JPH1078638A - Silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable simple and rapid image formation and also image formation even through a conventional color development process by incorporating photosensitive silver halide and a specified developing agent and a dye-forming coupler having a specified cationic releasable group in the photosensitive material. SOLUTION: The photosensitive material contains the photosensitive silver halide and one of the developing agents represents by formula I and the like and the dye-forming coupler having a cationic releasable group represented by formula II Cp-Y and a coupler having an anionic releasable group represented by formula III Cp-(Time)t -PUG, and in formulae I-III, each of R1 -R4 is an H or halogen atom or the like; R5 is an alkyl group or the like; Cp is a group for forming a dye at the site in which Y is not combined; Y is a group to be released as a cation at the time of a coupling reaction; Time is a timing group; PUG is a photographic useful group; and (t) is 0 or a positive integer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel silver halide color photographic material for recording an image.

[0002]

2. Description of the Related Art In a method usually called a color photograph, an image is recorded using a color negative film, image information recorded on the color negative film is converted into a color image by a development process, and the image information on the developed color negative film is converted into a color image. A color print is obtained by optically printing on color photographic paper.

[0003] At present, color photographs that are widely used adopt color reproduction by a subtractive color method. That is, in a general color negative film, a photosensitive layer using a silver halide emulsion, which is a photosensitive element having photosensitivity in the blue, green, and red regions, is provided on a transparent support. Contains a combination of so-called color couplers that form complementary hues of yellow, magenta, and cyan. The color negative film that has been subjected to imagewise exposure by photography is subjected to color development processing in a color developer containing an aromatic primary amine developing agent. The silver halide grains exposed at this time are developed or reduced by the developing agent in the developing solution, and the respective dyes are formed by the coupling reaction between the oxidized product of the developing agent and the above-described color coupler at the same time. Metallic silver (developed silver) generated by development and unreacted silver halide are removed by bleaching and fixing, respectively, to obtain a dye image. Optical exposure is applied to color photographic paper having the same combination of photosensitive wavelength range and color hue through a developed color negative film, and the same color development, bleaching, and fixing are applied to reproduce the original scene. A color print consisting of the dye image thus obtained can be obtained.

[0004] Although these systems are now widespread, the demand for increased simplicity and speed is increasing. First, the processing bath for performing the color development, bleaching and fixing processes described above requires precise control of the composition and temperature, and requires specialized knowledge and skilled operations. Second, these processing solutions contain compounds that must be environmentally regulated, such as color developing agents and iron chelates, which are bleaching agents. Often requires equipment. Third, although the development process has been shortened in recent years, these development processes require time and are still inadequate for the demand for quickly reproducing a recorded image.

On the other hand, many photothermographic materials have been proposed as systems which do not require a processing solution containing a color developing agent. For example, "Basics of Photographic Engineering", Non-silver salt photography (19
1982, Corona Co., Ltd.), pages 242 to 255, and U.S. Pat. No. 4,500,626. A photothermographic material using silver halide is a photographic method that has been widely practiced since it has superior photographic properties such as sensitivity and gradation as compared with methods such as electrophotography and diazo photography. One example is a color development method in which a dye image is formed by a coupling reaction between an oxidized form of a developing agent and a coupler. Regarding developing agents and couplers that can be used in this color development system, see US Pat. No. 3,531,256.
No. 3,761,270, p-phenylenediamine reducing agent and phenol or active methylene coupler.
No. 4, p-aminophenol-based reducing agent, 4,02
No. 1,240 proposes a combination of a sulfonamidophenol-based reducing agent and a 4-equivalent coupler, and the like.

[0006] As another thermal development method which does not require a processing solution containing a color developing agent, a photography method is provided by Fuji Photo Film Co., Ltd. In this method, a small amount of water is supplied to a photosensitive member containing a base precursor, and the photosensitive member is bonded to an image receiving material and heated to cause a development reaction. Japanese Patent Application No. Hei 7-180568 discloses a method in which a photographic material containing a developing agent and a coupler is used as a photographic material using a pictography method.
Nos. 7-244698, 7-26804, 8
No. -30103. This method is characterized in that the waste liquid treatment of the treatment liquid is not required.

However, at present, systems using developer processing are widely used, but in areas where new facilities for thermal development are not sufficiently used, only systems using thermal development are applicable. The system will not be able to process. Further, even in an area where a heat developing machine can be used, a user is required to distinguish between a conventional color negative film and a conventional film and to perform different processing, thereby giving the user trouble.

As a result of the study by the present inventors, the developing agent represented by the general formula (I) and / or (II) is combined with the general formula (III)
A photosensitive material containing a dye-forming coupler having a cationic leaving group represented by the formula (1) is a conventional developing solution processing method, that is, a developing solution containing a primary aromatic amine developing agent and a conventional developing solution. It has become clear that a color image can be obtained by using any of the subsequent bleaching and fixing processes.

This photosensitive material has good image quality, specifically, granularity during thermal development, but is usually mixed with a developer containing a primary aromatic amine developing agent, followed by a bleaching process. Investigations by the present inventors have revealed that when processed by the fixing process, the granularity is poor, the color reproducibility is poor, and the color turbidity due to the bleach-fixing failure is large.

[0010]

SUMMARY OF THE INVENTION A first object of the present invention is to provide a simple and rapid thermal development system capable of forming an image with less environmental load, and also capable of forming an image even in a conventional color development process. The second object is to provide a color photographic light-sensitive material having good image quality in any of the developing methods, specifically, in terms of graininess, color reproducibility, and prevention of color turbidity. An object of the present invention is to provide a silver halide color photographic light-sensitive material capable of obtaining an image and suitable for photographing.

[0011]

That is, the object of the present invention can be achieved by the following photographic materials. (1) at least a photosensitive silver halide on a support,
At least one developing agent represented by formula (I) or (II), a dye-forming coupler having a cationic leaving group represented by formula (III), and a dye-forming coupler represented by formula (IV) A silver halide color photographic material comprising a coupler having an anionic leaving group capable of releasing a photographically useful group.

[0012]

Embedded image

In the formula, R _{1 to} R ₄ are a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkylcarbonamide group, an arylcarbonamide group, an alkylsulfonamide group, an arylsulfonamide group, an alkoxy group, an aryloxy group. , Alkylthio, arylthio, alkylcarbamoyl, arylcarbamoyl, carbamoyl, alkylsulfamoyl, arylsulfamoyl, sulfamoyl, cyano, alkylsulfonyl, arylsulfonyl, alkoxycarbonyl, aryloxy Represents a carbonyl group, an alkylcarbonyl group, an arylcarbonyl group or an acyloxy group, and R ₅ represents an alkyl group, an aryl group or a heterocyclic group. Z represents an atomic group necessary for forming an aromatic ring or a heteroaromatic ring. When Z forms a substituted benzene ring, the total value of Hammett constant (σ) of the substituent is 1 or more. It is. General formula (III) Cp-Y In general formula (III), Cp is a developing agent and / or an aromatic first compound represented by general formula (I) and / or (II) at a position where Y is bonded. A group that forms a dye by coupling reaction with an oxidized form of a secondary amine developing agent.
Y is a group capable of leaving as a cation during the coupling reaction. General formula (IV) Cp- (Time) t-PUG In the formula, Cp has the same meaning as Cp in general formula (III). (T
ime) t-PUG is a group capable of leaving as an anion from the coupler of the general formula (IV) upon coupling reaction with an oxidized form of the developing agent, and Time represents a timing group. The timing group is anionic (Tim
e) t-PUG is a group having a function of generating PUG after leaving from the Cp portion. PUG represents a photographically useful group. t represents 0 or a positive integer, preferably 0,
1 or 2. (2) The silver halide color photographic material as described in (1) above, wherein the PUG released from the coupler having an anionic leaving group represented by the general formula (IV) is a development inhibiting substance. (3) A silver halide color photographic light-sensitive material which can be subjected to color development processing and heat development processing using a developer containing a primary aromatic amine developing agent (1) or (2). The silver halide color photographic light-sensitive material according to the above item.

That is, general formulas (I) and / or (I
The photosensitive material containing the developing agent represented by the formula (I) and the dye-forming coupler having a cationic leaving group represented by the general formula (III) can be prepared by (a) a thermal development method or (b) a conventional method. A developer image processing method, that is, a color image can be obtained using any of a processing method including a developing solution containing a primary aromatic amine developing agent and a bleaching process and a fixing process that is usually performed subsequently. A color image having substantially the same hue of the resulting dye can be obtained by either of the processes. Thus, it is completely unexpected that one silver halide color photographic light-sensitive material can be processed by any one of the two developing methods having different principles to form a color image. Therefore, the cost can be reduced and the processing efficiency can be improved.

When the photosensitive material is subjected to a heat development process, the image quality, specifically, the granularity is good, but the photosensitive material is usually followed by a developing solution containing a primary aromatic amine developing agent. When processed by the bleaching process and the fixing process, the granularity and color reproducibility are deteriorated, and color turbidity due to poor bleaching and fixing is increased. Therefore, the image quality of this photosensitive material is insufficient particularly for use in photographing.

However, in the above-mentioned light-sensitive material further containing a coupler having an anionic leaving group capable of releasing a photographically useful group represented by the general formula (IV), When processed with a developer containing a group III amine developing agent and a bleaching process and a fixing process which is usually performed subsequently, the graininess, color reproducibility, and color turbidity due to poor bleach-fixing were improved.

Further, in the case of a light-sensitive material to which a coupler having an anionic leaving group capable of releasing a photographically useful group was added, no coupler capable of releasing a photographically useful group was added in the case of heat development processing. The surprising result that the photosensitive material and photographic performance (specifically, sensitivity, gradation, etc.) hardly deteriorated was obtained.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The compound represented by the general formula (I) is a compound generically called sulfonamidophenol,
It is a compound known per se. In the formula, R _{1 to} R ₄ each represent a hydrogen atom, a halogen atom (for example, a chloro group or a bromo group), or an alkyl group (preferably having 1 to 30 carbon atoms).
For example, a methyl group, an ethyl group, an isopropyl group, an n-butyl group, a t-butyl group), an aryl group (preferably having 6 to 40 carbon atoms, such as a phenyl group, a tolyl group, a xylyl group), and an alkylcarbonamide group ( It preferably has 2 to 30 carbon atoms, for example, acetylamino group, propionylamino group, butyroylamino group, arylcarbonamide group (preferably, 7 to 40 carbon atoms, for example, benzoylamino group), alkylsulfonamide group (Preferably having 1 to 30 carbon atoms such as methanesulfonylamino group and ethanesulfonylamino group), arylsulfonamide group (preferably having 6 to 40 carbon atoms such as benzenesulfonylamino group and toluenesulfonylamino group), An alkoxy group (preferably having 1 to 30 carbon atoms, such as Shi group, an ethoxy group, a butoxy group),
An aryloxy group (preferably having 6 to 30 carbon atoms);
For example, a phenoxy group), an alkylthio group (preferably having 1 to 30 carbon atoms, such as a methylthio group, an ethylthio group, or a butylthio group), an arylthio group (preferably having a carbon number of 6 to 40, such as a phenylthio group, a tolylthio group), Alkylcarbamoyl group (preferably having 2 to 2 carbon atoms)
30 things. For example, a methylcarbamoyl group, a dimethylcarbamoyl group, an ethylcarbamoyl group, a diethylcarbamoyl group, a dibutylcarbamoyl group, a piperidylcarbamoyl group, a morpholylcarbamoyl group), an arylcarbamoyl group (preferably having 7 to 40 carbon atoms, for example, a phenylcarbamoyl group, Methylphenylcarbamoyl group, ethylphenylcarbamoyl group, benzylphenylcarbamoyl group), carbamoyl group, alkylsulfamoyl group (preferably having 1 to 30 carbon atoms, for example, methylsulfamoyl group, dimethylsulfamoyl group, ethylsulfamoyl group) Famoyl group, diethylsulfamoyl group, dibutylsulfamoyl group, piperidylsulfamoyl group, morpholylsulfamoyl group), arylsulfamoyl group (preferably having 6 to 6 carbon atoms) 0 ones. For example phenylsulfamoyl group, methylphenyl sulfamoyl group, ethylphenyl sulfamoyl group, benzyl phenyl sulfamoyl group), a sulfamoyl group, a cyano group, an alkylsulfonyl group (preferably having 1 to 30 carbon atoms
Stuff. For example, a methanesulfonyl group, an ethanesulfonyl group), an arylsulfonyl group (preferably having 6 to 4 carbon atoms)
0 things. For example, phenylsulfonyl group, 4-chlorophenylsulfonyl group, p-toluenesulfonyl group), alkoxycarbonyl group (preferably having 2 to 30 carbon atoms, such as methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group), aryloxycarbonyl group (Preferably having 7 to 40 carbon atoms, such as a phenoxycarbonyl group), an alkylcarbonyl group (preferably having 2 to 30 carbon atoms, such as an acetyl group, a propionyl group, and a butyroyl group), and an arylcarbonyl group (preferably having a carbon number of 7 to 30). 7 to 40, such as benzoyl group and alkylbenzoyl group, or acyloxy group (preferably having 2 to 30 carbon atoms, such as acetyloxy group,
(Propionyloxy group, butyroyloxy group).
Among R _{1 to} R ₄ , R ₂ and R ₄ are preferably a hydrogen atom. The sum of the Hammett constants σ _P values of R _{1 to} R ₄ is preferably 0 or more, and the upper limit is not particularly limited, but is preferably 5 or less.

R ₅ is an alkyl group (preferably having 1 to carbon atoms)
30 things. For example, a methyl group, an ethyl group, a butyl group, an octyl group, a lauryl group, a cetyl group, a stearyl group), an aryl group (preferably having 6 to 30 carbon atoms, for example, a phenyl group, a tolyl group, a xylyl group, a 4-methoxyphenyl) Group, dodecylphenyl group, chlorophenyl group, trichlorophenyl group, nitrochlorophenyl group, triisopropylphenyl group, 4-dodecyloxyphenyl group,
3,5-di- (methoxycarbonyl) group) or a heterocyclic group (preferably a 5- to 10-membered ring, for example, a pyridyl group). The compound represented by the general formula (II) is a compound generically called sulfonylhydrazine. It is a compound known per se. In the formula, R ₅ has the same meaning as in general formula (I), and Z represents an atomic group forming an aromatic ring.
The aromatic ring formed by Z needs to be sufficiently electron-attracting in order to impart silver developing activity to the present compound. For this reason, an aromatic ring which forms a nitrogen-containing aromatic ring or has an electron-withdrawing group introduced into a benzene ring is preferably used. As such an aromatic ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a quinoline ring, a quinoxaline ring and the like are preferable.

In the case of a benzene ring, the substituent is
Alkylsulfonyl group (for example, methanesulfonyl group, ethanesulfonyl group), halogen atom (for example, chloro group,
Bromyl group), alkylcarbamoyl group (eg, methylcarbamoyl group, dimethylcarbamoyl group, ethylcarbamoyl group, diethylcarbamoyl group, dibutylcarbamoyl group, piperidylcarbamoyl group, morpholylcarbamoyl group), arylcarbamoyl group (eg, phenylcarbamoyl group, methylphenyl) Carbamoyl group, ethylphenylcarbamoyl group, benzylphenylcarbamoyl group), carbamoyl group, alkylsulfamoyl group (for example, methylsulfamoyl group, dimethylsulfamoyl group, ethylsulfamoyl group, diethylsulfamoyl group, dibutylsulfamoyl group) A famoyl group, a piperidylsulfamoyl group, a morpholylsulfamoyl group), an arylsulfamoyl group (for example, a phenylsulfamoyl group,
Methylphenylsulfamoyl group, ethylphenylsulfamoyl group, benzylphenylsulfamoyl group),
Sulfamoyl group, cyano group, alkylsulfonyl group (for example, methanesulfonyl group, ethanesulfonyl group),
Arylsulfonyl group (for example, phenylsulfonyl group,
4-chlorophenylsulfonyl group, p-toluenesulfonyl group), alkoxycarbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group), aryloxycarbonyl group (for example, phenoxycarbonyl group), alkylcarbonyl group (for example, acetyl group, A propionyl group, a butyroyl group), or an arylcarbonyl group (for example, a benzoyl group or an alkylbenzoyl group). The preferred range of the carbon number of each of these substituents is the same as the value specifically described for the same substituent for R _{1 to} R ₄ . The sum of Hammett constant σ values of the above substituents is 1 or more, and the upper limit is not particularly limited, but is preferably 5 or less.

Hereinafter, specific examples of the compounds represented by formulas (I) and (II) are shown, but the compounds of the present invention are not limited thereto.

