JP2000267239A - Color developing agent which is new metallic complex compound, new color developing agent, silver halide color photographic sensitive material, image forming method, processing method and method for forming color dye - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silver halide color photographic sensitive material having superior color forming property and high sensitivity and excellent in image preservability by incorporating a color developing agent which is a metallic complex compound. SOLUTION: The color developing agent is represented by the formula, wherein M is a metal ion, X is a coordination compound capable of forming a complex by coordinate bond to the metal ion, Y is an anion, (m) is an integer of 1-3, (n) is an integer of 0-3 and plural symbols X may be the same or different. The coordination compound is, e.g. represented by the formula R1-NHNH-J-R2, wherein R1 is aryl or a heterocyclic group, R2 is alkyl, alkenyl, alkynyl, aryl or a heterocyclic group and J is -SO2-, -CO-, -COCO-, -CO-O- or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to a novel color developing agent, a silver halide color photographic material containing the same,
The present invention relates to an image forming method, a processing method, and a coloring dye forming method.

[0002]

2. Description of the Related Art Conventionally, in silver halide color photographic materials, it has been desired to reduce the amount of silver halide used, that is, the amount of silver used.
No. 48148, No. 63-20330, No. 63-203
No. 32, JP-A-3-111844 and the like, a silver-silver color photographic light-sensitive material is greatly reduced in silver by performing development intensification processing with a development intensifying solution containing hydrogen peroxide and a color developing agent. It is described that sufficient image density can be obtained even with a low silver content photographic element.

However, a detailed study was conducted on a method of forming a color image to be subjected to development intensification processing using a development intensification liquid containing the above-mentioned hydrogen peroxide and a color developing agent. It became clear that the preservability of the processing solution was extremely poor because the agent coexisted. In order to solve this problem, a technique for incorporating a p-phenylenediamine compound as a color developing agent into a photosensitive material is disclosed in JP-A-56-6235, JP-A-56-54430 and JP-A-56-54430.
No. 67842, JP-A-2-143247, etc., the compound has a serious problem in storage stability in a light-sensitive material.

On the other hand, European Patent Nos. 545,491 and 56
5,165, 572,054, 593,110
JP-A-7-134335 and JP-A-8-227131
And JP-A-8-286340 disclose a technique for incorporating a hydrazine-type color developing agent in a photosensitive material.
Although the storage stability of the compound in the light-sensitive material is greatly improved, it has a disadvantage that the color dye has low fastness.

As a means for improving the fastness of a coloring dye, Japanese Patent Publication No. 4-47811 discloses a technique for forming a metal chelate dye image by bringing the coloring dye into contact with a metal ion-containing compound. However, according to the method described in this patent, the chelation reaction rate of the dye is low, and a sufficient metal chelate dye cannot be obtained, so that the improvement in the fastness of the color forming dye has not yet been said to be a satisfactory level.

Further, as a technique for forming a coloring pigment,
Although it is used in a wide range of fields such as hair dyes, test reagents, and pharmaceuticals, a technique using a p-phenylenediamine-based compound as a color developing agent is conventionally known. However, it had a serious problem in storage stability.

In general, a silver halide color photographic light-sensitive material undergoes color development after exposure, whereby an oxidized p-phenylenediamine derivative and a coupler react to form an image. A p-phenylenediamine derivative in the form of an aqueous alkali solution is unstable and easily deteriorates with time, and has a serious problem in disposal. In order to solve these problems, a hydrazine-type developing agent is incorporated in a silver halide color photographic light-sensitive material as a method in which p-phenylenediamine or a compound having a similar function is contained in the light-sensitive material. The method is public,
For example, European Patent Nos. 545,491 and 565,16
No. 5, 572,054, 593,110, JP-A-7-134355, and 8-227131. However, even the sulfonylhydrazine-type compounds mentioned here are not sufficiently stable, and high-temperature, high-humidity due to long-term storage after treatment, or stain due to light is still at a practically problematic level. Further, the dye formed from sulfonylhydrazine is inferior in fastness, and when stored under high temperature and high humidity, the density of a color image is reduced, and the color developability is inferior, which is a practically problematic level. In view of the above problems, a technique for improving storage stability and a technique for improving coloration and sensitivity have been desired.

[0008]

SUMMARY OF THE INVENTION In view of the above-mentioned circumstances, an object of the present invention is to provide a color developing agent which is a novel metal complex compound and a silver halide color photographic light-sensitive material containing the developing agent. An object of the present invention is to provide a silver halide color photographic light-sensitive material having high sensitivities, high sensitivity and excellent image storability, an image forming method using the same, and a processing method thereof.

Another object of the present invention is to provide a method for forming a color dye by using a color developing agent which is a novel metal complex compound having excellent storage stability.

Another object of the present invention is to provide a novel color developing agent (not a metal complex compound), and to prevent deterioration over time by containing the novel color developing agent in a silver halide color photographic light-sensitive material. Can be treated with alkaline solution,
It is an object of the present invention to provide a silver halide color photographic light-sensitive material and an image forming method, in which stain due to long-term storage of the light-sensitive material before and / or after processing is reduced, and which has excellent color developability and excellent sensitivity.

[0011]

The above object of the present invention has been attained by the following constitutions (1 to 11, 12 to 17).

1. A silver halide color photographic material comprising a color developing agent which is a metal complex compound.

2. The color developing agent as the metal complex compound is represented by the following general formula (1):
The silver halide color photographic light-sensitive material described in the above.

[0014]

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[In the formula, M represents a metal ion. X is
Y represents an anion, m represents an integer of 1, 2 or 3, and n represents 0, 1, 2 or 3; Represents an integer. However, the plurality of coordination compounds X may be the same or different. ] 3. 3. The silver halide color photographic light-sensitive material according to 2, wherein the coordination compound represented by X in the general formula (1) is represented by the following general formula (2).

[0016]

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[In the formula, R ₁ represents an aryl group or a heterocyclic group, and R ₂ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. J is -SO ₂ -,
-CO-, -COCO-, -CO-O-, -CON (R
_{3) -, - COCO-O} -, - COCON (R 3) -, -
Represents SO ₂ —N (R ₃ ) — or —PO (R ₃ ) ₂ —. Here, R ₃ represents a hydrogen atom or the group described for R ₂ . ] 4. 3. The silver halide color photographic light-sensitive material according to 2, wherein the coordination compound represented by X in the general formula (1) is represented by the following general formula (3).

[0018]

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[Wherein R _{4 to} R ₇ each represent a hydrogen atom, a halogen atom, or a monovalent substituent. R ₈ is an alkyl group,
Represents an aryl group or a heterocyclic group. ] 5. 3. The silver halide color photographic material as described in 2, wherein the coordination compound represented by X in the general formula (1) is represented by the following general formula (4).

[0020]

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[Wherein, R _{9 to} R ₁₄ each represent a hydrogen atom, a halogen atom, or a monovalent substituent. 6]. 6. The silver halide color photographic material as described in any one of items 1 to 5, which comprises at least one kind of a hardly soluble metal oxide or a hardly soluble metal hydroxide.

7. An image forming method comprising forming a dye image comprising a metal complex dye using the silver halide color photographic light-sensitive material according to any one of the above 1 to 6.

8. After performing image exposure on the silver halide color photographic light-sensitive material according to any one of the above 1 to 6,
A processing method characterized by providing an alkaline solution for processing.

9. After performing image exposure on the silver halide color photographic light-sensitive material according to any one of the above 1 to 6,
A processing method characterized by processing by overlapping processing sheets.

10. A color developing agent which is a metal complex compound represented by the general formula (1).

11. A method for forming a coloring dye, comprising using a color developing agent that is a metal complex compound.

12. A silver halide color photographic material comprising at least one color developing agent represented by the following formula (I).

[0028]

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[In the formula, R ₁₁ represents an aryl group or a heterocyclic group, and R ₁₂ and R ₁₃ each represent a hydrogen atom or a substituent. 13. 13. The silver halide color photographic material as described in 12, wherein the color developing agent represented by the general formula (I) is represented by the following general formula (II) or (III).

[0030]

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[Wherein, R ₁₂ and R ₁₃ each represent a hydrogen atom or a substituent, and R ₁₄ represents a heterocyclic group.
X ₁ , X ₂ , X ₃ , X ₄ and X ₅ each represent a hydrogen atom or a substituent, and may be the same or different, and may combine with each other to form a ring. 14. An image forming method comprising forming a chelate dye using a silver halide color photographic light-sensitive material containing a coupler and a color developing agent represented by the above general formula (I).

15. 1. A silver halide color photographic light-sensitive material containing a metal ion-containing compound.
5. The image forming method according to item 4.

16. 15. The image forming method according to 14, wherein the metal ion-containing compound is provided from outside the silver halide color photographic light-sensitive material.

17. A color developing agent represented by the general formula (I).

Hereinafter, the present invention will be described in detail.

First, the first to eleventh aspects of the present invention will be described.

The color developing agent which is the metal complex compound of the present invention will be described.

The color developing agent which is the metal complex compound of the present invention may be any compound which reacts with a coupler to form a coloring dye, and is itself a metal complex compound.

The color developing agent which is the metal complex compound of the present invention is represented by the general formula (1).

[0040]

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[In the formula, M represents a metal ion. X is
Y represents an anion, m represents an integer of 1, 2 or 3, and n represents 0, 1, 2 or 3; Represents an integer. However, the plurality of coordination compounds X may be the same or different. In the general formula (1), a metal ion represented by M (a metal ion forming a metal complex) is represented by
Monovalent and polyvalent metal ions belonging to Groups VIII to VIII. And, among them, Al, Co, Cr, Cu, Fe, M
g, Mn, Mo, Ni, Sn, Ti, Pt, Pd, Zr
And metal ions of metals such as Zn and Ni, C
Metal ions of the metals u, Cr, Co, Zn, and Fe are particularly preferred.

In the general formula (1), examples of the anion represented by Y include enolate (acetylacetonate, hexafluoroacetylacetonate), halogen ion (fluoride, chloride, bromide, iodide, etc.), marine ion, sulfite ion, sulfate ion, alkyl or aryl sulfonate ion, nitrate ion, nitrite ion, carbonate ion, perchlorate ion, alkyl or aryl carboxylate ion, tetraalkyl borate, Sarishineto, benzoate, PF ₆ ^-, B
Preferred are F ₄ ⁻ , SbF ₆ ^{− and the} like.

In the general formula (1), the coordination compound represented by X may be a color developing agent itself or a compound which becomes a color developing agent only after being a metal complex compound.

The coordination compound represented by X is preferably a compound represented by the general formula (2), (3) or (4).

[0045]

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[In the formula, R ₁ represents an aryl group or a heterocyclic group, and R ₂ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. J is -SO ₂ -,
-CO-, -COCO-, -CO-O-, -CON (R
_{3) -, - COCO-O} -, - COCON (R 3) -, -
Represents SO ₂ —N (R ₃ ) — or —PO (R ₃ ) ₂ —. Here, R ₃ represents a hydrogen atom or the group described for R ₂ . ]

[0047]

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[Wherein, R _{4 to} R ₇ each represent a hydrogen atom, a halogen atom, or a monovalent substituent. R ₈ is an alkyl group,
Represents an aryl group or a heterocyclic group. ]

[0049]

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[In the formula, R _{9 to} R ₁₄ each represent a hydrogen atom, a halogen atom, or a monovalent substituent. In the general formula (2), the aryl group represented by R ₁ preferably has 6 to 14 carbon atoms, such as a phenyl group and a naphthyl group. Further, these may further have a substituent. The heterocyclic group represented by R ₁ 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 heterocyclic ring. Examples of the heterocycle represented by R ₁ include furanyl, thienyl, oxazolyl,
Thiazolyl, imidazolyl, triazolyl, pyrrolidinyl, benzoxazolyl, benzothiazolyl, pyridyl, pyridazyl, pyrimidinyl, pyrazinyl, triazinyl, quinolinyl, isoquinolinyl, phthalazinyl, quinoxalinyl, quinazolinyl, prinyl, pteridinyl, azepinyl, and benzoxinyl.

As the substituent which R ₁ may have,
Alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, heterocyclic oxy group, alkylthio group, arylthio group, heterocyclic thio group, acyloxy group, acylthio group, alkoxycarbonyloxy group, Aryloxycarbonyloxy group, carbamoyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, amino group, alkylamino group, amide group, alkoxycarbonylamino group,
Aryloxycarbonylamino group, ureido group, sulfonamide group, sulfamoylamino group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group,
Carbamoyl, acylcarbamoyl, carbamoylcarbamoyl, sulfonylcarbamoyl, sulfamoylcarbamoyl, alkylsulfonyl, arylsulfonyl, alkylsulfinyl, arylsulfinyl, alkoxysulfonyl, aryloxysulfonyl, sulfamoyl, acyl Sulfamoyl group, carbamoylsulfamoyl group, halogen atom, nitro group, cyano group, carboxyl group, sulfo group,
Examples include a phosphono group, a hydroxyl group, a mercapto group, an imide group, and an azo group.

R ₂ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. The alkyl group represented by R ₂ preferably has 1 to 1 carbon atoms.
6, linear, branched or cyclic, for example, methyl, ethyl, hexyl, dodecyl, 2-octyl, t-butyl,
Examples include groups such as cyclopentyl and cyclooctyl.

The alkenyl group is preferably a linear or cyclic alkenyl group having 2 to 16 carbon atoms.
-Octenyl, cyclohexenyl and the like.

The alkynyl group preferably has 2 to 16 carbon atoms and includes, for example, groups such as 1-butynyl and phenylethynyl.

As the aryl group and the heterocyclic group, the aforementioned R
Examples include the same groups as the specific examples of the aryl group and the heterocyclic group described in ₁ .

J is -SO _2- , -CO-, -COCO
-, - CO-O -, - CON (R 3) -, - COCO-
_{O -, - COCON (R 3} ) -, or -SO ₂ -N
(R ₃ ) —, —PO (R ₃ ) ₂ —, wherein R ₃ is the above R ₂
Is synonymous with

In the general formulas (2) and (3), R
_{4 to} R ₇ and R _{9 to} R ₁₄ each represent a hydrogen atom, a halogen atom,
Or a monovalent substituent. Examples of the monovalent substituent include an alkyl group, an aryl group, an alkylcarbonamide group, an arylcarbonamide group, an alkylsulfonamide group, an arylsulfonamide group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, and an alkylcarbamoyl group. , Arylcarbamoyl, carbamoyl, alkylsulfamoyl, arylsulfamoyl, sulfamoyl, cyano, alkylsulfonyl, arylsulfonyl, alkoxycarbonyl, aryloxycarbonyl, alkylcarbonyl, arylcarbonyl Or an acyloxy group.

R ₈ represents an alkyl group, an aryl group, or a heterocyclic group as described above.

R ₁₃ and R ₁₄ may combine with each other to form a double bond or a ring.

Hereinafter, a color developing agent which is a metal complex compound represented by the general formula (1), and the general formulas (2) to (4)
Specific examples of the coordination compound represented by are shown below, but the compound of the present invention is of course not limited thereto.

[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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[0072]

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[0073]

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[0074]

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Next, a synthesis example of a color developing agent which is the metal complex compound of the present invention will be described.

Synthesis of Exemplified Compound 1-1 Exemplified compound 1-1 is synthesized according to the following scheme.

[0077]

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2-aminobenzamide (ABA) 8.0
g was dissolved in ethyl acetate by heating.
4 ml was added, and the mixture was allowed to cool to room temperature. 11.0 g of picolinoyl chloride hydrochloride was added thereto, followed by stirring at room temperature for 2 hours. The precipitated crystals were collected by filtration and recrystallized from acetonitrile to obtain 8.0 g of crystals (intermediate 1).

3 g of the obtained crystal (intermediate 1) was dispersed in 70 ml of dehydrated toluene, and sodium methoxide 28%
2.87 g of methanol solution was added. The mixture was heated and refluxed for 4 hours while dehydrating. Drain the obtained insolubles and toluene solution as is in 100 ml of water,
Extracted with ethyl acetate. Drying yielded 1.7 g of white crystals (Intermediate 2).

0.6 g of the oxo form (intermediate 2) was
It was dissolved in 80 ml of dichloroethane, and 0.3 ml of phosphorus oxychloride was added dropwise thereto. The mixture was heated and refluxed for 2 hours. As a result of TLC confirmation that the raw material remained, 1.6 ml of phosphorus oxychloride was further added dropwise in two portions. After completion of the reaction, the reaction solution was allowed to cool, drained, neutralized with sodium hydrogen carbonate, and extracted with ethyl acetate. The solvent was distilled off to obtain 0.5 g of a pale yellow solid (intermediate 3) as 76.9%.
In a yield of

3.3 g of the obtained chlorinated product (intermediate 3)
Hydrazine (HZ) is dissolved in 80 ml of DMF and TE
After adding 2.3 ml of A, the mixture was stirred at room temperature overnight. This was drained into 250 ml of water, decanting and draining were repeated, and the obtained syrupy oil was washed with a two-phase system of water and ethyl acetate. Thereafter, it was dried and further purified by a column to obtain 3.8 g of a white crystal (intermediate 4).

10. The obtained hydrazine compound (intermediate 4)
0 g was dissolved in methanol. When 2.1 g of nickel chloride hexahydrate was added thereto at room temperature, it was initially in a dispersed state, but was completely dissolved later. The mixture was stirred at room temperature for 30 minutes, and the solvent was distilled off with an evaporator. 9.5 g of the obtained solid was dissolved in 9.5 ml of DMF, 38 ml of ethyl acetate was added, and the mixture was stirred for a while at room temperature to precipitate crystals. This was collected by filtration and washed with ethyl acetate to obtain 8.8 g of the desired product (Exemplified Compound 1-1). NMR, mass spectrum and elemental analysis confirmed that it was Exemplified Compound 1-1.

The silver halide photographic light-sensitive material containing the color developing agent which is the metal complex compound of the present invention may contain a coupler. In such a case, the amount of the color developing agent which is the metal complex compound is added. Has a wide range, but preferably 0.1 to 10 times the molar amount of the coupler.

The couplers which can be used in the present invention will be described below.

As couplers preferably used in the present invention, there are compounds having structures represented by the following formulas (5) to (16). These are compounds generally called active methylene, pyrazolone, pyrazoloazole, phenol, naphthol and the like, respectively.

[0086]

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[0087]

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Formulas (5) to (8) represent couplers referred to as active methylene couplers, wherein R ²⁴ represents an acyl group, a cyano group, a nitro group or an aryl group which may have a substituent. , A heterocyclic group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, and an arylsulfonyl group.

In the general formulas (5) to (7), R ²⁵ is an optionally substituted alkyl group, aryl group or heterocyclic group. In the general formula (8), R ²⁶ is an aryl group or a heterocyclic group which may have a substituent. R
Examples of the substituent which ²⁴ , R ²⁵ and R ²⁶ may have include, for example, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a cyano group, and a halogen atom. Examples of the substituent include various substituents such as an atom, an acylamino group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylamino group, an arylamino group, a hydroxyl group, and a sulfo group.
Preferred examples of R ²⁴ include an acyl group, a cyano group, a carbamoyl group, and an alkoxycarbonyl group.

