JP2002296742A - Silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide color photographic sensitive material excellent in processability and having good latent image preservability after photographing. SOLUTION: The silver halide color photographic sensitive material has one or more blue-sensitive silver halide emulsion layers, one or more green- sensitive silver halide emulsion layers and one or more red-sensitive silver halide emulsion layers on the base and contains one or more compounds of formula (A') and one or more of compounds of formulae (A-I)-(A-III) in the same layer. In the formula (A'), R'<a1> -R'<a5> are each H, alkyl, -O-R'<a0> (R'<a0> is alkyl, aryl or a heterocyclic group) or the like and two groups situated in o- positions may bond to each other to form a ring. In the formulae (A-I)-(A-III), Ra1 is acyl, alkyl or the like; Ra2 is alkyl, alkenyl or the like; X is a heterocyclic group; Rb1 is alkyl, alkenyl or the like; and Y is a group of nonmetallic atoms required to form a 5- or 6-membered ring together with -N=C- but X and Y are not 1,3,5-triazine rings.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a photographic light-sensitive material having excellent suitability for development processing and good storage stability of a latent image after photographing.

[0002]

2. Description of the Related Art Improving the storability of a latent image after photographing in a silver halide photographic light-sensitive material is an important subject for improving the performance of the light-sensitive material. However, there has been a case where the storage stability of a latent image after photographing has been impaired with the recent demand for higher sensitivity, and it has been difficult to achieve both high sensitivity and storage stability. Further, when a storage stability improving agent is added, the processing dependency often deteriorates, which has been a problem to be solved.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a photographic light-sensitive material which is excellent in development processing suitability and has good storage stability of a latent image after photographing.

[0004]

The object of the present invention has been attained by the following method. (1) A silver halide color photographic light-sensitive material having at least one blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer on a support, wherein 'And at least one compound represented by any one of formulas (AI) to (A-II)
A silver halide color photographic material comprising, in the same layer, at least one compound selected from the group of compounds represented by I).

[0005]

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In the general formula A ′, R ′ ^{a1 to} R ′ ^a5 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group or —O—R ′ ^a0 (R ′ ^a0 represents an alkyl group) , An aryl group or a heterocyclic group.). Where R ' ^a1 ~
'At least one of ^a5 is -O-R' R is ^a0. R ' ^{a1 to} R' ^a5
And two groups at the ortho position may be bonded to each other to form a ring. However, the compound represented by the general formula A 'is not a so-called phenol coupler in the art.

[0007]

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In the general formula (AI), R _a1 represents an alkyl group, alkenyl group, aryl group, acyl group, alkyl or arylsulfonyl group, alkyl or arylsulfinyl group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group and aryl. represents a group selected from the group consisting of oxycarbonyl group, R _a2 represents a group shown by hydrogen atom or Ra1.

In the general formula (A-II), X represents a heterocyclic group, and R _b1 represents an alkyl group, an alkenyl group or an aryl group. However, X is s-triazine (1,3,
5-triazine ring).

In the general formula (A-III), Y is -N =
A non-metallic atomic group necessary for forming a 5-membered ring together with the C- group, or a non-metallic atomic group necessary for forming a 6-membered ring together with the -N = C- group,末端 C—The carbon atom of the group bonded to the terminal of Y is represented by —N (R _c1 ) —, —C
(R _c2 ) (R _c3 )-, -C (R _c4 ) =, -〇- and -S
-A divalent group selected from the group consisting of-
N = C-). Where Y
Does not form an s-triazine (1,3,5-triazine) ring. R _{c1 to} R _c4 are each independently a hydrogen atom or a group consisting of an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylamino group, an arylamino group, and a halogen atom. Represents a group or an atom selected from

(2) The silver halide color photographic material as described in (1), wherein the compound-added layer is a red-sensitive layer.

(3) The silver halide color photographic material as described in (1), wherein the compound-added layer is a blue-sensitive layer.

(4) The silver halide color photographic material as described in (1), wherein the compound-added layer is a green light-sensitive layer.

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The embodiment of the photographic light-sensitive material of the present invention is optional, but it is particularly effective to apply it to a negative type color photographic light-sensitive material. In the present invention, each compound contained in the same layer (a compound represented by the general formula A ′ and a compound selected from the group of compounds represented by the general formulas (AI) to (A-III)) May be used alone or a plurality of different compounds may be used at the same time, and the amount used is preferably from 10 ^-6 mol to 10 ^-1 mol / m ² . When a plurality of compounds represented by the general formula A ′ are used, the used amount is the total amount of the compounds. When a plurality of compounds selected from the group of compounds represented by formulas (AI) to (A-III) are used, the total amount of the compounds is also used.

In the present invention, the same layer to which each compound is added means that a layer having the same spectral sensitivity is divided into layers having different sensitivities, for example, a high-sensitivity layer, a medium-sensitivity layer, and a low-sensitivity layer. Means a layer of each sensitivity. The same layer mentioned here may include a plurality of the above-mentioned layers having respective sensitivities, or may be any one of the layers.

Hereinafter, the compound represented by formula A 'of the present invention will be described in detail.

Formula A '

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R ′ ^{a1 to} R ′ ^a5 may be the same or different and each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, or —O—R ′ ^a0 . ^{Alternatively} , two groups of R ′ ^{a1 to} R ′ ^a5 which are in the ortho position may be bonded to each other to form a ring. R ′ ^a0 represents an alkyl group, an aryl group, or a heterocyclic group. At least one of R ′ ^{a1 to} R ′ ^a5 is —O—R ′ ^a0 . However, the compound represented by the general formula A 'is not a so-called phenol coupler in the art.

When R ′ ^{a1 to} R ′ ^a5 are halogen atoms, they represent, for example, chlorine, bromine and fluorine atoms. In the case of an alkyl group, it is a linear, branched or cyclic alkyl group, for example, methyl, ethyl, hexadecyl, isopropyl, t-
Butyl, t-octyl, cyclohexyl, 2'-hydroxybenzyl, 4'-hydroxybenzyl can be used. In the case of an aryl group, for example, phenyl, 2-naphthyl can be used, in the case of a heterocyclic group, for example, 2-pyridyl, 4-pyridyl, 2-imidazolyl, 2-oxazolyl, 2-thiazolyl Can be used. These substituents may further have a substituent. Examples of the substituent that can be taken include an alkyl group (including a cycloalkyl group and a bicycloalkyl group) and an alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group). , Alkynyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, halogen atom, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyl Oxy group, aryloxycarbonyloxy group, amino group (including anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, Al Luthio, arylthio, heterocyclic thio, sulfamoyl, sulfo, alkyl and arylsulfinyl, alkyl and arylsulfonyl, acyl, aryloxycarbonyl, alkoxycarbonyl, carbamoyl, imide, silyl As an example.

R ′ ^a0 represents an alkyl group, an aryl group, or a heterocyclic group. Wherein R ^{'groups a0} can take the R' is selected from the group that can be taken when ^a1 to R ^'a5 alkyl group, aryl group, heterocyclic group. The R ^'a0 may be further substituted with a substituent, the substituent as used herein R' are those selected from the same range as the substituent may take the ^a1 to R ^'a5.

Two of R ′ ^{a1 to} R ′ ^a5 which are ortho to each other
Two groups may combine to form a ring structure. The ring referred to here is a 4- to 12-membered ring, preferably a 5- to 8-membered ring, and particularly preferably a 6-membered ring. It is also preferred that one of the two substituents forming a ring is represented by ^-OR'a0 .
Further, a case where a chroman skeleton is formed is more preferable. The ring structure is R ^'a1 and R' ^a2, R ^'a2 and R' ^a3, R ^'a3 and R' ^a4,
R ^'a4 and R' ^a5, may be configured in any combination of, in the case of two selected from these combinations may form a ring structure at the same time.

When R ′ ^{a1 to} R ′ ^a5 are an alkyl group, an aryl group, an aromatic heterocyclic group or —O—R ′ ^a0 , each has 1 to 50 carbon atoms.
It is a group of. Preferably the total number of carbon atoms in R ^'a1 ~R' ^a5 1~100
And more preferably 2 to 50, and particularly preferably 3
~ 40.

Preferred compounds in terms of the effects of the present invention are compounds represented by the following general formulas A'-I to IV.

Formula A'-I

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Formula A'-II

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General formula A'-III

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General formula A'-IV

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Here, R ' ^a1 , R' ^a2 , R ' ^a3 , R' ^a5
Has the same meaning as described in the general formula A ′. And Z is a group of atoms necessary for constituting a chromane skeleton, optionally substituted with a group selected from among ^{R 'a1, R' a2,} R 'a3, R' a5 those previously described as substituents which may take It may be. ^{R 'a1, R' a2,} R preferable examples ^'a3, R' ^a5 represents a hydrogen atom or an alkyl group is used. In the case of an alkyl group, a group having 1 to 20, more preferably 1 to 10 carbon atoms is used, and particularly preferably a methyl group, an ethyl group, an isopropyl group, a t-butyl group, and a t-octyl group are used. The group to be substituted for Z is preferably a hydrogen atom or an alkyl group. In the case of an alkyl group, the number of carbon atoms is preferably 1 to 50, more preferably 1 to 40, and particularly preferably 1 to 30.

Among the compounds represented by the general formulas A'-I to IV, more preferred are the compounds represented by the general formulas A'-II and A'-II.
And particularly preferably represented by the general formula A′-I
It is represented by II.

The compound represented by the general formula A'-III is most preferably a tocol derivative. Tocol derivatives are α-tocopherol, β-tocopherol,
It is a group of compounds represented by γ-tocopherol, δ-tocopherol and the like. These compounds may be optically active or racemic, and when there are a plurality of stereocenters, they may be single diastereomers or diastereomeric mixtures. Further, when the olefin has an olefin bond, the cis / trans may be either, and the cis olefin and the trans olefin may be mixed in the same molecule. These compounds may be used alone or as a mixture of two or more.

The general formulas A ', A'-I, A'-II,
The compounds represented by A'-III and A'-IV may be contained anywhere in the photosensitive material, but are preferably contained in the photosensitive layer.

Formulas A ', A'-I, A'-II, A'-III,
As a method for adding the compound represented by A′-IV, the compound may be added after dissolving in water, alcohol, ester or ketone, or a mixed solvent thereof. Further, after dissolving in a high boiling point organic solvent, it may be dispersed and added. This method and the oil-soluble general formulas A ', A'-I, A'-II, A'-III, A'
It is preferable to combine the compound represented by -IV because the added compound is easily fixed to the added layer. It is also preferable to add so-called co-emulsified with couplers.