[0022]

Embedded image

[0023]

Embedded image

[0024]

Embedded image

[0025]

Embedded image

[0026]

Embedded image

The dye-forming coupler having a cationic leaving group that can be used in the present invention will be described. The dye-forming coupler having a cationic leaving group that can be used in the present invention is represented by the following general formula (III). General formula (III) Cp-Y In general formula (III), Cp performs a coupling reaction with an oxidized developing agent of general formula (I) and / or (II) at a position where Y is bonded to a dye. Is a group that forms Y is a group capable of leaving as a cation during the coupling reaction, and Cp is present when the elimination reaction between Cp and Y is performed.
The leaving group is characterized in that the bonding electron pair of -Y takes the form of moving to the Cp side. Y is a hydrogen atom, a formyl group, a carbamoyl group, a substituted methylene group (for example, an aryl group, a sulfamoyl group, a carbamoyl group, an alkoxy group, an amino group, a hydroxyl group), an acyl group, a sulfonyl group, or the like. And leaving groups.

The addition amount of the coupler represented by the general formula (III) used in the present invention depends on its molar extinction coefficient. When the dye to be formed is a coupler having an epsilon of about 5,000 to 500,000, the coating amount is 0.001 to 100 mmol / m 2, preferably 0.05 to 10 mmol / m 2, more preferably 0.1 to 5 mmol / m 2. is there. The amount of the color developing agent represented by the general formula (I) and / or (II) used in the present invention is 0.01 to 100 in a molar ratio with respect to all couplers.
Times, preferably 0.1 to 10 times, more preferably,
It is 0.2 to 4 times.

Cp will be specifically described. General formula (II
Cp in I) is preferably the following formulas (1) to (12)
It is represented by These are compounds generally referred to as active methylene, pyrazolone, pyrazoloazole, phenol, naphthol, and pyrrolotriazole, respectively, and are compounds known in the art.

[0030]

Embedded image

[0031]

Embedded image

[0032]

Embedded image

Formulas (1) to (4) represent couplers referred to as active methylene couplers, wherein R ¹⁴ represents an optionally substituted acyl group, cyano group, nitro group, aryl group, A heterocyclic residue, 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 residue. In the general formula (4), R ¹⁶ is an aryl group or a heterocyclic residue which may have a substituent. R
^14, as the R ^15, the substituent that may be R ¹⁶ has, include those mentioned as examples of substituents in Q of the above general formula (I).

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 referred to as a 5-pyrazolone 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.

In the 5-pyrazolone coupler represented by the general formula (5), R ¹⁷ is an aryl group or an acyl group,
A phenyl group in which ¹⁸ is substituted with one or more halogen atoms is preferred.

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 are organic groups linked by a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom. It is a substituent or a halogen atom.

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-based coupler, wherein R ¹⁹ represents a hydrogen atom or a substituent. Q ³ represents a group of nonmetallic atoms necessary for forming a 5-membered azole ring containing 2 to 4 nitrogen atoms, and the azole ring may have a substituent (including a condensed ring).

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

For details of the substituents on the azole ring represented by the substituents R ¹⁹ and Q ³ , see, for example, US Pat.
No. 0,654, column 2, line 41 to column 8, line 27. Preferably, JP-A-61-
No. 65245, a pyrazoloazole coupler having a branched alkyl group directly bonded to the 2, 3 or 6-position of the pyrazolotriazole group, and a sulfonamide group in the molecule described in JP-A-61-65245. A pyrazoloazole coupler having an alkoxyphenylsulfonamide ballast group described in JP-A-61-147254;
Pyrazolotriazole couplers having an alkoxy group or an aryloxy group at the 6-position described in JP-A-209457 or JP-A-63-307453;
22279 is a pyrazolotriazole coupler having a carboxamide group in the molecule.

The general formulas (7) and (8) are couplers called a phenol coupler and a naphthol coupler, respectively, wherein R ²⁰ is a hydrogen atom or —CONR ²² R
_{^{23, -SO 2 NR 22 R 23}} , -NHCOR 22, -NHCO
NR 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, 1 represents an integer selected from 0 to 2, and m represents an integer selected from 0 to 4. When l and m are 2 or more, R ²¹ may be different from each other. Examples of the substituent of R ^{21 to} R ²³ include those described as examples of the substituent of Q in the general formula (I).

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.
Nos. 2,166-9656, 2,5-diacylaminophenols, U.S. Pat. Nos. 3,446,622, 4,333,999, 4,451,559, and 4,427, No. 767, etc., and 2-phenylureido-5-acylaminophenols.

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-amido-1-naphthol type and the like.

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 for R ³² , R ³³ , and R ³⁴ include those described as examples of the substituent for Q in the general formula (I). Preferred examples of the pyrrolotriazole-based couplers represented by the general formulas (9) to (12) include European Patent Nos. 488,248A1 and 491,197A1.
And at least one of R ³² and R ³³ described in JP-A No. 545300/1990 is an electron-withdrawing group.

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

US Pat. Nos. 4,327,173 and 4,564,586 as 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.

The 5,5-fused heterocyclic couplers include:
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.

The 5,6-fused heterocyclic couplers include:
Pyrazolopyrimidine couplers described in U.S. Pat. No. 4,950,585, pyrrolotriazine couplers described in JP-A-4-204730, EP 556,70.
The couplers described in No. 0 can be used.

In the present invention, in addition to the above-mentioned couplers, West German Patent Nos. 3,819,051A 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 dye-forming coupler having a cationic leaving group that can be used in the present invention are shown below, but the present invention is not limited by these examples.

[0056]

Embedded image

[0057]

Embedded image

[0058]

Embedded image

[0059]

Embedded image

[0060]

Embedded image

[0061]

Embedded image

[0062]

Embedded image

[0063]

Embedded image

[0064]

Embedded image

[0065]

Embedded image

[0066]

Embedded image

[0067]

Embedded image

[0068]

Embedded image

[0069]

Embedded image

[0070]

Embedded image

Next, couplers having an anionic leaving group capable of releasing a photographically useful group which can be used in the present invention will be described. The coupler having an anionic leaving group capable of releasing a photographically useful group that can be used in the present invention is represented by the following general formula (IV).

Formula (IV) Cp- (Time) t-PUG

In the formula, Cp has the same meaning as Cp in formula (III). Cp is a group that performs a coupling reaction with an oxidized developing agent at a position where-(Time) t-PUG is bonded. This Cp does not need to have the same hue to be formed as Cp of the general formula (III) (it is only necessary to release PUG, and it is not necessary to develop color). (Time)
t-PUG is a group that is released as an anion during a coupling reaction with an oxidized developing agent, and Cp and (Ti
me) During the elimination reaction with t-PUG, Cp- (Tim
e) A leaving group characterized in that the bonding electron pair of t takes the form of moving to the (Time) t side. Time represents a timing group. The timing group is anionic (Tim
e) t-PUG is a group having a function of generating PUG after leaving from the Cp portion. PUG represents a photographically useful group. t represents 0 or a positive integer, preferably 0,
1 or 2.

In the present invention, the coupler of the general formula (IV) is used in an amount of from 0.01 mol to 10 mol of the coupler of the general formula (III). Preferably, the coupler of general formula (IV) is used in an amount of between 0.01 mol and 0.5 mol of the coupler of general formula (III).

The Time group represents a timing group. The timing group is a group having a function of generating a PUG after (Time) t-PUG is released from the Cp portion. Regarding groups having such a function, for example, US Pat.
146,396, 4,652,516 or 4,698,297, which utilize the cleavage reaction of hemiacetal, U.S. Pat. No. 4,248,962.
No. 4,847,185, 4,912,028 or 4,857,440, a timing group for causing a cleavage reaction using an intramolecular nucleophilic substitution reaction, U.S. Pat. 4,409,323, 5,034
No. 311, No. 5,055,385 or No. 4,42
U.S. Pat. No. 4,54,154 discloses a timing group for causing a cleavage reaction by utilizing an electron transfer reaction described in U.S. Pat.
No. 6,073, a group which causes a cleavage reaction by utilizing the hydrolysis of an imino ketal, or a cleavage reaction utilizing a hydrolysis reaction of an ester, which is described in British Patent No. 1,531,927. And groups that cause it.

Examples of the case where two Times are connected are described in US Pat. Nos. 4,861,701 and 5,026,6.
No. 28, 5,021, 322, 5,021, 32
No. 2, European Published Patent (EP) 499,279A
No. 438,129A. Time may be a timing group that releases two PUGs, such as the timing group described in EP-A-464,612A. Time represents a hetero atom contained therein, preferably an oxygen atom, a sulfur atom or a nitrogen atom, particularly preferably an oxygen atom, a sulfur atom,
binds to p.

[0099] Time preferably contains at least one diffusion-resistant group. The diffusion-resistant group contains a substituent having a total carbon number of 8 to 40, preferably 10 to 22. Preferred Time is the following (T-1),
(T-2) or (T-3).

Formula (T-1) * -W- (X = Y) jC (R ⁸¹ ) R ⁸² -** Formula (T-2) * -W-CO-** Formula (T-3) * -W-LINK-E-**

In the formula, * represents a position bonding to Cp in the general formula (II), ** represents a position bonding to PUG in the general formula (II), and W represents an oxygen atom, a sulfur atom or> N- R ⁸³ represents X and Y each represents a methine or nitrogen atom;
j represents 0, 1 or 2, and R ⁸¹ , R ⁸² and R ⁸³ each represent a hydrogen atom or a substituent. Here, when X and Y each represent a substituted methine, any two of the substituents, R ⁸¹ , R ⁸² and R ⁸³ , are linked to form a cyclic structure (for example, a benzene photosensitive material, a pyrazole ring). It may be either performed or not formed.
In the formula (T-3), E represents an electrophilic group, and LINK
Represents a linking group that sterically links W and E so that they can undergo an intramolecular nucleophilic substitution reaction. Specific examples of Time include, for example, the following.

[0080]

Embedded image

[0081]

Embedded image

[0082]

Embedded image

PUG represents a photographically useful group. Hereinafter, PUG will be specifically described. PUG is a development inhibitor, dye, nucleating agent, developer, coupler, bleaching accelerator,
Bleaching inhibitors, fixing accelerators, development accelerators, silver halide solvents, color toning agents, color image stabilizers, surfactants, hardeners, desensitizers, chelating agents, fluorescent brighteners or precursors thereof And so on. Examples of preferred photographically useful groups are described in U.S. Pat.
No. 248,962, a photographically useful group (in the patent, represented by the general formula PUG), U.S. Pat.
77,563; JP-A-61-201,247; JP-A-62-248,131.
Bleaching accelerators (parts of the leaving group released from the coupler) described in JP-A No. 195/1992, etc., and BARCs, DI (A) Rs described in Research Disclosure No. 37,038 (Feb. 1995), etc. And the leaving group moiety.

In the present invention, preferred as photographically useful groups are development inhibitors and bleaching accelerators, and particularly preferred are development inhibitors. Hereinafter, these preferred examples will be specifically described.

As an example of the development inhibitor, a compound having a mercapto group bonded to a hetero ring. For example, substituted or unsubstituted mercaptoazoles (specifically, 1-phenyl-5-mercaptotetrazole, 1- (4-carboxyphenyl) -5-mercaptotetrazole, 1- (3-
(Hydroxyphenyl) -5-mercaptotetrazole,
1- (4-sulfophenyl) -5-mercaptotetrazole, 1- (3-sulfophenyl) -5-mercaptotetrazole, 1- (4-sulfamoylphenyl) -5
-Mercaptotetrazole, 1- (3-hexanoylaminophenyl) -5-mercaptotetrazole, 1-ethyl-5-mercaptotetrazole, 1- (2-carboxyethyl) -5-mercaptotetrazole, 2-methylthio-5-mercapto -1,3,4-thiadiazole, 2- (2-carboxyethylthio) -5-mercapto-1,3,4-thiadiazole, 3-methyl-4-phenyl-5-mercapto-1,2,4-triazole ,
2- (2-dimethylaminoethylthio) -5-mercapto-1,3,4-thiadiazole, 1- (4-n-hexylcarbamoylphenyl) -2-mercaptoimidazole, 3-acetylamino-4-methyl-5 -Mercapto-1,2,4-triazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2
-Mercaptobenzothiazole, 2-mercapto-6-
Nitro-1,3-benzoxazole, 1- (1-naphthyl) -5-mercaptotetrazole, 2-phenyl-
5-mercapto-1,3,4-oxadiazole, 1-
{3- (3-methylureido) phenyl} -5-mercaptotetrazole, 1- (4-nitrophenyl) -5-
Mercaptotetrazole, 1-butyl-5-mercaptotetrazole, etc., substituted or unsubstituted mercaptoazaindenes (specifically, 6-methyl-4-mercapto-1,3,3a, 7-tetrazaindene, 6 -Methyl-2-benzyl-4-mercapto-1,3,3a, 7
-Tetrazaindene, 6-phenyl-4-mercaptotetrazaindene, 4,6-dimethyl-2-mercapto-
1,3,3a, 7-tetrazaindene, etc., substituted or unsubstituted mercaptopyrimidines (specifically, 2-
Mercaptopyrimidine, 2-mercapto-4-methyl-
6-hydroxypyrimidine, 2-mercapto-4-propylpyrimidine, etc.).

Heterocyclic compounds capable of forming imino silver, for example, substituted or unsubstituted benzotriazoles (specifically, benzotriazole, 5-nitrobenzotriazole, 5-methylbenzotriazole, 5,6-dichlorobenzotriazole, 5-bromobenzotriazole, 5-methoxybenzotriazole, 5-n-butylbenzotriazole, 5-nitro-6-chlorobenzotriazole, 5,6-dimethylbenzotriazole,
4,5,6,7-tetrachlorobenzotriazole, etc., substituted or unsubstituted indazoles (specifically, indazole, 5-nitroindazole, 3-cyanoindazole, 3-chloro-5-nitroindazole,
Substituted or unsubstituted benzimidazoles (specifically, 5-nitrobenzimidazole, 4-nitrobenzimidazole, 5,6-
Dichlorobenzimidazole, 5-cyano-6-chlorobenzimidazole, 5-trifluoromethyl-6-chlorobenzimidazole, and the like.

In addition, the development inhibitor is released in the development step to become a compound having a development inhibiting property, and further, it changes into a compound having substantially no development inhibiting property or having a significantly reduced development inhibiting property. It may be something.
Specifically, 1- (3-phenoxycarbonylphenyl)
-5-mercaptotetrazole, 1- (4-phenoxycarbonylphenyl) -5-mercaptotetrazole,
1- (3-maleimidophenyl) -5-mercaptotetrazole, 5- (phenoxycarbonyl) benzotriazole, 5- (p-cyanophenoxycarbonyl) benzotriazole, 2-phenoxycarbonylmethylthio-5-mercapto-1,3,4 -Thiadiazole, 5-
Phenoxycarbonyl-2-mercaptobenzimidazole, 5- (2,3-dichloropropyloxycarbonyl) benzotriazole, 5- (butylcarbamoylmethoxycarbonyl) benzotriazole, 5- (butoxycarbonylmethoxycarbonyl) benzotriazole, 1- (4 -Benzoyloxyphenyl) -5-mercaptotetrazole, 5- (2-methanesulfonylethoxycarbonyl) -2-mercaptobenzothiazole,
1- {4- (2-chloroethoxycarbonyl) phenyl} -2-mercaptoimidazole, 5-cinnamoylaminobenzotriazole, 1- (3-vinylcarbonylphenyl) -5-mercaptotetrazole, 5-succinimidomethylbenzotriazole, 2- (4-succinimidophenyl) -5-mercapto-1,3,4-
Oxadiazole, 6-phenoxycarbonyl-2-mercaptobenzoxazole and the like can be mentioned.

The PUG may be a dye, and the dye may be diffusible or non-diffusible, or may be water-soluble or water-insoluble. Can be. As the dye, azo dye, azomethine dye, indoaniline dye, indophenol dye, anthraquinone dye, triarylmethane dye, alizarin dye, nitro dye, quinoline dye, indigo dye,
Examples include phthalocyanine dyes, oxonol dyes, cyanine dyes, and merocyanine dyes. In addition, those leuco bodies, those in which the absorption wavelength is temporarily shifted, and those which change into a dye by an oxidation-reduction reaction such as a tetrazolium salt may be used. Further, these dyes may form a chelate dye with an appropriate metal, or may be a dye which forms a metal chelate during a development process or a subsequent step.

With respect to these dyes, for example, US Pat. Nos. 3,880,658, 3,931,144, 3,932,380, 3,932,381 and 3,942,987 And the compounds described in
No. 52,123, No. 3-223,750, No. 4-2
4,633 and EP 603,964 A2.

The dyes and dye precursors include azo dyes, azomethine dyes, indoaniline dyes, indophenol dyes and precursors thereof.

