JPS6275528A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enable reduction in the thickness of layers and to increase the sharpness of an image by combinedly incorporating one kind of specified coupler and one kind of specified compound and by forming a silver halide emulsion layer contg. core/shell type silver halide particles and/or flat silver halide particles. CONSTITUTION:This silver halide color photographic sensitive material contains combinedly at least one kind of coupler represented by formula I and at least one kind of compound represented by formula II and has a silver halide emulsion layer contg. core/shell type silver halide particles and/or flat silver halide particles. The coupler is an acrylacetamide type coupler having an aryloxy group as an eliminable group and is obtd. by halogenating the coupling position of a four-equiv. coupler and reacting the coupler with a phenolic compound in the presence of a base. Each of the core/shell type silver halide particles is composed of two or more layers having different silver iodide contents. Each of the flat silver halide particles has >=3, preferably 8-20 aspect ratio (ratio of diameter/thickness). The excessive development accelerating action of a released fogging agent is controlled by the moderate development retarding action of silver iodide.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide color photographic light-sensitive material that has high image sharpness and excellent color development.

[Prior art]

It is well known that after three exposures are given to a silver halide photographic light-sensitive material, an oxidized aromatic primary amine developer and a dye-forming coupler react to form a color image. In this method, a subtractive color reproduction method is usually applied, and red,
Cyan, magenta, and yellow color images, which are complementary colors to green and blue, are formed. The reaction between the coupler and the oxidation product of the color developing agent takes place at the active site of the coupler, and couplers with hydrogen atoms at this active site have 4
Equivalent couplers, ie, theoretically require stoichiometrically 4 moles of silver halide with development nuclei as oxidizing agent to form 1 mole of dye. On the other hand, those with anionically leaving (capable of) groups at the active sites are 2-equivalent couplers, i.e. couplers that require only 32 moles of silver halide with development nuclei to form 1 mole of dye; Compared to equivalent couplers, the amount of silver halide in the photosensitive layer can generally be reduced and the film thickness can be made three times thinner, making it possible to shorten the processing time of the photosensitive material and further improving the sharpness of the color image formed. do. Furthermore, the coupling activity of two-equivalent couplers with color developing agents can be varied widely depending on the nature of the leaving group.

Although the known two-equivalent couplers have a certain degree of performance, it has been desired to further improve the performance. In particular, it is unsatisfactory in terms of color development (reactivity), which poses a serious problem in high-temperature rapid processing, which has recently become obsolete. In order to compensate for this insufficient color development, in some cases, an organic solvent such as benzyl alcohol is added to the developer as a color development accelerator. However, when these organic solvents for promoting color development are added, problems arise such as adverse effects due to changes in concentration during development processing, deterioration of image storage stability due to remaining after processing, and pollution of waste liquid.

On the other hand, two Togawa couplers with increased reactivity of 3 have been proposed in the past, such as British Patent No. 1.077,874, U.S. Patent No. 3.419.391, U.S. Patent No. 3.476, 563.
Although aryloxy leaving type 2-equivalent couplers are disclosed in JP-A-50-87650, etc., these are still insufficient in terms of color-forming properties.
A coupler containing a diffusion-resistant group terminated with a p-hydroxyphenylsulfonyl group or a β-hydroxyphenylsulfinyl group, as described in No. 42045, is disclosed. Although this coupler was improved in terms of color development over conventional couplers due to the effect of the diffusion-resistant group, it was still not sufficient and also had the disadvantage of low solubility in organic solvents for coupler dispersion.

Also, JP-A No. 58-95346, No. 59-214854
Although the two-equivalent couplers disclosed in Japanese Patent No. 59-231538 and Japanese Patent No. 59-228649 are improved in terms of color development over conventional couplers, they are still not sufficient. On the other hand, in order to promote development and improve color development,
The use of development accelerators is also being considered, and in order to accelerate development, the addition of various development accelerators such as hydrazine compounds to the emulsion layer or developer has been considered, mainly for black-and-white sensitive materials, but none of them This is often accompanied by increased fog and worsened graininess3, making it impractical.

In contrast, JP-A-57-150845 and JP-A-59-5
No. 0439, No. 59-172640, etc. disclose that a fogging agent is released in an imagewise manner to accelerate development, enhance color development, and improve graininess. [Problems to be Solved by the Invention] Therefore, the first object of the present invention is to reduce the thickness of the layer and improve the sharpness of the image. The second objective is to provide a silver halide color photographic material with excellent color development, and the third objective is to provide a silver halide color photographic material with excellent color development. The object of the present invention is to provide a silver halide color photographic light-sensitive material which is improved in sensitivity and image graininess.

[Means for solving problems]

The present inventors have repeatedly studied the above-mentioned problems and found that in a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, a coupler represented by the following general formula [I] and at least one compound represented by the following general formula [II] in combination, and the silver halide emulsion layer contains a core/
It has been found that the above object can be achieved by a silver halide color photographic light-sensitive material characterized by containing shell-type silver halide grains and/or tabular silver halide grains.

General formula [I″l C0IJP 〇General formula CIOA-B [In the formula, C0UP represents a yellow dye-forming coupler (hereinafter simply referred to as Y coupler) residue from which one hydrogen atom at the coupling position has been removed, and X is Phenyl nucleus or naphthyl nucleus? Represents a nonmetallic atom group necessary for completion, R is a hydrogen atom, a halogen atom, (e.g. a chlorine atom, a fluorine atom)
Nitro group, cyano group, carboxy group, 7-alkyl group even if it has a substituent (for example, methyl group, ethyl group, propyl group, 15o-propyl group, butyl group, 5ec-butyl group, tert-butyl group) , pentyl group, octyl group, dodecyl group, octadecyl group), cycloalkyl group,
UJ (for example, cyclopentyl group, cyclohexyl group, norbornyl group), alkenyl group, (e.g. allyl group) aralkyl group, (e.g. benzyl group, β-phenylethyl group)
Aryl group, (e.g. evaphenyl group, naphthyl group) alkoxy group, (e.g. methoxy group, ethoxy group, propoxy group, 1so-propoxy group, butoxy group, tert-butoxy group, hexyloxy group, octyloxy group, dodecyl group) oxy group, hexadecyloxy group) aryloxy group (e.g. phenoxy group, tolyloxy group), argylcarbonyl group (e.g. aceto group, ethylcarbonyl group, t-butyΦcarbonyl group, dodecylcarbonyl group)
Arylcarbonyl group, (e.g. benzoyl group, tolyl group, naphthylcarbonyl group) alkoxycarbonyl group (
For example, methoxycarbonyl group, ethoxycarbonyl group% tert-butoxycarbonyl group, dodecyloxycarbonyl group, 2-ethoxyethyloxycarbonyl group, ■-dodecyloxycarbonyl ethoxycarbonyl group, 1-(2,4-di-tcrt-amylphenoxy carbonyl) ethoxycarbonyl group) aryloxycarbonyl group, (e.g. phenoxycarbonyl group, m-dodecyloxyphe/oxycarbonyl group, p-dodecyloxyphenoxycarbonyl group, p-tert-octylphenoxycarbonyl group, 2,4-tert -amylphenoxycarbonyl group, m-lauroylamidophenoxycarbonyl group) alkylsulfonyl group, methylsulfonyl group, ethylsulfonyl group, t-butylsulfonyl group, dodecylsulfonyl group) arylsulfonyl group, (e.g. phenylsulfonyl group, p -benzyloxyphenylsulfonyl group) carbamoyl group, (PJ
For example, ethylcarbamoyl group, dimethylcarbamoyl group,
N-methyl-phenylcarbamoyl group, N-phenylcarbamoyl group) alkylcarbamoyl group, arylcarbamoyl group, alkylcarbonamide group (e.g. acetamide group, pivaloylamide group, lauroylamide group, α-(2,4-di-tert-amyl group) phenoxy)butanamide group, γ-(2,4-di-tert-amylphenoxy)butanamide group, α-(m-dodecyloxyphenoxy)butanamide group, α-(m-butanesulfonamidophenoxy)tetradecanamide group, α-( p
-dimethylaminosulfonamidebuenoxy)tetradecanamide group)arylcarbonamide group (e.g. benzamide group, m-dodecyloxybenzamide group, m-
dodecylbenzenesulfonamide benzamide group, 3-
Chloro-4-dodecyloxybenzamide group, m-(2
, 4-di-tert-7-milphenoxy) carbonylbenzamide group, p-hexadecyloxycarbonylbenzamide group) sulfonamide group, alkylsulfonamide group (e.g. methanesulfonamide group, ethanesulfonamide group, butanesulfonamide group, octane Sulfonamide group, dodecanesulfonamide group, hexadecanesulfonamide group, ethoxyethanesulfonamide group, γ
-(2,4-di-ter,t-amylphenoxy)propanesulfonamide group)arylsulfonamide group, (
'[M Examples include benzenesulfonamide group, m-chlorobenzenesulfonamide group, p-butoxybenzenesulfonamide group, rn-lauroylamide benzenesulfonamide group, p-dodecylbenzenesulfonamide group, p-
dodecyloxybenzenesulfonamide group), alkyl sulf, moyl group ('9'lJ, t Cf N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group), arylsulfamoyl group (e.g. H'N-
7-arylsulfamoyl group, N-furkyl-N-arylsulfamoyl group, N,N-diarylsulfamoyl group), alkylsulfinyl M, (e.g., methylsulfinyl group, ethylsulfinyl group, t-butyl Sulfinyl group, dodecylsulfinyl group) Arylsulfinyl group (sidelight LJ phenylsulfinyl group, p-benzyloxyphenylsulfinyl group, p-tolylsulfinyl group) Represents a lyloxy group. ) N-acylcarboimidoyl group (e.g. N-acetocarboimidoyl group, N-pivaloylcarboimidoyl group,
N-benzoylcarboimidoyl group) N-alkyl or N-arylcarboimidoyl group (f!
methylcarboimidoyl group, N-ethylcarboimidoyl group, N-phenylcarboimidoyl group) Heterocyclic group (for example, a 5- or 6-membered heterocyclic ring containing a nitrogen atom, oxygen atom, or sulfur atom as a heteroatom, a fused A heterocyclic group, such as a pyridyl group, a quinolyl group, a furyl group, a benzothiazolyl group, an oxasilyl group, an imidazolyl group, a naphthoxacylyl group) (e.g. an alkylamino group (for example, an n-butylamino group, a methylamino group, a cyclo) xylamino group (7 groups, etc.), cycloamino group (e.g. evaphenylamino group, N-methylanilino group, diphenylami7 group, N-acetylanilino group, 2-chloro-5-tetradecanamide anilino group, etc.), cycloamino group ( (e.g., piperidi7 group, pyrrolidino group, etc.), heterocyclic amino groups (e.g., α-pyridylamino group, 2-benzoxasilylamino group), l/ide groups (e.g., methylureido group,
phenylureido group, tolylureido group), alkylcarbonyloxy group (e.g. acetoxy group, ethylcarbonyloxy group, t-butylcarbonyloxy group, dodecylcarbonyloxy group), arylcarbonyloxy group (e.g. benzoyloxy group, tolyloxy group) , naphthylcarbonyloxy group) the above Ri;! [It may have a substituent, and examples of the substituent in this case include an alkyl group, an alkenyl group, a cyclic alkyl group, an aralkyl group, a cyclic alkenyl group, a halogen atom, a nitro group, a cyano group,
Aryl group, alkoxy group, aryloxy group, carboxy group, alkoxycarbonyl group, aryloxycarbonyl group, sulfo group, sulfamoyl group, carbamoyl group, acylamino group, diacylamino group, ureido group,
Urethane group, sulfonamide group, heterocyclic group, arylsulfonyl group, alkylsulfonyl group, arylthio group,
Alkylthio grave, 7 alkylamides, 7 dialkylamides
group, anilino group, N-alkylanilino group, N-arylanilin7 group, N-acylanilino group, hydroxy group,
Examples include mercapto bases.

