JPS61267048A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the titled material having the excellent sharpness, graininess and storage stability by incorporating at most 1mol% a compd. capable of cleaving a developing restrainer or its precursor on the weight basis of the silver halide contd. in the photosensitive layer. CONSTITUTION:The compd. (the coupler capable of releasing a DIR coupler) in which the compd. cleaved by a coupling reaction with an oxidation product of a developing agent, is carried out the coupling reaction with an another oxidation product of the developing agent, thereby cleaving the developing restrainer or its precursor, is the compd. shown by the formula. The additional amount of the compd. is at most 1mol% per 1mol of the silver halide contd. in the same layer. If the compounding amount of the compd. is more than the value as mentioned above, the problems of lessening the photosensitivity and of softening and of the deterioration of the sharpness remarkably appear in the titled material. The additional amount of the compd. as mentioned above, is 0.003-0.3mol% per 1mol of the silver halide.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide color photographic light-sensitive material having excellent sharpness, graininess, and storage stability.

(Prior art) In recent years, silver halide photographic materials, especially photographic materials, have been developed using ultra-high-sensitivity materials such as ISO/6θθ films and /10-length image cameras and disc cameras. There is a growing demand for photosensitive materials having high image quality and high sharpness suitable for such small format cameras.

Conventionally, as one of the means to improve sharpness and graininess, a compound (hereinafter referred to as I)I8 compound that releases a development inhibitor in accordance with the density of an image during development has been used in silver halide color photographic photosensitive materials. It is known to be incorporated into materials.

This DIR compound is generally a compound that releases a development inhibitor by reacting with the acid chloride of an aromatic primary amine developing agent. So-called DIR couplers (for example, US Pat. No. 3,127.!
rAru issue, same J.

ri0/, 7g3 issue, u, 09, 9! :'I No. 9.114, 3,933. ! No. 00.

Compounds described in Id. u, luA, No. 394, Id. Dakuku, No. 563) are known. This is a compound in which, when subjected to a coupling reaction with an oxidized form of an aromatic primary amine developing agent, the Katzler matrix forms a dye while releasing a development inhibitor.

Compounds that form a colorless dye through a coupling reaction with the oxidized form of an aromatic primary amine developing agent while releasing a development inhibitor include, for example, U.S. Pat.
Jco, 3≠3, 3.91g, 0II1, 3.9
3g, No. 99.7, No. 3゜94/, No. 939, No. u,
OjJ+ko/J issue, JP-A-13-110! ;ko9, same3
Gu/? , 7.7.7, etc. are known.

In addition, so-called DIR hydroquine which releases a development inhibitor through a cross-oxidation reaction with an oxidized form of a developing agent includes, for example, U.S. Patent No. 3. Jri No. 9,319, 3
, 930, 163, etc.

However, these compounds have drawbacks such as deterioration in functionality and desensitization due to decomposition during storage of the film after coating, and their sharpness improvement effect has not been sufficient.

In addition, as a compound whose leaving group releases a development inhibitor with timing when coupled with an oxidized product of an aromatic primary amine developing agent, for example, U.S. Pat.
From No. 962 and Tokukaisho-! 4g37, etc.

It is true that when this type of compound is used, it is possible to exert the inhibitory effect at a position a particular distance away from the developed silver halide grains, so sharpness should be improved based on the so-called adjacent effect. However, these compounds did not improve the sharpness sufficiently because the timing was not sufficient. Furthermore, during film storage, hydrolysis or cleavage is unavoidable under conditions of high humidity, resulting in problems such as desensitization and deterioration of its functions.

On the other hand, a compound obtained by removing the development inhibitor portion from the compound of the present invention is disclosed in JP-A-Sho, t7-13g63&. This compound splits off when the component that scavenges the oxidized form of the color developing agent couples with the oxidized form of the developing agent, controls the diffusion and formation of this oxidized form, and improves sharpness and graininess. , as will be described later, is a completely different effect from that of the present invention.

In addition, the above compound and the compound of the present invention may be added to the highest sensitivity layer for silver halide contained in the same light-sensitive emulsion layer.
-U.S. Patent U states that adding a large amount of jt morch
, u'i'i, sbo, but it has become clear that the addition of such a large amount of the compound of the present invention causes a significant desensitization effect.

(Object of the Invention) An object of the present invention is to provide a silver halide color photographic light-sensitive material having excellent sharpness, graininess, and storage stability.

(Structure of the Invention) An object of the present invention is to provide a silver halide color photographic light-sensitive material having a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer on a support.
At least one photosensitive layer is composed of two or more layers having different sensitivities, and the highest sensitivity layer of the layers contains a compound cleaved by a coupling reaction with an oxidized main developing agent and another oxidized developing agent. This is achieved by a silver halide color photographic light-sensitive material characterized in that it contains at most 1 mole of a compound that cleaves a development inhibitor or its precursor through a ring reaction relative to the silver halide in the light-sensitive layer. Ta.

Here, the compound cleaved by the coupling reaction with the oxidant of the main development system undergoes a coupling reaction with another oxidant of the main development system, and the compound that cleaves the development inhibitor or its precursor (hereinafter referred to as DIR coupler The releasing coupler) is preferably represented by the following general formula.

General formula CI) CpTe-BT+v-CpT+-B-1-91 in the formula, C
po is caused by a coupling reaction with the oxidized developing agent,
(BT+v-cpT+body ``→'' represents a coupler residue that cleaves the molecule, B□ represents a linking group that cleaves Cp2 after cleavage from Cp, and Cr2 represents a linking group that cleaves Cp2 after cleavage from CpT-+B□). The coupler residue is in a form capable of ring reaction, and by reaction with the oxidized developing agent (
B2) is a group that cleaves i→, B2 represents a linking group that cleaves DI after dicleaving Cr2, DI represents an active inhibitor, and ■ and W each represent O or l.

In general formula (1), the coupler residues represented by Cp and Cr2 are preferably yellow coupler residues (e.g., open-chain ketomethylene coupler residues), magenta coupler residues (e.g., !-pyrazolone type coupler residues). cyan coupler residues (e.g., phenolic coupler residues, naphthol reducer residues).

Black coupler residues (e.g. resorcinol-type coupler residues)
Alternatively, colorless coupler residues (eg, indanone casolar residues, acetophenone disc coupler residues) may be mentioned.

When these coupler residues are Cr2, Cr
The coupling reaction with the oxidized developing agent becomes possible only after the bond with "HBl) is cleaved. That is, in the general formula (1), Cr2 is an open-chain ketomethylene coupler residue, an S-pyrazolone magenta coupler. When the residue is an indanone coupler residue or an acetophenone coupler residue, Cp7-+ B□)7 at the oxygen atom obtained by removing the hydrogen atom from the enol-type hydroxyl group
Combine with. When Cr2 is a resol monochrome coupler residue, a phenol coupler residue, or a naphthol coupler residue, it bonds to Cr8B□)7 at the oxygen atom obtained by removing the hydrogen atom from the human α-xyl group.

Furthermore, when Cr2 is a pyrazolotriazole coupler residue or a pyrazoloimidazole coupler residue, the carbon atom at the coupling position is tautomerized and SP
As it becomes 2 carbon, the hybrid orbital of the nitrogen atom in the vicinity changes from SF3 to SF3, and when the hydrogen atom is removed from the tautomerized imino group (SF3), the nitrogen atom becomes CpT- (B□) Combines with 7.

Furthermore, the present invention is particularly effective for general formula (1)
, Cpl has the following general formula (Cp-/), (Cp-
2), (Cp-j), (Cp-1, (Cp-j), (C
p-6), (Cp-7), (Cp-t>, (Cp-9)
, (Cp-10) is a coupler residue represented by (Cp-//). These coupler residues have a high coupling rate and are therefore preferred.

