JPH09152704A - Color developing agent, silver halide photographic sensitive material and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To attain satisfactory coloring at the time of development by using a specified color developing agent and to form an image having satisfactory coloring property even when a two-equiv. coupler is used. SOLUTION: This color developing agent is represented by the formula, wherein Z is carbamoyl, acyl, sulfonyl, sulfamoyl, alkoxycarbonyl, aryloxycarbonyl, amidino, imidoyl or phosphoryl, Q is a group of atoms forming an unsatd. ring in combination with C, each of Y<1> and Y<2> is a group having a dissociable group whose pKa is 1-12, each of (n) and (m) is an integer of 0-3, n+m>=1, in the case of n>=2, Y<1> 's may be different from each other, in the case of m>=2, Y<2> 's may be different from each other and each of Y<1> and Y<2> is preferably a group contg. -NHSO2 -, phenolic hydroxyl, -CONHCO-, -CONHSO2 -, -CON(R)-OH, -COOH or -SO2 NHSO.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material using a novel color developing agent and a new image forming method, and in particular, a silver halide photographic light-sensitive material having good color forming property during development. Materials and imaging methods.

[0002]

2. Description of the Related Art In a color photographic light-sensitive material, after the material is exposed to light and color-developed, an oxidized color-developing agent reacts with a coupler to form an image. In this method, a color reproduction method based on a subtractive color method is used. To reproduce blue, green, and red, yellow, magenta, and cyan color images having complementary colors are formed.

In color development, an exposed color photographic light-sensitive material is dissolved in an alkaline aqueous solution (developing solution) in which a color developing agent is dissolved.
Achieved by immersion. However, there is a problem that a color developing agent made of an aqueous alkaline solution is unstable and easily deteriorates with time, and it is necessary to frequently replenish the developing solution in order to maintain stable developing performance. Further, the used developer containing the developing agent needs to be discarded, and in combination with the above-mentioned frequent replenishment, the processing of the used developer discharged in large quantities is a major problem. Thus, there is a strong demand for achieving low replenishment and low discharge of the developer.

As one of effective means for solving the problem of low replenishment and low discharge of a developing solution, there is a method of incorporating an aromatic primary amine developing agent or a precursor thereof into a hydrophilic colloid layer. Examples of suitable developing agents include, for example, U.S. Patent Nos. 803,783, 3,342,597, and 3,7.
19,492, 4,060,418, British Patent 1,069,061, West German Patent 1,159,758
No., JP-B-58-14,671 and No. 58-14,67
No. 2, JP-A-57-76,543 and JP-A-59-81,6
No. 43 and the like. However, color photographic light-sensitive materials containing these aromatic primary amine developing agents or their precursors have the disadvantage that sufficient color formation cannot be obtained during color development. Another effective means is a method of incorporating a sulfonylhydrazine type developing agent in a hydrophilic colloid. Examples of the developing agent which can be incorporated include, for example, European Patent Nos. 545,491A1 and 565.
165A1 and the like. But,
Even with the developing agents mentioned here, sufficient color formation has not yet been obtained at the time of color development, and the sulfonylhydrazine type developing agent has a problem that almost no color is formed when a 2-equivalent coupler is used. Compared with 4-equivalent couplers, 2-equivalent couplers have advantages such as reduction of coupler-derived stains and easy control of coupler activity. Accordingly, there has been a strong demand for a developing agent capable of obtaining a sufficient color at the time of development even when the coupler is incorporated, and capable of obtaining an image having good color development even when a 2-equivalent coupler is used.

[0005]

The object of the present invention is to provide an image which, when a novel color-developing agent is used, provides sufficient color development during development and has a good color-forming property even when a 2-equivalent coupler is used. And a silver halide photographic light-sensitive material using the same and a method for forming an image. Another object of the present invention is to provide a color developing agent having improved processing temperature dependency (in particular, development temperature dependency) and an image forming method using the same.

[0006]

The object of the present invention has been attained by the following constitutions. (1) A color developing agent represented by the general formula (I).

[0007]

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In the formula, Z represents a carbamoyl group, an acyl group, a sulfonyl group, a sulfamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amidino group, an imidoyl group or a phosphoryl group. Q represents an atomic group that forms an unsaturated ring with C. Y ¹ and Y ² each represent a group having a dissociative group having a pKa of 1 or more and 12 or less, n and m each represent an integer of 0 to 3, and
n + m ≧ 1. When n and m are 2 or more, Y ¹ and Y
² may be the same or different. (2) In the general formula (I), Z is a carbamoyl group, and Y ¹ and Y ² have a pKa of 3 or more and 12 or less;
HSO ₂ -group, phenolic hydroxyl group, -CONHCO-
Group, —CONHSO ₂ — group or —SO ₂ NHSO ₂ —
A color developing agent which is a group having a dissociative group selected from the group. (3) The image-exposed silver halide photographic light-sensitive material in the presence of a color developing agent represented by the general formula (I) (for example, the main agent may be contained in the light-sensitive material, or in the processing solution). It may be contained), and an image forming method characterized by developing. (4) A silver halide photographic light-sensitive material characterized by containing at least one color developing agent represented by formula (I) in at least one hydrophilic colloid layer provided on a support. . (5) Diffusion transfer type silver halide containing at least one color developing agent represented by the general formula (I) in at least one hydrophilic colloid layer provided on a support. Color photographic light-sensitive material. (6) An image forming method, which comprises thermally developing the silver halide photographic light-sensitive material described in (4) or (5). (7) An image forming method, which comprises treating a silver halide light-sensitive material with an alkaline solution containing a color developing agent represented by the general formula (I).

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The compound represented by formula (I) used in the present invention will be described below in detail. The groups represented by Y ¹ and Y ² each have a pKa of 1 or more, 12
It is a group having the following dissociative groups. The value of pKa as used herein represents an acid dissociation constant when the compound represented by the general formula (I) is dissolved in tetrahydrofuran (THF) / water = 6/4 at room temperature. PKa of the group represented by Y ¹ and Y ²
Is more preferably 3 or more and 12 or less, and most preferably 5 or more and 11 or less. Preferred examples of Y ¹ and Y ² are —NHSO ₂ — group, phenolic hydroxyl group, —CONHCO— group, —CONHSO ₂ — group, and —C.
ON (R) -OH, -COOH or -SO ₂ NHSO
₂ - Although groups containing group include, -NHSO ₂ - group, a phenolic hydroxyl group, -CONHCO- group, -CONHS
O ₂ - group or a -SO ₂ NHSO ₂ - group are more preferable. R represents a hydrogen atom or a substituent. R is preferably an alkyl group, an aryl group, or a heterocyclic group. n and m each represent an integer from 0 to 3, and n + m ≧ 1. n is preferably 0, 1 or 2, and more preferably 1 or 2. m is preferably 0, 1 or 2. Preferably, n + m = 1 to 3. When n and m are 2 or more, Y ¹ and Y ² may be the same or different. The following are preferred examples of the method of substituting Y ¹ and Y ² for Z or Q. Alkyl group, alkenyl group, alkynyl group, aryl group, acyloxy group, carbamoyloxy group, carbonamido group, sulfonamide group, carbamoyl group, sulfamoyl group, alkoxy group, aryloxy group, aryloxycarbonyl group, alkoxycarbonyl group,
N-acyl sulfamoyl group, alkylsulfonyl group,
Arylsulfonyl group, alkoxycarbonylamino group, aryloxycarbonylamino group, amino group, alkylsulfinyl group, arylsulfinyl group, alkylthio group, arylthio group, ureido group, heterocyclic group, acyl group, sulfamoylamino group, silyl group .

In the general formula (I), Z represents a carbamoyl group, an acyl group, a sulfonyl group, a sulfamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amidino group or an imidoyl group. In the present invention, carbamoyl group is most preferable as Z in the general formula (I). The preferred carbamoyl group has 1 to 1 carbon atoms.
50 carbamoyl groups, more preferably 1 to 40 carbon atoms. Specifically, as a carbamoyl group,
CONHR ₁₁ is preferable, and R ₁₁ is preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an amide group, or an imide group, and more preferably an alkyl group, an aryl group, or a heterocyclic group. Specific examples include a carbamoyl group, a methylcarbamoyl group, an ethylcarbamoyl group, an isopropylcarbamoyl group, a cyclohexylcarbamoyl group, a t-octylcarbamoyl group,
Cyclopropylcarbamoyl group, dodecyloxycarbonylmethylcarbamoyl group, 3-dodecyloxypropylcarbamoyl group, 3- (3,5-tetradecyloxyphenoxy) propylcarbamoyl group, 3- (2,4-
t-pentylphenoxy) propylcarbamoyl group,
(2-chloro-5-hexadecyloxycarbonylphenyl) carbamoyl group, 4-octadecyloxyphenylcarbamoyl group, 2,4-dimethoxyphenylcarbamoyl group, 2,5-dichloro-4-dioctylsulfamoylphenylcarbamoyl group, dioctyl Examples thereof include a carbamoyl 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, 2-methylpropanoyl, cyclohexylcarbonyl, n-octanoyl, 2-hexyldecanoyl, dodecanoyl, chloroacetyl, trifluoroacetyl, benzoyl, 4- Dodecyloxybenzoyl group, 2-hydroxymethylbenzoyl group, 3- (N-hydroxy-N
-Methylaminocarbonyl) propanoyl group. The sulfonyl group is preferably a sulfonyl group having 1 to 50 carbon atoms, and more preferably 1 to 40 carbon atoms. Specific examples include methanesulfonyl group, ethanesulfonyl group, phenylsulfonyl group, 2-naphthalenesulfonyl group, 2-methoxy-5-t-octylphenylsulfonyl group, 4-dodecylsulfonyl group, 4-hexadecyloxyphenylsulfonyl group. Group, 2- (2-ethoxyethoxy) -5-hexadecylsulfonamidophenylsulfonyl group, n-dodecylsulfonyl group and the like.

The sulfamoyl group has 0 to 50 carbon atoms.
Is preferred, and more preferably has 0 to 40 carbon atoms. Specific examples include sulfamoyl, methylsulfamoyl, isopropylsulfamoyl, phenylsulfamoyl, dioctylsulfamoyl, (2-chloro-5- (2- (2,4-di-
t-Amylphenoxy) butyryl) aminophenyl) sulfamoyl group, 3-methanesulfonylaminophenylsulfamoyl group and the like. The alkoxycarbonyl group and the aryloxycarbonyl group each have 2 carbon atoms.
~ 50 alkoxycarbonyl groups and aryloxycarbonyl groups are preferred, more preferably 2 to 40 carbon atoms.
It is. Specific examples include a methoxycarbonyl group,
Ethoxycarbonyl group, isobutyloxycarbonyl group, cyclohexyloxycarbonyl group, dodecyloxycarbonyl group, benzyloxycarbonyl group, phenoxycarbonyl group, 4-octyloxyphenoxycarbonyl group, 2-hydroxymethylphenoxycarbonyl group, 2-dodecyloxyphenoxycarbonyl And the like.

The amidino group is preferably an amidino group having 1 to 50 carbon atoms, more preferably 1 to 40 carbon atoms. Specific examples include amidino group, 1-methylamidino group, 1,1-dibutylamidino group, 1-phenylamidino group, 1,3-diisoamylamidino group, 1,3-
And a dicyclohexylamidino group. The imidoyl group is preferably an imidoyl group having 1 to 50 carbon atoms, more preferably 1 to 40 carbon atoms. Specific examples include a methylimidoyl group, a phenylimidoyl group, an N-acetyldodecyloxyimidoyl group, an N-phenylsulfonylnonylimidoyl group, and a hexadecyloxyimidoyl group.

Q represents an atomic group forming an unsaturated ring together with C, and the unsaturated ring formed by Q and C is an aromatic hydrocarbon ring represented by a benzene ring, a naphthalene ring, or pyridine. A ring, a pyrimidine ring, a thiazole ring, an imidazole ring, a triazole ring, an azaindene ring, a thiophene ring, or an unsaturated heterocycle represented by a condensed ring type thereof is preferable. More specifically, in the case of an aromatic hydrocarbon ring such as a benzene ring and a naphthalene ring, at least one or more, preferably 2 to 4, more preferably 2 to
It is preferable that the substituent is substituted by three electron-withdrawing groups, and that the sum of Hammett's sigma constant σp values of the substituent bonded to this ring is 0.8 or more and 3.5 or less, Most preferably, the sum is 1.2 or more and 3.0 or less.

In the case of unsaturated heterocycle, various heterocycles are applicable. Examples of this ring include azines (pyridine ring, pyrimidine ring, pyrazine ring, triazine ring, etc.) and azoles (pyrrole ring, imidazole ring,
Pyrazole ring, triazole ring, tetrazole ring, oxazole ring, oxadiazole ring, thiazole ring, isothiazole ring, thiadiazole ring, etc.), thiophene ring, furan ring, pyran ring and the like are preferable. Other preferred examples include rings of the type in which the unsaturated rings exemplified above are fused. Examples thereof include an azanaphthalene ring (quinazoline ring, quinoxaline ring, quinoline ring, etc.) and an azaindene ring (indazole, benzimidazole, 1,3,3a, 7-tetrazaindene,
2,3,3a, 7-pentaazaindene), benzothiazole ring, benzoxazole ring, benzoisothiazole ring and the like. In these heterocycles, those in which at least one, preferably 1 to 3 electron-withdrawing groups are substituted are preferred. Here, the electron-withdrawing group is a Hammett's substituent constant having a positive value.

