JPH1062896A - Silver halide photographic sensitive material and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain sufficient color development at the time of development and an image good in color development performance and hue and superior in sharpness even in the case of using an active site substituted coupler by incorporating a specified color developing agent and a specified dye-forming coupler in one of photographic constituent layers. SOLUTION: One of the hydrophilic colloidal layers contains at least one of color developing agent represented by formula I and at least one kind of dye-forming coupler represented by one of formulae II-IV, and in formulae I-IV, R<11> is an aryl or heterocyclic group; R<12> is an alkyl, alkenyl, alkynyl, aryl, or heterocyclic group; X is a -SO2 - or -CO- group or the like; each of C1 -C3 is a coupler group to be released by coupling with the oxidation product of the color developing agent of formula I; each of M1 -M4 is a -O- or -COO- group or the like; each of (a), (b), (c), and (d) is 0 or 1; each of C'2 , D1 , and D2 is a divalent bonding group; and E is a trivalent bonding group.

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 novel image forming method, and in particular, has excellent color development during development and excellent sharpness. Silver photographic light-sensitive materials and image forming 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 to incorporate a sulfonylhydrazine-type developing agent into a hydrophilic colloid. Examples of developing agents that can be incorporated include, for example, U.S. Pat. No. 4,481,268 and European Patent 54.
Compounds described in 5,491A1 and 565,165A1 are exemplified. However, even with the developing agents listed here, sufficient color formation has not yet been obtained during color development, and this sulfonyl hydrazine type developing agent hardly develops color when an active site substituted coupler is used. There was a problem. A coupler having a substituted active site has advantages over a coupler having no active site substituted, such as reduction of coupler-derived stain and easy control of the activity of the coupler. 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 coloration even when a coupler having an active site substituted is used.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to obtain a sufficient color at the time of development by using a novel color developing agent and a coupler in combination, and to obtain a color developing property even when an active site substituent coupler is used. An object of the present invention is to provide a silver halide photographic light-sensitive material capable of obtaining an image having good hue and excellent sharpness, and an image forming method. It is a further object of the present invention to provide a silver halide photographic light-sensitive material and an image forming method which can provide a stable color image with respect to heat, humidity and light by using a novel color developing agent and a coupler in combination and have less stain. It is in.

[0006]

The object of the present invention has been achieved by the following constitutions. (1) In a silver halide color photographic material having at least one photographic component layer provided on a support,
At least one color developing agent represented by the following general formula (I) in at least one of the photographic constituent layers, and dye formation represented by at least one of the following general formulas (VIII-1) to (VIII-3) A silver halide photographic material comprising a coupler.

[0007]

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In the formula, R ¹¹ is an aryl group or a heterocyclic group, and R ¹² is an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. X is -SO ₂
-, -CO-, -COCO-, -CO-O-, -CON
(R ¹³ )-, -COCO-O-, -COCO-N
(R ¹³ ) — or —SO ₂ —N (R ¹³ ) —. Here, R ¹³ is a hydrogen atom or a group described for R ¹² .

[0009]

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In the formula, C ₁ , C ₂ and C ₃ each represent a dye-forming coupler residue capable of forming a dye by coupling reaction with an oxidized form of a color developing agent represented by the general formula (I); ₁ , M ₂ , M ₃ and M ₄ are respectively -O- and -C
OO -, - CO -, - NR 70 -, - CONR 70 -, - N
R ⁷⁰ CONR ⁷¹ —, —OCONR ⁷⁰ —, —SO ₂ NR ⁷⁰
-, -NR ⁷⁰ SO ₂ NR ^71- , -P (O) OR ⁷⁰ NR ⁷¹
—, —P (O) R ⁷⁰ NR ⁷¹ —, —S—, —SO—, or —SO ₂ —, wherein R ⁷⁰ and R ⁷¹ are each a hydrogen atom,
Represents an alkyl group, an alkenyl group, a cycloalkyl group, or an aryl group. a, b, c, and d each represent 0 or 1, and C ′ ₂ , D ₁ , D ₂ in the general formula VIII-2;
Represents a divalent linking group, and E represents a trivalent linking group.
C ₁ , C ₂ and C ₃ may be the same or different from each other. (2) The silver halide photographic material as described in the above item (1), wherein the compound represented by the general formula (I) is represented by the following general formula (II) or (III).

[0011]

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Wherein Z ¹ is an acyl group, a carbamoyl group,
Represents an alkoxycarbonyl group or an aryloxycarbonyl group, Z ² represents a carbamoyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group, and X ¹ , X ² , X ³ , X ⁴ and X ⁵ are each a hydrogen atom or Represents a substituent. However, the sum of the Hammett's substituent constant σ _p value of X ¹ , X ³ and X ^{5 and} the Hammett's substituent constant σ _m value of X ² and X ⁴ is 0.80 or more and 3.80 or less.
R ³ represents a heterocyclic group. (3) The silver halide photographic material as described in (2) above, wherein the compounds represented by formulas (II) and (III) are represented by formulas (IV) and (V), respectively. .

[0013]

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In the formula, R ¹ and R ² each represent a hydrogen atom or a substituent, and X ¹ , X ² , X ³ , X ⁴ and X ⁵ each represent a hydrogen atom or a substituent. However, the sum of the Hammett's substituent constant σ _p value of X ¹ , X ³ and X ^{5 and} the Hammett's substituent constant σ _m value of X ² and X ⁴ is 0.80 or more and 3.80 or less. R ³ represents a heterocyclic group. (4) The silver halide photographic material as described in the above item (3), wherein the compounds represented by the general formulas (IV) and (V) are represented by the general formulas (VI) and (VII), respectively. .

[0015]

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In the formula, R ⁴ and R ⁵ each represent a hydrogen atom or a substituent, and X ⁶ , X ⁷ , X ⁸ , X ⁹ and X ¹⁰ represent a hydrogen atom, a cyano group, a sulfonyl group, a sulfinyl group and a sulfamoyl group, respectively. , A carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, a trifluoromethyl group, a halogen atom, an acyloxy group, an acylthio group, or a heterocyclic group. However, X ⁶ , X ⁸ ,
The sum of the Hammett's substituent constant σ _p value of X ^{10 and} the Hammett's substituent constant σ _m value of X ⁷ and X ⁹ is 1.20 or more and 3.80.
It is as follows. Q ¹ represents a nonmetallic atom group necessary for forming a heterocyclic ring of 5- to 8-membered ring nitrogen-containing with C. (5) An image forming method, wherein the silver halide photographic light-sensitive material described in (1) to (4) above is developed by heat-treating the material at 50 ° C or more and 200 ° C or less. (6) An image forming method, comprising developing the silver halide photographic light-sensitive material according to any one of (1) to (4) in a solution. Preferred embodiments include the following. (1) A diffusion transfer type silver halide color photograph comprising a color developing agent represented by formula (I) and a dye-forming coupler represented by formulas (VIII-1) to (VIII-3). Photosensitive material. (2) An image forming method comprising thermally developing the photosensitive material of (1). (3) When the photosensitive material according to the present invention is processed with a processing solution, the processing solution does not contain the color developing agent of the present invention. In the present invention, the coating silver material is added in an amount of 0.003 to 0.3 g / m ^2.
A good image can be obtained even with a low silver photosensitive material,
It is suitable for environmental preservation, and can provide an image formed by scanning exposure with high density and little stain after storage, and is suitable for digital processing.

[0017]

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

Here, when the substituent in the compound of the present invention contains an aliphatic moiety (including an alkyl moiety, an alkenyl moiety, an alkynyl moiety, an alkylene moiety and an alkenylene moiety), unless otherwise specified, the aliphatic moiety is directly substituted. Even in the form of a chain, a branched chain, or a ring, even if it is saturated,
It may be unsaturated, substituted or unsubstituted. When the substituent in the compound of the present invention contains an aryl moiety, the aryl moiety is, unless otherwise specified.
It may be substituted or unsubstituted, and may be a single ring or a condensed ring. When the substituent in the compound of the present invention contains a heterocyclic moiety, the heterocyclic moiety may be substituted or unsubstituted, and may be a single ring or a condensed ring, unless otherwise specified. In the present invention, as the hetero ring, a 3- to 8-membered ring is preferably formed by a nonmetallic atom, and a 5- to 6-membered ring is more preferably formed. As the nonmetal atom, carbon, oxygen, nitrogen, sulfur and hydrogen are preferred, and carbon, hydrogen and nitrogen are more preferred. As the aliphatic moiety, an alkyl moiety is preferable unless otherwise specified.
As the substituent for the aliphatic moiety, preferably, for example, a halogen atom, an aryl group, a heterocyclic group, an aliphatic oxy group, an aryloxy group, an acyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an acylamino group , A sulfonamide group, an aliphatic sulfonyl group, an arylsulfonyl group, and the like. In the general formula (I), R ¹¹ represents an aryl group or a heterocyclic group which may have a substituent. The aryl group of R ^11, preferably that of 6 to 14 carbon atoms include, for example, phenyl or naphthyl. The heterocyclic group represented by R ¹¹ is preferably a saturated or unsaturated 5-, 6- or 7-membered ring containing at least one of nitrogen, oxygen, sulfur and selenium. These may be condensed with a benzene ring or a hetero ring. Examples of the hetero ring of R ¹¹ include furanyl, thienyl, oxazolyl, thiazolyl, imidazolyl, triazolyl, pyrrolidinyl, benzoxazolyl, benzothiazolyl, pyridyl, pyridazyl, pyrimidinyl, pyrazinyl, triazinyl, quinolinyl, isoquinolinyl, phthalazinyl, quinoxalinyl, and quinazolinyl. , Purinyl, pteridinyl, azepinyl, benzoxepinyl and the like.

