JPS63165849A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To increase the sensitivity and color density of a cyan image by incorporating a specified phenol type cyan coupler and diffusion resistant carboxylic acids developing no color. CONSTITUTION:A phenol type cyan coupler represented by formula I and diffusion resistant carboxylic acids developing no color are incorporated into at least one layer of a color photographic sensitive material having a multilayered structure. In the formula I, R1 is aryl, a hetero ring or the like, R2 is alkyl, aryl or the like, R3 is H, alkyl or the like and Z is H, halogen or the like. The carboxylic acids include a compd. represented by formula II (where R12 is a group providing diffusion resistance to the compd. represented by the formula II, M<n+> is an H ion, a metallic ion or the like and n=1-4). The coupler and carboxylic acids are preferably incorporated into the red-sensitive emulsion layer. The resulting sensitive material has high sensitivity, exhibits high color developability even in a processing soln. contg. no benzyl alcohol and gives a cyan image whose density hardly lowers or changes even when an exhausted bleaching or bleach-fixing bath is used.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention exhibits high color development, particularly in a processing solution free of benzyl alcohol, and furthermore, it is suitable for use in bleach baths or bleach-fix baths that have been exhausted by running during development processing. The present invention relates to a silver halide color photographic light-sensitive material which provides a cyan image with little reduction in color density or variation even when using a silver halide color photographic material, and which has excellent thermal durability of the cyan image after processing.

(Prior art) After exposing a silver halide light-sensitive material to light, a color development process is performed, whereby a developing agent such as an aromatic-class amine oxidized by silver halide reacts with a dye-forming coupler, resulting in color development. An image is formed. Generally, in this method, a subtractive color reproduction method is often used, and in order to actually reproduce green and red, yellow, magenta and cyan color images, which are complementary colors, are formed, respectively.

As cyan image forming couplers, phenols or 7-tols are often used.

Naphthols are generally not preferred for use in printing sensitive materials because the dyes formed absorb light at long wavelengths, and phenols have generally been used in printing sensitive materials. However, conventionally used cyan couplers, such as U.S. Patent No. z367.531J4 and U.S. Patent No. 2,36Q92,
No. 9, No. 2.42 R730 and No. 2801.17
The 2-7 cylaminophenol cyan coupler described in No. 1 and other publications has problems in that it has poor color image clarity and causes a decrease or fluctuation in cyan image density when used in bleaching or bleach-fixing solutions with weak oxidizing power. was there.

To overcome these drawbacks, U.S. Patent No. 2.772
, No. 162, No. 2.895826, No. 4124396
The 2,5-diacylaminophenol cyan coupler described in No. 1, No. 375a308, and the like was proposed.

It is true that the above-mentioned problems have been improved to a certain extent with these Kabu 2s, but it has become clear that the color development performance, particularly with a developer not containing benzyl alcohol, is insufficient.

On the other hand, Japanese Patent Publication No. 48-40422 claims that an alkyl-substituted phenoxyalkylcarboxylic acid is used as a solvent component of a coupler having an alkyl-substituted phenoxyalkanamide group as a diffusion-resistant group. However, this patent does not make any description of the cyan coupler of the present invention, and in this patent, it is not necessary for the coupler to have an alkyl-substituted phenoxyalkanamide group as in the patent, and furthermore, the carboxylic acid is not required to have an alkyl-substituted phenoxyalkanamide group. It does not need to be a phenoxyalkyl carboxylic acid,
The difference is obvious.

Further, European Patent Publication No. 7λ122 discloses the color development improvement effect and grain size improvement effect of a carboxylic acid compound having an ester group. However, the effect of the present invention can be exerted only by the cyan coupler within the present invention, and the effect can also be exerted by carboxylic acids other than those included in the patent.

(Problem that the invention seeks to solve).