When PUG is a developer, this developer may be a color developing agent. As a developer, a paraphenylenediamine developer, a paraaminophenol developer,
Parasulfonamide phenol developer, dihydroxybenzene developer, paraalkylaminophenol developer,
3-pyrazolidone developers.

When PUG is a bleaching accelerator, the bleaching accelerator is preferably a compound represented by HS-R- (Z) p.
In the formula, R represents a saturated or unsaturated aliphatic group, aromatic group, or heterocyclic group, Z represents an amino group, a hydroxyl group, a carboxyl group, or a sulfo group, and p represents an integer of 1 or more. Z is preferably a hydroxyl group or a carboxyl group, and p is preferably 1, 2 or 3.

Other PUGs are disclosed in Japanese Patent Application No. 60-7 / 1985.
No. 1,768 and U.S. Pat. No. 4,248,962 can be referred to.

In the general formula (I), (Time) t-P
When t of UG is 0, Cp and PUG are bonded. In this case, a preferable bonding mode is an oxygen atom present in PUG,
It is preferable that a nitrogen atom, a sulfur atom, a phosphorus atom, a selenium atom and an iodine atom bond to Cp, more preferably an oxygen atom, a sulfur atom and a nitrogen atom, and most preferably an oxygen atom and a sulfur atom.

Specific examples of the compound represented by the general formula (IV) that can be used in the present invention are shown below, but the present invention is not limited thereto.

[0096]

Embedded image

[0097]

Embedded image

[0098]

Embedded image

[0099]

Embedded image

[0100]

Embedded image

[0101]

Embedded image

[0102]

Embedded image

[0103]

Embedded image

[0104]

Embedded image

[0105]

Embedded image

[0106]

Embedded image

[0107]

Embedded image

[0108]

Embedded image

[0109]

Embedded image

The added layer of the coupler is not particularly limited, but the coupler of the general formula (III) is usually the same layer or an adjacent layer as the light-sensitive silver halide, preferably the same layer, and the coupler of the general formula (IV) is usually The coupler of the formula (III) may be the same layer or an adjacent layer in the same layer or an adjacent layer as the photosensitive silver halide.
The photosensitive material of the present invention basically has a photosensitive silver halide, a color developing agent, a coupler, and a binder on a support, and may further contain an organic metal salt oxidizing agent and the like as necessary. it can. These components are often added to the same layer, but they can be added separately in separate layers as long as they can react.

The hydrophobic additives such as couplers and color developing agents used in the present invention are described in US Pat. No. 2,322,027.
It can be introduced into the layer of the light-sensitive material by a known method such as the method described in the above. In this case, U.S. Pat.
No. 55,470, No. 4,536,466, No. 4,
No. 536,467, 4,587,206, 4,555,476, 4,599,296, and JP-B-3-62,256. 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 organic solvent is 10 g or less, preferably 5 g or less, more preferably 1 g to 0.1 g, per 1 g of the color image forming compound used. Further, 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.
Also, Japanese Patent Publication No. 51-39,853,
No. 9,943, JP-A-62-30,242 and JP-A-63-271339.
And the method of adding as a fine particle dispersion described in No. For compounds that are substantially insoluble in water,
In addition to the above-mentioned method, fine particles can be dispersed and contained in a binder. When dispersing the hydrophobic compound in the hydrophilic colloid, various surfactants can be used. For example, Japanese Patent Application Laid-Open No.
The surfactants described in RD magazines listed in pages 7) to (38) and listed 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. 0,626, columns 51 to 52.

In order to obtain a wide range of colors on a 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, 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 may 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, such as silver rhodan, silver sulfide, silver selenide, silver carbonate, silver phosphate, and organic acid silver, may be contained as separate grains or as part of silver halide grains. When rapid development and desilvering (bleaching, fixing and bleach-fixing) steps are 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, in the case of X-ray sensitive material, 0.1 to 15 mol%,
0.1-5 for graphic arts and micro-sensitive materials
Molar% is a preferred range. 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 preferred, and a silver halide containing 5 to 30 mol% is more preferred.
-20 mol%, particularly preferably 8-15 mol%.
It is preferable that silver iodobromide grains contain silver chloride in order to reduce lattice strain.

The silver halide emulsion of the present invention preferably has a distribution or a structure with respect to the halogen composition in the grains. A typical example is JP-B-43-131.
No. 62, JP-A-61-215540 and JP-A-60-2
No. 22845, JP-A-61-75337, etc. are core-shell or double-structured grains having a different halogen composition in the inside and the surface of the grains.
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 can be thinly applied on the surface of a double-structured grain in the core-shell.

In order to give a structure inside 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 joint structure, a combination of silver halides is of course possible, but a silver salt compound having no rock salt structure, such as silver rhodanate or silver carbonate, can be combined with silver halide to form a joint 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 such a structure, 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 boundary portions having different halogen compositions of grains having these structures may be clear boundaries or unclear boundaries. 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 are present as mixed crystals or with a structure, it is important to control the halogen composition distribution between the grains. The method for measuring the halogen composition distribution between grains is described in JP-A-60-254032. 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 silver chloride content 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 the 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. Examples include single twins containing one twin plane, parallel multiple twins containing two or more parallel twin planes, and non-parallel multiple twins containing two or more non-parallel twin planes. You can select and use it. 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. Furthermore, J
own of Imaging Science
As reported in Vol. 30, pp. 247 (1986), (h11) plane particles represented by the (211) plane, and (3)
The (hh1) plane particle represented by (31), the (hk0) plane particle represented by the (210) plane, and the (hk1) plane particle represented by the (321) plane also require adjustment methods, but depending on the purpose. You can select and use it. (100) face and (11)
1) a tetrahedral particle whose plane coexists in one particle, (10
Particles in which the (0) plane and the (110) plane coexist, 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 Th.
eory and Practice (1930)),
P.131; Gatov, Photographic Science and Engineering (Gutof, Photo)
graphic Science and Engin
eering), Vol. 14, pp. 248-257 (197
0), U.S. Patent Nos. 4,434,226 and 4,4,226.
No. 14,310, No. 4,433,048, No. 4,
439,520 and British Patent 2,112,157.
Can be prepared by the methods described in 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, particularly preferably 3 or more and 1 or less.
It is less than 0. Triangular, hexagonal,
You can choose a circle or the like. U.S. Pat. No. 4,798,
A regular hexagon having substantially equal lengths of six sides as described in Japanese Patent No. 354 is a preferred 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 grain 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. Further, particles described in JP-A-63-163451, in which the thickness of the particles and the distance between twin planes are specified, are also preferable.

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. Also, it is possible to select dislocations introduced linearly or distorted dislocations in a specific direction of the crystal orientation of the grains, to introduce them throughout the grains, or to introduce them only to 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 rounding treatment as disclosed in European Patent No. 96,412 B1 or the like, or a process described 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 sometimes preferable to intentionally form irregularities. JP-A-58-106532, JP-A-60-221
For example, a method of making a hole in a part of a crystal described in No. 320, for example, a vertex or a center of a plane, or a raffle particle described in US Pat. No. 4,643,966.

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, grains having a size of 0.1 to 3 microns are used as photosensitive silver halide grains.

The emulsion used in the present invention may be a polydisperse emulsion having a wide grain size distribution, or a monodisperse emulsion having a narrow size distribution. In some cases, the coefficient of variation of the projected area circle equivalent 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 the number or weight of particles. In order to satisfy the target gradation of the light-sensitive material, two or more monodispersed 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
lafkides, Chemie et Physiq
uePhotographique, Paul Mon
tel., 1967), Duffin, "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 simultaneous 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 in which pAg in a liquid phase in which silver halide is formed is kept 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.

No. 4,334,012, No. 4,301,241, No. 4,150,994. A method of adding previously precipitated silver halide grains to a reaction vessel for preparing an emulsion. 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 once, an addition in a plurality of times, or a continuous addition. It is also effective in some cases to add particles having various halogen compositions to modify the surface.

A method for converting most of the halogen composition of silver halide grains by a halogen conversion method is described in US Pat. Nos. 3,477,852 and 4,142,142.
No. 900, European Patent Nos. 273,429 and 273,
No. 430 and West German Patent No. 3,819,241, 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 sparingly soluble 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 of changing the concentration or changing the flow rate as described in the above-mentioned 4,242,445 is a preferable 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 an effective method. 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.

For the purpose of accelerating ripening, a silver halide solvent is useful. For example, it is known to have excess halide ions present in the reactor to promote ripening. Other ripening agents can also be used. These ripening agents can be incorporated in their entirety in a dispersion medium in a reactor before silver and halide salts are added,
A halide salt, silver salt or deflocculant can be added and introduced into the reactor. As another variant,
The ripening agent can also be introduced independently at the stage of halide and silver salt addition.

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 the like, and thione compounds (for example, tetrasubstituted thioureas described in JP-A-53-82408 and JP-A-55-77737, U.S. Pat. Compounds described in JP-A-143319, mercapto compounds capable of promoting the growth of silver halide grains described in JP-A-57-202531, and amine compounds (for example, JP-A-54-1007).
No. 17, etc.).

Gelatin is advantageously used 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, cellulose sulfate, sodium alginate, starch derivatives, gum arabic Saccharide derivatives such as natural compounds such as polysaccharides such as dextran, pullulan and the like; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole and the like Or various kinds of synthetic hydrophilic high-molecular substances such as a copolymer of the above. Also, vinyl having U.S. Patent No. 4,960,681, superabsorbent polymers described in JP-A-62-245,260, etc., i.e. -COOM or -SO ₃ M a (M is a hydrogen atom or an alkali metal) Copolymers with monomers or copolymers of these vinyl monomers or with other vinyl monomers (for example, sodium methacrylate, ammonium methacrylate, Sumikagel L-5H manufactured by Sumitomo Chemical Co., Ltd.) are 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. Use of low molecular weight gelatin described in JP-A-1-158426 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. There are benzotriazoles, fatty acids and other compounds described in Columns 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. Total coating amount of light-sensitive silver halide emulsion and the organic silver salt is 0.05 to 10 g / m ² in terms of silver, and preferably from 0.1-4 g / m ^2.

The emulsion of 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, but is preferably selected in the range of 5 to 20 ° C. 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. As a water washing method, a noodle water washing method, a dialysis method using a semipermeable membrane, a centrifugal separation method, a coagulation sedimentation method, or an ion exchange method can be used. 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.

When preparing the emulsion of the present invention, for example, during grain formation,
In the desalting step, at the time of chemical sensitization, the presence of a metal ion salt before coating is preferable depending on the purpose. When doping the grains, they are preferably added at the time of grain formation, when modifying the grain surface or when using as a chemical sensitizer, after grain formation and before the end of chemical sensitization. The case of doping the entire grain and the method of doping only the core portion, only the shell portion, only the epitaxial portion, or only the base grain of the grain can be selected. Mg, Ca, Sr, B
a, Al, Sc, Y, La, Cr, Mn, Fe, Co,
Ni, Cu, Zn, Ga, Ru, Rh, Pd, Re, O
s, Ir, Pt, Au, Cd, Hg, Tl, In, S
n, Pb, Bi or the like can be used. These metals can be added in the form of ammonium salts, acetates, nitrates, sulfates, phosphates, hydroxides, or salts that can be dissolved at the time of particle formation, such as six-coordinate complex salts and four-coordinate complex salts. For example, CdBr ₂ , CdCl ₂ , Cd (NO ₃ )
₂ , Pd (NO ₃ ) ₂ , Pb (CH ₃ COO) ₂ , K ₃
[Fe (CN) ₆ ], (NH ₄ ) ₄ [Fe (C
N) ₆ ], K ₃ IrCl ₆ , (NH ₄ ) ₃ RhCl ₆ ,
K ₄ Ru (CN) _{6 and the} like. The ligand of the coordination compound can be selected from halo, aquo, cyano, cyanate, thiocyanate, nitrosyl, thionitrosyl, oxo, and carbonyl. These may be used alone or in combination of two or more metal compounds.

A method of adding a chalcogen compound during preparation of an emulsion as described in US Pat. No. 3,772,031 is sometimes useful. In addition to S, Se, and Te, cyanide, thiocyanate, selenocyanate, carbonate, phosphate, and acetate may be present.

The silver halide grains of the present invention are sulfur-sensitized,
At least one of selenium sensitization, tellurium sensitization (these three are collectively referred to as chalcogen sensitization), noble metal sensitization, or reduction sensitization may be applied in any step of the production process of a silver halide emulsion. it can. 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 at 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.

Chemical sensitization which can be preferably carried out in the present invention is chalcogen sensitization and noble metal sensitization alone or in combination, and is described in TH James, The Photographic Process, 4th Edition. Macmillan, 1977 (TH James, The Ph.
otographic Process, 4the
d. Macmillan, 1977), pages 67-76, and can be carried out using active gelatin, or can be carried out using Research Disclosure Item 1.
2008 (April 1974); Item 13452
(June 1975); Item 307105 (198)
Nov. '09), U.S. Pat. Nos. 2,642,361, 3,297,446, 3,772,031, 3,857,711, and 3,901,714. issue,
Nos. 4,266,018 and 3,904,4
No. 15 and pAg 5-10, pH 5-8 and temperature 3 as described in GB 1,315,755.
At 0 to 80 ° C, sulfur, selenium, tellurium, gold, platinum, palladium, iridium or a combination of a plurality of these sensitizers can be used.

In the sulfur sensitization, an unstable sulfur compound is used. Specifically, thiosulfates (eg, hypo), thioureas (eg, diphenylthiourea, triethylthiourea, allylthiourea, etc.), rhodanine Kind,
Mercaptos, thioamides, thiohydantoins, 4
-Oxooxazolidine-2-thiones, di- or polysulfides, polythionates and elemental sulfur,
And US Patent Nos. 3,857,711 and 4,2
Known sulfur-containing compounds described in Nos. 66,018 and 4,054,457 can be used. Sulfur sensitization is often used in combination with noble metal sensitization.

The preferred amount of the sulfur sensitizer to be used for the silver halide grains of the present invention is 1 × 10 ^-7 to 10 ^-3 mol per mol of silver halide, more preferably 5 × 10 ^-7 to 10 ^-3 mol.
X 10 ^-7 to 1 X 10 ^-4 mol.

In the selenium sensitization, a known unstable selenium compound is used, for example, US Pat. No. 3,297,44.
No. 6,297,447 and the like, and specifically, colloidal metal selenium, selenoureas (for example, N, N-dimethylselenourea, tetramethylselenourea) Urea, etc.), selenoketones (eg, selenoacetone), selenoamides (eg, selenoacetamide), selenocarboxylic acids and esters, isoselenocyanates, selenides (eg, diethyl selenide, triphenylphosphine selenide), Selenophosphates (eg, tri-p
-Tolyl selenophosphate) and the like. Selenium sensitization may be preferably used in combination with sulfur sensitization and / or noble metal sensitization.

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

The 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, chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide,
Known compounds such as gold selenide can be used.
The palladium compound means a divalent palladium salt or a tetravalent salt. Preferred palladium compounds are R ₂ PdX ₆
Or it is represented by R ₂ PdX ₄ . Where R is a hydrogen atom,
Represents an alkali metal atom or an ammonium group. X represents a halogen atom, and represents a chlorine, bromine or iodine atom.

More specifically, K ₂ PdCl ₄ , (NH ₄ )
₂ PdCl ₆ , NaPdCl ₄ , (NH ₄ ) ₂ PdCl
₄ , Li ₂ PdCl ₄ , Na ₂ PdCl ₆ or K ₂ P
dBr ₄ is preferred. The gold compound and the palladium compound are preferably used in combination with a thiocyanate or a selenocyanate.

The emulsion of 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.

During the grain formation of the silver halide emulsion of the present invention,
It is preferable to perform reduction sensitization after grain formation and before or during chemical sensitization, or after chemical sensitization.

Here, reduction sensitization refers to a method in which a reduction sensitizer is added to a silver halide emulsion, or a pAg 1 called 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. Also, two or more methods can be used in combination.

The method of adding a reduction sensitizer is a preferable method because 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 as reduction sensitizer,
Aminoiminomethanesulfinic acid (common name: thiourea dioxide), dimethylamine borane, ascorbic acid and derivatives thereof are preferred compounds. Since the addition amount of the reduction sensitizer depends on the emulsion production conditions, it is necessary to select the addition amount, but an appropriate range is 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 sensitization aids include compounds known as azaindene, azapyridazine, azapyrimidine, which suppress fog during chemical sensitization and increase sensitivity. Examples of chemical sensitization aid modifiers are described in U.S. Pat.
Nos. 411,914 and 3,554,757, JP-A-58-126526 and the aforementioned "Emulsion Chemistry" by Duffin, pp. 138-143.