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

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

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

The general formula (II) and Z ¹ in the general formula (III) represents an acyl group, a carbamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group,, Z ²
Represents a carbamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group. The acyl group is preferably an acyl group having 1 to 50 carbon atoms, and more preferably 2 to 40 carbon atoms. Specific examples include acetyl, 2-methylpropanoyl, cyclohexylcarbonyl, n-octanoyl, 2-hexyldecanoyl, dodecanoyl, chloroacetyl, trifluoroacetyl, benzoyl, Dodecyloxybenzoyl group, 2-hydroxymethylbenzoyl group, 3
-(N-hydroxy-N-methylaminocarbonyl) propanoyl group. The case where Z ¹ and Z ² are carbamoyl groups will be described in detail in formulas (VI) to (VII).

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

X ¹ , X ² , X ³ , X ⁴ and X ⁵ represent a hydrogen atom or a substituent. Here, examples of the substituent include a linear or branched, chain or cyclic alkyl group having 1 to 50 carbon atoms (for example, 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 50 carbon atoms (Eg, vinyl, 1-methylvinyl, cyclohexen-1-yl, etc.), having 2 to 50 carbon atoms in total.
Alkynyl group (e.g., ethynyl, 1-propynyl, etc.), an aryl group having 6 to 50 carbon atoms (e.g., phenyl, naphthyl, anthryl, etc.), an acyloxy group having 1 to 50 carbon atoms (e.g.,

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

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

Methylthio, octylthio, cyclohexylthio, etc.), an arylthio group having 6 to 50 carbon atoms (eg, phenylthio, naphthylthio, etc.), 1 to 50 carbon atoms
Ureido group (eg, 3-methylureido, 3,3-
Dimethylureide, 1,3-diphenylureide, etc.),
A heterocyclic group having 2 to 50 carbon atoms (as a hetero atom, for example, a 3- to 12-membered monocyclic or condensed ring containing at least one or more of nitrogen, oxygen and sulfur;
Furyl, 2-pyranyl, 2-pyridyl, 2-thienyl,
2-imidazolyl, morpholino, 2-quinolyl, 2-benzimidazolyl, 2-benzothiazolyl, 2-benzoxazolyl, etc.), an acyl group having 1 to 50 carbon atoms (eg, acetyl, benzoyl, trifluoroacetyl, etc.), carbon Sulfamoylamino groups of numbers 0 to 50 (e.g., N-butylsulfamoylamino, N-phenylsulfamoylamino, etc.), silyl groups of 3 to 50 carbon atoms (e.g., trimethylsilyl, dimethyl-t-butylsilyl, Triphenylsilyl and the like, and a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom and the like). The above substituents may further have a substituent,
Examples of the substituent include the substituents mentioned here. X ¹ , X ² , X ³ , X ⁴ and X ⁵ may be bonded to each other to form a condensed ring. The condensed ring is preferably a 5- to 7-membered ring, more preferably a 5- to 6-membered ring.

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

In the general formula (II), X ¹ , X ² , X ³ ,
As for X ⁴ and X ⁵ , the sum of Hammett's substituent constant σ _p value of X ¹ , X ³ and X ⁵ and Hammett's substituent constant σ _m value of X ² and X ⁴ is 0.80 or more. 80 or less. Further, X ⁶ , X ⁷ , X ⁸ , X ⁹ , X ⁹ in the general formula (VI)
¹⁰ is a hydrogen atom, a cyano group, a sulfonyl group, a sulfinyl group, a sulfamoyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group,
Represents a trifluoromethyl group, a halogen atom, an acyloxy group, an acylthio group, or a heterocyclic group, which may further have a substituent and may be bonded to each other to form a condensed ring. X ¹ , X
² , X ³ , X ⁴ , and X ⁵ are the same as those described above. However, in the general formula (VI), the sum of the Hammett's substituent constant σ _p value of X ⁶ , X ⁸ and X ^{10 and} the Hammett's substituent constant σ _m value of X ⁷ and X ⁹ is 1.20 or more, 80 or less;
It is preferably from 1.50 to 3.80, and more preferably from 1.70 to 3.80. Here, if the sum of the σ _p value and the σ _m value is less than 0.80, there is a problem that the coloring property is not sufficient, and if it exceeds 3.80, it is difficult to synthesize and obtain the compound itself. Becomes

The Hammett's substituent constants σ _p and σ _m are described, for example, by Naoki Inamoto, “Hammet's Rule-Structure and Reactivity-” (Maruzen), “New Experimental Chemistry Course 14, Synthesis and Reaction of Organic Compounds V”. 2605 (edited by The Chemical Society of Japan, Maruzen), Tadao Nakaya, "Explanation of Theoretical Organic Chemistry", 217 pages (Tokyo Kagaku Dojin), Chemical Review (91), 165-195.
The book is described in detail in pages (1991).

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

In the general formulas (III) and (V), R ³ represents a heterocyclic group. The preferred heterocyclic group here has 1 to 1 carbon atoms.
50 heterocyclic groups, and the hetero atom is, for example,
A saturated or unsaturated 3- to 12-membered (preferably 3- to 8-membered) monocyclic or condensed ring containing at least one or more nitrogen, oxygen and sulfur atoms, and a specific example of the heterocyclic ring is furan. , Pyran, pyridine, thiophene, imidazole, quinoline, benzimidazole, henzothiazole, benzoxazole, pyrimidine, pyrazine, 1,2,4-thiadiazole, pyrrole, oxazole, thiazole, quinazoline, isothiazole,
Pyridazine, indole, pyrazole, triazole,
Quinoxaline and the like. These heterocyclic groups may have a substituent, and preferably have at least one electron-withdrawing group. Here, the electron-withdrawing group means a group having a positive Hammett σ _p value. In case of incorporating a color developing agent of the present invention in the photosensitive ^{material, Z 1, Z 2, R} 1 ~R 5, preferably it has a ballast group in at least one group of X ¹ to X ^10.
Examples of the heterocycle completed by Q ₁ are specific compound examples I-
16-I-74. The compounds represented by formula (I) of the present invention may be used alone or in combination of two or more.

Next, the novel color developing agent used in the present invention will be specifically described, but the scope of the present invention is not limited to these specific examples.

[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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Next, general formulas (VIII-1) to (VIII)
The dye-forming coupler represented by -3) will be described in detail. The active positions of these couplers may be substituted or unsubstituted, but in the present invention, it is preferable that all active positions are substituted.

In the general formulas (VIII-1) to (VIII-3), C
₁ , C ₂ and C _{3 each} represent a dye-forming coupler residue capable of forming a dye by a coupling reaction with an oxidized form of the color developing agent represented by the general formula (I). The term "dye-forming coupler residue" as used herein means a monovalent group obtained by removing one hydrogen atom from any part of the dye-forming coupler. C ₁ , C ₂ ,
C ₃ may be the same or different, but is preferably the same.

In the general formulas (VIII-1) to (VIII-3), M
₁ , M ₂ , M ₃ , and M ₄ are -O-, -COO-,
^{-CO -, - NR 70 -,} - CONR 70 -, - NR 70 CO
^{NR 71 -, - OCONR 70 -} , - SO 2 NR 70 -, - P
(O) OR ⁷⁰ NR ^71- , -P (O) R ⁷⁰ NR ^71- , -S
-, - SO-, or -SO ₂ - represents, preferably -
O -, - COO -, - CONR 70 -, - NR 70 CONR
^{71 -, - OCONR 70 -,} - SO 2 NR 70 -, or -
Represents SO ₂ —, more preferably —O—, —COO—,
—CONR ⁷⁰ — or —SO ₂ NR ⁷⁰ —. Here, R ⁷⁰ and R ⁷¹ each represent a hydrogen atom, an alkyl group (preferably having a C number of 1 to 20) and an alkenyl group (preferably having a C number of 2).
To 20), a cycloalkyl group (preferably having 3 to 2 carbon atoms)
0), an aryl group (preferably having 6 to 26 carbon atoms),
It preferably represents a hydrogen atom, an alkyl group or an aryl group, more preferably represents a hydrogen atom or an alkyl group, and still more preferably represents a hydrogen atom or a methyl group.

In the general formulas (VIII-1) and (VIII-3),
a, b, c, and d each represent 0 or 1, and preferably 1. General formulas (VIII-1) to (VIII-2)
In the above, D ₁ and D ₂ each represent a divalent linking group (preferably C
(Numbers 0 to 30), and preferably a divalent linking group as shown below.

[0053]

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Even more preferably, D ₁ and D ₂ represent a divalent linking group as shown below.

[0055]

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D ₁ and D ₂ may be the same or different,
It is preferred that they be the same. In the general formula (VIII-3), E represents a trivalent linking group (preferably having a C number of 0 to 20), preferably a linking group as shown below.

[0057]

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Even more preferably, E represents a trivalent linking group as shown below.

[0059]

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The dye-forming coupler of the present invention has the general formula (VIII)
-1) or (VIII-3), more preferably represented by the general formula (VIII-1).

