JPH09160192A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the silver halide photographic sensitive material capable of processing small in replenishment and discharge by incorporating a specified reducing agent for color development and a specified dye forming coupler in one of photographic constituent layers and specified silver halide grains in at least one layer. SOLUTION: This silver halide color photographic sensitive material contains at least one of the reducing agents of carbamoylhydrazines for color development represented by the formulae and the dye forming coupler, and the silver halide grains containing coordinated metal complex or metal ions derived from metal atoms of cycles 4, 5, and 6 and groups III-XIV of the periodic table in the crystal grating in at least one of the photographic constituent layers. In one of the formulae, R<12> is an optionally substituted alkyl or alkenyl group or the like; and X is -SO2 - or -CO- or the like.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to photographic technology, and more particularly to a silver halide photographic light-sensitive material excellent in environmental protection and safety, and having good color developability and hue even by simple and rapid processing, and an image forming method.

[0002]

2. Description of the Related Art Generally, a photographic light-sensitive material is subjected to color development after exposure, whereby an oxidized p-phenylenediamine derivative reacts with a coupler to form an image. In this method, the color reproduction method by the subtractive color method is used, and blue, green,
In order to reproduce red and red, yellow, magenta, and cyan color images having complementary colors are formed.

Color development is carried out by exposing the exposed photographic light-sensitive material to p.
-It is achieved by immersion in an aqueous alkali solution (color developing solution) in which a phenylenediamine derivative is dissolved. However, the p-phenylenediamine derivative in the form of an aqueous alkali solution is unstable and easily deteriorates with time, and there is a problem that it is necessary to frequently replenish the color developing solution to maintain stable developing performance. Further, the disposal of the used color developing solution containing the p-phenylenediamine derivative is complicated, and in combination with the frequent replenishment described above, the processing of a large amount of the used color developing solution is a big problem. There is.
Thus, there is a strong demand for achieving low replenishment and low discharge of the color developing solution.

As one of effective means for solving low replenishment and low discharge of the color developing solution, there is a method of incorporating an aromatic primary amine or a precursor thereof into a hydrophilic colloid layer,
Examples of the aromatic primary amine developing agent or a precursor thereof that can be incorporated include, for example, U.S. Pat. Nos. 2,507,114, 3,764,328, 4,060,418 and JP-A-56-
6235, the same 58-192031, etc. are mentioned. However, these aromatic primary amines and precursors thereof are unstable, and thus have a drawback that stain is generated during long-term storage or color development of unprocessed photosensitive materials. Another effective means is, for example, a method of incorporating a sulfone hydrazide type compound described in European Patent Nos. 0545491A1 and 565165A1 into a hydrophilic colloid layer. However, even the sulfone hydrazide type compounds listed here are not sufficiently stable, and the stain due to long-term storage after the treatment is still at a problematic level. Further, this sulfone hydrazide type compound has a problem that it hardly develops color when a 2-equivalent coupler is used. The 2-equivalent coupler has advantages over the 4-equivalent coupler in that the stain derived from the coupler can be reduced, the activity of the coupler can be easily adjusted, and the leaving group can have various functions.
In order to solve the above problems, a technique for increasing the coloring property, and further 2
It has been desired to develop a technique in which an equivalent coupler is used.

On the other hand, silver halide photographic light-sensitive materials are required to have high sensitivity, fine graininess and low fog as basic performance. One of the means for satisfying the demand is a metal doping technique for the purpose of improving the physical properties of silver halide grains and increasing the efficiency (quantum sensitivity) of converting photoelectrons into latent images that are active for development. The metal doping is a technique of incorporating (doping) metal ions alone or a metal complex containing a ligand into silver halide grains. This modifies the properties of the silver halide grains and can improve the performance of the emulsion as expected. Regarding metal doping techniques, Research Disclosure, 17643, Item IA, describes metal ions or metal complexes that can be introduced during grain formation.

An early representative example of metal complex doping technology is the metal complexes of platinum, palladium, iridium, rhodium and ruthenium shown in US Pat. No. 2,448,060. Doping with these metal complexes has the effect of preventing fogging and as a stabilizer,
In particular, it is disclosed that when a hexacoordinated metal complex of palladium (IV value) is added, sensitization is also performed. U.S. Pat. No. 3,690,888 discloses a method for producing a silver halide containing a polyvalent metal ion, the method including a step of producing silver halide grains in the presence of a peptizing agent mainly composed of an acrylic polymer. It is disclosed. Bivalent metal ions include bismuth, iridium, lead or osmium ions.

Japanese Patent Publication No. 48-35373 discloses that silver halide is doped with yellow blood salt and red blood salt which are hexacyano metal complexes of iron. U.S. Pat. No. 3,79
No. 0,390, iron by forming a stable compound,
Simple salts of 4th period elements such as cobalt and nickel, and VI
It is disclosed to use a hexacoordinated metal complex containing a cyano ligand in a group II metal, a hexacoordinated metal complex containing only ruthenium, rhodium, palladium, osmium, iridium simple salt or halide ligands. ing. Here, a silver halide emulsion containing a cyano complex of iron (II), iron (III) and cobalt (III) is described. European Patent 242,290 describes a halogenation of silver halide grains formed in the presence of one or more complexes of rhodium (III) with 3, 4, 5 or 6 cyano ligands. In silver emulsions, reduction of high illumination failure is disclosed.

JP-A-2-20853 and JP-A-2-2085
No. 4 describes a silver halide emulsion grained in the presence of a rhenium, ruthenium, osmium, or iridium complex having at least 4 or more cyano ligands. The effect is that the sensitivity and gradation are excellent in stability over time, and the low illuminance failure is improved. In JP-A-6-51423, an effect is obtained by doping a hexacyano metal complex in an internal latent image type direct positive silver halide emulsion. In addition to this, in JP-A-2-20852, JP-A-2-20855, JP-A-3-118535, and JP-A-3-118536, a ligand having a cyanide ion as one of bridging ligands is effective. It is described that it can be used in combination with a ligand such as NO, NS, CO or (O) ₂ . US Patent No. 53607
No. 12, 5457021, 5462849 disclose hexacoordinated metal complexes containing organic ligands containing one or more carbon-carbon, carbon-hydrogen, or carbon-nitrogen-hydrogen bonds. In these disclosures, a new concept is proposed in which a hexacoordinated metal complex is doped by replacing 7 silver vacancies of 1 silver ion and 6 adjacent halide ions inside the crystal. , Which is different from the conventional view on metal doping in which only metal ions are replaced by silver ions.

As described above, the metal doping technique exhibits excellent performance in silver halide photographic light-sensitive materials. As a result of intensive studies, the present inventors have found that excellent photographic properties are obtained by combining a photographic constituent layer containing a reducing agent for color formation of the present invention and a dye-forming coupler with a silver halide grain using a metal doping technique. I was found to be done.

[0010]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a light-sensitive material which has a low replenishment and a low discharge, has a reduced stain due to long-term storage of the light-sensitive material, has excellent granularity at high sensitivity, and has low fog. To provide.

[0011]

It has been found that the object of the present invention is achieved by the following method. (1) In a silver halide photographic light-sensitive material having at least one photographic constituent layer on a support, at least one color-forming reducing agent represented by the following general formula (I) in any of the photographic constituent layers, The silver halide grains containing at least one dye-forming coupler and contained in at least one of the photographic constituent layers are 4, 5 and 6 of the periodic table, 3 to 1
A silver halide photographic light-sensitive material comprising a coordinated metal complex containing a Group 4 element metal or a metal ion in a crystal lattice.

[0012]

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In the formula, R ¹¹ is an aryl group or a heterocyclic group which may have a substituent, and R ¹² is an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a hetero group which may have a substituent. It is a cyclic group. X is -SO ₂ -, - CO
-, - COCO -, - CO -O -, - CON (R 13)
-, - COCO-O -, - COCO-N (R 13) - or -SO ₂ -N (R ¹³⁾ - it is. Here, R ¹³ is a hydrogen atom or a group described for R ¹² . (2) The compound represented by the general formula (I) is represented by the general formula (II),
The silver halide photographic light-sensitive material according to (1), which is represented by (III).

[0014]

[Chemical 6]

Wherein Z ¹ is an acyl group, a carbamoyl group,
Represents an alkoxycarbonyl group or an aryloxycarbonyl group, Z ² represents a carbamoyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group;
X ¹ , X ² , X ³ , X ⁴ and X ⁵ represent a hydrogen atom or a substituent. However, the sum of the Hammett's substituent constant σp value of X ¹ , X ³ and X ^{5 and} the Hammett's substituent constant σm value of X ² and X ⁴ is 0.80 or more and 3.80 or less. R ³ represents a heterocyclic group.

(3) The silver halide photographic light-sensitive material according to (2), wherein the compounds represented by the general formulas (II) and (III) are represented by the general formulas (IV) and (V), respectively. material.

[0017]

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In the formula, R ¹ and R ² represent a hydrogen atom or a substituent, and X ¹ , X ² , X ³ , X ⁴ and X ⁵ represent a hydrogen atom or a substituent. However, the sum of the Hammett's substituent constant σp values of X ¹ , X ³ and X ^{5 and} the Hammett's substituent constant σm of X ² and X ⁴ is 0.80 or more and 3.80 or less. R ³ represents a heterocyclic group. (4) The silver halide photographic light-sensitive material according to (3), wherein the compounds represented by the general formulas (IV) and (V) are represented by the general formulas (VI) and (VII), respectively.

[0019]

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In the formula, R ⁴ and R ⁵ represent a hydrogen atom or a substituent, and X ⁶ , X ⁷ , X ⁸ , X ⁹ and X ¹⁰ represent a hydrogen atom, a cyano group, a sulfonyl group, a sulfinyl group, a sulfamoyl group, Carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, trifluoromethyl group, halogen atom, acyloxy group, acylthio group,
Or a heterocyclic group. However, the sum of the Hammett's substituent constant σp value of X ⁶ , X ⁸ and X ^{10 and} the Hammett's substituent constant σm value of X ⁷ and X ⁹ is 1.20 or more and 3.80 or less. Q ¹ represents a group of nonmetallic atoms necessary for forming a nitrogen-containing 5- to 8-membered heterocyclic ring together with C.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a specific configuration of the present invention will be described in detail. Hereinafter, the color-forming reducing agent used in the present invention will be described in detail. The color-forming reducing agent represented by the general formula (I) used in the present invention reacts directly with the exposed silver halide in an alkaline solution and is oxidized, or is oxidized by the exposed silver halide. A compound characterized by being oxidized by a redox reaction with a developing agent, and a compound characterized by reacting an oxidized form thereof with a dye-forming coupler to form a dye. Hereinafter, the structure of the color-forming reducing agent represented by the general formula (I) will be described in detail.

In the general formula (I), R ¹¹ represents an aryl group or a heterocyclic group which may have a substituent. The aryl group of R ^11, preferably that of 6 to 14 carbon atoms include, for example, phenyl or naphthyl. R ¹¹
As the heterocyclic group, preferably, nitrogen, oxygen, sulfur,
It is a saturated or unsaturated 5-, 6- or 7-membered ring containing at least one of selenium. These may be condensed with a benzene ring or a hetero ring. R
Examples of ¹¹ heterocycles include furanyl, thienyl, oxazolyl, thiazolyl, imidazolyl, triazolyl,
Pyrrolidinyl, benzoxazolyl, benzothiazolyl, pyridyl, pyridazyl, pyrimidinyl, pyrazinyl, triazinyl, quinolinyl, isoquinolinyl, phthalazinyl, quinoxalinyl, quinazolinyl, purinyl,
Pteridinyl, azepinyl, benzoxepinyl and the like can be mentioned.

The substituent which R ¹¹ has is an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group. , Acyloxy group, acylthio group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, carbamoyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, amino group, alkylamino group, arylamino group, amide group, alkoxycarbonylamino group , An aryloxycarbonylamino group, an ureido group, a sulfonamide group, a sulfamoylamino group,
Acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, acylcarbamoyl group,
Carbamoylcarbamoyl group, sulfonylcarbamoyl group, sulfamoylcarbamoyl group, alkylsulfonyl group, arylsulfonyl group, alkylsulfinyl group, arylsulfinyl group, alkoxysulfonyl group, aryloxysulfonyl group, sulfamoyl group,
Examples include acylsulfamoyl, carbamoylsulfamoyl, halogen, nitro, cyano, carboxyl, sulfo, phosphono, hydroxyl, mercapto, imide, and azo groups. R ¹² represents an optionally substituted alkyl group, alkenyl group, alkynyl group, aryl group or heterocyclic group.

The alkyl group represented by R ¹² is preferably a linear, branched or cyclic C 1-16 alkyl group such as methyl, ethyl, hexyl, dodecyl, 2-octyl, t-butyl, cyclopentyl, cyclooctyl. And the like. The alkenyl group for R ¹² is preferably a chain or cyclic group having 2 to 16 carbon atoms, and includes, for example, vinyl, 1-octenyl and cyclohexenyl.

The alkynyl group for R ¹² preferably has 2 to 16 carbon atoms, and examples thereof include 1-butynyl and phenylethynyl. As the aryl group and heterocyclic group for R ¹² , those described for R ¹¹ can be mentioned.
Examples of the substituent of R ¹² include those described for the substituent of R ¹¹ . X represents -SO _2- , -CO-, -C
OCO -, - CO-O - , - CONH (R 13) -, - C
OCO-O -, - COCO- N (R 13) - or -SO
₂ -NH (R ¹³⁾ - and the like. Here, R ¹³ is a hydrogen atom or a group described for R ¹² . Of these groups, -C
O-, -CONH (R < ¹³ >)-, and -CO-O- are preferable, and -CONH (R < ¹³ >) is particularly preferable in terms of excellent color development.
-Is particularly preferred. Among the compounds represented by the general formula (I), the compounds represented by the general formulas (II) and (III) are preferable, the compounds represented by the general formulas (IV) and (V) are more preferable, and the general formula (VI) and The compound represented by (VII) is more preferable. Hereinafter, the compounds represented by formulas (II) to (VII) will be described in detail.

In the general formulas (II) and (III), Z ¹ represents an acyl group, a carbamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group, and Z ²
Represents an acyl group, a carbamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group. The acyl group is preferably an acyl group having 1 to 50 carbon atoms, and more preferably 2 to 40 carbon atoms. Specific examples include acetyl group, 2-methylpropanoyl group, cyclohexylcarbonyl group, n-octanoyl group, 2-hexyldecanoyl group, dodecanoyl group, chloroacetyl group, trifluoroacetyl group, benzoyl group, 4- Examples thereof include a dodecyloxybenzoyl group, a 2-hydroxymethylbenzoyl group, and a 3- (N-hydroxy-N-methylaminocarbonyl) propanoyl group. When Z ¹ and Z ² are carbamoyl groups, they can be represented by the general formulas (VI) to (VI
Details are described in I).

The alkoxycarbonyl group and aryloxycarbonyl group are preferably an alkoxycarbonyl group having 2 to 50 carbon atoms and an aryloxycarbonyl group, and more preferably 2 to 40 carbon atoms. Specific examples include a methoxycarbonyl group, an ethoxycarbonyl group,
Isobutyloxycarbonyl group, cyclohexyloxycarbonyl group, dodecyloxycarbonyl group, benzyloxycarbonyl group, phenoxycarbonyl group, 4-octyloxyphenoxycarbonyl group, 2-hydroxymethylphenoxycarbonyl group, 2-dodecyloxyphenoxycarbonyl group and the like. Can be

X ¹ , X ² , X ³ , X ⁴ and X ⁵ represent a hydrogen atom or a substituent. Preferred examples of the substituents of X ¹ to X ⁵ are cyano, alkylsulfonyl, arylsulfonyl, alkylsulfinyl, arylsulfinyl,
Sulfamoylcarbamoyl, alkoxycarbonyl,
Each group (or each atom) of aryloxycarbonyl, acyl, trifluoromethyl, halogenacyloxy, and acylthio. Two adjacent groups of X ¹ to X ⁵ are
A condensed ring may be formed (a naphthalene ring, a quinoline ring, etc. are formed). Both sulfamoyl and carbamoyl groups may be substituted with 1 or 2 alkyl or aryl. In the above-mentioned substituents containing an alkyl group or an aryl group (alkylsulfonyl, arylsulfonyl and up to an acylthio group), the alkyl group or the aryl group may have a usual substituent. Examples of permissible substituents are hydroxy, alkoxy, aryloxy,
Halogen, alkoxycarbonyl, aryloxycarbonylcarbamoyl, sulfamoyl, alkylthio,
Each group (or each atom) of arylthio, which has a plurality of these substituents, and these groups (atoms) may be the same or different. The preferred carbon number range of each substituent containing the above-mentioned alkyl group is 1 to 50, more preferably 1 to 42, and most preferably 1 to 34. Similarly, the preferable carbon number range of each of the above-mentioned substituents including the aryl group has the same upper limit as that of the alkyl group, and the lower limit thereof is 6. An aromatic group containing a hetero atom is also useful as a substituent of the present invention in the same manner as an aryl group, in which case the upper limit of the carbon number range is the same as that of the alkyl group and the lower limit is 1
Becomes Specific examples of the heterocycle from which the aromatic group containing a heteroatom is derived are pyridine, furan, thiophene, pyrazole, imidazole and the like. Specific examples of the substituents represented by X ¹ to X ⁵ include a linear or branched, chain or cyclic alkyl group having 1 to 50 carbon atoms (eg, trifluoromethyl, methyl, ethyl, propyl, heptafluoro). Propyl, isopropyl, butyl, t-butyl,
t-pentyl, cyclopentyl, cyclohexyl, octyl, 2-ethylhexyl, dodecyl, etc.), C2-C2
50 straight or branched, chain or cyclic alkenyl groups (eg vinyl, 1-methylvinyl, cyclohexene-
1-yl), an alkynyl group having 2 to 50 carbon atoms (eg, ethynyl, 1-propynyl, etc.), an aryl group having 6 to 50 carbon atoms (eg, phenyl, naphthyl, anthryl, etc.), 1 to 50 carbon atoms. An acyloxy group of (for example,

Acetoxy, tetradecanoyloxy, benzoyloxy, etc.), carbamoyloxy group having 1 to 50 carbon atoms (eg, N, N-dimethylcarbamoyloxy, etc.), carbonamido group having 1 to 50 carbon atoms (eg, formamide) , N-methylacetamide, acetamide,
N-methylformamide, benzamide, etc.), having 1 carbon atom
To 50 sulfonamide groups (for example, methanesulfonamide, dodecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, etc.), 1 to 50 carbon atoms
Carbamoyl group (for example, N-methylcarbamoyl,
N, N-diethylcarbamoyl, N-mesylcarbamoyl, etc.), a sulfamoyl group having 0 to 50 carbon atoms (for example,
N-butylsulfamoyl, N, N-diethylsulfamoyl, N-methyl-N- (4-methoxyphenyl) sulfamoyl, etc.), an alkoxy group having 1 to 50 carbon atoms (for example, methoxy, propoxy, isopropoxy, Octyloxy, t-octyloxy, dodecyloxy, 2-
(2,4-di-t-pentylphenoxy) ethoxy and the like), an aryloxy group having 6 to 50 carbon atoms (for example, phenoxy, 4-methoxyphenoxy, naphthoxy and the like),
An aryloxycarbonyl group having 7 to 50 carbon atoms (for example, phenoxycarbonyl, naphthoxycarbonyl, etc.),

Alkoxycarbonyl group having 2 to 50 carbon atoms (eg, methoxycarbonyl, t-butoxycarbonyl, etc.), N-acylsulfamoyl group having 1 to 50 carbon atoms (eg, N-tetradecanoylsulfamoyl, N-
Benzoylsulfamoyl, etc.), an alkylsulfonyl group having 1 to 50 carbon atoms (eg, methanesulfonyl, octylsulfonyl, 2-methoxyethylsulfonyl, 2-hexyldecylsulfonyl, etc.), and an arylsulfonyl group having 6 to 50 carbon atoms (eg, Benzenesulfonyl, p-toluenesulfonyl, 4-phenylsulfonylphenylsulfonyl, etc.), an alkoxycarbonylamino group having 2 to 50 carbon atoms (eg, ethoxycarbonylamino, etc.), and an aryloxycarbonylamino group having 7 to 50 carbon atoms (eg, Phenoxycarbonylamino, naphthoxycarbonylamino, etc.), an amino group having 0 to 50 carbon atoms (eg, amino, methylamino, diethylamino, diisopropylamino, anilino, morpholino, etc.), cyano group, nitro group, carboxyl , A hydroxy group, a sulfo group, a mercapto group, etc.), an alkylsulfinyl group having 1 to 50 carbon atoms (eg, methanesulfinyl, octanesulfinyl, etc.), an arylsulfinyl group having 6 to 50 carbon atoms (eg, benzenesulfinyl, 4-chlorophenyl) Sulfinyl, p-toluenesulfinyl, etc.), having 1 to 5 carbon atoms
An alkylthio group of 0 (eg,

Methylthio, octylthio, cyclohexylthio, etc.), arylthio groups having 6 to 50 carbon atoms (eg phenylthio, naphthylthio, etc.), 1 to 50 carbon atoms.
Ureido group (eg, 3-methylureido, 3,3-
Dimethylureide, 1,3-diphenylureide, etc.),
A heterocyclic group having 2 to 50 carbon atoms (as a hetero atom, for example, a 3- to 12-membered monocyclic or condensed ring containing at least one or more of nitrogen, oxygen and sulfur;
Furyl, 2-pyranyl, 2-pyridyl, 2-thienyl,
2-imidazolyl, morpholino, 2-quinolyl, 2-benzimidazolyl, 2-benzothiazolyl, 2-benzoxazolyl, etc.), an acyl group having 1 to 50 carbon atoms (eg, acetyl, benzoyl, trifluoroacetyl, etc.), carbon Sulfamoylamino groups of numbers 0 to 50 (e.g., N-butylsulfamoylamino, N-phenylsulfamoylamino, etc.), silyl groups of 3 to 50 carbon atoms (e.g., trimethylsilyl, dimethyl-t-butylsilyl, Triphenylsilyl and the like, and a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom and the like). The above substituents may further have a substituent,
Examples of the substituent include the substituents mentioned here. Further, X ¹ , X ² , X ³ , X ⁴ and X ⁵ may combine with each other to form a condensed ring.

The carbon number of the substituent is preferably 50 or less, more preferably 42 or less, and most preferably 34 or less. Also, one or more is preferable.

