JPH1062894A - Silver halide photographic sensitive material and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable low replenishing and low discharge and to obtain superior color development performance and further to improve dependence on processing temperature by incorporating at least one kind of specified color developing agent and at least one kind of dye-forming coupler in at least one of the photographic constituent layers. SOLUTION: At least one of the photographic constituent layers contains at least one kind of color developing agent represented by formula I and at least one kind of dye-forming coupler represented by formula II, and in formulae I and II, Z is a carbamoyl or acyl or alkyl-or aryl-sulfonyl group or the like; Q is an atomic group necessary to form an unsaturated ring together with C; L<1> is an alkyl or aryl or heterocyclic group; each of L<2> and L<3> is an H atom or a substituent; Q<0> is a nonmetallic atomic group necessary to form a ring together with > C=N<+> < group; Y is an H atom or a group to be released by coupling reaction with a color developing agent of formula I; A is an anion; and (k) is 1 or 0.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color photographic technique, and more particularly to a silver halide photographic material and an image forming method which can cope with environmental preservation and simple and rapid processing, and have good color development and storage stability.

[0002]

2. Description of the Related Art Generally, a color photographic light-sensitive material undergoes color development after exposure, whereby an oxidized p-phenylenediamine derivative and a coupler react to form an image. In this method, a color reproduction method based on a subtractive color method is used, and in order to reproduce blue, green, and red, yellow, magenta, and cyan color images having respective complementary colors are formed. Color development is achieved by immersing the exposed color photographic light-sensitive material in an aqueous alkaline solution (color developing solution) in which a p-phenylenediamine derivative is dissolved.
However, the p-phenylenediamine derivative in the form of an aqueous alkali solution is unstable and easily deteriorates with time, and there is a problem that it is necessary to frequently replenish the color developing solution to maintain stable developing performance. Further, the waste color developing solution containing the p-phenylenediamine derivative is complicated in waste liquid treatment, and in combination with the above frequent replenishment, the waste liquid treatment of a large amount of used color developing solution discharged becomes a serious problem. ing. Thus, there is a strong demand for achieving low replenishment and low discharge of the color developing solution.

One of effective means for solving the problem of low replenishment and low discharge of a color developing solution is to incorporate an aromatic primary amine or a precursor thereof into a hydrophilic colloid layer.
Examples of the aromatic primary amine developing agent or its precursor that can be incorporated include compounds described in US Pat. No. 4,060,418. However, these aromatic primary amines and precursors thereof are unstable, and thus have a drawback that stain is generated during long-term storage or color development of unprocessed photosensitive materials. Another effective means is
For example, European Patent Nos. 0545491A1 and 56516
A method of incorporating a sulfonylhydrazine type compound described in No. 5A1 or the like into a hydrophilic colloid layer is exemplified. However, even the sulfonylhydrazine-type compounds mentioned here are not sufficiently stable, and high-temperature, high-humidity, and stains due to light during long-term storage after treatment are still at a problematic level. In response to the above problems, there has been a demand for the development of a technique for improving the color development and further a technique for improving the storage stability.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to enable low replenishment and low discharge, exhibit good color development, and to reduce high-temperature high-humidity and light-induced stain during long-term storage of a photosensitive material. A light-sensitive material.

[0005]

The object of the present invention can be achieved by the following constitutions. (1) In a silver halide photographic light-sensitive material having at least one photographic constituent layer on a support, at least one type of a color developing agent represented by the following general formula (I) is added to at least one of the photographic constituent layers; A kind of the following general formula (II)
A silver halide photographic material comprising a dye-forming coupler represented by the formula:

[0006]

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In the formula, Z represents a carbamoyl group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group, a heterocyclic sulfonyl group, a sulfamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amidino group, or an imidoyl group. Q represents an atomic group that forms an unsaturated ring with C.

[0008]

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In the formula, L ¹ represents an alkyl group, an aryl group or a heterocyclic group, and L ² and L ³ each represent a hydrogen atom or a substituent. Q ⁰ is -C = N ⁺ - with represents a nonmetallic atomic group necessary for forming a ring. Y represents a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidized form of the color developing agent represented by formula (I). L ² , L
^3. Two of Y do not form a double bond. A
Represents an anion ion. k represents 1 or 0. When the coupler of the general formula (II) forms an inner salt, k is 0.
Represents (2) The silver halide photographic material as described in the above item (1), wherein the general formula (II) is represented by the following general formula (III).

[0010]

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In the formula, L ¹ represents an alkyl group, an aryl group or a heterocyclic group, and L ² , L ³ , L ⁴ and L ⁵ each represent a hydrogen atom or a substituent. L ⁴ and L ⁵ may combine with each other to form a double bond or a ring. Q ¹ is -S -, - O -, - N (L 6) -, - Se -, - C (L 7)
(L ⁸ )-, -C (L ⁷ ) = C (L ⁸ )-, -C (L ⁷ ) = N
-Or -N = N-. L ⁶ , L ⁷ and L ⁸ each represent a hydrogen atom or a substituent. Q ² and Q ³ are C,
Represents N, O or S. l and m each represent 0 or 1. Y and A have the same meanings as those in formula (II). (3) In the general formula (I), Z represents an alkylsulfonyl group, an arylsulfonyl group, a heterocyclic sulfonyl group,
Or a carbamoyl group, the silver halide photographic material as described in the above item (2). (4) The silver halide photographic material as described in the above item (2), wherein Z in the general formula (I) is a carbamoyl group. (5) An image forming method, wherein the silver halide photographic light-sensitive material described in the above (1) is subjected to heat treatment at 65 ° C or more and 180 ° C or less to perform development. (6) An image forming method, comprising developing the silver halide photographic light-sensitive material according to the above (1) in a solution. (7) The image forming method according to the above (5), wherein the general formula (II) is represented by the general formula (III). (8) The image forming method according to the above (6), wherein the general formula (II) is represented by the general formula (III). (9) In the general formula (I), Z is an alkylsulfonyl group, an arylsulfonyl group, a heterocyclic sulfonyl group or a carbamoyl group.
2. The image forming method according to 1., (10) The image forming method according to the above (7), wherein in the general formula (I), Z is a carbamoyl group. (11) In the general formula (I), Z is an alkylsulfonyl group, an arylsulfonyl group, a heterocyclic sulfonyl group or a carbamoyl group.
2. The image forming method according to 1., (12) The image forming method according to the above (8), wherein in the general formula (I), Z is a carbamoyl group.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The compound represented by formula (I) used in the present invention will be described below in detail. In the general formula (I), Z represents a carbamoyl group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group, a heterocyclic sulfonyl group, a sulfamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amidino group, or an imidoyl group. In the present invention, Z in the general formula (I) is preferably an alkylsulfonyl group, an arylsulfonyl group, a heterocyclic sulfonyl group, or a carbamoyl group, and more preferably a carbamoyl group. The carbamoyl group is preferably a carbamoyl group having 1 to 50 carbon atoms, more preferably 1 to 40 carbon atoms.
Specifically, as the carbamoyl group, -CONHR ₁₁ is preferable, and R ₁₁ is preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an amide group, or an imide group, and more preferably an alkyl group or an aryl group. , A heterocyclic group. Specific examples include a carbamoyl group,
Methylcarbamoyl, ethylcarbamoyl, isopropylcarbamoyl, cyclohexylcarbamoyl, t-octylcarbamoyl, cyclopropylcarbamoyl, dodecyloxycarbonylmethylcarbamoyl, 3-dodecyloxypropylcarbamoyl,
3- (3,5-tetradecyloxyphenoxy) propylcarbamoyl group, 3- (2,4-t-pentylphenoxy) propylcarbamoyl group, (2-chloro-5-hexadecyloxycarbonylphenyl) carbamoyl group, 4- Octadecyloxyphenylcarbamoyl group,
2,4-dimethoxyphenylcarbamoyl group, 2,5-
Examples thereof include a dichloro-4-dioctylsulfamoylphenylcarbamoyl group and a dioctylcarbamoyl group.