During the production process of the emulsion of the present invention, an acid for silver is used.
It is preferable to use an agent. The oxidizing agent for silver is
Has the effect of converting to silver ions by acting on metallic silver
Say compound. Especially the formation process of silver halide grains and
Extremely small silver particles that replicate during the chemical sensitization process,
Compounds that can be converted to silver ions are effective. Generate here
Silver ions, such as silver halide, silver sulfide, silver selenide, etc.
It may form a silver salt that is hardly soluble in water.
A readily soluble silver salt may be formed. Oxidizing agent for silver is inorganic
It may be a substance or an organic substance. With an inorganic oxidant
Ozone, hydrogen peroxide and its adducts (eg
For example, NaBO_Two, H_TwoO_Two・ H_TwoO, 2NaCO_Three・ H
_TwoO_Two, Na_FourP_TwoO₇・ H_TwoO_Two, 2NaSO_Four・ H
_TwoO_Two・ 2H_TwoO), peroxyacid salts (eg, K_TwoS
_TwoO₈, K_TwoC_TwoO₆, K_TwoP_TwoO ₈) Peroxy complex
Compounds (eg, K_Two[Ti (O_Two) C_TwoO_Four] 3H
_TwoO, 4K_TwoSO_Four・ Ti (O_Two) OH ・ SO_Four・ 2H
_TwoO, Na_Three[VO (O_Two) (C_TwoO_Four)_Two] ・ 6H_Two
O), permanganate (eg, KMnO)_Four),chromium
Acid salts (eg, K_TwoCrO₇), Such as oxyacid salts, iodine
And halogens such as bromine and perhalates (for example,
Potassium periodate), high valent metal salts (e.g.,
Potassium hexacyanoferrate) and thiosulfonic acid
And salt.

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 of 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 reverse method, or a method of coexisting the two. 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 benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, amino Triazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially 1-phenyl-5-mercaptotetrazole); mercaptopyrimidine; mercaptotriazine;
Thioketo compounds such as oxazolinethione; azaindenes such as triazaindenes and tetraazaindenes (especially 4-hydroxy-6-methyl-1,
Many compounds known as antifoggants or stabilizers can be added, such as 3,3a, 7-tetraazaindene), pentaazaindenes and the like. For example, U.S. Patent Nos. 3,954,474 and 3,982,94
No. 7, JP-B-52-28660 can be used. One of the preferred compounds is Japanese Patent Application No. Sho 62
No. 47225. Antifoggants and stabilizers are used at various times before, during and after particle formation, during the water washing step, during dispersion after water washing, before chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. It can be added according to the purpose. Controls grain walls, reduces grain size, reduces grain solubility, controls chemical sensitization, in addition to exerting its inherent fogging prevention and stabilization effects during emulsion preparation It can be used for various purposes such as controlling the arrangement of dyes.

In the case where the photosensitive silver halide used in the present invention has green, red and infrared sensitivity, the photosensitive silver halide emulsion is spectrally sensitized with methine dyes 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, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hexoxonol dyes.
Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of 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, a pyridine nucleus and the like; an alicyclic hydrocarbon ring fused to these nuclei; and an aromatic hydrocarbon ring fused to these nuclei, ie, an indolenine nucleus, a benzindolenin nucleus, 5-64-hydroxy-6-methyl- such as indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, rhodanine nucleus, thiobarbituric acid nucleus and the like.
Heterocyclic nuclei can be applied. These nuclei may be substituted on carbon atoms. Specifically, U.S. Pat. No. 4,617,257, and JP-A-59-180,550.
No. 64-13,546, JP-A-5-45,828.
And sensitizing dyes described in JP-A-5-45,834.

In the merocyanine dye or the complex merocyanine dye, nuclei having a ketomethylene structure include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidin-2,4-dione nucleus, and a thiazolidine-2,4-nucleus.
5 such as dione nucleus, rhodanine nucleus and thiobarbituric acid nucleus
A 6-membered heterocyclic nucleus can be applied.

These dyes may be used alone or in combination, and a combination of sensitizing dyes is often used particularly for supersensitization and for controlling 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. 7,641, No. 3,617,293, No. 3,6
No. 28,964, No. 3,672,898, No. 3,
No. 679,428, No. 3,703,377, No. 3,769,301, No. 3,814,609, No. 3,837,862, No. 4,026,707,
British Patent Nos. 1,344,281 and 1,507,8
03, JP-B-43-4,936 and 53-12,3
No. 75, JP-A-52-110,618, JP-A-52-10
No. 9,925.

Along with the sensitizing dye, a dye which has no spectral sensitizing effect or a compound which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (for example, US Pat. No. 3,615,641, JP-A-63-23145, etc.).

The time when these sensitizing dyes are added 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 performed after completion of chemical sensitization and before coating, but US Pat. No. 3,628,96.
As described in JP-A-58-113 and JP-A No. 4,225,666, spectral sensitization may be carried out simultaneously with chemical sensitization by adding a chemical sensitizer at the same time. , 92
As described in No. 8, it can be carried out prior to chemical sensitization. Further, it can be added before the completion of silver halide grain precipitation to start spectral sensitization. Nos. 4,183,756 and 4,225,666.
The addition may be before or after the nucleation of the silver halide grains according to the formula (1), or a divided addition in which a part of the compound is added before the chemical sensitization and the remainder is added after the chemical sensitization.

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.

Type of Additive RD17643 RD18716 RD307105 1. Chemical sensitizer page 23 page 648 right column page 996 2. Sensitivity increasing agent, page 648, right column 3. Spectral sensitizers, pages 23 to 24, page 648, right column, 996 to 998, super sensitizers, page 649, right column. Brightener 24 page 647 page right column 998 5. 5. Light absorber, page 25-26, page 649, right column, page 1003, filter-page 650, left column, dye, ultraviolet absorber. Binder 26 pages 651 pages 1003 to 1004 7. 7. Plasticizer, page 27 650 page 1006 Lubricant 8. Coating aid, pages 26 to 27, page 650, 1005 left to surfactant 1006, right. Static page 27 page 650 right column 1006 to inhibitor 1007 page 10. Antifoggants 24 to 25 pages 649 pages 998 and stabilizers 1000 pages 11. Stain 25 page right column 650 page left-right inhibitor 12. 12. Dye image stabilizer page 25 Hardener 26 pages 651 left column 1004 right to 1005 left

As hardeners, in addition to the above, US Pat. No. 4,678,739, column 41, 4,791,04
No. 2, JP-A-59-116,655, and JP-A-62-24
5,261, 61-18,942, JP-A-4-24-2
18,044 and the like. More specifically, aldehyde hardeners (such as formaldehyde), aziridine hardeners, epoxy hardeners, and vinyl sulfone hardeners (N, N'-ethylene-bis (vinylsulfonylacetamide)) Ethane), an N-methylol-based hardening agent (such as dimethylol urea), or a polymer hardening agent (compounds described in JP-A-62-234157). These hardeners are used in an amount of 0.001 to 1 g, preferably 0.001 g / g of gelatin applied.
5 g to 0.5 g are 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. Examples of the matting agent include silicon dioxide, polyolefin and polymethacrylate.
No. 8,256 (29), benzoguanamine resin beads, polycarbonate resin beads, A
There are compounds such as S resin beads described in JP-A-63-274,944 and JP-A-63-274,952. 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 light-sensitive material of the present invention may contain a heat solvent, an antifoaming agent, a fungicide, a fungicide, colloidal silica, and the like. Specific examples of these additives are described in JP-A-61-88,256, pages (26) to (32), JP-A-3-11,338, and JP-B-2-51,496. The light-sensitive material of the present invention may contain a formalin antifoggant during storage.
Compounds SCV-1 to 28 described in 477, 932A, and the like. In the light-sensitive material of the present invention, compounds described in JP-A-7-239540 can be used for the purpose of improving latent image stability.

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, prevention of electrification, acceleration of development and the like. Specific examples of the surfactants are described in the above-mentioned RD Magazine, known technology No. 5 (199).
(Aztec Co., Ltd., March 22, 2013) 136-
138 pages, JP-A-62-173463, 62-1
No. 83,457. 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 Japanese Patent Publication No. 57
No. 9,053, columns 8-17, JP-A-61-20,94.
No. 4, Nos. 62-135, 836, etc., or a hydrophobic fluorine such as a fluorine-based surfactant, or an oily fluorine-based compound such as fluorine oil or a solid fluorine compound resin such as ethylene tetrafluoride resin Compounds.

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 a hindered amine and a hindered phenol partial structure in the same molecule as described in U.S. Pat. No. 4,268,593 are effective in preventing deterioration of a yellow dye image due to heat, humidity and light. give. Further, in order to prevent the deterioration of the magenta dye image, particularly the deterioration due to light, spiroindanes described in JP-A-56-159,644 and hydroquinone diethers described in JP-A-55-89,835 can be used. Monoether-substituted chromans give favorable 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. Specific examples of the above R
Magazine D, US Patent Nos. 5,089,378 and 4,50
0,627, 4,614,702, JP-A-64
-13,546 pages (7) to (9), (57) to (7)
1) and (81)-(97), U.S. Pat.
No. 75,610, No. 4,626,500, No. 4,
983,494, JP-A-62-174,747, JP-A-62-239,148, JP-A-63-264,747,
JP-A-1-150,135, 2-110,557
No. 2-178,650, RD. No. 17,64
No. 3 (1978), pages (24) to (25) and the like. These compounds are present in 5 moles per silver mole.
X 10 ^-6 to 1 x 10 ^-1 mol is preferred, and 1 x 10
^-5 to 1 × 10 ^-2 is preferably used.

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 the silver halide in the development process of silver halide development, and the auxiliary developing agent in the present invention is preferably a Kender loupe. It is an electron-emitting compound that obeys Ruth's rule.

The light-sensitive material of the present invention preferably has a slip property. The slip agent-containing layer is preferably used on both the photosensitive layer surface and the back surface. A preferable slip property is a dynamic friction coefficient of 0.25 or less and 0.01 or more. The measurement at this time represents the value when the stainless steel ball having a diameter of 5 mm was conveyed at 60 cm / min (25 ° C., 60% RH). In this evaluation, even when the surface of the photosensitive layer is replaced as the partner material, the values are almost the same level. Usable slip agents include polyorganosiloxanes, higher fatty acid amides, higher fatty acid metal salts, esters of higher fatty acids and higher alcohols, and polyorganosiloxanes include polydimethylsiloxane,
Polydiethylsiloxane, polystyrylmethylsiloxane, polymethylphenylsiloxane, or the like can be used. The additional layer is preferably the outermost layer of the emulsion layer or the back layer. Particularly, polydimethylsiloxane or an ester having a long-chain alkyl group is preferable.

In the light-sensitive material of the present invention, an antistatic agent is preferably used. Examples of such antistatic agents include polymers containing carboxylic acid and carboxylate and sulfonate, cationic polymers, and ionic surfactant compounds. The most preferred antistatic agents are ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ ,
n ₂ O ₃ , SiO ₂ , MgO, BaO, MoO ₃ , V ₂
At least one kind of volume resistivity selected from O ₅ is 1
0 ⁷ Ω · cm or less, more preferably 10 ⁵ Ω · cm or less.
n, S, Si, C, etc.), and fine particles of a sol-shaped metal oxide or a composite oxide thereof. Preferably 5 to 500 mg / m ² as the content of the sensitive material, particularly preferably from 10 to 350 mg / m ^2. The ratio of the amount of the conductive crystalline oxide or its composite oxide to the binder is preferably from 1/300 to 100/1, more preferably from 1/100 to 100/5.

The constitution of the light-sensitive material or the processing material described later (including the back layer) is used for the purpose of improving film physical properties such as dimensional stability, curl prevention, adhesion prevention, film crack prevention and pressure increase / decrease sensation. Various polymer latexes can be included. Specifically, JP-A-62-245258
And the polymer latexes described in JP-A Nos. 62-136648 and 62-110066 can be used.
In particular, when a polymer latex having a low glass transition point (40 ° C. or lower) is used for the mordant layer, cracking of the mordant layer can be prevented, and when a polymer latex having a high glass transition point is used for the back layer, the curl prevention effect is reduced. can get.

The light-sensitive material of the present invention preferably contains a matting agent. The matting agent may be on either the emulsion side or the back side, but is particularly preferably added to the outermost layer on the emulsion side. The matting agent may be soluble in the processing solution or insoluble in the processing solution, and preferably both are used in combination. For example, polymethyl methacrylate, poly (methyl methacrylate /
(Methacrylic acid = 9/1 or 5/5 (molar ratio)), polystyrene particles and the like are preferable. 0.8-1
0 μm is preferable, and the particle size distribution is preferably narrow,
It is preferable that 90% or more of the total number of particles is contained between 0.9 and 1.1 times the average particle size. It is also preferable to simultaneously add fine particles having a size of 0.8 μm or less in order to enhance the matting property.
μm), poly (methyl methacrylate / methacrylic acid =
9/1 (molar ratio, 0.3 μm)), polystyrene particles (0.25 μm), colloidal silica (0.03 μm)
Is mentioned. Specifically, it is described in JP-A-61-88256 (page 29). Other examples include benzoguanamine resin beads, polycarbonate resin beads, AS resin beads, and the like, as described in JP-A-63-274944 and JP-A-63-274944.
No. 74952. In addition, the compounds described in the aforementioned Research Disclosure can be used.

In the present invention, as the support of the light-sensitive material, a support which is transparent and can withstand the processing temperature is used. Generally, The Photographic Society of Japan, "Basics of Photographic Engineering-Silver Halide Photography", Corona Co., Ltd. (1979)
Photographic supports such as papers and synthetic polymers (films) described on pages (223) to (240). Specific examples include polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, and celluloses (for example, triacetyl cellulose). In addition, JP-A-62-253159 (29)-(31)
Page, JP-A-1-161,236 (14)-(17)
Page, JP-A-63-316,848, JP-A-2-22,
No. 651, No. 3-56,955, U.S. Pat.
The support described in No. 1,033 or the like can be used.

Particularly when heat resistance and curl characteristics are strictly required, JP-A-6-41281 discloses a support for a photosensitive material.
6-43581, 6-51426, 6-51
No. 437, No. 6-51442, Japanese Patent Application No. 4-25184
No. 5, 4-231825, 4-253545,
4-258828, 4-240122, 4-
No. 221538, No. 5-21625, No. 5-1592
6, No. 4-331919, No. 5-199704,
Supports described in JP-A-6-13455 and JP-A-6-14666 can be preferably used. Further, a support which is mainly a styrene polymer having a syndiotactic structure can also be preferably used.

In order to bond the support to the light-sensitive material constituting layer, it is preferable to perform a surface treatment. Surface activation treatments such as chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, ozone oxidation treatment, and the like. Among the surface treatments, ultraviolet irradiation treatment, flame treatment, corona treatment, and glow treatment are preferable.
Next, the undercoating method will be described. It may be a single layer or two or more layers. As the binder for the undercoat layer, vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, including copolymers starting from monomers selected from maleic anhydride, as a starting material, Examples include polyethyleneimine, epoxy resin, grafted gelatin, nitrocellulose, and gelatin. Compounds that swell the support include resorcinol and p-chlorophenol. In the undercoat layer, chromium salts (chromium alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates,
Active halogen compounds (such as 2,4-dichloro-6-hydroxy-s-triazine), epichlorohydrin resin,
Active vinyl sulfone compounds and the like can be mentioned.
SiO ₂ , TiO ₂ , inorganic fine particles or polymethyl methacrylate copolymer fine particles (0.01 to 10 μm) may be contained as a matting agent.

As a support, for example, JP-A-4-14-1
No. 24645, No. 5-40321, No. 6-35092
It is preferable to record photographic information and the like using a support having a magnetic recording layer described in Japanese Patent Application No. 5-58221 and Japanese Patent Application No. 5-106979.

The magnetic recording layer is obtained by coating a support with an aqueous or organic solvent-based coating liquid in which magnetic particles are dispersed in a binder. Magnetic particles include ferromagnetic iron oxide such as γFe ₂ O _3, Co deposited γFe ₂ O _3, Co coated magnetite, Co containing magnetite, ferromagnetic chromium dioxide, ferromagnetic metal, ferromagnetic alloy, hexagonal crystal systems Ba ferrite, Sr ferrite, Pb ferrite, Ca ferrite and the like can be used. Co-coated ferromagnetic iron oxide such as Co-coated γFe ₂ O ₂ is preferable. The shape may be any of needle shape, rice grain shape, spherical shape, cubic shape, plate shape and the like. Preferably 20 m ² / g or more S _BET is the specific surface area, 30 m ² /
g or more is particularly preferred. Saturation magnetization (σs) of ferromagnetic material
Is preferably 3.0 × 10 ^{4 to} 3.0 × 10 ⁵ A / m
And particularly preferably 4.0 × 10 ^{4 to} 2.5 × 10 ⁴
0 ⁵ A / m. The ferromagnetic particles may be subjected to a surface treatment with silica and / or alumina or an organic material. Further, the surface of the magnetic particles may be treated with a silane coupling agent or a titanium coupling agent as described in JP-A-6-161332. Also, magnetic particles having a surface coated with an inorganic or organic substance described in JP-A-4-259911 and JP-A-5-81652 can be used.