X ¹ in the general formulas (II) and (III),
Regarding X ² , X ³ , X ⁴ and X ⁵ , the sum of Hammett's substituent constant σp value of X ¹ , X ³ and X ⁵ and Hammett's substituent constant σm value of X ² and X ⁴ is 0.80. The above is 3.80 or less. In addition, X ⁶ , X ⁷ , X ⁸ in the general formula (VI),
X ⁹ and X ¹⁰ are hydrogen atom, cyano group, sulfonyl group, sulfinyl group, sulfamoyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, trifluoromethyl group, halogen atom, acyloxy group, acylthio group or It represents a heterocyclic group, which may further have a substituent and may be bonded to each other to form a condensed ring. X for specific examples
It is the same as that described for ¹ , X ² , X ³ , X ⁴ , and X ⁵ . However, in the general formula (VI), the sum of the Hammett's substituent constant σp value of X ⁶ , X ⁸ , and X ¹⁰ and the Hammett substituent constant σm value of X ⁷ , XX ⁹ is 1.20 or more and 3.80 or less. And is preferably 1.50 or more and 3.80 or less, and more preferably 1.70 or more and 3.80 or less. here,
If the sum of the σp value and the σm value is less than 0.80, there is a problem that the color developability is insufficient, and if it exceeds 3.80, it becomes difficult to synthesize and obtain the compound itself.

Regarding the Hammett's substituent constants σp and σm, for example, Naoki Inamoto, “Hammett's Rule-Structure and Reactivity-” (Maruzen), “New Experimental Chemistry Lecture 14, Synthesis and Reaction V of Organic Compounds” 2605. Page (edited by the Chemical Society of Japan, Maruzen), Tadao Nakaya, "Commentary on Theoretical Organic Chemistry", page 217 (Tokyo Kagaku Dojin), Chemical Review (Vol. 91), 165-195.
The book is described in detail in pages (1991).

R ¹ in the general formulas (IV) and (V),
R ⁴ and R ⁵ in R ² , (VI) and (VII) represent a hydrogen atom or a substituent, and specific examples of the substituent include X ¹ and
It has the same meaning as described for X ² , X ³ , X ⁴ and X ⁵ , but is preferably a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, or a substituted or unsubstituted alkyl group having 6 to 50 carbon atoms. It is a substituted aryl group or a substituted or unsubstituted heterocyclic group having 1 to 50 carbon atoms. More preferably, at least one of R ¹ and R ² and at least one of R ⁴ and R ⁵ are a hydrogen atom.

In the general formulas (III) and (V), R ³ represents a heterocyclic group. Preferred examples of the hetero ring of R ³ include:
Examples thereof include a 5- to 8-membered monocyclic or condensed-ring heterocycle containing nitrogen, which may further contain O and S atoms, and include pyridine, pyrimidine, pyridazine, pyrazine, 1,2,4-triazine, 1,3, and 3. Examples include 5-triazinepyrazole, imidazole, thiazole, isothiazole, oxazole, isoxazole, 1,2,4-thiadiazole, quinazoline, quinoxaline, phthalazine, quinoline, isoquinoline, benzothiazole, benzoxazole, benzimidazole, pteridine, and purine. To be The number of nitrogen atoms contained in these monocycles or condensed rings is preferably 1 to 4. In the general formula (VII), Q ¹ represents a group of non-metal atoms necessary for forming a nitrogen-containing 5- to 8-membered hetero ring together with C. Preferred examples of the heterocycle formed by Q ¹ together with C are the same as the above R ³ . R ³
The number of carbon atoms in the heterocycle is 1 to 50, preferably 1 to 42, and most preferably 1 to 3
4. A preferred heterocyclic group is a heterocyclic group having 1 to 50 carbon atoms, and the hetero atom includes, for example, at least one or more of nitrogen, oxygen and sulfur atoms, and a saturated or unsaturated 3 to 12 membered ring (preferably (3 to 8-membered ring) monocyclic or condensed ring, and specific examples of the heterocyclic ring include furan, pyran, pyridine, thiophene, imidazole, quinoline, benzimidazole, benzothiazole, benzoxazole, pyrimidine, pyrazine, 1,
2,4-thiadiazole, pyrrole, oxazole, thiazole, quinazoline, isothiazole, pyridazine,
Examples include indole, pyrazole, triazole, quinoxaline and the like. These heterocyclic groups may have a substituent, and those having one or more electron-withdrawing groups are preferable. Here, the electron-withdrawing group means a group having a positive Hammett σp value. When the color-forming reducing agent of the present invention is incorporated in a light-sensitive material, Z ¹ ,
At least one of Z ² , R ^{1 to} R ⁵ , and X ^{1 to} X ¹⁰ preferably has a ballast group.

Next, the novel color-forming reducing agents used in the present invention will be specifically shown, but the scope of the present invention is not limited to these specific examples.

[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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

[0060]

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[0061]

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[0062]

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The general formulas (1) to (4) represent couplers called active methylene couplers, in which R ¹⁴ represents an acyl group which may have a substituent, a cyano group, a nitro group, an 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 which may have a substituent or a heterocyclic residue. R
^14, as the R ^15, the substituent that may be R ¹⁶ has, include those mentioned as examples of X ¹ to X ⁵ as described above.

In the general formulas (1) to (4), Y is a hydrogen atom or a group which can be eliminated by a coupling reaction with an oxidant of the color-forming reducing agent. Examples of Y include a heterocyclic group (a heterocyclic atom is a saturated or unsaturated monocyclic or condensed 5- to 7-membered ring containing at least one nitrogen, oxygen, sulfur or the like, and examples thereof include succinimide and maleic Imide, phthalimide, diglycolimide, pyrrole, pyrazole, imidazole, 1,2,4-triazole, tetrazole, indole, benzopyrazole, benzimidazole, benzotriazole, imidazoline-2,4-dione, oxazolidin-2,4-dione , Thiazolidine-2,4-dione, imidazolidine-2-one, oxazolin-2-one, thiazoline-2
-One, benzimidazolin-2-one, benzoxazolin-2-one, benzothiazolin-2-one, 2-
Pyrrolin-5-one, 2-imidazolin-5-one, indoline-2,3-dione, 2,6-dioxypurine,
Parabanic acid, 1,2,4-triazolidine-3,5-dione, 2-pyridone, 4-pyridone, 2-pyrimidone,
6-pyridazone, 2-pyrazone, 2-amino-1,3,
4-thiazolidine, 2-imino-1,3,4-thiazolidin-4-one etc.), halogen atom (eg chlorine atom, bromine atom etc.), aryloxy group (eg phenoxy, 1-naphthoxy etc.), hetero Ring oxy group (eg pyridyloxy, pyrazolyloxy etc.), acyloxy group (eg acetoxy, benzoyloxy etc.),
Alkoxy group (eg, methoxy, dodecyloxy, etc.), carbamoyloxy group (eg, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, etc.), aryloxycarbonyloxy group (eg, phenoxycarbonyloxy, etc.), alkoxycarbonyloxy group (Eg, methoxycarbonyloxy, ethoxycarbonyloxy, etc.), arylthio groups (eg, phenylthio, naphthylthio, etc.), heterocyclic thio groups (eg, tetrazolylthio, 1,3,4-thiadiazolylthio, 1,3,4- Oxadiazolylthio, benzimidazolylthio, etc.), alkylthio group (eg, methylthio, octylthio, hexadecylthio, etc.), alkylsulfonyloxy group (eg, methanesulfonyloxy, etc.), arylsulfonyloxy Si group (eg, benzenesulfonyloxy, toluenesulfonyloxy, etc.), carbonamide group (eg, acetamide, trifluoroacetamide, etc.), sulfonamide group (eg, methanesulfonamide, benzenesulfonamide, etc.), alkylsulfonyl group ( For example, methanesulfonyl and the like, an arylsulfonyl group (eg, benzenesulfonyl), an alkylsulfinyl group (eg, methanesulfinyl), an arylsulfinyl group (eg, benzenesulfinyl), an arylazo group (eg, phenylazo, naphthylazo) Carbamoylamino group (for example, N-methylcarbamoylamino and the like).

Y may be substituted with a substituent,
Examples of the substituent for substituting Y include those described for X ^{1 to} X ⁵ .

Y is preferably a halogen atom, an aryloxy group, a heterocyclic oxy group, an acyloxy group, an aryloxycarbonyloxy group, an alkoxycarbonyloxy group or a carbamoyloxy group.

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.

The general formula (5) represents a coupler called a 5-pyrazolone type coupler, in which R ¹⁷ represents an alkyl group, 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.

Describing in detail about these preferable groups, R ¹⁷ is phenyl group, 2-chlorophenyl group, 2-methoxyphenyl group, 2-chloro-5-tetradecanamidophenyl group, 2-chloro-5- (3-octadecenyl group. -1-succinimido) 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. Y has the same meaning as described above.

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

The general formula (6) represents a coupler called a pyrazoloazole coupler, and in the formula, 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 type couplers represented by the general formula (6), in terms of the spectral absorption characteristics of the color forming dye,
Imidazo [1,2-b] pyrazoles described in US Pat. No. 4,500,630, US Pat.
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.

The details of the substituent of the azole ring represented by the substituents R ¹⁹ and Q ³ are described in, for example, US Pat. No. 4,54.
No. 0,654, column 2, line 41 to column 8, line 27. Preferably JP-A-61-1
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. Y has the same meaning as described above.

The general formulas (7) and (8) are couplers called phenol type couplers and naphthol type couplers, 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 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. As the substituents of R ^{21 to} R ^23, the above X ¹ to
Those mentioned as examples of X ⁵ may be mentioned. Y has the same meaning as described above.

Preferred examples of the phenolic coupler represented by the general formula (7) include US Pat. No. 2,369,9.
No. 29, No. 2,801,171, No. 2,772
No. 162, No. 2,895,826, No. 3,77
2,002 and the like, 2-acylamino-5-alkylphenols, U.S. Pat. Nos. 2,772,162, 3,758,308, 4,126,396;
Nos. 4,334,011, 4,327,173
No. 3,329,729, West German Patent Publication No.
2,5-diacylaminophenol-based compounds described in US Pat. No. 4,696,956, U.S. Pat. Nos. 3,446,622, 4,333,999, 4,451,559, and 4,427. Examples thereof include 2-phenylureido-5-acylaminophenol-based compounds described in No. 767 and the like. Y is the same as that described above.

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

The general formulas (9) to (12) are couplers called pyrrolotriazole, and R ³² , R ³³ and R ³⁴ represent a hydrogen atom or a substituent. Y is as described above. ^Examples of the substituent of R ³² , R ³³ and R ³⁴ include the aforementioned X
Include those mentioned above as examples of the ¹ to X ^5. Preferred examples of the pyrrolotriazole-based couplers represented by the general formulas (9) to (12) include European Patent 488,248.
A1, No. 491,197 A1, No. 545,30
A coupler in which at least one of R ³² and R ³³ described in No. 0 is an electron-withdrawing group can be mentioned. Y is the same as that described above.

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

As the condensed ring phenol type coupler, US Pat. Nos. 4,327,173 and 4,564,586 are known.
And the couplers described in JP-A Nos. 4,904,575 and the like can be used.

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

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

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

As the 5,5-fused heterocyclic type couplers,
Pyrrolopyrazole couplers described in U.S. Pat. No. 5,164,289 and pyrroloimidazole couplers described in JP-A-4-17429 can be used.

As the 5,6-condensed heterocyclic coupler,
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 coupler, West German Patent Nos. 3,819,051A and 3,823,049 are also included.
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,
No. 4-179949, No. 4-182645, No. 4-
Nos. 184437, 4-188138, 4-188
No. 139, No. 4-194847, No. 4-204532
The couplers described in JP-A No. 4-204731, JP-A No. 4-204732, and the like can also be used.

Specific examples of the coupler that can be used in the present invention are shown below, but the present invention is not limited thereto.

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The color-forming reducing agent of the present invention contains 0.01 to 10 mmol / m ² per layer in order to obtain a sufficient color density.
It is preferred to use. A more preferred amount is 0.0
It is 5 to 5 mmol / m ² , and the particularly preferred amount used is 0.1.
It is 1 to 1 mmol / m ² . The amount of the coupler in the color-forming layer in which the color-forming reducing agent of the present invention is used is preferably 0.05 to 20 times, more preferably 0.1 to 10 times, particularly preferably 0.1 to 10 times the molar amount of the color-forming reducing agent. Is 0.2 to 5 times.

The light-sensitive material of the present invention is basically formed by coating a support with a photographic constituent layer comprising at least one hydrophilic colloid layer, and any one of the photographic constituent layers is provided with a photosensitive silver halide, It contains a dye-forming coupler and a color-forming reducing agent. The dye-forming coupler and the color-forming reducing agent used in the present invention are most commonly added to the same layer, but if they are in a reactive state, they can be divided and added to different layers. These components are preferably added to a silver halide emulsion layer or a layer adjacent to the silver halide emulsion layer in the light-sensitive material, and particularly preferably added to a silver halide emulsion layer.

The color-forming reducing agent and coupler of the present invention can be introduced into a light-sensitive material by various known dispersion methods, dissolved in a high boiling organic solvent (a low boiling organic solvent is optionally used in combination), and emulsified in a gelatin aqueous solution. An oil-in-water dispersion method of dispersing and adding to a silver halide emulsion is preferred. The high boiling organic solvent that can be used in the present invention has a melting point of 100 ° C. or less and a boiling point of 140 ° C.
Any compound that is immiscible with water at a temperature of not less than ° C and is a good solvent for the color-forming reducing agent and coupler can be used. The melting point of the high boiling organic solvent is preferably 80 ° C. or lower. The boiling point of the high boiling organic solvent is preferably 160 ° C. or higher, more preferably 170 ° C. or higher. Details of these high-boiling organic solvents are described in JP-A-62-215272, page 137, lower right column to page 144, upper right column. In the present invention, when using a high boiling organic solvent, the amount of the high boiling organic solvent used may be any amount,
Preferably, the ratio of the high-boiling organic solvent / color-forming reducing agent to the color-forming reducing agent is 20 or less by weight, preferably 0.02 or less.
To 5 are more preferable, and 0.2 to 4 are particularly preferable. In the present invention, a known polymer dispersion method may be used. The steps and effects of the latex dispersion method as one of the polymer dispersion methods and specific examples of the latex for impregnation are described in US Pat.
No. 9,363, West German Patent Application No. (OLS) 2,541,
No. 274, No. 2,541, 230, JP-B 53-4
No. 1091 and European Patent Publication No. 029104, and a dispersion method using an organic solvent-soluble polymer is described in PCT International Publication No. WO88 / 00723.

The average particle size of the lipophilic fine particles containing the reducing agent for color development of the present invention may be any particle size. It is preferable to set the thickness to 0.05 to 0.3 µ from the viewpoint of color development. Further, 0.05 μ to 0.2 μ is more preferable.

Generally, in order to reduce the average particle size of the lipophilic fine particles, the kind of the surfactant is selected, the amount of the surfactant used is increased, the viscosity of the hydrophilic colloid solution is increased, and the lipophilicity is increased. This can be achieved by reducing the viscosity of the organic layer by using a low-boiling point organic solvent in combination, strengthening the shearing force such as increasing the rotation of the stirring blade of the emulsifying device, or lengthening the emulsifying time. The particle size of the lipophilic fine particles can be measured, for example, by a device such as Nanosizer manufactured by Coulter Co. of England.

In the present invention, when the dye formed from the color-forming reducing agent and the dye-forming coupler is a diffusible dye, it is preferable to add a mordant to the light-sensitive material. When the present invention is applied to such a form, it is not necessary to immerse in an alkali to form a color, and therefore, the image stability after the processing is remarkably improved. The mordant of the present invention may be used in any of the layers, but when added to a layer containing the color-forming reducing agent of the present invention, the stability of the color-forming reducing agent deteriorates.
It is preferable to use it in the layer not containing the color-forming reducing agent of the present invention. Furthermore, the dye formed from the color-forming reducing agent and the coupler diffuses through the swollen gelatin film during the treatment and dyes the mordant. Therefore, it is preferable that the diffusion distance is short in order to obtain good sharpness. Therefore, the layer to which the mordant is added is preferably added to the layer adjacent to the layer containing the color-forming reducing agent. Further, since the dye formed from the color-forming reducing agent of the present invention and the coupler of the present invention is a water-soluble dye, it may flow out into the processing solution. Therefore, the layer to which the mordant is added to prevent this is preferably on the side opposite to the support with respect to the layer containing the color-forming reducing agent. However, when the barrier layer as described in JP-A-7-168335 is provided on the side opposite to the support with respect to the layer to which the mordant is added, the layer to which the mordant is added contains a color-forming reducing agent. It is also preferred that it is on the same side of the support as the layer.

The mordant of the present invention may be added to a plurality of layers. Particularly, when there are a plurality of layers containing a reducing agent for color formation, the mordant should be added to each adjacent layer. Is also preferable.

The coupler forming the diffusible dye may be any coupler as long as the diffusible dye formed by coupling with the color-forming reducing agent of the present invention reaches a mordant, but the diffusivity formed The dye preferably has at least one dissociative group having a pKa (acid dissociation constant) of 12 or less, more preferably has at least one dissociating group of pKa of 8 or less, and particularly preferably has a dissociating group of pKa of 6 or less. The molecular weight of the diffusible dye formed is 200 or more 20
00 or less is preferable. Further, (molecular weight of dye formed / number of dissociative groups having pKa12 or less) is 100 or more and 2000
The following is preferable, and 100 or more and 1000 or less is more preferable. Here, as the value of pKa, a value measured using dimethylformamide: water = 1: 1 as a solvent is used.

The coupler forming the diffusible dye is 1 × 10 ^{−6 in} an alkaline solution having a solubility of the diffusible dye formed by coupling with the color-forming reducing agent of the present invention at 25 ° C. and pH 11.
It is preferable to dissolve at least mol / l and 1 × 10 ⁻⁵
It is more preferable that the amount is 1 mol / liter or more.
It is particularly preferable to dissolve ^0-4 mol / l or more. The coupler forming the diffusible dye is dissolved at a concentration of 10 ^-4 mol / liter in an alkaline solution having a diffusion constant of 25 ° C. and pH 11 of the diffusible dye formed by coupling with the reducing agent for color formation of the present invention. 1 × is preferably ^10-2 8 m ² / s ^-1 or more, further preferably ^{1 × 10 -7 m 2 / s} -1 or more when ^{the, 1 × 10 -6 m 2 /} s - It is particularly preferably ¹ or more.

The mordant which can be used in the present invention can be arbitrarily selected from the commonly used mordants.
Among them, a polymer mordant is particularly preferable. Here, the polymer mordant is a polymer having a tertiary amino group, a polymer having a nitrogen-containing heterocyclic moiety, a polymer having a quaternary cation group thereof, or the like.

Specific examples of homopolymers and copolymers containing a vinyl monomer unit having a tertiary imidazole group include US Pat. Nos. 4,282,305 and 4,11.
No. 5,124, No. 3,148,061, JP-A-60
No. 118834, No. 60-122941, No. 62-
No. 244043, No. 62-244036 and the like.

Preferred specific examples of homopolymers and copolymers containing a vinyl monomer unit having a quaternary imidazolium salt include British Patent Nos. 2,056,101, 2,093,041, and 1,594. , 961, U.S. Pat. Nos. 4,124,386, 4,115,12.
4, No. 4,450,224, JP-A-48-283.
No. 25, etc.

Other preferable specific examples of homopolymers and copolymers having a vinyl monomer unit having a quaternary ammonium salt include US Pat. No. 3,709,690.
No. 3,898,088, No. 3,958,99
No. 5, JP-A-60-57836 and JP-A-60-60643.
No. 60-122940, No. 60-122942
And No. 60-235134.

Others, US Pat. No. 2,548,564
No. 2,484,430 and 3,148,16
No. 3,756,814 and the like, vinylpyridine polymer and vinylpyridinium cationic polymer; US Pat. No. 3,625,694
No. 3,859,096, No. 4,128,53
8, polymer mordants crosslinkable with gelatin and the like disclosed in GB 1,277,453 and the like; US Pat. Nos. 3,958,995 and 2,721,852
No. 2,798,063, JP-A-54-1152
No. 28, No. 54-145529, No. 54-26027
Aqueous sol-type mordant disclosed in US Pat. No. 3,898,088; water-insoluble mordant disclosed in US Pat. No. 3,898,088; US Pat. No. 4,168,976 (Japanese Patent Laid-Open No. 54-137333) No. 3,709,690, 3,788,855, and 3,642,482; reactive mordants capable of forming a covalent bond with the dyes disclosed in the specification. No. 3,488,706,
No. 3,557,066, No. 3,271,147
No., JP-A-50-71332 and JP-A-53-30328.
Nos. 52-155528, 53-125, 5
Examples include mordants disclosed in the specification of JP-A-3-1024. Other US Pat. No. 2,675,316
And the mordants described in JP-A-2,882,156.

The molecular weight of the polymer mordant of the present invention is 1,0.
100 to 1,000,000 is suitable, and especially 10,000
00 to 200,000 is preferred. The above-mentioned polymer mordant is usually used by being mixed with a hydrophilic colloid. As the hydrophilic colloid, a hydrophilic colloid, a highly hygroscopic polymer or both of them can be used, and gelatin is most typical. The mixing ratio between the polymer mordant and the hydrophilic colloid, and the amount of the polymer mordant applied, are easily determined by those skilled in the art according to the amount of the dye to be morded, the type and composition of the polymer mordant, and the image forming process used. But the mordant / hydrophilic colloid ratio is 20/80
~ 80/20 (weight ratio), mordant applied amount is 0.2 ~ 15
g / m ² is suitable, preferably for use in the 0.5 to 8 g / m ^2.