General formula (Cp-/) General formula (Cp-riR, -N H- to -l(-(,' -N 1-1
-9,□General formula (Cp-3) General formula (Cp-4') General formula 1 (Cp-yo) General formula (Cp-1-) General formula (Cp-ri) General formula (Cp-4) General Formula (Cp-9) General formula (Cp-to) General formula (CI) -//) In the above formula, the free bond derived from the coupling position represents the bonding position TIt of the coupling-off group. In the above formula, R5□, R5□, R53, ordinary, 4, "55
- "56-"57- fL58-几59- R60
If ``61'' contains a diffusion-resistant group, it is selected such that the total number of carbon atoms is from g to 3, preferably io-coco; otherwise, the total number of carbons is preferably 15 or less.

Next, R5□ of the general formula (Cp-/) to (Cp-//)
~R6□, 1%m and p will be explained.

In the formula, 'fL5□ represents an aliphatic group, an aromatic group, an alkoxy group, or a heterocyclic group, and R5□ and R53 each represent an aromatic group or a heterocyclic group.

In the formula, the aliphatic group represented by 51 preferably has 1 to 22 carbon atoms, is substituted or unsubstituted, is linear or cyclic,
It may be either. Preferred substituents for the alkyl group include an alkoxy group, an aryloxy group, an amino group, an acylamino group, and a halo group, which themselves are further substituents. You may have it. Specific examples of aliphatic groups useful as R5 are as follows: isopropyl, isobutyl, tert-butyl, isoamyl, tert-amyl, t,i-dimethylbutyl.

/, /-dimethylhexyl group, l,l-diethylhexyl group, dodecyl group, hexadecyl group, octadecyl group,
cyclohexyl group, -1methoxyisopropyl group, -1phenoxyisopropyl group.

Co-p-tert-butylphenoxyisobrobyl group,
These include α-aminoisopropyl group, α-(diethylamino)isopropyl group, α-(succinimido)isopropyl group, α-(7talimido)isopropyl group, α-(benzenesulfonamido)isopropyl group, and the like.

When R5□, R5□ or RJ53 represents an aromatic group (7 enyl group in %), the aromatic group may be substituted. Aromatic groups such as phenyl groups include alkyl groups with a carbon number of 3J or less, alkenyl groups, alkoxy groups, alkoxycarbonyl groups, alkoxycarbonylamino groups, aliphatic amide groups, alkylsulfamoyl groups, alkyl sulfonamide groups, and alkylureido groups. The alkyl group may be substituted with a group, an alkyl-substituted succinimide group, etc., and in this case, the alkyl group may have an aromatic group such as phenylene interposed in the chain. The phenyl group can also be an aryloxy group, an aryloxycarbonyl group, an arylcarbamoyl group, an arylamido group, an arylsulfamoyl group, an arylsulfonamide group,
It may also be substituted with an ori-roureido group, etc., and the ori-ru group portion of these substituents further has a total number of carbon atoms of /~
-2 may be substituted with one or more alkyl groups.

The phenyl group represented by R+5□, R5□ or 'fL53 further includes an amino group, including one substituted with a lower alkyl group having carbon number/-4, hydroxyl, carboxy group, sulfo group, nitro group, cyano group, It may be substituted with a thiocyano group or a halogen atom.

Further, R+51, 几, □ or "53 may represent a substituent in which a phenyl group is fused with another ring, such as a naphthyl group, a quinolyl group, an isoquinolyl group, a chromanyl group, a coumaranyl group, a tetrahydronaphthyl group, etc. These substituents may themselves have further substituents.

When 几 and □ represent an alkoxy group, the alkyl portion represents a linear or branched alkyl group, alkenyl group, cyclic alkyl group, or cyclic alkenyl group having 1 to 31 carbon atoms, preferably 1 to 22 carbon atoms, These may be substituted with halogen atoms, aryl groups, alkoxy groups, etc.

When 51, 几, □ or R53 represents a heterocyclic group, the heterocyclic group is the carbon atom of the carbonyl group of the acyl group in alpha acylacetamide or the amide group, respectively, through one of the carbon atoms forming the ring. bond to the nitrogen atom of.Such heterocycles include thiophene, furan,
Pyran, pyrrole, pyrazole, pyridine, pyrazine,
Examples include pyrimidine, pyritazine, indolizine, imidazole, thiazole, oxazole, triazine, thiadiazine, oxazine, and the like. These may further have a substituent on the ring.

In the general formula (Cp-3), R55 is a linear or branched alkyl group having 1 to 1 carbon atoms, preferably 1 to 5 carbon atoms (e.g., methyl, impropyl, tert-butyl, hexyl, dodecyl group, etc.); Alkenyl groups (e.g., allyl group, etc.), cyclic alkyl groups (e.g., cyclopentyl group, cyclohexyl group, normenyl group, etc.)
, aralkyl group (e.g., eva, benzyl, β-phenylethyl group, etc.), cyclic alkenyl group (e.g., cyclointenyl, cyclohexenyl group, etc.), and these represent halogen atoms, nitro groups, cyano groups, aryl groups, alkoxy group, aryoloxy group, carboxy group, alkylthiocarbonyl group, arylthiocarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, sulfo group, sulfamoyl group 1, carbamoyl group, acylamino group, diacylamino group, ureido group, urethane group, thiourethane group, sulfonamide group, heterocyclic group, arylsulfonyl group, alkylsulfonyl group, arylthio group, alkylthio group, alkylamino group, dialkylamino group, anilino group, N-arylanilino group, N-alkylani It may be substituted with a lino group, an N-acylanilino group, a hydroxyl group, a mercapto group, or the like.

Furthermore, R55 is an aryl group (e.g., phenyl group, α-
or β-su7tyl group). The aryl group may have one or more substituents, such as an alkyl group, an alkenyl group, a cyclic alkyl group, an aralkyl group, a cyclic alkenyl group, a halogen atom,
Nitro group, cyano group, aryl group, alkoxy group, aryloxy group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, sulfo group, sulfamoyl group, carbamoyl group, acylamino group, diacylamino group, ureido group, urethane group, sulfoy y mil' group, '418 ring group, arylsulfonyl group, alkylsulfonyl group, arylthio group, alkylthio group,
alkylamino group, dialkylamino group, anilino group,
N-alkylanilino group, N-aryanilino group, N
- may have an acylanilino group, a hydroxyl group, etc.

Furthermore, R55 is a heterocyclic group (for example, a !- or 6-membered heterocyclic group containing a nitrogen atom, an oxygen atom, or a sulfur atom as a heteroatom, a fused heterocyclic group, a pyridyl group, a quinolyl group,
Furyl group, benzothiazolyl group 1. oxasilyl group, imidazolyl group, naphthoxacylyl group, etc.), a heterocyclic group substituted with the substituents listed for the above-mentioned aryl group, an aliphatic or aromatic acyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylcarbamoyl group, It may also represent an arylcarbamoyl group, an arylthiocarbazoyl group or an arylthiocarbamoyl group.

