained in the photosensitive layer of the photosensitive material include sensitizing dyes, organic silver salts, radical generators, various image formation accelerators, thermal polymerization inhibitors, thermal polymerization initiators, development terminators, and silica. Photowhitening agents, antifading agents, dyes or pigments for preventing halation or irradiation, pigments having the property of decolorizing by heating or light irradiation, matting agents, antismudge agents, plasticizers, water releasing agents, binders, photopolymerization initiation Agents, solvents for polymerizable compounds, water-soluble vinyl polymers and the like.

The sensitizing dye that can be used in the light-sensitive material is not particularly limited, and a silver halide sensitizing dye known in the photographic art can be used. The sensitizing dye, methine dye, cyanine dye, merocyanine dye, complex cyanine dye, holopolar cyanine dye, hemicyanine dye,
Examples include 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.

The sensitizing dye is preferably added at the stage of preparing a silver halide emulsion described below. Regarding a light-sensitive material obtained by adding a sensitizing dye in the step of forming silver halide grains, JP-A-62-947 discloses a sensitizing dye of a silver halide emulsion after formation of silver halide grains. Regarding the light-sensitive material obtained by adding in the preparation stage, Japanese Patent Application No. 61-5
Each is described in the specification of 5510. Further, specific examples of sensitizing dyes that can be used in the light-sensitive material are also described in the above-mentioned JP-A Nos. 62-947 and 61-55510. Further, as in the light-sensitive material described in Japanese Patent Application No. 61-208786, an infrared-sensitive sensitizing dye may be used in combination.

Addition of an organic silver salt to a light-sensitive material is particularly effective in heat development processing. 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. Examples of the organic compound that constitutes the organic silver salt include an aliphatic or aromatic carboxylic acid, 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 above organic silver salt is generally used in an amount of 0.01 to 10 mol, preferably 0.01 to 1 mol, per mol of silver halide. 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. A light-sensitive material using an organic silver salt is described in JP-A-62-3246. The above-mentioned organic silver salt is preferably used in the range of 0.1 to 10 mol per mol of silver halide, 0.01 to 1 mol.
More preferably, it is used in the molar range.

The above-mentioned radical generator which participates in the polymerization acceleration (or polymerization suppression) reaction of the reducing agent may be added to the photosensitive layer.
As the radical generator, a azo compound is used in Japanese Patent Application No. 61-38510 for a light-sensitive material using triazene silver, and a Japanese Patent Application No. 61-38511 for a light-sensitive material using silver diazotate. Japanese Patent Application Sho 61
-38512 specification describes each.

Various image formation accelerators can be used in the light-sensitive material. The image forming accelerator has a function of accelerating the redox reaction between the silver halide (and / or organic silver salt) and the reducing agent and the redox agent. The image forming accelerator is a base, a base precursor, an oil, a surfactant, a compound having an antifoggant function and / or a development promoting function, a thermal solvent, a compound having an oxygen removing function, etc. Is further classified into. 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 various image formation accelerators are shown below.

Examples of preferable bases include alkali metal or alkaline earth metal hydroxides as inorganic bases; alkali metal or alkaline earth metal tertiary phosphates, borates,
Carbonates, metaborates; combinations of zinc hydroxide or zinc oxide with chelating agents such as sodium picolinate;
Ammonium hydroxides; quaternary alkyl ammonium hydroxides; hydroxides of other metals, and the like, and organic bases include 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, and the like, with a pKa of 7 or more being particularly preferable.

Examples of the base precursor include salts of organic acids and bases that are decarboxylated by heating, compounds that release amines by reactions such as intramolecular nucleophilic substitution reaction, Rossen rearrangement, Beckmann rearrangement, etc. Compounds that release and generate a base by electrolysis are preferably used. Specific examples of the base precursor include guanidine trichloroacetic acid, piperidine trichloroacetic acid, morpholine trichloroacetic acid, p-toluidine trichloroacetic acid, 2-picoline trichloroacetic acid, phenylsulfonylacetic acid guanidine, 4-chlorophenylsulfonylacetic acid guanidine, and 4-methyl-. Examples thereof include guanidine sulfonylphenylsulfonylacetate and guanidine 4-acetylaminomethylpropiolate.