In the present invention, it is preferable to use an auxiliary developing agent and its precursor in the light-sensitive material, and these compounds will be described below. The auxiliary developing agent used in the present invention is a compound having an action of promoting electron transfer from a color-forming reducing agent to silver halide in the course of developing silver halide grains, and is preferably an exposed silver halide. A compound capable of developing particles and oxidizing the particles to oxidize a color-forming reducing agent (hereinafter referred to as cross-oxidation). As the auxiliary developing agent used in the present invention, pyrazolidones, dihydroxybenzenes, reductones or aminophenols are preferably used, and pyrazolidones are particularly preferably used. The diffusivity of these compounds in the hydrophilic colloid layer is preferably low. For example, the solubility in water (25 ° C.) is preferably 0.1% or less, more preferably 0.05% or less, and particularly preferably 0% or less. .01%
It is as follows. The precursor of the auxiliary developing agent used in the present invention is a compound which exists stably in the light-sensitive material but rapidly releases the auxiliary developing agent once treated with the processing solution. Also in this case, it is preferable that the diffusivity in the hydrophilic colloid layer is low. For example, the solubility in water (25 ° C.) is preferably 0.1% or less, more preferably 0.05% or less, and particularly preferably 0.01% or less. The solubility of the auxiliary developing agent released from the precursor is not particularly limited, but the auxiliary developing agent itself preferably has low solubility. The auxiliary developing agent precursor of the present invention is preferably represented by the general formula (A): general formula (A) A- (L) _n -PUG

A represents a block group in which the bond with (L) n-PUG is cleaved during development, and L is the bond between L and PUG after the bond between L and A in the general formula (A) is cleaved. Represents a linking group which is cleaved, n represents an integer of 0 to 3, and P
UG represents an antifoggant and a photographically useful group, but in the present invention, PUG represents an auxiliary developing agent. As the auxiliary developing agent, electron-emissive compounds other than p-phenylenediamine compounds according to the Kender-Rouperts law are used, and the above-mentioned pyrazolidones are preferably used. As the block group represented by A, the following publicly known ones can be applied. That is, U.S. Pat. No. 3,311,476
Block groups such as acyl groups and sulfonyl groups described in
Block groups utilizing a reverse Michael reaction described in JP-A-59-105642, block groups using a quinone methide or a compound similar to quinone methide by intramolecular electron transfer described in JP-A-2-280140, and the like. 63
-318555 (European Patent Publication No. 0295729) and other blocking groups utilizing an intramolecular nucleophilic substitution reaction, and JP-A-4-186344 and the like utilizing a nucleophilic addition reaction to a conjugated unsaturated bond. Blocking group, JP-A-62-1
No. 163051, a block group utilizing the β-elimination reaction, a block group utilizing the nucleophilic substitution reaction of diarylmethanes described in JP-A No. 61-188540, and a rosene described in JP-A No. 62-187850. Blocking group utilizing rearrangement reaction, blocking group utilizing reaction between N-acyl derivative of thiazolidine-2-thione and amine described in JP-A-62-147457, WO 93
No. / 03419, there are two electrophilic groups and a blocking group which reacts with a dinucleophile.

The group represented by L is a linking group capable of cleaving (L) _n -1-PUG after the group represented by A is removed from the group represented by A during the development processing, and any group can be used. good.

Specific examples of the auxiliary developing agent or its precursor are shown below, but the compounds used in the present invention are not limited to these specific examples.

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These compounds may be added to any of the photosensitive layer, the intermediate layer, the undercoat layer and the protective layer, but when an auxiliary developing agent is contained, they are preferably added to the non-photosensitive layer for use. As a method of incorporating these compounds into the photosensitive material, a method of dissolving in a water-miscible organic solvent such as methanol and directly adding the compound to the hydrophilic colloid layer, and coexisting with a surfactant to form an aqueous solution or a colloidal dispersion. The method of addition, after dissolving in a solvent or oil that is substantially immiscible with water,
A method of adding a substance dispersed in water or a hydrophilic colloid, a method of adding a dispersion in the form of a solid fine particle dispersion, and the like can be used, and a conventionally known method can be applied alone or in combination. The amount added to the light-sensitive material is 1 mo with respect to the color-forming reducing agent.
le% to 200mole%, preferably 5mole% to 100mole
%, More preferably 10 mole% to 50 mole%.

The coordinating metal complex or metal ion used in the present invention can be selected from elements of Groups 4 to 5, 5 and 6 in Groups 3 to 14 of the periodic table in which the group numbers are shown from left to right. These metals can also be used as metal ions by using them as metal salts such as ammonium salts, acetates, nitrates, sulfates, phosphates, and hydrates, but they can also be used as metal ions such as hexacoordinated complex salts and tetracoordinated complex salts. By using it as a mononuclear coordinated metal complex salt, a dinuclear metal complex salt, or a polynuclear metal complex salt, the performance depending on the structure of the ligand or complex salt can be brought out. As a ligand when a coordination metal complex is used, halo (X), aco (H ₂ O), azide (N
₃ ), cyano (CN), cyanate (OCN), thiocyanate (SCN), selenocyanate (SeCN),
Tellurocyanate (TeCN), Nitrosyl (NO),
Thionitrosyl (NS), oxo (O), carbonyl (CO) and the like are preferably used. Also disclosed in US Pat. No. 5,360,712,
It may include organic ligands containing one or more carbon-carbon, carbon-hydrogen, or carbon-nitrogen-hydrogen bonds such as 4,4′-bipyridine, pyrazine, thiazole and the like.

The coordinating metal complex or metal ion of the present invention is mixed with water or a suitable organic solvent miscible with water (for example, alcohols, ethers, glycols, ketones, esters, amides, etc.). It can be added after being dissolved in a mixed solvent of.

The silver halide emulsion used in the present invention is
It is preferable to allow a coordination metal complex or metal ion to be present during emulsion preparation, for example, during grain formation, desalting step, chemical sensitization, and before coating. When the grains are doped, it is preferably added during grain formation, after grain formation, or before chemical sensitization, when grain surface modification or as a chemical sensitizer is used. When doping the whole particle and only the core part of the particle,
Alternatively, a method of doping only the shell portion, only the epitaxial portion, or only the base particles can be selected.

When the silver halide grains are doped with the coordination metal complex or metal ion of the present invention, the silver halide grains are added directly to the reaction solution at the time of forming the silver halide grains, or for forming the silver halide grains. It is preferable to add it to a solution containing a halide ion or to a solution other than that, and then add it to the grain forming reaction solution. Further, various addition methods may be combined. When the silver halide grains are doped with the coordination metal complex or metal ion of the present invention,
The particles may be present uniformly inside the particles, and the method disclosed in JP-A-4-20
8936, JP-A-2-125245, JP-A3-1
As disclosed in U.S. Pat. No. 8,884,37, a higher concentration of doping may be achieved by the grain surface phase. Also, US Pat.
As disclosed in US Pat. Nos. 252,451 and 5,256,530, the grain surface phase may be modified by physical ripening with doped fine particles. In this way, a method is also preferred in which the doped fine grains are prepared, and the fine grains are added and physically ripened to dope the silver halide grains. Furthermore, you may use combining the said dope method.

The coordination metal complex or metal ion satisfying the requirements of the present invention has the same concentration per mol of silver as conventionally used in the transition metal doping.
It can be contained in silver halide grains. In this regard, an extremely wide range of densities are known, and it is disclosed in
1 per mole of silver as disclosed in 1-107129
From low concentrations of 0 ^-10 moles to US Patent 3,687,676
No. 3,690,891 in the high concentration range of ^10.sup.-3 mol per mol of silver disclosed in each of the specifications. The effective concentration depends largely on the halide content of the grains, the coordination metal complex or metal ion selected, its oxidation state, the type of ligand, if any, and the photographic effect desired.

The hydrogen ion concentration in the reaction solution when the coordination metal complex or metal ion used in the present invention is added is not particularly limited, but pH 3 or higher is preferable.

The doping amount and the doping ratio of the coordinated metal complex or metal ion in the silver halide grains in this study were determined by the atomic absorption method or ICP method (Inductively Coupled Method) for the doped coordinated metal complex or metal ion of the metal ion. Pl
asma Spectrometry; ICPMS (Inductively Coupled Plasma)
Mass spectrometry (inductively coupled plasma mass spectrometry) or the like can be used.

Specific examples of the coordinated metal complex or metal ion of the present invention include “Comprehensive Coordinati (“ Comprehensive Coordinati ”).
on Chemistry ")" (Pergamon Press (1987)).

The silver halide grains used in the present invention are silver bromide, silver chloride, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide,
It is silver chloroiodobromide. Other silver salts, such as rodin silver,
Silver sulfide, silver selenide, silver carbonate, silver phosphate, and organic acid silver may be contained as separate grains or as a part of silver halide grains. When it is desired to accelerate the development / desilvering (bleaching, fixing and bleach-fixing) steps, silver halide grains having a high silver chloride content are desirable. Further, in the case of suppressing development appropriately, it is preferable to contain silver iodide.
The preferred silver iodide content depends on the intended light-sensitive material.
For example, 0.1 to 15 mol% is preferable for X-ray sensitive material, and 0.1 to 5 mol% is preferable for graphic arts and micro sensitive material. 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, more preferably 5 to 20 mol%, and particularly preferably 8 to 15 mol%. is there. 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 structure with respect to the halogen composition in its grains. The typical one is Japanese Patent Publication No. 43-13162.
JP-A-61-215540, JP-A-60-222845, JP-A-60-1
It is a core-shell type or double structure type grain having a halogen composition in which the inside and the surface layer of the grain are different as disclosed in Japanese Patent No. 43331, JP-A-61-75337 and the like. Further, it is not a simple double structure but a triple structure as disclosed in JP-A-60-222844, or a multilayer structure of more than that, or a different composition on the surface of the core-shell double structure particles. It is possible to thinly apply a silver halide having.

In order to give a structure to the inside of the particle, not only the wrapping structure as described above but also a so-called junction structure can be prepared. Examples of these are JP-A-59-1
33540, JP-A-58-108526, European Patent 199,290A2
Japanese Patent Publication No. 58-24772 and Japanese Patent Application Laid-Open No. 59-16254. The crystal to be bonded can be formed by bonding to the edge, corner, or face 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, it is naturally possible to combine silver halides with each other, but a silver salt compound not having a rock salt structure such as silver rhodan and silver carbonate may 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 grains such as silver iodobromide having these structures, it is a preferred embodiment that the core portion has a higher silver iodide content than the shell portion. Conversely, grains having a low silver iodide content in the core and a high shell are sometimes preferred.
Similarly, grains having a junction structure may be grains having a high silver iodide content in the host crystal and relatively low silver iodide content in the junction crystal, or vice versa. Further, the boundary portions having different halogen compositions of the 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 exist as a mixed crystal or have a structure, it is important to control the halogen composition distribution between grains. A 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 where there is a correlation between grain size and halogen composition. For example, the larger the particles, the higher the iodine content,
On the other hand, there is a correlation such that the smaller the size, the lower the iodine content. 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 halogen composition near the grain surface. Increase the silver iodide content near the surface,
Alternatively, increasing the silver chloride content can be selected according to the purpose because the adsorption property 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, {100} plane and {1
This is the case where the halogen composition is changed only on one surface of the tetrahedral grain composed of 11} faces, or the halogen composition is changed on one of the main plane and the side face of the tabular grain.

The silver halide grains used in the present invention, even if they are normal crystals not containing twin planes, are as described in Japan Photographic Society, Basics of the Photographic Industry, Silver Salt Photographs (Corona Publishing Co.), P.163. For example, a single twin containing one twin plane, a parallel multiple twin containing two or more parallel twin planes, a non-parallel multiple twin containing two or more non-parallel twin planes, etc. It can be selected and used accordingly. An example of mixing particles having different shapes is disclosed in U.S. Pat.No. 4,865,964.
This method can be selected if necessary. In the case of a normal crystal, a cube having {100} faces, an octahedron having {111} faces, and a dodecahedron having {110} faces disclosed in JP-B-55-42737 and JP-A-60-222842. Particles can be used. Furthermore, Journal of Imaging Science
Volume 30 Page 247 {2 as reported in 1986
11} representative {h11} face particles, {331} representative {hh1} face grains, {210} face representative {hk0} face grains and {321} face representative {hk
Although the 1} plane grains also require some preparation method, they can be selected and used according to the purpose. A tetrahedral grain in which {100} planes and {111} planes coexist in one grain, a grain in which {100} planes and {110} planes coexist, or a grain in which {111} planes and {110} planes coexist, etc. Particles in which two surfaces or a large number of 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 the 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. Known tabular grains are a flat plate having a {111} plane as a main plane and a {100} plane as a main plane. Tabular grains whose principal planes are {111} planes are described by Cleve in "Theory and Practice of Photography" (Cleve, Photography Theory a
nd Practice (1930), p. 131; Gatov, Photography Science and Engineering (Gutof)
f, Photographic Science and Engineering), Volume 14, 2
48-257 (1970); U.S. Pat.Nos. 4,434,226, 4,4
It can be prepared by the method described in 14,310, 4,433,048, 4,439,520 and British Patent 2,112,157. The tabular grains having a {100} main plane can be prepared by the methods described in JP-A-51-88017, JP-B-64-8323 and JP-A-6-59360. The use of tabular grains has advantages such as an increase in covering power and an increase in color sensitization efficiency by a sensitizing dye, and they are described in detail in US Pat. No. 4,434,226 cited above. As an average aspect ratio of 80% or more of the total projected area of the grain,
1 or more and less than 100 is desirable. It is more preferably 2 or more and less than 20, and particularly preferably 3 or more and less than 10. As the shape of tabular grains, triangle, quadrangle, hexagon, circle, etc. can be selected. A regular hexagon with six sides of approximately equal length, as described in U.S. Pat. No. 4,797,354, is a preferred form. Also, a square having four equal sides is also a preferable form.

Although the diameter of the circle equivalent to the projected area is often used as the grain size of tabular grains, US Pat. No. 4,748,106 is used.
Particles having an average diameter of 0.6 μm or less, as described in No. 3, are preferable for improving image quality. US Patent
Emulsions with a narrow grain size distribution as described in 4,775,617 are also preferred. 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, grains described in JP-A-63-163451, in which the grain thickness and the distance between twin planes are defined, 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. It is also possible to select a dislocation or a dislocation that is introduced linearly with respect to a specific direction of the crystal orientation of the grain, or to introduce the entire grain, or to introduce only a specific portion of the grain, for example. The dislocation can be introduced only in the fringe portion of the particle. The introduction of dislocation lines is preferable not only in the case of tabular grains but also in the case of normal grains or irregular grains typified by potato grains. Also in this case, it is a preferable form 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 is a treatment for rounding grains as disclosed in European Patent Nos. 96,727B1 and 64412B1, or West German Patent No.
The surface may be modified as disclosed in JP-A-306,447C2 and JP-A-60-221320.

A structure having a flat particle surface is generally used.
It is preferable in some cases to form irregularities intentionally.
A part of the crystal described in JP-A-58-106532 and JP-A-60-221320, for example, a method of forming a hole at the apex or the center of the surface, or the ruffle particles described in U.S. Pat. This is an example.

The grain size of the emulsion used in the present invention depends on the circle-equivalent diameter of the projected area using an electron microscope, the sphere-equivalent diameter of the grain volume calculated from the projected area and the grain thickness, or the sphere-equivalent diameter of the volume determined by the Coulter counter method. Can be evaluated. Ultrafine particles having an equivalent sphere 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 so-called polydisperse emulsion having a wide grain size distribution or a monodisperse emulsion having a narrow size distribution, and can be selected and used according to the purpose. As a scale representing the size distribution, a variation coefficient of a circle equivalent diameter of a projected area of a particle or a sphere equivalent diameter of a volume may be used. When a monodispersed emulsion is used, the coefficient of variation is 25% or less,
It is more preferable to use an emulsion having a size distribution of 20% or less, more preferably 15% or less.

The monodisperse emulsion may be defined as a grain size distribution in which 80% or more of all grains fall within ± 30% of the average grain size in terms of number of grains or weight. In order to satisfy the target gradation of the light-sensitive material, the emulsion layers having substantially the same color sensitivity have different grain sizes.
One or more kinds of monodisperse silver halide emulsions can be mixed in the same layer or coated in different 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 Graphide, published by P. Montela (P.Glaf).
kides, Chemie et Phisique Photographique, Paul Mon
Tel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photographic Emulsion Ch
emistry, Focal Press, 1966), "Manufacturing and coating of photographic emulsions" by Zelikmann et al., published by Focal Press (VLZe
likman, et al. Making and Coating Photographic Emu
lsion, Focal Press, 1964) and the like. 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 one of a one-side mixing method, a simultaneous mixing method, and a combination thereof. Good. 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.

A method of adding pre-precipitated silver halide grains to a reaction vessel for emulsion preparation, US Pat.
334,012, 4,301,241, and 4,150,994 are preferable in some cases. 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 or only a part of the halogen composition of silver halide grains by the halogen conversion method is described in US Pat. Nos. 3,477,852 and 4,14.
2,900, EP 273,429, EP 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 soluble silver salt and halogen salt at a constant concentration and a constant flow rate for grain growth, British Patent No. 1,46
The particle formation method of varying the concentration or varying the flow rate as described in US Pat. No. 9,480, U.S. Pat. Nos. 3,650,757 and 4,242,445 is the preferred method. By changing the concentration or increasing the flow rate, the amount of silver halide to be supplied can be changed by a linear function, a quadratic function, or a more complicated function of the addition time. It is also preferable in some cases to reduce the amount of silver halide supplied if 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 halogen salt is described in US Pat. No. 2,996,287.
Nos. 3,342,605 and 3,415,650
No. 3,785,777, West German published patent 2,55
6,885 and 2,555,364.

A silver halide solvent is useful for the purpose of promoting ripening. For example, it is known to have an excess of halogen ions in the reactor to promote ripening. Other ripening agents can also be used. These ripening agents can be incorporated in their entirety in the dispersion medium in the reactor before adding the silver and halide salts,
A halide salt, silver salt or deflocculant can be added and introduced into the reactor. As another variant, the ripening agent can be introduced independently during the halide salt and silver salt addition steps.

Ammonia, thiocyanate (such as rhodan potassium, rhodan ammonium) and organic thioether compound (for example, US Pat. Nos. 3,574,628 and 3,021,215,
Same 3,057,724, same 3,038,805, same 4,276,374, same
4,297,439, 3,704,130, 4,782,013
And the compounds described in JP-A-57-104926. ), A thione compound (for example, JP-A-53-82408).
No. 55-77737, U.S. Pat. No. 4,221,8.
Tetrasubstituted thioureas described in JP-A-63-63, compounds described in JP-A-53-144319),
Examples thereof include a mercapto compound and an amine compound (for example, JP-A-54-100717) capable of promoting the growth of silver halide grains described in JP-A-57-202531.

Gelatin is advantageously used as a protective colloid used in the preparation of 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 hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfate, sugar derivatives such as sodium alginate and starch derivatives. A variety of synthetic hydrophilic polymers such as polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and other single or copolymers; A substance can be used.

As gelatin, in addition to lime-processed gelatin, acid-processed gelatin and Bull. Soc. Sci. Photo. Japan. No. 1
The enzyme-treated gelatin as described in 6.p30 (1966) may be used, and a hydrolyzed product or an enzymatically decomposed product of gelatin may also be used. Use of low molecular weight gelatin described in JP-A-1-158426 is preferred for preparing tabular grains.

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 it is preferably selected in the range of 5 ° to 20 ° C. The pH at the time of washing with water can also be selected according to the purpose, but it is preferably selected between 2 and 10. More preferably, it is in the range of 3 to 8. The pAg at the time of washing with water can also be selected according to the purpose, but it is preferably selected between 5 and 10. Noodle washing method, dialysis method using semi-permeable membrane,
It can be selected from centrifugation, coagulation sedimentation, and ion exchange. In the case of the coagulation sedimentation method, a method using a sulfate, a method using an organic solvent, a method using a water-soluble polymer, a method using a gelatin derivative, and the like can be selected.

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

The silver halide grain of the present invention has at least one of sulfur sensitization, selenium sensitization, tellurium sensitization (these three types are collectively called chalcogen sensitization), noble metal sensitization, or reduction sensitization. It can be applied at any step of the process for producing a silver halide emulsion. It is preferable to combine two or more sensitization methods. Various types of emulsions can be prepared depending on the step of chemical sensitization. There are a type of embedding a chemically sensitized nucleus inside the grain, a type of embedding at a shallow position from the grain surface, and a type of forming a chemically sensitized nucleus on the surface. In the emulsion of the present invention, the location of the chemically sensitized nucleus can be selected according to the purpose, but it is generally preferable that at least one type of chemically sensitized nucleus is formed near the surface.

The chemical sensitization which can be preferably carried out in the present invention is a chalcogen sensitization and a noble metal sensitization alone or in combination thereof, and is written by TH James in The Photographic Process, 4th edition, published by Macmillan. , 1977 (TH James, The Theor of the Photographic Process,
4th ed. Macmillan, 1977) pp. 67-76, using active gelatin, or Research Disclosure Item 12008 (1).
April 974); Item 13452 (June 1975)
), Item 307105 (November 1989), US Pat. Nos. 2,642,361 and 3,297,446.
No. 3,772,031, No. 3,857,711
No. 3,901,714, 4,266,018
And pAg 5-1 as described in US Pat. No. 3,904,415 and British Patent No. 1,315,755.
0, sulfur at pH 5-8 and temperature 30-80 ° C,
It can be carried out using selenium, tellurium, gold, platinum, palladium, iridium or a combination of a plurality of these sensitizers.

In the sulfur sensitization, an unstable sulfur compound is used, specifically, thiosulfate (eg, hypo),
Thioureas (eg, diphenylthiourea, triethylthiourea, allylthiourea, etc.), rhodanins, mercaptos, thioamides, thiohydantoins, 4-oxo-oxazolidine-2-thiones, di- or polysulfides, polythionic acid Salt and elemental sulfur, and U.S. Pat. Nos. 3,857,711, 4,266.
Known sulfur-containing compounds described in No. 018 and No. 4,054,457 can be used. Sulfur sensitization is often used in combination with noble metal sensitization.

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

In the selenium sensitization, known unstable selenium compounds are used, for example, US Pat. No. 3,297,44.
No. 6,297,447 and the like, and specific examples thereof include colloidal metal selenium and selenoureas (eg, N, N-dimethylselenourea, tetramethylselenourea). Etc.), seleno ketones (eg, selenoacetone), selenoamides (eg, selenoacetamide), selenocarboxylic acids and esters, isoselenocyanates, selenides (eg, diethyl selenide, triphenylphosphine selenide), Selenium compounds such as selenophosphates (for example, tri-p-tolyl selenophosphate) can be used. Selenium sensitization may be preferably used in combination with sulfur sensitization, precious metal sensitization, or both.

[0168] The amount of the selenium sensitizer, the selenium compound used, the silver halide grains will vary by the chemical ripening condition and the like, generally per mol of silver halide 10 ^-8 to 10 ^-4 mol, preferably 10 ^{- About 7} to 10 ^-5 mol is used.

The tellurium sensitizers used in the present invention include Canadian Patent 800,958 and British Patents 1,2.
Nos. 95,462 and 1,396,696, Japanese Patent Application No. 2-
The compounds described in No. 333819, No. 3-131598 and the like can be used, and specific tellurium sensitizers include colloidal tellurium and telluroureas (eg, tetramethyl tellurourea, N-carboxyethyl-N). ', N'
-Dimethyl tellurourea, N, N'-dimethylethylene tellurourea), isotellocyanates, telluroketones, telluroamides, tellurohydrazides, telluroesters, phosphine tellurides (for example, tributylphosphine telluride, butyl-diisopropyl) Phosphine telluride), other tellurium compounds (eg, potassium telluride, potassium tellurocyanate, telluropentathionate sodium salt) and the like.

The amount of the tellurium sensitizer used is 1 g of silver halide.
It is 10 ^{−7 to} 5 × 10 ⁻³ mol per mol, and more preferably 5 × 10 ⁻⁷ to 1 × 10 ⁻³ mol.

