JPH11153850A - Silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the silver halide color photographic sensitive material capable of forming a dye image superior in color developing performance and good in color reproducibility by incorporating a specified color developing agent and a specified dye-forming coupler in a blue-sensitive silver halide emulsion layer. SOLUTION: At least one of the blue-sensitive silver halide emulsion layer contains the color developing agent represented by formula I and the dye- forming coupler represented by formula II, and in formulae I and II, R1 is an alkyl or alkenyl group or the like: L1 is a -SO2 - or -CO- group or the like; Y1 is an alkyl or-OR5 group or the like; R6 is an alkyl or aryl group; n1 , is 1 or 2; X1 is a -CN or -CONR9 R10 group; each of R9 and R10 is an H atom or an alkyl group or the like; J1 is an H atom or a group releasable by reaction with the oxidation product of a color developing agent; Z1 is an H atom or a substituent; and (m) is an integer of 0-5.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material containing a color developing agent and a dye-forming coupler, and more particularly, to an excellent color developing property by containing a novel color developing agent and a dye-forming coupler. The present invention also relates to a silver halide color photographic light-sensitive material capable of obtaining a dye image having good color reproducibility.

[0002]

2. Description of the Related Art In a silver halide color photographic light-sensitive material, as couplers generally used, open-chain ketomethylene compounds, pyrazolone compounds, pyrazoloazole compounds, phenol compounds and naphthol compounds are known.

[0003] Such couplers form a dye image by reaction with an oxidized aromatic primary amine, and the dye image forming reaction involves converting an exposed silver halide color photographic material to an aromatic primary. This is achieved by immersing in a developer containing an amine at a predetermined temperature for a predetermined time. However, a developer containing an aromatic primary amine is liable to be colored by a decomposition product thereof, and processing of such used developer is also a serious problem.

As one means for solving such a problem, there is a method of incorporating an aromatic primary amine developing agent or a precursor thereof into a silver halide color photographic light-sensitive material. Examples of the main drug include US Patent Nos. 803,783, 3,342,597, 3,719,492, 4,060,418, British Patent 1,069,061, and West German Patent No. 1,159,
No. 758, No. 58-14671, No. 58-146
No. 72, JP-A-57-76543 and JP-A-59-8164.
No. 3 and the like. However, silver halide color photographic light-sensitive materials containing these aromatic primary amine developing agents or their precursors have a problem of poor color developability. Apart from this, as a means not using an aromatic primary amine, a method has been disclosed in which a sulfonylhydrazine type developing agent is incorporated in a silver halide color photographic light-sensitive material.
Nos. 91, 565, 165, 572, 054, 593, 110, JP-A-7-134355, and 8-
No. 227131 and the like. However, even with these developing agents, long-term development at a high temperature is required to obtain a sufficient color density. In order to further improve the color developing property, a carbamoylhydrazine type developing agent described in JP-A-8-286340, JP-A-8-234390
No. carbonylhydrazone type developing agents have been proposed, but the color developability has been improved but not yet sufficient,
There is also a problem that the color reproducibility of the generated dye image is insufficient.

[0005]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above problems, and an object of the present invention is to provide a silver halide capable of obtaining a dye image having excellent color development and good color reproducibility. A color photographic light-sensitive material is provided. Another object of the present invention is to provide a silver halide color photographic light-sensitive material capable of forming an image gently and quickly by treating such a silver halide color photographic light-sensitive material with a developing solution containing no aromatic primary amine.

[0006]

The above object of the present invention is achieved by the following constitution.

(1) A silver halide color photographic light-sensitive material having a photographic constituent layer including a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support, At least one layer of the blue-sensitive silver halide emulsion layer contains at least one color developing agent represented by the following general formula [I] and at least one dye-forming coupler represented by the following general formula [II]. A silver halide color photographic light-sensitive material, characterized in that:

[0008]

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Wherein R ₁ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group;
L ₁ is _{-SO 2 -, - CO -,} - COCO -, - COO
_{-, - CON (R 4)} -, - COCOO -, - COCO
N (R ₄₎ - or -SO ₂ N (R ₄₎ - represents a. Where R ₄
Represents a hydrogen atom, an alkyl group or an aryl group. Y ₁ represents an alkyl _{group, -OR 5, -SO 2 R 6} , -SO 2 NR 7 R 8 or halogen atom. Here, R ₅ represents an alkyl group or an aryl group, R ₆ represents an alkyl group, and R ₇ and R ₈
Represents a hydrogen atom, an alkyl group or an aryl group. n1 represents 1 or 2. n1 two Y ₁ when 2 represent different groups. ]

[0010]

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Wherein X ₁ is —CN or —CONR ₉ R ₁₀
Represents Here, R ₉ and R ₁₀ represent a hydrogen atom, an alkyl group or an aryl group. J ₁ represents a hydrogen atom or a group which can be eliminated by reaction with an oxidized form of the color developing agent, and Z ₁ represents a hydrogen atom or a substituent. m represents an integer from 0 to 5, but when m is 2 or more, a plurality of Z ₁ may be the same or different. (2) In a silver halide color photographic light-sensitive material having a photographic component layer comprising a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support, At least one of the light-sensitive silver halide emulsion layers contains at least one color developing agent represented by the following general formula [III] and at least one dye-forming coupler represented by the following general formula [IV] A silver halide color photographic light-sensitive material comprising:

[0012]

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Wherein R ₂ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group;
L ₂ is —SO ₂ —, —CO—, —COCO—, —COO
_{-, - CON (R 11)} -, - COCOO -, - COCO
N (R ₁₁₎ - or -SO ₂ N (R ₁₁₎ - represents a. Here, R ₁₁ represents a hydrogen atom, an alkyl group or an aryl group. Y
₂ represents an alkyl _{group, -OR 12, -SO 2 NR 13} R 14 or a halogen atom. Here, R ₁₂ represents an alkyl group or an aryl group, and R ₁₃ and R ₁₄ represent a hydrogen atom, an alkyl group or an aryl group. n2 represents an integer of 1 to 3;
Is 2 or more, a plurality of Y ₂ represent different groups. ]

[0014]

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Wherein X ₂ is a hydrogen atom or —SO ₂ NR ₁₅
Representing the R _16. Here, R ₁₅ and R ₁₆ represent a hydrogen atom, an alkyl group or an aryl group. J ₂ represents a group capable of leaving upon reaction with an oxidation product of a hydrogen atom or a color developing agent, Z ₂
Represents -NHSO ₂ R ₁₇ or -NHSO ₂ NR ₁₈ R _19.
Here, R ₁₇ represents an alkyl group or an aryl group, and R ₁₈ and R ₁₉ represent a hydrogen atom, an alkyl group or an aryl group. (3) In a silver halide color photographic light-sensitive material having a photographic component layer comprising a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support, At least one of the light-sensitive silver halide emulsion layers contains at least one kind of color developing agent represented by the following formula [V] and at least one kind of dye-forming coupler represented by the following formula [VI]. A silver halide color photographic light-sensitive material comprising:

[0016]

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Wherein R ₃ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group;
L ₃ is —SO ₂ —, —CO—, —COCO—, —COO
_{-, - CON (R 20)} -, - COCOO -, - COCO
N (R ₂₀₎ - or -SO ₂ N (R ₂₀₎ - represents a. Here, R ₂₀ represents a hydrogen atom, an alkyl group or an aryl group. Y
₃ represents an alkyl group, —OR ₂₁ , —SO ₂ R ₂₂ , —NO ₂ or —CN. Here, R ₂₁ represents an alkyl group or an aryl group, and R ₂₂ represents an alkyl group. and n3 represents 2 or 3, a plurality of Y ₃ represent different groups. ]

[0018]

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Wherein X ₃ is a hydrogen atom or —SO ₂ NR ₂₃
Representing the R _24. Here, R ₂₃ and R ₂₄ represent a hydrogen atom, an alkyl group or an aryl group. J ₃ represents a group capable of leaving upon reaction with an oxidation product of a hydrogen atom or a color developing agent, Z ₃
Represents -NHSO ₂ R ₂₅ or -NHSO ₂ NR ₂₆ R _27.
Here, R ₂₅ represents an alkyl group or an aryl group, and R ₂₆ and R ₂₇ represent a hydrogen atom, an alkyl group or an aryl group. (4) In a silver halide color photographic light-sensitive material having a photographic component layer including a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support, At least one of the light-sensitive silver halide emulsion layers contains at least one color developing agent represented by the above general formula [I] and at least one dye-forming coupler represented by the above general formula [II]; In addition, at least one of the green-sensitive silver halide emulsion layers has the above general formula (II)
At least one of the color developing agents represented by the formula (I) and at least one of the dye-forming couplers represented by the formula (IV)
And at least one of the red-sensitive silver halide emulsion layers contains at least one color developing agent represented by the above general formula [V] and a dye-forming coupler represented by the above general formula [VI]. A silver halide color photographic material comprising at least one of the following.

(5) A silver halide color photographic light-sensitive material characterized in that an image is formed from the silver halide color photographic light-sensitive material described in (4) by an activator process.

(6) An amplified image is formed by intensifying the silver halide color photographic light-sensitive material described in (4) above using a solution containing hydrogen peroxide or a compound releasing hydrogen peroxide. A silver halide color photographic light-sensitive material, characterized in that:

Hereinafter, the present invention will be described in detail.

The color developing agents represented by the general formulas [I], [III] and [V] of the present invention (hereinafter also referred to as color developing agents of the present invention) and the general formulas [II], [IV] and [VI]
The dye-forming coupler represented by (hereinafter, also referred to as the dye-forming coupler of the present invention or the coupler of the present invention) will be described.

In the general formula [I], R ₁ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group.

Examples of the alkyl group represented by R ₁ include a methyl group, an ethyl group, a propyl group, an isopropyl group,
tert-butyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, octyl group, dodecyl group and the like.

Examples of the alkenyl group represented by R ₁ include a vinyl group and an allyl group.

The alkynyl group represented by R ₁ includes, for example, a propargyl group.

Examples of the aryl group represented by R ₁ include a phenyl group and a naphthyl group.

Examples of the heterocyclic group represented by R ₁ include pyridyl, thiazolyl, oxazolyl, imidazolyl, furyl, pyrrolyl, pyrazinyl, pyrimidinyl, pyridazinyl, selenazolyl, sulfolanyl, piperidinyl and the like. Group, pyrazolyl group, tetrazolyl group and the like.

In the above general formula [I], L ₁ is -SO ₂
-, -CO-, -COCO-, -COO-, -CON
(R ₄ ) —, —COCO—, —COCON (R ₄ ) — or —SO ₂ N (R ₄ ) —. Where R ₄ is a hydrogen atom,
Represents an alkyl group or an aryl group.

Examples of the alkyl group represented by R ₄ include the same groups as the alkyl group represented by R ₁ .

Examples of the aryl group represented by R ₄ include the same groups as the aryl group represented by R ₁ .

In the above formula [I], Y ₁ represents an alkyl group, —OR ₅ , —SO ₂ R ₆ , —SO ₂ NR ₇ R ₈ or a halogen atom. Here, R ₅ represents an alkyl group or an aryl group, R ₆ represents an alkyl group, and R ₇ and R ₈ represent a hydrogen atom, an alkyl group or an aryl group.

Examples of the alkyl group represented by R ₅ include the same groups as the alkyl group represented by R ₁ .

As the aryl group represented by R ₅ , the same groups as the aryl group represented by R ₁ can be mentioned.

Examples of the alkyl group represented by R ₆ include the same groups as the alkyl group represented by R ₁ .

Examples of the alkyl group represented by R ₇ include the same groups as the alkyl group represented by R ₁ .

The aryl group represented by R _{7 includes the same} groups as the aryl group represented by R ₁ .

Examples of the alkyl group represented by R ₈ include the same groups as the alkyl group represented by R ₁ .

As the aryl group represented by R ₈ , the same groups as the aryl group represented by R ₁ can be mentioned.

In the general formula [I], n1 represents 1 or 2. n1 two Y ₁ when 2 represent different groups.

In the above general formula [I], a group represented by R ₁ , an alkyl group represented by R ₆ , R ₄ , R ₅ , R ₇ and R
_The alkyl group and the aryl group represented by ₈ may have a substituent, for example, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a halogen atom, an alkoxy group, an alkoxycarbonyl Group, aryloxycarbonyl group, sulfonamide group, sulfamoyl group, ureido group, acyl group, carbamoyl group,
Examples include an amide group, a sulfonyl group, an amino group, a cyano group, a nitro group, a sulfo group, a carboxyl group, a hydroxyl group, and the like. These groups may be further substituted with the above substituents.

In the general formula [II], X ₁ is -CN
Or represents -CONR ₉ R ₁₀ . Here, R ₉ and R ₁₀ represent a hydrogen atom, an alkyl group or an aryl group.

Examples of the alkyl group represented by R ₉ include the same groups as the alkyl group represented by R ₁ .

The aryl group represented by R ₉ includes the same groups as the aryl group represented by R ₁ .

As the alkyl group represented by R ₁₀ , R ₁
And the same groups as the alkyl groups represented by

Examples of the aryl group represented by R ₁₀ include the same groups as the aryl group represented by R ₁ .

In the general formula [II], R ₉ and R ₁₀ may have the same substituents as R ₁ in the general formula [I] may have.

In the general formula [II], J ₁ represents a hydrogen atom or a group which can be eliminated by reaction with an oxidized form of a color developing agent.

Examples of the group capable of leaving by reaction with the oxidized form of the color developing agent represented by J ₁ include, for example, a halogen atom (a chlorine atom, a bromine atom, a fluorine atom, etc.) and an alkoxy,
Aryloxy, heterocyclic oxy, acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio,
Examples include acylamino, sulfonamide, nitrogen-containing heterocycle linked by an N atom, alkyloxycarbonylamino, aryloxycarbonylamino, and carboxyl.

In the general formula [II], Z ₁ represents a hydrogen atom or a substituent.