The base or base precursor can be used in a wide range of amount in the light-sensitive material. The base or base precursor is suitably used in an amount of 100% by weight or less, more preferably 0.1% by weight to 4% by weight of the coating film of the photosensitive layer.
A range of 0% by weight is useful. In the present invention, the base and /
Alternatively, the base precursor may be used alone or as a mixture of two or more kinds.

A light-sensitive material using a base or a base precursor is described in Japanese Patent Application No. 60-227528. Regarding the photosensitive material using a tertiary amine as a base, Japanese Patent Application No. 61-13181 discloses a photosensitive material using a fine particle dispersion of a hydrophobic organic base compound having a melting point of 80 to 180 ° C. Is Japanese Patent Application No. 61-52992, the solubility is 0.1%
Japanese Patent Application No. 61-215637 describes a light-sensitive material using the following guanidine derivative, and Japanese Patent Application No. 61-96341 describes a light-sensitive material using a hydroxide or salt of an alkali metal or an alkaline earth metal. There is a description in each book.

Furthermore, Japanese Patent Application No. 61-167558 discloses a photosensitive material using an acetylide compound as a base precursor.
Japanese Patent Application No. 61-191000 discloses a photosensitive material containing a propiolic acid salt as a base precursor and further containing a silver compound or a copper compound as a catalyst for a base formation reaction.
Regarding the light-sensitive material containing the above-mentioned propiolic acid salt and the above-mentioned silver compound or copper compound in a state of being isolated from each other, Japanese Patent Application No.
-227769 describes a photosensitive material containing a ligand in a free state in addition to the above-mentioned propiolic acid salt and the above-mentioned silver compound or copper compound, Japanese Patent Application No. 61-243555 discloses propiolic acid as a base precursor. With salt,
Furthermore, regarding a light-sensitive material containing a heat-meltable compound as a reaction accelerator for a base formation reaction, Japanese Patent Application No. 61-191001 discloses that a sulfonyl acetate salt is used as a base precursor,
Further, regarding a light-sensitive material containing a heat-melting compound as a reaction accelerator of a base-forming reaction, Japanese Patent Application No. 61-193375 discloses a light-sensitive material using a compound in which an isocyanate or isothiocyanate is bound to an organic base as a base precursor. These are described in Japanese Patent Application No. 61-167558.

When using a base or a base precursor for the light-sensitive material,
It is preferable that a silver halide, a reducing agent, a polymerizable compound, and the like are contained in the microcapsules described above, and a base or a base precursor is present in the photosensitive layer outside the microcapsules. Alternatively, a base or a base precursor may be contained in another microcapsule as in the light-sensitive material described in Japanese Patent Application No. 61-52988. In addition to the above specification, a light-sensitive material containing microcapsules containing a base or a base precursor is a light-sensitive material containing a base or a base precursor dissolved or dispersed in an aqueous solution of a water retention agent in microcapsules.
No. 61-52989 discloses a light-sensitive material containing solid fine particles carrying a base or a base precursor in microcapsules, and has a melting point of 70 ° C. to 210 ° C.
Light-sensitive materials using microcapsules containing a base compound at ℃ are described in Japanese Patent Application No. 61-212149. Further, instead of the microcapsules containing the base or the base precursor, particles containing a base or a base precursor and a hydrophobic substance in a compatible state may be used as in the light-sensitive material described in Japanese Patent Application No. 61-243556. Good.

The base or base precursor is described in Japanese Patent Application No. 61-96340.
As described in the specification, it may be added to an auxiliary layer (a layer containing a base or a base precursor described later) other than the photosensitive layer. Furthermore, as described in Japanese Patent Application No. 61-176417, the above-mentioned support may be made porous and a base or a base precursor may be contained in this porous support.