The groups represented by Z and Q may further have a substituent, and examples of the substituent include linear or branched, chain or cyclic alkyl groups having 1 to 40 carbon atoms. Groups (eg trifluoromethyl, methyl, ethyl,
Propyl, heptafluoropropyl, isopropyl, butyl, t-butyl, t-pentyl, cyclopentyl, cyclohexyl, octyl, 2-ethylhexyl, dodecyl, etc.), linear or branched, chain or cyclic alkenyl group having 2 to 40 carbon atoms (For example, vinyl, 1-methylvinyl, cyclohexen-1-yl, etc.), having 2 to 40 carbon atoms in total.
(E.g., ethynyl, 1-propynyl, etc.), an aryl group having 6 to 40 carbon atoms (e.g., phenyl, naphthyl, anthryl, etc.), and an acyloxy group having 1 to 40 carbon atoms (e.g., acetoxy, tetradecanoyloxy) , Benzoyloxy, etc.), a carbamoyloxy group having 1 to 40 carbon atoms (eg, N, N-dimethylcarbamoyloxy), a carbonamide group having 1 to 40 carbon atoms (eg, formamide, N-methylacetamide, acetamide, N -Methylformamide, benzamide, etc.),
C1-C40 sulfonamide groups (e.g., methanesulfonamide, dodecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, etc.) and C1-C40 carbamoyl groups (e.g., N-methylcarbamoyl, N, N-diethylcarbamoyl, N-mesylcarbamoyl and the like, a sulfamoyl group having 0 to 40 carbon atoms (for example, N-butylsulfamoyl, N, N-diethylsulfamoyl, N-methyl-N- (4-methoxyphenyl) ) Sulfamoyl and the like, alkoxy groups having 1 to 40 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 40 carbon atoms (for example, phenoxy, 4 Methoxyphenoxy, naphthoxy, etc.), an aryloxycarbonyl group having 7 to 40 carbon atoms (eg, phenoxycarbonyl, naphthoxycarbonyl, etc.), and an alkoxycarbonyl group having 2 to 40 carbon atoms (eg, methoxycarbonyl, t-butoxycarbonyl, etc.) An N-acylsulfamoyl group having 1 to 40 carbon atoms (for example, N-tetradecanoylsulfamoyl, N-
Benzoylsulfamoyl, etc.), an alkylsulfonyl group having 1 to 40 carbon atoms (eg, methanesulfonyl, octylsulfonyl, 2-methoxyethylsulfonyl, 2-hexyldecylsulfonyl, etc.), and an arylsulfonyl group having 6 to 40 carbon atoms (eg, Benzenesulfonyl, p-toluenesulfonyl, 4-phenylsulfonylphenylsulfonyl, etc.), an alkoxycarbonylamino group having 2 to 40 carbon atoms (eg, ethoxycarbonylamino), an aryloxycarbonylamino group having 7 to 40 carbon atoms (eg, Phenoxycarbonylamino, naphthoxycarbonylamino, etc.), an amino group having 0 to 40 carbon atoms (eg, amino, methylamino, diethylamino, diisopropylamino, anilino, morpholino, etc.), cyano group, nitro group, carboxyl A hydroxy group, a sulfo group, a mercapto group, an alkylsulfinyl group having 1 to 40 carbon atoms (eg, methanesulfinyl, octanesulfinyl and the like), an arylsulfinyl group having 6 to 40 carbon atoms (eg, benzenesulfinyl, 4-chlorophenylsulfinyl, p-toluenesulfinyl, etc.), having 1 to 4 carbon atoms
0 alkylthio groups (eg, methylthio, octylthio, cyclohexylthio, etc.), arylthio groups having 6 to 40 carbon atoms (eg, phenylthio, naphthylthio, etc.),
A ureido group having 1 to 40 carbon atoms (for example, 3-methylureide, 3,3-dimethylureide, 1,3-diphenylureide and the like), a heterocyclic group having 2 to 40 carbon atoms (for example, nitrogen, A 3- to 12-membered monocyclic or condensed ring containing at least one or more oxygen and sulfur atoms, for example, 2-furyl, 2-pyranyl, 2-pyridyl, 2-thienyl, 2-imidazolyl, morpholino,
-Quinolyl, 2-benzimidazolyl, 2-benzothiazolyl, 2-benzoxazolyl, etc.), having 1 to 40 carbon atoms
(E.g., acetyl, benzoyl, trifluoroacetyl, etc.), and a sulfamoylamino group having 0 to 40 carbon atoms (e.g., N-butylsulfamoylamino, N
-Phenylsulfamoylamino, etc.), having 3 to 40 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 total carbon number of the compound represented by the general formula (I) is preferably 1 or more and 80 or less, and more preferably 2 or more and 6 or less.
0 or less, and most preferably 3 or more and 50 or less.
The Hammett's substituent constants σp and σm are described, for example, by Naoki Inamoto, “Hammet Rule—Structure and Reactivity—” (Maruzen), “New Experimental Chemistry Lecture 14, Synthesis and Reaction of Organic Compounds V”, page 2605 (Japan). Chemical Society, Maruzen), Tadao Nakaya, "Explanation on Theoretical Organic Chemistry", 217 pages (Tokyo Kagaku Dojin), Chemical Review (91), 165-195 (199)
(1 year). Next, the novel color developing agents used in the present invention are shown as a single body, but the scope of the present invention is not limited to these specific examples.

[0018]

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[0019]

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[0020]

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[0021]

[Chemical 6]

[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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The compound used in the present invention is generally a hydrazine (aryl hydrazine or heterocyclic hydrazine) having a ring portion formed by C and Q and an acid halide, acid anhydride or isocyanate of the acid moiety represented by Z. It can be easily synthesized by reacting an acid ester or the like. A typical synthesis example is shown below. Other compounds can be synthesized in the same manner as in this example. Synthesis Example 1 Synthesis of Exemplified Compound (3) It was synthesized by the following route.

[0032]

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Synthesis of Compound (A-2) 1,2-Dichloro-4,5-dicyanobenzene (A-
1) 53.1 g of (CAS Registry No.139152-08-2) was dissolved in 1.1 l of N, N-dimethylformamide (DMF), and a methyl mercaptan sodium salt aqueous solution (15
%) At room temperature over 1 hour.
The mixture was stirred at 60 ° C. for 1 hour. Cool the reaction to room temperature,
Poured into water and stirred for 30 minutes. The resulting white solid was collected by filtration, washed with water, and dried. Synthesis of Compound (A-3) 41.1 g of the compound (A-2) was suspended in 400 ml of acetic acid, and 89.3 g of potassium permanganate dissolved in 400 ml of water was added dropwise under water cooling over 1 hour. . After standing at room temperature overnight, 2 l of water and 2 l of ethyl acetate were added, and the mixture was filtered through celite. The filtrate was separated, and the organic layer was washed with water, an aqueous solution of sodium hydrosulfite, an aqueous solution of sodium bicarbonate and brine, and then dried over anhydrous magnesium sulfate. After filtration, the solvent was distilled off, and a mixed solvent of ethyl acetate and hexane was added to the residue for crystallization to obtain 29.4 g of compound (A-3) as a white solid.

Synthesis of compound (A-4) 29.4 g of compound (A-3) was dissolved in 200 ml of dimethyl sulfoxide (DMSO), and 8.7 g of hydrazine monohydrate was added dropwise over 15 minutes under water cooling. The mixture was stirred under water cooling for 10 minutes. The reaction solution was poured into water, and the generated yellow solid was collected by filtration, washed with water, and dried. Synthesis of compound (A-6) 27.8 g of m-nitrophenol, 53.6 g of N-3-bromopropylphthalimide, potassium carbonate 33.6.
g, 400 ml of dimethylformamide are mixed, and the temperature is 80 ° C.
For 4 hours. After the reaction was completed, it was poured into hydrochloric acid water, and the precipitated crystals of the target substance were collected by filtration and dried.

Synthesis of compound (A-7) 32.6 g of compound (A-6) was dissolved in ethyl acetate and hydrogenated directly in an autoclave using palladium / carbon as a catalyst. After completion of the reaction, the catalyst was filtered off and the filtrate was concentrated to obtain compound (A-7). Synthesis of compound (A-8) 23.7 g of compound (A-7) was dissolved in dimethylacetamide to prepare paramethoxybenzenesulfonyl chloride 1
7.4 g was added. Under water cooling, 15 ml of 2-picoline was added and reacted for 2 hours. After the reaction was completed, dilute hydrochloric acid was added to make the mixture acidic, and water was further added to precipitate crystals. The precipitated target crystal was collected by filtration and dried. Synthesis of compound (A-9) 20 g of compound (A-8) was suspended in ethanol, 10 g of hydrazine hydrate was added, and the mixture was heated under reflux for 4 hours. After cooling,
The precipitated crystals were filtered off and the filtrate was concentrated to give the compound (A-
The crude product of 9) was obtained. The crude product was produced by column chromatography using alumina gel to obtain the desired product having a purity that can be used in the next step.

Synthesis of Exemplified Compound (3). 15.2 g of the compound (A-9) and 220 m of acetonitrile
It was dissolved in 1 and 5.0 g of triphosgene was added under ice cooling. Furthermore, 11 ml of triethylamine was added dropwise to 30
Stirred for minutes. Compound (A-4) 11.8 was added to the reaction solution.
g was added, and the mixture was reacted under ice cooling for 1 hour and at room temperature for 1 hour.
After the reaction solution was poured into water to stop the reaction, ethyl acetate was added for extraction. The organic phase was dried over anhydrous magnesium sulfate, concentrated, and purified by silica gel column chromatography to obtain exemplary compound (3). Synthesis of Exemplified Compound (21) Exemplified Compound (21) was synthesized by the following route.

[0037]

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Synthesis of Compound (B-2) 190 g of m-nitrophenylhydrazine hydrochloride, 133 g of ethyl acetoacetate and 2.0 l of ethanol were mixed, and 8
Heated to reflux for an hour. After cooling, the precipitated crystals of the target substance were collected by filtration. Synthesis of Compound (B-3) 50 g of Compound (B-2) and 350 g of phosphorus oxychloride were mixed and reacted at 90 ° C. for 40 hours. The reaction mixture was cooled and then poured into ice water. The precipitated crystals of the target substance were collected by filtration, washed well with water and then dried. Synthesis of Compound (B-4) 200.0 g of methanesulfonic acid was heated to 70 ° C., and 119 g of thionyl chloride was slowly added dropwise. After dropping,
After reacting at 80 ° C. for 1 hour, the reaction solution was cooled to room temperature. Compound (B-3) (59 g) was added to the reaction solution, and trifluoromethanesulfonic acid (20 g) was added.
The reaction was carried out at 2 ° C. for 2 hours and 110 ° C. for 4 hours. The reaction mixture was cooled, poured into ice water, stirred for 1 hour, and extracted with ethyl acetate. The organic layer was concentrated and then purified by silica gel column chromatography to obtain the desired product (B-4).

Synthesis of compound (B-6) 15.8 g of compound (B-4) and 21 g of compound (B-5)
Dissolved in 300 ml of dimethylacetamide and heated at 110 ° C.
For 3 hours. After cooling, water and ethyl acetate were added, the desired product was extracted, washed with hydrochloric acid water, and then purified using silica gel column chromatography to obtain (B-6). Synthesis of Exemplified Compound (21) 12.6 g of Compound (B-6) was dissolved in ethyl acetate and hydrogenated directly in an autoclave using palladium / carbon as a catalyst. After completion of the reaction, the catalyst was filtered off, ice water was added to the ethyl acetate solution, and further 10 g of sodium hydrogencarbonate was added.
Was added, 4.6 g of methanesulfonyl chloride was added, and the mixture was reacted for 8 hours. After completion of the reaction, the organic phase was concentrated and purified by silica gel column chromatography to obtain exemplary compound (21).

The color developing agent of the present invention is used together with a compound (coupler) which forms a dye by an oxidative coupling reaction. This coupler is called "2 equivalent coupler", which is called in the system using the conventionally used para-phenylenediamine-based developing agent.
Although it may be an "equivalent coupler", in the present invention, when Z is other than a sulfonyl group, a "2-equivalent coupler" is preferable. Specific examples of couplers are described in Theory of the Photographic Process (4th. Ed., THJ
ames editing, Macmillan, 1977) 291
Pp. 334 to 354 and 354 to 361, JP-A-58
-12353, 58-149046, 58-1
No. 49047, No. 59-11114, No. 59-124
No. 399, No. 59-174835, No. 59-2315
No. 39, No. 59-231540, No. 60-2951
Nos. 60-14242, 60-23474 and 60-66249. Examples of the coupler preferably used in the present invention are listed below. The couplers preferably used in the present invention include compounds having the structures represented by the following general formulas (1) to (12). These are compounds generally referred to as active methylene, pyrazolone, pyrazoloazole, phenol, naphthol, and pyrrolotriazole, respectively, and are compounds known in the art.

[0041]

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[0042]

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[0043]

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The general formulas (1) to (4) represent couplers called active methylene couplers, in which R ¹⁴ is an optionally substituted acyl group, cyano group, nitro group, aryl group, A heterocyclic residue, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, and an arylsulfonyl group. In the general formulas (1) to (3), R ¹⁵ is an alkyl group, an aryl group or a heterocyclic residue which may have a substituent. In the general formula (4), R ¹⁶ is an aryl group which may have a substituent or a heterocyclic residue. R ¹⁴ , R1
5 and R ¹⁶ may have the above-mentioned Z, Q
Examples of the substituents described above can be given.

In the general formulas (1) to (4), G is a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidized product of a developing agent. Examples of G are a heterocyclic group (a hetero atom containing at least one of nitrogen, oxygen, sulfur, etc., and a saturated or unsaturated 5- to 7-membered monocyclic ring or condensed ring, examples of which include succinimide and malein. Imide, phthalimide, diglycolimide, pyrrole, pyrazole, imidazole, 1,2,4-triazole, tetrazole, indole, benzopyrazole,
Benzimidazole, benzotriazole, imidazoline-2,4-dione, oxazolidine-2,4-dione, thiazolidine-2,4-dione, imidazolidin-
2-one, oxazolin-2-one, thiazoline-2-
ON, 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-thiazolidine-4-one and the like), a halogen atom (for example, a chlorine atom,
A bromine atom, an aryloxy group (e.g., phenoxy, 1-naphthoxy, etc.), a heterocyclic oxy group (e.g.,
Pyridyloxy, pyrazolyloxy etc.), acyloxy group (eg acetoxy, benzoyloxy etc.), alkoxy group (eg methoxy, dodecyloxy etc.), carbamoyloxy group (eg N, N-diethylcarbamoyloxy, morpholinocarbonyloxy etc.) , An aryloxycarbonyloxy group (eg, phenoxycarbonyloxy), an alkoxycarbonyloxy group (eg, methoxycarbonyloxy, ethoxycarbonyloxy, etc.), an arylthio group (eg, phenylthio, naphthylthio, etc.), a heterocyclic thio group (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 group (eg, benzenesulfonyl) Oxy, toluenesulfonyloxy etc.), carbonamide group (eg acetamide, trifluoroacetamide etc.), sulfonamide group (eg methanesulfonamide, benzenesulfonamide etc.), alkylsulfonyl group (eg methanesulfonyl etc.), Arylsulfonyl group (eg, benzenesulfonyl etc.), alkylsulfinyl group (eg, methanesulfinyl etc.), arylsulfinyl group (eg, benzenesulfinyl etc.), arylazo group (eg. If, phenylazo, naphthylazo etc.), carbamoylamino group (e.g., N- methylcarbamoyl amino, etc.) and the like.

G may be substituted with a substituent,
Examples of the substituent for substituting G include the examples shown as the substituents for Z and Q. G 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. Formula (5) represents a coupler called a 5-pyrazolone-based coupler, and in the formula, 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 with one or more halogen atoms, alkyl groups, cyano groups, alkoxy groups, alkoxycarbonyl groups, or acylamino groups.

Among the 5-pyrazolone-based couplers represented by the general formula (5), R ¹⁷ is an aryl group or an acyl group, and R is
A phenyl group in which ¹⁸ is substituted with one or more halogen atoms is preferred. To describe these preferred groups in detail, R ¹⁷ is a phenyl group, a 2-chlorophenyl group, a 2-
Methoxyphenyl group, 2-chloro-5-tetradecanamidophenyl group, 2-chloro-5- (3-octadecenyl-1-succinimido) phenyl group, 2-chloro-5
An aryl group such as -octadecylsulfonamidophenyl group or 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-
(2,4-di-t-amylphenoxyacetamido) benzoyl group and like acyl groups, which may further have a substituent, which may be a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom. It is an organic substituent or a halogen atom to be linked. G has the same meaning as described above.