Next, R1 is a halogen atom (e.g., chlorine atom, heptadium atom), a cya group, a nitro group, a hydroxy group, a carboxy group, an alkyl group which may have a substituent (e.g., a methyl group, an ethyl group, a propyl group) , 1so-propyl group, butyl group, 5ee-butyl group, tert-butyl group, pentyl group, octyl group, dodecyl group, octadecyl group), cycloalkyl group (e.g. cyclopentyl group, cyclohexyl group, norbornyl group), aryl group (e.g. phenyl group, naphthyl group), aralkyl group (e.g. benzyl group, β-phenylethyl group), alkoxy group (e.g. hamethoxy group, ethoxy group, propoxy group, 1so-propoxy group, butoxy group, tcrt-butoxy group, hexyloxy group, octyloxy group, dodecyloxy group, hexadecyloxy group) aryloxy group (e.g. phenoxy group, tolyloxy group), alkoxycarbonyl group (e.g. methoxycarbonyl group, ethoxycarbonyl group, tcr
t-butoxycarbonyl group, dodecyloxycarbonyl group, 2-ethoxyethyloxycarbonyl group, ■-dodecyloxycarbonyl ethoxycarbonyl group, 1-(2
, 4-di-tert-amylphenoxycarbonyl)ethoxycarbonyl group), aryloxycarbonyl group (
For example, phenoxycarbonyl group, m-dodecyloxyphenoxycarbonyl group, p-dodecyloxyphenoxycarbonyl group, p-tert-octylphenoxycarbonyl group, 2I4-di-tert-amylphenoxycarbonyl group, m-lauroylamidophenoxycarbonyl group), alkyl Sulfonamide groups (e.g. methanesulfonamide group, ethanesulfonamide group, butanesulfonylamide group, octanesulfonamide group, dodecanesulfonamide group, hexadecanesulfonamide group, ethoxyethanesulfonamide group, te
rt-amylphenoxy)propanesulfonamide group)
, arylsulfonamide group (e.g. benzenesulfonamide group, m-chlorobenzenesulfonamide group, p-
butoxybenzenesulfonamide group, m-lauroylamide benzenesulfonamide group, p-dodecylbenzenesulfonamide group, p-dodecyloxybenzenesulfonamide group), alkylsulfamoyl group (e.g. N-
alkylsulfamoyl group, N-N'-dialkylsulfamoyl group), aryls/l/7amo, i# group (e.g. N-arylsulfamoyl group, N-alkyl-N
-arylsulfamoyl, M, N-IV-diarylsulfamoyl group), alkylcarboxamide groups (e.g. acetamido group, pivaloylamide group, lauroylamide group, α-(2,4-di-tert-amylphe/xy)butanamide group) group, γ-(214-di-tert-amylphenoxy)butanamide group, α-(m-dodecyloxyphenoxy)butanamide group, α-(m-butanesulfonamidophenoxy)tetradecanamide group, α-
(p-dimethylaminosulfonamidophenoxy)tetrazodamide group), arylcarboxamide group (e.g. benzamide group, m-dodecyloxybenzamide group,
m-dodecylbenzenesulfonamidobenzamide group,
3-chloro-4-dodecyloxybenzamide group, m-
(2,4-di-tert-amylpheoxy) carbonylbenzamide group, p-hexadecyloxycarbonylbenzamide group), amine group (e.g. alkylami 7 group (e.g. n-butyl amine 7 group, methylamino group, cyclohexyl amide group), 7 groups, etc.), 7 arylamino groups (e.g., phenylamino, N-methylanilino group, 7 diphenylamine groups, N-acetylanilino group, 7 groups of 2-chloro-5-tetradecanamide anilino groups, etc.), 7 cycloamide groups (e.g., piperidianilino group, 7 groups, etc.). 7 groups, pyrrolisif groups, etc.), heterocyclic amino groups (e.g. 4-pyridylamide 7 groups, 2-benzogisazolyl 7 groups), arylcarbamoyl groups (e.g. ethylcarbamoyl group, dimethylcarbamoyl group),
alkylsulfonyl group (e.g. methylsulfonyl group, ethylsulfonyl group, t-butylsulfonyl group, dodecylsulfonyl group), Arylsulfonyl groups (e.g. phenylsulfonyl group, p-benzyloxyphenylsulfonyl group), alkylcarbonyl groups (e.g. aceto group, ethylcarbonyl group, t-butylcarbonyl group, dodecylcarbonyl group), arylcarbonyl groups (e.g. benzoyl group, toluyl group) R1 may have a substituent B, and examples of the substituent in this case include an alkyl group, an alkenyl group, a cyclic alkyl group, an aralkyl group, a cyclic alkenyl group, a halogen atom, and a nitro group. , sia/group, aryl group, alkoxy group, aryloxy group, carboxy group, alfkidicarbonyl group, 7lyloxycarbonyl group, sulfo group, sulfamoyl group, carbamoyl group, acylamino group, diacylamino group, ureido- group, urethane group, sulfonamide group, min group, arylsulfonyl group, furkylsulfonyl group, arylthio group, alkylthio group, alkylami 7 group, dialkylami 7 group, anilino group, N-alkylanilino group, N-arylani group Examples include a lino group, an N-alkenyl group, a hydroxy group, and a mercapto group.

Further, as the divalent linking group represented by Xl, for example, an alkylene group, II II 11Oo
O or -C- group? can be mentioned.

Next, in the general formula [[], the substituent represented by R is more preferably a cyano group, a nitro group, a carboxy group, a halogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylcarbonyl group. Amide group, arylcarbonamide group, alkylsulfonamide group, arylsulfonamide group,
Examples include an alkylcarbonyl group, an arylcarbotyl group, an alkylcarbamoyl group, an arylcarbamoyl group, an alkylsulfamoyl group, an arylsulfamoyl group, an alkylsulfonyl group, and a ryylsulfonyl group.

In general formula [I], examples of the Y-coupler residue represented by C0UP include pivaloylacetanilide type,
Benzoylaceto 7 dilide type, malon diester type, malondiamide type, dibenzoylmethane type, benzothiazolyl ester 7mide type, malon ester monoamide type, pendithiazolylacetate type, benzoxacylylacetamide type, benzoxacylyl Coupler residues of the acetate type, benzimidazolylacetamide type or benzimidazolylacetate type, US Pat. No. 3.841
Coupler residues derived from heterocycle-substituted acetamides or heterocycle-substituted acetates included in US Pat. No. 3.770.446, British Patent No. 1.459
, No. 171, West German Patent (OLS) 2.503.0
Coupler residues derived from acylacetamides described in No. 99, Japanese Publication No. 5O-1139V38 or Research Disclosure No. 15737, or heterozygous coupler residues described in U.S. Pat. No. 4.046.574. Can be mentioned.

Furthermore, in the present invention, Y- represented by C0UP above
The coupler is represented by the following general formula [Seki, [v]]
Preferably it is a coupler residue.

General formula (IV) OO II II R2-C-CI(-C-NH-R3 ■ General formula [:V]OO II11 R4-NH-C-CH-C-NH-R3 ■ In the above formula, the coupling position The more derived free bond represents the attachment position of the coupling-off group.

In the above formula, if R2, Rs and R4 contain a diffusion-resistant group, it is selected such that the total number of carbon atoms is from 8 to 32, preferably from 10 to n; otherwise, the total number of carbon atoms is is preferably 15 or less.

R2, R3 and R4 will be explained below.

In the formula, R2 represents an aliphatic group, an aromatic group, an alkoxy group, or a heterocyclic group, and R3 and M each represent an aromatic group or a heterocyclic group.

In the formula, the aliphatic group represented by R2 preferably has 1 carbon number.
-22, and may be substituted or unsubstituted, linear or cyclic. Preferred substituents for the alkyl group include an alkoxy group, an aryloxy group, an acyl group, a halogen atom, and the like, which may themselves have further substituents. Specific examples of aliphatic groups useful as R2 are: isopropyl,
Isobutyl group, tert-butyl group, isoamyl group, t
ert-amyl group, 1,1-dimethylbutyl group, if-
Dimethylhexyl group, 1.1-diethylhexyl group, dodecyl group, hexadecyl group, octadecyl group, cyclohexyl group, 2-methoxyisopropyl group, 2-phenoxyisopropyl group, 2- p -terL-butylphenoxyisopropyl group, α-amino /isopropyl group, α
-(diethylamino)isopropyl group, α-(succinimido)isopropyl group, α-(phthalimido)isopropyl group, α-(benzenesulfonamido)isopropyl group, and the like.

When R2, R3 or R4 is an aromatic group (particularly a phenyl group), the aromatic group may be substituted. Aromatic groups such as phenyl groups include alkyl groups having carbon v132 or less, alkenyl groups, alkoxy groups, alkoxycarbonyl groups, alkoxycarbonylamino groups, aliphatic amide groups,
It may be substituted with an alkylsulfamoyl group, an alkylsulfonamide group, an alkylureido group, an alkyl-substituted succinimide group, etc. In this case, the alkyl group may have an aromatic group such as phenylene interposed in its chain. phenyl group or aryloxy group, aryloxycarbonyl group,
It may be substituted with an arylcarbamoyl group, an arylamide group, an arylsulfamoyl group, an arylsulfonamide group, an arylureido group, etc., and the aryl group portion of these substituents further has a total number of carbon atoms of 1 to 22. may be substituted with one or more alkyl groups.

The phenyl group represented by R2, R3 or R4 further includes an amide group, including one substituted with a lower alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group, a sulfo group, a nitro group, a sia/group, May be substituted with thiocya/groups or halogen atoms.

R2, R8 or R4 may also 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 chromanyl group, a tetrahydronaphthyl group, etc.

These substituents may themselves have further substituents.

When R2 represents an alkoxy group, the alkyl moiety represents a linear or branched alkyl group, alkenyl group, cyclic alkyl group, or cyclic alkenyl group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms. It may be substituted with a halogen atom, an aryl group, an alkoxy group, etc.

When R2, R8 or R4 is a heterocyclic group, the heterocyclic group is a carbon atom of the carbonyl group of the acyl group or the amide group in alpha-azila-heptamide, respectively. Combines with nitrogen atoms.

Examples of such heterocycles include thiophene, furan, pyran, virole, pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, indolizine, imidazole, thiazole, oxazole, triazine, thiadiazine, and oxazine. These may further have substituents at the top.

Representative forces, blurs, that can be used in the present invention are described below: R”・ 1 II IINHCG
(s C0CH, sO 2II II -NCCF, -COCH.

CH8 3II -H -CNT-72 Power, Blur J Hill B J%
I I-N)TCCH3 10-8O2CH, -H 〇-CI(2NI(CCI(.

Coupler ii B
Tl"-CNT-TNT-■CNH2 R" 18 II
II-NHCCH3C00(3 19II-I-I
-CN) T2 force, puller rot B R1
I coupler tiger B RI I
R12 yam 29 CIJ-5
NHCH2CH20H power, Blur 46 1'l
+ a T'L +.

3:3-CI I
I-CI-I=N-CCH.

34-OCH, CH, O pull, 11 COH 35-Not II -CNT(2 37Cl5O2NT-TC2H5 CT(3 38-C-CT (3-Dou ICC3F.

+ ll CH30 ■ -αI=N-CCT-I3 -3o2NI(C2N
.

R26 -CNHNHCNH2 O2 H H Pull O2 H H O2 Te H H O2 ○H C=0 H C=0 H Cabinet-■ C20 H NI( i -C C) T-C, □H25 " O2 H3 CO□Chochu.