In the general formulas (5) to (8), Y is a hydrogen atom or a group which can be eliminated by a coupling reaction with an oxidized developing agent. Examples of Y include groups acting as an anionic leaving group of a 2-equivalent coupler, such as a halogen atom (for example, chromium group, bromo group), an alkoxy group (for example, methoxy group, ethoxy group), an aryloxy group (for example, phenoxy group) , 4-cyanophenoxy group, 4-alkoxycarbonylphenyl group), alkylthio group (for example, methylthio group, ethylthio group, butylthio group), arylthio group (for example, phenylthio group, tolylthio group),
Alkylcarbamoyl group (for example, methylcarbamoyl group, dimethylcarbamoyl group, ethylcarbamoyl group,
Diethylcarbamoyl group, dibutylcarbamoyl group, piperidylcarbamoyl group, morpholylcarbamoyl group), arylcarbamoyl group (for example, phenylcarbamoyl group, methylphenylcarbamoyl group, ethylphenylcarbamoyl group, benzylphenylcarbamoyl group), carbamoyl group, alkylsulfamoyl Groups (eg, methylsulfamoyl, dimethylsulfamoyl, ethylsulfamoyl, diethylsulfamoyl, dibutylsulfamoyl, piperidylsulfamoyl, morpholylsulfamoyl), arylsulfamoyl Moyl group (for example, phenylsulfamoyl group, methylphenylsulfamoyl group, ethylphenylsulfamoyl group, benzylphenylsulfamoyl group), sulfamoyl group, cyano group Alkylsulfonyl groups (eg, methanesulfonyl group, ethanesulfonyl group), arylsulfonyl groups (eg, phenylsulfonyl group, 4-chlorophenylsulfonyl group, p-toluenesulfonyl group), alkylcarbonyloxy groups (eg, acetyloxy group, propionyloxy group, Butyloyloxy group), arylcarbonyloxy group (for example, benzoyloxy group, toluyloxy group, anisyloxy group), nitrogen-containing heterocyclic group (for example, imidazolyl group, benzotriazolyl group) and the like.

Examples of the group acting as a cationic leaving group of the 4-equivalent coupler include a hydrogen atom, a formyl group, a carbamoyl group and a methylene group having a substituent (substituents include an aryl group, a sulfamoyl group, a carbamoyl group, An alkoxy group, an amino group, a hydroxyl group, etc.), an acyl group,
And a sulfonyl group.

In the general formulas (5) to (8), R ²⁴ and R
²⁵ , R ²⁴ and R ²⁶ may combine with each other to form a ring.

The formula (9) represents a coupler called a 5-pyrazolone-based magenta coupler, wherein R ²⁷ represents an alkyl group, an aryl group, an acyl group, or a carbamoyl group. R ²⁸ represents a phenyl group or a phenyl group substituted by one or more halogen atoms, an alkyl group, a cyano group, an alkoxy group, an alkoxycarbonyl group, or an acylamino group. Y is the same as Y in general formulas (5) to (8).

Among the 5-pyrazolone magenta couplers represented by the general formula (9), those in which R ²⁷ is an aryl group or an acyl group and R ²⁸ is a phenyl group substituted by one or more halogen atoms are preferred.

To describe these preferred groups in detail, R ²⁷ is phenyl, 2-chlorophenyl, 2-methoxyphenyl, 2-chloro-5-tetradecanamidophenyl, 2-chloro-5- (3-octadecenyl-1-succinimide) Phenyl, 2-chloro-5-octadecylsulfonamidophenyl or 2-chloro-5- [2
-(4-hydroxy-3-t-butylphenoxy) tetradecanamido] aryl group such as phenyl, acetyl, pivaloyl, tetradecanoyl, 2- (2,4-
Di-t-pentylphenoxy) acetyl, 2- (2,4
Acyl groups such as -di-t-pentylphenoxy) butanoyl, benzoyl, and 3- (2,4-di-t-amylphenoxyacetamido) benzoyl; these groups may further have a substituent; Is an organic substituent or a halogen atom connected by a carbon atom, an oxygen atom, a nitrogen atom, or a sulfur atom.

R ²⁸ is 2,4,6-trichlorophenyl,
Substituted phenyl groups such as 2,5-dichlorophenyl and 2-chlorophenyl groups are preferred.

The formula (10) represents a coupler called a pyrazoloazole coupler, wherein R ²⁹ represents a hydrogen atom or a substituent. Z is 5 containing 2 to 4 nitrogen atoms
Represents a group of nonmetallic atoms necessary for forming a membered azole ring, and the azole ring may have a substituent (including a condensed ring). Y is the same as Y in general formulas (5) to (8).

Among the pyrazoloazole-based couplers represented by the general formula (10), imidazo [1,2] described in US Pat.
-B] pyrazoles, pyrazolo [1,5-b] [1, 2, 4] triazoles described in U.S. Pat. No. 4,540,654, and pyrazolo [US Pat. No. 3,725,067]. 5,1-c] [1,2,4] triazoles are preferable, and among these, pyrazolo [1,5-b] [1,2,4] triazole is preferable from the viewpoint of light fastness.

For details of the substituents on the azole ring represented by the substituents R ²⁹ , Y and Z, see, for example, US Pat.
No. 540,654, column 2, line 41 to column 8, line 27. Preferably, JP-A-61
Pyrazoloazole couplers in which a branched alkyl group is directly linked to the 2, 3 or 6 position of the pyrazolotriazole group as described in JP-A-65245;
Pyrazoloazole couplers containing a sulfonamide group in the molecule described in JP-A-61-147254
Pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group described in
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. 01443 is a pyrazolotriazole coupler having a carboxamide group in the molecule.

The general formulas (11) and (12) are couplers called a phenol coupler and a naphthol coupler, respectively, wherein R ³⁰ is a hydrogen atom or —NHCO
_{^{R 32, -SO 2 NR 32 R}} 33, -NHSO 2 R 32, -NHC
^{OR 32, -NHCONR 32 R 33,} -NHSO 2 NR 32 R
Represents a group selected from ³³ . R ³² and R ³³ represent a hydrogen atom or a substituent. In the general formulas (11) and (12), R
³¹ represents a substituent, p represents an integer selected from 0 to 2, and m represents an integer selected from 0 to 4. Y is the same as Y in general formulas (5) to (8). Examples of R ^{31 to} R ³³ include those described above as the substituents for R ^{24 to} R ²⁶ .

Preferred examples of the phenolic coupler represented by the general formula (11) include US Pat. No. 2,369,
No. 929, No. 2,801,171, No. 2,77
No. 2,162, No. 2,895,826, No. 3,7
2-alkylamino-5-alkylphenols described in U.S. Pat. No. 72,002 and the like, U.S. Pat. No. 2,772,162
No. 3,758,308, No. 4,126,39
No. 6, No. 4,334,011, No. 4,327,1
No. 73, West German Patent Publication No. 3,329,729, 2,5-diacylaminophenols described in JP-A-59-166956 and the like; U.S. Pat. Nos. 3,446,622 and 4,333. No. 999, No. 4,451,559,
And 4-phenylureido-5-acylaminophenols described in 4,427,767 and the like.

A preferred example of the naphthol coupler represented by the general formula (11) is described in US Pat. No. 2,474,2.
No. 93, 4,052, 212, 4,146
No. 396, No. 4,228,233, No. 4,29
Examples thereof include 2-carbamoyl-1-naphthol described in US Pat. No. 6,200 and the like and 2-carbamoyl-5-amide-1-naphthol described in U.S. Pat. No. 4,690,889 and the like.

The general formulas (13) to (16) are couplers called pyrrolotriazole, and R ⁴² , R ⁴³ and R ⁴⁴ each represent a hydrogen atom or a substituent. Y is the same as Y in general formulas (5) to (8). As the substituents for R ⁴² , R ⁴³ and R ⁴⁴ , those described above as the substituents for R ^{24 to} R ²⁶ can be mentioned. Preferable examples of the pyrrolotriazole-based couplers represented by the general formulas (13) to (16) include European Patent Nos. 488,248A1 and 491,1.
No. 97A1, No. 545, 300A1,
A coupler in which at least one of R ⁴² and R ⁴³ is an electron withdrawing group is exemplified.

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

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

The pyrrole coupler is described in JP-A No. 4-1.
The couplers described in Nos. 88137 and 4-190347 can be used.

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

As active methine couplers, couplers described in US Pat. Nos. 5,104,783 and 5,162,196 can be used.

The 5,5-fused heterocyclic couplers include
Pyrrolopyrazole couplers described in U.S. Pat. No. 5,164,289, pyrroloimidazole couplers described in JP-A-4-174429, and the like can be used.

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

In the present invention, in addition to the above-mentioned couplers, West German Patent Nos. 3,819,051A and 3,823,049.
No. 4,840,883, U.S. Pat.
No. 4,930, No. 5,051,347, No. 4,4
81,268, European Patent Nos. 304,856A2, 329,036A2, and 354,549A2,
No. 374, 781A2 and No. 379, 110A2
No. 386,930A1, JP-A-63-1410
No. 55, No. 64-32260, No. 64-32261
JP-A-2-29747, JP-A-2-44340,
2-110555, 3-7938, 3-16
0440, 3-172839, 4-17244
No. 7, 4-179949, 4-182645,
4-184337, 4-188138, 4-
Nos. 188139, 4-194847, 4-204
No. 532, No. 4-204731, No. 4-204732
The couplers described in the above publications can also be used.

Specific examples of the coupler usable in the present invention are shown below, but the present invention is of course not limited thereto.

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Further, the following functional couplers may be contained. As couplers for correcting unnecessary absorption of color-forming dyes, yellow colored cyan couplers described in European Patent No. 456,257A1, yellow colored magenta couplers described in the aforementioned European Patent, US Pat. No. 4,833,069 Magenta colored cyan coupler described in U.S. Pat. No. 4,837,136 (2);
Colorless masking couplers of formula (A) in claim 1 of WO 92/11575 (especially the exemplary compounds on pages 36-45). Compounds (including couplers) that react with oxidized developing agents to release photographically useful compound residues include the following. Development inhibitor releasing compound:
Compounds of formulas (I) to (IV) described on page 11 of EP 378,236 A1, EP 436,
Compounds represented by the formula (I) described on page 7 of 938A2, compounds represented by the formula (1) of Japanese Patent Application No. 4-134523, and described on pages 5 and 6 of EP 440,195A2. Compounds represented by formulas (I), (II) and (III),
No. 4,555,47. The compound of formula (I) -ligand releasing compound of claim 1 of U.S. Pat.
A compound represented by LIG-X according to claim 1 of Claim 8.

The amount of the coupler to be added depends on its molar extinction coefficient (ε), but in order to obtain an image density of 1.0 or more in reflection density, the ε of the dye formed by coupling is about 5,000 to 500,000. In the case of the coupler described above, 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 .

A hydrophobic additive such as a coupler or a color developing agent can be introduced into a layer of a light-sensitive material by a known method such as the method described in US Pat. No. 2,322,027. In this case, U.S. Pat. No. 4,555,470,
Nos. 4,536,466, 4,536,467, 4,587,206, 4,555,476, 4,599,296 and JP-B-3-62256. Such a high-boiling organic solvent may be used, if necessary,
It can be used in combination with an organic solvent having a low boiling point of from 1 to 160 ° C. Two or more of these dye-donating couplers and high-boiling organic solvents can be used in combination. The amount of the high boiling organic solvent is 10 g per 1 g of the hydrophobic additive used.
Or less, preferably 5 g or less, more preferably 1 g to 0.1 g.
1 g. Further, 1 cc or less, more preferably 0.5 cc or less, particularly 0.3 cc or less is suitable for 1 g of the binder. JP-B-51-39853, JP-A-51-59
A dispersion method using a polymer described in No. 943 or a method of adding a fine particle dispersion described in JP-A-62-30242 can be used. In the case of a compound which is 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, the surfactants described in Research Disclosure described below, pages (37) to (38) of JP-A-59-157636, can be used. Japanese Patent Application Nos. 5-204325 and 6-
Phosphate ester type surfactants described in 19247 and West German Patent Publication No. 1,932,299A can also be used.

The silver halide photographic light-sensitive material containing the color developing agent of the present invention may contain a hardly soluble metal oxide or a hardly soluble metal hydroxide. Hardly soluble metal oxides such as zinc oxide, nickel oxide, cobalt oxide, iron oxide, manganese oxide, calcium oxide, magnesium oxide, and aluminum oxide.

The hardly soluble metal hydroxide of the present invention includes metal hydroxides which are hardly soluble in water, such as zinc hydroxide, nickel hydroxide, cobalt hydroxide, iron hydroxide, manganese hydroxide, and the like.
Examples include calcium hydroxide, magnesium hydroxide, and aluminum hydroxide.

In the present invention, an auxiliary developing agent may be used. Here, the auxiliary developing agent has an effect of promoting the transfer of electrons from the color developing agent to the silver halide in the development process of silver halide development. Has a substance.

The auxiliary developing agent in the present invention is preferably an electron-emitting compound represented by the following general formula (B-1) or (B-2) according to the Kendall-Peltz rule. Among them, those represented by the general formula (B-1) are particularly preferable.

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In the formula, each of R ^{51 to} R ⁵⁴ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or a heterocyclic group.

R ^{55 to} R ⁵⁹ each represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, a cycloalkyloxy group, an aryloxy group, Ring 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, cycloalkyloxycarbonyl Oxy, aryloxycarbonyloxy, carbamoyloxy, sulfamoyloxy, alkanesulfonyloxy, arylsulfonyloxy, acyl, alkoxycarbonyl, cycloalkyloxycarbonyl, aryloxycarbonyl, carbamoy Group, carbonamide group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide group, sulfamoylamino group, alkylsulfinyl group, arenesulfinyl group, alkanesulfonyl group, arylsulfonyl group, Represents a sulfamoyl group, a sulfo group, a phosphinoyl group or a phosphinoylamino group.

Q represents an integer of 0 to 5, and when q is 2 or more, a plurality of R ⁵⁵ may be the same or different. R ⁶⁰ represents an alkyl group or an aryl group.

In the following, formula (B-1) or (B-2)
Specific examples of the compound represented by are shown below, but the auxiliary developing agent used in the present invention is not limited thereto.

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In the development processing of the present invention, development processing performed on conventionally known color negatives, color papers, color instant photographs, X-ray light-sensitive materials, light-sensitive materials for plate making, and the like can be preferably applied. Further, development can be carried out by heat treatment or activator treatment.

The heat treatment of the photosensitive material is known in the art.
For example, pages 553 to 555 of Basics of Photonics Engineering (Corona Corp., 1979), video information 40 issued in April 1978,
Page, Netlets Handbook of Ph
otography and Reprograph
y, 7th. Ed. (Van Nostrand an
d Reinhold Co. Pp. 32-33, U.S. Pat. Nos. 3,152,904 and 3,301,678,
Nos. 3,392,020 and 3,457,075, British Patent Nos. 1,131,108, 1,167,777, and RD17029 (June 1978), pp. 9-15. .

In the photothermographic material, various development terminators can be used for the purpose of always obtaining a constant image with respect to fluctuations in processing temperature and processing time during development. As used herein, the term "development terminator" refers to a compound that neutralizes a base or reacts with a base immediately after appropriate development to reduce the base concentration in the film and to stop development, or to interact with silver and / or a silver salt. Is a compound that suppresses development. Specific examples include an acid precursor that releases an acid when heated, an electrophilic compound that undergoes a substitution reaction with a coexisting base when heated, or a nitrogen-containing heterocyclic compound, a mercapto compound, and a precursor thereof.
For further details, see JP-A-62-253159, 31-32.
Page.

When the light-sensitive material of the present invention is used as a heat-developable light-sensitive material, the method of supplying a base is preferably a method of generating a base from a base precursor. Examples of the base precursor include a salt of an organic acid and a base which is decarboxylated by heat, a compound which decomposes by a reaction such as an intramolecular nucleophilic substitution reaction, a Rossen rearrangement or a Beckmann rearrangement, and releases amines, etc. Preference is given to compounds that wake up to release a base and compounds that generate a base by electrolysis or complexing reactions.

Examples of the former base precursor which generates a base by heating include salts of trichloroacetic acid described in British Patent No. 998,959 and the like, and US Pat. No. 4,060,420 as a further improved stability. Salts of propiolic acid described in JP-A-59-180537, U.S. Pat. No. 4,088,4.
No. 96, a 2-carboxycarbamide derivative, a salt with a thermally decomposable acid using an alkali metal or an alkaline earth metal in addition to an organic base as a base component (JP-A-59-19523).
No. 7), JP-A-59-1684 using Rossen dislocation
Hydroxam carbamates described in No. 40 and aldoxime carbamates described in JP-A-59-157637, which produces a nitrile upon heating, can be mentioned. In addition, UK Patent Nos. 998,945 and 2,079,480
No., JP-A-50-226225, U.S. Pat.
0,846, 4,514,493 and 4,65
7,848 and the known art No. 5 (March 22, 1991)
Base precursors described on pages 55-86 and the like are also useful.

When the photosensitive material is heated and developed, a processing sheet containing a base and / or a base precursor can be used. The processing sheet containing a base and / or a base precursor is for the purpose of assisting the development processing, and forms an image on the photosensitive layer after the processing.

The base and / or the base precursor contained in the treated sheet used in the present invention forms a complex with a basic metal compound which is hardly soluble in water and a metal ion constituting the basic metal compound in the presence of water. It is preferable to use a compound that can be used.

The compound capable of forming a complex in the present invention has an organic base, and has a stability constant of log K using a metal hydroxide or a metal ion constituting the metal oxide and water as a medium.
Is to purify a complex salt having a value of 1 or more.

These complex-forming compounds are described in, for example, AE Martel, R.E.
rtell, R .; M. Smith), “Critical Stability Konstanz (Critical S)
facility Constants), 1st to 5th
Vol. ", Plenum Press.

Specifically, aminocarboxylic acids, iminodiacetic acid and derivatives thereof, aniline carboxylic acids, pyridine carboxylic acids, aminophosphoric acids, carboxylic acids (mono, di, tri, tetracarboxylic acids and furthermore phosphono, hydroxy, oxo, ester, Compounds having a substituent such as amide, alkoxy, mercapto, alkylthio, and phosphino), salts with organic bases such as hydroxamic acids, polyacrylates, and polyphosphoric acids.

Preferred specific examples include picolinic acid,
2,6-pyridinedicarboxylic acid, 2,5-pyridinedicarboxylic acid, 4-dimethylaminopyridine-2,6-dicarboxylic acid, 5-ethylpyridine-2-carboxylic acid, quinoline-2-carboxylic acid, 2-pyridylacetic acid , Oxalic acid,
Citric acid, tartaric acid, isocitric acid, malic acid, gluconic acid, EDTA (ethylenediaminetetraacetic acid), NTA (nitrilotriacetic acid), CyDTA (1,2-cyclohexanediaminetetraacetic acid), hexametaphosphoric acid, tripolyphosphoric acid, tetraphosphoric acid, poly Acrylic acid, o-aminobenzoic acid,

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And the like and salts with organic bases.

Of these, an aromatic heterocyclic compound having at least one —CO ₂ HM and one nitrogen atom in the ring is preferable. The ring may be a single ring or a condensed ring, and examples thereof include a pyridine ring and a quinoline ring.
And it is particularly preferable that the position where —CO ₂ HM is bonded to the ring is α-position with respect to the N atom. Here, M is an organic base.

More preferable compounds include those represented by the following formula.

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In the above formula, R represents a hydrogen atom, an aryl group, a halogen atom, an alkoxy group, —CO ₂ HM, a hydroxycarbonyl group, an amino group, a substituted amino group,
Represents any one of electron donating groups such as an alkyl group.
Two Rs may be the same or different.