Examples of the substituent represented by Z ₁ include an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, an octyl group) , Dodecyl group, etc.), alkenyl group (eg, vinyl group, allyl group, etc.), alkynyl group (eg, propargyl group, etc.), aryl group (eg, phenyl group, naphthyl group, etc.), heterocyclic group (eg, pyridyl group) , Thiazolyl group, oxazolyl group, imidazolyl group, furyl group, pyrrolyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, selenazolyl group, sulfolanyl group, piperidinyl group, pyrazolyl group, tetrazolyl group, etc.), halogen atom (for example, chlorine atom, Bromine atom, iodine atom, fluorine atom, etc., alkoxy group (example For example, methoxy group, ethoxy group, propyloxy group, pentyloxy group, cyclopentyloxy group, hexyloxy group, cyclohexyloxy group, octyloxy group, dodecyloxy group, etc., aryloxy group (for example, phenoxy group, naphthyloxy group) Etc.), alkoxycarbonyl groups (eg, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl groups (eg, phenyloxycarbonyl group, naphthyloxy Carbonyl group), sulfonamide group (for example,
Methylsulfonylamino group, ethylsulfonylamino group, butylsulfonylamino group, hexylsulfonylamino group, cyclohexylsulfonylamino group, octylsulfonylamino group, dodecylsulfonylamino group, phenylsulfonylamino group, etc., sulfamoyl group (for example, aminosulfonyl group) , Methylaminosulfonyl, dimethylaminosulfonyl, butylaminosulfonyl, hexylaminosulfonyl, cyclohexylaminosulfonyl, octylaminosulfonyl, dodecylaminosulfonyl, phenylaminosulfonyl, naphthylaminosulfonyl, 2-pyridylaminosulfonyl Group), a ureido group (eg, a methylureido group, an ethylureido group, a pentylureido group, a cyclohexylureido group, Kuchiruureido group, dodecyl ureido group, a phenyl ureido group, Nafuchiruureido group,
2-pyridylaminoureido group, etc., acyl group (for example, acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, Naphthylcarbonyl group, pyridylcarbonyl group, etc.), carbamoyl group (for example, aminocarbonyl group,
Methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl Group, 2-pyridylaminocarbonyl group, etc.), amide group (for example, methylcarbonylamino group, ethylcarbonylamino group,
Dimethylcarbonylamino group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group, octylcarbonylamino group, dodecylcarbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group, etc.), sulfonyl Groups (eg, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.), amino group (eg, , Amino group, ethylamino group, dimethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino , Naphthylamino group, 2-pyridylamino group), a cyano group, a nitro group, a sulfo group, a carboxyl group, and hydroxyl group and the like, these groups may be further substituted by a substituent described above.

Z ₁ is preferably a hydrogen atom, a halogen atom or a sulfamoyl group.

In the general formula [II], m is 0 to 5
Represents an integer up to, but when m is 2 or more, a plurality of Z ₁ may be the same or different.

In the general formula [III], R ₂ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. These groups have the same meaning as the alkyl group, alkenyl group, alkynyl group, aryl group and heterocyclic group represented by R ₁ in the above formula [I].

In the general formula [III], L ₂ represents —SO
_2- , -CO-, -COCO-, -COO-, -CON
(R ₁₁ )-, -COCO-, -COCON (R ₁₁ )-
Or —SO ₂ N (R ₁₁ ) —. These groups include —SO ₂ — and —CO represented by L ₁ in the general formula [I].
-, - COCO -, - COO -, - CON (R 4) -,
—COCO—, —COCON (R ₄ ) — or —SO ₂ N
(R ₄₎ - synonymous.

In the above formula [III], Y ₂ represents an alkyl group, —OR ₁₂ , —SO ₂ NR ₁₃ R ₁₄ or a halogen atom.

Examples of the halogen atom represented by Y ₂ include a chlorine atom, a bromine atom, an iodine atom and a fluorine atom.

Examples of the alkyl group represented by Y ₂ include the same groups as the alkyl group represented by R ₁ .

-OR ₁₂ and -SO ₂ NR ₁₃ represented by Y ₂
R ₁₄ represents —O represented by Y ₁ in the general formula [I].
The same meaning as R ₅ and -SO ₂ NR ₇ R _8.

In the general formula [III], n2 represents an integer of 1 to 3, and when n2 is 2 or more, a plurality of Y ₂ represent different groups.

In the general formula [III], R ₂ , R ₁₁ ,
R ₁₂ , R ₁₃ and R ₁₄ may have the same substituents as R ₁ in the above general formula [I] may have.

In the general formula [IV], X ₂ represents a hydrogen atom or —SO ₂ NR ₁₅ R ₁₆ .

—SO ₂ NR ₁₅ R ₁₆ represented by X ₂ has the same meaning as —SO ₂ NR ₇ R ₈ represented by Y ₁ in the general formula [I].

In the formula [IV], J ₂ represents a hydrogen atom or a group which can be eliminated by a reaction with an oxidized form of a color developing agent.

[0066] a group capable upon reaction with an oxidation product of a color developing agent represented by J ₂ is a leaving upon reaction with an oxidation product of a color developing agent represented by J ₁ in the general formula (II) Synonymous with a detachable group.

In the general formula [IV], Z ₂ represents —NH
It represents an SO ₂ R ₁₇ or -NHSO ₂ NR ₁₈ R _19. Where R
₁₇ represents an alkyl group or an aryl group, and R ₁₈ and R ₁₉ represent a hydrogen atom, an alkyl group or an aryl group.

The alkyl group represented by R ₁₇ includes R ₁
And the same groups as the alkyl groups represented by

The aryl group represented by R ₁₇ includes R ₁
And the same groups as the aryl groups represented by

The alkyl group represented by R ₁₈ includes R ₁
And the same groups as the alkyl groups represented by

The aryl group represented by R ₁₈ includes R ₁
And the same groups as the aryl groups represented by

The alkyl group represented by R ₁₉ includes R ₁
And the same groups as the alkyl groups represented by

The aryl group represented by R ₁₉ includes R ₁
And the same groups as the aryl groups represented by

In the general formula [IV], R ₁₅ , R ₁₆ ,
The alkyl group and the aryl group represented by R ₁₇ , R ₁₈ and R ₁₉ may have a substituent, for example, an alkyl group, an alkenyl group, an alkynyl group, an aryl group,
Heterocyclic group, halogen atom, alkoxy group, alkoxycarbonyl group, aryloxycarbonyl group, sulfonamide group, sulfamoyl group, ureido group, acyl group,
Carbamoyl group, amide group, sulfonyl group, amino group,
Examples thereof include a cyano group, a nitro group, a sulfo group, a carboxyl group, a hydroxyl group, and the like, and these groups may be further substituted with the above substituents.

In the above formula [V], R ₃ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. These groups have the same meaning as the alkyl group, alkenyl group, alkynyl group, aryl group and heterocyclic group represented by R ₁ in the above formula [I].

In the general formula [V], L ₃ represents —SO ₂
-, -CO-, -COCO-, -COO-, -CON
(R ₂₀ )-, -COCO-, -COCON (R ₂₀ )-
Or -SO ₂ N (R ₂₀₎ - represents a. These groups include —SO ₂ — and —CO represented by L ₁ in the general formula [I].
-, - COCO -, - COO -, - CON (R 4) -,
—COCO—, —COCON (R ₄ ) — or —SO ₂ N
(R ₄₎ - synonymous.

In the above formula [V], Y ₃ represents an alkyl group, —OR ₂₁ , —SO ₂ R ₂₂ , —NO ₂ or —CN.

Examples of the alkyl group represented by Y ₃ include the same groups as the alkyl group represented by R ₁ .

-OR ₂₁ and -SO ₂ R represented by Y _3
22 is -OR ₅ represented by Y ₁ in the general formula [I].
And it is synonymous with -SO ₂ R _6.

In the above general formula [V], n3 represents 2 or 3, but a plurality of Y ₃ represent different groups.

In the general formula [V], R ₃ , R ₂₀ ,
R ₂₁ and R ₂₂ may have the same substituents as R ₁ in the above general formula [I] may have.

In the above general formula [VI], X ₃ represents a hydrogen atom or —SO ₂ NR ₂₃ R ₂₄ .

-SO ₂ NR ₂₃ R ₂₄ represented by X ₃ has the same meaning as -SO ₂ NR ₇ R ₈ represented by Y ₁ in formula [I].

In the above general formula [VI], J ₃ represents a hydrogen atom or a group which can be eliminated by reaction with an oxidized form of a color developing agent.

[0085] a group capable upon reaction with an oxidation product of a color developing agent represented by J ₃ are removed by reaction with an oxidation product of a color developing agent represented by J ₁ in the general formula (II) Synonymous with a detachable group.

In the general formula [VI], Z ₃ represents —NH
It represents an SO ₂ R ₂₅ or -NHSO ₂ NR ₂₆ R _27.

--NHSO ₂ R ₂₅ or --NH represented by Z ₃
SO ₂ NR ₂₆ R ₂₇ has the same meaning as —NHSO ₂ R ₁₇ or —NHSO ₂ NR ₁₈ R ₁₉ represented by Z ₂ in the general formula [IV].

In the general formula [VI], R ₂₃ , R ₂₄ ,
R ₂₅ , R ₂₆ and R ₂₇ may have the same substituents as R ₁ in the above formula [I] may have.

Hereinafter, the general formulas [I] and [III] of the present invention will be described.
And a representative compound example of a color developing agent represented by [V],
And typical examples of the dye-forming couplers represented by formulas [II], [IV] and [VI], but the present invention is not limited thereto.

[0090]

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[0091]

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[0092]

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[0093]

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[0094]

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[0095]

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[0096]

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[0097]

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[0098]

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[0099]

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[0100]

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[0101]

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[0102]

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[0103]

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Hereinafter, the general formulas [I] and [III] of the present invention will be described.
And a color developing agent represented by [V], and a general formula [I
Representative synthesis examples of representative compounds of the dye-forming couplers represented by I], [IV] and [VI] are shown below.

Synthesis Example 1 << Synthesis of Color Developing Agent D-10 >>

[0106]

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50.0 g of the compound [A] was added to 200 ml of acetic acid.
And 59.5 ml of concentrated hydrochloric acid was added with stirring. A solution obtained by dissolving 16.9 g of sodium nitrite in 26 ml of water was added dropwise while stirring the mixture under ice-cooling while maintaining the internal temperature at 10 ° C or lower. On the other hand, a solution prepared by dissolving 96.5 g of stannous chloride in 178 ml of concentrated hydrochloric acid was prepared, and the reaction solution was added to the prepared solution while maintaining the internal temperature at 15 ° C. or lower under ice cooling. After stirring at an internal temperature of 15 ° C. or lower for 1 hour, ethyl acetate was added for extraction. The ethyl acetate layer was washed five times with a saline solution, and then washed with an aqueous sodium hydroxide solution until the aqueous layer became alkaline. The obtained ethyl acetate layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure.
36.0 g of compound [B] was obtained as a pale yellow oil. Compound [B] was used in the next step without purification.

13.1 g of triphosgene was dissolved in 280 ml of tetrahydrofuran, and the compound [C] 38.6 was added thereto.
g was added dropwise at room temperature over 30 minutes, and 53.3 ml of triethylamine was further added dropwise at room temperature over 30 minutes. By reacting for 1 hour, a solution of compound [D] was obtained. 36.0 g of the compound [B] synthesized earlier was added to 30 parts of the reaction solution.
The mixture was added dropwise over a minute, and the mixture was further stirred for 2 hours. After completion of the reaction, the mixture was poured into water and extracted with ethyl acetate. The ethyl acetate layer was washed successively with aqueous hydrochloric acid, an aqueous solution of sodium hydrogen carbonate, and brine, dried over anhydrous magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure. The obtained residue was subjected to column chromatography (silica gel, developing solvent: ethyl acetate / n-
Hexane) to give 45.8 g of a pale yellow amorphous color developing agent D-10. Identification is M
Performed by ASS and NMR spectra, color developing agent D-
It was confirmed to be 10.

Synthesis Example 2 << Synthesis of Dye-Forming Coupler C-12 >>

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To 100 ml of tetrahydrofuran was added 15.9 g of 5-amino-1-naphthol, and 16.2 ml of pyridine was added with stirring. While stirring under ice-cooling, 36.1 g of the compound [E] was added in portions over 30 minutes. After completion of the addition, the mixture was returned to room temperature and stirred for 3 hours. After completion of the reaction, the mixture was poured into water and extracted with ethyl acetate. The ethyl acetate layer was washed successively with aqueous hydrochloric acid, an aqueous solution of sodium hydrogen carbonate, and brine, dried over anhydrous magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure. The obtained residue was recrystallized from acetonitrile to obtain 38.6 g of a dye-forming coupler C-12 as a white solid.

The identification was performed by MASS and NMR spectra, and it was confirmed that the dye-forming coupler was C-12.

The amount of the dye-forming coupler (hereinafter, also simply referred to as a coupler) used in the present invention is from 1 × 10 ⁻⁶ mol to 0.1 mol / m ² , preferably from 1 × 10 ⁻⁶ mol to 0.1 mol / m ² .
A suitable range is from × 10 ⁻⁵ mol to 1 × 10 ⁻² mol / m ² , more preferably from 1 × 10 ⁻⁴ mol to 5 × 10 ⁻³ mol / m ² .

The color developing agent of the present invention may be added in an amount of
0.01 to 100 times, preferably 0.1 to 100 times the coupler.
It is 1 to 10 times, more preferably 0.2 to 5 times.

In the present invention, an auxiliary developing agent can be preferably used. Here, the auxiliary developing agent means a substance having an action of promoting the transfer of electrons from the developing agent to the silver halide in the development process of silver halide development, and the auxiliary developing agent in the present invention is preferably represented by the general formula ( B-1) or an electron-emitting compound according to the Kendall-Peltz rule represented by the general formula (B-2). Among them, those represented by (B-1) are particularly preferred.

[0116]

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In the general formulas (B-1) and (B-2),
R ^{51 to} R ⁵⁴ represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, or a heterocyclic group.

