JP2001092091A - Silver halide color photographic sensitive material and heat developable color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silver halide color photographic sensitive material which contains a developing agent and which can be dry-processed without using a liquid agent and a heat developable color photographic sensitive material and to also obtain a silver halide color photographic sensitive material and a heat developable color photographic sensitive material each having good preservability and good discrimination. SOLUTION: The silver halide color photographic sensitive material contains a color developing agent of formula I, e.g. formula II.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silver halide color photographic light-sensitive material containing a color developing agent, and more particularly to a silver halide color photographic light-sensitive material containing a specific color developing agent and a heat-developable color photographic light-sensitive material.

[0002]

2. Description of the Related Art Reduction in processing time of silver halide color photographic light-sensitive materials (hereinafter, also simply referred to as light-sensitive materials) has always been demanded since the development of the light-sensitive materials. This is a subject that can be said to be an eternal theme of photosensitive materials.

Various efforts have been made to shorten the processing time of photosensitive materials. On the other hand, the developer used for processing the photosensitive material is strongly alkaline, and its handling requires great care.

A photothermographic material has been proposed as a means for solving these problems at once. The photothermographic material is
This is revolutionary in that the processing time is short and there is no need to handle the developer. However, in the case of a photothermographic material which does not use a developing solution, it is necessary to add a developing agent or a substitute thereof in advance to the photosensitive material, which is technically extremely difficult. Development was awaited.

Examples of photosensitive materials containing a developing agent include p-phenylenediamine derivatives described in JP-A-62-227141, and JP-A-8-286340 and JP-A-8-286340.
A photosensitive material containing a hydrazine derivative described in No. 27131 can be cited, but it has a problem that a large increase in yellow stain during image storage and discrimination (discrimination ability) are not sufficiently satisfactory.

A so-called diffusion transfer type photosensitive material has been proposed in which a diffusible dye is formed and the dye is transferred to an image receiving layer to form an image. , The sharpness is inevitably reduced due to the lateral diffusion of the dye during the transfer process, the transferred dye image is re-transferred, and waste containing silver halide, a heavy metal, is generated. The problem is that the cost is high because a support is required for both the light-sensitive material layer and the image receiving layer.

A photosensitive material which generates a sublimable dye by thermal development and transfers the dye to an image receiving paper has also been proposed. However, with respect to waste containing sharpness and heavy metals, the same as the above-mentioned diffusion transfer type photosensitive material has been proposed. Had a problem.

In addition, any of these heat-developable light-sensitive materials incorporating a developing agent has poor storage stability, and in particular, has not been able to solve the fatal drawbacks such as an increase in fog during storage and a decrease in the maximum density. Has reached.

[0009]

Accordingly, the first aspect of the present invention is as follows.
An object of the present invention is to provide a silver halide color photographic light-sensitive material and a heat-developable color photographic light-sensitive material containing a specific developing agent which can be dry-processed without using a liquid agent. Second
An object of the present invention is to provide a silver halide color photographic light-sensitive material and a heat-developable color photographic light-sensitive material having good storage stability and good discrimination.

[0010]

The above object of the present invention is attained by the following constitutions.

1. A silver halide color photographic material comprising a color developing agent represented by the following general formula [I].

[0012]

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Wherein Ra ₁ and Ra ₂ are each an alkyl group,
Or an aryl group, Ra ₃ represents a hydrogen atom or a substituent, and n represents an integer of 1 to 2. When n is 2, Ra ₃ may be the same or different. Za ₁ and Za ₂ each represent a nitrogen atom or CRa ₄ , at least one of which is CRa ₄ . Ra ₄ has the same meaning as Ra ₃ , but at least one is a substituent capable of forming a hydrogen bond. Xa represents a non-metallic atomic group necessary for forming a 5- to 6-membered aromatic heterocyclic ring or aromatic ring together with Za ₁ , Za ₂ and carbon atoms adjacent thereto. However, when Xa is a hetero atom and has 5 members, Za ₁ and Za ₂ need not be nitrogen atoms. La is -SO ₂ -,
_{-CO -, - SO 2 N (} Ra 5) -, - COO -, - CO
Represents NH- or -P (= O) (Ra ₆ )-. Ra ₅ and Ra ₆ have the same meanings as Ra ₃ and Ra _4. Ya represents an alkyl group, an aryl group or a heterocyclic group.

2. A silver halide color photographic material comprising a color developing agent represented by the following general formula [II].

[0015]

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In the formula, Rb ₁ represents a hydrogen atom or a substituent. Rb ₂ represents a substituent capable of forming a hydrogen bond. Rb ₃ represents a hydrogen atom or a substituent capable of leaving under alkaline conditions. 1 is an integer of 0 to 3;
Represents an integer of 4. Lb is _{-SO 2 -, - CO -,} - SO 2
_{N (Rb 4) -, -} COO -, - CONH- , or -P
_{(= O) (Rb 5)} - represents a. Rb ₄ and Rb ₅ have the same meanings as Ra ₅ and Ra _6. Yb represents an alkyl group, an aryl group, or a heterocyclic group.

3. A silver halide color photographic material comprising a color developing agent represented by the following general formula [III]:

[0018]

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In the formula, Rc ₂ and Rc ₃ represent a hydrogen atom or a substituent. Rc ₁ represents a substituent capable of forming a hydrogen bond. Rc ₄ represents an alkyl group or an aryl group, respectively, and may combine with Rc ₃ to form a 5- or 6-membered ring. Lc is _{-SO 2 -, - CO -,} - SO 2 N (Rc 5)
-, -COO-, -CONH- or -P (= O) (Rc
₆ ) represents-. Rc ₅ and Rc ₆ have the same meaning as Ra ₅ and Ra ₆ . Yc represents an alkyl group, an aryl group or a heterocyclic group. Xc represents a nonmetallic atom group necessary for forming a 5- or 6-membered ring together with a nitrogen atom and a carbon atom, and may have a substituent.

4. A silver halide color photographic material comprising a color developing agent represented by the following general formula [IV]:

[0021]

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In the formula, Rd _{1 to} Rd ₄ represent a hydrogen atom or a substituent. Rd ₅ and Rd ₆ represent each an alkyl group, or an aryl group, the total number of carbon atoms in Rd ₅ and Rd ₆ is 5 to 13
It is. Further, it contains at least one hydroxyl group. Ld
It is _{-SO 2 -, - CO -,} - SO 2 N (Rd 7) -, - C
OO -, - CONH-, or _{-P (= O) (Rd 8} ) - represents a. Rd ₇ and Rd ₈ have the same meanings as Ra ₅ and Ra _6.
Yd represents an alkyl group, an aryl group, or a heterocyclic group.

5. A photosensitive silver halide, a binder, a coupler and a color developing agent represented by the general formula [I], [II], [III] or [IV] described in any one of the above 1 to 4 on a support A heat-developable color photographic light-sensitive material comprising at least one developing agent selected from the group consisting of:

Hereinafter, the present invention will be described in more detail.

In the general formula [I], Ra ₁ and Ra ₂ are an alkyl group or an aryl group. As the alkyl group, preferred are methyl, ethyl, propyl, butyl and the like. These may be further substituted, and preferred substituents include a hydroxyl group and a sulfonamide group. Preferably diethylamino among -NRa ₁ Ra _2, dibutylamino, N- hydroxyethyl -N- ethylamino, N- hydroxypropyl -N- ethylamino, N- methanesulfonamidoethyl -N- ethyl dialkylamino amino such Group.

The aryl group is preferably a phenyl group.

The substituents represented by Ra ₃ and Ra ₄ are not particularly limited, but are typically alkyl, aryl, alkoxy, aryloxy, anilino, acylamino,
Examples include sulfonamide, alkylthio, arylthio, alkenyl, and cycloalkyl groups.In addition, halogen atoms and cycloalkenyl, alkynyl,
Heterocyclic, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, acyloxy, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonyl, aryloxycarbonyl, phosphonylamide, hydroxy, heterocyclic thio, etc., And spiro compound residues, bridged hydrocarbon compound residues, and the like.

The alkyl group represented by Ra ₃ and Ra ₄ preferably has 1 to 16 carbon atoms, and may be linear or branched.

The aryl group represented by Ra ₃ and Ra ₄ is preferably a phenyl group.

Examples of the alkoxy groups represented by Ra ₃ and Ra ₄ include a methoxy group, an ethoxy group, an i-propyloxy group, a t-butoxy group and the like.

Examples of the aryloxy group represented by Ra ₃ and Ra ₄ include a phenoxy group and a naphthoxy group.

The acylamino group represented by Ra ₃ and Ra ₄ includes an alkylcarbonylamino group, an arylcarbonylamino group and the like.

Examples of the sulfonamide group represented by Ra ₃ and Ra ₄ include an alkylsulfonylamino group and an arylsulfonylamino group.

The alkyl and aryl components of the alkylthio and arylthio groups represented by Ra ₃ and Ra ₄ include the alkyl and aryl groups represented by Ra _{1 to} Ra ₄ .

The alkenyl group represented by Ra ₃ and Ra ₄ is preferably a group having 2 to 32 carbon atoms, and the cycloalkyl group is preferably a group having 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms. It may be a branch.

As the cycloalkenyl group represented by Ra ₃ and Ra ₄ , those having 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms, are preferred.

As the heterocyclic groups represented by Ra ₃ and Ra ₄ , those having a 5- to 7-membered heterocyclic ring are preferable, and specific examples include a 2-furyl group, a 2-pyrimidinyl group and a 2-benzothiazole group. Is mentioned.

The sulfonyl groups represented by Ra ₃ and Ra ₄ include an alkylsulfonyl group and an arylsulfonyl group; the sulfinyl groups include an alkylsulfinyl group;
An arylsulfinyl group or the like; an alkylphosphonyl group or an arylphosphonyl group as a phosphonyl group; an alkylcarbonyl group or an arylcarbonyl group as an acyl group; an alkylcarbamoyl group as a carbamoyl group;
Arylcarbamoyl group and the like; sulfamoyl group as alkylsulfamoyl group and arylsulfamoyl group and the like; acyloxy group as alkylcarbonyloxy group and arylcarbonyloxy group as imide group as succinimide group and 3-heptadecylsuccinyl group Acid imide group,
Phthalimido group, glutarimido group, etc .; ureido group is alkylureido group, arylureido group, etc .; heterocyclic thio group is preferably a 5- to 7-membered heterocyclic thio group, specifically 2-pyridylthio group, A benzothiazolylthio group or the like; a spiro compound residue such as spiro [3.
3] heptane-1-yl and the like; as bridged hydrocarbon compound residues, bicyclo [2.2.1] heptane-1-yl, tricyclo [1.3.13.17] decan-1-yl,
7,7-dimethyl-bicyclo [2.2.1] heptane-
1-yl and the like.

These groups are further represented by Ra ₃ and R
It may be substituted by a substituent of a _4. Among these, alkyl, aryl, alkoxy, hydroxy,
Aryloxy, acylamino, sulfonamide, alkylthio, arylthio, halogen atom, sulfonyl,
Each group such as sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, acyloxy, ureido, sulfamoylamino, alkoxycarbonyl, aryloxycarbonyl, and phosphonylamido is preferable, and a halogen atom, an alkyl group, an alkoxy group, an acylamino group, and a sulfonamide are preferred. Groups, carbamoyl groups, ureido groups, phosphonylamido groups, and hydroxy groups are more preferred.

At least one substituent is a substituent capable of forming a hydrogen bond, and examples thereof include hydroxy, hydroxyalkyl, acylamino, sulfonamide, carbamoyl, sulfamoyl, ureido, sulfamoylamino, and phosphonylamido.

The aromatic heterocyclic ring in the present invention is a ring having a hetero atom such as a nitrogen atom, a sulfur atom or an oxygen atom in the ring and having aromaticity. However,
When Xa is a 5-membered hetero atom, Za ₁ and Za ₂ need not be nitrogen atoms. Xa, Za _1, Za ₂ and pyridine as aromatic heterocyclic 5-6 membered formed at the carbon atom adjacent to them, pyrimidine, pyridazine, pyrazine, triazine, tetrazine, pyrrole, thiazole,
Rings such as oxazole, imidazole, thiadiazole and oxadiazole are exemplified. These rings are represented by R
It may be substituted by the substituents mentioned for a ₃ and Ra ₄ , and among them, a pyridine ring is preferable.

La is -SO _2- , -CO-, -SO ₂ N
_{(Ra 5) -, - COO} -, - CONH- , or -P (=
O) (Ra ₆₎ - represents a, preferably -SO ₂ - it is. Ra ₅ and Ra ₆ have the same meaning as Ra ₃ and Ra _4, and are preferably each group such as an alkyl group, an alkoxy group, an aryl group or an aryloxy group.

Ya represents an alkyl group, an aryl group, or a heterocyclic group, and specific examples include those represented by Ra ₃ and Ra _4. Preferably, the aryl group is an aryl group or a heterocyclic group. Most preferred.

In the general formula [II], Rb ₁ represents a hydrogen atom or a substituent, and has the same meaning as Ra ₃ and Ra ₄ . These groups may be further substituted by substituents of Ra ₃ and Ra ₄ . Among these, alkyl, aryl, alkoxy, hydroxy, aryloxy, acylamino, sulfonamide, alkylthio, arylthio, halogen atom, sulfonyl, sulfinyl, phosphonyl,
Acyl, carbamoyl, sulfamoyl, cyano, acyloxy, ureido, sulfamoylamino, alkoxycarbonyl, aryloxycarbonyl, phosphonylamido, etc. are preferred, and halogen, alkyl, alkoxy, acylamino, sulfonamido, carbamoyl, ureido Groups, phosphonylamido groups, hydroxy groups, alkylthio groups and the like are more preferred.

Rb ₂ represents a substituent capable of forming a hydrogen bond, and includes hydroxy, hydroxyalkyl, acylamino,
Sulfonamide, carbamoyl, sulfamoyl, ureido, sulfamoylamino, phosphonylamido groups are preferred. More preferred are acylamino, sulfonamide, ureido, hydroxy, and phosphonylamido groups.

Rb ₃ represents a hydrogen atom or a group capable of leaving under alkaline conditions.

The substituent which is eliminated under alkaline conditions represented by Rb ₃ represents a substituent which is eliminated by a hydrolysis reaction or a nucleophilic substitution reaction. The substituent which is eliminated by the hydrolysis reaction is, for example, alkyl. Examples thereof include a carbonyl group, an arylcarbonyl group, an alkylsulfonyl group, and an arylsulfonyl group, which may be further substituted by the substituents represented by Ra ₃ and Ra ₄ described above. Examples of the substituent which is eliminated by the nucleophilic substitution reaction include, for example, US Pat.
Substituents described in JP-A-10-612, for example, those represented by the general formula [A] or [B];
6564 and the like, and the transition state of the nucleophilic reaction preferably forms a 5- or 6-membered ring.

[0048]

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In the general formula [A] or [B], Re ₁ to
Re ₆ represents a hydrogen atom or a substituent and has the same meaning as Ra ₃ and Ra ₄ , but is preferably an alkyl group or an aryl group. Re ₁ and Re ₂ , Re ₃ or Re ₄ and Re ₅ or Re ₆ may be bonded to each other to form a 5- to 6-membered ring, and Re ₁ and Re ₂ may form a ring. preferable. R
e ₇ and Re ₈ represent a hydrogen atom, an alkyl group, an alkylamino group, or an amino group. Further, the general formula [A] or [B] is bonded to the oxygen atom of the general formula [II] at the * part.

The formula may be represented by the general formula [C]. Here, Rf ₁ has the same meaning as Re ₇ and Re ₈ , n represents 1 or 2, and is bonded to an oxygen atom of the general formula [II] at *.

[0051]

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Lb is -SO _2- , -CO-, -SO ₂ N
_{(Rb 4) -, - COO} -, - CONH- , or -P (=
O) (Rb ₅₎ - represents preferably -SO ₂ - or -C
An O-, -SO ₂ - is most preferred. Rb ₄ and Rb
₅ has the same meaning as Ra ₅ and Ra ₆ above.

Yb represents an alkyl, aryl, or heterocyclic group, and has the same meaning as Ya described above, preferably an aryl or heterocyclic group, most preferably an aryl group.

Rc ₂ and Rc ₃ in formula (III) have the same meanings as Rb ₁ , but are preferably halogen, alkyl, aryl, alkoxy, acylamino, sulfonamido, carbamoyl, ureido, phosphonylamido, Preferably a hydroxy group, an alkylthio group, a hydrogen atom, a halogen atom, an alkyl group,
Aryl, acylamino and sulfonamide groups are more preferred.

Rc ₁ has the same meaning as Rb ₂ but is preferably hydroxy, hydroxyalkyl, acylamino, sulfonamide, carbamoyl, sulfamoyl,
Each group such as ureido, sulfamoylamino, phosphonylamide and the like is preferable. More preferably, they are groups such as acylamino, sulfonamide, ureido, hydroxy, and phosphonylamido.

Rc ₄ has the same meaning as Ra ₁ and Ra ₂ , but is preferably an alkyl group, an aryl group, and more preferably an alkyl group. Further, Rc ₄ and Rc ₃ may combine to form a 5- or 6-membered ring.

Xc represents a nitrogen atom or a carbon atom and 5 or 6
Represents a group of non-metallic atoms necessary for forming a membered ring, and may have a substituent.

Lc is —SO ₂ —, —CO—, —SO ₂ N
_{(Rc 5) -, - COO} -, - CONH- , or -P (=
O) (Rc ₆₎ - represents preferably -SO ₂ - or -C
An O-, -SO ₂ - is most preferred. Rc ₅ and Rc
₆ has the same meaning as Ra ₅ and Ra ₆ above.

Yc represents an alkyl, aryl, or heterocyclic group, and has the same meaning as Ya described above, but is preferably an aryl group.