The acyl group is preferably an acyl group having 1 to 50 carbon atoms, more preferably 2 to 40 carbon atoms. Specific examples include acetyl, 2-methylpropanoyl, cyclohexylcarbonyl, n-octanoyl, 2-hexyldecanoyl, dodecanoyl, chloroacetyl, trifluoroacetyl, benzoyl, 4-benzoyl, Dodecyloxybenzoyl group, 2-hydroxymethylbenzoyl group, 3- (N-hydroxy-N
-Methylaminocarbonyl) propanoyl group. The alkylsulfonyl group is preferably a sulfonyl group having 1 to 50 carbon atoms, and more preferably a sulfonyl group having 1 to 4 carbon atoms.
0. Specific examples include a methanesulfonyl group and an ethanesulfonyl group. The arylsulfonyl group is preferably an arylsulfonyl group having 6 to 50 carbon atoms, and more preferably 6 to 40 carbon atoms. Specific examples include phenylsulfonyl, 2-naphthalenesulfonyl, 2-methoxy-5-t-octylphenylsulfonyl, 4-dodecylsulfonyl, 4-hexadecyloxyphenylsulfonyl, 2- (2-ethoxy) Ethoxy) -5-hexadecylsulfonamidophenylsulfonyl group, n-dodecylsulfonyl group and the like. Examples of the heterocyclic sulfonyl group include those having 1 to 5 carbon atoms.
A heterocyclic sulfonyl group of 0 is preferable, and more preferably has 1 to 40 carbon atoms. The hetero ring is the same as that described later in the description of the hetero ring formed by Q and C. Specific examples include 2-pyridylsulfonyl, 2-furanylsulfonyl, and the like.

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

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

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

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

The groups represented by Z and Q may further have a substituent. Examples of the substituent include a linear or branched, chain or cyclic alkyl having 1 to 40 carbon atoms. Groups (eg, trifluoromethyl, methyl, ethyl,
Propyl, heptafluoropropyl, isopropyl, butyl, t-butyl, t-pentyl, cyclopentyl, cyclohexyl, octyl, 2-ethylhexyl, dodecyl, etc.), linear or branched, chain or cyclic alkenyl group having 2 to 40 carbon atoms (For example, vinyl, 1-methylvinyl, cyclohexen-1-yl, etc.), having 2 to 40 carbon atoms in total.
(E.g., ethynyl, 1-propynyl, etc.), an aryl group having 6 to 40 carbon atoms (e.g., phenyl, naphthyl, anthryl, etc.), and an acyloxy group having 1 to 40 carbon atoms (e.g., acetoxy, tetradecanoyloxy) , Benzoyloxy, etc.), a carbamoyloxy group having 1 to 40 carbon atoms (eg, N, N-dimethylcarbamoyloxy), a carbonamide group having 1 to 40 carbon atoms (eg, formamide, N-methylacetamide, acetamide, N -Methylformamide, benzamide, etc.),
C1-C40 sulfonamide groups (e.g., methanesulfonamide, dodecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, etc.) and C1-C40 carbamoyl groups (e.g., N-methylcarbamoyl, N, N-diethylcarbamoyl, N-mesylcarbamoyl and the like, a sulfamoyl group having 0 to 40 carbon atoms (for example, N-butylsulfamoyl, N, N-diethylsulfamoyl, N-methyl-N- (4-methoxyphenyl) ) Sulfamoyl and the like, alkoxy groups having 1 to 40 carbon atoms (for example, methoxy, propoxy, isopropoxy, octyloxy, t-octyloxy, dodecyloxy, 2- (2,4-di-t-pentylphenoxy) ethoxy and the like) ), An aryloxy group having 6 to 40 carbon atoms (for example, phenoxy, 4 Methoxyphenoxy, naphthoxy, etc.), an aryloxycarbonyl group having 7 to 40 carbon atoms (eg, phenoxycarbonyl, naphthoxycarbonyl, etc.), and an alkoxycarbonyl group having 2 to 40 carbon atoms (eg, methoxycarbonyl, t-butoxycarbonyl, etc.) An N-acylsulfamoyl group having 1 to 40 carbon atoms (for example, N-tetradecanoylsulfamoyl, N-
Benzoylsulfamoyl, etc.), an alkylsulfonyl group having 1 to 40 carbon atoms (eg, methanesulfonyl, octylsulfonyl, 2-methoxyethylsulfonyl, 2-hexyldecylsulfonyl, etc.), and an arylsulfonyl group having 6 to 40 carbon atoms (eg, Benzenesulfonyl, p-toluenesulfonyl, 4-phenylsulfonylphenylsulfonyl, etc.), an alkoxycarbonylamino group having 2 to 40 carbon atoms (eg, ethoxycarbonylamino), an aryloxycarbonylamino group having 7 to 40 carbon atoms (eg, Phenoxycarbonylamino, naphthoxycarbonylamino, etc.), an amino group having 0 to 40 carbon atoms (eg, amino, methylamino, diethylamino, diisopropylamino, anilino, morpholino, etc.), cyano group, nitro group, carboxyl A hydroxy group, a sulfo group, a mercapto group, an alkylsulfinyl group having 1 to 40 carbon atoms (eg, methanesulfinyl, octanesulfinyl and the like), an arylsulfinyl group having 6 to 40 carbon atoms (eg, benzenesulfinyl, 4-chlorophenylsulfinyl, p-toluenesulfinyl, etc.), having 1 to 4 carbon atoms
0 alkylthio groups (eg, methylthio, octylthio, cyclohexylthio, etc.), arylthio groups having 6 to 40 carbon atoms (eg, phenylthio, naphthylthio, etc.),
A ureido group having 1 to 40 carbon atoms (for example, 3-methylureide, 3,3-dimethylureide, 1,3-diphenylureide and the like), a heterocyclic group having 2 to 40 carbon atoms (for example, nitrogen, A 3- to 12-membered monocyclic or condensed ring containing at least one or more oxygen and sulfur atoms, for example, 2-furyl, 2-pyranyl, 2-pyridyl, 2-thienyl, 2-imidazolyl, morpholino,
-Quinolyl, 2-benzimidazolyl, 2-benzothiazolyl, 2-benzoxazolyl, etc.), having 1 to 40 carbon atoms
(E.g., acetyl, benzoyl, trifluoroacetyl, etc.), and a sulfamoylamino group having 0 to 40 carbon atoms (e.g., N-butylsulfamoylamino, N
-Phenylsulfamoylamino, etc.), having 3 to 40 carbon atoms
(E.g., trimethylsilyl, dimethyl-t
-Butylsilyl, triphenylsilyl and the like), and a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom and the like).

The compound represented by the general formula (I) preferably has a total carbon number of 1 or more and 80 or less, more preferably 2 or more and 6 or less.
0 or less, and most preferably 3 or more and 50 or less.
The Hammett's substituent constants σp and σm are described, for example, by Naoki Inamoto, “Hammet Rule—Structure and Reactivity—” (Maruzen), “New Experimental Chemistry Lecture 14, Synthesis and Reaction of Organic Compounds V”, page 2605 (Japan). Chemical Society, Maruzen), Tadao Nakaya, "Explanation on Theoretical Organic Chemistry", 217 pages (Tokyo Kagaku Dojin), Chemical Review (91), 165-195 (199)
(1 year). Next, the color developing agent represented by the general formula (I) used in the present invention will be specifically described, but the scope of the present invention is not limited to these specific examples.