Noble metal salts such as platinum, gold, palladium and iridium can be used in the noble metal sensitization, and gold sensitization, palladium sensitization and a combination of both are particularly 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. A preferred palladium compound is R ₂ PdX ₆
Alternatively, it is represented by R ₂ PdX ₄ . Here, R represents a hydrogen atom, an alkali metal atom or an ammonium group.
X represents a halogen atom, and represents a chlorine, bromine or iodine atom.

Specifically, K ₂ PdCl ₄ , (NH ₄ )
₂ PdCl ₆ , Na ₂ PdCl 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 combined with gold sensitization. The preferred amount of the gold sensitizer is 1 × 10 ^-7 to 1 × 10 ^-3 mol, and 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 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, the reduction sensitization is a method of adding a reduction sensitizer to a silver halide emulsion, pAg1 called silver ripening.
No. 7, a method of growing or aging in a low pAg atmosphere, and a method of growing or aging in a high pH atmosphere of pH 8 to 11 called high pH aging can be selected. Also, two or more methods can be used in combination.

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

As the reduction sensitizer, known reduction sensitizers such as stannous salt, ascorbic acid and its derivatives, amines and polyamines, hydrazine and its derivatives, formamidinesulfinic 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 the range of 10 ^-7 to 10 ^-3 mol is suitable per mol of silver halide.

The chemical sensitization can also be carried out in the presence of a so-called chemical sensitization aid. Useful chemical sensitization aids include compounds known to suppress fog and increase sensitivity during chemical sensitization, such as azaindene, azapyridazine and azapyrimidine. Examples of chemical sensitization aid modifiers are described in US Pat. Nos. 2,131,038 and 3,4.
11,914, 3,554,757, JP-A-58.
No. 126526 and the above-mentioned "Photographic Emulsion Chemistry" by Duffin, pp. 138-143.

It is preferable to use an oxidizing agent for silver during the process of producing the emulsion of the present invention. The oxidizing agent for silver is
It refers to a compound that acts on metallic silver to convert it into silver ions. In particular, a compound that converts extremely fine silver grains by-produced during the formation process of silver halide grains and the chemical sensitization process into silver ions is effective. The silver ions formed here may form a poorly water-soluble silver salt such as silver halide, silver sulfide, or silver selenide, or may form a readily soluble silver salt such as silver nitrate. Is also good. The oxidizing agent for silver may be an inorganic substance or an organic substance. Examples of the inorganic oxidant include ozone, hydrogen peroxide and its adducts (for example, NaBO ₂ · H ₂ O ₂ , 3H ₂ O, 2Na).
_{CO 3 · 3H 2 O 2,} Na 4 P 2 O 7 · 2H 2 O 2, 2
Na ₂ SO ₄ .H ₂ O ₂ .2H ₂ O), peroxy acid salts (eg, K ₂ S ₂ O ₈ , K ₂ C ₂ O ₆ , K ₂ P
₂ O ₈ ), a peroxy complex compound (for example, K ₂ [Ti
(O ₂ ) C ₂ O ₄ ] ・ 3H ₂ O, 4K ₂ SO ₄・ Ti
(O ₂ ) OH ・ SO ₄・ 2H ₂ O, Na ₃ [VO
_{(O 2) (C 2 O} 4) 2 · 6H 2 O ], permanganate (e.g., KMnO _4), chromates (e.g., K ₂ Cr ₂ O
₇ ) Oxygenates, halogen elements such as iodine and bromine, perhalogenates (eg potassium periodate), high valent metal salts (eg potassium hexacyanoferrate) and thiosulfonates. and so on.

As the organic oxidant, quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, compounds that release active halogen (for example, N-bromosuccinimide, chloramine T). , Chloramine B).

The preferred oxidizing agents of the present invention are ozone, hydrogen peroxide and its adducts, halogen elements, thiosulfonate inorganic oxidizing agents and quinones of organic oxidizing agents. It is a preferable embodiment to use the reduction sensitization and the oxidizing agent for silver in combination. The method can be selected from a method of performing reduction sensitization after using an oxidizing agent, a method reverse thereto, or a method of coexisting the two simultaneously. 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 of the light-sensitive material, during storage or during photographic processing, or stabilizing photographic performance. . That is, thiazoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially 1-phenyl-5-mercaptotetrazole)
Mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy-6-methyl (1,3,3a, 7 ) Tetraazaindene), many compounds known as antifoggants or stabilizers such as pentaazaindenes and the like can be added.
For example, US Pat. Nos. 3,954,474 and 3,98
Nos. 2,947 and 52-28660 can be used. One of the preferred compounds is the compound described in Japanese Patent Application No. 62-47225. Antifoggants and stabilizers are used at various times before, during and after particle formation, during the 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. In addition to adding the original antifoggant and stabilizing effects during emulsion preparation,
It can be used for various purposes such as controlling the crystal wall of grains, reducing the grain size, reducing the solubility of grains, controlling chemical sensitization, controlling the arrangement of dyes.

The photographic emulsion used in the present invention is preferably spectrally sensitized with a methine dye or the like in order to exert the effects of the present invention. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei usually used for cyanine dyes as basic 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; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these Nucleus of fused aromatic hydrocarbon ring, namely, indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus A nucleus, a quinoline nucleus, etc. can be applied. These nuclei may be substituted on carbon atoms.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidine-2,4-dione nucleus, a thiazolidine-2,4-
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 the combination of sensitizing dyes is often used especially for the purpose of supersensitization. Typical examples thereof are US Pat. Nos. 2,688,545 and 2,977,
No. 229, No. 3,397,060, No. 3,522,0
No. 52, No. 3,527, 641, No. 3, 617, 29
No. 3, No. 3,628,964, No. 3,666,480
Issue 3, Issue 3,672,898, Issue 3,679,428
No. 3,703,377, No. 3,769,301
Nos. 3,814,609 and 3,837,862
No. 4,026,707, British Patent No. 1,344.
No. 281, No. 1,507,803, Japanese Patent Publication No. 43-49
No. 36, No. 53-12, 375, JP-A-52-11
0,618 and 52-109,925.

Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a substance which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion.

The timing of adding the sensitizing dye to the emulsion may be at any stage in the emulsion preparation which has heretofore been known to be useful. Most commonly, it is carried out after the completion of chemical sensitization and before coating, but it is described in US Pat. No. 3,62.
As described in JP-A Nos. 8,969 and 4,225,666, spectral sensitization can be carried out simultaneously with chemical sensitization by simultaneous addition with a chemical sensitizer.
It can also be carried out prior to chemical sensitization as described in 3,928, or it can be added before the completion of silver halide grain precipitation to initiate spectral sensitization.
Still further, the separate addition of these compounds as taught in US Pat. No. 4,225,666, i.e., some of these compounds are added prior to chemical sensitization and the balance is chemically sensitized. It can be added after the sensation, and can be added at any time during the formation of silver halide grains, including the method disclosed in US Pat. No. 4,183,756.

The addition amount is 4 × per mol of silver halide.
It can be used in an amount of 10 ⁻⁶ to 8 × 10 ⁻³ mol, but in the case of a more preferable silver halide grain size of 0.2 to 1.2 μm, a drug of 5 × 10 ⁻⁵ to 2 × 10 ⁻³ mol is more effective. Is.

The above-mentioned various additives are used in the light-sensitive material of the present technology, but various additives other than the above can be used depending on the purpose.

These additives are described in more detail in Research Disclosure Item 17643 (January 1, 1978).
(February), Item 18716 (November 1979) and Item 307105 (November 1989), and the relevant parts are summarized in the table below.

[0191]

[Table 1]

The present invention is more effective below in tabular emulsions containing a large amount of silver chloride. In a silver halide emulsion containing at least a dispersion medium and silver halide grains, 50% or more, preferably 60% to 100%, and more preferably 70 to 100% of the total projected area of the silver halide grains has a main plane ( It is a tabular grain having an aspect ratio of 2 or more, which is a 100) or (111) plane. Here, the tabular grains are grains having an aspect ratio (diameter / thickness) larger than 1.
The major plane refers to the largest outer surface of the tabular grains. The thickness of the tabular grains is 0.35 μm or less and is 0.05 to 0.3 μm.
Is more preferable, and 0.05 to 0.25 μm is further preferable. A preferable aspect ratio is 2 or more, preferably 3 to 3
It is 0, more preferably 5 to 20. Here, the diameter is
The diameter of a circle having an area equal to the projected area of the tabular grains is inserted, and the thickness refers to the distance between two principal planes. Cl ^- content is 20 mol% or more, preferably 30 mol% to 100%,
More preferably 40 to 100 mol%, even more preferably 5
0-100 mol% is preferred.

The nucleation of the emulsion having the (111) plane as the principal plane among the emulsions of the present invention is described in JP-B-64-8326.
Nos. 64-8325, 64-8324, JP-A-1-250943, JP-B-3-14328, JP-B-4-81782, JP-B-5-40298, and 5-3
No. 9459, No. 5-12696 and JP-A-63-213.
No. 836, No. 63-218938, No. 63-2811
49, JP-A-62-218959 and the like, and regarding tabular grains having a (100) plane as a main plane, JP-A-5-204073 and 51
-88017, JP-A-63-24238, Japanese Patent Application No. 5
-264059 and the like.

In the present invention, any of the nucleation methods described in these prior arts can be used.
The method of crystal growth of the present invention by physical ripening in the presence of fine silver halide grains (fine grains are dissolved and substrate grains grow) is described below. In the fine grain emulsion addition method, it is 0.
An AgX fine grain emulsion having a diameter of 15 μm or less, preferably 0.1 μm or less, more preferably 0.06 to 0.006 μm is added, and the tabular grains are grown by Ostwald ripening. The fine grain emulsion can be added either continuously or continuously. Fine grain emulsion is AgNO in mixer provided in the vicinity of the reaction vessel ₃ solution and X ^-
The salt solution may be supplied and continuously prepared, and then immediately added continuously to the reaction vessel, or may be previously prepared in a batch manner in another vessel and then continuously or continuously added. The fine grain emulsion can be added in a liquid form or as a dry powder. The dry powder may be mixed with water immediately before addition, liquefied and added. The added fine particles are preferably added in such a manner that they disappear within 20 minutes, more preferably 10 seconds to 10 minutes. If the disappearance time becomes long, ripening occurs between the fine particles and the particle size becomes large, which is not preferable. Therefore, it is preferable not to add the entire amount at once. The fine particles preferably do not substantially contain multiple twin particles. Here, the multiple twin particles refer to particles having two or more twin planes per particle. "Substantially not contained" means that the ratio of the number of multiple twin grains is 5% or less, preferably 1% or less, more preferably 0.1% or less. Further, it is preferable that substantially no single twin particles are contained. Furthermore, it is preferable that the fine particles are substantially free of screw dislocation. Here, "substantially not included" complies with the above-mentioned rules.

The halogen composition of the fine particles is AgCl, AgB.
r, AgBrl (I ⁻ content is preferably 10 mol% or less, more preferably 5 mol% or less) and a mixed crystal of two or more thereof. For other details, refer to Japanese Patent Application No. 4-2141.
09 can be referred to. The total amount of fine grains added must be at least 20% of the total silver halide content.
It is preferably at least 40%, more preferably at least 50% and at most 98%. The Cl content of the fine particles is preferably 10% or more, more preferably 50% or more and 100% or less.

As the dispersion medium for nucleation, ripening and growth, a conventionally known dispersion medium for AgX emulsion can be used, but the methionine content is preferably 0 to 50 μmol / g, more preferably 0. -30 μmol / g gelatin can be preferably used. When the gelatin is used during ripening and growth, thinner tabular grains having a uniform diameter size distribution are preferably formed. In addition, Tokiko Sho 52
-16365, The Photographic Society of Japan, 29 (1), 1
7, 22 (1966), same 30 volumes (1), 10, 19
(1967), Volume 30 (2), 17 (1967)
), 33 (3), 24 (1967) can be preferably used as a dispersion medium. The pH at the time of growth by adding fine particles needs to be 2.0 or more, but is preferably 3 or more and 10 or less. More preferably, p
It is H4 or more and 9 or less. Also, pCl needs to be 1.0 or more, but is preferably 1.6 or more. More preferably, it is 2.0 or more and 3.0 or less. These growth conditions are particularly preferable for tabular grains having a (100) plane as a main plane. Here, pCl is defined as pCl = −log [Cl ⁻ ] with respect to the activity [Cl ⁻ ] of Cl ions in the solution. Written by THJames THE THEORY OF THE RHOTO
It is described in detail in Chapter 1 of the GRAPHIC PROCESS, 4th Edition.

When the pH is 2.0 or less, for example, in the case of tabular grains having the (100) plane as the main plane, lateral growth is suppressed and the aspect ratio is lowered, so that the emulsion covering power is reduced. Tends to be low, and the sensitivity becomes low. When the pH is 2.0 or higher, an emulsion having a high lateral growth rate and a high aspect ratio and a high covering power can be obtained, but the fog is high and the sensitivity is easily lowered. p
When Cl is 1.0 or less, the growth in the vertical direction is promoted, the aspect ratio is reduced, the covering power of the emulsion is low, and the sensitivity is lowered. When the pCl is 1.6 or more, the aspect ratio is increased to increase the covering power, but the fog is high and the sensitivity is easily reduced. At this time, when the substrate grains are grown with silver halide fine grains, the fog is low even at a pH of 6 or more and / or a pCl of 1.6 or more, resulting in a high sensitivity, a high aspect ratio, and a high covering power.

The monodispersity of the emulsion of the present invention is preferably 30% or less, and preferably 5% or more 25 % Or less is preferable. Particularly when used for a sensitive material having a high contrast, it is preferably 5% or more and 15% or less.

The support used in the present invention includes glass,
Any support such as paper and plastic film which can be coated with a photographic emulsion layer can be used as long as it is a transmission or reflection support. As the plastic film used in the present invention, a polyester film such as polyethylene terephthalate, polyethylene naphthalate, cellulose triacetate or cellulose nitrate, a polyamide film, a polycarbonate film, a polystyrene film and the like can be used. The "reflective support" that can be used in the present invention refers to a support that enhances reflectivity to sharpen a dye image formed in a silver halide emulsion layer. A substrate coated with a hydrophobic resin containing a light-reflective substance such as titanium oxide, zinc oxide, calcium oxide, or calcium sulfate, or a hydrophobic resin itself containing a light-reflective substance dispersed therein was used as a support. Things included. For example, polyethylene-coated paper, polyester-coated paper, polypropylene-based synthetic paper, supports provided with a reflective layer or combined with a reflective substance, for example, glass plates, polyester films such as polyethylene terephthalate, cellulose triacetate or cellulose nitrate, polyamide films , Polycarbonate film, polystyrene film, and vinyl chloride resin. As the polyethylene-coated paper, polyester-coated paper containing polyethylene terephthalate as a main component described in European Patent EP 0,507,489 is preferably used.

The reflective support used in the present invention is preferably a paper support whose both surfaces are coated with a water resistant resin layer and at least one of the water resistant resins contains fine white pigment particles. The white pigment particles are preferably contained at a density of 12% by weight or more, more preferably 14% by weight or more. As the light-reflective white pigment, it is preferable to sufficiently knead the white pigment in the presence of a surfactant, and it is preferable that the surface of the pigment particles is treated with a divalent to tetravalent alcohol. In the present invention, a support having a surface of diffuse reflection of the second kind can be preferably used. What is the second type diffuse reflectance?
Diffusive reflectivity obtained by imparting irregularities to a surface having a mirror surface and dividing the surface into minute mirror surfaces facing different directions to disperse the divided minute surface (mirror surface) directions. The unevenness of the surface of the second kind diffuse reflection has a three-dimensional average roughness of 0.1 to 2 μm, preferably 0.1
Is about 1.2 μm. Details of such a support are described in JP-A-2-239244.

In order to obtain a wide range of colors on the chromaticity diagram by using the three primary colors of yellow, magenta and cyan, a combination of at least three silver halide emulsion layers having photosensitivity in different spectral regions is used. To be For example, three layers of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer, and three layers of a green-sensitive layer, a red-sensitive layer, and an infrared-sensitive layer are coated on the support in combination. Each of the light-sensitive layers can take various arrangements and arrangements that are known in ordinary color light-sensitive materials. Each of these photosensitive layers may be divided into two or more layers as necessary.
The photographic material may be provided with a photographic constituent layer comprising the above-mentioned photosensitive layer and various protective layers such as a protective layer, an undercoat layer, an intermediate layer, an antihalation layer and a back layer. Further, various filter dyes may be added to the photographic constituent layers to improve the color separation property.

As the binder or protective colloid that can be used in the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can be used alone or together with gelatin. The calcium content of gelatin is preferably 800 ppm or less, more preferably 200 ppm or less, and the iron content of gelatin is preferably 5 ppm or less, more preferably 3 ppm or less. Further, in order to prevent various molds and bacteria that propagate in the hydrophilic colloid layer and deteriorate the image, Japanese Patent Application Laid-Open No.
It is preferable to add an antifungal agent as described in Japanese Patent No. 1247.

When the light-sensitive material of the present invention is exposed to a printer, it is preferable to use the band stop filter described in US Pat. No. 4,880,726. As a result, light color mixing is removed, and color reproducibility is significantly improved.

The light-sensitive material of the present invention is used not only in a printing system using a general negative printer but also in a solid state laser using a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser or a semiconductor laser as an excitation light source, and a nonlinear laser. It is preferably used for digital scanning exposure using monochromatic high-density light such as a second harmonic generation light source (SHG) combined with an optical crystal. Compact system,
In order to make it inexpensive, it is preferable to use a semiconductor laser, or a second harmonic generation light source (SHG) that is a combination of a semiconductor laser or a solid-state laser and a nonlinear optical crystal. Particularly, in order to design a device which is compact, inexpensive, and has a long life and high stability, it is preferable to use a semiconductor laser, and it is preferable to use a semiconductor laser as at least one of the exposure light sources.

When using such a scanning exposure light source,
The spectral sensitivity maximum of the light-sensitive material of the present invention can be arbitrarily set according to the wavelength of the scanning exposure light source used. Solid-state laser using a semiconductor laser as an excitation light source or SHG obtained by combining a semiconductor laser with a nonlinear optical crystal
In the light source, the oscillation wavelength of the laser can be halved, so that blue light and green light can be obtained. Therefore, the spectral sensitivity maximum of the photosensitive material can be provided in the usual three regions of blue, green and red. In order to use a semiconductor laser as a light source in order to make the device inexpensive, highly stable, and compact, it is preferable that at least two layers have a spectral sensitivity maximum at 670 nm or more. This is because currently available inexpensive and stable III-V semiconductor lasers have emission wavelengths only in the red to infrared regions. However, at the laboratory level, the oscillation of II-VI group semiconductor lasers in the green and blue regions has been confirmed, and these semiconductor lasers can be used inexpensively and stably if the manufacturing technology of semiconductor lasers is started. It is fully expected. In such a case, the necessity for at least two layers to have a spectral sensitivity maximum at 670 nm or more is reduced.

In such scanning exposure, the time for which the silver halide in the light-sensitive material is exposed is the time required for exposing a certain minute area. As the minute area, a minimum unit for controlling the amount of light from each digital data is generally used and is called a pixel. Therefore, the exposure time per pixel changes depending on the size of the pixel. The size of this pixel depends on the pixel density, and a practical range is 50 to 2000 dpi. The exposure time is preferably defined as ^10-4 seconds or less, and more preferably ^10-6 seconds or less, when the pixel density is defined as 400 dpi and the pixel size is defined as the exposure time.

The total coated silver particles in the light-sensitive material of the present invention are 0.003 to 1 g per 1 m ^{2 in} terms of silver, but the desilvering step can be omitted for faster processing, and the waste liquid load can be further reduced. Is preferred. The coated silver amount of each layer is preferably 0.001 to 0.4 g per photosensitive layer. Particularly when the light-sensitive material of the present invention is subjected to intensification processing, 0.003 to
0.3 g is preferable, and more preferably 0.01 to 0.1.
g, particularly preferably 0.015 to 0.05 g. In this case, it is preferably 0.001 to 0.1 g, and more preferably 0.003 to 0.03 g per photosensitive layer.
In the present invention, if the coating amount of silver in each light-sensitive material layer is less than 0.001 g per 1 m ² , the dissolution of the silver salt will proceed and a sufficient color development density will not be obtained. If it exceeds, Dmin increases and bubbles are generated, which makes it difficult to endure viewing.

In the photographic light-sensitive material of the present invention, for example, the following phosphors can be used as a fluorescent intensifying screen to preferably perform X-ray photography. Blue emitting phosphor Y ₂ O ₂ S: Tb, LaOBr: Tb, BaFCl: E
u Green light emitting phosphor Gd ₂ O ₂ S: Tb: LaO ₂ S: Tb, UV light emitting phosphor Titanium-free hafnium zirconium germanate phosphor described in JP-A-6-11804, YTaO ₄ , YT
aO ₄ : Nb, YTaO ₄ : Gd

The emission wavelength of the phosphor preferable in the present invention is 40
It is 0 nm or less, more preferably 370 nm or less.

A typical phosphor is M'phase YTaO.
₄ alone or Gd, Bi, Pb, Ce, Sr, Al,
Compounds containing Rb, Ca, Cr, Cd, Nb, etc.,
A compound obtained by adding Gd, Tm, Gd and Tm, Gd and Ce, Tb to LaOBr, a compound obtained by adding an oxide of HfZr alone or Ge, Ti alkali metal, etc.,
Y ₂ O ₃ alone or a compound to which Gd or Eu is added, Y
_There are compounds in which Gd is added to ₂ O ₂ S, compounds in which Gd, Tl, and Ce are used as activators in the matrix of various phosphors. Particularly preferred compounds include M ′ phase YTaO ₄ alone or a compound containing Gd and Sr added, and LaOBr containing G
Compound added with d, Tm, Gd and Tm, HfZr
Oxide or a compound to which Ge, Ti alkali metal or the like is added.

The particle size of the phosphor is preferably 1 μm or more and 20 μm or less, but can be changed depending on the required sensitivity and manufacturing problems. The coating amount is preferably 400 g / mm ² or more and 2000 g / mm ² or less, but it cannot be unequivocally determined depending on the required sensitivity and image quality. A single intensifying screen may be used to provide a particle size distribution from the vicinity of the support to the surface. In this case, it is generally known that particles on the surface are enlarged. The space filling rate of the phosphor is 40% or more, preferably 6
0% or more.

When the phosphor layers are provided on both sides of the light-sensitive material for photographing, the phosphor coating amount on the X-ray incident side and the opposite side can be changed. In general, it is known to reduce the coating amount of the intensifying screen on the X-ray incident side, especially when a high-sensitivity system is required for shielding by the intensifying screen on the X-ray incident side.

The support used in the screen used in the present invention may be paper, a metal plate, a polymer sheet or the like, but a flexible sheet such as polyethylene terephthalate is generally used. The support may be added with a reflecting agent or a light absorbing agent, if necessary, or may be provided as a separate layer on the surface.