The general formulas (VIII-1) to (VIII-) of the present invention
In the dye-forming coupler represented by 3), the dye-forming couplers C ₁ -H, C ₂ -H, and C ₃ -H (H represents a hydrogen atom bonded to a connecting portion of the dye-forming coupler residue)
Examples of all are Theory of Photographic Process (4th.Ed., edited by THJames, Macmilla
n, 1977) pages 291-334, and 354-36.
1 page, JP-A-58-12353 and 58-14904
No. 6, No. 58-149047, No. 59-11114
No. 59-124399, No. 59-174835
Nos. 59-231439 and 59-231540
No. 60-2951, No. 60-14242, No. 6
Nos. 0-23474 and 60-66249.

Dye-forming couplers C ₁ -H, C ₂ -H, C
_{As 3-} H, the following general formulas (1) to (1)
There is a compound having a structure as described in 2). These are compounds generally referred to as active methylene, pyrazolone, pyrazoloazole, phenol, naphthol, and pyrrolotriazole, respectively, and are compounds known in the art.

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Formulas (1) to (4) represent couplers referred to as active methylene couplers, wherein R ¹⁴ represents an optionally substituted acyl 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 or a heterocyclic residue which may have a substituent. R
^14, as the R ^15, the substituent that may be R ¹⁶ has, include those mentioned as examples of X ¹ to X ⁵ as described above.

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

Y may be substituted by a substituent,
Examples of the substituent for substituting Y include those described for X ^{1 to} X ⁵ . Y is preferably a halogen atom, an aryloxy group, a heterocyclic oxy group, an acyloxy group, an aryloxycarbonyloxy group, an alkoxycarbonyloxy group, or a carbamoyloxy group. General formula (1)
In (4), R ¹⁴ and R ¹⁵ , and R ¹⁴ and R ¹⁶ may be bonded to each other to form a ring. Formula (5) represents a coupler called a 5-pyrazolone-based coupler, wherein 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.

In the 5-pyrazolone coupler represented by the general formula (5), R ¹⁷ is an aryl group or an acyl group,
A phenyl group in which ¹⁸ is substituted with one or more halogen atoms is preferred. To describe these preferred groups in detail, R ¹⁷ is a phenyl group, a 2-chlorophenyl group, a 2-
Methoxyphenyl group, 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) is an acyl group such as a benzoyl group, and these groups may further have a substituent, and these groups may be a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom. It is a connecting organic substituent or a halogen atom. Y has the same meaning as described above.

R ¹⁸ is preferably a substituted phenyl group such as a 2,4,6-trichlorophenyl group, a 2,5-dichlorophenyl group and a 2-chlorophenyl group. The general formula (6) represents a coupler called a pyrazoloazole coupler, wherein R ¹⁹ represents a hydrogen atom or a substituent. Q ³ represents a group of nonmetallic atoms necessary for forming a 5-membered azole ring containing 2 to 4 nitrogen atoms, and the azole ring may have a substituent (including a condensed ring). Among the pyrazoloazole couplers represented by the general formula (6), imidazo [1,2-b] pyrazoles described in U.S. Pat. U.S. Patent No. 4,
No. 500,654, pyrazolo [1,5-b]-
1,2,4-triazoles, U.S. Pat.
No. 067, pyrazolo [5,1-c] -1,2,4
-Triazoles are preferred.

For details of the azole ring substituents represented by the substituents R ¹⁹ and Q ³ , see, for example, US Pat.
No. 0,654, column 2, line 41 to column 8, line 27. Preferably, JP-A-61-
No. 65245, a pyrazoloazole coupler having a branched alkyl group directly bonded to the 2, 3 or 6-position of the pyrazolotriazole group, and a sulfonamide group in the molecule described in JP-A-61-65245. A pyrazoloazole coupler having an alkoxyphenylsulfonamide ballast group described in JP-A-61-147254;
Pyrazolotriazole couplers having an alkoxy group or an aryloxy group at the 6-position described in JP-A-209457 or JP-A-63-307453;
No. 201443 is a pyrazolotriazole coupler having a carboxamide group in the molecule. Y has the same meaning as described above.

The general formulas (7) and (8) are couplers called a phenol coupler and a naphthol coupler, respectively, wherein R ²⁰ is a hydrogen atom or —CONR ²² R
_{^{23, -SO 2 NR 22 R 23}} , -NHCOR 22, -NHCO
NR ²² R ^23, represents a group selected from -NHSO ₂ NR ²² R ^23. R ²² and R ²³ represent a hydrogen atom or a substituent. In the general formulas (7) and (8), R ²¹ represents a substituent, 1 represents an integer selected from 0 to 2, and m represents an integer selected from 0 to 4. When l and m are 2 or more, R ²¹ may be different from each other. Examples of the substituent of R ^{21 to} R ²³ include those described as examples of X ^{1 to} X ^{5 in} the general formulas (II) and (IV). Y has the same meaning as described above.

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

Preferred examples of the naphthol coupler represented by the general formula (8) include US Pat. No. 2,474,29.
No. 3, 4,052, 212 and 4,146, 3
No. 96, No. 4,282,233, No. 4,296,
No. 200, etc., and 2-carbamoyl-1-naphthols described in US Pat. No. 4,690,889 and the like.
-Carbamoyl-5-amido-1-naphthol type and the like. Y is the same as described above. Formula (9) to (12) are couplers called ^{pyrrolotriazoles, R 32, R 33, R} 34 represents a hydrogen atom or a substituent. Y is as described above. As the substituents for R ³² , R ³³ and R ³⁴ , X ^{1 to} X
Examples described in ⁵ are given. General formula (9)
Preferable examples of the pyrrolotriazole coupler represented by (12) include EP 488,248 A1,
Couplers in which at least one of R ³² and R ³³ described in JP-A-491,197A1 and JP-A-545,300 are electron-withdrawing groups are exemplified. Y is the same as described above. In addition, couplers having a structure such as fused phenol, imidazole, pyrrole, 3-hydroxypyridine, active methylene, active methine, 5,5-fused heterocycle, and 5,6-fused heterocycle other than those described above can be used.

Examples of the fused phenol couplers include US Pat. Nos. 4,327,173 and 4,564,586.
And the couplers described in JP-A Nos. 4,904,575 and the like can be used. As the imidazole coupler, couplers described in U.S. Pat. Nos. 4,818,672 and 5,051,347 can be used. As the 3-hydroxypyridine-based coupler, couplers described in JP-A-1-315736 and the like can be used.

As active methylene and active methine couplers, US Pat. Nos. 5,104,783 and 5,16
The couplers described in 2,196 and the like can be used. 5,5
-As a fused heterocyclic coupler, US Pat.
Pyrrolopyrazole couplers described in JP-A-4,289, and pyrroleimidazole couplers described in JP-A-4-174429 can be used. Examples of 5,6-fused heterocyclic couplers include pyrazolopyrimidine couplers described in U.S. Pat. No. 4,950,585 and JP-A-4-20473.
No. 0, pyrrolotriazine couplers described in EP-A-556700, and the like can be used.

As C ₁ -H, C ₂ -H and C ₃ -H, besides the above-mentioned couplers, West German Patent No. 3,819,051A
No. 3,823,049, U.S. Pat.
No. 0,883, No. 5,024,930, No. 5,0
Nos. 51,347, 4,481,268, European Patent Nos. 304,856A2, 329,036, 354,549A2, 374,781A2, 379,110A2, No. 386,930A1,
JP-A-63-141055 and JP-A-64-32260,
JP-A-64-32261, JP-A-2-29747, JP-A-2-44340, JP-A-2-110555, and JP-A-3-79
No. 38, No. 3-160440, No. 3-172839
Nos. 4,172,447, 4,179,949, 4-182,645, 4-184,637 and 4-1
No. 88138, No. 4-188139, No. 4-1948
No. 47, No. 4-204532, No. 4-204731
And couplers described in JP-A-4-204732 and the like can also be used.

General formulas (VIII-1) to
Specific examples of the dye-forming coupler represented by (VIII-3) are shown below, but the present invention is of course not limited thereto.

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The amount of the coupler used in the present invention depends on its molar extinction coefficient (ε), but in order to obtain an image density of 1.0 or more in reflection density, the amount of the dye formed by the coupling is ε. Is about 5,000 to 500,000, the coating amount is 0.001 to 100 mmol /
m ² , preferably about 0.01 to 10 mmol / m ² , more preferably about 0.05 to 5 mmol / m ² .

When the color developing agent of the present invention is contained in a light-sensitive material, any layer (eg, emulsion layer, intermediate layer, etc.)
May be. Preferably, it is contained in the emulsion layer. When there are a plurality of emulsion layers, it is preferable to include them in all the layers. As the addition amount of the color developing agent of the present invention,
0.01 to 100 times, preferably 0.1 to 100 times the coupler.
It is 1 to 10 times, more preferably 0.2 to 5 times.

The color developing agent represented by the general formula (I) of the present invention may be capable of diffusing and transferring a produced dye to a layer coated with a mordant, depending on the coupling partner. In the present invention, an auxiliary developing agent can be preferably used. Here, the auxiliary developing agent means a substance having an action of promoting the transfer of electrons from the color developing agent to the silver halide in the development process of silver halide development, and the auxiliary developing agent in the present invention is preferably a compound of the general formula The compound is an electron-emitting compound represented by (B-1) or the general formula (B-2), which conforms to the Kendall-Peltz rule.
Among them, those represented by (B-1) are particularly preferred.

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In the general formulas (B-1) and (B-2),
R ^{51 to} R ⁵⁴ represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, or a heterocyclic group. R
^{55 to} R ⁵⁹ 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 from each other. R ⁶⁰ represents an alkyl group or an aryl group. Specific examples of the compound represented by formula (B-1) or (B-2) are shown below, but the auxiliary developing agent used in the present invention is not limited to these specific examples.