The purpose of the present invention is, firstly, to provide a silver halide color photographic material having a cyan image with high sensitivity and high color density; Another object of the present invention is to provide a silver halide color photographic light-sensitive material that can produce cyan images that do not cause a decrease in color development.The third object is to provide a silver halide color photographic material that can produce cyan images that do not cause a decrease in color development. It is an object of the present invention to provide a color photographic material that provides a cyan image without a decrease in color density or fluctuation even when the color density is changed.

(Means for Solving the Problems) These objects of the present invention are to provide a silver halide color photographic light-sensitive material having a multilayer structure having at least one silver halide emulsion layer on a support. This was achieved in a silver halide color photographic material characterized by containing a phenolic cyan coupler represented by the following general formula (I) and a non-color-forming, diffusion-resistant carboxylic acid.

General formula (I) (wherein R□ represents an alkyl group, a cycloalkyl group, a halogen atom, an alkyl group, or an alkoxy group.

2 represents a hydrogen atom, a halogen atom, or a group capable of being eliminated by reaction with an oxidized product of an aromatic primary amine color developing agent. ) The cyan coupler represented by the general formula (I) used in the present invention will be described in detail below.

R and R2 in the general formula (I) are alkyl groups having 1 to 32 carbon atoms (e.g. methyl group, ethyl group, propyl group, butyl group, pentyl group, tridecyl group, isopropyl group,
cyclohexyl group, allyl group, heptadecenyl group, etc.),
Aryl groups (e.g. phenyl group, naphthyl group, etc.) and heterocyclic groups (e.g. 2-pyridyl group, 2-imidazolyl group,
2-furyl group, 6-quinolyl group, etc.).

These groups can further include alkyl groups, aryl groups, heterocyclic groups, alkoxy groups (e.g., methoxy groups, 2-methoxyethoxy groups, etc.), aryloxy groups (e.g., 2,4
-di-tart-amylphenoxy group, 2-chlorophenoxy group, 4-cyanophenoxy group, etc.), alkenyloxy group (e.g., 2-pronyloxy group, etc.), acyl group (e.g., acetyl group, indiyl group, etc.), Ester groups (e.g., sthoxycarbonyl group, phenoxycarbonyl group, acetoxy group, knzoyloxy group, phthoxysulfonyl group, luenesulfonyloxy group, etc.), amyl group (e.g., acetylamine group, methanesulfonamide group, dipropylene group), pyrsulfamoylamino group, etc.), carbamoyl group (e.g., dimethyl carno 2 moyl group, ethyl carbamoyl group, etc.), sulfamoyl group (e.g., butylsulfamoyl group, etc.), imide 9 group (e.g., succinimyl group, hydantoinyl group, etc.) )
, clay r groups (e.g., phenylureido group, dimethyl clay r group, etc.), aliphatic or aromatic sulfonyl groups (e.g., methanesulfonyl group, phenylsulfonyl group, etc.), aliphatic or aromatic thio groups (e.g., ethylthio It may be substituted with a group selected from a group such as a phenylthio group, a hydroxyl group, a cyano group, a carboxy group, a nitro group, a sulfo group, a halogen atom, etc.

R3 is a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group having carbon a1 to a18 (for example, a methyl group, an ethyl group, an isopropyl group,
cyclohexyl group, dodecyl group, etc.) and carbon number 1 to 18
Alkoxy groups (eg, methoxy, ethoxy, methoxyethoxy, etc.) contain a pulling-off atom. The same applies below), examples of which are: 1 Alkoxy group (e.g., ethoxy group, hyPoxyethoxy group, dodecyloxy group, carboxymethoxy group, methoxyethylcarbamoylmethoxy group, carboxypropyloxy group, methylsulfonylethoxy group) group), aryloxy group (e.g., 4-chlorophenoxy group, 4-methoxyphenoxy group, 4-tert-octylphenoxy group, 4-tert-octylphenoxy group,
-carboxyphenoxy group, etc.), acyloxy group (e.g., acetoxy group, tetrazocallyloxy group, hanzoyloxy group, etc.), sulfonyloxy group (e.g.,
(methanesulfonyloxy group, toluenesulfonyloxy group, etc.), amyl group (e.g., dichloroacetylamino group, heptafluorobutyrylamino group, methanesulfonylamino group, toluenesulfonylamino group, etc.), alkoxycarbonyloxy group (e.g., ethoxy carbonyloxy group, benzyloxycarbonyloxy group, etc.)
, aryloxycarbonyloxy group (e.g., phenoxycarbonyloxy group, etc.), aliphatic or aromatic thio group (e.g., ethylthio group, phenylthio group, tetrazolylthio group, etc.), imir group (e.g., succinimide group, hydantoinyl group, etc.) , an aromatic azo group (for example, a phenylazo group), and the like. These leaving groups may include photographically useful groups.