R ¹⁸ is preferably a substituted phenyl group such as a 2,4,6-trichlorophenyl group, a 2,5-dichlorophenyl group and a 2-chlorophenyl group. The general formula (6) represents a coupler called a pyrazoloazole coupler, wherein R ¹⁹ represents a hydrogen atom or a substituent. Q3 represents a group of non-metal atoms necessary for forming a 5-membered azole ring containing 2 to 4 nitrogen atoms, and the azole ring may have a substituent (including a condensed ring). Among the pyrazoloazole couplers represented by the general formula (6), imidazo [1,2-b] pyrazoles described in U.S. Pat. U.S. Patent No. 4,
Pyrazolo [1,5-b]-described in No. 500,654
1,2,4-triazoles, U.S. Pat. No. 3,725,25
No. 067, pyrazolo [5,1-c] -1,2,4
-Triazoles are preferred. 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. 4,540,654, column 2, line 41 to column 8, line 27. Has been done. Preferably, a pyrazoloazole coupler in which a branched alkyl group is directly linked to the 2-, 3- or 6-position of the pyrazolotriazole group as described in JP-A-61-65245;
Pyrazoloazole couplers containing a sulfonamide group in the molecule described in JP-A 1-65245;
Pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group described in JP-A-147254, JP-A-62-209457 or 63-3.
Pyrazolotriazole couplers having an alkoxy group or an aryloxy group at the 6-position described in No. 07453,
And a pyrazolotriazole coupler having a carbonamide group in the molecule described in Japanese Patent Application No. 1-222279. G has the same meaning as described above.

The general formulas (7) and (8) are couplers called a phenol coupler and a naphthol coupler, respectively, wherein R ²⁰ is a hydrogen atom or —CONR ²² R
_{^{23, -SO 2 NR 22 R 23}} , -NHCOR 22, -NHCO
NR ²² R ^23, represents a group selected from -NHSO ₂ NR ²² R ^23. R ²² and R ²³ represent a hydrogen atom or a substituent. In the general formulas (7) and (8), R ²¹ represents a substituent, 1 represents an integer selected from 0 to 2, and m represents an integer selected from 0 to 4. When l and m are 2 or more, R ²¹ may be different from each other. Examples of the substituents of R ^{21 to} R ²³ include the examples shown as the substituents of Z and Q. Regarding G, it has the same meaning as described above. Preferable examples of the phenol-based coupler represented by the general formula (7) include US Pat. Nos. 2,369,929 and 2,801,171.
No. 2,772,162, No. 2,895,82
2-acylamino-5-alkylphenols described in US Pat. No. 6,7,002, US Pat.
No. 72,162, No. 3,758,308, No. 4,
126,396, 4,334,011, 4,327,173, West German Patent Publication 3,329,7.
29, 2, 5 described in JP-A-59-166956 and the like.
-Diacylaminophenol system, U.S. Pat. No. 3,44
No. 6,622, No. 4,333,999, No. 4,4
The 2-phenylureido-5-acylaminophenol system described in Nos. 51,559 and 4,427,767 can be mentioned. G 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. G 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. G is as described above. Examples of the substituent for R ³² , R ³³ , and R ³⁴ include the examples described above as the substituent for Z and Q. 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. G is the same as that described above.

In addition, 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 a condensed ring phenol type coupler, U.S. Pat. No. 4,327,173
No. 4,564,586 and 4,904,57
The couplers described in No. 5, etc. can be used. U.S. Pat. No. 4,818,672, as imidazole couplers,
The couplers described in JP-A-5,051,347 and the like can be used. As the 3-hydroxypyridine-based coupler, couplers described in JP-A-1-315736 and the like can be used. Active methylene and active methine couplers are described in US Pat. Nos. 5,104,783 and 5,162,196.
The couplers described in (1) and (2) can be used. 5,5-Fused heterocyclic couplers include US Pat. No. 5,164,289.
Pyrropyrazole-based couplers described in
Pyrroloimidazole couplers described in No. 74429 can be used. Examples of 5,6-fused heterocyclic couplers include pyrazolopyrimidine couplers described in U.S. Pat. No. 4,950,585, pyrrolotriazine couplers described in JP-A-4-204730, and EP 556.
The couplers described in No. 700 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 of course not limited thereto.

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[0059]

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The addition amount of the coupler used in the present invention depends on its molar absorption coefficient (ε). In the case of a coupler having a coating number of about 5000 to 500,000, the coating amount is 0.001 to 100 mmol / m.
^It is suitably about ² , preferably about 0.01 to 10 mmol / m ² , and more preferably about 0.05 to 5 mmol / m ² . The amount of the color developing agent of the present invention added to the light-sensitive material is 0.01 to 100 times, preferably 0.1 to 10 times, and more preferably 0.2 to 5 times, that of the coupler. Further, instead of being contained in the light-sensitive material, it may be contained in the processing solution for use. In this case, preferably 1
0.1 g to 100 g per liter, more preferably 1 g
-20g is contained. In the present invention, an auxiliary developing agent can be preferably used. Here, the auxiliary developing agent means a substance having an action of promoting the transfer of electrons from the color developing agent to silver halide in the development process of silver halide development, and the auxiliary developing agent in the present invention is preferably a compound of the general formula The compound is an electron-emitting compound represented by (D-1) or the general formula (D-2), which conforms to the Kendall-Peltz rule. Among them, those represented by (D-1) are particularly preferred.

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In the general formulas (D-1) and (D-2),
R ^{51 to} R ⁵⁴ represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, or a heterocyclic group. R
^{55 to} R ⁵⁹ represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group,
Heterocyclic group, alkoxy group, cycloalkyloxy group,
Aryloxy group, heterocyclic oxy group, silyloxy group, acyloxy group, amino group, anilino group, heterocyclic amino group, alkylthio group, arylthio group, heterocyclic thio group, silyl group, hydroxyl group, nitro group, alkoxycarbonyloxy group A cycloalkyloxycarbonyloxy group, an aryloxycarbonyloxy group, a carbamoyloxy group, a sulfamoyloxy group, an alkanesulfonyloxy group, an arenesulfonyloxy group,
Acyl group, alkoxycarbonyl group, cycloalkyloxycarbonyl group, aryloxycarbonyl group, carbamoyl group, carboxamide group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide group, sulfamoylamino Group, alkylsulfinyl group, arenesulfinyl group, alkanesulfonyl group, arenesulfonyl group, sulfamoyl group, sulfo group, phosphinoyl group,
Represents a phosphinoylamino group. q represents an integer of 0 to 5, and when q is 2 or more, R ⁵⁵ may be different. R ⁶⁰ represents an alkyl group or an aryl group.

The compounds represented by formula (D-1) or (D-2) are specifically shown, but the auxiliary developing agent used in the present invention is not limited to these examples.

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In the present invention, a blocked photographic reagent which releases a photographically useful group upon processing as represented by the general formula (A) can be used. 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 on the left side of L in the general formula (A). After that, the right side of L represents a linking group which is cleaved, n represents an integer of 0 to 3, and PUG represents a photographically useful group. Hereinafter, the group represented by formula (A) will be described. As the blocking group represented by A, the following known ones can be applied. In other words,
-9968, JP-A-52-8828 and 57-82.
No. 834, U.S. Pat. No. 3,311,476, and JP-B-47-44805 (U.S. Pat. No. 3,615,61).
No. 7) and the like, block groups such as acyl group and sulfonyl group, and JP-B-55-17369 (US Pat. No. 3,888,677) and JP-B-55-9696 (US Pat. No. 830), No. 55-34927 (U.S. Pat. No. 4,009,029), and JP-A-56-7.
No. 7842 (U.S. Pat. No. 4,307,175) and No. 5
No. 9-105640, JP-A-59-105641, and JP-A-59-105542, and a blocking group utilizing a reverse Michael reaction.
Nos. 3,674,478 and 3,932.
480, 3,993,661, JP-A-57-13
Nos. 5944, 57-135,945 (U.S. Pat. No. 4,420,554), 57-136640, 61-196239, and 61-196240 (U.S. Pat. No. 4,702,999). 61-185743
No. 61-124941 (U.S. Pat. No. 4,639,
No. 408) and JP-A-2-280140, etc., a block group utilizing the formation of quinone methide or a compound similar to quinone methide by intramolecular electron transfer,

US Pat. Nos. 4,358,525, 4,
No. 330,617, JP-A-55-53330 (U.S. Pat. No. 4,310,612), and JP-A-59-121328.
Nos. 59-218439 and 63-3185
No. 55 (European Patent Publication No. 0295729), a blocking group utilizing an intramolecular nucleophilic substitution reaction, and JP-A-57-76541 (U.S. Pat. No. 4,335,20).
No. 0) and No. 57-135949 (U.S. Pat.
No. 0,752), No. 57-179842, No. 59-1
Nos. 37945, 59-140445 and 59-21
No. 9741, No. 59-202059, No. 60-410
No. 34 (U.S. Pat. No. 4,618,563),
No. 59945 (U.S. Pat. No. 4,888,268) and No. 62-65039 (U.S. Pat. No. 4,772,537).
No. 62-80647, JP-A-3-236047.
Groups utilizing ring opening of a 5- or 6-membered ring described in JP-A-5-238445 and JP-A-3-238445.
No. 9-201057 (U.S. Pat. No. 4,518,685)
No. 61-95346 (U.S. Pat.
No. 885) and No. 61-95347 (U.S. Pat.
No. 92,811), JP-A-64-7035, JP-A-6-7035
4-42650 (U.S. Pat. No. 5,066,573)
No.), JP-A-1-245255 and 2-207249.
No. 2,235,055 (U.S. Pat. No. 5,118,5)
No. 96) and 4-186344 and the like, a blocking group utilizing the addition reaction of a nucleophile to a conjugated unsaturated bond,

JP-A-59-93442 and 61-32.
Nos. 839 and 62-163051 and 5-3
No. 7299 and the like, a blocking group utilizing a β-elimination reaction, a blocking group utilizing a nucleophilic substitution reaction of diarylmethanes described in JP-A-61-188540, No. 187850, a block group utilizing the Rossen rearrangement reaction.
Nos. 80646, 62-144163 and 62-
No. 147457, a block group utilizing the reaction of an N-acyl compound of thiazolidine-2-thione with an amine, JP-A-2-296240 (U.S. Pat.
No. 19,492), No. 4-177243, No. 4-17
No. 7244, No. 4-177245, No. 4-177724
No. 6, 4-177247, 4-177248,
4-177249, 4-179948, 4-
184337, 4-184338, WO92 / 21064, JP-A-4-330438, WO93 / 03419 and JP-A-5-4581.
JP-A-3-236047 and JP-A-3-238445, a blocking group having two electrophilic groups and reacting with a dinucleophile described in JP-A No. 6-360.

In the compound represented by the general formula (A), L
The group represented by may be any linking group capable of cleaving (L) n-1-PUG after being released from the group represented by A during the development processing. For example, a group utilizing cleavage of a hemiacetyl tar ring described in U.S. Pat. Nos. 4,146,396, 4,652,516 or 4,698,297;
8,962, 4,847,185 or 4,857,440, a timing group for causing an intramolecular nucleophilic substitution reaction, US Pat. No. 4,409,3.
No. 23 or 4,421,845, a timing group for causing a cleavage reaction utilizing an electron transfer reaction, and the hydrolysis reaction of an imino ketal described in US Pat. No. 4,546,073. To cause a cleavage reaction, a group to cause a cleavage reaction by utilizing a hydrolysis reaction of an ester described in West German Published Patent No. 2,626,317, or a sulfite ion described in European Patent No. 0572084. A group that causes a cleavage reaction by utilizing the reaction with

Next, the PUG in the general formula (A) will be described. PUG in the general formula (A) represents a photographically useful group such as an antifoggant or a photographic dye. In the present invention, the auxiliary development represented by the general formula (D-1) or (D-2) The main drug is particularly preferably used for PUG. When the auxiliary developing agent represented by the general formulas (D-1) and (D-2) corresponds to the PUG of the general formula (A), the bonding position is an oxygen atom or a nitrogen atom of the auxiliary developing agent. .

The light-sensitive material of the present invention basically has a photosensitive silver halide, a color developing agent, a coupler and a binder on a support and, if necessary, further contains an organometallic hydrochloric acid agent and the like. Can be made. These components are often added to the same layer, but they can be added separately in separate layers as long as they can react. Hydrophobic additives such as couplers and color developing agents used in the present invention can be incorporated into the layer of the light-sensitive material by a known method such as the method described in US Pat. No. 2,322,027. In this case, U.S. Pat. Nos. 4,555,470, 4,536,466, 4,536,467,
No. 4,587,206, No. 4,555,476
No. 4,599,296, Japanese Examined Patent Publication No. 3-62,25
A high-boiling point organic solvent as described in No. 6 and the like can be used in combination with a low-boiling point organic solvent having a boiling point of 50 to 160 ° C., if necessary. Further, two or more kinds of these dye donating compounds, diffusion resistant reducing agents, high boiling point organic solvents and the like can be used in combination. The amount of the high boiling point organic solvent is 10 g or less, preferably 5 g or less, relative to 1 g of the color image forming compound used,
More preferably, it is 1 g to 0.1 g. Also, 1 cc or less, further 0.5 cc or less, relative to 1 g of binder,
Particularly, 0.3 cc or less is suitable. In addition,
39,853, JP-A-51-59,943, the dispersion method using a polymer and JP-A-62-30,24.
No. 2, JP-A No. 63-271339, etc., and a method of adding a fine particle dispersion can also be used. In the case of a compound which is substantially unnecessary for water, fine particles can be dispersed and contained in a binder in addition to the above method. When dispersing the hydrophobic compound in the hydrophilic colloid, various surfactants can be used. For example, JP-A-5
It is possible to use those listed as the surfactants in RD magazines, which are shown in the following tables, pages (37) to (38) of 9-157,636. The light-sensitive material of the present invention includes
A compound for stabilizing an image simultaneously with activation of development can be used. Specific compounds preferably used are described in US Pat. No. 4,500,626, Nos. 51-5.
It is described in column 2.

In order to obtain a wide range of colors on the chromaticity diagram by using the three primary colors of yellow, magenta and cyan, at least three layers of silver halide emulsion layers having light sensitivity in different spectral regions are combined. To use. For example, there are combinations of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer, a green-sensitive layer, a red-sensitive layer and an infrared-sensitive layer. Each photosensitive layer can adopt various arrangement orders known for ordinary color photosensitive materials. Each of these photosensitive layers may be divided into two or more layers as necessary. The photosensitive material may be provided with various auxiliary layers such as a protective layer, an undercoat layer, an intermediate layer, an antihalation layer and a back layer. Further, various filter dyes can be added to improve color separation.

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

The silver halide emulsion of the present invention preferably has a distribution or structure with respect to the halogen composition in its grains. A typical example is JP-B-43-131.
No. 62, JP-A-61-215540 and JP-A-60-2
No. 22845, JP-A-61-75337, etc. are core-shell or double-structured grains having a different halogen composition in the inside and the surface of the grains.
Further, it is not a simple double structure, but is disclosed in JP-A-60-222844.
Or a multilayer structure having three or more layers as disclosed in the above-mentioned publication, or a silver halide having a different composition can be thinly applied on the surface of a double-structured grain in the core-shell.

In order to give a structure to the inside of the particle, not only the wrapping structure as described above but also a so-called junction structure can be produced. These examples are disclosed in
No. 133540, JP-A-58-108526, European Patent No. 199,290A2, JP-B-58-24772.
And JP-A-59-16254.
The crystal to be bonded can be formed by bonding to the edge, corner, or surface of the host crystal with a composition different from that of the host crystal. Such a junction crystal can be formed even if the host crystal is uniform in the halogen composition or has a core-shell structure. In the case of a junction structure, 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 or silver carbonate may be combined with silver halide to form a junction structure. Further, a non-silver salt compound such as lead oxide may be used as long as the bonding structure is possible.