The general formulas A ', A'-I, A'-II,
The addition amount of the compound represented by A′-III is preferably in the range of 1 × 10 ^{−4 to} 5 mol, more preferably in the range of 1 × 10 ⁻³ to 1 mol, per mol of silver halide in the layer to be added. And
Particularly preferably, it is in the range of 1 × 10 ^{−3 to} 0.5 mol.

Specific examples of the compound represented by the general formula A 'of the present invention are shown below, but it should not be construed that the invention is limited thereto.

[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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Next, the compounds represented by formulas (AI) to (A-III) will be described in more detail. The alkyl group referred to in the present invention is a linear, branched, or cyclic alkyl group, and may have a substituent.

In the general formula (AI), R _a1 is an alkyl group (preferably an alkyl group having 1 to 36 carbon atoms such as methyl, ethyl, i-propyl, cyclopropyl, butyl, isobutyl, cyclohexyl, t-octyl) , Decyl, dodecyl, hexadecyl, benzyl), an alkenyl group (preferably an alkenyl group having 2 to 36 carbon atoms such as allyl, 2-butenyl, isopropenyl, oleyl, vinyl) and an aryl group (preferably having 6 to 40 carbon atoms)
Aryl groups such as phenyl and naphthyl), and acyl groups (preferably acyl groups having 2 to 36 carbon atoms such as acetyl, benzoyl, pivaloyl, α- (2,4-di-te)
rt-amylphenoxy) butyryl, (3-cyclohexen-1-yl) -carbonyl, myristoyl, stearoyl, naphthoyl, m-pentadecylbenzoyl,
(5-norbornen-2-yl) carbonyl, isonicotinoyl), an alkyl or arylsulfonyl group (preferably an alkyl or arylsulfonyl group having 1 to 36 carbon atoms such as methanesulfonyl, octanesulfonyl,
Benzenesulfonyl, toluenesulfonyl), alkyl or arylsulfinyl group (preferably having 1 to 4 carbon atoms)
0 alkyl or arylsulfinyl groups such as methanesulfinyl and benzenesulfinyl), carbamoyl groups (including N-substituted carbamoyl groups, and preferably carbamoyl groups having 1 to 40 carbon atoms such as N-ethylcarbamoyl and N-phenylcarbamoyl; N, N-dimethylcarbamoyl, N-butyl-N-phenylcarbamoyl), a sulfamoyl group (including an N-substituted sulfamoyl group, preferably a sulfamoyl group having 1 to 40 carbon atoms such as N-methylsulfamoyl, N-diethylsulfamoyl, N-phenylsulfamoyl, N-cyclohexyl-N-phenylsulfamoyl, N-ethyl-N-dodecylsulfamoyl), alkoxycarbonyl group (preferably alkoxy having 2 to 36 carbon atoms) For example, a carbonyl group Alkoxycarbonyl, cyclohexyloxycarbonyl, benzyloxycarbonyl, isoamyl oxycarbonyl, hexadecyl oxycarbonyl)
Or an aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 40 carbon atoms, for example, phenoxycarbonyl, naphthoxycarbonyl).
R _a2 represents a hydrogen atom or the group represented by R _a1 .

In the general formula (A-II), the heterocyclic group represented by X is a 5- to 7-membered cyclic s having at least one of a nitrogen atom, a sulfur atom, an oxygen atom and a phosphorus atom as a ring-constituting atom.
A group that forms a heterocyclic ring other than a -triazine ring (1,3,5-triazine ring), and the bonding position of the heterocyclic ring (position of a monovalent group) is preferably a carbon atom;
-Triazin-3-yl, pyridin-2-yl, pyrazinyl, pyrimidinyl, purinyl, quinolyl, imidazolyl, 1,2,4-triazol-3-yl, benzimidazol-2-yl, thienyl, furyl, imidazolidinyl, pyrrolinyl, Represents tetrahydrofuryl, morpholinyl, phosphinolin-2-yl. R _b1 has the same meaning as the alkyl group, alkenyl group or aryl group for R _a1 in formula (AI).

In the general formula (A-III), Y is -N =
Non-metallic atomic groups necessary for forming a 5-membered ring together with C- (for example, when the formed ring group is imidazolyl, benzimidazolyl, 1,3-thiazol-2-yl, 2-imidazolin-2-yl, purinyl, 3H-indol-2-yl). Y is a group of nonmetallic atoms necessary for forming a 6-membered ring together with the -N = C- group, and -N
The terminal of Y bonded to the carbon atom of the ＣC— group is —N (R _c1 )
-, -C (R _c2 ) (R _c3 )-, -C (R _c4 ) =, _{-−- or} -S- (a group selected from -N =
C- carbon atom). However, it does not form an s-triazine (1,3,5-triazine) ring. R _{c1 to} R _c4 may be the same or different and each represents a hydrogen atom or a substituent (for example, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylamino group, an arylamino group, Halogen atom). Here, the alkyl group, the alkenyl group, and the aryl group are represented by R in the general formula (AI).
_Represents the same meaning as the alkyl group, alkenyl group or aryl group in _a1 , an alkoxy group, an alkylthio group,
The alkyl group of the alkylamino group, the aryloxy group, the arylthio group, and the aryl group of the arylamino group also have the same meanings as those described for R _a1 in formula (AI). Halogen atoms represent, for example, chlorine, bromine and fluorine atoms.

Examples of the 6-membered ring group formed by Y include quinolyl, isoquinolyl, phthalazinyl, quinoxalinyl, and 6H-1,2,5-thiadiazin-6-yl.

In formula (AI) or (A-II), R _a1 and R _a2 , X and R _b1 may be bonded to each other to form a 5- to 7-membered ring, for example, a succinimide ring, a phthalimide ring , A triazole ring, a urazole ring, a hydantoin ring, and a 2-oxo-4-oxazolidinone ring. However, the s-triazine ring (1,3,5-triazine) is excluded.

Each group of the compounds represented by the general formulas (AI) to (A-III) may be further substituted with a substituent. Examples of these substituents include an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a hydroxy group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an amino group, an acylamino group, a sulfonamide group, an alkylamino group, Arylamino group, carbamoyl group, sulfamoyl group, sulfo group, carboxyl group,
Examples include a halogen atom, a cyano group, a nitro group, a sulfonyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, and a hydroxyamino group.

In the general formula (AI), R_a2Is a hydrogen source
, An alkyl group, an alkenyl group, an aryl group,
One_a1Is an acyl group, alkyl or arylsulfonyl
Group, alkyl or arylsulfinyl group, carbamo
Yl group, sulfamoyl group, alkoxycarbonyl group,
Those which are aryloxycarbonyl groups are preferred,
More preferably, R_a2Is an alkyl or alkenyl group
And R_a1Is an acyl group, alkyl or aryl sulf
Honyl group, carbamoyl group, sulfamoyl group, alcohol
Xycarbonyl group and aryloxycarbonyl group
Compound. R _a2Is an alkyl group, and R_a1Is acyl
Those which are groups are most preferred.

In the general formula (A-II), R _b1 is preferably an alkyl group or an alkenyl group, more preferably an alkyl group. On the other hand, the general formula (A-II) is preferably represented by the following general formula (A-II-1).

[0058]

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In the general formula (A-II-1),_b1Haichi
R of general formula (A-II)_b1And X ₁Is -C = N- and
Non-metallic atomic groups necessary to form a 5- to 6-membered ring
I forgot. Compound represented by the general formula (A-II-1)
Chi, X₁Form a 5- to 6-membered heteroaromatic ring
preferable. However, no s-triazine ring is formed.
No.

Among the compounds represented by the general formula (A-III), it is preferable that Y is a group of non-metallic atoms necessary for forming a 5-membered ring, and is bonded to a carbon atom of a -N = C- group. More preferably, the terminal atom of Y is a nitrogen atom.
However, it does not form an s-triazine ring. Most preferably, Y forms an imidazoline ring. This imidazoline ring may be condensed with a benzene ring or a heterocyclic ring.

Of the compounds represented by the general formulas (AI) to (A-III), those having a total carbon number of 15 or less are preferable in that they act on layers other than the additive layer. Compounds having a total carbon number of 16 or more are preferred for the purpose of acting only on the additive layer. Formulas (AI) to (A)
-III), a compound represented by the general formula (A-
Preferred are those represented by I) and (A-II), and more preferred are those represented by formula (AI).

The general formulas (AI) to (A-) of the present invention are described below.
Specific examples of the compound represented by III) will be given below, but the invention is not limited thereto.

[0063]

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[0064]

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[0065]

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[0066]

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[0067]

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These compounds are represented by the general formula (AI)
Correspondence with (A-III) is as follows. General formula (AI): A-1 to A-9, A-11 to A-1
8, A-33 to A-55. General formula (A-II): A-10, A-20, A-30. General formula (A-III): A-19, A-21 to A-29,
A-31, A-32.

These compounds of the present invention are described in J. Org.
m., 27, 4054 ('62), J. Amer. Chem. Soc., 73, 298
1 ('51), JP-B-49-10692, or the like or a method analogous thereto.

In the present invention, the compounds represented by the general formulas (AI) to (A)
The compound represented by -III) may be added by dissolving in a water-soluble solvent such as methanol, ethanol, dimethylformamide (DMF) or dimethylsulfoxide (DMSO) or a mixed solvent thereof, or by emulsifying and dispersing. May be. Further, they may be added in advance during the preparation of the emulsion.

In the present invention, the compounds represented by the general formulas (AI) to (A)
-III) in combination of two or more of the compounds represented by
Is also good. The coating amounts of the compounds (AI) to (A-III)
0.01 to 200 mg / m per layer^TwoIs preferred. 0.
1 to 100 mg / m^TwoIs more preferable, and 1 to 50 mg /
m ^TwoIs more preferred.

The light-sensitive material of the present invention may have at least one layer of a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer on a support. A typical example is
This is a silver halide photographic material having at least one photosensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. The photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light, and in a multilayer silver halide color photographic material, the arrangement of the unit photosensitive layers is generally A red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are provided in this order from the support side. However, depending on the purpose, the order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between layers of the same color sensitivity. A non-light-sensitive layer may be provided between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer. These include couplers described later, DI
An R compound, a color mixing inhibitor, and the like may be included. The plurality of silver halide emulsion layers constituting each unit photosensitive layer are DE
As described in 1,121,470 or GB 923,045, it is preferable to arrange two layers of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer so that the sensitivity decreases sequentially toward the support. Also, JP-A-57-112751, 62-200350, 62-206541, 62-
As described in 206543, a low-speed emulsion layer may be provided on the side farther from the support, and a high-speed emulsion layer may be provided on the side closer to the support.