C)L NHCC, F.

c, Ho(t) CO,TT The coupler of the present invention can be synthesized by combining known methods. Synthesis of an acylacetamide type coupler having an aryloxy group as a leaving group is carried out by converting the coupling position of the nominal coupler to 10-gen and reacting it with a phenol compound in the presence of a base. Synthesis methods for these two-equivalent couplers are described in the following known documents. U.S. Patent Nos. 3.894.875 and 3.933.
No. 501, No. 4.296, No. 199, No. 3.227.5
No. 54, No. 3.476, No. 563, No. 4.296°20
No. 0, No. 4.234.678, No. 4.228.233
No. 4゜351, 897, No. 4.264.723, No. 4.366, 237, No. 3.408.194,
Japanese Patent Publication No. 57-70871, No. 57-9634
No. 3, No. 53-52423, etc.

Generally speaking, it is advantageous to synthesize a coupler mother nucleus and then introduce a leaving group. It is also possible to use a method in which a diffusion-resistant group is introduced after the formation of a diffusion-resistant group.

Next, a typical synthesis example of the coupler of the present invention will be specifically shown.

Synthesis Example (1) Synthesis of Illustrative Coupler α-Chloro-α-pivaloyl-2-chloro-5=(n-
Hexadecane sulfonamide) acetanilide 41.4
g, 4-acetylamino-2-cyanophenol 12
．． 9 g, E dimethylacetamide 150 ml and acetonitrile 100 m/! was dissolved under reflux.

11.7 ml of triethylamine was added dropwise over 30 minutes.
Afterwards, the mixture was reacted under reflux for 1 hour.

After cooling, the reaction mixture was poured into ice water (containing 1Qm/! of concentrated hydrochloric acid). Dissolve the oil in 200 m of ethyl acetate.
After washing with water twice, it was dried over magnesium sulfur and concentrated under reduced pressure to obtain a residue of 509. This residue was subjected to silica gel chromatography, the product-containing portion was concentrated under reduced pressure, and the residue was crystallized from n-hexane/isopropanol to obtain the exemplary coupler 27min 28I.

(Melting point 85-93°C) Synthesis Example (2) Synthesis of Exemplary Coupler 37 α-Chloro-α-pivaloyl-2-10 rho-5-(n-dodecyloxycarbonyl)acetani IJ
l”35,9, 2-chloro-4-ethylsulfamoylphenol 17.3gf dimethylacetamide 2
00ml and acetonitrile room/! was dissolved under reflux.

10.7++t/! of triethylamine to this mixture! was added dropwise, and the mixture was then reacted under reflux for 2 hours.

After cooling, the reaction mixture was poured into ice water (containing about 10 ml of hydrochloric acid) and 200 ml of ethyl acetate/oil was added.
! Extracted with.

Vinegar ethyl layer? After washing twice with water and drying over magnesium sulfate, the residue was concentrated under reduced pressure to obtain 46 g of residue.

This residue was subjected to silica gel chromatography, and the product? The contained portion was concentrated under reduced pressure, and the residue was dissolved in n-hexane/
Exemplary couplers 37 and 32i were crystallized with ethanol.
Obtained. (Melting point 82-89°C) Combination example (3) For the preparation of coupler shop 12 ↓ TMG/CH3CN 18.2 g (0.03 mol) (Da and 5,19
(0.03%) (7) Into a slurry of 2-acetamidomethylphenol in 50 ml of acetonitrile, while stirring,
7.07 (0.06 mol) of tetramethylguanidine (TMG) were added.

The reaction mixture was stirred at 20'C for 15 hours. The precipitated salt was collected, washed with cold ethyl acetate, and then methanol was added to make up to 200 ml. This solution was slowly poured into an ice water/hydrochloric acid mixture to decompose the salt, thus yielding coupler 2. Recrystallization from ethyl acetate gave 10.0 g (45%) of a white solid product, mp 177-181°C.

Synthesis Example (4) Preparation of coupler A24 CO□chu.

19.5 g (0,033 mol) and 6.7 g (0
,064 mol) of triethylamine in 150 m6 of acetonitrile while stirring.8.
1,! i' (0,033 mol) of methyl-3-methanesulfonamido-4-hydroxybenzoate was added. The mixture was heated on a steam bath with stirring for 3 hours. After cooling, the mixture was poured into ice water (containing 5 ml of concentrated hydrochloric acid). A gummy solid was collected, triturated with water, and dried.

Transfer the crude product to a silica gel column (eluted with dichloromethane)
Chromatographed through. Fractions containing pure product were collected and the solvent was removed under reduced pressure. A white residue was obtained. Recrystallization from isopropyl alcohol gave 16 g (61%) of a white solid, melting point 96-97°C.

Synthesis Example (5) Synthesis of Exemplary Coupler 52 α-Chloro-
α-pivaloyl-2-10rho-5-(n-hexadecanesulfonamide)acetanilide 44,9,3.3'
-Dichloro-4,4'-dihydroxydiphenylsulfone (112 g) was dissolved in 24 C1 cc of dimethylacetamide and 210 ml of acetonitrile under reflux.

9.7 cc of triethylamine was slowly added dropwise, and the reaction was then carried out under reflux for 5 hours.

The reaction mixture was 5% hydroxide) IJum solution 500ml
1 and extracted with 300 ml of ethyl acetate.

After washing the oil layer twice with water, it was dried over magnesium sulfate and concentrated under reduced pressure to obtain a residue of 15 [.1 g].

This residue? Silica gel chromatography 3 was carried out, and the part containing the product was concentrated under reduced pressure, and the residue was crystallized from n-hexane/ethanol (10/1 volume ratio) to obtain example coupler 5.
I got 2 for 45.9. (Moving point 91-96°C) Synthesis example (6
) Synthesis of Exemplary Coupler 53 α-chloro-α-pivaloyl-2-10 rho-5-(n-dodecyloxycarbonyl)acetamide l-” 33 g, 3,3'-dichloro-4,4'-dihydroxydiphenylsulfone 112
．． 19 M was dissolved in 300 ml of dimethylacetamide and 150 ml of acetonitrile under flowing conditions.

15 ml of triethylamine was added dropwise to this mixture, followed by reaction under reflux for 3 hours.

5% hydroxide of the reaction mixture)
0ml and ethyl acetate 300ml/! Extracted with.

The fiiF was washed with water three times, dried over magnesium sulfate, and concentrated under reduced pressure to obtain 58 g of residue.

This residue was subjected to silica gel chromatography, the part containing the product was concentrated under reduced pressure, and the residue was purified by n-hexane/
Crystallized with isopropanol, the exemplary coupler 53'5
:38.9 obtained. (Melting point 88-92°C) Synthesis example (7)
Synthesis of Exemplary Coupler 64 α-Chloro-α-pivaloyl-2-chloro-5-(n-hexadecanesulfonamido)acetanilide 35.5,9.8-acetylamino-
4-diethylsulfamoyl-1-naphthol 22.2
g & dimethylacetamide 200 mA' and 100 ml of acetonitrile and heated to 80°C to 85°C with stirring.
14 g of tetramethylguanidine was added at <0>C.

This reaction mixture was allowed to react at the same temperature for 5 hours.

After the reaction was completed, the mixture was poured into ice water (containing 10 ml of concentrated hydrochloric acid), and the precipitated oily substance was extracted with ethyl acetate.

The oil layer was washed twice with water, dried over sulfurized magnesium, and concentrated under reduced pressure to obtain 52 g of residue.

This residue was subjected to silica gel chromatography 3 times, the part containing the product was concentrated under reduced pressure, and the residue was purified with ethyl acetate/n
-Crystallization from hexane gave 23 g of exemplified coupler 64. (Melting point 126-139°C) Synthesis Example (8) Synthesis of Exemplary Coupler 75 α-Chloro-α-pivaloyl-2-chloro-5-(n-dodecyloxycarbonyl)acetanilide 30.0,9,2-chloro- 18.9 g of 8-dimethylsulfamoyl-1-naphthol to 150 m/! of dimethylformamide! and acetonitrile 150m/!
14 g of tetramethylguanidine was added to the mixture at 80°C while stirring.

The reaction mixture was allowed to react at the same temperature for 5 hours, and then filtered into ice water (containing 10 ml of concentrated hydrochloric acid), and the precipitated oily substance was extracted with ethyl acetate.

The oil layer was washed twice with water, dried over magnesium sulfate, and concentrated under reduced pressure to obtain 43 g of residue.

This residue was subjected to silica gel chromatography, and the part containing the product was determined. Concentration under reduced pressure and crystallization of the residue from n-hexane/ethyl alcohol gave Exemplary Coupler 75 at 18.9
Obtained. (Melting point: 115-123°C) In the present invention, photographic constituent layers include a photosensitive layer containing a photosensitive silver halide emulsion, and non-photosensitive layers such as an intermediate layer, a filter layer, an undercoat layer, and a protective layer. include.

In the silver halide color photographic light-sensitive material of the present invention, the photographic constituent layer to which the yellow coupler represented by the general formula [■] is added is preferably a silver halide emulsion layer and/or a non-photosensitive layer adjacent thereto. More preferably, the silver halide emulsion layer contains both.

The amount of the yellow coupler added according to the present invention is not limited, but is preferably from 1.times.10 mol to 5.0 mol, more preferably from 1.times.10 mol to 5.times.10 mol per mol of silver.

Next, the compound of general formula [TI] used in the present invention will be explained. General formula [TI] -B (where A is the activity of the compound that causes a coupling reaction with the oxidized product of the aromatic primary amine developer. Hydrogen atom 1 from position
B represents a group that exhibits a fogging effect in a developer after being separated by a coupling reaction. ) The compound represented by the general formula [n] used in the present invention will be explained below.

In general formula [11I], A specifically represents a cyan coupler, magenta coupler, yellow coupler or colorless coupler. Specifically, the group represented by B that exhibits a blurring effect is a reducing compound such as hydrazine, hydrazide, hydrazone, enamine, polyamine, hydroquinone, mininophenol, phenylenediamine, acetylene, aldehyde, thiourea, thiocarbamate, etc. It is a group having a partial structure of a compound capable of forming silver sulfide, such as a thiocarbonyl compound represented by , dithiocarbamate, rhodanine, and thiohydantoin.

Among the compounds represented by the general formula [n], those represented by the following general formula [1] are preferably used.

General formula [■'] A-(TIME)-FA In the formula, A is the same as A in general formula [n], and TIME is removed from A by a coupling reaction and then further FA in the developer. represents a timing group that releases n
represents O or l; when n is O, FA is a group that can be separated from A in the coupling reaction; when n is 1, it is a group that can be released from TIME, and FA is a group that can be released from TIME; This is a group that has adsorption properties to grains and has a substantial fogging effect on silver halide.

Here, the term "group having a substantial fogging effect on silver halide" refers to a group (compound) that produces a measurable fog when developed in the presence of the compound.

FA is, for example, a group represented by AD-(Il)m-X, or a group having both the effects or structure of AD and X in one group.

Here, AD represents a group that can be adsorbed to silver halide grains, L represents a divalent linking group, X is a reducing group or a group that can form silver sulfide during development, and m is O or 1.

When FA is a group represented by A p -(L), n-X, the position bonded to TIME is A D -(L). −
Any position of X may be used. Of course, as FA, one having both the effects of AD and X in one group is also preferably used.

Examples of the coupler residue represented by A include the following.

Cyan coupler residues include phenol couplers, naphthol couplers, and the like. Magenta coupler is 5
- pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotrizole couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, indacylon couplers, and the like. Examples of the yellow coupler residue include benzoylacetanilide coupler, pivaloyl ryoseto nilide coupler, malonzi ryo nilide coupler, and the like. Non-color forming coupler residues include open chain or cyclic active methylene compounds such as indanone, cyclopentanone, malonic acid diester, imidazolinone, oxazolidine, thiacillinone, etc.

Further, among the coupler residues represented by A, those preferably used in the present invention can be represented by the general formula % [X' ] or [Xr].

In the formula, R1 represents an acylamido group, anilino group or ureido group, and R; represents a phenyl group which may be substituted with one or more halogen atoms, alkyl groups, alkoxy groups or cyano groups.