Next, examples of preferred substituents in the cyan coupler represented by general formula (I) will be described.

Preferred R groups in general formula (I) are aryl groups and heterocyclic groups, such as halogen atoms, alkyl groups, alkoxy groups, aryloxy groups, acylamino groups, acyl groups, carbamoyl groups, sulfonamyl groups, sulfamoyl groups, and sulfonyl groups. , 9 sul7amito groups, oxycarbonyl group,
More preferably, it is an aryl group substituted with a cyano group.

R2 is preferably a substituted or unsubstituted alkyl group or aryl group, particularly preferably a substituted aryloxy alkyl group, and R3 is preferably a hydrogen atom.

2 is preferably a hydrogen atom, a halogen atom (particularly preferably a chlorine atom or a fluorine atom), an alkoxy group or a phenoxy group.

The cyan couplers represented by the general formula (I) are bonded to each other via a divalent or more polyvalent linking group in the substituent R□, R2, R8 or Z to form a dimer or more multimer. may also be R,,R2
, R3 or 2 may be a polymeric coupler that is bonded to the polymer main chain. In these cases,
The number of carbon atoms in each of the above substituents may be exceeded. Polymeric couplers are obtained by polymerizing together the ethylenic double bond sites contained in any of the substituents R1, R2, R3 or Z, and are homopolymers of fan coupler monomers as well as aromatic primary amines. It may also be a copolymer of an oxidized developer and a non-color-forming ethylene-like monomer that does not undergo a coupling reaction.

Acrylic acid, α
- Chloropacrylic acid, α-alkylacrylic acid (e.g. methacrylic acid, etc.) and esters or amide derived from these acrylic acids) # (e.g. acrylamide, n-butylacrylamide, t-butylacrylamide, diacetone) Acrylamide 9, methacrylamide r.

Methyl acrylate, ethyl acrylate), n-propyl acrylate, n-butyl acrylate, t-methyl acrylate), 1so-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate,
Lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β-
vinyl esters (e.g. vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylonitrile, aromatic vinyl compounds (e.g. styrene and its derivatives, vinyl toluene) , cyhinylbenzene, vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ether (
Examples include λ hahinyl ethyl ether), maleic acid, maleic anhydride, maleic esters, N-vinyl-2-pyrrolidone, N-vinylpyridine, and 2- and 4-vinylpyridine. Two or more non-color-forming ethylenically unsaturated monomers may be used together. Examples include n-butyl acrylate and methyl acrylate, styrene and methacrylic acid, methacrylic acid and acrylamide, methyl acrylate and diacetone acrylamide, and the like.

As is well known in the polymer color coupler art, the non-chromogenic ethylenically unsaturated monomer to be copolymerized with the solid water-insoluble monomer Kab2- Properties such as solubility, compatibility with binders such as gelatin of the photographic colloidal composition, its flexibility,
It can be selected so that thermal stability etc. are favorably influenced.

The polymer cassillator used in the present invention may be either water-soluble or water-insoluble, but polymer coupler latex is preferred.

The non-color-forming and diffusion-resistant carboxylic acids used in the present invention are represented by the following general formula (IV).

