JPH0623839B2 - Photosensitive material manufacturing method - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a method for producing a light-sensitive material having a light-sensitive layer containing a silver halide, a reducing agent, and a polymerizable compound on a support.

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 an image forming method in which the polymerizable compound is polymerized. Can be used for

An example of the image forming method is described in Japanese Examined Patent Publication Nos. 45-11149 and 4
7-20741, 49-10697, JP-A-57.
138632, 57-142638, 57-
176033, 57-211146, 58-1
07529, 58-121031, 58-16.
It is described in each publication of No. 9143. These methods are
When developing the exposed silver halide with a developer,
A coexisting polymerizable compound (eg, vinyl compound) initiates polymerization to form an image-like polymer compound. Therefore, the above method requires a development process using a liquid, and the process requires a relatively long time.

As an improvement of the above method, JP-A-61-69062 and JP-A-61-73145 each disclose a method capable of forming a polymer compound by a dry treatment. The above method uses a recording material (photosensitive material) in which a photosensitive layer comprising a photosensitive silver salt (silver halide), a reducing agent, a crosslinkable compound (polymerizable compound) and a binder is carried on a support. is there. Regarding the above-mentioned method and the light-sensitive material used therein, JP-A-61-183640 and JP-A-61-1
88 535 and 61-228441 each also have a description.

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.

Further, a method of polymerizing a polymerizable compound in a portion where a latent image of silver halide is not formed was also invented, and a patent application has already been filed (Japanese Patent Application No. 60-210657). This method
By thermal development, a reducing agent is caused to act on the portion where the latent image of silver halide is formed to suppress the polymerization of the polymerizable compound, and at the same time, the polymerization of many portions is promoted.

One of these photosensitive materials is a photosensitive material in which a polymerizable compound is dispersed in the photosensitive layer in the form of oil droplets. The light-sensitive material having the above structure is described in Japanese Patent Application No. 60-218603. The light-sensitive material in which the oil droplets of the polymerizable compound are in the form of microcapsules is described in Japanese Patent Application No. 60-261888. As described above, a photosensitive material in which the polymerizable compound is dispersed in the photosensitive layer in the form of oil droplets (including a photosensitive material using microcapsules)
Has the advantage that the sharpness of the obtained image is improved, and further research is being conducted.

[Summary of the Invention] An object of the present invention is to provide a method for producing a light-sensitive material capable of obtaining a clearer image.

The present invention (a) has a main chain substantially composed of a hydrocarbon chain, and a part of the main chain is substituted with a hydrophilic group containing a nitrogen atom having an lone electron pair or an -OH group in the terminal group. The polymer is dissolved in a liquid polymerizable compound,
(B) Liquid photosensitivity in which a silver halide and a reducing agent are contained in a polymerizable compound by adding a reducing agent to the polymerizable compound and emulsifying a silver halide emulsion in the polymerizable compound. The composition is prepared, and (c) the photosensitive composition is emulsified in an aqueous medium to prepare an aqueous emulsion in which oil droplets of the photosensitive composition are dispersed in the aqueous medium, and (d) the aqueous emulsification. Forming a shell on the oil droplets of the photosensitive composition in the composition to prepare a dispersion of microcapsules, and (e) coating the dispersion of microcapsules on a support. A photosensitive layer containing a silver halide, a reducing agent and a polymerizable compound on the body, and the silver halide, the reducing agent and the polymerizable compound being present in a microcapsule dispersed in the photosensitive layer. A method of manufacturing a material is provided.

[Effects of the Invention] In the light-sensitive material produced according to the present invention, since the silver halide exists in the oil droplets of the polymerizable compound, the polymerization of the polymerizable compound in the portion where the latent image of silver halide is formed. The accelerating reaction (or polymerization suppressing reaction) proceeds smoothly, and the contrast in the image between the portion where the latent image is formed and the portion where the latent image is not formed is improved. Therefore, the light-sensitive material produced according to the present invention can obtain a clear image.

In the method for producing a light-sensitive material of the present invention, the hydrophilicity has a main chain substantially consisting of a hydrocarbon chain, and a part of the main chain has a nitrogen atom having a lone electron pair or an -OH group in the end group. A polymer substituted with a group is used by dissolving it in a polymerizable compound. Since the above polymer has a hydrophilic group, the silver halide emulsion containing silver halide can be dispersed very finely in the oil droplets of the liquid photosensitive composition, and this dispersed state can be maintained.

Further, the above-mentioned polymer also has a function of aggregating silver halide on the surface of oil droplets of the liquid photosensitive composition. That is, it is presumed that the nitrogen atom having a lone electron pair or the —OH group contained in the hydrophilic group of the polymer functions as a ligand of silver halide. For details of the functions of nitrogen atoms having a lone pair of electrons and -OH groups as silver ligands, see "The Teory of the Photographi" by T. James.
c Process "4th edition, pages 8-9 (1966), and Research Disclosure No. 17643 (19).
1978) etc. The silver halide aggregated on the surface of the oil droplets of the liquid photosensitive composition and, as a result, on the surface of the microcapsules can easily and effectively utilize the light energy given from the outside of the photosensitive material. Therefore, the silver halide is dispersed in the droplets of the liquid photosensitive composition using the above polymer, and the light-sensitive material produced according to the present invention exhibits very high sensitivity.

DETAILED DESCRIPTION OF THE INVENTION The light-sensitive material produced according to the present invention has microcapsules containing a silver halide, a reducing agent and a polymerizable compound dispersed in a light-sensitive layer. The microcapsules may contain other optional components in the photosensitive layer such as a color image forming substance.

There are various means for accommodating silver halide in microcapsules, but nitrogen having a main chain substantially consisting of a hydrocarbon chain as described above, and a part of the main chain having a lone electron pair. Since it is the easiest method to use a polymer substituted with a hydrophilic group containing an atom or an -OH group in the end group and to dissolve the polymer in the polymerizable compound at the production stage of the photosensitive material, The present invention adopts this method.

The number of hydrophilic groups contained in the polymer is determined according to the solubility in the polymerizable compound and the dispersibility of the silver halide emulsion, but when the polarity of the polymerizable compound is high, the hydrophilic groups are It is preferable to increase the number of N and decrease the number of hydrophobic groups. Generally, the number of hydrophilic groups is 0.25% or more, preferably 0.5% or more, and more preferably 1% or more of the number of carbon atoms contained in the main chain of the polymer. preferable.

The above-OH group may be either alcohol or phenol, and may be contained in the carboxyl group.

An example of the terminal group of the hydrophilic group containing a nitrogen atom having a lone electron pair can be represented by the following formula (I).

[In the above formula (I), R ¹ and R ² are a hydrogen atom or a substituent in which the total number of carbon atoms of R ¹ and R ² is 5 or less] R ¹ and R ² are as described above. There is no particular limitation except that the total number of carbon atoms is 5 or less. Examples of R ¹ and R ² include a hydrogen atom, —COR ³ (R ³ has 4 carbon atoms.
The following substituents), —SO ₂ R ⁴ (R ⁴ is a substituent having 5 or less carbon atoms), a substituted or unsubstituted alkyl group having 5 or less carbon atoms, and the like. .

Further, R ¹ and R ² may form a 5-membered or 6-membered nitrogen-containing heterocycle with the adjacent nitrogen atom. Examples of the nitrogen-containing heterocycle are shown below.

When the polymer is composed of a plurality of repeating units, examples of the repeating unit having a hydrophilic group described above are shown using the following formulas (II) to (V).