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

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

The compound having an antifoggant function and / or a development promoting function can be used for the purpose of obtaining a clear image (image having a high S / N ratio) having a high maximum density and a low minimum density. Incidentally, Japanese Patent Application No. 60-294337 discloses a photosensitive material using an antifoggant as a compound having an antifoggant function and / or a development accelerating function, and a photosensitive material using a compound having a cyclic amide structure. Japanese Patent Application No. 60-294338, Japanese Patent Application No. 60-294339 for photosensitive materials using thioether compounds, Japanese Patent Application No. 60-294340 for photosensitive materials using polyethylene glycol derivatives. In Japanese Patent Application No. 60-294341 for a photosensitive material using a thiol derivative, and Japanese Patent Application No. 61-20438 for a photosensitive material using an acetylene compound, a photosensitive material using a sulfonamide derivative. Japanese Patent Application No. 61-25578, and Japanese Patent Application No. 61-238 for a photosensitive material using a quaternary ammonium salt.
The 871 specification describes each.

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. Patent No. 3347675, derivatives of acids such as oleic acid esters of polyethylene oxide, beeswax, glycerol monostearate, -SO ₂ - high dielectric constant compounds having and / or -CO- groups, U.S. Patent No. The polar substances described in Japanese Patent No. 3667959, 1,10-decanediol, methyl anisate, biphenyl suberate and the like described in Research Disclosure, December 1976, pages 26 to 28 are preferably used. The light-sensitive material using a hot solvent is described in Japanese Patent Application No. 60-227527.

The compound having a function of removing oxygen can be used for the purpose of eliminating the influence of oxygen during development (oxygen has a polymerization inhibiting action). Examples of the compound having an oxygen removing function include compounds having two or more mercapto groups. Regarding the photosensitive material using a compound having two or more mercapto groups, Japanese Patent Application No.
It is described in the specification of 61-53880.

The thermal polymerization initiator that can be used in the light-sensitive material is generally a compound that thermally decomposes under heating to generate a polymerization initiation species (particularly a radical), and is usually used as an initiator of radical polymerization. The thermal polymerization initiator is described on pages 6 to 18 of “Addition Polymerization / Ring-Opening Polymerization,” 1983, Kyoritsu Shuppan, edited by the Society of Polymer Science, Japan, Editorial Committee for Polymer Experiments. Specific examples of the thermal polymerization initiator include azobisisobutyronitrile, 1,1′-azobis (1-cyclohexanecarbonitrile), dimethyl-2,2′-azobisisobutyrate, 2,2-azobis ( 2-methylbutyronitrile), azo compounds such as azobisdimethylvaleronitrile, organic peroxides such as benzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, etc. Examples thereof include oxides, hydrogen peroxide, inorganic peroxides such as potassium persulfate and ammonium persulfate, and sodium p-toluenesulfinate. 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. In the system in which the polymerizable compound in the portion where the latent image of silver halide is not formed is polymerized, it is preferable to add a thermal polymerization initiator to the photosensitive layer. Regarding the photosensitive material using a thermal polymerization initiator, Japanese Patent Application No. 60-210657
It is described in the specification.

A development terminator that can be used in a light-sensitive material is a compound that interacts with a compound or silver and a silver salt that immediately neutralizes or reacts with a base to reduce the concentration of the base in the film to stop development after proper development. Is a compound that suppresses development. Specific examples thereof include an acid precursor 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. Examples of acid precursors include JP-A-60-10883.
Examples thereof include oxime esters described in JP-A Nos. 7 and 60-192939 and compounds releasing an acid by Rossen rearrangement described in JP-A-60-230133. Examples of electrophilic compounds that undergo a substitution reaction with a base upon heating include the compounds described in JP-A-60-230134.

Dyes or pigments may be added to the photosensitive layer of the photosensitive material for the purpose of preventing halation or irradiation. Incidentally, Japanese Patent Application No. 61-174402 describes a photosensitive material in which a white pigment is added to a photosensitive layer for the purpose of preventing halation or irradiation.

The photosensitive layer of the photosensitive material may contain a dye having a property of being decolorized by heating or light irradiation in the microcapsules. The dye having the property of being decolorized by heating or light irradiation can function as a yellow filter in a conventional silver salt photographic system. A light-sensitive material using a dye having the property of being decolorized by heating or irradiation with light as described above is described in Japanese Patent Application No. 61-243551.