Rd _{1 to} Rd ₄ in the general formula [IV] are Rb
_{The same as 1} , but preferably a halogen atom, an alkyl group, an aryl group, an alkoxy group, an acylamino group, a sulfonamide group, a carbamoyl group, a ureido group, a phosphonylamido group, a hydroxy group, an alkylthio group, and a hydrogen atom, halogen An atom, an alkyl group, an aryl group, an acylamino group and a sulfonamide group are more preferred.

Rd ₅ and Rd ₆ each represent an alkyl group or an aryl group, and the total number of carbon atoms of Rd ₅ and Rd ₆ is 5 to 1
3. Further, it contains at least one hydroxyl group. It is preferably an alkyl group, and the total number of carbon atoms is 5 to 9.

Ld is —SO ₂ —, —CO—, —SO ₂ N
_{(Rd 7) -, - COO} -, - CONH- , or -P (=
O) (Rd ₈₎ - represents preferably -SO ₂ - or -C
An O-, -SO ₂ - is most preferred. Rd ₇ and Rd
₈ has the same meaning as Ra ₅ and Ra ₆ above.

Yd represents an alkyl group, an aryl group, or a heterocyclic group, and has the same meaning as Ya described above, preferably an aryl group or a heterocyclic group, and most preferably an aryl group.

Next, the general formulas [I], [II] and [II]
Representative examples of the compounds represented by [I] and [IV] are shown below, but the present invention is not limited thereto.

[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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[0072]

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[0073]

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[0074]

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[0075]

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[0076]

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[0077]

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[0078]

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[0079]

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[0080]

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[0081]

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[0082]

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[0083]

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[0084]

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[0085]

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[0086]

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[0087]

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[0088]

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[0089]

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[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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Next, the compounds represented by the general formulas [I], [II] and [II]
The synthesis examples of the compounds represented by I] and [IV] are shown below.

[0105]

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I) Synthesis of Intermediate 1 Ethyl acetate (EA): 8.3 g of m-nitroaniline
Add 00 ml, 80 ml of water and 14.2 g of potassium acetate and dissolve with stirring. There acetyl chloride 2.95
g was added dropwise over 10 minutes and allowed to react at room temperature for 2 hours. Thereafter, the mixture is separated, neutralized and washed with water, and ethyl acetate is distilled off under reduced pressure. Since crystals precipitate, a small amount of ethyl acetate is added, and the mixture is suspended and filtered. 9.6 g of white crystals were obtained. It was identified by MASS, H-NMR, and IR spectrum, and it was confirmed to be Intermediate 1.

II) Synthesis of Intermediate 2 Intermediate 1: 9.0 g was dissolved in 200 ml of methanol.
3.0 g of 5% palladium carbon was added to carry out catalytic hydrogen reduction. After absorbing a specified amount of hydrogen, palladium carbon was filtered off, and the solvent in the filtrate was distilled off under reduced pressure. 8.0 g of white crystals were obtained. It was identified by MASS, H-NMR, and IR spectrum, and it was confirmed to be Intermediate 2.

III) Synthesis of Intermediate 3 Intermediate 2: 8.0 g of sodium bicarbonate was added to 8.0 g of
50 ml of water and 16.1 g of butyl bromide were added,
Heat and stir at 80-90 ° C for 8 hours. After completion of the reaction, the mixture was extracted with ethyl acetate, separated, neutralized, washed with water, and the solvent was distilled off under reduced pressure.
2 g of oil were obtained. It was identified by MASS, H-NMR, and IR spectrum, and it was confirmed to be Intermediate 3.

VI) Synthesis of Intermediate 4 Intermediate 3: 11.0 g was mixed with 40 ml of ice water and concentrated hydrochloric acid: 1
7.7 ml was added and stirred, and an aqueous solution in which 3.1 g of sodium nitrite was dissolved in 10 ml of water was added at 20 ° C. or lower, and the mixture was reacted for 1 hour. Further, a 10% aqueous sodium hydroxide solution is added and p
H-8 and stir for 1 hour. After completion of the reaction, the mixture was extracted with ethyl acetate, washed with water, the solvent was distilled off under reduced pressure, and the residue was purified by column chromatography to obtain 11.0 g of an oil. To this, 150 ml of methanol was added for dissolution, and 3.4 g of 5% palladium on carbon was added to carry out catalytic hydrogen reduction. After absorbing a specified amount of hydrogen, palladium carbon was filtered off, and the solvent in the filtrate was distilled off under reduced pressure. 10.0 g of milky white crystals were obtained. M
Identified by ASS, H-NMR, IR spectrum,
It was confirmed to be Intermediate 4.

V) Synthesis of Illustrative Compound I-1 70 ml of ethyl acetate, 50 ml of acetonitrile, 50 ml of water and 10.6 g of potassium acetate were added to and dissolved in 5 g of intermediate 4, and 2,4,6-triisopropylbenzenesulfonyl chloride 6 And react for 1 hour. After completion of the reaction, the mixture was separated, adjusted to pH-1 once with dilute hydrochloric acid, washed with neutralized water, the solvent was distilled off under reduced pressure, and the residue was purified by column chromatography to obtain a crude product. This was recrystallized from ethyl acetate and n-hexane to obtain 8.3 g of white crystals. MA
It was identified by SS, H-NMR, and IR spectra, and it was confirmed to be Exemplified Compound I-1.

[0111]

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I) Synthesis of Intermediate 1 4.0 g of pyridine and 150 ml of acetonitrile were added to 7.7 g of 3-nitro-4-aminophenol and stirred for 15 minutes, and 15.1 g of 2,4,6-triisopropylbenzenesulfonyl chloride was added. And react at 70-80 ° C. for 3 hours. After completion of the reaction, the solvent is distilled off under reduced pressure, and ethyl acetate is added to make the mixture acidic (pH = 1) with hydrochloric acid, followed by liquid separation, neutralization and washing with water. The obtained solid was recrystallized from ethyl acetate and n-hexane to obtain 24.1 g of crystals. It was identified by MASS, H-NMR, and IR spectrum, and it was confirmed to be Intermediate 1.

II) Synthesis of Intermediate 2 12.0 g of Intermediate 1 was dissolved in 500 ml of methanol, and 3.0 g of 5% palladium on carbon was added to carry out catalytic hydrogen reduction. After absorbing a specified amount of hydrogen, palladium carbon was filtered off, and the solvent in the filtrate was distilled off under reduced pressure. 10.9 g of white crystals were obtained. It was identified by MASS, H-NMR, and IR spectrum, and it was confirmed to be Intermediate 2.

III) Synthesis of Exemplified Compound II-11 Intermediate 2: 6.0 g was dissolved in 80 ml of acetonitrile, 5.6 g of N, N-dimethylaniline was added, and the mixture was stirred at room temperature for 15 minutes and then acetyl chloride: 2.6 g. Is added dropwise over 15 minutes. The mixture was stirred for 2 hours as it was. After the reaction was completed, the solvent was distilled off under reduced pressure.
H-1), liquid separation, neutralization, and washing with water, and the solvent is distilled off under reduced pressure. The obtained solid was recrystallized from ethyl acetate and n-hexane to obtain 6.2 g of crystals. MASS, H-NM
Exemplified compound II-1 identified by R and IR spectra
It was confirmed that it was 1.

[0115]

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I) Synthesis of Exemplified Compound III-11 Compound described in Reference 1: 5.5 g of acetonitrile 60
Then, 1.8 ml of pyridine was added, and the mixture was stirred for 15 minutes. Then, 6.38 g of 2,4,6-triisopropylbensensulfonyl chloride was added under cooling with water. Thereafter, the reaction is carried out at room temperature for 2 hours, and the solvent is distilled off under reduced pressure. Thereafter, ethyl acetate is added to make the mixture acidic with hydrochloric acid (pH〜1), separated, neutralized and washed with water, and the solvent is distilled off under reduced pressure. The resulting viscous oil was recrystallized from ethyl acetate and n-hexane to give 9.2.
g of Exemplified Compound III-11 was obtained. MASS, H-NM
R and IR spectra, and Compound III-
It was confirmed to be 11.

* Reference 1: J.I. Chem. , Soc. , P
erkin Trans. , II, 815 (1987).

[0118]

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I) Synthesis of Intermediate 1 N-ethyl-m-toluidine: 180.5 g was added to 500 ml of methanol, and 153.9 g of 3-chloro-1-propanol was further added. 115 g of sodium hydrogen carbonate was added thereto while stirring, and the mixture was heated under reflux for 32 hours.
The solvent was removed under reduced pressure, extracted with ethyl acetate, neutralized, washed with water, the organic layer was dried, and the solvent was distilled off under reduced pressure.
A fraction at 138 to 145 ° C with Hg: 140 g was collected.
It was identified by MASS, H-NMR, and IR spectrum, and it was confirmed to be Intermediate 1.

II) Synthesis of Exemplified Compound IV-8 To 19.0 g of Intermediate 1: 70 ml of water and 70 ml of concentrated hydrochloric acid were added, and the mixture was cooled in an ice-water bath, and 7.3 g of sodium nitrite was added to ０0 g
Add slowly at about ° C.

After the end of the reaction, 18 g of iron are added at ０0 ° C. After the completion of the reaction, sodium carbonate was added to adjust the pH to 7 to 8,
Extract with ethyl acetate, wash with water and remove the solvent under reduced pressure.
15.3 g of a viscous oil were obtained.

To this, 200 ml of ethyl acetate, 100 ml of acetonitrile, 100 ml of water and 28.times.
8 g was added and dissolved, and 2,4,6-triisopropylbenzenesulfonyl chloride (24.5 g) was added and reacted for 1 hour. After completion of the reaction, the mixture was separated, adjusted to pH-1 once with dilute hydrochloric acid, washed with neutralized water, the solvent was distilled off under reduced pressure, and the residue was purified by column chromatography to obtain a crude product. This was recrystallized from acetonitrile to obtain 29.2 g of white crystals. M
Identified by ASS, H-NMR, IR spectrum,
It was confirmed to be Exemplified Compound IV-8.

The other color developing agents of the present invention can also be synthesized according to the above.

The light-sensitive material of the present invention contains a color developing agent. These color developing agents are themselves oxidized by developing a silver salt, and it is necessary that the oxidized product can be coupled with a coupler described later to form a dye. Such a combination of a color developing agent and a coupler is described in US Pat. No. 3,531,256, p.
Phenylenediamines developing agents and phenol or active methylene couplers, p.
-Combinations of aminophenol-based developing agents and active methylene couplers can be used. US Patent 4,02
Combinations of a sulfonamide phenol and a 4-equivalent coupler as described in JP-A Nos. 1,240 and JP-A-60-128438 are excellent in raw storage when incorporated in a light-sensitive material, and are preferred combinations. When a color developing agent is incorporated, a precursor of the color developing agent may be used. For example, indoaniline compounds described in US Pat. No. 3,342,597, US Pat. No. 3,342,599
No., Research Disclosure No. 14,850
And the same No. 15,159, an aldol compound described in US Pat. No. 13,924, a metal salt complex described in US Pat. No. 3,719,492,
And urethane compounds described in JP-A-135628.

The developing agent contained in the light-sensitive material is required to be relatively stable during storage of the light-sensitive material and not to unnecessarily reduce silver salts. As a color developing agent satisfying such requirements, Japanese Patent Application Laid-Open No.
15806 and the like, JP-A-5-241282 and JP-A-8-234388.
No. 8-286340, No. 9-152700, No. 9-152701, No. 9-152702, No. 9-1
Hydrazine-based drugs described in JP-A-52703 and JP-A-9-152704, JP-A-7-202002, JP-A-8-234
And hydrazone-based drugs described in JP-A-390 / 390 and the like.

In the present invention, general formula (1-1):
(1-2), (1-3), (1-4) or (1-
The compound represented by 5) can be used in combination as a color developing agent.

Of these, the compounds of the general formula (1-1) or (1-4) are particularly preferably used. Hereinafter, these developing agents will be described in detail.

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The compound represented by the general formula (1-1) is a compound generally called sulfonamidophenol. In the general formula (1-1), R _{1 to} R ₄ each represent a hydrogen atom, a halogen atom (for example, a chloro atom or a bromo atom), an alkyl group (for example, a methyl group, an ethyl group, an isopropyl group, a butyl group, a t-butyl group) ), An aryl group (eg, phenyl group, tolyl group, xylyl group), an alkylcarbonamide group (eg, acetylamino group, propionylamino group,
Butyroylamino group), arylcarbonamide group (eg, benzoylamino group), alkylsulfonamide group (eg, methanesulfonylamino group, ethanesulfonylamino group), arylsulfonamide group (eg, benzenesulfonylamino group, toluenesulfonylamino group) An alkoxy group (for example, a methoxy group, an ethoxy group,
Butoxy group), aryloxy group (eg, phenoxy group), alkylthio group (eg, methylthio group, ethylthio group, butylthio group), arylthio group (eg, phenylthio group, tolylthio group), alkylcarbamoyl group (eg, methylcarbamoyl group, dimethylcarbamoyl group) , Ethyl carbamoyl group, diethyl carbamoyl group,
Dibutylcarbamoyl group, piperidylcarbamoyl group,
Morpholylcarbamoyl group), arylcarbamoyl group (eg, phenylcarbamoyl group, methylphenylcarbamoyl group, ethylphenylcarbamoyl group, benzylphenylcarbamoyl group), carbamoyl group, alkylsulfamoyl group (eg, methylsulfamoyl group, dimethylsulfa Moyl group, ethylsulfamoyl group, diethylsulfamoyl group, dibutylsulfamoyl group,
Piperidylsulfamoyl group, morpholylsulfamoyl group), arylsulfamoyl group (for example, phenylsulfamoyl group, methylphenylsulfamoyl group, ethylphenylsulfamoyl group, benzylphenylsulfamoyl group), sulfamoyl Group, cyano group, alkylsulfonyl group (eg, methanesulfonyl group, ethanesulfonyl group), arylsulfonyl group (eg, phenylsulfonyl group, 4-chlorophenylsulfonyl group, p-
Toluenesulfonyl group), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group), aryloxycarbonyl group (eg, phenoxycarbonyl group), alkylcarbonyl group (eg, acetyl group, propionyl group, butyroyl group), aryl Represents a carbonyl group (eg, a benzoyl group, an alkylbenzoyl group) or an acyloxy group (eg, an acetyloxy group, a propionyloxy group, a butyroyloxy group). Among R _{1 to} R ₄ , R ₂ and R ₄ are preferably a hydrogen atom. Further, it is preferable that the sum of the Hammett constant σp values of R _{1 to} R ₄ is 0 or more.

R ₅ is an alkyl group (for example, methyl group, ethyl group, butyl group, octyl group, lauryl group, cetyl group,
A stearyl group), an aryl group (e.g., phenyl, tolyl, xylyl, 4-methoxyphenyl, dodecylphenyl, chlorophenyl, trichlorophenyl, nitrochlorophenyl, triisopropylphenyl, 4-dodecyloxyphenyl, 3,5-di-
(Methoxycarbonyl) group) or a heterocyclic group (eg, a pyridyl group).

The compound represented by the general formula (1-2) is a compound generically called sulfonylhydrazine. The compound represented by the general formula (1-4) is a compound generally called carbamoylhydrazine.

In the general formulas (1-2) and (1-4), Z represents a group of atoms forming an aromatic ring. The aromatic ring formed by Z needs to be sufficiently electron-attracting in order to impart silver developing activity to the present compound. For this reason, an aromatic ring which forms a nitrogen-containing aromatic ring or has an electron-withdrawing group introduced into a benzene ring is preferably used. As such an aromatic ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a quinoline ring, a quinoxaline ring and the like are preferable.

In the case of a benzene ring, the substituent is
An alkylsulfonyl group (for example, methanesulfonyl group, ethanesulfonyl group), a halogen atom (for example, chloro atom, bromo atom), an alkylcarbamoyl group (for example, methylcarbamoyl group, dimethylcarbamoyl group, ethylcarbamoyl group, diethylcarbamoyl group, dibutylcarbamoyl group, Piperidylcarbamoyl group, morpholylcarbamoyl group), arylcarbamoyl group (eg, phenylcarbamoyl group, methylphenylcarbamoyl group, ethylphenylcarbamoyl group, benzylphenylcarbamoyl group), carbamoyl group, alkylsulfamoyl group (eg, methylsulfamoyl group) , Dimethylsulfamoyl group, ethylsulfamoyl group, diethylsulfamoyl group, dibutylsulfamoyl group, piperidylsulfamoyl group, Le Hori Rusuru sulfamoyl group),
Arylsulfamoyl group (for example, phenylsulfamoyl group, methylphenylsulfamoyl group, ethylphenylsulfamoyl group, benzylphenylsulfamoyl group), sulfamoyl group, cyano group, alkylsulfonyl group (for example, methanesulfonyl group, Ethanesulfonyl group), arylsulfonyl group (eg, phenylsulfonyl group, 4-chlorophenylsulfonyl group, p-toluenesulfonyl group), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group), aryloxycarbonyl group ( For example, phenoxycarbonyl group), alkylcarbonyl group (for example, acetyl group, propionyl group, butyroyl group), or arylcarbonyl group (for example, benzoyl group, alkylbenzoyl group) Although the like, the sum of the Hammett constants σ values of the substituents is 1 or more. R ₅ has the general formula (1)
-1) the same meaning as R ₅ in.

The compound represented by the general formula (1-3) is a compound generally called sulfonylhydrazone. The compound represented by the general formula (1-5) is a compound generally called carbamoylhydrazone.