[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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The compound represented by the general formula (I) used in the present invention is generally represented by Z and a hydrazine having an unsaturated ring portion formed by C and Q (arylhydrazine or heterocyclic hydrazine). The compound can be easily synthesized by reacting an acid halide, an acid anhydride or an isocyanate of the acid moiety. A typical synthesis example is shown below. Other compounds can be synthesized in the same manner as in this example.

Synthesis Example 1 Synthesis of Exemplified Compound (I-10) The compound was synthesized by the following synthetic route.

[0037]

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Synthesis of Compound (A-2) Compound (A-1) (CAS Registry No. 139152-08-2)
84.7 g and 89.8 g of potassium carbonate were added to DMF60.
0 ml of 2-methylbutyl mercaptan.
3 ml was added dropwise over 1 hour at room temperature. Further, the mixture was stirred at room temperature for 1 hour. The reaction mixture was poured into water and stirred for 10 minutes. The generated white solid was collected by filtration, washed with water, and dried. Yield 100.8 g, yield 88.5%

Synthesis of Compound (A-3) 98.0 g of Compound (A-2) was suspended in 500 ml of acetic acid and 500 ml of water, and 88.5 g of potassium permanganate was added.
g in 500 ml of water was added dropwise over 1 hour at room temperature. The mixture was further stirred at room temperature for 2 hours. Water 21 and ethyl acetate 21 were added, and the mixture was filtered through celite. The filtrate was separated, and the organic layer was washed with water, aqueous hydrosulfite solution, aqueous sodium bicarbonate and brine, and then dried over anhydrous magnesium sulfate. After filtration, the solvent was distilled off, and isopropyl alcohol was added to the residue for crystallization to give 53.2 g of compound (A-3).
Was obtained as a white solid. 48.4% yield

Synthesis of Compound (A-4) Compound (A-3) (50.5 g) was dissolved in DMSO (100 ml), and hydrazine monohydrate (17.0 g) was added dropwise over 10 minutes under ice-cooling. Stirred for minutes. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with water and dried over anhydrous magnesium sulfate. After filtration,
The solvent was distilled off, and the residue was purified by silica gel chromatography. Methylene chloride was used as eluent. Crystallization with ethyl acetate-hexane (1: 2) gave compound (A-
4) was obtained as a yellow solid in an amount of 31.4 g. Yield 63.2% Synthesis of Exemplified Compound (I-10) 4.6 g of triphosgene was dissolved in 100 ml of THF, and Compound (A-5) (CAS Registry No. 61053-26-7) 1
3.6 g was added dropwise at room temperature over 10 minutes, and 18.7 ml of triethylamine was added dropwise at room temperature over 10 minutes. The mixture was reacted for 30 minutes to obtain a solution of the compound (A-6). To this reaction solution, 13.0 g of compound (A-4) was added portionwise over 10 minutes at room temperature. After stirring for an additional hour, the mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with aqueous sodium hydrogen carbonate, aqueous hydrochloric acid, and brine, dried over anhydrous magnesium sulfate, filtered, and the solvent was distilled off. The residue was purified by silica gel column chromatography, and crystallized from a mixed solution of ethyl acetate / hexane = 1/10 to give the exemplified compound (I-1).
0) was obtained as a white solid. Yield 17.0 g, yield 6
1.3%

Synthesis Example 2 Synthesis of Exemplified Compound (I-16) The compound was synthesized by the following synthetic route.

[0042]

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Compound (A-6) prepared from 5.8 g of compound (A-5) in the same manner as in Synthesis Example 1 and compound (A-
7) 4.3 g (described in European Patent No. 545491 A1)
Was used to synthesize Exemplified Compound (I-16) as a white solid. Yield 6.7 g, 61.5% yield

Next, the couplers represented by formulas (II) and (III) used in the present invention will be described in detail.
In the general formulas (II) and (III), L ¹ represents an alkyl group, an aryl group, or a heterocyclic group. The alkyl group has 1 to 50 carbon atoms, preferably 1 to 40 carbon atoms.
Linear, branched, chain or cyclic alkyl group such as methyl, ethyl, isopropyl, trifluoromethyl, t-butyl, t-pentyl, octyl, 2-ethylhexyl, cyclohexyl, dodecyl and the like.
The aryl group has 6 to 50 carbon atoms, preferably 6 to 4 carbon atoms.
0 monocyclic or fused-ring aryl groups such as phenyl,
Naphthyl, anthryl, 4-methylphenyl and the like can be mentioned. Examples of the heterocyclic group include a heterocyclic group having 1 to 50, preferably 1 to 40 carbon atoms. The heteroatom includes, for example, one or more and nine or less nitrogen, oxygen and sulfur atoms. A 12-membered ring (preferably a 3- to 8-membered ring) or a condensed ring, and specific examples of the hetero ring include furan, pyran, pyridine, thiophene,
Examples include imidazole, quinoline, benzimidazole, benzothiazole, benzoxazole, pyrimidine, pyrazine, 1,2,4-thiadiazole, pyrrole, oxazole, thiazole, quinazoline, isothiazole, pyridazine, indole, pyrazole, triazole, quinoxaline and the like.

L ¹ is preferably an alkyl group. In the general formula (II), Q ⁰ is a group of non-metallic atoms necessary for forming a ring together with -C = N ⁺ -. As this ring, those described in the description of the formula (III) are preferable. In the general formulas (II) and (III), L ² ,
L ³ represents a hydrogen atom or a substituent. Examples of the substituent include those described as the substituent which Z and Q may have.

In the general formulas (II) and (III), Y is a hydrogen atom or a group which can be eliminated by a coupling reaction with an oxidized form of the color developing agent represented by the general formula (I). 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, thiazolin-2-one, benzimidazolin-2-one, benzooxazolin-2-one , Benzothiazolin-2-one, 2-pyrrolin-5-
On, 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.), heterocyclic oxy group (eg, pyridyloxy , Pyrazolyloxy, etc.), acyloxy groups (eg, acetoxy, benzoyloxy, etc.), alkoxy groups (eg, methoxy, dodecyloxy, etc.), carbamoyloxy groups (eg, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, etc.), aryl Oxycarbonyloxy group (for example, phenoxycarbonyloxy, etc.), alkoxy Carbonyl group (e.g.,
Methoxycarbonyloxy, ethoxycarbonyloxy, etc.), arylthio groups (eg, phenylthio, naphthylthio, etc.), heterocyclic thio groups (eg, tetrazolylthio, 1,3,4-thiadiazolylthio, 1,3,4-oxadiazoli) Ruthio, benzimidazolylthio, etc.), alkylthio groups (eg, methylthio, octylthio, hexadecylthio, etc.), alkylsulfonyloxy groups (eg, methanesulfonyloxy, etc.), arylsulfonyloxy groups (eg, benzenesulfonyloxy, toluenesulfonyloxy, etc.) , A carbonamide group (eg, acetamide, trifluoroacetamide, etc.), a sulfonamide group (eg, methanesulfonamide, benzenesulfonamide, etc.), an alkylsulfonyl group (eg,
Methanesulfonyl, etc.), arylsulfonyl group (eg, benzenesulfonyl), alkylsulfinyl group (eg, methanesulfinyl), arylsulfinyl group (eg, benzenesulfinyl), arylazo group (eg, phenylazo, naphthylazo), carbamoyl And an amino group (eg, N-methylcarbamoylamino).

