JPH11184055A - Image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an image forming method applicable to the conventional silver halide color photographic sensitive material for photographing superior in storage stability with the lapse of time and the good image forming easy method. SOLUTION: The silver halide color photographic sensitive material contains a coupler and silver halide and a binder on a support and it is imagewise exposed and processed with a developing solution containing a color developing agent and then, processed by overlaying the fixing material on the photosensitive layer so as to oppose the photosensitive layer of the photosensitive material to the fixing layer of the fixing material, and a color image is formed by dissolving a part or the total part of the silver halide.

Description

DETAILED DESCRIPTION OF THE INVENTION

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BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming method using a silver halide color photographic light-sensitive material for photographing. The present invention relates to a simple and good image forming method using a silver halide color photographic light-sensitive material for photography, which has excellent stability over time of the material.

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2. Description of the Related Art In a silver halide color photographic light-sensitive material, a latent image formed on the surface of the silver halide by exposure is reduced to silver during a developing process to form an image. Undeveloped silver halide and developed silver are removed in a bleach-fixing step subsequent to a developing step, and a color photographic material from which a negative image can be obtained can obtain a dye image by using a coupler. The color print is obtained by projecting the color negative, exposing the print photosensitive material, and performing the same developing and fixing / bleaching steps. As described above, the usual wet development, bleaching, and fixing processes are complicated, and wastewater treatment of each processing solution is required.
The load is large from an environmental point of view. Further, in recent years, with the spread of personal computers, information on a color negative film is photoelectrically read and used as a digital signal as a new storage method of a negative film and for processing image information. However, there is a problem that it takes a long time to obtain the image because it must be read by a scanner after being developed once in a photo store.

On the other hand, as a processing method of a photosensitive material using silver halide, a simple and quick method using heat development has been developed. Examples of such products include 3M Dry Silver, Fuji Photo Film Co., Ltd.'s Pictography, and Pictrostat. However, these are black-and-white or color print materials, and there has been no known photosensitive material for photography by thermal development. These heat-developable light-sensitive materials have a built-in developing agent, so that it is hard to say that the storage stability is good. Therefore, it is preferable not to incorporate a developing agent into the photosensitive material for photographing, that is, the color film, and it is desired that a digital image signal can be obtained by simpler processing.

Although an image formed on a light-sensitive material is relatively stable without additional development stop processing, image information is photoelectrically obtained without fixing processing and with silver halide remaining. When reading, there is a problem that the remaining silver halide raises the haze, etc., and the light diffusion becomes noise, degrading the information. Even if it is attempted to reproduce the image from the information obtained as it is, the deterioration of the image quality such as sharpness and graininess Is remarkable.

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SUMMARY OF THE INVENTION Accordingly, the object of the present invention can be applied to conventional silver halide color photographic light-sensitive materials for photography, and the silver halide color photographic light-sensitive material for photography has excellent temporal stability. An object of the present invention is to provide a simple and good image forming method using a silver halide color photographic light-sensitive material for photography.

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[Means for Solving the Problems] A silver halide photographic light-sensitive material containing a coupler, silver halide and a binder is provided on a support, and a developer containing a color developing agent is applied after imagewise exposure to form a dye image. An image forming method comprising forming a dye image by dissolving a part or all of silver halide by performing a superposing process in such a manner that a fixing layer and a fixing layer face each other.

[0007] 2. A silver halide photographic material containing a coupler, silver halide and a binder on a support,
After imagewise exposure, a developer containing a color developing agent is provided to form a dye image, and then a photosensitive material and a fixing material are overlapped with each other so that the photosensitive layer and the fixing layer face each other. An image forming method comprising: forming a dye image by dissolving a colorant; optically or electrically converting the image information to obtain the image information; and then obtaining a color image on another recording material.

[0008] 3. A silver halide photographic material containing a coupler, silver halide and a binder on a support,
After imagewise exposure, a developing solution containing a color developing agent is applied to form a dye image, and then a photosensitive material and a fixing material are superposed on each other so that the photosensitive layer and the fixing layer face each other. 3. The image forming method according to 1 or 2, wherein a dye image is formed by dissolving part or all of silver halide.

4. A silver halide photographic material containing a coupler, silver halide and a binder on a support,
After forming a dye image by providing a developer containing a color developing agent after imagewise exposure, a photosensitive material and a fixing material are superposed on each other with the photosensitive layer and the fixing layer facing each other, and processed at 40 ° C to 100 ° C. A dye image is formed by dissolving part or all of silver halide, the image information is converted optically or electrically to obtain image information, and then a color image is obtained on another recording material. Image forming method.

[0010] 5. The total amount of silver halide contained in the silver halide photographic light-sensitive material before the development processing is 0.7 to 3.5 g.
/ M ² , the image forming method according to 1, 2, 3 or 4.

That is, in the present invention, the haze and the like can be reduced by dissolving a part or all of the residual silver halide using the fixing material, and the noise at the time of reading an image can be successfully reduced. Thus, it is possible to provide a simple and good image forming method which is excellent in stability over time of a photosensitive material.

Hereinafter, the present invention will be described in detail.

The coupler preferably used in the present invention will be described.

As couplers preferably used in the present invention, there are compounds having structures represented by the following general formulas (1) to (12). These are compounds generally referred to as active methylene, pyrazolone, pyrazoloazole, phenol, naphthol, and pyrrolotriazole, respectively, and are compounds known in the art.

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Formulas (1) to (4) represent couplers referred to as active methylene couplers, wherein R ¹⁴ represents an optionally substituted acyl, cyano, nitro or aryl group. , A heterocyclic group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, and an arylsulfonyl group.

In the general formulas (1) to (3), R ¹⁵ is an optionally substituted alkyl group, aryl group or heterocyclic group. In the general formula (4), R ¹⁶ is an aryl group or a heterocyclic group which may have a substituent.

Examples of the substituent which R ¹⁴ , R ¹⁵ and R ¹⁶ may have include, for example, a linear or branched chain or cyclic alkyl group having 1 to 50 carbon atoms (for example, methyl, ethyl, Propyl, isopropyl, butyl, t-butyl, t
-Amyl, cyclopentyl, cyclohexyl, octyl, 2-ethylhexyl, dodecyl, trifluoromethyl, heptafluoropropyl and the like, a linear or branched linear or cyclic alkenyl group having 2 to 50 carbon atoms (for example, vinyl, 1-methyl Vinyl, cyclohexen-1-yl, etc.), an alkynyl group having a total of 2 to 50 carbon atoms (eg, ethynyl, 1-propynyl, etc.), an aryl group having a carbon number of 6 to 50 (eg, phenyl, naphthyl, anthryl, etc.), carbon An acyloxy group having a number of 1 to 50 (for example, acetoxy,
A carbamoyloxy group having 1 to 50 carbon atoms (e.g., N, N-
Dimethylcarbamoyloxy, etc.), a carbonamide group having 1 to 50 carbon atoms (for example, formamide, N-methylformamide, acetamide, N-methylacetamide,
Benzamide), a sulfonamide group having 1 to 50 carbon atoms (eg, methanesulfonamide, dodecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, etc.), a carbamoyl group having 1 to 50 carbon atoms (eg, N-methyl) Carbamoyl, N, N-diethylcarbamoyl, N-mesylcarbamoyl, etc.), having 0 to 50 carbon atoms
(E.g., N-butylsulfamoyl, N, N-diethylsulfamoyl, etc.) having 1 to 1 carbon atoms
50 alkoxy groups (e.g., methoxy, propoxy, isopropoxy, octyloxy, t-octyloxy,
Dodecyloxy, etc.), an aryloxy group having 6 to 50 carbon atoms (eg, phenoxy, 4-methoxyphenoxy, naphthoxy, etc.), an aryloxycarbonyl group having 7 to 50 carbon atoms (eg, phenoxycarbonyl, naphthoxycarbonyl, etc.), carbon A C2-50 alkoxycarbonyl group (e.g., methoxycarbonyl, t-butoxycarbonyl, etc.), a C1-C50 N-acylsulfamoyl group (e.g., N-tetradecanoylsulfamoyl, N-
Benzoylsulfamoyl, etc.), an alkylsulfonyl group having 1 to 20 carbon atoms (eg, methanesulfonyl, octanesulfonyl, etc.), an arylsulfonyl group having 6 to 50 carbon atoms (eg, benzenesulfonyl, p-toluenesulfonyl, etc.), carbon An alkoxycarbonylamino group having 2 to 50 carbon atoms (e.g., ethoxycarbonylamino); an aryloxycarbonylamino group having 7 to 50 carbon atoms (e.g., phenoxycarbonylamino, naphthoxycarbonylamino); Groups (for example, amino, methylamino, diethylamino, diisopropylamino, anilino, etc.), cyano group, nitro group, carboxy group, hydroxy group, sulfo group, mercapto group, carbon number 1
Alkylsulfinyl group (e.g., methanesulfinyl, octanesulfinyl, etc.) having 6 to 50 carbon atoms
Arylsulfinyl group (e.g., benzenesulfinyl, p-toluenesulfinyl, etc.) having 1 to 50 carbon atoms
Alkylthio group (e.g., methylthio, octylthio, etc.), acylthio group (e.g., acetylthio group, etc.) having 2 to 50 carbon atoms, arylthio group having 6 to 50 carbon atoms (e.g., phenylthio, naphthylthio, etc.), 1 to 50 carbon atoms
Ureido group (eg, 3-methylureido, 3,3-
Dimethylureide, 1,3-diphenylureide, etc.),
A heterocyclic group having 2 to 50 carbon atoms (as a hetero atom, for example, containing at least one or more of nitrogen, oxygen and sulfur,
A 3- to 12-membered monocyclic or condensed ring, for example, 2-furyl,
2-pyranyl, 2-thienyl, 2-pyridyl, 2-imidazolyl, 4-morpholyl, 2-quinolyl, etc.), an acyl group having 1 to 50 carbon atoms (eg, acetyl, benzoyl, etc.), a sulfone having 1 to 50 carbon atoms. A famoylamino group (eg, N-butylsulfamoylamino, N-phenylsulfamoylamino, etc.), a silyl group having 3 to 50 carbon atoms (eg, trimethylsilyl, dimethyl-t-butylsilyl, triphenylsilyl, etc.), Examples include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and the like).

In the general formulas (1) to (4), Y is a hydrogen atom or a group which can be removed by a coupling reaction with an oxidized developing agent. Examples of Y include a carboxy group, a formyl group, a halogen atom (for example, chlorine, bromine, iodine), a carbamoyl group, a methylene group having a substituent (for the substituent, an aryl group, a sulfamoyl group, a carbamoyl group, an alkoxy group, Amino group, hydroxy group, etc.), acyl group, sulfo group and the like. In this,
As described above, Y is preferably a hydrogen atom.