In the general formulas (1-3) and (1-5), R ₆ represents a substituted or unsubstituted alkyl group (for example, a methyl group or an ethyl group). X represents an oxygen atom, a sulfur atom, a selenium atom or an alkyl- or aryl-substituted tertiary nitrogen atom, preferably an alkyl-substituted tertiary nitrogen atom. R ₇ , R ₈ , R ₉ , and R ₁₀ represent a hydrogen atom or a substituent, and R ₇ and R ₈ may combine with each other to form a double bond or a ring. R ₅ has the same meaning as R ₅ in the general formula (1-1).

Specific examples of the compounds represented by formulas (1-1) to (1-5) are described in JP-A-11-95383, 10-3.
It is described on page 0.

The developing agent of the present invention and the developing agent which can be preferably used in the present invention include a color-forming layer and 0.0
It is preferable to use 5 to 10 mmol / m ² . A more preferred amount is 0.1 to 5 mmol / m ² , and a particularly preferred amount is 0.2 to 2.5 mmol / m ² .

Next, the coupler will be described. The coupler in the present invention is a compound that forms a dye by a coupling reaction with an oxidized form of the color developing agent. Examples of the coupler preferably used in the present invention include compounds represented by the following general formulas Cp-1 to Cp-12. These are compounds generally referred to as compounds having an active methylene group, pyrazolone compounds, pyrazoloazole compounds, phenol compounds and naphthol compounds, respectively.

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The general formulas Cp-1 to Cp-4 represent couplers called active methylene couplers, wherein R ₂₄ represents an acyl group, a cyano group, a nitro group or an aryl group which may have a substituent. , A heterocyclic group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, and an arylsulfonyl group.

In the general formulas Cp-1 to Cp-3, R ₂₅
Is an alkyl group, an aryl group, or a heterocyclic group which may have a substituent. In the general formula Cp-4, R ₂₆ is an aryl group or a heterocyclic group which may have a substituent. Examples of the substituent which R ₂₄ , R ₂₅ and R ₂₆ may have include:
For example, an alkyl group, a cycloalkyl group, an alkenyl group,
Alkynyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, cyano group, halogen atom, acylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylamino group, aryl Examples include various substituents such as an amino group, a hydroxyl group, and a sulfo group. Preferred examples of R ₂₄ include an acyl group, a cyano group, a carbamoyl group, and an alkoxycarbonyl group.

In the general formulas Cp-1 to Cp-4, Y is a hydrogen atom or a group which can be eliminated by a coupling reaction with an oxidized developing agent. As examples of Y, groups acting as an anionic leaving group of a 2-equivalent coupler include a halogen atom (eg, a chloro atom, a bromo atom), an alkoxy group (eg, a methoxy group, an ethoxy group), an aryloxy group (eg, a phenoxy group, 4-cyanophenoxy group,
4-alkoxycarbonylphenyl group), alkylthio group (for example, methylthio group, ethylthio group, butylthio group), arylthio group (for example, phenylthio group, tolylthio group), alkylcarbamoyl group (for example, methylcarbamoyl group, dimethylcarbamoyl group, ethylcarbamoyl group, Diethylcarbamoyl, dibutylcarbamoyl, piperidylcarbamoyl, morpholylcarbamoyl, arylcarbamoyl (eg, phenylcarbamoyl, methylphenylcarbamoyl, ethylphenylcarbamoyl, benzylphenylcarbamoyl), carbamoyl, alkylsulfamoyl Groups (eg, methylsulfamoyl, dimethylsulfamoyl, ethylsulfamoyl, diethylsulfamoyl, dibutylsulfamoyl, Amoiru group, piperidyl sulfamoyl group, morpholinocarbonyl Rusuru sulfamoyl group), an aryl sulfamoyl group (e.g., phenyl sulfamoyl group,
Methylphenylsulfamoyl group, ethylphenylsulfamoyl group, benzylphenylsulfamoyl group),
Sulfamoyl group, cyano group, alkylsulfonyl group (for example, methanesulfonyl group, ethanesulfonyl group),
Arylsulfonyl group (for example, phenylsulfonyl group,
4-chlorophenylsulfonyl group, p-toluenesulfonyl group), alkylcarbonyloxy group (eg, acetyloxy group, propionyloxy group, butyroyloxy group), arylcarbonyloxy group (eg, benzoyloxy group, toluyloxy group, anisyloxy group), Examples include a nitrogen heterocyclic group (for example, an imidazolyl group and a benzotriazolyl group).

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

In the general formulas Cp-1 to Cp-4, R ₂₄
And R ₂₅ , and R ₂₄ and R ₂₆ may combine with each other to form a ring.

The general formula Cp-5 represents a coupler called a 5-pyrazolone-based magenta coupler, wherein R ₂₇ represents an alkyl group, an aryl group, an acyl group, or a carbamoyl group. R ₂₈ represents a phenyl group substituted by one or more halogen atoms, an alkyl group, a cyano group, an alkoxy group, an alkoxycarbonyl group, or a phenyl group substituted by an acylamino group. For Y, the general formulas Cp-1 to Cp
Same as -4.

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

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

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

The general formula Cp-6 represents a coupler called a pyrazoloazole coupler, wherein R ₂₉ represents a hydrogen atom or a substituent. Z represents a nonmetallic atom group necessary for forming a 5-membered azole ring containing 2 to 4 nitrogen atoms, and the azole ring may have a substituent (including a condensed ring). Y is the same as in general formulas Cp-1 to Cp-4.

Among the pyrazoloazole-based couplers represented by the general formula Cp-6, the imidazo [1,1] described in US Pat.
2-b] pyrazoles, U.S. Pat. No. 4,540,654
[1,5-b] [1,2,4] triazoles described in US Pat. No. 3,725,067, and pyrazolo [5,1-c] [1,2,4] triazole described in US Pat. No. 3,725,067. Are preferred, and among these, pyrazolo [1,5-b] [1,2,4] triazole is preferred from the viewpoint of light fastness.

For details of the substituents on the azole ring represented by the substituents R ₂₉ , Y and Z, see, for example, US Pat.
No. 540,654, column 2, line 41 to column 8, line 27. Preferably, JP-A-61
Pyrazoloazole couplers in which a branched alkyl group is directly linked to the 2, 3 or 6 position of the pyrazolotriazole group as described in JP-A-65245;
Pyrazoloazole couplers containing a sulfonamide group in the molecule described in JP-A-61-147254
Pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group described in
Pyrazolotriazole couplers having an alkoxy group or an aryloxy group at the 6-position described in JP-A-209457 or JP-A-63-307453;
No. 01443 is a pyrazolotriazole coupler having a carboxamide group in the molecule.

Formulas Cp-7 and Cp-8 are couplers called phenol couplers and naphthol couplers, respectively, wherein R ₃₀ is a hydrogen atom or -NHCO
_{R 32, -SO 2 NR 32 R} 33, -NHSO 2 R 32, -NHC
_{OR 32, -NHCONR 32 R 33,} -NHSO 2 NR 32 R
Represents a group selected from ₃₃ . R ₃₂ and R ₃₃ represent a hydrogen atom or a substituent. In the general formulas Cp-7 and Cp-8, R
₃₁ represents a substituent, o represents an integer selected from 0 to 2, and p represents an integer selected from 0 to 4. For Y, the general formula C
Same as p-1 to Cp-4. Examples of the substituent for R _{31 to} R ₃₃ include those described above as the substituent for R _{24 to} R ₂₆ .

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

Preferred examples of the naphthol coupler represented by the general formula Cp-8 include US Pat.
No. 93, 4,052, 212, 4,146
No. 396, No. 4,228,233, No. 4,29
Examples thereof include 2-carbamoyl-1-naphthol described in US Pat. No. 6,200 and the like and 2-carbamoyl-5-amide-1-naphthol described in U.S. Pat. No. 4,690,889 and the like.

Formulas Cp-9 to Cp-12 are couplers referred to as pyrrolotriazoles, and include R ₄₂ , R ₄₃ , and R ₄₄
Represents a hydrogen atom or a substituent. For Y, the general formula C
Same as p-1 to Cp-4. As the substituents for R ₄₂ , R ₄₃ and R ₄₄ , those described above as the substituents for R _{24 to} R ₂₆ can be mentioned. Preferable examples of the pyrrolotriazole couplers represented by the general formulas Cp-9 to Cp-12 include European Patent Nos. 488,248A1 and 491,1.
No. 97A1, No. 545,300, R ₄₂ , R
_A coupler in which at least one of ₄₃ is an electron-withdrawing group.

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

Examples of the fused phenol couplers include US Pat. Nos. 4,327,173 and 4,564,586.
And the couplers described in JP-A Nos. 4,904,575 and the like can be used.

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

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

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

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

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

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

In the present invention, in addition to the couplers described above, West German Patent Nos. 3,819,051A and 3,823,049.
No. 4,840,883, US Pat.
No. 4,930, No. 5,051,347, No. 4,4
No. 81,268, European Patent Nos. 304,856A2, 329,036, 354,549A2, 374,781A2, 379,110A2, 386,930A1, 63-141055
Nos. 64-32260 and 32261, JP-A No. 2
No. -297475, No. 2-44340, No. 2-110
555, 3-7938, 3-160440,
Nos. 3-172839, 4-172247, 4-
No. 179949, No. 4-182645, No. 4-184
Nos. 437, 4-188138, 4-188139
And couplers described in JP-A-4-194847, JP-A-4-204532, JP-A-4-204731, and JP-A-4-204732.

In the silver halide color photographic light-sensitive material of the present invention, compounds generally known as a yellow coupler, a magenta coupler and a cyan coupler can be used. These compounds are used in general color photography, and when developed with a paraphenylenediamine-based color developing agent, each of them has a blue region (wavelength: 350 to 500 nm).
m), a compound having a spectral absorption maximum wavelength in a green region (wavelength 500 to 600 nm) and a red region (wavelength 600 to 750 nm). However, the general formula (1) related to the present invention
-1) to (1-5), in particular, the general formula (1-2)
When used together with the developing agents of (1) to (1-5), the dye formed by the coupling may have a spectral absorption maximum in a wavelength region different from these wavelengths. Accordingly, it is necessary to appropriately select the type of the coupler. Similarly, the color developing agents [I] to [IV] of the present invention may also have different spectral absorption wavelengths, but the light-sensitive material of the present invention does not always have the color-forming dyes in the above-mentioned blue region, green region, and red region. It need not be designed to have a spectral absorption maximum wavelength in the region. The coloring dye may have a spectral absorption in an ultraviolet region or an infrared region, or may be used in combination with the absorption in the visible light region.

In the couplers usable in the present invention, the diffusion-resistant group may form a polymer chain. Further, either a 4-equivalent coupler or a 2-equivalent coupler can be used, but it is preferable to use different couplers depending on the type of the color developing agent. First, it is preferable to use a 4-equivalent coupler for the developing agents of the general formulas (1-1), (1-2) and (1-3), and the general formulas (1-4) and (1-5) It is preferred to use a two-equivalent coupler for the developing agent of (1). For the color developing agents [I] to [IV] of the present invention, it is preferable to use a 4-equivalent coupler. Specific examples of the coupler include a four-equivalent and a two-equivalent of the theory of the photographic process (4th Ed.THJ James).
s Editing, Macmillan, 1977) p. 291-3
Page 34, and pages 354 to 361, JP-A-58-12
No. 353, No. 58-149046, No. 58-1490
No. 47, No. 59-11114, No. 59-124399
Nos. 59-174835 and 59-231439
No. 59-231540, No. 60-2951, No. 60-14242, No. 60-23474, No. 60-
No. 66249, JP-A-8-110608 and 8-146
552, 8-146578, 9-204031, etc., and the above-mentioned documents and patents.

The light-sensitive material of the present invention may contain the following functional coupler. EP 456,257A1 as a coupler for correcting unnecessary absorption of a coloring dye
, A yellow colored magenta coupler described in the EP, a magenta colored cyan coupler described in US Pat. No. 4,833,069, and (2) of US Pat. No. 4,837,136.
Colorless masking couplers of formula (A) in claim 1 of WO 92 / 11,575 (especially the exemplified compounds on pages 36 to 45). Compounds (including couplers) that react with oxidized developing agents to release photographically useful compound residues include the following. Development inhibitor releasing compounds: compounds represented by formulas (I) to (IV) described on page 11 of EP 378,236 A1, EP 436,93
A compound represented by the formula (I) described on page 7 of No. 8A2,
Compounds represented by formula (1) of Japanese Patent Application No. 4-134523, compounds represented by formulas (I), (II) and (III) described on pages 5 and 6 of EP 440,195A2. 325564. The compound of formula (I) -ligand releasing compound of claim 1 of U.S. Pat.
A compound represented by LIG-X according to claim 1 of No. 478.

The couplers used in the present invention can be used alone or in combination of two or more, and can be used in combination with other types of couplers. The coupler is preferably added to the same layer as the developing agent and silver halide of the present invention, and its preferred amount is from 0.05 to 20 mol, more preferably from 0.1 to 20 mol, per mol of the developing agent. It is 10 mol, particularly preferably 0.2 to 5 mol. In the present invention, the coupler is preferably used in an amount of 0.01 to 1 mol per mol of silver halide.
0.02-0.6 mol is more preferred. This range is preferred in that a sufficient color density can be obtained.

A hydrophobic additive such as a coupler or a color developing agent can be introduced into a layer of a light-sensitive material by a known method such as the method described in US Pat. No. 2,322,027. In this case, U.S. Pat. No. 4,555,470,
Nos. 4,536,466, 4,536,467, 4,587,206, 4,555,476, 4,599,296 and JP-B-3-62256. Such a high-boiling organic solvent may be used, if necessary,
It can be used in combination with an organic solvent having a low boiling point of from 1 to 160 ° C.

Further, two or more of these couplers, high boiling point organic solvents and the like can be used in combination. The amount of the high boiling organic solvent is usually 10 g or less, preferably 5 g or less, more preferably 1 g to 0.1 g per 1 g of the hydrophobic additive used.
g. Further, 1 ml or less per 1 g of the binder,
Further, 0.5 ml or less, particularly 0.3 ml or less is suitable. JP-B-51-39853, JP-A-51-5994
No. 3, a dispersion method using a polymer described in
No. 30,242 and the like can also be used. In the case of a compound which is substantially insoluble in water, it can be dispersed and contained as fine particles in a binder in addition to the above method. When dispersing the hydrophobic compound in the hydrophilic colloid, various surfactants can be used. For example, the surfactants described in Research Disclosure described in JP-A-59-157636, pages (37) to (38) can be used. Japanese Patent Application Nos. 5-204325 and 6-19
No. 247 and West German Patent Application No. 1,932,299A.

In the present invention, an organic metal salt can be used in combination with the photosensitive silver halide as an oxidizing agent. Among such organic metal salts, an organic silver salt is particularly preferably used. Organic compounds that can be used to form the above-described organic silver salt oxidizing agents include US Pat.
There are benzotriazoles, fatty acids and other compounds described in No. 0,626, columns 52 to 53 and the like. The acetylene silver described in U.S. Pat. No. 4,775,613 is also useful. Two or more organic silver salts may be used in combination. The above organic silver salt is used in an amount of 0.01 to 1 mol per mole of the photosensitive silver halide.
10 mol, preferably 0.05 to 3 mol, can be used in combination. The total coating amount of the photosensitive silver halide 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 silver halide used in the present invention may have any halogen composition such as silver bromide, silver iodobromide, silver chloride, silver chlorobromide, silver chloroiodobromide, or silver iodochloride. . Generally, silver iodobromide, silver bromide, and silver chloroiodobromide are preferably used when sensitivity is important, and silver chloride, silver chlorobromide and the like are preferably used when processing speed is important. Silver halide emulsions containing these grains were prepared by Simmy & Physics Photographic by Paul Grafkides (Paul Montel, Inc., USA).
1967); Photographic Emulsion Chemistry by GF Duffin (The Fo)
Cal Press, 1966); Making and Coating Photographic Emulsion (The Foc) co-authored by V. El Jerikmmann et al.
al Press, 1964), and JP-A-51-39027, 55-142329.
Nos. 58-113928, 54-48521 and 58-4938, and 60-138538, and pages 88 of the Abstracts of the 58th Annual Meeting of the Photographic Society of Japan. 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 is a one-sided mixing method, a double-mixing method, a combination thereof, or a method in which grains are excessively silver ion. (Reverse mixing method), a method of supplying a soluble silver salt and a soluble halide salt to a fine seed crystal and growing the same.

The silver halide grain size distribution of the silver halide photographic emulsion may be either narrow or wide, but is preferably monodisperse with uniform grain sizes. Specifically, when the width of the distribution is defined by the relative standard deviation (coefficient of variation) expressed by (standard deviation of particle size / average particle size) × 100 = width (%) of particle size distribution, 25% or less is defined. Is preferred, and more preferably 20% or less. The average grain size of the silver halide grains used in the present invention is not particularly limited, but the length of one side when the volume is converted to a cube is 0.05 to 2.0.
0 μm, preferably 0.1 to 1.2 μm.

The silver halide grains contained in the silver halide emulsion of the present invention may have a regular shape such as a cubic, octahedral or tetradecahedral shape, or an irregular shape such as a flat twin. The mixture may be a mixture of both, but preferably contains tabular grains. The tabular silver halide grains preferably used in the present invention have an average ratio (average aspect ratio) of grain diameter / thickness (aspect ratio) of 2 or more, and an average aspect ratio of preferably 3 to 20, More preferably, it is 4 to 15. In these tabular silver halide grains, the outer wall of the crystal may substantially consist almost of {111} planes or may consist of {100} planes. In addition, it may have both the {111} plane and the {100} plane.

