JPH0619568B2 - Photosensitive material manufacturing method - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a method for producing a photosensitive material having a photosensitive 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 is negatively or positively polymerized by the action of the reducing agent. It can be used in an image forming method in which a polymerizable compound is polymerized.

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

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

The above image forming method is a method of polymerizing the polymerizable compound in the portion where the latent image of silver halide is formed. The present inventors have further invented a method capable of polymerizing a polymerizable compound in a portion where a latent image of silver halide is not formed, and this invention has already been applied for a patent (Japanese Patent Application No. 60-
210657). This method, by heating,
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 thermal polymerization initiator is used to accelerate the polymerization of other portions.

The present inventors have found that, as an excellent light-sensitive material that can be used in the image forming method as described above, a silver halide, a reducing agent, a polymerizable compound and a 5- or 6-membered nitrogen-containing complex are formed on a support. A light-sensitive material having a light-sensitive layer containing a compound having a ring structure was invented, and the invention has been applied for a patent (Japanese Patent Laid-Open Nos. 62-151838 and 62-151).
841). 5 or 6 in the above light-sensitive material
The member having a nitrogen-containing heterocyclic structure has a fog-preventing function and / or a development-accelerating function. Therefore, the above light-sensitive material can obtain a clear image having a low minimum density and a high maximum density.

SUMMARY OF THE INVENTION An object of the present invention is to provide an excellent method for producing the above-mentioned light-sensitive material.

The present invention has a 5-membered nitrogen-containing heterocyclic structure selected from the group consisting of a diazole ring, a triazole ring and a tetrazole ring (a benzene ring or a naphthalene ring may be fused to the diazole ring and the triazole ring). Then
In the presence of a compound in which at least one of the carbon atoms constituting the nitrogen-containing heterocyclic structure has a thiol group, formation or ripening of silver halide grains is carried out, whereby the above compounds are adsorbed on the silver halide grains. And a photosensitive coating solution containing the above-mentioned silver halide emulsion, a reducing agent and a polymerizable compound is coated on a support. The present invention provides a method for manufacturing the same.

[Effect of the Invention] In the present invention, in the preparation of a silver halide emulsion, silver halide grains are formed or ripened at the same time as or after the addition of the compound having a 5- or 6-membered nitrogen-containing heterocyclic structure. It is characterized by doing.

By using the silver halide emulsion prepared as described above, most of the above compounds are adsorbed on silver halide. Therefore, the light-sensitive material produced according to the present invention has a remarkable fog-preventing function and / or a development-accelerating function, which the above-mentioned compounds exhibit, and a clearer image can be obtained.

Further, by using the above silver halide emulsion, it is possible to prevent alteration of the emulsion during the production process, particularly, undesirable change in photographic characteristics when the coating solution is left for a very long time. Further, it is possible to prevent the photosensitive material from being deteriorated over time after the production of the photosensitive material. Therefore, by using the manufacturing method of the present invention, it is possible to obtain a light-sensitive material that is stable in quality and hardly deteriorates during and after the manufacturing process.

[Detailed Description of the Invention] The compound having a 5- or 6-membered nitrogen-containing heterocyclic structure that can be used in the production method of the present invention is known as an additive used in general photographic technology, and these are included. Various types of compounds can be used.

Examples of the compound having a 5- or 6-membered nitrogen-containing heterocyclic structure are shown by the following formulas (I) to (XX).

[In the above formulas (I) and (II), A is a substituted or unsubstituted alkyl group, alkenyl group,
A monovalent group selected from the group consisting of an alkynyl group, an aralkyl group, an alicyclic hydrocarbon group and an aryl group, and B
Is a substituted or unsubstituted hydrocarbon divalent group, X is an anion, and Z is a non-metal atom group that forms a heterocycle with a nitrogen atom.] Preferred examples of B in the above formula (II) Can include the following divalent groups.

_{- (CH 2) n - -CH} 2 O- (CH 2) n -O-CH 2 - —CH ₂ —O—CH ₂ — [In the above formulas, n is an integer 1 to 12] [In the formulas (III) to (XV), R ¹ , R ² , R ³ and R ⁴ are each a hydrogen atom, an alkyl group, an aralkyl group, an alkenyl group, an alkoxy group, an aryl group, -NRR ', -COOR. , -SO ₃ M, -CONRR ', -NHSO ₂ R, -SO ₂ NRR', -NO ₂ , a halogen atom, -CN and a monovalent group selected from the group consisting of -OH (the above R and R'is a monovalent group selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group and an aralkyl group, and M is a hydrogen atom or an alkali metal atom) (R ¹ , R ² , R ³ and R ⁴ may be the same or different from each other), or R ¹ and R ² are bonded to each other to form an aliphatic carbocycle, and R ⁵ is a hydrogen atom or a carbon atom number 1 Through 5 a A monovalent group selected from the group consisting of an alkyl group and —SR ″ (the above R ″ is a monovalent group selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group and an aralkyl group), R ⁶ is a hydrogen atom or an alkyl group, R ⁷ is a monovalent group selected from the group consisting of a hydrogen atom, an alkyl group and an aryl group, R ⁸ is an alkyl group, an aryl group, a benzyl group and a pyridyl group Is a monovalent group selected from the group consisting of, R ⁹ is a monovalent group selected from the group consisting of an alkyl group, an alkenyl group and an aryl group, and R ₁₀ and R ₁₁ are an alkyl group, an alkenyl group and a monovalent group that is one selected from the group consisting of aryl groups (R ₁₀ and R ₁₁ may be independently identical or different), or aromatic attached R ₁₀ and R ₁₁ are mutually To form a] [In the formula (XVI), Q is a divalent group selected from the group consisting of an oxygen atom, a sulfur atom and —NR ″ ″, and (wherein R ″ is a hydrogen atom, an alkyl group or an alkenyl group). , A monovalent group selected from the group consisting of an alkynyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted aralkyl group) Y and G are carbon atoms or nitrogen atoms, and R ₁₂ and R ₁₃ is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, -SR "" and -N
Is a monovalent group selected from the group consisting of H ₂ (wherein R ″ ″ is a hydrogen atom, an alkyl group, an aryl group,
An aralkyl group, an alkylcarboxylic acid or an alkali metal salt thereof and a alkylsulfonic acid or an alkali metal salt thereof, which is a monovalent group) (R ₁₂ and R ₁₃ may be the same or different. R) when both Y and G are carbon atoms.
₁₂ and R ₁₃ are bonded to each other to form a substituted or unsubstituted aromatic ring] Of the above compounds having a 5- or 6-membered nitrogen-containing heterocyclic structure, a thiazole ring, a diazole ring, a triazole ring and A compound having a 5-membered nitrogen-containing heterocyclic structure selected from the group consisting of a tetrazole ring (a thiazole ring, a diazole ring and a triazole ring may be condensed with a benzene ring or a naphthalene ring) is particularly preferable.