The binder used for the magnetic particles may be a thermoplastic resin, a thermosetting resin, a radiation-curable resin, a reactive resin, an acid, an alkali or a biodegradable polymer, a natural product described in JP-A-4-219569. Polymers (cellulose derivatives, sugar derivatives, etc.) and mixtures thereof can be used. Tg of the above resin is −40 ° C. to 300 ° C.,
The weight average molecular weight is from 2,000 to 1,000,000. Examples thereof include vinyl copolymers, cellulose diacetate, cellulose triacetate, cellulose derivatives such as cellulose acetate propionate, cellulose acetate butyrate, and cellulose tripropionate, acrylic resins and polyvinyl acetal resins, and gelatin is also preferable. Particularly, cellulose di (tri) acetate is preferable. The binder can be cured by adding an epoxy-based, aziridine-based, or isocyanate-based crosslinking agent. Examples of the isocyanate-based crosslinking agent include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate,
Isocyanates such as xylylene diisocyanate, and reaction products of these isocyanates with polyalcohol (for example, 3 mol of tolylene diisocyanate)
Reaction product of 1 mol of trimethylolpropane and trimethylolpropane) and polyisocyanates formed by condensation of these isocyanates.
No. 357.

As a method for dispersing the above-mentioned magnetic substance in the binder, a kneader, a pin type mill, an annular type mill and the like are preferably used, as in the method described in JP-A-6-35092. JP-A-5-08828
The dispersant described in No. 3 and other known dispersants can be used. The thickness of the magnetic recording layer is 0.1 μm to 10 μm, preferably 0.2 μm to 5 μm, more preferably 0.3 μm to
3 μm. The weight ratio between the magnetic particles and the binder is preferably 0.5: 100 to 60: 100, and more preferably 1: 100 to 30: 100. The coating amount of the magnetic particles is 0.005 to 3 g / m ² , preferably 0.0
1-2 g / m ² , more preferably 0.02-0.5 g
/ M ² . The transmission yellow density of the magnetic recording layer is 0.
It is preferably from 0.01 to 0.50, more preferably from 0.03 to 0.20, and particularly preferably from 0.04 to 0.15. The magnetic recording layer can be provided on the whole surface or in a stripe form by coating or printing on the back surface of the photographic support. As a method for applying the magnetic recording layer, air doctor, blade, air knife, squeeze, impregnation, reverse roll, transfer roll, gravure, kiss, cast, spray, dip, bar, extrusion, etc. can be used. The coating solution described in 341436 is preferred.

In the magnetic recording layer, lubricity improvement, curl control,
It may have functions such as antistatic, antiadhesion, and head polishing, or may provide another functional layer to provide these functions. At least one of the particles has a Mohs hardness of 5 or more. Abrasives of the above non-spherical inorganic particles are preferred. As the composition of the non-spherical inorganic particles, oxides such as aluminum oxide, chromium oxide, silicon dioxide, titanium dioxide and silicon carbide, carbides such as silicon carbide and titanium carbide, and fine powders such as diamond are preferable. These abrasives may have their surfaces treated with a silane coupling agent or a titanium coupling agent. These particles may be added to the magnetic recording layer, or may be overcoated (for example, a protective layer, a lubricant layer, etc.) on the magnetic recording layer. As the binder used at this time, the above-mentioned binders can be used, and the same binder as the binder for the magnetic recording layer is preferable. For a light-sensitive material having a magnetic recording layer, see US Pat. No. 5,336,589,
Nos. 5,250,404, 5,229,259, 5,215,874 and EP 466,130.

The polyester support preferably used for the light-sensitive material having the above-mentioned magnetic recording layer will be further described below. (Invention Association; 1994. 3.15). Polyester is formed with diol and aromatic dicarboxylic acid as essential components, and 2,6-, 1,5 as aromatic dicarboxylic acid.
-, 1,4-, and 2,7-naphthalenedicarboxylic acid,
Terephthalic acid, isophthalic acid, phthalic acid, and diols include diethylene glycol, triethylene glycol, cyclohexanedimethanol, bisphenol A, and bisphenol. Examples of the polymer include homopolymers such as polyethylene terephthalate, polyethylene naphthalate, and polycyclohexanedimethanol terephthalate. Particularly preferred is 2,6-naphthalenedicarboxylic acid in an amount of 50 mol% to 10 mol%.
It is a polyester containing 0 mol%. Among them, polyethylene 2,6-naphthalate is particularly preferred. The average molecular weight ranges from about 5,000 to 200,000. The Tg of the polyester is 50 ° C. or higher, and 9
0 ° C. or higher is preferred.

Next, the polyester support is subjected to a heat treatment at a heat treatment temperature of 40 ° C. or more and less than Tg, more preferably Tg−20 ° C. or more and less than Tg in order to make it difficult to form a curl. The heat treatment may be performed at a constant temperature within this temperature range, or may be performed while cooling. The heat treatment time is from 0.1 hour to 1500 hours, more preferably from 0.5 hour to 200 hours. The heat treatment of the support may be performed in the form of a roll, or may be performed while being transported in the form of a web. Irregularities may be imparted to the surface (for example, conductive inorganic fine particles such as SnO ₂ or Sb ₂ O ₅ may be applied) to improve the surface state. In addition, it is desirable to take measures such as applying knurls to the ends and making the ends slightly higher so as to prevent the cut end of the winding core from being imaged. These heat treatments may be performed at any stage after the formation of the support, after the surface treatment, after the application of the back layer (antistatic agent, slip agent, etc.), and after the application of the undercoat. Preferably after application of the antistatic agent. An ultraviolet absorber may be incorporated into this polyester. In order to prevent light piping, the purpose can be achieved by kneading a commercially available dye or pigment for polyesters such as Diaresin manufactured by Mitsubishi Kasei and Kayaset manufactured by Nippon Kayaku.

Next, a film cartridge in which a photosensitive material can be loaded will be described. The main material of the patrone used in the present invention may be metal or synthetic plastic. Preferred plastic materials are polystyrene, polyethylene, polypropylene, polyphenyl ether and the like. Further, patrone may contain various antistatic agents, such as carbon black, metal oxide particles, nonions,
Anionic, cationic and betaine-based surfactants or polymers can be preferably used. These antistatic patrones are disclosed in JP-A-1-312537,
No. 1-312538. Especially 25 ° C,
The resistance at 25% RH is preferably 10 ¹² Ω or less. Usually, a plastic patrone is manufactured using a plastic into which carbon black, a pigment, or the like is kneaded in order to impart light shielding properties. The size of the patrone may be the same as the current 135 size.
It is also effective to make the diameter of a 35 mm 25 mm cartridge 22 mm or less. The volume of the patrone case is preferably 30 cm ³ or less, more preferably 25 cm ³ or less. The weight of the plastic used for the patrone and the patrone case is preferably 5 g to 15 g.

Further, a patrone for feeding a film by rotating a spool may be used. Further, a structure may be employed in which the leading end of the film is housed in the patrone main body, and the leading end of the film is sent out from the port portion of the patrone by rotating the spool shaft in the film sending direction. These are U
S4,834,306 and 5,226,613. The above light-sensitive materials are disclosed in
And a film unit with a lens described in JP-B-3-39784.

The light-sensitive material of the present invention can be subjected to both thermal development and development with a developing solution containing a developing agent and a base as a method for developing after exposure.

The method of thermal development will be described. Heat treatment of photosensitive materials is known in the art. For example, a photothermographic material and its process are described in, for example, pages 553 to 555 of Basics of Photographic Engineering (Corona, 1979).
Pages, April 1978, Video Information 40 pages, Neblet
ts Handbook of Photograph
y and Reprography 7th Ed.
(Van Norstrand and Reihol
dCompany), pages 32-33, U.S. Pat.
No. 52,904, No. 3,301,678, No. 3,
Nos. 392,020 and 3,457,075; British Patent Nos. 1,131,108 and 1,167,777.
And Research Disclosure Magazine, June 1978
This is described in the monthly publication, pages 9 to 15 (RD-17029).

In the heat development step, the air is shut off during heat development, the material is prevented from volatilizing from the light-sensitive material, the processing material is supplied to the light-sensitive material, and the light-sensitive material becomes unnecessary after the development. In order to remove a raw material (YF dye, AH dye, sensitizing dye, etc.) or an unnecessary component generated during development, a material different from the photosensitive material may be superposed on the photosensitive material surface and heated. Another material used in this case is called a processing sheet. As the support and the binder used for the processing sheet, the same ones as the photosensitive material can be used. The processing sheet is preferably hardened with a hardener similarly to the photosensitive member. The same hardening agent as that for the photosensitive member can be used. A mordant may be added to the treated sheet for the purpose of removing the above-mentioned dye or for other purposes. As the mordant, those known in the field of photography can be used, and US Pat. No. 4,500,62.
No. 6, columns 58-59, JP-A-61-88256, 31.
Pp. 41 to 41, JP-A-62-244036, JP-A-62-44036
And mordants described in JP-A-244043. Further, a dye-receiving polymer compound described in U.S. Pat. No. 4,463,079 may be used.

In the light-sensitive material of the present invention, it is preferable to use a base or a base precursor for the purpose of accelerating the heat development and the dye formation reaction. It is preferable to include a base or a base precursor in the above-mentioned processing sheet from the viewpoint of raw storage stability of the light-sensitive material. As the base, an inorganic or organic base can be used. Examples of the inorganic base include hydroxides of alkali metals or alkaline earth metals described in JP-A-62-209448 (eg, potassium hydroxide, sodium hydroxide, lithium hydroxide, calcium hydroxide, magnesium hydroxide, etc.), Phosphates (eg, secondary or tertiary phosphates such as dipotassium hydrogen phosphate, disodium hydrogen phosphate, ammonium sodium phosphate, calcium hydrogen phosphate, etc.), carbonates (eg, potassium carbonate, sodium carbonate) , Sodium bicarbonate, magnesium carbonate, etc.), borates (eg, potassium borate, sodium borate, sodium metaborate, etc.), and organic acid salts (eg, potassium acetate, sodium acetate, potassium oxalate, sodium oxalate, potassium tartrate) , Sodium tartrate, sodium malate, sodium palmitate , Sodium stearate, etc.), Sho 63-252
No. 08 acetylide of an alkali metal or alkaline earth metal. Examples of the organic base include ammonia, aliphatic or aromatic amines (for example, primary amines (for example, methylamine, ethylamine, butylamine, n-hexylamine, cyclohexylamine, 2-ethylhexylamine, allylamine, ethylenediamine, 1,4 -Diaminobutane, hexamethylenediamine, aniline, anisidine, p-toluidine, α
-Naphthylamine, m-phenylenediamine, 1,8-
Diaminonaphthalene, benzylamine, phenethylamine, ethanolamine, thallium, etc., and secondary amines (eg, dimethylamine, diethylamine, dibutylamine, diallylamine, N-methylaniline, N-methylbenzylamine, N-methylethanolamine, diethanolamine, etc.) Tertiary amines (for example, JP-A-62-1
70954, N-methylmorpholine, N-hydroxyethylmorpholine, N-methylpiperidine, N-hydroxyethylpiperidine, N, N'-dimethylpiperazine, N, N'-dihydroxyethylpiperazine, diazabicyclo [2,2,2 Octane, N, N-dimethylethanolamine, N, N-dimethylpropanolamine, N-methyldiethanolamine, N-methyldipropanolamine, triethanolamine, N, N,
N ', N'-tetramethylethylenediamine, N, N,
N ', N'-tetrahydroxyethylethylenediamine, N, N, N', N'-tetramethyltrimethylenediamine, N-methylpyrrolidine, etc., polyamines (diethylenetriamine, triethylenetetramine, polyethyleneimine, polyallylamine, polyvinylbenzyl) Amine, poly- (N, N-diethylaminoethyl methacrylate), poly- (N, N-dimethylvinylbenzylamine, etc.), hydroxylamines (eg, hydroxylamine, N-hydroxy-N-methylaniline, etc.), heterocyclic amine (Eg, pyridine, lutidine, imidazole, aminopyridine, N, N-dimethylaminopyridine, indole, quinoline, isoquinoline, poly-4-
Vinylpyridine, poly-2-vinylpyridine, etc., amidines (for example, monoamidine, (for example, acetamidine, imidazotan, 2-methylimidazole, 1,4,4)
5,6-tetrahydropyrimidine, 2-methyl-1,
4,5,6-tetrahydropyrimidine, 2-phenyl-
1,4,5,6-tetrahydropyrimidine, iminopiperidine, diazabicyclononene, diazabicycloundecene (DBU), bis or tris or tetraamidine, guanidines (for example, water-soluble monoguanidine (for example, guanidine, dimethyl Guanidine, tetramethylguanidine, 2-aminoimidazoline, 2-amino-1,4,5-tetrahydropyrimidine, etc.), water-insoluble mono- or bisguanidine, bis or tris described in JP-A-63-70845. Tetraguanidine, quaternary ammonium hydroxide (eg, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide) , Trioctylmethylammonium hydroxide, methylpyridinium hydroxide, etc. Examples of the base precursor include a decarboxylation type, a decomposition type, a reaction type, and a complex salt formation type. The amount used is 0.1-20 g / m ² , preferably 1-1.
0 g / m ² .

A thermal solvent may be added to the light-sensitive material of the present invention for the purpose of promoting thermal development. Examples include U.S. Pat. Nos. 3,347,675 and 3,667,667.
Organic compounds having a polar group such as described in US Pat. Specifically, amide derivatives (such as benzamide), urea derivatives (such as methyl urea and ethylene urea), sulfonamide derivatives (such as the compounds described in Japanese Patent Publication Nos. 1-40974 and 4-133701), polyols Compounds (such as sorbitol) and polyethylene glycols. When the heat solvent is insoluble in water, it is preferably added to the photosensitive material as a solid dispersion. The layer to be added may be a photosensitive material or a processing sheet, and may be a photosensitive layer or a non-photosensitive layer depending on the purpose. The amount of the hot solvent is from 10% by weight to 500% of the binder to be added.
% By weight, preferably 20% to 300% by weight.

When heat development is performed using a processing sheet,
A solvent may be used for the same purpose as the hot solvent. In particular,
U.S. Pat. Nos. 4,704,245 and 4,470,4
No. 45P, and JP-A-61-238056. In this method, the heating temperature is preferably lower than the boiling point of the solvent used. For example, when the solvent is water, 50 ° C. to 10
0 ° C. is preferred. Specific examples of the solvent to be used include water, a basic aqueous solution containing an inorganic alkali metal salt or an organic base, a low-boiling solvent or a mixed solution of a low-boiling solvent and water or the basic aqueous solution. Further, a surfactant, an antifoggant, a compound forming a complex with a hardly soluble metal salt, a fungicide, and a bactericide may be contained in the solvent. Water is preferably used as the solvent, but any water may be used as long as it is generally used. Specifically, distilled water,
Tap water, well water, mineral water and the like can be used. As a method for applying water, there is a method in which a photosensitive material or a processing sheet is immersed in water and excess water is removed with a squeeze roller. In the heat development process using the photosensitive material and the processing sheet of the present invention, water may be used up or circulated. In the latter case, water containing components eluted from the material will be used. However,
It is preferable to apply a certain amount of water to the light-sensitive material or the processing sheet. Further, a plurality of nozzles for injecting water are arranged at a certain interval along a method intersecting the conveying direction of the photosensitive material or the processing sheet and the nozzles are displaced toward the photosensitive material or the processing sheet on the conveying path. A method of spraying water with a water application device having an actuator is particularly preferable. The temperature of the applied water is preferably 30C to 60C. As a method for applying water, for example, JP-A-63-144354 and JP-A-63-1
44355, 62-38460, JP-A-3-21
No. 5,555, JP-A-62-235159, page 5, and JP-A-63-85544 can be used.

When heat development is performed in the presence of a small amount of water or a solvent, as described in European Patent Publication No. 210,660 and US Pat. Compound which can form a complex with a basic metal compound and a metal ion constituting the basic metal compound using water as a medium (referred to as a complex-forming compound)
It is effective to adopt a method of generating a base by a combination of the above. In this case, the basic metal compound which is hardly soluble in water is preferably added to the light-sensitive material, and the complex-forming compound is preferably added to the processing sheet, and vice versa.