[In the above formula (II), R ⁵ , R ⁶ and R ⁷ are a hydrogen atom, a methyl group and -C
H ₂ CO ₂ R ²⁰ is a monovalent group selected from the group consisting of (R ²⁰ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, And a monovalent group selected from the group consisting of aralkyl groups having 7 to 20 carbon atoms), L ¹ is an alkylene group, an arylene group, an aralkylene group, —CO ₂ —R ⁸ —, and —CO. -NR ⁹ -R ⁸ -
Is a divalent group selected from the group consisting of (R ⁸ is a divalent group selected from the group consisting of an alkylene group, an arylene group, and an aralkylene group, and R ⁹ is a hydrogen atom,
An alkyl group having 1 to 6 carbon atoms, having 6 carbon atoms
To 10 aryl groups and 7 to 2 carbon atoms
A 0 a monovalent group selected from the group consisting of aralkyl group), m1 is 0 or 1, and Q ¹ is a hydroxyl ^{group, -NR 10 R 11, -CONR 10} R
_{^{11, -NR 10 COR 11, -SO}} 2 NR
¹⁰ R ¹¹ , —NR ¹⁰ SO ₂ R ¹¹ , and a monovalent group selected from the group consisting of groups having a 5- or 6-membered nitrogen-containing heterocycle (R ¹⁰ and R ¹¹ are hydrogen atoms,
Or an alkyl group or a substituted alkyl group in which the total number of carbon atoms of R ¹⁰ and R ¹¹ is 5 or less, or R 10
¹⁰ and R ¹¹ together with the adjacent atom or atomic group form a 5- or 6-membered nitrogen-containing heterocyclic group)].

[In the above formula (III), R ¹² and R ¹³ represent a hydrogen atom, a methyl group and -C.
H ₂ CO ₂ R ²⁰ is a monovalent group selected from the group consisting of (R ²⁰ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, And a monovalent group selected from the group consisting of aralkyl groups having 7 to 20 carbon atoms), L ² is —CO ₂ —R ⁸ —, or —CO—NR ⁹ —R.
⁸ - and, ^{L 3} is an alkylene group, an arylene group, an aralkylene group, _-CO 2 -R ⁸ -, and ^-CO-NR 9 -R ⁸ -
Is a divalent group selected from the group consisting of (R ⁸ is a divalent group selected from the group consisting of an alkylene group, an arylene group, and an aralkylene group, and R ⁹ is a hydrogen atom,
An alkyl group having 1 to 6 carbon atoms, having 6 carbon atoms
To 10 aryl groups and 7 to 2 carbon atoms
A 0 a monovalent group selected from the group consisting of aralkyl group), m @ 2 and m3 is 0 or 1, and Q ² and ^{Q 3} represents a hydroxyl ^group, -NR ¹⁰ R 11, -CO
^{NR 10 R 11, -NR 10 COR} 11, -SO 2 NR
¹⁰ R ¹¹ , —NR ¹⁰ SO ₂ R ¹¹ , and a monovalent group selected from the group consisting of groups having a 5- or 6-membered nitrogen-containing heterocycle (R ¹⁰ and R ¹¹ are hydrogen atoms,
Or an alkyl group or a substituted alkyl group in which the total number of carbon atoms of R ¹⁰ and R ¹¹ is 5 or less, or R 10
¹⁰ and R ¹¹ together with the adjacent atom or atomic group form a 5- or 6-membered nitrogen-containing heterocyclic group)].

[In the above formula (IV), R ¹⁴ and R ¹⁵ represent a hydrogen atom, a methyl group and -C.
H ₂ CO ₂ R ²⁰ is a monovalent group selected from the group consisting of (R ²⁰ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, and the number of carbon atoms from 7 to 20 amino monovalent group selected from the group consisting of aralkyl group), ^{L 4} represents an alkylene group, an arylene group, an aralkylene group, _-CO 2 -R ⁸ and, -CO- NR ⁹ —R ⁸ — is a divalent group selected from the group consisting of (R ⁸ is a divalent group selected from the group consisting of an alkylene group, an arylene group, and an aralkylene group, and R ⁹ is hydrogen. Atoms, alkyl groups having 1 to 6 carbon atoms, aryl groups having 6 to 10 carbon atoms, and 7 to 20 carbon atoms
Is a monovalent radical selected from the group consisting of pieces of aralkyl group), m4 is 0 or 1, and Q ⁴ are a hydroxyl ^{group, -NR 10 R 11, -CONR 10} R
_{^{11, -NR 10 COR 11, -SO}} 2 NR
¹⁰ R ¹¹ , —NR ¹⁰ SO ₂ R ¹¹ , and a monovalent group selected from the group consisting of groups having a 5- or 6-membered nitrogen-containing heterocycle (R ¹⁰ and R ¹¹ are hydrogen atoms,
Or an alkyl group or a substituted alkyl group in which the total number of carbon atoms of R ¹⁰ and R ¹¹ is 5 or less, or R 10
¹⁰ and R ¹¹ together with the adjacent atom or atomic group form a 5- or 6-membered nitrogen-containing heterocyclic group)].

[In the above formula (V), R ¹⁶ , R ¹⁷ and R ¹⁸ are a hydrogen atom or a methyl group, X is an oxygen atom or —NH—, n is an integer 1 to 6, and Q ⁵ is a hydroxyl group. An amino group, an amino group substituted by 1 or 2 alkyl groups having 1 to 6 total carbon atoms, a hydroxyphenyl group, a group having a 5- or 6-membered nitrogen-containing heterocycle, and- It is a monovalent group selected from the group consisting of NHSO ₂ CH ₃ ].

Among these, the repeating unit represented by the formula (V) is preferable. In the formula (V), n is an integer of 2 to 4, and Q ⁵ is preferably a hydroxyl group or a dimethylamino group.

Specific examples of the above polymers are shown below.

(P-1) (P-2) (P-3) (P-4) (P-5) (P-6) (P-7) (P-8) (P-9) (P-10) (P-11) The above polymer may form a copolymer containing a hydrophobic repeating unit in addition to the repeating unit having a hydrophilic group as described above. As the hydrophobic repeating unit, an ethylenic group such as olefins, vinyl ethers, vinyl esters, styrenes, acrylic acid esters, methacrylic acid esters, itaconic acid esters, maleic acid esters and the like having no hydrophilic group It is preferably a repeating unit derived from an unsaturated monomer.

Specific examples of the ethylenically unsaturated monomer include ethylene, butadiene, isobutylene, acrylonitrile,
Methyl vinyl ether, vinyl benzyl ether, vinyl acetate, vinyl propionate, styrene, vinyl toluene, chloromethyl styrene, p-chlorostyrene, methyl acrylate, ethyl acrylate, n-butyl acrylate, iso-butyl acrylate, n-hexyl acrylate, cyclohexyl Acrylate, 2-ethylhexyl acrylate, benzyl acrylate, tetrahydrofurfuryl acrylate, 2-methoxyethyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, Benzyl methacrylate, tetrahydrofurfuryl methacrylate It may be mentioned furfuryl methacrylate, phenyl methacrylate, 2-methoxyethyl methacrylate, itaconic acid diethyl, and dibutyl maleate. Among these, esters of acrylic acid or methacrylic acid with an alkyl alcohol having 1 to 6 carbon atoms or cyclohexyl alcohol are particularly preferable.

Specific examples of the copolymer that can be used as the above-mentioned polymer are shown below. In each example, the repeating unit shown on the left corresponds to the repeating unit having the hydrophilic group described above, and the repeating unit shown on the right corresponds to the hydrophobic repeating unit.

(P-12) (P-13) (P-14) (P-15) (P-16) (P-17) (P-18) (P-19) (P-20) (P-21) (P-22) (P-23) (P-24) (P-25) (P-26) (P-27) (P-28) (P-29) (P-30) (P-31) (P-32) (P-33) The molecular weight of the above-mentioned polymer is determined according to the viscosity and dispersion ability of the solution when the polymer is dissolved in a polymerizable compound (which can also function as a solvent or a dispersion medium in the production of the light-sensitive material of the present invention). . That is,
Regarding the molecular weight of the polymer, if the molecular weight of the polymer is too large, the solution viscosity becomes too high, and it becomes difficult to stir to disperse the droplets of the silver halide emulsion. Consider the decrease in Usually, the molecular weight is in the range of 5,000 to 10,000,000, preferably 10,000 to 2,000,000.