In the case of 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. On the contrary, in some cases, grains having a low silver iodide content in the core portion and a high shell portion are preferable. Similarly, with respect to the grains having a junction structure, the grains having a high silver iodide content in the host crystal and the grains having a relatively low silver iodide content in the junction crystal may be used, or vice versa. In addition, the boundary portions having different halogen compositions of grains having these structures may be clear boundaries or unclear boundaries. In addition, a configuration in which the composition is positively and continuously changed is also a preferable embodiment. In the case of silver halide grains in which two or more silver halides exist as mixed crystals or with a structure, it is important to control the halogen composition distribution between grains. The method for measuring the halogen composition distribution between grains is described in JP-A-60-254032. Uniform halogen distribution between grains is a desirable property. In particular, a highly uniform emulsion having a coefficient of variation of 20% or less is preferable. Another preferred form is an emulsion where there is a correlation between grain size and halogen composition. As an example, there is a correlation such that the iodine content is higher for larger size particles, while the iodine content is lower for smaller size particles. Depending on the purpose, an inverse correlation or a correlation with another halogen composition can be selected. For this purpose, it is preferable to mix two or more emulsions having different compositions.

It is important to control the silver halide composition near the surface of the grain. Increasing the amount of silver iodide in the vicinity of the surface or increasing the silver chloride content can be selected according to the purpose because the adsorption of the dye and the developing speed are changed. When changing the halogen composition in the vicinity of the surface, either a structure that wraps the entire grain or a structure that adheres only to a part of the grain can be selected. For example, the halogen composition may be changed only on one side of the tetrahedral grain composed of the (100) plane and the (111) plane, or the halogen composition on one of the main plane and the side face of the tabular grain may be changed. Even if the silver halide grains used in the present invention are normal crystals that do not contain twin planes, examples such as those described on page 163, edited by The Photographic Society of Japan, Fundamentals of Photography Industry, Silver Salt Photography (Corona Publishing Co., Ltd.), for example, Select from twin twins containing one twin plane, parallel multiple twins containing two or more parallel twin planes, and non-parallel multiple twins containing two or more non-parallel twin planes. Can be used.
An example of mixing particles having different shapes is disclosed in U.S. Pat.
Although disclosed in Japanese Patent No. 865,964, this method can be selected if necessary. In case of normal crystal (100)
Cubes composed of planes, octahedrons composed of (111) planes, and dodecahedral particles composed of (110) planes disclosed in JP-B-55-42737 and JP-A-60-222842 can be used. In addition, the Journal of Imaging Scienc
e30, 247 (1986), as described in (211) (h11) plane grains,
(Hh1) plane particles represented by (331), (210)
The (hk0) plane particles typified by the plane and the (hkl) plane particles typified by the (321) plane may be selected and used according to the purpose although some adjustment methods are required. A tetrahedral grain in which the (100) plane and the (111) plane coexist in one grain,
Depending on the purpose, particles having two or many surfaces such as particles having both (100) surface and (110) surface or particles having both (111) surface and (110) surface may be selected and used according to the purpose. You can

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. Tabular grains are described in Cleav, Photography Theory and Practice.
(1930)), p. 131; Gatov, Photographic
Science and Engineering (Gutof, Photo
graphic Science and Engineering), Volume 14, 248
~ 257 (1970), U.S. Pat. No. 4,434,2
No. 26, No. 4,414, 310, No. 4,433.
It can be prepared by the method described in, for example, 048, 4,439,520 and British Patent 2,112,157. When tabular grains are used, there are advantages such as an increase in covering power and an increase in color sensitization efficiency by a sensitizing dye, and the like. U.S. Pat.
No. 6 describes this in detail. 80 of the total projected area of the grain
It is desirable that the average aspect ratio of 1% or more is 1 or more and less than 100. It is more preferably 2 or more and less than 20 and particularly preferably 3 or more and less than 10. As the shape of the average particle, a triangle, a hexagon, a circle, or the like can be selected. A regular hexagon having approximately equal six sides as described in U.S. Pat. No. 4,798,354 is a preferred form.
The equivalent circle diameter of the projected area is often used as the average particle size. However, particles having an average diameter of 0.6 μm or less as described in US Pat. preferable. Also preferred are emulsions having a narrow grain size distribution as described in U.S. Pat. No. 4,775,617. It is preferable to limit the grain thickness of the tabular grains to 0.5 μm or less, more preferably 0.3 μm or less, in order to increase sharpness. Further, an emulsion having a highly uniform thickness having a variation coefficient of grain thickness of 30% or less is also preferable. Further, JP-A-63-163
No. 451 is also preferable, in which the thickness of the grains and the distance between twin planes are specified.

In the case of tabular grains, dislocation lines can be observed with a transmission electron microscope. It is preferable to select a particle containing no dislocation line, a particle containing several dislocations, or a particle containing many dislocations according to the purpose. Also, it is possible to select dislocations introduced linearly or distorted dislocations in a specific direction of the crystal orientation of the grains, to introduce them throughout the grains, or to introduce them only to a specific portion of the grains, For example, dislocations can be introduced only in the fringe portion of the particles. Introduction of dislocation lines is preferable not only in the case of tabular grains, but also in the case of irregular grains typified by normal crystal grains or potato grains. Also in this case, it is a preferable embodiment to limit to a specific portion such as a vertex or a ridge of the particle. The silver halide emulsion used in the present invention is a treatment for rounding grains as disclosed in European Patent No. 96,412B1 or the like, or West German Patent No. 2,306,447C2, JP-A-60-.
The surface may be modified as disclosed in 221320.

A structure having a flat particle surface is generally used.
It is sometimes preferable to intentionally form irregularities. JP-A-58-106532, JP-A-60-221
For example, a method of making a hole in a part of a crystal described in No. 320, for example, a vertex or a center of a plane, or a raffle particle described in US Pat. No. 4,643,966. The grain size of the emulsion used in the present invention can be evaluated by the equivalent circle diameter of the projected area using an electron microscope, the equivalent sphere diameter of the particle volume calculated from the projected area and the grain thickness, or the equivalent sphere diameter of the volume by the Coulter counter method. Ultrafine particles having a sphere equivalent diameter of 0.05 μm or less and coarse particles exceeding 10 μm can be selected and used. Preferably, grains having a size of 0.1 to 3 microns are used as photosensitive silver halide grains.

The emulsion used in the present invention may be a 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. In some cases, the coefficient of variation of the projected area circle equivalent diameter or sphere equivalent diameter of a particle is used as a scale representing the size distribution. When a monodisperse emulsion is used, it is preferable to use an emulsion having a size distribution with a coefficient of variation of 25% or less, more preferably 20% or less, and still more preferably 15% or less. The monodisperse emulsion may be defined as the average grain size distribution in terms of grain number or weight.
In order to satisfy the target gradation of the light-sensitive material, two or more monodispersed silver halide emulsions having different grain sizes are mixed in the same layer or different layers in an emulsion layer having substantially the same color sensitivity. Can be applied in layers. 2 more
It is also possible to use a mixture of more than one kind of polydisperse silver halide emulsion or a combination of monodisperse emulsion and polydisperse emulsion or to form a multilayer.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Graphide, published by Paul Monte (P.Glaf).
kides, Chemie et Phisique Photographique, Paul Mon
Tel, 1967), "Photographic Emulsion 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 (VLZeli
kman, et al., Making and Coating Photographic Emul
Any of the silver halide emulsions prepared by the method described in Sion, Focal Press, 1964) can be used. That is, any of an acidic method, a neutral method, an ammonia method, and the like may be used, and a method of reacting a soluble silver salt and a soluble halide may be any of a one-sided mixing method, a simultaneous mixing method, a combination thereof, and the like. . A method of forming grains in the presence of excess silver ions (a so-called reverse mixing method) can also be used. As one type of the double jet method, a method in which pAg in a liquid phase in which silver halide is formed is kept constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained. In some cases, a method of adding silver halide grains preliminarily formed in a reaction vessel for emulsion preparation, U.S. Pat. preferable. 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.

Most of the halogen composition of silver halide grains is converted by a halogen conversion method, and a method of converting the halogen composition is described in US Pat. Nos. 3,477,852 and 4,142.
No. 900, European Patent Nos. 273,429 and 273,
No. 430 and West German Patent No. 3,819,241, which are effective particle forming methods. A solution of a soluble halogen or silver halide grains can be added to convert the silver salt into a sparingly soluble silver salt. It can be selected from methods such as converting at once, converting into a plurality of times, or converting continuously. In addition to the method of adding soluble silver salt and halogen salt at a constant concentration and a constant flow rate for grain growth, British Patent No. 1,469,480, US Pat. Nos. 3,650,757, and 4,242,445. The particle formation method in which the concentration is changed or the flow rate is changed as described in (4) is a preferable method. By changing the concentration or increasing the flow rate, the amount of silver halide to be supplied can be changed by a linear function, a quadratic function, or a more complicated function of the addition time. It is also preferable in some cases to reduce the amount of silver halide supplied 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.
No. 3,342,605 and No. 3,415,65
No. 0, No. 3,785,777, West German Patent No. 2,
556,885 and 2,555,364. Silver halide solvents are useful for the purpose of accelerating ripening. For example, it is known to have excess halide ions present in the reactor to promote ripening. Other ripening agents can also be used. The total amount of these ripening agents can be blended in the dispersion medium in the reactor before adding the silver and halide salts, and the halide salt, silver salt or peptizer can be added in the reactor as well. Can also be introduced. As another variant, the ripening agent can be introduced independently during the halide salt and silver salt addition steps.

Ammonia, thiocyanate (Rhodan potassium, Rhodan ammonium, etc.), organic thioether compound (for example, US Pat. Nos. 3,574,628 and 3,3).
Nos. 021, 215, 3,057,724, 3,038,805, 4,276,374, 4,297,439, 3,704,130,
No. 4,782,013, JP-A-57-104926
Compounds and thione compounds (for example, tetrasubstituted thioureas described in JP-A Nos. 53-82408 and 55-77737, U.S. Pat. No. 4,221,863, and JP-A-53- No. 144319), mercapto compounds and amine compounds described in JP-A-57-202531, which can promote the growth of silver halide grains (for example, JP-A-54-1007).
No. 17, etc.).

As the protective colloid used in the preparation of the emulsion of the present invention and as the binder of the other hydrophilic colloid layers, it is advantageous to use gelatin, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxycellulose, carboxymethylcellulose, cellulose sulfate, sodium alginate, starch derivatives, gum arabic, dextran, Sugar derivatives such as natural compounds such as pullulan and other polysaccharides; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Alternatively, various synthetic hydrophilic polymer substances such as copolymers can be used. Also, U.S. Pat. No. 4,960,6
81 No., superabsorbent polymers described in JP-A-62-245,260, etc., i.e. -COOM or -SO ₃ M
A copolymer with a vinyl monomer having (M is a hydrogen atom or an alkali metal) or these vinyl monomers,
Alternatively, a copolymer with another vinyl monomer (for example, sodium methacrylate, ammonium methacrylate, Sumika Gel L-5H manufactured by Sumitomo Chemical Co., Ltd.) is also used. These binders can be used in combination of two or more kinds. Combinations of gelatin and the above binders are also preferred.

Examples of gelatin include lime-processed gelatin,
It suffices to select from so-called demineralized gelatin with a reduced content of acid-processed gelatin and calcium, and it is also preferable to use them in combination. Bull.Soc.Sci.Photo.Japan.N
The enzyme-treated gelatin as described in o.16.p30 (1966) may be used, and a hydrolyzate or an enzymatic hydrolyzate of gelatin may also be used. Use of low molecular weight gelatin described in JP-A-1-158426 is preferred for preparing tabular grains.

In the case of a heat-developable light-sensitive material, an organic silver salt oxidizing agent may be used together with the light-sensitive silver halide emulsion. Organic compounds which can be used for forming the same are described in US Pat. There are benzotriazoles, fatty acids and other compounds described in columns 52 to 53 of No. 500,626. The acetylene silver described in U.S. Pat. No. 4,775,613 is also useful. Two or more organic silver salts may be used in combination.
The above organic silver salts are
0.01 to 10 mol, preferably 0.01 to 1 mol can be used in combination. Total coating amount of light-sensitive silver halide emulsion and the organic silver salt is 0.05 to 10 g / m ² in terms of silver, and preferably from 0.1-4 g / m ^2.

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

During preparation of the emulsion of the present invention, for example, during grain formation,
In the desalting step, at the time of chemical sensitization, the presence of a metal ion salt before coating is preferable depending on the purpose. When doping the grains, they are preferably added at the time of grain formation, when modifying the grain surface or when using as a chemical sensitizer, after grain formation and before the end of chemical sensitization. The case of doping the entire grain and the method of doping only the core portion, only the shell portion, only the epitaxial portion, or only the base grain of the grain can be selected. Mg, Ca, Sr, B
a, Al, Sc, Y, La, Cr, Mn, Fe, Co,
Ni, Cu, Zn, Ga, Ru, Rh, Pd, Re, O
s, Ir, Pt, Au, Cd, Hg, Tl, In, S
n, Pb, Bi or the like can be used. These metals can be added in the form of salts such as ammonium salts, acetates, nitrates, sulfates, phosphates, hydrates or hexacoordinated complex salts and tetracoordinated complex salts which can be dissolved at the time of grain formation. . For example, CdBr ₂ , CdCl ₂ , Cd (NO ₃ )
₂ , Pd (NO ₃ ) ₂ , Pb (CH ₃ COO) ₂ , K ₃
[Fe (CN) ₆ ], (NH ₄ ) ₄ [Fe (C
N) ₆ ], K ₃ IrCl ₆ , (NH ₄ ) ₃ RhCl ₆ ,
K ₄ Ru (CN) _{6 and the} like. The ligand of the coordination compound can be selected from halo, aquo, cyano, cyanate, thiocyanate, nitrosyl, thionitrosyl, oxo, and carbonyl. These may be used alone or in combination of two or more metal compounds. U.S. Pat. No. 3,772,0
In some cases, a method of adding a chalcogen compound during emulsion preparation as described in No. 31 is useful. S, Se,
In addition to Te, cyanate, thiocyanate, selenocyanate, carbonate, phosphate and acetate may be present.

The silver halide grains of the present invention are sulfur sensitized,
At least one of selenium sensitization, tellurium sensitization (these three are collectively referred to as chalcogen sensitization), noble metal sensitization, or reduction sensitization may be applied in any step of the production process of a silver halide emulsion. it can. It is preferable to combine two or more sensitization methods. Various types of emulsions can be prepared depending on the step of chemical sensitization. There are a type 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 that 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. 1
977 (TH James, The Photographic Process, 4th
ed. Macmillan, 1977) pp. 67-76 with active gelatin, and Research Disclosure Item 12008 (1).
April 974); Item 13452 (6 June 1975).
Month); Item 307105 (November 1989),
U.S. Pat. Nos. 2,642,361 and 3,297,4
No. 46, No. 3,772,031, No. 3,857,
No. 711, No. 3,901,714, No. 4,26
6,018, and 3,904,415 and pAg 5-10, pH 5-8 and temperature 30-80 ° C as described in British Patent 1,315,755.
Can be performed by combining sulfur, selenium, tellurium, gold, platinum, palladium, iridium or a plurality of these sensitizers.