Y may be substituted by a substituent,
Examples of the substituent that substitutes for Y include those described as the substituent that the group represented by Z or Q may have. In the general formula (I), when Z is other than an alkylsulfonyl group, an arylsulfonyl group or a heterocyclic sulfonyl group,
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. When Z in the general formula (I) is an alkylsulfonyl group, an arylsulfonyl group, or a heterocyclic sulfonyl group, Y is preferably a hydrogen atom.

In the general formula (III), L ⁴ and L ⁵
Each represents a hydrogen atom or a substituent. Examples of the substituent include those described as the substituent which the group represented by Z or Q may have. L ⁴ and L ⁵ may combine with each other to form a double bond or a ring. L ⁴ , L
^As the ring formed by ⁵ , a benzene ring, a naphthalene ring,
An aromatic hydrocarbon ring such as an anthracene ring or the aforementioned L ¹
Is a heterocyclic group.

In the general formula (III), Q ¹ represents —S—, —O
^{-, - N (L 6)} -, - Se -, - C (L 7) (L 8) -, -
^{C (L 7) = C (} L 8) -, - C (L 7) = N-, or -N
= N-. L ⁶ , L ⁷ , and L ⁸ each represent a hydrogen atom or a substituent, and examples of the substituent include those described above as the substituents that Z and Q may have. L ⁷ ,
L ⁸ may form a double bond, a carbonyl group, a thiocarbonyl group or a ring. Q ² and Q ³ are C, N,
Represents O or S. l and m each represent 0 or 1. L ⁴ and Q ² or L ⁵ and Q ³ may form a double bond, a carbonyl group, a thiocarbonyl group, or an imide group.

In the general formulas (II) and (III), A represents a negative ion. This negative ion may be a monovalent ion or a polyvalent ion, or may be a mixture of two or more. Examples include a halogen anion (eg, a fluorine anion, a chlorine anion, a bromine anion, an iodine anion, etc.), a carboxylate anion (eg, an acetate anion, a trifluoroacetate anion, etc.), a sulfonate anion (eg, a methanesulfonate anion, benzene Sulfonate anion, p-toluenesulfonic acid anion, etc.), alkyl sulfate anion (eg, methyl sulfate anion), sulfate anion, nitrate anion, carbonate anion, aryloxy anion (eg, phenoxy anion), alkoxy anion (eg, methoxy anion)
And the like. When the coupler of the general formula (II) or the general formula (III) forms an inner salt, for example, an anionic group such as a sulfonic acid group, a carboxylic acid group or a sulfate group is added to any of L ^{1 to} L ⁵ and Y. Have.

The total carbon number of the couplers represented by the general formulas (II) and (III) is preferably from 3 to 80, more preferably from 3 to 60, and most preferably 3 to 60.
Not less than 50. In particular, those having a ballast group in the coupler body are preferred. Next, couplers represented by formulas (II) and (III) used in the present invention will be specifically described, but the scope of the present invention is not limited to these specific examples.

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[0053]

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[0054]

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[0055]

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[0057]

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[0059]

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[0061]

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The method for synthesizing the coupler represented by the general formula (II) of the present invention is well known in the field of photographic industry as a method for synthesizing an intermediate of a sensitizing dye, and includes a heterocyclic ring containing a nitrogen atom. And various alkylating agents. For more information, see the review by FMHamer (The Chemistr
y of Heterocyclic Compounds, Vol. 18, The CyanineDyes
and Related Compounds, A.Weissberger, ed., Interscie
nce, New York, 1964) or a review by GEFicken (The Ch
emistry of Synthetic Dyes, Vol. 4, K. Venkataraman, e
d., Academic Press, New York, 1971, p. 211.).

A typical synthesis example is shown below. Other compounds can be synthesized in the same manner as in this example. Synthesis Example 1 Synthesis of Exemplified Compound II-1 1.5 g of 5-chloro-2-methylbenzothiazole and 3.4 g of tridecyl p-chlorobenzenesulfonate
Was reacted at 150 ° C. for 4 hours. Crystallized from a mixed solvent of ethyl acetate and hexane, 1.74 g of Exemplified Compound II
-1 was obtained. Synthesis Example 2. Synthesis of Exemplified Compound II-2 10 g of 2,5-dimethylbenzothiazole and 25 g of octyl p-toluenesulfonate were reacted at 150 ° C. for 11 hours. Crystallization from a mixed solvent of ethyl acetate and hexane gave 4.5 g of Exemplified Compound II-2.

In the present invention, other couplers can be used together with the couplers represented by the general formulas (II) and (III). This coupler may be a so-called "4-equivalent coupler" or "2-equivalent coupler" which is used in a system using a conventionally used paraphenylenediamine developing agent. An example of a coupler is Theory of the Photographic Process (4th. Ed., Edited by THJames, Macmillan, 197).
7) pages 291 to 334, and pages 354 to 361,
JP-A-58-12353 and JP-A-58-149046,
Nos. 58-149047, 59-11114, 5
Nos. 9-124399, 59-174835, 59
No. 231538, No. 59-231540, No. 60-
No. 2951, No. 60-14242, No. 60-2347
No. 4, No. 60-66249, and the like.

The amount of the couplers represented by the general formulas (II) and (III) used in the present invention depends on the molar extinction coefficient (ε), but the reflection density of the image is 1.0 or more. In order to obtain a concentration, in the case of a coupler having a ε of about 5,000 to 500,000 in the dye formed by coupling, the coating amount is about 0.001 to 100 mmol / m ² , preferably 0.01 to 10 mmol / m ^2. And more preferably about 0.05 to 5 mmol / m ² . The amount of the color developing agent used in the present invention to the photosensitive material,
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. In the present invention, an auxiliary developing agent can be preferably used. Here, the auxiliary developing agent means a substance having an action of promoting the transfer of electrons from the color developing agent to silver halide in the development process of silver halide development, and the auxiliary developing agent in the present invention is preferably a compound of the general formula The compound is an electron-emitting compound represented by (D-1) or the general formula (D-2), which conforms to the Kendall-Peltz rule. Among them, those represented by (D-1) are particularly preferred.

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In the general formulas (D-1) and (D-2),
R ^{51 to} R ⁵⁴ represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, or a heterocyclic group. R
^{55 to} R ⁵⁹ represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group,
Heterocyclic group, alkoxy group, cycloalkyloxy group,
Aryloxy group, heterocyclic oxy group, silyloxy group, acyloxy group, amino group, anilino group, heterocyclic amino group, alkylthio group, arylthio group, heterocyclic thio group, silyl group, hydroxyl group, nitro group, alkoxycarbonyloxy group A cycloalkyloxycarbonyloxy group, an aryloxycarbonyloxy group, a carbamoyloxy group, a sulfamoyloxy group, an alkanesulfonyloxy group, an arenesulfonyloxy group,
Acyl group, alkoxycarbonyl group, cycloalkyloxycarbonyl group, aryloxycarbonyl group, carbamoyl group, carboxamide group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide group, sulfamoylamino Group, alkylsulfinyl group, arenesulfinyl group, alkanesulfonyl group, arenesulfonyl group, sulfamoyl group, sulfo group, phosphinoyl group,
Represents a phosphinoylamino group. q represents an integer of 0 to 5, and when q is 2 or more, R ⁵⁵ may be different. R ⁶⁰ represents an alkyl group or an aryl group. Specific examples of the compound represented by formula (D-1) or (D-2) are shown below, but the auxiliary developing agent used in the invention is not limited to these specific examples.