In the method for producing a light-sensitive material of the present invention, the polymer is
It is preferably used in the range of 0.1 to 20% by weight, more preferably 0.1 to 10% by weight, and more preferably 0.5 to 5% by weight, based on the silver halide emulsion.
It is more preferable to use in the range of.

Some of the above-mentioned polymers are already on the market, but they can be prepared by polymerizing the above-mentioned monomers. Or hydrolyzing various polymers,
It can be obtained by modification such as acetalization.

An example of polymer synthesis by the method of copolymerizing monomers is shown below. Other polymers can be synthesized by the same method.

[Synthesis Example 1] Synthesis of poly- (N, N-dimethylaminoethyl methacrylate-co-methyl methacrylate-co-n-butyl methacrylate (P-20)) In a 300 m three-necked flask, N, N-dimethylaminoethyl was used. 12.6 g of methacrylate, 24.0 g of methyl methacrylate, 11.4 g of butyl methacrylate and 190 m of toluene were put in. The flask was heated to 80 ° C. with stirring, and 2,2′-azobis- (2,2'-
4-dimethylvaleronitrile) 0.298 g to 10 m
Was dissolved in toluene, and heating was continued for 2 hours, the same amount was added, and heating and stirring were continued for 2 hours. The reaction solution was allowed to cool to room temperature, then gradually poured into n-hexane (1), and the precipitate was collected by filtration. This is 200m
The product was washed twice with n-hexane and then dried to obtain 43.7 g of the title polymer as a white product. The yield was 91%.

Hereinafter, the silver halide, the reducing agent, the polymerizable compound, and the support which compose the light-sensitive material will be sequentially described. In addition,
Hereinafter, the light-sensitive material having the above structure will be simply referred to as "light-sensitive material".

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 multiple structures having different compositions on the surface and inside, JP-A-57-154232 and 58-10853 are known.
3, 59-48755, 59-52237, U.S. Pat. No. 4,433,048 and European Patent No. 1.
No. 00984 is described in each specification. Also, Japanese Patent Application Sho 61
A silver halide grain having a high proportion of silver iodide in the shell portion may be used as in the light-sensitive material described in Japanese Patent No. 25576.

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.

As the silver halide grains, Japanese Patent Application No. 61-2
It is preferable to use silver halide grains having a relatively low fog value as in the light-sensitive material described in 14580 specification.

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,
More preferably, it is 001 to 2 μm.

The amount of silver halide contained in the photosensitive layer is 0.1 mg to 10 in terms of silver including an organic silver salt which is an optional component described later.
It is preferably in the range of g / m ² . In terms of silver halide alone, it is preferably 0.1 g / m ^2, and particularly preferably 1 mg to 90 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, sulfonamidepyrazolobenzimidazoles, sulfonamidepyrazolotriazoles, α-sulfonamidoketones, hydrazines, etc. There is. 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 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, JP-A Nos. 61-183640 and 61-188535, and Japanese Patent Application Nos. 60-68874 and 60-210.
No. 657, No. 60-226084, No. 60-2275.
No. 27, No. 60-227528, No. 61-42746.
In each specification (including those described as a developing agent or a hydrazine derivative). Regarding the reducing agent, see “The Theory of the Photographic Pr” by T. James.
ocess ", 4th edition, pp. 291-334 (1977), Research Disclosure Vol. 170, June 1978.
No. 17029 of the Moon (pages 9 to 15), and Vol. 17 of the same magazine.
6, 17643, December 1978 (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-phenyl Sulfonylamino-4-t-butyl-5-hexadecyloxyphenol, 2- (N-butylcarbamoyl) -4-phenylsulfonylaminonaphthol, 2- (N-methyl-N-toctadecylcarbamoyl) -4-sulfonylamino Naphthol, 1-acetyl-2-phenethylhydrazine, 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} 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- (methoxy Carbonylbenzohydryl) -2- (2,4-dichlorophenyl) hydrazine, 1-trityl-2-[{2- (N-ethyl-N-octylsulfamoyl) -4-methanesulfonyl} phenyl] hydrazine, 1 -Benzoyl-2-
Trityl hydrazine, 1- (4-butoxybenzoyl)
-2-Tritylhydrazine, 1- (2,4-dimethoxybenzoyl) -2-tritylhydrazine, 1- (4dibutylcarbamoylbenzoyl) -2-tritylhydrazine, 1- (1-naphthoyl) -2-tritylhydrazine, 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
It is preferable to use compounds of (° C. or higher). 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 described later, when a transfer image is formed using an image receiving material, Japanese Patent Application No. 61-15007
It is preferable to use a highly viscous substance as the polymerizable compound, as in the light-sensitive material described in No. 9.

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. Acids, maleic acid esters, itaconic acid esters, styrenes, vinyl ethers, vinyl esters, N-vinyl heterocycles, allyl ethers,
There are 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. A substance obtained by introducing a polymerizable functional group such as a vinyl group or a vinylidene group into the chemical structure of the above-mentioned reducing agent or an optional component described later, which is a color image forming substance, can also be used as the polymerizable compound. Needless to say, use of a substance that serves as both a reducing agent and a polymerizable compound or a color image forming substance and a polymerizable compound as described above is also included in the embodiment of the light-sensitive material.

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 preferable range of use is 12 to 120.
It is 00 parts by weight.

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. Examples of 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, polyethylene. Examples thereof include films such as terephthalate, and paper laminated with a resin material or a polymer such as polyethylene.

When the support is made of a porous material such as paper, the support used in the photosensitive material described in Japanese Patent Application No. 61-52996 has a certain degree of 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. Paper support having a certain Beck's smoothness, Japanese Patent Application No. 61-
Paper support with low shrinkage like the light-sensitive material described in No. 227766, paper support with low air permeability like the light-sensitive material described in Japanese Patent Application No. 61-227768, 1986 by the present applicant. It is also possible to use a paper support or the like having a pH value of 5 to 9 like the light-sensitive material described in the specification of "Light-sensitive material" on October 14, (2).

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 portion is dispersed in the photosensitive layer in the form of oil droplets, and the silver halide is contained in the oil droplets of the polymerizable compound. The oil droplets of the polymerizable compound are more preferably in the form of microcapsules.

The wall material forming the outer shell of the microcapsule is not particularly limited. Regarding the photosensitive material using microcapsules having an outer shell made of a polyamide resin and / or a polyester resin, Japanese Patent Application No. 61-53871.
Japanese Patent Application No. 61-53872 describes a photosensitive material using a microcapsule having an outer shell made of a polyurea resin and / or a polyurethane resin, and a microcapsule having an outer shell made of an amino-aldehyde resin. Japanese Patent Application No. 61-
Japanese Patent Application No. SHO 61-61, for a light-sensitive material using microcapsules having an outer shell made of gelatin is described in Japanese Patent No. 53873.
Regarding the photosensitive material using a microcapsule having an outer shell made of an epoxy resin in No. 53874, a microcapsule having a composite resin outer shell containing a polyamide resin and a polyurea resin is disclosed in Japanese Patent Application No. 61-53875. Regarding the photosensitive material used, Japanese Patent Application No. 61-53877
Japanese Patent Application No. 61-53878 describes a light-sensitive 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 level, as in the light-sensitive material described in Japanese Patent Application No. 61-176415 by the present applicant.

Further, 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 a color image forming substance which is an optional component described later 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. Regarding a light-sensitive material in which two or more types of microcapsules are used in combination, Japanese Patent Application No. 61-42
No. 747 specification.

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

As an optional component that can be contained in the photosensitive layer of the photosensitive material, a color image forming substance, a sensitizing dye, an organic silver salt, a radical generator, various image forming accelerators, a thermal polymerization inhibitor, a thermal polymerization initiator, Development stopper, fluorescent whitening agent, anti-fading agent, dye or pigment for preventing halation or irradiation, dye having a property of decolorizing by heating or light irradiation, matting agent, anti-smudge agent, plasticizer, water releasing agent, Examples include binders, photopolymerization initiators, solvents for polymerizable compounds, water-soluble vinyl polymers and the like.