If necessary, the surface of the support may be slightly uneven, or an adhesive layer for increasing the adhesion to the phosphor layer or a conductive layer may be provided as an undercoat. Examples of the reflecting agent include zinc oxide, titanium oxide, barium sulfate, etc., but titanium oxide and barium sulfate are preferable because the phosphor has a short emission wavelength. The reflecting agent may be present not only in the support or between the support and the phosphor layer, but also in the phosphor layer. When it is present in the phosphor layer, it is preferred that it is localized near the support.

Examples of the binder used in the screen of the present invention include proteins such as gelatin, polysaccharides such as dextran and corn starch, and natural polymer substances such as gum arabic; polyvinyl butyral, polyvinyl acetate, polyurethane, polyalkyl acrylate, and chloride. Examples thereof include synthetic polymer substances such as vinylidene, nitrocellulose, fluorine-containing polymers and polyesters, and mixtures and copolymers thereof. Preferred binders include:
The basic performance is high transmittance for light emitted from the phosphor. In this regard, gelatin,
Examples thereof include corn starch, acrylic polymers, fluorine-containing olefin polymers, polymers containing fluorine-containing olefins as copolymer components, and styrene / acrylonitrile copolymers. These binders may have functional groups that are crosslinked by the crosslinking agent. Further, depending on the desired image quality performance, an absorber for the light emitted from the phosphor may be added to the binder, or a binder having a low transmittance may be used. Examples of the absorbent include a pigment, a dye, and an ultraviolet absorbing compound. The ratio of the phosphor to the binder is generally 1: 5 to 5 in volume ratio.
It is 0: 1, preferably 1: 1 to 1: 5: 1. The ratio between the phosphor and the binder may be uniform or non-uniform in the thickness direction.

The phosphor layer is usually formed by a coating method using a coating liquid in which the phosphor is dispersed in a binder solution.
Examples of the solvent for the coating liquid include water or alcohols, chlorine-containing hydrocarbons, organic solvents such as ketones, esters and ether aromatic compounds, and mixtures thereof.
Phosphoric acid, stearic acid,
A dispersion stabilizer such as caproic acid and a surfactant, and a plasticizer such as a phosphate, a phthalate, a glycolate, a polyester, and a polyethylene glycol may be added.

In the screen used in the present invention, a protective layer can be provided on the phosphor layer. As the protective layer, a method of coating on the phosphor layer or a method of separately forming a protective layer film and laminating is used. In the coating method, the coating may be performed simultaneously with the phosphor layer, or may be performed after the phosphor layer is coated and dried. The protective layer may be the same substance as the binder of the phosphor layer or a different substance. Examples of the substance used for the protective layer include the substances listed as the binder for the phosphor layer, as well as cellulose derivatives, polyvinyl chloride, melamine, phenol resins, epoxy resins and the like.
Preferred materials include gelatin, corn starch, acrylic polymers, fluorine-containing olefin polymers, polymers containing fluorine-containing olefins as copolymer components, and styrene / acrylonitrile copolymers. The thickness of the protective layer is generally 1 μm or more 2
0 μm or less, preferably 2 μm or more and 10 μm or less, 2
More preferably, it is not less than μm and not more than 6 μm. It is preferable to emboss the surface of the protective layer of the present invention. Further, a matting agent may be present in the protective layer, or a substance having a light-scattering property for light emission depending on the image to be obtained, such as titanium oxide may be present.

[0218] The protective layer of the screen used in the present invention may have surface slipperiness. Examples of preferable slip agents include polysiloxane skeleton-containing oligomers and perfluoroalkyl group-containing oligomers. You may give electroconductivity to the protective layer of this invention. Examples of the conductivity imparting agent include white and transparent inorganic conductive substances and organic antistatic agents. As a preferable inorganic conductive substance, Z
Examples thereof include nO powder, whiskers, SnO ₂ and ITO.

The light-sensitive material of the present invention is particularly effective when it has at least one silver halide emulsion layer on each side of the support. When the present invention is applied to a light-sensitive material having an emulsion on both sides of such a support, in addition to the effects described above, there is a feature that an image with high image quality and high sharpness can be obtained. It also has the unexpected effect of not polluting the tank or rollers.

The silver amount of the light-sensitive material of the present invention is preferably 0.5 g / m ^{2 to} 5 g / m ² (on one side), more preferably 0.7 g / m ^{2 to} 3.4 g / m ² (on one side). ). It is preferable that the rapid processing suitability does not exceed 5 g / m ² .

As various additives and the like used in the photographic light-sensitive material of the present invention, for example, those described in the following relevant parts can be used. Item This section 1) Silver halide emulsion and JP-A-2-68539, page 8, right lower column, bottom 6 from its production line to page 10, upper right column, line 12 2) Chemical sensitization method Kaihei 2-68539, page 10, upper right column, line 13 to same, lower left column, line 16 3) Antifoggant, stability JP-A-2-68539, page 10, lower left column, line 17 Agent to same, page 11 upper left Column line 7 and page 3, lower left column, line 2 to page 4, lower left column. 4) Color tone improving agent JP-A-62-276539, page 2, lower left column, line 7 to page 10, left lower column, line 20; JP-A-3-94249, page 6, lower left column, line 15 to Page 11, right upper column, line 19 5) Spectral sensitizing dye From JP-A-2-68539, page 4, lower right column, line 4 to page 8, lower right column. 6) Surfactant, antistatic JP-A-2-68539, page 11, upper left column, line 14 Stopping agent to page 12, upper left column, line 9 7) Matting agent, slip agent, JP-A-2-68539, page 12, upper left column, line 10 Plasticizer to the same upper right column, line 10; page 14, lower left column, line 10 to right lower column, line 1 8) Hydrophilic colloid JP-A-2-68539, page 12, upper right column, line 11 to lower left column, line 16 9) Hardener JP-A-2-68539, page 12, lower left column, line 17 to page 13, upper right column, line 6 10) Support, JP-A-2-68539, page 13, upper right column, lines 7 to 20. 11) Crossover JP-A-2-264944, page 4, upper right column, line 20: From the cutting method, page 14, upper right column

The photographic light-sensitive material of the present invention can be image-formed by using a silver image and a dye image together. This ratio of concentration interests can be changed in any way. However, in the X-ray image forming system, the density ownership ratio of the silver image and the dye image is preferably 1:10 to 10: 1, and particularly 3: 3.
7 to 7: 3 is preferably used. The total processing time of the photographic light-sensitive material of the present invention in an automatic processor is preferably 90 seconds or less, more preferably 60 seconds or less. In a medical X-ray image forming system using a combination of a phosphor screen and a photographic light-sensitive material, the sharpness of the image is an important factor in improving the diagnostic ability. On the other hand, since the present invention uses a silver image and a dye image together, the sharpness of the image is likely to be lowered depending on the spread of the dye cloud. Therefore, in order to improve this problem, the sharpness of the image is improved by another method. It is important to raise. As a result of intensive studies, the present inventors have found that the sensitivity reduction is smaller when the crossover light is 20% or less than when a development inhibitor releasing coupler or the like generally used in color light-sensitive materials is used. It has been found that an image having excellent sharpness can be provided. The crossover light is more preferably 15% or less, further preferably 10% or less. As a method for reducing the crossover light, a method using a solid disperse dye or a method disclosed in JP-A No. 1-1228, as described in JP-A No. 1-172828.
No. 6645, a technique of mordanting a crossover light absorbing dye in a film undercoat layer, and a method of increasing the crossover light absorptivity of a silver halide emulsion by using a spectral sensitizing dye, and further, substantially improving the photosensitivity. A method may be used in which the dye is adsorbed on a fine grain emulsion or a fine grain tabular emulsion which does not have the dye and the dye is applied to the lower layer of the emulsion layer.

The processing material and processing method used in the present invention will be described in detail. In the present invention, the photosensitive material is subjected to development (silver development / cross-oxidation of a built-in reducing agent), desilvering, and washing or stabilization. After the washing or stabilizing treatment, a treatment for enhancing color development such as alkali addition may be performed.

In the development processing of the light-sensitive material of the present invention, the developer functions as a developing agent for silver halide, and /
Alternatively, a compound having a function of cross-oxidizing a color-forming reducing agent contained in a light-sensitive material by an oxidized product of a developing agent generated in silver development is used. Preferred are pyrazolidones, dihydroxybenzenes, reductones and aminophenols, and particularly preferred are pyrazolidones.

As the pyrazolidones, 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 and the like.

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

As the reductone, ascorbic acid or a derivative thereof is preferable, and the compounds described on pages 3 to 10 of JP-A-6-148822 can be used. Particularly, sodium L-ascorbate and sodium erythorbate are preferred.

As p-aminophenols, N-methyl-p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, N- (4-hydroxyphenyl) glycine, 2-methyl-p- Aminophenol, etc.

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

Examples of preservatives used in the developer of the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, sodium formaldehyde bisulfite and hydroxyamine / sulfate. The amount used is 0.1 mol / liter or less, preferably 0.001 to
It may be used in the range of 0.02 mol / liter. When a high silver chloride emulsion is used in the light-sensitive material, the above compound may be contained in an amount of 0.001 mol / liter or less, and preferably not contained at all. In the present invention, it is preferable to contain diethylhydroxylamine, sialylhydroxylamines described in JP-A-4-97355, and an organic preservative in place of the hydroxyamine and sulfite ion.

In the present invention, the developer contains halogen ions such as chlorine ions, bromine ions and iodine ions. Here, the halide may be directly added to the developing solution, or may be eluted from the light-sensitive material to the developing solution during the development processing.

The developing solution used in the present invention preferably has a pH of 8 to 13, and more preferably 9 to 12. The above p
In order to retain H, it is preferable to use various buffers. Preference is given to using carbonates, phosphates, tetraborates and hydroxybenzoates.

The amount of the buffer added to the developing solution is 0.05.
Mol / liter or more, preferably 0.1 mol / liter or more.
It is particularly preferred that the molar ratio is from mol to 0.4 mol / liter.

In addition, various chelating agents can be used as a precipitation inhibitor of calcium or magnesium in the developing solution or for improving the stability of the developing solution. The amount of these chelating agents added may be an amount sufficient to mask the metal ions in the developing solution, and is, for example, about 0.1 g to 10 g per liter.

In the present invention, any antifoggant can be added if necessary. As the antifoggant, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide and nitrogen-containing heterocyclic compounds are used. The addition amount of the nitrogen-containing heterocyclic compound is 1 × 10 ⁻⁵
~ 1 x 10 ^-2 mol / l, preferably 2.5 x 1
It is 0 ⁻⁵ to 1 × 10 ⁻³ mol / liter.

Any development accelerator can be added to the developing solution, if necessary.

The developer preferably contains a fluorescent whitening agent. In particular, it is preferable to use a 4,4'-diamino-2,2'-disulfostilbene compound.

The processing temperature of the developing solution applied to the present invention is 2
The temperature is 0 to 50 ° C, preferably 30 to 45 ° C. The processing time is 5 seconds to 2 minutes, preferably 10 seconds to 1 minute. It is preferable that the replenishing amount is small, but 15 to ⁶ per 1 m ^{2 of} light-sensitive material
00 ml, preferably 25 to 200 ml, more preferably 3
5 to 100 ml.

After the development, desilvering processing is performed. The desilvering process includes a fixing process and a bleaching and fixing process. When the bleaching and fixing treatments are carried out, the bleaching treatment and the fixing treatment may be carried out individually or simultaneously (bleach-fixing treatment). Further, processing in two continuous bleach-fixing baths, fixing before bleach-fixing, or bleaching after bleach-fixing can be arbitrarily performed according to the purpose. Also, without desilvering after development,
It is also preferable in some cases to perform the stabilizing treatment to stabilize the silver salt or the color image.

Further, after development, West German Patent (OLS) 1,
813,920, 2,044,993, 2,7
35,262, JP-A-48-9728, and 49-8
No. 4240, No. 49-102314, No. 51-538
No. 26, No. 52-13336, No. 52-73731, etc. can be subjected to an image reinforcing treatment (intensification) using a peroxide, a halogenous acid, an iodoso compound and a cobalt (III) complex compound. . In order to further enhance the image reinforcement, an oxidizing agent for reinforcing the image may be added to the developer, and the development and the image intensification may be simultaneously performed in one bath.
In particular, hydrogen peroxide is preferable because of its high amplification factor. These image intensification methods can significantly reduce the amount of silver in the photosensitive material, so that bleaching is not required and it is not necessary to discharge silver (or silver salt) for stabilization, etc. This is a preferable treatment method.

Examples of the bleaching agent used in the bleaching solution and the bleach-fixing solution include iron (III), cobalt (III) and chromium (I
V), compounds of polyvalent metals such as copper (II), peracids, quinones and nitro compounds. Among these, ethylenediaminetetraacetic acid iron (III) complex salts and 1,3-diaminopropanetetraacetic acid iron (III) complex salts of aminopolycarboxylic acid iron (II
I), hydrogen peroxide, persulfate and the like are preferable from the viewpoint of rapid treatment and prevention of environmental pollution. PH of bleaching solution or bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts
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.

For the bleaching solution, the bleach-fixing solution and the fixing solution, conventionally known additives such as a rehalogenating agent, a pH buffering agent and a metal corrosion inhibitor can be used. Especially, in order to prevent bleach stain, the acid dissociation constant (pka) is 2 to 7
It is preferable that the organic acid is contained.

Examples of the fixing agent used in the fixing solution or the bleach-fixing solution include thiosulfate, thiocyanate, thioureas, a large amount of iodide and JP-A-4-365037, pages 11 to 2.
Examples thereof include a nitrogen-containing heterocyclic compound having a sulfide group, a mesoionic compound, and a thioether compound described on page 1 and 5-66540, pages 1088 to 1092. 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.

The fixing solution and the bleach-fixing solution may further contain various fluorescent whitening agents, defoaming agents, surfactants, polyvinylpyrrolidone, methanol and the like.

The processing temperature of the desilvering step is 20 to 50 ° C, preferably 30 to 45 ° C. The processing time is 5 seconds to 2 minutes, preferably 10 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. 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 step and a stabilizing step in which a stabilizing bath containing a dye stabilizing agent and a surfactant represented by processing of a color light-sensitive material for photographing is used as a final bath may be performed. Sulfite salts; hard water softeners such as inorganic phosphoric acid, polyaminocarboxylic acid, organic aminophosphonic acid; metal salts such as Mg salt, Al salt, Bi salt; surfactants; hardeners A film agent; a pH buffering agent; an optical brightening agent; a silver salt forming agent such as a nitrogen-containing heterocyclic compound can be used. 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 4-9, preferably 5-8. The treatment temperature is 15 to 45 ° C, preferably 25 ° C to 40 ° C. The processing time is 5 seconds to 2 minutes, preferably 10 seconds 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 the stabilizing solution can be set within 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 25 to 120 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 the method in a multistage countercurrent system.

In the present invention, water obtained by treating the overflow liquid or the liquid in the tank with a reverse osmosis membrane can be used for saving water. For example, the treatment by reverse osmosis is preferably performed on the water in the second tank and subsequent tanks for multistage countercurrent washing and / or stabilization.

In the present invention, it is preferable that the stirring is strengthened as much as possible. Specific methods of strengthening the stirring are described in JP-A-62-183460 and JP-A-62-1834.
No. 61, a method of impinging a jet jet of a processing liquid on an emulsion surface of a light-sensitive material, a method of increasing a stirring effect by using a rotating means of 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 stirring improving means include a developing solution, a bleaching solution, a fixing solution, a bleach-fixing solution, a stabilizing solution,
It is useful in any washing. 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.

In the present invention, the liquid opening ratio [air contact area (cm ² ) / liquid volume (cm ³ )] of any bath shows excellent performance, but from the viewpoint of stability of liquid components. The liquid opening ratio is preferably ⁰ to 0.1 cm ^-1 . In continuous treatment, the range of 0.001 cm ^{-1 to} 0.05 cm ^-1 is preferable in practical use, and more preferably 0.002 to 0.03 cm.
It is ^-1 .

The automatic developing machine used for the light-sensitive material of the present invention is disclosed in JP-A-60-191257 and 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, and is highly effective in preventing the performance of the processing solution from deteriorating. Such an effect is particularly effective for shortening the processing time of each step and reducing the replenishing amount of the processing solution. In order to shorten the processing time, it is preferable to shorten the crossover time (air time).
For example, Japanese Patent Application Laid-Open No. 4-86659, FIG.
Also, a method in which each process described in FIG. 4 or FIG. 5 of JP-A-5-66540 is conveyed via a blade having a shielding effect is preferred. In the case where each processing solution is concentrated by evaporation in the continuous processing, it is preferable to add water to correct the concentration.

The processing time of the step in the present invention means the time required from the start of the processing of the photosensitive material in one step to the start of the 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, the speed is preferably 500 to 2500 mm / min. The total processing step, that is, the processing time 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 the immersion of the photosensitive material in the developing solution to the exit from the drying section of the processor.

Various additives are used in the treatment agent of the present technology, and more specifically, Research Disclosure
It is described in Item 36544 (September 1994), and the relevant parts are summarized below.

Processing Agent Type Page Developer 536 Preservative for developer 537 Left column Antifoggant 537 Chelating agent 537 Right column Buffer 537 Right column Surfactant 538 Left column and 539 Left column Bleach 538 Bleach accelerator 538 right column to 539 left column bleaching chelating agent 539 left column rehalogenating agent 539 left column fixing agent 539 right column fixing agent preservative 539 right column fixing chelating agent 540 left column stabilizing surfactant 540 Left side Stabilization scum agent 540 Right side Stabilizing chelating agent 540 Right side Antibacterial and antifungal agent 540 Right side Color image stabilizer 540 Right side

For details of the water saving technology of this technology, see Research Disclosure Item 36544 (199).
(September 4, 2004) 540, right column to 541, left column.

[0258]

The present invention will be further described with reference to the following examples. Example 1 Preparation of {100} AgCl tabular emulsion A-1 1582 ml of an aqueous gelatin solution (gelatin-1) was placed in a reaction vessel.
(Deionized alkali-treated bone gelatin with a methionine content of about 40 μmol / g) 19.5 g, HNO ₃ 1N solution 7.8 ml, pH 4.3, NaCl-1 solution (10)
13 ml of 10 g of NaCl was added to 0 ml, and while maintaining the temperature at 40 ° C, Ag-1 solution (AgN in 100 ml was added).
O ₃ (including 20 g) and solution X-1 (NaC in 100 ml)
17.0 ml at 62.4 ml / min.
Were added simultaneously. After stirring for 3 minutes, 80.6 ml of Ag-2 solution (100 g contains AgNO ₃ 2 g) and X-2 solution (100 ml contains KBr 1.4 g).
Simultaneously mixed 28.2 ml / min. After stirring for 3 minutes, the Ag-1 solution and the X-1 solution were added at 62.4 ml / min at 46.8.
ml was added simultaneously. After stirring for 2 minutes, 203 ml of gelatin aqueous solution (oxidized gelatin 11.3 g, Na
Cl 1.3 g, NaO to adjust pH to 5.5
(Including H1N solution) was added to adjust the pCl to 1.8, the temperature was raised to 75 ° C., the pCl was adjusted to 1.8, and the mixture was aged for 10 minutes. Then, the disulfide compound A was added in an amount of 1 × 10 ⁻⁴ mol per mol of silver halide, and AgCl was added.
2.68 × 1 fine particle emulsion (average particle diameter 0.1 μm)
It was added for 20 minutes at an addition rate of AgCl of 0 ^-2 mol / min.
After aging for 10 minutes after addition, a precipitating agent was added and the temperature was adjusted to 35
It was lowered to ℃ and washed with sedimented water. Add gelatin aqueous solution, 60
The pH was adjusted to 6.0 at ° C.

[0259]

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A transmission electron microscope photographic image (hereinafter referred to as TEM) of the replica of the particles was observed. The emulsion obtained is
High silver chloride {100} tabular grains containing 0.44 mol% of AgBr based on silver. The shape characteristic values of the particles were as follows. (Total projected area of tabular grains having an aspect ratio larger than 2 / sum of projected areas of all AgX grains) × 100 = a ₁ = 90% (average aspect ratio (average diameter / average thickness) of tabular grains) = a ₂ = 9.3 (average diameter of the tabular grains) = a ₃ = 1.67 .mu.m (average thickness) = a ₄ = 0.18 .mu.m

Preparation of (111) AgCl Tabular Emulsion A-2 Silver chloride tabular grains were prepared as follows.

[0262]

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[0263]

Solution (2) and solution (3) were simultaneously added to solution (1) kept at 35 ° C. with stirring at a constant addition rate over 1 minute, and the temperature of the solution was raised to 70 ° C. over 15 minutes. Let At this point, grains corresponding to about 5.7% of the total silver were formed. Next, the solution (4) and the solution (5) were
The solution (6) and the solution (7) were simultaneously added over 40 minutes at a constant addition rate, and pCl = 1.0 over 40 minutes.
A silver chloride tabular emulsion was obtained by making the addition rate of the silver nitrate solution constant and growing by the control double jet method. After the emulsion was washed with water and desalted by a precipitation method, 30 g of gelatin and H ₂ O were added, 2.0 g of phenoxyethanol and 0.8 g of sodium polystyrene sulfonate as a thickener were added, and the pH was adjusted to 6 with caustic soda.
Redispersion was performed so as to be 0. The emulsion thus obtained is
a ₁ = 90%, a ₃ = 1.55 μm, a ₄ = 0.18 μm
m, a ₂ = 8.6, coefficient of variation of projected area diameter equivalent to circle 19%
Is a tabular silver chloride emulsion having the (111) plane as the main plane.

Preparation of {111} AgBr Tabular Grain A-3 6.0 g of potassium bromide and average molecular weight of 1 in 1 liter of water.
An aqueous solution containing 37 cc of an aqueous silver nitrate solution (4.00 g of silver nitrate) and 5.9 g of potassium bromide was added to a container kept at 55 ° C. while adding 7.0 g of low-molecular-weight gelatin of 15,000 and stirring.
8 cc was added in 37 seconds by the double jet method. Next, after adding 18.6 g of gelatin, the temperature was raised to 70 ° C., and 89 cc of an aqueous silver nitrate solution (9.80 g of silver nitrate) was added over 22 minutes. Here, 7 cc of 25% aqueous ammonia solution was added and physically aged at the same temperature for 10 minutes, then 10
6.5 cc of 0% acetic acid solution was added. Followed by silver nitrate 1
An aqueous solution of 53 g and an aqueous solution of potassium bromide were added to pAg 8.5.
While maintaining the above value, it was added by the control double jet method over 35 minutes. Next, 2N potassium thiocyanate solution 1
5 cc was added. After physical ripening at the same temperature for 5 minutes, the temperature was lowered to 35 ° C. a ₁ = 95%, average projected area diameter a ₃ = 1.50 μm, thickness a ₄ = 0.185 μm
m, average aspect ratio a ₂ = 8.1, diameter variation coefficient 1
8.5% monodispersed pure silver bromide tabular grains were obtained. After this,
Soluble salts were removed by sedimentation. The temperature was raised again to 40 ° C., and 30 g of gelatin and 2.35 g of phenoxyethanol were obtained.
Then, 0.8 g of sodium polystyrene sulfonate was added as a thickener, and the solution was adjusted to pH 5.0 with a solution of sodium hydroxide and silver nitrate.
90, pAg 8.00.