In the formula, R54 is a hydrogen atom, a linear or branched alkyl having from 1 to 31 carbon atoms, preferably 1 to 3 carbon atoms, an alkenyl% cyclic alkyl group, an aralkyl group, a cyclic alkenyl group (
These groups may have the substituents listed for R55 above), aryl groups and heterocyclic groups (which may have the substituents listed for R55 above), alkoxycarbonyl groups (e.g. , methoxycarbonyl group, methoxycarbonyl group, stearyloxycarbonyl group, etc.), aryloxycarbonyl group (e.g., phenoxycarbonyl group, naphthoxycarbonyl group, etc.),
Aralkyloxycarbonyl group (e.g. Eva, benzyloxycarbonyl group, etc.), alkoxy group (e.g., methoxy group, ethoxy group, heptadecyloxy group, etc.), aryloxy group (e.g., TTF, phenoxy group, tolyloxy group, etc.), alkylthio groups (e.g. ethylthio group,
dodecylthio group, etc.), arylthio group (e.g., 7-enylthio group, α-naphthylthio group, etc.), carboxyl group, acylamino group (e.g., acetylamino group, 3-
C(2+''-di-tert-amylphenol)acetamide]benzamide group, etc.), diacylamino group%N
- an alkyl acylamino group (e.g., N-methylpropionamide group, etc.), an N-arylacylamino group (e.g., N-phenylacetamide group, etc.), a ureido group (e.g., ureido, N-arylureido, N-alkylfreido group) ), urethane group, thiourethane group,
Arylamino groups (e.g., phenylamino, hemethylanilino, diphenylamino, N-acetylanilino, cochrolow!-tetradecanabadoanilino, etc.), alkylamino groups (e.g., n-butylamino, methyl amino group, cyclohexylamino group, etc.)
, cycloamino group (e.g., lysino group, pyrrolidino group, etc.), heterocyclic amino group (e.g., derbylidylamino group, -1penzoxazolylamino group, etc.), alkylcarbonyl group (e.g., methylcarbonyl group) nato),
Arylcarbonyl groups (e.g. Eva, phenylcarbonyl groups, etc.), sulfonamide groups (e.g. alkylsulfonamide groups, arylsulfonamide groups, etc.), carbamoyl groups (e.g. ethylcarbamoyl group, dimethylcarbamoyl M, N-methyl-phenyl) Carbamoyl, N-
phenylcarbamoyl, etc.), sulfamoyl group (e.g., N-alkylsulfamoyl, N,N-dialkylsulfa-7yl group, N-arylsulfamoyl group, N-arylsulfamoyl group,
-furkyl-N-arylsulfamoyl group, N, N-
It represents any one of a diarylsulfamoyl group, a cyano group, a hydroxy group, and a sulfo group.

In the formula, "56 represents a hydrogen atom or a carbon number of 7 to 31, preferably a straight or branched chain alkyl group, an alkenyl group, a cyclic alkyl group, an aral group, or a cyclic alkenyl group, These may have the substituents listed for "55" above.

Further, 'FL56 may represent an aryl group or a heterocyclic group, and these may have the substituents listed for 5 above.

In addition, R56 is a cyano group, an alkoxy group, an aryloxy group, a halogen atom, a carboxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a sulfo group, an acyl group, a sulfamoyl group, a carbamoyl group, an acylamino group, Diacylamino group, ureido group, urethane group, sulfonamido group, arylsulfonyl group, aryl sulfonyl group, iri-ruthio group, alkylthio group, alkylamino group, sialylamino group, anilino group, N-arylanilino group , a healkylanilino group, or a heacylanilino group.

R57, R'ss and "59 each represent a group used in a normal f-type phenol or α-naphthol coupler. Specifically, R57 represents a hydrogen atom, a halogen atom, an alkoxycarbonylamino group, an aliphatic carbonization group, etc. Hydrogen residue, hairarylureido group, acylamino group, -0-R, 2-fi or -8-R, □ (however, R6
2 is an aliphatic hydrocarbon residue), and when one or more R57 exists in the same molecule, one or more TL57
may be different groups, and the aliphatic hydrocarbon residues include those having substituents. - When these substituents include an aryl group, the aryl group may have the substituents listed for R55 above.

R58 and , , are aliphatic hydrocarbon residues.

Examples include groups selected from aryl groups and heterocyclic residues, one of which may be a hydrogen atom, and these groups include those having substituents. Furthermore, R'ss and R59 may jointly form an N-containing heterocyclic nucleus.

The aliphatic hydrocarbon residues may be either saturated or unsaturated, and may be straight-chain, branched, or
Any ring-shaped one may be used. and preferably an alkyl group (e.g., methyl, ethyl, propyl, isopropyl, butyl, t-butyl, inbutyl, dodecyl, octadecyl, cyclobutyl, cyclohexyl, etc.),
Alkenyl groups (e.g. allyl, octenyl, etc.)
It is. Typical aryl groups include phenyl and naphthyl groups, and typical heterocyclic residues include pyridinyl, quinolyl, chenyl, piperidyl, and imidazolyl. These aliphatic hydrocarbon residues, aryl groups and hetero 3iJ! Substituents introduced into residues include halogen atom, nitro, hydroΦ, calhosyl, amino, &substituted amino, sulfo, alkyl, alkenyl, aryl, heterocycle, alkoxy, aryloxy, arylthio, arylazo, acylamino. , carbamoyl,
Examples include groups such as ester, acyl, acyloxy, sulfonamide, sulfamoyl, sulfonyl, and morpholino.

represents an integer of /-g, m represents an integer of 1 to 3, and p represents an integer of 1 to SO.

R2O is an arylcarbonyl group, preferably a colcoco alkanoyl group, an arylcarbamoyl group, an alkanecarbamoyl group having 3 carbon atoms, preferably 11 carbon atoms, carbon number/-JJ, preferably 1L< represents an alkoxycarbonyl group or an aryloxycarbonyl group of 1 to 1, which may have a substituent, and examples of the substituent include an alkoxy group, an alkoxycarbonyl group,
Examples include an acylamino group, an alkylsulfamoyl group, an alkylsulfonamide group, an alkylsuccinimide group, a halogen atom, a nitro group, a carboxyl group, a nitrile group, an alkyl group, and an aryl group.

R61 is an arylcarbamoyl group having -3 carbon atoms.

Preferably, Colcoco's alkanoyl group, carbon number 7 to 3, preferable! L< is 1A-2-alkoxycarbonyl group or aryloxycarbonyl group, carbon number 1 to 3λ,
Preferably 7 to -1 alkylsulfonyl group, arylsulfonyl group, aryl group, 3- or 6-membered heterocyclic group (the hetero atom is selected from nitrogen atom, oxygen atom, sulfur atom, for example, triazolyl group, imidazolyl group) group, 7-thallimide group, succinimide group, furyl group, pyridyl group, or benzotriazolyl group), which may have the 9 substituents mentioned above for R60.

Among the above coupler residues, as a yellow coupler residue, in the general formula (Cp-i), 几6 is a t-butyl group I or a substituted or unsubstituted aryl group, and 几52 is a substituted or unsubstituted aryl group. represents an aryl group, and in general formula (Cp--2), R52 and R'sa
is preferably a substituted or unsubstituted 7-aryl group.

Preferred magenta coupler residues are of the general formula (C
p-3)+; When R54 represents an acylamino group, a ureido group, or an arylamino group, and R'ss represents a substituted aryl group, "54" in general formula (Cp-1) represents an acylamino group, a ureido group, or an arydo group. and arylamino group, when R'sa represents a hydrogen atom, and when the general formula (C
R54 and R in p-, t) and (cp-6)
'sa represents a linear or branched alkyl group, alkenyl group, cyclic alkyl group, aralkyl group, or cyclic alkenyl group.

Preferred cyan coupler residues are those represented by the general formula (C
When R57 in p-7) represents an acylamino group or ureido group at the 2nd position, an acylamino group or an alkyl group at the 3rd position, and a hydrogen atom or a chlorine atom at the 6th position, and when R57 in the general formula (Cp-9) , a hydrogen atom at the 3-position, an acylamino group, a sulfonamide group, an alkoxycarbonyl group, R58 is a hydrogen atom, and R5
This is the case where 9 represents a phenyl group, an alkyl group, an alkenyl pentacyclic alkyl group, an aralkyl group, or a cyclic alkenyl group.

Preferred colorless coupler residues have the general formula (Cp
-10), when R56 represents an acylamino group, a sulfonamide group, or a sulfamoyl group, the general formula (
Cp-//), R60 and R61 represent an alkoxycarbonyl group.

In addition, any part of R5□ to R6□ may form a multimer of bis form or more, and a polymer of a monomer having an ethylenically unsaturated group in any part of these groups or a non-bis polymer may be formed. It may also be a copolymer with a color-forming monomer.