As the anti-smudge agent used in the light-sensitive material, solid particles at room temperature are preferable. As a specific example, British Patent No. 12
32347 starch particles, U.S. Pat.
Polymer powder as described in the specification, microcapsule particles containing no color former as described in British Patent No. 1235991, cellulose powder as described in U.S. Pat.No. 2711375, talc, kaolin, bentonite, wax Inorganic particles such as stone, zinc oxide, titanium oxide and alumina can be used. The average particle size of the above 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 microcapsules.

The binder that can be used in the light-sensitive material can be contained in the light-sensitive layer alone 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. For the photosensitive material using a binder, see
It is described in Japanese Patent Publication No. 61-69062. A light-sensitive material using a binder together with microcapsules is described in Japanese Patent Application No. 61-52994.

When a solvent for a polymerizable compound is used in the light-sensitive material, it is preferably used by enclosing it in a microcapsule different from the microcapsule containing the polymerizable compound. A photosensitive material using an organic solvent miscible with a polymerizable compound encapsulated in microcapsules is described in Japanese Patent Application No. 61-52993.

A water-soluble vinyl polymer may be adsorbed on the above-described silver halide grains for use. A light-sensitive material using a water-soluble vinyl polymer as described above is described in Japanese Patent Application No. 61-238870.

In addition to the above, examples of optional components that can be contained in the photosensitive layer and usage thereof are also described in the application specification regarding the series of photosensitive materials described above, and Research Disclosure Magazine Vol. 170, June 1978. 17029 (pages 9 to 15).

The photosensitive layer of the photosensitive material comprising the components described above preferably has a pH value of 7 or less as in the photosensitive material described in Japanese Patent Application No. 61-104226.

Examples of layers that can be optionally provided in the light-sensitive material include an image receiving layer, a heating element layer, an antistatic layer, an anti-curl layer, a peeling layer,
Examples thereof include a cover sheet or a protective layer, a layer containing a base or a base precursor, a base barrier layer, and an antihalation layer (colored layer).

Regarding the light-sensitive material using the heating element layer, Japanese Patent Application No. 60-135
No. 568, Japanese Patent Application No. 61-55507 for a photosensitive material provided with a cover sheet or a protective layer, and Japanese Patent Application No. 61-96340 for a photosensitive material provided with a layer containing a base or a base precursor. Japanese Patent Application No. 61-246901 discloses a photosensitive material provided with a colored layer as an antihalation layer.
, Respectively. Further, regarding a light-sensitive material provided with a base barrier layer, the above-mentioned Japanese Patent Application No. 61-963
There is a description in No. 40 specification. Further, examples of other auxiliary layers and usage modes thereof are also described in the application specification of the series of photosensitive materials described above.

The method for producing the photosensitive material will be described below.

Although various methods can be used as a method for producing a photosensitive material, the general method is to prepare a photosensitive composition by dissolving, emulsifying or dispersing the components of the photosensitive layer in an appropriate solvent. The method comprises the steps of microcapsulating this and preparing a coating solution containing the capsule dispersion and the curing agent of the present invention, and coating and drying the coating solution on a support.

Generally, each 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 so as 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. .

With respect to the main components contained in the photosensitive layer, a method for preparing a liquid composition and a coating liquid is shown below.

The halogenated emulsion can be prepared by any known method such as an acidic method, a neutral method or an ammonia method.

As the reaction mode of the soluble silver salt and the soluble halogen salt,
Either a one-sided mixing method, a double-sided mixing method or a combination thereof may be used. The back-mixing method in which grains are formed under conditions of excess silver ions and the controlled double-jet method in which pAg is kept constant can also be adopted. Further, in order to accelerate the grain growth, the addition concentration, the addition amount or the addition rate of the silver salt and the halogen salt to be added may be increased (JP-A-55-158124 and JP-A-5-158124).
5-158124, and U.S. Pat. No. 3,650,757).