Further, a compound in which at least one of the carbon atoms constituting the nitrogen-containing heterocyclic structure has a thiol group is also particularly preferable.

Including the compounds represented by the above formulas (I) to (XVI),
Representative specific examples of the compound having a 5- or 6-membered nitrogen-containing heterocyclic structure are shown below.

(1) (2) (3) (Four) (Five) (6) (7) (8) (9) (Ten) (11) (12) (13) (14) (15) (16) (17) (18) (19) (20) (twenty one) (twenty two) (twenty three) (twenty four) (twenty five) (26) (27) (28) (29) (30) (31) (32) (33) (34) (35) (36) (37) (38) (39) (40) (41) (42) (43) (44) (45) (46) (47) (48) (49) (50) (51) (52) (53) (54) (55) (56) (57) (58) (59) (60) (61) (62) (63) (64) (65) (66) (67) (68) (69) (70) (71) (72) (73) (74) As another example of the compound having a 5- or 6-membered nitrogen-containing heterocyclic structure, a compound in which the nitrogen-containing heterocyclic structure is a 5- or 6-membered cyclic amide structure can be mentioned.
The cyclic amide structure is represented by the following formula (XVII).

[In the above formula (XVII), X is an atomic group necessary to form a 5-membered or 6-membered ring together with -NH-CO-] The amide hydrogen in the ring may be dissociated. In this case, the cyclic amide compound can form a salt as an anion.

Further, the 5- or 6-membered ring formed may be saturated or unsaturated.

The atomic group constituting X may be composed only of carbon atoms, or may contain another hetero atom (N, O, S, etc.).

A substituent may be bonded to the atomic group constituting X above. Examples of the substituent include a substituted or unsubstituted alkyl group (preferably having 1 to 12 carbon atoms; eg, methyl group, n-butyl group, t-octyl group, n-dodecyl group), substituted or Unsubstituted aralkyl group (preferably having 7 to 14 carbon atoms; benzyl group, β-phenethyl group, α-
Methylbenzyl group), alkoxy group (preferably having 1 to 12 carbon atoms;
Examples: ethoxy group, methoxyethoxy group), halogen atom (chlorine atom, bromine atom, iodine atom), and substituted or unsubstituted sulfamoyl group (preferably having 1 to 12 carbon atoms; example, sulfamoyl group, dimethylsulfa group) Moyl group, octylsulfamoyl group) and the like.

The cyclic amide structure may form a condensed ring with another ring. Examples of the ring capable of forming a condensed ring with the cyclic amide include a substituted or unsubstituted cycloalkane or cycloalkene having 3 to 10 carbon atoms (eg, cyclohexane, cyclohexene, norbornane), a substituted or unsubstituted aromatic ring (eg, , Benzene ring, naphthalene ring), and a substituted or unsubstituted heterocycle (eg, imidazole ring, pyridine ring, pyrimidine ring, pyrazine ring) and the like.

The ring substituent capable of forming a condensed ring with the above cyclic amide includes a halogen atom (eg, chlorine atom, bromine atom), a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms (eg, methyl group, ethyl group). Group), a substituted or unsubstituted sulfamoyl group (eg, octylsulfamoyl group, diethylsulfamoyl group) and an alkoxy group having 1 to 8 carbon atoms (eg, methoxy group, ethoxy group, methoxyethoxy group), etc. Can be mentioned.

Among the compounds having the above cyclic amide structure, compounds having a pKa of amide hydrogen in the ring of 18 or less are preferable. Further, preferable compounds for the cyclic amide structure are shown by the following formulas (XVIII) to (XX).

[In the above formula (XVIII), X ¹ is an atomic group necessary for forming a 5-membered or 6-membered ring together with —CO—NH—CO— (the formed cyclic amide is different from another ring). It may form a condensed ring, and may be saturated or unsaturated)].

[In the above formula (XIX), X ² is an atom or an atomic group necessary for forming a 5-membered or 6-membered ring together with —CY ¹ ═N—NH—CO— (the formed cyclic amide is , May form a condensed ring with another ring, and may be saturated or unsaturated), and Y ¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, an alkoxy group. , A monovalent group selected from the group consisting of a halogen atom and a substituted or unsubstituted sulfamoyl group].

[In the above formula (XX), X ³ is an atomic group necessary for forming a 5-membered or 6-membered ring together with —CNY ² —NH—CO— (the formed cyclic amide is another ring. And may form a condensed ring,
It may be saturated or unsaturated), and Y ² is a monovalent group selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group and an alkoxy group].