Z ₁ and Z ₂ are the same as defined for R, and Z ₁ and Z ₂ may combine to form a ring fused to a pyridine ring.

M is an organic base as described above.

As the organic base, those having a pKa of 7 or more and a carbon number of 12 or less are preferable.
It is a low-volatile base having a10 or more and a boiling point of 150 ° C. or more, and particularly preferred are guanidines, cyclic guanidines, amidines, cyclic amidines, and tetraalkylammonium hydroxides. Preferred examples of the organic base include piperidine, piperazine, ethylenediamine, N, N'-dimethylethylenediamine, acetamidine, diazabicyclononene, diazabicycloundecene, tetramethylammonium hydroxide, tetraethylammonium hydroxide,

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And the like.

In the silver halide photographic light-sensitive material of the present invention, the obtained coloring dye preferably has a chelating group and forms a chelate. Examples of the chelating group include a group containing an atom having a non-covalent atom pair (such as a nitrogen, oxygen, or sulfur atom) (such as an amino, imino, ether, alcohol, thioether, thiol, pyrrole, pyridyl, furyl, or thiofuryl group). Can be Particularly preferred groups among the chelating groups include a nitrogen atom on a heterocycle, a sulfonamide group and a sulfamoyl group.

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 these components are often added to the same layer. If it can react, it can be added in separate layers.

The hydrophobic additive such as a coupler used in the present invention can be introduced into a layer of a light-sensitive material by a known method such as the method described in US Pat. No. 2,322,027. In this case, US Pat. No. 4,555,470
No. 4,536,466 and No. 4,536,46
No. 7, No. 4,587,206, No. 4,555, 4
No. 76, No. 4,599,296, Tokuhei 3-622
A high-boiling organic solvent as described in No. 56 or the like can be used in combination with a low-boiling organic solvent having a boiling point of 50 to 160 ° C. as necessary. Two or more of these color developing agents, couplers, high-boiling organic solvents and the like can be used in combination. The amount of the high boiling point organic solvent is 10 g or less, preferably 5 g or less, more preferably 1 to 0.1 g, based on 1 g of the color image forming compound used. Also, 1 cc or less, more preferably 0.5 cc or less, especially 0.3 cc per 1 g of the binder.
cc or less is appropriate. In addition, Japanese Patent Publication No. 51-39853
And the dispersion method using a polymer described in JP-A-51-59943, JP-A-62-30242 and JP-A-62-30242.
No. 271339 can be used. In the case of a compound that is substantially unnecessary 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, the RD shown in the list below, pages (37) to (38) of JP-A-59-157636.
Those mentioned as surfactants described in magazines 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, and 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 light-sensitive 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 grains used in the present invention are silver bromide, silver chloride, silver chlorobromide, silver chloroiodide, silver iodobromide, and silver chloroiodobromide. Other silver salts, for example, silver rhodan silver sulfide, silver selenide, silver carbonate, silver phosphate, and organic acid silver may be contained as separate grains or as part of halogen atom grains. Development and desilvering (bleaching, fixing and bleach-fixing)
When speeding up the process is desired, silver halide grains having a high silver chloride content are desirable.

The silver halide emulsion used in the present invention preferably has a distribution or a structure with respect to the halogen composition in the grains. A typical example is Japanese Patent Publication No. 43-1
No. 3162, Japanese Patent Application Laid-Open No. 61-215540, Japanese Patent Application Laid-Open
These are core-shell type or double structure particles having a halogen composition in which the inside and the surface of the grains have different halogen compositions, as disclosed in JP-A-22845 and JP-A-61-75337.
In addition, it is not a simple double structure.
Or a multilayer structure having three or more layers as disclosed in the above-mentioned publication, or a silver halide having a different composition can be thinly applied to the surface of a core-shell type double structure grain.

In order to provide a structure inside the particle, not only the wrapping structure as described above but also a particle having a so-called junction structure can be produced. These examples are disclosed in
No. 133540, JP-A-58-108526, European Patent No. 199,290A2, JP-B-58-24772.
And JP-A-59-16254.
The crystal to be bonded can be formed by bonding to the edge, corner, or surface of the host crystal with a composition different from that of the host crystal. Such a junction crystal can be formed even if the host crystal is uniform in the halogen composition or has a core-shell structure.

In the case of a junction structure, a combination of silver halides is of course possible, but a silver halide compound having no silver salt structure such as rhodan silver or silver carbonate can be combined with silver halide to form a junction structure. Further, a non-silver salt compound such as lead oxide may be used as long as the bonding structure is possible.

It is important to control the silver halide composition near the surface of the grains. Increasing the amount of silver iodide in the vicinity of the surface or increasing the content of silver chloride can be selected according to the purpose because the adsorption of the dye and the developing speed are changed. When changing the halogen composition in the vicinity of the surface, either a structure that wraps the entire grain or a structure that adheres only to a part of the grain can be selected. For example, the halogen composition may be changed on only one side of the tetrahedral grain composed of the (100) plane and the (111) plane, or the halogen composition on one of the main plane and the side face of the tabular grain may be changed.

The silver halide grains used in the present invention may be normal crystals containing no twin planes, as described in the Photographic Society of Japan, Basics of the Photographic Industry, Silver Salt Photography (Corona), p. 163. Examples include single twins containing one twin plane, parallel multiple twins containing two or more parallel twin planes, and non-parallel multiple twins containing two or more non-parallel twin planes. You can select and use it. An example of mixing particles having different shapes is disclosed in U.S. Pat. No. 4,865,964, but this method can be selected as necessary. In the case of a normal crystal, a cube consisting of (100) planes, (111)
Octahedral particles composed of planes and dodecahedral particles composed of (110) planes disclosed in JP-B-55-42737 and JP-A-60-222842 can be used. Jou
rnalof Imaging Science 30
Volume, page 247 (1986), (h11) plane particles represented by the (211) plane, and (33)
1) The (hh1) plane particle representing the plane, the (hk0) plane particle represented by the (210) plane, and the (hk1) plane particle represented by the (321) plane also require some contrivance in the adjustment method. They can be selected and used according to the requirements. (100) face and (11)
1) a tetrahedral particle whose plane coexists in one particle, (10
0) and (110) coexisting particles, or (11)
Particles in which two surfaces or many surfaces coexist, such as particles in which 1) and (110) surfaces coexist, can be selected and used according to the purpose.

The value obtained by dividing the circle equivalent diameter of the projected area by the grain thickness is called an aspect ratio, and defines the shape of tabular grains. Tabular grains having an aspect ratio of greater than 1 can be used in the present invention. Tabular grains are described in "Theory and Practice of Photography" by Cleave (Cleav, Photography The).
ory and Practice (1930)), 1
Page 31; Gatov, Photographic Science
And Engineering (Gutof, Photog
raphic science and engineering
ering), 14, 248-257 (1970).
U.S. Pat. Nos. 4,434,226 and 4,41.
No. 4,310, No. 4,433,048, No. 4,4
39,520 and British Patent No. 2,112,157. When tabular grains are used, there are advantages such as an increase in covering power and an increase in the efficiency of color sensitization by a sensitizing dye, which is described in detail in U.S. Pat. No. 4,434,226 cited above. . The average aspect ratio of 80% or more of the total projected area of the grains is desirably 1 or more and less than 100. It is more preferably 2 or more and less than 20 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. U.S. Pat. No. 4,798,35
No. 4, a regular hexagon having substantially equal lengths of six sides is a preferable form.

Although the circle equivalent diameter of the projected area is often used as the average particle size, US Pat.
No. 8,106 has an average diameter of 0.6.
Submicron particles are preferred for high image quality. Also preferred are emulsions having a narrow grain size distribution as described in U.S. Pat. No. 4,775,617. It is preferable to limit the grain thickness of the tabular grains to 0.5 μm or less, more preferably 0.3 μm or less, in order to increase sharpness. Further, an emulsion having a highly uniform thickness having a variation coefficient of grain thickness of 30% or less is also preferable. JP 63
Also preferred are particles described in JP-A-163451 in which the thickness of the particles and the distance between twin planes are specified.

In the case of tabular grains, dislocation lines can be observed with a transmission electron microscope. It is preferable to select a particle containing no dislocation line, a particle containing several dislocations, or a particle containing many dislocations according to the purpose. It is also possible to select dislocations introduced linearly or bent dislocations in a specific direction of the crystal orientation of the grains, or to introduce them all over the grains, or to introduce them only into a specific portion of the grains, For example, dislocations can be introduced only in the fringe portion of the particles. Introduction of dislocation lines is preferable not only in the case of tabular grains, but also in the case of irregular grains typified by normal crystal grains or potato grains. Also in this case, it is a preferable embodiment to limit to a specific portion such as a vertex or a ridge of the particle.

The silver halide emulsion used in the present invention may be prepared by subjecting a grain to a roundness as disclosed in European Patent No. 96,412B1 or the like, or by a method described in West German Patent No. 2,30.
The surface may be modified as disclosed in JP-A-6-447C2 and JP-A-60-221320.

A structure having a flat particle surface is generally used.
It is preferable in some cases to form irregularities intentionally.
JP-A-58-106532, JP-A-60-22132
0, for example, a method of making a hole in a part of a crystal, for example, a vertex or a center of a face, or US Pat.
Raffle particles described in U.S. Pat. No. 3,966 are examples.

The grain size of the emulsion used in the present invention is determined by a circle equivalent diameter of a projected area using an electron microscope, a sphere equivalent diameter of a particle volume calculated from the projected area and the grain thickness, or a sphere equivalent diameter of a volume by the Coulter counter method. Can be evaluated. Ultrafine particles having a sphere equivalent diameter of 0.05 μm or less and coarse particles exceeding 10 μm can be selected and used. Preferably 0.1 micron or more 3
Submicron grains can be used as the photosensitive silver halide grains.

The emulsion used in the present invention may be a polydisperse emulsion having a wide grain size distribution, or a monodisperse emulsion having a narrow size distribution. In some cases, a variation coefficient of the projected area circle equivalent diameter or sphere equivalent diameter of a particle is used as a scale representing the size distribution. When a monodisperse emulsion is used, it is preferable to use an emulsion having a variation coefficient of 25% or less, more preferably 20% or less, and still more preferably 15% or less.

A monodisperse emulsion may be defined as an average grain size distribution by grain or weight. In order to satisfy the target gradation of the light-sensitive material, two or more kinds of monodispersed silver halide emulsions having different grain sizes are mixed in the same layer or different layers in an emulsion layer having substantially the same color sensitivity. Can be applied in layers. Further, two or more kinds of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion can be used as a mixture or as a mixture.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Grafkid, published by Paul Monte Co. (PG
refkides, Chemie et Physiq
uePhotographique, Paul Mon
tel., 1967), Duffin, "Photographic Emulsion Chemistry", published by Focal Press (GF Duffin, Phot).
optic Emulsion Chemist
ry, FocalPress, 1966), "Production and Coating of Photographic Emulsions", by Zerikman et al., published by Focal Press (VL Zelikman, et al., Maki).
ng and Coating Photograph
ic Emulsion, Focal Press, 1
964), etc., any of which can be used. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt and a soluble halide may be any one of a one-side mixing method, a double-mixing method, and a combination thereof. . A method of forming grains in the presence of excess silver ions (a so-called reverse mixing method) can also be used. As one type of the double jet method, a method of keeping the pAg of a liquid phase in which silver halide is formed constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.

A method of adding previously precipitated silver halide grains to a reaction vessel for preparing an emulsion, US Pat. No. 4,33
No. 4,012, No. 4,301,241, No. 4-1
50,994 is optionally preferred. These can be used as seed crystals, and are also effective when supplied as silver halide for growth. In the latter case, it is preferable to add an emulsion having a small grain size, and the addition method can be selected from a total amount addition at a time, a plurality of additions, or a continuous addition. Also,
It is sometimes effective to add particles of various halogen compositions to modify the surface.

A method for converting most or only a part of the halogen composition of silver halide grains by a halogen conversion method is described in US Pat. Nos. 3,477,852 and 4,14.
No. 2,900, European Patent Nos. 273,429 and 27
No. 3,430, West German Patent No. 3,819,241, etc., which are effective particle forming methods. A solution of a soluble halogen or silver halide grains can be added to convert the silver salt into a more insoluble silver salt. It can be selected from methods such as converting at once, converting into a plurality of times, or converting continuously.

In addition to the method of adding a soluble silver salt and a halogen salt at a constant concentration and a constant flow rate for grain growth, British Patent No. 1
469,480; U.S. Pat. No. 3,650,757;
The particle formation method in which the concentration is changed or the flow rate is changed as described in US Pat. No. 4,242,445 is a preferred method. By changing the concentration or increasing the flow rate, the amount of silver halide to be supplied can be changed by a linear function, a quadratic function, or a more complicated function of the addition time. It is also preferable in some cases to reduce the amount of silver halide supplied as necessary. Further, when adding a plurality of soluble silver salts having different solution compositions or adding a plurality of soluble halide salts having different solution compositions, an addition method of increasing one and decreasing the other is also an effective method. It is.

A mixer for reacting a solution of a soluble silver salt and a soluble halide salt is disclosed in US Pat. No. 2,996,287.
No. 3,342,605 and No. 3,415,65
No. 0, No. 3,785,777, West German Patent No. 2,
556,885 and 2,555,364.

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

Ammonia, thiocyanates (rhodancali, rhodanammonium, etc.), and organic thioether compounds (eg, US Pat. Nos. 3,574,628 and 3,574)
Nos. 021, 215, 3,057,724, 3,038,805, 4,276,374, 4,297,439, 3,704,130,
No. 4,782,013, JP-A-57-104926
And thione compounds (for example, tetra-substituted thioureas described in JP-A-53-82408 and JP-A-55-77737, U.S. Pat. Compounds described in JP-A-144319, mercapto compounds capable of promoting the growth of silver halide grains described in JP-A-57-202531, and amine compounds (for example, JP-A-54-1007).
No. 17, etc.).

It is advantageous to use gelatin as a protective colloid used in preparing the emulsion of the present invention and as a binder for other hydrophilic colloid layers, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxycellulose, carboxymethylcellulose and cellulose sulfate, sodium alginate, starch derivatives, gum arabic , Dextran, sugar derivatives such as natural compounds such as polysaccharides such as pullulan, polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. And various kinds of synthetic hydrophilic high-molecular substances such as a single or copolymer. Further, superabsorbent polymers described in U.S. Pat. No. 4,960,681 and JP-A-62-245260, that is, -COOM or -SO
₃ M (M represents a hydrogen atom or an alkali metal) copolymer (for example, sodium methacrylate and a copolymer or a vinyl monomer together or with other vinyl monomers, a vinyl monomer having, ammonium methacrylate, Sumitomo Chemical (Co. Sumikagel L-5H)) is also used. These binders can be used in combination of two or more kinds. Combinations of gelatin and the above binders are also preferred.

As the gelatin, in addition to lime-processed gelatin,
It may be selected from acid-treated gelatin and so-called demineralized gelatin having a reduced content of calcium and the like, and it is also preferable to use them in combination. Bull. Soc. Sci. P
photo. Japan. No. 16. p30 (196
Enzyme-treated gelatin as described in 6) may be used, and hydrolysates or enzymatic degradation products of gelatin can also be used. The use of low molecular weight gelatin described in JP-A-1-58426 is preferred for preparing tabular grains.

In the case of a photothermographic material, an organic silver salt oxidizing agent may be used together with the photosensitive silver halide emulsion. Examples of the organic compound which can be used for forming the same include 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. The total coating amount of the photosensitive silver halide emulsion and the organic silver salt is preferably from 0.7 to 3.5 g / m ² in terms of silver. More preferably, 1.0 to 2.0 g /
m ² . If the amount of silver increases, the desilvering process may be insufficient. If the amount is too low, the image density is too low, which may affect image information.

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

The silver halide grains used in the present invention are at least one of sulfur sensitization, selenium sensitization, tellurium sensitization (these three are collectively referred to as chalcogen sensitization), noble metal sensitization, or reduction sensitization. Can be applied in any step of the production process of the silver halide emulsion. It is preferable to combine two or more sensitization methods. Various types of emulsions can be prepared depending on the step of chemical sensitization. There are a type in which a chemical sensitizing nucleus is embedded inside the grain, a type in which the chemical sensitizing nucleus is embedded in a position shallow from the grain surface, and a type in which a chemical sensitizing nucleus is formed on the surface. In the emulsion of the present invention, the location of the chemical sensitization nucleus can be selected according to the purpose. Generally, the case where at least one type of chemical sensitization nucleus is formed near the surface is preferred.

The chemical sensitization which can be preferably carried out in the present invention is a combination of chalcogen sensitization and noble metal sensitization alone or in combination, and is described in TH James, The.
Photographic Process, 4th Edition, published by Macmillan, 1977 (TH James, The Pho
graphical Process, 4th ed.
Macmillan, 1977), pages 67-76, and can be performed using active gelatin, or can be performed using Research Disclosure Item 120.
08 (April 1974), Item 13452 (19
June 1975), Item 307105 (January 1989)
January), US Patent Nos. 2,642,361 and 3,2
No. 97,446, No. 3,772,031, No. 3,
PAg 5-10 as described in 857,711, 3,901,714, 4,266,018 and 3,904,415 and British Patent 1,315,755. , Selenium, tellurium, gold, platinum, palladium, iridium or a combination of a plurality of these sensitizers at a pH of 5 to 8 and a temperature of 30 to 80 ° C.

In sulfur sensitization, an unstable sulfur chemical is used, specifically, thiosulfate (eg, hypo),
Thioureas (eg, diphenylthiourea, triethylthiourea, allylthiourea, etc.), rhodanines, mercaptos, thioamides, thiohydantoins, 4-oxooxazolidin-2-thiones, di- or polysulfides, polythionates And elemental sulfur, and U.S. Patent Nos. 3,857,711 and 4,266,018.
And the known sulfur-containing compounds described in U.S. Pat. No. 4,054,457. Sulfur sensitization is often used in combination with noble metal sensitization.

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

In selenium sensitization, a known unstable selenium compound is used, for example, US Pat. No. 3,297,446.
No. 3,297,447 and the like, and specifically, colloidal metal selenium, selenoureas (for example, N, N-dimethylselenourea, tetramethylselenium urea) Etc.), seleno ketones (eg, selenoacetone), selenoamides (eg, selenoacetamide), selenocarboxylic acids and esters, isoselenocyanates, selenides (eg, diethyl selenide, triphenylphosphine selenide), seleno Phosphates (eg, tri-p-
Selenium compounds such as trisylselenophosphate) can be used. It may be preferable to use selenium sensitization in combination with sulfur sensitization and / or precious metal sensitization.

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

The tellurium sensitizers used in the present invention include Canadian Patent No. 800,958 and British Patent Nos. 1,2.
No. 95,462, No. 1,396,696, Japanese Patent Application No. 2
Compounds described in JP-A-333819 and JP-A-3-131598 can be used. Specific examples of tellurium sensitizers include colloidal tellurium and telluroureas (for example, tetramethyltellurourea, N-carboxyethyl-N ', N'
-Dimethyltellurourea, N, N'-dimethylethylenetellurourea), isotellurocyanates, telluroketones, telluramides, tellurohydrazides, telluroesters, phosphine tellurides (eg, tributylphosphine telluride, butyldiisopropylphosphine) Telluride), other tellurium compounds (eg, potassium tellurocyanate, sodium telluropentathionate)
And the like.