R ^{55 to} R ⁵⁹ are a hydrogen atom, a halogen atom, a cyano atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, a cycloalkyloxy group, an aryloxy group, a heterocyclic oxy group. 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, cycloalkyloxycarbonyloxy group, aryloxycarbonyloxy group, carbamoyloxy group, sulfamoyloxy group, alkanesulfonyloxy group, arenesulfonyloxy group, acyl group, alkoxycarbonyl group,
Cycloalkyloxycarbonyl group, aryloxycarbonyl group, carbamoyl group, carbonamide group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide group,
Represents a sulfamoylamino group, an alkylsulfinyl group, an arenesulfinyl group, an alkanesulfonyl group, an arenesulfonyl group, a sulfamoyl group, a sulfo group, a phosphinoyl group, and a phosphinoylamino group.

Q represents an integer of 0 to 5, and when q is 2 or more, R ⁵⁵ may be different from each other. R ⁶⁰ represents an alkyl group or an aryl group.

Specific examples of the compound represented by formula (B-1) or (B-2) are given below, but the auxiliary developing agent used in the present invention is not specifically limited to these.

[0121]

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[0122]

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[0123]

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[0124]

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[0125]

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[0126]

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[0127]

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In the present invention, a blocked photographic reagent which releases a photographically useful group upon processing as represented by the general formula (A) can be used.

General Formula (A) A- (L) n-PUG A represents a block group that cleaves a bond with (L) n-PUG during development processing, and L represents the left side of L in the general formula (A). After the bond is cleaved, the bond on the right side of L is cleaved, n is an integer of 0 to 3, and PUG is a photographically useful group.

The group represented by formula (A) will be described below. As the blocking group represented by A, the following known ones can be applied. In other words,
-9968, JP-A-52-8828 and 57-82.
834, U.S. Pat. No. 3,311,476, and JP-B-47-44805 (U.S. Pat. No. 3,615,617).
No. 55-17369 (U.S. Pat. No. 3,017,369), which is a blocking group such as an acyl group or a sulfonyl group described in US Pat.
888,677), 55-9696 (U.S. Pat. No. 3,791,830), 55-34927 (U.S. Pat.No. 4,009,029), and JP-A-56-7784.
No. 2 (U.S. Pat. No. 4,307,175);
Nos. 05640, 59-105641, and 59-
No. 5,064,972, and the like. U.S. Pat. No. 3,674,478, U.S. Pat.
No. 3,993,661, JP-A-57-135944
No. 57-135945 (U.S. Pat.
No. 554), Nos. 57-136640 and 61-196.
Nos. 239 and 61-196240 (U.S. Pat.
No. 02,999), No. 61-185743, No. 61-
No. 4,249,408 (US Pat. No. 4,639,408) and JP-A-2-280140, and the like. 35
Nos. 8,525 and 4,330,617;
Nos. 53330 (U.S. Pat. Nos. 4,310,612), 59-121328, 59-218439, and 63-318555 (European Patent No. 295,72).
No. 9) and the like, and a blocking group utilizing an intramolecular nucleophilic substitution reaction, JP-A-57-76541 (U.S. Pat. No. 4,335,200) and 57-135949 (U.S. Pat. , 350, 752), 57-17984.
No. 2, No. 59-137945, No. 59-140445
Nos. 59-219741 and 59-202449
No. 60-41034 (U.S. Pat. No. 4,618,5).
No. 63) and 62-59945 (U.S. Pat.
No. 8,268), No. 62-65039 (U.S. Pat. No. 4,772,537), No. 62-80647, and JP-A-3-236047 and JP-A-3-238445. A block group utilizing ring cleavage of a 6-membered ring, disclosed in JP-A-59-201057 (U.S. Pat.
No. 18,685), No. 61-95346 (U.S. Pat. No. 4,690,885), No. 61-95347 (U.S. Pat. No. 4,892,811), and JP-A-64-7035.
No. 64-42650 (US Pat. No. 5,066,5).
No. 73), JP-A-1-245255, JP-A-2-2072
Nos. 49 and 2-235055 (U.S. Pat.
No. 8,596) and 4-186344, and a blocking group utilizing the addition reaction of a nucleophile to a conjugated unsaturated bond, JP-A-59-93442 and JP-A-61-32.
Nos. 839 and 62-163051 and 5-37
No. 299, etc .; a blocking group utilizing a nucleophilic substitution reaction of diarylmethanes described in JP-A-61-188540; No. 187850, a block group utilizing the Rossen rearrangement reaction.
Nos. 0646, 62-144163 and 62-14
No. 7457, which describes a blocking group utilizing a reaction between an N-acyl compound of thiazolidine-2-thione and an amine, and JP-A-2-296240 (U.S. Pat.
No. 9,492), No. 4-177243, No. 4-177
No. 244, No. 4-177245, No. 4-177246
Nos. 4-177247, 4-177248, 4-177249, 4-179948, 4-1-1
Nos. 84337 and 4-184338, International Patent No. 9
2/21064, JP-A-4-330438, WO93 / 03419 and JP-A-5-45816, a block having two electrophilic groups and reacting with a dinucleophile. And JP-A-3-236047 and JP-A-3-238445.

In the compound represented by formula (A), L
The group represented by may be any linking group capable of cleaving (L) n-1-PUG after leaving from the group represented by A during the development processing. For example, a group utilizing cleavage of a hemiacetyl tar ring described in U.S. Pat. Nos. 4,146,396, 4,652,516 or 4,698,297;
962, 4,847,185 or 4,85
7,440, a timing group for causing an intramolecular nucleophilic substitution reaction, and cleavage using an electron transfer reaction described in U.S. Pat. No. 4,409,323 or 4,421,845. A timing group for causing a reaction, a group for causing a cleavage reaction by utilizing a hydrolysis reaction of imino ketanol described in U.S. Pat. And a group that causes a cleavage reaction by utilizing a reaction with a sulfite ion described in EP 572,084.

Next, PUG in the general formula (A) will be described.

PUG in the general formula (A) represents a photographically useful group such as an antifoggant and a photographic dye. In the present invention, PUG is represented by the general formulas (B-1) and (B-2). Auxiliary developing agents are particularly preferably used for PUG.

When the auxiliary developing agents represented by the general formulas (B-1) and (B-2) correspond to the PUG of the general formula (A), the bonding position is an oxygen atom or a nitrogen atom of the auxiliary developing agent. Is an atom.

The light-sensitive material of the present invention basically has a light-sensitive silver halide, a color developing agent, a coupler and a binder on a support, and further contains, if necessary, an organic metal salt oxidizing agent and the like. Can be done. These components are often added to the same layer, but they can be added separately in separate layers as long as they can react.

The hydrophobic additives such as couplers and color developing agents used in the present invention are described in US Pat. No. 2,322,027.
It can be introduced into the layer of the light-sensitive material by a known method such as the method described in the above. In this case, U.S. Pat.
No. 55,470, No. 4,536,466, No. 4,
No. 536,467, No. 4,587,206, No. 4,555,476, No. 4,599,296, and Japanese Patent Publication No. 3-62256 require a high boiling point organic solvent. Can be used in combination with a low-boiling organic solvent having a boiling point of 50 to 160 ° C. depending on the solvent. Two or more of these dye-donating compounds, nondiffusible reducing agents, 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 per 1 g of the binder, and more preferably 0.1 cc.
5 cc or less, especially 0.3 cc or less is appropriate. Also,
A dispersion method using a polymer described in JP-B-51-39853 and JP-A-51-59943, and JP-A-62-3
No. 0242, JP-A-63-271339, and the like, and a method of adding it as a fine particle dispersion can also be used.
Compounds substantially unnecessary in water can be dispersed and contained as fine particles in a binder in addition to the above-mentioned method. When dispersing the hydrophobic compound in the hydrophilic colloid, various surfactants can be used. For example, JP
The surfactants listed as surfactants in RD magazines shown in the following table on pages (37) to (38) of No. 9-157636 can be used. In the light-sensitive material of the present invention, a compound for stabilizing an image simultaneously with activation of development can be used. Specific compounds preferably used are described in U.S. Pat. No. 4,500,626, Nos. 51-52.
Column.

In order to obtain a wide range of colors on 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 photosensitive material can be provided with various auxiliary layers such as a protective layer, an undercoat layer, an intermediate layer, an antihalation layer, and a back layer. Further, various filter dyes can be added to improve color separation.

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

The silver halide emulsion of the present invention preferably has a distribution or a structure with respect to the halogen composition in the grains. A typical example is JP-B-43-1316.
No. 2, JP-A-61-215540, JP-A-60-22
No. 2,845, JP-A-61-75337, etc. are core-shell or double-structure grains having a halogen composition in which the inside and the surface of the grains are different. In addition to a mere double structure, a triple structure as disclosed in JP-A-60-222844 or a multilayer structure of more than that, or a different composition on the surface of the core-shell double structure particles Or a thin silver halide having the following formula:

In order to impart a structure to the inside of 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 bonding result can be generated by bonding to a host crystal, an edge, a corner portion, or a surface portion 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 salt compound having no rock salt structure such as silver rhodanate 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.

In the case of particles of silver iodobromide or the like having these structures, it is a preferred embodiment that the core portion has a higher silver iodide content than the shell portion. Conversely, grains having a low silver iodide content in the core and a high shell are sometimes preferred. Similarly, grains having a bonding structure may be grains having a high silver iodide content of the host crystal and relatively low silver iodide content of the bonding crystal, or vice versa. In addition, the boundary portions having different halogen compositions of grains having these structures may be clear boundaries or unclear boundaries. In addition, a configuration in which the composition is positively and continuously changed is also a preferable embodiment.

In the case of silver halide grains in which two or more silver halides are present as mixed crystals or with a structure, it is important to control the halogen composition distribution between the grains.
Regarding the method of measuring the halogen composition distribution between grains, see
No. 0-254032. Uniform halogen distribution between grains is a desirable property. In particular, a highly uniform emulsion having a coefficient of variation of 20% or less is preferable. Another preferred form is an emulsion having a correlation between the grain size and the halogen composition. As an example, there is a correlation such that the iodine content is higher for larger size particles, while the iodine content is lower for smaller size particles. Depending on the purpose, an inverse correlation or a correlation with another halogen composition can be selected. For this purpose, it is preferable to mix two or more emulsions having different compositions.

It is important to control the silver halide composition near the surface of the 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 only on one side of a 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, Fundamentals of the Photographic Industry, Silver Salt Photography (Corona), page 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 according to the purpose. 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. Furthermore, Jo
urnal of Imaging Science
(H11) plane particles represented by (211) as reported in Vol. 30, page 247 (1986);
The (hh1) plane particles represented by (1), the (hk0) plane particles represented by the (210) plane, and the (hk1) plane particles represented by the (321) plane also require some devising method for adjustment, but depending on the purpose. You can select and use it. (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 Th.
eory 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
No. 14,310, No. 4,433,048, No. 4,
No. 439,520 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 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. 4,798,354
A regular hexagon having substantially equal lengths of the six sides as described in the item is a preferred form.

Although the circle equivalent diameter of the projected area is often used as the particle size of the average particle, 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 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 the grains described in JP-A-163451 in which the thickness of the grains and the distance between twin planes are specified.

In the case of tabular grains, dislocation lines can be observed with a transmission electron microscope. It is preferable to select a particle containing no dislocation line, a particle containing several dislocations, or a particle containing many dislocations according to the purpose. In addition, dislocations introduced linearly or bent dislocations with respect to a specific direction of the crystal orientation of the grains can be selected, or introduced over the entire grains, or introduced 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. 96,412 B1 or the like, or a process described in West German Patent No. 2,30.
The surface may be modified as disclosed in JP-A-6-447 C2 and JP-A-60-221320.

A structure having a flat particle surface is generally used.
It is sometimes preferable to intentionally form irregularities. JP-A-58-106532, JP-A-60-221
No. 320, for example, a method for drilling 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. 643,966 are examples.

The particle 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
The use of submicron grains as 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, depending on the purpose. In some cases, a variation coefficient of the projected area equivalent circle diameter or sphere equivalent diameter of a particle is used as a scale representing the size distribution. When a monodisperse emulsion is used, it is preferable to use an emulsion having a size distribution with a coefficient of variation of 25% or less, more preferably 20% or less, and still more preferably 15% or less.

A monodisperse emulsion is sometimes defined as an average particle size distribution by the number or weight of particles. In order to satisfy the target gradation of the light-sensitive material, two or more monodisperse 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. As the emulsion used in the present invention, an emulsion containing the above-mentioned grains is used. Here, as one of the embodiments for carrying out the present invention, an embodiment in which the active ingredient of the present invention and an emulsion composed of tabular grains having a silver chloride content of 50 mol% or more are not used can be adopted.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Grafkid, published by Paul Monte Co. (PG
lafkides, Chemie et Physiq
uePhotograhique, Paul Mont
el, 1967), Duffin, "Photographic Emulsion Chemistry", published by Focal Press (GF Duffin, Photo).
graphic Emulsion Chemistr
y, Focal Press, 1966), Zerikman et al., "Manufacture and Coating of Photographic Emulsion," Focal Press (VL Zelikman, et al., Mak.
ing and Coating Photograph
hic Emulsion, Focal Press,
1964), 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 of a one-sided mixing method, a double-sided mixing method, a combination thereof and the like. . A method of forming grains in the presence of excess silver ions (a so-called reverse mixing method) can also be used. As one type of the double jet method, a method in which pAg in a liquid phase in which silver halide is formed is kept constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide photographic 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. Nos. 4,334,012, 4,301,241, and 4,150,994. 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. It is also effective in some cases to add particles having various halogen compositions to modify the surface.

The method of converting most of the halogen composition of silver halide grains by a halogen conversion method is disclosed in US Pat. Nos. 3,477,852 and 4,142,
No. 900, European Patent Nos. 273,429 and 273,
No. 430 and West German Patent No. 3,819,241, which are effective particle forming methods. A solution of a soluble halogen or silver halide grains can be added to convert the silver salt into a 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, UK 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 effective. It is.

A mixer for reacting a solution of a soluble silver salt with 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 silver halide salt, a silver salt or a deflocculant can be added and introduced into the reactor. As another variant, the ripening agent can be introduced independently during the halide and silver salt addition stage.