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In the present invention, a known color developing agent is used.
It can be used together with the color developing agent of the present invention. Known color developing agents include West German Patent No. 1,158,8.
No. 36, UK Patent No. 2,018,453, US Pat. No. 3,734,735, US Pat. No. 3,809,906.
JP-A-47-37,539, JP-A-52-42,
No. 725, JP-A-52-57,827, JP-A-54-57
No. 31,737, U.S. Pat. No. 4,126,461, JP-B-63-36,487, and JP-A-58-33,238.
No., JP-A-59-53,831, Japanese Patent Publication No. 2-4,89.
No. 0, No. 3-60,418, No. 4-20,1
No. 77, Tokuhei 5-48,901, Tokuhei 5-48,
No. 902, Japanese Patent Publication No. 4-69,776, JP-A-60-1
81,742, JP-A-60-191,251, JP-A-62-227,141, JP-A-62-288,833.
5, JP-A-3-15,052, JP-A-3-33,7
No. 43, JP-A-3-125145, JP-A-5-22
No. 4,381, JP-A-49-46,427, JP-B-2
No. 15,855, JP-B No. 2-15,856, JP-A-59-111,148, U.S. Pat. No. 4,430,42
No. 0, JP-B-46-7,782, JP-B-45-9,0
No. 31, Belgian Patent No. 602,250, U.S. Pat. No. 3,357,203, JP-B-48-39,165,
JP-B-3-74,817, JP-A-62-131,25
No. 3, Tokuhei 5-33, 781, Tokuhei 5-33, 7
No. 82, JP-A-63-8,645, JP-A-63-12
3,043, JP-A-63-123,044, JP-A-63-123,045, JP-A-63-123,046
No., EP 545,491A1, EP 56
The color developing agents described in 5,165A1 are preferably used. These color developing agents may be added to the light-sensitive material or may be present in the developer.

The light-sensitive material of the present invention basically has a light-sensitive silver halide, a color developing agent, a coupler and a binder on a support, and further contains, if necessary, an organic metal salt oxidizing agent and the like. Can be done. These components are often added to the same layer (a photosensitive layer or a non-photosensitive layer), but can be added separately to another layer as long as they can react. Hydrophobic additives such as couplers and color developing agents used in the present invention are described in U.S. Pat. No. 2,322,027.
It can be introduced into the layer of the light-sensitive material by a known method such as the method described in the above. In this case, U.S. Pat.
No. 55,470, No. 4,536,466, No. 4,
No. 536,467, No. 4,587,206, No. 4,555,476, No. 4,599,296, and Japanese Patent Publication No. 3-62256 require a high boiling point organic solvent. Can be used in combination with a low-boiling organic solvent having a boiling point of 50 to 160 ° C. depending on the solvent. Further, two or more of these couplers, color developing agents (diffusion-resistant reducing agents), high-boiling organic solvents and the like can be used in combination. The amount of the high boiling organic solvent is 10 to 1 g of the color image forming compound used.
g or less 0 or more, preferably 5 g or less, more preferably 1 or less.
g to 0.1 g. In addition, 1 to 1 g of binder
cc or less, more preferably 0.5 cc or less, especially 0.3 cc or less and 0 or more is suitable. Also, a dispersion method using a polymer described in JP-B-51-39853 and JP-A-51-59943, JP-A-62-30242 and JP-A-63-27 are disclosed.
No. 1339 can be used. When the hydrophobic additive is a compound substantially insoluble in water, it can be dispersed and contained as fine particles in a binder other than the above method. When dispersing the hydrophobic compound in the hydrophilic colloid, various surfactants can be used. For example, JP
The surfactants described in the RD magazine shown in pages (37) to (38) of JP-A-157636 and the following list can be used. In the light-sensitive material of the present invention, a compound for stabilizing an image simultaneously with activation of development can be used. Specific compounds preferably used are described in U.S. Pat. No. 4,500,626, columns 51-52.

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

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

The silver halide emulsion which can be used in the present invention includes:
Any of silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide, and silver chloroiodobromide may be used. The silver halide emulsion used in the present invention may be a surface latent image type emulsion or an internal latent image type emulsion. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent or light fogging. Also,
It may be a so-called core-shell emulsion in which the inside of the grain and the surface layer of the grain have different phases, or silver halides having different compositions may be joined by epitaxial joining. The silver halide emulsion may be monodispersed or polydispersed, and a method of adjusting the gradation by mixing monodispersed emulsions as described in JP-A-1-167,743 and JP-A-4-223,643 is preferably used. . The particle size is preferably from 0.1 to 2 μm, particularly preferably from 0.2 to 1.5 μm. The crystal habits of silver halide grains include those having regular crystals such as cubic, octahedral, and tetrahedral, those having irregular crystal systems such as spheroids and high aspect ratio tabular, and those having twin planes. It may be one having such a crystal defect, or a composite system thereof, or any other. Specifically, US Pat. No. 4,500,626
No. 50, No. 4,628,021, Research Disclosure Magazine (hereinafter abbreviated as RD) No. 17,0
29 (1978), No. 17, 643 (December, 1978), pp. 22-23, and No. 18, 716 (1979).
No. 307, 105 (198).
Nov. 9, pp. 863-865, JP-A-62-253,
No. 159, No. 64-13,546, JP-A-2-23
No. 6,546, No. 3-110, 555, and Grafkid, "Physics and Chemistry of Photography", published by Paul Monte (P.Gl.
afkides, Chemieet Phisique Photographique, Paul Mont
el, 1967), Duffin's "Photoemulsion Chemistry", published by Focal Press (GFDuffin, Photographic Emulsion C)
hemistry, Focal Press, 1966), "Production and Coating of Photographic Emulsions", by Zerikman et al.
L. Zelikman et al., Making and Coating Photographic
Emulsion, Focalpress, 1964) can be used.

The photosensitive silver halide emulsion used in the present invention may contain heavy metals such as iridium, rhodium, platinum, cadmium, zinc, thallium, lead, iron, osmium and chromium for various purposes. These compounds may be used alone or in combination of two or more. In addition, these compounds can be added as salts such as chlorides, bromides, and cyanides, as well as various complex salts. The amount of addition depends on the purpose of use, but is generally about 10 ^-9 to 10 ^-3 mol per mol of silver halide.
Also, when it is contained, it may be uniformly introduced into the particles,
Further, it may be localized inside or on the surface of the particle. Specifically, Japanese Patent Application Laid-Open Nos. 2-236542 and 1-11663
No. 7, JP-A-5-181246 and the like are preferably used. The light-sensitive silver halide emulsion is usually a chemically sensitized silver halide emulsion. For the chemical sensitization of the photosensitive silver halide emulsion of the present invention, known sulfur sensitization, selenium sensitization, chalcogen sensitization such as tellurium sensitization,
A noble metal sensitization method and a reduction sensitization method using gold, platinum, palladium or the like can be used alone or in combination (for example, JP-A-3-110,555, JP-A-5-105).
No. 241267). These chemical sensitizations can be carried out in the presence of a nitrogen-containing heterocyclic compound (Japanese Patent Laid-Open No. Sho 62-2).
53, 159). Further, an antifoggant described later can be added after the completion of the chemical sensitization. Specifically, the methods described in JP-A-5-45,833 and JP-A-62-40,446 can be used. The pH at the time of chemical sensitization is preferably 5.3 to 10.5, more preferably 5.5 to 8.
5, and the pAg is preferably 6.0 to 10.5, more preferably 6.8 to 9.0. The coating amount of the photosensitive silver halide emulsion used in the present invention is 1 mg in terms of silver.
To 10 g / m ² .

In order to give the photosensitive silver halide used in the present invention green sensitivity, red sensitivity, and infrared sensitivity, the photosensitive silver halide emulsion is spectrally sensitized with methine dyes or the like. . If necessary, the blue-sensitive emulsion may be subjected to spectral sensitization in the blue region. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, heminanine dyes, styryl dyes and hemioxonol dyes. Specifically, U.S. Pat.
Sensitizing dyes described in JP-A-617,257, JP-A-59-180,550, JP-A-64-13,546, JP-A-5-45,828 and JP-A-5-45,834. These sensitizing dyes may be used alone, or a combination thereof may be used. The combination of sensitizing dyes is often used particularly for the purpose of supersensitization or wavelength adjustment of spectral sensitivity. Along with the sensitizing dye, a dye which does not itself have a spectral sensitizing effect or a compound which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (for example, US Pat. 615,641, JP-A-63-23145, etc.). These sensitizing dyes may be added to the emulsion at or before or after chemical ripening, or according to U.S. Pat. Nos. 4,183,756 and 4,225,666 before and after nucleation of silver halide grains. Good. These sensitizing dyes and supersensitizers may be added as a solution of an organic solvent such as methanol, a dispersion of gelatin or the like, or a solution of a surfactant. The amount of addition is generally about 10 ^-5 to 10 ^-2 mol per mol of silver halide. Known photographic additives that can be used in the light-sensitive material and the dye-fixing material used in such a process and the RDNO. 17, 643 and RD.
16 and Nos. 307 and 105, and the relevant portions are summarized in the following table.