When the coupler residue represented by Cpo represents a polymer, it is derived from a monomer coupler represented by the following general formula (Cp-/co) and has a repeating unit represented by the general formula (Cp-/3). A copolymer with one or more non-chromogenic monomers containing at least one ethyl group that does not have the ability to coalesce or couple with an oxidized form of an aromatic primary amine developing agent. means. Here, more than one monomer coupler may be polymerized at the same time.

General formula (Cp -/ko) 几Cf(7C+AsA3+r-(-A-iQ General formula (Cp
-／、? ) ■ (At1 dimension T trajectory i8 In the formula, R represents a hydrogen atom, the number of carbon atoms/-4 represents a lower alkyl group, or a chlorine atom, and A□ represents CON R'-
1-N R'CON R,'-1-NB,'COO-1
-COO-1-so, -co-1-NR,C0-1
-SO□N B,'-1-NR'802-1-OCO-
1-OCONR'-1-N R'- or -〇-, A2 represents -CON R'- or -COO-, R
′ represents a hydrogen atom, an aliphatic group, or an aryl group,
-If there are more than one molecule in the molecule, they may be the same or different.

A3 represents an unsubstituted or substituted alkylene group, an aralkylene group, or an unsubstituted or substituted arylene group having -70 carbon atoms, and the alkylene group may be linear or branched.

(Examples of alkylene groups include methylene, methylmethylene, dimethylmethylene, dimethylene, trimethylene,
Tetramethylene, pentamethylene, hexamethylene, tetramethylene, aralkylene groups such as benzylidene, arylene groups such as phenylene, naphthylene, etc.) Q is a general formula (Cp-/) to (Cp-/
Any part of R5□ to R'cti of /) represents a coupler residue that becomes a -valent group.

i, j, and k represent Omanoha l\\.

Here, the alkylene group and arylene group represented by A3 are substituents of the arylene group such as aryl group (for example, phenyl group), nitro group, hydroxyl group, cyano group, sulfo group, and alkoxy group! iC series, t, methoxy group), aryoloxy group (e.g., phenoxy group), alkylene group (e.g., acetoxy group), acylamino group (e.g.,
acetate (amino group), sulfonamide group (e.g.
methanesulforamide group), sulfamoyl i (e.g., t
(e.g., methylsulfamoyl group), hydrogen atom (e.g., fluorine, chlorine, bromine, etc.), carboxy group, carbamoyl group (e.g., methylsulfamoyl group), alkoxycarbonyl group (e.g., methoxycarbonyl group) etc.), and sulfonyl groups (eg, methylsulfonyl group). When there are λ or more substituents, they may be the same or different.

Next, non-color-forming ethylene-like monomers that do not couple with the oxidation products of aromatic-grade amine developers include acrylic acid, α-chloroacrylic acid, α-alkyl acrylic acid, and derivatives of these acrylic acids. Examples include esters or amides, methylenebisacrylamide, vinyl esters, acrylonitrile, aromatic vinyl compounds, maleic acid derivatives, and vinylpyridines. Two or more kinds of the non-color-forming ethylenically unsaturated monomers used here can also be used at the same time.

In general formula (I), Cp2 is preferably represented by the following general formula (
Cp-ihiro), (Cp-/!), (Cp-76
), (Cp -tri), (Cp -/za), (Cp-7
9), (Cp-J+!:l), (CI)-J/), (
Cp-ako), (Cp-ko3) or (Cp-J<<
) is the coupler residue represented by These couplers are preferred because of their high coupling speed. Here, the * mark represents the position where Cpr+B is combined, and the ** mark represents the position where it is combined with →BiDI.

General formula (Cp-itI) ** General formula (Cp-is) General formula (Cp-/A) General formula (Cp-/ri) "56 General formula (Cp-/l) General formula (C: p-/ 9) * General formula (Cp-CoO)! ** General formula (Cp-Two) ** General formula (Cp-22) ** General formula (Cp-13) Y * General formula (Cp--q) ★ In the formula, -13+ m r p+ "51- "52*
R54m ”55-R'sa, R'sy, R'ss,
R59 and "61 are general formulas (Cp-/), (Cp-co), (Cp-J), (Cp-Hiroshi), (Cp-, t), (
Cp-1, (Cp-ri) (Cp-za), (Cp-9),
It has the same meaning as defined in (Cp −/ 0 ) and (Cp −/ / ).

Development inhibition fllJ represented by DI in general formula (I)
The agent is preferably a tetrazolylthio group, /-fi or cocopenzotrizolyl group, ! -Penzoindazolyl group, benzimidazolylthio group, benzoxazolylthio group, imidazolylthio group, oxazolylthio group, triazolylthio group, oxadiazolylthio group, thiadiazolylthio group, or N-aryl-/, Tip 3. Hiro-thiatriazole-3-amino group is mentioned. Here N-
Allie Roots, Ko, 3. The q-thiatriazole-3-amino group itself (after being cleaved) does not have an inhibitory effect on development, but it undergoes a rearrangement reaction to generate j-mercapto-/-phenyltetrazole and exhibits an inhibitory effect (as described in West German Published Patent Application No. 3.30'?, !06A).

The development inhibitors listed above also include cases where they have one or more substituents at substitutable positions.

Preferred substituents include aliphatic groups (e.g., methyl group, ethyl group, propyl group), aromatic groups (e.g., phenyl group, methoxycarbonylphenyl group), halogen atoms (e.g., chloro atom, propyl group), seven atoms), alkoxy groups (e.g., methoxy group, benzyloxy group), alkylthio groups (e.g., ethylthio group), aryloxy groups (e.g., phenyloxy group), arylthio groups (
For example, phenylthio group), carbamoyl group (for example,
N-ethylcarbamoyl group), alkoxycarbonyl group (e.g., dicarbonyl group), aryloxycarbonyl group (e.g., phenoxycarbonyl group), sulfonyl group (e.g., benzenesulfonyl group), sulfamoyl group (For example, N-butylsulfuryl moyl group)
, acylamino group (e.g., acetamido group, benzamide group)% sulfonamide group (e.g., benzenesulfonamide group), acyl group (e.g., benzoyl group), nitroso group, nitro group, acyloxy group (e.g., benzoyloxy 2NG), ureido group (e.g., 3-phenylureido group), imide group (e.g., succinimide group), heterocyclic group (heterocyclic group with a v- or e-membered ring selected from a nitrogen atom, an oxygen atom, or a sulfur atom as a heteroatom) For example, cofuryl group, copyridyl group, l-imidazolyl group, normorpholino fG), hydroxyl group,
Alkoxycarbonylamino groups (e.g. methoxycarbonylamino groups), aryloxycarbonylamino groups (e.g. phenoxycarbonylamino groups), amine groups, aryl, amino groups (e.g.

(e.g., anilino group), aliphatic amines (e.g., diethylamino group), sulfinyl crystals (e.g., ethylsulfinyl group), thioureido groups (e.g., 3-phenylthioureido group), or heterocyclic amino groups (e.g., imidazolylamino group), etc.

When there is an aliphatic group in the partial structure of the above substituent, the number of carbon atoms is /-, Z, preferably /-10, and chain or t is cyclic, straight chain or branched, saturated or unsaturated, Replacement°
Mayu is an unsubstituted aliphatic group.

Further, when the partial structure of the substituents listed above includes an aromatic group, the number of carbon atoms is 6 to IO, and preferably a substituted or unsubstituted phenyl group.

In general formula (1), DI is particularly preferably a tetrazolylthio group or a benzotriazolyl group.

The groups represented by B1 and B2 in general formula (1) are preferably the following.

(1) A group that utilizes the cleavage reaction of hemiacetal, for example, U.S. Patent No. 6,394, Patent Application Showa Tade-7θ
6ko λ3, same! 9-101. Coco Q and J? -7
! ; A group described in No. Il'ljr and represented by the following general formula.