In the general formulas (1) to (4), R ¹⁴ and R
¹⁵ , R ¹⁴ and R ¹⁶ may combine with each other to form a ring.

Formula (5) represents a coupler called a 5-pyrazolone-based coupler, wherein R ¹⁷ is an alkyl group,
Represents an aryl group, an acyl group or a carbamoyl group. R ¹⁸
Represents a phenyl group or a phenyl group substituted by one or more halogen atoms, alkyl groups, cyano groups, alkoxy groups, alkoxycarbonyl groups or acylamino groups.

Among the 5-pyrazolone couplers represented by the general formula (5), R ¹⁷ is an aryl group or an acyl group, and R ^{18 is}
Is preferably a phenyl group substituted by one or more halogen atoms.

To describe these preferred groups in detail, R ¹⁷ is a phenyl group, a 2-chlorophenyl group, a 2-methoxyphenyl group, a 2-chloro-5-tetradecanamidophenyl group, a 2-chloro-5- (3-octadecenyl) group. -1-succinimide) phenyl group, 2-chloro-5-
An aryl group such as an octadecylsulfonamidophenyl group or a 2-chloro-5- [2- (4-hydroxy-3-t-butylphenoxy) tetradecanamido] phenyl group, or an acetyl group, 2- (2,4-di- t-pentylphenoxy) butanoyl group, benzoyl group, 3- (2,
Acyl groups such as 4-di-t-amylphenoxyacetamido) benzoyl group, and these groups may further have a substituent, and these groups may be an organic group linked by a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom. It is a substituent or a halogen atom. Y has the same meaning as described above.

R ¹⁸ is preferably a substituted phenyl group such as a 2,4,6-trichlorophenyl group, a 2,5-dichlorophenyl group and a 2-chlorophenyl group.

The general formula (6) represents a coupler called a pyrazoloazole coupler, wherein R ¹⁹ represents a hydrogen atom or a substituent. Q ³ represents a nonmetallic atom group necessary for forming a 5-membered azole ring containing 2 to 4 nitrogen atoms,
The azole ring may have a substituent (including a condensed ring).

Among the pyrazoloazole couplers represented by the general formula (6), the imidazo [1,1] described in US Pat. No. 4,500,630 in terms of the spectral absorption characteristics of the coloring dye.
2-b] pyrazoles, U.S. Pat. No. 4,500,654
[1,5-b] -1,2,4-triazoles described in US Pat. No. 3,725,067, and pyrazolo [5,1-c] -1,2,4-triazole described in US Pat. No. 3,725,067. Are preferred.

For details of the azole ring substituents represented by the substituents R ¹⁹ and Q ³ , see, for example, US Pat.
No. 0,654, column 2, line 41 to column 8, No. 27. Preferably, JP-A-61-
No. 65245, a pyrazoloazole coupler in which a branched alkyl group is directly bonded to the 2, 3 or 6 position of a pyrazolotriazole group, and a sulfonamide group in the molecule described in JP-A-61-65245. A pyrazole coupler having an alkoxyphenylsulfonamide ballast group described in JP-A-61-147254;
No. 457 or 63-307453, pyrazolotriazole couplers having an alkoxy group or an aryloxy group at the 6-position, and Japanese Patent Application No. 1-222279.
Pyrazolotriazole couplers having an intramolecular carboxamide group described in the above item. Y has the same meaning as described above.

The general formulas (7) and (8) are couplers referred to as phenol couplers and naphthol couplers, respectively, wherein R ²⁰ is a hydrogen atom or —CONR ²² R ²³ ,
_{^{-SO 2 NR 22 R 23, -NHCOR}} 22, -NHCONR
²² R ²³ represents a group selected from —NHSO ₂ NR ²² R ²³ . R ²² and R ²³ represent a hydrogen atom or a substituent. In the general formulas (7) and (8), R ²¹ represents a substituent, and k is 0
And m represents an integer selected from 0 to 4. When k and m are 2 or more, R ²¹ may be different from each other. As the substituents of R ^{21 to} R ²³ , R ^{14 to} R
Examples of the ¹⁶ substituents include those described above. Y has the same meaning as described above.

Preferred examples of the phenolic coupler represented by the general formula (7) include US Pat. No. 2,369,9.
No. 29, No. 2,801,171, No. 2,772
No. 162, No. 2,895,826, No. 3,77
2,002 and the like, 2-acylamino-5-alkylphenols, U.S. Pat. Nos. 2,772,162, 3,758,308, 4,126,396;
Nos. 4,334,011, 4,327,173
No. 3,329,729, West German Patent Publication No.
2,166-9656, 2,5-diacylaminophenol, U.S. Pat. Nos. 3,446,622, 4,333,999, 4,451,559, and 4,427, No. 767, etc., and 2-phenylureido-5-acylaminophenols. Y is the same as described above.

Preferred examples of the naphthol coupler represented by the general formula (8) include US Pat. No. 2,474,29.
No. 3, 4,052, 212 and 4,146, 3
No. 96, No. 4,282,233, No. 4,296,
No. 200, etc., and 2-carbamoyl-1-naphthols described in US Pat. No. 4,690,889 and the like.
Carbamoyl-5-amide-1-naphthol and the like can be mentioned. Y is the same as described above.

Formulas (9) to (12) are couplers called pyrrolotriazoles, and R ³² , R ³³ and R ³⁴ represent a hydrogen atom or a substituent. Y is as described above. ^Examples of the substituent of R ³² , R ³³ and R ³⁴ include the aforementioned R ¹⁴
Those mentioned as examples of the substituent to R ¹⁶ can be mentioned. Preferred examples of the pyrrolotriazole-based couplers represented by the general formulas (9) to (12) include EP 488,2.
No. 48A1, No. 491, 197A1, No. 545
No. 300 includes a coupler in which at least one of R ³² and R ³³ is an electron-withdrawing group. Y is the same as described above.

In addition, couplers having structures such as condensed phenol, imidazole, pyrrole, 3-hydroxypyridine, active methylene, active methine, 5,5-condensed heterocycle, and 5,6-condensed heterocycle can be used.

US Pat. Nos. 4,327,173 and 4,564,586 disclose fused ring phenol couplers.
And the couplers described in JP-A Nos. 4,904,575 and the like can be used.

As the imidazole coupler, couplers described in US Pat. Nos. 4,818,672 and 5,051,347 can be used.

As the 3-hydroxypyridine-based coupler, couplers described in JP-A-1-315736 can be used.

Active methylene and active methine couplers are described in US Pat. Nos. 5,104,783 and 5,16.
The couplers described in 2,196 and the like can be used.

As the 5,5-fused heterocyclic coupler,
Pyrrolopyrazole couplers described in U.S. Pat. No. 5,164,289, pyrroloimidazole couplers described in JP-A-4-174429, and the like can be used.

As the 5,6-fused heterocyclic coupler,
Pyrazolopyrimidine couplers described in U.S. Pat. No. 4,950,585, pyrrolotriazine couplers described in JP-A-4-204730, EP 556,700.
And the like.

In the present invention, in addition to the couplers described above, West German Patent Nos. 3,189,051A and 3,823,049.
No. 4,840,883, US Pat.
No. 4,930, No. 5,051,347, No. 4,4
No. 81,268, European Patent Nos. 304,856A2, 329,036, 354,549A2, 374,781A2, 379,110A2, 386,930A1, 63-141055
Nos. 64-32260, 64-32261, JP-A-2-29747, JP-A-2-44340, and 2-
No. 110555, No. 3-7938, No. 3-16044
No. 0, No. 3-172839, No. 4-17247,
4-179949, 4-182645, 4-
Nos. 184437, 4-188138, 4-188
No. 139, No. 4-194847, No. 4-204532
And the couplers described in JP-A Nos. 4-207473 and 4-204732 can also be used.

Specific examples of the coupler usable in the present invention are shown below, but the present invention is of course not limited thereto.

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The amount of the coupler used in the present invention depends on its molar extinction coefficient (ε), but in order to obtain an image density of 1.0 or more in reflection density, ε of the dye formed by coupling is required. Is about 5000 to 500000, the coating amount is 0.001 to 100 mmol / m
² , preferably from 0.01 to 10 mmol / m ² , more preferably from 0.05 to 5 mmol / m ² .

In the present invention, an auxiliary developing agent can be preferably used. Here, the auxiliary developing agent means a substance having an action of promoting the transfer of electrons from the color developing agent to silver halide in the development process of silver halide development, and the auxiliary developing agent in the present invention is preferably a compound of the general formula It is an electron-emitting compound according to the Kendall-Peltz rule represented by (B-1) or the general formula (B-2). Among them, those represented by (B-1) are particularly preferred.

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In the general formulas (B-1) and (B-2),
R ^{51 to} R ⁵⁴ represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, or a heterocyclic group.

R ^{55 to} R ⁵⁹ are a hydrogen atom, a halogen atom, a cyano group, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, a cycloalkyloxy group, an aryloxy group, a heterocyclic oxy group. Group, silyloxy group, acyloxy group, amino group, anilino group, heterocyclic amino group, alkylthio group, arylthio group, heterocyclic thio group, silyl group, hydroxyl group,
Nitro group, alkoxycarbonyloxy group, cycloalkyloxycarbonyloxy group, aryloxycarbonyloxy group, carbamoyloxy group, sulfamoyloxy group, alkanesulfonyloxy group, arenesulfonyloxy group, acyl group, alkoxycarbonyl group,
Cycloalkyloxycarbonyl group, aryloxycarbonyl group, carbamoyl group, carbonamide group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide group,
Represents a sulfamoylamino group, an alkylsulfinyl group, an arenesulfinyl group, an alkanesulfonyl group, an arenesulfonyl group, a sulfamoyl group, a sulfo group, a phosphinoyl group, and a phosphinoylamino group.

Q represents an integer of 0 to 5, and when q is 2 or more, R ⁵⁵ may be different from each other. R ⁶⁰ represents an alkyl group or an aryl group.

Specific examples of the compound represented by formula (B-1) or (B-2) are shown below, but the auxiliary developing agent used in the present invention is not limited to these specific examples.

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The light-sensitive material of the present invention is basically a material having a light-sensitive silver halide, a coupler, and a binder on a support, and these components are often added to the same layer, but are reactive. If it is in a state, it can be added in separate layers.