Types of additives RD17643 RD18716 RD307105 1. Chemical sensitizer page 23 page 648 right column page 866 2. Sensitivity increasing agent, page 648, right column 3. Spectral sensitizers, pages 23 to 24, page 648, right column 866 to 868, super sensitizers, page 649, right column 4. Optical brightener page 24 page 648 right column page 868 5. Fogging prevention page 24-25 page 649 right column 868-870 page Agents, stabilizers 6. Light absorbers, pages 25 to 26, page 649, right column, page 873, filters-page 650, left column, dyes, ultraviolet absorbers 7. Stain prevention page 25 right column 650 page left column page 872 Stopper to right column 8. Dye image page 25 page 650 left column page 872 stabilizer 10. Hardener page 26 page 651 left column pages 874-875 Binder page 26 page 651 left column pages 873 to 874 11. 11. Plasticizer, page 27, page 650, right column, page 876, lubricant. Coating aid, pages 26 to 27, page 650, right column, pages 875 to 876 Surfactant 13. Static 27 pages 650 right column 876-877 Inhibitors 14. Matting agent 878-879

A hydrophilic binder is preferably used as a binder for the constituent layers of the photosensitive material. Examples thereof include the above-mentioned Research Disclosure and JP-A-64-13 / 1988.
No. 546, pages (71) to (75). Specifically, a transparent or translucent hydrophilic binder is preferable, and examples thereof include gelatin and gelatin derivatives. The gelatin may be selected from lime-processed gelatin, acid-processed gelatin, and so-called demineralized gelatin having a reduced content of calcium and the like according to various purposes, and it is also preferable to use them in combination.

Examples of the method of exposing and recording an image on a photosensitive material include a method of directly photographing a landscape or a person using a camera or the like, a method of exposing through a reversal film or a negative film using a printer or a enlarger, Scanning and exposing the original image through slits and the like using a copier exposure device, etc., light emitting diodes and various lasers (laser diodes,
A method of performing scanning exposure by emitting light from a gas laser or the like (JP-A-2-129625, JP-A-5-17614).
No. 4, No. 5-199372, No. 6-127022), image information is output to an image display device such as a CRT, a liquid crystal display, an electroluminescence display, a plasma display, etc., directly or through an optical system. Exposure method. As the light source for recording an image on the photosensitive material, natural light, a tungsten lamp, a light emitting diode, a laser light source,
US Patent No. 4,500,626 56
Column, JP-A-2-53,378 and JP-A-2-54,672 can be used. Also, image exposure can be performed using a wavelength conversion element in which a non-linear optical material and a coherent light source such as laser light are combined. Here, the non-linear optical material is a material that can exhibit nonlinearity between polarization and electric field that appears when a strong optical electric field such as laser light is applied, and lithium niobate,
Potassium dihydrogen phosphate (KDP), lithium iodate, B
Inorganic compounds represented by aB ₂ O _{4 and the} like, urea derivatives, nitroaniline derivatives, for example, nitropyridine-N-oxide derivatives such as 3-methyl-4-nitropyridine-N-oxide (POM); 61-5346
Compounds described in Nos. 2 and 62-210432 are preferably used. As a form of the wavelength conversion element, a single crystal optical waveguide type, a fiber type and the like are known, and any of them is useful. The image information includes an image signal obtained from a video camera, an electronic still camera, a television signal represented by the Nippon Television Signal Standards (NTSC), and an image obtained by dividing an original image into a number of pixels such as a scanner. An image signal generated using a computer represented by a signal, CG, or CAD can be used.

The method of developing the photosensitive material having the color developing agent of the present invention after it is exposed is as follows: an activator processing method of developing with an alkaline processing solution not containing a color developing agent, and an auxiliary developing agent / base. There is a method of processing with a processing solution containing, a method of developing the alkaline processing solution on a photosensitive material by a diffusion transfer method, and a method of processing by thermal development.

Activator processing refers to a processing method in which a color developing agent is incorporated in a light-sensitive material and is developed with a processing solution containing no color developing agent. In the present invention, the "activator liquid" is characterized in that it does not substantially contain a p-phenylenediamine-based color developing agent as conventionally used, and other components (eg, alkali, halogen, chelating agent, etc.) ) May be included. In some cases, it is preferable that a reducing agent is not contained in order to maintain processing stability. In this case, it is preferable that an auxiliary developing agent, hydroxyamines, sulfites, and the like are not substantially contained. Here, “substantially not contained” means preferably 0.5 mmol / l or less, more preferably 0.1 mmol / l or less. In particular, it is preferable not to contain at all. The pH of the alkaline treatment liquid is preferably from 9 to 14, and particularly preferably from 10 to 13. For the activator processing photosensitive material and its processing,
For example, Japanese Patent Application Nos. 7-63572 and 7-334190.
Nos. 7-334192, 7-334197 and 7-344396.

The process of developing an alkaline processing solution by the diffusion transfer method is known in the art as an instant processing system, and includes at least one photosensitive layer / dye-forming layer (the photosensitive layer and the dye-forming layer are composed of the same layer). The photosensitive material having a mordant layer for capturing and mordanting the diffusible dye formed from the photosensitive layer / dye-forming layer on the same support or on a separate support is subjected to alkaline treatment. This means that the liquid is developed with a thickness of 500 μm or less, preferably 50 to 200 μm. When an auxiliary developing agent is incorporated, it is preferable that the alkaline processing liquid does not contain the auxiliary developing agent for production and storage of the processing solution. In the case of the diffusion transfer method, the pH of the alkaline treatment liquid is preferably from 10 to 14, and particularly preferably from 12 to 14. See THJames, The Theory of Photog for the process of instant materials.
The fourth edition of the raphic Process (1977, Macmillan) and the specific composition of the film unit is disclosed in
No. 3-226649. Examples of the materials included in the film unit and various layers including the same are described below. The dye image-receiving layer and the mordant contained therein are described in JP-A-61-2.
No. 5,551,551, U.S. Pat. Nos. 2,548,564, 3,756,814, 4,124,386 and 3,625,694. The neutralizing layer for lowering the pH of the light-sensitive material after developing the alkaline processing solution is described in JP-B-7-122753, U.S. Pat. No. 4,139,383, and RD-NO. 16102. The timing layer used in combination with the neutralizing layer is described in JP-A-54-136328, U.S. Pat. Nos. 4,267,262 and 4,009,030.
No. 4,268,604. Although any emulsion can be used as the silver halide emulsion, preferred auto-positive emulsions for photographic light-sensitive materials include JP-A-7-333770 and JP-A-7-33771. In addition, if necessary, a light shielding layer, a reflection layer, an intermediate layer, an isolation layer, an ultraviolet absorption layer, a filter layer,
An overcoat layer, an adhesion improving layer, and the like can be provided. The processing solution for processing the above-mentioned light-sensitive material contains processing components necessary for development, and usually contains a thickening agent and spreads uniformly on the light-sensitive material. Thickening agents such as carboxymethylcellulose and hydroxyethylcellulose are preferable as the thickener. Details of the photosensitive layer and the processing solution are described in JP-A-7-33377.
1.

The heat treatment in the heat development of the light-sensitive material is known in the art and can be applied to the light-sensitive material of the present invention. The photothermographic material and its process are described, for example, in Photo Industry Fundamentals (1979, published by Corona Co., Ltd.).
53-555 pages, 40 pages of video information issued in April 1978,
Nebletts Handbook of Photography and Reprography,
32 of 7th Ed. (Van Nostrand and Reinhold Company)
~ 33 pages, U.S. Patent No. 3,152,904,
Nos. 301,678, 3,392,020 and 3,457,075, British Patent 1,131,108
No. 1,167,777, and Research Disclosure Magazine, June 1978, pp. 9-15 (RD-1
7029).

The light-sensitive material of the present invention may contain, for the purpose of accelerating silver development and dye formation reaction, US Pat.
Nos. 4,657,848 and 5 (published by Aztec Co., Ltd. on March 22, 1991), pages 55 to 86, etc. No. 660, U.S. Pat.
It is preferable to apply the base generation method described in No. 0,445. To the light-sensitive material of the present invention, a heat solvent described in U.S. Pat. Nos. 3,347,675 and 3,667,959 may be added for the purpose of accelerating thermal development. When the light-sensitive material of the present invention is subjected to heat treatment, in order to promote development and / or diffusion transfer of the processing material,
Water, an aqueous solution containing an inorganic alkali metal salt or an organic base,
It is also preferable to include a low-boiling solvent or a mixed solvent of a low-boiling solvent and water or the above-mentioned basic aqueous solution in a light-sensitive material or a processing sheet and heat-treat it. As a method using water, JP-A-63-144354 and JP-A-63-14 are known.
4,355, 62-38,460, JP-A-3-2
10,555, JP-A-62-253,159, and 6
3-85,544, EP 210,660 and U.S. Pat. No. 4,740,445. The present invention relates to JP-A-7-261336 and JP-A-7-26.
No. 8045, No. 8-30103, No. 8-46822, and No. 8-97344. The heating temperature in the thermal development step is about 50 ° C. to 200 ° C.
A temperature of 0 ° C. to 150 ° C. is useful, and when a solvent is used, it is preferably used at a temperature not higher than its boiling point.