When the above-mentioned linking group is B1, in the formula, the mark * represents the position bonded to Cpl, and the mark ** represents the position bonded to C20. Also, when the above linking group is B2, the * mark in the formula is C
20, and the ** mark represents the position where it is bonded to DI.

In the formula, W represents an oxygen atom or -N- group (G3 represents an organic direct substituent), G and G2 represent a hydrogen atom or an organic substituent, t represents 1 or 9, and t is 2
When λ, each of G1 and G2 may be the same or different, and it also includes the case where any two of G□, G2 and G3 are joined together to form a cyclic structure.

(2) A group that causes a cleavage reaction using an intramolecular nucleophilic direct exchange reaction. For example, US Patent No. DA! <4ff.

The timing group described in No. 962.

(3) A group that causes a cleavage reaction using an electron transfer reaction along a conjugated system. For example, U.S. Pat.

No. 09,323 or a group represented by the following general formula (British Patent No. A, OQB).

Riff,? Groups listed in item A).

When the above linking group is B1, in the formula, * mark is cp11=
The bonding position is indicated, and the mark ** indicates the bonding position to C20. Moreover, when the above-mentioned connecting group is B2, in the formula,
The * mark represents the bonding position to C20, and the ** mark represents 1) I
represents the position where it is bonded to. In the formula, G4 and G5 represent a hydrogen atom or an organic substituent.

A particularly preferred coupler in general formula (I) is when V and W are both O.

Specific examples of the DIR coupler releasing coupler used in the present invention are shown below, but the invention is not limited thereto.

N-thickness N Δ=N These compounds of the present invention are disclosed in JP-A-37-tSt6J6.
U.S. Patent No. Q, Dakuku! It can be easily synthesized from known compounds by the method described in the specification attached to Patent Layer (A) filed on Q. 72, 1985, No. RL, No. D, 1985.

The compounds of the present invention may be used in combination for one or more layers, or the same compound may be used in layers other than the highest sensitivity silver halide emulsion layer (for example, a low sensitivity silver halide emulsion layer having substantially the same color sensitivity). layers, such as non-light-sensitive emulsion layers adjacent simultaneously to silver halide emulsion layers of different sensitivities with substantially the same color sensitivity).

The compound of the present invention is added to the highest sensitivity layer of a silver halide emulsion layer having a sensitivity of I4, which has substantially the same color sensitivity as that of a silver halide color photographic light-sensitive material. The amount is at most 1 mole per mole of silver halide, and if the amount added is greater than this, problems such as desensitization, softening, and deterioration of sharpness become noticeable. The amount added per mole of silver halide is preferably 0.0θ01 mole or C)O.
, t molar ratio, more preferably 0.001 molar ratio, O
, S molar ratio, more preferably 0.003 molar ratio, O
03 mol.

The color-sensitive silver halide emulsion layer to which the compound of the present invention is added requires at least two or more silver halide emulsion layers, but these may or may not be adjacent. . Further, these layers may be further divided into layers having different sensitivities. Further, a color-insensitive skin may be placed adjacent to these layers at the same time.

The multilayer color photographic material of the present invention usually has at least one each of a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer on a support. The order of these layers can be arbitrarily selected as required. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case.

In the same or other photographic emulsion layer or non-light-sensitive layer of the photographic light-sensitive material made using the present invention, in addition to the above-mentioned DIR coupler-emitting couplers, color couplers, i.e., aromatic primary amine developers in the color development process, are used. (For example, a compound capable of developing color by oxidative coupling with a phenylenediamine rust conductor, an aminophenol derivative, etc.) may be used.

The silver halide multilayer color photographic light-sensitive material C:L using the present invention usually uses yellow, magenta, 2, and cyan color-forming couplers, but the couplers of the present invention can be used for all three colors, and if necessary. Therefore, a part of the coupler of the present invention may be replaced with a conventionally known color coupler.

Useful color couplers are cyan, magenta and yellow colored couplers, examples of which include naphthol or phenolic compounds - pyrazolones or pyrazoloazoles and open chain or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers used in the present invention are provided in Research Disclosure.
sclosure) tybaJ (/9ri3/71)■
- and in the patents cited in 4/979/I).

The color coupler incorporated in the light-sensitive material preferably has a ballast group or is made into a polymer so that it has diffusion resistance. A two-hit color coupler substituted with a leaving group can reduce the amount of coated silver and provide higher sensitivity than a four-hit color coupler in which the coupling active position is a hydrogen atom. Couplers in which the color-forming dye has appropriate diffusivity, non-color-forming couplers, or DIR couplers that release a development inhibitor or couplers that release a development accelerator upon coupling reaction can also be used.

A representative example of the yellow coupler' that can be used in the present invention is the azila-heptamide coupler of OIL PROTIK) W. Specific examples include U.S. Patent Nos.
Aoy, alO issue, same number -, 17! , No. 037 and No. 3. It is written in Koroyo, Yo 04, etc. As a bivalent yellow coupler, U.S. Patent No. 3. Gor,i
Qa No. J, G&? , No. 92g, No. 3. q3
3. ! ; No. 01 and the oxygen atom separation type yellow couplers described in No. 01 and No. 620, etc., or Tokko Sho! ; g-10-39, U.S. Patent No. g, <t.

1, Ri No. 31, Su No. 3, Komei No. 3, RD/10
! 3 (/97 wa month), UK special plan 1st, it
, oco No. 0, West German application publication tube 2. Ko/? .

qt'r, same No. 2. Kobt, 3b/J4F, same No. ko.

3 pieces 9, 1g and 2nd. 33. A representative example of this is the yellow coupler described in No. g/co, etc., which has a t nitrogen atom separation disk. α-piparoylacetanilide couplers have excellent coloring dye stability, particularly optical stability, while α-benzoylacetanilide couplers provide high color density.

Magenta couplers that can be used in the present invention include oil-protected indacylon or cyanoacetyl couplers, preferably pyrazoloazole couplers such as yoichi pyrazolone and pyrazolotriazoles. ! The pyrazolone coupler is preferably a coupler in which the J-position is substituted with an arylamino group (4L) (is an acylamino group) from the viewpoint of the hue and color density of the coloring dye. , No. 17g-, No. 2
゜3g J, 7Q, No. 7, No. 6, 6θ0, 7gj,
Same number, 901, ! rri No. 3, same No. 3,062,6
! J No. 3. isco, Za No. 96 and No. J.

It is described in q3b, ois issue, etc. Two equivalents of 3-
As a leaving group for pyrazolone couplers, U.S. Pat.
Particularly preferred are the nitrogen atom leaving groups described in Jlo, No. 4/9, or the arylthio groups described in US Pat.

Further, the pyrazolone coupler having a pallast group described in European Patent No. 73,436 can provide a high color density.

As a pyrazoloazole coupler, US Patent 11t
3. JA9. Pyrazolobenzimidazoles as described in U.S. Patent No. 3. Pyrazolo [! , /-c] (/, ko, 9) Triryozole, Research Group Disclosure Corico 2Q (
19! pyrazolotetrazoles and Research Disclosure λ1I2so (i
Examples include birafuropizoles described in qtu, year A month). The imidazo C'e cob] pyrazoles described in European Patent Nos. 1/9 and 9141 are preferred from the viewpoint of low yellow sub-absorption of coloring dyes and light intensity, and European Patent Nos. 1/9 and 8: Pyrazolo C'5z-b described in No. 40:
l[:z, ko, hiro] triazoles are particularly preferred.

Cyan couplers that can be used in the present invention include oil-protected 7-tall and phenolic couplers, as described in US Patent No. J, tta.