The hydrophobic additive such as a coupler used in the present invention can be introduced into a layer of a light-sensitive material by a known method such as the method described in US Pat. No. 2,322,027. In this case, US Pat. No. 4,555,470
No. 4,536,466 and No. 4,536,46
No. 7, No. 4,587,206, No. 4,555, 4
No. 76, No. 4,599,296, Tokuhei 3-622
A high-boiling organic solvent as described in No. 56 or the like can be used in combination with a low-boiling organic solvent having a boiling point of 50 to 160 ° C. as necessary. Two or more of these dye-donating compounds, nondiffusible reducing agents, high-boiling organic solvents, and the like can be used in combination. The amount of the high boiling point organic solvent is 10 g or less, preferably 5 g or less, more preferably 1 to 0.1 g, based on 1 g of the color image forming compound used. Also, 1 cc or less, more preferably 0.5 cc or less, particularly 0.3 cc or less is suitable for 1 g of the binder. In addition, Tokiko Sho 51-3
No. 9853, JP-A-51-59943, and a dispersion method using a polymer and a method of adding a fine particle dispersion described in JP-A-62-30242, JP-A-62-271339, and the like. Can also be used. In the case of a compound that is substantially unnecessary in water, it can be dispersed and contained as fine particles in a binder in addition to the above method. When dispersing the hydrophobic compound in the hydrophilic colloid, various surfactants can be used. For example, JP-A-59-157
No. 636, pages (37) to (38), and those listed as surfactants in the RD magazine shown in the list below can be used. In the light-sensitive material of the present invention, a compound for stabilizing an image simultaneously with activation of development can be used. Specific compounds preferably used are described in U.S. Pat. No. 4,500,626, columns 51-52.

To obtain a wide range of colors on the chromaticity diagram using the three primary colors of yellow, magenta and cyan, at least three silver halide emulsion layers having photosensitivity in different spectral regions are combined. Used. For example, there are a combination of three layers of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer, and a combination of a green-sensitive layer, a red-sensitive layer, and an infrared-sensitive layer. Each photosensitive layer can adopt various arrangement orders known for ordinary color photosensitive materials. Each of these photosensitive layers may be divided into two or more layers as necessary.

The photosensitive material can be provided with various auxiliary layers such as a protective layer, an undercoat layer, an intermediate layer, an antihalation layer, and a back layer. Further, various filter dyes can be added to improve color separation.

The silver halide grains used in the present invention are silver bromide, silver chloride, silver chlorobromide, silver chloroiodide, silver iodobromide and silver chloroiodobromide. Other silver salts, for example, silver rhodan silver sulfide, silver selenide, silver carbonate, silver phosphate, and organic acid silver may be contained as separate grains or as part of halogen atom grains. Development and desilvering (bleaching, fixing and bleach-fixing)
When speeding up the process is desired, silver halide grains having a high silver chloride content are desirable. In order to appropriately suppress development, it is preferable to contain silver iodide. The preferred silver iodide content depends on the intended light-sensitive material. For example, the preferred range is 0.1 to 15 mol% for X-ray photographic materials and 0.1 to 5 mol% for graphic arts and micro photographic materials. In the case of a photographic light-sensitive material represented by a color negative, a silver halide containing 1 to 30 mol% of silver iodide is preferable, and 5 to 20 mol% is more preferable.
Especially preferably, it is 8 to 15 mol%. It is preferable that silver iodobromide grains contain silver chloride in order to reduce lattice strain.

The silver halide emulsion used in the present invention preferably has a distribution or a structure with respect to the halogen composition in the grains. A typical example is Japanese Patent Publication No. 43-1
No. 3162, Japanese Patent Application Laid-Open No. 61-215540, Japanese Patent Application Laid-Open
These are core-shell type or double structure particles having a halogen composition in which the inside and the surface of the grains have different halogen compositions, as disclosed in JP-A-22845 and JP-A-61-75337.
In addition, it is not a simple double structure.
Or a multilayer structure having three or more layers as disclosed in the above-mentioned publication, or a silver halide having a different composition may be thinly applied to the surface of a core-shell double-structured grain.

In order to impart a structure to the inside of the particle, not only the wrapping structure as described above, but also a particle having a so-called junction structure can be produced. These examples are disclosed in
No. 133540, JP-A-58-108526, European Patent No. 199,290A2, JP-B-58-24772.
And JP-A-59-16254.
The crystal to be bonded can be formed by bonding to the edge, corner, or surface of the host crystal with a composition different from that of the host crystal. Such a junction crystal can be formed even if the host crystal is uniform in the halogen composition or has a core-shell structure.

In the case of a junction structure, a combination of silver halides is naturally possible, but a silver salt compound having no silver salt structure, such as silver rhodanate or silver carbonate, can be combined with silver halide to form a junction structure. Further, a non-silver salt compound such as lead oxide may be used as long as the bonding structure is possible.

In the case of silver iodobromide grains having these structures, it is a preferred embodiment that the core portion has a higher silver iodide content than the shell portion. Conversely, grains having a low silver iodide content in the core and a high shell are sometimes preferred. Similarly, grains having a bonding structure may be grains having a high silver iodide content of the host crystal and relatively low silver iodide content of the bonding crystal, or vice versa. In addition, the environmental portions having different halogen compositions of the particles having these structures may be a clear environment or an unclear environment. In addition, a configuration in which the composition is positively and continuously changed is also a preferable embodiment.

In the case of silver halide grains in which two or more silver halides exist as mixed crystals or have a structure, it is important to control the distribution of the halogen composition between the grains.
Regarding the method of measuring the halogen composition distribution between grains, see
No. 0-254032. Uniform halogen distribution between grains is a desirable property. In particular, a highly uniform emulsion having a coefficient of variation of 20% or less is preferable. Another preferred form is an emulsion having a correlation between the grain size and the halogen composition. As an example, there is a correlation such that the iodine content is higher for larger size particles, while the iodine content is lower for smaller size particles. Depending on the purpose, an inverse correlation or a correlation with another halogen composition can be selected. For this purpose, it is preferable to mix two or more emulsions having different compositions.

It is important to control the silver halide composition near the surface of the grains. Increasing the amount of silver iodide in the vicinity of the surface or increasing the content of silver chloride can be selected according to the purpose because the adsorption of the dye and the developing speed are changed. When changing the halogen composition in the vicinity of the surface, either a structure that wraps the entire grain or a structure that adheres only to a part of the grain can be selected. For example, the halogen composition may be changed only on one side of a tetrahedral grain composed of the (100) plane and the (111) plane, or the halogen composition on one of the main plane and the side face of the tabular grain may be changed.

The silver halide grains used in the present invention may be normal crystals containing no twin planes, as described in the Photographic Society of Japan, Fundamentals of the Photographic Industry, Silver Salt Photography (Corona), page 163. For example, a single twin containing one twin plane, a parallel multiple twin containing two or more parallel twin planes, a non-parallel multiple twin containing two or more non-parallel twin planes, and so on They can be selected and used according to the requirements. An example of mixing particles having different shapes is disclosed in U.S. Pat. No. 4,865,964, but this method can be selected as necessary. In the case of a normal crystal, a cube consisting of (100) planes, (111)
Octahedral particles composed of planes and dodecahedral particles composed of (110) planes disclosed in JP-B-55-42737 and JP-A-60-222842 can be used. Jou
rnalof Imaging Science 30
Volume, page 247 (1986), (h11) plane particles represented by the (211) plane, and (33)
1) The (hh1) plane particle representing the plane, the (hk0) plane particle represented by the (210) plane, and the (hk1) plane particle represented by the (321) plane also require some contrivance in the adjustment method. They can be selected and used according to the requirements. (100) face and (11)
1) a tetrahedral particle whose plane coexists in one particle, (10
0) and (110) coexisting particles, or (11)
Particles in which two surfaces or many surfaces coexist, such as particles in which 1) and (110) surfaces coexist, can be selected and used according to the purpose.

The value obtained by dividing the circle equivalent diameter of the projected area by the grain thickness is called an aspect ratio, and defines the shape of tabular grains. Tabular grains having an aspect ratio of greater than 1 can be used in the present invention. Tabular grains are described in "Theory and Practice of Photography" by Cleave (Cleav, Photography The).
ory and Practice (1930)), 1
Page 31; Gatov, Photographic Science
And Engineering (Gutof, Photog
raphic science and engineering
ering), 14, 248-257 (1970).
U.S. Pat. Nos. 4,434,226 and 4,41.
No. 4,310, No. 4,433,048, No. 4,4
39,520 and British Patent No. 2,112,157. When tabular grains are used, there are advantages such as an increase in covering power and an increase in the efficiency of color sensitization by a sensitizing dye, which is described in detail in U.S. Pat. No. 4,434,226 cited above. . The average aspect ratio of 80% or more of the total projected area of the grains is desirably 1 or more and less than 100. It is more preferably 2 or more and less than 20 and particularly preferably 3 or more and less than 10. As the shape of the average particle, a triangle, a hexagon, a circle, or the like can be selected. U.S. Pat. No. 4,798,35
No. 4, a regular hexagon having substantially equal lengths of six sides is a preferable form.

Although the circle equivalent diameter of the projected area is often used as the particle size of the average particle, US Pat.
No. 8,106 has an average diameter of 0.6.
Submicron particles are preferred for high image quality. Also preferred are emulsions having a narrow grain size distribution as described in U.S. Pat. No. 4,775,617. It is preferable to limit the thickness of the tabular grains to 0.5 μm or less, more preferably 0.3 μm or less, in order to increase sharpness. Further, an emulsion having a highly uniform thickness having a variation coefficient of grain thickness of 30% or less is also preferable. JP 63
Also preferred are the grains described in JP-A-163451 in which the thickness of the grains and the distance between twin planes are specified.

In the case of tabular grains, dislocation lines can be observed with a transmission electron microscope. It is preferable to select a particle containing no dislocation line, a particle containing several dislocations, or a particle containing many dislocations according to the purpose. In addition, dislocations introduced linearly or bent dislocations with respect to a specific direction of the crystal orientation of the grains can be selected, or introduced over the entire grains, or introduced only into a specific portion of the grains, For example, dislocations can be introduced only in the fringe portion of the particles. Introduction of dislocation lines is preferable not only in the case of tabular grains, but also in the case of irregular grains typified by normal crystal grains or potato grains. Also in this case, it is a preferable embodiment to limit to a specific portion such as a vertex or a ridge of the particle.

The silver halide emulsion used in the present invention may be prepared by subjecting a grain to a roundness as disclosed in European Patent No. 96,412B1 or the like, or by a method disclosed in West German Patent No. 2,30.
The surface may be modified as disclosed in JP-A-6-447C2 and JP-A-60-221320.

A structure having a flat particle surface is generally used.
It is preferable in some cases to form irregularities intentionally.
JP-A-58-106532, JP-A-60-22132
0, for example, a method of making a hole in a part of a crystal, for example, a vertex or a center of a face, or US Pat.
Raffle particles described in U.S. Pat. No. 3,966 are examples.