General formula (IV) (R,2-Coo'), Mne R□, represents a substituent that imparts diffusion resistance to the compound of general formula (IV), and Mne represents a hydrogen ion, a metal ion, or an ammonium ion. where n represents an integer of 1 to 4.

The group represented by R12 that imparts diffusion resistance to the compound of general formula (IV) has a total carbon number of 8 to 40. Preferably 12
to 32, a linear or branched alkynyl group (e.g. methyl group, ethyl group, n-propyl group, n-butyl group,
1so-butyl L n-pentyl ft% n-hephthyl L n-nonyl Ln-'; F-decyl group, n-)lysosyl group, etc.), alkenyl group (e.g. allyl group, decenyl group, to9-decenyl group).

oleyl group, etc.), cycloalkyl group (e.g., cyclopropyl group, cyclointyl group, cyclohexyl group, norbornyl group, etc.), alkynyl group (e.g., pronorgyl group, etc.), aralkyl group (e.g., benzyl group, phenethyl group, etc.), cycloalkenyl group Group 11. cyclopentenyl group, cyclohexenyl group, etc.), aryl group (e.g. phenyl group, α-naphthyl group, β-naphthyl group, etc.) or heterocyclic group (i.e. at least a nitrogen atom, an oxygen atom or a sulfur atom as a hetero atom) A 5- to 7-membered monocyclic or condensed heterocyclic group in which one atom is a ring constituent, such as 2-pyridyl group, 4-pyridyl group, 2-quinolyl group, 2-furyl group, 2-furyl group, -chenyl group, 4-pyrazolyl group, 4-imidazolyl group, etc.), which are substituted so that the total number of carbon atoms is in the range of 8 to 40, and the number of substituents may be one or more. good. (However, among these groups, those having 8 or more carbon atoms may be unsubstituted.) Examples of substituents for these groups include halogen atoms (e.g. fluorine atom, chlorine atom, bromine atom, iodine atom) etc.), nitro group, cyano group, hydroxy group, carboxy group, sulfo group, mercapto group, alkoxy group (e.g. methoxy group, methoxy group, dodecyloxy group, etc.),
Aryloxy groups (e.g. phenoxy group, 2-4-di-tart-inchylphenoxy group, 3-tert-butyl-4-hydroxyphenoxy group, 3-intertadecylkenoxy group, 2-chloro-4-tert- acylphenoxy group, 2-cyanophenoxy group, 4-tert
-octylphenoxy group, 4-ydecyloxyphenoxy group, etc.), alkylthio group (e.g., methylthio group, ethylthio group, to9decylthio group, etc.), arylthio group (e.g., phenylthio group, 4-t"decyl phenylthio group,
4-octyloxyphenylthio group, etc.), alkylsulfonyl group (methylsulfonyl group, benzylsulfonyl group,), decylsulfonyl group 1, arylsulfonyl group (
For example, phenylsulfonyl group, p-)! J sulfonyl group, 4-)"7' sylphenyl sulfonyl group, 4-)
'decyloxyphenylsulfonyl group 71), carbonamide group (e.g. acetamide 0 group, hardenzamide group, N-phenylacetamide 9 group, tetradecanamide group, etc.), sulfonamide group 3 (e.g. methylsulfonamide group, phenylsulfonamide group) 'ts, p-tolylsulfonand group, hexadecylsulfonamino group, anilino group, etc.), carbamoyl group (e.g. carbamoyl group,
N,N-dimethylcarbamoyl group, N-Ydecylcarbazoyl group, etc.), alkoxycarbonyl group (e.g., methoxycarbonyl group, ethoxycarbonyl group, indyloxycarbonyl group, to9decyloxycarbonyl group, etc.),
Aryloxycarbonyl group (e.g. phenoxycarbonyl group, p-”rt-butylphenoxycarbonyl i
s>, acyloxy group (e.g., acetoxy group, etc.), sulfamoyl group (e.g., sulfamoyl group, dimethylsulfamoyl group, dimethylcarbamoyl group, etc.), acyl group (e.g., acetyl group, indiyl group, etc.), imide group (e.g., Kono-Ri). (acid imide 9 groups, etc.), urei r group (e.g. 3
, 3-dimethylurein group, etc.), alkoxycarbonylamino group (e.g., ethoxycarbonylamino group, etc.), aryl group (e.g., phenyl group, p-)'J group, p-methoxyphenyl group, α-su7tyl group , β-su7tyl group, etc.) and heterocyclic groups (e.g. 1-imidazolyl group, 1-pyrazolyl group, 2-pyridyl group, 4-pyridyl group, 2-quinolyl group, 2-furyl group, 2-chenyl group, 1-benzotriazolyl group, phthalimide 9 groups, etc.).