[0116]

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

Example 1 A surface of a paper support laminated on both sides with polyethylene was subjected to a corona discharge treatment, and then a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided. Further, three types of photographic constituent layers were coated. A photographic paper (100) having a three-layer structure shown in Table 2 was produced. The coating solution was prepared as follows. Coating solution for second layer 18.3 g of coupler (ExY-1), color developing agent (I
-16) 19.2 g of a solvent (Solv-1) and 80 g of a solvent were dissolved in ethyl acetate, and this solution was emulsified and dispersed in 400 g of a 16% gelatin solution containing 10% sodium dodecylbenzenesulfonate and citric acid to obtain an emulsified dispersion A. Was prepared. On the other hand, silver chlorobromide emulsion A (cubic, 3: 7 mixture of large-size emulsion A having an average grain size of 0.10 μm and small-size emulsion A having an average grain size of 0.08 μm (silver mole ratio). 0.08 and 0.10, respectively, and 0.3 mol% of silver bromide in each size emulsion was locally contained in a part of the surface of the silver chloride-based grain). This emulsion contained the following blue-sensitive sensitizing dyes A, B, and C in an amount of 7.0.times.10
^-4 mol, and for small size emulsion A, respectively.
5 × 10 ^-4 mol is added. The chemical ripening of this emulsion was optimally performed 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 coating solution for the second layer so as to have the following composition. The emulsion coating amount indicates a silver equivalent coating amount.

The coating solutions for the first and third layers were prepared in the same manner as the coating solution for the second layer. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. Cpd-2, Cpd-
3, the total amount of each of Cpd-4 and Cpd-5 was 15.0.
^{mg / m 2, 60.0mg / m} 2, 50.0mg / m 2 and 10.
0 mg / m ² was added. The following spectral sensitizing dyes were used in the silver chlorobromide emulsion of the second layer.

[0119]

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Also, 1- (5-methylureidophenyl)
^-3 -Mercaptotetrazole was added in an amount of 3.0 × 10 ^-3 mol per mol of silver halide. (Layer Structure) The composition of each layer is shown below. The number is the coating amount (g
/ M ² ). The silver halide emulsion represents a coating amount in terms of silver. The fine solid dispersion of 1,5-diphenyl-3-pyrazolidone added to the first layer is disclosed in JP-A-2-23504.
It was prepared by the method described on page 20 of No. 4. Support Polyethylene laminated paper [The first layer side polyethylene contains white pigment (TiO ₂ 15% by weight) and bluish dye (ultramarine)]

First layer Gelatin 1.12 1,5-Diphenyl-3-pyrazolidone 0.02 (fine-particle solid dispersion state) Second layer The above-mentioned silver chlorobromide emulsion A 0.01 Gelatin 1.50 Yellow coupler (ExY -1) 0.18 Color developing agent (I-16) 0.19 Solvent (Solv-1) 0.80

Third 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 Second layer Samples (101) to (111) were prepared in exactly the same manner as in the preparation of Sample (100), except that the yellow coupler and the color developing agent in the coating solution of Example 1 were replaced with the yellow coupler and the color developing agent shown in Table a in equimolar amounts. ) Was prepared. However, the yellow coupler of the present invention was replaced by 1/2 mole.
Further, silver chlorobromide emulsion A in the coating solution of the second layer was replaced with silver chlorobromide emulsion B shown below with an equal silver amount, and the coupler and the color developing agent were changed to magenta couplers and color developing agents shown in Table b. Samples (200) to (211) were prepared in exactly the same manner as Sample (100) except that each was replaced by an equimolar amount.
However, the magenta coupler of the present invention was replaced by 1/2 mole. Silver chlorobromide emulsion B: cubic, average grain size 0.10 μm
1: 3 mixture of a large-size emulsion B and a small-size emulsion B of 0.08 μm (Ag molar ratio). The coefficient of variation of the grain size distribution was 0.10 and 0.08, respectively, and 0.8 mol% of AgBr was locally contained in a part of the grain surface containing silver chloride as a base in each size emulsion. The following spectral sensitizing dyes were used for silver chlorobromide emulsion B, respectively.

[0123]

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(The sensitizing dye D was used in an amount of 1.5 × 10 ⁻³ mol for a large-sized emulsion, 1.8 × 10 ⁻³ mol for a small-sized emulsion, and Sensitizing dye E was used in an amount of 2.0 × 10 ^-4 mol per mol of silver halide and 3.5 mol per mol of silver halide.
× 10 ^-4 mol of sensitizing dye F per mol of silver halide, 1.0 × 10 ^-3 mol for large-size emulsion, and 1.4 × 10 ^-3 mol for small-size emulsion. Was added. In addition, silver chlorobromide emulsion A in the coating solution for the second layer was replaced with silver chlorobromide emulsion C shown below with an equal silver amount, and the coupler and color developing agent were cyan couplers and color developing agent shown in Table c. Samples (300) to (310) were prepared in exactly the same manner as for Sample (100) except that each was replaced by an equimolar. However, the cyan coupler of the present invention was replaced with 1/2 mole. Silver chlorobromide emulsion C: cubic, average grain size 0.10 μm
1: 4 mixture (Ag molar ratio) of the large size emulsion C of the formula (1) and the small size emulsion of 0.08 μm. The coefficient of variation of the grain size distribution was 0.09 and 0.11, and AgBr was used for each size emulsion.
0.8 mol% was locally contained in a part of the surface of the silver chloride-based grain. The following spectral sensitizing dyes were used for silver chlorobromide emulsion C, respectively.

[0125]

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(Each mole of silver halide was added in an amount of 2.5 × 10 ^-4 mol for a large-sized emulsion and 4.0 × 10 ^-4 mol for a small-sized emulsion.)

[0127]

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[0128]

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[0129]

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[0130]

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The samples (100) to (111) prepared as described above using a FWH type photometer (color temperature of light source: 3200 ° K) manufactured by Fuji Film Co., Ltd. were filtered with a blue filter for sensitometry. , Samples (200) to (2)
11) was subjected to gradation exposure using a green filter for sensitometry, and samples (300) to (310) were subjected to gradation exposure using a red filter for sensitometry. The exposed sample was processed in the following processing steps using the following processing solutions. Processing Step 1 Processing Step Temperature Time Current Image 40 ° C. 45 seconds Rinse Room Temperature 45 seconds Developing Solution (Alkaline Activating Solution Containing Hydrogen Peroxide) Water 600 ml Potassium Phosphate 40 g KCl 5 g Hydroxyethylidene-1,1-diphosphonic acid ( 30 ml) 4 ml H ₂ O ₂ 10 ml Water was added and 1000 ml pH (at 25 ° C./potassium hydroxide) 11.5 The rinse solution was previously sterilized with chlorinated sodium isocyanurate (0.02 g / l). Deionized water (conductivity 5 μS / cm or less) was used. This pH was 6.5.

For the samples (100) to (111), the maximum color density portion of the processed sample was set to the blue light and the sample (2).
00) to (211), green light, sample (300)
(310) was measured with red light. The results are shown in Tables a, b, and c, respectively.

[0133]

[Table 1]

[0134]

[Table 2]

[0135]

[Table 3]

As is clear from Tables a, b, and c, when the color developing agent and the dye-forming coupler of the present invention were used, the auxiliary developing agent was incorporated in the light-sensitive material and intensified with hydrogen peroxide. However, it can be seen that a higher color density can be obtained with a known coupler.

Example 2 A corona discharge treatment was applied to the surface of a paper support laminated on both sides with polyethylene, and then a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided. Further, various photographic constituent layers were coated. A multilayer color photographic paper (400) having the indicated layer configuration was produced. The coating solution was prepared as follows.

First layer coating solution Coupler (ExY-3) 20 g, color developing agent (I-3)
2) 16.6 g and 80 g of a solvent (Solv-2) were dissolved in ethyl acetate, and this solution was emulsified and dispersed in 400 g of a 16% gelatin solution containing 10% sodium dodecylbenzenesulfonate and citric acid to obtain emulsified dispersion A. Prepared.
On the other hand, silver chlorobromide emulsion D (cubic, average grain size 0.8
3: 7 mixture of 8 μm large emulsion D and 0.70 μm small emulsion D (silver molar ratio). The coefficient of variation of the grain size distribution was 0.08 and 0.10, respectively, and 0.3 mol% of silver bromide was locally contained in a part of the grain surface based on silver chloride in each size emulsion). did. This emulsion contained the blue-sensitive sensitizing dyes A, B and C used in Example 1 in an amount of 1.4 × 10 5 per silver mole of the emulsion D, respectively.
^-4 mol, and for small size emulsion D, respectively 1.
7 × 10 ^-4 mol is added. The chemical ripening of this emulsion was optimally performed by adding a sulfur sensitizer and a gold sensitizer. The emulsified dispersion A and the silver chlorobromide emulsion D were mixed and dissolved to prepare a coating solution for the first layer having the following composition. The emulsion coating amount indicates a silver equivalent coating amount.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. Cpd-2, Cpd-
3, the total amount of each of Cpd-4 and Cpd-5 was 15.0.
^{mg / m 2, 60.0mg / m} 2, 50.0mg / m 2 and 10.
0 mg / m ² was added. The following spectral sensitizing dyes were used for the silver chlorobromide emulsion of each photosensitive emulsion layer.

Blue-Sensitive Emulsion Layer The following amounts of the blue sensitizing dyes A, B and C used in Example 1 were used. (Per mol of silver halide, 1.4 × 10 ^-4 mol was added to the large-size emulsion and 1.7 × 10 ^-4 mol was added to the small-size emulsion, respectively.)