The silver halide emulsion used for producing the light-sensitive material may be either 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. Internal latent image type emulsions suitable for this purpose are described in U.S. Pat. Nos. 2,592,250 and 3,761,276, JP-B-58-3534, JP-A-58-136641, and the like. Preferred nucleating agents to be combined with the above emulsions are U.S. Pat. Nos. 3,227,552, 4,245,037, 4,255,511, 42,66013, 4,276,364 and West German Published Patent (OL).
S) No. 2635316 is described in each specification.

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. Examples of hydrophilic colloids are gelatin, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; hydroxyethyl cellulose, carboxymethyl cellulose,
Cellulose derivatives such as cellulose sulfates and the like, sugar derivatives such as sodium alginate and starch derivatives, and polyvinyl alcohol, polyvinyl alcohol partial acetals, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole. Examples thereof include various kinds of synthetic hydrophilic polymer substances such as a single or copolymer such as polyvinylpyrazole. Of these, gelatin is preferred. As the gelatin, lime-processed gelatin, acid-processed gelatin or enzyme-processed gelatin may be used, and a hydrolyzed product or an enzymatically-decomposed product of gelatin may also be used.

The silver halide emulsion contains ammonia, an organic thioether derivative (see JP-B-47-386) and a sulfur-containing compound (see JP-A-53-144319) as a silver halide solvent in the step of forming silver halide grains. 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, water-soluble iridium salts such as iridium chloride (III or IV) and hexachloroiridium ammonium for the purpose of improving high illumination failure and low illumination failure,
Alternatively, a 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 sedimentation method. The silver halide emulsion may be used as it is without being post-ripened, but it is usually chemically sensitized before use. In the emulsion for a conventional type photosensitive material, known sulfur sensitizing method, reduction sensitizing method, noble metal sensitizing method and the like can be used alone or in combination. These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-58-1).
26526 and 58-215644).

When a sensitizing dye is added to the silver halide emulsion,
It is preferably added at the stage of preparing a silver halide emulsion like the light-sensitive materials described in Japanese Patent Application Nos. 60-139746 and 61-55510. When a nitrogen-containing heterocyclic compound is added as the compound having the fog-preventing function and / or the development-accelerating function, it should be added in the step of forming silver halide grains or the ripening step in the preparation of a silver halide emulsion. Is preferred. Regarding the method for producing a light-sensitive material in which a nitrogen-containing heterocyclic compound is added in the step of forming silver halide grains or the ripening step,
It is described in the specification of Japanese Patent Application No. 61-3024.

When the above-mentioned organic silver salt is contained in the photosensitive layer, the organic silver salt emulsion can be prepared by a method similar to the method for preparing the silver halide emulsion.

In the production of a light-sensitive material, the polymerizable compound can be used as a medium for preparing the composition of other components in the light-sensitive layer. For example, a silver halide (including a silver halide emulsion), a reducing agent, and a substance (for example, a color former) which causes a color-forming reaction are dissolved, emulsified or dispersed in a polymerizable compound to produce a light-sensitive material. Can be used for In particular, when one of the substances that cause a color forming reaction is added, it is preferable to include it in the polymerizable compound. Further, as described later, when oil droplets of the polymerizable compound are microencapsulated, components such as wall material necessary for microencapsulation may be included in the polymerizable compound.

The photosensitive composition containing a polymerizable compound containing silver halide can be prepared using a silver halide emulsion.
In addition to the silver halide emulsion, a silver halide powder prepared by freeze-drying or the like can be used for the preparation of the photosensitive composition. 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 repeating unit. Regarding a photosensitive composition containing the above copolymer, Japanese Patent Application No. 60-2
It is described in the specification of 61887.

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. The photosensitive composition containing microcapsules containing the silver halide emulsion as a core substance is described in Japanese Patent Application No. 61-5750.

The polymerizable compound (including those containing other constituents such as the above-mentioned photosensitive composition) is preferably used as an emulsion emulsified in an aqueous solvent. It is also possible to add a wall material necessary for microencapsulation to the emulsion and then perform a treatment for forming the outer shell of the microcapsule at the stage of the emulsion. Further, a reducing agent or another optional component may be added at the stage of the above emulsion.