The grain size of the emulsion used in the present invention is determined by a circle equivalent diameter of a projected area using an electron microscope, a sphere equivalent diameter of a particle volume calculated from the projected area and the grain thickness, or a sphere equivalent diameter of a volume by the Coulter counter method. Can be evaluated. Ultrafine particles having a sphere equivalent diameter of 0.05 μm or less and coarse particles exceeding 10 μm can be selected and used. Preferably 0.1 micron or more 3
Submicron grains can be used as the photosensitive silver halide grains.

Emulsions used in the present invention may be selected from so-called polydisperse emulsions having a wide grain size distribution, and monodisperse emulsions having a narrow size distribution, depending on the purpose. In some cases, a variation coefficient of the projected area equivalent circle diameter or sphere equivalent diameter of a particle is used as a scale representing the size distribution. When a monodisperse emulsion is used, it is preferable to use an emulsion having a size distribution with a coefficient of variation of 25% or less, more preferably 20% or less, and still more preferably 15% or less.

A monodisperse emulsion may be defined as an average particle size distribution by grain or weight. In order to satisfy the target gradation of the light-sensitive material, two or more monodisperse silver halide emulsions having different grain sizes are mixed in the same layer or different layers in an emulsion layer having substantially the same color sensitivity. Can be applied in layers. Further, two or more kinds of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion can be used as a mixture or as a mixture.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Grafkid, published by Paul Monte Co. (PG
refkides, Chemie et Physiq
uePhotographique, Paul Mon
tel., 1967), Duffin's "Photographic Emulsion Chemistry", published by Focal Press (GF Duffin, Phot).
optic Emulsion Chemist
ry, FocalPress, 1966), "Production and Coating of Photographic Emulsions", by Zerikman et al., published by Focal Press (VL Zelikman, et al., Maki).
ng and Coating Photograph
ic Emulsion, Focal Press, 1
964), etc., any of which can be used. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt and a soluble halide may be any of a one-sided mixing method, a double-sided mixing method, a combination thereof and the like. . A method of forming grains in the presence of excess silver ions (a so-called reverse mixing method) can also be used. As one type of the double jet method, a method of keeping the pAg of a liquid phase in which silver halide is formed constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.

A method of adding previously precipitated silver halide grains to a reaction vessel for preparing an emulsion, US Pat. No. 4,33
No. 4,012, No. 4,301,241, No. 4-1
50,994 is optionally preferred. These can be used as seed crystals, and are also effective when supplied as silver halide for growth. In the latter case, it is preferable to add an emulsion having a small grain size, and the addition method can be selected from a total amount addition at a time, a plurality of additions, or a continuous addition. Also,
It is sometimes effective to add particles of various halogen compositions to modify the surface.

The method of converting most or only a part of the halogen composition of silver halide grains by a halogen conversion method is described in US Pat. Nos. 3,477,852 and 4,14.
No. 2,900, European Patent Nos. 273,429 and 27
No. 3,430, West German Patent No. 3,819,241, etc., which are effective particle forming methods. A solution of a soluble halogen or silver halide grains can be added to convert the silver salt into a more insoluble silver salt. It can be selected from methods such as converting at once, converting into a plurality of times, or converting continuously.

In addition to the method of adding a soluble silver salt and a halogen salt at a constant concentration and a constant flow rate for grain growth, British Patent No. 1
469,480; U.S. Pat. No. 3,650,757;
The particle formation method in which the concentration is changed or the flow rate is changed as described in US Pat. No. 4,242,445 is a preferred method. By changing the concentration or increasing the flow rate, the amount of silver halide to be supplied can be changed by a linear function, a quadratic function, or a more complicated function of the addition time. It is also preferable in some cases to reduce the amount of silver halide supplied as necessary. Further, when adding a plurality of soluble silver salts having different solution compositions or adding a plurality of soluble halide salts having different solution compositions, an addition method of increasing one and decreasing the other is also effective. It is.

A mixer for reacting a solution of a soluble silver salt and a soluble halide salt is disclosed in US Pat. No. 2,996,287.
No. 3,342,605 and No. 3,415,65
No. 0, No. 3,785,777, West German Patent No. 2,
556,885 and 2,555,364.

A silver halide solvent is useful for the purpose of accelerating ripening. For example, it is known to have excess halide ions present in the reactor to promote ripening. Other ripening agents can be used. These ripening agents can be incorporated in their entirety in the dispersion medium in the reactor before adding the silver and halide salts, or can be added together with the halide salts, silver salts or deflocculants and added to the reactor. Can also be introduced. As another variant, the ripening agent can be introduced independently during the silver halide and silver salt addition step.

Ammonia, thiocyanates (rhodancali, rhodanammonium, etc.) and organic thioether compounds (for example, US Pat. Nos. 3,574,628 and 3,
Nos. 021, 215, 3,057,724, 3,038,805, 4,276,374, 4,297,439, 3,704,130,
No. 4,782,013, JP-A-57-104926
And thione compounds (for example, tetra-substituted thioureas described in JP-A-53-82408 and JP-A-55-77737, U.S. Pat. -144319), mercapto compounds capable of promoting the growth of silver halide grains described in JP-A-57-202531, amine compounds (for example, JP-A-54-100717) and the like. Is mentioned.

It is advantageous to use gelatin as a protective colloid used in preparing the emulsion of the present invention and as a binder for other hydrophilic colloid layers, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxycellulose, carboxymethylcellulose and cellulose sulfate, sodium alginate, starch derivatives, gum arabic , Dextran, sugar derivatives such as natural compounds such as polysaccharides such as pullulan, polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. And various kinds of synthetic hydrophilic high-molecular substances such as a single or copolymer. Further, superabsorbent polymers described in U.S. Pat. No. 4,960,681 and JP-A-62-245260, that is, -COOM or -SO
₃ M (M represents a hydrogen atom or an alkali metal) copolymer (for example, sodium methacrylate and a copolymer or a vinyl monomer together or with other vinyl monomers, a vinyl monomer having, ammonium methacrylate, Sumitomo Chemical (Co. Sumikagel L-5H)) is also used. These binders can be used in combination of two or more kinds. Combinations of gelatin and the above binders are also preferred.

As gelatin, in addition to lime-processed gelatin,
It may be selected from acid-treated gelatin and so-called demineralized gelatin having a reduced content of calcium and the like, and it is also preferable to use them in combination. Bull. Soc. Sci. P
photo. Japan. No. 16. p30 (196
Enzyme-treated gelatin as described in 6) may be used, and hydrolysates or enzymatic degradation products of gelatin can also be used. The use of low molecular weight gelatin described in JP-A-1-58426 is preferred for preparing tabular grains.

In the case of a photothermographic material, an organic silver salt oxidizing agent may be used together with the photosensitive silver halide emulsion. Examples of the organic compound which can be used for forming the same include US Pat. There are benzotriazoles, fatty acids and other compounds described in column Nos. 52 to 53 of 500,626. The acetylene silver described in U.S. Pat. No. 4,775,613 is also useful. Two or more organic silver salts may be used in combination.
The above organic silver salt is used per mole of the photosensitive silver halide,
0.01 to 10 mol, preferably 0.01 to 1 mol, can be used in combination. The total coating amount of the photosensitive silver halide emulsion and the organic silver salt is preferably from 0.7 to 3.5 g / m ² in terms of silver. More preferably, 1.0 to 2.0 g /
m ² . If the amount of silver increases, the desilvering process may be insufficient. If the amount is too low, the image density is too low, which may affect image information.

The emulsion used in the present invention is preferably washed with water for desalting and dispersed in a newly prepared protective colloid. The temperature of water washing can be selected according to the purpose,
It is preferable to select within the range. The pH at the time of washing can be selected depending on the purpose, but is preferably selected from 2 to 10. More preferably, it is in the range of 3 to 8. The pAg at the time of washing can be selected according to the purpose, but is preferably selected from 5 to 10. The method for washing can be selected from noodle washing, dialysis using a semipermeable membrane, centrifugal separation, coagulation sedimentation, and ion exchange. In the case of the coagulation sedimentation method, a method using a sulfate, a method using an organic solvent, a method using a water-soluble polymer, a method using a gelatin derivative, and the like can be selected.

The silver halide grains used in the present invention are at least one of sulfur sensitization, selenium sensitization, tellurium sensitization (these three are collectively referred to as chalcogen sensitization), noble metal sensitization, or reduction sensitization. Can be applied in any step of the production process of the silver halide emulsion. It is preferable to combine two or more sensitization methods. Various types of emulsions can be prepared depending on the step of chemical sensitization. There are a type in which a chemical sensitizing nucleus is embedded inside the grain, a type in which the chemical sensitizing nucleus is embedded in a position shallow from the grain surface, and a type in which a chemical sensitizing nucleus is formed on the surface. In the emulsion of the present invention, the location of the chemical sensitization nucleus can be selected according to the purpose. Generally, the case where at least one type of chemical sensitization nucleus is formed near the surface is preferred.

The chemical sensitization which can be preferably carried out in the present invention is chalcogen sensitization and noble metal sensitization alone or in combination thereof, and is described in TH James, The.
Photographic Process, 4th Edition, Macmillan, 1977 (TH James, The Pho
graphical Process, 4th ed.
Macmillan, 1977), pages 67-76, and can be performed using active gelatin, or can be performed using Research Disclosure Item 120.
08 (April 1974), Item 13452 (19
June 1975), Item 307105 (January 1989)
January), US Patent Nos. 2,642,361 and 3,2
No. 97,446, No. 3,772,031, No. 3,
PAg 5-10 as described in 857,711, 3,901,714, 4,266,018 and 3,904,415 and British Patent 1,315,755. , Selenium, tellurium, gold, platinum, palladium, iridium or a combination of a plurality of these sensitizers at a pH of 5 to 8 and a temperature of 30 to 80 ° C.

In sulfur sensitization, an unstable sulfur chemical is used, specifically, thiosulfate (eg, hypo),
Thioureas (eg, diphenylthiourea, triethylthiourea, allylthiourea, etc.), rhodanines, mercaptos, thioamides, thiohydantoins, 4-oxooxazolidin-2-thiones, di- or polysulfides, polythionates And elemental sulfur, and U.S. Patent Nos. 3,857,711 and 4,266,018.
And the known sulfur-containing compounds described in U.S. Pat. No. 4,054,457. Sulfur sensitization is often used in combination with noble metal sensitization.

The preferable amount of the sulfur sensitizer used for the silver halide grains used in the present invention is 1
The amount is 1 × 10 ⁻⁷ × 10 ⁻³ mol per mol, more preferably 5 × 10 ⁻⁷ to 1 × 10 ⁻⁴ mol.