Preparation of {100} AgBrCl Tabular Emulsion A-4 1582 ml of gelatin aqueous solution (gelatin-1) was placed in a reaction vessel.
(Deionized alkali-treated bone gelatin with a methionine content of about 40 μmol / g) 19.5 g, HNO ₃ 1N solution 7.8 ml, pH 4.3, NaCl-1 solution (10)
13 ml of 10 g of NaCl was added to 0 ml, and while maintaining the temperature at 40 ° C, Ag-1 solution (AgN in 100 ml was added).
O ₃ (including 20 g) and solution X-1 (NaC in 100 ml)
17.0 ml at 62.4 ml / min.
Were added simultaneously. After stirring for 3 minutes, Ag-2 solution (AgNO ₃ including 2g in 100ml) and X-2 solution (containing KBr 1.4 g in 100ml) 80.6Ml
Simultaneously mixed 28.2 ml / min. After stirring for 3 minutes, the Ag-1 solution and the X-1 solution were added at 62.4 ml / min at 46.8.
ml was added simultaneously. After stirring for 2 minutes, 203 ml of an aqueous gelatin solution (13 g of gelatin-1, NaCl
1.3g, NaOH 1N to adjust PH to 5.5
Solution, and pCl was adjusted to 1.8.
The temperature was raised to 5 ° C., the pCl was adjusted to 1.8, and the mixture was aged for 10 minutes. After this, Ag-3 solution (100% Ag in 100 ml)
NO ₃ (including 50 ml), X-3 solution (N in 100 ml)
aCl 23.5 g and KBr 71.4 g) are prepared, the addition rate of silver nitrate is set to 2.68 × 10 ⁻² mol / min, and pCl is controlled by the control double jet method.
= 1.8, it was made to grow for 20 minutes. After aging for 10 minutes after the addition, a precipitant was added, the temperature was lowered to 35 ° C., and the precipitate was washed by settling. An aqueous gelatin solution was added, and the pH was adjusted to 6.0 at 60 ° C. A transmission electron micrograph image (hereinafter referred to as TEM) of a replica of the particles was observed. The obtained emulsion had a high silver chloride content of about 53 mol% AgBr based on silver {1.
00} tabular grains. The shape characteristic values of the particles were as follows. (Total projected area of tabular grains having an aspect ratio larger than 1 / sum of projected areas of all AgX grains) × 100 = a ₁ = 90% (average aspect ratio (average diameter / average thickness) of tabular grains) = a ₂ = 9.3 (average diameter of the tabular grains) = a ₃ = 1.67 .mu.m (average thickness) = a ₄ = 0.18 .mu.m

Preparation of {111} AgBrCl Tabular Emulsion A-5 Silver chloride tabular grains were prepared as follows.

[0268]

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[0269]

Solution (2) and solution (3) were simultaneously added to solution (1) kept at 35 ° C. with stirring at a constant addition rate over 1 minute, and the temperature of the solution was raised to 70 ° C. over 15 minutes. Let At this point, grains corresponding to about 5.7% of the total silver were formed. Here, 1 × 10 ⁻⁴ mol of the disulfide compound-B was added to 1 mol of silver halide, and then the solution (4) and the solution (5) were simultaneously added at a constant addition rate over 24 minutes. The solution 6) and the solution (7) were grown for 40 minutes by the control double jet method while the addition rate of the silver nitrate solution was kept constant so that pCl was 1.8, and a silver chloride tabular emulsion was obtained. The emulsion was washed with water and desalted by a precipitation method, 30 g of gelatin and H ₂ O were added, 2.0 g of phenoxyethanol and 0.8 g of sodium polystyrene sulfonate as a thickener were added, and the pH was adjusted to 6.0 with caustic soda. Redistributed.
The emulsion thus obtained contains about 50% Br and a ₁ =
90%, a ₃ = 1.55 μm, a ₄ = 0.18 μm, a
₂ = 8.6, the variation coefficient of the projected area diameter equivalent to a circle is 19% ((1
11) A silver chloride tabular emulsion having the plane as the main plane.

[0271]

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Preparation of Monodisperse Cubic Silver Halide Emulsion A-6 32 g of gelatin was dissolved in 1 liter of water, and 0.3 g of potassium bromide and 5 g of sodium chloride were placed in a container heated at 53 ° C.
g and compound [I]

[0273]

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After the addition of 46 mg, 444 ml of an aqueous solution containing 80 g of silver nitrate and 452 ml of an aqueous solution containing 45 g of potassium bromide and 5.5 g of sodium chloride were added over about 20 minutes by the double jet method, and then 80 g of silver nitrate was added. 415 ml of an aqueous solution containing 400 ml of an aqueous solution, 46.4 g of potassium bromide, 5.7 g of sodium chloride and potassium hexachloroiridium (III) (10 ^-7 mol / mol silver)
Is added by a double jet method over about 25 minutes to obtain a cubic monodispersed silver chlorobromide particle having an average grain size (projected area diameter) of 0.34 μm (coefficient of variation of projected area diameter of 10).
%). After desalting this emulsion by a coagulation method,
62 g of gelatin and 1.75 g of phenoxyethanol were added to adjust to pH 6.5 and pAg 8.5.

Preparation of emulsions doped with metal compounds

Preparation of {100} AgCl Tabular Emulsion B-1 When preparing an AgCl fine grain emulsion to be added during tabular grain growth, K ₄ [Fe (CN) ₆ ] was dissolved in an aqueous halogen solution to prepare [Fe ( CN) ₆ ] ^4- doped AgCl fine particles were prepared. At this time, K ₄ [Fe (C
The amount of N) ₆ ] was such that the local concentration in the {100} AgCl tabular grains was 5 × 10 ⁻⁵ mol / mol silver.
By replacing the AgCl fine particles doped with [Fe (CN) ₆ ] ^4- with the undoped AgCl fine particles on the way, the outside of the {100} AgCl tabular grains can be adjusted to a silver amount of 3
The shell portion corresponding to 0% was doped with [Fe (CN) ₆ ] ^4- . Otherwise, {100} AgCl tabular emulsion A-1
Was prepared in exactly the same way.

Preparation of {111} AgCl Tabular Emulsion B-2 Solution (8) in {111} AgCl Tabular Emulsion A-2.
As an example, an aqueous solution of K ₄ [Ru (CN) ₆ ] was prepared and added as a third jet while the solution (6) and the solution (7) were being added. [Ru (CN) ₆ ] ⁴⁻ has a local concentration of 5 × on the outside of the grain and in the shell portion corresponding to 30% of the silver amount.
The concentration of the aqueous solution and the addition rate were adjusted so as to be 10 ⁻⁵ mol / mol silver. Other than that, {111} AgCl tabular emulsion A
-2 was prepared in exactly the same manner.

Preparation of {111} AgBr Tabular Emulsion B-3 In the preparation of {111} AgBr tabular grains A-3, [I] was added to the outside of the grains and to the shell portion corresponding to 30% of the silver amount.
As a third jet, K ₃ [Ir (CN) ₃ ] was used so that the local concentration of r (CN) ₆ ] ³⁻ was 5 × 10 ⁻⁵ mol / mol silver.
₆ ] An aqueous solution was added. Other than that, {111} AgBr
A tabular emulsion A-3 was prepared in exactly the same manner.

Preparation of {100} AgBrCl Tabular Emulsion B-4 In {100} AgBrCl tabular emulsion A-4, [Fe was added to the outside of the grains and in the shell portion corresponding to 30% in silver amount.
As the third jet, K ₃ [Fe (CN) ₆ ] is added so that the local concentration of (CN) ₆ ] ³⁻ becomes 5 × 10 ⁻⁵ mol / mol silver.
An aqueous solution was added. Other than that, {100} AgBrCl
A tabular emulsion A-4 was prepared in exactly the same manner.

Preparation of {111} AgBrCl Tabular Emulsion B-5 In {111} AgBrCl tabular emulsion A-5, [Re was added to the outside of the grains and at the shell portion corresponding to a silver amount of 30%.
(CN) ₆ ] ⁴⁻ has a local concentration of 5 × 10 ⁻⁵ mol / mol silver, and K ₄ [Re (CN) ₆ ] is used as the third jet.
An aqueous solution was added. Other than that, {111} AgBrCl
A tabular emulsion A-5 was prepared in exactly the same manner.

Preparation of Monodisperse Cubic Emulsion B-6 In Monodisperse Cubic Emulsion A-6, [Co (CN) ₆ ] ^3-at the outside of the grains and in the shell portion corresponding to 30% of the silver amount.
So that the local concentration is 5 × 10 ^-5 mol / mol silver.
An aqueous solution of K ₃ [Co (CN) ₆ ] was added as a jet. Otherwise, it was prepared in exactly the same manner as the monodisperse cubic emulsion A-6.

Chemical Sensitization The particles prepared as described above were subjected to chemical sensitization while being kept at 60 ° C. with stirring. First, 10 ^-4 mol of thiosulfonic acid compound-I was added per 1 mol of silver halide, and then AgBr fine particles having a diameter of 0.10 μm was added in an amount of 1.0 mol% with respect to the total amount of silver. After 5 minutes, 1% was added. KI solution of 10 ^-3 mol per mol of silver halide was added, and after 3 minutes, 1 × 10 ^-6 mol / mol Ag of thiourea dioxide was added.
The mixture was kept as it was for 1 minute to perform reduction sensitization. Next, 3 × 10 ⁻⁴ mol / mol Ag of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene was added to sensitizing dye-1,
2 were each added. Further calcium chloride was added. Further, 1 × 10 ⁻⁵ mol / mol Ag of chloroauric acid and 3.0 × 10 ⁻³ mol / mol Ag of potassium thiocyanate were added, and then sodium thiosulfate (6 × 10 ⁻⁶ mol / mol Ag) was added.
Mol Ag) and selenium compound-I (4 × 10 ⁻⁶ mol / mol Ag). After another 3 minutes, the nucleic acid (0.5 g /
Mol Ag) was added. After 40 minutes, water-soluble mercapto compound-1 was added and cooled to 35 ° C. Thus, preparation of the emulsion (chemical ripening) was completed.

[0283]

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Example 2 (Preparation of Auxiliary Developing Agent Coating Layer) Auxiliary developing agent ETA-1 (methanol solution) Auxiliary developing agent ETA-2 (solid fine particle dispersion) was added at 1 × 10 1 per mol of silver halide. ^{It was} applied as if it were applied at ^-2 mol. In this way, the gelatin coating amount was set to 0.5 g / m ² .

[0285]

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(Preparation of emulsion coating layer) The chemicals listed below and Table 2 per mol of silver halide were used for the chemically sensitized emulsion.
The emulsion was added to prepare an emulsion coating solution. -Gelatin (including gelatin in emulsion) 111 g-Dextran (average molecular weight 39,000) 21.5 g-Sodium polyacrylate (average molecular weight 400,000) 5.1 g-Sodium polystyrene sulfonate (average molecular weight 600,000) 1.2 g Hardener 1,2-bis (vinylsulfonylacetamido) ethane Addition amount is adjusted so that the swelling ratio becomes 230%. Compound-I 42.1 mg Compound-II 10.3 g Compound-III 0.11 g Compound-IV 8.5 mg Compound-V 0.43 g Compound-VI 0.004 g Compound-VII 0.1 g Compound-VIII 0.1 g Adjusted to pH 6.1 with NaOH

[0287]

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[0288]

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[0289]

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For the above coating solution, ultraviolet absorbing dye-I to
A sample was prepared in which the dye emulsion S was added to the emulsion subbing layer so that III was 5 mg / m ^{2 on} each side.

[0291]

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(Preparation of Dye Emulsion S) Dyes I to II
20 g each, and 62.degree.
8 g, 62.8 g of high boiling organic solvent-II and 333 g of ethyl acetate were dissolved at 60 ° C. Next, 65 cc of a 5% aqueous solution of sodium dodecyl sulfonate, 94 g of gelatin and 581 cc of water were added, and the mixture was emulsified and dispersed at 60 ° C. for 30 minutes with a dissolver. Next, 2 g of the following compound-IX and water 6
One liter was added and the temperature was lowered to 40 ° C. Next, using Asahi Kasei's ultrafiltration laboratory module ACP1050, the total amount was concentrated to 2 kg, and 1 g of the compound-IX was added to obtain a dye emulsion S.

[0293]

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The color-forming coupler and the color-forming reducing agent were dissolved in 73 cc of ethyl acetate and 52 g of solvent Solv-1 as shown in Table 2, and this solution was dissolved in 12% gelatin aqueous solution containing 10% sodium dodecylbenzenesulfonate and citric acid.
An emulsion as shown in Table 2 was prepared by emulsifying and dispersing to 0 cc.

[0295]

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[0296]

[Table 2]

(Preparation of Coating Solution for Surface Protective Layer) A coating solution for surface protective layer was prepared so that each component had the following coating amount.・ Gelatin 0.780 g / m ²・ Sodium polyacrylate (average molecular weight 400,000) 0.035 g / m ²・ Sodium polystyrene sulfonate (average molecular weight 600,000) 0.0012 g / m ²・ Polymethyl methacrylate (average particle size 3.7 μm) ) 0.072 g / m ²・ Coating aid-I 0.020 g / m ²・ Coating aid-II 0.037 g / m ²・ Coating aid-III 0.0080 g / m ²・ Coating aid-IV 0.0032 g / m ²・ Coating aid-V 0.0025 g / m ²・ Compound-VII 0.0022 g / m ²・ Proxel 0.0010 g / m ² (pH adjusted to 6.8 with NaOH)

[0298]

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(Preparation of Support) (1) Preparation of Dye Dispersion B for Undercoat Layer The following Dye-II was ball-milled by the method described in JP-A-63-197943.

[0300]

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434 cc of water and Triton X200® surfactant (6.7% of TX-200®)
791 cc of the aqueous solution was placed in a 2 liter ball mill. 20 g of the dye were added to this solution. Zirconium oxide (Zr
400 ml of O ₂ ) beads (2 mm diameter) were added and the contents were milled for 4 days. After this, 12.5% gelatin 160g
Was added. After defoaming, the ZrO ₂ beads were removed by filtration. Observation of the obtained dye dispersion showed that the pulverized dye had a wide range of particle diameters from 0.05 to 1.15 .mu.m, and the average particle diameter was 0.37 .mu.m. Furthermore, dye particles having a size of 0.9 μm or more were removed by centrifugation. Thus Dye Dispersion B
I got

(2) Preparation of support Corona discharge was performed on a biaxially stretched polyethylene terephthalate film having a thickness of 175 μm, and the coating amount of the first undercoating liquid having the following composition was 4.9 cc / m ^2. Thus, it was applied by a wire converter and dried at 185 ° C. for 1 minute. Next, a first undercoat layer was similarly provided on the opposite surface. The polyethylene terephthalate used is a dye-
The one containing 0.06 wt% of IV and 0.06 wt% of Dye-V was used.

[0303]

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* Butadiene-styrene copolymer latex solution (solid content 40% butadiene / styrene weight ratio = 31/69) 158 cc * 2,4-dichloro-6-hydroxy-s-triazine sodium salt 4% solution 41 cc・ Distilled water 801 cc * The latex solution contains 0.4 wt% of the following compounds as an emulsifying dispersant based on the latex solids.

[0305]

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(3) Coating of undercoat layer A second undercoat layer having the following composition is coated on the above-mentioned first undercoat layers on both sides, one side at a time so that the coating amount is as described below. To the wire bar coder method,
It was dried at 155 ° C.・ Gelatin 80 mg / m ²・ Dye Dispersion B (as dye solid content) 8 mg / m ²・ Coating aid-VI 1.8 mg / m ²・ Compound-X 0.27 mg / m ²・ Mat agent Average particle size 2 0.5 μm polymethylmethacrylate 2.5 mg / m ²

[0307]

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(Preparation of Photographic Material) On the support prepared as described above, the auxiliary developing agent layer, the emulsion layer and the surface protective layer were combined and coated on both sides by the simultaneous extrusion method. The coated silver amount per one side was 0.80 g / m ² . In this way, the samples shown in Table 3 were prepared.

[0309]

[Table 3]

(Evaluation of Photographic Performance) Fuji Photo Film Co., Ltd.'s HR-4 screen, HGM screen, and DuPont's UV rapid screen were used to make close contact with each other for 0.05 seconds. Exposure was performed and X-ray sensitometry was performed. The adjustment of the exposure amount was performed by changing the distance between the X-ray tube and the cassette. After the exposure, the film was subjected to automatic developing machine processing using the following developing solution and fixing solution.

(Processing) Automatic processor: CEPROS manufactured by FUJIFILM Corporation
-30 was modified to form a rinse layer between the fixing layer and the washing layer.

Developer-1 Tank Solution Replenisher Water 800 ml 800 ml Tripotassium phosphate 30 g 39 g 5-Nitrobenzotriazole 0.1 g 0.25 g Disodium-N, N-bis (sulfonate ethyl) hydroxylamine 3.3 g 6 0.6 g Potassium chloride 10 g-Hydroxyethylidene-1,1-diphosphonic acid (30% solution) 4 ml 4 ml 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 1.5 g 1.5 g Water was added to 1 liter pH 12.0 pH 12.0

Developer-2 (Alkali Activation Solution) A solution obtained by removing the auxiliary developing agent (1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone) from the above developer was used.

<Fixer> (Same as tank solution and replenisher) Ammonium thiosulfate (70 wt / vol%) 3000 ml Ethylenediaminetetraacetic acid / disodium dihydrate 0.45 g Sodium sulfite 225 g Boric acid 60 g 1- (N , N-diethylamine) -ethyl-5-mercaptotetrazole 15 g Tartaric acid 48 g Glacial acetic acid 675 g Sodium hydroxide 225 g Sulfuric acid (36N) 58.5 g Aluminum sulfate 150 g Water 6000 ml pH 4.68

(Rinse Solution) K ₃ CO ₃ 30 g Tetrabutylammonium bromide 8 g Acetic acid 6.8 g Water was added to 1 liter pH 10.00 The washing tank was filled with tap water.

As a water stain inhibitor, 0.4 g of actinomycetes supported on perlite having an average particle size of 100 μm and an average pore size of 3 μm was covered with a polyethylene bottle (the bottle opening was covered with a 300-mesh nylon cloth. Prepare three pieces filled with water and fungi from the cloth), two of them at the bottom of the washing tank, and one at the bottom of the stock tank for washing water (liquid volume 0.2 liters). I sunk each. As shown in Table 4, in the evaluation of sensitometry, the light-sensitive material of the present invention showed good results when Developer-2 was used. In Developer-1 as well, the light-sensitive material of the present invention showed good photographic properties.

[0317]

[Table 4]

Example 3 An emulsion was prepared in the same manner as in Example 2, except that Solv-2 was used in place of the solvent Solv-1 when the color-forming coupler and the color-forming reducing agent were dissolved. A coated sample was prepared in the same manner. When this was evaluated and processed for photographic performance in exactly the same manner as in Example except for the rinse step, the sample of the present invention showed good photographic performance.

[0319]

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The light-sensitive materials of the present invention produced in Examples 2 and 3 were kept in an environment of 50 ° C. and 70% for 5 days. This condition is a compulsory condition corresponding to about 2 years of normal temperature and normal humidity conditions of 25 ° C. and 60%. When the same sensitometry was evaluated after the passage of time, the photosensitive material of the present invention showed good performance which was the same as before the passage of time.

Example 4 A surface of a paper support laminated on both sides with polyethylene was subjected to a corona discharge treatment and then provided with a gelatin subbing layer containing sodium dodecylbenzenesulfonate, and two types of photographic constituent layers were further coated thereon. A photographic printing paper (100) having a two-layer structure shown in 1 was prepared. The coating solution was prepared as follows. First layer coating liquid Coupler (ExY) 17 g, color-forming reducing agent (I-61)
20 g and a solvent (Solv-1) 80 g were dissolved in ethyl acetate, and this solution was added to a 16% gelatin solution 400% containing 10% sodium dodecylbenzenesulfonate and citric acid.
Then, emulsified dispersion A was prepared by emulsifying and dispersing the mixture in an amount of 1 g. On the other hand, silver chlorobromide emulsion A (cubic, 3: 7 mixture of large size emulsion A having an average grain size of 0.88 μm and small size emulsion A having a grain size of 0.70 μm (silver molar ratio). Coefficient of variation of grain size distribution. Of 0.08 and 0.10, respectively, and 0.3 mol% of silver bromide in each size emulsion was locally contained in a part of the surface of the grain based on silver chloride). At this time, in each size emulsion, K is formed on a part of the grain surface where silver bromide is extremely present.
₂ IrCl ₆ was added to dope so that the Ir content would be 5 × 10 ⁻⁷ mol per mol of silver in the entire grain. Also,
In each size emulsion, K ₄ [Fe (CN) ₆ ] was doped to the outside of the grain and to the shell portion where the amount of silver was 20% so as to be 2 × 10 ⁻⁵ mol per mol of silver of the whole grain. In this emulsion, blue-sensitive sensitizing dyes A, B and C shown below were added to the large-sized emulsion A per mol of silver in an amount of 1.4 × 1 each.
0 ^-4 mol, and to the small size emulsion A, 1.7 x 10 ^-4 mol each was added. The chemical ripening of this emulsion was carried out by adding a sulfur sensitizer and a gold sensitizer. The emulsified dispersion A and the silver chlorobromide emulsion A were mixed and dissolved to prepare a first layer coating solution having the following composition. The emulsion coating amount is the silver equivalent coating amount.

[0322]

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The coating solution for the second layer was also prepared in the same manner as the coating solution for the first layer. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. Also, Cpd-2, Cpd-3, Cpd
-4 and Cpd-5 are each 15.0 mg / m
² , 60.0 mg / m ² , 50.0 mg / m ² and 1
It was added to a concentration of 0.0 mg / m ² . The following spectral sensitizing dyes were used in the first layer silver chlorobromide emulsion.

[0324]

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1- (5-methylureidophenyl)
^-3 -Mercaptotetrazole was added in an amount of 3.0 × 10 ^-3 mol per mol of silver halide. (Layer constitution) The composition of each layer is shown below. The number is the coating amount (g
/ M ² ). The silver halide emulsion represents a coating amount in terms of silver.