As an example of the above microencapsulation method, US Pat.
Methods utilizing coacervation of hydrophilic wall-forming materials described in 2800457 and 2800458; U.S. Pat. No. 3,287,154 and British Patent 990443, and Japanese Patent Publications Nos. 38-19574 and 42. -446 and 42-771, interfacial polymerization method described in U.S. Pat. Nos. 3,418,250 and 3,
No. 660304 Method by precipitation of polymer described in each specification; Method using isocyanate-polyol wall material described in US Pat. No. 3,966,669; Method using isocyanate wall material described in US Pat. No. 3,914,511; US patent No. 4001140, No. 4087376 and No. 4089802, the method using the urea-formaldehyde-based or urea-formaldehyde-resylcinol-based wall-forming material; melamine-formaldehyde resin and hydroxy described in U.S. Pat. No. 4025455. A method using a wall forming material such as propyl cellulose; in situ by polymerization of monomers described in JP-B-36-9168 and JP-A-51-9079.
Examples thereof include a polymerization dispersion cooling method described in British Patent Nos. 927807 and 965074, and a spray drying method described in U.S. Patent No. 3111407 and British Patent No. 930422. The method of microencapsulating the oil droplets of the polymerizable compound 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 photosensitive microcapsules that can be used for producing the light-sensitive material are described in Japanese Patent Application Nos. 61-11556 and 61-115.
57, 61-53871, 61-53872, 61-53873, 61
61-53874, 61-53875, 61-53877, 61-53878
No. There is a description in each specification.

The photosensitive composition is microencapsulated using the microencapsulation technique as described above to prepare a microcapsule dispersion.

Further, to the microcapsule dispersion liquid, the other substance that causes the above-mentioned color development reaction (for example, a color developer) and the curing agent according to the present invention are added to prepare a coating liquid for forming a photosensitive layer, which is applied to the support described above. Then, the photosensitive material is manufactured by drying. The coating of the coating liquid on the support can be easily carried out according to known techniques.

The method of using the photosensitive material will be described below.

The light-sensitive material may be imagewise exposed at the same time or after imagewise exposure.
It is used after being developed.

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 is subjected to development processing simultaneously with the imagewise exposure or after the imagewise exposure. The light-sensitive material may be subjected to development processing using a developing solution described in JP-B-45-11149.
In addition, as described above, the heat development treatment is performed as described in JP-A-61-690.
Since the method described in Japanese Patent Laid-Open No. 62-62 is a dry process, it has the advantages that the operation is simple and the process can be performed in a short time. Therefore, the latter is particularly excellent in the development processing of the photosensitive material.

As a heating method in the heat development treatment, various conventionally known methods can be used. Further, like the light-sensitive material described in JP-A-61-294434, the light-sensitive material may be provided with a heating element layer and used as a heating means.
Further, as in the image forming method described in Japanese Patent Application No. 61-55506, the heat development treatment may be carried out while suppressing the amount of oxygen present in the photosensitive layer. Heating temperature is generally 80 ℃ to 20
The temperature is 0 ° C, preferably 100 ° C to 160 ° C. The heating time is generally 1 second to 5 minutes, preferably 5 seconds to 1 minute.

Instead of incorporating the above-mentioned base or base precursor into the light-sensitive material, development processing may be carried out while adding the base or base precursor to the light-sensitive layer or immediately after the addition. As a method for adding a base or a base precursor, a method using a sheet containing a base or a base precursor (base sheet) is the easiest and preferable. An image forming method using the above-mentioned base sheet is described in Japanese Patent Application No. 61-176417.

The light-sensitive material can be subjected to the heat development treatment as described above to polymerize the polymerizable compound in the portion where the latent image of silver halide is formed or the portion where the latent image of silver halide is not formed. Incidentally, in the light-sensitive material, the polymerizable compound in the portion where the latent image of silver halide is formed is generally polymerized in the above heat development treatment.
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 kind and amount of the reducing agent as in the light-sensitive material described in the specification of No. 657.

As described above, the photosensitive material can obtain a polymer image on the photosensitive layer.