Green-Sensitive Emulsion Layer The following amounts of the green sensitizing dyes D, E and F used in Example 1 were used. (The amount of sensitizing dye D per mol of silver halide is 3.0 × 10 ^-4 mol for large-size emulsion, 3.6 × 10 ^-4 mol for small-size emulsion, and sensitizing dye E Per mole of silver halide, 4.0 for large emulsions.
× 10 ^-5 mol, 7.0 × 10 ^-5 for small size emulsions
Sensitizing dye F was added in an amount of 2.0 × 10 ^-4 mol for a large-size emulsion and 2.8 × 10 ^-4 mol for a small-size emulsion per mol of silver halide. )

Red-Sensitive Emulsion Layer The red sensitizing dyes G and H used in Example 1 were used in the following amounts. Fifth layer (red) (addition of 5.0 × 10 ⁻⁵ mol for large-size emulsion and 8.0 × 10 ⁻⁵ mol for small-size emulsion per mol of silver halide) Sensitive layer)
Further, 2.6 × 10 ^-2 mol of the following compound was added per mol of silver halide.

[0143]

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The blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer were treated with 1- (5-methylureidophenyl)-
5-mercaptotetrazole was replaced by silver halide 1
3.5 × 10 ^-4 mole, 3.0 × 10 ^-3 mole per mole,
2.5 × 10 ^-4 mol was added. In addition, 4-hydroxy-6-methyl-1, 4-hydroxy-6-methyl-1,
3,3a, 7-Tetrazaindene was added in an amount of 1 × 10 ⁻⁴ mol and 2 × 10 ⁻⁴ mol per mol of silver halide, respectively. To prevent irradiation, the following dyes were added to the emulsion layer (the values in parentheses indicate the coating amount).

[0145]

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(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver. Support Polyethylene laminated paper [The first layer side polyethylene contains white pigment (TiO ₂ 15% by weight) and blue dye (ultramarine)] First layer (blue-sensitive emulsion layer) Silver chlorobromide emulsion D 0 .20 gelatin 1.50 yellow coupler (ExY-3) 0.20 color developing agent (I-32) 0.17 solvent (Solv-1) 0.80

Second layer (color mixture preventing layer) Gelatin 1.09 Color mixture inhibitor (Cpd-6) 0.11 Solvent (Solv-2) 0.19 Solvent (Solv-3) 0.07 Solvent (Solv-4) 0.25 solvent (Solv-5) 0.09 1,5-diphenyl-3-pyrazolidone 0.03 (fine particle solid dispersion state)

Third Layer (Green-Sensitive Emulsion Layer) Silver chlorobromide emulsion E (cubic, 1: 3 mixture of large-size emulsion E having an average grain size of 0.55 μm and small-size emulsion E having a size of 0.39 μm (Ag The variation coefficient of the grain size distribution was 0.10 and 0.08, respectively, and 0.8 mol% of AgBr was locally contained in a part of the grain surface having silver chloride as a base in each size emulsion. ) 0.20 Gelatin 1.50 Magenta coupler (ExM-2) 0.26 Color developing agent (I-32) 0.17 Solvent (Solv-1) 0.80

Fourth layer (color mixture preventing layer) Gelatin 0.77 Color mixture inhibitor (Cpd-6) 0.08 Solvent (Solv-2) 0.14 Solvent (Solv-3) 0.05 Solvent (Solv-4) 0.14 Solvent (Solv-5) 0.06 1,5-diphenyl-3-pyrazolidone 0.02 (fine particle solid dispersion state)

Fifth Layer (Red-Sensitive Emulsion Layer) Silver chlorobromide emulsion F (cubic, 1: 4 mixture of large-sized emulsion F having an average grain size of 0.5 μm and small-sized emulsion F of 0.41 μm (Ag The variation coefficient 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 based on silver chloride in each size emulsion.) 0 .20 Gelatin 1.50 Cyan coupler (ExC-1) 0.27 Color developing agent (I-16) 0.21 Solvent (Solv-1) 0.80

Sixth layer (ultraviolet absorbing layer) Gelatin 0.64 Ultraviolet absorbing agent (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

[0153]

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[0154]

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(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver. Samples (401) to (401) were prepared in exactly the same manner as in the preparation of sample (400) except that the coupler and the color developing agent were replaced with the coupler and the color developing agent shown in Table d in equimolar amounts to sample (400). 406). However, the coupler of the present invention was replaced with 1/2 mole. For all samples prepared as described above, a FWH type sensitometer manufactured by FUJIFILM Corporation (color temperature of light source 3200 °)
K) was used to give a gradation exposure of a three-color separation filter for sensitometry.

The exposed sample was processed in the following processing steps using the following processing solutions. Processing Step Temperature Time Current image 40 ° C. 35 seconds Bleaching and fixing 40 ° C. 45 seconds Rinse room temperature 90 seconds Developing solution (alkali activating solution) Water 600 ml Potassium phosphate 40 g KCl 5 g Hydroxyethylidene-1,1-diphosphonic acid (30 %) 4 ml water and 1000 ml pH (at 25 ° C / potassium hydroxide) 12

Bleaching / fixing solution Water 600 ml Ammonium thiosulfate (700 g / l) 93 ml Ammonium sulfite 40 g Ammonium iron (III) ethylenediaminetetraacetate 55 g Ethylenediaminetetraacetic acid 2 g Nitric acid (67%) 30 g Water was added to the mixture. 5.8 As the rinsing liquid, the rinsing liquid used in Example 1 was used. The maximum color density portion of the processed sample was measured with red light, green light, and blue light. The results are shown in Table d.

[0158]

[Table 4]

As can be seen from Table d, when the color developing agent and the dye-forming coupler of the present invention are used in the case of a multi-layered light-sensitive material in which the auxiliary developing agent is incorporated in the light-sensitive material, when a known coupler is used. It can be seen that a high color density can be obtained with respect to. Further, since the maximum color density per weight of the dye formed from the coupler of the present invention is higher than that of the known coupler, as a result, there is an advantage that the photosensitive material can be made thinner and the sharpness is excellent. Further, the light-sensitive material of the present invention was excellent in hue, stability, and fastness.

Example 3 A corona discharge treatment was applied to the surface of a paper support laminated on both sides with polyethylene, and then a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided. Further, three types of photographic constituent layers were coated. A photographic paper (500) having a three-layer structure shown in Table 2 was produced. The coating solution was prepared as follows. First layer coating solution 17 g of coupler (ExY-4), color developing agent (I-3)
2) 16.6 g and 80 g of the solvent (Solv-2) are dissolved in ethyl acetate, and this solution is emulsified and dispersed in a 16% gelatin solution containing 10% sodium dodecylbenzenesulfonate and citric acid to prepare an emulsified dispersion D. did. The emulsified dispersion A and the silver chlorobromide emulsion D used in Example 2 were mixed and dissolved to prepare a first layer coating solution having the following composition. The emulsion coating amount indicates a silver equivalent coating amount.

The coating solutions for the second and third layers were prepared in the same manner as the coating solution for the first layer. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. Cpd-2, Cpd-
3, the total amount of each of Cpd-4 and Cpd-5 was 15.0.
^{mg / m 2, 60.0mg / m} 2, 50.0mg / m 2 and 10.
0 mg / m ² was added. The same amount of the blue sensitizing dyes A, B, and C used in Example 2 as in Example 2 was used for the first layer silver chlorobromide emulsion. Further, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added in an amount of 3.0 × 10 ⁻³ mol per mol of silver halide. (Layer Structure) The composition of each layer is shown below. The number is the coating amount (g
/ M ² ). The silver halide emulsion represents a coating amount in terms of silver. Support Polyethylene laminated paper [The first layer side polyethylene contains white pigment (TiO ₂ 15% by weight) and bluish dye (ultramarine)]

First layer Silver chlorobromide emulsion D 0.20 Gelatin 1.50 Yellow coupler (ExY-4) 0.17 Color developing agent (I-32) 0.17 Solvent (Solv-2) 80

Second Layer Gelatin 3.17 Mordant (Cpd-8) 3.21

Third 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

[0165]

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[0166]

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The sample (50) was prepared by replacing the yellow coupler and the color developing agent in the coating solution of the first layer with the yellow coupler and the color developing agent shown in Table e in equimolar amounts.
Sample (501) was produced in exactly the same manner as in the production of (0). However, the coupler of the present invention was replaced with 1/2 mole. The silver chlorobromide emulsion D in the coating solution of the first layer was prepared in Example 2.
Except that the silver chlorobromide emulsion E used in Example 2 was replaced by an equal amount of silver, and the coupler and the color developing agent were replaced by the magenta coupler shown in Table f and the color developing agent by an equimolar amount, the same as the sample (500). Thus, samples (600) to (601) were produced. Green sensitizing dyes D, E, and F used in Example 2 were used in silver chlorobromide emulsion E in the same amounts as those used in Example 2. However, the coupler of the present invention was replaced with 1/2 mole.

The silver chlorobromide emulsion D in the coating solution for the first layer was replaced by the silver chlorobromide emulsion F used in Example 2 with an equal silver amount, and the coupler and the color developing agent were as shown in Table g. , And color developing agents were replaced in equimolar amounts, respectively.
Samples (700) to (701) in exactly the same manner as
Was prepared. Red sensitizing dyes G and H used in Example 2 were used in silver chlorobromide emulsion F in the same amounts as those used in Example 2. However, the coupler of the present invention was replaced with 1/2 mole. FWH type sensitometer manufactured by FUJIFILM Corporation (color temperature of light source 32
00K) using the sample (50 ° C) prepared as described above.
Samples (700) to (70) are blue filters for sensitometry for (0) to (501), and green filters for sensitometry for samples (600) to (601).
In 1), gradation exposure was given by a red filter for sensitometry.