As a specific example, from the side farthest from the support,
Low sensitivity blue photosensitive layer (BL) / High sensitivity blue photosensitive layer (BH) / High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (GL) / High sensitivity red photosensitive layer (RH) / In the order of the low-sensitivity red photosensitive layer (RL), or in the order of BH / BL / GL / GH / RH / RL, or BH / BL / GH /
They can be installed in the order of GL / RL / RH.

As described in JP-B-55-34932, the blue-sensitive layer / GH /
They can be arranged in the order of RH / GL / RL. Also, JP-A-56
As described in -25738 and 62-63936, the layers may be arranged in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support.

As described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is a layer having a higher sensitivity than the middle layer. An example is an arrangement in which a silver halide emulsion layer having a low sensitivity is arranged and three layers having different sensitivities are sequentially reduced in sensitivity toward a support. Even when such a three-layer structure having different photosensitivity is used,
As described in JP-A-59-202464, in the same color-sensitive layer, the layers may be arranged in the order of medium-speed emulsion layer / high-speed emulsion layer / low-speed emulsion layer from the side away from the support.

In addition, a high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or a low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer may be arranged in this order. The arrangement may be changed as described above even in the case of four or more layers.

In order to improve color reproducibility, US Pat. No. 4,663,27
1, 4,705,744, 4,707,436, JP-A-62-160448,
It is preferable to arrange a donor layer (CL) having a multilayer effect having a spectral sensitivity distribution different from that of the main photosensitive layers such as BL, GL, and RL described in the specification of JP-A-63-89850, adjacent to or adjacent to the main photosensitive layer.

Preferred silver halides for use in the present invention are silver iodobromide, silver iodochloride, or silver iodochlorobromide containing up to about 30 mole percent silver iodide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide.

The silver halide grains in the photographic emulsion include those having regular crystals such as cubic, octahedral and tetradecahedral, those having irregular crystal forms such as spherical and plate-like,
It may have a crystal defect such as a twin plane or a composite form thereof. The silver halide may be fine grains having a grain size of about 0.2 μm or less or large grains having a projected area diameter of about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion.

The silver halide photographic emulsion usable in the present invention is, for example, Research Disclosure (hereinafter referred to as RD).
No. 17643 (December 1978), pp. 22-23, "I. Emulsion preparation and types", and No. 18716 (November 1979), p. 648, pp. 307105 (1989
Nov., pp. 863-865, and Grafkid, "Physics and Chemistry of Photography", published by Paul Montell (P. Glafkides, Chimi)
e et Phisique Photographiques, Paul Montel, 1967)
, Duffin, Photographic Emulsion Chemistry, GF Duffin, Photographic Emulsion Chemistry, F
ocal Press, 1966), "Production and Coating of Photographic Emulsions", by Zelikman et al., Published by Focal Press (VL Zelikman, et.
al., Making and Coating Photographic Emulsion, Fo
cal Press, 1964). US 3,574,628, US 3,655,394 and GB
Monodisperse emulsions described in 1,413,748 are also preferred.

Tabular grains having an aspect ratio of about 3 or more can be used in the present invention. Tabular grains are described in Gatoff, Photographic Science and Engineering (Gutoff, Photographic Science and E).
ngineering), Vol. 14, pp. 248-257 (1970); US 4,43.
It can be easily prepared by the methods described in 4,226, 4,414,310, 4,433,048, 4,439,520 and GB 2,112,157.

The crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, or may have a layered structure. Silver halides having different compositions may be joined by an epitaxial junction, or may be joined to a compound other than silver halide such as, for example, silver rhodanate or lead oxide. Also, a mixture of particles of various crystal forms may be used.

The above emulsion may be either a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which the latent image is formed inside the grains, or a type having a latent image on both the surface and the inside. Type emulsion. Among the internal latent image types, core / shell type internal latent image type emulsions described in JP-A-63-264740 may be used.
-133542. The thickness of the shell of this emulsion varies depending on the development process and the like, but is preferably 3 to 40 nm, and 5 to 40 nm.
20 nm is particularly preferred.

As the silver halide emulsion, usually, those subjected to physical ripening, chemical ripening and spectral sensitization are used. The additives used in such a process are RD No. 17643, RD No. 187
16 and No. 307105, and the relevant portions are summarized in the table below.

The light-sensitive material of the present invention comprises a light-sensitive silver halide emulsion having a grain size, a grain size distribution, a halogen composition,
Two or more emulsions differing in at least one characteristic of grain shape and sensitivity can be mixed and used in the same layer.

Silver halide grains having a fogged surface described in US Pat. No. 4,082,553, US Pat. No. 4,626,498, JP-A-59-214852.
It is preferable to apply the silver halide grains and colloidal silver having the inside of the grains described in (1) to the light-sensitive silver halide emulsion layer and / or the substantially light-insensitive hydrophilic colloid layer. The term "silver halide particles having a fogged interior or surface" refers to silver halide grains that can be uniformly (non-imagewise) developed regardless of unexposed portions and exposed portions of the photosensitive material. , Its preparation method is described in US Pat.
It is described in 214852. The silver halide forming the internal nucleus of the core / shell type silver halide grain having the inside of the grain fogged may have a different halogen composition. Any of silver chloride, silver chlorobromide, silver bromoiodide and silver chloroiodobromide can be used as the silver halide having the inside or the surface of the grain fogged. The average grain size of these fogged silver halide grains is 0.01 to 0.75 μm, particularly 0.05
~ 0.6 μm is preferred. The grains may be regular grains or polydisperse emulsions, but may be monodisperse (at least 95% of the mass or number of silver halide grains has a grain size within ± 40% of the average grain size). Is preferable.

In the present invention, it is preferable to use non-photosensitive fine grain silver halide. Non-photosensitive fine grain silver halide is silver halide fine grains that are not exposed during imagewise exposure to obtain a dye image and are not substantially developed in the developing process, and are preferably not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may contain silver chloride and / or silver iodide as needed. Preferably, it contains 0.5 to 10 mol% of silver iodide. The fine grain silver halide has an average grain size (average value of the circle equivalent diameter of the projected area).
It is preferably from 0.01 to 0.5 μm, more preferably from 0.02 to 0.2 μm.

The fine grain silver halide can be prepared in the same manner as in the case of ordinary light-sensitive silver halide. The surface of the silver halide grains does not need to be optically sensitized, and no spectral sensitization is required. However, before adding this to the coating solution, a triazole-based, azaindene-based,
It is preferable to add a known stabilizer such as a benzothiazolium-based or mercapto-based compound or a zinc compound. Colloidal silver can be contained in the fine grain silver halide grain-containing layer. Coated silver amount of the light-sensitive material of the present invention is preferably 6.0 g / m ² or less, 4.5 g / m ² or less is most preferred.

The photographic additives which can be used in the present invention are also described in the RD, and the relevant portions are shown in the following table. Type of additive RD17643 RD18716 RD307105 Chemical sensitizer page 23, page 648, right column, page 866 2. 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column 866 to 868 Super sensitizer, page 649, right column Brightener page 24 page 647 page right column page 868 5. 5. Light absorbers, pages 25 to 26, page 649, right column, page 873 Filters, page 650, left column, dyes, ultraviolet absorbers Binder page 26 page 651 left column pages 873 to 874 7. 7. Plasticizer, page 27 page 650, right column, page 876 Lubricant Coating aid, pages 26 to 27, page 650, right column, pages 875 to 876 Surfactant 9. Static 27 pages 650 pages right column pages 876-877 Inhibitors 10. Matsuto 878-879.

Various dye-forming couplers can be used in the light-sensitive material of the present invention, and the following couplers are particularly preferable. Yellow couplers: couplers represented by formulas (I) and (II) in EP 502,424A; couplers represented by formulas (1) and (2) in EP 513,496A (especially Y-28 on page 18); EP 568,037A Claim 1
A coupler represented by the general formula (I) in column 1, lines 45 to 55 of US 5,066,576; a coupler represented by the general formula (I) in paragraph 0008 of JP-A-4-274425; Couplers described in claim 1 on page 40 of EP 498,381 A1 (especially D-35 on page 18); Couplers of formula (Y) on page 4 of EP 447,969A1 (especially Y-1 (page 17), Y- 54 (p. 41)); US
Couplers represented by formulas (II) to (IV) in columns 7, 36 to 58 of column 4,476,219 (particularly II-17, 19 (column 17), II-24 (column 19)).

Magenta coupler; JP-A-3-39737 (L-57 (1
L-68 (lower right of page 12), L-77 (lower right of page 13); EP 456,
257, A-4 -63 (p. 134), A-4 -73, -75 (p. 139); EP 486,
965 M-4, -6 (p. 26), M-7 (p. 27); EP 571, 959A M-45 (19
(M-1) of JP-A-5-204106 (page 6); M-22 of paragraph 0237 of JP-A-4-32631.

Cyan coupler: CX-1, described in JP-A-4-04843
3,4,5,11,12,14,15 (pages 14 to 16); JP-A-4-43345, C-7,
10 (page 35), 34, 35 (page 37), (I-1), (I-17) (pages 42 to 43); Japanese Patent Application Laid-Open No. 6-67385, claim 1 wherein the general formula (Ia) or (Ib) ).

Polymer coupler: P-1, described in JP-A-2-44345
P-5 (page 11). US 4,366,237, GB 2,125,570, EP 96,873 B,
Those described in DE 3,234,533 are preferred.

Couplers for correcting the unnecessary absorption of the coloring dye are described in formulas (CI), (CII) and (CI) described on page 5 of EP 456,257A1.
II), yellow colored cyan couplers represented by (CIV) (especially YC-86 on page 84), yellow colored magenta couplers ExM-7 (page 202), EX-1 (page 249), EX
-7 (p. 251), Magenta colored cyan coupler CC-9 (column 8), CC-13 (column 10) described in US 4,833,069, US
4,837,136 (2) (column 8), a colorless masking coupler of the formula (A) in claim 1 of WO 92/11575 (especially 36
-Exemplified compounds on page 45).