The amount of water or solvent applied to the light-sensitive material may be applied to either the light-sensitive material or the processing sheet.
The amount of water or solvent interposed between the photosensitive material and the processing sheet is preferably 0.1 to 1 times the amount corresponding to the maximum swelling volume of the photosensitive material and the processing sheet due to the solvent used. In the present invention, the photosensitive material and / or the processing sheet are bonded and heated in a swollen state. The state of the film at the time of swelling is unstable, and it is important to limit the amount of water to the above range to prevent local uneven coloring. The amount of solvent required in the order of maximum swelling is determined by immersing the photosensitive material or processing sheet with the coating film to be measured in the solvent to be used, measuring the film thickness where it swells sufficiently, calculating the maximum swelling amount, and then calculating the maximum swelling amount. Can be obtained by reducing the weight of
An example of a method for measuring the degree of swelling is described in Photographic Science Engineering, Vol. 16, p. 449 (1972).
There is also a description.

The preferred thermal development system in the present invention has a weight of water obtained by subtracting the weight of the entire coated film from the weight of water corresponding to the maximum swelling volume of the coated film excluding the processing sheet and the photosensitive material and both backs. The photosensitive material and the processing sheet are overlapped with the photosensitive layer and the processing layer facing each other so that an amount of water equivalent to 0.1 times to 1 time is sandwiched between the photosensitive material and the processing sheet, and at a temperature of 60 ° C to 100 ° C. This is a method of heating for 5 to 120 seconds.

The heating temperature in the heat development step is about 50 ° C. to 2 ° C.
The temperature is 50 ° C., but especially 60 ° C. to 150 ° C. is useful. As a heating method, a method of contacting with a heated block or plate, contacting with a hot plate, a hot plate, a heat roller, a heat drum halogen lamp heater, infrared and far-infrared lamp heater, etc., or passing through a high-temperature atmosphere Etc. Examples of the method of superposing the processing sheet and the photosensitive material include the methods described in JP-A-62-253159 and JP-A-61-147244.

Any of various heat developing apparatuses can be used in the heat developing process of the present invention. For example, see JP-A-59-752.
No. 47, 59-1777547, 59-18135
No. 3, No. 60-18951, Shokai 62-25944
No., Japanese Patent Application No. 4-277517 and No. 4-243072
And the devices described in JP-A Nos. 4-24493, 6-164421, and 6-164422 are preferably used. As a commercially available apparatus, there can be used a Pictrostat 100, a Pictrostat 200, a Pictrostat 300, a Pictrostat 330, a Pictrostat 50, a Pictrography 2000, a Pictrography 3000, and the like manufactured by Fuji Photo Film Co., Ltd.

The light-sensitive material of the present invention and the processing sheet used for processing may have a form having a conductive heating element layer as a heating means for heat development. As the elements of the present invention, those described in JP-A-61-145544 can be used. In the present invention, a development stop agent may be included in the processing sheet, and the development stop agent may act simultaneously with the development. The term "development terminator" as used herein means that after appropriate development, the base is quickly neutralized or reacts with the base to reduce the base concentration in the film, and interact with a compound that stops development or silver and silver salts to suppress development. Compound. Specific examples include an acid precursor that releases an acid when heated, an electrophilic compound that causes a substitution reaction with a coexisting base when heated, or a nitrogen-containing heterocyclic compound, a mercapto compound, and a precursor thereof. For further details, see JP-A-62-25
No. 3,159, pages (31) to (32).
Further, a combination in which a zinc salt of mercaptocarboxylic acid described in Japanese Patent Application No. 6-190529 or the like is contained in a photosensitive material and the above-mentioned complex forming compound is contained in a processing sheet is advantageous.

Similarly, a printout inhibitor of silver halide may be included in the processing sheet so that its function can be exhibited simultaneously with the development. Examples of the printout inhibitor include a monohalogen compound described in JP-B-54-164, a trihalogen compound described in JP-A-53-46020, and a halogen described in JP-A-48-45228 bonded to an aliphatic carbon atom. And polyhalogen compounds represented by tetrabromoxylene described in JP-B-57-8454. Also, UK Patent No. 1,005,1
Development inhibitors such as 1-phenyl-5-mercaptotetrazole described in No. 44 are also effective. Also,
The viologen compounds described in Japanese Patent Application No. 6-337531 are also effective. The use amount of the printout inhibitor is preferably 10 ^-4 to 1 mol / Ag1 mol, particularly preferably 10 ^-3 to 10 ^-1 mol / Ag1 mol. The processing sheet may contain a physical development nucleus and a silver halide solvent, solubilize the silver halide of the photosensitive member and fix it to the processing layer simultaneously with the development.

The physical development nucleus is for converting soluble silver salt diffused from the light-sensitive material into physical developed silver by reduction, and fixing it to the processing layer. Physical development nuclei include zinc, mercury,
Heavy metals such as lead, cadmium, iron, chromium, nickel, tin, cobalt, copper, ruthenium, or noble metals such as palladium, platinum, silver, gold, or sulfur thereof;
All known physical development nuclei such as colloidal particles of chalcogen compounds such as selenium and tellurium can be used. These physical development nuclei substances reduce the corresponding metal ions with a reducing agent such as ascorbic acid, sodium borohydride, hydroquinone, etc. to form a metal colloid dispersion,
Alternatively, it is obtained by mixing a soluble sulfide, selenide or telluride solution to form a colloidal dispersion of water-insoluble metal sulfide, metal selenide or metal telluride. These dispersions are preferably formed in a hydrophilic binder such as gelatin. A method for preparing colloidal silver particles is described in U.S. Pat. No. 2,688,601. If necessary, a desalting method for removing an excessive salt known in the method for preparing a silver halide emulsion may be performed. The size of these physical development nuclei is 2 to
Those having a particle size of 200 nm are preferably used. These physical development nuclei are usually added to the processing layer in an amount of 10 ^{-3 to} 100 mg.
/ M ² , preferably 10 ^{−2 to} 10 mg / m ² .

The physical development nucleus can be separately prepared and added to a coating solution. However, in a coating solution containing a hydrophilic binder, for example, silver nitrate and sodium sulfide, or
It may be prepared by reacting gold chloride with a reducing agent or the like. Silver, silver sulfide, palladium sulfide and the like are preferably used as physical development nuclei. When using physically developed silver transferred to the complexing agent sheet as an image, palladium sulfide, silver sulfide, etc.
It is preferably used because min is short and Dmax is high. Known silver halide solvents can be used.
For example, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; sulfites such as sodium sulfite and sodium bisulfite; thiocyanates such as potassium thiocyanate and ammonium thiocyanate;
Thioether compounds such as 1,8-di-3,6-dithiaoctane, 2,2'-thiodiethanol, and 6,9-dioxa-3,12-dithiatetradecane-1,14-diol described in 7-1386. , Japanese Patent Application No. 6-32535
Compounds having a 5- or 6-membered imide ring such as uracil and hydantoin described in JP-A No. 07-143431.
The compound of the following general formula (I) described in No. 9 can be used. Analytica Chemica Acta (Analyti
ca Chemica Acta) 248 volumes 604-6
Also preferred are trimethyltriazolium thiolate and meso-ion thiolate compounds described on page 14 (1991).
The compounds capable of fixing and stabilizing silver halide described in Japanese Patent Application No. 6-206331 can also be used as a silver halide solvent.

General Formula (I) N (R ¹ ) (R ² ) —C (＝ S) —X—R ^{3 In the} formula, X represents a sulfur atom or an oxygen atom. R ¹ and R ² may be the same or different and each represents an aliphatic group, an aryl group, a heterocyclic residue or an amino group.
R ³ represents an aliphatic or aryl group. R ¹ and R ² or R ² and R ³ may combine with each other to form a 5- or 6-membered heterocycle. The above-mentioned silver halide solvents may be used in combination. Among the above compounds, compounds having a 5- or 6-membered imide ring, such as sulfites, uracil and hydantoin, are particularly preferred. In particular, when uracil or hydantoin is added as a potassium salt, it is preferable in that gloss reduction during storage of the treated sheet can be improved.

The total content of the silver halide solvent in the processing layer is from 0.01 to 50 mmol / m ² , preferably from 0.1 to 30 mmol / m ² . More preferably, it is 1 to 20 mmol / m ² . The molar ratio is 1/20 to 20 times, preferably 1/10 to 10 times, and more preferably 1/3 to 3 times, relative to the amount of silver applied to the light-sensitive material. The silver halide solvent may be added to a solvent such as water, methanol, ethanol, acetone, dimethylformamide, methylpropylglycol, or an alkali or acidic aqueous solution, or may be added to a coating solution after dispersing solid fine particles.

Further, by incorporating a polymer having a repeating unit of vinylimidazole and / or vinylpyrrolidone described in Japanese Patent Application No. 6-325350 into the processing layer, the density of the silver image in the photosensitive material can be increased. Is possible. The processing sheet may have a protective layer, an undercoat layer, a back layer, and other various auxiliary layers as in the case of the photosensitive material. The processing sheet is preferably provided with a processing layer on a continuous web. The continuous web of the processing sheet referred to here is such that the length of the processing sheet is sufficiently longer than the long side of the corresponding photosensitive material at the time of processing, and is used without cutting a part when used for processing, A form having a length that allows use of a plurality of photosensitive materials. Generally, it means that the length of the processing sheet is 5 times or more and 1000 times or less of the width. The width of the processing sheet is arbitrary, but is preferably equal to or larger than the width of the corresponding photosensitive material.

It is also preferable that a plurality of light-sensitive materials are processed in parallel, that is, a plurality of light-sensitive materials are arranged and processed. In this case, the width of the processing sheet is preferably equal to or more than the width of the photosensitive material × the number of simultaneous processing. Such a continuous web processing sheet is particularly effective when the length of the photosensitive material is 50 cm or more and when a plurality of photosensitive materials are continuously processed. Also, when using such a continuous web processing sheet,
After the development, the photosensitive material and the processing sheet can be easily separated. Preferably, the continuous web processing sheet is supplied from an unwinding roll, wound up on a take-up roll and discarded. Especially in the case of large-sized photosensitive materials,
Easy to dispose. As described above, the handling property of the continuous web processing sheet is remarkably improved as compared with the conventional sheet-like member.

The thickness of the support used in the treatment sheet of the present invention is arbitrary, but is preferably thin, particularly preferably 4 μm or more and 40 μm or less. In this case, the amount of the processing sheet per unit volume increases, so that the processing sheet roll can be made compact. The material of the support is not particularly limited, and a material that can withstand the processing temperature is used. In general, papers and synthetic polymers (films) described in the Photographic Society of Japan, "Basics of photographic engineering-silver halide photography-", pages 223 to 240, published by Corona Co., Ltd. (1979). And photographic supports.
Specifically, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyvinyl chloride,
Polystyrene, polypropylene, polyimide, celluloses (for example, triacetyl cellulose) or those containing pigments such as titanium oxide in these films,
Further, synthetic paper made from polypropylene or the like, mixed paper made from synthetic resin pulp such as polyethylene and natural pulp, Yankee paper, baryta paper, coated paper (especially cast-coated paper) and the like are used.

These can be used alone,
It can also be used as a support laminated on one or both sides with a synthetic polymer such as polyethylene. In addition, JP-A-62-253159 (29)-(31)
Page, JP-A-1-161,236 (14)-(17)
Page, JP-A-63-316,848, JP-A-2-22,
No. 651, No. 3-56,955, U.S. Pat.
The support described in No. 1,033 or the like can be used.
Further, a support which is mainly a styrene polymer having a syndiotactic structure can also be preferably used.

On the surface of these supports, a hydrophilic binder and a semiconductive metal oxide such as alumina sol or tin oxide,
Carbon black or another antistatic agent may be applied. A support on which aluminum is deposited can also be preferably used.

The method of developing with a processing solution containing a developing agent / base is described in RD. No. 17643, pp. 28-29, N
o. No. 18716, page 651, left column to right column;
The method is the same as the method described on pages 880 to 881 of 307105. The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution mainly containing an aromatic primary amine color developing agent. Aminophenol compounds are also useful as the color developing agent, but p-phenylenediamine compounds are preferably used. Representative examples and preferred examples thereof are EP55.
6700A, page 28, lines 43-52. These compounds can be used in combination of two or more depending on the purpose. Color developing solutions include alkali metal carbonates, pH buffers such as borates or phosphates, chlorides, bromides, iodides, benzimidazoles,
It generally contains a development inhibitor such as benzothiazoles or a mercapto compound or an antifoggant. If necessary, various preservatives such as hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazide, trimethanolamine, catecholsulfonic acid, ethylene glycol, Organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts,
Development accelerators such as amines, dye-forming couplers, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity-imparting agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, phosphonos Various chelating agents represented by carboxylic acids, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo -N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N,
N-tetramethylene phosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and their salts are added.

The color developing solution generally has a pH of 9 to 12. The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per square meter of the light-sensitive material, and 500 ml by reducing the bromide ion concentration in the replenishing solution.
It can also be: When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area with the air in the processing tank. The processing effect due to the contact between the photographic processing solution and the air in the processing tank depends on the aperture ratio (=
[Contact area between treatment liquid and air cm ² ] ÷ [capacity of treatment liquid cm ³ ]). This aperture ratio is
It is preferably 0.1 or less, more preferably 0.1.
001 to 0.05. As a method for reducing the aperture ratio, a method of providing a movable lid described in JP-A-1-82032, a method of providing a movable lid described in JP-A-1-82032, besides providing a shield such as a floating lid on the photographic processing liquid surface of the processing tank. And the slit developing method described in the above item. The aperture ratio is preferably reduced not only in both the color development and black-and-white development steps but also in the subsequent steps, for example, in all of the steps such as bleaching, bleach-fixing, fixing, washing, stabilization, and the like.
The amount of replenishment can also be reduced by using means for suppressing the accumulation of bromide ions in the developer. The time for the color developing process is usually set between 2 and 5 minutes, but the processing time can be further shortened by using a high temperature, a high pH and using a high concentration of the color developing agent.
Preservatives used in the developer of the present invention include sodium sulfite, potassium sulfite, lithium sulfite, sodium formaldehyde sodium bisulfite, and hydroxylamine sulfate, and the amount of use is 0.1 mol / l or less, preferably It may be used in the range of 0.001 to 0.02 mol / liter. When a high silver chloride emulsion is used for the light-sensitive material, the above compound may be contained in an amount of 0.001 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 oxidation of a developing agent by air or the like, among which hydroxylamine derivatives (excluding hydroxylamine), hydroxamic acids, hydrazines, phenols, α-hydroxyketones, α-hydroxyketones Aminoketones, 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-63-4235.
No.-5341, No.63-30845, No.63-216
No. 47, No. 63-44655, No. 63-46454
No. 63-53551, No. 63-43140, No. 63-56654, No. 63-58346, No. 63-
No. 43138, No. 63-146041, No. 63-44
657, 63-44656, U.S. Pat.
No. 5,503, No. 2,494,903, Tokubo Sho48
-30496 and the like. Other preservatives include JP-A-57-44148 and JP-A-57-537.
Various metals described in JP-A No. 49-180588
Salicylic acids, alkanolamines described in JP-A-54-3532, polyethyleneimines described in JP-A-56-94349, U.S. Pat. No. 3,746,54
An aromatic polyhydroxy compound described in No. 4 or the like may be contained as necessary. It is particularly preferable to contain alkanolamines described in JP-A-4-97355, pp. 631-632, and dialkylhydroxylamine described in JP-A 627-630. Further, a dialkylhydroxylamine and / or a hydrazine derivative may be used in combination with an alkanolamine, or may be a dialkylhydroxylamine and glycine represented by dialkylhydroxylamine and glycine described in EP 530,921 A1.
-It is also preferable to use amino acids in combination. The amount of these compounds used is preferably 1 ×
10 ^{-3 to} 5 × 10 ^-1 mol, more preferably 1 × 10 ^-2 to
2 × 10 ^-1 mol.

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 bromide ions in an amount of 0.5 × 10 ^{-5 to} 1.0 × 10 ^-3 mol / l, more preferably 3.0 × 10 ^-3 mol / l.
^{-5 to} 5 × 10 ^-4 mol / liter. 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 developer, 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, trishydroxylamine methane 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 boric acid. 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 is preferably at least 0.05 mol / l, particularly preferably from 0.1 mol to 0.4 mol / l.

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 diaminetetraacetic acid, ethylenediamine orthohydroxy Phenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 1,2-dihydroxybenzene-4,6-disulfonic acid and alkali metal salts thereof. . These chelating agents may be used in combination of two or more as necessary. The addition amount of these chelating agents may be an amount sufficient to mask metal ions in the developer, for example, 0.1 g to 10 g per liter.
g.