When R1□ is an aryl group, a heterocyclic group, or an aralkyl group, substituents for these groups include, in addition to the above substituents, an alkyl group (e.g., a methyl group, an ethyl group, a 1so-propyl group, a tert-butyl group, tart-pentyl group, t
ert-hexyl group, 1,1.3°3-tetramethylbutyl group, etc.), alkenyl group (e.g. allyl group, hexenyl group, oleyl group, etc.), alkynyl group (e.g. propargyl group, etc.), and cycloalkyl group (e.g. cycloalkyl group) (propyl group, cycloyntyl group, cyclohexyl group, etc.) can be mentioned as examples.

As R□2 of the compound represented by general formula (IV),
An alkyl group substituted with a substituted phenoxy group or an aryl group substituted with a carbonamide group or an alkoxy group is preferred.

Mne is an ion of group 1 of the periodic table (for example, H69, H
ae, niΦ, Cs@, etc.), group II ions (e.g. Mg 28, q, 28, Ba"Φ, etc.), group 1 ions (e.g. F'e2e, Fe3Φ, Co2e, C
o3e.

(N12@, etc.) and ammonium ion is, preferably ions of Group 1, Group 2, and ammonium ions of the periodic table. %, preferably H', Nae, Ke, and NH4e, most preferably HΦ.

Here, R13, R□4, Ryu6, and Rlg are hydrogen atoms, alkyl groups (e.g., methyl, ethyl, t-butyl, etc.), substituted alkyl groups, aralkyl groups (e.g., benzyl, phenethyl, etc.) ), substituted aralkyl group, aryl group (e.g. phenyl group, naphthyl group, etc.) and substituted aryl group, and the number of carbon atoms from R□3 to R□6 does not exceed 20, and between R13 and R16, They may form a ring and may be the same or different.

ζ Here, substituents for alkyl, aralkyl, and aryl groups include nitro group, hydroxyl group, cyano group, sulfo group, alkoxy group (e.g., methoxy group), aryloxy group (e.g., phenoxy group), acyloxy group (e.g., acetoxy group). group), carbonamide group (e.g. acetamide V group), sulfonamide group (e.g. methylsulfonamide 9 group), sulfamoyl group (e.g. methylsulfamoyl group), halogen atom (e.g. fluorine, chlorine, bromine), carboxy group, Carbamoyl group (such as methylcarbamoyl group), alkoxycarbonyl group (
For example, methoxycarbonyl group nato), sulfonyl ts
Examples include methylsulfonyl group. When there are two or more of these substituents, they may be the same or different.

Preferred specific examples of the couplers represented by formula (I) will be shown below, but the invention is not limited thereto.

(C-5) H (C-6) (C-7) (C-8) N (C-9) (C-10) (C-11) (C-12) (C-13) (C-14) vinegar (C-15) (C-17) (C-18) Haruka CR3 (C-19) (C-20) (C-21) (C-24) (“C3H11 (t)C5H11 (C-26) N (C-28) (C-29) (C-30) (t)05H□l 5C2H.

5CH2CH2Co□CH3 (C-34) (The composition ratio is a weight ratio, the same applies hereinafter) (C-35) (C-36) H These phenolic cyankabu 2- represented by the general formula (I) are disclosed in, for example, the US patent ) No. 4454143
No. 67, No. 450Q635 and No. 4557.99
It can be synthesized by the method described in No. 9 and Japanese Patent Application Laid-Open No. 60-24547.