The coupler releasing a photographically useful group includes the following. Development inhibitor releasing compound:
Compounds of the formulas (I), (II), (III) and (IV) described on page 11 of EP 378,236A1 (especially T-101 (page 30), T-104 (page 31), T-11
3 (page 36), T-131 (page 45), T-144 (page 51), T-158 (page 58)), EP 4
Compounds represented by formula (I) described on page 7 of 36,938A2 (especially D-49 (page 51)), compounds represented by formula (1) of EP 568,037A (especially (23) (page 11)), Compounds of the formulas (I), (II) and (III) described on pages 5 to 6 of EP 440,195 A2 (especially on page 29)
I- (1)); Bleaching accelerator releasing compounds: compounds represented by the formulas (I) and (I ′) on page 5 of EP 310,125A2 (especially (60) and (6) on page 61)
1)) and a compound represented by formula (I) of claim 1 of JP-A-6-59411 (particularly (7) (page 7)); Ligand releasing compound: US
A compound represented by LIG-X described in claim 1 of 4,555,478 (especially a compound on line 21 to 41 of column 12); a leuco dye-releasing compound: compound 1 of column 3 to 8 of US 4,749,641
~ 6; fluorescent dye releasing compound: of claim 1 of US 4,774,181
Compound represented by COUP-DYE (especially compounds 1 to 11 in columns 7 to 10); Development accelerator or fogging agent releasing compound: US
Compounds represented by the formulas (1), (2) and (3) in column 3 of 4,656,123 (especially (I-22) in column 25) and EP 450,637A2
ExZK-2, p. 75, lines 36-38; Compound which releases a group which becomes a dye only after leaving: Formula (I) of claim 1 of US 4,857,447
(Particularly Y-1 to Y-1 of columns 25 to 36)
9).

As the additives other than the coupler, the following are preferable. Dispersion medium of oil-soluble organic compound: P-3,5, JP-A-62-215272
16,19,25,30,42,49,54,55,66,81,85,86,93 (140-144
Page); Latex for impregnation of oil-soluble organic compounds: US 4,199,3
Latex according to 63; oxidized developing agent scavenger: a compound represented by the formula (I) in columns 54 to 62 of column 2, US 4,978,606 (especially I-, (1), (2), (6), (12 ) (Column 4 ~
5), US Pat. No. 4,923,787, columns 5 to 10 of formula (particularly compound 1 (column 3); stain inhibitor: EP 298321A 4
Formulas (I) to (III) on page 30-33, especially I-47, 72, III-1, 27 (24
-48 pages); Anti-fading agent: A-6, 7, 20, 21, 23, 2 of EP 298321A
4,25,26,30,37,40,42,48,63,90,92,94,164 (pp.69-118),
US 5,122,444 columns 25-38 II-1 to III-23, especially III-
10, EP 471347A, pages 8-12, I-1 to III-4, especially II-2, US
5,139,931 columns 32-40 A-1 to 48, especially A-39,42; Materials that reduce the amount of color enhancer or color mixture inhibitor used:
EP 411324A pages 5--24, 1-1-1-15, especially I-46; formalin scavenger: EP 477932A pages 24-29, SCV-1-28,
Especially SCV-8; hardener: H-1, 4, 6, on page 17 of JP-A-1-214845,
Formulas (VII) to (XII) of columns 13 to 23 of 8,14, US 4,618,573
(H-1 to 54), a compound (H-1 to 76) represented by the formula (6) on the lower right of page 8 of JP-A-2-214852, especially H-14, US
Compound described in claim 1 of 3,325,287; Development inhibitor precursor: P-24,37,39 of JP-A-62-168139 (pages 6 to 7);
Compounds described in claim 1 of US 5,019,492, especially 28,29 of column 7; Preservatives, fungicides: column 3, US 4,923,790
-15 to I-1 to III-43, especially II-1,9,10,18, III-25; Stabilizer, antifoggant: US Pat.
~ (14), especially I-1,60, (2), (13), US 4,952,483
Compounds 1 to 65 of 25 to 32, especially 36: Chemical sensitizer: triphenylphosphine selenide, compound 5 of JP-A-5-40324
0; dyes: a-1 to b-20 on pages 15 to 18 of JP-A-3-156450, especially
a-1,12,18,27,35,36, b-5, V-1-23 on pages 27-29, especially V-1,
EP 445627A FI-1 to F-II-43 on pages 33 to 55, especially FI-1
1, III-36 on pages 17-28 of F-II-8, EP 457153A, especially I
II-1,3, microcrystalline dispersion of Dye-1 to 124 of 8 to 26 of WO 88/04794, compounds 1 to 22 of EP 319999A, pages 6 to 11, especially compound 1, formula (1) of EP 519306A Or a compound represented by (3)
D-1 to 87 (pages 3 to 28), compounds 1 to 22 (columns 3 to 10) represented by formula (I) of US 4,268,622, and compounds (1) to (31) represented by formula (I) of US 4,923,788. ) (Columns 2-9); UV absorbers:
Compounds (18b) to (18) represented by formula (1) of JP-A-46-3335
r), 101 to 427 (pages 6 to 9), the compounds (3) to (66) (pages 10 to 44) represented by the formula (I) and the compound HBT-1 represented by the formula (III) in EP 520938A. Compounds (1) to (31) represented by Formula (1) of EP 10521823A (columns 2 to 9).

The present invention can be applied to various color photographic materials such as color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers. In addition, 2-26,315 and 3,
It is suitable for a film unit with a lens described in -39784.

Suitable supports that can be used in the present invention include, for example, the aforementioned RD. No. 17643, page 28, RD. No. 18716, page 647, right column to page 648, left column, and RD. It is described in.

In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, further preferably 18 μm or less, and more preferably 16 μm or less. Particularly preferred. Further, the film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. T _1/2 is defined as 90% of the maximum swollen film thickness reached when the color developing solution is processed at 30 ° C. for 3 minutes and 15 seconds as a saturated film thickness.
It is defined as the time until the film thickness reaches 1/2. The film thickness means a film thickness measured under humidity control at 25 ° C. and a relative humidity of 55% (2 days), and T _1/2 is a value obtained by A. Green et al. In Photographic Science and Engineering. (Photogr. Sci. Eng.), Vol. 19, pp. 2,124-129, which can be used for measurement. T _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. The swelling ratio is
150-400% is preferred. The swelling ratio is calculated from the maximum swelling film thickness under the conditions described above by the formula: (maximum swelling film thickness-film thickness)
/ Thickness can be calculated.

In the light-sensitive material of the present invention, a hydrophilic colloid layer having a total dry film thickness of 2 to 20 μm (referred to as a back layer) is preferably provided on the side opposite to the side having the emulsion layer. In this back layer, the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder,
It is preferable to include a plasticizer, a lubricant, a coating aid, and a surfactant. The swelling ratio of the back layer is preferably from 150 to 500%.

The light-sensitive material of the present invention is obtained by using the above-mentioned RD.
No. 18716, No. 18716, 651 left column to right column, and N
o. 307105, pages 880 to 881.

Next, the processing solution for a color negative film used in the present invention will be described. The color developing solution used in the present invention is described in JP-A-4-121739, page 9, upper right column, line 1 to
The compounds described in page 11, lower left column, line 4, can be used. Particularly, color developing agents for rapid processing include 2-methyl-4- [N-ethyl-N- (2-hydroxyethyl) amino] aniline and 2-methyl-4- [N
-Ethyl-N- (3-hydroxypropyl) amino] aniline and 2-methyl-4- [N-ethyl-N- (4-hydroxybutyl) amino] aniline are preferred.

These color developing agents are used in an amount of 0.01 to 0.08 per liter of a color developing solution (hereinafter also referred to as “L”).
It is preferable to use it in a molar range, particularly from 0.015 to
Preferably, it is used in an amount of 0.06 mol, more preferably 0.02 to 0.05 mol. Also, the replenisher of the color developing solution has this concentration.
It is preferable to contain 1.1 to 3 times the color developing agent, particularly preferably 1.3 to 2.5 times.

As a preservative for the color developing solution, hydroxylamine can be used in a wide range. If higher preservation is required, substitution with an alkyl group, a hydroxyalkyl group, a sulfoalkyl group, a carboxyalkyl group, or the like is required. A hydroxylamine derivative having a group is preferable, and specifically, N, N-di (sulfoethyl) hydroxylamine, monomethylhydroxylamine, dimethylhydroxylamine, monoethylhydroxylamine, diethylhydroxylamine, N, N-di (carboxyethyl) Hydroxylamines are preferred. Among the above, N, N-di (sulfoethyl) hydroxylamine is particularly preferred. These may be used in combination with hydroxylamine, but it is preferable to use one or more of them instead of hydroxylamine.

The preservative is preferably used in an amount of 0.02 to 0.2 mol per liter, particularly 0.03 to 0.15 mol, more preferably 0.03 to 0.15 mol.
It is preferable to use it in the range of 0.04 to 0.1 mol. As in the case of the color developing agent, the replenisher preferably contains a preservative at a concentration of 1.1 to 3 times the concentration of the mother liquor (processing tank solution).

In the color developing solution, a sulfite is used as an anti-tarring agent for the oxide of the color developing agent. The sulfite is preferably used in a range of 0.01 to 0.05 mol per liter, particularly preferably in a range of 0.02 to 0.04 mol. In the replenisher, it is preferable to use the replenisher at a concentration 1.1 to 3 times the above.

The pH of the color developing solution is preferably in the range of 9.8 to 11.0, particularly preferably 10.0 to 10.5, and the replenisher is set to a higher value in the range of 0.1 to 1.0 from these values. Preferably. In order to stably maintain such a pH, a known buffer such as carbonate, phosphate, sulfosalicylate, and borate is used. The replenishment rate of the color developing solution preferably has light-sensitive material 1 m ² per 80～1300ML, from the viewpoint of reducing environmental pollution load, it less is preferable, and specific examples 80～600ML, even 80~400mL
Is preferred.

The bromide ion concentration in the color developing solution is usually 0.01 to 0.06 mol per liter. However, while maintaining sensitivity, fog is suppressed, discrimination is improved, and graininess is improved. From the purpose, per 1L
It is preferably set to 0.015 to 0.03 mol. When the bromide ion concentration is set in such a range, the replenisher may contain bromide ions calculated by the following formula. However, when C becomes negative, it is preferred that the replenisher does not contain bromide ions.

C = A−W / V C: bromide ion concentration in the color developing replenisher (mol / L) A: target bromide ion concentration in the color developing solution (mol / L) W: 1 m ² photosensitivity Amount (mol) of bromide ions eluted from the light-sensitive material into the color developer when the material is color-developed. V: Replenishment amount (L) of the color-developing replenisher for 1 m ² of the light-sensitive material.

When the replenishment amount is reduced or when the bromide ion concentration is set to a high level, 1-phenyl-3-pyrazolidone or 1-phenyl-
Pyrazolidones represented by 2-methyl-2-hydroxymethyl-3-pyrazolidone and 3,6-dithia-1,8
It is also preferable to use a development accelerator such as a thioether compound represented by octanediol.

The compounds and processing conditions described in JP-A-4-125558, page 4, lower left column, line 16 to page 7, lower left column, line 6 can be applied to the processing solution having bleaching ability in the present invention. . The bleaching agent preferably has an oxidation-reduction potential of 150 mV or more, and specific examples thereof include JP-A-5-72694 and JP-A-5-7333.
The compounds described in No. 12 are preferred, and 1,3-diaminopropanetetraacetic acid, particularly, a ferric complex salt of the compound of Example 1 on page 7 of JP-A-5-73312 is preferred.