The tellurium sensitizer was used in the amount of silver halide 1
1 × 10 ^{−7 to} 5 × 10 ⁻² mol per mol, preferably 5 × 10 ⁻² mol
It is about × 10 ⁻⁷ to 1 × 10 ⁻³ mol.

In the noble metal sensitization, noble metal salts such as platinum, gold, palladium and iridium can be used. Among them, gold sensitization, palladium sensitization and a combination of both are preferable. In the case of gold sensitization, known compounds such as chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, and gold selenide can be used. The palladium compound means a divalent salt or a tetravalent salt of palladium. Preferred palladium compounds are R ₂ PdX ₆ or R
₂ PdX ₄ Here, R represents a hydrogen atom, an alkali metal atom or an ammonium group. X represents a halogen atom, and represents a chlorine, urea or iodine atom.

Specifically, K ₂ PdCl ₄ , (NH ₄ ) ₂ P
dCl ₅ , NaPdCl ₄ , (NH ₄ ) ₂ PdCl ₄ , Li ₂
PdCl ₄ , Na ₂ PdCl ₆ or K ₂ PdBr ₄ is preferred. The gold compound and the palladium compound are preferably used in combination with a thiocyanate or a selenocyanate.

The emulsion used in the present invention is preferably used in combination with gold sensitization. The preferred amount of the gold sensitizer is 1 × 10 ^-7 to 1 × 10 ^-3 mol, more preferably 5 × 10 ^{-7 to} 5 × 10 ^-4 mol, per mol of silver halide. The preferred range of the palladium compound is 5 × 10 ^-7 to 1 × 10 ^-3 mol. The preferred range of the thiocyan compound or selenocyan compound is 1 × 10 ^{−6 to} 5 × 10 ⁻² mol.

The silver halide emulsion of the present invention is preferably subjected to reduction sensitization during grain formation, after grain formation and before or during chemical sensitization, or after chemical sensitization.

Here, reduction sensitization refers to a method in which a reduction sensitizer is added to a silver halide emulsion, or a pAg 1
7, a method of growing or ripening in a low pAg atmosphere, or a method of growing or ripening in a high pH atmosphere of pH 8-11 called high pH ripening can be selected. Also, two or more methods can be used in combination.

The method of adding a reduction sensitizer is a preferable method because it has an advantage that the level of reduction sensitization can be finely adjusted.

As the reduction sensitizer, known reduction sensitizers such as stannous salts, ascorbic acid and its derivatives, amines and polyamines, hydrazine and its derivatives, formamidine sulfinic acid, silane compounds and borane compounds are selected. And two or more compounds can be used in combination. Stannous chloride, aminoiminomethanesulfinic acid (common name: thiourea dioxide) as reduction sensitizer,
Dimethylamine borane, ascorbic acid and its derivatives are preferred compounds. Since the addition amount of the reduction sensitizer depends on the emulsion production conditions, it is necessary to select the addition amount, but an appropriate range is 10 ^-7 to 10 ^-3 mol per mol of silver halide.

Chemical sensitization can be carried out in the presence of a so-called chemical sensitization aid. Useful chemical sensitizers include compounds known as azaindene, azapyridazine, azapyrimidine, which suppress fog in the course of chemical sensitization and increase sensitivity. Examples of chemical sensitization aid modifiers are described in US Pat. Nos. 2,131,038 and 3,4,
No. 11,914, No. 3,554,757;
No. 8-126526 and the above-mentioned book by Duffin, "Photographic Emulsion Chemistry, pp. 138-143".

The emulsion used in the present invention preferably contains an oxidizing agent for silver during the production process. The oxidizing agent for silver refers to a compound having an effect of acting on metallic silver to convert it into silver ions. In particular, a compound that converts extremely fine silver grains that are replicated in the course of forming silver halide grains and in the course of chemical sensitization into silver ions is effective. The silver ions generated here may form a silver salt that is hardly soluble in water such as silver halide, silver sulfide, silver selenide, or a silver salt that is easily soluble in water such as silver nitrate. good. The oxidizing agent for silver may be inorganic or organic. Examples of the inorganic oxidizing agent include ozone, hydrogen peroxide and adducts thereof (for example, NaBO ₂ , H ₂ O ₂ .H ₂ O, 2NaCO _3.
H ₂ O ₂ , Na ₄ P ₂ O ₇ .H ₂ O ₂ , 2NaSO ₄ .H ₂ O _2.
2H ₂ O), peroxy acid salts (eg, K ₂ S ₂ O ₈ , K ₂
C ₂ O ₆ , K ₂ P ₂ O ₈ ) peroxy complex compound (for example,
K _{2 [Ti (O 2) C 2 O} 4 ] _{· 3H 2 O, 4K 2 SO} 4 · T
i (O ₂ ) OH.SO ₄ .2H ₂ O, Na ₃ [VO (O ₂ )
(C ₂ O ₄ ) ₂ ] · 6H ₂ O), permanganate (eg, K
Oxyacids such as MnO ₄ ), chromates (eg, K ₂ CrO ₇ ), halogen elements such as iodine and bromine, perhalates (eg, potassium periodate), and salts of high-valent metals (eg, , Potassium hexacyanoferrate) and thiosulfonates.

Examples of the organic oxidizing agent include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogens (eg, N-bromosuccinimide, chloramine). T, chloramine B) are mentioned by way of example.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the photographic material, or stabilizing photographic performance. . That is, thiazoles such as benzothiazole salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiazoles, aminotriazoles , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-
Phenyl-5-mercaptotetrazole), mercaptopyrimidine, mercaptotriazine such as thioketo compounds such as oxazolinethione, azaindenes such as triazaindenes and tetraazaindenes (especially 4-hydroxy-6-methyl-1,3,3) Many compounds known as antifoggants or stabilizers can be added, such as 3a, 7-tetraazaindene), pentaazaindenes and the like. For example, US Pat.
No. 474, No. 3,982,947, Japanese Patent Publication No. 52-2
No. 8660 can be used. One of the preferred compounds is a compound described in Japanese Patent Application No. 62-47225. Antifoggants and stabilizers are used at various times before, during and after particle formation, during the washing step, during dispersion after washing, before chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. It can be added according to the purpose.
In addition to exhibiting the original fogging prevention and stabilizing effects when added during emulsion preparation, it also controls grain walls, reduces grain size, reduces grain solubility, and controls chemical sensitization. It can be used for various purposes such as controlling the arrangement of dyes.

When the photosensitive silver halide used in the present invention has green, red, and infrared sensitivity, it 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.

The dyes used in the present invention include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, complex cyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei usually used for cyanine dyes as base heterocyclic nuclei can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, such as an alicyclic hydrocarbon ring fused to these nuclei, and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus,
That is, indolenine nucleus, benzindolenin nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus,
Heterocyclic nuclei such as a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a thiobarbituric acid nucleus and the like can be applied. These nuclei may be substituted on carbon atoms. Specific examples include sensitizing dyes described in U.S. Pat. No. 4,617,257, JP-A-59-180550, JP-A-64-13546, Japanese Patent Application Nos. 5-45828, 5-45834, and the like. Can be

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

These dyes may be used alone or in combination, and a combination of sensitizing dyes is often used for the purpose of supersensitization and wavelength adjustment of spectral sensitivity. A representative example is U.S. Pat. No. 2,688,5.
No. 45, No. 3,397,060, No. 2,977,
No. 229, No. 3,522,052, No. 3,52
No. 7,64, No. 3,617,293, No. 3,62
No. 8,964, No. 3,672,898, No. 3,6
No. 79,428, No. 3,703,377, No. 3,
Nos. 769,301, 3,814,609, 3,837,862, 4,026,707, British Patents 1,344,281, and 1,507,80.
No. 3, JP-B-43-4936, and JP-B No. 53-12375
JP-A-52-110618, JP-A-52-110992
No.5.

In addition to the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a compound which does not substantially absorb visible light and exhibits supersensitization (for example, U.S. Pat. No. 3,615,641 and those described in JP-A-63-23145).

The timing of adding these sensitizing dyes to the emulsion may be at any stage in the preparation of the emulsion which has hitherto been known to be useful.

Most commonly, the reaction is carried out after completion of chemical sensitization but before coating, but US Pat. No. 3,628,96
As described in JP-A-58-113928, the addition of a chemical sensitizer at the same time as that described in JP-A Nos. Can be performed prior to chemical sensitization as described in (1). Further, it can be added before the completion of precipitation of silver halide grains to start spectral sensitization. Further, according to U.S. Pat. Nos. 4,183,756 and 4,225,666, the sensitization may be performed before or after the nucleation of silver halide grains. Separate additions, such as those added later, are also possible.

These sensitizing dyes and supersensitizers may be added as a solution of an organic solvent such as methanol, a dispersion of gelatin or the like, or a solution of a surfactant.

The addition amount is generally about 4 × 10 ^-6 to 8 × 10 ^-3 mol per mol of silver halide, but about 5 × when the silver halide grain size is more preferably 0.2 to 1.2 μm. 10 ^{-5 to} 2 × 10 ^-3 mol is more effective.

The above-mentioned various additives are used in the light-sensitive material of the present invention. In addition, various additives can be used according to the purpose.

These additives are described in more detail in Research Disclosure Item 17643 (December 1978) and Item 18716 (November 1979).
And Item 307105 (November 1989), and the relevant portions are summarized in the table below.

[0248]

[Table 1]

As hardeners, in addition to the above, US Pat. No. 4,678,739, column 41, 4,791,04
No. 2, JP-A-59-116655 and JP-A-62-2452.
No. 61, 61-18942, JP-A-4-21804
No. 4 and the like. More specifically,
Aldehyde hardener (such as formaldehyde), azirine hardener, epoxy hardener, vinyl sulfone hardener (N, N'-ethylene-bis (vinylsulfonylacetamide) ethane, etc.), N-methylol Hardeners (such as dimethylol urea) or polymeric hardeners (JP-A-6
2-234157). These hardeners are used in an amount of 0.001 g to 1 g, preferably 0.005 g to 0.5 g per g of gelatin applied.
Is used. The layer to be added may be any of constituent layers such as a light-sensitive material and a dye-fixing material, or may be added in two or more layers.

In the light-sensitive material of the present invention, a matting agent can be used for the purpose of preventing adhesion, improving slipperiness, and giving a non-glossy surface. Matting agents such as silicon dioxide, polyolefin and polymethacrylate are disclosed in JP-A-61-882.
JP-A-63-274944 and JP-A-63-2, such as benzoguanamine resin beads, polycarbonate resin beads, and AS resin beads, in addition to the compounds described on page 56 (29).
No. 74952. In addition, the compounds described in the aforementioned RD magazine can be used. These matting agents can be added not only to the uppermost layer (protective layer) but also to the lower layer as needed. In addition, the constituent layers of the photothermographic material may contain a thermal solvent, an antifoaming agent, an antibacterial agent, a fungicide, colloidal silica, and the like. Specific examples of these additives are disclosed in
No. 88256, pages 26 to 32, JP-A-3-113
No. 38, JP-B-2-51496 and the like.

In the constituent layers of the light-sensitive material of the present invention, various surfactants can be used for the purpose of coating aid, improvement of releasability, improvement of slipperiness, antistatic, acceleration of development and the like. Specific examples of the surfactant are described in the above-mentioned RD Magazine and JP-A-62-1746.
No. 3, No. 62-183457 and the like. In the case of a photothermographic material, it is also preferable to include an organic fluoro compound in the constituent layers for the purpose of improving slipperiness, preventing static charge, improving releasability, and the like. Representative examples of organic fluoro compounds include JP-B-57-9053, columns 8-17, and JP-A-61-9053.
No. -20944, No. 62-135836 and the like, or a hydrophobic fluorine compound such as an oily fluorine compound such as fluorine oil or a solid fluorine compound resin such as ethylene tetrafluoride resin Is mentioned.

A known anti-fading agent can be used in the light-sensitive material of the present invention. Organic anti-fading agents include hydroquinones, 5-hydroxychromans, 5-hydroxycoumarins, paraalkoxyphenols, hindered phenols mainly including bisphenols, gallic acid derivatives, methylenedioxybenzenes, amino Representative examples include phenols, hindered amines, and ether or ester derivatives in which the phenolic hydroxyl group of each of these compounds is silylated or alkylated. Further, a metal complex represented by a (bissalicylaldoximato) nickel complex and a (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used. Compounds having both hindered amine and hindered phenol partial structures in the same molecule as described in U.S. Pat. No. 4,268,593 have been found to be effective in preventing deterioration of the yellow dye image due to heat, humidity and light. give. Further, spiroindanes described in JP-A-56-159644 may be used to prevent the deterioration of magenta dye images, especially deterioration due to light.
And chromans substituted with hydroquinone diether or monoether described in JP-A-55-89835 give preferable results.

In the constituent layers of the light-sensitive material of the present invention, various antifoggants or photographic stabilizers and precursors thereof can be used. As a specific example, the RD
Magazine, U.S. Pat. Nos. 5,089,378 and 4,50.
0,627, 4,614,702, JP-A-64
No. 13546, pages (7) to (9), (57) to (71)
Page and pages (81)-(97), U.S. Pat.
No. 610, No. 4,626,500, No. 4,98
No. 3,494, JP-A-62-174747, JP-A-62-274.
239148, 63-264747, JP-A-1-
No. 150135, No. 2-110557, No. 2-178
No. 650, Research Disclosure 17643 (1
978), pages 24 to 25, and the like. These compounds are 5 × 10 ^-6 per mole of silver.
To 1 × 10 ^−1, more preferably 1 × 10 ⁻⁵ to 1 × 10 ^−2.
Is preferably used.

Suitable supports that can be used in the present invention include synthetic plastic films such as polyolefins such as polyethylene and polypropylene, polycarbonates, cellulose acetate, polyethylene terephthalate, polyethylene naphthalate and polyvinyl chloride, as well as photographic base paper and printing. Paper supports such as paper, baryta paper, and resin-coated paper; and supports in which a reflective layer is provided on the above-mentioned plastic film, JP-A-62-253195 (29-3)
1) described as a support. Page 28 of the aforementioned Research Disclosure 17643,
No. 18716, from the right column on page 647 to the left column on page 648; Those described on page 879 of 307105 can also be preferably used. Syndiotactic polystyrenes are also preferred. These are disclosed in JP-A-62-1770.
No. 8, JP-A-1-46912 and JP-A-1-178505. These supports include U.S. Pat. No. 4,141,7.
As described in No. 35, by performing a heat treatment of Tg or less, it is possible to use a material which is less likely to have a curl. The surface of these supports may be subjected to surface treatment for the purpose of improving the adhesion between the support and the emulsion undercoat layer. In the present invention, glow discharge treatment, ultraviolet irradiation treatment, corona treatment, and flame treatment can be used as the surface treatment. Further known technology No. 5
No. (issued by Aztec Co., Ltd. on March 22, 1991) at pages 44 to 149 can also be used.
A transparent support such as polyethylene dinaphthalenedicarboxylate or a support obtained by applying a transparent magnetic substance thereon can be used.

The method of exposing and recording an image on the light-sensitive material of the present invention includes, for example, a method of directly photographing a landscape or a person using a camera or the like, and a method of exposing through a reversal film or a negative film using a printer or a enlarger. Scanning method using an exposure device of a copier to scan and expose the original image through slits, etc., and scan by emitting light emitting diodes and various lasers (laser diodes, gas lasers, etc.) via image information and electric signals. A method of exposing (a method described in JP-A-2-129625), a method of outputting image information to an image display device such as a CRT, a liquid crystal display, an electroluminescence display, and a plasma display, and exposing directly or via an optical system. and so on.

As the light source for recording an image on a photosensitive material,
As described above, U.S. Pat. No.4, such as natural light, tungsten lamp, light emitting diode, laser light source, CRT light source, etc.
500,626, column 56, JP-A-2-53378,
The light source and the exposure method described in JP-A-2-54672 can be used. Also, image exposure can be performed using a wavelength conversion element in which a non-linear optical material and a coherent light source such as laser light are combined. Here, the nonlinear optical material is
It is a material that can exhibit nonlinearity between localization and electric field that appears when a strong optical electric field such as laser light is applied, such as lithium niobate, potassium dihydrogen phosphate (KDP), lithium iodate, and BaB ₂ O ₄ Such as inorganic compounds,
Urea derivatives, nitroaniline derivatives, for example, nitropyridine-N-oxide derivatives such as 3-methyl-4-nitropyridine-N-oxide (POM);
Compounds described in JP-A-53462 and JP-A-62-210432 can be preferably used. As a form of the wavelength conversion element, a single crystal optical waveguide type, a fiber type, and the like are known, and any of them is useful.

The image information is obtained by dividing an image signal obtained from a video camera, an electronic still camera, or the like, a television signal represented by the Nippon Television Signal Standard (NTSC), or an original image into a plurality of pixels such as a scanner. Image signal,
Images created using a computer represented by CG and CAD can be used.

Next, the invention according to claims 12 to 17 will be described.

First, the color developing agent represented by formula (I) (color developing agent which is not a metal complex compound) of the present invention will be described.

Among the coordination compounds represented by the general formula (2) which are the coordination compounds represented by X in the color developing agent which is the metal complex compound of the present invention represented by the above general formula (1), J is -PO (R ₃₎ is a _bidentate compound i.e. formula (I) color developing agent represented by (color developer not a metal complex compound), a color developing agent (the color developing agent is not a metal complex compound) As well as a new and superior performance.

Hereinafter, the color developing agent represented by the general formula (I) (color developing agent which is not a metal complex compound) according to the twelfth aspect of the present invention will be described.

In the general formula (I), R ₁₁ represents an aryl group or a heterocyclic group. The aryl group represented by R _11, preferably that of 6 to 14 carbon atoms include, for example, a phenyl group or a naphthyl group.

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. It is. These may be condensed with a benzene ring or a heterocyclic ring. Examples of the heterocyclic group represented by R ₁₁ include furanyl, thienyl, oxazolyl, thiazolyl,
Imidazolyl, triazolyl, pyrrolidinyl, benzoxazolyl, benzothiazolyl, pyridyl, pyridazyl, pyrimidinyl, pyrazinyl, triazinyl, quinolinyl, isoquinolinyl, phthalazinyl, quinoxalinyl, quinazolinyl, purinyl, pteridinyl, azepinyl, benzooxepinyl, etc. .

R ₁₁ may be substituted, and examples of the substituent which R ₁₁ may have include, for example, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, Heterocyclic oxy group, alkylthio group, arylthio group, heterocyclic thio group, acyloxy group, acylthio group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, carbamoyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, amino group, Alkylamino group, amide group, alkoxycarbonylamino group, aryloxycarbonylamino group, ureido group, sulfonamide group, 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, acylsulfamoyl group, carbamoylsulfamoyl group, halogen atom, nitro group, cyano group,
Examples thereof include a carboxyl group, a sulfo group, a phosphono group, a hydroxyl group, a mercapto group, an imide group, and an azo group.

R ₁₂ and R ₁₃ represent a hydrogen atom or a substituent. Examples of the substituent represented by R ₁₂ and R ₁₃ include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group, Aryloxy group, heterocyclic oxy group, alkylthio group, arylthio group, heterocyclic thio group,
Acyloxy group, acylthio group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, carbamoyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, amino group, alkylamino group,
Amide group, alkoxycarbonylamino group, aryloxycarbonylamino group, ureido group, sulfonamide group, 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, acylsulfamoyl group, carbamoylsulfamoyl group, Examples include 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. Ku is 1 hydrogen or carbon atoms
50 substituted or unsubstituted alkyl groups, 6 to 5 carbon atoms
0 substituted or unsubstituted aryl group, 1 to 50 carbon atoms
Is a substituted or unsubstituted heterocyclic group.