When silver iodobromide or silver bromide tabular grains are used, at least 50% of the grain surfaces are {111} faces, more preferably 60% to 90% are {111} faces. Particularly preferably, particles in which 70 to 95% are {111} planes are preferred. It is preferable that the plane other than the {111} plane is mainly the {100} plane. This surface ratio utilizes the difference in the adsorption dependency between the {111} plane and the {100} plane in the adsorption of the sensitizing dye [T. Tani, J .; Ima
ging Sci. , 29, 165 (1985)].

The tabular (iodo) bromide grains are preferably hexagonal. Hexagonal tabular grains (hereinafter sometimes referred to as hexagonal tabular grains) refer to the main plane (# 11).
(1｝ plane) is hexagonal, and the maximum adjacency ratio is 1.0 to 2.0. Here, the maximum adjacent side ratio is the ratio of the length of the side having the maximum length to the length of the side having the minimum length forming a hexagon. If the maximum adjacent side ratio is 1.0 to 2.0, the hexagonal tabular grains may have rounded corners, and may have more corners, and may be substantially circular tabular grains. The length of a side having a rounded corner is represented by the distance between the intersection of the extended straight line portion of the side and the extended straight line portion of the adjacent side. Each side forming the hexagon of the hexagonal tabular grain preferably has a half or more of substantially a straight line, and more preferably has an adjacent side ratio of 1.0 to 1.5.

The tabular (iodo) bromide grains preferably have dislocations. Dislocations of halogenated grains are described, for example, in J. Am. F. Hamilton, Photogr. Sci.
Eng. , 57 (1967); Shiozaw
a, J. et al. Soc. Photogr. Sci. Japan
n, 35, 213 (1972), which can be observed by a direct method using a transmission electron microscope at a low temperature. It is desirable that the dislocation positions of the silver halide grains are generated in a region from 0.58 to 1.0 L from the center of the silver halide grains toward the outer surface, but more preferably 0.80 to 1.0 L. It occurs in the area of 98L. The direction of the dislocation line is approximately from the center to the outer surface, but often meanders. Regarding the number of dislocations in the silver halide grains, it is desirable that grains containing one or more dislocations exist in an amount of 50% (number) or more, and the higher the ratio (number) of the number of tabular grains having dislocation lines, the more preferable.

In the present invention, silver chloride, silver chlorobromide, silver chloroiodide or silver chloroiodobromide tabular grains can be used. In this case, tabular grains having a {100} plane as a main plane,
Any tabular grain having a {111} plane as a main plane can be used. For silver chloride tabular grains having {100} faces, see US Pat. No. 5,314,798, E.
P-534,395A, EP-617,321A,
EP-617,317A, EP-617,318A
No., EP-617,325A, WO94 / 22,05
No. 1, EP-616,255A, U.S. Pat.
No. 6,764, U.S. Pat. No. 5,320,938, U.S. Pat. No. 5,275,930, JP-A-5-204073.
Nos. 5-281640, 7-225441 and 6-30116. In addition, various reports have been made on tabular grains mainly composed of {111} planes. For example, US Pat.
No. 39,520 and the like. Also, US Patent No. 5,250,403 discloses an equivalent circle equivalent diameter of 0.7.
It describes a so-called ultrathin tabular grain having a thickness of not less than μm and a thickness of not more than 0.07 μm. In addition, U.S. Pat.
No. 35,501 discloses a technique for growing a silver salt epitaxially on the surface of tabular grains.

In the tabular grains, the particle diameter is a diameter when a projected image of the grains is converted into a circular image having the same area. The projected area of a particle can be determined from the sum of the particle areas.
In any case, a silver halide crystal sample distributed on a sample table to such an extent that the grains do not overlap can be obtained by observing with an electron microscope. The average projected area diameter of the tabular silver halide grains is represented by the circle-equivalent diameter of the projected area of the grains, and is preferably 0.30 μm or more, more preferably 0.30 to 5 μm, and still more preferably 0.40 μm. ~ 2μ
It is. The particle size can be obtained by projecting the particles at a magnification of 10,000 to 70,000 times with an electron microscope and actually measuring the projected area on the print. The average particle diameter (φ) can be obtained by the following equation, where n is the number of measured particle diameters and ni is the frequency of particles having the particle diameter φi.

Average particle diameter (φ) = (Σniφi) / n (The number of particles to be measured is assumed to be 1,000 or more indiscriminately.) The thickness of the particles is determined by observing the sample obliquely with an electron microscope. Obtainable. The preferred thickness of the tabular grains of the present invention is from 0.03 to 1.0 µm, more preferably from 0.05 to 0.5 µm. The tabular silver halide grains used in the present invention preferably have a small thickness distribution. Specifically, when the width of distribution is defined by (standard deviation of thickness / average thickness) × 100 = width (%) of thickness distribution, it is preferably 25% or less, more preferably 20% or less. These are:

Further, taking into account the factors of the aspect ratio and the grain thickness, tabularity represented by the following equation: A = ECD / b2
Is preferably 20 or more. Here, ECD indicates the average projected diameter (μ) of tabular grains, and (b) indicates the thickness of the grains. Here, the average projected diameter represents the number average of the diameter of a circle having an area equal to the projected area of the tabular grains.

Further, the distribution of the halogen content of each grain in the tabular silver halide grain emulsion of the present invention is preferably small. Specifically, when the width of distribution is defined by (standard deviation of halogen content / average halogen content) × 100 = width (%) of halogen content, it is preferably 25% or less, more preferably. 20% or less.

The silver halide grains used in the present invention are:
The silver halide grains may have a core / shell type structure having at least two layer structures having substantially different halogen compositions or a uniform composition. The average silver iodide content of the silver halide emulsion according to the present invention is preferably 20 mol% or less,
More preferably, it is 0.1 to 10 mol%.

In the present invention, so-called halogen conversion type (conversion type) particles may be used. The halogen conversion amount is preferably from 0.2 to 2.0 mol% based on the silver amount, and the conversion may be carried out during physical ripening or after physical ripening. As a method of halogen conversion, an aqueous halogen solution or fine silver halide particles having a solubility product with silver smaller than the halogen composition on the grain surface before the halogen conversion is usually added. The fine particle size at this time is preferably 0.2 μm or less, more preferably 0.02 to 0.1 μm.

Further, during the process of forming and / or growing the silver halide grains, cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (including complex salts),
At least one metal ion selected from a rhodium salt (including a complex salt) and an iron salt (including a complex salt) can be added, and these metal elements can be contained inside the particle and / or in the particle surface layer.

In the silver halide photographic emulsion used in the present invention, at the end of the growth of silver halide grains, unnecessary soluble salts may be removed or may be kept contained. When the salts are removed, Research Disclosure (hereinafter abbreviated as RD) No. It can be performed based on the method described in 17643 No. II.

In the present invention, two or more kinds of silver halide emulsions each formed separately can be arbitrarily mixed and used.

The photosensitive silver halide emulsion is usually a chemically sensitized silver halide emulsion. For the chemical sensitization of the photosensitive silver halide emulsion of the present invention, a sulfur sensitization method, a selenium sensitization method, a chalcogen sensitization method such as a tellurium sensitization method, gold, platinum, and the like, which are known for an emulsion for a normal type photosensitive material, A noble metal sensitization method and a reduction sensitization method using palladium or the like can be used alone or in combination (for example, see JP-A-3-110555).
No., Japanese Patent Application No. 4-75798).

As the chalcogen sensitizer applied to the silver halide emulsion, a sulfur sensitizer and a selenium sensitizer are preferably used. As sulfur sensitizers, thiosulfate, allyl thiocarbamide thiourea, allyl isothiocyanate,
Examples include cystine, p-toluenethiosulfonate, rhodanine, inorganic sulfur and the like. The addition amount of the sulfur sensitizer is preferably changed depending on the kind of the silver halide emulsion to be applied, the expected effect size, and the like, but 5 × 10 ^{−10 to} 5 × 10 ⁻ per mol of silver halide. A range of ⁵ mol, preferably 5 × 10 ^{−8 to} 3 × 10 ⁻⁵ mol is preferred.

Examples of the gold sensitizer include chloroauric acid and gold sulfide.
Other various gold complexes can be added. Used
Dimethyl rhodanine, thiocyane
Formic acid, mercaptotetrazole, mercaptotriazo
And the like. The amount of gold compound used is
Types of silver halide emulsions, types of compounds used, ripening strips
Although it is not uniform depending on the situation, usually silver halide 1
1 × 10 per mole^-Four~ 1 × 10^-8Preferably a mole
Good. More preferably 1 × 10^-Five~ 1 × 10 ^-8In mole
is there.

These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-62-253159).
issue). Further, an antifoggant described later can be added after the completion of the chemical sensitization. Specifically, Japanese Patent Application Laid-Open No. 5-4583
No. 3, JP-A-62-40446. The pH at the time of chemical sensitization is preferably 5.3 to 1
0.5, more preferably 5.5 to 8.5, and pAg
Is preferably 6.0 to 10.5, more preferably 6.8.
９9.0. The coating amount of the photosensitive silver halide used in the present invention is in the range of 1 mg to 10 g / m ² in terms of silver.

In the preparation of the silver halide of the present invention,
Reduction sensitization can also be used in combination. By placing the silver halide emulsion in an appropriate reducing atmosphere, a reduction sensitizing nucleus can be provided inside the silver halide grains and / or on the surface of the grains. The reduction sensitization is preferably performed during the growth of silver halide grains described below. As a method of applying during the growth, not only a method of performing reduction sensitization in a state where silver halide grains are growing, but also a method of performing reduction sensitization in a state where growth of silver halide grains is interrupted, and then performing reduction sensitization. The method also includes a method of growing the perceived silver halide grains, specifically, by adding a reducing agent and / or a water-soluble silver salt to the silver halide emulsion.

Preferred examples of the reducing agent include thiourea dioxide, ascorbic acid and derivatives thereof. Another preferred reducing agent is hydrazine,
Examples thereof include polyamines such as diethylenetriamine, dimethylamine borane, and sulfite. The amount of the reducing agent added depends on the type of reduction sensitizer, the particle size of the silver halide grains,
It is preferable to change the composition depending on environmental conditions such as composition, crystal habit, temperature of reaction system, pH, pAg and the like. For example, in the case of thiourea dioxide, 0.01 mol per mol of silver halide is used.
A range of ２2 mg is preferred. In the case of ascorbic acid, the range is preferably 0.2 to 50 g per mol of silver halide. Conditions for the reduction sensitization are as follows: temperature is 40 to 80 ° C., time is 10 to 200 minutes, pH is 5 to 11, pAg is 1 to 1
A range of 0 is preferred.

As the water-soluble silver salt, silver nitrate is preferably used. By adding a water-soluble silver salt, so-called silver ripening, which is a kind of reduction sensitization technique, is performed. PAg at the time of silver ripening is 1
-6 is suitable, more preferably 2-4. The conditions such as temperature, time and pH are preferably in the above ranges.

Further, the action of the reducing agent added at the desired point in time of the formation of the particles is such that the oxidizing agent such as hydrogen peroxide (water) and its adduct, peroxoacid salt, ozone, I ₂ , thiosulfonic acid, etc. is added at the desired point in time. It is preferable to deactivate the compound by adding it, and to suppress or stop the reducing agent. The oxidizing agent may be added at any time from when the silver halide grains are formed to before the addition of a gold sensitizer (or a chemical sensitizer if no gold sensitizer is used) in the chemical sensitization step.

In order to impart color sensitivity such as green sensitivity and red sensitivity to the photosensitive silver halide used in the present invention, the photosensitive silver halide emulsion is spectrally sensitized with a methine dye or the like. If necessary, the blue-sensitive emulsion may be subjected to spectral sensitization in the blue region. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Specifically, 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. These sensitizing dyes may be used alone, or a combination thereof may be used. The combination of sensitizing dyes is often used for the purpose of adjusting the wavelength of supersensitization or spectral sensitization. . Along with the sensitizing dye, a dye which has no spectral sensitizing effect or a compound which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (for example, US Pat. , 615, 641, and JP-A-63-23145). These sensitizing dyes may be added to the emulsion at or before chemical ripening, or before or after nucleation of silver halide grains according to U.S. Pat. Nos. 4,183,756 and 4,225,666. Good. These sensitizing dyes and supersensitizers may be added as a solution of an organic solvent such as methanol, a dispersion such as gelatin, or one solution of a surfactant. The amount added is generally 1 silver halide.
It is about 10 ^-8 to 10 ^-2 mol per mol.

The hydrophilic protective colloid used for producing the silver halide color photographic light-sensitive material of the present invention includes:
Product Licensing Index, Volume 92 P
108, gelatin derivatives such as acetylated gelatin and phthalated gelatin, water-soluble cellulose derivatives, and other synthetic or natural hydrophilic compounds, in addition to the gelatin used in ordinary silver halide emulsions as described in the section of "Vehicles". Functional polymers.

In the silver halide color photographic light-sensitive material of the present invention, various techniques and additives known in the art can be used as needed. For example, in addition to the photosensitive silver halide emulsion layer, auxiliary layers such as a protective layer, a filter layer, an antihalation layer, a crossover light cut layer, and a backing layer can be provided. Sensitizers, precious metal sensitizers, photosensitive dyes, supersensitizers, couplers,
High boiling point solvent, antifoggant, stabilizer, development inhibitor, bleaching accelerator, fixing accelerator, color mixture inhibitor, formalin scavenger, color tone, hardener, surfactant, thickener, plasticizer, slipping agent , An ultraviolet absorber, an anti-irradiation dye, a filter light-absorbing dye, a sunscreen, a polymer latex, a heavy metal, an antistatic agent, a matting agent and the like can be contained by various methods.

These additives described above are described in more detail in Research Disclosure, Vol. 176, Item /
17643 (December 1978), Volume 184 Item
/ 18431 (August 1979), 187 Items
/ 18716 (November 1979) and 308 It
em / 308119 (December 1989).

The types of compounds and the locations described in these three Research Disclosures are listed below.

Additives RD-17643 RD-18716 RD-308119 page classification page classification page classification chemical sensitizer 23 III 648 upper right 996 III sensitizing dye 23 IV 648-649 996-8 IV desensitizing dye 23 IV 998 IV dye 25-26 VIII 649-650 1003 VIII Development accelerator 29 XXI 648 Upper right antifoggant / stabilizer 24 IV 649 Upper right 1006-7 VI Brightener 24 V 998 V Hardener 26 X 651 Left 1004-5 X Surface activity Agent 26-7 XI 650 right 1005-6 XI antistatic agent 27 XII 650 right 1006-7 XIII plasticizer 27 XII 650 right 1006 XII sliding agent 27 XII matting agent 28 XVI 650 right 1008-9 XVI binder 26 XXII 1003-4 IX support 28 XVII 1009 XVII The light-sensitive material of the present invention includes various antifoggants, You may use photographic stabilizers and their precursors. Specific examples thereof include the aforementioned Research Disclosure, U.S. Pat. Nos. 5,089,378 and 4,5.
Nos. 00,627 and 4,614,702,
No. 135564, pages (7) to (9), (57) to (71)
Pp. (81)-(97), U.S. Pat.
5,610, 4,626,500, 4,98
No. 3,494, JP-A-62-174747, JP-A-62-274.
239148, JP-A-1-150135, 2-1
No. 10557, No. 2-178650, RD17643
No. (1978), pages (24) to (25). These compounds are 5 × per mole of silver
It is preferably 10 ^-6 to 1 × 10 ^-1 mol, more preferably 1 × 10 ^-5 mol.
１1 × 10 ^-2 mol is preferably used.

In the light-sensitive material of the present invention, a protective layer and a protective layer are provided between the silver halide emulsion layers and as the uppermost layer and the lowermost layer.
Various non-photosensitive layers such as an undercoat layer, an intermediate layer, a yellow filter layer and an antihalation layer may be provided, and various auxiliary layers such as a back layer can be provided on the side opposite to the support. Specifically, US Pat. No. 5,051,335
No. undercoat layer, JP-A-1-1677838,
Intermediate layers having solid pigments as described in JP-A-61-20943, JP-A-1-120553 and JP-A-5-3488.
Nos. 4 and 2-64634 and reducing agents such as DIR
Interlayer with compound, US Pat. No. 5,017,454
No. 5,139,919, JP-A-2-235044
Intermediate layer having an electron transfer agent as described in
A protective layer having a reducing agent as described in JP-A-249245 or a layer obtained by combining them can be provided.

In the silver halide color photographic light-sensitive material of the present invention, dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and halation. Colloidal silver fine particles have often been used in the yellow filter layer and antihalation layer of conventional color light-sensitive materials. However, it is necessary to provide a bleaching step to remove the colloidal silver after developing the light-sensitive material. For the purpose of the present invention, which requires simple processing, a light-sensitive material which does not require a bleaching step is preferable. Therefore, in the present invention, it is preferable to use a dye, in particular, a dye which decolors or elutes and transfers during development processing and has a small contribution to the density after processing, instead of colloidal silver. When the dye is decolored or removed at the time of development, the amount of the dye remaining after the processing is 1/3 or less, preferably 1/10 or less immediately before coating, and the dye component is developed at the time of development. May be eluted or transferred into a processing material, or may be converted to a colorless compound by reacting during development.

These dyes may be added to a silver halide emulsion layer or a non-photosensitive layer. From the viewpoint of achieving both sensitivity and sharpness, a dye that absorbs light in the same wavelength range is added to the side opposite to the exposure source to the layer where the silver halide emulsion sensitive to a certain wavelength range exists. preferable. As the dye used in the light-sensitive material of the present invention, a known dye can be used. For example, a dye that dissolves in the alkali of the developing solution, or a type of dye that reacts with the components in the developing solution, sulfite ions, the base agent, or the alkali to be decolorized can be used.

Specifically, European Patent Application EP549,4
No. 89A and the dye described in JP-A-7-152129.
xF2 to 6 dyes. These dyes can be used when developing a photosensitive material with a processing solution, but are particularly preferable when the photosensitive material is thermally developed using a processing sheet described later.