The photosensitive material can obtain a polymer image by the constitution of the photosensitive layer described above, but a color image can also be formed by including a color image forming substance as an optional component in the photosensitive layer.

The color image-forming substance that can be used in the light-sensitive material is not particularly limited, and various types can be used. That is, a substance that is itself colored (dye or pigment), or energy that is colorless or light-colored but is external (heat, pressure, light irradiation, etc.) or contact with another (developing agent) A substance (color former) that develops color by is included in the color image forming substance. Incidentally, the general light-sensitive material using a color image forming substance is described in the above-mentioned JP-A-61-73145. Further, a photosensitive material using a dye or a pigment as a color image forming substance is described in Japanese Patent Application No. 61-29987, and a photosensitive material using a leuco dye is Japanese Patent Application No.
No. 1-53876, Japanese Patent Application No. 61-96339 for a light-sensitive material using a triazene compound, and Japanese Patent Application Nos. 61-133091 and 61-61 for a light-sensitive material using a yellow color-forming leuco dye. -133
The specification of Japanese Patent Application No. 61-197963 describes the light-sensitive material using a cyan color-forming leuco dye in the specification of No. 092.

Dyes and pigments, which are themselves colored substances, are commercially available as well as various documents (eg, "Handbook of Dyes" edited by the Society of Synthetic Organic Chemistry, published in 1970, "Handbook of Latest Pigments" edited by the Japan Pigment Technology Association, Known ones described in 1975 can be used. These dyes or pigments are used after being dissolved or dispersed.

On the other hand, examples of the substance that develops color by some energy such as heating, pressurization, and light irradiation are thermochromic compounds,
Known are piezochromic compounds, photochromic compounds, and leuco bodies such as triarylmethane dyes, quinone dyes, indigoid dyes, and azine dyes. All of them develop color by heating, pressurizing, light irradiation or air oxidation.

Examples of the substance that develops a color upon contact with another component include various systems that develop a color by an acid-base reaction between two or more components, a redox reaction, a coupling reaction, a chelate formation reaction and the like. For example, pressure-sensitive copying paper (pages 29 to 58) and azography (87 to 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.

When two types of substances that cause a color reaction in a contact state are used as the above-mentioned color image forming substances, one of the substances that cause the color reaction and the polymerizable compound are contained in microcapsules. Then, a color image can be formed on the photosensitive layer by allowing another substance among the substances that cause the above-mentioned color forming reaction to exist outside the microcapsules containing the polymerizable compound. A light-sensitive material capable of obtaining a color image without using an image receiving material as described above is described in Japanese Patent Application No. 61-53881.

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 10 ^{−8 to} 10 per mol of silver halide.
It is about ^-2 mol.

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, Japanese Patent Application No. 60-139746 discloses a silver halide emulsion after the formation of silver halide grains. The light-sensitive materials obtained by adding them in the preparation stage are described in Japanese Patent Application No. 61-55510. Further, specific examples of sensitizing dyes that can be used in the light-sensitive material are described in the above-mentioned Japanese Patent Application Nos. 60-139746 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 0.0 mol, per mol of silver halide.
Use 1 to 1 mole. Instead of the organic silver salt, an organic compound (for example, benzotriazole) that constitutes it
The same effect can be obtained by adding to the photosensitive layer. A light-sensitive material using an organic silver salt is described in Japanese Patent Application No. 60-141799. The organic silver salt as described above is preferably used in the range of 0.1 to 10 mol, and more preferably 0.01 to 1 mol, based on 1 mol of silver halide.

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.
Japanese Patent Application No. 61-38510 discloses a photosensitive material using silver triazene as the above-mentioned radical generator, and Japanese Patent Application No. 61-38510 discloses a photosensitive material using silver diazotate.
No. 38511 and Japanese Patent Application No. 61-38512 describe the light-sensitive material using an azo compound.

Various image formation accelerators can be used in the light-sensitive material. The image forming accelerator includes a silver halide (and / or an organic silver salt) and a reducing agent for promoting the redox reaction between the redox agent and the photosensitive material to the image receiving material or image receiving layer (these will be described later). It has the function of promoting the movement of image forming substances. The image formation accelerator is a base, a base precursor, an oil, a surfactant, a
It is further classified into a compound having an antifoggant function and / or a development promoting function, a heat agent, a compound having an oxygen removing function, and the like. 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-sulfonyl. Examples thereof include guanidine phenylsulfonylacetate 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 appropriately used in an amount of 100% by weight or less, more preferably 0.1% by weight, based on the weight of the photosensitive layer coating film.
A range of from 40% by weight is useful. In the present invention, the base and / or 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 a light-sensitive material using a tertiary amine as a base, Japanese Patent Application No. 61-13181 discloses a light-sensitive 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
Japanese Patent Application No. 61-215637 discloses a photosensitive material using a guanidine derivative having a solubility of 0.1% or less.
Japanese Patent Application Laid-Open No. Sho 61-61, for a light-sensitive material using a hydroxide or salt of an alkali metal or an alkaline earth metal.
-96341 has a description.

Further, regarding a light-sensitive material using an acetylide compound as a base precursor, Japanese Patent Application No. 61-167558 discloses that a propiolic acid salt is used as a base precursor, and silver, copper, a silver compound or a copper compound is used as a catalyst for the base formation reaction. Japanese Patent Application No. 61-
For the light-sensitive material containing the above-mentioned propiolic acid salt and the above-mentioned silver, copper, silver compound or copper compound in the state of being isolated from each other, there is disclosed in Japanese Patent Application No. 61-227769, the above-mentioned Japanese Patent Application No. 61-227769. As for a light-sensitive material containing a free ligand in addition to copper, a silver compound, or a copper compound, the applicant of the present invention, 1986 10
In Japanese Patent Application No. 61-61, the specification of "Photosensitive Material" filed on Apr. 14, 2014, uses a propiolic acid salt as a base precursor and further contains a heat-meltable compound as a reaction accelerator for a base formation reaction. No. 191001,
Regarding a light-sensitive material containing a sulfonylacetate as a base precursor and further containing a heat-meltable compound as a reaction accelerator for a base-forming reaction, Japanese Patent Application No. 61-193375 discloses that an organic base is an isocyanate or isothiocyanate as a base precursor. The light-sensitive materials using the combined compounds 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 and a polymerizable compound are contained in the microcapsules described above, and a base or a base precursor is present in the photosensitive layer outside the microcapsules. Alternatively, Japanese Patent Application No. 61-5298
A base or a base precursor may be contained in another microcapsule like the light-sensitive material described in No. 8. 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. 5,29,89 discloses a light-sensitive material containing solid fine particles carrying a base or a base precursor in microcapsules, and Japanese Patent Application No. 61-52995 discloses a light-sensitive material containing a micro compound containing a base compound having a melting point of 70 ° C. to 210 ° C. Japanese Patent Application No. Sho 61 for a light-sensitive material using capsules.
-212149 specification, respectively.
Further, in place of the microcapsules containing the above-mentioned base or base precursor, the applicant of the present invention, October 14, 1986
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 the specification of “Light-sensitive material” in Japanese application (6).

The base or base precursor is described in Japanese Patent Application No. 61-9.
It may be added to an auxiliary layer (a layer containing a base or a base precursor described later) other than the photosensitive layer as described in the specification of 6340. Furthermore, Japanese Patent Application No. 61-1
As described in Japanese Patent No. 76417, 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.

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.

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. As for the photosensitive material using an antifoggant as a compound having an antifoggant function and / or a development accelerating function, Japanese Patent Application No. 60-294337 discloses a photosensitive material using a compound having a cyclic amide structure. Japanese Patent Application No. 60-294338 discloses a light-sensitive material using a thioether compound in Japanese Patent Application No.
Japanese Patent Application No. 60-294 discloses a light-sensitive material using a polyethylene glycol derivative.
No. 340, Japanese Patent Application No. 60-294341 for a photosensitive material using a thiol derivative, and Japanese Patent Application No. 61-2 for a photosensitive material using an acetylene compound.
No. 0438, Japanese Patent Application No. 61-25578 describes a photosensitive material using a sulfonamide derivative.
The photosensitive material using the quaternary ammonium salt is described in the specification of "Photosensitive Material" by the applicant of the present application on October 6, 1986 (2).