Representative specific examples of compounds having a 5- or 6-membered cyclic amide structure, including the compounds represented by the above formulas (XVII) to (XX), are shown below.

(1) (2) (3) (Four) (Five) (6) (7) (8) (9) (Ten) (11) (12) (13) (14) (15) (16) (17) (18) (19) (20) (twenty one) (twenty two) (twenty three) (twenty four) (twenty five) (26) (27) (28) (29) (30) (31) (32) (33) (34) (35) (36) In the production method of the present invention, the compounds described above may be used alone or in combination of several kinds.

In the production method of the present invention, the above compound is used in the range of 0.001 to 10 mol% with respect to the total amount of silver used in the production (including silver halide described below and an organic silver salt which is an optional component). It is preferable. A more preferable range of use is 0.05 to 5 mol%.

In the method for producing a light-sensitive material of the present invention, silver halide is prepared as a silver halide emulsion. There are various methods known in the photographic art for preparing a halogenated emulsion, but the manufacturing method of the present invention is not particularly limited. The silver halide emulsion can be implemented by any of the acidic method, the neutral method and the ammonia method. As the reaction mode of the soluble silver salt and the soluble halogen salt, a one-sided mixing method,
Either a double jet method or a combination thereof may be used. Back-mixing method and pA for forming grains under silver ion excess conditions
A controlled double jet method that keeps g constant can also be adopted. Further, the silver halide emulsion may be a surface latent image type in which a latent image is mainly formed on the surface of a grain, or an internal latent image type in which a latent image is formed inside the grain. A direct reversal emulsion in which an internal latent image type emulsion and a nucleating agent are combined can also be used.

In the preparation of the above silver halide emulsion, the silver halide grains formed are not particularly limited. Any of silver chloride, silver bromide, silver iodide or silver chlorobromide, silver chloroiodide, silver iodobromide and silver chloroiodobromide can be used in the production method of the present invention. The halogen composition of the silver halide grains may be uniform or non-uniform on the surface and inside. In the present invention, the silver halide grains preferably have an average grain size of 0.001 μm to 10 μm,
Those having a thickness of 0.001 μm to 5 μm are particularly preferable. Two or more kinds of silver halides having different crystal habits, halogen compositions, grain sizes and the like can be used in combination. The amount of silver halide used in the production method of the present invention is in the range of 1 mg to 10 g per 1 m ² of the light-sensitive layer of the light-sensitive material to be produced, in terms of silver containing an organic silver salt which is an optional component described later. It is preferable.

In the preparation of the silver halide emulsion used for producing the light-sensitive material of the present invention, it is preferable to use a hydrophilic colloid as a protective colloid. By preparing a silver halide emulsion using a hydrophilic colloid, the sensitivity of a light-sensitive material produced using this emulsion is improved. The silver halide emulsion contains ammonia, an organic thioether derivative (see JP-B-47-386) and a sulfur-containing compound (see JP-A-53-144319) as a silver halide solvent in the step of forming silver halide grains. Etc. can be used. Further, in the process of grain formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt or the like may be allowed to coexist. Further, for the purpose of improving the high illuminance failure and the low illuminance failure, a water-soluble iridium salt such as iridium chloride (III valence or IV valence), hexachloroiridium ammonium salt, 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 without ripening, but it is usually chemically sensitized before use. In the emulsion for conventional type sensitizers, known sulfur sensitization method, reduction sensitization method, noble metal sensitization method, or a sensitization method using a sensitizing dye described in Japanese Patent Application No. 60-139746, which will be described later, is used alone or It can be used in combination.

The compound having a 5-membered or 6-membered nitrogen-containing heterocyclic structure of the present invention is added and used in the stage of preparing a silver halide emulsion as described above. The addition of the compound of the present invention to the silver halide emulsion is carried out at the same time as or before the step of forming or ripening the silver halide grains. That is, when ripening the silver halide grains, the ripening of the silver halide grains is performed at the same time as or after the addition of the compound of the present invention. When the ripening of the silver halide grains is not carried out, the silver halide grains are formed simultaneously with or after the addition of the compound of the present invention. When the compound of the present invention is added before the formation of silver halide grains, it can be used by adding it to either one of the salt solutions to be mixed.

As a method of adding the above compound to the silver halide emulsion,
Various methods can be used. For example, the above compound is a water-miscible organic solvent (eg, methanol, ethanol,
Acetone, dimethylform, etc.) or a mixed solution of these organic solvents and water, and the resulting solution can be added to the silver halide emulsion. It can also be added to the silver halide emulsion by an emulsion dispersion method (described in US Pat. No. 2322029) using an organic solvent having a high boiling point. Alternatively, a method of dispersing fine grains in a silver halide emulsion (described in JP-A-59-17830) can be used.

In the present invention, a light-sensitive material is manufactured using the silver halide emulsion prepared as described above. That is, by providing a photosensitive layer containing the silver halide, the compound, the reducing agent and the polymerizable compound on the support, the photosensitive layer containing the silver halide, the reducing agent, the polymerizable compound and the compound is provided on the support. A light-sensitive material having a layer is manufactured.

As the method for forming the photosensitive layer, various methods including known methods can be used. The general forming method is a coating liquid prepared by dissolving, emulsifying or dispersing the components of the photosensitive layer in a suitable solvent. Is prepared, and the coating solution is applied to a support and dried to form a photosensitive layer.