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

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

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

In the compound represented by formula (A), L
Any group can be used as long as it is capable of cleaving (L) n-1 -PUG after leaving from the group represented by G during the development processing. For example, a group utilizing cleavage of a hemiacetyl tar ring described in U.S. Pat. Nos. 4,146,396, 4,652,516 or 4,698,297;
No. 962, No. 4,847,185 or No. 4,8
No. 57,440, a timing group for causing an intramolecular nucleophilic substitution reaction, and cleavage using an electron transfer reaction described in US Pat. No. 4,409,323 or 4,421,845. The timing groups that trigger the reaction,
U.S. Pat. No. 4,546,073 describes a group that causes a cleavage reaction by utilizing the hydrolysis reaction of an imino ketal, and utilizes a hydrolysis reaction of an ester described in West German Patent No. 2,626,317. And a group which causes a cleavage reaction by utilizing a reaction with a sulfite ion described in EP 0572840.

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 in addition to the above method. When dispersing the hydrophobic compound in the hydrophilic colloid, various surfactants can be used. For example, JP
No. 157636, pages (37) to (38), and those listed as surfactants in the RD magazine shown in the list below can be used. In the light-sensitive material of the present invention, a compound for stabilizing an image simultaneously with activation of development can be used. Specific compounds preferably used are described in U.S. Pat. No. 4,500,626, Nos. 51-52.
Column.

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

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

The silver halide 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, column 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 M
ontel, 1967), Duffin's "Photoemulsion Chemistry", Focal Press (GFDuffin, Photographic Emulsi)
on Chemistry, Focal Press, 1966), "Production and Coating of Photographic Emulsions", by Zerikman et al., Published by Focal Press (VLZelikman et al., Making and Coating Photograp).
hic Emulsion, Focal Press, 1964), etc., any of which can be used.

The use of the above tabular grains has advantages such as an increase in covering power and an increase in the color sensitization efficiency of a sensitizing dye, and is described in detail in US Pat. No. 4,434,226. I have. The average aspect ratio of 80% or more of the total projected area of the grains is desirably 1 or more and less than 100. It is more preferably 2 or more and less than 20 and particularly preferably 3 or more and less than 10. As the shape of the average particle, a triangle, a hexagon, a circle, or the like can be selected. A regular hexagon having approximately equal six sides as described in U.S. Pat. No. 4,798,354 is a preferred form. The equivalent circle diameter of the projected area is often used as the average particle size. However, particles having an average diameter of 0.6 μm or less as described in US Pat. preferable. Also, U.S. Pat.
Emulsions having a narrow grain size distribution as described in US Pat. No. 5,617 are also preferred. It is preferable to limit the grain thickness of the tabular grains to 0.5 μm or less, more preferably 0.3 μm or less, in order to increase sharpness. Further, an emulsion having a highly uniform thickness having a variation coefficient of grain thickness of 30% or less is also preferable. Further, particles described in JP-A-63-163451, in which the thickness of the particles and the distance between twin planes are specified, are also preferable. In the case of tabular grains, dislocation lines can be observed with a transmission electron microscope. It is preferable to select a particle containing no dislocation line, a particle containing several dislocations, or a particle containing many dislocations according to the purpose. Also, it is possible to select dislocations introduced linearly or distorted dislocations in a specific direction of the crystal orientation of the grains, to introduce them throughout the grains, or to introduce them only to a specific portion of the grains, For example, dislocations can be introduced only in the fringe portion of the particles. Introduction of dislocation lines is preferable not only in the case of tabular grains, but also in the case of irregular grains typified by normal crystal grains or potato grains. Also in this case, it is a preferable embodiment to limit to a specific portion such as a vertex or a ridge of the particle.

The 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
7, and the emulsions described in JP-A-5-181246 are preferably used. Further, in order to accelerate the grain growth, the addition concentration, the addition amount and the addition speed of the added silver salt and halogen salt may be increased (Japanese Patent Application Laid-Open No. 55-142,329).
No. 55-158,124; U.S. Pat.
No. 0,757). Further, the method of stirring the reaction solution may be any known stirring method. The temperature and pH of the reaction solution during the formation of silver halide grains may be set in any manner depending on the purpose. The preferred pH range is between 2.2 and 8.5, more preferably between 2.5 and 7.5.

In the case of a photothermographic material, an organic silver salt oxidizing agent may be used together with the photosensitive silver halide emulsion. Examples of the organic compound which can be used for forming the same are US Pat. There are benzotriazoles, fatty acids and other compounds described in column Nos. 52 to 53 of 500,626. The acetylene silver described in U.S. Pat. No. 4,775,613 is also useful. Two or more organic silver salts may be used in combination.
The above organic silver salt is used per mole of the photosensitive silver halide,
0.01 to 10 mol, preferably 0.01 to 1 mol, can be used in combination. Total coating amount of light-sensitive silver halide emulsion and the organic silver salt is 0.05 to 10 g / m ² in terms of silver, and preferably from 0.1-4 g / m ^2. The light-sensitive silver halide emulsion is usually a chemically sensitized silver halide emulsion. Chemical sensitization of the photosensitive silver halide emulsion of the present invention includes:
Known sulfur sensitization method, selenium sensitization method, chalcogen sensitization method such as tellurium sensitization method, noble metal sensitization method using gold, platinum, palladium and the like, reduction sensitization method and the like may be used alone or in combination. (For example, see JP-A-3-110,5)
55, JP-A-5-241,267, etc.). Examples of tellurium sensitizers include Canadian Patent No. 800,958, British Patent Nos. 1,295,462 and 1,396,696.
And compounds described in Japanese Patent Application Nos. 2-333819 and 3-131598 can be used. Specific tellurium sensitizers include colloidal tellurium, telluroureas (for example, tetramethyltellurourea, N-carboxyethyl-
N ′, N′-dimethyltellurourea, N, N′-dimethylethylenetellurourea), isotellurocyanates, telluroketones, telluramides, tellurohydrazides, telluroesters, phosphine tellurides (for example, tributylphosphine) Butyldiisopropylphosphine telluride), other tellurium compounds (for example, potassium tellurocyanate, telluropentathionate sodium salt) and the like. The amount of tellurium sensitizer used is about 10 ^{-7 to} 5 × 10 ^-2 mol, preferably about 5 × 10 ^-7 to 10 ^-3 mol, per mol of silver halide. It is preferable to use an oxidizing agent for silver during the production process of the silver halide emulsion. Preferred oxidants are ozone, hydrogen peroxide and its adducts, halogen elements, inorganic oxidants of thiosulfonates and organic oxidants of quinones. It is a preferred embodiment to use the above-described reduction sensitization and an oxidizing agent for silver in combination. After using the oxidizing agent, the method can be selected from a method of performing reduction sensitization, a reverse method thereof, or a method of coexisting the two at the same time. These methods can be selectively used in both the grain formation step and the chemical sensitization step. These chemical sensitizations can also be performed in the presence of a nitrogen-containing heterocyclic compound (JP-A-62-253,159).
issue). Further, an antifoggant described later can be added after the completion of the chemical sensitization. Specifically, Japanese Patent Application Laid-Open No. 5-45,8
No. 33 and JP-A-62-40446 can be used. The pH during chemical sensitization is preferably 5.3.
１10.5, more preferably 5.5-8.5, p
Ag 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 from 1 mg to 10 mg in terms of silver.
g / m ² .