In order to improve the biodegradability of the bleaching agent, JP-A-4-251845, JP-A-4-268552, EP588,289, and 591,
934, a compound ferric complex salt described in JP-A-6-208213 is preferably used as a bleaching agent. The concentration of these bleaching agents is preferably 0.05 to 0.3 mol per liter of a liquid having bleaching ability, and particularly preferably 0.1 mol to 0.15 mol for the purpose of reducing the amount discharged to the environment. When the liquid having bleaching ability is a bleaching liquid, it is preferable to contain 0.2 mol to 1 mol of bromide per liter, especially 0.3 to 0.8 mol.
It is preferable to include a mole.

The replenisher of the solution having the bleaching ability basically contains the concentration of each component calculated by the following formula. Thereby, the concentration in the mother liquor can be kept constant. CR = CT × (V1 + V2) / V1 + CP CR: Concentration of component in replenisher CT: Concentration of component in mother liquor (processing tank solution) CP: Concentration of component consumed during processing V1: 1 m ² for photosensitive material Replenishment amount of replenisher having bleaching ability (mL) V2: Amount (mL) brought in from a prebath by a photosensitive material of 1 m ² .

In addition, the bleaching solution preferably contains a pH buffer, particularly preferably a dicarboxylic acid having a low odor, such as succinic acid, maleic acid, malonic acid, glutaric acid and adipic acid. Also, JP-A-53-9
It is also preferred to use the known bleaching accelerators described in US Pat. No. 5,630, RD No. 17129, US Pat.

The bleaching solution contains 50 to 1000 per m ² of the light-sensitive material.
It is preferable to replenish the bleaching replenisher of mL, especially 80 to
It is preferred to replenish 500 mL, more preferably 100-300 mL. Further, it is preferable to perform aeration on the bleaching solution.

The processing solution having a fixing ability is described in
The compounds and processing conditions described on page 7, lower left column, line 10 to page 8, lower right column, line 19 of 4-125558 can be applied. Particularly, in order to improve the fixing speed and the preservability, the compounds represented by the general formulas (I) and (II) of JP-A-6-301169 are contained alone or in combination in a processing solution having a fixing ability. Is preferred. In addition to p-toluenesulfinate, it is also possible to use sulfinic acid described in JP-A-1-2224762,
It is preferable from the viewpoint of improvement of preservation.

It is preferable to use ammonium as a cation in the solution having the bleaching ability or the solution having the fixing ability from the viewpoint of improving the desilvering property. However, from the viewpoint of reducing environmental pollution, ammonium is reduced or reduced to zero. Is more preferred. In the bleaching, bleach-fixing and fixing steps, JP-A-1-30
It is particularly preferred to carry out jet stirring as described in 9059. The replenishment amount of the replenisher in the bleach-fixing or fixing process is
100 to 1000 mL per 1 m ^{2 of} photosensitive material, preferably 150 to 1000 mL
700700 mL, particularly preferably 200-600 mL.

In the bleach-fixing and fixing steps, it is preferable to install various silver recovery devices in-line or off-line to recover silver. By installing in-line, the processing can be carried out with a reduced silver concentration in the solution, so that the replenishment amount can be reduced. It is also preferable to recover silver off-line and reuse the remaining liquid as a replenisher.

The bleach-fixing step and the fixing step can be constituted by a plurality of processing tanks, and it is preferable that each tank is cascaded to form a multistage countercurrent system. From the balance with the size of the developing machine, a two-tank cascade configuration is generally efficient, and the ratio of the processing time in the former tank and the latter tank is preferably in the range of 0.5: 1 to 1: 0.5. In particular, the range of 0.8: 1 to 1: 0.8 is preferable.

It is preferable that a free chelating agent not forming a metal complex is present in the bleach-fixing solution or the fixing solution from the viewpoint of improvement in preservation. These chelating agents are described in connection with the bleaching solution. Preferably, a biodegradable chelating agent is used.

The washing and stabilizing steps are described in the above-mentioned JP-A-4-125558, page 12, lower right column, line 6 to page 13, lower right column, line 16.
The contents described in the line can be preferably applied. In particular, EP 504,60 replaces formaldehyde in stabilizers.
9. Use of the azolylmethylamines described in 519,190 and N-methylolazoles described in JP-A-4-362943, and the use of an interface free of image stabilizers such as formaldehyde by dimerizing a magenta coupler. It is preferable to use a liquid of the activator from the viewpoint of preserving the working environment. Further, in order to reduce the adhesion of dust to the magnetic recording layer applied to the photosensitive material, a stabilizer described in JP-A-6-289559 can be preferably used.

The amount of washing and replenishment of the stabilizing solution can be adjusted according to the photosensitive material 1
80 to 1000 mL per m ² is preferable, and particularly 100 to 500 mL, and more preferably 150 to 300 mL, is a preferable range in terms of both securing a washing or stabilizing function and reducing waste liquid for environmental protection. In the treatment performed with such a replenishing amount, thiabendazole, 1, 1
2-benzoisothiazoline-3-one, 5-chloro-2-
It is preferable to use a known fungicide such as methylisothiazolin-3-one, an antibiotic such as gentamicin, or water deionized with an ion exchange resin.
It is more effective to use a combination of deionized water and a bactericide or antibiotic.

Further, the liquid in the washing or stabilizing liquid tank is
JP-A-3-46652, 3-53246, -355542, 3-121448,
It is also preferable to reduce the replenishment amount by performing the reverse osmosis membrane treatment described in the above-mentioned 3-126030, and in this case, the reverse osmosis membrane is preferably a low pressure reverse osmosis membrane.

In the process of the present invention, it is particularly preferable to carry out the correction of the evaporation of the processing liquid disclosed in the Invention Association of Japan, Technical Publication No. 94-4992. In particular, a method of performing correction using temperature and humidity information of a developing machine installation environment based on (Equation 1) on page 2 is preferable. The water used for evaporation correction is preferably collected from a replenishment tank for washing,
In that case, it is preferable to use deionized water as the washing replenishing water.

As the treating agent used in the present invention, those described in page 3, right column, line 15 to page 4, left column, line 32 of the above-mentioned published technical report are preferable. In addition, as a developing machine used for this,
The film processor described on page 3, right column, lines 22 to 28 is preferred. Specific examples of preferred processing agents, automatic developing machines, and evaporation correction methods for carrying out the present invention are described in the above-mentioned published technical report from page 5, right column, line 11 to page 7, right column, last line. .

The supply form of the treating agent used in the present invention is as follows.
It may be in any form, such as a liquid preparation in the form of a liquid used or a concentrated form, or granules, powders, tablets, pastes, and emulsions. As an example of such a treating agent, JP-A-63-1
7453 discloses a liquid agent contained in a container having low oxygen permeability,
19655, 4-230748, vacuum-packed powder or granules, 4-221951, granules containing water-soluble polymer,
JP-A-51-61837 and JP-A-6-102628 describe tablets and JP-A-57-5
Discloses a paste-like treating agent, which can be preferably used, but from the viewpoint of simplicity at the time of use,
It is preferable to use a liquid that has been prepared in advance in a concentration for use.

[0127] Polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, nylon and the like are used alone or as a composite material in the container for storing these treating agents. These are selected according to the required level of oxygen permeability. For an easily oxidizable liquid such as a color developing solution, a material having low oxygen permeability is preferable, and specifically, a polyethylene terephthalate or a composite material of polyethylene and nylon is preferable. These materials have a thickness of 500 to 1500 μm and are used for containers, and preferably have an oxygen permeability of 20 mL / m ² · 24 hrs · atm or less.

Next, a processing solution for a color reversal film used in the present invention will be described. Regarding the processing for the color reversal film, see page 1, line 5 to page 10, line 5, and page 15, line 8 to page 24, 2 of the publicly known technique No. 6 (April 1, 1991) issued by Aztec Co., Ltd. Each row is described in detail, and any of the contents can be preferably applied.

In processing a color reversal film, an image stabilizer is contained in a conditioning bath or a final bath. Such image stabilizers include, in addition to formalin, formaldehyde sodium bisulfite and N-methylolazole, and from the viewpoint of working environment, sodium formaldehyde sodium bisulfite or N-methylolazole is preferable, and N-methylol is preferred. As the azoles, N-methyloltriazole is particularly preferred. Further, the contents relating to the color developing solution, the bleaching solution, the fixing solution, the washing water and the like described in the processing of the color negative film can be preferably applied to the processing of the color reversal film. Examples of preferred color reversal film processing agents containing the above contents include Eastman Kodak E-6 processing agent and Fuji Photo Film Co., Ltd.
CR-56 treating agent.

The color photographic light-sensitive material of the present invention is also suitable as a negative film for an advanced photo system (hereinafter, referred to as an AP system). NEXI
Films processed into the AP system format such as AF and NEXIA H (in order, ISO 200/100/400) and stored in special cartridges can be mentioned. These APs
The cartridge film for the system is used by being loaded into a camera for an AP system such as an Epion series (Epion 300Z, etc.) manufactured by Fujifilm. Further, the color photographic light-sensitive material of the present invention is also suitable for a film with a lens such as a super slim, which is a Fujicolor photograph run made by Fuji Film.

The film photographed by the above is printed in the minilab system through the following steps. (1) Acceptance (exposed cartridge film received from customer) (2) Detach process (transfer the film from cartridge to intermediate cartridge for development process) (3) Film development (4) Rear touch process (developed negative (Return the film to its original cartridge.) (5) Print (C / H / P3 type prints and index prints on color paper (preferably made by Fujifilm)
SUPER FA8]) (6) Collation and shipping (cartridge and index print
Check with ID number and ship with print).

These systems include Fujifilm Minilab Champion Super FA-298 / FA-278 / FA-258 / F
A-238 and Fujifilm Digital Lab System Frontier are preferred. FP922AL / FP562B / FP562B, AL / FP362B / FP as minilab champion film processors
362B, AL, and the recommended treatment chemicals are Fujicolor Justit CN-16L and CN-16Q. As a printer processor, PP3008AR / PP3008A / PP1828AR / PP1828A / PP12
58AR / PP1258A / PP728AR / PP728A, and the recommended treatment chemicals are Fujicolor Justit CP-47L and CP-40FAII. For Frontier System, Scanner & Image Processor SP-1000 and Laser Printer & Paper Processor LP-1000P or Laser Printer L
P-1000W is used. The detacher used in the detaching step and the reattacher used in the rear attaching step are preferably DT200 / DT100 and AT200 / AT100 of Fujifilm, respectively.