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

In the method for producing a light-sensitive material of the present invention, the polymerizable compound is
It can be used as a solvent when preparing a composition of other components in the photosensitive layer. For example, a silver halide (including a silver halide emulsion), a reducing agent or a color image-forming substance which is an optional component described later may be dissolved, emulsified or dispersed in a polymerizable compound to be used in the production of a light-sensitive material. it can. In particular, when a color image forming substance is contained in the photosensitive layer, it is preferable to include the color image forming substance in the polymerizable compound.

The photosensitive composition in which a polymerizable compound contains silver halide can be prepared using the silver halide emulsion described above. The photosensitive composition containing silver halide can be obtained by stirring a mixture of a silver halide emulsion and a polymerizable compound with a homogenizer, a blender, a mixer or other commonly used stirrers.

In addition, in the polymerizable compound used for the preparation of the photosensitive composition, it is preferable to dissolve a copolymer composed of a hydrophilic repeating unit and a hydrophobic group repeating unit. Regarding the photosensitive composition containing the above copolymer, Japanese Patent Application No.
No. 0-261887 and the photosensitive materials using the above copolymers are described in Japanese Patent Application No. 60-281888.

The polymerizable compound (including those containing other constituents such as the photosensitive composition) is preferably used as an emulsion emulsified in an aqueous solvent. Also, Japanese Patent Application Sho 60
When the oil droplets of the polymerizable compound are microencapsulated as in the light-sensitive material described in -117089, the wall material necessary for microencapsulation is added to this emulsion,
Further, it is preferable to carry out the treatment for forming the wall surface at the stage of this emulsion. Further, a reducing agent or other optional component may be added at the stage of the above emulsion.

Among the emulsions of the above-mentioned polymerizable compound, those in which the polymerizable compound is a photosensitive composition containing silver halide can be used as they are as a coating solution for a photosensitive material. Emulsions other than the above can be mixed with the composition of other components such as a silver halide emulsion and optionally an organic silver salt emulsion to prepare a coating solution. Other components may be added at the stage of this coating solution as in the case of the above emulsion.

The photosensitive material according to the present invention can be produced by applying the coating solution prepared as described above onto a support described later and drying it. The coating of the coating liquid on the support can be easily carried out according to known techniques.

Hereinafter, a reducing agent used in the method for producing a light-sensitive material of the present invention,
The polymerizable compound and the support will be sequentially described.

The reducing agent that can be used in the production method of the present invention has a function of reducing silver halide and / or a function of promoting 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-virazolones, 5-aminouracils, 4,5-Dihydroxy-6-aminopyrimidines, reductones, aminoreductones, o- or p-sulfonamidophenols, o- or p-sulfonamidonaphthols, 2-
Sulfonamide indanones, 4-sulfonamido-5
-Pyrazolones, 3-sulfonamidoindoles, sulfonamidepyrazolobenzimidazoles, sulfonamidepyrazolotriazoles, α-sulfonamidoketones, hydrazines and the like.

Regarding various reducing agents having the above functions, Japanese Patent Application Nos. 60-22980, 60-29894 and 60-
68874, 60-226084, 60-22
No. 7527 and No. 60-227528. Regarding the reducing agent, "The Theory of the Photographic Process" 4th edition by T. James,
291-334 (1977), Research Disclosure, Vol. 170, June 1978, 17029.
Issue (pages 9 to 15) and Vol.176, 1987, 1
It is also described in February 17643 (pages 22 to 31). Also in the production method of the present invention, the reducing agents (including those described as a developing agent or a hydrazine derivative) described in the above specifications and references can be effectively used. Therefore, the “reducing agent” in the present specification includes the reducing agents described in the above respective specifications and documents.

These reducing agents may be used alone or as a mixture of two or more reducing agents as described in the above specification. When two or more reducing agents are used in combination, the reducing agents may interact with each other by first promoting the reduction of silver halide (and / or organic silver salt) by so-called superadditivity. 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 Etc. are possible. 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- (N-phenylsulfamoyl) -4-hexadodecyloxy-5-octylphenol, 2- (N-phenylsulfamoyl) -4-
t-butyl-5-hexadodecyloxyphenol, 2
-(N-butylcarbamoyl) -4- (N-phenylsulfamoyl) naphthol, 2- (methyl-N-octadecylcarbamoyl) -4- (N-phenylsulfamoyl) naphthol, 1-acetyl-2-phenyl Hydrazine, 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 penta Decyl fluorocaprylate, 3-indazolinone, 1- (3,5-dichlorobenzoyl) -2-phenylhydrazine, 1-trityl-2
-[{2-N-butyl-N-octylsulfamoyl)
-4-Methanesulfonyl} phenyl] hydrazine, 1-
{4- (2,5-di-t-pentylphenoxy) butyroyl} -2-{(p or o) -methoxyphenyl} hydrazine, 1- (methoxycarbonylbenzohydryl)
-2-Phenylhydrazine, 1-formyl-2- [4-
{2- (2,4-di-t-pentylphenoxy) butylamido} phenyl] hydrazine, 1-acetyl-2-
[4- {2- (2,4-di-t-pentylphenoxy)
Butylamido} phenyl] hydrazine, 1-trityl-
2-[{2,6-dichloro-4- (N, N-di-2-ethylhexyl) carbamoyl} phenyl] hydrazine,
1- (methoxycarbonylbenzohydryl) -2-
(2,4-dichlorophenyl) hydrazine, and 1-
Examples thereof include trityl-2-[{2- (N-ethyl-N-octylsulfamoyl) -4-methanesulfonyl} phenyl] hydrazine.

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

The polymerizable compound that can be used in the production method of the present invention is not particularly limited, and known polymerizable compounds can be used.
When a heat development process is planned as a method of using the manufactured light-sensitive material, it is preferable to use a compound having a high boiling point (for example, a boiling point of 80 ° C. or higher) that is hard to volatilize during heating. When a color image-forming substance is used as an optional component of the photosensitive layer, the photosensitive material produced is intended to immobilize the color image-forming substance by polymerization of the polymerizable compound. A crosslinkable compound having a plurality of polymerizable functional groups in the molecule is preferable.