The light-sensitive material is subjected to development processing as described above, and then pressed by a commonly used pressing means to destroy the microcapsules containing the unpolymerized polymerizable compound and the like. And
The unpolymerized polymerizable compound contacts with the above-mentioned curing agent on the outside of the capsule to polymerize and cure (fix). In addition, two kinds of substances that cause a coloring reaction at the same time as the destruction of the microcapsules come into contact with each other to develop a color. Thus, a cured color image can be obtained on the photosensitive material.

The present applicant has already applied for a patent for various image recording apparatuses suitable for carrying out the series of image forming methods described above using a photosensitive material. Typical of these devices are an exposure device that forms a latent image by imagewise exposure, a heating and developing device that hardens and immobilizes a portion corresponding to the formed latent image, and a developed photosensitive material. A transfer device that superimposes an image receiving material on a material and pressurizes the image receiving material (Japanese Patent Application No. 60-289703), and at least light-irradiating the image receiving material on which the image is further transferred to the above configuration, For example, there is a fixing device attached to perform either pressurization or heating (Japanese Patent Application No. 60-289703).

Photosensitive materials include black and white or color imaging and printing materials, printing materials, printing plates, X-ray materials, medical materials (for example, ultrasonic diagnostic machine CRT imaging materials), computer graphic hard copy materials, There are many applications such as sensitive materials for copiers.

Examples and comparative examples of the present invention will be described below.

[Example 1] [Preparation of light-sensitive material] Preparation of silver halide emulsion 117 g of potassium bromide was added to a stirring gelatin aqueous solution (containing 1200 g of water containing 25 g of seratin and 1.5 g of sodium chloride and kept at 60 ° C). An aqueous solution containing 600 ml and an aqueous silver nitrate solution (600 ml of water in which 0.74 mol of silver nitrate were dissolved) were simultaneously added at an equal flow rate over 15 minutes. Five minutes after this was completed, 200 m of an aqueous solution further containing 4.3 g of potassium iodide
l was added over 5 minutes. This emulsion was washed with water and desalted, 24 g of gelatin was added, and the mixture was stirred at 50 ° C. for 30 minutes to prepare a silver halide emulsion with a yield of 1000 g.

Preparation of Photosensitive Composition 100.00 g of trimethylolpropane triacrylate (trade name; Aronix M-309, manufactured by Toagosei Kagaku Co., Ltd.), 0.40 g of the following copolymer, and Vargus Script Red I-6-B
(Ciba Geigy Co., Ltd.) 10.00 g was dissolved. Add 18.00 g of the above solution to the following hydrazine derivative (reducing agent) 1.29.
g, 1.22 g of the following developing agent (reducing agent), 0.20 g of a 1% ethyl acetate solution of the following thiol derivative (antifoggant) and 0.36 g of Emarex NP-8 (manufactured by Nippon Emulsion Co., Ltd.) were dissolved. To this solution, 4.00 g of methylene chloride was further added to make a uniform solution. Further, 3.00 g of the silver halide emulsion prepared as described above and 0.69 g of a 10% aqueous solution of potassium bromide were added, and the mixture was stirred with a homogenizer at 15,000 rpm for 3 minutes to obtain a photosensitive composition.

(Copolymer) (Thiol derivative) (Hydrazine derivative) (Developer) Preparation of photosensitive microcapsule solution 10.51 g of 18.6% aqueous solution of Isoban (manufactured by Kuraray Co., Ltd.) and 48.56 g of 2.89% aqueous solution of pectin were added, and 10% sulfuric acid was used.
The above photosensitive composition was added to an aqueous solution whose pH was adjusted to 4.0, and the mixture was stirred at 7,000 rpm for 2 minutes using a homogenizer to emulsify the above photosensitive composition in an aqueous solvent.

Urea 40% aqueous solution 8.32 g, resorcin 11.3% aqueous solution 2.82 g, formalin 37% aqueous solution 8.56 g, and ammonium sulfate 8.00% aqueous solution 3.00 g were sequentially added to this aqueous emulsion 72.5 g, 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 photosensitive microcapsule dispersion liquid.