The AP system can also be enjoyed by a photojoy system centered on Fujifilm's Aladdin 1000 digital image workstation. For example, you can directly load a developed AP system cartridge film into the Aladdin 1000, or transfer image information from negative film, positive film, and print to a 35mm film scanner FE.
The digital image data obtained by inputting using the -550 or PE-550 flat head scanner can be easily processed and edited. The data are stored in a digital color printer NC-550AL using a light fixing type thermal color printing system and a pictograph 3000 using a laser exposure thermal development transfer system.
Or as prints with existing lab equipment through a film recorder. The Aladdin 1000 can also output digital information directly to a floppy (registered trademark) disk or Zip disk, or to a CD-R via a CD writer.

On the other hand, at home, the developed AP system cartridge film is transferred to a Fujifilm photo player AP.
You can enjoy photos on TV just by loading it in -1,
By loading it onto a Fujifilm AS-1 photo scanner, image information can be continuously and rapidly captured on a personal computer. To enter a film, print, or three-dimensional object into a computer, use Fujifilm PhotoVision FV-10 / FV.
-5 is available. Furthermore, image information recorded on a floppy disk, Zip disk, CD-R, or hard disk can be variously processed and enjoyed on a personal computer using Fujifilm's application software Photo Factory. In order to output high-quality prints from a personal computer, a digital color printer NC-2 / NC-2D manufactured by Fujifilm of a light fixing type thermal color print system is suitable.

In order to store the developed AP system cartridge film, the Fuji Color Pocket Album AP-5 POP L, AP-1 POP L, AP-1 POP KG or the cartridge file 16 is preferable.

[0136]

Examples of the present invention will be described below. However, the present invention is not limited to this embodiment. Example 1) Support The support used in this example was produced by the following method. 1) First layer and undercoat layer For a polyethylene naphthalate support having a thickness of 90 μm, a treatment atmosphere pressure of 2.66 × 10
Pa, H ₂ O partial pressure of 75% in the atmosphere gas, a discharge frequency 3
0 kHz, output 2500 W, processing intensity 0.5 kV ・ A ・
A glow discharge treatment was performed at a rate of min / m ² . On this support,
For the first layer, a coating solution having the following composition was used: Japanese Patent Publication No. 58-4589.
The coating was performed at a coating amount of 5 mL / m ² by using a bar coating method described in Japanese Patent Application Laid-Open No. H10-260,036.

Conductive fine particle dispersion (SnO ₂ / Sb ₂ O ₅ particle concentration 50 parts by mass 10% aqueous dispersion. Secondary aggregate having a primary particle diameter of 0.005 μm and an average particle diameter of 0.05 μm) Gelatin 0.5 parts by mass Water 49 parts by mass Polyglycerol polyglycidyl ether 0.16 parts by mass Poly (degree of polymerization 20) oxyethylene 0.1 parts by mass Sorbitan monolaurate.

Further, after the first layer was applied, it was wound around a stainless steel core having a diameter of 20 cm, and was heated at 110 ° C. (Tg of the PEN support: 119 ° C.) for 48 hours, subjected to heat history and annealed. Thereafter, a coating solution having the following composition was applied to the side opposite to the first layer side as an undercoat layer for the emulsion at a coating amount of 10 mL / m ² by using a bar coating method.

Gelatin 1.01 part by mass Salicylic acid 0.30 part by mass Resorcin 0.40 part by mass Poly (degree of polymerization 10) oxyethylene nonylphenyl ether 0.11 part by mass Water 3.53 parts by mass Methanol 84.57 parts by mass n -Propanol 10.08 parts by weight.

Further, a second layer and a third layer described later are sequentially coated on the first layer, and finally, a color negative photosensitive material having a composition described later is coated on the opposite side in a multi-layered manner to form a silver halide emulsion layer. A transparent magnetic recording medium was manufactured.

2) Second layer (transparent magnetic recording layer) Dispersion of magnetic material Co-coated γ-Fe ₂ O ₃ magnetic material (average major axis length: 0.25 μm)
m, S _BET : 39 m ² / g, Hc: 6.56 × 10 ⁴ A /
^{m, σs: 77.1Am 2 /kg,σr:37.4Am 2} /
kg) 1100 parts by mass, 220 parts by mass of water and 165 parts by mass of a silane coupling agent [3- (poly (degree of polymerization 10) oxyethynyl) oxypropyl trimethoxysilane] were added, and the mixture was kneaded well with an open kneader for 3 hours. . The coarsely dispersed viscous liquid was dried at 70 ° C. for 24 hours to remove water, and then heated at 110 ° C. for 1 hour to produce surface-treated magnetic particles.

Further, the mixture was kneaded again in an open kneader for 4 hours according to the following formulation. The above-mentioned surface-treated magnetic particles 855 g Diacetyl cellulose 25.3 g Methyl ethyl ketone 136.3 g Cyclohexanone 136.3 g Further, the particles were finely dispersed in a sand mill (1/4 G sand mill) at 2,000 rpm for 4 hours according to the following formulation. As the media, 1 mmφ glass beads were used.

The above kneading liquid 45 g diacetyl cellulose 23.7 g methyl ethyl ketone 127.7 g cyclohexanone 127.7 g Further, a magnetic substance-containing intermediate liquid was prepared according to the following formulation.

Preparation of Magnetic Substance-Containing Intermediate Solution 674 g of the above magnetic substance fine dispersion liquid 24280 g (solid content: 4.34%, solvent: methyl ethyl ketone / cyclohexanone = 1/1) cyclohexanone 46 g After mixing these, The mixture was stirred with a disper to prepare a "magnetic substance-containing intermediate liquid".

An α-alumina abrasive dispersion of the present invention was prepared according to the following formulation. (A) Sumicorundum AA-1.5 (average primary particle diameter 1.5 μm, specific surface area 1.3 m ² / g) Preparation of particle dispersion Sumicorundum AA-1.5 152 g Silane coupling agent KBM903 (Shin-Etsu 0.48 g Diacetylcellulose solution 227.52 g (solid content 4.5%, solvent: methyl ethyl ketone / cyclohexanone = 1/1) Ceramic-coated sand mill (1/1)
(4G sand mill) at 800 rpm for 4 hours. The media used was zirconia beads of 1 mmφ. (B) Colloidal silica particle dispersion (fine particles) "MEK-ST" manufactured by Nissan Chemical Industries, Ltd. was used. This is a dispersion liquid of colloidal silica having an average primary particle diameter of 0.015 μm using methyl ethyl ketone as a dispersion medium,
The solids content is 30%.

Preparation of Second Layer Coating Solution The above magnetic substance-containing intermediate solution 19053 g Diacetyl cellulose solution 264 g (solid content: 4.5%, solvent: methyl ethyl ketone / cyclohexanone = 1/1) Colloidal silica dispersion “MEK-ST” [Dispersion b] 128 g (solid content 30%) AA-1.5 dispersion [dispersion a] 12 g Millionate MR-400 (manufactured by Nippon Polyurethane Industries, Ltd.) Diluent 203 g (solid content 20%, diluent solvent: methyl ethyl ketone) / Cyclohexanone = 1/1) methyl ethyl ketone 170 g cyclohexanone 170 g.

[0147] The coating solution obtained by mixing and stirring the above with a wire bar, was applied so that the coating amount of 29.3 mL / m ^2. Drying was performed at 110 ° C. The thickness of the dried magnetic layer was 1.0 μm.

3) Third Layer (High Fatty Acid Ester Slip Agent-Containing Layer) Preparation of Dispersion Stock Solution of Slip Agent The following solution A was heated and dissolved at 100 ° C., added to Solution A, and dispersed with a high-pressure homogenizer. Was prepared.

[0149] A solution following compound 399 parts by weight _{C 6 H 13 CH (OH)} (CH 2) 10 COOC 50 H 101 The following compound 171 parts by weight _{n-C 50 H 101 O (} CH 2 CH 2 O) 16 H Cyclohexanone 830 Parts by mass.

Solution A Cyclohexanone 8600 parts by mass.

Preparation of Spherical Inorganic Particle Dispersion A spherical inorganic particle dispersion [c1] was prepared according to the following formulation.

Isopropyl alcohol 93.54 parts by mass Silane coupling agent KBM903 (manufactured by Shin-Etsu Silicone) Compound 1-1: (CH ₃ O) ₃ Si— (CH ₂ ) ₃ —NH ₂ ) 5.53 parts by mass Compound 1 2.93 parts by mass

Embedded image Sea hosta KEP50 88.00 parts by mass (amorphous spherical silica, average particle size 0.5 μm, manufactured by Nippon Shokubai Co., Ltd.).

After stirring for 10 minutes with the above formulation, the following is further added. Diacetone alcohol 252.93 parts by mass. While the above liquid is cooled with ice and stirred, an ultrasonic homogenizer “SONIFIER450 (BRANSON Co., Ltd.)
)) For 3 hours to obtain a spherical inorganic particle dispersion c1.
Was completed.

Preparation of Spherical Organic Polymer Particle Dispersion A spherical organic polymer particle dispersion [c2] was prepared according to the following formulation. XC99-A8808 (manufactured by Toshiba Silicone Co., Ltd., spherical crosslinked polysiloxane particles, average particle size 0.9 μm) 60 parts by mass methyl ethyl ketone 120 parts by mass cyclohexanone 120 parts by mass (solid content: 20%, solvent: methyl ethyl ketone / cyclohexanone = 1/1) While cooling with ice and stirring, the ultrasonic homogenizer “SONI”
FIER450 (manufactured by BRANSON Co., Ltd.) "for 2 hours to complete a spherical organic polymer particle dispersion c2.

Preparation of Third Layer Coating Solution The following was added to 542 g of the above-mentioned slip agent dispersion stock solution to prepare a third layer coating solution.

Diacetone alcohol 5950 g Cyclohexanone 176 g Ethyl acetate 1700 g The above-mentioned Seahosta KEP50 dispersion [c1] 53.1 g The above-mentioned spherical organic polymer particle dispersion [c2] 300 g FC431 2.65 g (3M Corporation) BYK310 5.3 g (manufactured by BYK Chemi Japan, solid content 25%). Apply the above third layer coating solution to the second layer at 10.35 mL / m ^2.
And dried at 110 ° C.
After a minute, it was dried.

4) Coating of photosensitive layer Next, on the side opposite to the support of the back layer obtained above, each layer having the following composition was applied in multiple layers to prepare a color negative film. (Composition of photosensitive layer) The number corresponding to each component indicates the coating amount in g / m ² , and the coating amount in terms of silver is shown for silver halide.