In order to impart green, red and infrared sensitivity to the photosensitive silver halide used in the present invention, the photosensitive silver halide emulsion is spectrally sensitized with a methine dye or the like. . If necessary, the blue-sensitive emulsion may be subjected to spectral sensitization in the blue region. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine 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 addition amount is generally 10 ^-5 to 10 per mol of silver halide.
^-2 moles.

The additives used in such a process and known photographic additives which can be used in the light-sensitive material and the dye-fixing material are described in the above-mentioned RD Nos. 17, 643 and 18, 71.
No. 6 and Nos. 307, 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 enhancer, page 648, right column 3. Spectral sensitizer, page 23-24, page 648, right column-866- Page 868 Supersensitizer 649 right column 4. Fluorescent brightener 24 page 648 right column 868 5. Antifoggant, 24-24 page 649 right column 868-870 stabilizer 6. Light absorber 25-26 page 649 right column-873 filter dye, page 650 left column UV absorber 7.Stain inhibitor 7 page right column 650 page left column-872 right column 8. Dye image stabilizer page 25 page 650 Left column page 872 9. Hardener page 26 page 651 left column page 874-875 10. Binder page 26 page 651 left column 873-874 11. Plasticizers and lubricants page 27 650 page right column page 876 12. Coating Auxiliaries, pages 26 to 27, page 650, right column, pages 875 to 876 Surfactants 13.Static 27, page 650, right column, pages 876 to 877 Inhibitors 14. Matting agents, pages 878 to 879

As the binder for the constituent layers of the photosensitive material, hydrophilic binders are preferably used. 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.

Other techniques and inorganic / organic materials which can be used in the color photographic light-sensitive material of the present invention are described in the following portions of European Patent 436,938A2 and the patents cited below. 1. Layer structure: page 146, line 34 to page 147, line 25 2. Antiseptic / antifungal agent: page 150, lines 25-28. 3. Formalin Scavenge: page 149, lines 15 to 17 Other additives: page 153, lines 38 to 47; EP 421,453A1, page 75, line 21 to page 84, line 56, page 27, line 40 to page 37, line 40 Eyes 5. 5. Dispersion method: page 150, 4th line to 24th line 6. Supporter: page 150, lines 32 to 34 7. Film thickness / film physical properties: page 150, lines 35 to 49 8. Desilvering process: page 151, line 48 to page 152, line 53 Automatic developing machine: page 152, line 54 to page 153, line 2 Washing and stabilization process: page 153, lines 3 to 37

As a method of exposing and recording an image on a photosensitive material, for example, 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 an exposure device of a copier, 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-5-1761-1)
No. 44, 5-199, 372, 6-127, 02
No. 1 etc.), a method of outputting image information to an image display device such as a CRT, a liquid crystal display, an electroluminescence display, a plasma display, etc., and exposing directly or via an optical system.

As a light source for recording an image on a photosensitive material,
As described above, U.S. Pat. No. 4,500,626, column 56, natural light, tungsten lamp, light emitting diode, laser light source, CRT light source, etc., JP-A-2-53,37.
No. 8, No. 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 capable of expressing nonlinearity between polarization and electric field that appears when a strong optical electric field such as laser light is applied, and is composed of lithium niobate, potassium dihydrogen phosphate (K
DP), lithium iodate, BaB ₂ O _{4 and} other inorganic compounds, urea derivatives, nitroaniline derivatives,
For example, nitropyridine-N-oxide derivatives such as 3-methyl-4-nitropyridine-N-oxide (POM), JP-A-61-53462 and JP-A-62-121032.
The compounds described in (1) 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. In addition, the image information includes an image signal obtained from a video camera, an electronic still camera, and the like, and the Nippon Television Signal Standard (NTS).
A television signal represented by C), an image signal obtained by dividing an original image into a large number of pixels such as a scanner, and an image signal created by using a computer represented by CG and CAD can be used.

The light-sensitive material incorporating the color-forming reducing agent of the present invention is exposed to light, and then subjected to a developing process. , A method of developing the alkaline processing solution into a photosensitive material by a diffusion transfer method, and a method of performing thermal development. Activator processing refers to a processing method in which a color-forming reducing agent is incorporated in a photosensitive material, and development is performed using a processing solution that does not contain a color-forming developing agent. In the present invention, the “activator liquid” is a p-activator as conventionally used.
-It is characterized in that it does not substantially contain a phenylenediamine-based color developing agent, and may contain other components (alkali, halogen, chelating agent, etc.). 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 that each is preferably 0.5 mmol / liter or less, more preferably 0.1 mm / liter or less.
ol / liter or less. In particular, it is preferable not to contain at all. The pH of the alkaline treatment liquid is preferably 9 to
14, particularly preferably 10-13. The activator processing photosensitive material and the processing thereof are described in, for example, Japanese Patent Application Nos. 7-63572, 7-334190, and 7-3.
Nos. 34192, 7-334197 and 7-34
No. 4396.

In the present invention, when the photosensitive material is developed using a developing solution, the developing solution functions as a silver halide developing agent and / or an oxidized developing agent generated in silver development contains an oxidized developing agent in the photosensitive material. A compound having a function of cross-oxidizing a color-forming reducing agent (color-developing agent) contained in the toner may be used. Preferred are pyrazolidones, dihydroxybenzenes, reductones and aminophenols, and particularly preferred are pyrazolidones.
In addition, regarding additives, processing formulas (methods), processing conditions, and the like used in the processing of development, bleaching, fixing, and washing (stabilization), see JP-A-8-101484, page 13, column 24, 33.
What is described from line to page 19, column 35, line 28 is preferably applicable. If the amount of silver halide used is small,
Desilvering can be omitted. The actual processing time in a developing machine using a processing solution is usually determined by the linear velocity and the capacity of the processing bath.
/ Min. Especially in the case of a small developing machine,
2500 mm / min is preferred. The processing time from the entire processing step, that is, from the developing step to the drying step, is preferably 360 seconds or less, more preferably 120 seconds or less, and particularly preferably 90 to 30 seconds. Here, the processing time is the time from when the photosensitive material is immersed in the developing solution to when it comes out of the drying section of the processor.

The process of developing an alkaline processing solution in a diffusion transfer system 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 a 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 about 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.
raphic Process 4th edition (1977, Macmillan)
The structure of a specific film unit is described in JP-A-63-226649. Examples of the materials included in the film unit and various layers including the same are described below. The dye receiving layer and the mordant contained therein are described in
No. 1-252551, U.S. Pat. No. 2,548,564.
No. 3,756,814, No. 4,124,38
No. 6, No. 3,625,694. For the neutralizing layer for lowering the pH of the photosensitive material after developing the alkaline processing solution, JP-B-7-122753,
U.S. Pat. No. 4,139,383, RD-No. 1610
The timing layer used in combination with the neutralizing layer is described in JP-A-54-136328.
No. 4,267,262, US Pat.
No. 9,030 and 4,268,604. Although any emulsion can be used as the silver halide emulsion, preferred auto-positive emulsions as photographic light-sensitive materials are described in JP-A-7-333770 and JP-A-7-337377.
No. can be given. In addition, if necessary, a light-shielding layer, a reflective layer, an intermediate layer, an isolation layer, an ultraviolet absorbing 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
No. 3,337,771.

The heat treatment in the heat development of the light-sensitive material is known in the art, and is 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, 7
thEd. (Van Nostrand and Reinhold Company) 32
~ 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 is prepared in accordance with 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.