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 the like, and thione compounds (for example, tetra-substituted thioureas described in JP-A-53-82408 and JP-A-55-77737, U.S. Pat. No. 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.).

Gelatin is advantageously used 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 or a vinyl monomer each other with vinyl monomers having,
Alternatively, a copolymer with another vinyl monomer (for example, sodium methacrylate, ammonium methacrylate, Sumikagel L-5H manufactured by Sumitomo Chemical Co., Ltd.) is also used. These binders can be used in combination of two or more kinds. Combinations of gelatin and the above binders are also preferred.

As 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. Use of low molecular weight gelatin described in JP-A-1-158426 is preferred for preparing tabular grains.

The silver halide color photographic light-sensitive material of the present invention can form an image by thermal development. In the case of a photothermographic material, an organic silver chloride may be used together with the photosensitive silver halide emulsion.
No. 626, columns 52 to 53, benzotriazoles, fatty acids and other compounds. U.S. Pat.
The acetylene silver described in 775,613 is also useful. Two or more organic silver salts may be used in combination. The above organic silver salt is used in an amount of 0.01 to 10 per mole of the photosensitive silver halide.
Mole, preferably 0.01 to 1 mole can be used in combination. The total coating amount of the photosensitive silver halide emulsion and the organic silver salt is 0.05 to 10 g / m ^{2 in} terms of silver, preferably 0.1 to 0.1 g / m ² .
４4 g / m ² is suitable.

The emulsion of the present invention is preferably washed with water for desalting and dispersed in a newly prepared protective colloid. The temperature of water washing can be selected according to the purpose, but is preferably selected in the range of 5 to 20 ° C. The pH at the time of washing can be selected depending on the purpose, but is preferably selected from 2 to 10. More preferably, it is in the range of 3 to 8. The pAg at the time of washing can be selected according to the purpose, but is preferably selected from 5 to 10. Noodle washing method, dialysis method using semi-permeable membrane,
It can be selected from centrifugation, coagulation sedimentation, and ion exchange. In the case of the coagulation sedimentation method, a method using a sulfate, a method using an organic solvent, a method using a water-soluble polymer, a method using a gelatin derivative, and the like can be selected.

When preparing the emulsion of the present invention, for example, during grain formation,
In the desalting step, at the time of chemical sensitization, the presence of a metal ion salt before coating is preferable depending on the purpose. When doping the grains, it is preferable to add them at the time of grain formation, when modifying the grain surface or as a chemical sensitizer, after grain formation and at the end of chemical sensitization. The case of doping the whole grain and the method of doping only the core portion, only the shell portion, only the epitaxial portion, or only the base grain of the grain can be selected. Mg, Ca, Sr, Ba, Al,
Sc, Y, La, Cr, Mn, Fe, Co, Ni, C
u, Zn, Ga, Ru, Rh, Pd, Re, Os, I
r, Pt, Au, Cd, Hg, Tl, In, Sn, P
b, Bi, etc. can be used. These metals may be in the form of a salt that can be dissolved at the time of particle formation, such as ammonium salt, acetate, nitrate, sulfate, phosphate, hydroxide, or 6-coordinate acetate, 4-coordinate acetate. Can be added. For example, CdBr ₂ , CdCl ₂ , Cd (NO ₃ ) ₂ , Pd
(NO ₃ ) ₂ , Pb (CH ₃ COO) ₂ , K ₃ [Fe (C
N) ₆ ], (NH ₄ ) ₄ [Fe (CN) ₆ ], K ₃ IrC
l _6, and the like _{(NH 4) 3 RhCl 6,} K 4 Ru (CN) 6. The ligand of the coordination compound can be selected from halo, aquo, cyano, cyanate, thiocyanate, nitrosyl, thionitrosyl, oxo, and carbonyl. These may use only one type of metal compound, or may use two or more types in combination.

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

The silver halide grains of the present invention are sulfur-sensitized,
At least one of selenium sensitization, tellurium sensitization (these three are collectively referred to as chalcogen sensitization), noble metal sensitization, or reduction sensitization can be applied in any step of the production process of a silver halide emulsion. it can. It is preferable to combine two or more sensitization methods. Various types of emulsions can be prepared depending on the step of chemical sensitization. There are a type 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 chalcogen sensitization and noble metal sensitization alone or in combination thereof, and is described in TH James, The.
Photographic Process, 4th Edition, Macmillan, 1977 (TH James The Pho
graphical Process, 4thed, M
ecmillan, 1977), pages 67-76, and can also be performed using active gelatin, as well as 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
97,446, 3rd, 772,031, 3rd
PAg5 as described in 857,711, 3,901,714, 4,266,018, and 3,904,415 and British Patent 1,315,755. 10, pH 5-8 and temperature 30-80 ° C
Can be carried out by combining sulfur, selenium, tellurium, gold, silver, palladium, iridium or a plurality of these sensitizers.

In the sulfur sensitization, an unstable sulfur compound is used, and specifically, thiosulfates (eg, hypo), thioureas (eg, diphenylthiourea, triethylthiourea, allylthiourea, etc.), rhodanine Kind,
Mercaptos, thioamides, thiohydantoins, 4
-Oxooxazolidine-2-thiones, di- or polysulfides, polythionates and elemental sulfur, and U.S. Patent Nos. 3,857,711, 4,266.
Known sulfur-containing compounds described in No. 018 and 4,054,457 can be used. Sulfur sensitization is often used in combination with noble metal sensitization.

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

In the selenium sensitization, a known unstable selenium compound is used, for example, US Pat. No. 3,297,44.
No. 6,297,447 and the like, and specifically, colloidal metal selenium, selenoureas (for example, N, N-dimethylselenourea, tetramethylselenourea) Urea, etc.), seleno ketones (eg, selenoacetone), selenoamides (eg, selenoacetamide), selenocarboxylic acids and esters, isoselenocyanates, selenides (eg, diethyl selenide, triphenylphosphine selenide), Selenophosphates (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.

[0174] The amount of the selenium sensitizer, the selenium compound used, the silver halide grains will vary by the chemical ripening condition and the like, generally, per mol of silver halide 10 ^-8 to 10 ^-4
Mol, preferably 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, and specific 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 an amount of 1 silver halide.
10 ^{-7 to} 5 × 10 ^-2 mol per mol, preferably 5 × 1
It is about ^0-7 to ^10-3 mol.

In the noble metal sensitization, noble metal salts such as silver, gold, palladium and iridium can be used, and 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, bromine or iodine atom.

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

The emulsion of 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.

During the grain formation of the silver halide emulsion of the present invention,
It is preferable to perform reduction sensitization after grain formation and before or during chemical sensitization, or after chemical sensitization.

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

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

As the reduction sensitizer, known reduction sensitizers such as stannous 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 novolane, 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 sensitization aids include compounds known as azaindene, azapyridazine, azapyrimidine, which suppress fog during chemical sensitization and increase sensitivity. Examples of chemical sensitization aid modifiers are described in U.S. Pat.
Nos. 411,914 and 3,554,757, JP-A-58-126526 and the aforementioned "Photographic Emulsion Chemistry" by Duffin, pp. 138-143.

It is preferable to use an oxidizing agent for silver during the production process of the emulsion of the present invention. The oxidizing agent for silver is
A compound that acts on metallic silver to convert silver ions. In particular, a compound that converts very fine silver grains that are replicated during the formation of silver halide grains and the chemical sensitization process 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. As the inorganic oxidizing agent, ozone, hydrogen peroxide and its adducts (for example, Na
BO ₂ , H ₂ O ₂ .H ₂ O, 2NaCO ₃ .H ₂ O ₂ , Na ₄ P
₂ O ₇ · H ₂ O ₂ , 2NaSO ₄ · H ₂ O ₂ · 2H ₂ O), peroxy acid salts (eg, K ₂ S ₂ O ₈ , K ₂ C ₂ O ₆ , K ₂ P ₂ O
₈ ) Peroxy complex compound (for example, K ₂ [Ti (O ₂ )
C ₂ O _{4] · 3H 2 O, 4K 2 SO} 4 · Ti (O 2) OH · S
_{O 4 · 2H 2 O, Na} 3 _{[VO (O 2) (C 2} O 4) 2 ] · 6
Oxyacids such as H ₂ O), permanganate (eg, KMnO ₄ ), chromate (eg, K ₂ CrO ₇ ), halogen elements such as iodine and bromine, and perhalates (eg, periodate) Potassium), high valent metal salts (eg, potassium hexacyanoate) 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.

Preferred oxidizing agents of the present invention are ozone, hydrogen peroxide and its adducts, halogen elements, inorganic oxidizing agents of thiosulfonates and organic oxidizing agents of quinones. It is a preferred embodiment to use the above-described reduction sensitization and an oxidizing agent for silver in combination. A method of performing reduction sensitization after using an oxidizing agent,
The reverse method or a method in which both coexist simultaneously can be selected and used. These methods can be selectively used in both the grain formation step and the chemical sensitization step.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the photographic material, or stabilizing photographic performance. . That is, thiazoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, amino Triazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially,
1-phenyl-5-mercaptotetrazole), mercaptopyrimidine, mercaptotriazine, thioketo compounds such as oxazolinethione, azaindene rings such as triazaindenes, tetraazaindenes, (especially 4-hydroxy-6-methyl-1 , 3,3
Many compounds known as antifoggants or stabilizers can be added, such as a, 7-tetraazaindene), pentaazaindenes and the like. For example, those described in U.S. Pat. Nos. 3,954,474 and 3,982,947 and JP-B-52-28660 can be used. One of the preferred compounds is disclosed in Japanese Patent Application No. 62-472.
There is a compound described in No. 25. 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. Besides controlling the crystal wall of the grains, reducing the grain size, reducing the solubility of the grains, and controlling the chemical sensitization, in addition to exhibiting the original fogging prevention and stabilizing effects by adding during emulsion preparation. It can be used for various purposes such as controlling the arrangement of dyes.

When the photosensitive silver halide used in the present invention 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 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. 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 alicyclic hydrocarbon ring is fused to these nuclei such as an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, and a pyridine nucleus. Nuclei in which hydrogen rings are fused, i.e., indolenine nucleus, benzindolenin nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, rhodanine nucleus, thione A 5-64-hydroxy-6-methyl-heterocyclic nucleus such as a barbituric acid nucleus can be applied. These nuclei may be substituted on carbon atoms. Specifically, US Patent 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.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazoline-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. The combination of sensitizing dyes is often used for the purpose of supersensitization and adjusting the wavelength 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.

Along with the sensitizing dye, a dye which does not itself have a spectral sensitizing effect or a compound which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (for example, US Pat. No. 3,615,641 and those described in JP-A-63-23145).

The timing of adding these sensitizing dyes to the emulsion may be any means of preparing an emulsion which has hitherto been known to be useful.

Most commonly, the reaction is carried out after completion of chemical sensitization and before coating, but US Pat. No. 3,628,96
As described in JP-A-58-113928, it is also possible to simultaneously add a chemical sensitizer and carry out spectral sensitization simultaneously with chemical sensitization, as described in JP-A Nos. Can be performed prior to chemical sensitization as described in Further, it can be added before the completion of silver halide grain precipitation to start spectral sensitization. Further, according to U.S. Pat. Nos. 4,183,756 and 4,255,666, the compounds may be added before or after nucleation of silver halide grains, a part of the compound is added before chemical sensitization, and the remainder is subjected to chemical sensitization. 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 according to the present technology, but other 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 18176 (November 1979).
And Item 307105 (November 1989), and the relevant portions are summarized below.

Types of Additives RD17643 RD18716 RD307105 Chemical sensitizer page 23 page 648 right column page 996 2. 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer Supersensitizer 23 to 24 pages 648 right column to 649 right column 996 to 998 Brightener page 24 page 647 page right column page 998 5. 5. Light absorber, filter dye, ultraviolet absorber page 25-26 page 649 right column-page 650 left column page 1003 Binder 26 pages 651 pages 1003 to 1004 7. 7. Plasticizers and lubricants Page 27 Page 650 Page 1006 8. Coating aids, surfactants 26 to 27 pages 650 pages 1005 left to 1006 right 10. Antistatic agent, page 27, page 650, right column, pages 1006 to 1007 Antifoggants and stabilizers 24 to 25 p. 649 p. 998 to 1000 p. Stain inhibitor 25 pages right column 650 pages left to right 12. Dye image stabilizer page 25 13. Hardening agents page 26, page 651, left column, page 1004 right to page 1005 left In addition to the above, hardening agents are described in U.S. Pat.
739, column 41, 4,791,042, JP-A-59-116655, JP-A-62-245261, and 6
Hardening agents described in, for example, JP-A-1-19422 and JP-A-4-218044 are exemplified. More specifically, aldehyde hardeners (such as formaldehyde), aziridine hardeners, epoxy hardeners, vinyl sulfone hardeners (N,
N'-ethylene-bis (vinylsulfonylacetamide)
Ethane, etc.), N-methylol hardener (dimethylolurea, etc.), or polymer hardener (JP-A-62-234).
157 etc.). These hardeners are used in an amount of 0.001 to 1 g of gelatin applied.
1 g, preferably 0.005 to 0.5 g 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.

A matting agent can be used in the light-sensitive material of the present invention 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 Nos. 63-274944 and 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, an antifungal agent, colloidal silica and the like. Specific examples of these additives are disclosed in
-88256, pages 26 to 32, JP-A-3-11
No. 338, 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 lubricity, prevention of electrification, 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 heat-developable photosensitive 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 or 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.