In selenium sensitization, a known unstable selenium compound is used, for example, US Pat. No. 3,297,446.
No. 3,297,447 and the like, and specifically, colloidal metal selenium, selenoureas (for example, N, N-dimethylselenourea, tetramethylselenium urea) Etc.), seleno ketones (eg, selenoacetone), selenoamides (eg, selenoacetamide), selenocarboxylic acids and esters, isoselenocyanates, selenides (eg, diethyl selenide, triphenylphosphine selenide), seleno Phosphates (eg, tri-p-
Selenium compounds such as trisylselenophosphate) can be used. It may be preferable to use selenium sensitization in combination with sulfur sensitization and / or precious metal sensitization.

The amount of the selenium sensitizer varies depending on the selenium compound used, silver halide grains, chemical ripening conditions and the like, but is generally 10 ^-8 to 10 ^-4 per mol of silver halide.
Mol, preferably about 10 ^-7 to 10 ^-5 mol.

Examples of tellurium sensitizers used in the present invention include Canadian Patent No. 800,958 and British Patent Nos. 1,2.
No. 95,462, No. 1,396,696, Japanese Patent Application No. 2
Compounds described in JP-A-333819 and JP-A-3-131598 can be used, and specific tellurium sensitizers include colloidal tellurium and telluroureas (for example, tetramethyltellurourea, N-carboxyethyl-N ', N'
-Dimethyltellurourea, N, N'-dimethylethylenetellurourea), isotellurocyanates, telluroketones, telluramides, tellurohydrazides, telluroesters, phosphine tellurides (eg, tributylphosphine telluride, butyldiisopropylphosphine) Telluride), other tellurium compounds (eg, potassium tellurocyanate, sodium telluropentathionate)
And the like.

The tellurium sensitizer was used in an amount of 1 silver halide.
10 ^{-7 to} 5 × 10 ^-2 mol per mol, preferably 5 × 1
It is about ^0-7 to ^10-3 mol.

In the noble metal sensitization, noble metal salts such as platinum, gold, palladium and iridium can be used, and among them, gold sensitization, palladium sensitization and a combination of both are preferable. In the case of gold sensitization, known compounds such as chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, and gold selenide can be used. The palladium compound means a divalent salt or a tetravalent salt of palladium. Preferred palladium compounds are R ₂ PdX ₆ or R
₂ PdX ₄ Here, R represents a hydrogen atom, an alkali metal atom or an ammonium group. X represents a halogen atom, and represents a chlorine, urea or iodine atom.

Specifically, K ₂ PdCl ₄ , (NH ₄ ) ₂ P
dCl ₅ , NaPdCl ₄ , (NH ₄ ) ₂ PdCl ₄ , Li ₂
PdCl ₄ , Na ₂ PdCl ₆ or K ₂ PdBr ₄ is preferred. The gold compound and the palladium compound are preferably used in combination with thiocyanate or selenocyanate.

The emulsion used in the present invention is preferably used in combination with gold sensitization. The preferred amount of the gold sensitizer is 1 × 10 ^-7 to 1 × 10 ^-3 mol, more preferably 5 × 10 ^{-7 to} 5 × 10 ^-4 mol, per mol of silver halide. The preferred range of the palladium compound is 5 × 10 ^-7 to 1 × 10 ^-3 mol. The preferred range of the thiocyan compound or selenocyan compound is 1 × 10 ^{−6 to} 5 × 10 ⁻² mol.

The silver halide emulsion of the present invention is preferably subjected to reduction sensitization during grain formation, after grain formation and before or during chemical sensitization, or after chemical sensitization.

Here, reduction sensitization is a method in which a reduction sensitizer is added to a silver halide emulsion, and pAg1 to silver ripening.
7, a method of growing or ripening in a low pAg atmosphere, or a method of growing or ripening in a high pH atmosphere of pH 8-11 called high pH ripening can be selected. Also, two or more methods can be used in combination.

The method of adding a reduction sensitizer is a preferable method because of the advantage that the level of reduction sensitization can be finely adjusted.

As the reduction sensitizer, known reduction sensitizers such as stannous salts, ascorbic acid and its derivatives, amines and polyamines, hydrazine and its derivatives, formamidine sulfinic acid, silane compounds and borane compounds are selected. And two or more compounds can be used in combination. Stannous chloride, aminoiminomethanesulfinic acid (common name: thiourea dioxide) as reduction sensitizer,
Dimethylamine borane, ascorbic acid and its derivatives are preferred compounds. Since the addition amount of the reducing agent sensitizer depends on the emulsion production conditions, it is necessary to select the addition amount, but an appropriate range is from 10 ^-7 to 10 ^-3 mol per mol of silver halide.

Chemical sensitization can be carried out in the presence of a so-called chemical sensitization auxiliary. Useful chemical sensitizers include compounds known as azaindene, azapyridazine, azapyrimidine, which suppress fog in the course of chemical sensitization and increase sensitivity. Examples of chemical sensitization aid modifiers are described in US Pat. Nos. 2,131,038 and 3,4,
No. 11,914, No. 3,554,757;
No. 8-126526 and the above-mentioned book by Duffin, "Photographic Emulsion Chemistry, pp. 138-143".

It is preferable to use an oxidizing agent for silver in the emulsion used in the present invention during the production process. The oxidizing agent for silver refers to a compound having an effect of acting on metallic silver to convert it into silver ions. In particular, a compound that converts extremely fine silver grains that are replicated in the course of forming silver halide grains and in the course of chemical sensitization into silver ions is effective. The silver ions generated here may form a silver salt that is hardly soluble in water such as silver halide, silver sulfide, silver selenide, or a silver salt that is easily soluble in water such as silver nitrate. good. The oxidizing agent for silver may be inorganic or organic. Examples of the inorganic oxidizing agent include ozone, hydrogen peroxide and adducts thereof (for example, NaBO ₂ , H ₂ O ₂ .H ₂ O, 2NaCO ₃ .H ₂ O
₂ , Na ₄ P ₂ O ₇ .H ₂ O ₂ , 2NaSO ₄ .H ₂ O ₂ .2H ₂
O), peroxyacid salts (eg, K ₂ S ₂ O ₈ , K ₂ C)
₂ O ₆ , K ₂ P ₂ O ₈ ) peroxy complex compound (for example, K _{2
[Ti (O 2) C 2 O} 4 ] _{· 3H 2 O, 4K 2 SO} 4 · Ti
(O ₂ ) OH.SO ₄ .2H ₂ O, Na ₃ [VO (O ₂ )
(C ₂ O ₄ ) ₂ ] · 6H ₂ O), permanganate (eg, K
Oxyacids such as MnO ₄ ), chromates (eg, K ₂ CrO ₇ ), halogen elements such as iodine and bromine, perhalates (eg, potassium periodate), and salts of high-valent metals (eg, , Potassium hexacyanoferrate) and thiosulfonates.

Examples of the organic oxidizing agent include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogen (eg, N-bromosuccinimide, chloramine). T, chloramine B) are mentioned by way of example.

Preferred oxidizing agents used in the present invention are ozone, hydrogen peroxide and its adducts, halogen elements, inorganic oxidizing agents of thiosulfonates and organic oxidizing agents of quinones. It is a preferred embodiment to use the above-described reduction sensitization and an oxidizing agent for silver in combination. After using the oxidizing agent, the method can be selected from a method of performing reduction sensitization, a method in which the sensitizing agent is used in the opposite direction, or a method of simultaneously coexisting both. These methods can be selectively used in both the grain formation step and the chemical sensitization step.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the photographic material, or stabilizing photographic performance. . That is, thiazoles such as benzothiazole salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiazoles, aminotriazoles , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-
Phenyl-5-mercaptotetrazole), mercaptopyrimidine, mercaptotriazine such as thioketo compounds such as oxazolinethione, azaindenes such as triazaindenes and tetraazaindenes (especially 4-hydroxy-6-methyl-1,3,3) Many compounds known as antifoggants or stabilizers can be added, such as 3a, 7-tetraazaindene), pentaazaindenes and the like. For example, US Pat.
No. 474, No. 3,982,947, Japanese Patent Publication No. 52-2
No. 8660 can be used. One of the preferred compounds is a compound described in Japanese Patent Application No. 62-47225. Antifoggants and stabilizers are used at various times before, during and after particle formation, during the washing step, during dispersion after washing, before chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. It can be added according to the purpose.
In addition to exhibiting the original fogging prevention and stabilizing effects when added during emulsion preparation, it also controls grain walls, reduces grain size, reduces grain solubility, and controls chemical sensitization. It can be used for various purposes such as controlling the arrangement of dyes.

When the light-sensitive silver halide used in the present invention has green-, red- and infrared-sensitive color sensitivity, the light-sensitive silver halide emulsion is spectrally sensitized with a methine dye or the like. . If necessary, the blue-sensitive emulsion may be subjected to spectral sensitization in the blue region.

The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, complex cyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei usually used for cyanine dyes as base heterocyclic nuclei can be applied to these dyes.
That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, such as an alicyclic hydrocarbon ring fused to these nuclei, and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus, i.e., indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, 5-64-hydroxy-6-methyl- such as rhodanine nucleus and thiobarbituric acid nucleus
Heterocyclic nuclei can be applied. These nuclei may be substituted on carbon atoms. Specifically, US Pat. No. 4,617,257, JP-A-59-180550,
No. 64-13546, Japanese Patent Application No. 5-45828, No. 5
Sensitizing dyes described in US Pat.

In the merocyanine dye or the complex merocyanine dye, nuclei having a ketomethylene structure include a pyrazoline-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidin-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, 5 to 5 such as rhodanine nucleus and thiobarbituric acid nucleus
Six-membered heterocyclic nuclei can be applied.

These dyes may be used alone or in combination, and a combination of sensitizing dyes is often used for the purpose of supersensitization and adjusting the wavelength of spectral sensitivity. A representative example is U.S. Pat. No. 2,688,5.
No. 45, No. 3,397,060, No. 2,977,
No. 229, No. 3,522,052, No. 3,52
No. 7,64, No. 3,617,293, No. 3,62
No. 8,964, No. 3,672,898, No. 3,6
No. 79,428, No. 3,703,377, No. 3,
Nos. 769,301, 3,814,609, 3,837,862, 4,026,707, British Patents 1,344,281, and 1,507,80.
No. 3, JP-B-43-4936, and JP-B No. 53-12375
JP-A-52-110618, JP-A-52-110992
No.5.

Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a compound which does not substantially absorb visible light and exhibits supersensitization (for example, U.S. Pat. No. 3,615,641 and those described in JP-A-63-23145).

The timing of adding these sensitizing dyes to the emulsion may be at any stage in the preparation of the emulsion which has hitherto been known to be useful.