Support Polyethylene laminated paper [Polyethylene on the first layer side contains a white pigment (TiO ₂ ) and a bluish dye (ultraviolet)]

First Layer Silver Chlorobromide Emulsion A 0. 20 Gelatin 1.50 Yellow coupler (ExY) 0.17 Coloring reducing agent (I-61) 0.20 Solvent (Solv-1) 0.80

Second Layer (Protective Layer) Gelatin 1.01 Polyvinyl alcohol acrylic modified copolymer (modification degree 17%) 0.04 Liquid paraffin 0.02 Surfactant (Cpd-1) 0.01

Completely the same as the preparation of Sample (100) except that the yellow coupler and the color-forming reducing agent in the coating solution for the first layer were replaced with the yellow coupler and the color-forming reducing agent shown in Table 5 in equimolar amounts. Then, a sample (101) was prepared.

Further, silver chlorobromide emulsion A in the coating solution for the first layer was replaced with silver chlorobromide emulsion B shown below in an equal silver amount, and couplers and color-forming reducing agents were replaced with magenta couplers shown in Table 5. A sample (200) was prepared in exactly the same manner as the sample (100) except that the reducing agent for color formation was replaced with an equimolar amount.

Silver chlorobromide emulsion B: Cubic, 1: 3 mixture of large size emulsion B having an average grain size of 0.55 μm and small size emulsion B having a grain size of 0.39 μm (Ag molar ratio). The coefficient of variation of the grain size distribution was 0.10 and 0.08, respectively, and 0.8 mol% of AgBr was contained in a part of the grain surface based on silver chloride in each size emulsion. At this time, in each size emulsion, K is formed on a part of the grain surface where silver bromide is extremely present.
₂ IrCl ₆ was added to dope so that the Ir content would be 5 × 10 ⁻⁷ mol per mol of silver in the entire grain. Also,
In each size emulsion, K ₄ [Fe (CN) ₆ ] was doped to the outside of the grain and to the shell portion where the amount of silver was 20% so as to be 2 × 10 ⁻⁵ mol per mol of silver of the whole grain.

The following spectral sensitizing dyes were used in the silver chlorobromide emulsion B, respectively.

[0333]

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(Sensitizing dye D per mol of silver halide was 3.0 × 10 ^-4 mol for large size emulsion, 3.6 × 10 ^-4 mol for small size emulsion, and Sensitizing dye E per mol of silver halide was 4.0 × 10 ⁻⁵ mol for large size emulsion and 7.0 for small size emulsion.
× 10 ^-5 mol, and 2.0 × 10 ^-4 mol of sensitizing dye F per mol of silver halide per mol of silver halide and 2.8 × 10 ^-4 mol per mol of silver emulsion. Added)

Further, silver chlorobromide emulsion A in the coating solution for the first layer was replaced with silver chlorobromide emulsion C shown below in an equal silver amount, and the coupler and the color-forming reducing agent were cyan couplers shown in Table 5, A sample (300) was produced in exactly the same manner as the sample (100) except that the reducing agent for color formation was replaced with an equimolar amount. Silver chlorobromide emulsion C: Cubic, 1: 4 mixture of large size emulsion C having an average grain size of 0.5 μm and small size emulsion of 0.41 μm (Ag molar ratio). The coefficient of variation of the grain size distribution was 0.09 and 0.11, and AgBr was used for each size emulsion.
0.8 mol% was locally contained in a part of the surface of the grain based on silver chloride. At this time, in each size emulsion, K ₂ IrCl ₆ was added to a part of the surface of the grain in which silver bromide was extremely present so that the Ir content was 5 × 10 ⁻⁷ per 1 mol of silver in the whole grain.
Doped to be molar. In addition, for each size emulsion, K is added to the outside of the grain and to the shell portion where the silver amount is 20%.
₄ [Fe (CN) ₆ ] is added 2 × per 1 mol of silver in the whole particle
Doping was performed so that the concentration became 10 ^-5 mol.

The following spectral sensitizing dyes were used in the silver chlorobromide emulsion C, respectively.

[0337]

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(5.0 × 10 ⁻⁵ mol was added to the large size emulsion and 8.0 × 10 ⁻⁵ mol was added to the small size emulsion, per mol of silver halide).

[0339]

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[0340]

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[0341]

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For samples (100) to (101) prepared as described above using an FWH type sensitometer manufactured by Fuji Film Co., Ltd. (color temperature of light source: 3200 ° K), a blue filter for sensitometry was used. Sample (200) was subjected to gradation exposure with a green filter for sensitometry, and sample (300) was subjected to gradation exposure with a red filter for sensitometry.

The exposed sample was processed in the following processing steps using the following processing solutions. Treatment process Temperature Time Development 40 ℃ 20 seconds Bleach-fix 40 ℃ 45 seconds Rinse room temperature 45 seconds Alkaline treatment Room temperature 30 seconds

Developer Water 600 ml Potassium phosphate 40 g Disodium-N, N-bis (sulfonate ethyl) hydroxylamine 10 g KCl 5 g Hydroxyethylidene-1,1-diphosphonic acid (30%) 4 ml 1- Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 1 g Water was added to 1000 ml pH (25 ° C./potassium hydroxide) 12

Bleach-fixing solution Water 600 ml Ammonium thiosulfate (700 g / l) 93 ml Ammonium sulfite 40 g Ethylenediaminetetraacetic acid iron (III) ammonium 55 g Ethylenediaminetetraacetic acid 2 g Nitric acid (67%) 30 g Water was added 1000 ml pH (25 ° C / acetic acid and aqueous ammonia) 5.8

Rinsing solution Sodium chlorinated isocyanurate 0.02 g Deionized water (conductivity 5 μS / cm or less) 1000 ml pH 6.5

Alkaline-treated solution Water 800 ml Potassium carbonate 30 g Water was added to 1000 ml pH (with 1N sulfuric acid or 1N potassium hydroxide) 10

For the samples (100) to (101), the maximum color density portion of the processed sample was measured using blue light and sample (2).
00) with green light and sample (300) with red light.

[0349]

[Table 5]

It was found that high color density can be obtained by using the color-forming reducing agent of the present invention.

Example 5 A surface of a paper support laminated on both sides with polyethylene was subjected to a corona discharge treatment, and thereafter provided with a gelatin subbing layer containing sodium dodecylbenzenesulfonate, and three types of photographic constituent layers were further coated thereon. A photographic printing paper (400) having a three-layer structure shown in (3) was prepared. The coating solution was prepared as follows. First layer coating liquid Coupler (ExY) 17 g, color-forming reducing agent (I-61)
20 g and 80 g of the solvent (Solv-2) were dissolved in ethyl acetate, and this solution was emulsified and dispersed in a 16% gelatin solution containing 10% sodium dodecylbenzenesulfonate and citric acid to prepare an emulsified dispersion A. The emulsified dispersion A and the silver chlorobromide emulsion A used in Example 4 were mixed and dissolved to prepare a coating solution for the first layer having the composition shown below. The emulsion coating amount is the silver equivalent coating amount.

The coating solutions for the second and third layers were prepared in the same manner as the coating solution for the first layer. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. Cpd-2, Cpd-
3, the total amount of each of Cpd-4 and Cpd-5 was 15.0.
^{mg / m 2, 60.0mg / m} 2, was added to a 50.0 mg / m ² and 10.0 mg / m ^2. The blue sensitizing dye A used in Example 4 was used for the first layer of silver chlorobromide emulsion,
B and C were used in the same amounts as those used in Example 4.

1- (5-methylureidophenyl)
^-3 -Mercaptotetrazole was added in an amount of 3.0 × 10 ^-3 mol per mol of silver halide. (Layer constitution) The composition of each layer is shown below. The number is the coating amount (g
/ M ² ). The silver halide emulsion represents a coating amount in terms of silver.

Support Polyethylene laminated paper [Polyethylene on the first layer side contains a white pigment (TiO ₂ ) and a bluish dye (ultraviolet)]

First Layer Silver Chlorobromide Emulsion A 0.20 Gelatin 1.50 Yellow Coupler (ExY) 0.17 Coloring Reducing Agent (I-61) 0.20 Solvent (Solv-2) 0.80

Second Layer Gelatin 3.17 Mordant (Cpd-6) 3.21

Third Layer (Protective Layer) Gelatin 1.01 Polyvinyl alcohol acrylic modified copolymer (modification degree 17%) 0.04 Liquid paraffin 0.02 Surfactant (Cpd-1) 0.01

[0358]

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Completely the same as the preparation of Sample (400) except that the yellow coupler and the color-forming reducing agent in the coating solution for the first layer were replaced with the yellow coupler and the color-forming reducing agent shown in Table 6 in equimolar amounts. Then, a sample (401) was prepared.

Further, the silver chlorobromide emulsion A in the coating solution for the first layer was replaced with the silver chlorobromide emulsion B used in Example 4 in the same silver amount,
Sample (4) except that the coupler and the color-forming reducing agent were replaced with the magenta coupler and the color-forming reducing agent shown in Table 6 in equimolar amounts.
Sample (500) was prepared in exactly the same manner as 00).
For the silver chlorobromide emulsion B, the green sensitizing dye D used in Example 1 was used.
E and F were used in the same amounts as those used in Example 4.

The silver chlorobromide emulsion A in the coating solution for the first layer was replaced with the silver chlorobromide emulsion C used in Example 4 in the same silver amount, and the coupler and the color-forming reducing agent shown in Table 6 were cyan. A sample (600) was produced in exactly the same manner as the sample (400) except that the coupler and the color-forming reducing agent were replaced with equimolar amounts. For the silver chlorobromide emulsion C, the red sensitizing dyes G and H used in Example 4 were used in the same amounts as those used in Example 4.

Using the FWH type sensitometer manufactured by FUJIFILM Corporation (color temperature of light source: 3200 ° K), the samples (400) to (401) prepared as described above were subjected to a sensitometric blue filter. The sample (500) was subjected to gradation exposure with a green filter for sensitometry, and the sample (600) was subjected to gradation exposure with a red filter for sensitometry.

The exposed sample was processed in the following processing steps using the following processing solutions. Processing Step Temperature Time Development 40 ° C 20 seconds Bleaching and fixing 40 ° C 45 seconds Rinse Room temperature 45 seconds

As the developing solution, the bleach-fixing solution and the rinsing solution, the developing solution, the bleach-fixing solution and the rinsing solution used in Example 4 were used.

For the samples (400) to (401), the maximum color density portion of the processed sample was measured using blue light and sample (5).
00) with green light and sample (600) with red light.

[0366]

[Table 6]

It was found that by using the color-forming reducing agent of the present invention, a high color-forming density can be obtained even when a mordant is contained in the light-sensitive material.

Example 6 A surface of a paper support laminated on both sides with polyethylene was subjected to a corona discharge treatment and then provided with a gelatin subbing layer containing sodium dodecylbenzenesulfonate. A photographic printing paper (700) having a three-layer structure shown in 1 was prepared. The coating solution was prepared as follows. Second layer coating liquid Coupler (ExY) 17 g, reducing agent for color development (I-61)
20 g of a solvent (Solv-2) and 80 g of a solvent were dissolved in ethyl acetate, and this solution was emulsified and dispersed in a 16% gelatin solution containing 10% sodium dodecylbenzenesulfonate and citric acid to prepare an emulsified dispersion D. The emulsified dispersion D and the silver chlorobromide emulsion A used in Example 4 were mixed and dissolved to prepare a second layer coating solution having the composition shown below. The emulsion coating amount is the silver equivalent coating amount.

The coating solutions for the first and third layers were prepared in the same manner as the coating solution for the second layer. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. Cpd-2, Cpd-
3, the total amount of each of Cpd-4 and Cpd-5 was 15.0.
^{mg / m 2, 60.0mg / m} 2, was added to a 50.0 mg / m ² and 10.0 mg / m ^2. The blue sensitizing dye A used in Example 4 was used for the first layer of silver chlorobromide emulsion,
B and C were used in the same amounts as those used in Example 1.

1- (5-methylureidophenyl)
^-3 -Mercaptotetrazole was added in an amount of 3.0 × 10 ^-3 mol per mol of silver halide. (Layer constitution) The composition of each layer is shown below. The number is the coating amount (g
/ M ² ). The silver halide emulsion represents a coating amount in terms of silver.

Support Polyethylene laminated paper [Polyethylene on the first layer side contains a white pigment (TiO ₂ ) and a bluish dye (ultraviolet)]

First layer Gelatin 1.12 1,5-diphenyl-3-pyrazolidone 0.02 (fine particle solid dispersion state)

Second Layer Silver Chlorobromide Emulsion A 0.20 Gelatin 1.50 Yellow Coupler (ExY) 0.17 Coloring Reducing Agent (I-61) 0.20 Solvent (Solv-2) 0.80

Third Layer (Protective Layer) Gelatin 1.01 Polyvinyl alcohol acrylic modified copolymer (modification degree 17%) 0.04 Liquid paraffin 0.02 Surfactant (Cpd-1) 0.01

Except that the yellow coupler and the color-forming reducing agent in the coating solution for the second layer were replaced with the yellow coupler and the color-forming reducing agent shown in Table 7 in equimolar amounts. Then, a sample (701) was prepared.

Further, the silver chlorobromide emulsion A in the coating solution for the first layer was replaced with the silver chlorobromide emulsion B used in Example 4 in the same silver amount,
Sample (7) except that the coupler and the color-forming reducing agent were replaced with the magenta coupler and the color-forming reducing agent shown in Table 7 in equimolar amounts.
Sample (800) was prepared in exactly the same manner as 00).
The silver chlorobromide emulsion B contains the green sensitizing dye D used in Example 4,
E and F were used in the same amounts as those used in Example 4.

The silver chlorobromide emulsion A in the coating solution for the first layer was replaced with the silver chlorobromide emulsion C used in Example 4 in the same silver amount, and the coupler and the color-forming reducing agent shown in Table 7 were used. A sample (900) was produced in exactly the same manner as the sample (700), except that the coupler and the color-forming reducing agent were replaced by equimolar amounts. For the silver chlorobromide emulsion C, the red sensitizing dyes G and H used in Example 4 were used in the same amounts as those used in Example 4.

Using a FWH type sensitometer manufactured by FUJIFILM Corporation (color temperature of light source: 3200 ° K), a blue filter for sensitometry was prepared for each of the samples (700) to (701) prepared as described above. The sample (800) was subjected to gradation exposure with a green filter for sensitometry, and the sample (900) was subjected to gradation exposure with a red filter for sensitometry.

The exposed sample was processed in the following processing steps using the following processing solutions. Processing Step Temperature Time Development 40 ° C 20 seconds Bleaching and fixing 40 ° C 45 seconds Rinse Room temperature 45 seconds

Developer (alkali activating solution) Water 600 ml Potassium phosphate 40 g KCl 5 g Hydroxyethylidene-1,1-diphosphonic acid (30%) 4 ml Water was added to 1000 ml pH (25 ° C / hydroxylation). With potassium) 12

The developing solution, the bleach-fixing solution and the rinsing solution used in Example 4 were used as the bleach-fixing solution and the rinsing solution.

For the samples (700) to (701), the maximum color density portion of the processed sample was measured using blue light and sample (8).
00) with green light and sample (900) with red light.

[0383]

[Table 7]

It is understood that by using the color-forming reducing agent of the present invention, a high color-developing density can be obtained even when the auxiliary developing agent is incorporated in the light-sensitive material.

Example 7 A surface of a paper support laminated on both sides with polyethylene was subjected to a corona discharge treatment and then provided with a gelatin subbing layer containing sodium dodecylbenzenesulfonate, and three types of photographic constituent layers were further coated. A photographic printing paper (1000) having a three-layer structure shown in 1 was produced. The coating solution was prepared as follows. Second layer coating liquid Coupler (ExY) 17 g, reducing agent for color development (I-61)
20 g and 80 g of the solvent (Solv-2) were dissolved in ethyl acetate, and this solution was added to a 16% gelatin solution 400 containing 10% sodium dodecylbenzenesulfonate and citric acid.
An emulsified dispersion D was prepared by emulsifying and dispersing in g. On the other hand, silver chlorobromide emulsion D (cubic, 3: 7 mixture of large size emulsion D having an average grain size of 0.10 μm and small size emulsion D having an average grain size of 0.08 μm (silver molar ratio). Coefficient of variation of grain size distribution. Of 0.08 and 0.10, respectively, and 0.3 mol% of silver bromide in each size emulsion was locally contained in a part of the surface of the grain based on silver chloride). At this time, in each size emulsion, K is formed on a part of the grain surface where silver bromide is extremely present.
₂ IrCl ₆ was added to dope so that the Ir content would be 5 × 10 ⁻⁷ mol per mol of silver in the entire grain. Also,
In each size emulsion, K ₄ [Fe (CN) ₆ ] was doped to the outside of the grains and to the shell portion where the amount of silver was 20% so as to be 2 × 10 ⁻⁵ mol per mol of silver of the whole grains. In this emulsion, blue-sensitive sensitizing dyes A, B, and C shown below were added to the large-sized emulsion D per mol of silver in an amount of 7.0 × 1 each.
^0-4 mol, and 8.5 × 10 ^-4 mol were added to the small-sized emulsion D, respectively. The chemical ripening of this emulsion was carried out by adding a sulfur sensitizer and a gold sensitizer. The above emulsified dispersion D and this silver chlorobromide emulsion D were mixed and dissolved to prepare a coating solution for the second layer having the composition shown below. The emulsion coating amount is the silver equivalent coating amount.

The coating solutions for the first layer and the third layer were prepared in the same manner as the coating solution for the second layer. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. Cpd-2, Cpd-
3, the total amount of each of Cpd-4 and Cpd-5 was 15.0.
^{mg / m 2, 60.0mg / m} 2, was added to a 50.0 mg / m ² and 10.0 mg / m ^2.

1- (5-methylureidophenyl)
^-3 -Mercaptotetrazole was added in an amount of 3.0 × 10 ^-3 mol per mol of silver halide. (Layer constitution) The composition of each layer is shown below. The number is the coating amount (g
/ M ² ). The silver halide emulsion represents a coating amount in terms of silver.

Support: Polyethylene laminated paper [Polyethylene on the first layer side contains a white pigment (TiO ₂ ) and a bluish dye (ultraviolet)]

First layer Gelatin 1.12 1,5-diphenyl-3-pyrazolidone 0.02 (fine particle solid dispersion state)

Second Layer Silver Chlorobromide Emulsion D 0.01 Gelatin 1.50 Yellow Coupler (ExY) 0.17 Coloring Reducing Agent (I-61) 0.20 Solvent (Solv-2) 0.80

Third Layer (Protective Layer) Gelatin 1.01 Polyvinyl Alcohol Acrylic Modified Copolymer (Modification Degree 17%) 0.04 Liquid Paraffin 0.02 Surfactant (Cpd-1) 0.01

Same as the preparation of Sample (1000) except that the yellow coupler and the color-forming reducing agent in the coating solution for the second layer were replaced with the yellow coupler and the color-forming reducing agent shown in Table 8 in equimolar amounts. Then, a sample (1001) was prepared.

Further, the silver chlorobromide emulsion D in the coating solution for the second layer was replaced with the silver chlorobromide emulsion E shown below in an equal silver amount, and the coupler and the color-forming reducing agent were changed to the magenta coupler shown in Table 8. Sample (1000) except that the reducing agent for color formation was replaced with an equimolar amount
A sample (1101) was prepared in exactly the same manner as in (1).

Silver chlorobromide emulsion E: Cubic, 1: 3 mixture of large size emulsion B having an average grain size of 0.10 μm and small size emulsion B of 0.08 μm (Ag molar ratio). The coefficient of variation of the grain size distribution was 0.10 and 0.08, respectively, and 0.8 mol% of AgBr was contained in a part of the grain surface based on silver chloride in each size emulsion. At this time, in each size emulsion, K is formed on a part of the grain surface where silver bromide is extremely present.
₂ IrCl ₆ was added to dope so that the Ir content would be 5 × 10 ⁻⁷ mol per mol of silver in the entire grain. Also,
In each size emulsion, K ₄ [Fe (CN) ₆ ] was doped to the outside of the grain and to the shell portion where the amount of silver was 20% so as to be 2 × 10 ⁻⁵ mol per mol of silver of the whole grain.

For the silver chlorobromide emulsion E, the green sensitizing dyes D, E and F used in Example 4 were used in the amounts shown below.

(Sensitizing dye D per mol of silver halide is 1.5 × 10 ⁻³ mol for large size emulsion, 1.8 × 10 ⁻³ mol for small size emulsion, and Sensitizing dye E per mol of silver halide is 2.0 × 10 ⁻⁴ mol for large size emulsion, 3.5 × 10 ⁻⁴ mol for small size emulsion, and sensitizing dye F is halogen. Silver oxide 1
(1.0 × 10 ⁻³ mol was added to the large-sized emulsion and 1.4 × 10 ⁻³ mol was added to the small-sized emulsion).

Further, silver chlorobromide emulsion D in the coating solution for the second layer was replaced with silver chlorobromide emulsion F shown below in an equal silver amount, and the coupler and the color-forming reducing agent were cyan couplers shown in Table 8, A sample (1200) was prepared in exactly the same manner as the sample (1000), except that the color-forming reducing agent was replaced with an equimolar amount.

Silver chlorobromide emulsion F: Cubic, 1: 4 mixture of large size emulsion C having an average grain size of 0.10 μm and small size emulsion of 0.08 μm (Ag molar ratio). The coefficient of variation of the grain size distribution was 0.09 and 0.11, and 0.8 mol% of AgBr was locally contained in a part of the grain surface having silver chloride as a base in each size emulsion. At this time, in each size emulsion, K ₂ Ir was formed on a part of the grain surface where silver bromide was extremely present.
Cl ₆ was added to dope so that the Ir content would be 5 × 10 ⁻⁷ mol per mol of silver in the entire grain. In addition, in each size emulsion, K ₄ [Fe (CN) ₆ ] was doped to the outside of the grain and to the shell portion having a silver amount of 20% so as to be 2 × 10 ⁻⁵ mol per mol of silver of the whole grain. .

For the silver chlorobromide emulsion F, the red sensitizing dyes G and H used in Example 4 were used in the amounts shown below.

(2.5 × 10 ⁻⁴ mol for each large-sized emulsion and 4.0 × 10 ⁻⁴ mol for each small-sized emulsion were added per mol of silver halide).

A blue filter for sensitometry was used for samples (1000) to (1001) prepared as described above using an FWH type sensitometer manufactured by FUJIFILM Corporation (color temperature of light source: 3200 ° K). , Sample (1100)
Is a green filter for sensitometry.
(00) was subjected to gradation exposure with a red filter for sensitometry.