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

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

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

The polymerizable compounds may be used alone or in combination of two or more. It should be noted that 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 a color image forming substance which is an optional component described later can also be used as the polymerizable compound of the present invention. Needless to say, the use of a substance that serves as 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 aspect of the present invention.

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

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

In the production method of the present invention, a photosensitive layer containing a silver halide, a reducing agent, a polymerizable compound and a compound having a 5- or 6-membered nitrogen-containing heterocyclic structure as described above is provided on a support. There are no particular restrictions on this support,
When heat development processing is planned as a method of using the manufactured light-sensitive material, it is preferable to use a material that can withstand this processing temperature. 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.

With the light-sensitive material produced according to the present invention, a polymer image can be obtained by polymerizing the polymerizable compound with the above-mentioned constitution, but a light-sensitive material capable of forming a color image can also be produced. That is, by adding a color image forming substance as an optional component to the coating liquid, a photosensitive material in which the photosensitive layer further contains the color image forming substance can be produced. The color image-forming substance that can be used in the method for producing the light-sensitive material of the present invention 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 pale but is external (heat, pressure, light irradiation, etc.) or another component (developing agent) Substances that develop color by contact (color former)
Are also included in the color image forming substance. When a plurality of the color image-forming substances are used, they are combined with at least three kinds of silver halide emulsions (the silver halide emulsion will be described later) having photosensitivity in mutually different spectral regions,
A light-sensitive material capable of easily forming a color image can be produced by using each emulsion so as to correspond thereto. For examples of color image forming substances that can be used in the light-sensitive material, see Japanese Patent Application No. 59-19540.
There is a description in No. 7.

Dyes and pigments that 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 pigments 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, an oxidation-reduction reaction, a coupling reaction, a chelate formation reaction, etc. between two or more components. For example, pressure-sensitive copying paper (pages 29-58) and Azography (87-) described in "Introduction to Special Paper Chemistry" by Hiroyuki Moriga (published in 1975).
95), thermosensitive coloring due to chemical changes (118-120)
Page) and other well-known color development systems, or a seminar by Kinki Chemical Industry Association "Latest dye chemistry-Attractive utilization as a functional dye and new development-" Proceedings 26-32, (19
The coloring system described in June 19, 80) can be used. Specifically, a color-developing system composed of a colorant having a partial structure such as lactone, lactam, and spiropyran used for pressure-sensitive paper and an acidic substance (developing agent) such as acid clay or phenol; an aromatic diazonium salt or Diazotate, diazosulfonates and naphthols,
Systems utilizing azo coupling reactions of anilines and active methylenes; reactions of hexamethylenetetramine with ferric ions and gallic acid, reactions of phenolphthalein-complexones with alkaline earth metal ions, etc. Chelate forming reaction; a redox reaction such as a reaction between ferric stearate and pyrogallol or a reaction between silver behenate and 4-methoxy-1-naphthol can be used.

When using the color image-forming substance, in the production method of the present invention, the polymerizable compound contains a color image-forming substance,
Then, it is preferable to use a method of emulsifying the polymerizable compound in an aqueous solvent and preparing a coating liquid containing the emulsion of the polymerizable compound and a reducing agent. By using the above method, the polymerizable compound is dispersed in the photosensitive layer in the form of oil droplets, and among the components contained in the photosensitive layer, at least the color image-forming substance is present in the oil droplets of the polymerizable compound. It is possible to manufacture a photosensitive material having The oil droplets may contain other components in the photosensitive layer such as silver halide and a reducing agent. For an example of a photosensitive material in which the above polymerizable compound is dispersed in the photosensitive layer in the form of oil droplets, see Japanese Patent Application No. 60-1170.
89.

It is more preferable that the oil droplets of the polymerizable compound are produced in a microcapsule state by subjecting the emulsion of the polymerizable compound described above to microencapsulation. There are no particular restrictions on the microencapsulation method, and various known techniques can be applied. For an example of a light-sensitive material using microcapsules, Japanese Patent Application No. 60-11708.
There is a description in No. 9 specification.

As an example of the above-mentioned known technique, US Pat.
US Pat. No. 3,287,154 and British Patent No. 990443, and Japanese Patent Publication Nos. 38-19574 and 42. −
U.S. Pat. No. 3,418,250 and U.S. Pat. No. 3,603,603 described in U.S. Pat.
No. 04, a method by precipitation of the polymer described in US Pat. No. 4,967,691; isocyanates described in US Pat. No. 3,796,669.
Method using polyol wall material; US Pat. No. 39145.
A method using the isocyanate wall material described in No. 11; US Pat. Nos. 4,001,140 and 4,087,376.
And U.S. Pat. No. 4,089,802. Urea-formaldehyde-based or urea-formaldehyde-resilicinol-based wall forming materials; US Pat.
Method using a wall forming material such as melamine-formaldehyde resin and hydroxypropyl cellulose described in Japanese Patent No. 25455; JP-B-36-9163 and JP-A-51-51.
-9079 in sit by polymerization of monomers
u method; US Pat. Nos. 927,807 and 96,507.
No. 4, polymerization dispersion cooling method; US Pat. No. 311
1407 and British Patent No. 930422, the spray drying method etc. which are described can be mentioned. The microencapsulation method is not limited to the above, but a method of emulsifying the core substance and then forming a polymer film as the microcapsule wall is particularly preferable.