In the case of treating with a treatment solution, JP-A-3-251840 discloses a dye having absorption in the visible region.
Dyes of AI-1 to 11 described on page 08;
The dye described in JP-A-3770 is preferably used. Examples of the infrared absorbing dye include general formulas (I), (II) and (II) described in the lower left column of page 2 of JP-A-1-280750.
The compound represented by the formula (I) has preferable spectral characteristics, does not affect the photographic characteristics of the silver halide photographic emulsion, and is preferably free from contamination by residual color. Specific examples of preferred compounds include Exemplified Compounds (1) to (45) listed on page 3, lower left column to page 5, lower left column of the same publication.

Further, the mordant and the binder may be dyed with a mordant. In this case, as the mordant and the dye, those known in the field of photography can be used.
No. 0,626, columns 58 to 59 and JP-A-61-8825.
No. 6, pages 32 to 41, JP-A-62-244043, JP-A-62-244036 and the like. Further, by using a compound that reacts with a reducing agent to release a diffusible dye and a reducing agent, the mobile dye can be released with an alkali at the time of development and eluted in a processing solution or transferred and removed to a processing sheet. Specifically, U.S. Patent Nos. 4,559,290 and 4,783,369, European Patent No. 220,746A2, and Published Technical Report 87-6119.
And Japanese Patent Application No. 6-259805, paragraphs 0080-0081.

A decolorizable leuco dye or the like can also be used. Specifically, JP-A-1-150132 discloses a silver halide photosensitive material containing a leuco dye which has been colored in advance with a developer of a metal salt of an organic acid. Since the leuco dye and the developer complex react with heat or an alkali agent to decolor, when performing thermal development in the present invention, the combination of the leuco dye and the developer is preferable.
Known leuco dyes can be used, and are described in Moriga and Yoshida, “Dyes and Chemicals”, p. 84, page 84 (Chemical Products Industry Association), “New Edition Dye Handbook”, p. 242 (Maruzen, 1970), R. Garner
"Reportson the Progress o
f Appl. Chem ", 56, 199 (197
1), "Dyes and Chemicals", p. 19, 230 (Chemical Products Association, 1974), "Coloring Materials", p. 62, 288 (198)
9), “Dye industry”, 32, 208 and the like. As the developer, a metal salt of an organic acid is preferably used in addition to the acid clay-based developer and phenol formaldehyde resin.

As the binder for the constituent layers of the light-sensitive material, hydrophilic binders are preferably used. Examples are the above-mentioned Research Disclosure and JP-A-64-135.
No. 46, pages (71) to (75). Specifically, transparent or translucent hydrophilic binders are preferable, for example, gelatin, proteins such as gelatin derivatives or cellulose derivatives, starch, gum arabic, dextran, pullulan, natural compounds such as polysaccharides such as carrageenan, and polysaccharides. Synthetic polymer compounds such as vinyl alcohol, polyvinylpyrrolidone, and acrylamide polymer are exemplified.

Also, US Pat. No. 4,960,681,
Superabsorbent polymers described in JP-62-245260 Patent etc., i.e. -COOM or -SO ₃ M (M is a hydrogen atom or an alkali metal) homopolymer or a vinyl monomer together or with other vinyl vinyl monomer having Copolymers with monomers (eg, sodium methacrylate, ammonium methacrylate, potassium acrylate, etc.) are also used. These binders may be used in combination of two or more kinds. Particularly, a combination of gelatin and the above binder is preferable. The gelatin may be selected from lime-processed gelatin, acid-processed gelatin, and so-called demineralized gelatin having a reduced content of calcium and the like according to various purposes, and it is also preferable to use them in combination. In the present invention, the coating amount of the binder is preferably 20 g or less per 1 m ² , and particularly preferably 10 g or less.

The light-sensitive material of the present invention is preferably hardened with a hardener. U.S. Pat.
678,739, column 41, 4,791,042,
JP-A-59-116655 and JP-A-62-245261.
No., 61-18942, 61-249054,
Hardening agents described in JP-A-61-245153 and JP-A-4-218044 are exemplified. More specifically, aldehyde hardeners (such as formaldehyde), aziridine hardeners, epoxy hardeners, and vinyl sulfone hardeners (N, N'-ethylene-bis (vinylsulfonylacetamide)) Ethane, etc.), N-methylol hardeners (dimethylolurea, etc.), boric acid, metaboric acid and polymer hardeners (compounds described in JP-A-62-234157). Among these hardeners, it is preferable to use a vinyl sulfone hardener or a chlorotriazine hardener alone or in combination. These hardeners are used in an amount of 0.001 to 1 g, preferably 0.005 to 0.5 g, per 1 g of the hydrophilic binder.

As the support that can be used in the present invention, synthetic plastic films such as polyolefins such as polyethylene and polypropylene, polycarbonates, cellulose acetate, polyethylene terephthalate, polyethylene naphthalate and polyvinyl chloride can also be preferably used. Syndiotactic polystyrenes are also preferred. These can be obtained by polymerizing according to the methods described in JP-A Nos. 62-117708, 1-46912 and 178505.

Further, a support which can be used in the light-sensitive material of the present invention includes a paper support such as photographic base paper, printing paper, baryta paper and resin-coated paper, and a support in which a reflective layer is provided on the above-mentioned plastic film. No. 253195 (pages 29 to 31).

The RD. No. 17643, page 28,
No. No. 18716, from the right column on page 647 to the left column on page 648 and the same No. Those described on page 879 of 307105 can also be preferably used. Syndiotactic polystyrenes are also preferred. These are disclosed in JP-A-62-117.
No. 708, JP-A-1-46912 and 1-178050
It can be obtained by polymerization according to the method described in No. 5.

These supports are disclosed in US Pat.
By performing a heat treatment of Tg or less as in 1,735,
It is possible to use a material having a hard curl. The surface of these supports may be subjected to surface treatment for the purpose of improving the adhesion between the support and the emulsion undercoat layer. In the present invention, glow discharge treatment, ultraviolet irradiation treatment, corona treatment, and flame treatment can be used as the surface treatment. Further, the supports described in the publicly known technique No. 5 (Aztec Co., Ltd., March 22, 1991), pp. 44 to 149 can also be used. A transparent support such as polyethylene dinaphthalenedicarboxylate or a support on which a transparent magnetic substance is applied can be used.

Examples of the support which can be used in the light-sensitive material according to the present invention include, for example, the aforementioned RD-17643-2
8 and page 1009 of RD-308119, and those described in the “Products Licensing Index”, Vol. 92, P108, “Supports”.

When the light-sensitive material of the present invention is used in a heat development process described later, it is necessary to use a support capable of withstanding the processing temperature.

As a support, for example, JP-A-4-14-1
No. 24645, No. 5-40321, No. 6-35092
Photographic information can also be recorded using a support having a magnetic recording layer described in Japanese Patent Application Laid-Open Nos. 5-58221 and 5-106979.

The magnetic recording layer is obtained by coating an aqueous or organic solvent-based coating solution in which magnetic particles are dispersed in a binder on a support. Magnetic particles include ferromagnetic iron oxide such as γ-Fe ₂ O _3, Co deposited γ-Fe ₂ O _3, Co coated magnetite, Co containing magnetite, ferromagnetic chromium dioxide, ferromagnetic metal, ferromagnetic alloy, Hexagonal Ba ferrite, Sr ferrite, Pb ferrite, Ca ferrite and the like can be used. Co-coated γ-Fe ₂ O ₃ Any Co-coated ferromagnetic iron oxide is preferred. Needle shape, rice grain shape,
Any of spherical, cubic, and plate shapes may be used. Preferably at least 20 m ² / g in SBET is the specific surface area, and particularly preferably equal to or greater than 30 m ² / g. The saturation magnetization (σs) of the ferromagnetic material is preferably from 3.0 × 10 ^{4 to} 3.0 × 10 ⁵ A / m,
Particularly preferably, it is 4.0 × 10 ^{4 to} 2.5 × 10 ⁵ A / m. The ferromagnetic particles may be subjected to a surface treatment with silica and / or alumina or an organic material. Further, the surface of the magnetic particles may be treated with a silane coupling agent or a titanium coupling agent as described in JP-A-6-161332. JP-A-4-259911
And magnetic particles having a surface coated with an inorganic or organic substance described in JP-A-5-81652.

The binder used for the magnetic particles may be a thermoplastic resin, a thermosetting resin, a radiation-curable resin, a reactive resin, an acid, an alkali or a biodegradable polymer, a natural product described in JP-A-4-219569. Polymers (cellulose derivatives, sugar derivatives, etc.) and mixtures thereof can be used. Tg of the above resin is −40 ° C. to 300 ° C.,
The weight average molecular weight is from 2,000 to 1,000,000. Examples thereof include vinyl copolymers, cellulose derivatives such as cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, and cellulose tripropionate, acrylic resins, and polyvinyl acetal resins, and gelatin is also preferable. Particularly, cellulose di (tri) acetate is preferable.

The binder can be cured by adding an epoxy-based, aziridine-based, or isocyanate-based crosslinking agent.

Examples of the isocyanate-based crosslinking agent include isocyanates such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, and xylylene diisocyanate;
Reaction products of these isocyanates with polyalcohols (for example, a reaction product of 3 mol of tolylene diisocyanate and 1 mol of trimethylolpropane), and polyisocyanates formed by condensation of these isocyanates are mentioned. Kaihei 6-5935
No. 7.

As a method for dispersing the above-mentioned magnetic substance in the binder, a kneader, a pin type mill, an annular type mill and the like are preferably used, as in the method described in JP-A-6-35092. JP-A-5-08828
The dispersant described in No. 3 and other known dispersants can be used.

The thickness of the magnetic recording layer is usually from 0.1 μm to 10 μm.
μm, preferably 0.2 μm to 5 μm, more preferably 0.3 μm to 3 μm. The weight ratio between the magnetic particles and the binder is preferably 0.5: 100 to 60: 100, and more preferably 1: 100 to 30: 100.

The coating amount of the magnetic particles is usually 0.005 to 3
g / m ^2, preferably not 0.01 to 2 g / m ^2, more preferably at 0.02 to 0.5 g / m ^2. The transmission yellow density of the magnetic recording layer is preferably 0.01 to 0.50,
0.03 to 0.20 is more preferable, and 0.04 to 0.1
5 is particularly preferred.

The magnetic recording layer can be provided on the entire back surface of the photographic support by coating or printing or in the form of stripes. Examples of the method of applying the magnetic recording layer include an air doctor, a blade, an air knife, a squeeze, an impregnation, a reverse roll, a transfer roll, a gravure, a kiss, a cast, a spray, a dip, a bar, and an extrusion. The coating solution described in 341436 is preferred.

In the magnetic recording layer, lubricity improvement, curl control,
It may have functions such as antistatic, antiadhesion, and head polishing, or may provide another functional layer to provide these functions. At least one of the particles has a Mohs hardness of 5 or more. Abrasives of the above non-spherical inorganic particles are preferred. As the composition of the non-spherical inorganic particles, oxides such as aluminum oxide, chromium oxide, silicon dioxide, titanium dioxide and silicon carbide, carbides such as silicon carbide and titanium carbide, and fine powders such as diamond are preferable.

These abrasives may have their surfaces treated with a silane coupling agent or a titanium coupling agent. These particles may be added to the magnetic recording layer, or may be overcoated (for example, a protective layer, a lubricant layer, etc.) on the magnetic recording layer. As the binder used at this time, the above-mentioned binders can be used, and the same binder as the binder for the magnetic recording layer is preferable. Regarding photosensitive materials having a magnetic recording layer, US Pat. Nos. 5,336,589 and 5,25.
0,404, 5,229,259, 5,21
No. 5,874, EP 466,130.

The polyester support preferably used for the above-mentioned photosensitive material having a magnetic recording layer will be further described. The details including the photosensitive material, the processing, the cartridge, and the examples are described in Published Technology, Official Technical Publication No. 94-6023.
(Invention Association; 1994. 3.15).

The polyester is formed with a diol and an aromatic dicarboxylic acid as essential components. As the aromatic dicarboxylic acids, 2,6-, 1,5-, 1,4- and 2,7-naphthalenedicarboxylic acid, terephthalic acid, Examples of isophthalic acid, phthalic acid, and diol include diethylene glycol, triethylene glycol, cyclohexane dimethanol, bisphenol A, and bisphenol.

Examples of the polymer include homopolymers such as polyethylene terephthalate, polyethylene naphthalate and polycyclohexane dimethanol terephthalate. Particularly preferred is a polyester containing 50 to 100 mol% of 2,6-naphthalenedicarboxylic acid. Among them, polyethylene-2,6-naphthalate is particularly preferred. The average molecular weight ranges from about 5,000 to 200,000. The Tg of the polyester is 50 ° C. or higher, preferably 90 ° C. or higher.

Next, the polyester support is heat-treated at a heat treatment temperature of 40 ° C. or more and less than Tg, more preferably Tg−20 ° C. or more and less than Tg in order to make it difficult to form a curl. The heat treatment may be performed at a constant temperature within this temperature range, or may be performed while cooling.

The heat treatment time ranges from 0.1 hour to 1500 hours.
Time, more preferably 0.5 to 200 hours. The heat treatment of the support may be performed in the form of a roll, or may be performed while being transported in the form of a web. Irregularities may be imparted to the surface (for example, conductive inorganic fine particles such as SnO ₂ or Sb ₂ O ₅ may be applied) to improve the surface state. It is also desirable to take measures such as applying knurls to the ends and making the ends slightly higher so as to prevent the cut end of the core from appearing. These heat treatments may be performed at any stage after the formation of the support, after the surface treatment, after the application of the back layer (antistatic agent, slip agent, etc.), and after the application of the undercoat. Preferably after application of the antistatic agent. An ultraviolet absorber may be incorporated into this polyester.

In order to prevent light pumping, Diaresin manufactured by Mitsubishi Kasei and Kayase manufactured by Nippon Kayaku were used.
The object can be achieved by applying a commercially available dye or pigment for polyesters such as t.

One of the preferable processing modes of the light-sensitive material of the present invention is an activator processing. Activator processing means that a color developing agent is built in a photosensitive material,
It refers to a processing method in which development processing 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.). Activator treatment is described in European Patent Nos. 545,491A1 and 565,16.
This is exemplified in known literature such as 5A1. The pH of the activator treatment liquid used in the present invention is preferably 9 or more, more preferably 10 or more.

When the light-sensitive material of the present invention is subjected to an activator treatment, an auxiliary developer is preferably used. Here, the auxiliary developer is a substance having an action of promoting the transfer of electrons from the color developing agent to the silver halide in the development process of silver halide development.

The auxiliary developer may be added to the activator processing solution, but may be incorporated in the photosensitive material in advance. A method of developing with an aqueous alkali solution containing an auxiliary developer is described in RD. No. No. 17643, pages 28 to 29;
No. 18716, 651 left column to right column; 307
105, pages 880-881.

The auxiliary developing agent in the present invention is preferably an electron-emitting compound represented by the general formula (ETA-I) or the general formula (ETA-II) according to the Kendall-Peltz rule. Among them, those represented by (ETA-I) are particularly preferred.

[0240]

Embedded image

In the general formulas (ETA-I) and (ETA-II), 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 group, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, a cycloalkyloxy group, an aryloxy group, 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.

Formula (ETA-I) or (ETA-II)
Specific examples of the compound represented by No. 10-44518 by the present applicant are described in p. Compounds (ETA-1) to (ETA-32) described in 26 to 30.

When the auxiliary developer is incorporated in the light-sensitive material, the auxiliary developer may be incorporated in the form of a precursor in order to enhance the storage stability of the light-sensitive material. The auxiliary developer precursor used herein is described in JP-A-1-13855.
No. 6 and the like. These compounds are dissolved in a suitable solvent such as water, alcohols, acetone, dimethylformamide, glycols,
Alternatively, it can be applied by dispersing in a fine solid dispersion or dispersing in a high boiling point organic solvent such as tricresyl phosphate and then dispersing the fine particles in a hydrophilic binder, and applying. These auxiliary developer precursors may be used in combination of two or more, or may be used in combination with an auxiliary developer.

Another preferred processing mode of the light-sensitive material of the present invention is a heat development processing. In the heat development, it is preferable to use a processing material different from the photosensitive material. Examples of the treatment material include a sheet having a treatment layer containing a base and / or a base precursor on a support.
It is preferable that the treatment layer is composed of a hydrophilic binder. After the photosensitive material is imagewise exposed, the photosensitive material and the processing material are bonded on the photosensitive layer surface of the photosensitive material and the processing layer surface of the processing material and heated to form an image. A method of performing color development by supplying water equivalent to 1/10 to 1 time of water required for maximum swelling of the entire coating film constituting the photosensitive material and the processing material to the photosensitive material or the processing material, and then bonding and heating the color development. Is preferably used. Further, it is also possible to use a method in which the auxiliary developer is incorporated in the photosensitive material or the processing material as required, or is applied together with water.

The heat treatment of the photosensitive material is known in the art.
For example, the basics of photo engineering (Corona, 1970)
553-555, April 1978, video information 4
Page 0, Nabletts Handbook of P
photography and Reprograph
y 7th Ed. (Vna Nostrand an
d Reinhold Company) 32-33
, U.S. Patent Nos. 3,152,904 and 3,30
Nos. 1,678, 3,392,020, 3,4
57,075, British Patent Nos. 1,131,108 and 1,167,777, and Research Disclosure, June 1978, pp. 9-15 (RD-1702).
9). The heating temperature in the heat development step is usually from 50 ° C to 250 ° C, and particularly preferably from 60 ° C to 150 ° C.