In the light-sensitive material of the present invention, known brown inhibitors can be used. Organic brown inhibitors include hydroquinones, 5-hydroxychromans, 5-hydroxycoumarins, paraalkoxyphenols, hindered phenols, mainly bisphenols, gallic acid derivatives, methylenedioxybenzenes, amino acids 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, metal complexes represented by (bissalicylaldoximato) nickel complex and (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used. Compounds having both partial structures of hindered amine and hindered phenol in the same molecule, as described in U.S. Pat. No. 4,268,593, are effective in preventing the 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, US Patent 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, RD. No. 17643 (1978)
Compounds described on pages (24) to (25) and the like are included.
These compounds are used in an amount of from 5 × 10 ^-6 to 1 × 10 per mol of silver.
^-1 mol is preferable, and 1 × 10 ⁻⁵ to 1 × 10 ⁻² is more 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.
Page)). The RD. No. No. 17643, page 28; 1871
No. 6 from the right column on page 647 to the left column on page 648, and 30
Those described on page 879 of 7105 can also be preferably used. These supports include U.S. Pat. No. 4,141,73.
As described in No. 5, by applying 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, a glow discharge treatment, an ultraviolet irradiation treatment, a corona treatment, and a flame treatment can be used as the surface treatment. Further, the publicly known technology No. 5 (issued by Aztec Co., Ltd. on March 22, 1991)
The supports described on pages 4-149 can also be used. A transparent support such as polyethylene dinaphthalenedicarboxylate or a support obtained by applying a transparent magnetic substance thereon can also be used.

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" means that after appropriate development, the base is immediately neutralized or reacted with the base to reduce the base concentration in the film, and interact with a compound or silver and silver salt that stops the development to effect development. It is a compound that suppresses. 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. Further details are described in JP-A-62-253159, pages (31) to (32).

When the light-sensitive material of the present invention is used as a photothermographic material, a method for supplying a base is preferably a method of generating a base from a base precursor. Examples of the base precursor used in the present invention include a salt of an organic acid and a base that is decarboxylated by heat, a compound that decomposes by a reaction such as an intramolecular nucleophilic substitution reaction, a Rossen rearrangement or a Beckmann rearrangement, and releases amines, and the like. A compound that causes a certain reaction to release a base and a compound that generates a base by an electrolysis or a complex formation reaction are preferably used. Examples of the former base precursors that generate 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 which further improves stability. Salts of α-sulfonylacetate described, propiolic acid described in Japanese Patent Application No. 58-55700, 2-carboxycarbamide derivatives described in US Pat. No. 4,088,496, and organic bases other than organic bases. With a thermally decomposable acid using an alkali metal or alkaline earth metal (Japanese Patent Application No. 58-69597); hydroxam carbamates described in Japanese Patent Application No. 58-43860 using Rossen rearrangement; And aldoxime carbamates described in Japanese Patent Application No. 58-31614. Others, UK Patent 998,945
No. 2,079,480, JP-A-50-2262
No. 25, U.S. Pat. Nos. 3,220,846 and 4,5,5;
The base precursors described in JP-A Nos. 14,493, 4,657,848, and Known Technique No. 5 (March 22, 1991, Aztec Co., Ltd.), pp. 55-86, are also useful.

The method of exposing and writing 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, or a method of exposing through a reversal film or a negative film using a printer or a enlarger. Scanning, exposing the original image through slits, etc. using an exposure device of a copying machine, and scanning by emitting light emitting diodes and various lasers (laser diodes, gas lasers, etc.) via image information and electric signals. Exposure method (JP-A-2-129629, Japanese Patent Application No. 3-3381)
No. 82, No. 4-93388, No. 4-281442), image information is transferred to a CRT, a liquid crystal display,
There is a method of outputting to an image display device such as an electroluminescence display and a plasma display and exposing the image directly or via an optical system.

As a light source for recording an image on a photosensitive material,
As described above, U.S. Pat.
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-2-210432 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.

The color developing agent of the present invention is used for all silver halide photosensitive materials such as color negatives, color papers, color instant photographs and X-ray photographic materials for forming color images or color images, and photographic materials for plate making. be able to. Further, the color developing agent of the present invention can be added to a silver halide photosensitive material, and can also be added to a processing solution.

When the color developing agent of the present invention is added to a silver halide photosensitive material, development can be carried out by heat treatment or activator treatment.

The heat treatment of photosensitive materials is known in the art.
For example, the basics of the photography industry (1979, published by Corona)
Pages 553-555, published April 1978, video information 4
Page 0, Neblets Handbook of Ph
Otography and Reprography
7th Ed. (Van Nostrand and
Reinhold Company), pages 32-33,
U.S. Pat. Nos. 3,152,904 and 3,301,6
No. 78, No. 3,392,020, No. 3,457,
No. 075, British Patent No. 1,131,108,
167,777 and Research Disclosure, June 1978, pages 9-15 (RD-17029).

Activator processing refers to a processing method in which a color developing agent is incorporated in a photosensitive material and development is performed using a processing solution 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 (for example, an alkali, an auxiliary developing agent, etc.). Regarding the activator treatment, European Patent No. 545,
No. 491A1, No. 565, 165A1, and the like. In the present invention, the “developer” means a processing solution containing a color developing agent or a processing solution containing no main agent (for an activator).

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

In the present invention, when the photosensitive material is subjected to development processing using a developer, the developer functions as a silver halide developing agent and / or an oxidized developing agent generated in silver development is incorporated in the photosensitive material. It is preferable to use a compound having a function of cross-oxidizing the color developing agent (auxiliary developing agent). Preferred are pyrazolidones, dihydroxybenzenes, reductones and aminophenols, and particularly preferred are pyrazolidones.

The pyrazolidones include 1-phenyl-3
-Pyrazolidones are preferable, 1-phenyl-3-pyrazolidone, 1-phenyl4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4, 4-dihydroxydimethyl-3-pyrazolidone, 1-phenyl-5
-Methyl-3-pyrazolidone, 1-phenyl-5-phenyl-3-pyrazolidone, 1-p-tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-p-
Chlorophenyl-4-methyl-4-hydroxymethyl-
3-pyrazolidone, 1-phenyl-2-hydroxymethyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-2-acetyl-3-pyrazolidone, 1-phenyl-
2-hydroxymethyl-5-phenyl-3-pyrazolidone, 1- (2-chlorophenyl) -4-hydroxymethyl-4-methyl-3-pyrazolidone and the like.

Examples of the dihydroxybenzenes include hydroquinone, chlorohydroquinone, bromohydrokinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,5-dimethylhydroquinone,
And potassium hydroquinone monosulfonate.

Reductones include N-methyl-p-
Aminophenol, N- (β-hydroxyethyl) -p
-Aminophenol, N- (4-hydroxyphenyl)
Glycine, 2-methyl-p-aminophenol and the like.

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

In the present invention, when an auxiliary developing agent such as pyrazolidones is incorporated in the light-sensitive material, it is preferable that the developing solution does not contain the above-mentioned developing agent. That is, the treatment is preferably performed using an intensifier-containing alkaline solution that does not contain an auxiliary developing agent. Hereinafter, the intensifier-containing liquid not containing the auxiliary developing agent is also referred to as a developer or a developing intensifier. Examples of the intensifier include West German Patents (OLS) 1,813,920, 2,044,993, 2,735,262, JP-A-48-9728, JP-A-49-84240, and 49. −
No. 102314, No. 51-53826, No. 52-13
No. 336, No. 52-73731, etc., peroxides, halogenous acids, iodoso compounds and cobalt (II
I) Complex compounds are used. Particularly, hydrogen peroxide is preferable because of its high amplification factor. In the present invention, compounds that release hydrogen peroxide such as perboric acid and percarbonate are also preferred. In the developer,
Hydrogen peroxide is contained in an amount of 0.005 mol to 1 mol / l, preferably 0.01 to 0.5 mol / l, more preferably 0.02 to 0.25 mol / l. The developer according to the present invention is an alkaline solution containing an intensifier, and contains various compounds described below.

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

In the present invention, an organic preservative is preferably contained in place of the above-mentioned hydroxylamine and sulfite ions. Here, the term "organic preservative" refers to all organic compounds that reduce the rate of deterioration of the developing agent by being added to a developer.
That is, organic compounds having a function of preventing the developing agent from being oxidized by air or the like, among which hydroxylamine derivatives (excluding hydroxylamine), hydroxamic acids, hydrazines, phenols, α-hydroxyketones, and α-hydroxyketones Amino ketones, sugars, monoamines, diamines, polyamines, quaternary ammoniums, nitroxy radicals, alcohols, oximes, diamide compounds, condensed amines, and the like are particularly effective organic preservatives. These are disclosed in JP-A-63-4235 and JP-A-63-53.
No. 41, 63-30845, 63-21647
No. 63-44655, No. 63-46454, No. 63-53551, No. 63-43140, No. 63-
No. 56654, No. 63-58346, No. 63-431
No. 38, No. 63-146041, No. 63-44657
No. 63-44656, U.S. Pat. No. 3,615,5
No. 03, No. 2,494, 903, JP-B-48-30
496, etc. Other preservatives include various metals described in JP-A-57-44148 and JP-A-57-53749, salicylic acids described in JP-A-59-180588, and alkanolamines described in JP-A-54-3532. Polyethyleneimines described in JP-A-56-94349, aromatic polyhydroxy compounds described in U.S. Pat. No. 3,746,544, and the like, if necessary. In particular, alkanolamines described in JP-A-4-97355, pp. 631 to 632,
It preferably contains the dialkylhydroxylamine described on pages 27 to 630. Furthermore, the use of a dialkylhydroxylamine and / or a hydrazine derivative in combination with an alkanolamine, or the use of a dialkylhydroxylamine described in EP 530,921 A1 in combination with an α-amino acid represented by glycine. Is also preferred.

The use amount of these compounds is preferably 1 × 10 ^{−35 to} 5 × 10 ⁻¹ mol, more preferably 1 × 10 ⁻² to 2 × 10 ⁻¹ mol, per liter of developer.

In the present invention, the developing solution contains halogen ions such as chlorine ions, bromine ions and iodine ions. In particular, when a high silver chloride emulsion is used, it preferably contains 3.5 × 10 ^{−3 to} 3.0 × 10 ⁻¹ mol / l of chloride ions, more preferably 1 × 10 ⁻² to 2 × 10 ^−2.
× 10 ^-1 mol / l, and / or preferably contains 0.5 × 10 ^{-5 to} 1.0 × 10 ^-3 mol / l of bromine ions, more preferably 3.0 × 10 ^-5. ~
5 × 10 ^-4 mol / l. Here, the halide may be directly added to the developer or may be eluted from the photosensitive material into the developer during the development processing.

When added to the developing solution, the supply materials include the respective sodium salts, potassium salts, ammonium salts, lithium salts, and magnesium salts.

When eluted from the light-sensitive material, it is mainly supplied from a silver halide emulsion, but may be supplied from other sources.

The developer used in the present invention preferably has a pH of 8 to 13, more preferably 9 to 12. The above p
In order to retain H, it is preferable to use various buffers. Buffers include carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycine salt, N, N
-Dimethylglycine salt, leucine salt, norleucine salt,
Guanic acid, 3,4-dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-methyl-1,3-propanediol salt, valine salt, proline salt, trishydroxylaminomethane salt, lysine salt, etc. Can be used. In particular, carbonate, phosphate, tetraborate, and hydroxybenzoic acid have solubility and pH 9.0 or higher.
It is preferable to use these buffers because they have excellent buffering capacity in the H region and do not adversely affect photographic performance even when added to a developer.

Specific examples of these buffers include lithium carbonate, sodium carbonate, potassium carbonate, potassium bicarbonate, tripotassium phosphate, trisodium phosphate, dipotassium phosphate, disodium phosphate, potassium borate, and boric acid. Examples include sodium, sodium tetraborate, potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), and the like. The amount of the buffer added to the developer is preferably at least 0.05 mol / l, particularly preferably from 0.1 mol to 0.4 mol / l.

In addition, various chelating agents can be used in the developer as a precipitation inhibitor for calcium or magnesium, or for improving the stability of the developer. For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylenesulfonic acid, 1,2-diaminopropanetetraacetic acid Glycol ether diamine tetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 1,2-dihydroxybenzene-4,6-disulfone Acids and their alkali metal salts. These chelating agents may be used in combination of two or more as necessary. The addition amount of these chelating agents may be an amount sufficient to mask metal ions in the developer, for example, 0.1 g to 10 g per liter.
It is about.

In the present invention, an optional antifoggant can be added as required. As the antifoggant, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide and nitrogen-containing heterocyclic compounds are used. Examples of the nitrogen-containing heterocyclic compound include benzotriazole, 5-nitrobenzotriazole,
-Methylbenzotriazole, 5-nitrobenzimidazole, 5-nitroindazole, 2-thiazolylbenzimidazole, indazole, hydroxyazaindolizine, adenine, 1-phenyl-5-mercaptotetrazole or derivatives thereof are mentioned as typical examples. Can be. The addition amount of the nitrogen-containing heterocycle is 1 × 10 ⁻⁵ to 1 × 1.
0 ^-2 mol / l, preferably 2.5-10 ^-5 to 1 ×
10 ⁻³ mol / l.

An optional development accelerator can be added to the developer if necessary. As development accelerators, JP-B-37-16
No. 088, No. 37-5987, No. 38-7826,
Thioether compounds represented by JP-A Nos. 44-12380 and 45-9019 and U.S. Pat. No. 3,813,247;
No. 54, p-phenylenediamine compound disclosed in JP-A-50-137726, JP-B-44-30074.
And JP-A-56-156826 and JP-A-52-4342.
No. 9, quaternary ammonium salts described in US Pat.
494,903, 3,128,182, 4,2
No. 30,796, No. 3,253,919, Japanese Patent Publication No. 41
-11431, U.S. Pat. Polyalkylene oxides and imidazoles described in U.S. Pat. No. 3,532,501 can be added as necessary.

The developer preferably contains a fluorescent whitening agent. In particular, it is preferable to use a 4,4-diamino-2,2'-disulfostilbene compound. Specifically, commercially available optical brighteners, for example, "Stained Note 19th Edition"
Compounds described on pages 165 to 168 and JP-A No. 4-24
The compounds described on page 3 to page 7 of 2943 can be used. The addition amount is 0.1 g to 10 g / l, preferably 0.5 g to 5 g / l.

The processing temperature of the developer used in the present invention is 2
The temperature is 0 to 50 ° C, preferably 30 to 45 ° C. The processing time is 5 seconds to 2 minutes, preferably 10 seconds to 1 minute. While replenishing amount is desirably small, the photosensitive material 1 m ² per 15
The volume is 600 ml, preferably 25 to 200 ml, more preferably 35 to 100 ml.