In the production method of the present invention, other optional components that can be contained in the photosensitive layer include sensitizing dyes, organic silver salts, various image forming accelerators (eg, bases or base precursors,
Oils, surfactants, thermal solvents, etc.), thermal polymerization inhibitors, thermal polymerization initiators, development terminators, fluorescent whitening agents, anti-fading agents, antihalation or irradiation dyes, matting agents, antismudge agents (eg. , Starch particles), plasticizers, water release agents, binders, etc.

Examples of sensitizing dyes that can be used in the production of light-sensitive materials are described in Japanese Patent Application No. 60-139746.
Examples of organic silver salts are described in Japanese Patent Application No. 60-141799. For a light-sensitive material using a base or a base precursor, see Japanese Patent Application No.
No. 227528, and a photographic material using a thermal polymerization initiator is described in Japanese Patent Application No. 60-223347. Further, a photosensitive material using a polyethylene glycol derivative as a heat solvent is described in the specification of "Photosensitive Material and Image Forming Method" filed on Dec. 2, 1985 (4) by the present applicant. Examples of other components and usage thereof are also described in the specification of the above-mentioned series of applications relating to the light-sensitive material and Research Disclosure Vol. 170, June 1978, No. 17029 (pages 9 to 15). is there.

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

In the method for producing a light-sensitive material of the present invention, the use of an organic silver salt is particularly effective when heat development processing is planned as a method for using the light-sensitive material. That is, when heated to a temperature of 80 ° C. or higher, the organic silver salt is considered to participate in the redox reaction using the latent image of silver halide as a catalyst. In this case, it is preferable that the silver halide and the organic silver salt are in contact with or in close proximity to each other. 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. Of these, penzotriazole is particularly preferred. The above organic silver salt is generally used in an amount of 0.01 to 10 moles, preferably 0.
01 to 1 mol is used. It should be noted that instead of the organic silver salt, an organic compound (for example, benzotriazole) that constitutes it is used.
The same effect can be obtained by adding to the photosensitive layer.

Various image forming accelerators can be used in the method for producing the light-sensitive material of the present invention. The image-forming accelerator includes a silver halide (and / or an organic silver salt) and a reducing agent, which promotes the redox reaction between the reducing agent and the redox agent, and from the light-sensitive material to the image-receiving material or image-receiving layer (which will be described later). It has functions such as promoting the movement of the forming substances. The image forming accelerator is a base or a base precursor, from the viewpoint of physicochemical function,
It is classified into oil, surfactant, hot solvent, etc. However,
These substance groups generally have a complex function, and usually have some of the above-mentioned accelerating effects together. Therefore, the above classification is convenient, and in reality, one compound often has a plurality of functions.

Examples of bases, base precursors, oils, surfactants and hot solvents are shown below.

Examples of preferable bases include alkali metal or alkaline earth metal hydroxides as inorganic bases, secondary or tertiary phosphates, borates, carbonates, quinolinates, metaborates; ammonium hydroxides. Quaternary alkylammonium hydroxide; 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, Examples thereof include cyclic guanidines, and those having a pKa of 8 or more are particularly preferable.

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

The base or the base precursor can be used in a wide range of amount in the method for producing the light-sensitive material of the present invention. The base or base precursor is suitably used in an amount of 50% by weight or less, more preferably 0.01% by weight to 40% by weight in terms of the coating film of the photosensitive layer to be produced. In the present invention, the base and / or the base precursor may be used alone or as a mixture of two or more kinds.

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

Examples of the surfactant include pyridinium salts, ammonium salts, phosphonium salts described in Japanese Patent Application No. 59-74547 and polyalkylene oxides described in Japanese Patent Application No. 59-57231.

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

The thermal polymerization initiator that can be used in the method for producing the light-sensitive material of the present invention is generally a compound that thermally decomposes under heating to generate a polymerization initiation species (particularly a radical), and is usually used as an initiator for radical polymerization. There is something. Regarding the thermal polymerization initiator, "Additional Polymerization / Ring-Opening Polymerization" edited by Editorial Committee for Polymer Experiments, Polymer Society of Japan, 1983, Kyoritsu Shuppan), No. 6
Pages to page 18 and the like. Specific examples of the thermal polymerization initiator include azbisisobutyronitrile and 1,1′-
Azo compounds such as azobis (1-cyclohexanecarbonitrile), dimethyl-2,2′azobisisobutyrate, 2,2-azobis (2-methylbutyronitrile) and azobisdimethyldimethylvaleronitrile, benzoyl peroxide,
Di-t-peroxide, dicumyl peroxide, t
Examples thereof include organic peroxides such as -butylhydroperoxide and cumene hydroperoxide, and inorganic peroxides such as sodium p-toluenesulfinate, hydrogen peroxide, potassium persulfate and ammonium persulfate. By using the above thermal polymerization initiator and adjusting the amount of the reducing agent, etc., the polymerizability of either the portion where the latent image of silver halide is formed or the portion where the latent image is not formed is polymerized. It is also possible to produce a light-sensitive material capable of polymerizing a compound. The thermal polymerization initiator is preferably used in the range of 0.1 to 120% by weight, more preferably 1 to 10% by weight, based on the polymerizable compound.

The development terminator that can be used in the method for producing a light-sensitive material of the present invention is a compound or silver that, after proper development, rapidly neutralizes or reacts with a base to lower the concentration of the base in the film and stop development. It is a compound that interacts with a silver salt to suppress 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 are Japanese Patent Application Nos. 58-216928 and 59-48305.
No. 59-8, oxime esters described in each specification
Examples thereof include compounds that release an acid by the Rossen rearrangement described in Japanese Patent No. 5834, and electrophilic compounds that undergo a substitution reaction with a base upon heating include, for example, Japanese Patent Application No. 59-85836.
Examples thereof include the compounds described in the specification.