To the light-sensitive material of the present invention, a thermal solvent may be added for the purpose of promoting thermal development. The hot solvent is a compound that liquefies when heated and has an action of promoting image formation.
At room temperature, it is preferably white and in a solid state, and it is desired that volatility during heating is small. Preferred melting point is 70
１７０170 ° C. Examples include U.S. Pat.
Organic compounds having a polarity as described in JP-A Nos. 47,675 and 3,667,959 may be mentioned.
Specifically, amide derivatives (benzamide etc.), urea derivatives (methyl urea, ethylene urea etc.), sulfonamide derivatives (JP-B-1-40974 and JP-B-4-137)
No. 01), polyol compounds sorbitols, and polyethylene glycols.

In addition, examples of the thermal solvent which can be used in the present invention include, for example, US Pat. Nos. 3,347,675, 3,438,776, 3,666,477, and 3,667,959. RD17643, JP-A-Sho 51
195525, 53-24829, 53-60
No. 223, No. 58-118640, No. 58-1980
No. 38, No. 59-68730, No. 59-84236
No. 59-229556, No. 60-14241,
Nos. 60-191251, 60-232525, 61-52643, 62-42153 and 62-
No. 44737, No. 62-78554, No. 62-136
No. 645, No. 62-139545, No. 63-5354
No. 8, 63-161446, JP-A-1-22475
No. 1, No. 1-227150, No. 2-863, No. 2-
Compounds described in JP-A Nos. 120739 and 2-123354 can be exemplified.

Further, as specific examples of preferred thermal solvents used in the present invention, JP-A-2-297548, 8
TS-1 to TS-21 described in the upper left of page 9 to the upper left of page 9 are exemplified. The thermal solvents of the present invention can be used in combination of two or more.

In the light-sensitive material and / or processing material of the present invention, it is preferable to use a base or a base precursor for the purpose of promoting silver development and a dye-forming reaction. Examples of the base precursor include a salt of an organic acid and a base that are decarboxylated by heat, and a compound that releases an amine by an intramolecular nucleophilic substitution reaction, Lossen rearrangement, or Beckmann rearrangement.

Specific examples thereof are described in US Pat. No. 4,514,4.
Nos. 93, 4,657,848 and No. 5 (March 22, 1991, Aztec Co., Ltd.), pp. 55-86. A method of generating a base with a combination of a basic metal compound which is hardly soluble in water and a compound capable of forming a complex with metal ions constituting the basic metal compound using water as a medium (referred to as a complex forming compound) is also preferably used.

Such base generation methods are described in EP 210,660 and US Pat. No. 4,740,445. When such a base generation method is used, in the present invention, a basic metal compound which is hardly soluble in water is added to the photosensitive material, and the processing material is complexed with a metal ion constituting the basic metal compound and water as a medium. It is preferable to include a compound capable of forming reaction (referred to as a complex-forming compound). With such a configuration, the storage stability of the photosensitive material can be improved.

The processing material used in the heat development step of the present invention contains the above-mentioned base and / or base precursor, and further shuts off air during heat development,
The material is prevented from volatilizing from the light-sensitive material, the processing material other than the base is supplied to the light-sensitive material, the material (YF dye, AH dye, etc.) in the light-sensitive material which becomes unnecessary after development, or is generated at the time of development. It can also have a function of removing unnecessary components.

Further, the processing material may have a desilvering function. For example, when a part or all of the silver halide and / or the developed silver is soluble when the photographic material is superposed with the imagewise exposed post-processing material, the processing material may contain a fixing agent as a silver halide solvent. You can leave it.

As the support and the binder for the processing material, the same materials as those for the photosensitive material can be used. A mordant may be added to the processing material for the purpose of removing the above-mentioned dye or other purposes. As the mordant, those known in the field of photography can be used, and U.S. Pat. No. 4,50,626, columns 58 to 59, JP-A-61-88256, pages 32-41,
Examples include mordants described in JP-A-2-244043 and JP-A-62-244036. Further, a dye-receiving polymer compound described in U.S. Pat. No. 4,463,079 may be used. Further, the above-mentioned thermal solvent may be contained.

The treatment layer of the treatment material contains a base or a base precursor. The base may be either an organic base or an inorganic base. As the inorganic base, JP-A-62
Hydroxides (eg, potassium hydroxide, sodium hydroxide, lithium hydroxide, calcium hydroxide, magnesium hydroxide, etc.), phosphates (eg, dipotassium hydrogen phosphate) described in US Pat. Secondary or tertiary phosphates such as disodium hydrogen phosphate, ammonium sodium phosphate, calcium hydrogen phosphate, etc.), carbonates (eg, potassium carbonate, sodium carbonate, sodium hydrogen carbonate, magnesium carbonate, etc.), Borate (eg, potassium borate, sodium borate, sodium metaborate, etc.), organic acid salt (eg, potassium acetate, sodium acetate, potassium oxalate, sodium oxalate, potassium tartrate, sodium tartrate,
Sodium malate, sodium palmitate, sodium stearate, etc.), acetylides of alkali metals or alkaline earth metals described in JP-A-63-25208,
And the like.

As the organic base, ammonia,
Aliphatic or aromatic amines (e.g., primary amines (e.g., methylamine, ethylamine, butylamine, n-
Hexylamine, cyclohexylamine, 2-ethylhexylamine, allylamine, ethylenediamine, 1,
4-diaminobutane, hexamethylenediamine, aniline, anisidine, p-toluidine, α-naphthylamine, m-phenylenediamine, 1,8-diaminonaphthalene, benzylamine, phenethylamine, ethanolamine, etc., and secondary amine (for example, dimethylamine) , Diethylamine, dibutylamine, diallylamine, N-methylaniline, N-methylbenzylamine, N-methylethanolamine, diethanolamine, etc., tertiary amines (for example, N-methylmorpholine, N-methyl morpholine described in JP-A-62-170954). Hydroxyethylmorpholine, N-
Methylpiperidine, N-hydroxyethylpiperidine,
N, N'-dimethylpiperazine, N, N'-dihydroxyethylpiperazine, diazabicyclo [2,2,2] octane, N, N-dimethylethanolamine, N, N-
Dimethylpropanolamine, N-methyldiethanolamine, N-methyldipropanolamine, triethanolamine, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetrahydroxyethylethylenediamine, N , N, N ', N'-tetramethyltrimethylenediamine, N-methylpyrrolidine, etc.), polyamines (diethylenetriamine, triethylenetetramine, polyethyleneimine, polyallylamine, polyvinylbenzylamine, poly- (N, N-diethylaminoethylmethacrylate) ), Poly- (N, N-
Dimethylvinylbenzylamine)), hydroxylamines (e.g., hydroxylamine, N-hydroxy-
N-methylaniline, etc.), heterocyclic amines (for example, pyridine, lutidine, imidazole, aminopyridine,
N, N-dimethylaminopyridine, indole, quinoline, isoquinoline, poly-4-vinylpyridine, poly-
2-vinylpyridine, etc., amidines (eg, monoamidine, (eg, acetamidine, imidazotan, 2-methylimidazole, 1,4,5,6-tetrahydropyrimidine, 2-methyl-1,4,5,6-tetrahydropyrimidine) , 2-phenyl-1,4,5,6-tetrahydropyrimidine, iminopiperidine, diazabicyclononene, diazabicycloundecene (DBU), etc.), bis or tris, tetraamidine, guanidines (for example, water-soluble Monoguanidine (eg guanidine,
Dimethylguanidine, tetramethylguanidine, 2-aminoimidazoline, 2-amino-1,4,5-tetrahydropyrimidine, etc.)), water-insoluble mono- or bisguanidine, bis or tris described in JP-A-63-70845. Tetraguanidine, quaternary ammonium hydroxide (eg, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide,
Trimethylbenzylammonium hydroxide,
Trioctylmethylammonium hydroxide,
Methylpyridinium hydroxide, etc.).

When a complex forming compound for a metal ion of a poorly water-soluble basic compound is used as the base precursor, for example, an aminocarboxylic acid such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid or a salt thereof is used. , Aminophosphonic acid or a salt thereof,
2-picolinic acid, pyridine-2,6-dicarboxylic acid, 5
Pyridylcarboxylic acid such as -ethyl-2-picolinic acid or a salt thereof, iminodiacetic acid such as benzyliminodiacetic acid, α-picolineliminodiacetic acid or a salt thereof and the like can be used. As the complex-forming compound, it is preferable to use a salt neutralized with an organic base such as guanidine or an alkali metal such as potassium. The preferable addition amount of the base or the base precursor or the complex-forming compound in the treatment material is 0.1 to 20 g / m ² , more preferably 0.5 to 10 g / m ² .

On the other hand, as the water-insoluble basic compound to be contained in the light-sensitive material, a metal hydroxide or a metal oxide is preferably used, and among these, zinc hydroxide or zinc oxide is particularly preferable. Is preferred.

In thermal development using the processing material, it is preferable to use a small amount of water for the purpose of promoting development, promoting transfer of the processing material, and promoting diffusion of unnecessary substances. As described above, when a method of generating a base with a combination of a basic metal compound which is hardly soluble in water and a metal ion constituting the basic metal compound and a complex forming compound is employed, it is essential to use water. is there. The water may contain an inorganic alkali metal salt, an organic base, a low-boiling solvent, a surfactant, an antifoggant, a complex-forming compound with a poorly soluble metal salt, a fungicide, and a bactericide. Any water may be used as long as it is generally used. Specifically, distilled water, tap water, well water, mineral water and the like can be used.

In the thermal developing apparatus using the light-sensitive material and the processing material of the present invention, the water may be used up, or the water may be circulated and used repeatedly. In the latter case, water containing components eluted from the material will be used. JP-A-63-144354 and JP-A-63-144355.
And water described in JP-A-62-38460 and JP-A-3-210555. Water can be applied to the photosensitive material, the processing material, or both. The amount used is 1/1/3 of the amount required for maximally swelling all coating films (excluding the back layer) of the photosensitive material and the processing material.
This is an amount equivalent to 10 to 1 times. As a method for applying the water, for example, JP-A-62-253159 (5)
Page, JP-A-63-85544 and the like are preferably used.

In addition, the solvent can be used by being encapsulated in a microcapsule or incorporated in advance in a light-sensitive material or a processing material or both in the form of a hydrate. The temperature of the water to be applied may be 30 ° C. to 60 ° C. as described in JP-A-63-85544.

When the photosensitive material of the present invention is thermally developed, known heating means can be applied, for example, a method of contacting with a heated heat block or a surface heater, or a method of contacting with a heat roller or a heat drum. A method of contacting with an infrared or far-infrared lamp heater, a method of passing through an atmosphere maintained at a high temperature, a method of using a high-frequency heating method, or the like can be used.

In addition, a method in which a heat-generating conductive substance such as a carbon black layer is provided on the back surface of the photosensitive material or the image receiving member, and Joule heat generated by energization can be applied. The heating element of this heat generation is disclosed in
What is described in 1-1145544 etc. can be used. A method of superposing a photosensitive material and a processing material in such a manner that the photosensitive layer and the processing layer face each other is described in JP-A-62-253159 and JP-A-6-253159.
The method described in 1-1147244, page 27, can be applied. The heating temperature is preferably from 70C to 100C.

For processing the photographic element of the present invention, any of various heat developing apparatuses can be used. For example, JP-A-59-7
No. 5247, No. 59-177547, No. 59-181
No. 353, No. 60-18951, Shokai 62-259
No. 44, Japanese Patent Application No. 4-277517, No. 4-24307
No. 2, 4-24493, 6-164421,
An apparatus described in JP-A-6-164422 or the like is preferably used. As a commercially available device, there can be used Pictrostat 100, Pictrostat 200, Pictrostat 300, Pictrostat 330, Pictrostat 50, Pictrograph 3000, Pictograph 2000, etc., manufactured by Fuji Photo Film Co., Ltd. .

In the heat development processing of the present invention, a processing stop agent may be included in the processing member, and the development stop agent may act simultaneously with the development. The term "development terminator" as used herein means that after appropriate development, the base is quickly neutralized or reacts with the base to reduce the base concentration in the film, and interact with a compound that stops development or silver and silver salts to suppress development. Compound. Specific examples include an acid precursor that releases an acid when heated, an electrophilic compound that causes a substitution reaction with a coexisting base when heated, or a nitrogen-containing heterocyclic compound, a mercapto compound, and a precursor thereof. For further details, see JP-A-62-253.
No. 159, pages (31) to (32).

Further, a combination in which a zinc salt of mercaptocarboxylic acid described in Japanese Patent Application No. 6-190529 or the like is contained in a photosensitive member and the above-mentioned complex-forming compound is contained in a processing member is advantageous. Similarly, a silver halide printout preventing agent may be included in the processing member, and the function may be developed simultaneously with the development. Examples of the printout inhibitor include a monohalogen compound described in JP-B-54-164, a trihalogen compound described in JP-A-53-46020, and a halogen described in JP-A-48-45228 bonded to an aliphatic carbon atom. And polyhalogen compounds represented by tetrabromoxylene described in JP-B-57-8454. Also, UK Patent No. 1,005,
A development inhibitor such as 1-phenyl-5-mercaptotetrazole described in No. 144 is also effective.

The viologen compounds described in Japanese Patent Application No. 6-337531 are also effective. The use amount of the printout inhibitor is preferably 10 ^-4 to 1 mol / Ag.
It is 1 mol, particularly preferably 10 ^-3 to 10 ^-1 mol / Ag1 mol.

In the heat development processing of the present invention, a silver oxidizing agent acting as a bleaching agent is contained in the processing material in order to remove the developed silver generated in the photosensitive material by the heat development, These reactions can take place. Further, after the development of the image formation is completed, the second material containing the oxidizing agent for silver can be bonded to the photosensitive material to remove the developed silver. However, it is preferable that the developed silver is not bleached during processing because the processing is simple.

As the bleaching agent that can be used in the processing material of the present invention, any commonly used silver bleaching agent can be used. Such bleaches are disclosed in U.S. Pat. No. 1,315,464.
No. 1,946,640 and Photogr
aphic Chemistry ol2, chapter
er 30, Foundation Press Lo
ndon England. These bleaches effectively oxidize and solubilize photographic silver images. Examples of useful silver bleaches include alkali metal dichromates, alkali metal ferricyanides. Preferred bleaches are those that are soluble in water, and ninhydrin, indandione, hexaketocyclohexane, 2,4-dinitrobenzoic acid, benzoquinone, benzenesulfonic acid,
Includes 2,5-dinitrobenzoic acid. Metal-organic complexes such as ferric salts of cyclohexyldialkylaminotetraacetic acid and ferric salts of ethylenediaminetetraacetic acid;
There is a ferric salt of citric acid. With respect to the binder, the support, and other additives that can be used for the second processing material, the same materials as the processing material (first processing material) for developing the photosensitive material can be used. The amount of the bleaching agent to be applied should be changed according to the silver content of the light-sensitive material to be laminated.
It is used in the range of from 0.1 mol to 10 mol / mol of coated silver of the photosensitive material. The molar ratio is preferably 0.1 to 3 mol / mol of silver applied to the light-sensitive material, and more preferably 0.1 to 2 mol / mol of silver applied to the light-sensitive material.

In order to remove unnecessary silver halide after image formation, a compound having a fixing function can be contained in the processing material. One specific example of such a method is a method in which a physical development nucleus and a silver halide solvent are included in a processing material, and the silver halide of the photosensitive material is solubilized during heating and fixed to the processing layer. Is mentioned. The physical development nucleus converts soluble silver salt diffused from the light-sensitive material into physical developed silver and fixes it to the processing layer.

As physical development nuclei, zinc, mercury, lead, cadmium, iron, chromium, nickel, tin, cobalt, copper,
Heavy metals such as ruthenium, or palladium, platinum,
Any known physical development nuclei such as colloidal particles of noble metals such as silver and gold or chalcogen compounds such as sulfur, selenium and tellurium can be used.

These physical development nuclei substances are prepared by reducing the corresponding metal ions with a reducing agent such as ascorbic acid, sodium borohydride, or hydroquinone to form a metal colloid dispersion, or by dissolving a soluble sulfide or selenide. Alternatively, it is obtained by mixing a telluride solution to form a colloidal dispersion of a water-insoluble metal sulfide, metal selenide or metal telluride.

These dispersions are preferably formed in a hydrophilic binder such as gelatin. A method for preparing colloidal silver particles is described in U.S. Pat. No. 2,688,601. If necessary, a desalting method for removing an excessive salt known in the method for preparing a silver halide emulsion may be performed. The size of these physical development nuclei is 2 to 200.
Those having a particle size of nm are preferably used. These physical development nuclei are usually added to the processing layer in an amount of 10 ^{−3 to} 100 mg /
m ² , preferably 10 ^{−2 to} 10 mg / m ² .
Physical development nuclei can be separately prepared and added to a coating solution, but in a coating solution containing a hydrophilic binder, for example, silver nitrate and sodium sulfide, or gold chloride and a reducing agent are reacted. It may be produced. Silver, silver sulfide, palladium sulfide and the like are preferably used as physical development nuclei.

When silver halide is fixed by such a method, a reducing agent capable of causing physical development in a layer containing physical development nuclei needs to be present. When a non-diffusible reducing agent is used, it is necessary to add it to the layer. However, when a diffusible reducing agent is used, the reducing agent is added to any layer of the photosensitive material or the processing material. No problem. As the reducing agent having such a function, the above-mentioned auxiliary developer is preferably used.

The silver halide may be fixed without using a physical development nucleus or a reducing agent. In this case, it is desired that silver ions are subjected to salt substitution by a so-called silver halide solvent to produce a non-photosensitive silver salt.

In any case, known silver halide solvents can be used. For such uses, compounds generally known as silver halide solvents and fixing agents can be optionally used, but are preferably used.