R ₁₄ represents a heterocyclic group. The heterocyclic group represented by R _14, a heterocyclic group represented as heterocyclic groups of R ₁₁ can be mentioned.

X ₁ , X ₂ , X ₃ , X ₄ and X ₅ each represent a hydrogen atom or a substituent. Examples of the substituent represented by X ₁ , X ₂ , X ₃ , X ₄ and X ₅ include groups having the same meaning as the substituent represented by R ₁₂ or R ₁₃ .

In the following, formulas (I), (II) and (II)
Typical specific examples of the color developing agent represented by I) are shown below, but the compounds of the present invention are not limited thereto.

[0269]

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[0270]

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[0271]

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Hereinafter, typical examples of the synthesis of the color developing agents represented by formulas (I), (II) and (III) of the present invention are shown.

Synthesis of Illustrative Color Developing Agent I-3-6 Synthesis Route

[0274]

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2-Aminobenzamide (ABA) 8.0
g was dissolved in ethyl acetate while heating.
9 g was added, and the mixture was allowed to cool to room temperature. Thereto, 13.0 g of trifluoroacetic anhydride was added dropwise, followed by stirring at room temperature for 2 hours. The precipitated crystals were collected by filtration and recrystallized from acetonitrile to obtain 11.3 g of crystals (intermediate I).

The obtained crystals (intermediate I) were dissolved in 80 ml of 1,2-dichloroethane, and 9.7 g of phosphorus oxychloride was dissolved.
Was added dropwise. Thereafter, the mixture was heated under reflux for 3 hours, allowed to cool to room temperature, and drained into 150 ml of water. After neutralizing with sodium bicarbonate and extracting with ethyl acetate,
The solvent was distilled off under reduced pressure, dried, and recrystallized from acetonitrile to obtain 9.3 g of a chloro form (intermediate II) as white crystals.

9.3 g of the obtained chlorinated product (intermediate II) was dissolved in 25 ml of DMF, and 6 ml of TEA was added. 9 g of hydrazine hydrate was added dropwise thereto, and the mixture was stirred at room temperature for 4 hours. Thereafter, the mixture was drained into 200 ml of water, and 6.5 g of a hydrazine compound (intermediate III) was collected by filtration.

The obtained hydrazine derivative (intermediate III) 6.
5 g was dissolved in 30 ml of ethyl acetate, and 4.5 g of TEA was added. Here, diphenyl phosphate chloride (DPP)
C) was added dropwise, and the mixture was stirred at room temperature for 4 hours.
The obtained crystals were collected by filtration. The crystals were dispersed and washed in methanol at room temperature and purified to obtain 9.7 g of a desired illustrative color developing agent I-3-6 in a yield of 74%. NMR, mas
The compound was identified as Exemplified Compound I-3-6 by s-spectrum and elemental analysis.

The compounds of the general formulas (I), (II) and (II)
The addition amount of the color developing agent represented by I) has a wide range, but it is preferably from 0.01 to 100 mol times, more preferably from 0.1 to 10 mol times, based on the coupler.

Next, the coupler used in the present invention will be described.

The couplers preferably used in the present invention are the same as the couplers used in the first to eleventh aspects of the present invention.

In the present invention, a metal ion-containing compound (hereinafter, also referred to as a metal source) refers to a compound that supplies a metal ion that chelates a chelating group of a coupler, a color developing agent or a dye. Examples of such a metal source include inorganic or organic salts and metal complexes of metal ions, and among them, organic acid salts and complexes are preferable. Examples of the metal include monovalent and polyvalent metals belonging to Groups I to VIII of the periodic table. Among them, Al, Co, Cr,
Cu, Fe, Mg, Mn, Mo, Ni, Sn, Ti and Zn are preferred, and particularly Ni, Cu, Cr, Co and Zn
Is preferred.

As specific examples of the metal source, Ni ²⁺ ,
^Examples include salts of Cu ²⁺ , Cr ²⁺ , Co ^2+, and Zn ²⁺ with aliphatic acids such as acetic acid and stearic acid, and salts with aromatic carboxylic acids such as benzoic acid and salicylic acid. Further, the ligand may be a precursor of a coupler, and is preferably used from the viewpoint of coloring properties.

The complex represented by the following formula (M) can be particularly preferably used.

[0285] Formula _{(M) [M (Q 1} ) s (Q 2) t (Q 3) u] + r · (T -) in _r formula, M is a metal ion, preferably Ni ^2+, Cu ^{2 +} , C
r ²⁺ , Co ²⁺ , and Zn ²⁺ . Q ₁ , Q ₂ and Q ₃ each represent a coordination compound capable of coordinating with the metal ion represented by M, and may be the same or different. These coordination compounds can be selected, for example, from the coordination compounds described in Chelate Science (5) (Nankodo). T ⁻ represents an organic anion group, and specific examples include a tetraphenylboron anion and an alkylbenzenesulfonic acid anion. s, t and u each represent an integer of 0 to 3;
Seating coordination or, or is determined by whether 6-coordinated, or is determined by Q _1, the number of ligands Q ₂ and Q _3. r
Represents 1 or 2.

Of the complexes represented by the general formula (M), the following general formula (M-1) (when s, t, u = 0) is more preferable.

Formula (M-1) M ₁₂ ⁺ · (W ⁻ ) _{2 In the} formula, M ₁₂ ⁺ represents a divalent transition metal ion, and W ⁻ forms a complex with a divalent metal ion. Represents a coordination compound represented by the following general formula (M-2).

[0288] formula _{(M-2) R 11 COC} (Z 11) = C (R 12) O - wherein, Z ₁₁ represents an alkyl group, an aryl group, an aryloxycarbonyl group, an alkoxy group, an alkoxycarbonyl group, a halogen Represents an atom or a hydrogen atom. R ₁₁ and R ₁₂ each represent an alkyl group or an aryl group, and may be the same or different, and R ₁₁ and Z or R ₁₂ and Z may combine to form a ring. However, when Z is a hydrogen atom, R ₁₁ and R ₁₂ are not both methyl groups.

Examples of typical compounds of the metal source are shown below, but the present invention is not limited to these.

[0290]

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[0291]

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One form for forming a metal chelate image is to perform treatment with a solution containing a metal source. This solution may be the color developing solution itself,
It may be a subsequently used processing solution, such as an alkaline fixing solution, or a separate metal chelating solution.
Metal chelation can be carried out at pH 5.0 to 12.0 at normal processing temperatures.

When a metal source is added to a processing solution, the compound can be selected so as to be easily dissolved in a processing solution, for example, a fixing solution. 0.1-120g for metal sauce
/ L, preferably 1-30 g / l.

When processing is performed with a solution containing a metal source, the processing can be performed by immersing the photosensitive material in the solution. Alternatively, the solution may be sprayed or applied to the photosensitive material. Chelation with a metal source may be performed before or after development, and can be performed before or after bleach-fixing.

Another form for forming a metal chelate image is a processing method using a sheet containing a metal ion compound. The sheet may be the same as a processing sheet for color development. That is, an alkali precursor, a bleach-fixing agent, a mordant and the like may be simultaneously contained, or only a metal source may be contained.

The chelated sheet can be used as it is or with the addition of water. As a method of adding water, a method of applying a small amount of water to a light-sensitive material or a processing sheet or spraying water can be used. Alternatively, the photosensitive material may be immersed in a water bath, and excess water may be squeezed for use.

Another mode for forming a metal chelate image is to add a metal source to a light-sensitive material. The layer to be added may be the same layer as the coupler or a layer adjacent thereto. The metal source may be water-soluble or oil-soluble, but when the coupler is oil-soluble, the metal source is preferably oil-soluble, and can be added by dissolving it in a high-boiling solvent like the coupler.

The amount of the metal source to be added is 0.01 to 100 times, preferably 0.1 to 10 times, more preferably 0.2 to 5 times as much as the weight of the coupler.

The light-sensitive material used in 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 an organic metal salt oxidizing agent, if necessary. It can be contained. These components are often added to the same layer, but they can be added separately in separate layers as long as they can react.

The photosensitive material preferably has at least three or more photosensitive layers having three or more types of photosensitivity.

The silver halide grains used in the light-sensitive material include silver bromide, silver chloride, silver chlorobromide, silver chloroiodide, silver bromoiodide,
It is silver chloroiodobromide. Other silver salts, for example, silver rhodan silver sulfide, silver selenide, silver carbonate, silver phosphate, organic acid silver, etc.
It may be included as a separate particle or as a part of a halogen atom particle.

When rapid development and desilvering (bleaching, fixing and bleach-fixing) steps are desired, silver halide grains having a high silver chloride content are desirable. In order to appropriately suppress development, it is preferable to contain silver iodide. The preferred silver iodide content depends on the intended light-sensitive material. For example X
-The preferred range is 0.1 to 15 mol% for lay sensitive materials, and 0.1 to 5 mol% for printed and microsensitive materials. In the case of a photographic material represented by a color negative, preferably 1
The range is suitably from 30 to 30 mol%, more preferably from 5 to 30 mol%.
It is 20 mol%, particularly preferably 8 to 15 mol%. It is preferable that silver iodide grains contain silver chloride in order to reduce lattice distortion.

When the light-sensitive material is a heat-developable light-sensitive material, an organic silver salt oxidizing agent may be used together with the light-sensitive silver halide emulsion. No. 4,500,626, benzotriazoles, fatty acids and other compounds described in columns 52 to 53. 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 a photosensitive silver halide 1
0.01 to 10 mol per mol, preferably 0.01 to 10 mol
One mole can be used in combination.

[0304] total coating amount of light-sensitive silver halide emulsion and the organic silver salt, 0.05 to 10 g / m ² in terms of silver, preferably is 0.1-4 g / m ² suitably.

The silver halide grains used in the present invention are:
At least one of sulfur sensitization, selenium sensitization, tellurium sensitization (these three are collectively referred to as chalcogen sensitization), noble metal sensitization or reduction sensitization is performed in any step of the silver halide emulsion production process. be able to. It is preferable to combine two or more sensitization methods.

Various types of emulsions can be prepared depending on the step in which chemical sensitization is performed. There are a type in which a chemical sensitizing nucleus is embedded inside the grain, a type in which the chemical sensitizing nucleus is embedded at a position shallow from the grain surface, and a type in which a chemical sensitizing nucleus is formed on the surface.

In the present invention, the location of the chemical sensitization nucleus can be selected according to the purpose. Generally, the case where at least one type of chemical sensitization nucleus is formed near the surface is preferred.

When the photosensitive silver halide is to have green sensitivity, red sensitivity, and infrared sensitivity, the silver halide emulsion is spectrally sensitized with methine dyes or the like. If necessary, the blue-sensitive emulsion may be subjected to spectral sensitization in the blue region.

The spectral sensitizing dyes used include cyanine dyes, merocyanine dyes, composite cyanine dyes, composite merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes.

For these dyes, any of nuclei usually used for cyanine dyes as basic heterocyclic nuclei can be applied. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, and the like. Are fused, i.e., indolenine, benzoindolenine, indole, benzoxazole, naphthoxazole, benzothiazole, naphthothiazole,
5- to 6-membered heterocyclic nuclei such as benzoselenazole, benzimidazole, rhodanine, thiobarbituric acid and the like can be applied. These nuclei may have substituents on carbon atoms.

Specifically, US Pat. No. 4,617,257
No. JP-A-59-180550, JP-A-64-13546
And sensitizing dyes described in JP-A-5-45828 and JP-A-5-45834.

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

These dyes may be used alone, or may be used in combination. The combination of sensitizing dyes is often used for the purpose of supersensitization and wavelength adjustment of spectral sensitivity. A representative example is U.S. Pat. No. 2,688,54.
No. 5, 3,977,060, 2,977,229
Nos. 3,522,052, 3,617,293
No. 3,628,964 and 3,672,898
No. 3,679,428 and 3,703,377
Nos. 3,769,301 and 3,814,609
No. 3,837,862, No. 4,026,707
No. 1,344,281 and 1,507,8
No. 03, JP-B-43-4936, JP-B No. 53-12375
JP-A-52-110618, JP-A-52-110992
No. 5, etc.

Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a compound which does not substantially absorb visible light and exhibits supersensitization (US Patent No. 3,615,641, JP-A-63
23145).

The time when these sensitizing dyes are added to the emulsion may be at any stage during the preparation of the emulsion which has hitherto been known to be useful. 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 4 × 10 ⁻⁶ to 8 × 10 ⁻³ mol per mol of silver halide. In the case of a more preferable silver halide grain size of 0.2 to 1.2 μm, about 4 × 10 ⁻⁶ to 8 × 10 ⁻³ mol. 5 × 10 ^{−5 to} 2 × 10 ⁻³ mol is more effective.

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 developing process of silver halide development.

The auxiliary developing agent in the present invention is preferably an electron-emitting compound represented by the following general formula (B-1) or (B-2) according to the Kendall-Peltz rule. Among them, those represented by the general formula (B-1) are particularly preferable.

[0319]

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In the formula, each of R ^{51 to} R ⁵⁴ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or a heterocyclic group.

R ^{55 to} R ⁵⁹ each represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, a cycloalkyloxy group, an aryloxy group, Ring 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, cycloalkyloxycarbonyl Oxy, aryloxycarbonyloxy, carbamoyloxy, sulfamoyloxy, alkanesulfonyloxy, arylsulfonyloxy, acyl, alkoxycarbonyl, cycloalkyloxycarbonyl, aryloxycarbonyl, carbamoy Group, carbonamide group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide group, sulfamoylamino group, alkylsulfinyl group, arenesulfinyl group, alkanesulfonyl group, arylsulfonyl group, Represents a sulfamoyl group, a sulfo group, a phosphinoyl group or a phosphinoylamino group.

Q represents an integer of 0 to 5. When q is 2 or more, a plurality of R ⁵⁵ may be the same or different. R ⁶⁰ represents an alkyl group or an aryl group.

In the following, formula (B-1) or (B-2)
Specific examples of the compound represented by are shown below, but the auxiliary developing agent used in the present invention is not limited thereto.

[0324]

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[0325]

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[0326]

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The above-mentioned various additives are used in the photographic light-sensitive material of the present invention. In addition, various additives can be used according to the purpose.

These additives are described in more detail in Research Disclosure (RD) 17643 (Jan.
Feb. 23-27, 18176 (November 1979)
Month) page 647 right column to page 651 and 307105 (1
Nov. 989), pp. 996-1007.

Suitable supports that can be used for the light-sensitive material include synthetic plastic films such as polyolefins such as polyethylene and polypropylene, polycarbonates, cellulose acetate, polyethylene terephthalate, polyethylene naphthalate, and polyvinyl chloride; photographic base paper; Paper supports such as paper, baryta paper, and resin-coated paper; and supports in which a reflective layer is provided on the above-mentioned plastic film, JP-A-62-253195, 29-3.
One described as a support on page 1 can be mentioned. or,
28 pages of RD17643 and 647 of 18716
Those described on page right column to page 648, left column, and page 879 of 307105 can also be preferably used.

These supports include those described in US Pat.
By applying a heat treatment at Tg (glass transition temperature) or lower as in the case of 1,735, it is possible to use a material which is hard to have a curl. The surface of the support may be subjected to surface treatment for the purpose of improving the adhesion between the support and the emulsion undercoat layer. As the surface treatment, glow discharge treatment, ultraviolet irradiation treatment, corona treatment, flame treatment and the like can be used. Further, a support described in Known Technology No. 5 (March 22, 1991, published by Aztec Co., Ltd.), pp. 44 to 149, can also be used. A transparent support such as polyethylene dinaphthalenedicarboxylate or a support obtained by applying a transparent magnetic substance thereon can be used.

The method of exposing and recording an image on the light-sensitive material of the present invention includes, for example, a method of directly photographing a landscape or a person using a camera or the like, and a method of exposing through a reversal film or a negative film using a printer or a enlarger. Scanning, exposure of original images through slits using a copier exposure device, etc., scanning exposure by emitting light emitting diodes, various lasers (laser diodes, gas lasers, etc.) via image information and electric signals, etc. (Japanese Patent Application Laid-Open No. 2-129625, Japanese Patent Application No. 3-338182)
And the image information is output to an image display device such as a CRT, a liquid crystal display, an electroluminescence display, and a plasma display, and is exposed directly or via an optical system. There are methods.

As a light source for recording an image on a photosensitive material,
As described above, U.S. Pat. Nos. 4,5,5 and 5, such as natural light, tungsten lamp, light emitting diode, laser light source and CRT light source
00,626, column 56, JP-A-2-53378,
The light source and the exposure method described in JP-A-2-54672 can be used. Image exposure can also 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 localization and electric field that appears when a strong optical electric field such as laser light is applied, and includes lithium niobate, potassium dihydrogen phosphate (KDP), and iodic acid. Inorganic compounds represented by lithium, BaB 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), Kaisho 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 is obtained by dividing an image signal obtained from a video camera, an electronic still camera, or the like, a television signal represented by the Nippon Television Signal Standard (NTSC), or an original image into a plurality of pixels such as a scanner. Image signal, C
Images created using a computer represented by G and CAD can be used.

The light-sensitive material of the present invention can be applied to all photographic light-sensitive materials such as color negatives, color papers, color instant photographs, X-ray light-sensitive materials for color reversal or for forming color images and light-sensitive materials for plate making. it can.

In the development processing of the present invention, development processing performed on conventionally known color negatives, color papers, color instant photographs, X-ray light-sensitive materials, light-sensitive materials for plate making, and the like can be preferably applied. Further, development can be performed by a heat treatment or an activator treatment. Among them, development by heat treatment is preferable.

Heat treatment of photosensitive materials is known in the art.
For example, pages 553 to 555 of Basics of Photonics Engineering (Corona Corp., 1979), video information 40 issued in April 1978,
Page, Netlets Handbook of Ph
otography and Reprograph
y, 7th. Ed. (Van Nostrand an
d Reinhold Co. Pp. 32-33, U.S. Pat. Nos. 3,152,904 and 3,301,678,
Nos. 3,392,020 and 3,457,075, British Patent Nos. 1,131,108, 1,167,777, and RD17029 (June 1978), pp. 9-15. .

In the photothermographic material, various development terminators can be used for the purpose of always obtaining a constant image with respect to fluctuations in processing temperature and processing time during development. As used herein, the term "development terminator" refers to a compound that neutralizes a base or reacts with a base immediately after appropriate development to reduce the base concentration in the film and to stop development, or to interact with silver and / or a silver salt. Is a compound that suppresses development. Specific examples include an acid precursor that releases an acid when heated, an electrophilic compound that undergoes a substitution reaction with a coexisting base when heated, or a nitrogen-containing heterocyclic compound, a mercapto compound, and a precursor thereof.
For further details, see JP-A-62-253159, 31-32.
Page.

When the light-sensitive material of the present invention is used as a heat-developable light-sensitive material, the method of supplying a base is preferably a method of generating a base from a base precursor. Examples of the base precursor include a salt of an organic acid and a base which is decarboxylated by heat, a compound which decomposes by a reaction such as an intramolecular nucleophilic substitution reaction, a Rossen rearrangement or a Beckmann rearrangement, and releases amines, etc. Preference is given to compounds that wake up to release a base and compounds that generate a base by electrolysis or complexing reactions.