The binder that can be used in the method for producing the light-sensitive material of the present invention and in the production of the image-receiving material described later can be contained in the light-sensitive layer or the image-receiving layer (described later) 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 proteins such as gelatin, gelatin derivatives, and cellulose derivatives, natural substances such as starch and polysaccharides such as arabic gum, polyvinyl alcohol, and polyvinyl alcohol. Includes synthetic polymeric materials such as water soluble polyvinyl compounds such as pyrrolidone, acrylamide polymers. Other synthetic polymeric materials include disperse vinyl compounds in the form of latices, which in particular increase the dimensional stability of photographic materials.

Examples of layers that can be optionally provided in the light-sensitive material produced according to the present invention include an image-receiving layer, a heating element layer, a protective layer, an antistatic layer, an anti-curl layer, a peeling layer, and a matting agent layer. .

The light-sensitive material produced according to the present invention can form an image by transferring the color image-forming substance to the image-receiving material in the embodiment in which the light-sensitive layer contains the color image-forming substance. The image receiving material comprises an image receiving layer having a function of fixing a color image forming substance released from the light sensitive material, and a support. Instead of using the image-receiving material, the image-receiving layer can be coated on the support common to the photosensitive layer as an optional layer of the photosensitive material as described above.

The image-receiving layer can be configured in various forms using various compounds according to the color-forming system of the color image-forming substance described above. 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 composed of at least one layer containing a mordant. The mordant 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 mordants having different mordant strengths may be used to form the image receiving element with two or more image receiving layers. When the image receiving layer is located on the surface of the light-sensitive material or the image receiving material, it is preferable to further provide a protective layer.

An example of an image receiving material that can be used together with a light-sensitive material and an image-receiving layer that can be provided in the light-sensitive material are described in Japanese Patent Application No. 60-212284, and a light-sensitive material using a heating element layer is Japanese Patent Application No. -135568, respectively. In addition, examples of other auxiliary layers and usage modes thereof are also described in the specification of the above-mentioned series of photosensitive materials.

Regarding the method of using the light-sensitive material produced according to the present invention,
This will be described below.

The light-sensitive material is used after being subjected to a polymerization treatment at the same time as the imagewise exposure or after the imagewise exposure.

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

The light-sensitive material produced according to the present invention is disclosed in JP-B-45-11.
By performing the development treatment using the liquid described in JP-A-149, etc., the polymerizable compound in the portion where the latent image exists can be polymerized. In addition, the method described in Japanese Patent Application No. 59-191353, which performs the polymerization treatment by heating as described above, has a merit that the operation is simple and the treatment can be performed in a short time because it is a dry treatment. There is. therefore,
The method of using the light-sensitive material produced according to the present invention,
The latter is particularly preferred.

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

The light-sensitive material produced according to the present invention as described above,
A polymer image can be obtained. Further, a dye or a pigment may be fixed to the polymer to obtain a dye image.

The light-sensitive material produced according to the present invention, in an embodiment using a color image-forming substance, is subjected to the polymerization and curing treatment of the polymerizable compound as described above, thereby immobilizing the color image-forming substance in the cured portion, and then the cured portion. The color image forming substance in the uncured portion can be transferred to the image receiving material by pressurizing the image receiving material in a state of being superimposed on the photosensitive material on which the color image forming substance is immobilized. Various conventionally known methods can be used for the pressing means. An image forming method using an image receiving element such as an image receiving material is described in the above-mentioned Japanese Patent Application No. 60-112284.

The light-sensitive material produced according to the present invention includes black-and-white or color image-sensing and printing light-sensitive materials, printing light-sensitive materials, printing plates, X-ray light-sensitive materials, medical light-sensitive materials (for example, ultrasonic diagnostic machine CRT imaging light-sensitive materials), computers. Graphic hard copy material
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] Preparation of silver chlorobromide emulsion containing 2-mercaptobenzimidazole Aqueous gelatin solution (gelatin 2 in 1000 ml of water was stirred).
0 g and 3 g of sodium chloride kept at 75 ° C), 21 g of sodium chloride and 35 g of sodium bromide
(A) in which 600 ml of water is dissolved and 100 g of silver nitrate
The solution (B) in which 600 ml of water was dissolved was added simultaneously at an equal flow rate over 40 minutes.

At the time of the above addition, a solution prepared by dissolving 1.3 g of 2-mercaptobenzimidazole in 150 ml of methanol was added at an equal flow rate for 40 minutes from 1 minute after the start of addition of the solutions (A) and (B). After washing the above emulsion with water and desalting,
Was adjusted to 6.4. The yield of emulsion was 600 g.

Preparation of benzotriazole silver emulsion 28 g of gelatin and 13.2 g of benzotriazole were added to 3 parts of water.
Dissolved in 000 ml. This solution was stirred while maintaining the temperature at 40 ° C., and a solution prepared by dissolving 17 g of silver nitrate in 100 ml of water was added over 2 minutes. By adjusting the pH of the resulting emulsion,
Excess salt was precipitated and removed. Thereafter, the pH was adjusted to 6.30 to obtain a benzotriazole silver emulsion. Emulsion yield is 4
It was 00 g.

Preparation of Emulsion of Polymerizable Compound To a mixture of 28 g of trimethylolpropane triacrylate and methyl methacrylate, 1 g of Pergascript Red I-6-B (manufactured by Ciba Geigy Co., Ltd.) dissolved in 6 g of methylene chloride was added. The above mixture was stirred and mixed in 60 g of a 10% aqueous polyvinyl alcohol solution containing 0.5 g of sodium dodecylbenzenesulfonate, and then emulsified and dispersed at 18,000 rpm for 5 minutes with a homogenizer. Thus, an emulsion of a polymerizable compound having an average particle size of 0.5 μm was prepared.