[■”] [V' ]fIVr] In the formula, R↓ represents a halogen atom, an acylamido group, or an aliphatic residue, and R: and Rmi each represent an aliphatic residue, an aromatic residue, or a heterocyclic residue. Also, R'4 and R-
One of them may be a hydrogen atom. a is an integer from 1 to 4,
b represents an integer from 0 to 3, and C represents an integer from 0 to 5.

] In the formula, R; represents a tertiary alkyl group or an aromatic residue,
R↓ represents a hydrogen atom, a halogen atom, or an alkoxy group. Rλ represents an acylamido group, an aliphatic residue, an alkoxycarbonyl group, a sulfuryl group, a carbamoyl group, an alkoxy group, a halogen atom, or a sulfonamide group.

In the formula, RQ is an aliphatic residue, an alkoxy group, a mercapto group,
Alkylthio group, acyl group, nido'g, alkoxycarbonyl group, sulfonamido group, carbamoyl group, sulfamoyl group, alkoxysulfonyl group, aryoxysulfonyl group, acyl group, diacylamino group, alkylsulfonyl group or ryylsulfonyl group represents a group, R
:. represents a hydrogen atom, a halogen atom, an alkoxy group, a silyl group, a nitro group, an alkylsulfonyl group or an alkylsulfonyl group. Enol esters of indanone can also be used in the present invention.

In the formula, R11 represents an aliphatic residue or an aromatic residue.

■ represents an oxygen atom, sulfur atom or nitrogen atom.

[, light “] Ri2-C”-Ris peek o o o o
o.

However, R:4, R:, and Ri6 each represent a hydrogen atom, an aliphatic residue, an aromatic residue, or a heterocycle, and W is a nonmetallic atom necessary to form a 5- to 6-membered ring with a nitrogen atom. represents a group. R1□ and R: may form a 5- to 6-membered ring together with a necessary nonmetallic atomic group.

The timing group represented by TIMEli is one that leaves A by a coupling reaction and then leaves FA by an intramolecular substitution reaction, as described in U.S. Pat. , British Patent No. 2,072,363A, JP 5'7-154234
No. 57-188035, etc., which removes FA by electron transfer via a conjugated system, JP-A-57-11
Examples include coupling components such as No. 1526, which are capable of releasing FA through a cambling reaction with an oxidized product of an aromatic primary amine developer. These reactions may occur in one step or in multiple steps.

FA is AD-CL). In the case of a group containing -X, AD'b''- may be directly bonded to the carbon atom at the coupling position, or if it can be separated by the Knobrbling reaction, these may be coupled. It may be bonded to carbon.Also, what is known as a so-called 2-equivalent leaving group may be present between the coupling carbon and AD.These groups include an alkoxy group (
Examples include methoxy groups, aryloxy groups (e.g., phenoxy groups), alkylthio groups (e.g., ethylthio groups), arylthio groups (e.g., phenylthio groups), heterocyclic oxy groups (e.g., tetrazolyloxy), heterocyclic thio groups (
For example, pyridylthiono, heterocyclic groups (such as hydantoinyl group, pyrazolyl group, triazolyl group, benzotriazolyl group, etc.).
1.391 can be used as the FA.

Groups that can be adsorbed to the halogenated compound represented by AD include nitrogen heterocycles with dissociable hydrogen atoms (pyrrole, imidazole, pyrazole, trizoole, tetrazole, benzimidazole, benzopyrazole,
benzotriazole, uracil, tetrazynden,
imidazotetrazole, pyrazolotrizole, pentalyzaindene, etc.], heterocycles with at least one nitrogen atom and another heteroatom (oxygen atom, sulfur atom, selenium atom, etc.) in the ring (ogisazole, thiazole, thiazoline, Heterocycles with mercapto groups (2-mercaptobenzothiazole, 2-mercaptopyrimidine, 2-mercaptobenzoxazole,
-7enyl-5-mercaptotetrazole, etc.), quaternary salts (tertiary amines, pyridine, quinoline, benzothiazole, benzimidazole, benzoxazole, etc. quaternary salts), thiophyl/-ols, alkylthiol compounds (e.g. Thiourea, dithiocarbamate, thiouramide,
rhodanine, thiacyridinethione, thiohydantoin,
Ciobal bir RL! '4) etc.

The divalent linking group represented by L in FA includes commonly used alkylene, alkenylene, phenylene, naphthylene, -o-1-s-1-so-1-SO2-1-N=
It is composed of a ring selected from N-, carbonyl, amide, thiourimide, sulfonylamide, ureido, thioureido, heterocycle, and the like.

The group represented by
1-phenyl-3-pyrazolidinone, enamine, aldehyde, polyamine, acetylene, aminoborane, tetrazolium salt, ethylene bispyridium salt, etc.) or a compound that can form silver sulfide during development (e.g., thiourea , thiohydantoin, dithiocarbamate, rhodanine, thiohydantoin, thiohydantoin, etc.). Among the groups represented by .

FA is an adsorption site for silver halide grains (for example, nitrogen VK of benzotriazole, 1-phenyl-5
- sulfur atom of mercaptotetrazole, etc.) may be bonded to TIME or A, but this is not necessarily the case. In this case, either a hydrogen atom is bonded to the adsorption site, or the adsorption site is a group that can be hydrolyzed in the developer (
For example, it is preferable to block with a cetyl group, a benzoyl group, a methanesulfonyl group, or a removable group (eg, a 2-cyanoethyl group, a 2-methanesulfonylethyl group).

An example of AD is shown below.

C1(3 0H.

CH.

An example of L is shown below.

-CH2-1-0H, CH2-1-00H2-1-0C
! H,C! H2-1-3CH2-, -NHNHC! HO, -NHNHOOOH, -NHN
HSO, (H,, -NHNHC!0OF-N-NHCH
O C00C2H.

-CONHNHG! H,-(1!0NHNH2 Further, preferred specific examples of FA in general formula [I] are shown below.

H3 (Jf2CM, CHn CH5 0H5 0H, (1!H2NHOC!H8) Specific examples of the compounds used in the present invention are as follows.

(1) 0H (2) OH 2H5 OH OH (OH2)4NHCOH.

CH.

CH.

OH (2sn”4 (z7) OH OH OH H H n-C!HH37000CHCOO(!11H37-n
(3s OH.

(39y OH) The compound represented by the general formula [I] of the present invention is
-138636, 57-150845 and Tokken Sho 5
7-161515.

Two or more kinds of the compounds of general formula [I] of the present invention may be used simultaneously.

Compounds of general formula [I] of the present invention and JP-A-57-1519
DIR compound releasing a diffusible leaving group disclosed in No. 44, JP-A-57-154234, JP-A No. 57-188035
It can be used in combination with a DIR compound having a timing adjustment function disclosed in US Pat.

Compounds of general formula [TI] of the present invention and JP-A-57-828
It may be preferable to use a coupler in which the formed dye has diffusive properties, such as those described in No. 37, in that the granularity is further improved.

It is also possible to use the compound of general formula [n] of the present invention in combination with hydroquinones or a compound having the ability to scavenge an oxidized developing agent described in U.S. Pat. No. 4,252,893, U.S. Pat. It may be preferable in terms of improving properties.

The amount of the compound represented by the general formula [II] of the present invention is 1 mol or less, preferably 0.2 mol or less, per 1 mol of silver in the same layer.
The amount is 10 mol or less, more preferably 0.1 mol or less and 10 mol or more. In particular, the amount of the compound represented by the general formula [■゛] added is 0.1 mole or less, preferably 0.05 mole or less, and 10 mole or more per mole of silver in the same layer.
More preferably 10 moles or less. It is preferable that the amount is mol or more.

The core/shell type silver halide grains according to the present invention are:
It is preferable to use particles with a grain structure consisting of two or more layers having different silver iodide contents, and the average silver iodide content in the outermost layer (shell part) of the two or more layers is It is preferable that the silver iodide content is lower than that of the inner layer (core portion).

In the present invention, the silver iodide content in the outermost layer (shell portion) of the silver halide grains having the above composition is desirably as low as possible, and is preferably close to 0%.

Furthermore, the core portion inside the grain may be formed as two or more layers having different silver iodide contents. Further, the difference between a layer with a high silver iodide content and a layer with a low silver iodide content may have a sharp boundary, or may have a continuous change in which the boundary is not necessarily obvious.

The distribution state of silver iodide in the above silver halide grains is as follows:
It can be measured by various physical measurement methods, and can also be investigated by measuring luminescence at low temperatures as described in the Abstracts of the 1986 Annual Conference of the Photographic Society of Japan.

The core/shell type silver halide grains according to the present invention have a core portion made of silver halide having a high silver iodide content, and a content of silver iodide coating the core portion that is higher than the content in the core portion. Preferably, the grains are silver halide grains consisting of a shell part made of low silver halide and a shell part having a thickness of 0.001 to 0.1 .mu.m.

In a preferred embodiment of the silver halide grains of the present invention, the average silver iodide content is C1., 1 mol% or more and 7.
．． The emulsion consists of 0 mol% or less.

The silver iodide content in each of the core parts is preferably 60% to 70% of the total, and the silver iodide content in the shell part is 0 to 40%.
A composition containing is preferred.

The silver halide grains in the present invention preferably contain silver bromide as a silver halide composition other than the above-mentioned silver iodide, but may contain silver chloride as long as the effects of the present invention are not impaired. In this case, the content of silver chloride is approximately 1 mol%
Less than is preferred.

The shape of the silver halide grains according to the present invention may be, for example, hexahedral, octahedral, dodecahedral, plate-like, spherical, etc., or may be a mixture of these various shapes. , octahedral, and tetradecahedral particles are preferred.

The silver halide emulsion containing silver halide grains having the specific layer structure of the present invention can be produced by using monodisperse silver halide grains as a core part and coating the core part with a shell part.

To produce monodisperse silver halide grains in the core portion, grains of a desired size can be obtained, for example, by a double jet method while keeping pAg constant. Furthermore, in order to obtain highly monodispersed silver halide grains,
The method described in Japanese Patent No. 4-48521 can be applied.

For example, it is produced by a method in which a potassium iodobromide-gelatin aqueous solution and an ammoniacal silver nitrate aqueous solution are added to a gelatin aqueous solution containing silver halide seed particles while changing the addition rate as a function of time. In this case, the time function of the addition rate,
By appropriately selecting pH, pAg, temperature, etc., highly monodisperse silver halide grains can be obtained.

Next, the thickness of the shell portion covering the core portion is preferably a thickness that does not hide the desirable qualities of the 77 part, and conversely, a thickness sufficient to hide the unfavorable qualities of the core portion. . That is, the thickness is preferably limited to a narrow range defined by such upper and lower limits. Such a shell portion can be formed by depositing a soluble halogen compound solution and a soluble silver salt solution on the core portion of monodisperse silver halide grains by a double jet method.

Regarding the production method of the above-mentioned core/shell type silver halide grains, for example, West German Patent No. 1,169,290, British Patent No. 1.027.146, JP-A-57-1
542328., Japanese Patent Publication No. 51-1417, etc.

The substantially monodisperse silver halide grains as used in the present invention are:
Silver halide grains have a particle size distribution in which the variation in grain size is less than a certain ratio with respect to the average grain size as shown below. Since the grain size distribution of an emulsion (hereinafter referred to as a monodisperse emulsion) consisting of a group of photosensitive silver halide grains with almost uniform grain morphology and small grain size variations is almost a normal distribution, the standard deviation can be easily determined. The width of the distribution of the silver halide grains according to the present invention is preferably 25% or less, more preferably monodispersity of 15% or less, when the width of the distribution and coefficient of variation are defined by the relational expression It is.

The relationship between grain size distribution is "sensitome in photographic emulsion" I
"Empirical relationship between J-distribution and particle size distribution" The Photographic Journal, Volume LXXIX (1949)
This can be determined using the method described in the article by Tribelli and Smith on pages 330-338.