293, preferably the naphthol couplers described in U.S. Pat. r2.21A, same No. DA.

lq&,, No. 194, q1.2, a, t,
Typical examples include the two-equivalent naphthol-based couplers for dissociation of silicic atoms described in Nos. 2 and 2, No. 9A, and No. -0a. Specific examples of maku phenolic cutlets are:
U.S. Patent No. 2,369,929, co, toi, t
ri No. 1, same No. 1. Kukuko, 16J, same tiga+tq
It is written in r*t coro issue etc. Cyan couplers that are sensitive to humidity and temperature are preferably used in the present invention, and are typically described in US patent m3. Kukuko, 0
A phenolic cyan coupler having an alkyl group greater than an ethyl group at the meta-position of the phenol nucleus described in No. 01, US patent! ! Ko, Kukuko, /I-2, same No. 3.7s
r, 5otr, same no.μ, lyu no.4,391゜, same no.μ, J3da, 0//, same jlr & I JJri.

No. 173, West German Patent Publication No. 3. JJ9,729 and Japanese Patent Application No. 5G-Ko 261, etc., and the 9-13-diacylamino substituted phenolic couplers and U.S. Patent No. 3. Sanko 6.6 Coco No. 6, No. 333,999,
Hiroshi Dodai! r/, No. 319 and Daihiro, Dako? ,
76? It has a phenylureido group at this position and is described in the issue! These include phenolic couplers having an acylamino group at the - position.

In order to correct unnecessary absorption in the short wavelength range of dyes generated from magenta and cyan couplers, it is preferable to use colored couplers in combination with color sensitive materials for photographing. U.S. Patent No. g,/A, 7. The yellow-colored magenta coupler M9 described in Ari No. 0 and Japanese Patent Publication No. 5 Ku1 No. 39≠13 is disclosed in U.S. Pat.
/3g, -St and British Patent No. 1. ItI4,34
Typical examples include the magenta-colored cyan coupler described in No. 1 and the like.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Such blur couplers are described in US Pat. No. 70 has a specific example of a magenta coupler.
European patent number again? A.

Specific examples of yellow, magenta or cyan couplers are described in No. 370 and DE 3,1 J da, 333.

Dye-forming couplers and special couplers listed above.

A dimer or higher polymer may also be formed. Typical examples of polymerized dye-forming couplers are described in U.S. Patent No. 3. Hiro s-
i, tko no. 0 and same Daihiro, ogo.

It is described in No. 411. Specific examples of polymerized magenta couplers are given in British Patent No. J, /117J, /
No. 73 and U.S. Special IFF Ghiro, No. 347.2g2.

These couplers may be either q-equivalent or 1-equivalent to silver ions. It may also be a colored coupler that has a color correction effect or a coupler that releases a development inhibitor during development (so-called DIR coupler).

In addition to DIR cutler, there is also colorless D, which has a colorless coupling reaction product and releases a development inhibitor.
IR coupling compounds may also be included. In addition to the DIR coupler, the light-sensitive material may contain a compound that releases a development inhibitor during development.

In order to satisfy the characteristics required for photosensitive materials, each of the above couplers can be used in combination in the same layer of the photographic layer, or in two or more different layers of the same compound. It can also be introduced.

The couplers of the present invention and couplers that can be used in combination can be introduced into the silver halide emulsion layer by known methods, for example, US Pat. The method described in this issue is used. For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. Ltd, acetyl citric acid) tributyl)% benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, diethyl azelate),
Trimesic acid esters (e.g. tributyl trimesate), etc., or boiling point of 30°C to /j-0'C
is dissolved in an organic solvent such as lower alkyl acetate such as ethyl acetate or butyl acetate, ethyl propionate, co-butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc., and then dispersed in a hydrophilic colloid. be done. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be used in combination.

Also, Tokko Akira/-39t! , No. 1, Tokukai Shoj-/-! 9
The polymer dispersion method described in No. 9e3 can also be used.

When the coupler has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use seratin, but other hydrophilic colloids can also be used alone or together with gelatin.

In the present invention, gelatin can be used even if it has been lime-treated.
It doesn't matter if it was processed using . For details on how to make gelatin, see Arthur Vuai x
The Macromolecule Chemistry of Gelatin
ar Chemistry of Ge1ati
n)% (Academic P
ress), published in 1996).

Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as silver halide in the photographic emulsion layer of the photographic light-sensitive material used in the present invention. Preferred silver halide is silver iodobromide containing 7.1 moles of silver iodide or less. Particularly preferred is silver iodobromide containing from 2 to 71 moles of silver iodide.

The average grain size of the silver halide grains in a photographic emulsion (grain diameter for spherical or near-spherical grains).

In the case of cubic particles, the wavelength is taken as the particle size and is expressed as an average based on the projected area. ) is not particularly limited, but is preferably 3μ or less.

The particle size may be narrow or wide.

Silver halide grains in photographic emulsions may have regular crystal bodies such as cubic or octahedral, or may have spherical,
It may have an irregular crystalline shape such as a plate shape, or it may have a composite shape of these crystalline shapes. It may also consist of a mixture of particles of various crystalline forms.

Further, an emulsion may be used in which ultratabular silver halide grains having a grain diameter of five times or more the grain thickness occupy 50% or more of the total projected area.

The silver halide grains may have different phases, such as a circular part and a surface layer. It may be a particle in which a solid latent image is mainly formed on the surface, or it may be a particle in which a latent image is mainly formed inside the particle.

The photographic emulsion used in the present invention is B. gracchide (P
, Glafkides), “Chimie etPhy Photographic”
Paul Montel
Publishing, 1944), V.L. Zerichman (
V.L.

Zelikman), Others, 6 Ma Young and Coating Photographic Emulsions (Ma
King and Coating Photogra
phicEmulsion” (The Focal Press, 1q.
It can be adjusted using the method described in 2010). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble norogen salt may be a one-sided mixing method, a simultaneous mixing method, a combination thereof, etc. Good too.

It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).

One type of simultaneous mixing method is a method in which the pAg in the liquid phase in which silver halide is produced is kept constant.

A so-called Chondrold double jet method may also be used.

According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

One or more silver halide emulsions formed separately may be used in combination.

In the process of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be allowed to coexist.

Silver halide emulsions are usually chemically sensitized.

For chemical sensitization, for example, Etch Free Easer (
H,, Fr1eser), 1 Die Grundrakender@Photographischen
lagender photography
Prozesse mit 5ilber Halog
eniden)” (Akademische Ver.
lagsgesellschaft), lq6g),
No. 67! The method described on pages 73g to 73g can be used.

That is, sulfur sensitization using sulfur-containing compounds that can react with active gelatin and silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines); reducing substances (e.g., stannous salts, amines, hydrazine fatty conductors, formamidine sulfinic acid, silane compounds); noble metal compounds (e.g., total complex salts, Pt,
A noble metal sensitization method using complex salts of metals in group I of the periodic table such as Ir and pct can be used alone or in combination.
can be done.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. That is, azoles such as penzothiazolicum salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles,
Mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially l-phenyl-!-mercaptotetrazole), etc.; mercaptopyrimidines; mercaptotriazines ; for example, thioketo compounds such as oxadorinthione; azaindenes, for example triazaindenes, tetraazaindenes (especially ←-hydroxy substituted ('I'l'
1) Tetraazaindenes), pentaazaindenes-1, T; Known as antifoggants or stabilizers such as henchiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. Many compounds can be added.

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material prepared using the present invention include coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and photographic property improvement (e.g.,
Various surfactants may be included for various purposes such as development acceleration, contrast enhancement, sensitization, etc.

The photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, the following:
It may also contain polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, quaternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like.

The photographic light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability. For example, alkyl acrylate, alkyl methacrylate, alkoxyalkyl acrylate, alkoxyalkyl methacrylate, glycidyl acrylate, glycidyl methacrylate, acrylamide, methacrylamide, vinyl ester (e.g. vinyl acetate), acrylonitrile, olefin, styrene, etc. alone or in combination, or these. and acrylic acid, methacrylic powder,
A polymer containing a combination of α,β-unsaturated dicarboxylic acid, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, sulfoalkyl acrylate, sulfoalkyl methacrylate, styrene sulfonic acid, etc. as a monomer component can be used.