In sulfur sensitization, unstable sulfur compounds are used, and specifically, thiosulfates (eg, hypo), thioureas (eg, diphenylthiourea, triethylthiourea, allylthiourea, etc.), rhodanine. Kind,
Mercaptos, thioamides, thiohydantoins, 4
-Oxooxazolidine-2-thiones, di- or polysulfides, polythionates and elemental sulfur,
And US Patent Nos. 3,857,711 and 4,2
Known sulfur-containing compounds described in Nos. 66,018 and 4,054,457 can be used. Sulfur sensitization is often used in combination with noble metal sensitization. The preferred amount of sulfur sensitizer used for the silver halide grains of the present invention is 1 × 10 ^-7 to 10 ^-3 mol, and more preferably 5 mol / mol of silver halide.
X 10 ^-7 to 1 X 10 ^-4 mol.

In the selenium sensitization, known unstable selenium compounds are used. For example, US Pat. No. 3,297,44 is used.
No. 6,297,447 and the like, and specifically, colloidal metal selenium, selenoureas (for example, N, N-dimethylselenourea, tetramethylselenourea) Urea, etc.), selenoketones (eg, selenoacetone), selenoamides (eg, selenoacetamide), selenocarboxylic acids and esters, isoselenocyanates, selenides (eg, diethyl selenide, triphenylphosphine selenide), Selenophosphates (eg, tri-p
-Tolyl selenophosphate) and the like. Selenium sensitization may be preferably used in combination with sulfur sensitization and / or noble metal sensitization. The amount of the selenium sensitizer used varies depending on the selenium compound used, the silver halide grains, the chemical ripening conditions, etc., but is generally 10 ^-8 to 1 per mol of silver halide.
^0-4 mol, preferably about ^10-7 to ^10-5 mol is used.

The tellurium sensitizers used in the present invention include Canadian Patent 800,958 and British Patents 1,2.
No. 95,462, No. 1,396,696, Japanese Patent Application No. 2
The compounds described in US Pat. ', N'
-Dimethyl tellurourea, N, N'-dimethylethylene tellurourea), isotellurocyanates, telluroketones, telluroamides, tellurohydrazides, telluroesters, phosphine tellurides (for example, tributylphosphine telluride, butyldiisopropylphosphine) Telluride), other tellurium compounds (eg potassium tellurocyanate, telluropentathionate sodium salt)
And the like. The amount of the tellurium sensitizer used is 10 ^{−7 to} 5 × 10 ⁻² mol, preferably 5 per mol of silver halide.
It is about 10 ⁻⁷ to 10 ⁻³ mol.

In the noble metal sensitization, a noble metal salt such as platinum, gold, palladium or iridium can be used, and among them, gold sensitization, palladium sensitization and a combination of both are preferable. In the case of gold sensitization, chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide,
Known compounds such as gold selenide can be used.
The palladium compound means a divalent palladium salt or a tetravalent salt. A preferred palladium compound is R ₂ PdX ₆
Or it is represented by R ₂ PdX ₄ . Where R is a hydrogen atom,
Represents an alkali metal atom or an ammonium group. X represents a halogen atom, and represents a chlorine, bromine or iodine atom. Specifically, K ₂ PdCl ₄ , (NH ₄ ) ₂ PdC
l ₆ , NaPdCl ₄ , (NH ₄ ) ₂ PdCl ₄ , Li
₂ PdCl ₄ , Na ₂ PdCl ₆ or K ₂ PdBr ₄
Is preferred. The gold compound and the palladium compound are preferably used in combination with a thiocyanate or a selenocyanate. The emulsion of the present invention is preferably used in combination with gold sensitization. The amount of the gold sensitizer is preferably 1 × 10 ⁻⁷ to 1 × 10 ⁻³ mol, and more preferably 5 per mol of silver halide.
It is ^{x10 -7 to} 5 x 10 ^-4 mol. The preferred range of the palladium compound is 5 × 10 ^-7 to 1 × 10 ^-3 mol. The preferable 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, a method of growing in a low pAg atmosphere of pAg 1 to 7 called silver ripening, or a method of ripening, a pH 8 to 11 called high pH ripening. Any of the method of growing or aging in a high pH atmosphere 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 can be selected and used. It is also possible to use two or more compounds in combination. Stannous chloride, aminoiminomethanesulfinic acid (commonly known as thiourea dioxide), dimethylamine borane, ascorbic acid and derivatives thereof are preferred compounds as reduction sensitizers. Since the addition amount of the reduction sensitizer depends on the emulsion production conditions, it is necessary to select the addition amount, but an appropriate range is 10 ^-7 to 10 ^-3 mol per mol of silver halide.

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 as azaindene, azapyridazine, azapyrimidine, which suppress fog during chemical sensitization and increase sensitivity. Examples of chemical sensitization aid modifiers are described in U.S. Pat.
Nos. 411,914 and 3,554,757, JP-A-58-126526 and the aforementioned "Emulsion Chemistry" by Duffin, pp. 138-143.

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, extremely fine silver grains that replicate during the formation and chemical sensitization processes of silver halide grains,
Compounds that can be converted to silver ions are effective. The silver ions generated here may form a silver salt which is hardly soluble in water such as silver halide, silver sulfide, silver selenide, or a silver salt which is easily soluble in water such as silver nitrate. good. The oxidizing agent for silver may be an inorganic substance or an organic substance. Examples of the inorganic oxidizing agent include ozone, hydrogen peroxide and adducts thereof (for example, NaBO ₂ , H ₂ O ₂ .H ₂ O, 2NaCO ₃ .H
₂ O ₂ , Na ₄ P ₂ O ₇ · H ₂ O ₂ , 2NaSO ₄ · H
₂ O ₂ · 2H ₂ O), peroxy acid salts (eg, K ₂ S
₂ O ₈ , K ₂ C ₂ O ₆ , K ₂ P ₂ O ₈ ) peroxy complex compound (for example, K ₂ [Ti (O ₂ ) C ₂ O ₄ ] / 3H
₂ O, 4K ₂ SO ₄ · Ti (O ₂ ) OH · SO ₄ · 2H
₂ O, Na ₃ [VO (O ₂ ) (C ₂ O ₄ ) ₂ ] ・ 6H ₂
O), permanganate (eg, KMnO ₄ ), chromate (eg, K ₂ CrO ₇ ) and other oxyacid salts, halogen elements such as iodine and bromine, and perhalogenates (eg,
Potassium periodate), high valent metal salts (eg,
Potassium hexacyanoferrate) and thiosulfonate. Examples of the organic oxidant include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogen (for example, N-.
Bromsuccinimide, chloramine T, chloramine B)
Is given as an example. Preferred oxidants of the present invention are ozone, hydrogen peroxide and its adducts, halogen elements, inorganic oxidants of thiosulfonates and organic oxidants of quinones. It is a preferable embodiment to use the reduction sensitization and the oxidizing agent for silver in combination. After using the oxidizing agent, the method can be selected from a method of performing reduction sensitization, a reverse method thereof, or a method of coexisting the two at the same time. 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, amino Triazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially 1-phenyl-5-mercaptotetrazole); mercaptopyrimidine; mercaptotriazine;
Thioketo compounds such as oxazolinethione; azaindenes such as triazaindenes and tetraazaindenes (especially 4-hydroxy-6-methyl-1,
Many compounds known as antifoggants or stabilizers can be added, such as 3,3a, 7-tetraazaindene), pentaazaindenes and the like. For example, U.S. Patent Nos. 3,954,474 and 3,982,94
No. 7, JP-B-52-28660 can be used. One of the preferred compounds is Japanese Patent Application No. Sho 62
No. 47225. Antifoggants and stabilizers are used at various times before, during and after particle formation, during the water washing step, during dispersion after water washing, before chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. It can be added according to the purpose. Controls grain walls, reduces grain size, reduces grain solubility, controls chemical sensitization, in addition to exerting its inherent fogging prevention and stabilization effects during emulsion preparation It can be used for various purposes such as controlling the arrangement of dyes.

When the photosensitive silver halide used in the present invention is provided with green-sensitive, red-sensitive and infrared-sensitive color sensitivities, the photosensitive silver halide emulsion is spectrally sensitized with methine dyes or the like. .. If necessary, the blue-sensitive emulsion may be spectrally sensitized in the blue region. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of nuclei usually used for cyanine dyes as base heterocyclic nuclei can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus,
Thiazoline nuclei, pyrrole nuclei, oxazole nuclei, thiazole nuclei, selenazole nuclei, imidazole nuclei, tetrazole nuclei, pyridine nuclei, etc .; these nuclei fused with alicyclic hydrocarbon rings; and these nuclei containing aromatic hydrocarbon rings Fused nuclei, i.e., indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, rhodanine nucleus, thiobarbituric acid A 5-64-hydroxy-6-methyl-heterocyclic nucleus such as a nucleus can be applied. These nuclei may be substituted on carbon atoms.
Specifically, U.S. Pat. No. 4,617,257, JP-A-5
Examples include sensitizing dyes described in JP-A Nos. 9-180,550, 64-13,546, and JP-A-5-45,828 and 5-45,834. 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 5- or 6-membered heterocyclic nucleus such as a 2-thiooxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus or a thiobarbituric acid 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 or wavelength adjustment of spectral sensitivity. A representative example is U.S. Pat. No. 2,688,5.
No. 45, No. 3,397,060, No. 2,977,
No. 229, No. 3,522,052, No. 3,52
7,64, 3,617,293, 3,62
No. 8,964, No. 3,672,898, No. 3,6
79,428, 3,703,377, and 3,
769,301, 3,814,609, 3,837,862, 4,026,707, British Patents 1,344,281, 1,507,80.
No. 3, Japanese Patent Publication No. 43-4,936, No. 53-12, 37
No. 5, JP-A Nos. 52-110,618 and 52-10.
No. 9,925. Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a compound that does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (for example, US Pat. 61
5,641 and those described in JP-A-63-23,145). When to add these sensitizing dyes to the emulsion,
It may be at any stage in the preparation of emulsions heretofore 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. 3,628,96.
As described in JP-A-58-113 and JP-A No. 4,225,666, spectral sensitization may be carried out simultaneously with chemical sensitization by adding a chemical sensitizer at the same time. , 92
As described in No. 8, it can be carried out prior to chemical sensitization. Further, it can be added before the completion of silver halide grain precipitation to start spectral sensitization. Further, U.S. Pat. Nos. 4,183,756 and 4,225,666.
The addition may be before or after the nucleation of the silver halide grains according to the formula (1), or a divided addition in which a part of the compound is added before the chemical sensitization and the remainder is added after the chemical sensitization. These sensitizing dyes and supersensitizers may be added in a solution of an organic solvent such as methanol, a dispersion of gelatin or the like, or a solution of a surfactant. The amount added is generally 1 silver halide.
It is about 4 × 10 ⁻⁶ to 8 × 10 ⁻³ mol per mol, and more preferable silver halide grain size is 0.2 to 1.
In the case of 2 μm, about 5 × 10 ⁻⁵ to 2 × 10 ⁻³ mol is more effective.

Although the above-mentioned various additives are used in the light-sensitive material of the present technology, other various additives can be used depending on the purpose. These additives are
For more details, Research Disclosure Item1
7643 (December 1978), Item 18176.
(November 1979) and Item 307105.
(November 1989), and the relevant parts are summarized in the table below. Type of additive RD17643 RD18716 RD307105 Chemical sensitizer page 23 page 648 right column page 996 2. 2. Sensitivity increasing agent, page 648, right column Spectral sensitizers 23 to 24 pages 648 right column 996 to 998 supersensitizers to 649 right column 4. Whitening agent Page 24 Page 647 Right column Page 998 5. Light absorber, pages 25-26, page 649, right column, page 1003, filter, page 650, left column, dye, ultraviolet absorber 6. Binder 26 pages 651 pages 1003 to 1004 7. Plasticizer, page 27, page 650, page 1006, lubricant 8. Coating aid, pages 26 to 27, page 650, page 1005 left to surface active agent, page 1006 right 9. Static page 27 page 650 right column 1006-inhibitor 1007 page 10. Antifoggant page 24-25 page 649 page 998-1000 and stabilizer 11. Stain, page 25, right column, page 650, left-right inhibitor 12. Dye image stabilizer, page 25 13. Hardener page 26 page 651 left column 1004 right to 1005 left

In addition to the hardeners mentioned above, US Pat. No. 4,678,739, column 41, US Pat. No. 4,791,04.
2, JP-A-59-116,655, and JP-A-62-24.
5,261, 61-18,942, Japanese Patent Laid-Open No. 4-2.
Examples include hardeners described in No. 18,044. More specifically, aldehyde hardeners (formaldehyde etc.), aziridine hardeners, epoxy hardeners, vinyl sulfone hardeners (N, N'-ethylene-bis (vinylsulfonylacetamide)) Ethane, etc.), N-methylol type hardeners (dimethylolurea, etc.), or polymer hardeners (compounds described in JP-A-62-234,157). These hardeners are used in an amount of 0.001 to 1 g, preferably 0.001 g per 1 g of coated gelatin.
5 g to 0.5 g are used. Further, the layer to be added may be any of constituent layers such as a light-sensitive material and a dye fixing material, or may be divided into two or more layers and added.

A matting agent can be used in the light-sensitive material of the present invention for the purpose of preventing adhesion, improving slipperiness, and providing a non-glossy surface. Examples of matting agents include silicon dioxide, polyolefin, and polymethacrylate.
No. 8,256 (29) page, benzoguanamine resin beads, polycarbonate resin beads, A
There are compounds described in JP-A-63-274,944 and JP-A-63-274,952, such as S resin beads. In addition, the compounds described in the aforementioned RD magazine can be used. These matting agents can be added not only to the uppermost layer (protective layer) but also to the lower layer as needed. In addition, the constituent layers of the photothermographic material may contain a thermal solvent, an antifoaming agent, an antibacterial agent, an antifungal agent, colloidal silica and the like. Specific examples of these additives are described in JP-A-61-88,256, pages (26) to (32), JP-A-3-11,338, JP-B-2-51-51,496 and the like. There is.

In the constituent layers of the light-sensitive material of the present invention, various surfactants can be used for the purposes of coating aid, improvement of releasability, improvement of slipperiness, antistatic property, acceleration of development and the like. Specific examples of the surfactant are described in RD magazine, JP-A-62-173,4.
63, 62-183, 457 and the like. In the case of a heat-developable photosensitive material, it is also preferable that the constituent layer contains an organic fluoro compound for the purpose of improving slipperiness, preventing electrification, improving peelability and the like. Typical examples of organic fluoro compounds include fluorine-based surface active agents described in JP-B No. 57-9,053, columns 8 to 17, JP-A Nos. 61-20,944 and 62-135,836. Agents, or oily fluorine-based compounds such as fluorine oil or hydrophobic fluorine compounds such as solid fluorine compound resins such as tetrafluoroethylene resin.

A known anti-fading agent can be used in the light-sensitive material of the present invention. Organic anti-fading agents include hydroquinones, 5-hydroxychromans, 5-hydroxycoumarans, paraalkoxyphenols, hindered phenols centering on bisphenols, gallic acid derivatives, methylenedioxybenzenes, amino Typical examples are phenols, hindered amines, and ether or ester derivatives obtained by silylated and alkylated phenolic hydroxyl groups of these compounds.
Further, a metal complex represented by (bissalicylaldoximato) nickel complex and (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used. A compound having both a hindered amine and a hindered phenol partial structure in the same molecule, as described in U.S. Pat. No. 4,268,593, gives good results in preventing deterioration of a yellow dye image by heat, humidity and light. give. Further, in order to prevent the deterioration of the magenta dye image, particularly the deterioration by light, spiroindanes described in JP-A-56-159,644 and hydroquinone diethers described in JP-A-55-89,835 or Monoether substituted chromans give favorable results.