The former base precursors that generate a base by heating include the salts of trichloroacetic acid described in British Patent No. 998,959 and the like, and US Pat. No. 4,060,420 as a further improved stability. Salts of propiolic acid described in JP-A-59-180537, U.S. Pat. No. 4,088,4.
No. 96, a 2-carboxycarbamide derivative, a salt with a thermally decomposable acid using an alkali metal or an alkaline earth metal in addition to an organic base as a base component (JP-A-59-19523).
No. 7), JP-A-59-1684 using Rossen dislocation
Hydroxam carbamates described in No. 40 and aldoxime carbamates described in JP-A-59-157637, which produces a nitrile upon heating, can be mentioned. In addition, UK Patent Nos. 998,945 and 2,079,480
No., JP-A-50-226225, U.S. Pat.
0,846, 4,514,493 and 4,65
7,848 and the known art No. 5 (March 22, 1991)
Base precursors described on pages 55-86 and the like are also useful.

When the light-sensitive material is heated and developed, a processing sheet containing a base and / or a base precursor can be used. The processing sheet containing a base and / or a base precursor is for the purpose of assisting the development processing, and forms an image on the photosensitive layer after the processing.

The base and / or base precursor contained in the treated sheet used in the present invention is complexed with a basic metal compound which is hardly soluble in water and metal ions constituting the basic metal compound in the presence of water. It is preferable to use a compound that can be used.

Furthermore, the processing sheet may have a desilvering function. When the photosensitive material is subjected to imagewise exposure and then superposed with the processing material, when a part or all of the silver halide and / or developed silver is soluble, a fixing agent is included in the processing material as a silver halide solvent. May be placed.

Known silver halide solvents can be used. As fixing agents, thiosulfates, sulfites, thiocyanates, thioether compounds and JP-A-4-365037
No., pages 11 to 21 and 5-66540, 1088-1.
Examples of the compound include a nitrogen-containing heterocyclic compound having a sulfide group, a mesoionic compound, and a thioether compound described on page 092.

The processing material may be provided with a physical development nucleus, and the solubilized silver halide may be immobilized on the processing material. The physical development nucleus is a substance that reduces silver halide that has been solubilized and diffused from the photosensitive material to be fixed as a physical development nucleus. Known as physical development nuclei are zinc, mercury, lead, cadmium, iron, chromium, nickel,
Examples include heavy metals such as tin, cobalt, copper, and ternium; noble metals such as palladium, platinum, silver, and gold; and colloid particles of chalcogen compounds such as sulfur, selenium, and tellurium, all of which can be used.

Before the photosensitive material and the processing sheet or the image receiving sheet are overlaid, water may be applied. When supplying water, any of tap water, distilled water, ion exchange water, and well water can be used. The supply amount of the developing solution is preferably from 10 to 200 ml per 1 m ² of the photosensitive material, more preferably from 15 to 120 ml, and still more preferably from 20 to 8 ml.
0 ml is most preferred.

The light-sensitive material of the present invention may have a form having a conductive heating element layer as a heating means for heat development. The heat generating element in this case is described in JP-A-61-1455.
No. 44 etc. can be used. The heating temperature in the heat development step is about 75 to 180 ° C, preferably 80 to 1 ° C.
The temperature is 50 ° C, more preferably 80 to 130 ° C. The heating time is from 0.1 to 60 seconds, preferably from 0.1 to 30 seconds.

As a heating method in the developing step, a heated block or plate is brought into contact, or a hot plate, a hot presser, a heated roller, a heated drum, a halogen lamp heater, an infrared or far-infrared lamp heater, or the like is contacted. Or passing through a high-temperature atmosphere. A method of superposing a photothermographic material and a dye fixing material is described in JP-A-62-253159 and JP-A-61-147244,
The method described on page 27 can be applied.

Activator processing refers to a processing method in which a color developing agent is incorporated in a photosensitive material and is developed with a processing solution (activator) containing no color developing agent. The processing solution in this case is characterized in that it does not contain a color developing agent contained in a normal developing solution component, and may contain other components (alkali, auxiliary developing agent, etc.). Regarding the activator treatment, European Patent 545,
Examples thereof are known documents such as 491A1 and 565,165A1.

Next, a processing material and a processing method used in the case of the activator processing in the present invention will be described.

In the present invention, the photosensitive material is developed (silver development / cross-oxidation of a built-in color developing agent). After development, it may be subjected to desilvering and washing or stabilizing treatment. In addition, a treatment (alkali treatment) for enhancing color development such as application of an alkali may be performed.

When the photosensitive material is developed using an activator solution, the activator solution has a function as a silver halide developing agent and / or an oxidized developing agent generated in silver development built in the photosensitive material. It is preferable to use an auxiliary developing agent having a function of cross-oxidizing a certain color developing agent. Preferred are pyrazolidones, dihydroxybenzenes, reductones and aminophenols, and particularly preferred are pyrazolidones.

These compounds are usually used alone, but it is also preferable to use two or more of them in combination to enhance the development and cross-oxidation activities. The amount of these compounds used in the activator solution is 2.5 × 10 ^{−4 to} 0.2 mol / L, preferably 0.0025 to 0.1 mol / L,
More preferably, it is 0.001 to 0.05 mol / liter.

The activator liquid used in the present invention includes:
The pH is preferably 8 to 13, and more preferably 9 to 12. In order to maintain the above pH, it is preferable to use various buffers. Buffers include carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycine salt,
N, N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3,4-dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-
Methyl-1,3-propanediol salt, valine salt, proline salt, trishydroxylaminomethane salt, lysine salt and the like can be used. In particular, carbonates, phosphates, tetraborates, and hydroxybenzoic acids are excellent in solubility and buffering capacity in the pH range of 9.0 or more, and do not adversely affect photographic performance even when added to an activator solution. It is preferable to use a buffer solution of

The processing temperature of the activator solution is 20 to 50.
° C, preferably 30 to 45 ° C. Processing time is 5 seconds ~
It is 2 minutes, preferably 10 seconds to 1 minute. It is preferable that the replenishment amount is small, but 15 to 600 m per 1 m ^{2 of} the light-sensitive material.
1, preferably 25-200 ml, more preferably 35
１００100 ml.

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

Examples of the bleaching agent used in the bleaching solution or the bleach-fixing solution include compounds of polyvalent metals such as iron (III), cobalt (III), chromium (IV) and copper (II), peracids and quinones. And nitro compounds. Representative compounds include iron chloride, ferricyanide, bichromate,
Organic complex salts of iron (III) (ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diaminepropanetetraacetic acid, methyliminodiacetic acid and aminopolyamines described in JP-A-4-365036, pp. 5-17) Carboxylic acids and metal salts), persulfates,
Examples include permanganate, bromate, hydrogen peroxide and its releasing compounds (such as percarbonate and perboric acid), and nitrobenzenes. Among them, ethylenediaminetetraacetic acid (III) complex salt, 1,3-diaminopropanetetraacetic acid iron (III) complex aminopolycarboxylate iron (III), hydrogen peroxide, persulfate, etc. are rapidly treated and polluted. It is preferable from the viewpoint of prevention.

These iron (III) aminopolycarboxylates
The pH of the bleaching solution or the bleach-fix using is 3 to 8, preferably 5 to 7. The pH of the bleaching solution using persulfate or hydrogen peroxide is used at 4 to 11, preferably 5 to 10.

Examples of the fixing agent used in the fixing solution or the bleach-fixing solution include thiosulfates, thiocyanates, thioureas, a large amount of iodide salts and JP-A-4-365037, 11-2.
Examples thereof include a nitrogen-containing heterocyclic compound having a sulfide group, a mesoionic compound, and a thioether compound described on page 1 or 5-66540, pages 1088 to 1092. Of these, the use of thiosulfates is common,
Ammonium thiosulfate is most widely used. or,
Thiosulfates and thiocyanates, thioether compounds,
Combinations with thioureas, mesoionic compounds, etc. are also preferred.

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

The light-sensitive material of the present invention may be subjected to a washing step after desilvering. When the stabilization treatment is performed, the washing step may be omitted. In such a stabilization process,
JP-A Nos. 57-8543, 58-14834, and 6
0-220345 and JP-A-58-127.
No. 926, No. 58-137837, No. 58-1407
All known methods described in No. 41 can be used.
Further, a washing-stabilizing step may be performed such that a stabilizing bath containing a dye stabilizer and a surfactant typified by processing of a color photographic material for photography is used as a final bath.

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

In the present invention, when converting image information into optical information or electric information, a scanner is preferably used. A scanner is a device that optically scans a photosensitive material and converts optical density of reflection or transmission into image information. When scanning, it is common and recommended to scan the required area of the photosensitive material by moving the optical part of the scanner in a direction different from the direction of movement of the photosensitive material. Then, only the optical part of the scanner may be moved, or only the photosensitive material may be moved to fix the optical part of the scanner. Further, a combination of these methods may be used.

When reading the image information of the photosensitive material,
A method of irradiating the entire surface with light in a wavelength region where at least three dyes can be absorbed or slit scanning to measure the amount of reflected light or transmitted light is preferable. In this case, it is preferable to use diffused light, because information such as a matting agent and a scratch on the film can be removed as compared with the use of parallel light. It is preferable that a semiconductor image sensor (such as an area CCD or a CCD line sensor) is used for the light receiving unit. Also, the presence or absence of the processing sheet at the time of image reading is not important.

According to the present invention, an image signal thus read can be output to form an image on another recording material. As an output method, normal projection exposure may be used, or image information may be read photoelectrically by measuring the density of transmitted light, and output using the signal. The material to be output need not be a photosensitive material, and may be, for example, a sublimation type thermosensitive recording material, an ink jet material, a full color direct thermosensitive recording material, or the like.

In a preferred embodiment, after forming a color image by thermal development, image information is diffused using a CCD image sensor and diffused light, with or without additional processing to remove the remaining silver halide and developed silver. After reading through the transmission density measurement and converting it to a digital signal, perform image processing,
It is output by any of the above methods. Since the digital signal can be arbitrarily processed and edited, the photographed image can be freely modified, deformed, processed and output.

[0366]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto.

Hereinafter, the inventions according to claims 1 to 11 will be described.

Example 1 <Preparation of photosensitive material sample 110> After a corona discharge treatment was applied to the surface of a paper support laminated on both sides with polyethylene,
A gelatin undercoat layer containing sodium dodecylbenzenesulfonate was provided, and two types of photographic constituent layers were further coated and dried to obtain a two-layered photosensitive material (photographic paper) sample 11 shown below.
0 was produced. The coating solution was prepared as follows.

(Preparation of Coating Solution for First Layer) Coupler (C-1)
51) 16.0 g, color developing agent (1-1) 21.7
(g) and 80 g of a solvent (Solv-1) were dissolved in ethyl acetate, and this solution was emulsified and dispersed in a 16% gelatin solution containing 10% sodium dodecylbenzenesulfonate and citric acid to prepare an emulsified dispersion A.

On the other hand, silver chlorobromide emulsion A (cubic, 1: 4 mixture of a large-size emulsion having an average grain size of 0.5 μm and a small-size emulsion of 0.41 μm (silver molar ratio). The variation coefficients of the grain size distribution of the size emulsions were 0.09 and 0.11, respectively, and both emulsions were AgB
r0.8 mol% was locally contained in a part of the surface of the silver chloride-based grain).

The following spectral sensitizing dyes (SD-1 and SD-2) were used for the silver chlorobromide emulsion A, and 5.0 × 10 ^-5 for the large-size emulsion per mole of silver halide. Mol and 8.0 × 10 ^-5 mol for the small-sized emulsion, respectively.

Solv-1: tricresyl phosphate

[0373]

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The emulsion was chemically ripened by adding a sulfur sensitizer and a gold sensitizer.

The above emulsified dispersion A and this silver chlorobromide emulsion A
Were mixed and dissolved to prepare a first layer coating solution so as to have a composition shown as the first layer in the following layer structure. The emulsion coating amount indicates a silver equivalent coating amount.

(Preparation of Coating Solution for Second Layer) The coating solution for the second layer was prepared in the same manner as the coating solution for the first layer so as to have the composition shown below as the second layer in the following layer constitution.

H-1 was used as a gelatin hardener for each layer. In addition, preservatives (Cpd-2, Cpd-3, C
pd-4 and Cpd-5), each having a total volume of 1 m
15.0 mg, 60.01 mg, 50.0 mg per ²
And 10.0 mg.

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

Support Polyethylene laminated paper [the first layer side polyethylene contains white content (TiO ₂ ) and bluish dye (ultra blue)] First layer Silver chlorobromide emulsion A 0.20 gelatin 1.50 Cyan coupler (C-151) 0.10 Color developing agent (1-1) 0.17 Solvent (Solv-1) 0.80 Second 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 H-1: 2,4-dichloro-6-hydroxy-s-triazine sodium Cpd-2: Benzoisothiazolone- 3 Cpd-3: butyl p-hydroxybenzoate Cpd-5: 2-phenoxyethanol

[0380]

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Next, the light-sensitive material samples 100 to 104 were prepared in exactly the same manner as the sample 110 except that the couplers and the color developing agents in the coating solution for the first layer were replaced with the couplers and the color developing agents shown in Table 2 in equimolar amounts. , 111-118.

After subjecting the samples 100 to 104 and 110 to 118 to gradation exposure using a wedge, the samples were developed according to the following processing steps.

Development Processing Temperature Step Development 40 ° C. 15 seconds Bleaching and Fixing 40 ° C. 45 seconds Rinse room temperature 45 seconds Alkaline processing room temperature 30 seconds Processing solution composition (developer) Water 800 ml Potassium phosphate 40 g Disodium-N , N-bis (sulfonatoethyl) hydroxylamine 10 g Potassium chloride 5 g Hydroxyethylidene-1,1-disulfonic acid (30%) 4 ml 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 1 g Water was added. 1000 ml pH (at 25 ° C./potassium hydroxide) 12.0 (bleach-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 Water is added and 1000 ml pH (at 25 ° C./acetic acid and aqueous ammonia) 5.8 (rinse solution) 0.02 g of chlorinated sodium isocyanurate Deionized water (conductivity 5 μS / cm or less) 1000 ml pH 6.5 ( Alkali processing solution) Water 800 ml Potassium carbonate 30 g Water is added and 1000 ml pH (at 25 ° C./sulfuric acid) 10.0 The above treated samples 100 to 104 and 110 to 118
Was measured using a KD-7 densitometer (manufactured by Konica Corporation) to determine the maximum color density (Dmax).
Further, each treated sample was subjected to high temperature and high humidity (60 ° C, 80% R
H) The samples were allowed to stand in an atmosphere for 14 days, and the heat resistance and humidity resistance of the dye images were examined. Irradiation was performed for 7 days using a xenon lamp to examine the light fastness of the dye image.

The results are shown in Table 3. However, the light resistance, heat resistance and moisture resistance of the dye image are represented by the residual ratio (%) after the light resistance, heat resistance and moisture resistance test with respect to the initial density of 1.0.

[0385]

[Table 2]

[0386]

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[0387]

[Table 3]

As is clear from Table 3, Sample 11 containing a color developing agent which is a novel metal complex compound of the present invention.
0 to 118 (claims 1 to 5, 7, 8, 10, 1 of the present invention)
Configuration 1) of the invention) is higher than that of Samples 100 to 104 containing a color developing agent which is not a metal complex compound.
It can be seen that max, light resistance, heat resistance, and moisture resistance are improved.

Example 2 A high-density polyethylene was laminated on both sides of a paper pulp weighing 180 g / m ² to prepare a paper support. However, on the side to which the emulsion layer was applied, a molten polyethylene containing surface-treated anatase-type titanium oxide dispersed at a content of 15% by weight was laminated to form a reflective support. After subjecting this reflective support to a corona discharge treatment, a gelatin undercoat layer was provided, and each layer having the following constitution was further provided to prepare a silver halide photographic light-sensitive material. The coating solution was prepared as follows.

(Preparation of First Layer Coating Solution) Coupler (C-1)
51) 16.0 g, color developing agent (1-1) 21.7
g, solvent (Solv-1) 80 g, high boiling organic solvent (D
BP) 1.56 g and high boiling organic solvent (DNP) 0.8
To 3 g, 30 ml of ethyl acetate was added and dissolved, and emulsified and dispersed in 110 ml of a 10% aqueous gelatin solution containing 3.5 ml of 20% surfactant (SU-1) using an ultrasonic homogenizer to prepare a dispersion.

Also, (H-1), (H-
2) was added. Surfactants (SU
-2) and (SU-3) were added to adjust the surface tension.
The total amount of the preservative (F-1) was 0.04 g / m ² in each layer.
Was added so that

SU-1: sodium tri-i-propylnaphthalenesulfonate SU-2: di (2-ethylhexyl) sodium sulfosuccinate sodium salt SU-3: di (2,2,3,3,4) sulfosuccinate , 4,
5,5-octafluoropentyl) · sodium salt DBP: dibutyl phthalate DNP: dinonyl phthalate (Preparation method of zinc hydroxide dispersion) 31 g of zinc hydroxide powder having a primary particle size of 0.2 μm as a dispersant 1.6 g of carboxymethyl cellulose and 0.4 g of sodium polyacrylate, lime-processed ossein gelatin 8.5
g of water and 158.5 ml of water were mixed and dispersed in a mill using glass beads for 1 hour. After the dispersion, the glass beads were separated by filtration to obtain 188 g of a dispersion of zinc hydroxide.

(Preparation of Silver Halide Emulsion) The following (solution A) and (solution B) were adjusted to pAg = 7.3 and pH = 3.0 in 1 liter of a 2% aqueous gelatin solution kept at 40 ° C. Simultaneous addition over 30 minutes, and the following (solution C) and (D
Liquid) at pAg = 8.0 and pH = 5.5 while controlling
Co-added over 0 minutes. At this time, the pAg was controlled by the method described in JP-A-59-45437, and the pH was controlled using sulfuric acid or an aqueous sodium hydroxide solution.

(Solution A) 3.42 g of sodium chloride 0.03 g of potassium bromide 200 ml with addition of water (Solution B) 10 g of silver nitrate 200 ml with addition of water (Solution C) 102.7 g of sodium chloride 102.7 g of K ₂ IrCl ₆ 4 × 10 ^-8 mol / mol Ag K ₄ Fe (CN) ₆ 2 × 10 ^-5 mol / mol Ag Potassium bromide 1.0 g Add water 600 ml (Solution D) Silver nitrate 300 g Add water 600 ml after completion of addition, Kao Atlas After desalting using a 5% aqueous solution of Demol N and 20% aqueous solution of magnesium sulfate, the mixture was mixed with an aqueous gelatin solution to give an average particle size of 0.71 μm.
m, coefficient of variation of particle size distribution 0.07, silver chloride content 99.
A 5 mol% monodispersed cubic emulsion EMP-1 was obtained.

Next, EMP was performed except that the addition time of (solution A) and (solution B) and the addition time of (solution C) and (solution D) were changed.
In the same manner as -1, a monodispersed cubic emulsion EMP-1B having an average particle size of 0.64 μm, a coefficient of variation of 0.07, and a silver chloride content of 99.5 mol% was obtained.

The above-mentioned EMP-1 was optimally subjected to chemical sensitization at 60 ° C. using the following compounds. Also, EMP-1B
Similarly, after the optimal chemical sensitization, the sensitized E
MP-1 and EMP-1B were mixed at a silver ratio of 1: 1 to obtain a blue-sensitive silver halide emulsion (Em-B).