First Layer (First Antihalation Layer) Black Colloidal Silver Silver 0.122 0.07 μm Silver Iodobromide Emulsion Silver 0.01 Gelatin 0.919 ExM-1 0.066 ExC-1 0.002 ExC -3 0.002 Cpd-2 0.001 F-8 0.001 HBS-1 0.050 HBS-2 0.002.

Second Layer (Second Antihalation Layer) Black Colloidal Silver Silver 0.055 Gelatin 0.425 ExF-1 0.002 F-8 0.001 Solid Disperse Dye ExF-7 0.120 HBS-1 074.

Third layer (intermediate layer) ExC-2 0.050 Cpd-1 0.090 Polyethyl acrylate latex 0.200 HBS-1 0.100 Gelatin 0.700.

Fourth layer (low-sensitivity red-sensitive emulsion layer) Em-D silver 0.577 Em-C silver 0.347 ExC-1 0.188 ExC-2 0.011 ExC-3 0.075 ExC-40 .121 ExC-5 0.010 ExC-6 0.007 ExC-8 0.050 ExC-9 0.020 Cpd-2 0.025 Cpd-4 0.025 UV-2 0.047 UV-3 0.086 UV-4 0.018 HBS-1 0.245 HBS-5 0.038 gelatin 0.994.

Fifth Layer (Medium Speed Red Sensitive Emulsion Layer) Em-B Silver 0.431 Em-C Silver 0.432 ExC-1 0.154 ExC-2 0.068 ExC-3 0.018 ExC-40 .103 ExC-5 0.023 ExC-6 0.010 ExC-8 0.016 ExC-9 0.005 Cpd-2 0.036 Cpd-4 0.028 HBS-1 0.129 Gelatin 0.882.

Sixth layer (high-sensitivity red-sensitive emulsion layer) Em-A silver 1.108 ExC-1 0.180 ExC-3 0.035 ExC-6 0.029 ExC-8 0.110 ExC-9 020 Cpd-2 0.064 Cpd-4 0.077 HBS-1 0.329 HBS-2 0.120 Gelatin 1.245.

Seventh layer (intermediate layer) Cpd-1 0.094 Cpd-6 0.369 Solid disperse dye ExF-4 0.030 HBS-1 0.049 Polyethyl acrylate latex 0.088 Gelatin 0.886.

Eighth Layer (Layer that Gives Layering Effect to Red Sensitive Layer) Em-J Silver 0.153 Em-K Silver 0.153 Cpd-4 0.030 ExM-2 0.120 ExM-3 0.016 ExM -4 0.026 ExY-1 0.016 ExY-4 0.036 ExC-7 0.026 HBS-1 0.218 HBS-3 0.003 HBS-5 0.030 Gelatin 0.610.

Ninth layer (low-sensitivity green-sensitive emulsion layer) Em-H silver 0.329 Em-G silver 0.333 Em-I silver 0.088 ExM-2 0.378 ExM-3 0.047 ExY-1 0.017 ExC-7 0.007 HBS-1 0.098 HBS-3 0.010 HBS-4 0.077 HBS-5 0.548 Cpd-5 0.010 Gelatin 1.470.

Tenth Layer (Medium Speed Green Sensitive Emulsion Layer) Em-F Silver 0.457 ExM-2 0.032 ExM-3 0.029 ExM-4 0.029 ExY-3 0.007 ExC-6 0.0. 010 ExC-7 0.012 ExC-8 0.010 HBS-1 0.065 HBS-3 0.002 HBS-4 0.020 HBS-5 0.020 Cpd-5 0.004 Gelatin 0.446.

Eleventh Layer (High Sensitive Green Sensitive Emulsion Layer) Em-E Silver 0.794 ExC-6 0.002 ExC-8 0.010 ExM-1 0.013 ExM-2 0.011 ExM-30 030 ExM-4 0.017 ExY-3 0.003 Cpd-3 0.004 Cpd-4 0.007 Cpd-5 0.010 HBS-1 0.148 HBS-3 0.003 HBS-4 0.020 HBS -5 0.037 polyethyl acrylate latex 0.099 gelatin 0.939.

12th layer (yellow filter layer) Cpd-1 0.094 Solid disperse dye ExF-2 0.070 Solid disperse dye ExF-5 0.010 Oil-soluble dye ExF-6 0.010 HBS-1 0.049 Gelatin 0.630.

13th layer (low-sensitivity blue-sensitive emulsion layer) Em-O silver 0.112 Em-M silver 0.320 Em-N silver 0.240 ExC-1 0.027 ExC-7 0.013 ExY-1 0.002 ExY-2 0.890 ExY-4 0.058 Cpd-2 0.100 Cpd-3 0.004 HBS-1 0.222 HBS-5 0.074 Gelatin 1.553.

Fourteenth layer (high-sensitivity blue-sensitive emulsion layer) Em-L silver 0.714 ExY-2 0.211 ExY-4 0.068 Cpd-2 0.075 Cpd-3 0.001 HBS-10 124 gelatin 0.678.

Fifteenth layer (first protective layer) 0.07 μm silver iodobromide emulsion Silver 0.301 UV-1 0.211 UV-2 0.132 UV-3 0.198 UV-4 0.026 F -11 0.009 S-1 0.086 HBS-1 0.175 HBS-4 0.050 gelatin 1.984.

Sixteenth layer (second protective layer) H-1 0.400 B-1 (diameter 1.7 μm) 0.050 B-2 (diameter 1.7 μm) 0.150 B-3 0.050 S- 10.20 Gelatin 0.750.

Further, in order to improve the storability, processability, pressure resistance, fungicide / antibacterial properties, antistatic properties and coatability of each layer, W-1 to W-6, B-4 to B -6, F
-1 to F-18, and lead salts, platinum salts, iridium salts, and rhodium salts.

Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 of the twelfth layer was dispersed by the following method. ExF-2 wet cake (containing 17.6% by weight of water) 2.800 kg Sodium octylphenyldiethoxymethanesulfonate (31% by weight aqueous solution) 0.376 kg F-15 (7% aqueous solution) 0.011 kg water 4 0.020 kg Total 7.210 kg (adjusted to pH = 7.2 with NaOH).

After the slurry having the above composition was roughly dispersed by stirring with a dissolver, using an agitator mill LMK-4,
Circumferential speed 10m / s, discharge rate 0.6kg / min, 0.3m
The dispersion was dispersed until the absorbance ratio of the dispersion became 0.29 at a filling rate of zirconia beads of m diameter of 80% to obtain a solid fine particle dispersion. The average particle size of the fine dye particles was 0.29 μm.

Similarly, ExF-4 and ExF-7
Was obtained. The average particle size of the fine dye particles was 0.28 μm and 0.49 μm, respectively. ExF-5
Was dispersed by a microprecipitation dispersion method described in Example 1 of European Patent No. 549,489A. The average particle size was 0.06 μm.

[0178]

[Table 1]

In Table 1, Emulsions A to C were optimally sensitized with gold, sulfur, and selenium to which spectral sensitizing dyes 1 to 3 were added in optimal amounts. Emulsions E to G are spectral sensitizing dyes 4 to 6
In an optimum amount, and are optimally sensitized with gold, sulfur, and selenium. Emulsion J was added with optimal amounts of spectral sensitizing dyes 7 and 8 and optimally sensitized with gold, sulfur and selenium. Emulsion L was added with an optimal amount of spectral sensitizing dyes 9 to 11,
Optimally gold, sulfur and selenium sensitized. Emulsion O was optimally gold sensitized and sulfur sensitized with optimal amounts of spectral sensitizing dyes 10-12 added. Emulsions D, H, I, K,
For M and N, the spectral sensitizing dyes shown in Table 2 were added in optimal amounts, and gold sensitization, sulfur sensitization, and selenium sensitization were optimally performed.

[0180]

[Table 2] The sensitizing dyes described in Table 2 are shown below.

[0181]

Embedded image

[0182]

Embedded image

[0183]

Embedded image

[0184]

Embedded image

[0185]

Embedded image

[0186]

Embedded image

[0187]

Embedded image

[0188]

Embedded image

[0189]

Embedded image

[0190]

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[0191]

Embedded image

[0192]

Embedded image

[0193]

Embedded image

The preparation of tabular grains is described in JP-A-1-1584.
According to the example described in No. 26, low molecular weight gelatin is used. Emulsions A to K contain optimum amounts of Ir and Fe. Emulsions L to O were reduction sensitized during grain preparation. When a high-pressure electron microscope is used for tabular grains, see JP-A-3-2.
Dislocation lines as described in No. 37450 are observed.

Emulsions A to C and J were subjected to dislocation introduction using an iodine ion releasing agent according to the examples described in JP-A-6-11782. Emulsion E was translocated using silver iodide fine particles prepared immediately before addition in a separate chamber having a magnetic coupling induction type stirrer described in JP-A-10-43570. The compounds used for each layer are shown below.

[0196]

Embedded image

[0197]

Embedded image

[0198]

Embedded image

[0199]

Embedded image

[0200]

Embedded image

[0201]

Embedded image

[0202]

Embedded image

[0203]

Embedded image

[0204]

Embedded image

[0205]

Embedded image

The silver halide color photographic light-sensitive material was used as Sample 101. Sample 001 was exposed for 1/100 second through a gelatin filter SC-39 manufactured by FUJIFILM Corporation and a continuous wedge.

The development was performed by an automatic developing machine F manufactured by Fuji Photo Film Co., Ltd.
Performed as follows using P-360B. In addition, the remodeling was performed so that the overflow solution of the bleaching bath was not discharged to the post-bath, but was entirely discharged to the waste liquid tank. This FP-360B is equipped with the evaporation correction means described in Publication Technique No. 94-4992 (issued by the Invention Association).

The processing steps and the composition of the processing solution are shown below. (Processing process) Process Processing time Processing temperature Replenishment amount * Tank capacity Color development 3 minutes 5 seconds 37.8 ° C 20 mL 11.5L Bleaching 50 seconds 38.0 ° C 5 mL 5L Fixing (1) 50 seconds 38.0 ° C-5L fixing (2) 50 38.0 ℃ 8mL 5L Washing with water 30sec 38.0 ℃ 17mL 3L stable (1) 20sec 38.0 ℃-3L stable (2) 20sec 38.0 ℃ 15mL 3L Drying 1min 30sec 60.0 ℃ 35mm per 1.1m width (equivalent to one shot per 24 shots).

The stabilizing solution and the fixing solution were of a countercurrent type from (2) to (1), and the overflow of the washing water was all introduced into the fixing bath (2). The amount of the developer brought into the bleaching step, the amount of the bleaching liquid brought into the fixing step, and the amount of the fixing liquid brought into the washing step were 35 mm in width of the photosensitive material and 1.1 m in width.
2.5 mL, 2.0 mL, and 2.0 mL, respectively. The crossover time is 6 seconds in each case, and this time is included in the processing time of the previous step.