The light-sensitive material of the present invention may have a form having a conductive heating 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 65 ° C to 180 ° C, preferably about 7 ° C.
0 ° C to 180 ° C, about 75 ° C to 180 ° C, particularly preferably 80 ° C to 150 ° C, and more preferably 80 ° C to 135 ° C. The heating time is preferably 0.1
Seconds to 120 seconds, more preferably 0.1 seconds to 60 seconds, and particularly preferably 0.1 seconds to 30 seconds.

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

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 continuous bleach-fixing baths, fixing before bleach-fixing, or bleach-fixing after bleach-fixing can be arbitrarily performed according to the purpose. In some cases, it is also preferable to carry out a stabilization treatment without performing a desilvering treatment after the development to stabilize a silver salt or a color image.

Examples of the bleaching agent used in the bleaching solution 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 compounds, dichromates, and organic complex salts of iron (III) (eg, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid). , Methyliminodiacetic acid and JP-A-4-365036, p.
Aminopolycarboxylic acids and metal salts described on page 17, persulfates, permanganates, bromates, hydrogen peroxide and its releasing compounds (such as percarbonate and perboric acid), and nitrobenzenes. it can. Of these, ethylenediaminetetraacetic acid (III) complex salt, 1,3-diaminopropanetetraacetic acid iron (III) complex salt of aminopolycarboxylate iron (II)
I), hydrogen peroxide, persulfate and the like are preferable from the viewpoint of rapid processing and prevention of environmental pollution. The pH of the bleaching solution or bleach-fixing solution using these iron (III) aminopolycarboxylates is 3
-8, preferably 5-7. The pH of the bleaching solution using persulfate or hydrogen peroxide is used at 4 to 11, preferably 5 to 10.

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

Regarding the accelerator for persulfuric acid bleaching, see JP-A-6
-214365 (European Patent No. 602600A1)
A complex salt of the described iron (III) ion with 2-pyridinecarboxylic acid or 2,6-pyridinedicarboxylic acid is effective. Regarding the hydrogen peroxide bleaching accelerator, see JP-B-61-1.
The metal salts of organic acids described in Nos. 6067 and 61-19024 are effective.

The bleaching solution, the bleach-fixing solution and the fixing solution include a rehalogenating agent such as ammonium bromide and ammonium chloride, ammonium nitrate, acetic acid, boric acid, citric acid or a salt thereof, tartaric acid or a salt thereof, succinate or a salt thereof. Known additives such as salts, pH buffers such as imidazole, and metal corrosion inhibitors such as ammonium sulfate can be used. In particular, it is preferable to contain an organic acid in order to prevent bleaching stain. The organic acid is a compound having an acid dissociation constant (pKa) of 2 to 7, specifically, acetic acid,
Succinic acid, citric acid, propionic acid and the like are preferred.

Examples of the fixing agent used in the fixing solution or the bleach-fixing solution include thiosulfates, thiocyanates, thioureas, large amounts of iodides, and JP-A-4-365037, page 11 to
21 and 5-66540, pp. 1088-1092, nitrogen-containing heterocyclic compounds having a sulfide group, mesoionic compounds, and thioether compounds. Of these, thiosulfates are generally used, and ammonium thiosulfate is most widely used.
It is also preferable to use a combination of a thiosulfate with a thiocyanate, a thioether compound, a thiourea, a mesoionic compound, or the like.

As a preservative of the fixing solution or the bleach-fixing solution, a sulfite, a bisulfite, a carbonyl bisulfite adduct or a sulfinic acid compound described in EP-A-294769A is preferable. Furthermore, various aminopolycarboxylic acids and organic phosphonic acids (eg, 1-hydroxyethylidene-1,1-1-) are added to the fixing solution, the bleaching solution and the bleach-fixing solution for the purpose of stabilizing the solution.
Diphosphonic acid, N, N, N ', N'-ethylenediaminetetraphosphonic acid, 2-phosphonobutane-1,2,4-
It is preferred to add tricarboxylic acid) sodium stannate.

The fixing solution and the bleach-fixing solution further contain various fluorescent whitening agents, defoamers, surfactants, polyvinylpyrrolidone,
Methanol or the like can be contained.

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. The replenishment amount is preferably smaller, but 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 generally undergoes a washing step after desilvering. When the stabilization treatment is performed, the washing step may be omitted. In such a stabilization process, JP-A-57-8543 and JP-A-58-1483 are used.
Nos. 4 and 60-220345, and JP-A-5-220345.
8-127926, 58-13837, 58
All known methods described in JP-A-140741 can be used. Further, a washing-stabilizing step may be performed in which a stabilizing bath containing a dye stabilizer and a surfactant, which is typified by processing of a color light-sensitive material for photography, is used as a final bath.

The washing solution and the stabilizing solution include hard water softeners such as sulfite, inorganic phosphoric acid, polyaminocarboxylic acid and organic aminophosphonic acid, metal salts such as Mg salt, Al salt and Bi salt, and surfactants. Agents, hardeners, pH buffers, optical brighteners, silver salt-forming agents such as nitrogen-containing heterocyclic compounds, and the like can be used. Examples of the dye stabilizer of the stabilizing solution include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine and aldehyde sulfite adducts.

The pH of the washing and 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.

The amount of washing water and / or stabilizing solution can be set in a wide range depending on various conditions.
15 to 360 ml per ² is preferable, and 25 to 120 m
l is more preferred. In order to reduce the amount of replenishment water, it is preferable to use a plurality of tanks and carry out a multi-stage countercurrent system. In particular, it is preferable to use 2 to 5 tanks. In order to prevent the propagation of bacteria which occur when the amount of water is reduced and the contamination of the resulting suspended matter to the photosensitive material, isothiazolone compounds, siapentazoles, and chlorinated compounds described in JP-A-57-8542 are used. Fungicides such as sodium isocyanurate, other benzotriazoles, etc., by Hiroshi Horiguchi, "The Chemistry of Fungicides and Fungicides" (1986, Sankyo Publishing), edited by the Society of Sanitary and Fungicides, "Sterilization, Sterilization, and Fungicide Technology for Microorganisms". (1982, Industrial Technology Association), the bactericide described in "Encyclopedia of Fungicides and Fungicides" edited by the Japan Society of Fungicides and Fungi (1986). The method of reducing Mg and Ca ions described in JP-A-62-288838 is also particularly preferably used.

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

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

In the present invention, it is preferable that the stirring is strengthened as much as possible. Specific methods for strengthening the stirring are described in JP-A-62-183460 and JP-A-62-183.
No. 461, a method of impinging a jet jet of a processing liquid on an emulsion surface of a light-sensitive material, a method of increasing stirring efficiency by using a rotating means disclosed in JP-A-62-183461, and a wiper blade provided in a liquid. A method in which the photosensitive material is moved while bringing the emulsion surface into contact with the emulsion surface to make the emulsion surface turbulent, thereby improving the stirring effect, and a method of increasing the circulation flow rate of the entire processing solution. Such a stirring improving means is useful in any of a developing solution, a bleaching solution, a bleach-fixing solution, a stabilizing solution, and washing with water. These methods are effective in that the supply of the effective component in the liquid into the photosensitive material and the diffusion of the unnecessary component in the photosensitive material are promoted.

In the present invention, the liquid opening ratio [air contact area (cm ² ) / liquid volume (cm ³ )] of any bath shows excellent performance in any state, but from the viewpoint of stability of liquid components. The liquid aperture ratio is preferably from ⁰ to 0.1 cm ^-1 . In a continuous process, 0.001 cm ^{-1 to} 0.0
5 cm ^-1 is preferable, and more preferably 0.002 to 0.1 cm.
03 cm ^-1 .

The automatic developing machine used for the light-sensitive material of the present invention is described in JP-A-60-191257 and JP-A-60-19125.
No. 8, No. 60-191259. Such a transport means can significantly reduce the carry-in of the processing solution from the pre-bath to the post-bath,
The effect of preventing performance deterioration of the processing liquid is high. Such an effect is effective in shortening the processing time of each step and in reducing the amount of processing replenishment. In order to shorten the processing time, it is preferable to shorten the crossover time (air time). For example, FIG. 4, FIG. The method of transporting between the processes described in 5 through a blade having a shielding effect is preferable. Further, when the respective processing liquids are concentrated by evaporation in the continuous processing, it is preferable to correct the concentration by adding water.

The processing time of the process in the present invention means the required time from the start of processing of the photosensitive material in one step to the start of processing in the next step. The actual processing time in an automatic developing machine is usually determined by the linear velocity and the capacity of the processing bath.
000 mm / min. In particular, in the case of a small developing machine, the speed is preferably 500 to 2500 mm / min. The entire processing step, that is, the processing time from the development step to the drying step is preferably 360 seconds or less, more preferably 120 seconds or less, and particularly preferably 3 seconds or less.
Preferably, it is used for 0 to 90 seconds. Here, the processing time is the time from when the photosensitive material is immersed in the developing solution to when it comes out of the drying unit of the processor.

[0257]

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

Example 1 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 be coated with the emulsion layer, a molten polyethylene containing surface-treated anatase-type titanium oxide dispersed at a content of 15% by weight was laminated to produce 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 (Y-1), 6.68 g of color developing agent (1), 3.33 of high boiling organic solvent (DBP)
g and 1.67 g of a high boiling point organic solvent (DNP) were added and dissolved in 60 ml of ethyl acetate, and this solution was dissolved in a 10% aqueous gelatin solution containing 7 ml of a 20% surfactant (SU-1).
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 to seventh layers were prepared in the same manner as the coating solution for the first layer so that the coating amounts were as shown in Tables 1 and 2.

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

[0262]

[Table 1]

[0263]

[Table 2]

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 DOP: dioctyl phthalate DIDP: di-i-decyl phthalate PVP: polyvinylpyrrolidone H-1: tetrakis (vinylsulfonylmethyl) methane H-2 : 2,4-dichloro-6-hydroxy-s-triazine sodium HQ-2: 2,5-di-sec-dodecylhydroquinone HQ-3: 2,5-di-sec-tetradecylhydroquinone HQ-4: 2 -Sec-dodecyl-5-sec-tetradecylhydroquinone HQ-5: 2,5-di [(1,1-dimethyl-4-hexyloxycarbonyl) butyl] hydroquinone

[0265]

Embedded image

[0266]

Embedded image

[0267]

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(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) 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.
As in the case of -1, the average particle size is 0.64 μm, and the variation coefficient is 0.
07, a monodispersed cubic emulsion EMP-1B having 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 (green-sensitive silver halide emulsion Preparation) (Solution A) and (Solution B)
The average particle diameter 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 stability 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 diameter 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 In the red-sensitive emulsion, SS-1 was used per mole of silver halide. 2.0 × 10 ^{-3 was} added.

[0278]

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[0279]

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The light-sensitive material prepared as described above was used for Sample 1
01.

Next, Sample 102 was prepared in exactly the same manner as in Sample 101, except that the color developing agent and coupler were replaced with the color developing agent and coupler shown in Table 3 in equimolar amounts.

These samples were subjected to light wedge exposure (blue light exposure for yellow image evaluation, green light exposure for magenta image evaluation, and red light exposure for cyan image evaluation) by a conventional method, followed by development processing described below. A development process was performed by the process.

Processing step Processing temperature Time Color development 40.0 ± 0.3 ° C. 30 seconds Bleaching and fixing 40.0 ± 0.5 ° C. 45 seconds Rinse room temperature 30 seconds Alkaline processing room temperature 30 seconds Drying 60-80 ° C. The composition of the developing solution for 30 seconds is shown below.

Color developer Water 600 ml Potassium phosphate 40 g KCl 5 g Hydroxyethylidene-1,1-disulfonic acid (30%) 4 ml Add water 1000 ml pH (25 ° C./potassium hydroxide) 12 Bleaching fixer water 600 ml Ammonium thiosulfate ( (700 g / l) 93 ml Ammonium iron (III) ethylenediaminetetraacetate 55 g Ethylenediaminetetraacetic acid 2 g Nitric acid (67%) 30 g pH (at 25 ° C./acetic acid and ammonium water) 5.8 Rinse liquid 0.02 g chlorinated sodium isocyanurate Deionized water (dielectric constant 5 μm / cm or less) 1000 ml pH 6.5 Alkaline treatment liquid 800 ml Potassium carbonate 30 g Add water 1000 ml pH (with 1N sulfuric acid or 1N potassium hydroxide) 10 Use the sample after treatment Rating It was.

<< Dmax >> The maximum color density was measured with blue light, green light and red light.

<< Color Reproducibility >> First, a color checker manufactured by Macbeth Co., Ltd. was photographed using a color negative film (Konica Color JX-400: manufactured by Konica Corporation) and a camera (Konica FT-1MOTOR: manufactured by Konica Corporation). . Subsequently, color negative development processing (CNK-4: Konica Corporation)
Manufactured by the Konica Color Printer CL-P2000 (manufactured by Konica Corporation). Prints were made on 101 and 102 to a size of 82 mm × 117 mm, and practical prints were obtained in the same manner as described above.
Printer conditions at the time of printing were set for each sample so that the gray on the color checker became gray on the print. The obtained practical prints were visually evaluated for color reproducibility.

The results are shown in Table 3.

[0288]

[Table 3]

As is clear from Table 3, Sample 102 using the combination of the color developing agent of the present invention and a coupler was used.
Is yellow, magenta,
It can be seen that both the cyan density and the maximum color density are high.
Further, it can be seen that the sample 102 of the present invention has good color reproducibility for all of blue, green and red.

Example 2 In the sample 101 of Example 1, the blue light-sensitive silver halide emulsion of the first layer was 0.026 g / m ² , and the green light-sensitive silver halide emulsion of the third layer was 0.014 g / m 2. ^2. The red-sensitive silver halide emulsion of the fifth layer was 0.021 g / m ^2, and the coupler of the red-sensitive layer was EC-2 having the following structure in an equimolar amount to EC-1.
Sample 101 except that the coupler in the green sensitive layer was changed to EM-2 having the following structure in an equimolar amount to EM-1 and the coupler in the blue sensitive layer was changed to EY-2 in the following structure having an equimolar amount to EY-1. A sample 201 was produced in exactly the same manner as described above.