Various antifoggants or photographic stabilizers and their precursors can be used in the constituent layers of the light-sensitive material of the present invention. Specific examples of the above R
D magazine, US Pat. Nos. 5,089,378 and 4,50.
0,627, 4,614,702, JP-A-64
-13,546 (7) to (9), (57) to (7)
1) and (81)-(97), U.S. Pat.
No. 75,610, No. 4,626,500, No. 4,
983,494, JP-A-62-174,747, 62-239,148, 63-264,747,
JP-A-1-150,135, 2-110,557
No. 2-178,650, RD. No. 17,64
No. 3 (1978), pages (24) to (25) and the like. These compounds are present in 5 moles per silver mole.
× 10 ^-6 to 1 × 10 ^-1 mol is preferable, and further 1 × 10
^-5 to 1 × 10 ^-2 mol is preferably used.

Suitable supports usable in the present invention include polyolefins such as polyethylene and polypropylene, polycarbonates, cellulose acetate, polyethylene terephthalate, polyethylene naphthalate, synthetic plastic films such as polyvinyl chloride, photographic base paper and printing. Paper support such as paper, baryta paper, and resin-coated paper, and a support provided with a reflection layer on the above plastic film, JP-A-62-253,159 (29).
Up to page 31). The RD. No. 17643, page 28, No. 17643. 1
8716, page 647, right column to page 648, left column, and ibid.
o. Those described on page 879 of 307105 can also be preferably used. These supports include US Pat.
By applying heat treatment below Tg like No. 1,735,
It is possible to use a material that has less curling tendency. Further, the surface of these supports may be surface-treated for the purpose of improving the adhesion between the support and the emulsion undercoat layer. In the present invention, glow discharge treatment, ultraviolet irradiation treatment, corona treatment, and flame treatment can be used as the surface treatment. Further, the support described on pages 44 to 149 of Known Technology No. 5 (published by Aztec Co., Ltd. on March 22, 1991) can also be used. A transparent support such as polyethylene dinaphthalene dicarboxylate or a support having a transparent magnetic material coated thereon can also be used.

In the photothermographic material, various development stoppers can be used for the purpose of always obtaining a constant image with respect to variations in processing temperature and processing time during development. The term "development terminating agent" as used herein means that after proper development, the base is promptly neutralized or reacted with the base to lower the concentration of the base in the film, and the development is stopped by interacting with a compound or silver and a silver salt which stop the development. It is a compound that suppresses. Specific examples thereof include an acid precursor that releases an acid by heating, an electrophilic compound that causes a substitution reaction with a coexisting base by heating, or a nitrogen-containing heterocyclic compound, a mercapto compound and a precursor thereof. More specifically, JP-A-62-253,159 (3
It is described on pages 1) to (32). The color developing agent of the present invention can be used in all silver halide light-sensitive materials such as color negatives, color papers, X-ray sensitive materials for color reversal or forming a color image, and sensitive materials for plate making. The color developing agent of the present invention can be added to the silver halide light-sensitive material and also to the processing solution.

When the color developing agent of the present invention is added to a silver halide light-sensitive material, it can be developed by heat treatment or activator treatment. The heat treatment of a light-sensitive material is known in the art, and the heat-developable light-sensitive material and the process thereof are described in, for example, pages 553 to 555 of Fundamentals of Photographic Engineering (1979, Corona Publishing Co.),
Video information published in April 1978, page 40, Nablets
Handbook of Photography
and Reprography 7th Ed. (V
an Nostrand and ReinholdC
Company), pages 32-33, US Pat. No. 3,15.
No. 2,904, No. 3,301,678, No. 3,3
92,020, 3,457,075, British Patents 1,131,108, 1,167,777 and Research Disclosure, June 1978, pages 9-15 (RD-17029). )It is described in.

The activator processing means a processing method in which a developing agent (color developing agent) is contained in the light-sensitive material and the developing processing is carried out with a processing solution containing no developing agent. The processing liquid in this case is characterized in that it does not contain the developing agent contained in the usual developing processing liquid components, and may contain other components (for example, alkali, auxiliary developing agent, etc.). Regarding the activator treatment, European Patent No. 545,
It is illustrated in known documents such as 491A1 and 565,165A1. Next, the processing material and processing method used in the case of the activator processing in the present invention will be described in detail. In the present invention, the light-sensitive material is subjected to development (silver development / cross oxidation of built-in reducing agent), desilvering, washing with water, or stabilization treatment. After the washing or stabilizing treatment, a treatment for enhancing color development such as alkali addition may be performed.

When the light-sensitive material of the present invention is used as a heat-developable light-sensitive material, a method of generating a base from a base precursor is preferable as a method of supplying a base. Examples of the base precursor used in the present invention include salts of organic acids and bases that are decarboxylated by heat, compounds that decompose by reactions such as intramolecular nucleophilic substitution reaction, Rossen rearrangement or Beckmann rearrangement, and release amines. A compound that releases a base by causing some reaction by the above, and a compound that generates a base by electrolysis or a complex formation reaction are preferably used. As the former type of base precursor that generates a base by heating, a salt of trichloroacetic acid described in British Patent No. 998,959, etc., and further improved stability are described in US Pat. No. 4,060,420. Salt of α-sulfonylacetic acid, a salt of propiolic acid described in Japanese Patent Application No. 58-55,700, a 2-carboxycarbamide derivative described in US Pat. No. 4,088,496, and an organic base as a base component. In addition, a salt with a thermally decomposable acid using an alkali metal or an alkaline earth metal (Japanese Patent Application No. 58-69,597) and a hydroxamum carbamate described in Japanese Patent Application No. 58-43,860 using Rossen rearrangement. And the aldoxime carbamates described in Japanese Patent Application No. 58-31,614 which produce nitriles by heating. Others, British Patent No. 9
98,945, 2,079,480, JP-A-5
0-226,225, U.S. Pat. No. 3,220,846.
No. 4,514,493, 4,657,84
The base precursors described in No. 8 and No. 5 of the related art (March 22, 1991, issued by Aztec Co., Ltd.), pages 55 to 86, etc. are also useful.

The method of exposing and recording an image on the light-sensitive material of the present invention includes, for example, a method of directly photographing a landscape or a person using a camera or the like, and a method of exposing through a reversal film or a negative film using a printer or an enlarger. Method, a method of scanning and exposing an original image through a slit, etc. using an exposure device of a copying machine, and scanning by emitting light from a light emitting diode, various lasers (laser diode, gas laser, etc.) via image information and electric signals. Method of exposing (Japanese Patent Application Laid-Open No. 2-129,625, Japanese Patent Application No. 3-338,
No. 182, No. 4-9, 388, No. 4-281, 442
No.), image information is output to an image display device such as a CRT, a liquid crystal display, an electroluminescence display, and a plasma display, and exposed directly or through an optical system.

As a light source for recording an image on a photosensitive material,
As described above, the natural light, tungsten lamp, light emitting diode, laser light source, CRT light source, etc.
500,626, column 56, JP-A-2-53,378.
No. 2, 2-54, 672, the light source and the exposure method can be used. Image exposure can also be performed using a wavelength conversion element in which a nonlinear optical material and a coherent light source such as laser light are combined. Here, the non-linear optical material is a material capable of exhibiting the non-linearity between the electric field and the division that appears when a strong optical electric field such as laser light is applied.
Lithium niobate, potassium dihydrogen phosphate (KDP),
Inorganic compounds represented by lithium iodate, BaB ₂ O _4, etc., urea derivatives, nitroaniline derivatives, for example,
3-methyl-4-nitropyridine-N-oxide (PO
Nitropyridine-N-oxide derivatives such as M) and the compounds described in JP-A Nos. 61-53,462 and 62-210,432 can be preferably used. As the form of the wavelength conversion element, a single crystal optical waveguide type, a fiber type and the like are known, and any of them is useful. Further, the image information is an image signal obtained from a video camera, an electronic still camera or the like, a television signal represented by Nippon Television Signal Standard (NTSC), an image signal obtained by dividing an original image into many pixels such as a scanner. , CG, CAD
An image created using a computer represented by can be used.

When the light-sensitive material of the present invention is developed using a developing solution, the developing solution functions as a developing agent for silver halide and / or an oxidized product of a developing agent generated by silver development is incorporated in the photosensitive material. A compound having a function of cross-oxidizing the existing reducing agent for coloring is used. Preferred are pyrazolidones, dihydroxybenzenes, reductones and aminophenols, and particularly preferred are pyrazolidones. 1 for pyrazolidones
-Phenyl-3-pyrazolidones are preferable, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-
4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxydimethyl-3-pyrazolidone,
1-phenyl-5-methyl-3-pyrazolidone, 1-phenyl-5-phenyl-3-pyrazolidone, 1-p-tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-p-chlorophenyl-4 -Methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-2
-Hydroxymethyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-2-acetyl-3-pyrazolidone, 1-phenyl-2-hydroxymethyl-5-phenyl-3-pyrazolidone, 1- (2-chlorophenyl) −
4-hydroxymethyl-4-methyl-3-pyrazolidone and the like. The dihydroxybenzenes include hydroquinone, chlorohydroquinone, bromhydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,5-dimethylhydroquinone,
And potassium hydroquinone monosulfonate.

As the reductones, N-methyl-p-
Aminophenol, N- (β-hydroxyethyl) -p
-Aminophenol, N- (4-hydroxyphenyl)
Glycine, 2-methyl-p-aminophenol and the like. These compounds are usually used alone, but it is also preferable to use two or more 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 / liter, preferably 0.0025 mol / liter to 0.1 mol / liter, and more preferably 0.1. It is 001 mol / liter to 0.05 mol / liter.

Preservatives used in the developer of the present invention include sodium sulfite, potassium sulfite, lithium sulfite, sodium formaldehyde bisulfite and hydroxylamine / sulfate, and the amount used is 0.1 mol / mol.
Liter or less, preferably 0.001 to 0.02 mol /
It may be used in the liter range. When a high silver chloride emulsion is used in the light-sensitive material, the above compound is 0.00
It may be 1 mol / liter or less, preferably not contained at all.

In the present invention, it is preferable to contain an organic preservative in place of the hydroxylamine and sulfite ion. Here, the term "organic preservative" refers to all organic compounds that reduce the rate of deterioration of the developing agent by being added to a developer.
That is, organic compounds having a function of preventing oxidation of a developing agent by air or the like, among which hydroxylamine derivatives (excluding hydroxylamine), hydroxamic acids, hydrazines, phenols, α-hydroxyketones, α-hydroxyketones Aminoketones, sugars, monoamines, diamines, polyamines, quaternary ammoniums,
Nitroxy radicals, alcohols, oximes, diamide compounds, condensed amines and the like are particularly effective organic preservatives. These are disclosed in JP-A-63-4235 and JP-A-63-4235.
No.-5341, No.63-30845, No.63-216
No. 47, No. 63-44655, No. 63-46454
No. 63-53551, No. 63-43140, No. 63-56654, No. 63-58346, No. 63-
No. 43138, No. 63-146041, No. 63-44
657, 63-44656, U.S. Pat.
No. 5,503, No. 2,494,903, Tokubo Sho48
-30496 and the like. Other preservatives include JP-A-57-44148 and JP-A-57-537.
Various metals described in JP-A No. 49-180588
Salicylic acids, alkanolamines described in JP-A-54-3532, polyethyleneimines described in JP-A-56-94349, U.S. Pat. No. 3,746,54
An aromatic polyhydroxy compound described in No. 4 or the like may be contained as necessary. It is particularly preferable to contain alkanolamines described in JP-A-4-97355, pp. 631-632, and dialkylhydroxylamine described in JP-A 627-630. Further, a dialkylhydroxylamine and / or a hydrazine derivative may be used in combination with an alkanolamine, or may be a dialkylhydroxylamine and glycine represented by dialkylhydroxylamine and glycine described in EP 530,921 A1.
-It is also preferable to use amino acids in combination. The amount of these compounds used is preferably 1 ×
10 ^{-3 to} 5 × 10 ^-1 mol, more preferably 1 × 10 ^-2 to
It is 2 × 10 ⁻¹ .

In the present invention, the developer contains halogen ions such as chlorine ion, bromine ion and iodine ion. Particularly when a high-silver chloride emulsion is used, it is preferable to contain chlorine European Patent Office at 3.5 × 10 ^{−3 to} 3.0 × 10 ⁻¹ mol / liter, and more preferably 1 × 10 ^−2.
To 2 × 10 ⁻¹ mol / liter, and / or bromine ion content of 0.5 × 10 ^{−5 to} 1.0 × 10 ⁻³ mol / liter is preferable, and 3.0 × is more preferable.
It is 10 ^{−5 to} 5 × 10 ⁻⁴ mol / liter. Here, the halide may be directly added to the developer or may be eluted from the photosensitive material into the developer during the development processing. When added to the developer, each sodium salt as a feed substance,
Examples thereof include potassium salt, ammonium salt, lithium salt and magnesium salt. When eluted from the light-sensitive material, it is mainly supplied from a silver halide emulsion, but may be supplied from other sources.

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

Specific examples of these buffers include lithium carbonate, sodium carbonate, potassium carbonate, potassium bicarbonate, tripotassium phosphate, trisodium phosphate, dipotassium phosphate, disodium phosphate, potassium borate, boric acid. Examples thereof include sodium, sodium tetraborate, potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate). The amount of the buffer added to the developer is preferably at least 0.05 mol / l, particularly preferably from 0.1 mol to 0.4 mol / l.
In addition, as a precipitation inhibitor of calcium and magnesium in the developer, or for improving the stability of the developer,
Various chelating agents can be used. For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylenesulfonic acid, 1,2-diaminopropanetetraacetic acid. , Glycol ether diamine tetraacetic acid, ethylenediamine orthohydroxyphenyl acetic acid, 2-phosphonobutane-1,
2,4-tricarboxylic acid, 1-hydroxyethylidene-
Examples include 1,1-diphosphonic acid, 1,2-dihydroxybenzene-4,6-disulfonic acid and alkali metal salts thereof. These chelating agents may be used in combination of two or more as necessary. The amount of these chelating agents added is
The amount is sufficient to conceal the metal ions in the developer, 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. Examples of the nitrogen-containing heterocyclic compound include, for example,
Benzotriazole, 5-nitrobenzotriazole,
5-methylbenzotriazole, 5-nitrobenzimidazole, 5-nitroindazole, 2-thiazolylbenzimidazole, indazole, hydroxyazaindolizine, adenine, 1-phenyl-5-mercaptotetrazole or derivatives thereof are mentioned as typical examples. be able to. The addition amount of the nitrogen-containing heterocycle is 1 × 10 ⁻⁵ to 1
× 10 ⁻² / liter, preferably 2.5 to 10 ⁻⁵ to 1 ×
It is 10 ^-3 mol / liter.