The exposed sample was processed in the following processing steps using the following processing solutions. Processing step 1 Processing step Temperature Time Development 40 ° C 40 seconds Rinse room temperature 45 seconds

Developer water 600 ml Potassium phosphate 40 g KCl 5 g Hydroxyethylidene-1,1-diphosphonic acid (30%) 4 ml H ₂ O ₂ 10 ml Water was added to 1000 ml pH (25 ° C./hydroxylation). 11.5 in potassium)

As the rinse liquid, the rinse liquid used in Example 4 was used.

The maximum color density part of the sample after treatment was blue light for samples (1000) to (1001), green light for sample (1100), and red light for sample (1200). It was measured at.

[0406]

[Table 8]

It can be seen that by using the color-forming reducing agent of the present invention, a high color-developing density can be obtained even when the auxiliary developing agent is incorporated in the light-sensitive material and subjected to intensification processing with hydrogen peroxide.

Example 8 A surface of a paper support laminated on both sides with polyethylene was subjected to a corona discharge treatment and then provided with a gelatin subbing layer containing sodium dodecylbenzenesulfonate, and various photographic constituent layers were further coated thereon. A multilayer color photographic paper (1300) having the layer structure shown was produced. The coating solution was prepared as follows.

First layer coating liquid Coupler (ExY) 17 g, color-forming reducing agent (I-61)
20 g and 80 g of the solvent (Solv-1) were dissolved in ethyl acetate, and this solution was emulsified and dispersed in a 16% gelatin solution containing 10% sodium dodecylbenzenesulfonate and citric acid to prepare an emulsified dispersion A. The emulsified dispersion A and the silver chlorobromide emulsion A used in Example 1 were mixed and dissolved to prepare a coating solution for the first layer having the composition shown below. The emulsion coating amount is the silver equivalent coating amount.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. Cpd-2, Cpd-
3, the total amount of each of Cpd-4 and Cpd-5 was 15.0.
^{mg / m 2, 60.0mg / m} 2, was added to a 50.0 mg / m ² and 10.0 mg / m ^2. For the silver chlorobromide emulsions of the first layer, the third layer and the fifth layer, the blue sensitizing dyes A, B and C, the green sensitizing dyes D and E used in Example 4 were used.
F and red sensitizing dyes G and H were used in the same amounts as those used in Example 4.

The following compounds were further added to the fifth layer (red-sensitive layer) in an amount of 2.6 × 10 ^-2 mol per mol of silver halide.

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For the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer, 1- (5-methylureidophenyl)-
5-mercaptotetrazole was replaced by silver halide 1
3.5 × 10 ^-4 mole, 3.0 × 10 ^-3 mole per mole,
2.5 × 10 ^-4 mol was added. In addition, 4-hydroxy-6-methyl-1, 4-hydroxy-6-methyl-1,
3,3a, 7-Terrazaindene was added in an amount of 1 × 10 ⁻⁴ mol and 2 × 10 ⁻⁴ mol per mol of silver halide, respectively. Further, in order to prevent irradiation, the following dye (the amount in parentheses represents the coating amount) was added to the emulsion layer.

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(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver.

Support Polyethylene laminated paper [Polyethylene on the first layer side contains a white pigment (TiO ₂ ) and a bluish dye (ultraviolet)]

First Layer (Blue Sensitive Emulsion Layer) The silver chlorobromide emulsion A 0.20 gelatin 1.50 yellow coupler (ExY) 0.17 color-forming reducing agent (I-61) 0.20 solvent (Solv -2) 0.80

Second Layer (Color Mixing Prevention Layer) Gelatin 1.09 Color mixing inhibitor (Cpd-7) 0.11 Solvent (Solv-1) 0.19 Solvent (Solv-3) 0.07 Solvent (Solv-4) 0.25 solvent (Solv-5) 0.09 1,5-diphenyl-3-pyrazolidone 0.03 (fine particle solid dispersion state)

Third Layer (Green Sensitive Emulsion Layer) The silver chlorobromide emulsion B 0.20 Gelatin 1.50 Magenta coupler (ExM) 0.24 Coloring reducing agent (I-61) 0.20 Solvent (Solv -2) 0.80

Fourth Layer (Color Mixing Prevention Layer) Gelatin 0.77 Color mixing inhibitor (Cpd-7) 0.08 Solvent (Solv-1) 0.14 Solvent (Solv-3) 0.05 Solvent (Solv-4) 0.14 Solvent (Solv-5) 0.06 1,5-Diphenyl-3-pyrazolidone 0.02 (fine particle solid dispersion state)

Fifth Layer (Red Sensitive Emulsion Layer) Silver Chlorobromide Emulsion C 0.20 Gelatin 0.15 Cyan Coupler (ExC) 0.21 Coloring Reducing Agent (I-61) 0.20 Solvent (Solv -2) 0.80

Sixth Layer (UV Absorbing Layer) Gelatin 0.64 UV Absorbing Agent (UV-1) 0.39 Color Image Stabilizer (Cpd-8) 0.05 Solvent (Solv-6) 0.05

Seventh Layer (Protective Layer) Gelatin 1.01 Acryl-modified copolymer of polyvinyl alcohol (modification degree 17%) 0.04 Liquid paraffin 0.02 Surfactant (Cpd-1) 0.01

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[0425]

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A sample (1301) was prepared in exactly the same manner as the preparation of the sample (1300) except that the coupler (1300) was replaced with the coupler shown in the color-forming reducing agent and the color-forming reducing agent in an equimolar amount. It was made.

For all the samples prepared as described above, the FWH type sensitometer manufactured by FUJIFILM Corporation (color temperature of light source 3
(200 ° K.) to give a gradation exposure of a three-color separation filter for sensitometry.

The exposed sample was processed in the following processing steps using the following processing solutions. Processing process Temperature Time Color development 40 ° C 30 seconds Bleaching and fixing 40 ° C 45 seconds Rinse Room temperature 90 seconds

As the color developing solution, the bleach-fixing solution and the rinse solution, the developing solution, the bleach-fixing solution and the rinse solution used in Example 6 were used.

The maximum color density portion of the processed sample was measured with red light, green light and blue light.

It can be seen that high color density can be obtained also in the case of a multi-layered light-sensitive material having an auxiliary developing agent incorporated in the light-sensitive material.

Example 9 (Comparative Example) Preparation of Photosensitive Material Incorporating Reducing Agent for Coloring and Auxiliary Developing Agent (1) Preparation of Emulsion Containing Coupler and Reducing Agent for Coloring Cyan Coloring Coupler (ExC-1) 22.5 g And ExC
-6.82 g, reducing agent for color development (I-7) 27.8 g
52 g of high-boiling organic solvent (Solv-1) and ethyl acetate 7
It is dissolved in 3 cc, and this solution is a 12% gelatin aqueous solution containing sodium dodecylbenzenesulfonate and citric acid 4
Emulsion A was prepared by emulsifying and dispersing in 20 cc. Emulsion B was changed to Emulsion B and Yellow color coupler (ExY-1) to prepare Emulsion C in the same manner except that the magenta color forming coupler (ExM-1) was used.

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(2) Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 shown below was dispersed by the following method. That is, water 2
1.7 ml and 3 ml of a 5% aqueous solution of sodium p-octylphenoxyethoxyethoxyethoxyethanesulfonate and 0.5 g of a 5% aqueous solution of 0.5 g of p-octylphenoxypolyoxyethylene ether (polymerization degree 10) were put into a 700 ml pot mill. , Dye ExF-
5.0 g and zirconium oxide beads (diameter 1 mm) 5
00 ml was added and the contents were dispersed for 2 hours.
For this dispersion, a BO type vibration ball mill manufactured by Chuo Koki was used. After the dispersion, the contents were taken out, added to 8 g of a 12.5% aqueous gelatin solution, and the beads were removed by filtration to obtain a gelatin dispersion of the dye. The average particle size of the dye particles is 0.44μ
m.

In the same manner, solid dispersions of ExF-3, ExF-4 and ExF-6 were obtained. The average particle diameter of the fine dye particles is 0.24 μm, 0.45 μm, and 0.52 μm, respectively.
Met. ExF-5 is European Patent Application Publication (EP) No. 5
Dispersion was carried out by the microprecipitation dispersion method described in Example 1 of the specification of No. 49,489A. The average particle size was 0.06 μm.

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Example 10 (3) Preparation of {100} Silver Chlorobromide Tabular Emulsion Emulsions prepared by the following methods were respectively sensitized to red-sensitive, green-sensitive and blue-sensitive color sensitivities and optimum sensitivity was obtained. It was adjusted by a conventionally known method so as to obtain it. Further, for use in the high-sensitivity layer, medium-sensitivity layer, and low-sensitivity layer, the size of silver halide grains was adjusted by a known method, and optimum color sensitization and chemical sensitization were performed to prepare emulsions. Sensitizing dyes ExS-1, ExS-2, ExS-3 for red-sensitive emulsions and sensitizing dyes ExS-4, ExS-5, ExS- for green-sensitive emulsions.
6 and ExS-7 was used as a blue-sensitive emulsion to perform color sensitization. In a reaction vessel, 1582 ml of an aqueous gelatin solution (gelatin-1 (deionized alkali-treated bone gelatin having a methionine content of about 40 μmol / g) 19.5 g, HNO ₃
1N solution (7.8 ml, pH 4.3), NaCl-1 solution (100 ml contains 10 g of NaCl) 13 ml, and while keeping the temperature at 40 ° C, Ag-1 solution (100 ml).
20g of AgNO ₃ ) and solution X-1 (7.05g of NaCl in 100ml) at 62.4ml / min.
5.6 ml were added simultaneously. After stirring for 3 minutes, X
-Part 2 (containing 1.1 g of KBr in 100 ml) 8
28.2 ml were mixed simultaneously at 0.6 ml / min. After stirring for 3 minutes, Ag-1 solution and X-1 solution were mixed at 62.4 ml / min for 4 minutes.
6.8 ml were added simultaneously. After stirring for 2 minutes, 203 ml of gelatin aqueous solution (gelatin-1 13 g, NaC
l 1.3 g, containing NaOH 1N solution for adjusting the pH to 6.5) was added to adjust the pCl to 1.75, and the temperature was adjusted to 6
The temperature was raised to 5 ° C., and the mixture was adjusted to pCl 1.95 and aged for 3 minutes. After that, Ag-2 liquid (AgNO ₃ 50 in 100 ml)
g) and solution X-4 (NaCl in 100 ml 16.
CDJ (controlled including 4g and KBr 2.5g)
double jet), the Ag-3 solution was added at a constant flow rate for 20 minutes until the added amount reached 182 ml. At this time, [Fe]
(CN) ₆ ] ⁴⁻ is 1 × 10 1 per mol of silver in the whole grain.
-K ₄ as the third jet so that it is ^-5 mol / mol
A [Fe (CN) ₆ ] aqueous solution was added. Then, AgBr fine particles having an average equivalent spherical diameter of 0.03 μm were added in an amount of 0.2 mol% per mol of silver halide and ripened for about 5 minutes to complete the halogen conversion. At this time the Ag
For the Br fine particles, when preparing the fine particles, K ₂ IrCl ₆
And 5 × 10 ^-5 mol of I per 1 mol of fine silver particles are added.
It was doped with r ions. Add a precipitating agent and increase the temperature to 35 ° C.
And washed with sedimented water. Add gelatin aqueous solution, 60 ℃
The pH was adjusted to 6.0. A TEM image of a replica of the particles was observed. The resulting emulsion was AgBr based on silver.
Was a silver chlorobromide {100} tabular grain containing 6.95 mol% of. (4) Preparation of multilayer coating sample Emulsions A to C and solid disperse dye dispersion described in Example 9 Using the above emulsion, each layer having the following composition was formed on a transparent support by a conventional known method. Multi-layer coating was performed to prepare a light-sensitive material. This is designated as Sample 10-1. (Composition of photosensitive layer) The main materials used for each layer are classified as follows; ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: Gelatin hardening agent ExS: Sensitizing dye (Specific compounds are given in the following description, followed by a numeral and a chemical formula) The numeral corresponding to each component is g / m ² unit The coating amount represented by is shown, and for silver halide, the coating amount in terms of silver is shown. However, as for the sensitizing dye, the coating amount is shown in mol unit with respect to 1 mol of silver halide in the same layer.

First layer (antihalation layer) Black colloidal silver Silver 0.09 Gelatin 1.60 ExF-1 2.0 × 10 ^-3 Solid disperse dye ExF-2 0.030 Solid disperse dye ExF-3 0.040 HBS-1 0.15 HBS-2 0.02 Second Layer (intermediate layer) 0.07 μm Silver bromide emulsion Silver 0.065 Polyethyl acrylate latex 0.20 Gelatin 1.04 Third layer (low sensitivity red sensitive emulsion layer) Silver chloride tabular emulsion Silver 0.50 ExS-1 6.0 × 10 ^-4 ExS-2 3.2 × 10 ^-5 ExS-3 9.0 × 10 ^-4 ExC-1 0.33 ExC-2 0.10 Coloring reducing agent I-7 0.30 Cpd-2 0.025 HBS-1 0.10 Gelatin 0.87 Fourth layer (medium-sensitive red-sensitive emulsion layer) Chloride Silver tabular emulsion Silver 0.70 ExS-1 4.5 × 10 ^-4 ExS-2 2.0 × 10 ^-5 ExS-3 6.5 × 10 ^-4 ExC-1 0.31 ExC-2 0.05 Color reducing agent I-7 0.023 HBS-1 0.10 Gelatin 0.75 Fifth layer (high-sensitivity red-sensitive emulsion layer) Chloride Tabular emulsion silver ^{1.40 ExS-1 3.0 × 10 -4} ExS-2 1.6 × 10 -5 ExS-3 4.5 × 10 -4 ExC-1 0.175 color-forming reducing agent I-7 0.15 Cpd-2 0.050 HBS-1 0.22 HBS- 2 0.050 Gelatin 1.10 6th layer (intermediate layer) Auxiliary developing agent precursor (ETA-49) 0.07 Cpd-1 0.090 Solid disperse dye ExF-4 0.030 HBS-1 0.050 Polyethyl acrylate latex 0.15 Gelatin 1.10 7th layer (low sensitivity) Green-sensitive emulsion layer) Silver chloride tabular emulsion Silver 0.35 ExS-4 3.8 × 10 ^-5 ExS-5 2.9 × 10 ^-4 ExS-6 9.8 × 10 ^-4 ExM-1 0.41 Coloring reducing agent I-7 0.30 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73 Eighth layer (medium sensitivity green emulsion layer) Silver chloride tabular emulsion Silver 0.80 ExS-4 4.0 × 10 ^-5 ExS-5 2.0 × 10 ^-4 ExS-6 5.0 × 10 ^-4 ExM- 1 0.18 Coloring reducing agent I-7 0.15 HBS-1 0.13 HBS-3 4.0 × 10 ^-3 Gelatin 0.80 9th layer (high-sensitivity green emulsion layer) Silver chloride tabular emulsion Silver 1.25 ExS-4 7.9 × 10 ^-5 ExS-5 1.4 × 10 ^-4 ExS-6 0.4 × 10 ^-4 ExM-1 0.095 Coloring reducing agent I-7 0.10 Cpd-3 0.040 HBS-1 0.25 Polyethyl acrylate latex 0.15 Gelatin 1.33 10th layer (yellow filter layer) Yellow colloidal silver Silver 0.015 Cpd-1 0.16 Solid disperse dye ExF-5 0.060 Solid disperse dye ExF-6 0.060 Oil-soluble dye ExF-7 0.010 Auxiliary developer precursor (ETA-49) 0.07 HBS-1 0.60 Gelatin 0.60 11th layer (low-sensitivity blue emulsion layer) Silver chloride tabular emulsion Silver 0.18 ExS-7 4.0 × 10 ^-4 ExC -1 7.0 × 10 ^-3 ExY-1 0.79 Coloring reducing agent I-7 0.70 Cpd-2 0.10 Cpd-3 4.0 × 10 ^-3 HBS-1 0.28 Gelatin 1.20 12th layer (high-sensitivity blue-sensitive emulsion layer) Silver chloride Tabular emulsion Silver 1.00 ExS-7 2.0 × 10 ^-4 ExY-10 .22 Coloring reducing agent I-7 0.20 Cpd-2 0.10 Cpd-3 1.0 × 10 ^-3 HBS-1 0.070 Gelatin 0.70 13th layer (1st protective layer) UV-1 0.19 UV-2 0.075 UV-3 0.065 HBS -1 5.0 × 10 ^-2 HBS-4 5.0 × 10 ^-2 Gelatin 1.8 14th layer (2nd protective layer) 0.07 μm Silver bromide emulsion Silver 0.10 H-1 0.40 B-1 (1.7 μm diameter) 5.0 × 10 ^-2 B-2 (1.7 μm diameter) 0.15 B-3 0.05 S-1 0.20 Gelatin 70

Further, in order to improve storage stability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property, each layer may be provided with W-1 to W-3, B-4 to B-. 6, F
-1 to F-17, and iron salts, lead salts, gold salts, platinum salts,
It contains a palladium salt, an iridium salt, and a rhodium salt.

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[0442]

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[0445]

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[0446]

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[0447]

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[0448]

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Each sample was stored at 40 ° C. and 70% for 16 hours and then stored in a sensitometer (manufactured by Fuji Photo Film Co., Ltd., FW type,
A light source color temperature of 4800 ° K) was used and wedge exposure was performed using R, G and B filters. The exposed sample was continuously processed using the processing solution composition described below until the tank volume of the developing solution was replenished.

Treatment process Temperature Replenishment amount ^* Time Tank capacity (liter) Current image 40 ° C. 30 ml 20 sec 1.0 Bleach fixing 40 ° C. 30 ml 15 sec 1.0 Rinse 30 ° C.-3 sec 0.3 Rinse 30 ° C.− 3 seconds 0.3 Rinse 30 ℃ -3 seconds 0.3 Rinse 30 ℃ -3 seconds 0.3 Rinse 30 ℃ 60ml 3 seconds 0.3 Alkaline treatment 30 ℃ 30ml 5 seconds 0.3 Dry 80 ℃ 10 seconds (* Replenishment amount per 1 m ^{2 of} light-sensitive material) (Rinse → 5 tank countercurrent method)

In the above treatment, the rinse water was pumped to the reverse osmosis membrane, the permeated water was supplied to the rinse, and the concentrated water that did not permeate the reverse osmosis membrane was returned to the rinse for treatment. In addition,
In order to shorten the crossover time between the rinses, a blade was installed between the tanks and the blades were passed between them.

Developer-1 (Alkaline active solution) Tank solution Replenisher Water 800 ml 800 ml Tripotassium phosphate 30 g 39 g 5-Nitrobenzotriazole 0.1 g 0.25 g Disodium-N, N-bis (sulfonate ethyl) hydroxyl Amine 3.3 g 6.6 g Potassium chloride 10 g-Hydroxyethylidene-1,1-diphosphonic acid (30% solution) 4 ml 4 ml Water was added to 1 liter pH 12.0

Bleach-fixing solution Tank solution Replenishing solution Water 600 ml 150 ml Ammonium thiosulfate (700 g / l) 100 ml 250 ml Ammonium sulfite monohydrate 40 g 40 g Ethylenediaminetetraacetic acid iron (III) ammonium 77 g 154 g Ethylenediaminetetraacetic acid 5 g 10 g Ammonium bromide 10 g 20 g Acetic acid (50%) 70 ml 140 ml Add water 1000 ml 1000 ml Rinse water Tap water Alkaline potassium carbonate 30.0 g Add water 1 liter pH 10.0

The image densities of yellow, magenta and cyan after continuous processing under the respective conditions were measured through B, G and R filters corresponding to the respective dyes. The present invention
It was confirmed that it showed excellent photographic performance.

Claims (4)

[Claims] 1. A silver halide photographic light-sensitive material having at least one photographic constituent layer on a support, wherein at least one color-forming reducing agent represented by the following general formula (I) is present in any of the photographic constituent layers. And a coordination metal containing at least one dye-forming coupler, wherein the silver halide grains contained in at least one of the photographic constitutional layers contain a metal of elements of Groups 4 to 5 and 6 of the periodic table. A silver halide photographic light-sensitive material characterized by containing a complex or a metal ion in a crystal lattice. Embedded image In the formula, R ¹¹ is an aryl group or a heterocyclic group which may have a substituent, and R ¹² is an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group which may have a substituent. is there. X is _{-SO 2 -, - CO -,} - COC
O -, - CO-O - , - CON (R 13) -, - COCO
-O -, - COCO-N ( R 13) - or -SO ₂ -N
(R ¹³ ) −. Here, R ¹³ is a hydrogen atom or a group described for R ¹² . 2. A compound represented by the general formula (I) is represented by the general formula:
It is represented by (II) or (III).
The silver halide photographic light-sensitive material described in. Embedded imageWhere Z¹Is an acyl group, a carbamoyl group, an alkoxy group
Represents a carbonyl group or an aryloxycarbonyl group.
Then Z^TwoIs a carbamoyl group, an alkoxycarbonyl group,
Or an aryloxycarbonyl group, X¹,
X^Two, X^Three, X^Four, X ^FiveRepresents a hydrogen atom or a substituent
You. Where X¹, X^Three, X^FiveHammett's substituent constant σ
p-value and X^Two, X^FourThe sum of Hammett's substituent constant σm values is
It is 0.80 or more and 3.80 or less. R^ThreeIs a heterocyclic group
Represents 3. The silver halide photographic light-sensitive material according to claim 2, wherein the compounds represented by the general formulas (II) and (III) are represented by the general formulas (IV) and (V), respectively. . Embedded image In the formula, R ¹ and R ² represent a hydrogen atom or a substituent,
X ¹ , X ² , X ³ , X ⁴ and X ⁵ represent a hydrogen atom or a substituent. However, the sum of the Hammett's substituent constant σp values of X ¹ , X ³ and X ^{5 and} the Hammett's substituent constant σm of X ² and X ⁴ is 0.80 or more and 3.80 or less. R ³ represents a heterocyclic group. 4. The silver halide photographic light-sensitive material according to claim 3, wherein the compounds represented by the general formulas (IV) and (V) are represented by the general formulas (VI) and (VII), respectively. . Embedded image In the formula, R ⁴ and R ⁵ represent a hydrogen atom or a substituent,
X ⁶ , X ⁷ , X ⁸ , X ⁹ , and X ¹⁰ represent a hydrogen atom, a cyano group,
Represents a sulfonyl group, a sulfinyl group, a sulfamoyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, a trifluoromethyl group, a halogen atom, an acyloxy group, an acylthio group, or a heterocyclic group. However, the sum of the Hammett's substituent constant σp value of X ⁶ , X ⁸ and X ^{10 and} the Hammett's substituent constant σm value of X ⁷ and X ⁹ is 1.20 or more and 3.80 or less. Q ¹
Represents a nonmetallic atom group necessary for forming a nitrogen-containing 5- to 8-membered heterocycle together with C.