[0291]

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Next, Sample 202 was prepared in exactly the same manner as in Sample 201 except that the color developing agent and coupler in Sample 201 were replaced with the color developing agent and coupler shown in Table 4 in equimolar amounts.

After exposing these samples in the same manner as in Example 1, the samples were treated with the following processing solutions using the following processing solutions.

Processing Step Processing Temperature Amplification Developer (CDA-1) 33.0 ± 0.5 ° C. 60 seconds, 70 seconds Bleaching / Fixing Solution (BF-1) 35.0 ± 0.5 ° C. 20 Second stabilizing solution 30-34 ° C 60 seconds Drying 60-80 ° C 30 seconds The composition of the processing solution is shown below.

Amplification developer (CDA-1) Pure water 800 ml Potassium bromide 0.001 g Potassium chloride 0.35 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 4 0.0 g N, N-diethylhydroxylamine 4.7 g Diethylenetriaminepentaacetic acid sodium salt 2.0 g 1-hydroxyethylidene-1,1'-diphosphonic acid 0.35 g Fluorescent whitening agent (4,4'-diaminostilbene disulfonic acid derivative 2.0 g Potassium carbonate 20 g Hydrogen peroxide (30%) 5.0 g Add water to make the total volume 1 liter, and adjust to pH = 10.3.

Bleaching-fixing solution (BF-1) Pure water 700 ml Diethylenetriaminepentaacetate ammonium ferric dihydrate 65 g Diethylenetriaminepentaacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml 2-amino-5-mercapto-1,3,4 -Thiadiazole 2.0 g Ammonium sulfite (40% aqueous solution) 27.5 ml Add water to make the total volume 1 liter, and adjust the pH to 5.0 with potassium carbonate or glacial acetic acid.

Stabilizing liquid Pure water 800 ml o-phenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4-isothiazolin-3-one 0.02 g diethylene glycol 1 0.0 g fluorescent whitening agent (Tinopearl SFP) 2.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 1.8 g bismuth chloride (45% aqueous solution) 0.65 g magnesium sulfate heptahydrate 0.2 g PVP (polyvinylpyrrolidone) 1.0 g ammonia water (25% aqueous solution of ammonium hydroxide) 2.5 g nitrilotriacetic acid / trisodium salt 1.5 g Water was added to make the total volume 1 liter, and the pH was adjusted to 7.5 with sulfuric acid or ammonia water. .

Using the sample after the treatment, D
The evaluation was performed for max and color reproducibility. Table 4 shows the results.

[0299]

[Table 4]

As is clear from Table 4, Sample 202 using the combination of the color developing agent of the present invention and a coupler was used.
Is compared with the comparative sample 201, yellow, magenta,
It can be seen that both the cyan density and the maximum color density are high.
Further, it can be seen that the sample 202 of the present invention has good color reproducibility for all of blue, green and red.

Example 3 Preparation of Magnetic Recording Medium << Preparation of Support >> 0.1 part by weight of calcium acetate hydrate as a transesterification catalyst was added to 100 parts by weight of dimethyl 2,6-naphthalenedicarboxylate and 60 parts by weight of ethylene glycol. After the addition, a transesterification reaction was carried out according to a conventional method.
To the obtained product, 0.05 parts by weight of antimony trioxide,
0.03 parts by weight of trimethyl phosphate was added.
Then, gradually raise the temperature and reduce the pressure, 290 ° C, 0.05 mm
Polymerization was performed under the conditions of Hg to obtain polyethylene-2,6-naphthalate having an intrinsic viscosity of 0.60.

This was vacuum-dried at 150 ° C. for 8 hours, melt-extruded in a layer form from a T-die at 300 ° C., brought into close contact with a cooling drum at 50 ° C. while applying static electricity, cooled and solidified, and an unstretched sheet was obtained. Obtained. This unstretched sheet was stretched 3.3 times in the machine direction at 135 ° C. using a roll-type longitudinal stretching machine.

The obtained uniaxially stretched film was stretched in a first stretching zone at 145 ° C. by 50% of the total transverse stretching ratio using a tenter type transverse stretching machine, and further at a second stretching zone at 155 ° C. at a total transverse stretching ratio of 3. The film was stretched three times. Then 10
Heat treated at 0 ° C for 2 seconds, and further heat-fixed zone 200 ° C
For 5 seconds and a second heat setting zone at 240 ° C. for 15 seconds. Next, the film was gradually cooled to room temperature over 30 seconds while relaxing in a transverse direction by 5% to obtain a polyethylene naphthalate film having a thickness of 85 μm.

This is wound around a stainless steel core and
A heat treatment (annealing treatment) was performed at 10 ° C. for 48 hours to produce a support.

On both sides of the support, 12 W / m ² / min
Of the undercoating coating solution B-1
Is applied to a dry film thickness of 0.4 μm, and 1
A 2 W / m ² / min corona discharge treatment was applied, and the undercoat coating solution B-2 was applied so as to have a dry film thickness of 0.06 μm.

On the other surface subjected to the corona discharge treatment of 12 W / m ² / min, the undercoating coating solution B-3 was dried to a thickness of 0.
2 μm, and 12 W / m ² / m
An in-corona discharge treatment was performed, and a coating solution B-4 was applied so as to have a dry film thickness of 0.2 μm.

Each of the layers was dried at 90 ° C. for 10 seconds after the application, and after the four layers were applied, heat-treated at 110 ° C. for 2 minutes, and then cooled at 50 ° C. for 30 seconds.

<Undercoat Coating Solution B-1> A copolymer latex liquid of 30% by weight of butyl acrylate, 20% by weight of t-butyl acrylate, 25% by weight of styrene and 25% by weight of 2-hydroxyethyl acrylate (solid content: 30% 125 g Compound (UL-1) 0.4 g Hexamethylene-1,6-bis (ethylene urea) 0.05 g Finish with water 1000 ml <Subbing coating solution B-2> Hydroxidation of styrene-maleic anhydride copolymer Sodium aqueous solution (solid content 6%) 50 g Compound (UL-1) 0.6 g Compound (UL-2) 0.09 g Silica particles (average particle size 3 μ) 0.2 g Finish with water 1000 ml <Coating solution B-3> Butyl 30% by weight of acrylate, 20% by weight of t-butyl acrylate, 25% by weight of styrene and 25 of 2-hydroxyacrylate The amount% of copolymer latex solution (solid content 30%) 50 g Compound (UL-1) 0.3 g Hexamethylene-1,6-bis (ethyleneurea) 1000 ml finish in 1.1g water

[0309]

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<Coating Solution B-4> 60 mol% of dimethyl terephthalate, 30 mol% of dimethyl isophthalate, 10 mol% of sodium salt of dimethyl 5-sulfoisophthalate, 50 mol% of ethylene glycol as a glycol component, Diethylene glycol 50 mol%
Was copolymerized by a conventional method. The copolymer was stirred in hot water at 95 ° C. for 3 hours to obtain a 15% by weight aqueous dispersion A.

Water dispersion of tin oxide-antimony oxide composite fine particles (average particle size: 0.2 μm) (solid content: 40% by weight) 109 g Water dispersion A 67 g Finished with water 1000 ml << Coating of magnetic recording layer >> Undercoat layer B of treated support
4 On the layer coated with the coating solution, a magnetic recording layer coating solution having the following composition was dried with a precision extrusion coater to a dry film thickness of 0.
The coating was applied so as to have a thickness of 8 μm, and at the same time as drying, the magnetic substance was oriented in the application direction in an orientation magnetic field while the coating film was not dried, thereby achieving high output during magnetic recording and reproduction.

[Composition and Preparation of Magnetic Recording Layer Coating Solution M-1] Cobalt-containing gamma iron oxide (average major axis length 0.12 μm, minor axis length 0.015 μm, Fe ²⁺ / Fe ³⁺ = 0.2, Specific surface area 40 m ² / g, Hc = 750 Oe) 10 parts by weight Alumina (α-Al ₂ O ₃ , average particle size 0.2 μm) 3 parts by weight Diacetyl cellulose (manufactured by Teijin Limited) 150 parts by weight Polyurethane (N3132, Japan Polyurethane Co., Ltd. 15 parts by weight Stearic acid 2 parts by weight Cyclohexanone 920 parts by weight Acetone 920 parts by weight After thoroughly mixing and dispersing the above, and then dispersing with a sand mill, Coronate-3041 of polyisocyanate (manufactured by Nippon Polyurethane Co., Ltd., solid (50% by weight), and then sufficiently stirred and mixed to obtain a magnetic coating material M-1.

<< Application of Lubricating Layer >> A lubricant coating liquid (wax liquid described below) was prepared by dispersing a carnauba wax on the magnetic recording layer so as to contain 0.1% of carnauba wax in a water / methanol mixed solution. Was applied so that the coating weight of was 15 mg / m ² . The raw material after the wax application was passed through a heat treatment zone at 100 ° C. for 5 minutes to dry, and then left in an oven at 40 ° C. for 5 days to sufficiently perform a crosslinking reaction of isocyanate.

(Preparation of Wax Liquid) Polyoxyethylene lauryl ether 4 was added to 100 parts by weight of water heated to 90 ° C.
Parts by weight, and 40 parts by weight of carnauba wax separately melted at 90 ° C. were added thereto, followed by sufficiently stirring using a high-speed stirring homogenizer to prepare a carnauba wax dispersion liquid (WAX1). .

Next, 995 parts by weight of water, 900 parts by weight of methanol and propylene glycol monomethyl ether 10
0 parts by weight, and 5 parts by weight of WAX1 was added thereto.
By stirring, a wax liquid was prepared.

On the side of the magnetic recording medium opposite to the magnetic recording layer side, a photographic component layer having the following composition was provided.
01. The addition amount is expressed in grams per 1 m ^2.
However, silver halide and colloidal silver were converted to the amount of silver, and sensitizing dyes (indicated by SD) were shown in moles per mole of silver.

First Layer (Antihalation Layer) Black Colloidal Silver 0.16 UV-1 0.3 OIL-1 0.044 Gelatin 1.33 Second Layer (Intermediate Layer) Polyethylacrylate Latex 0.20 Gelatin 1. 40 Third layer (low-sensitivity red-sensitive layer) Silver iodobromide a 0.12 Silver iodobromide b 0.50 SD-1 3.0 × 10 ^-5 SD-4 1.5 × 10 ^-4 SD -3 3.0 × 10 ^-4 SD-6 3.0 × 10 ^-6 EC-3 0.51 Color developing agent (1) 0.54 OIL-2 0.45 Gelatin 1.40 4th layer (medium sensitivity) Red-sensitive layer) Silver iodobromide c 0.64 SD-1 3.0 × 10 ^-5 SD-2 1.5 × 10 ^-4 SD-3 3.0 × 10 ^-4 EC-3 0.22 Color developing agent (1) 0.28 OIL-2 0.21 Gelatin 0.87 Fifth layer (high-sensitivity red-sensitive layer) Silver iodobromide c 0.13 silver iodobromide d 1.14 SD-1 3.0 × 10 ^-5 SD-2 1.5 × 10 ^-4 SD-3 3.0 × 10 ^-4 EC-3 0.169 Color development Active agent (1) 0.20 OIL-2 0.23 Gelatin 1.23 6th layer (intermediate layer) Polyethyl acrylate latex 0.23 Gelatin 1.00 7th layer (Low sensitivity green color sensitive layer) Iodobromide Silver a 0.245 Silver iodobromide b 0.105 SD-6 5.0 × 10 ^-4 SD-5 5.0 × 10 ^-4 EM-3 0.21 Color developing agent (1) 0.23 OIL- 1 0.25 Gelatin 0.98 Eighth layer (medium-speed green-sensitive layer) Silver iodobromide e 0.87 SD-7 3.0 × 10 ^-4 SD-8 6.0 × 10 ^-5 SD- 9 4.0 × 10 ^-5 EM-3 0.17 Color developing agent (1) 0.20 OIL-1 0.29 Gelatin 1.43 Ninth layer (high sensitivity green feeling Color layer) Silver iodobromide f 1.19 SD-7 4.0 × 10 ^-4 SD-8 8.0 × 10 ^-5 SD-9 5.0 × 10 ^-5 EM-3 0.09 Color development Active agent (1) 0.12 OIL-1 0.11 gelatin 0.78 10th layer (yellow filter layer) Yellow colloidal silver 0.05 polyethyl acrylate latex 0.20 gelatin 1.00 11th layer (low sensitivity blue feeling) Color layer) Silver iodobromide g 0.29 Silver iodobromide h 0.19 SD-10 8.0 × 10 ^-4 SD-11 3.1 × 10 ^-4 EY-3 0.91 Color developing agent ( 1) 0.90 OIL-1 0.37 Gelatin 1.29 12th layer (high-sensitivity blue-sensitive layer) Silver iodobromide h 0.13 Silver iodobromide i 1.00 SD-10 4.4 × ^{10 -4 SD-11 1.5 × 10} -4 EY-3 0.48 color developing agent (1) 0.49 OIL-1 0 . 1 gelatin 1.55 thirteenth layer (first protective layer) silver iodobromide j 0.30 UV-1 0.055 UV-2 0.110 OIL-2 0.63 gelatin 1.32 14th layer (second Protective layer) PM-1 0.15 PM-2 0.04 WAX-1 0.02 D-1 0.001 Gelatin 0.55 In addition to the above composition, coating aids SU-1 and SU-
2, SU-3, dispersing aid SU-4, viscosity modifier V-1,
Stabilizers ST-1, ST-2, antifoggant AF-1 (weight average molecular weight: 10,000, AF-2 weight average molecular weight: 1,100,000), suppressors AF-3, AF-
4, AF-5, hardeners H-1 and H-2 were added.

The structure of the compound used in the above sample is shown below.

Table 5 shows the characteristics of the silver iodobromide.

[0320]

[Table 5]

[0321]

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[0322]

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[0323]

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[0324]

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[0325]

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[0326]

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Incidentally, as a preferred example of forming silver halide grains of the present invention, a production example of silver iodobromide d and f will be shown below.