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 photosensitive material using a hot solvent is described in the specification of 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. The photosensitive material using a compound having two or more mercapto groups is described in Japanese Patent Application No. 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 and the like of "Addition Polymerization / Ring-Opening Polymerization", edited by Editorial Committee for Polymer Experiments, Polymer Society of Japan, 1983, Kyoritsu Shuppan). 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 azobismethylvaleronitrile, 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. Further, a light-sensitive material using a thermal polymerization initiator is described in Japanese Patent Application No. 60-210657.

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-60-1
Examples thereof include oxime esters described in each of Nos. 08837 and 60-192939, and compounds that release an acid by the Rossen rearrangement described in JP-A-60-230133. Further, as an example of the electrophilic compound which causes a substitution reaction with a base upon heating, there is disclosed in JP-A-60-230.
Examples thereof include compounds described in JP-A-134.

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 light-sensitive material in which a white pigment is added to a light-sensitive layer for the purpose of preventing halation or irradiation.

When the light-sensitive layer of the light-sensitive material is a mode in which the above-mentioned microcapsules are used, the microcapsules may contain a dye having a property of decoloring by heating or light irradiation. 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. As for the light-sensitive material using the dye having the property of being decolorized by heating or light irradiation as described above, the "light-sensitive material" filed on Oct. 14, 1986 by the present applicant (1)
There is a description in the specification.

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. 1
Starch particles described in US Pat. No. 2,322,347, fine polymer powders described in US Pat. No. 3,625,736, microcapsule particles containing no color-developing agent described in British Patent No. 12359991, US Pat. No. 2,711,375. Examples thereof include the finely divided cellulose powder, talc, kaolin, bentonite, pyrophyllite, zinc oxide, titanium oxide, and inorganic particles such as alumina. The average particle size of the agate is 3 to 50 μm in volume average diameter.
The range of m is preferable, and the range of 5 to 40 μm is more preferable. As described above, when the oil droplets of the polymerizable compound are in the microcapsule state, it is more effective that the particles are larger than the 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 light-sensitive material using a binder, see JP-A-61-6
It is described in Japanese Patent No. 9062. The light-sensitive material using a binder together with microcapsules is described in Japanese Patent Application No. 61-52994.

A photopolymerization initiator may be added to the photosensitive layer of the photosensitive material for the purpose of polymerizing the unpolymerized polymerizable compound after image transfer. A light-sensitive material using a photopolymerization initiator is described in Japanese Patent Application No. 61-3025.

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. Regarding a photosensitive material using an organic solvent miscible with a polymerizable compound encapsulated in microcapsules, see Japanese Patent Application No. 61-5299.
There is a description in No. 3 specification.

A water-soluble vinyl polymer may be adsorbed on the above-described silver halide grains for use. As for the light-sensitive material using the water-soluble vinyl polymer as described above, the applicant of the present invention shows it in Showa 6
It is described in the specification of "Photosensitive Material" filed on October 6, 1 (1).

In addition to the above, examples of optional components that can be contained in the photosensitive layer and the usage thereof are also described in the application specification regarding the series of photosensitive materials described above, and Research Disclosure Vol. 170, June 1978. The 17th
No. 029 (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).

Instead of using an image receiving material described later as a method of using the photosensitive material, the image receiving layer may be provided on the photosensitive material and an image may be formed on this layer. The image receiving layer provided on the photosensitive material may have the same structure as the image receiving layer provided on the image receiving material. Details of the image receiving layer will be described later.

For the photosensitive material using the heating element layer, Japanese Patent Application No.
-135568, 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. In the specification, the light-sensitive material provided with a coloring layer as an antihalation layer is described in the specification of "Light-sensitive material", filed (2), filed on Oct. 17, 1986 by the present applicant. Further, a light-sensitive material provided with a base barrier layer is also described in the above-mentioned Japanese Patent Application No. 61-96340. Furthermore, examples of other auxiliary layers and their usages are also described in the specification of the above-mentioned series of photosensitive materials.

The method for producing the photosensitive material will be 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 solution. It comprises a step of obtaining a light-sensitive material by applying the liquid to the support as described above and drying.

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 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, an oily (or aqueous) composition containing one or more components is
Further, a method of preparing a secondary composition by emulsifying 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 silver halide is preferably prepared as a silver halide emulsion. The halogenated emulsion can be prepared by any known method such as an acidic method, a neutral method or an 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, 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-51-158124 and JP-A-55-1581).
24, each publication and U.S. Pat. No. 3,650,757).

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. Internal latent image type emulsions suitable for this purpose are described in US Pat. No. 2,592,250.
Nos. 3,761,276 and Japanese Patent Publication No. 58-
No. 3534, JP-A No. 58-136641, and the like. Preferred nucleating agents for combination with the above emulsions are U.S. Pat. Nos. 3,227,552, 4245037.
No. 4,255,511, No. 4266013, No. 4,276,364 and West German Published Patent (OLS) No. 2,635,316.

In preparing a silver halide emulsion, 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; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sodium alginate. , Sugar derivatives such as starch derivatives; and homopolymers or copolymers of polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. A variety of synthetic hydrophilic polymer substances can be mentioned. 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. Iridium chloride (III or IV) for the purpose of improving high illumination failure and low illumination failure,
A water-soluble iridium salt such as hexachloroiridium salt ammonium or 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 conventional emulsion for a sensitive material, a known sulfur sensitization method, reduction sensitization method, noble metal sensitization method, or a sensitization method using a sensitizing dye described in the above-mentioned Japanese Patent Application No. 60-139746 is used. Alternatively, they 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 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, a color image-forming substance and the like can be dissolved, emulsified or dispersed in a polymerizable compound and used for producing a light-sensitive material. In the production of the light-sensitive material of the present invention, silver halide is dispersed in a polymerizable compound. When a color image forming substance is added, it is preferably contained in the polymerizable compound. Further, as described below, when the oil droplets of the polymerizable compound are microencapsulated,
Components such as wall materials 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 the preparation of the photosensitive composition, the polymer described above is dissolved in the polymerizable compound.

The photosensitive composition in which a silver halide is dispersed in a polymerizable compound is used as an emulsion emulsified in an aqueous solvent. Further, as in the light-sensitive material described in Japanese Patent Application No. 60-117089, in order to microencapsulate oil droplets of a polymerizable compound, a wall material necessary for microencapsulation is added to this emulsion. Further, the treatment for forming the outer shell of the microcapsule can be carried out at the emulsion stage. Further, a reducing agent or any other component may be added at the stage of the above emulsion.

As an example of the microencapsulation method, a method utilizing coacervation of the hydrophilic wall-forming material described in US Pat. Nos. 2,800,457 and 2,800,458; US Pat. No. 3,287,154 and British Patent No. 990443. Each specification and Japanese Patent Publication No. 38-1957
No. 4, 42-446 and 42-771; interfacial polymerization method; method by polymer precipitation described in US Pat. Nos. 3,418,250 and 3,660,304; US Pat. No. 3,796,669. Method using the described isocyanate-polyol wall material; Method using the isocyanate wall material described in US Pat. No. 3,914,511; US Pat. Nos. 4,001,140, 4;
No. 087376 and U.S. Pat. No. 4,089,802, a method of using a urea-formaldehyde-based or urea-formaldehyde-resilicinol-based wall forming material; walls of melamine-formaldehyde resin, hydroxypropyl cellulose, etc. described in US Pat. No. 4,025,455. In situ method by polymerization of monomers described in JP-B-36-9168 and JP-A-51-9079; Polymerization-dispersion cooling described in British Patents 927807 and 965074. Law; U.S. Pat. No. 3,111,407 and British Patent No. 930422.
The spray drying method described in each specification can be used. 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 emulsion of the above-mentioned photosensitive composition (including the microcapsule liquid subjected to the microencapsulation treatment) can be used as it is as a coating liquid for a photosensitive material. Other components may be added at the stage of this coating solution as in the case of the above emulsion.