In the present invention, the silver halide grains in at least two silver halide emulsion layers having different silver iodide contents contain the monodisperse silver halide grains in an amount of 70% or more of the total grains in the same silver halide emulsion layer. It is particularly preferred that all the grains are monodisperse silver halide grains. Further, the core/shell type silver halide emulsion advantageously used in the present invention has an average grain size of 01 to 1.2 .mu.m, preferably monodisperse grains of 0.2 to 0.9 .mu.m.

Next, core/shell type silver halide emulsions that can be used in the present invention include those written by T. H. James and C.E.K. Meese (T. H. James).
, C.K., K. Mees) The Theory of the Photographic Process, Volume 3, published by Macmillan;
Published by An Publishing: P. Grafikides) "Hemy...
Photographic”, published by Benny Montel (Pan
It can be prepared by various methods such as the commonly used ammonia method, neutral method, acid method, etc., which are also described in "Leaving method" such as "iMoute 1". Further, a single jet method, a double jet method, a controlled jet method, etc. may be used, or two or more types of silver halide emulsions prepared separately may be mixed. After forming such silver halide grains, they are washed with water to remove by-product water-soluble salts (for example, when silver bromide is made using silver nitrate and potassium bromide, potassium nitrate is removed from the system), and then heat treated. Chemical sensitizers (e.g. thiosulfate) IJum, N, N
, N'-)limethylthiourea, -side thiocyanate complex salt, thiosulfate complex salt, stannous chloride, hexamethylenetetramine, etc., the sensitivity can be increased without coarsening the particles. These general laws are set out above.

In addition to the above chemical sensitizers, for example, U.S. Patent No. 2.3
No. 99,083, No. 2,597,856, No. 2.
Gold compounds such as chlorauric acid salts and gold trichloride as shown in each specification of No. 597,915, U.S. Patent No. 2,448.06
No. 0, No. 2.540.086, No. 2,566.2
No. 45, No. 2,566,263, No. 2.5g8,
Platinum, palladium, as shown in each specification of No. 079,
Salts of noble metals such as iridium, rhodium, and ruthenium, U.S. Pat. Nos. 1.574.944 and 2,410
, No. 689, No. 3,189,458, No. 3,50
Sulfur compounds that react with silver salts to form silver sulfide, such as those described in U.S. Pat.
No. 487.850, No. 2゜518.698, No. 2
, 521,925, 2.521.926, 2.694.637, 2.983.610, and 3.201.254. Examples include stannous salts, amines, and other reducing substances.

The tabular grains according to the present invention have an asbestos ratio (diameter/thickness ratio of 3 or more, but preferably an aspect ratio of 5).
Above, it is particularly preferably 8-20. The diameter here is the diameter of the circumscribed circle of the particle, preferably 0.5 to 10 μm
1, more preferably 1.0 to 6.0 μm. Thickness is 2
In a tabular crystal with two parallel faces, these two objects are intersecting.

The silver halide composition of the tabular grains is a composition consisting essentially of silver iodobromide with a silver iodide content of 0.5 to 10 mol%, and the silver chloride content is less than 1 mol%. is desirable. Although the composition distribution of silver iodide may be uniform, it is preferable that the composition is different between the outer part of the grain and the inner part thereof.

Furthermore, an emulsion whose outer portion has a low iodine content is more preferable.

The particle structure was determined by J., K., Goldstein, and B.
X-ray analysis in Williams l'-TKM/ATPM, scanning electron microscopy (
1977) Vol. 1 P, 651.

Tabular grains with low iodide in the outer part are iodobromide grains in which the outer part has a silver iodide content of 0 to 5 mol % and the central region has a silver iodide content of 4 to 20 mol %. Silver is preferred. Such an emulsion can be produced by changing the composition of the halide solution added in JP-A-58-113927, but the silver iodide content in the nucleation area must be kept at 2 mol% or less. preferable. The halogen composition of such an emulsion can also be analyzed by the method described above.

(Tabular twinned grains consisting of lljj planes have exactly parallel external planes and one or more twinned planes parallel to the external planes. Regarding the morphology of twinned grains, see "Fundamentals of Photographic Engineering: Silver Salt Photography") Net” Corona Publishing (1979, 9) is classified in detail.

Further, the tabular silver iodobromide grains have first and second opposing parallel major faces and a central region extending between the two major faces, and further have at least one lateral region extending between the two major faces. It is preferable that the particle has an outer region displaced in the direction (parallel to the main surface) and has an internal structure in which the iodide content in the central region and the iodide content in the outer region are different. More preferred among these grains are grains having an internal structure in which the iodide content in the outer region is lower than the iodide content in the central region.Also, preferably, the central region is formed so that the outer region forms a ring in the lateral direction. It forms a composition distribution surrounding .

Incidentally, the change in the legal content in the boundary layer between the central region and the outer region may have a sharp boundary surface, or may have a continuous change in which the boundary is not necessarily obvious.

In the layer containing the tabular silver halide grains of the present invention, the tabular grains are present in a weight ratio of 4 to all silver halide grains in the layer.
It is preferably present in an amount of 0% or more, particularly 60% or more.

The tabular silver halide grains according to the present invention may be polydisperse or monodisperse, but monodisperse is more preferable.

Preferably, monodispersity is such that the variation coefficient of the particle size distribution (this particle size is defined as the diameter of the circumscribed circle of the particle as described above) is 25% or less.

As a method for preparing an emulsion consisting of monodisperse tabular grains, the methods described in JP-A-51-3-027, JP-A-54-118823 and JP-A-55-211143 can be used.

In addition, as a preferred method for obtaining an emulsion consisting of monodisperse tabular grains, a seed population consisting of monodisperse spherical grains is obtained by physically ripening core grains consisting of multiple twins in the presence of a silver halide solvent. A method that can be used is to create one and then grow it. More preferably, a tetrazaindene compound is present during the growth of tabular grains to increase the proportion of tabular grains and to improve monodispersity. When tabular grains are mixed with other silver halide grains, they are preferably used as a highly sensitive silver halide emulsion, and have the same color sensitivity and have two or more silver halide emulsion layers. In a silver halide multilayer photographic material, it is preferably used in a silver halide emulsion layer that requires higher sensitivity.

Emulsions containing tabular silver halide grains according to the present invention are disclosed in JP-A-52-153428 and JP-A-58-55426.
No. 58-113928, No. 58-113927, etc., or by referring to the methods described therein.

The tabular grains of the present invention may be doped with various metal salts or metal complex salts during silver halide precipitation, during grain growth, or after grain growth. For example, metal salts or complex salts such as gold, platinum, palladium, iridium, rhodium, bismuth, cadmium, copper, and combinations thereof can be used. In addition, in the method for producing an emulsion containing the above-mentioned particles, the Tardel water washing method, dialysis method, or coagulation precipitation method, which is commonly used in general emulsions, can be appropriately used as a means for desalting.

Furthermore, the above silver halide emulsion may contain sulfur sensitizers such as allylthiocarbamide, thiourea, cystine, etc., active or inactive selenium sensitizers, and reduction sensitizers.
For example, stannous salts, polyamines, etc., noble metal sensitizers, such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-oresulfopenztheazole methyl chloride, etc., or, for example, ruthenium, rhodium, Chemical sensitization can be carried out using a water-soluble salt sensitizer such as iridium, specifically ammonium chloroparadate, potassium chlorooleate, sodium chloroparadite, etc. alone or in combination as appropriate.

The silver halide used in the present invention has an appropriate sensitizing dye added thereto at 5 x 10-8 to 3 x 10 mol per mol of silver halide in order to impart photosensitivity to the desired wavelength range. It may also be optically sensitized.

Various sensitizing dyes can be used, and each sensitizing dye can be used alone or in combination of two or more. Examples of the sensitizing dyes advantageously used in the present invention include the following.

That is, examples of sensitizing dyes used in the blue-sensitive silver halide emulsion layer include West German Patent No. 929,080, US Pat. No. 2,231,658, US Pat. , No. 2,519,001, No. 2
, No. 912,329, No. 3,656,959, No. 3,
No. 672,897, No. 3,694,217, No. 4.0
No. 25,349, No. 4,046,572, British Patent 1
．． No. 242,588, Special Publication No. 44-14030, No. 5
Examples include those described in No. 2-24844. Examples of sensitizing dyes used in green-sensitive silver halide emulsions include, for example, U.S. Pat.
Typical examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in British Patent No. 505.979 and British Patent No. 505.979. Further, as sensitizing dyes used in red-sensitive silver halide emulsions, for example, U.S. Pat.
No. 34, No. 2,270,378, No. 2,442,71
No. 0, No. 2,454,629, No. 2,776,280
Typical examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. Furthermore, U.S. Patent 2,213,9
No. 95, No. 2.493.748, No. 2.519. O
Cyanine dyes, merocyanine dyes or composite cyanine dyes such as those described in German Patent No. 01, West German Patent No. 929,080, etc. can be advantageously used in green-sensitive silver halide emulsions or red-sensitive silver halide emulsions.

These sensitizing dyes may be used alone or in combination.

The photographic material of the present invention may be optically sensitized in a desired wavelength range by a spectral sensitization method using cyanine or merocyanine dyes alone or in combination, if necessary.

A typical particularly preferred spectral sensitization method is, for example, Japanese Patent Publication No. 43-493 concerning the combination of benzimidazolocarbocyanine and benzoxazolocarbocyanine.
No. 6, No. 43-22883, No. 45-18433,
No. 47-37443, No. 48-28293, No. 49
No.-6209, No. 53-12375, JP-A-52-2
No. 3931, No. 52-51932, No. 54-8011
No. 8, No. 58-153926, No. 59-116646
No. 59-116647 and the like.

Further, regarding the combination of carbocyanine having a benzimidazole nucleus with other cyanine or merocyanine, for example, Japanese Patent Publication Nos. 45-25831 and 47-11
No. 114, No. 47-25379, No. 48-38406
No. 48-38407, No. 54-34535, No. 55-1569, JP-A-50-33220, No. 50
-38526, 51-107127, 51-1
No. 15820, No. 51-1355'28, No. 52-1
No. 04916, No. 52-104917, and the like.

Furthermore, regarding combinations of benzoxazolocarbocyanine (oxa-carbocyanine) and other carbocyanines, for example, Japanese Patent Publication Nos. 44-32753 and 46
-11627, Japanese Unexamined Patent Publication No. 1483/1983, and Japanese Patent Publication No. 38408/1983 regarding merocyanine.
No. 48-41204, No. 50-40662, JP-A No. 56-25728, No. 58-10753, No. 5
No. 8-91445, No. 59-116645, No. 50-
No. 33828 etc. are mentioned.

Regarding combinations of thiacarbocyanin and other carbocyanins, for example, Japanese Patent Publications Nos. 43-4932, 43-4933, 45-26470, and 46
-18107, No. 47-8741, JP-A-59-1
No. 14533, etc., and the method described in Japanese Patent Publication No. 49-6207 using zeromethine, dimethine merocyanine monomethine, or trimethine cyanine and styryl dye can be advantageously used.

In order to add these sensitizing dyes to a silver halide emulsion, a hydrophilic organic solvent such as methyl alcohol, ethyl alcohol, acetone, dimethylformamide, or fluorinated alcohol described in Japanese Patent Publication No. 40659/1984 is prepared in advance as a dye solution. It is used by dissolving it in a solvent.

The addition may be made at any time such as at the start of chemical ripening of the silver halide emulsion, during ripening, or at the end of ripening, and in some cases, it may be added at a step immediately before coating the emulsion.