Sodium thiosulfate 0.8 mg / mol AgX Chloroauric acid 0.5 mg / mol AgX Stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX Stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX Stable Agent STAB-3 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-1 4 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-2 1 × 10 ⁻⁴ mol / mol AgX STAB-1: 1- ( 3-acetamidophenyl) -5-mercaptotetrazole STAB-2: 1-phenyl-5-mercaptotetrazole STAB-3: 1- (4-ethoxyphenyl) -5-mercaptotetrazole

[0398]

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The light-sensitive material thus prepared was used as a sample 2
It is assumed to be 10.

Next, the light-sensitive material samples 200 to 204, 211 to 211 were prepared in exactly the same manner as the sample 210 except that the couplers and the color developing agents in the coating solution were replaced with the couplers and the color developing agents shown in Table 4 in equimolar amounts. 218 were produced.

<Preparation of treatment sheet>
Polyethylene terephthalate (PE)
T) Prepared on base. The amount of addition was expressed in mg / m ² .

Fourth Layer Gelatin 220 Water-soluble polymer (1) 60 Water-soluble polymer (2) 200 Potassium nitrate 12 Palladium sulfide 3 Matting agent (silica) 10 Surfactant (3) 7 Surfactant (4) 7 Surfactant (5) 10 additive (6) 80 third layer gelatin 240 water soluble polymer (2) 24 hardener (7) 180 surfactant (8) 9 second layer gelatin 2400 water soluble polymer (2) 360 water soluble Polymer (9) 700 Water-soluble polymer (10) 600 High boiling solvent (11) 2000 Guanidine picolinate 2910 Additive (12) 170 Additive (13) 190 Potassium quinophosphate 225 Sodium quinophosphate 180 Surfactant (8) 24 First layer Gelatin 280 Water-soluble polymer (1) 12 Surfactant (8) 14 Hardener ( 7) 185 Water-soluble polymer (1): κ-carrageenan Water-soluble polymer (2): Sumikagel L-5H (manufactured by Sumitomo Chemical) Water-soluble polymer (9): Dextran (molecular weight 70,000) Water-soluble polymer (10): MP polymer 102 (manufactured by Kuraray Co.) surfactant (3): sulfosuccinate sodium di (2-ethylhexyl) surfactant _{(4): C 8 F 17} SO 2 N (C 3 H 7) CH 2 COOK surfactant _{(5): C 13 H 27} CONH (CH 2) 3 N + (CH 3) 2 CH 2 COO - hardener (7): ethylene glycol di (glycidyl) ether and high boiling solvent (11): salt para 40 (Made of Ajinomoto)

[0403]

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The above photosensitive material samples 200 to 204 and 210
To 218 were each subjected to gradation exposure using a wedge, then water was applied to the photosensitive layer of the exposed sample, and then superposed on a processing sheet, and heat-developed with a heat drum heated to 80 ° C. for 20 seconds. did. When the samples were peeled, images (print samples) were obtained.

Each of the obtained print samples was 200 to 2
Density of each of Nos. 04 and 210 to 218 was measured using a KD-7 densitometer (manufactured by Konica Corporation), and the maximum color density (Dmax) was determined. In addition, each processed sample is heated to high temperature,
The dye image was allowed to stand in a high humidity (60 ° C., 80% RH) atmosphere for 14 days, and the heat resistance and humidity resistance of the dye image were examined. Irradiation was performed for 7 days using a xenon lamp to examine the light fastness of the dye image.

Table 5 also shows the results. However, the light resistance, heat resistance and moisture resistance of the dye image are represented by the residual ratio (%) after the light resistance, heat resistance and moisture resistance test with respect to the initial density of 1.0.

[0407]

[Table 4]

[0408]

[Table 5]

As is clear from Tables 4 and 5, the samples 210 to 218 containing the color-developing agent of the present invention (the constitution of the invention according to claim 6 or 9 of the present invention) did not exhibit a color development which was not a metal complex compound. Samples 200 to 204 containing a developing agent
It can be seen that Dmax, light resistance, heat resistance, and moisture resistance are improved as compared with.

Example 3 A high-density polyethylene was laminated on both sides of a paper pulp having a basis weight of 180 g / m ² to prepare a paper support. However, on the side to which the emulsion layer was applied, a molten polyethylene containing surface-treated anatase-type titanium oxide dispersed at a content of 15% by weight was laminated to form a reflective support. After the reflective support was subjected to corona discharge treatment, a gelatin undercoat layer was provided thereon, and each layer having the following constitution was further provided thereon to prepare a silver halide photographic light-sensitive material. The coating solution was prepared as follows.

First layer coating solution 5.68 g of yellow coupler (C-25), 6.68 g of color developing agent (1-1), high boiling organic solvent (DBP)
To 3.33 g and 1.67 g of a high boiling point organic solvent (DNP), 60 ml of ethyl acetate was added and dissolved, and a 10% aqueous gelatin solution containing 7 ml of 20% surfactant (SU-1) 2
20 ml was emulsified and dispersed using an ultrasonic homogenizer to prepare a yellow coupler dispersion. This dispersion was mixed with a blue-sensitive silver halide emulsion prepared under the following conditions to prepare a first layer coating solution.

The coating solutions for the second layer to the seventh layer were prepared in the same manner as the coating solution for the first layer so that the coating amounts were as shown in Tables 6 and 7.

(H-1), (H-2)
Was added. Surfactants (SU-
2) and (SU-3) were added to adjust the surface tension.
The total amount of the preservative (F-1) was 0.04 g / m ² in each layer.
Was added so that

[0414]

[Table 6]

[0415]

[Table 7]

SU-1: Sodium tri-i-propylnaphthalenesulfonate SU-2: Di (2-ethylhexyl) sulfosuccinate sodium salt SU-3: Di (2,2,3,3,4) sulfosuccinate , 4,
5,5-octafluoropentyl) · sodium salt DBP: dibutyl phthalate DNP: dinonyl phthalate DOP: dioctyl phthalate DIDP: di-i-decyl phthalate DPhP: 1,5-diphenyl-3-pyrazolidone PVP: polyvinylpyrrolidone H-2 : Tetrakis (vinylsulfonylmethyl) methane HQ-1: 2,5-di-t-octylhydroquinone HQ-2: 2,5-di-sec-dodecylhydroquinone HQ-3: 2,5-di-sec-tetradecyl Hydroquinone HQ-4: 2-sec-dodecyl-5-sec-tetradecyl hydroquinone HQ-5: 2,5-di [(1,1-dimethyl-4-hexyloxycarbonyl) butyl] hydroquinone

[0417]

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[0418]

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

(Preparation of Blue-Sensitive Silver Halide Emulsion) 40 ° C.
In a liter of a 2% aqueous gelatin solution kept warm in
Solution) and (solution B) were added simultaneously over 30 minutes while controlling pAg = 7.3 and pH = 3.0, and the following (solution C) and (solution D) were further added at pAg = 8.0, pH = 5.5 and added simultaneously over 180 minutes. At this time, pAg was controlled by the method described in JP-A-59-45437.
H was controlled using sulfuric acid or an aqueous solution of sodium hydroxide.

(Solution A) 3.42 g of sodium chloride 0.03 g of potassium bromide 200 ml with addition of water (Solution B) 10 g of silver nitrate 200 ml with addition of water (Solution C) 102.7 g of sodium chloride 102.7 g of K ₂ IrCl ₆ 4 × 10 ^-8 mol / mol Ag K ₄ Fe (CN) ₆ 2 × 10 ^-5 mol / mol Ag Potassium bromide 1.0 g Add water 600 ml (Solution D) Silver nitrate 300 g Add water 600 ml after completion of addition, Kao Atlas After desalting using a 5% aqueous solution of Demol N and 20% aqueous solution of magnesium sulfate, the mixture was mixed with an aqueous gelatin solution to give an average particle size of 0.71 μm.
m, coefficient of variation of particle size distribution 0.07, silver chloride content 99.
A 5 mol% monodispersed cubic emulsion EMP-1 was obtained.

Next, except that the addition time of (Solution A) and (Solution B) and the addition time of (Solution C) and (Solution D) were changed,
In the same manner as -1, a monodispersed cubic emulsion EMP-1B having an average particle size of 0.64 μm, a coefficient of variation of 0.07, and a silver chloride content of 99.5 mol% was obtained.

The above-mentioned EMP-1 was optimally subjected to chemical sensitization at 60 ° C. using the following compounds. Also, EMP-1B
Similarly, after the optimal chemical sensitization, the sensitized E
MP-1 and EMP-1B were mixed at a silver ratio of 1: 1 to obtain a blue-sensitive silver halide emulsion (Em-B).

Sodium thiosulfate 0.8 mg / mol AgX Chloroauric acid 0.5 mg / mol AgX Stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX Stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX Stable Agent STAB-3 3 × 10 ^-4 mol / mol AgX sensitizing dye BS-1 4 × 10 ^-4 mol / mol AgX sensitizing dye BS-2 1 × 10 ^-4 mol / mol AgX (green-sensitive silver halide emulsion Preparation) (Solution A) and (Solution B)
The average particle size was 0.40 μm in the same manner as in EMP-1 except that the addition time of (C) and (C solution) and (D solution) were changed.
m, a coefficient of variation 0.08, and a monodispersed cubic emulsion EMP-2 having a silver chloride content of 99.5%.

Next, a monodispersed cubic emulsion EMP-2B having an average particle size of 0.50 μm, a coefficient of variation of 0.08, and a silver chloride content of 99.5% was obtained.

The above-mentioned EMP-2 was optimally subjected to chemical sensitization at 55 ° C. using the following compounds. Also, EMP-2B
Similarly, after the optimal chemical sensitization, the sensitized E
MP-2 and EMP-2B were mixed at a silver amount of 1: 1 to obtain a green-sensitive silver halide emulsion (Em-G).

Sodium thiosulfate 1.5 mg / mol AgX Chloroauric acid 1.0 mg / mol AgX Stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX Stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX Stable Agent STAB-3 3 × 10 ^-4 mol / mol AgX Sensitizing dye GS-1 4 × 10 ^-4 mol / mol AgX (Preparation of red-sensitive silver halide emulsion) (solution A) and (solution B)
The average particle size was 0.40 μm in the same manner as in EMP-1 except that the addition time of (C) and (C solution) and (D solution) were changed.
m, a coefficient of variation 0.08 and a monodisperse cubic emulsion EMP-3 having a silver chloride content of 99.5%. The average particle size is 0.38
A monodisperse cubic emulsion EMP-3B having a particle size of 0.08, a coefficient of variation of 0.08 and a silver chloride content of 99.5% was obtained.

The above-mentioned EMP-3 was optimally subjected to chemical sensitization at 60 ° C. using the following compounds. Also, EMP-3B
Similarly, after the optimal chemical sensitization, the sensitized E
MP-3 and EMP-3B were mixed at a silver amount of 1: 1 to obtain a red-sensitive silver halide emulsion (Em-R).

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stability Agent STAB-3 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-1 1 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-2 1 × 10 ⁻⁴ mol / mol AgX STAB-1: 1- ( 3-acetamidophenyl) -5-mercaptotetrazole STAB-2: 1-phenyl-5-mercaptotetrazole STAB-3: 1- (4-ethoxyphenyl) -5-mercaptotetrazole A color sensitizer (SS-1) was added in an amount of 2.0 × 10 ⁻³ per mol of silver halide.

[0430]

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[0431]

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The light-sensitive material thus prepared was used as a sample 3
It is assumed to be 10.

Next, the photosensitive material samples 300 to 304 and 311 to 314 were prepared in exactly the same manner as the sample 310 except that the color developing agents were replaced with the color developing agents shown in Table 8 in equimolar amounts.
Was prepared.

<Preparation of processing sheet>
Processing sheet A has been substracted to polyethylene terephthalate (P
ET) Made on base. The amount of addition was expressed in mg / m ² .

Fourth Layer Gelatin 220 Water-soluble polymer (1) 60 Water-soluble polymer (2) 200 Potassium nitrate 12 Palladium sulfide 3 Matting agent (silica) 10 Surfactant (3) 7 Surfactant (4) 7 Surfactant (5) 10 additive (6) 80 third layer gelatin 240 water soluble polymer (2) 24 hardener (7) 180 surfactant (8) 9 second layer gelatin 2400 water soluble polymer (2) 360 water soluble Polymer (9) 700 Water-soluble polymer (10) 600 High boiling solvent (11) 2000 Guanidine picolinate 2910 Additive (12) 170 Additive (13) 190 Potassium quinophosphate 225 Sodium quinophosphate 180 Surfactant (8) 24 First layer Gelatin 280 Water-soluble polymer (1) 12 Surfactant (8) 14 Hardener ( 7) 185 Water-soluble polymer (1): κ-carrageenan Water-soluble polymer (2): Sumikagel L-5H (manufactured by Sumitomo Chemical) Water-soluble polymer (9): Dextran (molecular weight 70,000) Water-soluble polymer (10): MP polymer 102 (manufactured by Kuraray Co.) surfactant (3): sulfosuccinate sodium di (2-ethylhexyl) surfactant _{(4): C 8 F 17} SO 2 N (C 3 H 7) CH 2 COOK surfactant _{(5): C 13 H 27} CONH (CH 2) 3 N + (CH 3) 2 CH 2 COO - hardener (7): ethylene glycol di (glycidyl) ether and high boiling solvent (11): salt para 40 (Made of Ajinomoto)

[0436]

Embedded image

[0437] A person and a Macbeth chart are photographed, and C-4
1 processed negative color film LV-400 (manufactured by Konica Corporation).
10 to 314, respectively. After water was applied to the photosensitive layer of the exposed sample, it was superposed on each of the processing sheets and developed by heating with a heat drum heated to 80 ° C. for 20 seconds. When the sample is peeled, the samples 300 to 304, 31
Images were obtained at 0 to 314, respectively.

The evaluation of the images was performed by subjective evaluation using 10 monitors. Each of the two types of prints was evaluated by a method of giving priority to comparison. Table 8 shows the results.

[0439]

[Table 8]

According to Example 3, it was confirmed that a silver halide light-sensitive material containing the color-developing agent of the present invention (the constitution of the invention according to claim 6 or 9 of the present invention) can provide an image having preferable image quality. .

Example 4 (Preparation of Silver Halide Emulsion) Three kinds of emulsions, which were spectrally sensitized, were red-sensitive, green-sensitive and blue-sensitive, were prepared as follows.

Silver iodobromide emulsion for red-sensitive emulsion layer (average particle size 0.7 μm, average iodine content 7.5 mol%) 0.9 g Sensitizing dye (S-1) 1.7 × 10 ^-4 Mol sensitizing dye (S-2) 1.6 × 10 ^-4 mol sensitizing dye (S-3) 0.1 × 10 ^-4 mol Silver iodobromide emulsion for green-sensitive emulsion layer (average particle size 0.7 μm) 0.9 g of sensitizing dye (S-4) 1.1 × 10 ⁻⁴ mol of sensitizing dye (S-5) 2.0 × 10 ⁻⁴ mol of sensitizing dye (S-6) 0.3 × 10 ^-4 mol <for blue-sensitive emulsion layer> Silver iodobromide emulsion (average particle size 0.8 μm, average iodine content 8.5 mol%) 0.5 g sensitizing dye (S-7) 3 × 10 ^-4 mol Sensitizing dye (S-8) 1.2 × 10 ^-4 mol

[0443]

Embedded image

[0444]

Embedded image

(Preparation of silver benzotriazole emulsion) A silver benzotriazole emulsion (organic silver salt) was prepared according to the following formulation.

28 g of gelatin and benzotriazole 1
A solution of 3.2 g dissolved in 300 ml of water was stirred at 40 ° C. A solution in which 17 g of silver nitrate was dissolved in 100 ml of water was added to this solution over 2 minutes. The pH of the benzotriazole silver emulsion was adjusted, sedimented, and excess salts were removed.
Thereafter, the pH was adjusted to 6.30 to obtain 400 g of a silver benzotriazole emulsion.

The coupler and the color developing agent are dissolved in a mixture of a high-boiling solvent and ethyl acetate, mixed with an aqueous gelatin solution containing a surfactant, and then mixed with a high-speed rotary mixer as described below. After emulsification and dispersion, they were added directly to the emulsion.

Using the material thus obtained, a heat-developable color light-sensitive material (sample 40
1) was produced. The color developing agents of the first layer, the third layer and the fifth layer of the sample 401 were equimolar to the comparative color developing agent-1.
A sample 402 was prepared in the same manner except that the sample 402 was changed.

Addition amount (mg / m ² ) Sixth layer Protective layer Lime-treated gelatin 1940 Matting agent (silica) 200 Surfactant (d) 50 Surfactant (e) 300 Base precursor (f) 1400 Water-soluble polymer ( g) 120 5th layer Yellow developing layer Lime-processed gelatin 2000 Blue-sensitive silver halide emulsion Silver equivalent 1250 Benzotriazole silver emulsion Silver equivalent 300 Yellow coupler (C-171) 460 Color developing agent (1-5) 480 Antifoggant ( a) 16 High boiling point solvent (b) 774 Surfactant (c) 80 Hot solvent (h) 1400 Surfactant (e) 70 Water-soluble polymer (g) 40 Fourth layer Middle layer Lime-treated gelatin 970 Surfactant ( d) 50 surfactant (e) 300 base precursor (f) 1400 water-soluble polymer (g) 60 Layer Magenta coloring layer Lime-processed gelatin 1000 Green-sensitive silver halide emulsion Silver equivalent 625 Benzotriazole silver emulsion Silver equivalent 150 Magenta coupler (C-133) 240 Color developing agent (1-5) 240 Antifoggant (a) 8 High boiling point Solvent (b) 490 Surfactant (c) 40 Thermal solvent (h) 700 Surfactant (e) 35 Water-soluble polymer (g) 20 Second layer Middle layer Lime-treated gelatin 970 Surfactant (d) 50 Surfactant Agent (e) 300 Base precursor (f) 1400 Water-soluble polymer (g) 60 First layer Cyan coloring layer Lime-treated gelatin 1000 Red-sensitive silver halide emulsion Silver equivalent 625 Benzotriazole silver emulsion Silver equivalent 150 Cyan coupler (C-119) ) 240 color developing agent (1-5) 240 antifoggant (a) 8 high boiling point Medium (b) 410 Surfactant (c) 40 Thermal solvent (h) 700 Surfactant (e) 35 Water-soluble polymer (g) 20 Transparent PET base (102 μm) Antifoggant (a): 2-mercaptobenzimidazole High boiling point solvent (b): Tricresyl phosphate Surfactant (c): Sodium p-dodecylbenzenesulfonate Surfactant (d): Dioctyl sodium sulfosuccinate sodium salt Base precursor (f): (H ₂ N) ₂ C = N ⁺ H ₂ · CCl ₃ COO ⁻

[0450]

Embedded image

The samples 401 and 4 thus obtained
02 was exposed for 1 second at 2000 lux through B, G, R filters of continuously varying density. The exposed sample was heat-developed for 10 seconds while the base side was in contact with a heat drum heated to 140 ° C. After processing, when the drum was released from the drum, cyan, magenta, and yellow color images were clearly obtained corresponding to the exposed filters.

Immediately after the treatment, the highest concentration part of the sample (D _max )
Table 9 shows the results obtained by measuring the minimum density part (D _min ) with an X-rite densitometer.