A photosensitive material is manufactured by coating the support with the coating solution for the photosensitive layer prepared as described above and 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 and the exposure
Sensitive wavelength of silver halide (when dye sensitization is performed,
It can be selected according to the sensitized wavelength) and the sensitivity. Further, 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 photosensitive material is Japanese Patent Publication No. 45-111.
You may perform the development process using the developing solution of Unexamined-Japanese-Patent No. 49 grade. As described above, the method described in Japanese Patent Application Laid-Open No. 61-69062, which carries out heat development processing, has the advantage that the operation is simple and the processing can be performed in a short time because it is a dry processing. Therefore, the development process of the photosensitive material is
The latter is especially good.

As a heating method in the heat development treatment, various conventionally known methods can be used. Further, as in the light-sensitive material described in Japanese Patent Application No. 60-135568, 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. 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.

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 heat development treatment described above.
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 210657.

As described above, the photosensitive material can obtain a polymer image on the photosensitive layer. Further, a dye or a pigment may be fixed to the polymer to obtain a dye image.

When the light-sensitive material is constituted as the light-sensitive material described in Japanese Patent Application No. 61-53881, the developed light-sensitive material is pressed to destroy the microcapsules and cause a color-developing reaction. A color image can be formed on the light-sensitive material by bringing different kinds of substances into contact with each other.

Further, the image receiving material can be used to form an image on the image receiving material.

The image receiving material will be described below. An image forming method using an image receiving material or an image receiving layer is generally described in Japanese Patent Application No. 60-112284.

As the support for the image receiving material, in addition to the support that can be used for the light-sensitive material described above, variator paper can be used. When a porous material such as paper is used as the support of the image receiving material, it preferably has a certain smoothness like the image receiving material described in Japanese Patent Application No. 61-52990. . An image receiving material using a transparent support is described in Japanese Patent Application No. 61-52991.

The image receiving material generally has an image receiving layer provided on a support. The image receiving layer is in accordance with the coloring system of the color image forming substance described above,
Various compounds can be used to make up any form. When a polymer image is formed on an image receiving material, a dye or a pigment is used as a color image forming substance, the image receiving material may be composed of only the above support.

For example, when a color-developing system comprising a color-developing agent and a color-developing agent is used, the image-receiving layer may contain the color-developing agent. Further, the image receiving layer may be configured as at least one layer containing a medium-beaming agent. The medium-beaming agent can be selected from compounds known in the photographic art and the like in consideration of conditions such as the type of color image-forming substance and used. If necessary, a plurality of medium beam agents having different medium beam forces may be used to form two or more image receiving layers.

The image receiving layer preferably contains a polymer as a binder. As the binder, the binder that can be used in the photosensitive layer of the photosensitive material described above can be used. A polymer having low oxygen permeability may be used as a binder, such as the image receiving material described in Japanese Patent Application No. 61-53879.

The image receiving layer may contain a thermoplastic compound. When the image receiving layer contains a thermoplastic compound, it is preferable that the image receiving layer itself is formed as an aggregate of thermoplastic compound fine particles. The image-receiving layer having the above-described structure has an advantage that a transfer image can be easily formed and a glossy image can be obtained by heating after the image formation. The thermoplastic compound is not particularly limited and can be arbitrarily selected and used from known plastic resins (plastics) and waxes. However, the glass transition point of the thermoplastic resin and the melting point of the wax are preferably 200 ° C. or lower. Regarding the image receiving material having the image receiving layer containing the above-mentioned thermoplastic compound fine particles, Japanese Patent Application No. 61-12
Nos. 4952 and 61-124953 are described.

The image receiving layer may contain a photopolymerization initiator or a thermal polymerization initiator. In image formation using an image receiving material,
The color image forming substance is transferred together with the unpolymerized polymerizable compound as described later. Therefore, a photopolymerization initiator or a thermal polymerization initiator can be added to the image-receiving layer for the purpose of smoothly proceeding the curing treatment (fixing treatment) of the unpolymerized polymerizable compound. An image receiving material having an image receiving layer containing a photopolymerization initiator is described in Japanese Patent Application No. 61-3025, and an image receiving material having an image receiving layer containing a thermal polymerization initiator is described in Japanese Patent Application No. 61-55502. Are described in each.

The dye or pigment may be contained in the image receiving layer for the purpose of writing characters, symbols, frames, etc. on the image receiving layer or for the purpose of making the background of the image a specific color. Further, dyes or pigments may be contained in the image receiving layer for the purpose of facilitating the front / back discrimination of the image receiving material. As the dye or pigment, various known substances including dyes or pigments that can be used in image formation can be used, but the dye or pigment may impair the image formed in the image receiving layer. In some cases, it is preferable to lower the dyeing density of the dye or pigment (for example, the reflection density is below), or to use a dye or pigment having the property of being decolorized by heating or light irradiation.
An image receiving material having an image receiving layer containing a dye or pigment having a property of being decolorized by heating or light irradiation is described in Japanese Patent Application No. 61-96339.

Further, when a white pigment such as titanium dioxide or barium sulfate is added to the image receiving layer, the image receiving layer can function as a white reflective layer. When the image receiving layer is made to function as a white reflective layer, the white pigment is 10 g per 1 g of the thermoplastic compound.
It is preferably used in the range of 100 to 100 g.

When the dye or pigment as described above is contained in the image receiving layer, it may be uniformly contained or may be partially distributed. For example, a support described below is made of a material having a light-transmitting property, and a part of the reflection image can be a projection image by including the white pigment in a part of the image receiving layer. By doing so, unnecessary image information in the projected image can be written as a reflected image in the image receiving layer portion containing the white pigment.

The image receiving layer may be composed of two or more layers depending on the functions as described above. The thickness of the image receiving layer is 1 to 1
The thickness is preferably 00 μm, more preferably 1 to 20 μm.

A protective layer may be further provided on the image receiving layer. Further, a layer made of an aggregate of fine particles of a thermoplastic compound may be further provided on the image receiving layer. An image receiving material having a layer comprising an aggregate of fine particles of a thermoplastic compound provided on the image receiving layer is described in Japanese Patent Application No. 61-55503.

Further, a layer containing an adhesive or an adhesive and release paper may be sequentially laminated on the surface of the support opposite to the surface on which the image receiving layer is provided. Regarding the sticker-shaped image receiving material having the above structure, Japanese Patent Application No. 61-16926 of the present applicant
There is a description in No. 4 specification.

The photosensitive material is subjected to development processing as described above, and by pressing the image receiving material in a state of being superposed, the unpolymerized polymerizable compound is transferred to the image receiving material, and a polymer image can be obtained on the image receiving material. it can. Regarding the pressing means,
Various conventionally known methods can be used.

Further, in the embodiment in which the photosensitive layer contains a color image-forming substance,
By carrying out the development processing in the same manner, the polymerizable compound is polymerized and cured, thereby immobilizing the color image forming substance in the cured portion. Then, by pressing the photosensitive material and the image receiving material in a superposed state, the color image forming substance in the uncured portion is transferred to the image receiving material, and a color image can be obtained on the image receiving material.

After forming an image on the image receiving material as described above,
The image receiving material may be heated as in the image forming method described in Japanese Patent Application No. 61-55501. In the above method, the unpolymerized polymerizable compound transferred onto the image receiving material is polymerized,
There is also an advantage that the storability of the obtained image is improved.