If necessary, any development accelerator can be added to the developing solution. As development accelerators, JP-B-37-16
No. 088, No. 37-5987, No. 38-7826,
Thioether compounds described in JP-A Nos. 44-12380 and 45-9019 and U.S. Pat. No. 3,813,247;
P-phenylenediamine compounds represented by JP-A-5554, JP-A-50-137726, JP-B-44-300
No. 74, JP-A-56-156826 and JP-A-52-4
Quaternary ammonium salts represented by 3429, U.S. Pat. Nos. 2,494,903, 3,128,182, 4,230,796, 3,253,919, and Japanese Patent Publication No. 41- 11431, US Pat. No. 2,482,546
Nos. 2,596,926 and 3,582,34
No. 6, etc., and the amine compounds described in JP-B-37-1608.
No. 8, No. 42-25201, U.S. Pat.
No. 501, etc., polyalkylene oxides and imidazoles can be added as needed.

The developer preferably contains a fluorescent whitening agent. Particularly, it is preferable to use a 4,4-diamino-2,2′-disulfostilbene compound. Specifically, commercially available optical brighteners such as "Dyeing Note 19th Edition"
The compounds described on pages 165 to 168 and JP-A-4-24
The compounds described in No. 2943, pages 3 to 7 can be used. The addition amount is 0.1 g to 10 g / liter, preferably 0.5 g to 5 g / liter. The processing temperature of the developer applied to the present invention is 20 to 50 ° C., preferably 30.
~ 45 ° C. Treatment time is 5 seconds to 2 minutes, preferably 1
It is 0 second to 1 minute. The replenishment amount is preferably small, but 15 to 600 ml, preferably 25, per 1 m ^{2 of} the light-sensitive material.
~ 200 ml, more preferably 35-100 ml.

The light-sensitive material of the present invention may have a form having a conductive heating element layer as a heating means for heat development. The heat generating element in this case is disclosed in JP-A-61-145,
No. 544 can be used. The heating temperature in the heat development step is about 75 ° C to 180 ° C, preferably 8 ° C.
0 ° C to 150 ° C, more preferably 80 ° C to 13 ° C
5 ° C. The heating time is 0.1 second to 60 seconds, preferably 0.1 second to 30 seconds. As the heating method in the developing process, it is brought into contact with a heated block or plate, or brought into contact with a hot plate, a hot presser, a heat roller, a heat drum, a halogen lamp heater, an infrared or far infrared lamp heater, or a high temperature. There is a method of passing through the atmosphere. The method described in JP-A-62-253,159 and 61-147,244, page (27) can be applied to the method of superimposing the heat-developable light-sensitive material and the dye-fixing material.

After development, desilvering processing can be carried out.
The desilvering process includes a fixing process and a bleaching and fixing process. In the case of bleaching and fixing, the bleaching treatment and the fixing treatment may be performed separately or simultaneously (bleach-fixing treatment). Further, processing in two continuous bleach-fixing baths, fixing before bleach-fixing, or bleach-fixing after bleach-fixing can be arbitrarily performed according to the purpose. In some cases, it is also preferable to carry out a stabilization treatment without performing a desilvering treatment after the development to stabilize a silver salt or a color image.

Examples of the bleaching agent used in the bleaching solution and the bleach-fixing solution include compounds of polyvalent metals such as iron (III), cobalt (III), chromium (IV) and copper (II), peracids and quinones. And nitro compounds. Typical compounds include iron chloride, ferricyanide compounds, dichromates, and organic complex salts of iron (III) (eg, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid). , Methyliminodiacetic acid and JP-A-4-365036
Nos. 5 to 17, aminopolycarboxylic acids and metal salts), persulfates, permanganates, bromates, hydrogen peroxide and its releasing compounds (percarbonic acid, perboric acid, etc.), nitrobenzenes, etc. Can be mentioned. Among them, ethylenediaminetetraacetic acid (III) complex salt, 1,3-diaminopropanetetraacetate iron (III) complex salt of aminopolycarboxylic acid iron (III), hydrogen peroxide, persulfate, etc. It is preferable from the viewpoint of preventing environmental pollution. The pH of the bleaching solution or bleach-fixing solution using these iron (III) aminopolycarboxylates is 3-8.
It is preferably 5 to 7. The pH of the bleaching solution using persulfate or hydrogen peroxide is 4 to 11, and preferably 5 to 5.
It is 10.

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

Regarding the accelerator for persulfuric acid bleaching, Japanese Patent Laid-Open Publication No. 6-58242
-214365 (European Patent No. 602600A1)
The complex salts of the iron (III) ions described with 2-pyridinecarboxylic acid or 2,6-pyridinedicarboxylic acid are effective. Regarding hydrogen peroxide bleaching accelerator, Japanese Patent Publication 6
The metal salts of organic acids described in Nos. 1-16067 and 61-19024 are effective. For bleaching solutions, bleach-fixing solutions and fixing solutions, rehalogenating agents such as ammonium bromide and ammonium chloride; ammonium nitrate, acetic acid, boric acid, citric acid or its salts, tartaric acid or its salts, succinic acid or its salts, imidazole. A known additive such as a pH buffering agent such as the following; a metal corrosion inhibitor such as ammonium sulfate can be used. In particular, it is preferable to contain an organic acid in order to prevent bleaching stain. The organic acid is a compound having an acid dissociation constant (pKa) of 2 to 7, specifically, acetic acid, succinic acid, citric acid, propionic acid and the like.

As the fixing agent used in the fixing solution or the bleach-fixing solution, thiosulfates, thiocyanates, thioureas, a large amount of iodide salts, and JP-A-4-365037, pages 11 to 21 and 5-66540. No. 1088 to 1092, a nitrogen-containing heterocyclic compound having a sulfide group,
Mesoionic compounds and thioether compounds can be mentioned. Of these, thiosulfates are generally used, and ammonium thiosulfate is most widely used.
It is also preferable to use a combination of a thiosulfate with a thiocyanate, a thioether compound, a thiourea, a mesoionic compound, or the like. As a preservative for the fixing solution or the bleach-fixing solution, sulfite, bisulfite, carbonyl bisulfite adduct or sulfinic acid compounds described in EP 294769A are preferable. In addition, various aminopolycarboxylic acids and organic phosphonic acids (for example, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N, N ′, N′-Ethylenediaminetetraphosphonic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid) or sodium oxalate is preferably added. The fixing solution or the bleach-fixing solution may further contain various fluorescent whitening agents; antifoaming agents; surfactants; polyvinylpyrrolidone; The processing temperature of the desilvering process is 20
-50 degreeC, Preferably it is 30-45 degreeC. The processing time is 5 seconds to 2 minutes, preferably 5 seconds to 1 minute. It is preferable that the replenishing amount is small, but 15 to 60 per 1 m ^{2 of} the light-sensitive material
It is 0 ml, preferably 25 to 200 ml, and more preferably 35 to 100 m. Just to compensate the amount of evaporation with water,
It is also preferable to process without supplementation.

The light-sensitive material of the present invention generally undergoes a washing step after desilvering. When the stabilization treatment is performed, the washing step may be omitted. In such a stabilization process, JP-A-57-8543 and JP-A-58-1483 are used.
Nos. 4 and 60-220345, and JP-A-5-220345.
8-127926, 58-13837, 58
All known methods described in JP-A-140741 can be used. Further, a washing-stabilizing step may be performed in which a stabilizing bath containing a dye stabilizer and a surfactant, which is typified by processing of a color light-sensitive material for photography, is used as a final bath. 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 to 9, preferably 5 to 8. The treatment temperature is 15 to 45 ° C, preferably 25 to 40 ° C
It is. Treatment time is 5 seconds to 2 minutes, preferably 5 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 in a wide range depending on various conditions, but the replenishing amount is preferably 15 to 360 ml per 1 m ² of the light-sensitive material, and 25 to 12 ml.
0 ml is more preferred. In order to reduce the amount of replenishment water, it is preferable to use a plurality of tanks and carry out a multi-stage countercurrent system. In particular, it is preferable to use 2 to 5 tanks. In order to prevent the propagation of bacteria which occur when the amount of water is reduced and the contamination of the resulting suspended matter to the photosensitive material, isothiazolone compounds and siapentazoles described in JP-A-57-8542, Fungicides such as sodium isocyanurate, and other benzotriazoles, etc., written by Hiroshi Horiguchi, "Chemistry of Fungicides and Fungicides" (1986)
(Published by Sankyo Publishing Co., Ltd.), "Sterilization, Sterilization, and Antifungal Techniques of Microorganisms" (edited by the Japan Society of Industrial Technology), edited by the Japan Society of Sanitary and Fungicides (1982); Can be used. Also, JP-A-62-28
The method of reducing Mg and Ca ions described in No. 8838 is also particularly preferably used.

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

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

In the present invention, it is preferable that the stirring is strengthened as much as possible. Specific methods for strengthening stirring are disclosed in JP-A Nos. 62-183460 and 62-183.
No. 461, a method of causing a jet jet of a processing solution to collide with the emulsion surface of the light-sensitive material, a method of increasing stirring efficiency by using a rotating means of JP-A-62-183461, and a wiper blade provided in the solution. Examples include a method of moving the light-sensitive material while bringing the emulsion surface into contact with the emulsion surface to make the emulsion surface turbulent, thereby improving the stirring effect, and a method of increasing the circulation flow rate of the entire processing solution. Such a stirring improving means is useful in any of the developing solution, the bleaching solution, the bleach-fixing solution, the stabilizing solution and the washing with water. These methods are effective in that the supply of the effective component in the liquid into the photosensitive material and the diffusion of the unnecessary component in the photosensitive material are promoted. In the present invention, the liquid opening ratio [air contact area (cm ² ) / liquid volume (cm ³ )] of any of the baths shows excellent performance in any state.
From the viewpoint of stability of liquid components, the liquid opening ratio is 0 to 0.1c.
m ^-1 is preferred. In continuous processing, practically, it is 0.1.
Preferably 001cm ^-1 ~0.05cm ^-1, more preferably from 0.002~0.03cm ^-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,
The effect of preventing performance deterioration of the processing liquid is high. Such an effect is effective in shortening the processing time of each step and in reducing the amount of processing replenishment. In order to shorten the processing time, it is preferable to shorten the crossover time (air time). For example, FIG. 4, FIG. The method of transporting between the processes described in 5 through a blade having a shielding effect is preferable. Further, when the respective processing liquids are concentrated by evaporation in the continuous processing, it is preferable to correct the concentration by adding water.
The processing time of the process 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 processor is usually determined by the linear velocity and the capacity of the processing bath,
In the present invention, a linear velocity of 500 to 4000 mm /
Minutes. Particularly in the case of a small developing machine, 500 to 2
500 mm / min is preferred. The processing time from the entire processing step, that is, from the developing step to the drying step, is preferably 360 seconds or less, more preferably 120 seconds or less, and particularly preferably 90 to 30 seconds. Here, the processing time is the time from when the photosensitive material is immersed in the developing solution to when it comes out of the drying unit of the processor.

[0146]

EXAMPLES The present invention will be specifically described below with reference to examples, but of course the present invention is not limited thereto.

Example 1 The surface of a paper support laminated on both sides with polyethylene was subjected to corona discharge treatment,
Providing a gelatin subbing layer containing sodium dodecylbenzenesulfonate, and further coating various photographic constituent layers,
A multilayer color photographic paper (101) having the following layer structure was produced. The coating solution was prepared as follows. First layer coating liquid Yellow coupler (C-21) 22.4 g, color developing agent (EXCD-1) 16.8 g, solvent (Solv-1)
80 g was 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 liquid A. On the other hand, silver chlorobromide emulsion A (cubic, 3: 7 mixture of large size milk A having an average grain size of 0.88 μm and small size emulsion of 0.70 μm (silver molar ratio)). The coefficient of variation of the grain size distribution was 0.08 and 0.10, respectively. In each size emulsion, 0.3 mol% of silver bromide was locally contained in a part of the grain surface based on silver chloride. did. In this emulsion, blue-sensitive sensitizing dyes A, B, and C shown below were added in an amount of 1.4 × 1 for each large-sized emulsion A per mol of silver.
0 ^-4 mol, and to the small size emulsion A, 1.7 x 10 ^-4 mol each was added. The emulsion was chemically ripened 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.

[0148]

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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. In addition, Cpd-2, Cpd
-3, Cpd-4 and Cpd-5 each having a total amount of 1
^{5.0mg / m 2, 60.0mg / m} 2, 50.0mg
/ M ² and 10.0 mg / m ² were added. The following spectral sensitizing dyes were used for the silver chlorobromide emulsion in each photosensitive emulsion layer. (Blue-sensitive emulsion layer)

[0150]

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(Green-sensitive emulsion layer)

[0152]

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(Sensitizing dye D per mol of silver halide was 3.0 × 10 ^-4 mol for a large-sized emulsion, 3.6 × 10 ^-4 mol for a small-sized emulsion, and sensitized dye) 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. Was added. ) (Red-sensitive emulsion layer)

[0154]

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(5.0 × 10 ⁻⁵ mol was added to the large-sized emulsion and 8.0 × 10 ⁻⁵ mol was added to the small-sized emulsion per mol of silver halide.) The following compound (S) was added in an amount of 2.6 × 10 ^-2 mol per mol of silver halide. Also, a blue-sensitive emulsion layer,
The green-sensitive emulsion layer and the red-sensitive emulsion layer, 1- (5-methyl) -5-mercaptotetrazole per mol of silver halide 3.5 × 10 ^-4 mol, 3.0 ×
10 ⁻³ mol and 2.5 × 10 ⁻⁴ mol were added. Further, 4-hydroxy-6- to the blue-sensitive emulsion layer and the green-sensitive emulsion layer.
Methyl-1,3,3a, 7-tetrazaindene was used in an amount of 1 × 10 ^-4 mol and 2 × 1 per mol of silver halide.
^0-4 moles were added. In order to prevent irradiation, the following dyes were added to the emulsion layer (the values in parentheses indicate the coating amount).
Was added.

[0156]

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(Layer Constitution) 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 White Content (TiO ₂ ) and Blue Tint (Ultramarine)] First Layer (Blue Sensitive Emulsion Layer) Silver chloride emulsion A 0.40 described above Gelatin 3.00 Yellow coupler (C-21) 0.45 Color developing agent (EXCD-1) 0.34 Solvent (Solv-1) 1.30 Second layer (color mixing prevention layer) Gelatin 1.09 Color mixing inhibitor ( Cpd-6) 0.11 solvent (Solv-1) 0.19 solvent (Solv-3) 0.07 solvent (Solv-4) 0.25 solvent (Solv-5) 0.09

Third Layer (Green-Sensitive Emulsion Layer) Silver Chlorobromide Emulsion: Cubic, large size emulsion B having an average grain size of 0.55 μm, and 0. 1: 3 mixture with 39 μm small size emulsion B (silver molar ratio). The coefficient of variation of the grain size distribution was 0.10 and 0.08, respectively, and in each emulsion, 0.8 mol% of AgBr was contained in a part of the grain surface based on silver chloride. 0.20 Gelatin 1.50 Magenta coupler (C-40) 0.26 Color developing agent (EXCD-1) 0.17 Solvent (Solv-2) 0.65 Fourth layer (color mixing prevention layer) Gelatin 0.77 Color mixing Inhibitor (Cpd-6) 0.08 Solvent (Solv-1) 0.14 Solvent (Solv-3) 0.05 Solvent (Solv-4) 0.14 Solvent (Solv-5) 0.06

Fifth Layer (Red-Sensitive Emulsion Layer) Silver Chlorobromide Emulsion: Cubic, large size emulsion C having an average grain size of 0.5 μm, and 0. 1: 4 mixture with small size emulsion C of 41 μm (silver 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 of which the base was silver chloride in each size emulsion. 0.20 Gelatin 0.15 Cyan coupler (C-43) 0.22 Color developing agent (EXCD-1) 0.17 Solvent (Solv-1) 0.15 Sixth layer (UV absorbing layer) Gelatin 0.64 UV Absorber (UV-1) 0.39 Color image stabilizer (Cpd-7) 0.05 Solvent (Solv-6) 0.05

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

[0162]

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[0163]

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[0164]

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[0165]

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Sample (102) to Sample (102) were prepared in the same manner as in Sample (101) except that the coupler and the color developing agent were replaced with equimolar amounts of the coupler and the color developing agent shown in Table 1. (105) was produced.