[0094]

【Example】

Example 1 A surface of a paper support laminated on both sides with polyethylene was subjected to a corona discharge treatment, followed by providing a gelatin subbing layer containing sodium dodecylbenzenesulfonate, and further coating two kinds of photographic constituent layers. A photographic paper (100) having a layer configuration was produced. The coating solution was prepared as follows. First layer coating solution Coupler (EXCY-1) 23 g, color developing agent (EX
19 g of CD-1) and 80 g of a solvent (Solv-1) 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 A (cubic, 3: 7 mixture of large-size emulsion A having an average grain size of 0.88 μm and small-size emulsion A having an average grain size of 0.70 μm (silver molar ratio). 0.08 and 0.10, respectively, and 0.3 mol% of silver bromide in each size emulsion was localized and contained in a part of the surface of silver chloride-based grains). This emulsion contains the following blue-sensitive sensitizing dyes A, B, and C in an amount of 1.4 × for the large-size emulsion A per mole of silver.
10 For ^-4 mol to the small size emulsion A, is 1.7 × 10 ^-4 mol each addition. 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 first layer coating solution having the following composition. The emulsion coating amount indicates a silver equivalent coating amount.

The coating solution for the second layer was prepared in the same manner as the coating solution for the first layer. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. Also, Cpd-2, Cpd-3, Cpd
-4 and Cpd-5 in a total amount of 15.0 mg / m ² , 6
0.0 mg / m ² , 50.0 mg / m ² and 10.0 mg / m ² were added.

[0096]

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[0097]

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2.8 × 10 ^-3 mol of 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to the first layer 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 [white pigment (TiO ₂ 15wt.
%) And a bluish dye (ultramarine)] First layer The above-mentioned silver chlorobromide emulsion A 0.20 Gelatin 1.50 Yellow coupler (EXCY-1) 0.23 Color developing agent (EXCD-1) 0.19 Solvent (Solv-1) 0.80

Second layer (protective layer) Gelatin 1.01 Acrylic modified copolymer of polyvinyl alcohol 0.04 (degree of modification 17%) Liquid paraffin 0.02 Surfactant (Cpd-1) 0.01

The sample (10) was prepared except that the yellow coupler and the color developing agent in the coating solution of the first layer were replaced with the yellow coupler and the color developing agent shown in Table a in equimolar amounts.
Samples (101) to (10)
7) was produced.

[0101]

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Further, silver chlorobromide emulsion A in the coating solution for the first layer was replaced by silver chlorobromide emulsion B shown below with an equivalent silver amount, and the coupler and color developing agent were respectively replaced by the coupler shown in Table b and color development. The samples (1
Samples (200) to (207) in exactly the same manner as in (00).
Was prepared.

Silver chlorobromide emulsion B: cubic, 1: 3 mixture of large-size emulsion B having an average grain size of 0.55 μm and small-size emulsion B having an average grain size of 0.39 μm (Ag molar ratio). The coefficient of variation of the grain size distribution was 0.10 and 0.08, respectively, and 0.8 mol% of AgBr was contained in each of the emulsions in a portion of the grain surface having silver chloride as a base.

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

[0105]

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(The sensitizing dye D was used in an amount of 3.0 × 10 ^-4 mol for a large-size emulsion, 3.6 × 10 ^-4 mol for a small-size emulsion, and Sensitizing dye E was used in an amount of 4.0 × 10 ^-5 mol per mol of silver halide and 7.0 mol per mol of silver halide.
× 10 ⁻⁵ mol, or 2.0 × 10 ⁻⁴ mol of the sensitizing dye F per mol of silver halide for a large size emulsion,
2.8 × 10 ^-4 mol was added to the small size emulsion)

[0107]

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[0108]

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[0109]

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The samples (100) to (107) prepared as above using a FWH type photometer (color temperature of light source: 3200 ° K) manufactured by Fuji Film Co., Ltd. were subjected to a blue filter for sensitometry. , Samples (200) to (2)
07) was subjected to gradation exposure with a green filter for sensitometry.

The exposed sample was processed in the following processing steps 1 and 2 using the following processing solutions. Processing Step 1 Processing Step Temperature Time Current Image 40 ° C 18 seconds Bleaching and Fixing 40 ° C 45 seconds Rinse Room Temperature 45 seconds Alkaline Processing Room Temperature 25 seconds Processing Step 2 Processing Step Temperature Time Current Image 40 ° C 18 seconds Bleaching and Fixing 40 ° C 45 Second 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-1.5 g 3-pyrazolidone Water was added 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 ml Ammonium iron (III) ethylenediaminetetraacetate 55 g Ethylenediaminetetraacetic acid 2 g Nitric acid (67%) 30 g Add water to 1000 ml pH (at 25 ° C / acetic acid and aqueous ammonia) 5.8

Rinse solution Chlorinated sodium isocyanurate 0.02 g Deionized water (conductivity 5 μS / cm or less) 1000 ml pH 6.5 Alkaline treatment solution Water 800 ml Potassium carbonate 30 g Add water 1000 ml pH 10

Both the sample processed in the processing step 1 and the sample processed in the processing step 2 have the color density portion as the sample (100).
To (107) blue light, samples (200) to (2)
07) was measured with green light. The densities of the highest color portion and the lowest color portion of the sample processed in the processing step 1 are set to Damax and Damin, respectively, and the densities of the highest color portion and the lowest color portion of the sample processed in the process step 2 are set to Dnmax and Dnmin, respectively. The results are shown in Tables a and b, respectively. Two unexposed and unprocessed samples were prepared, and desilvering was performed in the above-described bleach-fixing step. One sheet was subjected to an alkali treatment, and the other sheet was not subjected to the alkali treatment, and was subjected to a forced thermo test at a temperature of 50 ° C. and a humidity of 70% for one week. After the thermotest, the samples (100) to (107) for both the alkali-treated sample and the non-alkali-treated sample
Was measured with blue light, and samples (200) to (207) were measured with green light. The concentration of the sample subjected to the alkali treatment is designated as Das, and the concentration of the sample not subjected to the alkali treatment is designated as Dns. The results are shown in Tables a and b.

[0116]

[Table 1]

[0117]

[Table 2]

As is clear from Tables a and b, the samples using the color developing agent for comparison and the coupler do not develop color without alkali treatment. However, when the alkali treatment is performed, the increase in the density of the unexposed portion due to the storage under the moist heat condition increases. On the other hand, in the sample using the color developing agent of the present invention and the coupler, a sufficient color developing density was obtained without performing the alkali treatment, and under the condition where the alkali treatment was not performed, the density of the unexposed portion was almost increased. It can be seen that it has good storage stability.

Example 2 <Method for Preparing Photosensitive Silver Halide Emulsion> A well-stirred aqueous gelatin solution (inert gelatin 3
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 prepare a silver iodobromide emulsion having an iodine content of 3 mol% and an average sphere equivalent particle diameter of 0.76 μm. The equivalent sphere diameter was measured with a Coulter Counter Model TA-II. Potassium thiocyanate, chloroauric acid, and sodium thiosulfate were added to the above emulsion at 56 ° C. for optimal chemical sensitization. Sensitizing dyes corresponding to the respective spectral sensitivities were added to the emulsion at the time of preparing the coating solution to give color sensitivity.

<Preparation method of zinc hydroxide dispersion> 31 g of zinc hydroxide powder having a primary particle size of 0.2 μm,
1.6 g of carboxymethylcellulose, 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> Table 1
The oil phase component and the water phase component having the compositions shown in
Make a homogeneous solution at 0 ° C. The oil phase component and the aqueous phase component were combined, and placed in a 1-liter stainless steel container at 10,000 rpm with a dissolver equipped with a 5 cm diameter disperser.
Dispersed for 0 minutes. To this, warm water in the amount shown in Table 1 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.