Most commonly, it is carried out after completion of chemical sensitization and before coating, but US Pat. No. 3,628,96
As described in JP-A-58-113928, the addition of a chemical sensitizer at the same time as that described in JP-A Nos. Can be performed prior to chemical sensitization as described in (1). Further, it can be added before the completion of precipitation of silver halide grains to start spectral sensitization. Further, according to U.S. Pat. Nos. 4,183,756 and 4,225,666, the sensitization may be performed before or after the nucleation of silver halide grains. Separate additions, such as those added later, are also possible.

These sensitizing dyes and supersensitizers may be added as a solution of an organic solvent such as methanol, a dispersion of gelatin or the like, or a solution of a surfactant.

The addition amount is generally about 4 × 10 ^-6 to 8 × 10 ^-3 mol per mol of silver halide, but about 5 × when the silver halide grain size is more preferably 0.2 to 1.2 μm. 10 ^{-5 to} 2 × 10 ^-3 mol is more effective.

The above-mentioned various additives are used in the light-sensitive material according to the present technology, but other various additives can be used according to the purpose.

These additives are described in more detail in Research Disclosure Item 17643 (December 1978) and Item 18176 (November 1979).
And Item 307105 (November 1989), and the relevant portions are summarized in the table below.

[0135]

[Table 1]

As hardeners, in addition to the above, US Pat. No. 4,678,739, column 41 and 4,791,04.
No. 2, JP-A-59-116655 and JP-A-62-2452.
No. 61, 61-18942, JP-A-4-21804
No. 4 and the like. More specifically,
Aldehyde hardener (such as formaldehyde), azirine hardener, epoxy hardener, vinyl sulfone hardener (N, N'-ethylene-bis (vinylsulfonylacetamide) ethane, etc.), N-methylol Hardeners (such as dimethylol urea) or polymeric hardeners (JP-A-6
2-234157). These hardeners are used in an amount of 0.001 g to 1 g, preferably 0.005 g to 0.5 g per g of gelatin applied.
Is used. The layer to be added may be any of constituent layers such as a light-sensitive material and a dye-fixing material, or may be added in two or more layers.

In the light-sensitive material of the present invention, a matting agent can be used for the purpose of preventing adhesion, improving slipperiness, and giving a non-glossy surface. Matting agents such as silicon dioxide, polyolefin and polymethacrylate are disclosed in JP-A-61-882.
JP-A Nos. 63-274944 and 63-2, such as benzoguanamine resin beads, polycarbonate resin beads, and AS resin beads, in addition to the compounds described on page 56 (29).
No. 74952. In addition, the compounds described in the aforementioned RD magazine can be used. These matting agents can be added not only to the uppermost layer (protective layer) but also to the lower layer as needed. In addition, the constituent layers of the photothermographic material may contain a thermal solvent, an antifoaming agent, an antibacterial agent, a fungicide, colloidal silica, and the like. Specific examples of these additives are disclosed in
No. 88256, pages 26 to 32, JP-A-3-113
No. 38, JP-B-2-51496 and the like.

In the constituent layers of the light-sensitive material of the present invention, various surfactants can be used for the purpose of coating aid, improvement of releasability, improvement of slipperiness, antistatic, acceleration of development and the like. Specific examples of the surfactant are described in the above-mentioned RD Magazine and JP-A-62-1746.
No. 3, No. 62-183457 and the like. In the case of a photothermographic material, it is also preferable to include an organic fluoro compound in the constituent layers for the purpose of improving slipperiness, preventing static charge, improving releasability, and the like. Representative examples of organic fluoro compounds include JP-B-57-9053, columns 8-17, and JP-A-61-9053.
No. -20944, No. 62-135836 or the like, or a hydrophobic fluorine compound such as an oily fluorine compound such as fluorine oil or a solid fluorine compound resin such as ethylene tetrafluoride resin Is mentioned.

In the light-sensitive material of the present invention, known anti-fading agents can be used. Organic anti-fading agents include hydroquinones, 5-hydroxychromans, 5-hydroxycoumarins, paraalkoxyphenols, hindered phenols mainly including bisphenols, gallic acid derivatives, methylenedioxybenzenes, amino Representative examples include phenols, hindered amines, and ether or ester derivatives in which the phenolic hydroxyl group of each of these compounds is silylated or alkylated. Further, metal complexes represented by (bissalicylaldoximato) nickel complex and (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used. Compounds having both hindered amine and hindered phenol partial structures in the same molecule as described in U.S. Pat. No. 4,268,593 have been found to be effective in preventing deterioration of the yellow dye image due to heat, humidity and light. give. Further, spiroindanes described in JP-A-56-159644 may be used to prevent the deterioration of magenta dye images, especially deterioration due to light.
And chromans substituted with hydroquinone diether or monoether described in JP-A-55-89835 give preferable results.

In the constituent layers of the light-sensitive material of the present invention, various antifoggants or photographic stabilizers and precursors thereof can be used. As a specific example, the RD
Magazine, U.S. Pat. Nos. 5,089,378 and 4,50.
0,627, 4,614,702, JP-A-64
No. 13546, pages (7) to (9), (57) to (71)
Page and pages (81)-(97), U.S. Pat.
No. 610, No. 4,626,500, No. 4,98
No. 3,494, JP-A-62-174747, JP-A-62-274.
239148, 63-264747, JP-A-1-
No. 150135, No. 2-110557, No. 2-178
No. 650, Research Disclosure 17643 (1
978), pages 24 to 25, and the like. These compounds are 5 × 10 ^-6 per mole of silver.
To 1 × 10 ^−1, more preferably 1 × 10 ⁻⁵ to 1 × 10 ^−2.
Is preferably used.

Suitable supports that can be used in the present invention include synthetic plastic films such as polyolefins such as polyethylene and polypropylene, polycarbonates, cellulose acetate, polyethylene terephthalate, polyethylene naphthalate and polyvinyl chloride, as well as photographic base paper and printing. Paper supports such as paper, baryta paper, and resin-coated paper; and supports in which a reflective layer is provided on the above-mentioned plastic film, JP-A-62-253195 (29-3)
1) described as a support. Page 28 of the aforementioned Research Disclosure 17643,
No. 18716, from the right column on page 647 to the left column on page 648; Those described on page 879 of 307105 can also be preferably used. Syndiotactic polystyrenes are also preferred. These are disclosed in JP-A-62-1770.
No. 8, JP-A-1-46912 and JP-A-1-178505. These supports include U.S. Pat. No. 4,141,7.
As described in No. 35, by performing a heat treatment of Tg or less, it is possible to use a material which is less likely to have a curl. The surface of these supports may be subjected to surface treatment for the purpose of improving the adhesion between the support and the emulsion undercoat layer. In the present invention, glow discharge treatment, ultraviolet irradiation treatment, corona treatment, and flame treatment can be used as the surface treatment. Further known technology No. 5
No. (issued by Aztec Co., Ltd. on March 22, 1991) at pages 44 to 149 can also be used.
A transparent support such as polyethylene dinaphthalenedicarboxylate or a support on which a transparent magnetic substance is applied can be used.

The method of exposing and recording an image on the light-sensitive material of the present invention includes, for example, a method of directly photographing a landscape or a person using a camera or the like, and a method of exposing through a reversal film or a negative film using a printer or a enlarger. Scanning method using an exposure device of a copier to scan and expose the original image through slits, etc., and scan by emitting light emitting diodes and various lasers (laser diodes, gas lasers, etc.) via image information and electric signals. Exposure method (JP-A-2-129625, Japanese Patent Application No. 3-33818)
2, 4-9388, 4-281442), image information is output to an image display device such as a CRT, a liquid crystal display, an electroluminescence display, a plasma display, etc., directly or through an optical system. Exposure method.

As a light source for recording an image on a photosensitive material,
As described above, U.S. Pat.
500,626, column 56, JP-A-2-53378,
The light source and the exposure method described in JP-A-2-54672 can be used. Also, image exposure can be performed using a wavelength conversion element in which a non-linear optical material and a coherent light source such as laser light are combined. Here, the nonlinear optical material is
It is a material that can exhibit nonlinearity between localization and electric field that appears when a strong optical electric field such as laser light is applied, such as lithium niobate, potassium dihydrogen phosphate (KDP), lithium iodate, and BaB ₂ O ₄ Such as inorganic compounds,
Urea derivatives, nitroaniline derivatives, for example, nitropyridine-N-oxide derivatives such as 3-methyl-4-nitropyridine-N-oxide (POM);
Compounds described in JP-A-53462 and JP-A-62-210432 can be preferably used. As a form of the wavelength conversion element, a single crystal optical waveguide type, a fiber type, and the like are known, and any of them is useful.

The image information is obtained by dividing an image signal obtained from a video camera, an electronic still camera or the like, a television signal typified by the Nippon Television Signal Standard (NTSC), or an original image into a plurality of pixels such as a scanner. Image signal,
Images created using a computer represented by CG and CAD can be used.

The preservatives used in the developer of the present invention include sodium sulfite, potassium sulfite, lithium sulfite, sodium formaldehyde sodium bisulfite, and hydroxylamine / sulfate.
Liter or less, preferably 0.001 to 0.02 mol /
May be used in the liter range. When a high silver chloride emulsion is used for the light-sensitive material,
It may not be contained at 1 mol / l or less, preferably at all.

In the present invention, an organic preservative is preferably contained in place of the above-mentioned hydroxylamine and sulfite ions. Here, the term "organic preservative" refers to all organic compounds that reduce the rate of deterioration of the developing agent by being added to a developer.
That is, organic compounds having a function of preventing the developing agent from being oxidized by air or the like, among which hydroxylamine derivatives (excluding hydroxylamine), hydroxamic acids, hydrazines, phenols, α-hydroxyketones, and α-hydroxyketones Amino ketones, sugars, monoamines, diamines, polyamines, quaternary ammoniums, nitroxy radicals, alcohols, oximes, diamide compounds, condensed amines, and the like are particularly effective organic preservatives. These are disclosed in JP-A-63-4235 and JP-A-63-53.
No. 41, 63-30845, 63-21647
No. 63-44655, No. 63-46454, No. 63-53551, No. 63-43140, No. 63-
No. 56654, No. 63-58346, No. 63-431
No. 38, No. 63-146041, No. 63-44657
No. 63-44656, U.S. Pat. No. 3,615,5
No. 03, No. 2,494, 903, JP-B-48-30
496, etc. Other preservatives include various metals described in JP-A-57-44148 and JP-A-57-53749, salicylic acids described in JP-A-59-180588, and alkanolamines described in JP-A-54-3532. Polyethyleneimines described in JP-A-56-94349, aromatic polyhydroxy compounds described in U.S. Pat. No. 3,746,544, and the like, if necessary. In particular, alkanolamines described in JP-A-4-97355, pp. 631 to 632,
It preferably contains the dialkylhydroxylamine described on pages 27 to 630. Furthermore, it is also possible to use a dialkylhydroxylamine and / or a hydrazine derivative in combination with an alkanolamine, or to use a dialkylhydroxylamine described in EP 530,921A1 in combination with an α-amino acid represented by glycine. preferable. The amount of these compounds to be used is preferably 1 × 10 ^{−3 to} 5 × 10 ⁻¹ mol, more preferably 1 × 10 ⁻² to 2 × 10 ⁻¹ , per liter of developer.