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

Preparation of photosensitive material (A) Photosensitive microcapsule liquid prepared as described above 5.
0 g, developer-containing dispersion 5.0 g, Emalex NP-8 (manufactured by Nippon Emulsion Co., Ltd.) 5% aqueous solution 0.5 g, and compound (I) [base] 20 g shown below in polyvinyl alcohol 3% aqueous solution 8
Dispersion 12.4 in which solid was dispersed using Dynomill in 0 g
g and 0.40 g of a 30% aqueous solution of polyethyleneimine [curing agent] were added to prepare a coating solution for forming a photosensitive layer. Next, the coating solution is applied onto polyethylene terephthalate (support; thickness 100 μm) using a # 60 wire bar, and the temperature is about 40 ° C.
It was dried for 1 hour to prepare a light-sensitive material (A) according to the present invention.

[Examples 2 to 3] In the same manner as in Example 1 except that each of the compounds shown in Table 1 below was used in place of polyethyleneimine [curing agent] when producing a light-sensitive material. By operation, the light-sensitive materials (B) and (C) according to the present invention corresponding to them were prepared.

Comparative Example 1 A photosensitive material for comparison (D) was prepared in the same manner as in Example 1 except that distilled water was used in place of polyethyleneimine when the photosensitive material was prepared. )made.

In addition, Table 1 also shows Example 1 and Comparative Example 1.

[Evaluation as Photosensitive Material] The photosensitive materials (A) to (D) obtained as described above were evaluated by measuring the image density at each stage according to the following procedure.

(1) Each of the above light-sensitive materials was passed through a continuous filter with a transmission density of 0 to 2.0 using a tungsten bulb to 5000
Imagewise exposure at lux for 1 second. Further, these were placed on a hot plate heated to 140 ° C. and heated for 10 seconds. Then, each light-sensitive material was passed through a pressure roller of 500 kg / cm ² , and the density (Dmax) of the magenta positive color image obtained on each light-sensitive material was measured with a Macbeth reflection densitometer.

(2) Subsequently, these photosensitive materials were further superposed on plain paper for a copying machine and passed through a pressure roller of 500 kg / cm ² , and magenta transferred from each photosensitive material onto each plain paper. Image was obtained. The density of the obtained image was measured using a Macbeth reflection densitometer in the same manner as above.

The above results are summarized in Table 2.

As is clear from the results shown in Table 2, the images obtained on the light-sensitive materials (A to C) according to the present invention containing a curing agent have good image fixing due to the action of the curing agent, and are fixed on plain paper. There was little transcription. On the other hand, the image obtained on the light-sensitive material containing no curing agent was considerably transferred onto plain paper.

Claims (10)

[Claims] 1. A light-sensitive material having a support and a light-sensitive layer provided thereon, which contains a silver halide, a reducing agent, a polymerizable compound, and two kinds of substances that cause a color-forming reaction by contacting each other, One of the substances that cause the color reaction and the polymerizable compound are contained in microcapsules, and the outside of the microcapsules, the polymerizable compound is polymerized without the need for external energy application. A photosensitive material comprising a curing agent that can be cured. 2. The photosensitive material according to claim 1, wherein the curing agent is a compound containing two or more nucleophilic groups in the same molecule. 3. The photosensitive material according to claim 1, wherein the nucleophilic group is a functional group selected from the group consisting of an imino group, an amino group and a sulfinic acid group. 4. The curing agent is polyethyleneimine, 1,3
A photosensitive material according to claim 3, which is -diamino-2-hydroxypropane or sodium polyvinylbenzenesulfinate. 5. The photosensitive material according to claim 1, wherein the color-forming agent is contained in microcapsules together with the polymerizable compound, and the color-developing agent is present outside the microcapsules. material. 6. The photosensitive material according to claim 1, wherein the curing agent is contained in the polymerizable compound in an amount of 0.1 to 200 mol%. 7. The photosensitive material according to claim 1, wherein the polymerizable compound is an ester of acrylic acid or an amide of acrylic acid. 8. The light-sensitive material according to claim 1, wherein the silver halide is contained in the microcapsules. 9. The photosensitive material according to claim 1, wherein the reducing agent is contained in the microcapsules. 10. The photosensitive material according to claim 1, which is for thermal development.