The silver halide emulsion according to the present invention is used to increase sensitivity, increase contrast, and to accelerate development, for example, the polyalkylene oxide described in U.S. Pat. No. 2,441,389, and the polyalkylene oxide described in U.S. Pat. Ethers, esters, and amides of polyalkylene oxides described in British Patent No. 1,14, 5,186, Japanese Patent Publication No. 10989/1989, Japanese Patent Publication No. 45-15188, British Patent No. 48-
No. 43435, No. 47-8106, No. 47-8106
Other polyalkylene oxide derivatives described in each publication; U.S. Patent Nos. 3,046,132 to 3.046
．． 135, thioether compounds described in Japanese Patent Publication No. 45-9019 and Japanese Patent Publication No. 47-11119, thiomorpholines described in Japanese Patent Publication No. 47-28325; U.S. Patent No. 3,772,021 quaternary ammonium compounds described in Japanese Patent Publication No. 45-27037; pyro IJ dine, etc. described in Japanese Patent Publication No. 45-27037; urethane or urea derivatives described in Japanese Patent Publication No. 40-23465;
Imidazole derivatives described in Publication No. 541; Japanese Patent Publication No. 1973
-Polymer described in Publication No. 26471; Japanese Patent Publication No. 45-2
3-pyrazolidones described in Japanese Patent No. 7670 may also be included.

Furthermore, various compounds can be added to the photographic emulsion of the silver halide photographic light-sensitive material according to the present invention in order to prevent a decrease in sensitivity and the occurrence of capri during the manufacturing process, storage, or processing of the light-sensitive material. These compounds include, for example, 4
- Hydroxy-6-methyl-1,3,3a, 7-chitrazaindene, 3-methyl-benzothiazole, 1-phenyl-5-mercaptotetrazole, as well as heterocyclic compounds, mercury-containing compounds, mercapto compounds, metal salts, etc. Many compounds are known.

Specific examples of compounds that can be used include HoJames, T.;
The Theory of the Photographic Process', 3rd edition (1966), written by C.E. K0Mees, published by Macmillan Inc. In addition to citing the original document, U.S. Patent No. 1 ,75
No. 8.576, No. 2,110,178, No. 2,1
No. 31.038, No. 2.173.628, No. 2.
697.040, 2.30.4.962, 2.324.123, 2,394,198, 2,444.605 to 2,444,608 issue,
2,566.245, 2,694,716, 2,697.099, 2,708,162
No. 2,728.663 to No. 2,728,665
No. 2.476゜536, No. 2,824,00
No. 1, No. 2.843゜491, No. 2,886,4
No. 37, No. 3.052゜544, No. 3.137.
No. 577, No. 3.220゜839, No. 3,226
, No. 231, No. 3.236゜652, No. 3,25
No. 1,691, No. 3.252゜799, No. 3.2
No. 87.135, No. 3.326゜661, No. 3.
420.668, British Patent No. 3.622゜339, British Patent No. 893,428, British Patent No. 403,789, British Patent No. 1,173,609, British Patent No. 1.200.188
Examples include those listed in the product specifications and the like.

Specifically, the method of incorporating the coupler and compound of the present invention into a photographic constituent layer is as follows: When the coupler and compound of the present invention are alkali-soluble, they may be added as an alkaline solution; In some cases, for example, U.S. Pat.
No. 0, No. 2,801,171, No. 2,272,191
No. 2,304,940 and the respective specifications. According to the method described therein, the couplers and compounds of the present invention are dissolved in a high boiling point solvent, if necessary in combination with a low boiling point solvent, and dispersed in the form of fine particles. It is preferable to add it to a silver halide emulsion or a coating solution for other photographic constituent layers. Hydrophilic colloids used at this time include gelatin, gelatin conductor known as a photographic binder, gelatin graft polymers, various cellulose derivatives, polyvinyl alcohol partial oxide, sodium alginate, poly-N-vinylpyrrolidone, etc. Can be widely used. At this time, if necessary, other hydroquinone derivatives, ultraviolet absorbers, anti-fading agents, etc. may be used in combination.

In addition to the above methods, methods using other polymers such as latex dispersion are known.

Further, in detailing the method of adding preferred couplers and compounds of the present invention to a silver halide emulsion in the present invention, one or more couplers and compounds of the present invention may be added to other non-inventive couplers as necessary. couplers, hydroquinone derivatives, anti-fading agents, ultraviolet absorbers, etc., as well as organic acid amides, carbamates, esters, ketones, urea derivatives, ethers, hydrocarbons, etc., especially di-n-butyl phthalate, trichloride, etc. diyl phosphate, triphenyl phosphate, di-isooctyl azelate, di-
n-butyl sebacate, tri-hexyl phosphate, N,N-di-ethyl-caprylamidobutyl, N,
N-diethyl laurylamide, n-pentadecyl phenyl ether, di-n-octyl phthalate, di-1so
-dodecyl phthalate, di-n-7 nylphthalate, 2
,4-di-tert-hentylphenol, n-/
High boiling point solvents such as nilphenyl-/L/, 3-hentatecylphenyl ethyl ether, 2+ 5'/5ec-amylphenyl butyl ether, monophenyl-di-chlorophenyl phosphate or fluoroparaffin, and/or methyl acetate, ethyl acetate , propyl acetate, butyl acetate, butyl propionate, cyclohexanol, diethylene glycol monoacetate, nitromethane, carbon tetrachloride, chloroform, cyclohexane tetrahydrofuran, methyl alcohol, acetotrino L1, dissolved in a low boiling point solvent such as dimethylformamide, dioxane, methyl ethyl ketone, alkylbenzene Anionic surfactants such as sulfonic acids and alkylnaphthalene sulfonic acids and/or nonionic surfactants and/or cationic surfactants such as sorbicunseschioleate and sorbitan monolaurate, hydrophilic surfactants such as gelatin, etc. The mixture is mixed with an aqueous solution containing a binder, emulsified and dispersed using a high-speed rotary mixer, colloid mill, ultrasonic dispersion device, etc., and then added to a silver halide emulsion.

In addition, the above-mentioned latex dispersion method and its effects are disclosed in JP-A-49-74538, JP-A-51-59943, and JP-A-54.
-32552 Yongyong Publication and Research Disclosure +-
No. 14850, pp. 77-79, August 19th, 6th year.

Suitable latexes include, for example, styrene, acrylate,
Lobetyl acrylate, n-butyl methacrylate,
2-acetoacetoxyethyl methacrylate, 2-(methacryloyloxy)ethyltrimethylammonium methosulfate, 3-(methacryloyloxy)propane-1-sulfonic acid sodium salt, N-isopropylacrylamide, N-(2-(2-methyl-4 -oxopentyl)]acrylamide, 2-acrylamide-2-
Seven-dimensional homopolymers, copolymers and terpolymers such as methylpropanesulfonic acid and the like.

The support used in the photosensitive material using the silver halide emulsion of the present invention is a flexible paper such as paper laminated with an a-olefin polymer (for example, polyethylene, polypropylene, ethylene/butene co-electrolyte), or synthetic paper. Reflective supports, films made of semi-synthetic or synthetic polymers such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, polyamide, etc., and flexible supports in which these films are provided with reflective layers; Includes glass, metal, ceramics, etc.

The silver halide material of the present invention can be used directly or after subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc. as necessary, or to improve the adhesion, antistatic property, dimensional stability, etc. of the support surface.
It may be applied through one or more subbing layers to improve abrasion resistance, hardness, antihalation properties, frictional properties, and/or other properties.

It is advantageous to use gelatin as the binder (or protective colloid) in the silver halide emulsion of the present invention.
In addition, hydrophilic colloids such as gelatin derivatives, graft polymers of gelatin and other polymers, proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as single or copolymers can also be used.

The photographic emulsion layer and other hydrophilic colloid layers of the silver halide emulsion of the present invention are hardened by using alone or in combination with a hardening agent that cross-links Pine Goo (or protective colloid) molecules and increases the film strength. . It is desirable to add the hardening agent in an amount that can harden the photosensitive material to such an extent that it is not necessary to add the hardening agent to the processing solution, but it is also possible to add the hardening agent to the processing solution.

A plasticizer can be added for the purpose of increasing the flexibility of the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material.

A dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer can be contained in the photographic emulsion layer or other hydrophilic colloid layer of a light-sensitive material for the purpose of improving dimensional stability.

In the emulsion layer of the silver halide emulsion, a dye is formed by a coupling reaction with an oxidized product of an aromatic primary amine developer (for example, a p-7 enylene noamine derivative or an aminophenol derivative) during color development processing. , dye-forming couplers are used.

The dye-forming couplers are typically selected for each emulsion layer to form a dye that absorbs light in the emulsion layer's sensitive spectrum, with a yellow dye-forming coupler for the blue light-sensitive emulsion layer. However, a magenta dye-forming coupler is used in the green light-sensitive emulsion layer, and a cyan dye-forming coupler is used in the red light-sensitive emulsion layer. However, depending on the purpose, a silver halide color photographic light-sensitive material may be produced using the above-mentioned combinations.

In addition to the couplers of the present invention, yellow dye-forming couplers include acylacetamide couplers (e.g., benzoylacetanilides, pivaloylacetanilides),
Examples of magenta dye-forming couplers include 5-pyrazolone couplers, virazolobenlimigzole couplers, pyrazolotriazoles, and open-chain acylacetamide couplers, and cyan dye-forming couplers include lotus 7 toll couplers and phenol couplers.

These dye-synthesizing couplers preferably have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. In addition, even if these dye-forming couplers are 4-equivalent, in which 4 molecules of silver ions need to be reduced in order to form 1 molecule of dye, only 2 molecules of silver ions need to be reduced. Either equivalence is acceptable.

For hydrophobic compounds such as dye-forming couplers that do not need to be adsorbed onto the silver halide crystal surface, various methods such as solid dispersion, latex dispersion, and oil-in-water emulsion dispersion can be used. It can be selected as appropriate depending on the chemical path of the hydrophobic compound, etc. The oil-in-water emulsion dispersion method can be applied to conventionally known methods for dispersing hydrophobic additives such as couplers. Usually, a solvent with a high boiling point of 150'C or higher is used, and if necessary, a low-boiling, Direct, and/
Or, dissolve it in combination with a water-soluble organic solvent and mix it with a surfactant in a hydrophilic binder such as an aqueous gelatin solution, using a stirrer,
It may be emulsified and dispersed using a dispersing means such as a homogenizer, a colloid mill, a 70-jet mixer, or an ultrasonic device, and then added to the desired hydrophilic colloid layer. A step of removing the low-boiling, α-organic solvent may be included simultaneously with the dispersion or dispersion.

Examples of high boiling point oils include phenol derivatives that do not react with the oxidized form of the developing agent, heptatarate, phosphate, citric acid ester, benzoic R ester, alkylamide,
Boiling point of fatty acid ester, trimesic acid ester, etc. 150
An organic solvent having a temperature of ℃ or higher is used.

Anionic active agents and 7-ionic surfactants are used as dispersion aids when a hydrophobic compound is dissolved in a low boiling point solvent alone or in combination with a high boiling point solvent and dispersed in water using a machine or ultrasound. , cationic surfactants can be used.

The oxidized form of the developing agent or the electron transfer agent may migrate between the emulsion layers of the silver halide emulsion of the present invention (between the same color-sensitive layers and/or between different color-sensitive layers), resulting in color turbidity or sharpness. Color antifoggants are used to prevent deterioration and graininess from becoming noticeable.

The color antifoggant may be used in the emulsion layer itself, or in an intermediate layer provided between adjacent emulsion layers.

A hydrophilic colloid layer such as a protective layer or an intermediate layer of a photosensitive material contains an ultraviolet absorber to prevent fogging caused by discharge caused by charging of the photosensitive material due to friction, etc., and to prevent image deterioration due to UV light. Moyo 1%.

The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and/or an antiirradiation layer. These layers and/or the emulsion layer may contain dyes that flow out of the color light-sensitive material or are bleached during development.

A matting agent can be added to the silver halide emulsion grooves and other hydrophilic colloid layers of the light-sensitive material for the purpose of reducing the gloss of the light-sensitive material, increasing the writability, and preventing the light-sensitive materials from sticking to each other.

A lubricant can be added to reduce the sliding friction of the photosensitive material.