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

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 and Comparative Example 1] Preparation of silver halide emulsion 40 g of ceratin and 23.8 g of potassium bromide were dissolved in water 3, heated to 50 ° C., and silver nitrate 3 was added while stirring.
What melt | dissolved 4 g in 200 m of water was added in 10 minutes. Then, a solution prepared by dissolving 3.3 g of potassium iodide in 100 m of water was added over 2 minutes. The pH of the silver iodobromide emulsion thus obtained was adjusted, precipitated, and after removing excess salts, the pH was adjusted to 6.0 to obtain a silver iodobromide emulsion in a yield of 400 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 resulting emulsion, excess salt was precipitated and removed. Then adjust the pH to 6.30
And a benzotriazole silver emulsion having a yield of 400 g was obtained.

Preparation of Photosensitive Composition In 100 g of trimethylolpropane triacrylate, 0.40 g of the following polymer, Pergasscript Red I
6.00 g of -6-B (manufactured by Ciba-Geigy Co., Ltd.) was dissolved. 0.61 g of the following hydrazine derivative and 1.22 of the following developing agent as a reducing agent in 18.00 g of the above solution
A solution of g in 1.80 g methylene chloride was added.
Further, 4.06 g of the silver halide emulsion and 3.35 g of benzotriazole silver emulsion were added, and the mixture was stirred with a homogenizer at 15,000 rpm for 5 minutes to obtain a photosensitive composition.

(polymer) (Hydrazine derivative) (Developer) Preparation of microcapsule solution 18.6% aqueous solution of Isoban (manufactured by Kuraray Co., Ltd.) 1
0.51 g, 48.56 g of 2.89% aqueous pectin solution
The above-mentioned photosensitive composition was added to the aqueous solution added with, and the mixture was stirred by a homogenizer at 7,000 rpm for 2 minutes to emulsify the photosensitive composition in an aqueous solvent.

Urea 40% aqueous solution 8.32 was added to 72.5 g of this aqueous emulsion.
g, resorcin 11.2% aqueous solution 2.82 g, formalin 37% aqueous solution 8.56 g, and ammonium sulfate 8.76% aqueous solution 2.74 g were sequentially added, and heating was continued at 60 ° C. for 2 hours while stirring. After that, the pH was adjusted to 7.0 with 10% sulfuric acid, and sodium bisulfite was added to 30.9.
% Aqueous solution 3.62 g was added to prepare a microcapsule solution.

Preparation of light-sensitive material Microcapsule liquid 10.0 prepared as described above
To 10 g, 1.0 g of 10% aqueous solution of Emalex NP-8 (trade name; manufactured by Nippon Emulsion Co., Ltd.) and 3.69 g of 10% guanidine trichloroacetate (volume ratio of water / ethanol = 50/50) were added. , 100 μm thick polyethylene terephthalate was coated with a # 40 coating rod and dried at 40 ° C. to prepare a light-sensitive material (T-1) according to the present invention.

Further, the light-sensitive materials (T-2) and (T-) according to the present invention were used in exactly the same manner except that the following polymers were used instead of the polymers used in the preparation of the photosensitive composition described above.
3), (T-4), (T-5), and comparative photosensitive materials (S-1) and (S-2) were prepared.

(T-2) (T-3) (T-4) (T-5) (S-1) (S-2) Preparation of image receiving material To 125 g of water, 11 g of 40% sodium hexametaphosphate aqueous solution was added, and further 34 g of zinc 3,5-di-α-methylbenzylsalicylate and 82 g of 55% calcium carbonate slurry were mixed and roughly dispersed by a mixer. The liquid was dispersed with a Dynamill 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. This mixed solution was applied evenly on an art paper having a weight of 43 g / m ² so as to have a wet film thickness of 30 μm, and then dried to form an image receiving element.

Evaluation of Photosensitive Material Each of the obtained photosensitive materials was used for 200
After imagewise exposure at 0 lux for 1 second, it was heated for 40 seconds on a hot plate heated to 125 ° C. Then, stack each light-sensitive material with the above-mentioned image-receiving element to 350 kg / cm ²
The density was measured with a Macbeth reflection densitometer for the magenta positive color image obtained on the image receiving element through a pressure roller.

The above measurement results are shown in Table 1 below.

With any of the light-sensitive materials containing silver halide in microcapsules, clear images could be obtained. As is clear from the results shown in Table 1, the light-sensitive materials (T-1) to (T-5) using the above-mentioned polymers have a low minimum density and give a good positive image with high contrast. I understand.

[Example 2 and Comparative Example 2] 4.06 g of the silver halide emulsion used in Example 1
To a light-sensitive material (T-6 according to the present invention) was used in the same manner as in Example 1 except that 0.6 m of a 0.04% methanol solution of the following dye was added and stirred for 5 minutes to use as a silver halide emulsion. ), (T-7), (T-8), (T-
9), (T10-), and comparative light-sensitive material (S-
3) and (S-4) were created respectively. The above light-sensitive materials are (T-1) of Example 1 and Comparative Example 1, respectively.
(T-2), (T-3) (T-4), (T-5), (S
-1) and the same polymer as (S-2) are used.

(Pigment) Evaluation of Photosensitive Material Each of the obtained photosensitive materials was subjected to a green filter (500 to 6) whose density was continuously changed using a tungsten bulb.
Imagewise exposure for 1 second at 2000 lux through (transmitting light of 00 nm) 4 on a hot plate heated to 125 ° C.
Heated for 0 seconds. Then, each light-sensitive material was superposed on the above-mentioned image receiving element and passed through a 350 kg / cm ² pressure roller, and the density of the magenta positive color image obtained on the image receiving element was measured by a Macbeth reflection densitometer.

The above measurement results are shown in Table 2 below.

With any of the light-sensitive materials containing silver halide in microcapsules, clear images could be obtained. As is clear from the results shown in Table 1, the light-sensitive materials (T-6) to (T-10) using the above-mentioned polymers have a low minimum density and give a good positive image with high contrast. I understand.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP 61-275742 (JP, A) JP 61-278849 (JP, A) JP 62-78552 (JP, A) JP 62- 81635 (JP, A)

Claims (19)