[0453]

[Table 9]

As is clear from Table 9, in the case of the sample 402 containing the comparative color developing agent, an image excellent in discrimination was not obtained, whereas the color developing method which is a novel metal complex compound of the present invention was not obtained. Sample 40 containing main drug
In No. 1, an image excellent in discrimination was obtained. Further, the sample of the present invention also had good image storability.

[0455] Hereinafter, the invention according to claims 12 to 17 will be described.

Example 5 <Preparation of Photosensitive Material Sample 101 '> 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. Photosensitive material (photographic paper) sample 1 having the following two-layer structure was coated and dried.
01 'was prepared. The coating solution was prepared as follows.

(Preparation of Coating Solution for First Layer) Coupler (C-
2) 18.0 g, color developing agent I-2-2: 16.8
g, 80 g of the solvent (Solv-1) was dissolved in ethyl acetate,
This solution was emulsified and dispersed in a 16% gelatin solution containing 10% sodium dodecylbenzenesulfonate and citric acid to prepare an emulsified dispersion A.

On the other hand, silver chlorobromide emulsion A (cubic, 1: 4 mixture of a large-size emulsion having an average grain size of 0.5 μm and a small-size emulsion of 0.41 μm (silver molar ratio). The variation coefficients of the grain size distribution of the size emulsions were 0.09 and 0.11, respectively, and both emulsions were Ag
0.8 mol% of Br was locally contained on a part of the surface of a silver chloride-based grain).

The following spectral sensitizing dyes (SD-1 and SD-2) were used for the silver chlorobromide emulsion A, and 5.0 × 10 ^-5 for the large-size emulsion per mole of silver halide. Mol and 8.0 × 10 ^-5 mol for the small-sized emulsion, respectively.

Solv-1: tricresyl phosphate

[0461]

Embedded image

The emulsion was chemically ripened by adding a sulfur sensitizer and a gold sensitizer.

The above-mentioned emulsified dispersion A and this silver chlorobromide emulsion A
Were mixed and dissolved to prepare a first layer coating solution so as to have a composition shown as the first layer in the following layer structure. The emulsion coating amount indicates a silver equivalent coating amount.

(Preparation of Coating Solution for Second Layer) The coating solution for the second layer was prepared in the same manner as the coating solution for the first layer so as to have the composition shown below as the second layer in the following layer constitution.

H-1 was used as a gelatin hardener for each layer. In addition, preservatives (Cpd-2, Cpd-3, C
pd-4 and Cpd-5), each having a total volume of 1 m
15.0 mg, 60.01 mg, 50.0 mg per ²
And 10.0 mg.

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

Support Polyethylene laminated paper [polyethylene on the first layer side contains white content (TiO ₂ ) and blue dye (ultra blue)] First layer Silver chlorobromide emulsion A 0.20 gelatin 1.50 Cyan coupler (C-2) 0.10 Color developing agent (Exemplified compound I-2-2) 0.17 Solvent (Solv-1) 0.80 Second layer (protective layer) Gelatin 1.01 Acrylic modification of polyvinyl alcohol Copolymer (degree of modification 17%) 0.04 Liquid paraffin 0.02 Surfactant (Cpd-1) 0.01 H-1: 2,4-dichloro-6-hydroxy-s-triazine sodium Cpd-2 : Benzoisothiazolone-3 Cpd-3: butyl p-hydroxybenzoate Cpd-5: 2-phenoxyethanol

[0468]

Embedded image

Next, a photosensitive material sample 100 'containing no color developing agent was prepared as a comparative example. Photosensitive material samples 102 'to 10' were prepared in exactly the same manner as Sample 101 'except that the coupler and color developing agent in the coating solution for the first layer were replaced with the coupler and color developing agent shown in Table 10 in equimolar amounts.
5 'was prepared.

After subjecting the samples 100 'to 105' to gradation exposure using a wedge, the samples were processed according to the following processing steps. The development was performed under the development conditions and the developer shown in Table 10.

Processing Step Temperature Time Development A 40 ° C. 60 seconds Development B 40 ° C. 15 seconds Bleach-fix 40 ° C. 45 seconds Rinse room temperature 45 seconds Alkaline processing room temperature 30 seconds The composition of each processing solution is as follows.

(Developer A) 10% aqueous solution of sodium carbonate 800 ml Color developing agent (Exemplified Compound I-2-2) 1.6 g (Developer B) Water 800 ml Potassium phosphate 40 g Disodium-N, N-bis (sulfo (Natoethyl) hydroxylamine 10 g Potassium chloride 5 g Hydroxyethylidene-1,1-disulfonic acid (30%) 4 ml 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 1 g Water was added to the mixture 1000 ml pH (25 ° C. / 12.0 (with bleach-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 1000m l 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 liquid) Water 800 ml Potassium carbonate 30 g Add water 1000 ml pH (at 25 ° C./sulfuric acid) 10.0 For the above treated samples 100 ′ to 105 ′, KD
The density was measured using a -7 type densitometer (manufactured by Konica Corporation), and the maximum color density (Dmax) was determined.

The results are shown in Table 10.

[0474]

[Table 10]

As is clear from the results shown in Table 10, the samples 101 'to 105' containing the color developing agent (the constitution of the invention according to the twelfth or thirteenth aspect of the present invention) are compared with the light-sensitive material 100 'not containing the same. As a result, it can be seen that the color development was high with a short development time.

Example 6 In Example 5, after the development treatment, a metal chelating bath having the following composition was immersed for 5 minutes (21 ° C.), washed for 10 minutes (30 ° C.), and dried. Samples 110 'to 11
5 ′ were also prepared.

(Metal chelating bath) Nickel sulfate heptahydrate 10g Water 180ml 0.8% ammonia aqueous solution 2.32g Samples 110-11 subjected to the above metal chelating bath treatment
5 (corresponding to 100 to 105 respectively), KD-
The concentration was measured using a type 7 densitometer (manufactured by Konica Corporation),
The maximum color density (Dmax) was determined. Further, each of the treated samples is placed in a high temperature, high humidity (60 ° C., 80% RH) atmosphere
After leaving for 4 days, the dye image was examined for heat resistance and moisture resistance. Irradiation was performed for 7 days using a xenon lamp to examine the light fastness of the dye image.

The results are shown in Table 11. However, the light resistance, heat resistance and moisture resistance of the dye image are represented by the residual ratio (%) after the light resistance, heat resistance and humidity resistance test with respect to the initial density of 1.0.

[0479]

[Table 11]

As is clear from the results shown in Table 11, samples 111 'to 115' containing the color developing agent of the present invention (the constitution of the invention according to claim 12 or 13 of the present invention) did not contain the color developing agent. It can be seen that high color development is exhibited in a short development time as compared with 110 ′. Further, chelation is performed (the structure of the invention according to claims 14 and 16 of the present invention).
Thus, light resistance, heat resistance, and moisture resistance are improved.

Example 7 A high-density polyethylene was laminated on both sides of a paper pulp weighing 180 g / m ² to prepare a paper support. However, on the side to which the emulsion layer was applied, a molten polyethylene containing surface-treated anatase-type titanium oxide dispersed at a content of 15% by weight was laminated to form a reflective support. After subjecting this reflective support to a corona discharge treatment, a gelatin undercoat layer was provided, and each layer having the following constitution was further provided to prepare a silver halide photographic light-sensitive material. The coating solution was prepared as follows.

(Preparation of Coating Solution for First Layer) Coupler (C-1)
51) 16.0 g, 21.7 of color developing agent I-2-2
g, solvent (Solv-1) 80 g, high boiling organic solvent (D
BP) 1.56 g and high boiling organic solvent (DNP) 0.8
To 3 g, 30 ml of ethyl acetate was added and dissolved, and emulsified and dispersed in 110 ml of a 10% aqueous gelatin solution containing 3.5 ml of 20% surfactant (SU-1) using an ultrasonic homogenizer to prepare a dispersion.

Further, (H-1), (H-
2) was added. Surfactants (SU
-2) and (SU-3) were added to adjust the surface tension.
The total amount of the preservative (F-1) was 0.04 g / m ² in each layer.
Was added so that

SU-1: Sodium tri-i-propylnaphthalenesulfonate SU-2: Di (2-ethylhexyl) sodium sulfosuccinate sodium salt SU-3: Di (2,2,3,3,4) sulfosuccinate , 4,
5,5-octafluoropentyl) · sodium salt DBP: dibutyl phthalate DNP: dinonyl phthalate (Preparation method of zinc hydroxide dispersion) 31 g of zinc hydroxide powder having a primary particle size of 0.2 μm as a dispersant 1.6 g of carboxymethyl cellulose and 0.4 g of sodium polyacrylate, lime-processed ossein gelatin 8.5
g of water and 158.5 ml of water were mixed and dispersed in a mill using glass beads for 1 hour. After the dispersion, the glass beads were separated by filtration to obtain 188 g of a dispersion of zinc hydroxide.

(Preparation of Silver Halide Emulsion) The following (Solution A) and (Solution B) were adjusted to pAg = 7.3 and pH = 3.0 in 1 liter of a 2% aqueous gelatin solution kept at 40 ° C. Simultaneous addition over 30 minutes, and the following (solution C) and (D
Liquid) at pAg = 8.0 and pH = 5.5 while controlling
Co-added over 0 minutes. At this time, the pAg was controlled by the method described in JP-A-59-45437, and the pH was controlled using sulfuric acid or an aqueous sodium hydroxide solution.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Water was added to 200 ml (Solution B) Silver nitrate 10 g Water was added to 200 ml (Solution C) Sodium chloride 102.7 g K ₂ IrCl ₆ 4 × 10 ^-8 mol / mol Ag K ₄ Fe (CN) ₆ 2 × 10 ^-5 mol / mol Ag Potassium bromide 1.0 g Add water 600 ml (Solution D) Silver nitrate 300 g Add water 600 ml after completion of addition, Kao Atlas After desalting using a 5% aqueous solution of Demol N and 20% aqueous solution of magnesium sulfate, the mixture was mixed with an aqueous gelatin solution to give an average particle size of 0.71 μm.
m, coefficient of variation of particle size distribution 0.07, silver chloride content 99.
A 5 mol% monodispersed cubic emulsion EMP-1 was obtained.

Next, EMP was performed except that the addition time of (solution A) and (solution B) and the addition time of (solution C) and (solution D) were changed.
In the same manner as -1, a monodispersed cubic emulsion EMP-1B having an average particle size of 0.64 μm, a coefficient of variation of 0.07, and a silver chloride content of 99.5 mol% was obtained.

The above-mentioned EMP-1 was optimally subjected to chemical sensitization at 60 ° C. using the following compounds. Also, EMP-1B
Similarly, after the optimal chemical sensitization, the sensitized E
MP-1 and EMP-1B were mixed at a silver ratio of 1: 1 to obtain a blue-sensitive silver halide emulsion (Em-B).

Sodium thiosulfate 0.8 mg / mol AgX Chloroauric acid 0.5 mg / mol AgX Stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX Stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stability Agent STAB-3 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-1 4 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-2 1 × 10 ⁻⁴ mol / mol AgX STAB-1: 1- ( 3-acetamidophenyl) -5-mercaptotetrazole STAB-2: 1-phenyl-5-mercaptotetrazole STAB-3: 1- (4-ethoxyphenyl) -5-mercaptotetrazole

[0490]

Embedded image

The light-sensitive material prepared as described above was used for Sample 2
10 '.

Next, the coupler and the color developing agent are shown in Table 1.
Photosensitive material samples 200 ', 201' and 211 'to 213' shown in Table 12 were prepared in exactly the same manner as in Sample 210 'except that the couplers and color developing agents shown in Fig. 2 were used in equimolar amounts.

Next, a sample 214 ′ was prepared in the same manner as the sample 211 ′ except that 0.1 g / m ² of the metal ion-containing compound MS-2 was added to each of the first, third and fifth layers of the sample 211 ′. '.

<Preparation of treatment sheet>
Polyethylene terephthalate (PE)
T) Prepared on base. The amount of addition was expressed in mg / m ² .

Fourth Layer Gelatin 220 Water-soluble polymer (1) 60 Water-soluble polymer (2) 200 Potassium nitrate 12 Palladium sulfide 3 Matting agent (silica) 10 Surfactant (3) 7 Surfactant (4) 7 Surfactant (5) 10 additive (6) 80 third layer gelatin 240 water soluble polymer (2) 24 hardener (7) 180 surfactant (8) 9 second layer gelatin 2400 water soluble polymer (2) 360 water soluble Polymer (9) 700 Water-soluble polymer (10) 600 High boiling solvent (11) 2000 Guanidine picolinate 2910 Additive (12) 170 Additive (13) 190 Potassium quinophosphate 225 Sodium quinophosphate 180 Surfactant (8) 24 First layer Gelatin 280 Water-soluble polymer (1) 12 Surfactant (8) 14 Hardener ( 7) 185 Water-soluble polymer (1): κ-carrageenan Water-soluble polymer (2): Sumikagel L-5H (manufactured by Sumitomo Chemical) Water-soluble polymer (9): Dextran (molecular weight 70,000) Water-soluble polymer (10): MP polymer 102 (manufactured by Kuraray Co.) surfactant (3): sulfosuccinate sodium di (2-ethylhexyl) surfactant _{(4): C 8 F 17} SO 2 N (C 3 H 7) CH 2 COOK surfactant _{(5): C 13 H 27} CONH (CH 2) 3 N + (CH 3) 2 CH 2 COO - hardener (7): ethylene glycol di (glycidyl) ether and high boiling solvent (11): salt para 40 (Made of Ajinomoto)

[0496]

Embedded image

[0497] A person and a Macbeth chart are photographed, and C-4
The negative-treated color negative film LV-400 (manufactured by Konica Corp.)
1 'and 211' to 213 '.

The photosensitive material samples 200 ', 201', 2
After giving gradation exposure to each of 11 ′ to 213 ′ using a wedge, water is applied to the photosensitive layer of each exposed sample, and then superimposed on the processing sheet.
Heat development was performed for 20 seconds using a heat drum heated to 80 ° C.
When the samples were peeled off, images were obtained.

For each of the print samples thus obtained, the density was measured using a KD-7 densitometer (manufactured by Konica Corporation), and the maximum color density (Dmax) was determined. Further, each treated sample was subjected to high temperature and high humidity (60 ° C, 80% R
H) The samples were allowed to stand in an atmosphere for 14 days, and the heat resistance and humidity resistance of the dye images were examined. Irradiation was performed for 7 days using a xenon lamp to examine the light fastness of the dye image.

Table 13 also shows the results. However, the light resistance, heat resistance and moisture resistance of the dye image are represented by the residual ratio (%) after the light resistance, heat resistance and moisture resistance test with respect to the initial density of 1.0.

[0501]

[Table 12]

[0502]

[Table 13]

As is clear from the results in Table 13, the samples 210 'to 214' containing the color developing agent of the present invention (the constitution of the invention according to claims 12 to 16 of the present invention) have comparative color developing agents. It can be seen that Dmax, light resistance, heat resistance, and moisture resistance are improved as compared with the contained samples 200 'to 201'.

[0504]

According to the present invention, a color developing agent which is a novel metal complex compound, and a silver halide color photographic light-sensitive material containing the color developing agent have excellent color developing properties.
A silver halide color photographic light-sensitive material having high sensitivity and excellent image storability, an image forming method using the same, and a processing method thereof can be provided.

Further, it was possible to provide a method for forming a color dye by using a color developing agent which is a novel metal complex compound having excellent storage stability.

Also, separately, a novel color developing agent (not a metal complex compound) and an alkaline solution which is hardly deteriorated with time by containing the novel color developing agent in a silver halide color photographic light-sensitive material, It is possible to provide a silver halide color photographic light-sensitive material and an image forming method which have reduced stain due to long-term storage of the light-sensitive material before and / or after processing, and have excellent color developability and excellent sensitivity.

Claims (17)

[Claims] 1. A silver halide color photographic light-sensitive material comprising a color developing agent which is a metal complex compound. 2. The silver halide color photographic light-sensitive material according to claim 1, wherein said color developing agent which is a metal complex compound is represented by the following general formula (1). Embedded image [Wherein, M represents a metal ion. X represents a coordination compound capable of forming a complex by coordinating with a metal ion; Y represents an anion; m represents an integer of 1, 2 or 3; Or, represents an integer of 3. However, the plurality of coordination compounds X may be the same or different. ] 3. The silver halide color photographic light-sensitive material according to claim 2, wherein the coordination compound represented by X in the general formula (1) is represented by the following general formula (2). Embedded image [In the formula, R ₁ represents an aryl group or a heterocyclic group, and R ₂ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. J is _{-SO 2 -, - CO -,} - CO
CO -, - CO-O - , - CON (R 3) -, - COC
O-O -, - COCON ( R 3) -, - SO 2 -N
(R ₃ ) — or —PO (R ₃ ) ₂ —. Here, R ₃ represents a hydrogen atom or the group described for R ₂ . ] 4. The silver halide color photographic light-sensitive material according to claim 2, wherein the coordination compound represented by X in the general formula (1) is represented by the following general formula (3). Embedded image [Wherein, R _{4 to} R ₇ each represent a hydrogen atom, a halogen atom, or a monovalent substituent. R ₈ is an alkyl group, an aryl group,
Or a heterocyclic group. ] 5. The silver halide color photographic light-sensitive material according to claim 2, wherein the coordination compound represented by X in the general formula (1) is represented by the following general formula (4). Embedded image [Wherein, R _{9 to} R ₁₄ each represent a hydrogen atom, a halogen atom, or a monovalent substituent. ] 6. A silver halide color photographic light-sensitive material according to claim 1, which contains at least one kind of a hardly soluble metal oxide or a hardly soluble metal hydroxide. 7. An image forming method using the silver halide color photographic light-sensitive material according to claim 1 to form a dye image comprising a metal complex dye. 8. After performing image exposure on the silver halide color photographic light-sensitive material according to any one of claims 1 to 6,
A processing method characterized by providing an alkaline solution for processing. 9. After imagewise exposing the silver halide color photographic light-sensitive material according to any one of claims 1 to 6,
A processing method characterized by processing by overlapping processing sheets. 10. A color developing agent which is a metal complex compound represented by the general formula (1). 11. A method for forming a color-forming dye, comprising using a color developing agent which is a metal complex compound. 12. A silver halide color photographic material comprising at least one color developing agent represented by the following general formula (I). Embedded image [In the formula, R ₁₁ represents an aryl group or a heterocyclic group, and R ₁₂ and R ₁₃ each represent a hydrogen atom or a substituent. ] 13. The silver halide color photographic light-sensitive material according to claim 12, wherein the color developing agent represented by the general formula (I) is represented by the following general formula (II) or (III). material. Embedded image [Wherein, R ₁₂ and R ₁₃ each represent a hydrogen atom or a substituent, and R ₁₄ represents a heterocyclic group. X ₁ , X ₂ , X ₃ ,
X ₄ and X ₅ each represent a hydrogen atom or a substituent, and may be the same or different, and may combine with each other to form a ring. ] 14. An image forming method comprising forming a chelate dye using a silver halide color photographic light-sensitive material containing a coupler and a color developing agent represented by the above general formula (I). 15. The image forming method according to claim 14, wherein a compound containing a metal ion is contained in a silver halide color photographic light-sensitive material. 16. The image forming method according to claim 14, wherein the metal ion-containing compound is provided from outside the silver halide color photographic light-sensitive material. 17. A color developing agent represented by the above general formula (I).