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, for example,
Benzotriazole, 5-nitrobenzotriazole,
5-methylbenzotriazole, 5-nitrobenzimidazole, 5-nitroindazole, 2-thiazolylbenzimidazole, indazole, hydroxyazaindolizine, adenine, 1-phenyl-5-mercaptotetrazole or derivatives thereof are mentioned as typical examples. be able to. The addition amount of the nitrogen-containing heterocycle is 1 × 10 ⁻⁵ to 1
× 10 ⁻² mol / liter, preferably 2.5 × 10 ⁻⁵
１1 × 10 ⁻³ mol / l. In the present invention, when a photosensitive material is subjected to development processing using a developer, the developer functions as a silver halide developing agent, and / or an oxidized developing agent generated in silver development is incorporated in the photosensitive material. A compound having a function of cross-oxidizing a color-forming reducing agent may be used. Preferred are pyrazolidones, dihydroxybenzenes, reductones and aminophenols, and particularly preferred are pyrazolidones.

The pyrazolidones include 1-phenyl-3
-Pyrazolidones are preferred, and 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4 , 4-Dihydroxymethyl-3-pyrazolidone, 1-phenyl-
5-methyl-3-pyrazolidone, 1-phenyl-5-phenyl-3-pyrazolidone, 1-p-tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-p
-Chlorophenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-2-hydroxymethyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-2-acetyl-3-pyrazolidone, 1-phenyl -2-hydroxymethyl-5-phenyl-3-pyrazolidone, 1- (2-chlorophenyl) -4-hydroxymethyl-4-methyl-3-pyrazolidone and the like.

Examples of the dihydroxybenzenes include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,5-dimethylhydroquinone,
And potassium hydroquinone monosulfonate.

Reductones include N-methyl-p-
Aminophenol, N- (β-hydroxyethyl) -p
-Aminophenol, N- (4-hydroxyphenyl)
Glycine, 2-methyl-p-aminophenol and the like.

These compounds are usually used alone, but it is also preferable to use two or more of them in combination to enhance the development and cross-oxidation activities. The amount of these compounds used in the developer is from 2.5 × 10 ⁻⁴ mol / l to 0.2 mol / l, preferably from 0.0025 mol / l to 0.1 mol / l.
1 mol / l, more preferably 0.001 mol / l
Liter to 0.05 mol / liter.

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 described in JP-A Nos. 44-12380 and 45-9019 and U.S. Pat. No. 3,813,247;
P-phenylenediamine compound represented by JP-A-5-554, JP-A-50-137726, JP-B-44-300
No. 74, JP-A-56-156826 and JP-A-52-4
Quaternary ammonium salts described in US Pat. Nos. 2,494,903, 3,123,182, 4,230,796, and 3,253,919; No. 11431, U.S. Pat. No. 2,482,546
Nos. 2,596,926 and 3,582,34
No. 6, etc., and the amine compounds described in JP-B-37-1608.
No. 8, No. 42-25201, U.S. Pat.
No. 501, etc., polyalkylene oxides and imidazoles can be added as needed.

The light-sensitive material of the present invention may be subjected to a washing and / or stabilizing step after the development processing. The desilvering process can be performed after the development regardless of whether thermal development is performed or processing with a developer is performed. The desilvering process includes a fixing process and a bleaching and fixing process. In the case of bleaching and fixing, the bleaching and fixing may be performed separately or simultaneously (bleach-fixing). Further, processing in two continuous bleach-fixing baths, fixing before bleach-fixing, or bleach-fixing after bleach-fixing can be arbitrarily performed according to the purpose. In some cases, it is also preferable to carry out a stabilization treatment without performing a desilvering treatment after the development to stabilize a silver salt or a color image.

Examples of the bleaching agent used in the bleaching solution and the bleach-fixing solution include iron (III), cobalt (III), chromium (I
V), compounds of polyvalent metals such as copper (II), peracids, quinones and nitro compounds. Representative compounds include iron chloride, ferricyanide compounds, iron dichromate, and organic complex salts of iron (III) (for example, ethylenediaminetetraacetic acid,
Diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, methyliminodiacetic acid and aminopolycarboxylic acids and metal salts described in JP-A-4-365036, pp. 5-17), persulfates, persulfates Manganates, bromates, hydrogen peroxide and its releasing compounds (such as percarbonate and perboric acid), nitrobenzenes and the like can be mentioned. Among these, ethylenediaminetetraacetic acid (III) complex salt, 1,3-diaminopropanetetraacetic acid iron (III) complex aminopolycarboxylate iron (III), hydrogen peroxide, persulfate, etc. It is preferable from the viewpoint of preventing environmental pollution. PH of bleaching solution or bleach-fixing solution using these iron (III) aminopolycarboxylates
Is used in 3 to 8, preferably 5 to 7. The pH of the bleaching solution using persulfate or hydrogen peroxide is used at 4 to 11, preferably 5 to 10.

In the bleaching solution, the bleach-fixing solution and the prebath thereof, a bleaching accelerator can be used if necessary.
Specific examples of useful bleach accelerators include US Pat.
No. 93,856, West German Patent No. 1,290,812, JP-A-53-95630, Research Disclosure No. Compounds having a mercapto group or a disulfide bond described in No. 17129 (July, 1978);
Thiazolidine derivatives described in JP-A-50-140129; thiourea derivatives described in US Pat. No. 3,706,561; iodide salts described in JP-A-58-16235; West German Patent 2,748, No. 430; polyamine compounds described in JP-B-45-9936; bromide ions, and the like. Among them, compounds having a mercapto group or a disulfide group are preferred because they have a large promoting effect. These bleaching accelerators are particularly effective in desilvering color photographic materials for photography.

With respect to the accelerator for persulfuric acid bleaching, see
-214365 (European Patent No. 602600A1)
A complex salt of the described iron (III) ion with 2-pyridinecarboxylic acid or 2,6-pyridinedicarboxylic acid is effective. Regarding the hydrogen peroxide bleaching accelerator, see JP-B-61-1.
The metal salts of organic acids described in Nos. 6067 and 61-19024 are effective.

The bleaching solution, the bleach-fixing solution and the fixing solution include a rehalogenating agent such as ammonium bromide or ammonium chloride; ammonium nitrate, acetic acid, boric acid, citric acid or a salt thereof, tartaric acid or a salt thereof, succinic acid or a salt thereof. salt,
Known additives such as a pH buffer such as imidazole; a metal corrosion inhibitor such as ammonium sulfate can be used. In particular, it is preferable to contain an organic acid in order to prevent bleaching stain. The organic acid is a compound having an acid dissociation constant (pKa) of 2 to 7, specifically, acetic acid, succinic acid, citric acid, propionic acid and the like.

Examples of the fixing agent used in the fixing solution or the bleach-fixing solution include thiosulfates, thiocyanates, thioureas, a large amount of iodides, and JP-A-4-365037, pp. 11-21 and 5-1. 66540, pages 1088 to 1092, nitrogen-containing heterocyclic compounds having a sulfide group, mesoionic compounds, and thioether compounds. Of these, thiosulfates are generally used, and ammonium thiosulfate is most widely used. It is also preferable to use a combination of a thiosulfate with a thiocyanate, a thioether compound, a thiourea, a mesoionic compound, or the like.

As a preservative of the fixing solution or the bleach-fixing solution, a sulfite, a bisulfite, a carbonyl bisulfite adduct, or a sulfinic acid compound described in EP-A-294769A is preferable. Furthermore, various aminopolycarboxylic acids and organic phosphonic acids (for example, 1-hydroxyethylidene-1, 1
1-diphosphonic acid, N, N, N ′, N′-ethylenediaminetetraphosphonic acid, 2-phosphonobutane-1,2,2
Addition of sodium tristannate (4-tricarboxylic acid) is preferred.

The fixing solution or the bleach-fixing solution may further contain various fluorescent whitening agents; defoaming agents; surfactants; polyvinylpyrrolidone;

The processing temperature in the desilvering step is from 20 to 50 ° C., preferably from 30 to 45 ° C. The processing time is 5 seconds to 2 minutes, preferably 5 seconds to 1 minute. The replenishment amount is preferably smaller, but is preferably 15 to 600 ml, preferably 25 to 200 ml, more preferably 35 to 100 ml per m ^{2 of} the light-sensitive material.
ml. It is also preferable to perform the treatment without replenishment, to the extent that the evaporation amount is supplemented with water.

The light-sensitive material of the present invention generally undergoes a washing step after desilvering. When the stabilization treatment is performed, the washing step may be omitted. In such a stabilization process, JP-A-57-8543 and JP-A-58-1483 are used.
Nos. 4 and 60-220345, and JP-A-5-220345.
8-127926, 58-13837, 58
All known methods described in JP-A-140741 can be used. Further, a washing-stabilizing step may be performed in which a stabilizing bath containing a dye stabilizer and a surfactant, which is typified by processing of a color light-sensitive material for photography, is used as a final bath.

The washing and stabilizing solutions include sulfites; hard water softeners such as inorganic phosphoric acid, polyaminocarboxylic acid and organic aminophosphonic acid; metal salts such as Mg salt, Al salt and Bi salt; Agents; hardeners; pH buffers; fluorescent brighteners; silver salt-forming agents such as nitrogen-containing heterocyclic compounds; Examples of the dye stabilizer of the stabilizing solution include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine and aldehyde sulfite adducts.

The pH of the washing or stabilizing solution is 4 to 9, preferably 5 to 8. The processing temperature is from 15 to 45C, preferably from 25 to 40C. Processing time is 5 seconds ~
2 minutes, preferably 5 to 40 seconds. The overflow solution accompanying the washing and / or replenishment of the stabilizing solution can be reused in other steps such as a desilvering step.

The amount of washing water and / or stabilizing solution can be set in a wide range depending on various conditions, but the replenishing amount is preferably 15 to 360 ml per 1 m ² of the light-sensitive material, and more preferably 25 to 12
0 ml is more preferred. In order to reduce the amount of replenishment water, it is preferable to use a plurality of tanks and carry out a multi-stage countercurrent system. In particular, it is preferable to use 2 to 5 tanks. In order to prevent the propagation of bacteria which occur when the amount of water is reduced and the contamination of the resulting suspended matter to the photosensitive material, isothiazolone compounds and siapentazoles described in JP-A-57-8542, Fungicides such as sodium isocyanurate, and other benzotriazoles, etc., written by Hiroshi Horiguchi, "Chemistry of Fungicides and Fungicides" (1986)
(Published by Sankyo Publishing Co., Ltd.), "Sterilization, Sterilization, and Antifungal Techniques of Microorganisms" (edited by the Japan Society of Industrial Technology), edited by the Japan Society of Sanitary and Fungicides (1982); Can be used. Also, JP-A-62-28
The method of reducing Mg and Ca ions described in No. 8838 is also particularly preferably used.

In the present invention, water obtained by treating an overflow liquid or a liquid in a tank with a reverse osmosis membrane to save water can be used. For example, the treatment by reverse osmosis is preferably performed on water in the second and subsequent tanks for multi-stage countercurrent washing and / or stabilization. Specifically, in the case of a two-tank configuration, the water in the second or fourth tank is treated with a reverse osmosis membrane in the case of a four-tank configuration, and the permeated water is treated in the first tank (reverse osmosis membrane treatment). (A tank from which water has been collected) or a subsequent washing and / or stabilizing tank. One solution is to return the concentrated liquid to a tank upstream of the same tank and return to a desilvering bath.

As a material of the reverse osmosis membrane, cellulose acetate,
Crosslinked polyamide, polyether, polysulfone, polyacrylic acid, polyvinylene carbonate and the like can be used.
The liquid sending pressure in the use of these membranes is preferably 2 to
10 kg / cm ² , particularly preferably 3 to 7 kg / cm ²
It is.

In the present invention, it is preferable that the stirring is strengthened as much as possible. Specific methods for strengthening the stirring are described in JP-A-62-183460 and JP-A-62-183.
No. 461, a method of impinging a jet jet of a processing liquid on an emulsion surface of a light-sensitive material, a method of increasing stirring efficiency using a rotating means disclosed in JP-A-62-183461, and a wiper blade provided in a liquid A method of improving the stirring effect by moving the photosensitive material while bringing the emulsion surface into contact with the emulsion surface to make the emulsion surface turbulent, and a method of increasing the circulation flow rate of the entire processing solution. Such an agitation improving means is useful in any of a developing solution, a bleaching solution, a bleach-fixing solution, a stabilizing solution, and washing with water. These methods are effective in that the supply of the effective component in the liquid into the photosensitive material and the diffusion of the unnecessary component in the photosensitive material are promoted.

The automatic developing machine used for the light-sensitive material of the present invention is described in JP-A-60-191257 and JP-A-60-19125.
No. 8, No. 60-191259. Such a transport means can significantly reduce the carry-in of the processing solution from the pre-bath to the post-bath,
The effect of preventing performance deterioration of the processing liquid is high. Such an effect is effective in shortening the processing time of each step and in reducing the amount of processing replenishment. In order to shorten the processing time, it is preferable to shorten the crossover time (air time). For example, FIG. 4, FIG. The method of transporting between the processes described in 5 through a blade having a shielding effect is preferable. Further, when the respective processing liquids are concentrated by evaporation in the continuous processing, it is preferable to correct the concentration by adding water.

The processing time of the step in the present invention means the time required from the start of processing of the photosensitive material in one step to the start of processing in the next step. The actual processing time in an automatic developing machine is usually determined by the linear velocity and the capacity of the processing bath.
000 mm / min. In particular, in the case of a small developing machine, it is preferably 500 to 2500 mm / min. The processing time from the entire processing step, that is, from the developing step to the drying step, is preferably 360 seconds or less, more preferably 120 seconds or less, and particularly preferably 90 to 30 seconds. Here, the processing time is the time from when the photosensitive material is immersed in the developing solution to when it comes out of the drying unit of the processor.

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, exposing the original image through slits, etc. using an exposure device of a copying machine, and scanning by emitting light emitting diodes and various lasers (laser diodes, gas lasers, etc.) via image information and electric signals. Exposure method (Japanese Patent Application Laid-Open No. 2-129625, Japanese Patent Application No. 3-338,
No. 182, No. 4-9,388, No. 4-281, 442
And a method of outputting image information to an image display device such as a CRT, a liquid crystal display, an electroluminescence display, and a plasma display, and exposing directly or via an optical system.

As the light source for recording an image on a photosensitive material,
As described above, U.S. Pat.
No. 500,626, column 56, JP-A-2-53,378.
And the light source and the exposure method described in JP-A Nos. 2-54 and 672 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 a material capable of expressing nonlinearity between localization and an electric field that appears when a strong optical electric field such as laser light is applied.
Lithium niobate, potassium dihydrogen phosphate (KDP),
Inorganic compounds represented by lithium iodate, BaB ₂ O _{4 and the} like, urea derivatives, nitroaniline derivatives, for example,
3-methyl-4-nitropyridine-N-oxide (PO
Nitropyridine-N-oxide derivatives such as M) and the compounds described in JP-A Nos. 61-53,462 and 62-210,432 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 represented 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.

Hereinafter, the present invention will be described in more detail by way of examples.

[0255]

【Example】

<Method for Preparing Photosensitive Silver Halide Emulsion>

A well stirred gelatin aqueous solution (water 10
30 g of inert gelatin, potassium bromide 2 in 00 ml
g) as a solvent, ammonia / ammonium nitrate was added as a solvent, and the temperature was maintained at 75 ° C. Then, 1000 ml of an aqueous solution containing 1 mol of silver nitrate and 1000 ml of an aqueous solution containing 1 mol of potassium bromide and 0.03 mol of potassium iodide were added to the mixture.
Added simultaneously over minutes. After washing with water and desalting, the mixture was redispersed by adding inert gelatin to prepare a silver iodobromide emulsion having an equivalent sphere diameter of 0.76 μm and an iodine content of 3 mol%. The sphere equivalent diameter is
It was measured by Coulter Counter Model TA-II.
Potassium thiocyanate, chloroauric acid, and sodium thiosulfate were added to the above emulsion at 56 ° C. for optimal chemical sensitization. Sensitizing dyes corresponding to the respective spectral sensitivities were added to the emulsion at the time of preparing the coating solution to give color sensitivity.

<Preparation method of zinc hydroxide dispersion>

31 g of zinc hydroxide powder having a primary particle size of 0.2 μm, 1.6 g of carboxymethylcellulose as a dispersant and 0.4 g of sodium polyacrylate
g, lime-treated ossein gelatin 8.5 g, water 158.5
ml, and the mixture was dispersed in a mill using glass beads for 1 hour. After the dispersion, the glass beads were separated by filtration to obtain 188 g of a dispersion of zinc hydroxide.