Preferred specific examples of the compound represented by the general formula (f'v') will be shown below, but the invention is not limited thereto.

(A-1) (t)C,H□1 (A-2) (t)05H11 (A-3) (A-4) C□,H3,C00eNHe (A-5) (A-6') ( A-7) (A-8) C1, H3□00011! (A-9 (A-10) (A-11) (A-12) (A-13) (A-14) 0M2-Goon (A-15) (n) H25C□2- CH-C0OHCH2-C00
H C5”1□(I) (A-18) 12H25 (A-19) (A-20) (A-21) (t)05H11 (A-22) (A-23) N (A-24) ( A-25) (A-26) (A-27) (t)C,Hll (A-28) (A-29) (A-30) (t)C5H1l (A-31) (A-32) ( A-33) (A-35) The cyan coupler of the present invention is added to the same layer as the carboxylic acids of the present invention, but the amount of the cyan coupler added is 0.
01-117m2, preferably 0.05-015fi/
m", preferably 0.1 to 0.3117 m2. The carboxylic acids of the present invention have a weight ratio of 0.01 to 100 m" to the cyan coupler of the present invention contained in the same layer.
times, preferably 0.05 to 20 times, more preferably 0.
1 to 5 times.

The cyan coupler of the present invention and the carboxylic acid of the present invention may be used in any layer in the light-sensitive material as long as they are used in the same layer, but they are preferably in the red-sensitive silver halide emulsion layer or its adjacent layer, and more preferably in the red-sensitive silver halide emulsion layer or its adjacent layer. This is a red-sensitive emulsion layer.

The cyan coupler of the present invention can be dispersed and mixed with the carboxylic acids of the present invention alone or in combination of two or more thereof, and can also be used in combination with a conventionally known high-boiling organic solvent as described below.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing about 30 mole or less silver iodide. Particularly preferred are silver bromides containing from about 2 moles of silver iodide to about 25 moles of silver iodide.

Silver halide grains in photographic emulsions include those with regular crystals such as cubes, octahedrons, and tetradecahedrons, those with irregular crystal shapes such as spherical and plate shapes, and those with twin planes. may have crystal defects, or a composite form thereof.

The grain size of the silver halide may be fine grains of about 0.2 microns or less, or large grains with a projected area diameter of up to about 10 microns, and may be a polydisperse emulsion or a monodisperse emulsion.

Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (RD) 1. %17643(
December 1978), pp. 22-23, 1■, Emulsion Production (
Emulsion pre, parition and
types)”, and same/%18716 (I97
November 9), 648 pages, “Physics and Chemistry of Photography” by Grafkide, published by Paul Montell (P, G1afkj4es)
.

Chemic et Ph1sique Photog
raphique, paul mont, el, 19
67), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G,!', Duffin, Photogra
-phic Emulsion Chemistry
(Focal Press.

1966)), “Manufacture and Coating of Photographic Emulsions” by Zelikman.
, 7 Oichi Cal Press (V, L, Zelilcma)
n etal, Making and Coatin
g Photographic Fau'1eion.

Focal Press, 1964).

Monodisperse emulsions such as those described in U.S. Pat. No. 3,574,628, U.S. Pat.

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described by Gutoff, Photographic Inc. Science and Engineering (Gutoff, Photograμc 5cien
ceancl Engineering), Volume 14,
Pages 248-257 (I970): U.S. Patent No. 4434
No. 226, No. 4414310, No. 4433048,
It can be easily prepared by the method described in British Patent No. 4,438,520 and British Patent No. 2,112,157.

The crystal structure may be uniform, the inside and outside may have different halogen compositions, it may have a layered structure, or silver halides with different compositions may be joined by epitaxial bonding. It may also be bonded with a compound other than 710 silver germide, such as silver rhodan or lead oxide.