In the present invention, the developer contains halogen ions such as chlorine ions, bromine ions and iodine ions. In particular, when a high silver chloride emulsion is used, it preferably contains 3.5 × 10 ^{−3 to} 3.0 × 10 ⁻¹ mol / l of chloride ions, more preferably 1 × 10 ⁻² to 2 × 10 ^−2.
× 10 ^-1 mol / l, and / or preferably contains 0.5 × 10 ^-5 to 1 × 10 ^-3 mol / l of bromine ions, more preferably 3.0 × 10 ^{-5 to} 5 × 10 ^-5 mol / l. ×
10 ^-4 mol / l. Here, the halide may be directly added to the developer or may be eluted from the photosensitive material into the developer during the development processing.

When added to the developing solution, the supply material includes the respective sodium, potassium, ammonium, lithium and magnesium salts.

When eluted from the light-sensitive material, it is mainly supplied from a silver halide emulsion, but may be supplied from other sources.

The developer used in the present invention preferably has a pH of 8 to 13, more preferably 9 to 12. The above p
In order to retain H, it is preferable to use various buffers. Buffers include carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycine salt, N, N
-Dimethylglycine salt, leucine salt, norleucine salt,
Guanine salts, 3,4-dihydroxyphenylalanine salts, alanine salts, aminobutyrate salts, 2-amino-2-methyl-1,3-propanediol salts, valine salts, proline salts, trishydroxylaminomethane salts, lysine salts, etc. Can be used. In particular, carbonate, phosphate, tetraborate, and hydroxybenzoic acid have solubility and pH 9.0 or higher.
It is preferable to use these buffers because they have excellent buffering capacity in the H region and do not adversely affect photographic performance even when added to a developer.

Specific examples of these buffers include lithium carbonate, sodium carbonate, potassium carbonate, potassium bicarbonate, tripotassium phosphate, trisodium phosphate, dipotassium phosphate, disodium phosphate, potassium borate, and borate. Examples include sodium, sodium tetraborate, potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), and the like. The amount of the buffer added to the developer was 0.05
Mol / liter or more, preferably 0.1 mol / liter or more.
It is particularly preferred that the molar ratio is from mol to 0.4 mol / liter.

In addition, various chelating agents can be used in the developer as a precipitation inhibitor for calcium or magnesium, or for improving the stability of the developer. For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylenesulfonic acid, 1,2-diaminopropanetetraacetic acid Glycol ether diamine tetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 1,2-dihydroxybenzene-4,6-disulfone Acids and their alkali metal salts. These chelating agents may be used in combination of two or more as necessary. These chelating agents may be added in an amount sufficient to mask the metal ions in the developer, for example, about 0.1 g to 10 g per liter.

In the present invention, an optional antifoggant can be added as required. As the antifoggant, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide and nitrogen-containing heterocyclic compounds are used. Examples of the nitrogen-containing heterocyclic compound include benzotriazole, 5-nitrobenzotriazole,
-Methylbenzotriazole, 5-nitrobenzimidazole, 5-nitroindazole, 2-thiazolylbenzimidazole, indazole, hydroxyazaindolizine, adenine, 1-phenyl-5-mercaptotetrazole or derivatives thereof are mentioned as typical examples. Can be. The addition amount of the nitrogen-containing heterocycle is 1 × 10 ⁻⁵ to 1 × 1.
0 ^-2 mol / l, preferably 2.5-10 ^-5 to 1 ×
10 ⁻³ mol / l.

An optional development accelerator can be added to the developer if necessary. As development accelerators, JP-B-37-16
No. 088, No. 37-5987, No. 38-7826,
Thioether compounds represented by JP-A Nos. 44-12380 and 45-9019 and U.S. Pat. No. 3,813,247;
No. 54, p-phenylenediamine compound disclosed in JP-A-50-137726, JP-B-44-30074.
And JP-A-56-156826 and JP-A-52-4342.
No. 9, quaternary ammonium salts described in US Pat.
494,903, 3,128,182, 4,2
No. 30,796, No. 3,253,919, Japanese Patent Publication No. 41
-11431, U.S. Pat. Polyalkylene oxides and imidazoles described in U.S. Pat. No. 3,532,501 can be added as necessary.

The developer preferably contains a fluorescent whitening agent. In particular, it is preferable to use a 4,4-diamino 2,2'-disulfostilbene compound. In particular,
Commercially available optical brighteners, for example, "Stained Note 19th Edition" 16
Compounds described on pages 5 to 168 and JP-A-4-2429.
No. 43, pages 3 to 7 can be used. The addition amount is 0.1 g to 10 g / l, preferably 0.5 g to 5 g / l.

The supply amount of the developing solution applied to the present invention is preferably from 10 to 200 ml per 1 m ² of the photosensitive material.
１２０120 ml, more preferably 20-8
Most preferably, it is 0 ml.

The developing solution applied to the present invention may be one solution containing a color developing agent, but may be divided into two solutions, a solution containing an alkali agent and a solution containing a color developing agent. .

The light-sensitive material of the present invention may have a form having a conductive heating layer as a heating means for heat development or fixing processing. The heat generating element in this case is disclosed in
The thing described in 1-1145544 can be used. The heating temperature in the heat development or fixing step is preferably from 40 to 100C, more preferably from 50 to 95C, particularly preferably from 60 to 90C. or,
The heating time is 0.1 to 120 seconds, preferably 2 to 6 seconds.
0 seconds.

As a heating method in the developing step, a heating block, a plate, a hot plate, a hot presser, a heat roller, a heat drum, a halogen lamp heater, an infrared and far-infrared lamp heater, or the like is used. Or passing through a high-temperature atmosphere.
The method described in JP-A-62-253159 and JP-A-61-147244, page 27, can be applied to the method of superposing the photothermographic material and the dye fixing material.

As the color developing agent in the present invention, a p-phenylenediamine compound having a water-soluble group can be preferably used because it has good color reproducibility and little fog.

The p-phenylenediamine-based compound having a water-soluble group has less contamination of the photosensitive material and has less skin damage than a para-phenylenediamine-based compound having no water-soluble group such as N, N-diethyl-p-phenylenediamine. It has the advantage that the skin is hard to rash.

Examples of the water-soluble group include those having at least one on the amino group or benzene nucleus of the p-phenylenediamine-based compound.
_{(CH 2) n -CH 2 OH} , - (CH 2) m -NHSO 2 -
_{(CH 2) n CH 3,} - (CH 2) m -O- (CH 2) n -C
_{H 3, - (CH 2 CH} 2 O) n C m H 2m + 1 (m, n represents an integer of 0 or more, respectively), - COOH, group of -SO ₃ H and the like as preferred.

Specific examples of the color developing agent preferably used in the present invention include (C-1) to (C-1) described in JP-A-4-86674, pp. 7-9.
6).

The above color developing agents are usually used in the form of salts such as hydrochloride, sulfate and p-toluenesulfonate.

The color developing agents may be used alone or in combination of two or more, and if desired, used in combination with a black and white developing agent such as phenidone, 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone or methol. You may use it.

In the present invention, in order to dissolve a part or all of the silver halide by superimposing the photosensitive material with the fixing material after the development processing, a fixing agent is contained in the fixing material as a silver halide solvent. There is a way to keep it.

As the silver halide solvent, known substances can be used. As fixing agents, thiosulfates, sulfites, thiocyanates, thioether compounds and JP-A-4-365037
Nos. 11 to 21 and 5-66540, 1088 to 1
Examples thereof include a nitrogen-containing heterocyclic compound having a sulfide group, a mesoionic compound, and a thioether compound described on page 092.

The fixing material may contain physical development nuclei, and the solubilized silver halide may be fixed on the fixing material.

The physical development nuclei are those which reduce the silver halide which has been solubilized and diffused from the light-sensitive material and is fixed as physical development nuclei. Known as physical development nuclei are zinc, mercury, lead, cadmium, iron, chromium, nickel,
Examples thereof include heavy metals such as tin, cobalt, copper, and ternium; noble metals such as palladium, platinum, silver, and gold; and colloid particles of chalcogen compounds such as sulfur, selenium, and tellurium, all of which can be used.

Examples of the method of applying the developer include spray coating, gravure coating, dip coating, and reverse coating. Preferably, it is better to spray or apply the developing solution in such an amount that it substantially permeates the photosensitive material. Regardless of the method of ejecting the developer, the developer may be ejected while moving a single movable nozzle, or may be ejected using a plurality of fixed nozzles. The injection may be performed while the photosensitive material is fixed and the nozzle is moved, or the injection may be performed while the nozzle is fixed and the photosensitive material is moved. A combination of these may be used. The coating amount of the developer is used in the range of 0.01 to 10 mol of the amount of silver applied per unit area of the photosensitive member / mol of silver applied to the photosensitive member. Preferably 0.
1 to 5 mol / mol of coated silver of the photosensitive member. Further, the temperature of the developer is preferably 30 to 60 ° C.

In the present invention, the scanner is a device that optically scans a photosensitive material and converts reflection or transmission optical density into image information. When scanning, it is common to scan the required area of the photosensitive material by moving the optical part of the scanner in a direction different from the direction of movement of the photosensitive material, and it is recommended that the photosensitive material be fixed. Then, only the optical part of the scanner may be moved, or only the photosensitive material may be moved to fix the optical part of the scanner.
Alternatively, a combination of these may be used.

Light sources for reading image information include a tungsten lamp, a fluorescent lamp, a light emitting diode, a laser beam, and the like.
Tungsten lamps are preferred because they can be used without particular limitation and are inexpensive, and laser beams are preferred because they are stable, have high brightness, and are not easily affected by scattering. The reading method is not particularly limited, but it is preferable to read the transmitted light in terms of sharpness.

[0173]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.

Example 1 << Preparation of Silver Halide Emulsion >> As silver halide emulsions, three kinds of red-sensitive, green-sensitive and blue-sensitive emulsions which had been spectrally sensitized were prepared as follows.