The opening area of the above processor was 10
0cm ² , 120cm ^{2 for} bleaching solution, about 1 other processing solution
00 cm ² . The composition of the treatment liquid is shown below.

(Color developing solution) Tank solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 3.0 3.0 Catechol-3,5-disulfonate disodium 0.3 0.3 Sodium sulfite 3.9 5.9. 3 Potassium carbonate 39.0 39.0 Disodium-N, N-bis (2-sulfonatoethyl) hydroxylamine 1.5 2.0 Potassium bromide 1.3 0.3 Potassium iodide 1.3mg-4-Hydroxy -6-methyl-1,3,3a, 7-tetrazaindene 0.05-hydroxylamine sulfate 2.4 3.3 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino Aniline sulfate 4.5 6.5 Add water 1.0 L 1.0 L pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.18.

(Bleaching solution) Tank solution (g) Replenisher solution (g) Ferric ammonium 1,3-diaminopropanetetraacetate monohydrate 113 170 Ammonium bromide 70 105 Ammonium nitrate 14 21 Succinic acid 34 51 Maleic acid 28 42 Water was added and 1.0 L 1.0 L pH [adjusted with aqueous ammonia] 4.6 4.0.

(Fixing (1) tank solution) A mixture of the above bleaching tank solution and the following fixing tank solution in a ratio of 5 to 95 (volume ratio) (pH
6.8).

(Fixing (2)) Tank solution (g) Replenisher (g) Ammonium thiosulfate aqueous solution 240 mL 720 mL (750 g / L) Imidazole 7 21 Ammonium methanethiosulfonate 515 Ammonium methanesulfinate 10 30 Ethylenediaminetetraacetic acid 13 39 Add water 1.0 L 1.0 L pH [adjusted with aqueous ammonia and acetic acid] 7.4 7.45.

(Washing water) Tap water was replaced with H-type strongly acidic cation exchange resin (Amberlite IR- manufactured by Rohm and Haas Company).
120B) and a mixed bed column packed with an OH type strongly basic anion exchange resin (Amberlite IR-400) to reduce the calcium and magnesium ion concentration to 3 m.
g / L or less, followed by 20 mg / L of sodium diisocyanurate and 150 mg / L of sodium sulfate.
Was added. The pH of this solution was in the range of 6.5 to 7.5.

(Stabilizing solution) Common to tank solution and replenisher (unit g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether 0.2 (Average degree of polymerization 10) 1,2-benzo Isothiazolin-3-one sodium 0.10 Disodium ethylenediaminetetraacetate 0.05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0. 75 Add water to 1.0 L pH 8.5.

From the sample 101, the fourth layer, the fifth layer,
Samples 110 to 110 were prepared in the same manner except that the sixth layer was replaced as shown in Table 3, and a sample having a
% For 7 days. The following performance was investigated using these samples.

(Preservation over time) Using the above sample, 1/100 exposure was performed through a continuous wedge with a gelatin filter SC-39 manufactured by FUJIFILM Corporation. One set is 6
Store at 0 ° C and 30% relative humidity for 4 days.
After storing at 5 ° C. and a relative humidity of 65% for 4 days, the developed sample was subjected to concentration measurement. From the characteristic curve, the logarithm of the reciprocal of the exposure amount that gives a density of fog +0.1 as the sensitivity was determined, and the difference between the same sample number and the sample stored at 30 ° C. relative humidity of 30% and 25 ° C. relative humidity of 65%. R
The difference in concentration (ΔS) was calculated. The difference (Δfog) was also determined for the fog density.

(Bleach Stain) The above two samples were subjected to development processing by the above-mentioned development processing and the development processing B described later without exposure, and the B density was measured between the same sample numbers to obtain a density difference (ΔB). I asked.

(Processing method) Step Processing time Processing temperature Color development 3 minutes 15 seconds 38 ° C. Bleaching 3 minutes 00 seconds 38 ° C. Rinse 30 seconds 24 ° C. Fixing 3 minutes 00 seconds 38 ° C. Rinse (1) 30 seconds 24 ° C. Rinse (2 ) 30 seconds 24 ° C Stable 30 seconds 38 ° C Drying 4 minutes 20 seconds 55 ° C.

Next, the composition of the processing solution will be described. (Color developing solution) (unit: g) diethylenetriaminepentaacetic acid 1.0 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 sodium sulfite 4.0 potassium carbonate 30.0 potassium bromide 1.4 potassium iodide 1.5 mg hydroxylamine sulfate 2.4 4- [N- Ethyl-N- (β-hydroxyethyl) 4.5 amino] -2-methylaniline sulfate Water was added to adjust the pH to 1.0 L (adjusted with potassium hydroxide and sulfuric acid) 10.05.

(Bleach-fixing solution) (Unit g) Ferric ethylenediaminetetraacetate 100.0 Sodium trihydrate Disodium ethylenediaminetetraacetate 10.0 3-Mercapto-1,2,4-triazole 0.03 Ammonium bromide 140.0 Ammonium nitrate 30.0 Ammonia water (27%) 6.5 mL water was added to 1.0 L pH (adjusted with aqueous ammonia and nitric acid) 6.0.

(Fixing solution) Ethylenediaminetetraacetic acid disodium salt 0.5 Ammonium sulfite 20.0 Ammonium thiosulfate aqueous solution (700 g / L) 295.0 mL Acetic acid (90%) 3.3 Water is added to 1.0 L pH (adjusted with ammonia water and acetic acid) 6.7 .

(Stabilizing solution) (unit g) p-nonylphenoxypolyglycidol (glycidol average polymerization degree 10) 0.2 ethylenediaminetetraacetic acid 0.05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazole) -1-ylmethyl) piperazine 0.75 hydroxyacetic acid 0.02 hydroxyethylcellulose 0.1 (Daicel Chemical HEC SP-2000) 1,2-benzisothiazolin-3-one 0.05 Water was added to 1.0 L pH 8.5.

From Table 3, it is clear that the use of the compound of the present invention provides excellent storage stability over time after photographing, a small density difference between the two processes, and excellent development processing suitability. That is, the B stain concentration of the sample 101 is 1.02 in both treatments and the B stain difference is 0.00, but the storage stability over time after photographing is poor, and is not acceptable at all. On the other hand, the B stain concentration of the sample 103 is 1.04, 1.
02, and the B stain difference was 0.02, but the storage stability over time after photographing was good, and the total performance of the light-sensitive material was Sample 101.
Sample 103 clearly wins.

[0226]

[Table 3]

Example 2 Samples 202 to 208 prepared in the same manner as in Example 1 except that the sample 201 from which the fourth layer and the fifth layer Cpd-2 of the sample 101 were removed were replaced as shown in Table 4 were used. The same results as in Example 1 were obtained.

[0228]

[Table 4]

Example 3 A sample 30 was prepared in the same manner as in Example 1 except that the ninth to eleventh layers of the sample 101 were replaced as shown in Table 5.
1 to 306 were created. As a result of performing the same evaluation as in Example 1 (evaluation of the G concentration for the storage stability over time), the use of the compound of the present invention resulted in excellent storage stability over time after photographing, a small difference in density between the two processes, and a development process. It is clear that the suitability is excellent.

[0230]

[Table 5]

Example 4 The Cpds of the 10th to 11th layers of the sample 101 of Example 1
The same results as in Example 3 were obtained for samples 402 to 407 which were the same except that the sample 401 from which -5 was removed was replaced as shown in Table 6.

[0232]

[Table 6]

Example 5 A sample 50 was prepared in the same manner as in Example 1 except that the thirteenth and fourteenth layers of the sample 101 were replaced as shown in Table 7.
1 to 504 were created. As a result of performing the same evaluation as in Example 1 (evaluating the B concentration for the storage stability over time), the use of the compound of the present invention as in Example 1 resulted in excellent storage stability over time after photographing, and the concentration between the two treatments. It is clear that the difference is small and the suitability for development processing is excellent.

[0234]

[Table 7]

Embodiment 6 The Cpds of the thirteenth and fourteenth layers from the sample 101 of the first embodiment are shown.
The same results as in Example 5 were obtained for Samples 602 to 605, which were the same except that Sample 601 from which Sample-2 was removed was replaced as shown in Table 8.

[0236]

[Table 8]

 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 2H016 BD00 BD01 BD05 2H023 CC02 CD00 CD03

Claims (1)

[Claims] An at least one blue-sensitive silver halide emulsion layer, at least one green-sensitive silver halide emulsion layer on a support,
And a silver halide color photographic light-sensitive material having a red-sensitive silver halide emulsion layer, wherein at least one kind of the compound represented by the general formula A 'is represented by the general formulas (AI) to (A).
At least one selected from the group of compounds represented by -III)
A silver halide color photographic light-sensitive material comprising a seed and the same layer. Embedded image In the general formula A ′, R ′ ^{a1 to} R ′ ^a5 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group or —O—R ′ ^a0 (R ′ ^a0 represents an alkyl group, an aryl group, Or a heterocyclic group). However, at least one of R ′ ^{a1 to} R ′ ^a5 is —O—R ′ ^a0 . Two of the groups R ' ^{a1 to} R' ^a5 which are in the ortho positions may be bonded to each other to form a ring. However, the compound represented by the general formula A 'is not a so-called phenol coupler in the art. Embedded image In the general formula (AI), _Ra1 represents an alkyl group, an alkenyl group, an aryl group, an acyl group, an alkyl or arylsulfonyl group, an alkyl or arylsulfinyl group,
It represents a carbamoyl group, a sulfamoyl group, a group selected from the group consisting of alkoxycarbonyl group and an aryloxycarbonyl group, R _a2 represents a group shown by hydrogen atom or Ra1. In Formula (A-II), X represents a heterocyclic group, and R _b1 represents an alkyl group, an alkenyl group, or an aryl group. However, X is s-triazine (1,
3,5-triazine ring). General formula (A-III)
In the formula, Y represents a nonmetallic atom group necessary for forming a 5-membered ring together with the -N = C- group, or a nonmetallic atom necessary for forming a 6-membered ring together with the -N = C- group. A group wherein the terminal of Y bonded to the carbon atom of the -N = C- group is-
N ( _Rc1 )-, -C ( _Rc2 ) ( _Rc3 )-, -C ( _Rc4 )
=, A divalent group selected from the group consisting of -〇- and -S- (bonded to the carbon atom of -N = C- on the left side of each group). However, Y does not form an s-triazine (1,3,5-triazine) ring. R _{c1 to} R _c4 each independently represent a hydrogen atom, an alkyl group, an alkenyl group,
Represents a group or an atom selected from the group consisting of an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylamino group, an arylamino group, and a halogen atom.