[0122]

[Table 3]

[0123]

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[0124]

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Using the thus obtained raw materials, heat-developable color photosensitive materials 301 having a multilayer structure shown in Tables 4 and 5 were produced.

[0126]

[Table 4]

[0127]

[Table 5]

[0128]

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[0129]

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[0130]

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Further, a processing material R-1 having the contents shown in Tables 6, 7, and 8 was prepared.

[0132]

[Table 6]

[0133]

[Table 7]

[0134]

[Table 8]

[0135]

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[0136]

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Next, as shown in Table 9, photosensitive materials 302 to 312 having exactly the same composition as 301 except that the coupler and the developing agent were changed were prepared. The photosensitive materials 301 to 312 thus formed are passed through a B, G, R filter having a continuously changed density to 2500 l.
Exposure for 0.01 second with ux. 40 ° C on the exposed photosensitive material surface
15 ml / m ² of hot water, treated sheet (image receiving sheet)
After the film surfaces were overlaid on each other, heat development was performed at 80 ° C. for 35 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 processing, the highest density portion (Dmax) and the lowest density portion (Dmin) of the yellow dye image of the B exposed portion, the magenta image of the G exposed portion, and the cyan image of the R exposed portion of this sample.
Is shown in Table 10 by using an X-rite densitometer.

[0138]

[Table 9]

[0139]

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[0140]

[Table 10]

From Table 10, it can be seen that the combination of the developing agent and the coupler of the present invention gives a high maximum concentration to the comparative compound, and the minimum concentration hardly changes, giving good discrimination.

[0142]

According to the present invention, low replenishment and low discharge can be achieved, and stain due to long-term storage of the photosensitive material is reduced.
In addition, an image with a high color density can be obtained.

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[Procedure amendment]

[Submission date] January 31, 1997

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0013

[Correction method] Change

[Correction contents]

The acyl group is preferably an acyl group having 1 to 50 carbon atoms, more preferably 2 to 40 carbon atoms. Specific examples include acetyl, 2-methylpropanoyl, cyclohexylcarbonyl, n-octanoyl, 2-hexyldecanoyl, dodecanoyl, chloroacetyl, trifluoroacetyl, benzoyl, 4- Dodecyloxybenzoyl group, 2-hydroxymethylbenzoyl group, 3- (N-hydroxy-N
-Methylaminocarbonyl) propanoyl group. The alkylsulfonyl group is preferably a sulfonyl group having 1 to 50 carbon atoms, and more preferably a sulfonyl group having 1 to 4 carbon atoms.
0. Specific examples include a methanesulfonyl group and an ethanesulfonyl group. The arylsulfonyl group is preferably an arylsulfonyl group having 6 to 50 carbon atoms, and more preferably 6 to 40 carbon atoms. Specific examples include a phenylsulfonyl group, a 2-naphthalenesulfonyl group, a 2-methoxy-5-t-octylphenylsulfonyl group, a 4-dodecylphenylsulfonyl group,
A hexadecyloxyphenylsulfonyl group, 2- (2
-Ethoxyethoxy) -5-hexadecylsulfonamidophenylsulfonyl group, n-dodecylsulfonyl group and the like. The heterocyclic sulfonyl group is preferably a heterocyclic sulfonyl group having 1 to 50 carbon atoms, more preferably 1 to 40 carbon atoms. The hetero ring is the same as that described later in the description of the hetero ring formed by Q and C. Specific examples include 2-pyridylsulfonyl, 2
-Furanylsulfonyl and the like.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0021

[Correction method] Change

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[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0056

[Correction method] Change

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[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0096

[Correction method] Change

[Correction contents]

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[Procedure amendment 5]

[Document name to be amended] Statement

[Correction target item name]

[Correction method] Change

[Correction contents]

As is clear from Tables a and b, the samples using the color developing agent for comparison and the coupler do not develop color without alkali treatment. However, when the alkali treatment is performed, the density of the unexposed portion increases due to storage under a wet heat condition. On the other hand, in the sample using the color developing agent of the present invention and the coupler, a sufficient color developing density was obtained without performing the alkali treatment, and under the condition where the alkali treatment was not performed, the density of the unexposed portion was almost increased. It can be seen that it has good storage stability.

[Procedure amendment 6]

[Document name to be amended] Statement

[Correction target item name] 0121

[Correction method] Change

[Correction contents]

<Method for Preparing Emulsified Dispersion of Coupler> Table 3
The oil phase component and the water phase component having the compositions shown in
Make a homogeneous solution at 0 ° C. The oil phase component and the aqueous phase component were combined, and placed in a 1-liter stainless steel container at 10,000 rpm with a dissolver equipped with a 5 cm diameter disperser.
Dispersed for 0 minutes. Warm water in the amount shown in Table 3 was added thereto 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.

[Procedure amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0122

[Correction method] Change

[Correction contents]

[0122]

[Table 3]

[Procedure amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0126

[Correction method] Change

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[0126]

[Table 4]

[Procedure amendment 9]

[Document name to be amended] Statement

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[0127]

[Table 5]

──────────────────────────────────────────────────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 photographic material having at least one photographic constituent layer on a support, wherein at least one of the photographic constituent layers contains a color developing agent represented by the following general formula (I): A silver halide photographic material comprising at least one dye-forming coupler represented by the following general formula (II). Embedded image In the formula, Z represents a carbamoyl group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group, a heterocyclic sulfonyl group, a sulfamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amidino group, or an imidoyl group. Q represents an atomic group that forms an unsaturated ring with C. Embedded image In the formula, L ¹ represents an alkyl group, an aryl group or a heterocyclic group, and L ² and L ³ each represent a hydrogen atom or a substituent. Q ⁰ is -C = N ⁺ - with represents a nonmetallic atomic group necessary for forming a ring. Y represents a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidized form of the color developing agent represented by formula (I). ^{Two of} L ² , L ³ and Y do not form a double bond. A represents a negative ion. k represents 1 or 0, and k is 0 when the coupler of the general formula (II) forms an inner salt. 2. The silver halide photographic material according to claim 1, wherein the general formula (II) is represented by the following general formula (III). Embedded image In the formula, L ¹ represents an alkyl group, an aryl group, or a heterocyclic group, and L ² , L ³ , L ⁴ , and L ⁵ each represent a hydrogen atom or a substituent. L ⁴ and L ⁵ may combine with each other to form a double bond or a ring. Q ¹ is -S-, -O
^{-, - N (L 6)} -, - Se -, - C (L 7) (L 8) -, -
^{C (L 7) = C (} L 8) -, - C (L 7) = N-, or -N
= N-. L ⁶ , L ⁷ and L ⁸ each represent a hydrogen atom or a substituent. Q ² and Q ³ represent C, N, O or S. l and m each represent 0 or 1. Y, A and k
Has the same meaning as that of formula (II). 3. The silver halide photographic light-sensitive material according to claim 2, wherein in the general formula (I), Z is an alkylsulfonyl group, an arylsulfonyl group, a heterocyclic sulfonyl group or a carbamoyl group. 4. The silver halide photographic material according to claim 2, wherein Z in the general formula (I) is a carbamoyl group. 5. An image forming method, wherein the silver halide photographic material according to claim 1 is subjected to a heat treatment at 65 ° C. or more and 180 ° C. or less to perform development. 6. An image forming method, comprising developing the silver halide photographic material according to claim 1 in a solution.