An antistatic agent can be added to the photosensitive material for the purpose of preventing static electricity. Antistatic agents are sometimes used in the antistatic layer on the side of the support on which the emulsion is not laminated, and they are also used to protect the emulsion layer and/or the emulsion layer on the side of the support other than the emulsion layer on which the emulsion layer is laminated. It may also be used in colloid layers.

The photographic emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material has the following properties: improving coating properties, preventing static electricity, improving slipperiness, dispersing emulsions, preventing adhesion, and (accelerating development, increasing contrast, sensitizing, etc.) Various surfactants are used for the purpose of improving properties.

The photographic emulsion layer of silver halide emulsion, other layers are baryta layer or paper laminated with α-olefin poly÷-1, etc., flexible reflective support such as R1 paper, cellulose acetate,
It can be applied to films made of semi-synthetic or synthetic polymers such as cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, and polyamide, as well as rigid bodies such as glass, metal, and ceramics.

After subjecting the support surface to corona discharge, ultraviolet irradiation, flame treatment, etc. as necessary, the silver herodenide material of the present invention can be used directly or on the support surface to improve adhesion, antistatic properties, dimensional stability, etc.
It may be applied through one or more subbing layers to improve friction, hardness, antihalation, friction properties, and/or other properties.

When coating the photosensitive material, a thickener may be used to improve coating properties. Particularly useful coating methods are extrusion coating and curtain coating, which allow two or more layers to be applied simultaneously.

The silver halide emulsion of the present invention can be exposed using electromagnetic waves in the spectral region to which the emulsion layer constituting the light-sensitive material of the present invention is sensitive. As a light source, natural light (sunlight),
Tungsten electric lamps, fluorescent lamps, mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, l1fi ray tube flying spots, various laser beams, light emitting lights, electron beams, X-rays, gamma rays, alpha rays, etc. Any known light source can be used, such as light emitted from an excited phosphor.

Exposure times include not only exposure times of 1 millisecond to 1 second that are normally used with cameras, but also exposures shorter than 1 microsecond, such as 100 microseconds to 100 microseconds using a cathode ray tube or xenon flash lamp.
Microsecond exposures can be used, or longer exposures of 1 second or more are possible. The exposure may be performed continuously or intermittently.

The silver halide emulsion of the present invention can be used to form an image by color development known in the art.

The aromatic primary amine color developing agents used in the color developing state of the present invention include known ones that are widely used in various color photographic processes. These developers include aminophenol and 1]-phenylenediamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, since they are more stable than in the free state. Moreover, these compounds are generally used in about 0.1 g to about 30.0 g per 1 unit of color developer. concentration of,
Preferably from about 1 g to about 1.0 g for 1 q of color development 'e.
Use at a concentration of 5.

Examples of aminophenol-based developers include 〇-Ami/
Phenol, p-aminophenol, 5-amino-2-
Oxytoluene, 2-ami/-3-oxytoluene, 2
-oxy-3-amino-1°4-tmethylbenzene and the like.

Especially useful! tS primary aromatic amino color developer contains N,
It is an N'-dialkyl-1)-phenylenecyamine-based compound, and the alkyl group and V-phenyl group may be substituted with any substituent. Among them, a particularly useful compound example is N,N'-diethyl. -p-phenylenediamine [
I[, N-methyl-p-phenylenediamine hydrochloride, N
, N'-tumethyl-1)-phenylenediamine hydrochloride,
2-7mi/-5-(N-ethyl-N-dodecylami/)
-) toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-ami/7niline sulfate, N
-ethyl-N-β-hydroxyethylaminoaniline,
Examples include 4-amino/-3-methyl-N,N'-noethylaniline, 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-p-)luenesulfonate, and the like. can.

In addition to the above-mentioned primary aromatic amine color developer, the color developer used in the processing contains various components that are normally added to color developers, such as sodium hydroxide,
Optionally contain alkaline agents such as sodium carbonate and potassium carbonate, alkali metal sulfites, alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides, benol alcohol, water softeners, thickeners, etc. You can also do it. The pH value of this color developer is
Usually 7 or more, most commonly about 10 to about 13.

In the present invention, after color development processing, T! 1. However, if the processing liquid having the fixing ability is a fixing liquid, a bleaching process is performed before that.

A metal complex salt of an organic acid is used as a bleaching agent in the bleaching process, and the metal complex salt has the effect of oxidizing the metallic silver produced during development and converting it into silver halide, and at the same time coloring the uncolored areas of the coloring agent. It has a structure in which metal ions such as iron, cobalt, and copper are coordinated with amide/polycarboxylic acid or organic acids such as oxalic acid and citric acid.

The most preferred organic acids used to form such organic acid metal complexes include polycarboxylic acids or polycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids are alkali metal salts,
It may be an ammonium salt or a water-soluble amine salt.

Specific representative examples of these include the following.

[1] Ethylenediaminetetraacetic acid [2] Nitrirotriacetic acid [3] Imi7noacetic acid [4] Disodium ethylenecyaminetetraacetic acid [5]
Ethylenenoaminetetraacetic acid tetra(trimethylammonium) salt [6] Ethylenediaminetetraacetic acid tetrasodium salt (7) Di) Lilotriacetic acid sodium salt Bleach solution used The bleach-fix solution is a bleaching agent containing a metal complex salt of an organic acid as described above. It can contain various additives. As additives, it is particularly desirable to include rehalogenating agents, metal salts, and chelating agents such as alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, and ammonium bromide. In addition, pH buffering agents such as borates, oxalates, acetates, carbonates, and phosphates, alkylamines, polyethylene oxides, and other substances known to be added to normal bleaching solutions) are added as appropriate. can do.

Furthermore, the fixer and bleach-fixer contain ammonium sulfite,
Potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, sulfites such as ammonium bisulfite, potassium metabisulfite, sodium metabisulfite, boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, It may contain one or more pH buffers consisting of various salts such as potassium carbonate, sodium bisulfite, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide.

When carrying out the process of the present invention while replenishing the bleach-fix solution (bath) with a bleach-fix replenisher, the bleach-fix solution (bath) may contain thiosulfate, thiocyanate, sulfite, etc. These salts are added to the bleach-fixing replenisher. ! , may be commonly supplemented.

In order to increase the activity of the bleach-fix solution, air or oxygen may be blown into the bleach-fix bath and the bleach-fix replenisher storage tank, if desired, or a suitable oxidizing agent such as peroxide may be added. Hydrogen, bromate, persulfate, etc. may be added as appropriate.

(Effect of the invention) In order to increase the reactivity of the two-equivalent coupler of the invention A, a compound that releases a fogging agent in an imagewise manner was combined to accelerate development, but such a compound cannot be quantitatively controlled. This was a problem because it was subtle and often caused an increase in fog or a decrease in graininess.

Therefore, when a core/shell type silver rhodanide having a high internal silver iodide content was used as a silver halide emulsion,
The imagewise moderate development-inhibiting action of silver iodide was able to suppress the excessive development-promoting action caused by the above-mentioned released fogging agent, thus solving the conventional problems and achieving the above-mentioned object of the present invention. was able to achieve this.

Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

Example 1 (1) Preparation of a core/shell type monodisperse emulsion A silver halide seed emulsion was placed in a reaction vessel containing an aqueous gelatin solution, and was mixed with an aqueous silver nitrate solution while controlling the PAg and pH in the reaction vessel. After adding Tenshinka potassium aqueous solution at the same time while controlling the addition time, Kao Atlas Demol N aqueous solution and magnesium sulfate aqueous solution were added, precipitation desalting was performed, gelatin was added, PAg = 7.8,
The seed particles and the gelatin aqueous solution were prepared by adjusting the pH to 6.0, and then the ammoniacal silver nitrate aqueous solution and Tenshinka potassium aqueous solution were added to the reaction vessel while controlling the PAg and pH in the reaction vessel. The aqueous potassium bromide solution was replaced with a potassium bromide solution or another aqueous potassium bromide solution at an appropriate particle size, added in proportion to the increase in surface area during growth, and subsequently added. In the same way as the seed emulsion, precipitate and desalt, add gelatin, and adjust to PAg 7.8 and pH 6.
, 0 emulsion was obtained. Furthermore, sodium thiosulfate, chloroauric acid and rhodan ammonium were added, and chemical ripening was performed.
-Hydroxy-6-methyl-1,3,3a,7-titrazaindene and 6-nitropenzimidazole were added, and gelatin was further added to obtain a monodisperse core/shell silver iodobromide emulsion. By changing the ratio of potassium iodide and potassium bromide, the silver iodide molar ratio can be changed as shown in Table 1, and by changing the amounts of ammoniacal silver nitrate and potassium halide, the grain size can be changed. and also,
By changing the grain size when changing the potassium iodobromide aqueous solution during silver halide grain growth to a potassium bromide aqueous solution or another potassium iodobromide aqueous solution, the shell thickness is changed as shown in Table 1. Monodisperse emulsion samples A, B, O, D, E, o as shown in the table.

H and I were prepared.

Here, the shell thickness is expressed as a ratio of the shell thickness to the average grain size of monodisperse silver halide grains.

(2) Preparation of tabular emulsion Silver halide emulsion (Tensin silver emulsion containing 7 moles of silver iodide and having an average grain size of 3 μm and an average aspect ratio of 10:1) Similar to that described in JP-A-58-113928. prepared by the method. That is, 5.01 g of a 0.8% gelatin solution containing 59.5 g of potassium bromide was stirred at 80°C by the double jet method to obtain 8.33 g of potassium bromide.
3 m9 of an aqueous solution 5B to which was added and an aqueous solution to which 11.9 g of silver nitrate was added; ffl 58.3 mQ were added at the same flow rate. Next, a solution containing 176 parts of phthalated gelatin 80 parts
0mA was applied. Next, add a silver nitrate solution to a PBr of 1.40.
Added until reaching . Next, potassium iodide 38.79
, 2.61 of an aqueous solution of 3409 of monopotassium bromide was processed by the double jet method to prepare an aqueous solution of 2.61 g containing 525 g of silver nitrate.
1 was added at equal flow rates. During this time, PBr was maintained at 1.40.

After setting the temperature to 40'C and washing the precipitate with water, gelatin was
1, redispersed and solidified at 20°C, 2.0 I
Silver halide emulsion J of Q was prepared.

Silver halide emulsion (silver iodobromide emulsion with an average grain size of 2.8 μm and an average aspect ratio of 7:1, internal silver iodide of 10 moles and external silver iodide of 2 moles) containing 10.7jj of potassium bromide, 5 Stir gelatin aqueous solution 31 at 70°C 11) H5.8,
11.9 mQ of an aqueous solution containing 2.54 g of potassium bromide
and aqueous a11.9+nQ with nitric acid m13.96.9
were added at equal flow rates by double jet method while maintaining PB r 0.9. Next, 2.81 of an aqueous solution containing 33.75 g of silver nitrate and 2.81 g of an aqueous solution containing 214 y of potassium bromide and 33.2 g of potassium iodide were mixed into PBrl.
, 2 were added at equal flow rates by the double jet method. An aqueous solution containing 224.19 silver nitrate in the following 1.9
e and potassium bromide 155.5.9 and potassium iodide 4.
427 was added and an aqueous solution of 1.91 was added at equal flow rates by double jet method while maintaining PBrl and 2 to form tabular grains with a diameter of 2.8 μm, a diameter of 0.4 μm, and an aspect ratio of 7.1. did. Afterwards, the mixture was desalted at 40'C, piratin was added thereto, redispersed, and solidified by cooling at 20'C to obtain 1.5 kg of silver halide emulsion K.

Silver halide emulsion (silver iodobromide emulsion with an average grain size of 2.6 μm and an average aspect ratio of 7:1, internal silver iodide of 2 molar ratio and external silver iodide of 10 molar ratio) containing 50.67j of potassium bromide. , 5 Tigelatin aqueous solution 2.51 was added to it at 65°C while stirring, by the double jet method, while maintaining 9PBr at 0.8, silver nitrate 5.70, l! Aqueous solution containing 7 (solution A)llc
c and potassium bromide4. Aqueous solution containing Og (solution B) li
After adding ce and PBr at equal flow rates, silver nitrate was added and PBr was added at 1.
Adjusted to 4.