The photographic emulsions used in the present invention may be spectrally sensitized with methine dyes and others. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, and holopolar cyanine colors2. Included are hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus,
Pyridine nucleus, etc.; Nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, i.e., indolenine nucleus, benzindolenine nucleus, indole nucleus, benz An oxazole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus, etc. are applicable. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes contain pyrazoline-! as a core having a ketomethylene structure. -on nucleus, thiohydantoin nucleus, kothioxazolidine---<t-dione nucleus, thiazolidine---1 μm dione nucleus,
3- to 6-membered heterocyclic nuclei such as rhodanine nuclei and thiobarbic acid nuclei can be applied.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may be included in the emulsion. for example,
Aminostyl compounds substituted with nitrogen-containing heterocyclic groups (e.g., US Pat.

No. 933.390, same J, la J! , No. 7), aromatic organic acid formaldehyde condensates (for example, those described in US Pat. No. 3.7ψ3., No. 10), cadmium salts, azaindene compounds, and the like.

The photographic material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer.

For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, geltaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (co, 3-dihydroxy dioxane, etc.), active vinyl compounds ('13#yo-1 triacryloyl-hexahydro-5-1 riazine, 11
3-vinylsulfonyl-cozorononol, etc.), active halogen compounds (Y, ψ-dichloro-6-hydroxy-B-), 9azinato), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), etc. Can be used alone or in combination.

In the photosensitive material produced using the present invention, when dyes, ultraviolet absorbers, etc. are contained in the hydrophilic colloid layer, they may be mordanted with a cationic polymer or the like.

The light-sensitive material produced using the present invention may contain a hydroquinone derivative, an amine phenol derivative, a gallic acid derivative, an ascorbic acid derivative, or the like as a color antifoggant.

The photosensitive material produced using the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, benzotriazole compounds substituted with aryl groups (e.g., those described in U.S. Pat.
No. 91, same J, J! benzophenone compounds (for example, those described in JP-A No. 6-7GA), cinnamate ester compounds (for example, those described in U.S. Pat. No. 3,7oz, Gos. No. 3), .7Qt, those described in No. 3 Rima), butadiene compounds (e.g.

or benzoxazole compounds (e.g., those described in U.S. Pat.
? ,100,4! ! ! (described in No. r) can be used. UV-absorbing couplers (e.g. α-
A naphthol-based cyan dye-forming coupler) or an ultraviolet-absorbing polymer may also be used. These ultraviolet absorbers may be mordanted in specific layers.

The photosensitive material produced using the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful.

In carrying out the present invention, the following known anti-fading agents may be used in combination, and the color image stabilizers used in the present invention may be used alone or in combination. Known antifading agents include hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenols, p-OΦdiphenol derivatives, and bisphenols.

Photographic processing of layers comprising photographic emulsions made using the present invention includes, for example, Research Disclosure (R+e
Any of the known methods and known treatment liquids as described in Search Disclosure)/7A, pages 2t-30 can be applied. Processing temperatures are typically from /g'C! The temperature is selected between σ0C, but the temperature may be lower than 1t0C or above 30°C.

Color developers generally consist of an alkaline aqueous solution containing a color developing agent. The color developing agent is a known primary aromatic amine developer, such as phenylenediamines (e.g.
Hiro-amino-N, N-diethylaniline, 3-methyl-
q-amino-N,N-diethylaniline% q-amino-
N-ethyl-N-β-hydroxyethylaniline, 3-
) f-u-7minor N-ethyl-N-β-hydroxyethylaniline, 3-methyl-q-amino-ethyl-N-β-methanesulfamide ethylaniline, d-amino-3-methyl-heethyl-N-β- methoxyethylaniline, etc.) can be used.

In addition, F.N. Mason (F, A.

Photographic Processing Chemistry (Photographic Processing Chemistry)
ssing Chemistry)” (Focal Φ
Published by Focal Press, 7966)
, 2nd page to 9th page, US Special Edition, iq, y,.

No. 13, same, Yoriko, No. 36 % JP-A-Shoμg-Aμ?
,? You may use those described in No.j.

Color developers may also contain pH buffering agents such as alkali metal sulfites, carbonates, borates, and phosphates, development inhibitors or antifoggants such as bromides, iodides, and organic antifoggants. can include. Also, if necessary, water softeners, preservatives such as hydroxylamine,
Organic solvents such as benzyl alcohol, diethylene glycol, polyethylene glycol, quaternary ammonium salts,
Development accelerators such as amines, 1 dye-forming power pullers, competitive couplers, sodium boron high tri) (7) fogging agents, auxiliary developers such as /-phenyl-J-pyrazolidone, tackifiers, polycarboxylic acids. It may also contain a chelating agent, an antioxidant, etc.

After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. As a bleach.

For example, iron (It), cobalt (■), chromium (VI)
, compounds of polyvalent metals such as copper (If), peracids, quinones, nitroso compounds, etc. are used.

For example, ferricyanide, dichromate, iron (III)
) or copal) (III), such as ethylenediaminetetraacetic acid, nitrilotriacetic acid,! .

Aminopolycarboxylic acids such as 3-diamino-coprobanoltetraacetic acid, citric acid, and tartaric acid.

Complex salts of organic acids such as malic acid; persulfates, permanganates, nitrosophenols, etc. can be used. Of these, potassium ferricyanide, sodium ferric ethylenediaminetetraacetate (n[), and ammonium ferric ethylenediaminetetraacetate (Iff) are particularly useful. Ethylenediaminetetraacetic acid iron(III) complex salts are useful in both stand-alone bleach solutions and -bath bleach-fix solutions.

As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used. The fixing solution may contain a water-soluble aluminum salt as a hardening agent.

Here, after the fixing step or bleach-fixing step, washing with water,
It is common practice to perform treatment steps such as stabilization, but it is also possible to perform only a water washing step or, conversely, to perform only a stabilization floating step without providing a substantial water washing step (Japanese Patent Application Laid-Open No. 37-1999)
It is also possible to use a simple processing method such as Trzas Publication).

The rinsing water used in the rinsing step can contain known additives, if necessary. For example, inorganic phosphoric acid, aminopolycarboxylic acid, organic acid.

Use chelating agents such as acid, bactericides and antifungal agents to prevent the growth of various bacteria and algae, hardening agents such as magnesium salts and aluminum salts, surfactants to prevent drying load and unevenness, etc. I can do it. Or L.E.
West (L, E.

West), 1Water Quality Criteria
)"7 Otographic Science and Eng 7 Rings (Photo, 8ci, and Eng,)
, Vol, De/I6A page 34444~
．． ? Compounds described in J-9(/fA&) etc. can also be used.

tx, the washing process may be carried out using cypress of more than one tank if necessary, and the washing water may be saved by carrying out multi-stage countercurrent washing (for example, - to 9 stages).

As the stabilizing solution used in the stabilization step, a processing solution that stabilizes the dye image is used. for example.

A solution having a buffering capacity of pH 7 to O, a solution containing an aldehyde (for example, formalin), etc. can be used. A fluorescent brightener, a chelating agent, a bactericide, a fungicide, a hardening agent, a surfactant, and the like can be used in the stabilizing liquid as necessary.

In addition, the stabilization process may be carried out using cypress of more than one tank if necessary, and multi-stage countercurrent stabilization (for example, - to 9 stages) can save the stabilizing liquid and further omit the water washing process. You can also do that.

(Examples) The present invention will be described in detail below using Examples, but the present invention is not limited to these Examples.

Example: A multilayer color photosensitive material consisting of each layer having the composition shown below on a transparent triacetylcellulose film support (
10/) was created.