<Method for Preparing Emulsified Dispersion of Coupler>

An oil phase component and an aqueous phase component having the compositions shown in Table 1 are each dissolved to form a uniform solution at 60 ° C. Combine the oil phase component and the water phase component in a 1 liter stainless steel container,
The mixture was dispersed at 10,000 rpm for 20 minutes by a tisol bar equipped with a 5 cm diameter disperser. To this, warm water of the amount shown in Table 1 was added as post-hydration, and 2000 rpm
m for 10 minutes. Thus, an emulsified dispersion of couplers of three colors of cyan, magenta and yellow was prepared.

[0262]

[Table 1]

Using the material thus obtained, a heat-developable color light-sensitive material 10 having a multilayer structure shown in Tables 2 and 3 was used.
1 was produced.

[0264]

[Table 2]

[0265]

[Table 3]

[0266]

Embedded image

[0267]

Embedded image

[0268]

Embedded image

[0269]

Embedded image

Furthermore, B-1, B-2, W-1 to W- are preferably added to each layer to improve the storage stability, processing property, pressure resistance, fungicide / bacteriostatic property, antistatic property and coatability. 4, F-1 to F-
17 and iron, lead, platinum, palladium, iridium and rhodium salts.

[0271]

Embedded image

[0272]

Embedded image

[0273]

Embedded image

Further, the processing materials R having the contents shown in Tables 4 and 5
-1 was produced.

[0275]

[Table 4]

[0276]

[Table 5]

[0277]

Embedded image

[0278]

Embedded image

Then, in the same manner as in the emulsion shown in Table 1,
As shown in Table 6, a cyan coupler emulsion to which a coupler capable of releasing a photographically useful group by reacting with an aromatic primary amine developing agent usable in the present invention was prepared. Light-sensitive materials 102 to 106 having exactly the same composition as the light-sensitive material 101 except that the above-mentioned second coupler was added to the first layer were prepared using this emulsion. Table 7 shows the compositions of the first layers of the photosensitive materials 102 to 106. The photosensitive materials 101 to 106 thus produced were exposed for 0.01 second at 2000 Lux through B, G, and R optical filters having continuously changed densities. 15 ml / m 2 of 40 ° C. warm water is applied to the exposed photosensitive material, and the processing material R-1 and the coated surfaces are superimposed so that they come into contact with each other.
By performing heat treatment for 7 seconds, thermal development was performed, and the processing material R-1 was promptly peeled off. Photosensitive material 10 after peeling
1, 104, 105, and 106 include cyan, magenta,
Although a yellow color image was clearly obtained, the photosensitive material 102 in which the first cyan color-forming layer was a combination of the developing agent of the present invention and a coupler having an anionic leaving group, and the first cyan color-forming layer Photosensitive material 10 from which developing agent has been removed
Sample No. 3 did not develop cyan color, and only magenta and yellow images were obtained.

[0280]

[Table 6]

[0281]

[Table 7]

Photosensitive materials 101, 104, 105, 106
Was exposed through a neutral gray optical filter having a continuously changed density at 2,000 Lux for 0.01 second, and the same heat development step was performed. Photosensitive material 10 immediately after processing
The transmission cyan densities of 1, 104, 105, and 106 were measured to obtain a so-called characteristic curve. In the characteristic curve of the transmission cyan density, the reciprocal of the exposure amount that gives a density 0.15 higher than the fog density is defined as the relative R sensitivity.
Table 8 shows relative values where 1 is set to 100. In the characteristic curve of the density of transmitted cyan, the difference between the exposure amount giving a density 0.2 higher than the fog density and the exposure amount giving a density 1.5 times higher than the fog density is indicated by a logarithm as the R gradation. .
Table 8 shows the fog density, relative R sensitivity, and R gradation.

Next, photosensitive materials 101, 104, 105, 1
To examine the granularity of No. 06, exposure was performed with white light giving a density of 1.0 higher than the fog density of the cyan density, and a color sample was prepared by the same heat development.
8 micron diameter aperture size cyan density RM
The S granularity was measured. This is defined as RMS granularity (R). Table 8 shows the results.

[0284]

[Table 8]

The results in Table 8 show that the photosensitive materials 104, 105, and 106 to which the coupler having an anionic leaving group capable of releasing a photographically useful group of the present invention was added had a change in photographic properties during thermal development. Does not occur.

(Example 2) The photosensitive materials 101 to 106 prepared in Example 1 were exposed for 0.01 second at 2000 Lux through B, G, and R optical filters having continuously changed densities. With leadal processing. Cyan, magenta, and yellow images were clearly obtained on the processed photosensitive material. The processing steps and the composition of the processing solution are shown below.

(Processing step) Step Processing time Processing temperature Replenishment amount * Tank capacity Color development 3 minutes 5 seconds 38.0 ° C 20 ml 17 liter Bleaching 50 seconds 38.0 ° C 5 ml 5 liters Fixing (1) 50 seconds 38.0 ° C -5 Liter Settling (2) 50 seconds 38.0 ° C 8 ml 5 liter Rinse 30 seconds 38.0 ° C 17 ml 3.5 liter Stability (1) 20 seconds 38.0 ° C-3 liter Stability (2) 20 seconds 38.0 ° C 15 ml 3 liter Dry Drying 1 minute 30 seconds 60 ° C * The replenishment amount is 35 mm width of photosensitive material 1.1 m (equivalent to 24 Ex. 1 bottle) The stabilizing solution is a countercurrent method from (2) to (1). All were introduced into fixing (2). The fixing solution is also connected from (2) to (1) by a countercurrent pipe. The amount of the developer brought into the bleaching step, the amount of the bleaching solution brought into the fixing step, and the amount of the fixing solution brought into the washing step were 2.5 ml and 2.0 ml, respectively, per 35 mm width of 1.1 mm photosensitive material. , 2.0 ml. The crossover time is 6 seconds in each case, and this time is included in the processing time of the previous step. The opening area of the above processor is 100 cm with the color developer.
^2. Bleaching solution 120cm ² , other processing solution about 100
cm ² .

The composition of the processing liquid is shown below. (Color developing solution) Tank solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 2.0 2.0 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 2.0 Sodium sulfite 3.9 5.3 Carbonic acid Potassium 37.5 39.0 Potassium bromide 1.4 0.4 Potassium iodide 1.3 mg-Disodium-N, N-bis (sulfonatoethyl) hydroxylamine 2.0 2.0 Hydroxylamine sulfate 2. 4 3.3 2-Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 4.5 6.4 Add water and add 1.0 liter 1.0 liter pH (hydroxylated (Adjusted with potassium and sulfuric acid) 10.05 10.18

(Bleaching solution) Tank solution (g) Replenisher solution (g) 1,3-diaminopropanetetraacetic acid ferric ammonium ammonium monohydrate 118 180 Ammonium bromide 80 115 Ammonium nitrate 14 21 Succinic acid 40 60 Maleic acid 33 50 Add water 1.0 liter 1.0 liter pH [adjusted with aqueous ammonia] 4.4 4.0

(Fixing solution) Tank solution (g) Replenisher (g) Ammonium methanesulfinate 10 30 Ammonium methanethiosulfonate 4 12 Aqueous ammonium thiosulfate (700 g / L) 280 mL 840 mL Imidazole 7 20 Ethylenediaminetetraacetic acid 15 45 Add water 1.0 liter 1.0 liter pH [adjusted with ammonia water and acetic acid] 7.4 7.45

(Rinse water) Tap water was replaced with H-type strongly acidic cation exchange resin (Amberlite IR- manufactured by Rohm and Haas Co.)
120B) and a mixed bed column filled with an OH type strongly basic anion exchange resin (Amberlite IR-400) to reduce the calcium and magnesium ion concentrations to 3
The treatment was carried out at a concentration of not more than mg / l, followed by addition of 20 mg / l of sodium diisocyanurate and 150 mg / l of sodium sulfate. The pH of this solution is 6.
It was in the range of 5-7.5.

(Stabilizing solution) Common to tank solution and replenisher (unit: g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.2 Disodium ethylenediaminetetraacetate Salt 0.05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 1,2-benzisothiazolin-3-one 0.10 water 1.0 liter pH 8.5

The photosensitive materials 101 to 106 were exposed to 2,000 Lux for 0.01 second through a neutral gray optical filter having a continuously changed density, and subjected to a redal process in the same color processing step. Photosensitive materials 101 to 1 after processing
The transmission densities of 06 yellow, magenta, and cyan were measured to obtain a so-called characteristic curve. In the characteristic curve of the cyan density, the reciprocal of the exposure amount that gives a density 0.15 higher than the fog density is defined as the relative R sensitivity, and the photosensitive material 1
Table 9 shows the relative values with 01 being 100. Further, in the characteristic curve of the cyan density, the difference between the exposure amount that gives a density 0.2 higher than the fog density and the exposure amount that gives a density 1.5 higher than the fog density is indicated by a logarithm as the R gradation. Table 9 shows the cyan fog density, relative R sensitivity, and R gradation.

Next, to examine the granularity of the light-sensitive materials 101 to 106, exposure was performed with white light giving a cyan density 1.0 higher than the fog density, and a color-developed sample was prepared in the same color processing step as in the lead color processing. Then, as in Example 1, R
MS granularity (R) was determined. Table 9 shows the results.

[0295]

[Table 9]

In summary, the light-sensitive material 101 obtained by combining the developing agent of the present invention and a dye-forming coupler having a cation leaving group has a clear cyan, magenta,
Although a yellow image was provided, clear cyan, magenta, and yellow images were provided by the processing of the color developing solution. However,
In the case of processing with a color developing solution, the graininess is poor. The photosensitive material 102 of the combination of the anion-withdrawing coupler capable of releasing a photographically useful group and the developing agent of the present invention is, in thermal development,
A color image cannot be obtained, and a color developing solution can provide a color image but has low sensitivity. The photosensitive material 103 using a dye-forming coupler having a cation leaving group in combination with a coupler having an anionic leaving group capable of releasing a photographically useful group and not using the developing agent of the present invention is a color image in thermal development. Cannot be obtained. Photosensitive materials 104, 105, and 106 using a combination of the developing agent of the present invention, a dye-forming coupler having a cation leaving group, and a coupler having an anionic leaving group capable of releasing a photographically useful group.
As in the case of heat development, clear cyan, magenta, and yellow images were obtained even when the color developing solution was processed. Photosensitive material 10
In Nos. 4, 105 and 106, the relative sensitivity is lower than that of the light-sensitive material 101, and it can be estimated that the coupler of the present invention reacted with the developing agent in the color developing solution to release the development inhibitor. Photosensitive material 104 to which the coupler of the present invention is added,
The particles 105 and 106 have a smaller granularity than the non-added 101, and it is apparent that the granularity has been improved by the coupler having an anionic leaving group which releases the photographically useful group of the present invention. It is.

The results of Examples 1 and 2 show that the developing agent of the present invention, a dye-forming coupler having a cation leaving group, and a coupler having an anionic leaving group capable of releasing a photographically useful group are combined. The light-sensitive material used gave a clear color image using either heat development or color development processing, and had good graininess in both heat development and color development processing. The material can provide a photosensitive material having excellent color reproducibility, sensitivity, and granularity both in heat development and color development processing.

Example 3 Next, an anionic leaving group capable of releasing a photographically useful group usable in the present invention as shown in Table 10 in the same manner as in the emulsion shown in Table 1 Were prepared by adding a coupler having the formula (1) to the emulsions shown in Table 1 to prepare yellow, magenta and cyan coupler emulsions, respectively. Using this emulsion, a light-sensitive material 107 having exactly the same composition as the light-sensitive material 101 was prepared except that the above couplers were added to the first, third, and fifth layers. The composition of the photosensitive material 107 includes a first layer, a third layer,
Coupler C-127, 31.2 mg respectively in the fifth layer
/ M ^2, coupler C-111,76.7mg / m ^2, except that the added coupler C-103,85.0mg / m ^2, the same composition as the photosensitive material 101.

[0299]

[Table 10]

The photosensitive materials 101 and 107 were exposed to 2,000 Lux for 0.01 second through a neutral gray optical filter having a continuously changed density, and the same heat development process as in Example 1 was performed. Photosensitive materials 101 and 10 immediately after processing
The transmission densities of yellow, magenta, and cyan were measured to obtain a so-called characteristic curve. Relative sensitivities and gradation fog densities were determined for the three colors yellow, magenta, and cyan under the same definitions as in Example 1. The results are shown in Table 11. After preparing a color sample by thermal development in the same manner as in Example 1, the RMS granularity of yellow, magenta, and cyan densities was measured using a diffuse light source with an aperture size of 48 microns. Table 11 shows the results.

[0301]

[Table 11]

Next, the photosensitive materials 101 and 107 were subjected to a lead processing with a color developing solution in the same manner as in Example 2, and the relative sensitivity and the gradation fog density were determined for the three colors of yellow, magenta and cyan with the same definition. , And Table 12. RMS granularity of yellow, magenta and cyan densities was measured in the same manner. Table 12 shows the results.

[0303]

[Table 12]

From the results shown in Tables 11 and 12, the light-sensitive material 107 of the present invention, when compared with the light-sensitive material 101, was developed with a developing solution containing an aromatic primary amine color developing agent even when thermally developed. It is clear, however, that it gives good granular images.

Example 4 The photosensitive materials 101 and 107 were cut and pierced for a general color negative film, loaded into a camera, and two persons of the same scene were photographed of a person and a Macbeth chart. One of the photographed films was subjected to thermal development processing, and one of the films was subjected to lead development with the developing solution of Example 2.
After processing the negative film as a manuscript, read it with a digital scanner, perform image processing so that the hue of each color on the Macbeth chart is closest to the actual chart, and then use Fuji Photo Film Output was performed at 3000, and a print was obtained. The photosensitive material 101 of the comparative example had excellent graininess during heat development and excellent color reproducibility. However, when processed with a color developing solution, the graininess was remarkably bad, roughness was conspicuous, and color turbidity was sufficient in image processing. Although it could not be corrected, the photosensitive material 107 of the present invention was excellent in granularity, sharpness, and hue saturation in both heat development and processing solution development.

[0306]

According to the silver halide color photographic light-sensitive material of the present invention, it is possible to form an image by a processing method which is simple and quick and has a low environmental load. The light-sensitive material of the present invention can be used in a heat-development process and a processing step using a developing solution containing a primary aromatic amine developing agent without causing photographic performance (sensitivity reduction and _Dmax reduction) during heat development processing. In any of the processing steps, a color image excellent in graininess, color reproducibility and prevention of color turbidity can be formed.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical display location G03C 8/40 503 G03C 8/40 503 505 505

Claims (3)

[Claims] 1. A support comprising at least a photosensitive silver halide, at least one developing agent represented by formula (I) or (II), and a cationic compound represented by formula (III) A silver halide color comprising a dye-forming coupler having a leaving group and a coupler having an anionic leaving group capable of releasing a photographically useful group represented by the general formula (IV). Photosensitive material. Embedded image In the formula, R _{1 to} R ₄ are a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkylcarbonamide group, an arylcarbonamide group, an alkylsulfonamide group, an arylsulfonamide group, an alkoxy group, an aryloxy group, an alkylthio group. An arylthio group, an alkylcarbamoyl group, an arylcarbamoyl group, a carbamoyl group,
Alkylsulfamoyl group, arylsulfamoyl group, sulfamoyl group, cyano group, alkylsulfonyl group, arylsulfonyl group, alkoxycarbonyl group,
Aryloxycarbonyl group, alkylcarbonyl group,
Represents an arylcarbonyl group or an acyloxy group;
₅ represents an alkyl group, an aryl group or a heterocyclic group.
Z represents an atomic group necessary for forming an aromatic ring or a heteroaromatic ring. When Z forms a substituted benzene ring, the total value of Hammett constant (σ) of the substituent is 1 or more. It is. General formula (III) Cp-Y In general formula (III), Cp is a developing agent and / or an aromatic first compound represented by general formula (I) and / or (II) at a position where Y is bonded. A group that forms a dye by coupling reaction with an oxidized form of a secondary amine developing agent.
Y is a group capable of leaving as a cation during the coupling reaction. General formula (IV) Cp- (Time) t-PUG In the formula, Cp has the same meaning as Cp in general formula (III). (T
ime) t-PUG is a group capable of leaving as an anion from the coupler of the general formula (IV) upon coupling reaction with an oxidized form of the developing agent, and Time represents a timing group. The timing group is anionic (Tim
e) t-PUG is a group having a function of generating PUG after leaving from the Cp portion. PUG represents a photographically useful group. t represents 0 or a positive integer. 2. The silver halide color photographic light-sensitive material according to claim 1, wherein the PUG released from the coupler having an anionic leaving group represented by the general formula (IV) is a development inhibiting substance. 3. A silver halide color photographic light-sensitive material which can be subjected to color development processing and heat development processing using a developing solution containing a primary aromatic amine developing agent. The silver halide color photographic light-sensitive material described in the above.