Next, a solution containing 590 g of silver nitrate (solution C)・2.5
1 and potassium iodide 14.1 g and potassium bromide 330 g
A solution containing g (solution 1D) 21 was mixed with P by the double jet method.
Br was added at a constant rate while maintaining it at 1.5, and after the addition was completed, PBr was added to 1.5 mQ of solution C and 50 mQ of a solution containing 11.3 g of potassium iodide and 73.0 g of potassium bromide.
It was added at a constant speed by a double jet method while maintaining the temperature at 5. The temperature was set to 40°C, and after washing the precipitate with water, gelatin was added, redispersed, and solidified at 20°C.2. An emulsion of OKg silver halide was prepared.

Example 2 Coating solution (a) was coated on a cellulose triacetate support provided with an undercoat layer so that the amount of silver was 2.25 g/m2, and a protective layer was provided on top of this to obtain sample [1]. Ta.

Coating solution (a): Exemplary coupler (12) 100.9 was dissolved in 100 parts of dibutyl phthalate and 100 parts of ethyl acetate, and the solution was stirred at high speed with 1 kg of a 10% gelatin aqueous solution containing 1 g of sodium dodecylbenzenesulfonate. emulsion 3
50I was mixed with 1 kg of blue sensitized emulsion (C),
A coating solution (a) was prepared by adding 50 mQ of an aqueous solution of 2-hydroxy-4,6-dichloro-8-triazine Na salt as a gelatin hardening agent.

The protective layer was provided by applying an aqueous solution of 5tigelatin to a dry film thickness of 1 μm.

Coating 1 In addition to the coupler in (a), the compound of the present invention shown in the above specific example was added in a 10 molar proportion of the coupler, and the emulsion was changed to A-0.
(b) to (J) were made. Using these coating liquids, samples were prepared in the same manner as Sample [1] 1, and samples were designated as Samples [2] to [10] in accordance with the coatings used.

After the samples [1] to [10] were exposed to white light for sensitometry, they were developed at 38°C in the following processing steps.

(1) Color development...3 minutes 15 seconds (2) Bleaching...6 minutes 30 seconds (3) Water
Washing... 3 minutes 15 seconds (4) Fixing...
... 6 minutes 30 seconds (5) Washing with water ... 3 minutes 15
Seconds (6) Stable... 3 minutes 15 seconds The composition of the processing solution used in each step is as follows.

(Color developer) Sodium nitrite 1.0g Sodium sulfite 4.0. Sodium carbonate 30.0 g Potassium bromide 1.4 g Hydroxylamine sulfate 2.4 g -1-(N-ethyl-N-β-hydroxyethylamino)-2-methyl-aniline sulfate 4.5 g Water 1 plus 11 (bleaching solution) ammonium bromide 160.0,
! 9 Ammonia water (28%) 25.
0 mQ ethylenediamine-tetraacetic acid sodium iron salt 13
0. 9 Glacial acetic acid 14 mQ Add water 11 (fixing solution) Sodium tetrapolyphosphate 2.0.9 Sodium sulfite 4.0 Ammonium thiosulfate:=rum (70%) 175.0
mi! Sodium bisulfite 4.6
g Water was added 11 (stabilizing solution) Formalin 8.0 mQ Water was added 11 The treated sample was measured using blue light. The results obtained are as follows.

Photographic sensitivity was expressed as a relative value, with the exposure amount giving a density of fog +0.3 as 100, which was the white exposure value of sample 1.

The effect of improving image sharpness is due to the MTF (Modu) of the dye image.
transfer function)
Find the frequency when the MTF value becomes 80% (mains/
mm ) were compared using relative values (the comparative sample is set as 100).

In addition, the effect of improving image graininess is that the dye image density is
The relative value (
The comparative sample was set as 100).

From the results in the table above, it can be seen that the additives of the present invention (grades 2 to 10) have higher sensitivity, higher maximum concentration, and smaller increase in capri capri than the comparative samples.

Example 3 Cellulose provided with an undercoat layer) A coating solution (IO was coated on an IJ acetate support so that the silver amount was 2.25 g/m', a protective layer was provided on this, and a sample [11 ] was obtained.

Application 1(k): 100 g of exemplary coupler (27) are dissolved in 10 g of dibutyl phthalate and 100 cr of ethyl acetate, and 1! of sodium dodecylbenzenesulfonate is added. Emulsion 3 obtained by high speed stirring with 11 kg of 10% gelatin aqueous solution containing i
50 g was mixed with 1 kg of blue sensitized emulsion A, and 2-hydroxy-4,6-dichloro0-
3-) Add and apply divalent aqueous solution of riazine Na salt i5Qm9* (10 was made.

The protective layer was provided by applying an aqueous solution of 5tigelatin to a dry film thickness of 1 μm.

Coating liquid (In addition to the coupler in IO, 10% of the compound of the present invention shown in the above specific example was added to the coupler to prepare coating liquids (k) to (1) shown below in the same manner and used the above. Samples [11] to [20] were exposed to white light for sensitometry, and then developed according to the method described in Example 2. Results of measuring the density of the processed samples using blue light is as follows.

From the results in the table above, it can be seen that the samples [12] to [20] of the present invention have higher sensitivity and improved graininess, and have a smaller increase in fog compared to the comparative samples. Sample [21] was prepared by sequentially coating the following layers on a transparent support made of drawn cellulose triacetate film. (Hereinafter, in all Examples, the amount added to the silver halide photographic light-sensitive material was 1 m
2, and silver halide emulsions and colloidal silver are shown in terms of silver. ) Layer 1I Antihalation layer containing 0.3 g of black colloidal silver and 2 g of gelatin.

Layer 2: Intermediate layer containing 1.0 g of gelatin.

Layer 3: Silver iodobromide emulsion with an average silver iodide content of 6 mol%, which was chemically sensitized with gold and sulfur and color sensitized with a sensitizing dye.
A low-sensitivity red-sensitive silver iodobromide emulsion layer (1,5
g of gelatin and 0.9 g of cyan coupler (0-
1) and 0.079 colored cyan coupler (CC
-1) Further contains a high boiling point solvent (HBS-1) of 0.6.9 in which 0.02 g of DIR compound (D-1) is dissolved. ] Layer 4: Gold/sulfur sensitized and dye sensitized emulsion of Table 1 (H
) A highly sensitive red-sensitive silver iodobromide emulsion layer containing 1.5 g of gelatin and a cyan coupler (C-1) of 0.17,!i', a colored cyan coupler (C-1) of 0.03I QC-1) and 0.20 g of high boiling point solvent QH in which 0.02.!7 of DIR compound (D-1) was dissolved.
BS-1). ].

Layer 5I An intermediate layer identical to layer 2.

Layer 6: Low-sensitivity green-sensitive silver iodobromide emulsion layer [1,51 Gelatin, as well as 0
．． 8 g magenta coupler (M-1), 0.12 g colored magenta coupler (CM-1) and 0.02 g
,! 9 (7) 0 in which DIR compound (D-2) was dissolved,
959 high boiling point solvent (HBS-1)].

Layer 7: Gold/sulfur sensitized and dye sensitized emulsion of Table 1 (H
), a high-sensitivity green-sensitive silver iodobromide emulsion layer containing 1,5,9 gelatin, and 0179 magenta coupler (M-1), 0.05,9 colored magenta coupler (CM -1) and 0.0, 3.p high boiling point solvent (H
B, 9-1)].

Layer s: o, 1 g yellow colloidal silver, 0.06 g high boiling solvent (I
(BS-2) and one layer of yellow filter containing 1.5 g gelatin.

Layer 9: A low-speed blue-sensitive silver iodobromide emulsion layer containing 0.9 g of silver iodobromide emulsion containing gold-sulfur sensitized and dye-sensitized 9 molar silver iodide [1,0I of gelatin, and 1
．． 0,3.9 high boiling point solvent (HBS-1) in which 5 g of diro coupler (Y-1) and 0.06 g of DIR compound (D-2) were dissolved].

Layer 10゛ Gold/sulfur sensitized and dye sensitized emulsion of Table 1 (
G) 1. A highly sensitive blue-sensitive silver iodobromide emulsion layer containing OI (1.0p of gelatin and 0.3.9 of a yellow coupler of the present invention (Example 12) and 0.039 of a compound of the present invention (Example 8) Contains a high boiling point solvent (HBS-1) with a concentration of 0.01?

Layer 11: Preservation layer containing 1.5 g of gelatin.

The materials used in this example are as follows.

(C-1) OCH2CONH(CH2)20CH3(CC-1) (t) CsHl.

(J (BS-1) (CM-1) I (M-1) (HQ-1) H (HBS-2) 2H5 2H5 (Y-1) I (D-1) (D-2) Further lowering The samples were coated in the following layer order on a support made of processed cellulose acetate film [
Sample [22] was prepared in the same manner as [21].

Furthermore, Sample [23] was prepared in the same manner as Sample [21] except that the compound of the present invention was removed from layer 10 of Sample [21]. The above samples [21] to (23) were exposed to K white light for sensitometry, and then developed in the same manner as in Example 2. The results obtained by measuring the treated sample using blue light are shown below.

The above results show that samples [21] and [22] of the present invention have higher sensitivity and better sharpness than comparative sample [23], and have less fog.

Claims (1)

[Scope of Claims] A silver halide color photographic material having at least one silver halide emulsion layer on a support, comprising at least one coupler represented by the following general formula [I] and the following general formula [I]. II] in combination, and the silver halide emulsion layer contains core/shell type silver halide grains and/or tabular silver halide grains. Silver halide color photographic material. General formula [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [II] A-B [In the formula, COUP is a yellow dye-forming coupler with one hydrogen atom removed at the coupling position (hereinafter simply Y coupler) X represents a nonmetallic atom group necessary to complete the phenyl nucleus or naphthyl nucleus, and R represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a carboxy group, or a group having a substituent. Alkyl group, cycloalkyl group, alkenyl group, aralkyl group, aryl group, alkoxy group, aryloxy group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylsulfonyl group, arylsulfonyl group group, carbamoyl group, alkylcarbamoyl group, arylcarbamoyl group, alkylcarbonamide group, arylcarbonamide group, sulfonamide group,
Alkylsulfonamide group, arylsulfonamide group, alkylsulfamoyl group, arylsulfamoyl group, alkylsulfinyl group, arylsulfinyl group, phosphinyl group, N-acylcarboimidoyl group, N
-Alkylcarboimidoyl group, N-arylcarboimidoyl group, heterocyclic group, amino group, ureido group, alkylcarbonyloxy group, arylcarbonyloxy group,
Or represents the following general formula [III]. Further, n represents an integer of 0 to 4, and when n is 2 or more, R may be the same or different. General formula [III] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_1 is a halogen atom, a cyano group, a nitro group, a hydroxy group, a carboxy group, an alkyl group that may have a substituent, or a cycloalkyl group, respectively. , aryl group, aralkyl group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, alkylsulfonamide group, arylsulfonamide group, alkylsulfamoyl group, arylsulfamoyl group, alkylcarboxamide group, It represents an arylcarboxamide group, an amino group, an alkylcarbamoyl group, an arylcarbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylcarbonyl group, or an arylcarbonyl group. X_1 represents a divalent organic linking group. l represents 0 or 1, m represents 0, 1, 2, 3 or 4, and m represents 2
In the above cases, R_1 may be the same or different. Further, in the formula, A represents a residue obtained by removing one hydrogen atom from the active position of a compound that can cause a coupling reaction with the oxidized form of a color developing agent, and B represents a residue that is removed by a coupling reaction and then fogged with a developer. Represents a group that exhibits an action. )