[Claims] 1. A hydrophilic group having a main chain substantially consisting of a hydrocarbon chain, and a part of the main chain having a nitrogen atom having a lone electron pair or an --OH group in the terminal group. The substituted polymer is dissolved in a liquid polymerizable compound,
(B) Liquid photosensitivity in which a silver halide and a reducing agent are contained in a polymerizable compound by adding a reducing agent to the polymerizable compound and emulsifying a silver halide emulsion in the polymerizable compound. The composition is prepared, and (c) the photosensitive composition is emulsified in an aqueous medium to prepare an aqueous emulsion in which oil droplets of the photosensitive composition are dispersed in the aqueous medium, and (d) the aqueous emulsification. Forming a shell on the oil droplets of the photosensitive composition in the composition to prepare a dispersion of microcapsules, and (e) coating the dispersion of microcapsules on a support. A photosensitive layer containing a silver halide, a reducing agent and a polymerizable compound on the body, and the silver halide, the reducing agent and the polymerizable compound being present in a microcapsule dispersed in the photosensitive layer. Material manufacturing method. 2. In the step (a) or (b) above,
The method for producing a light-sensitive material according to claim 1, wherein the color image-forming substance is dissolved or dispersed in the polymerizable compound. 3. The method for producing a light-sensitive material according to claim 1, wherein the hydrophilic group of the polymer contains a nitrogen atom having a lone electron pair in the terminal group represented by the following formula (I): [In the above formula (I), R ¹ and R ² are hydrogen atoms or substituents in which the total number of carbon atoms of R ¹ and R ² is 5 or less]. 4. The method for producing a photosensitive material according to claim 3, wherein R ¹ in the above formula (I) is a hydrogen atom. 5. The method for producing a light-sensitive material according to claim ³ , wherein R ¹ in the formula (I) is —COR ³ , and R ³ is a substituent having 4 or less carbon atoms. 6. R ¹ in the above formula (I) is —SO ₂ R ⁴
Wherein R ⁴ is a substituent having 5 or less carbon atoms, and the method for producing a photosensitive material according to claim 3. 7. The production of a light-sensitive material according to claim 3, wherein at least one of R ¹ and R ² in the above formula (I) is a substituted or unsubstituted alkyl group having 5 or less carbon atoms. Method. 8. The light-sensitive material according to claim 3, wherein R ¹ and R ² in the above formula (I) form a 5-membered or 6-membered nitrogen-containing heterocycle with the adjacent nitrogen atom. Production method. 9. The number of the hydrophilic groups contained in the polymer is 0. 1 of the number of carbon atoms contained in the main chain of the polymer.
25% or more, The manufacturing method of the photosensitive material of Claim 1. 10. The photosensitive material according to claim 1, wherein the number of the hydrophilic groups contained in the polymer is 0.25% or more of the number of carbon atoms contained in the main chain of the polymer. Manufacturing method. 11. The number of the hydrophilic groups contained in the polymer is 1 of the number of carbon atoms contained in the main chain of the polymer.
The method for producing a photosensitive material according to claim 1, wherein the content is at least%. 12. The polymer comprises repeating units,
The method for producing a light-sensitive material according to claim 1, wherein 5% or more of the completely repeating units constituting the polymer are repeating units represented by the following formula (II): [In the above formula (II), R ⁵ , R ⁶ and R ⁷ represent a hydrogen atom, a methyl group and-
CH ₂ CO ₂ R ²⁰ is a monovalent group selected from the group consisting of (R ²⁰ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms,
And a monovalent group selected from the group consisting of aralkyl groups having 7 to 20 carbon atoms), L ¹ is an alkylene group, an arylene group, an aralkylene group, —CO ₂ —R ⁸ —, and —CO. -NR ⁹ -R ⁸ -
Is a divalent group selected from the group consisting of (R ⁸ is a divalent group selected from the group consisting of an alkylene group, an arylene group, and an aralkylene group, and R ⁹ is a hydrogen atom,
An alkyl group having 1 to 6 carbon atoms, having 6 carbon atoms
To 10 aryl groups and 7 to 2 carbon atoms
A 0 a monovalent group selected from the group consisting of aralkyl group), m1 is 0 or 1, and Q ¹ is a hydroxyl ^{group, -NR 10 R 11, -CONR 10} R
_{^{11, -NR 10 COR 11, -SO}} 2 NR
¹⁰ R ¹¹ , —NR ¹⁰ SO ₂ R ¹¹ , and a monovalent group selected from the group consisting of groups having a 5- or 6-membered nitrogen-containing heterocycle (R ¹⁰ and R ¹¹ are hydrogen atoms,
Or an alkyl group or a substituted alkyl group in which the total number of carbon atoms of R ¹⁰ and R ¹¹ is 5 or less, or R 10
¹⁰ and R ¹¹ together with the adjacent atom or atomic group form a 5- or 6-membered nitrogen-containing heterocyclic group)]. 13. The polymer comprises repeating units,
The method for producing a light-sensitive material according to claim 1, wherein 5% or more of the completely repeating units constituting the polymer are repeating units represented by the following formula (III): [In the above formula (III), R ¹² and R ¹³ represent a hydrogen atom, a methyl group and -C.
H ₂ CO ₂ R ²⁰ is a monovalent group selected from the group consisting of (R ²⁰ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, And a monovalent group selected from the group consisting of aralkyl groups having 7 to 20 carbon atoms), L ² is —CO ₂ —R ⁸ —, or —CO—NR ⁹ —R.
⁸ - and, ^{L 3} is an alkylene group, an arylene group, an aralkylene group, _-CO 2 -R ⁸ -, and ^-CO-NR 9 -R ⁸ -
Is a divalent group selected from the group consisting of (R ⁸ is a divalent group selected from the group consisting of an alkylene group, an arylene group, and an aralkylene group, and R ⁹ is a hydrogen atom,
An alkyl group having 1 to 6 carbon atoms, having 6 carbon atoms
To 10 aryl groups and 7 to 2 carbon atoms
A 0 a monovalent group selected from the group consisting of aralkyl group), m @ 2 and m3 is 0 or 1, and Q ² and ^{Q 3} represents a hydroxyl ^group, -NR ¹⁰ R 11, -CO
^{NR 10 R 11, -NR 10 COR} 11, -SO 2 NR
¹⁰ R ¹¹ , —NR ¹⁰ SO ₂ R ¹¹ , and a monovalent group selected from the group consisting of groups having a 5- or 6-membered nitrogen-containing heterocycle (R ¹⁰ and R ¹¹ are hydrogen atoms,
Or an alkyl group or a substituted alkyl group in which the total number of carbon atoms of R ¹⁰ and R ¹¹ is 5 or less, or R 10
¹⁰ and R ¹¹ together with the adjacent atom or atomic group form a 5- or 6-membered nitrogen-containing heterocyclic group)]. 14. The polymer comprises repeating units,
The method for producing a light-sensitive material according to claim 1, wherein 5% or more of the repeating units constituting the polymer are repeating units represented by the following formula (IV): [In the above formula (IV), R ¹⁴ and R ¹⁵ represent a hydrogen atom, a methyl group and -C.
H ₂ CO ₂ R ²⁰ is a monovalent group selected from the group consisting of (R ²⁰ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, and the number of carbon atoms from 7 to 20 amino monovalent group selected from the group consisting of aralkyl group), ^{L 4} represents an alkylene group, an arylene group, an aralkylene group, _-CO 2 -R ⁸ -, and -CO -NR ⁹ -R ⁸ -
Is a divalent group selected from the group consisting of (R ⁸ is a divalent group selected from the group consisting of an alkylene group, an arylene group, and an aralkylene group, and R ⁹ is a hydrogen atom,
An alkyl group having 1 to 6 carbon atoms, having 6 carbon atoms
To 10 aryl groups and 7 to 2 carbon atoms
A 0 a monovalent group selected from the group consisting of aralkyl group), m4 is 0 or 1, and Q ⁴ are a hydroxyl ^{group, -NR 10 R 11, -CONR 10} R
_{^{11, -NR 10 COR 11, -SO}} 2 NR
¹⁰ R ¹¹ , —NR ¹⁰ SO ₂ R ¹¹ , and a monovalent group selected from the group consisting of groups having a 5- or 6-membered nitrogen-containing heterocycle (R ¹⁰ and R ¹¹ are hydrogen atoms,
Or an alkyl group or a substituted alkyl group in which the total number of carbon atoms of R ¹⁰ and R ¹¹ is 5 or less, or R 10
¹⁰ and R ¹¹ together with the adjacent atom or atomic group form a 5- or 6-membered nitrogen-containing heterocyclic group)]. 15. The polymer comprises repeating units,
The method for producing a light-sensitive material according to claim 1, wherein 5% or more of the completely repeating units constituting the polymer are repeating units represented by the following formula (V): [In the above formula (V), R ¹⁶ , R ¹⁷ and R ¹⁸ are a hydrogen atom or a methyl group, X is an oxygen atom or —NH—, n is an integer 1 to 6, and Q ⁵ is a hydroxyl group. An amino group, an amino group substituted by 1 or 2 alkyl groups having 1 to 6 total carbon atoms, a hydroxyphenyl group, a group having a 5- or 6-membered nitrogen-containing heterocycle, and- It is a monovalent group selected from the group consisting of NHSO ₂ CH ₃ ]. 16. In the formula (V), n is an integer of 2 to 4.
16. The method for producing a light-sensitive material according to claim 15, wherein Q ⁵ is a hydroxyl group or a dimethylamino group. 17. The method for producing a light-sensitive material according to claim 1, wherein the polymer is used in the range of 0.1 to 20% by weight based on the silver halide emulsion. 18. The method for producing a photosensitive material according to claim 1, wherein the polymerizable compound is a compound having an ethylenically unsaturated group. 19. The polymerizable compound is added in an amount of 5 to 12 with respect to 1 part by weight of silver halide contained in the silver halide emulsion.
The method for producing a light-sensitive material according to claim 1, which is used in an amount of 10,000 parts by weight.