Examples of the silver halide solvent used in the present invention include thiosulfates, sulfites, thiocyanates, thioether compounds, mercapto compounds, thiouracils and JP-A-4-365037, pp. 11-21 and 5-1. -6
No. 6540, pp. 1088-1092, nitrogen-containing heterocyclic compounds having a sulfide group, mesoionic compounds, nitrogen-containing heterocyclic compounds such as tetraazaindenes, uracils, benzotriazoles, hydantoins, etc. Can be mentioned.

In each case, known silver halide solvents can be used. For example, thiosulfate,
Sulfites, thiocyanates, 1,8-di-3,6-dithiaoctane, 2,2 'described in JP-B-47-11386
Thioether compounds such as -thiodiethanol, 6,9-dioxa-3,12-dithiatetradecane-1,14-diol; uracils described in Japanese Patent Application No. 6-325350, and 5- or 6-membered ring imides such as hydantoin Compounds having a ring, mercapto compounds, thiouracils, JP-A-4-365037, pp. 11-21 and 5-6654.
No. 0, pages 1088 to 1092, nitrogen-containing heterocyclic compounds having a sulfide group, described in JP-A-53-1443.
The compound of the general formula (I) described in No. 19 can be used.

Analytical Chemika Acta (Anal)
ytica ChemicaActa) 248 60
Also preferred are trimethyltriazolium thiolate and meso-ion thiolate compounds described on pages 4-614 (1991). The compounds capable of fixing and stabilizing silver halide described in Japanese Patent Application No. 6-206331 can also be used as a silver halide solvent. These silver halide solvents may be used in combination.

Of the above compounds, particularly preferred are compounds having a 5- or 6-membered imide ring, such as sulfites, uracil and hydantoin. In particular, uracil or hydantoin is preferably added as a potassium salt in that gloss reduction during storage of the treated material can be improved.

The total content of the silver halide solvent in the processing layer is usually from 0.01 to 100 mmol / m ² , preferably from 0.1 to 50 mmol / m ² . More preferably, it is 1 to 30 mmol / m ² . The molar ratio is usually from 1/20 to 20 times, preferably from 1/10 to 10 times, more preferably from 1/3 to 10 times, relative to the amount of silver coated on the light-sensitive material.
It is three times.

The silver halide solvent may be added to a solvent such as water, methanol, ethanol, acetone, dimethylformamide, methylpropyl glycol, or an alkali or acidic aqueous solution, or may be dispersed in solid fine particles and added to a coating solution. Is also good.

The processing material can have at least one timing layer. The purpose of this timing layer is to delay the bleaching reaction and the fixing reaction until the reaction of the desired silver halide with the developing agent and further with the coupler is substantially completed. The timing layer can be made of gelatin, polyvinyl alcohol, or polyvinyl alcohol-polyvinyl acetate.

This layer may also be used, for example, in US Pat.
A barrier timing layer as described in US Pat. No. 6,394, 4,061,496 and 4,229,516 may be used.

In the heat development process of the present invention, two materials having different functions such as a processing material for performing color development and a processing material for performing bleaching and / or fixing (hereinafter referred to as a second processing material) are used. It is also possible to superpose the above-mentioned processing material and the photosensitive material in order and to perform the heat treatment. In this case, it is preferable that the processing material for development does not contain a compound having a bleaching or fixing function as described above.

As a method of heating the photosensitive material by superimposing it on the processing material for development and then bleaching it again using the second processing material, the photosensitive material, the second processing material, the photosensitive layer and the processing layer are respectively opposed to each other. It is overlaid together. At this time, water equivalent to 0.1 to 1 times the amount required for maximizing the swelling of the entire coating film except for both back layers is previously supplied to the photosensitive material or the second processing material.

In this state, at a temperature of 40 ° C. to 100 ° C., 5
By heating for seconds to 60 seconds, a bleaching process and a fixing process are performed. With respect to the amount of water, the type of water, the method of applying water, and the method of superimposing the photosensitive material and the processing material, the same materials as the processing materials for development can be used.

In order to use the light-sensitive material of the present invention for storage or appreciation for a long period after processing, it is preferable to perform the above-mentioned bleaching or fixing. However, when the photosensitive material of the present invention is read by a scanner or the like immediately after processing and is used for conversion into an electronic image as described later, bleaching processing and fixing processing are not necessarily required.

However, it is usually preferable to perform the fixing process. This is because the remaining silver halide has an absorption in the visible wavelength range, and adversely affects an electronic image obtained as a noise source during scanner reading. In order to realize a simple process of development only without performing a fixing process, it is preferable to use the above-mentioned thin tabular silver halide grains or silver chloride grains. In particular, silver chloride tabular grains are preferably used.

In the light-sensitive material and the processing material of the present invention, various surfactants can be used for the purpose of coating aid, improvement of peeling property, improvement of sliding property, antistatic property, acceleration of development and the like. Specific examples of the surfactant are known in the art No. 5 (March 22, 1991, Aztec Co., Ltd.), 136-13.
8 pages, JP-A-62-173463 and JP-A-62-1834.
No. 57, etc. The photosensitive material may contain an organic fluoro compound for the purpose of preventing slippage, preventing static charge, improving peelability, and the like. Representative examples of organic fluoro compounds are described in JP-B-57-9053, columns 8-17,
Hydrophobic surfactants such as fluorine-based surfactants described in JP-A Nos. 1-20944 and 62-135826, oily fluorine-containing compounds such as fluorine oil, and solid fluorine-containing compounds such as tetrafluoroethylene resin Compounds.

It is preferable that the photosensitive material and the processing material have a slip property. The content of the slip agent is preferably used for both the photosensitive layer surface and the back surface. A preferable slip property is 0.25 to 0.01 in terms of dynamic friction coefficient. The measurement at this time represents the value when the stainless steel ball having a diameter of 5 mm was conveyed at 60 cm / min (25 ° C., 60% RH). In this evaluation, even when the surface of the photosensitive layer is replaced as the partner material, the values are almost the same level.

Usable slip agents include polyorganosiloxanes, higher fatty acid amides, higher fatty acid metal salts, esters of higher fatty acids and higher alcohols, and the like, and polyorganosiloxanes include polydimethylsiloxane,
Polydiethylsiloxane, polystyrylmethylsiloxane, polymethylphenylsiloxane, or the like can be used. The additional layer is preferably the outermost layer of the emulsion layer or the back layer. Particularly, polydimethylsiloxane or an ester having a long-chain alkyl group is preferable.

In the light-sensitive material of the present invention, an antistatic agent is preferably used. Examples of such antistatic agents include polymers containing carboxylic acid and carboxylate and sulfonate, cationic polymers, and ionic surfactant compounds.

The most preferred antistatic agent is Z
nO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO
₂ , at least one kind of volume resistivity selected from MgO, BaO, MoO ₃ , and V ₂ O ₅ is usually 10 ⁷ Ω · cm or less;
More preferably, it is a fine particle of a crystalline metal oxide having a particle size of 0.005 to 1.0 μm or less and a composite oxide thereof having a particle size of 10 ⁵ Ω · cm or less. Preferably 5 to 500 mg / m ² as a content of the photosensitive material, particularly preferably from 10 to 350 mg / m ^2. The ratio of the amount of the conductive crystalline oxide or its composite oxide to the binder is 1/3.
It is preferably from 100 to 100/1, more preferably 1/10.
0 to 100/5.

The constitutions of the photosensitive material and the processing material (including the back layer) include various materials for the purpose of improving film properties such as stabilization of dimensions, prevention of curling, prevention of adhesion, prevention of cracks in the film, and prevention of pressure increase / decrease. A polymer latex can be included.

Specifically, Japanese Patent Application Laid-Open No. 62-245258
And the polymer latexes described in JP-A Nos. 62-136648 and 62-110066 can be used.
In particular, when a polymer latex having a low glass transition point (40 ° C. or lower) is used for the mordant layer, cracking of the mordant layer can be prevented, and when a polymer latex having a high glass transition point is used for the back layer, the curl prevention effect is reduced. can get.

The light-sensitive material of the present invention preferably contains a matting agent. The matting agent may be on either the emulsion side or the back side, but is particularly preferably added to the outermost layer on the emulsion side.

The matting agent may be soluble in the processing solution or insoluble in the processing solution, and preferably both are used in combination. For example, polymethyl methacrylate, poly (methyl methacrylate / methacrylic acid = 9/1 or 5/5 (molar ratio)), polystyrene particles and the like are preferable. The particle size is preferably 0.8 to 10 μm, and the particle size distribution is preferably narrow. It is preferable that 90% or more of the total number of particles be contained between 0.9 and 1.1 times the average particle size. .

Further, 0.8 μm
It is also preferable to add the following fine particles at the same time, for example, polymethyl methacrylate (0.2 μm), poly (methyl methacrylate / methacrylic acid = 9/1 (molar ratio)).
0.3 μm)), polystyrene particles (0.25 μm),
Colloidal silica (0.03 μm) is exemplified. Specifically, it is described in JP-A-61-88256 (page 29). In addition, there are compounds described in JP-A-63-274944 and JP-A-63-274952, such as benzoguanamine resin beads, polycarbonate resin beads, and AS resin beads. Other compounds described in Research Disclosure can be used.

Next, a film cartridge in which a photosensitive material can be loaded will be described. The main material of the patrone used in the present invention may be metal or synthetic plastic. Preferred plastic materials are polystyrene, polyethylene, polypropylene, polyphenyl ether and the like. Further, patrone may contain various antistatic agents, such as carbon black, metal oxide particles, nonions,
Anions, cations and betaine-based surfactants or polymers can be preferably used. These antistatic patrones are disclosed in JP-A-1-312537,
No. 3,12,538. Especially 25 ° C, 25
The resistance at% RH is preferably 10 ¹² Ω or less. Usually, a plastic patrone is manufactured using a plastic into which carbon black, a pigment, or the like is kneaded to impart light-shielding properties. The size of the patrone may be the same as the current 135 size.
It is also effective to set the diameter of a cartridge having a size of 25 mm to 22 mm or less. The volume of the patrone case is
It is preferably 30 cm ³ or less, more preferably 25 cm ³ or less. The weight of the plastic used for the patrone and the patrone case is preferably 5 g to 15 g.

A cartridge that rotates the spool to feed the film may also be used. Further, a structure may be employed in which the leading end of the film is housed in the cartridge body, and the leading end of the film is sent out from the port of the cartridge by rotating the spool shaft in the film sending direction. These are disclosed in U.S. Patent Nos. 4,834,306 and 5,226,613.
Issue.

The light-sensitive material of the present invention can be used by loading it on a commercially available film unit with a lens. The light-sensitive material of the present invention is disclosed in Japanese Patent Application No. 10-1584.
No. 27, No. 10-170624, No. 10-18898
It can be preferably used by loading it into the film unit with lens described in No. 4.

When the light-sensitive material of the present invention is used as a light-sensitive material for photographing, it is common to directly photograph landscapes, people, and the like using a camera or the like. The case where the above-described lens-attached film unit is used by being mounted thereon is similar to this.
In addition, the photosensitive material of the present invention is a method of exposing through a reversal film or a negative film using a printer or a stretching machine, a method of scanning and exposing an original image through a slit or the like using an exposing device of a copying machine, etc. A method of scanning and exposing a light-emitting diode, various lasers (laser diode, gas laser, etc.) and the like via electric signals (method described in JP-A-2-129625), image information on CRT, liquid crystal display, electroluminescence It is also used for a method of outputting to an image display device such as a display or a plasma display and exposing directly or via an optical system.

As a light source for recording an image on a photosensitive material,
As described above, U.S. Pat. No.4, such as natural light, tungsten lamp, light emitting diode, laser light source, CRT light source, etc.
500,626, column 56, JP-A-2-53378,
The light source and the exposure method described in JP-A-2-54672 can be used. Also, image exposure can be performed using a wavelength conversion element in which a non-linear optical material and a coherent light source such as laser light are combined.

Here, the non-linear optical material is a material capable of exhibiting the nonlinearity between the localization and the electric field that appears when a strong optical electric field such as laser light is applied.
Potassium dihydrogen phosphate (KDP), lithium iodate, B
inorganic compounds such as aB ₂ O ₄ , urea derivatives,
Nitroaniline derivatives, for example, nitropyridine-N-oxide derivatives such as 3-methyl-4-nitropyridine-N-oxide (POM), JP-A-61-53462.
And compounds described in JP-A Nos. 62-210432 can be preferably used. As a form of the wavelength conversion element, a single crystal optical waveguide type, a fiber type, and the like are known, and any of them is useful.

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

An image obtained by the present invention can be read using a scanner or the like and converted into electronic image information. In the present invention, the scanner is a device that optically scans a photosensitive material and converts the optical density of reflection or transmission into image information. When scanning, it is common to scan the required area of the photosensitive material by moving the optical part of the scanner in a direction different from the direction of movement of the photosensitive material, and it is recommended that the photosensitive material be fixed. Then, only the optical part of the scanner may be moved, or only the photosensitive material may be moved to fix the optical part of the scanner. Alternatively, a combination of these may be used.

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

[0311] The image data thus obtained can be viewed using various image display devices. As the image display device, an arbitrary device such as a color or monochrome CRT, a liquid crystal display, a plasma light emitting display, and an EL display is used.

In the present invention, an image can be formed on another recording material by outputting the image signal thus read. The output material is silver halide photosensitive material,
Various hard copy devices are used. For example, various systems such as an ink jet system, a sublimation type thermal transfer system, an electrophotographic system, a cycolor system, a thermoautochrome system, a method of exposing a silver halide color paper, and a silver halide heat development system are used. The effect of the present invention is sufficiently exhibited by any of the methods.

In the present invention, the main purpose is to capture image information obtained by development as digital data. However, according to the conventional method, photographed information is converted to a print material such as color paper by an analog optical method. It can also be used after exposure.

[0314]

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

Example 1 <Preparation of seed emulsion T-1> Seed emulsion T-1 having two parallel twin planes was prepared by the following method.

(A-1 solution) Ossein gelatin 38.0 g Potassium bromide 11.7 g Finish to 34.0 L with water (B-1 solution) Silver nitrate 810.0 g Finish to 815 ml with water (C-1 solution) Odor 567.3 g of potassium iodide Make up to 815 ml with water (D-1 solution) Ossein gelatin 163.4 g HO (CH ₂ CH ₂ O) m (CH (CH ₃ ) CH ₂ O) _19.8 (CH ₂ CH ₂ O) nH (M + n = 9.77) 10% methanol solution 5.5 ml Make up to 3961 ml with water (E-1 solution) Sulfuric acid (10%) 91.1 ml (F-1 solution) 56% acetic acid aqueous solution Required amount (G-1) Solution) Ammonia water (28%) 105.7 ml (H-1 solution) Potassium hydroxide aqueous solution (10%) Required amount Using a stirrer described in JP-A-62-160128, 3
Solution E-1 was added to solution A-1 which was vigorously stirred at 0 ° C. Then, 279 ml each of solution B-1 and solution C-1 were added at a constant rate for 1 minute by a double jet method to obtain silver halide nuclei. Was generated.

Thereafter, the solution D-1 was added, the temperature was raised to 60 ° C. over 31 minutes, the solution G-1 was further added, the pH was adjusted to 9.3 with the solution H-1, and 6.5 minutes. Aging was performed.

Then, the pH was adjusted to 5.8 with the F-1 solution, and then the remaining B-1 solution and the C-1 solution were acceleratedly added by the double jet method in 37 minutes, and immediately followed by the usual method. Desalting was performed. Observation of this seed emulsion with an electron microscope revealed that ECD = 0.72 having two twin planes parallel to each other.
It was a monodisperse tabular seed emulsion having a particle size distribution of 16 μm and a variation coefficient of 16%.

<Preparation of Tabular Grain Emulsion Em-1> Emulsion Em-1 was prepared using Seed Emulsion T-1 and the following solutions.

(A-2 solution) Ossein gelatin 519.9 g HO (CH ₂ CH ₂ O) m (CH (CH ₃ ) CH ₂ O) _19.8 (CH ₂ CH ₂ O) nH (m + n = 9.77) 10% methanol solution 4.5 ml Seed emulsion T-1 5.3 mol equivalent Equivalent to 18.0 liters with water (Solution B-2) 3.5N silver nitrate aqueous solution 2787 ml (Solution C-2) Potassium bromide 1020 g Potassium iodide 29.1 g Finish with water to 2500 ml (D-2 solution) Potassium bromide 618.5 g Potassium iodide 8.7 g Finish with water to 1500 ml (E-2 solution) Potassium bromide 208.3 g Finish with water to 1000 ml (F Solution-2) 56% acetic acid aqueous solution Required amount (solution G-2) Potassium bromide 624.8 g Finish up to 1500 ml with water (solution H-2) 3.0% by weight of gelatin and silver iodide The particles (ECD = 0.05 .mu.m) fine grain emulsion 0.672 mole equivalent preparation consisting of the following.

Containing 0.254 mol of potassium iodide
To 9942 ml of 0% gelatin solution, 3092 ml of an aqueous solution containing 10.59 mol of silver nitrate and 10.59 mol of potassium iodide were added at a constant speed over 35 minutes to form fine particles. The temperature during the formation of fine particles was controlled at 40 ° C, and the pH,
The EAg was established.

(Solution I-2) 10 ml of an aqueous solution containing 1.4 × 10 ⁻⁶ mol of thiourea dioxide per mol of silver halide (Solution J-2) Sodium ethylthiosulfonate per mol of silver halide. Aqueous solution containing 3 × 10 ^-5 mol 100 ml (K-2 solution) 10% aqueous potassium hydroxide solution Required amount Add the A-2 solution into the reaction vessel and add the I-2 solution while stirring vigorously at 75 ° C. After that, solution B-2, solution C-2
Solution D-2 and Solution D-2 were added by the simultaneous mixing method in accordance with the combinations shown in Table 1, seed crystals were grown, and Comparative Emulsion Em-1 was prepared. Here, B-2 solution, C-2 solution, D
-2 The addition rate of the liquid is changed in a function-wise manner with respect to the addition time in consideration of the critical growth rate, and the generation of small particles other than the seed particles growing and the particle size distribution due to Ostwald ripening between the growing particles. To prevent deterioration.