[0167]

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All the samples prepared as described above were subjected to gradation exposure of a three-color separation filter for sensitometry using an FWH type sensitometer manufactured by Fuji Film Co., Ltd. (color temperature of light source: 3200 ° K). Was given. The exposed sample was processed in the following processing steps using the following processing solutions. Treatment process Temperature Time Image 40 ° C 15 seconds Bleach-fix 40 ° C 45 seconds Rinse room temperature 45 seconds Alkaline treatment Room temperature 30 seconds

(Developer) Water 800 ml Potassium phosphate 40 g Disodium-N, N-bis (sulfonate ethyl) hydroxylamine 10 g KCl 5 g Hydroxyethylidene-1,1-disulfonic 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) 12.0

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

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

(Alkaline treatment liquid) Water 800 ml Potassium carbonate 30 g Water was added thereto 1000 ml pH (at 25 ° C./sulfuric acid) 10.0 The maximum color density part of the sample after treatment was treated with red light, green light,
It was measured with blue light. Table 1 shows the results.

[0173]

[Table 1]

As is clear from Table 1, the compounds of the present invention show higher color forming properties than the comparative compounds.

Example 2 The following photosensitive material 201 was prepared as a color diffusion transfer material. Photosensitive Material 201 Each layer was coated on a polyethylene terephthalate transparent support as follows to prepare a photosensitive sheet. Back layer: (a) Light-shielding layer containing carbon black 4.0 g / m ² and gelatin 2.0 g / m ² . Emulsion layer side: (1) Red-sensitive internal latent type direct positive silver bromide emulsion (with a silver content of 0.
6 g / m ² ), gelatin 2.0 g / m ² , the following nucleating agent 0.015 mg / m ² , 2-sulfo-5-n-pentadecylhydroquinone sodium salt 0.06 g / m ² , and the following cyan dyes. Donor compound (addition amount shown in parentheses), tricyclohexyl phosphate 0.15 g / m
A layer containing ² and 2,5-di-t-pentadecylhydroquinone 0.009 g / m ² .

[0176]

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[0177] (2) 2,5-di -t- pentadecyl hydroquinone 0.43 g / m ^2, trihexyl phosphate 0.1 g / m ² and a layer containing gelatin 0.4 g / m ^2. (3) Green-sensitive internal latent type direct positive silver bromide emulsion (with a silver content of 0.
42 g / m ² ), gelatin 1.4 g / m ² , the same nucleating agent as layer (1) 0.013 mg / m ² , 2-sulfo-5-n
-0.07 g of pentadecylhydroquinone sodium salt
/ M ² , the following magenta dye-donating compound (addition amount is shown in parentheses), tricyclohexyl phosphate 0.1
Layer containing 1 g / m ² and 2,5-di -t- pentadecyl hydroquinone 0.009 g / m ^2.

[0178]

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(4) The same layer as (2). (5) Blue-sensitive internal latent type direct positive silver bromide emulsion (with a silver amount of 0.1%).
6 g / m ² ), gelatin 1.8 g / m ² , the same nucleating agent as layer (1) 0.019 mg / m ² , 2-sulfo-5-n-
Pentadecylhydroquinone sodium salt 0.05g /
m ² , the following yellow dye-donating compound (addition amount is shown in parentheses), tricyclohexyl phosphate 0.22
layer containing g / m ² and 2,5-di -t- pentadecyl hydroquinone 0.014 g / m ^2.

[0180]

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(6) A layer containing 1.0 g / m ² of gelatin. Next, a dye fixing material having the constitution shown in Table 2 was prepared.

[0182]

[Table 2]

[0183]

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Polymer latex (1): Polymer latex obtained by emulsion polymerization of styrene / butyl acrylate / acrylic acid / N-methylol acrylamide at a weight ratio of 49.7 / 42.3 / 4/4 Polymer latex (2): methyl methacrylate / Acrylic acid / N-methylol acrylamide weight ratio 93
/ 3/4 emulsion polymerized polymer latex

The formulation of the treatment liquid is shown below. 0.8 g of a treatment liquid having the following composition was filled into a breakable container. 1-p-tolyl-4-hydroxymethyl-4-methyl-3-pyrazolidone 10.0 g 1-phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone 4.0 g potassium sulfite (anhydrous) 4.0 g hydroxyethyl cellulose 40.0 g Potassium hydroxide 64.0 g Benzyl alcohol 2.0 g Water was added and the total amount was 1 kg

Photosensitive materials 202 to 305 were prepared in exactly the same manner except that the cyan dye-donor compound, magenta dye-donor compound and yellow dye-donor compound of the light-sensitive material 201 were changed to those shown in the table. did. The light-sensitive materials 201 to 205 are exposed through a color chart on which wedges of cyan, magenta, yellow, and gray whose densities are continuously changed are recorded, and then the light-sensitive materials 201 and 205 are overlapped with a dye-fixing material. The treatment liquid was developed to have a thickness of 60 μm. (Development was done with the help of pressure rollers.) Treatment was at 25 ° C,
90 seconds after the treatment, the light-sensitive material and the dye-fixing material were peeled off, naturally dried and the density was measured. The density was measured by measuring the reflection density using a measuring device X Light 404 manufactured by X-Light Co., and measuring and evaluating the maximum density (Dmax) and the minimum density (Dmin). The results are shown in Table 3.

[0187]

[Table 3]

From Table 3, as compared with the light-sensitive element 201, the maximum density of the light-sensitive elements 202 to 205 of the present invention is significantly improved in the range where the minimum density hardly increases, and the object of the present invention is achieved. It indicates that Further, the density was measured while changing the time until peeling to 60 seconds, 90 seconds, and 120 seconds, but the density difference was remarkably small in the light-sensitive material using the developing agent of the present invention.

Example 3 <Preparation Method of Photosensitive Silver Halide Emulsion> Photosensitive silver halide emulsion (1) [for red-sensitive emulsion layer] Well stirred gelatin aqueous solution (16 g of gelatin in 540 ml of water, 0.24 g of potassium bromide, sodium chloride 1.
6 g and 24 mg of the compound (a) were added and heated to 55 ° C.), and the liquids (1) and (2) in Table 1 were added at the same time.
Add at an equal flow rate for minutes. Five minutes later, solution (3) and solution (4) in Table 1 were simultaneously added at an equal flow rate for 24 minutes. After washing with water and desalting in a conventional manner, lime-treated ossein gelatin 1
7.6 g and compound (b) 56 mg were added to adjust the pH to 6.
2. Adjust the pAg to 7.7 and add 0.41
g, and trimethylthiourea 1.02 mg were added, and the temperature was 60 ° C.
The optimum chemical sensitization. After this, 4-hydroxy-6-
Methyl-1,3,3a, 7-tetrazaindene 0.18
g, sensitizing dye (c) 64 mg, potassium bromide 0.41 g
Were added successively and then cooled. Thus, a monodisperse cubic silver chlorobromide emulsion 59 having an average grain size of 0.30 μm was obtained.
0 g was obtained.

[0190]

[Table 4]

[0191]

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Photosensitive Silver Halide Emulsion (2) [For Green Sensitive Emulsion Layer] Well stirred gelatin aqueous solution (20 ml of gelatin in 600 ml of water, 0.30 g of potassium bromide, 2.0 g of sodium chloride and compound (a)). The solution (1) and the solution (2) shown in Table 2 were simultaneously added to the solution obtained by adding 30 mg and heating to 46 ° C.) at an equal flow rate for 10 minutes. After 5 minutes, solution (3) and solution (4) in Table 2 were added simultaneously at the same flow rate for 30 minutes. One minute after the addition of the solutions (3) and (4) was completed, 60 ml of a solution of the sensitizing dye in methanol (sensitizing dye (d1) 360
mg and 73.4 mg of sensitizing dye (d2) were added all at once. After washing with water and desalting by a conventional method (performed with a precipitating agent (e) at pH 4.0), 22 g of lime-treated ossein gelatin was added to adjust pH to 6.0 and pAg to 7.6.
Then, 1.8 mg of sodium thiosulfate and 180 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene were added, and optimum chemical sensitization was performed at 60 ° C.
Next, 90 mg of antifoggant (f), 70 mg of compound (b) and 3 ml of compound (g) as preservatives were added and then cooled. Thus, 635 g of a monodispersed cubic silver chlorobromide emulsion having an average grain size of 0.30 μm was obtained.

[0193]

[Table 5]

[0194]

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[0195]

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Light-Sensitive Silver Halide Emulsion (3) [For Blue-Sensitive Emulsion Layer] Well-stirred aqueous gelatin solution (31.6 g of gelatin, 2.5 g of potassium bromide, and 13 mg of compound (a) in 584 ml of water) In addition, the solution (2) shown in Table 3 was first added to the solution heated to 70 ° C., and after 10 seconds, the addition of the solution (1) was started. Thereafter, the liquids (1) and (2) were added over 30 minutes. (2) After the completion of the addition of the solution, 5 minutes later, the addition of the solution (4) in Table 3 was started, and 10 seconds later, (3)
The addition of liquid was started. (3) Liquid is 27 minutes 50 seconds, (4)
The liquid was added over 28 minutes. After washing with water and desalting (pH was set to 3.9 using a precipitating agent (e)) by a conventional method, 24.6 g of lime-treated ossein gelatin and 56 of the compound (b).
The pH was adjusted to 6.1 and the pAg was adjusted to 8.5 by adding mg, and 0.55 mg of sodium thiosulfate was added to the mixture at 65 ° C.
The optimum chemical sensitization. Then, sensitizing dye (h) 0.35
g, 56 mg of the antifoggant (f) and 2.3 ml of the compound (g) as a preservative were added and cooled. Thus, 582 g of a monodispersed octahedral silver bromide emulsion having an average grain size of 0.55 μm was obtained.

[0197]

[Table 6]

[0198]

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<Preparation Method of Zinc Hydroxide Dispersion> 31 g of zinc hydroxide powder having a primary particle size of 0.2 μm,
1.6 g of carboxymethylcellulose, 0.4 g of sodium polyacrylate, 8.5 g of lime-treated ossein gelatin, and 158.5 ml of water were mixed as a dispersant, and the mixture was dispersed for 1 hour by a mill using glass beads. After the dispersion, the glass beads were filtered off, and a dispersion 188 of zinc hydroxide was obtained.
g was obtained. <Preparation Method of Emulsified Dispersion of Coupler> The oil phase component and the water phase component having the compositions shown in Table 7 are dissolved to obtain a uniform solution at 60 ° C. The oil phase component and the aqueous phase component were combined and dispersed in a 1 l stainless container with a dissolver equipped with a disperser having a diameter of 5 cm at 10,000 rpm for 20 minutes. To this, hot water in an amount shown in Table 7 was added as post-hydration and mixed at 2000 rpm for 10 minutes. Thus, an emulsified dispersion of couplers of three colors of cyan, magenta and yellow was prepared.

[0200]

[Table 7]

[0201]

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Using the materials thus obtained, the heat-developable dry color light-sensitive material 301 having a multilayer structure shown in Table 8 is obtained.
Was prepared.

[0203]

[Table 8]

[0204]

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Then, as shown in Table 9, photosensitive materials 302 to 305 having the same composition as 301 were prepared, except that the developing agent and coupler in each layer were changed.
To these samples, an FWH sensitometer manufactured by FUJIFILM Corporation (color temperature of light source: 3200 ° K) was used to perform gradation exposure through B, G, and R filters for sensitometry whose densities were continuously changed. Gave. Exposed photosensitive material 4
After immersing in water kept at 0 ° C. for 2.5 seconds, it was squeezed with a roller and immediately superposed so that the treated sheet R301 and the film surface were in contact with each other. Then, using a heat drum whose temperature has been adjusted so that the water-absorbed film surface temperature is 80 ° C., it is heated for 30 seconds and the processing sheet is peeled off from the photosensitive material. Cyan, magenta, and yellow color images were clearly obtained. Immediately after processing, the highest density part (Dmax) and the lowest density part (Dmi) of this sample
The results of measuring the concentration of n) with an X-LITE densitometer are shown in Table 9.
Shown in

[0206]

[Table 9]

[0207]

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Table 1 shows the configuration of the processing sheet R301 used.
0 is shown.

[0209]

[Table 10]

[0210]

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[0211]

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[0212]

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[0213]

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From Table 9, it can be seen that the developing agents of the present invention give high maximum densities to the comparative compounds, with little change in the minimum densities, and good discrimination. Also, the temperature of the film surface is 75 ° C, 85
When the temperature of the heat drum was adjusted so that the temperature became 0 ° C., and the above-described photosensitive material was processed in the same manner, the method using the color developing agent of the present invention showed a color density higher than that of the method using the comparative color developing agent. It can be seen that the difference is remarkably small and the development temperature dependency is small.

[0215]

By using the color-developing agent of the present invention, not only the color-forming property can be remarkably improved, but also the processing temperature dependency, especially the development temperature dependency can be remarkably improved.

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

Claims (7)

[Claims] 1. A color developing agent represented by formula (I). Embedded image In the formula, Z is a carbamoyl group, an acyl group, a sulfonyl group,
It represents a sulfamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amidino group, or an imidoyl group. Q represents an atomic group that forms an unsaturated ring with C. Y ¹ and Y ² each represent a group having a dissociative group having a pKa of 1 or more and 12 or less, and n and m are 0 respectively.
Represents an integer from 1 to 3, and n + m ≧ 1. When n and m are 2 or more, Y ¹ and Y ² may be the same or different. 2. In the general formula (I), Z is a carbamoyl group, and Y ¹ and Y ² have a pKa of 3 or more and 12 or less,
-NHSO ₂ - group, a phenolic hydroxyl group, -CONHC3H6N
O- group, -CONHSO ₂ - group or a -SO ₂ NHSO
A color-developing agent, which is a group having a dissociative group selected from ₂ -groups. 3. An image forming method comprising developing an image-exposed silver halide photographic light-sensitive material in the presence of a color-developing agent represented by formula (I) according to claim 1. 4. A hydrophilic colloid layer of at least one layer provided on a support contains at least one color developing agent represented by the general formula (I) of claim 1. Silver halide photographic light-sensitive material. 5. At least one of the color developing agents represented by the general formula (I) of claim 1 is contained in at least one hydrophilic colloid layer provided on a support. Diffusion transfer type silver halide color photographic light-sensitive material. 6. An image forming method, which comprises thermally developing the silver halide photographic light-sensitive material according to claim 4 or 5. 7. An image forming method comprising treating a silver halide photographic material with an alkaline solution containing a color developing agent according to claim 1.