<For Red-Sensitive Emulsion Layer> Silver iodobromide emulsion (average particle diameter 0.7 μm) (average iodine content 7.5 mol%) 0.9 g Sensitizing dye (S-1) 1.7 × 10 ^-4 mol of sensitizing dye (S-2) 1.6 × 10 ^-4 mol of sensitizing dye (S-3) 0.1 × 10 ^-4 mol <for green-sensitive emulsion layer> Silver iodobromide emulsion (average grain (Diameter 0.7 μm) (average iodine content 7.5 mol%) 0.9 g sensitizing dye (S-4) 1.1 × 10 ⁻⁴ mol sensitizing dye (S-5) 2.0 × 10 ⁻⁴ Molar sensitizing dye (S-6) 0.3 × 10 ⁻⁴ mol <for blue-sensitive emulsion layer> Silver iodobromide emulsion (average particle size 0.8 μm) (average iodine content 8.5 mol%) 5 g Sensitizing dye (S-7) 3 × 10 ^-4 mol Sensitizing dye (S-8) 1.2 × 10 ^-4 mol

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The coupler and the color developing agent are dissolved in a mixed solution of a high boiling point solvent and ethyl acidate as described in the following layer constitution, mixed with a gelatin aqueous solution containing a surfactant, and then mixed with a high speed ink. After being emulsified and dispersed using a rotary mixer, it was added directly to the emulsion.

<Preparation of Photosensitive Material> Using the material thus obtained, a photosensitive material 101 (comparative example) having the following multilayer structure was prepared on a subbed transparent PEN base. The addition amount was mg / m ^2, and silver halide and colloidal silver were expressed in terms of silver.

Photosensitive material 101 7th layer Gelatin 1940 Matting agent (silica) 200 Surfactant (a) 50 Surfactant (b) 300 Water-soluble polymer (c) 120 6th layer Gelatin 2000 Blue-sensitive silver halide Emulsion 1250 Yellow coupler (C-2) 460 Color developing agent (CD-1) 500 High boiling solvent (d) 774 Surfactant (b) 80 Surfactant (f) 70 Water-soluble polymer (c) 40 Antifoggant (J) 1.6 Fifth layer Gelatin 970 Yellow colloidal silver 35 Additive (g) 35 Additive (h) 35 Additive (i) 6 High boiling solvent (d) 75 Auxiliary developing agent (ETA-19) 30 Fourth layer Gelatin 1000 Green-sensitive silver halide emulsion 625 Magenta coupler (C-83) 240 Color developing agent (CD-1) 250 High boiling point Medium (d) 490 Antifoggant (j) 0.8 Surfactant (b) 40 Surfactant (f) 35 Water-soluble polymer (c) 20 Third layer Gelatin 970 Surfactant (a) 50 Surfactant Agent (b) 300 Water-soluble polymer (c) 60 Auxiliary developing agent (ETA-19) 30 Second layer Gelatin 1000 Red-sensitive silver halide emulsion 625 Cyan coupler (C-60) 240 Color developing agent (CD-1) 250 Surfactant (b) 40 Surfactant (f) 35 High boiling solvent (d) 410 Antifoggant (j) 0.8 Water-soluble polymer (c) 700 First layer Gelatin 800 Black colloidal silver 75 Ultraviolet absorption Agent (k) 200 High boiling point solvent (l) 200

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As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. Further, Cpd-2, Cpd-3, Cpd
-4 and Cpd-5 each in a total amount of 15.0 mg / m
² , 60.01 mg / m ² , 50.0 mg / m ² and 1
0.0 mg / m ² was added.

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The color developing agent (CD-1) was removed from the second, fourth and sixth layers of the photosensitive material 101, and the auxiliary developing agent (ETA-19) was used from the third and fifth layers. Except that the yellow coupler C-83 of the sixth layer was changed to C-29 and the cyan coupler C-60 of the second layer was changed to C-61, and the photosensitive material 102 was changed in the same manner as the photosensitive material 101. Produced.

<Preparation of Developing Solution> Color developing solutions 1 and 2 having the following structures were prepared.

(Composition of Color Developing Solution 1) Water 800 ml Potassium carbonate 30 g Sodium bicarbonate 2.5 g Potassium sulfite 3.0 g Sodium bromide 1.3 g Potassium iodide 1.2 mg Hydroxyamine sulfate 2.5 g Sodium chloride 6 g 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulfate (CD-4) 10.0 g Diethylenetetraaminepentaacetic acid 3.0 g Potassium hydroxide 1.2 g Water was added. Work up to 1.0 l and adjust to pH 10.06 with potassium hydroxide or 20% sulfuric acid.

(Composition of Color Developing Solution 2) Color developing solution 1 was obtained by removing 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulfate (CD-4) from Color developing solution 1. Liquid 2 was prepared.

<Preparation of Fixing Material> A fixing material was prepared on a subbed PEN base with the following structure. The amount added is m
g / m ² and silver halide and colloidal silver were expressed in terms of silver.

Fourth layer Gelatin 220 Water-soluble polymer (1) 60 Water-soluble polymer (2) 200 Potassium nitrate 12 Matting agent (silica) 10 Surfactant (4) 7 Surfactant (5) 7 Surfactant (6) 10) Additive (7) 40 Colloidal silver 20 Third layer Gelatin 240 Water-soluble polymer (2) 24 Hardener (8) 180 Surfactant (9) 9 Second layer Gelatin 2400 Water-soluble polymer (2) 360 Water-soluble polymer (10) 700 Water-soluble polymer (11) 600 High boiling solvent (12) 2000 Additive (13) 2750 Additive (14) 765 Additive (15) 20 Surfactant (9) 24 First layer Eye Gelatin 280 Water-soluble polymer (1) 12 Surfactant (9) 14 Hardener (8) 185

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A part of the prepared photosensitive material was heated at 55 ° C. and 80%
It was stored for one week in the environment of RH. The photosensitive material before and after storage was cut into a normal 135-negative film size, punched, and loaded into a camera, and then a person and a Macbeth chart were photographed. 55 ° C after dip coating a developer on this sample
And then heated and developed. After processing, a color negative image was obtained on the light-sensitive material.
When the fixing material was overlapped and heated on a heat drum heated to 60 ° C. for 50 seconds, and the processing sheet and the photosensitive material were peeled off, a part of the dissolved silver halide was transferred to the fixing material.

The processed sample was treated with a scanner Q-s manufactured by Konica Corporation.
The image is read using a CAN, and the image is processed on a personal computer.
The results were as shown in Table 2 when output at C and visually evaluated.

[0196]

[Table 2]

As is clear from Table 2, the image quality was improved by using the fixing material, and the temporal stability of the photosensitive material was improved by applying the color developing agent without incorporating it in the photosensitive material.

Example 2 A sample (206) was prepared from the sample (201) in the same manner as in Example 1 except that the coating amount of the silver halide emulsion in each layer of the light-sensitive material 102 was changed as shown in Table 3 in terms of silver. Was spray-coated and evaluated in the same manner (Table 3). Some of the samples were evaluated for processing at a fixing temperature of 35 ° C. and 120 ° C. (Table 4).

[0199]

[Table 3]

[0200]

[Table 4]

According to Table 3, the total amount of silver in the light-sensitive material was 0.7 to
In the case of 3.5 g, better image quality was obtained. Further, from Table 4, a good image was obtained when the fixing temperature was 60 ° C. 35
At 120C, the image was dark, and at 120C, bubbles were generated during processing, causing unevenness in the processing.

Example 3 Processing was evaluated in the same manner as in Example 1 except that the fixing time of Konica Color LV100 (manufactured by Konica Corporation) was changed to 90 seconds. As a result, a good quality image was obtained.

Example 4 The photosensitive material 102 was cut into a normal 135-negative film size, punched, and loaded into a camera, and then a person and a Macbeth chart were photographed. After applying a color developing solution to the sample by dip coating, the sample was brought into contact with a heat drum heated to 55 ° C. from the back side and developed by heating. After processing, a color negative image was obtained on the light-sensitive material. Before overlapping with the fixing material, a bleaching solution shown below was spray-coated on the photosensitive layer, contacted from the back with a heat drum heated to 55 ° C. from the back side, and heated and bleached.

(Bleaching solution composition) Water 800 ml 1,3-Diaminopropanetetraacetate ammonium iron (III) salt 125 g ethylenediaminetetraacetic acid 2 g sodium nitrate 40 g ammonium bromide 150 g glacial acetic acid 40 g Alternatively, adjust the pH to 4.4 using glacial acetic acid.

Table 5 shows the results.

[0206]

[Table 5]

As is clear from Table 5, when the images were compared with and without the bleaching process, although the noise caused by the residual developed silver and silver halide was reduced by bleaching, good images were obtained. There has occurred.

As is apparent from the above description, the present invention can provide a simple and good image forming method which can be applied to conventional photographic materials and has excellent stability over time of the photographic materials.

[0209]

According to the present invention, the silver halide color photographic light-sensitive material for photography can be applied to conventional silver halide color photographic light-sensitive materials for photography, and the silver halide color photographic light-sensitive material for photography has excellent stability over time. It was possible to provide a simple and good image forming method using the material.

Claims (5)

[Claims] 1. A silver halide photographic light-sensitive material containing a coupler, silver halide and a binder is provided on a support, a developing solution containing a color developing agent is formed after imagewise exposure, and a dye image is formed. An image forming method comprising forming a dye image by dissolving a part or all of silver halide by subjecting a fixing material to an overlapping process with a photosensitive layer and a fixing layer facing each other. 2. A silver halide photographic light-sensitive material containing a coupler, silver halide and a binder is provided on a support, and a developer containing a color developing agent is formed after imagewise exposure to form a dye image. The dyeing image is formed by dissolving part or all of the silver halide by superposing the fixing material with the photosensitive layer and the fixing layer facing each other, and optically or electrically converting the image information. An image forming method comprising obtaining a color image on another recording material after obtaining image information. 3. A silver halide photographic light-sensitive material containing a coupler, silver halide and a binder is provided on a support, and a developer containing a color developing agent is formed after imagewise exposure to form a dye image. The dye image is formed by dissolving a part or all of the silver halide without removing the developed silver by subjecting the fixing material to an overlapping process with the photosensitive layer and the fixing layer facing each other. Item 3. The image forming method according to Item 1 or 2. 4. A silver halide photographic light-sensitive material containing a coupler, silver halide and a binder is provided on a support, and a developer containing a color developing agent after imagewise exposure is provided to form a dye image. The fixing material is overlapped with the photosensitive layer and the fixing layer facing each other and processed at 40 ° C. to 100 ° C. to form a dye image by dissolving a part or all of the silver halide. An image forming method characterized by obtaining a color image on another recording material after obtaining image information by optical or electrical conversion. 5. The silver halide photographic light-sensitive material before development processing has a total silver content of 0.7 to 3.5 g / silver halide.
Claim 1, 2, 3 or 4 image forming method wherein it is m ^2.