First, the first growth was carried out by controlling the solution temperature in the reaction vessel to 75 ° C., the pAg to 8.9, and the pH to 5.8. In the first addition, 6 of solution B-2 was used.
5.8% was added. Thereafter, the solution J-2 was added, the solution temperature in the reaction vessel was lowered to 40 ° C. in 30 minutes, and the pAg was raised to 1
The solution was adjusted to 0.3, the entire amount of the H-2 solution was added at a constant speed for 2 minutes, and the second addition was immediately performed. The second addition was performed while controlling the solution temperature in the reaction vessel to 40 ° C., the pAg to 10.3, and the pH to 5.0, and added all the rest of the B-2 solution. For controlling pAg and pH, Solution E-2, Solution F-2, Solution G-2 and Solution K-2 were added as needed.

After the particles are formed, desalting treatment is performed according to the method described in JP-A-5-72658, gelatin is added and dispersed, and pAg 8.06 at 40 ° C., pH 5.0.
8 were obtained.

When the silver halide grains in this emulsion were observed with an electron microscope, the ECD (projected area circle equivalent grain size)
= 1.50 μm, hexagonal tabular monodispersed silver halide grains having an average aspect ratio of 7.0 and a variation coefficient of the particle size distribution of 14%.

[0326]

[Table 1]

<Chemical Sensitization and Spectral Sensitization> Em-1 was divided into small portions, and the following spectral sensitizing dyes were added to each of them. Further, optimal amounts of sodium thiocyanate, sodium thiosulfate, triethylthiourea, chloroauric acid, 1- (3-acetamidophenyl) -5-mercaptotetrazole (AF-
5) was added and heated to 50 ° C. After ripening for each of the optimum reaction times, the mixture was cooled, and a stabilizing agent ST-1 and an antifoggant AF-5 were added thereto to obtain a red-sensitive silver halide emulsion.
1, green-sensitive silver halide emulsion-1 and blue-sensitive silver halide emulsion-1 were obtained. The types and amounts of sensitizing dyes added to each emulsion are as follows. The addition amount was shown as an addition amount per mole of silver halide.

Red-Sensitive Silver Halide Emulsion-1 Sensitizing Dye (SD-1) 0.04 mmol Sensitizing Dye (SD-2) 0.07 mmol Sensitizing Dye (SD-3) 0.04 mmol Sensitizing Dye (SD-4) 0.13 mmol green-sensitive silver halide emulsion-1 sensitizing dye (SD-5) 0.04 mmol sensitizing dye (SD-6) 0.03 mmol sensitizing dye (SD-7) 0 .17 mmol sensitizing dye (SD-8) 0.02 mmol sensitizing dye (SD-9) 0.02 mmol sensitizing dye (SD-10) 0.02 mmol blue-sensitive silver halide emulsion-1 sensitizing dye (SD-11) 0.19 mmol Sensitizing dye (SD-12) 0.06 mmol The structural formulas of the compounds used in this example are shown below.

[0329]

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[0330]

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[0331]

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[0332]

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[0333]

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[0334]

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[0335]

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[0336]

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[0337]

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[0338]

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[0339]

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[0340]

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<Preparation of Photosensitive Material 101> The emulsion thus obtained and a compound described below were used to prepare a subbed transparent PEN.
Photosensitive layers having the following composition were sequentially applied on a base (thickness: 85 μm) to prepare a photosensitive material 101 having a multilayer structure. Amount of each material added mg of coating amount per 1 m ² /
It is shown in units of m ² . However, silver halide was expressed in terms of silver.

Addition amount of the first layer (mg / m ² ) Gelatin 3000 Zinc oxide 565 SU-490 Hardener (H-2) 45 Second layer Gelatin 1800 Green-sensitive silver halide emulsion-1 800 Color developing agent ( D-1) 0.70 * Magenta coupler (M-1) 0.55 * High boiling solvent (OIL-1) 350 High boiling solvent (OIL-2) 70 SU-31 Thickener (V-1) 8 Third layer Gelatin 600 Matting agent (PM-2) 40 Antifungal agent (F-1) 1 Surfactant (SU-3) 2 Hardening agent (H-1) 30 Slip agent (WAX-1) 40 *: Expressed in mmol / m ² .

Further, photosensitive materials 102 to 116 were produced in the same manner as in producing photosensitive material 101, except that the developing agent of the second layer was replaced as shown in Table 2.

<Preparation of Processing Sheet P-1> (Note: Developing Sheet) A layer of the following composition was sequentially applied on a subbed transparent PEN base (85 μm thick) to prepare a processing sheet P-1. did. Amount of each material added mg of coating amount per 1 m ² /
It is shown in units of m ² .

Addition amount (mg / m ² ) of first layer Gelatin 280 Water-soluble polymer (PS-2) 12 Surfactant (SU-3) 14 Hardener (H-5) 185 Second layer Gelatin 2400 Water-soluble Polymer (PS-3) 360 Water-soluble polymer (PS-1) 700 Water-soluble polymer (PS-4) 600 High boiling point solvent (OIL-3) 2000 Guanidine picolinate 2800 Potassium quinolinate 225 Sodium quinolinate 180 Surfactant ( SU-3) 24 third layer gelatin 240 water-soluble polymer (PS-1) 24 hardener (H-5) 180 surfactant (SU-3) 9 fourth layer gelatin 220 water-soluble polymer (PS-2) Reference Signs List 60 water-soluble polymer (PS-3) 200 potassium nitrate 12 matting agent (PM-2) 10 surfactant (SU-3) 7 surfactant Surfactant (SU-5) 7 Surfactant (SU-6) 10 <Evaluation of sample> Photosensitive material 1 prepared as described above
01 to 116 through an optical wedge and a green filter
Exposure was performed at 0 lux for 1/100 second. After applying 15 ml / m ² of warm water of 40 ° C. to the surface of the photosensitive material after the exposure, and superposing the processing sheet P-1 and each other film surface,
Heat development was performed at 80 ° C. for 30 seconds using a heat drum. When the photosensitive material was peeled off after the processing, a wedge-shaped image of magenta color was obtained. For the obtained sample, the maximum density (Dmax) and the minimum density part (Dmi) were measured with an X-rite densitometer (green light).
n) was measured.

Further, those stored for 7 days at 40 ° C. and 80% RH were treated in the same manner.

[0347]

[Table 2]

As is clear from Table 2, all of the samples 104 to 116 using the compound of the present invention have excellent coloring properties, small fog and good discrimination. Also, regarding the raw preservability, Dmin of Samples 101 to 103 is increased, whereas Samples 104 to 104 of the present invention are increased.
116 is not remarkable, indicating that it has excellent raw preservability.

Example 2 In the preparation of the light-sensitive material 101, a green light-sensitive emulsion of the second layer was prepared.
Photosensitive material 2 was prepared in the same manner except that 1 was replaced with red photosensitive emulsion-1, and the coupler and the developing agent were replaced as shown in Table 3.
01 to 213 were produced.

<Evaluation of Samples> The photosensitive materials 201 to 213 prepared as described above were exposed to light at 1000 lux for 1/100 second through an optical wedge and a red filter.
15 ml / m of 40 ° C warm water is applied to the surface of the photosensitive material after exposure.
² and then the processing sheet P-1 and the respective film surfaces were overlapped with each other, and then heat-developed at 80 ° C. for 30 seconds using a heat drum. When the photosensitive material was peeled off after the processing, a wedge-shaped image of cyan color was obtained. X-write
The highest density (Dmax) and the lowest density part (Dmin) were measured with a densitometer (red light).

Further, those stored for 7 days at 40 ° C. and 80% RH were treated in the same manner.

[0352]

[Table 3]

As is clear from Table 3, all of the samples 204 to 113 using the compound of the present invention have excellent coloring properties, small fog and good discrimination. Also, regarding the raw preservability, Dmin of Samples 201 to 203 is increased, whereas Samples 204 to 203 of the present invention are increased.
As for 113, it is not remarkable, indicating that it has excellent raw preservability.

Example 3 <Preparation of silver halide emulsion> A silver iodide content of 3 mol%, E
Example 1 was prepared using a silver halide emulsion containing monodispersed silver iodobromide tabular grains having a CD (projected area circle equivalent grain size) of 0.59, an average aspect ratio of 3.4, and a variation coefficient of the grain size distribution of 16%. By performing spectral sensitization and chemical sensitization in the same manner as described above, a red-sensitive silver halide emulsion-2 and a green-sensitive silver halide emulsion-
2 and blue-sensitive silver halide emulsion-2. The types and amounts of sensitizing dyes added to each emulsion are as follows. The addition amount was shown as an addition amount per mole of silver halide.

Red-sensitive silver halide emulsion-2 Sensitizing dye (SD-1) 0.08 mmol Sensitizing dye (SD-3) 0.08 mmol Sensitizing dye (SD-4) 0.42 mmol Green-sensitive halogen Silver halide emulsion-2 Sensitizing dye (SD-5) 0.04 mmol Sensitizing dye (SD-6) 0.15 mmol Sensitizing dye (SD-7) 0.35 mmol Sensitizing dye (SD-9) 0 0.05 mmol Blue-sensitive silver halide emulsion-2 Sensitizing dye (SD-11) 0.38 mmol Sensitizing dye (SD-12) 0.11 mmol <Preparation of photosensitive material 301> Halogen thus obtained Using a silver halide emulsion and the silver halide emulsion prepared in Example 1, a subbed transparent PEN base (85 μm thick)
m) A photographic constituent layer having the composition shown below is sequentially coated on
A photosensitive material 301 having a multilayer structure was manufactured. The amount of each material added is indicated in units of mg / m ² as the coating amount per 1 m ^2.
However, silver halide was expressed in terms of silver.

First layer (antihalation layer) Gelatin 800 Ultraviolet absorber (UV-1) 200 High boiling solvent (OIL-2) 200 Zinc hydroxide 500 Dye (AI-1) 280 Dye (AI-2) 240 Dye (AI-3) 400 Second layer (cyan coloring layer) Gelatin 1000 Red-sensitive silver halide emulsion-1 350 Red-sensitive silver halide emulsion-2 290 Color developing agent (D-1) 0.93 * Cyan coupler (C -1) 0.59 * High boiling solvent (OIL-1) 460 High boiling solvent (OIL-2) 130 Antifoggant (AF-6) 1 Third layer (intermediate layer) Gelatin 800 Dye (AI-2) 160 Additive (HQ-2) 20 High boiling point solvent (OIL-2) 60 Water-soluble polymer (PS-1) 60 Zinc hydroxide 500 Fourth layer (magenta coloring layer) Gelatin 18 00 Green-sensitive silver halide emulsion-1 350 Green-sensitive silver halide emulsion-2 290 Color developing agent (D-1) 0.93 * Magenta coupler (M-1) 0.74 * High boiling solvent (OIL-1) 460 High boiling point solvent (OIL-2) 90 Antifoggant (AF-6) 1 Water-soluble polymer (PS-1) 20 Fifth layer (intermediate layer) Gelatin 800 Dye (AI-1) 320 Additive (HQ-1) 6) Additive (HQ-2) 20 High boiling solvent (OIL-1) 75 Zinc hydroxide 300 6th layer (yellow color forming layer) Gelatin 3200 Blue-sensitive silver halide emulsion-1 670 Blue-sensitive silver halide emulsion-2 550 Color developing agent (D-1) 0.93 * Yellow coupler (Y-1) 1.48 * High boiling solvent (OIL-1) 450 High boiling solvent (OIL-2) 300 Antifoggant (A F-6) 2 Water-soluble polymer (PS-1) 40 7th layer (intermediate layer) Gelatin 1500 Water-soluble polymer (PS-1) 60 Zinc hydroxide 700 8th layer (protective layer) Gelatin 1000 Matting agent (WAX-) 1) 200 Water-soluble polymer (PS-1) 120 *: expressed in mmol / m ² .

Incidentally, in addition to the above composition, a coating aid SU-
1, SU-2, SU-3, dispersion aid SU-4, stabilizer S
T-1, ST-2, antifoggants AF-1, AF-2,
AF-3, AF-4, AF-5, hardeners H-1, H-
2, H-3 and H-4 were added. Also, F-2, F-
3, the total amount of F-4 and F-5 was 15.0 mg /
m ² , 60.01 mg / m ² , 50.0 mg / m ² and 1
It was distributed and added to each layer to 0.0 mg / m ² .

Light-sensitive materials 302 to 311 were prepared in the same manner except that the developing agents of the second, fourth and sixth layers were changed as shown in Table 4.

<Evaluation of Sample> The photosensitive materials 301 to 311 prepared as described above were subjected to an optical wedge by 1000 watts.
A 1/100 second exposure was performed with lux. 15 ml / m ² of 40 ° C. hot water was applied to the surface of the photosensitive material after the exposure, and the processing sheet P-1 and the respective film surfaces were overlapped with each other, and then heat-developed at 80 ° C. for 30 seconds using a heat drum. . When the photosensitive material was peeled off after the processing, a gray wedge-shaped image was obtained.
With respect to the obtained sample, the maximum density (Dmax) and the minimum density part (Dmin) were measured with blue light, green light, and red light, respectively, using an X-rite densitometer.

[0360]

[Table 4]

As is clear from Table 4, the samples 304 to 311 using the compound of the present invention have excellent color development, small fog and good discrimination even in the multilayer system.

[0362]

The silver halide color photographic light-sensitive material and the heat-developable color photographic light-sensitive material according to the present invention contain a specific developing agent which can be dry-processed without using a liquid agent, and have excellent storage stability and discrimination. Is also good and has an excellent effect.

Claims (5)

[Claims] 1. A silver halide color photographic material comprising a color developing agent represented by the following general formula [I]. Embedded image [Wherein, Ra ₁ and Ra ₂ each represent an alkyl group or an aryl group, Ra ₃ represents a hydrogen atom or a substituent, and n represents 1
Represents an integer of ２2. When n is 2, Ra ₃ may be the same or different. Za ₁ and Za ₂ are each a nitrogen atom or C
It represents ra _4, at least one of which is CRa _4. Ra ₄
Has the same meaning as Ra ₃ , but at least one is a substituent capable of forming a hydrogen bond. Xa represents a non-metallic atomic group necessary for forming a 5- to 6-membered aromatic heterocyclic ring or aromatic ring together with Za ₁ , Za ₂ and carbon atoms adjacent thereto. However, when Xa is a hetero atom and has 5 members, Za ₁ and Za ₂ need not be nitrogen atoms. La is -SO _2- , -CO
_{-, - SO 2 N (Ra} 5) -, - COO -, - CONH-
Or -P (= O) (Ra ₆ )-. Ra ₅ and Ra ₆
Has the same meaning as Ra ₃ and Ra ₄ . Ya represents an alkyl group, an aryl group or a heterocyclic group. ] 2. A silver halide color photographic material comprising a color developing agent represented by the following general formula [II]. Embedded image [In the formula, Rb ₁ represents a hydrogen atom or a substituent. Rb ₂ represents a substituent capable of forming a hydrogen bond. Rb ₃ represents a hydrogen atom or a substituent capable of leaving under alkaline conditions. In addition, 1 represents an integer of 0 to 3 and m represents an integer of 1 to 4. Lb is _{-SO 2 -, - CO -,} - SO 2 N (Rb 4)
-, -COO-, -CONH- or -P (= O) (Rb
₅ ) represents-. Rb ₄ and Rb ₅ have the same meanings as Ra ₅ and Ra _6. Yb represents an alkyl group, an aryl group or a heterocyclic group. ] 3. A silver halide color photographic material comprising a color developing agent represented by the following general formula [III]. Embedded image [Wherein, Rc ₂ and Rc ₃ represent a hydrogen atom or a substituent.
Rc ₁ represents a substituent capable of forming a hydrogen bond. Rc ₄ represents an alkyl group or an aryl group;
combine with c ₃ may combine to form a 5- or 6-membered ring. Lc is —SO ₂ —, —CO—, —SO ₂ N (Rc ₅ ) —, —CO
O -, - CONH-, or _{-P (= O) (Rc 6} ) - represents a. Rc ₅ and Rc ₆ have the same meanings as Ra ₅ and Ra _6.
Yc represents an alkyl group, an aryl group or a heterocyclic group. Xc represents a nonmetallic atom group necessary for forming a 5- or 6-membered ring together with a nitrogen atom and a carbon atom, and may have a substituent. ] 4. A silver halide color photographic material comprising a color developing agent represented by the following general formula [IV]. Embedded image [Wherein, Rd _{1 to} Rd ₄ represent a hydrogen atom or a substituent. R
d ₅ and Rd ₆ each represents an alkyl group or an aryl group,
Total number of carbon atoms in Rd ₅ and Rd ₆ is 5 to 13. Further, it contains at least one hydroxyl group. Ld is -SO ₂
-, - CO -, - SO 2 N (Rd 7) -, - COO -, -
CONH- or _{-P (= O) (Rd 8} ) - represents a. Rd ₇
And Rd ₈ have the same meanings as Ra ₅ and Ra ₆ . Yd represents an alkyl group, an aryl group, or a heterocyclic group. ] 5. A photosensitive silver halide, a binder, a coupler and a compound represented by the general formula [I], [II], [III] or [IV] according to any one of claims 1 to 4 on a support. A heat-developable color photographic material comprising at least one developing agent selected from the color developing agents represented.