Also, mixtures of particles of various crystal forms may be used.

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization. Additives used in such processes are listed in Research Disclosure/l6
17643 and 18716, and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant descriptions are shown in the table below.

Additives Class 81 RD17643 RD187
161 Chemical sensitizer page 23 Page 648 right column 2 Sensitivity enhancer Same as above 3
Spectral sensitizers, pages 23-24, page 648, right column - Super sensitizers, page 648, right column 4
Brightener, page 24 5 Anti-fog agent, page 24-25, right column on page 649 - and stabilizer 6 Light absorber, fill, page 25-26, right column on page 649 - Tardye, page 650, left column Ultraviolet absorber 7 Anti-stain agent Page 25, right column, page 650, left to right column 8
Dye image stabilizer page 25 9 Hardener 26 members page 651 left image 10 Binder page 26 Same as above 1
1 Plasticizers, lubricants Page 27 650 Right column 12 m Fabric aids, different surfaces Pages 26-27 Same as above Various color couplers can be used in the present invention,
A specific example is the research disclosure (RD) mentioned above.
)/l617643, ■-〇-G.

As a yellow coupler, for example, US Pat. No. 3933
No. 501, No. 4022.620, No. 432 02
No. 4, No. 4401.752, Special Publication No. 58-1073
9, British Patent No. L42 to 020, British Patent No. L47676
Those described in No. 0, etc. are preferred.

As magenta turnip 2-, 5-pyrazolone and pyrazoloazole compounds are preferred, and US Pat. No. 431Q
No. 619, No. 4351.897, European Patent No. 7a6
No. 36, U.S. Patent No. 306L432, U.S. Patent No. 72
No. 67, Research Disclosure 24220 (
June 1984), JP-A No. 60-33552, Research Disclosure/1624230 (I984
(June), Japanese Patent Application Publication No. 60-43659, U.S. Patent No. 45
Particularly preferred are those described in No. 0Q630 and No. 454Q654.

Examples of cyan couplers include phenolic and naphthol couplers, such as U.S. Pat. No. 4052.212, U.S. Pat.
Same No. 429@200, No. 236a929, No. 280
No. 1.171, No. 2.895826, No. 1774
002, US Patent No. A44%622, US Patent No. 433-999, US Patent No. 4451.559, US Patent No. 4427.7
67, European Patent No. 16λ626A, etc. are preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are available from Research Disclosure Scrap 17643.
-G section, U.S. Patent No. 4163670, Japanese Patent Publication No. 1983-3
9413, U.S. Patent No. 4004929, U.S. Patent No. 413
Preference is given to those described in British Patent No. 1.14a368.

Couplers whose coloring dyes have appropriate diffusivity include U.S. Patent No. 4,366,237 and British Patent No. 2,12457.
No. 0, European Patent No. 94570, West German Patent (Publication) No. 3
．． The one described in No. 234533 is preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat.
It is stated in the number etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. Current inhibitor releasing DIR couplers include RD17643, previously described;
Patent listed in Section W-1, JP-A-57-151944
Preferred are those described in No. 57-154234, No. 60-184248, and US Pat. No. 424a962.

As a coupler that releases a nucleating agent or a development accelerator imagewise during development, British Patent No. 2.097゜140;
No. 2,131,188, I? iF Kaisho 5 Kaikai 157
Those described in No. 638 and No. 59-170840 are preferred.

Other couplers that can be used in the photosensitive material of the present invention include competitive couplers described in U.S. Pat. No. 413Q427, etc., U.S. Pat.
&393, 431Q618, etc., DIR redox compound releasing couplers described in JP-A-60-185950, etc., European Patent No. 173302
Examples include couplers that release a dye that recovers color after separation as described in Item A.

The couplers used in the present wAK can be introduced into photosensitive materials by various known dispersion methods.

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027 and the like.

The steps and effects of latex dispersion methods and specific examples of latex for impregnation are described in U.S. Pat.
No. 541,230, etc.

Suitable supports that can be used in the present invention are described, for example, in the above-mentioned RD, shoulder 17643, page 28, and the same layer 18716, page 647 right column to page 648 left column.

The color photographic material according to the present invention includes the above-mentioned RD, /
% 17643, pages 28 to 29, and the same layer 18716, 651 left column to right column.

The color photographic material of the present invention is usually subjected to a water washing treatment or a stabilization treatment after development, bleach-fixing or fixing treatment.

In the washing process, two or more tanks are generally used for countercurrent washing to save water. As a stabilizing treatment, water washing process water DK is used.
A typical example is a multistage countercurrent stabilization treatment as described in JP-A-57-8543.

(Examples) The present invention will be explained in detail below using Examples, but the present invention is not limited thereto.

Example 1 A multilayer color photographic material 101 was prepared by coating the first layer (bottom @) to the seventh layer (top layer) shown in Table 1 on a paper support laminated on both sides with polyethylene. Sodium 2-oxy-4,6-dichloro-5-triazine was used as the gelatin hardening agent for each layer.

(Samples 102 to 114) The cyan coupler (k) of Sample 101 was replaced by 1 in an equimolar amount, and the compound of the present invention was added to the fifth layer in an amount of 0.07. l
Samples 102 to 114
It was created.

These samples were subjected to imagewise exposure and the following color development was performed.

Processing (a) Bleach fixing 33℃ 1 minute 30 seconds washing
Drying at 24-34°C for 3 minutes 80°C 1. The components of the published treatment solution are the following.

Diethylenetriaminepentaacetic acid 3.0
II Benzyl Alcohol 1
5-Diethylene glycol 10-Sodium sulfite 2.
0g fruit potassium
o, s g potassium carbonate
30.0gN-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 5.09
and droxyamine sulfate 4.0
g Fluorescent brightener (4,4'-distilbene type)
Add 1.0g water 1
000d (pH (zs℃): 10.10) Bleach-fix solution: Water 400
+gj thiosulfurized ammonium A (70111 liquid)
150Wll sodium sulfite
189 Iron (III) ethylenediaminetetraacetate Ammonium 55II Ethylenediaminetetraacetate 2Na 5y The following spectral sensitizers were used for each emulsion.

Blue-sensitive emulsion layer; (Addition of 10-' mol of b4.Ox per 1 mol of silver halide.) Green-sensitive emulsion layer; (Addition of 3. oxto-' mol per 1 mol of silver halide.) (91.0 x 10 moles added per mole.) The following dyes were used as the dyes for preventing staining in each emulsion layer.

Green-sensitive emulsion layer: The structural formulas of the compounds used in this example, such as couplers, are as shown below.

H 1:5:3 mixture (molar ratio) of 0H (j) (iao CgHlgO(P-0 (k) E3 ji3 02H.

[2f15 Table 2] In addition, a color developer obtained by removing indyl alcohol from the color developer (A) was treated as a treatment (B).

Furthermore, the above bleach-fix solution was continuously processed with 7 Dicolor ENO (manufactured by Fuji Photo Film Co., Ltd.) using an automatic color developing machine, and the processed solution in a steady state was used as a forced deterioration bleach-fix solution.

Table 2 shows the layer fruits obtained using these treatment solutions.

Table 2 shows that the samples of the present invention have little dependence of color development on processing with and without benzyl alcohol, have high sensitivity in both cases, and show almost no decrease in density even when a forced deterioration bleach-fix solution is used. it is obvious.

Claims (1)

[Scope of Claims] A multilayered silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, in which at least one layer contains a phenolic cyan coupler represented by the following general formula (I). and a silver halide color photographic light-sensitive material characterized by containing a non-color-forming and diffusion-resistant carboxylic acid. General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. (R_3 represents a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group. Z represents a hydrogen atom, a halogen atom, or a group that can be separated by reaction with an oxidized product of an aromatic primary amine color developing agent.)