Preparation of Photosensitive Material 3.7 g of a silver chlorobromide emulsion containing 2-mercaptobenzimidazole, 4 g of a benzotriazole silver emulsion, and 5 g of a polymerizable compound emulsion prepared as described above were further added to a 10% polyvinyl alcohol aqueous solution. Add 2 g and starch 0.5 g and mix, then para-acinophenol 0.0
2 g and β-acetylphenylhydrazine 0.04 g
What was dissolved in 1 ml of methanol was added and mixed to prepare a coating solution. This coating solution was applied onto a polyethylene terephthalate film so as to have a wet film thickness of 20 μm and dried to prepare a light-sensitive material (A) according to the present invention.

[Comparative Example 1] Preparation of silver chlorobromide emulsion Aqueous gelatin solution (gelatin 2 in 1000 ml of water was stirred).
0 g and 3 g of sodium chloride kept at 75 ° C), 21 g of sodium chloride and 35 g of sodium bromide
Aqueous solution containing 600ml and silver nitrate aqueous solution (water 600ml
40% simultaneously dissolved in 0.59 mol of silver nitrate)
Added at equal flow rate over minutes. The above emulsion was washed with water and desalted, and then the pH was adjusted to 6.4. The yield of emulsion was 600 g. Thus, a monodisperse cubic silver chlorobromide emulsion (bromine 80 mol%) having an average grain size of 0.35 μm was prepared.

Preparation of Photosensitive Material A silver chlorobromide emulsion 3.7 containing 2-mercaptobenzimidazole was added to 3.7 g of the silver chlorobromide emulsion prepared as described above.
Comparative Photosensitive Material (B) was prepared in the same manner as in Example 1 except that 0.01 g of 2-mercaptobenzimidazole dissolved in 1 ml of methanol was added to the coating solution. did.

Comparative Example 2 Preparation of Light-Sensitive Material The silver chlorobromide emulsion 3.7 g used in Comparative Example 1 was added to 2-
Silver chlorobromide emulsion containing mercaptobenzimidazole 3.
A comparative photosensitive material (C) was prepared in the same manner as in Example 1 except that 7 g was used.

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 further dispersed with a Dynamill disperser to obtain 200
To 50 g, 6 g of 50% SBR latex and 55 g of 8% polyvinyl alcohol were added and mixed uniformly.

30 μm of this mixed solution on 43 g / m ² art paper
After uniformly coating so as to have a wet film thickness, the image receiving material was prepared by drying.

Evaluation of Photosensitive Material The photosensitive material (A) obtained in Example 1 and the photosensitive materials (B) and (C) obtained in Comparative Examples 1 and 2 were imagewise exposed and then heated at 125 ° C. for 40 seconds. .

Then, the light-sensitive material and the image-receiving material are overlaid on each other to 200
When it was passed through a kg / cm ² pressure roller, a sharp magenta positive image having gradation corresponding to the unexposed area was obtained on the image receiving element. The image density at this time was measured using a Macbeth reflection densitometer (RD519).

The above measurement results are shown in Table 1.

As is clear from the above results, the light-sensitive material (A) produced according to the present invention can obtain a clearer image having a low minimum density while maintaining the maximum density value.

Example 2 Example 1 was repeated except that the following compounds (75) and (76) were used in equimolar amounts instead of 2-mercaptobenzimidazole used in the preparation of the silver chlorobromide emulsion of Example 1. Similarly, the light-sensitive materials (A2) and (A3) according to the present invention were produced.

(75) (76) The prepared silver halide emulsion was subjected to centrifugal sedimentation, and the amounts of the compounds (75) and (76) contained in the supernatant were quantified, whereby the compounds (75) and (76) were
It was confirmed that all were adsorbed on the silver halide grains.

[Comparative Example 3] Instead of the 2-mercaptobenzimidazole used in the preparation of the photosensitive material of Comparative Example 1, the above compound (7
Comparative Example 1 except that 5) and (76) were used in equimolar amounts
In the same manner as in Comparative Photosensitive Materials (B2) and (B
3) was produced.

Was manufactured.

Each of the light-sensitive materials obtained in Example 2 and Comparative Example 3 was processed in the same manner as in Example 1, Comparative Examples 1 and 2 to form an image on the image-receiving material. The density of the obtained image was measured using a Macbeth reflection densitometer. The results are shown in Table 2.

Claims (3)

[Claims] 1. A 5-membered nitrogen-containing heterocyclic structure selected from the group consisting of a diazole ring, a triazole ring and a tetrazole ring (a benzene ring or a naphthalene ring may be fused to the diazole ring and the triazole ring). Having, in the presence of a compound having at least one of the carbon atoms constituting the nitrogen-containing heterocyclic structure having a thiol group,
The formation or ripening of silver halide grains is carried out to obtain a silver halide emulsion in which the above compound is adsorbed on the silver halide grain, and a light-sensitive material containing the above silver halide emulsion, a reducing agent and a polymerizable compound. A method for producing a photosensitive material having a photosensitive layer on a support, which comprises applying the coating liquid on the support. 2. The photosensitive material according to claim 1, wherein the compound having a 5- or 6-membered nitrogen-containing heterocyclic structure is used in the range of 0.001 to 10 mol% with respect to silver halide. Material manufacturing method. 3. The photosensitive material according to claim 2, wherein the compound having a 5- or 6-membered nitrogen-containing heterocyclic structure is used in the range of 0.005 to 5 mol% with respect to silver halide. Material manufacturing method.