The exposed sample was processed in the following processing steps using the following processing solutions. Processing process Temperature Time Current image 40 ° C 20 seconds Bleaching and fixing 40 ° C 45 seconds Rinse room temperature 45 seconds

Developer Water 600 ml Potassium phosphate 40 g Disodium-N, N-bis (sulfonatoethyl) hydroxylamine 10 g KCl 5 g Hydroxyethylidene-1,1-diphosphonic acid (30%) 4 ml 1-phenyl-4-methyl -4-Hydroxymethyl-3-pyrazolidone 1 g Add water to 1000 ml pH (at 25 ° C / potassium hydroxide) 12

As the bleach-fixing solution and the rinsing solution, the developing solution, the bleach-fixing solution and the rinsing solution used in Example 2 were used. Samples (500) to (50) represent the maximum color density portion of the processed sample.
For 1), blue light, samples (600) to (601)
Was measured with green light, and samples (700) to (701) were measured with red light. Tables e, f, and
It is shown in Table g.

[0172]

[Table 5]

[0173]

[Table 6]

[0174]

[Table 7]

As is clear from Tables e, f and g, the use of the color developing agent and the dye-forming coupler of the present invention allows the use of a mordant in a light-sensitive material as compared with the case where a known coupler is used. It can be seen that a high color density can be obtained.

Example 4 <Method for Preparing a Light-Sensitive Silver Halide Emulsion> A well-stirred gelatin aqueous solution (inert gelatin 3 in 1000 ml of water)
0 g, potassium bromide 2 g) and ammonia
Add ammonium nitrate as a solvent and keep the temperature at 75 ° C.
To this, 1,000 ml of an aqueous solution containing 1 mol of silver nitrate and 1000 ml of an aqueous solution containing 1 mol of potassium bromide and 0.03 mol of potassium iodide were simultaneously added over 78 minutes. After washing with water and desalting, the mixture was redispersed by adding inert gelatin to obtain a sphere equivalent diameter of 0.1.
A silver iodobromide emulsion having an iodine content of 3 .mu.% Of 76 .mu.m was prepared. The ball equivalent diameter is a model TA from Coulter Counter
Measured at -II. Potassium thiocyanate, chloroauric acid, and sodium thiosulfate were added to the above emulsion at 56 ° C. for optimal chemical sensitization. Sensitizing dyes corresponding to the respective spectral sensitivities were added to the emulsion at the time of preparing the coating solution to give color sensitivity.

<Preparation method of zinc hydroxide dispersion> 31 g of zinc hydroxide powder having a primary particle size of 0.2 μm,
1.6 g of carboxymethylcellulose, 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 in a mill using glass beads for 1 hour. After the dispersion, the glass beads were filtered off, and a dispersion 188 of zinc hydroxide was obtained.
g was obtained. <Method for Preparing Emulsified Dispersion of Coupler> An oil phase component and an aqueous phase component having the compositions shown in Table h are dissolved to form a uniform solution at 60 ° C. The oil phase component and the aqueous phase component were combined and dispersed in a 1-liter stainless steel container at 10,000 rpm for 20 minutes by a dissolver equipped with a 5 cm diameter disperser. To this, warm water in the amount shown in Table 7 was added as post-water and mixed at 2000 rpm for 10 minutes. Thus, an emulsified dispersion of couplers of three colors of cyan, magenta and yellow was prepared.

[0178]

[Table 8]

[0179]

Embedded image

Using the materials thus obtained, a heat-developable color light-sensitive material 801 having a multilayer structure shown in Table i was produced.

[0181]

[Table 9]

[0182]

[Table 10]

[0183]

Embedded image

[0184]

Embedded image

[0185]

Embedded image

[0186]

Embedded image

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

[0188]

[Table 11]

[0189]

[Table 12]

[0190]

Embedded image

Next, as shown in Table 1, a light-sensitive material 8 having exactly the same composition as 801 except that the color developing agent and the coupler were changed in equimolar amounts (the coupler of the present invention was モ ル mole).
02 to 809, respectively. The light-sensitive materials 801 to 809 thus produced are passed through B, G, and R filters having continuously changed densities at 2500 lux and 0.0
Exposure was for 1 second. Apply 40 ° C. warm water to the exposed photosensitive material surface
After applying 5 ml / m ² , the processing sheet (image-receiving material) and the respective film surfaces were overlapped with each other, and then heat-developed at 83 ° C. for 30 seconds using a heat drum. When the image receiving material was peeled off after the processing, clear color images of cyan, magenta and yellow were obtained corresponding to the filters exposed on the light-sensitive material side. Immediately after the treatment, the highest density part (Dmax) and the lowest density part (Dmax)
min) was measured with an X-rite densitometer, and the results are shown in Table m.

[0192]

[Table 13]

[0193]

[Table 14]

The results in Table m indicate that the samples using the color developing agents and the dye-forming couplers of the present invention provide images with excellent discrimination compared to known couplers. From the above, the effect of the present invention is clear. Further, the light-sensitive material of the present invention was remarkably excellent in hue, dye stability and light fastness.

[0195]

By using the color developing agent of the present invention in combination with a coupler, the color developing properties are remarkably improved, the hue is largely improved, and the fastness (in particular, light fastness) is also significantly improved. Also, sharpness can be improved by thinning. Here, a significant improvement in hue means that the absorption of the formed dye becomes remarkably sharp. When the color developing agent of the present invention is used, the formed dye itself becomes very stable, and the stability of an image can be greatly improved.

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

Claims (6)

[Claims] 1. A silver halide color photographic light-sensitive material having at least one photographic constituent layer provided on a support, wherein at least one of the photographic constituent layers is represented by the following general formula (I). A silver halide photographic light-sensitive material containing a color developing agent and at least one dye-forming coupler represented by any of the following formulas (VIII-1) to (VIII-3). Embedded image Wherein, R ¹¹ is an aryl group or a heterocyclic group, R ¹²
Is an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. X is -SO ₂ -, - CO
-, - COCO -, - CO -O -, - CON (R 13)
—, —COCO—O—, —COCO—N (R ¹³ ) — or —SO ₂ —N (R ¹³ ) —. Here, R ¹³ is a hydrogen atom or a group described for R ¹² . Embedded image In the formula, C ₁ , C ₂ and C ₃ represent a dye-forming coupler residue capable of forming a dye by coupling reaction with an oxidized form of the color developing agent represented by the general formula (I), and M ₁ , M ₂ ,
M ₃ and M ₄ are each —O—, —COO—, —CO—,
^{-NR 70 -, - CONR 70 -} , - NR 70 CONR 71 -,
-OCONR ^70- , -SO ₂ NR ^70- , -NR ⁷⁰ SO ₂
NR ^71- , -P (O) OR ⁷⁰ NR ^71- , -P (O) R ⁷⁰
NR ⁷¹ —, —S—, —SO—, or —SO ₂ —, and R ⁷⁰ and R ⁷¹ each represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, or an aryl group. a, b, c, and d each represent 0 or 1,
D ₁ and D ₂ each represent a divalent linking group, and E represents a trivalent linking group. C ₁ , C ₂ and C ₃ may be the same or different. 2. The silver halide color photographic light-sensitive material according to claim 1, wherein the compound represented by the general formula (I) is represented by the following general formula (II) or (III). Embedded image Wherein, Z ¹ represents an acyl group, a carbamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group,, Z ² represents a carbamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group,, X ^1,
X ² , X ³ , X ⁴ and X ⁵ each represent a hydrogen atom or a substituent. However, the sum of the Hammett's substituent constant σ _p value of X ¹ , X ³ and X ^{5 and} the Hammett's substituent constant σ _m value of X ² and X ⁴ is 0.80 or more and 3.80 or less. R ³ represents a heterocyclic group. 3. The silver halide color photograph according to claim 2, wherein the compounds represented by formulas (II) and (III) are represented by formulas (IV) and (V), respectively. Photosensitive material. Embedded image In the formula, R ¹ and R ² each represent a hydrogen atom or a substituent, and X ¹ , X ² , X ³ , X ⁴ and X ⁵ each represent a hydrogen atom or a substituent. However, the sum of the Hammett's substituent constant σ _p value of X ¹ , X ³ and X ^{5 and} the Hammett's substituent constant σ _m value of X ² and X ⁴ is 0.80 or more and 3.80 or less.
R ³ represents a heterocyclic group. 4. The silver halide color photograph according to claim 3, wherein the compounds represented by formulas (IV) and (V) are represented by formulas (VI) and (VII), respectively. Photosensitive material. Embedded image In the formula, R ⁴ and R ⁵ each represent a hydrogen atom or a substituent, and X ⁶ , X ⁷ , X ⁸ , X ⁹ , and X ¹⁰ each represent a hydrogen atom, a cyano group, a sulfonyl group, a sulfinyl group, a sulfamoyl group, and a carbamoyl. Represents a group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, a trifluoromethyl group, a halogen atom, an acyloxy group, an acylthio group, or a heterocyclic group. However, X ⁶ , X ⁸ ,
The sum of the Hammett's substituent constant σ _p value of X ^{10 and} the Hammett's substituent constant σ _m value of X ⁷ and X ⁹ is 1.20 or more and 3.80.
It is as follows. Q ¹ represents a nonmetallic atom group necessary for forming a heterocyclic ring of 5- to 8-membered ring nitrogen-containing with C. 5. An image forming method, wherein the silver halide photographic light-sensitive material according to claim 1 is heat-treated at a temperature of 50 ° C. or more and 200 ° C. or less to perform thermal development. 6. An image forming method comprising developing the silver halide photographic material according to claim 1 in a solution.