1st layer; antihalation layer black colloidal silver Q・-Φ・・o, lz f/m2 ultraviolet absorber U-i・・o, oza 17m2 same
Gelatin layer first layer containing U-2---θ, / J 77m''; intermediate layer Co,!-Jt, Zinter-0,1g?/m2 Decylhydroquinone coupler C-/-...= 3rd layer of gelatin layer containing 0.//f/ln"; 1st red-sensitive emulsion layer as@as/, cof/m" Sensitizing dye I...1.daX per mole of silver / 0 = the same mole ■... o for 1 mole of silver, @xtθ-4 mole the same ■---... j, A x / 0-4 mole for 1 mole of silver ■... θX / 0-' mole coupler C-2...1 mole silver (=06051 mole coupler C-,?e o, oouo mole coupler C-a...silver for 1 mole silver) Gelatin layer qth layer containing o, oouo moles per mole; red-sensitive emulsion layer--, --/, O97m'' Sensitizing dye I...z,,5xio for 7 moles of silver Same mole 1 @ * a a For 1 mole of silver /, j;
/Q mole same l...for 1 mole of silver, / 0, θo6t molar coupler C-s...O, ooqs molar coupler C-,7...Jth layer of gelatin layer containing θ,00 dat mole relative to 7 moles of silver; Intermediate layer Yu! -G-t-Penta...θ, Otf/m" Gelatin layer containing decylhydroquinone No. 6; 1st green-sensitive emulsion layer #,,, *00 gof/m" Sensitizing dye V...... 1 mole of silver For 3, jfXlo mole is the same ■...0 for 1 mole of silver 3, QXlo mole is the same ■... @ for 1 mole /, O x 10 mole coupler C-A... for 1 mole of silver 7th layer of gelatin layer containing 0.0 acumol coupler C-ri... 0.0 cocomol Kab 5-c-g... 0.003 g mol per 7 moles of silver; 1st green Sensitizing emulsion layer,,, -o, trr9-/m2 Sensitizing dye V... 1 mole of silver per 1 mole of silver, 10 moles of silver ■..., 1 mole of /, fXlo
Same mole ■... 7 for silver l mole 2, j
Molkab 5-c-7... 0.00-0 mol per 1 mol C of silver Compound (2) of the present invention o, oos per 1 mol C of silver
G layer of gelatin layer containing mole; yellow filter layer yellow colloidal silver...o, o g t/m2
s, z-di-t-penta...0,0? O7% /
Gelatin Jl containing tn2 decylhydroquinone 9th layer; gg/blue-sensitive emulsion layer...-0,37y/rn" Sensitizing dye......Size per mole of silver, μ x 70 mol Coupler C-9 ...0.26 mol coupler C-q per 1 mol of silver 00075 mol per 1 mol silver 1st theta layer; first blue-sensitive emulsion layer Io, ss f/m2 Sensitizing dye ■...・Gelatin layer containing J, θX/θ molar coupler C-9 for 1 mol of silver...0.0!r7 mol for 7 mol of silver C2 1st/layer: 1st protective layer UV absorber U-1 ... o, i hirof / m” same
Gelatin layer 1st J layer containing U-Co-Ilo, xsy-7m2; Protective layer aO, 2! ;f/? F! In addition to the above composition, a gelatin hardening agent H-7 and a surfactant were applied to each layer of the gelatin layer containing polymethacrylate particles--o, 1 of p/m2 (diameter/, jμ).

(Samples 10 to 1i3) The compound of the present invention added to the layer of sample /Q/ (
Samples 10 to // and 7 were prepared in the same manner as sample /θ/ except that the amount added and the species of 2) were changed as shown in Table 1.

These samples were adjusted to 4A t 00'K using a light source with a single color temperature conversion filter, exposed to 0CMS, and subjected to the following color development at 0C.

Color development 3 minutes 75 seconds Bleach White 6 minutes 30 seconds Water Wash - Minutes θ seconds Fixed Arrival: Kobunko O seconds Water Wash J minutes 13 seconds Safe, stable, 1 minute 03 seconds The composition of the treatment liquid used in each factory was as follows.

Color developer diethylenetriaminepentaacetic acid /, 0? /-Hydroxyethylidene-co, Ot i, i-diphosphonic acid sodium sulfite Hiroshi, ol potassium carbonate Jo, Of potassium bromide
1. potassium iodide
1.3 ■ Hydroxylamine sulfate, l
0g fμ-(N-ethyl-N-β-Hiroshi, 3?Hydroxyethylamino) Add coco methylaniline sulfuric acid water /, 0J3p
H10, θ Bleach Liquid ethylenediaminetetraacetic acid 2nd 100. Of/iron ammonium salt ethylene diamine tetra vinegar vanina io, oy thorium term beautification ammonium /! ;0. OLt Ammonicum no θ, θ? add water
/, θJpHA, O Fixer ethylenediaminetetraacetic acid 1. Oy-trilum salt sodium sulfite Hiroshi, oy ammonium thiosulfate aqueous solution /1! , θ Go (Ri 0 Chi) Sodium Bisulfite G, 6y-Add water / , OJ3pH
6,6 Stabilizing liquid formalin (qO staff) Ko, o1! tl polyoxyethylene-p-mo 0. , If tunonylphenyl ether (in average degree of polymerization / θ), water was added / , exposed through a pattern for O40 1 MTF' measurement, and the above color development process was carried out to obtain a The MTF value was measured.

The results obtained are summarized in Table 7.

Table 1 shows that when the compound of the present invention is added in a certain amount or more, the effect of inhibiting development is too large, resulting in a significant decrease in sensitivity. In addition, compared to samples that had almost the same sensitivity by adding conventional DIB couplers or couplers with quinone scavenging ability, samples to which the amount of addition of the present invention was applied had a large MTF value and excellent sharpness. I understand.

Example 2 (Sample-oi) The DIR coupler added to the 6th layer of Sample 10/ was removed, and the following intermediate layer was installed between the 6th layer and the 7th layer,
Further, the fourth layer of silver iodide emulsion was made with 9 mol of silver iodide and the average grain size was (II), Aμ.
Sample 0/ was prepared in the same manner as i.

Intermediate layer coupler C-b---・o, osf/? F! 2 pieces, S-
G-t-octyl nomidoid・0.0/1%/ff1
20 Quinone Gelatin #ll11#-θ, t? /rn2 (Sample Co0 - Co10) Sample CoQ except that the comparative compound and the compound of the present invention were added to the seventh layer of Sample 20/ in the amounts shown in Table 2.
/ Samples-〇〇-〇〇〇 were prepared in the same manner.

These samples were tested for sensitivity and MTF in the same manner as in Example 1.
The values were determined and summarized in Table 2.

From the gJ table, the embodiment of the present invention also has high sensitivity.

It is also clear that the sharpness is excellent.

Structure of the compound used in Example 1 and Co. U-t U-co-j C-a (U.S. Pat. ! ? Compound 4c9) Ni3 C-7- α -t C-deCHrCH-802CH, -CON[CH,), NHC described in lsJ issue
O-CH-early MH2C-/θ (U.S. patent
Compound (7)) C-ti (US Patent J, J
Compounds included in Koku, Yo No. 3Q, etc.) C-tJ (Compound (12) of U.S. Patent No. 360) μ
'yt, rt, o (U.S. patent u, ett, sho)
No. Compound (7)) Sensitizing dye■ (CH2)4503Na (CH2)3SO3Na (CH2)2SO3■ Patent applicant Fuji Photo Film Co., Ltd. Procedural amendment 1985 month/l? Day

Claims (1)

[Claims] In a silver halide color photographic light-sensitive material having a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer on a support, at least one light-sensitive layer has two different sensitivities. A development inhibitor or its precursor is added to the highest sensitivity layer through a reaction in which a compound cleaved by a coupling reaction with an oxidized developing agent couples with another oxidized developing agent. 1. A silver halide color photographic light-sensitive material, characterized in that it contains a cleavable compound in an amount of at most 1 mol % based on the silver halide in the light-sensitive layer.