Preparation of Seed Crystal Emulsion-1 A seed crystal emulsion was prepared as follows.

JP-B-58-58288, 58-58
No. 289, a silver nitrate aqueous solution (1.161 mol) was added to the following solution A1 adjusted to 35 ° C.
And a mixed aqueous solution of potassium bromide and potassium iodide (potassium iodide 2 mol%) while maintaining the silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) at 0 mV. For 2 minutes to form nuclei. Subsequently, the temperature of the solution was raised to 60 ° C. over a period of 60 minutes, the pH was adjusted to 5.0 with an aqueous solution of sodium carbonate, and then an aqueous solution of silver nitrate (5.902 mol), potassium bromide and iodide were added. A mixed aqueous solution of potassium (2 mol% of potassium iodide) was added over 42 minutes by a double jet method while keeping the silver potential at 9 mV. After the addition was completed, the temperature was lowered to 40 ° C., and desalting and washing were immediately performed using a normal flocculation method.

The resulting seed crystal emulsion had an average sphere-equivalent diameter of 0.24 μm, an average aspect ratio of 4.8, and a maximum side ratio of 1.0% or more of 90% or more of the total projected area of silver halide grains.
~ 2.0 hexagonal tabular grains.
This emulsion is referred to as seed emulsion-1.

[Solution A1] Ossein gelatin 24.2 g Potassium bromide 10.8 g HO (CH ₂ CH ₂ O) _m (CH (CH ₃ ) CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) (10% ethanol solution 6.78 ml 10% nitric acid 114 ml H ₂ O 9657 ml Preparation of silver iodide fine grain emulsion SMC-1 6.0% by weight gelatin aqueous solution containing 0.06 mol of potassium iodide 5 Liters with vigorous stirring.
2 liters of an aqueous silver nitrate solution and 2 liters of a 7.06 mol aqueous potassium iodide solution were added over 10 minutes. During this time, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the particles are prepared, the pH is adjusted using an aqueous sodium carbonate solution.
Was adjusted to 5.0. The average particle size of the obtained silver iodide fine particles was 0.05 μm. This emulsion is designated as SMC-1.

Preparation of silver iodobromide d Seed emulsion-1 equivalent to 0.178 mol and HO (CH ₂ CH ₂
O) _m (CH (CH ₃ ) CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n
H (m + n = 9.77) in 10% ethanol solution 0.5
4.5% by weight of an aqueous inert gelatin solution 70
0 ml at 75 ° C., pAg 8.4, pH 5.0.
Then, particles were formed by the simultaneous mixing method with vigorous stirring by the following procedure.

1) A 2.1 mol aqueous solution of silver nitrate and 0.19
5 mol of SMC-1 and an aqueous solution of potassium bromide were added to pA
g while maintaining the pH at 8.4 and the pH at 5.0.

2) Subsequently, the temperature of the solution was lowered to 60 ° C., and pAg
Was adjusted to 9.8. Then, 0.071 mol of SMC
-1 was added and aging was performed for 2 minutes (introduction of dislocation lines).

3) 0.959 mol silver nitrate aqueous solution and 0.1 mol
03 mol of SMC-1 and an aqueous solution of potassium bromide were added to p
Ag was added at 9.8 and the pH was maintained at 5.0.

Each solution was added at an optimum rate throughout the particle formation so as to prevent the formation of new nuclei and the Ostwald ripening between particles from proceeding. After completion of the addition, the resultant was subjected to a water washing treatment at 40 ° C. using a normal flocculation method, and then gelatin was added and redispersed to adjust the pAg to 8.1 and the pH to 5.8.

The obtained emulsion had a particle size (cubic 1 of the same volume).
The emulsion was composed of tabular grains having a halogen composition of 0.75 μm in side length, an average aspect ratio of 5.0, and a halogen composition of 2 / 8.5 / X / 3 mol% (X is a dislocation line introduction position) from the inside of the grains. . When this emulsion was observed with an electron microscope, five or more dislocation lines were observed both in the fringe portion and in the inside of the grain in 60% or more of the total projected area of the grain in the emulsion. The surface silver iodide content was 6.7 mol%.

Preparation of silver iodobromide f In the preparation of silver iodobromide d, pAg was adjusted to 8.8 in step 1).
8, and silver iodobromide f was prepared in exactly the same manner as silver iodobromide d except that the amount of silver nitrate added in step 3) was 0.92 mol and the amount of SMC-1 was 0.069 mol. .

The emulsion obtained had a particle size (cubic 1 of the same volume).
Edge length) 0.65 μm, average aspect ratio 6.5, silver iodide content 2 / 8.5 / X / 7 mol% in order from the inside of the grain
The emulsion was composed of tabular grains having a halogen composition of (X is a dislocation line introduction position). When this emulsion was observed with an electron microscope, five or more dislocation lines were observed both in the fringe portion and in the inside of the grain in 60% or more of the total projected area of the grain in the emulsion. The surface silver iodide content was 11.9 mol%.

After the above-mentioned sensitizing dyes were added to each of the above emulsions and ripened, triphosphine selenide, sodium thiosulfate, chloroauric acid and potassium thiocyanate were added, and the fog and sensitivity were optimized according to a conventional method. Chemical sensitization was applied to obtain.

Silver bromoiodides a, b, c, e, g, h, and i were also subjected to spectral sensitization and chemical sensitization in accordance with d and f described above.

Next, Sample 302 was prepared in exactly the same manner as in Sample 301 except that the color developing agent and coupler were replaced with the color developing agent and coupler shown in Table 6 in equimolar amounts.

After exposing these samples in the same manner as in Example 1, the samples were processed in the following processing steps using the following developing solution.

(Processing Step) Process Processing time Processing temperature Color development 120 seconds 38 ° C. Bleaching 90 seconds 38 ° C. Fixing 120 seconds 38 ° C. Stable (1) 30 seconds 38 ° C. stable (2) 30 seconds 38 ° C. stable (3) ) 30 seconds 38 ° C. Drying 90 seconds 60 ° C. * The stability was a countercurrent method from (3) to (1).

The composition of the processing solution is shown below.

(Color developing solution) 30 g of tripotassium phosphate 0.1 g of 5-nitrobenzotriazole 0.1 g of disodium-N, N-bis (sulfonatoethyl) hydroxylamine 3.3 g of potassium chloride 10 g of hydroxyethylidene-1,1-diphosphone Acid (30% solution) 4 ml 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 1.5 g Add water 1.0 liter pH (adjusted with potassium hydroxide and sulfuric acid) 12.00 (bleach Liquid) Ammonium ferric 1,3-diaminopropanetetraacetate-hydroxide 140 g 1,3-Diaminopropanetetraacetic acid 3 g Ammonium bromide 80 g Ammonium nitrate 15 g Hydroxyacetic acid 25 g Acetic acid (98%) 40 g Add water 1.0 L pH (adjusted with aqueous ammonia and acetic acid) 4.3 (Fixing solution Ethylenediaminetetraacetic acid disodium salt 15 g Ammonium sulfite 19 g Imidazole 15 g Ammonium thiosulfate (70 wt%) 280 ml Add water 1.0 liter pH (adjusted with ammonia water and acetic acid) 7.4 (Stabilized solution) p-toluenesulfinic acid Sodium 0.03 g Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.2 g Ethylenediaminetetraacetic acid disodium salt 0.05 g 1,2,4-triazole 1.3 g 1,4-bis (1 , 2,4-triazol-1-ylmethyl) piperazine 0.75 g Water was added and 1.0 liter pH (adjusted with ammonia water and acetic acid) 9.5 Dmax in the same manner as in Example 1 using the sample after the treatment. Was evaluated. Table 6 shows the results.

[0347]

[Table 6]

As is clear from Table 6, Sample 302 using the combination of the color developing agent of the present invention and a coupler was used.
Is yellow, magenta,
It can be seen that both the cyan density and the maximum color density are high.

[0349]

According to the present invention, it is possible to provide a silver halide color photographic light-sensitive material which is excellent in color developability and can provide a dye image having good color reproducibility. Further, by processing such a silver halide color photographic light-sensitive material with a developing solution containing no aromatic primary amine, a silver halide color photographic light-sensitive material capable of forming an image gently and quickly can be provided. .

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03C 7/384 G03C 7/384 7/407 501 7/407 501

Claims (6)

[Claims] 1. A silver halide color photographic light-sensitive material having a photographic component layer comprising a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support. At least one of the blue-sensitive silver halide emulsion layers contains at least one color developing agent represented by the following general formula [I] and at least one dye-forming coupler represented by the following general formula [II]. A silver halide color photographic light-sensitive material, characterized in that: Embedded image [Wherein, R ₁ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and L ₁ represents —SO
_2- , -CO-, -COCO-, -COO-, -CON
(R ₄ ) —, —COCO—, —COCON (R ₄ ) — or —SO ₂ N (R ₄ ) —. Where R ₄ is a hydrogen atom,
Represents an alkyl group or an aryl group. Y ₁ is an alkyl group,
—OR ₅ , —SO ₂ R ₆ , —SO ₂ NR ₇ R ₈ or a halogen atom. Here, R ₅ represents an alkyl group or an aryl group, R ₆ represents an alkyl group, R ₇ and R ₈ represent a hydrogen atom,
Represents an alkyl group or an aryl group. n1 represents 1 or 2. n1 two Y ₁ when 2 represent different groups. [Chemical formula 2] [In the formula, X ₁ represents —CN or —CONR ₉ R ₁₀ . Here, R ₉ and R ₁₀ represent a hydrogen atom, an alkyl group or an aryl group. J ₁ represents a hydrogen atom or a group which can be eliminated by reaction with an oxidized form of the color developing agent, and Z ₁ represents a hydrogen atom or a substituent. m represents an integer from 0 to 5, where m is 2
In the above case, a plurality of Z ₁ may be the same or different. ] 2. A silver halide color photographic light-sensitive material having a photographic component layer comprising a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support. At least one layer of the green-sensitive silver halide emulsion layer contains at least one color developing agent represented by the following general formula [III] and at least one dye-forming coupler represented by the following general formula [IV]. A silver halide color photographic light-sensitive material, characterized in that: Embedded image [Wherein, R ₂ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and L ₂ represents -SO
_2- , -CO-, -COCO-, -COO-, -CON
(R ₁₁ )-, -COCO-, -COCON (R ₁₁ )-
Or —SO ₂ N (R ₁₁ ) —. Here, R ₁₁ represents a hydrogen atom, an alkyl group or an aryl group. Y ₂ represents an alkyl group, —OR ₁₂ , —SO ₂ NR ₁₃ R ₁₄ or a halogen atom. Here, R ₁₂ represents an alkyl group or an aryl group, and R ₁₃ and R ₁₄ represent a hydrogen atom, an alkyl group or an aryl group. n2 represents an integer of 1 to 3, and when n2 is 2 or more, a plurality of Y ₂ represent different groups. [Formula 4] [In the formula, X ₂ represents a hydrogen atom or —SO ₂ NR ₁₅ R ₁₆ .
Here, R ₁₅ and R ₁₆ represent a hydrogen atom, an alkyl group or an aryl group. J ₂ represents a hydrogen atom or a group capable of leaving by reaction with an oxidized form of a color developing agent, and Z ₂ represents —NHSO ₂
It represents an R ₁₇ or -NHSO ₂ NR ₁₈ R _19. Here, R ₁₇ represents an alkyl group or an aryl group, and R ₁₈ and R ₁₉ represent a hydrogen atom, an alkyl group or an aryl group. ] 3. A silver halide color photographic light-sensitive material having a photographic component layer comprising a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support. At least one layer of the red-sensitive silver halide emulsion layer contains at least one color developing agent represented by the following general formula [V] and at least one dye-forming coupler represented by the following general formula [VI]. A silver halide color photographic light-sensitive material, characterized in that: Embedded image Wherein R ₃ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and L ₃ represents —SO
_2- , -CO-, -COCO-, -COO-, -CON
(R ₂₀ )-, -COCO-, -COCON (R ₂₀ )-
Or -SO ₂ N (R ₂₀₎ - represents a. Here, R ₂₀ represents a hydrogen atom, an alkyl group or an aryl group. Y ₃ represents an alkyl group, —OR ₂₁ , —SO ₂ R ₂₂ , —NO ₂ or —CN. Here, R ₂₁ represents an alkyl group or an aryl group;
₂₂ represents an alkyl group. and n3 represents 2 or 3, a plurality of Y ₃ represent different groups. [Formula 6] [In the formula, X ₃ represents a hydrogen atom or —SO ₂ NR ₂₃ R ₂₄ .
Here, R ₂₃ and R ₂₄ represent a hydrogen atom, an alkyl group or an aryl group. J ₃ represents a hydrogen atom or a group which can be eliminated by reaction with an oxidized form of a color developing agent, and Z ₃ represents —NHSO ₂
It represents an R ₂₅ or -NHSO ₂ NR ₂₆ R _27. Here, R ₂₅ represents an alkyl group or an aryl group, and R ₂₆ and R ₂₇ represent a hydrogen atom, an alkyl group or an aryl group. ] 4. A silver halide color photographic light-sensitive material comprising a support having thereon a photographic component layer comprising a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer. At least one of the blue-sensitive silver halide emulsion layers contains at least one color developing agent represented by the above general formula [I] and at least one dye-forming coupler represented by the above general formula [II]. And at least one of the green-sensitive silver halide emulsion layers, at least one of a color developing agent represented by the above general formula [III] and at least one of a dye-forming coupler represented by the above general formula [IV] And at least one of the red-sensitive silver halide emulsion layers contains at least one color developing agent represented by the above general formula [V] and a dye-forming coupler represented by the above general formula [VI]. Less of A silver halide color photographic light-sensitive material, characterized in that it contains at least one of the following. 5. A silver halide color photographic light-sensitive material, wherein an image is formed from the silver halide color photographic light-sensitive material according to claim 4 by an activator process. 6. An amplified image is formed by intensifying the silver halide color photographic light-sensitive material according to claim 4 with a liquid containing hydrogen peroxide or a compound that releases hydrogen peroxide. A silver halide color photographic light-sensitive material comprising: