JPH0566572B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a multilayer silver halide color photographic light-sensitive material, more specifically, it has good color development, improved color reproducibility, improved image storage stability, and does not disrupt color balance. The present invention relates to a multilayer silver halide color photographic light-sensitive material (hereinafter referred to as a light-sensitive material) containing a combination of a cyan coupler and a magenta coupler. (Background Art) Silver halide color sensitive materials have a multilayer structure consisting of three types of silver halide emulsion layers that are selectively sensitized to have sensitivity to blue light, green light, and red light. coated on a support. For example, in so-called color photographic paper (hereinafter referred to as color paper), a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer are coated in order from the side that is normally exposed, and between each light-sensitive layer. etc., are provided with an intermediate layer that prevents color mixing, a UV absorbing layer, a protective layer, etc. Furthermore, in a so-called color positive film, a green-sensitive emulsion layer, a red-sensitive emulsion layer, and a blue-sensitive emulsion layer are generally coated in order from the side farthest from the support, that is, from the side to be exposed. Color negative films have a wide variety of layer arrangements, and are generally coated in the order of a blue-sensitive emulsion layer, a green-sensitive emulsion layer, and a red-sensitive emulsion layer from the exposed side. In light-sensitive materials having two or more different emulsion layers, there are some light-sensitive materials in which emulsion layers with different color sensitivities are arranged between the emulsion layers, and a bleachable yellow filter layer, intermediate layer, protective layer, etc. are inserted. be done. In order to form a color photographic image, three color photographic couplers of yellow, magenta and cyan are contained in the photosensitive layer, and the exposed photosensitive material is subjected to color development treatment using a so-called color developing agent. The oxidized product of the aromatic primary amine undergoes a coupling reaction with the coupler to give a coloring element, and the coupling rate at this time is as high as possible to give high coloring density within a limited development time.
Those with good color development are preferred. Furthermore, the coloring dyes are all required to be bright cyan, magenta, and yellow dyes with little side absorption and to provide color photographic images with good color reproducibility. On the other hand, the formed color photographic images are required to have good storage stability under various conditions. In order to meet this requirement, the rate of fading or discoloration of chromophores of different hues must be slow, and the rate of fading must be as uniform as possible over the entire image density, so that the color balance of the remaining dye image does not change. is important. Conventional light-sensitive materials, particularly color papers, suffer from severe deterioration of cyan dye images due to long-term fading due to the influence of humidity and heat, which tends to cause variations in color balance, and improvements are therefore strongly desired. Regarding cyan dye images, there have traditionally been strong contradictory tendencies such as resistant to fading and poor hue, and extremely poor photobleaching/photobleaching (temporary cyan discoloration caused by light). , improvements are strongly requested. On the other hand, regarding magenta dye images, in conventional photosensitive materials, especially color papers, magenta dye images derived from the commonly used 5-pyrazolone magenta couplers have sub-absorption near 430 nm, and have sub-absorption at longer wavelengths. Not only is the edge of the 5-pyrazolone coupler not sufficiently cut, and improvements are desired in terms of color reproduction, but also the color fading of the dye image due to light is large, and the stability of the 5-pyrazolone coupler itself to light is insufficient. Yellow staining occurred, and improvements in color image preservation were desired. In order to partially solve these problems, specific combinations of couplers have been proposed in the past, such as Japanese Patent Publication No. 52-7344 and Japanese Patent Application Laid-open No. 57-200037.
Examples thereof are described in No. 59-57238 and Japanese Patent Application No. 58-35178. However, with these combinations, the coloring properties are insufficient, the hue of the coloring dye is poor, causing problems in color reproduction, and the color balance of the remaining dye image changes due to deterioration due to light or heat. However, it has not yet been possible to comprehensively eliminate various disadvantages such as cyan discoloration or temporary cyan discoloration caused by light. (Objective of the Invention) The present invention aims to solve the above-mentioned problems at the same time.More specifically, the object of the present invention is to achieve good color development by a novel combination of cyan and magenta couplers, To provide a multilayer silver halide color photographic light-sensitive material in which the color reproducibility of the obtained color photographic image is improved, the image storage stability is improved, and in particular, the color balance does not change over a long period of time either in the dark or under light exposure. It is in. (Specific Structure of the Invention) The above objects of the present invention are to contain a coupler represented by the following general formula () in the red-sensitive photosensitive layer and a coupler represented by the following general formula () in the green-sensitive photosensitive layer. This was achieved using a distinctive multilayer silver halide color photographic material.

[Formula] General formula () In the formula, R represents a substituted or unsubstituted aliphatic, aromatic, heterocyclic group, or amino group, and W represents at least one hetero atom forming a 5- to 6-membered ring. Z represents a hydrogen atom, a halogen atom, or a coupling-off group.

[Formula] General formula () In the formula, X represents a hydrogen atom or a coupling-off group, and R ¹ represents a hydrogen atom or a substituent.
Za, Zb and Zc represent methine, substituted methine, methylene, substituted methylene, =N- or -NH-, and one of the Za-Zb bond and Zb-Zc bond is a double bond, and the other is a single bond. be. Furthermore, R ¹
Alternatively, X may form a dimer. Also, Za,
When Zb or Zc is a substituted methine, the substituted methine may form a dimer. The cyan dye-forming coupler represented by the general formula () is preferably one represented by the general formula ().

[Formula] General formula () In the formula, R and Z are as described above, V represents a halogen atom and a mono- or divalent organic group, n represents an integer from 0 to 4, and n is 2 or more. When V may be the same or different, they may mutually form a ring. R, V in general formulas () and (),
W and Z will be explained in detail. In the general formulas () and (), R is an aliphatic group having 1 to 22 carbon atoms (e.g., methyl group, butyl group, cyclohexyl group, octadecyl group, octadecenyl group, etc.), an aromatic group (e.g., phenyl group, naphthyl group, etc.) etc.), heterocyclic groups (for example, pyridyl group, pyrimidyl group, imidazoyl group, thiadiazol group, etc.), which may be fused with a benzene ring, etc., and in the case of a fused ring, may be bonded with a hetero ring, may be bonded through a benzene ring, etc.) or an amino group (e.g., anilino group, dibutylamino group, 2-pyridylamino group, etc.), and these represent an alkyl group, aryl group, heterocyclic group, alkoxy group (e.g., methoxy group, 2-
methoxyethoxy group, etc.), aryloxy group (e.g., 2,4-di-tert-amylphenoxy group, 2-chlorophenoxy group, 4-cyanophenoxy group, etc.), alkenyloxy group (e.g., 2
-propenyloxy group), acyl group (e.g.
acetyl group, benzoyl group, etc.), ester group (e.g., butoxycarbonyl group, phenoxycarbonyl group, acetoxy group, benzoyloxy group, butoxysulfonyl group, toluenesulfonyloxy group, etc.), amide group (e.g., acetylamino group, ethylcarbamoyl group, dimethylcarbamoyl group, methanesulfonamide group, butylsulfamoyl group, etc.), sulfamide group (e.g.
dipropylsulfamoylamino group, etc.), imide group (e.g., succinimide group, hydantoinyl group, etc.), ureido group (e.g., phenylureido group, dimethylureido group, etc.), aliphatic or aromatic sulfonyl group (e.g., methanesulfonyl group) , phenylsulfonyl group, etc.), aliphatic or aromatic thio group (e.g., ethylthio group, phenylthio group, etc.), hydroxy group, cyano group,
It may be substituted with a group selected from a carboxyl group, a nitro group, a sulfo group, a halogen atom, etc. In the general formula (), W represents a group of nonmetallic atoms for forming a 5- to 6-membered nitrogen-containing heterocycle containing at least one heteroatom, and examples thereof include the following. −N=CH−CH=CH−,

【formula】

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【formula】

[Formula] −OCH ₂ O−, −OCH ₂ CH ₂ CH ₂ −, −OCH ₂ CH ₂ −,
-O-CH ₂ CH ₂ -O-, etc., the bond direction may be left or right, where R ₂ and R ₃ represent a hydrogen atom, an alkyl group, an aryl group, or an acyl group, and -
The methylene group represented by CH ₂ - and the methine group represented by -CH= may be substituted with a substituent allowed by R, an alkylidene group, an imino group, etc. in place of the hydrogen atom, and these may form a ring. It's okay. In the general formulas () and (), Z represents a hydrogen atom or a coupling-off group, such as a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, etc.), an alkoxy group (e.g.,
ethoxy group, dodecyloxy group, methoxyethylcarbamoylmethoxy group, carboxypropyloxy group, methylsulfonylethoxy group), aryloxy group (e.g. 4-chlorophenoxy group, 4-methoxyphenoxy group, 4-carboxyphenoxy group) enoxy group), acyloxy group (e.g.
acetoxy group, tetradecanoyloxy group, benzoyloxy group, etc.), sulfonyloxy group (e.g., methanesulfonyloxy group, toluenesulfonyloxy group, etc.), amide group (e.g., dichloroacetylamino group, heptafluorobutyrylamino group, methanesulfonylamino group, toluenesulfonylamide group, etc.), alkoxycarbonyloxy group (e.g., ethoxycarbonyloxy 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.), imide group (e.g., succinimide group, hydantoinyl group, etc.) ,and so on. These leaving groups may include photographically useful groups. In the general formula (), V is a halogen atom and a mono- or divalent organic group (examples include permissible substituents for R, an alkylidene group, an imino group, etc.). In the general formula (), n represents an integer from 0 to 4, and when n is 2 or more, V may be the same or different, or may mutually form a ring. In the general formula (), W is preferably nitrogen-containing, and more preferably represented by the general formula (). In the general formulas () and (), Z is preferably a hydrogen atom, a halogen atom, an alkoxy group, or an aryloxy group. In the general formulas () and (), R is preferably an aryl group which may have a substituent. Next, couplers included in general formulas () and () are illustrated below, but the couplers used in the present invention are not limited to these. (C-1)

[Formula] (C-2)

[Formula] (C-3) (C-4) (C-5) (C-6) (C-7) (C-8) (C-9) (C-10) (C-11) (C-12) (C-13)

[Formula] (C-14) (C-15) (C-16) (C-17) Among the 5-5 membered fused nitrogen heterocyclic couplers represented by the general formula (), preferred ones are represented by the following general formulas (), (), (), (), and ().

【formula】

【formula】

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【formula】

[Formula] General formula (), (), (), () and ()
Preferably, R ¹¹ , R ¹² , and R ¹³ each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group,
heterocyclic group, cyano group, alkoxy group, aryloxy group, heterocyclic oxy group, acyloxy group,
Carbamoyloxy group, silyloxy group, sulfonyloxy group, acylamino group, anilino group, ureido group, imide group, sulfamoylamino group,
Carbamoylamino group, alkylthio group, arylthio group, heterocyclic thio group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide group, carbamoyl group, acyl group, sulfamoyl group, sulfonyl group, sulfinyl group, alkoxycarbonyl group, aryl It represents an oxycarbonyl group, and X represents a hydrogen atom, a halogen atom, a carboxy group, or a group that bonds with the carbon at the coupling position via an oxygen atom, nitrogen atom, or sulfur atom and is decoupled. R ¹¹ , R ¹² , R ¹³ or X may be a divalent group and form a bis body. More specifically, R ¹¹ , R ¹² , and R ¹³ are each a hydrogen atom, a halogen atom (e.g., chlorine atom, bromine atom, etc.), an alkyl group (e.g., methyl group, propyl group, t-butyl group, trifluoromethyl group, etc.). basis,
tridecyl group, 3-(2,4-di-t-amylphenoxy)propyl group, 2-[α-(2,4-di-
t-amylphenoxy)octanamide] ethyl group, allyl group, 2-dodecyloxyethyl group, 3
-phenoxypropyl group, 2-hexylsulfonyl-ethyl group, 2-(2-octadecyloxy-
(5-t-octylbenzenesulfonamide) ethyl group, cyclopentyl group, benzyl group, etc.), aryl group (e.g., phenyl group, 4-t-butylphenyl group, 2,4-di-t-amyl phenyl group, 4-tetradecane) amidophenyl group, etc.),
Heterocyclic groups (e.g., 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl, etc.), cyano groups, alkoxy groups (e.g.,
methoxy group, ethoxy group, 2-methoxyethoxy group, 2-dodecyloxyethoxy group, 2-methanesulfonylethoxy group, etc.), aryloxy group (e.g., phenoxy group, 2-methylphenoxy group, 4-t-butylphenoxy group, etc.), heterocyclic oxy groups (e.g., 2-benzimidazolyloxy group, etc.), acyloxy groups (e.g., acetoxy group, hexadecanoyloxy group, etc.), carbamoyloxy groups (e.g., N-phenylcarbamoyloxy group) , N-ethylcarbamoyloxy group, etc.), silyloxy group (e.g., trimethylsilyloxy group, etc.), sulfonyloxy group (e.g., dodecylsulfonyloxy group, etc.), acylamino group (e.g., acetamide group, benzamide group, tetradecaneamide group) group, α-(2,4-
di-t-amylphenoxy)butyramide group, γ
-(3-t-butyl-4-hydroxyphenoxy)
butyramide group, α-{4-(4-hydroxyphenylsulfonyl)phenoxy}decaneamide group,
etc.), anilino group (e.g., phenylamino group,
2-chloroanilino group, 2-chloro-5-tetradecanamideanilino group, 2-chloro-5-dodecyloxycarbonylanilino group, N-acetylanilino group, 2-chloro-5-{α-(3-t -butyl-4-hydroxyphenoxy)dodecaneamide}anilino group, etc.), ureido group (e.g. phenylureido group, methylureido group, N,N-
dibutylureido group, etc.), imide group (e.g.
N-succinimide group, 3-benzylhydantoynyl group, 4-(2-ethylhexanoylamino)
phthalimide group, etc.), sulfamoylamino group (e.g., N,N-dipropylsulfamoylamino group, N-methyl-N-decylsulfamoylamino group, etc.), alkylthio group (e.g., methylthio group, octylthio group, tetradecylthio group, 2-phenoxyethylthio group, 3-phenoxypropylthio group, 3-(4-t-butylphenoxy)propylthio group, etc.), arylthio group (e.g., phenylthio group, -butoxy-5-
t-octylphenylthio group, 3-pentadecylphenylthio group, 2-carboxyphenylthio group, 4-tetradecanamidophenylthio group,
), heterocyclic thio groups (e.g., 2-benzothiazolylthio group, etc.), alkoxycarbonylamino groups (e.g., methoxycarbonylamino group, tetradecyloxycarbonylamino group, etc.), aryloxycarbonylamino groups (e.g. , phenoxycarbonylamino group, 2,4-di-tert-
butylphenoxycarbonylamino group, etc.), sulfonamide group (e.g. methanesulfonamide group, hexadecanesulfonamide group, benzenesulfonamide group, p-toluenesulfonamide group, octadecanesulfonamide group, 2-methyloxy-5 -t-butylbenzenesulfonamide group, etc.), carbamoyl group (e.g., N-ethylcarbamoyl group, N,N-dibutylcarbamoyl group, N-(2-dodecyloxyethyl)carbamoyl group, N-methyl-N-dodecyl group) carbamoyl group, N-{3-(2,4-di-tert-amylphenoxy)propyl}carbamoyl group, etc.), acyl group (e.g., acetyl group, (2,4-di-tert-
amylphenoxy)acetyl group, benzoyl group,
), sulfamoyl group (e.g., N-ethylsulfamoyl group, N,N-dipropylsulfamoyl group, N-(2-dodecyloxyethyl)sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group , N,N-diethylsulfamoyl group, etc.), sulfonyl group (e.g. methanesulfonyl group, octanesulfonyl group, benzenesulfonyl group, toluenesulfonyl group, etc.), sulfinyl group (e.g. octanesulfinyl group, dodecyl group) Sulfinyl group, phenylsulfinyl group,
), alkoxycarbonyl groups (e.g., methoxycarbonyl group, butyloxycarbonyl group, dodecylcarbonyl group, octadecylcarbonyl group, etc.), aryloxycarbonyl groups (e.g.,
phenyloxycarbonyl group, 3-pentadecyloxy-carbonyl group, etc.), and X is linked by a hydrogen atom, a halogen atom (e.g., a chlorine atom, a bromine atom, an iodine atom, etc.), a carboxy group, or an oxygen atom (e.g., acetoxy group, propanoyloxy group, benzoyloxy group, 2,
4-dichlorobenzoyloxy group, ethoxyoxaloyloxy group, pyruvinyloxy group, cinnamoyloxy group, phenoxy group, 4-cyanophenoxyl group, 4-methanesulfonamidophenoxy group, 4-methanesulfonylphenoxy group cy group, α-
naphthoxy group, 3-pentadecylphenoxy group,
benzyloxycarbonyloxy group, ethoxy group, 2-cyanoethoxy group, benzyloxy group,
2-phenethyloxy group, 2-phenoxyethoxy group, 5-phenyltetrazolyloxy group, 2-
benzothiazolyloxy group, etc.), a group linked via a nitrogen atom (e.g. benzelsulfonamide group,
N-ethyltoluenesulfonamide group, peptafluorobutanamide group, 2,3,4,5,6-pentafluorobenzamino group, octanesulfonamide group, p-cyanophenylureido group, N,
N-diethylsulfamoylamino group, 1-piperidyl group, 5,5-dimethyl-2,4-dioxo-3-oxazolidinyl group, 1-benzyl-ethoxy-3-hydantoynyl group, 2N-1,1-dioxo- 3(2H)-oxo-1,2-benzisothiazolyl group, 2-oxo-1,2-dihydro-
1-pyridinyl group, imidazolyl group, pyrazolyl group, 3,5-diethyl-1,2,4-triazol-1-yl, 5- or 6-bromobenzotriazol-1-yl, 5-methyl-1,2, 3,
4-triazol-1-yl group, benzimidazolyl group, 3-benzyl-1-hydantoynyl group,
1-benzyl-5-hexadecyloxy-3-hydantoynyl group, 5-methyl-1-tetrazolyl group, etc.), arylazo group (e.g. 4-methoxyphenylazo group, 4-pivaloylaminophenylazo group) , 2-naphthylazo group, 3-methyl-4
-hydroxyphenylazo group, etc.), groups linked by a sulfur atom (e.g., phenylthio group, 2-carboxyphenylthio group, 2-methoxy-5-t
-octylphenylthio group, 4-methanesulfonylphenylthio group, 4-octanesulfonamidophenylthio group, 2-butoxyphenylthio group,
2-(2-hexanesulfonylethyl)-5-tert
-octylphenylthio group, benzylthio group, 2
-cyanoethylthio group, 1-ethoxycarbonyltridecylthio group, 5-phenyl-2,3,4,
5-tetrazolylthio group, 2-benzothiazolylthio group, 2-dodecylthio-5-thiophenylthio group, 2-phenyl-3-dodecyl-1,2,4
-triazolyl-5-thio group, etc.). In the couplers of general formulas () and (), R ¹² and R ¹³ are bonded to form a 5- to 7-membered saturated ring,
It may form an unsaturated ring or an aromatic ring. When R ¹¹ , R ¹² , R ¹³ or X becomes a divalent group to form a bis body, preferably R ¹¹ , R ¹² , R ¹³
is a substituted or unsubstituted alkylene group (e.g., methylene group, ethylene group, 1,10-decylene group, -
_{CH2CH2 -} O- _CH2CH2- , etc.), substituted or _{unsubstituted} phenylene groups (e.g., 1,4-phenylene group, 1,3-phenylene group,

【formula】

[Formula] etc.), -NHCO-R ¹⁴ -CONH- group (R ¹⁴ represents a substituted or unsubstituted alkylene group or phenylene group, for example -NHCOCH ₂
CH ₂ CONH−,

[Formula], etc.), -S- R ¹⁴ -S- group (R ¹⁴ represents a substituted or unsubstituted alkylene group, for example, -S-CH ₂ CH ₂ -S-,

[Formula], etc.), and X represents the above monovalent group converted into a divalent group at an appropriate position. Among the 5-5 membered fused nitrogen heterocyclic couplers represented by the general formula (), particularly preferred ones are represented by the general formulas () and (). Couplers included in general formula () and general formulas () to () are illustrated below, but are not limited thereto. (M-1)

[Formula] (M-2) (M-3) (M-4) (M-5) (M-6) (M-7) (M-8) (M-9) (M-10) (M-11) (M-12) (M-13) (M-14) (M-15) (M-16) (M-17) (M-18) (M-19) (M-20) (M-21) (M-22) (M-23) (M-24) (M-25) (M-26) (M-27) (M-28) (M-29)

[Formula] Coupler of general formula (), () is JP-A-56-
104333, JP-A-58-105229, and JP-A-59-164554. Couplers of general formula () and general formulas () to () are disclosed in JP-A-59-162548 and RD24222, respectively.
U.S. Patent No. 3725067, Japanese Patent Application Publication No. 171956/1983,
It can be synthesized by the method described in RD24220. The amount of the couplers of the present invention used is 1.times.10.sup.- ³ to 5.times.10.sup. ^- 1 mol, preferably 1.times.10.sup. ^-2 to 5.times.10.sup.- ¹ mol per mol of silver halide. Further, the coupler of the present invention may be mixed with a known coupler described below, but the effect of the present invention is remarkable when the molar ratio of the coupler of the present invention is 20 mol% or more, preferably 40 mol% or more. . The photosensitive material of the present invention is used for color photosensitive materials such as color paper, color reversal paper, color negative film, color reversal film, and color positive film, and is particularly preferred as a printing photosensitive material. In the present invention, the coupler can be introduced into the silver halide emulsion layer using known methods, such as those disclosed in the US Pat.
The method described in No. 2322027 is used. For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, etc.)
dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate),
benzoic acid esters (e.g. octyl benzoate),
Alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, diethyl azelate), trimesates (e.g. tributyl trimesate), etc., or organic solvents with a boiling point of about 30°C to 150°C, e.g. Lower alkyl acetates such as ethyl acetate and butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-
After being dissolved in ethoxyethyl acetate, methyl cellosolve acetate, etc., it is dispersed in a hydrophilic colloid. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be used in combination. Further, the dispersion method using a polymer described in Japanese Patent Publication No. 51-39853 and Japanese Patent Application Laid-open No. 51-59943 can also be used. When the coupler has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution. Binders or protective colloids that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention include:
Although gelatin is advantageously used, other hydrophilic colloids can also be used alone or in conjunction with gelatin. In the present invention, the gelatin may be either lime-treated or acid-treated. For more information about gelatin production, see Arthur Vuis, The Macromolecular Chemistry of Gelatin, (Academic Press,
Published in 1964). Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as silver halide in the photographic emulsion layer of the photographic light-sensitive material used in the present invention. The preferred silver halide is silver iodobromide containing up to 15 mole percent silver iodide. The average grain size of the silver halide grains in the photographic emulsion (the grain size is the grain diameter in the case of spherical or approximately spherical grains, the ridge length in the case of cubic grains,
Expressed as an average based on projected area. ) is not particularly limited, but is preferably 3μ or less. The particle size may be narrow or wide. The silver halide grains in the photographic emulsion may have regular crystal structures such as cubic or octahedral shapes, or may have irregular crystal structures such as spherical or plate shapes, or may have irregular crystal structures such as spherical or plate shapes. It can also be a composite of shapes. It may also consist of a mixture of particles of various crystalline forms. Further, an emulsion may be used in which ultratabular silver halide grains having a grain diameter of five times or more the grain thickness occupy 50% or more of the total projected area. The silver halide grains may have different phases inside and on the surface. Further, the particles may be particles in which the latent image is mainly formed on the surface, or may be particles in which the latent image is mainly formed inside the particles. The photographic emulsion used in the present invention is described in "Chimie et Physique Photography" by P. Glafkides.
Photographique”, Paul Montel
Montel) (1967), GF Duffin (GF
Dtffin), “Photographic Emulsion Chemistry”
Chemistry)”, Focal Press (Focal
Prcss) (1966), VL Zerikmann (V.
“Making and Coating Photographic Emulsion” by L. Zelikman et al.
Emulsion)”, Focal Press (1964)
It can be adjusted using the method described in et al. That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. good. It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).
One type of simultaneous mixing method is a method of keeping pAg constant in the liquid phase in which silver halide is produced, that is,
A so-called controlled double jet method may also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained. Two or more types of silver halide emulsions formed separately may be mixed and used. In the process of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be allowed to coexist. Silver halide emulsions are usually chemically sensitized.
For chemical sensitization, see, for example, H. Frieser, ed.
Grundlagender Photographischen Prozesse
mit Silberhalogeniden”, Akademische Fuerlagsgesellschaft
Verlagsgesellschaft (1968), pp. 675~
The method described on page 734 can be used. That is, sulfur sensitization using sulfur-containing compounds that can react with active gelatin and silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines); reducing substances (e.g., stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds) reduction sensitization method;
Noble metal compounds (e.g., gold complex salts, Pt, Ir,
A noble metal sensitization method using complex salts of metals in the periodic table group such as Pd can be used alone or in combination. The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, amino Triazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), etc.; mercaptopyrimidines; mercaptotriazines; thioketo compounds, such as oxadorinthione; azaindenes, e.g. triazaindenes, tetraazaindenes (especially 4-hydroxy substituted (1,3,
3a, 7) Tetraazaindenes, pentaazaindenes, etc.; many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfonic acid, benzenesulfonic acid amide, etc. can be added. The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material produced using the present invention contains coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and improvement of photographic properties (e.g., development acceleration, high contrast , sensitization)
Various surfactants may be included for various purposes. The photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholins, and quaternary ammonium salts for the purpose of increasing sensitivity, increasing contrast, or accelerating development. compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like. The photographic light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability. For example, alkyl (meth)acrylate, alkoxyalkyl (meth)
Acrylate, glycidyl (meth)acrylate, (meth)acrylamide, vinyl ester (e.g. vinyl acetate), acrylonitrile, olefin, styrene, etc. alone or in combination, or together with acrylic acid, methacrylic acid, α,β-unsaturated dicarboxylic acid, Hydroxyalkyl (meth)
Polymers containing a combination of acrylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, etc. as monomer components can be used. The photographic emulsions used in the present invention may be spectrally sensitized with methine dyes and others. The pigments used include cyanine pigments, merocyanine pigments,
Included are complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of Imidazole nuclei, quinoline nuclei, etc. can be applied.
These nuclei may be substituted on carbon atoms. The merocyanine dye or composite merocyanine dye includes a nucleus having a ketomethylene structure such as a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, A 5- to 6-membered heteroartic ring nucleus such as a thiobarbituric acid nucleus can be applied. These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization. For example, aminostyryl compounds substituted with nitrogen-containing heterocyclic groups (e.g.,
2933390 and 3635721), aromatic organic acid formaldehyde condensates (for example, those described in US Pat. No. 3743510), cadmium salts, azaindene compounds, and the like. The invention is also applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support. A multilayer natural color photographic material usually has at least one each of a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer on a support. The order of these layers can be arbitrarily selected as required. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case. In the same or other photographic emulsion layer or non-light-sensitive layer of the photographic light-sensitive material prepared using the present invention, in addition to the coupler represented by the general formula () or (), other dye-forming couplers may be used, namely: In the color development process, a compound that can develop color by oxidative coupling with an aromatic primary amine developer (for example, a phenylene diamine derivative, an aminophenol derivative, etc.) may be used. For example, magenta couplers include 5-pyrazolone couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, etc., yellow couplers include acylacetamide couplers (e.g. benzoylacetanilides, pivaloylacetanilides), and cyan couplers. As,
These include naphthol couplers and phenol couplers. These couplers are preferably non-diffusible and have a hydrophobic group called a ballast group in their molecules, or are polymerized. The coupler may be either 4-equivalent or 2-equivalent to silver ions. Also, colored couplers that have a color correction effect, or couplers that release a development inhibitor during development (so-called DIR couplers).
It may be. In addition to the DIR coupler, the coupling reaction product is colorless and may contain a colorless DIR coupling compound that releases a development inhibitor.
In addition to the DIR coupler, the light-sensitive material may contain a compound that releases a development inhibitor during development. The coupler of the present invention and the above-mentioned couplers can be used in combination in the same layer in order to satisfy the characteristics required for a photosensitive material, or the same compound can be added in two or more different layers. Of course it doesn't matter. The photographic material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.),
Dioxane derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol, etc.), active halogen compounds (2,3-dihydroxydioxane, etc.), (4-dichloro-6-hydroxy-s-triazine, etc.), mucohalogen acids (mucochloric acid, mucocoenoxychloroic acid, etc.), and the like can be used alone or in combination. In the photosensitive material produced using the present invention, when dyes, ultraviolet absorbers, etc. are contained in the hydrophilic colloid layer, they may be mordanted with a cationic polymer or the like. The light-sensitive material produced using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifoggant. The photosensitive material produced using the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, benzotriazole compounds substituted with aryl groups (such as those described in U.S. Pat. No. 3,533,794), 4-thiazolidone compounds (such as those described in U.S. Pat.
3314794 and 3352681), benzophenone compounds (for example, those described in JP-A-46-2784), cinnamic acid ester compounds (for example, those described in U.S. Pat. No. 3705805 and 3707375), butadiene Compounds such as those described in US Pat. No. 4,045,229 or benzoxide compounds (such as those described in US Pat. No. 3,700,455) can be used. An ultraviolet absorbing coupler (for example, an α-naphthol cyan dye-forming coupler) or an ultraviolet absorbing polymer may be used. These ultraviolet absorbers may be mordanted in specific layers. The photosensitive material produced using the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include
Included are oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful. In carrying out the present invention, the following known anti-fading agents may be used in combination, and the color image stabilizers used in the present invention may be used alone or in combination of two or more. Known antifading agents include hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenols, p-oxyphenol derivatives, and bisphenols. For the photographic processing of the layer consisting of the photographic emulsion produced using the present invention, any of the known methods and known processing solutions, such as those described in Research Disclosure No. 176, pages 28-30, can be applied. can do. The treatment temperature is usually chosen between 18°C and 50°C, but it may also be lower than 18°C or above 50°C. Color developers generally consist of an alkaline aqueous solution containing a color developing agent. The color developing agent is a known primary aromatic amine developer, such as phenylenediamines (e.g., 4-amino-N,N-diethylaniline, 3-methyl-4-amino-N,N-diethylaniline, 4-amino- N-ethyl-N-
β-hydroxyethylaniline, 3-methyl-4
-Amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfamide ethylaniline, 4-amino-3-methyl-N-ethyl-N −
β-methoxyethylaniline, etc.) can be used. In addition, written by LFA Mason,
“Photographic Processing Chemistry”
pp. 226-229 (Focal Press, 1966),
U.S. Patent No. 2193015, U.S. Patent No. 2592364, Japanese Unexamined Patent Publication No. 1973-
Those described in No. 64933 may also be used. Color developers may also contain pH buffering agents such as alkali metal sulfites, carbonates, borates, and phosphates, development inhibitors or antifoggants such as bromides, iodides, and organic antifoggants. can include. If necessary, water softeners, preservatives such as hydroxylamine, organic solvents such as benzyl alcohol and diethylene glycol, development accelerators such as polyethylene glycol, quaternary ammonium salts, and amines, dye-forming couplers, competitive couplers, It may also contain a fogging agent such as sodium boron hydride, an auxiliary developer such as 1-phenyl-3-pyrazolidone, a viscosity imparting agent, a polycarboxylic acid chelating agent, an antioxidant, and the like. After color development, the photographic emulsion layer is usually bleached. The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. As a bleach,
For example, iron (), cobalt (), chromium (),
Compounds of polyvalent metals such as copper, peracids, quinones, nitroso compounds, etc. are used. For example, ferricyanide, dichromate, organic complex salts of iron () or cobalt (), such as ethylenediaminetetraacetic acid, nitrilotriacetic acid,
Complex salts of aminopolycarboxylic acids such as 1,3-diamino-2-propanoltetraacetic acid or organic acids such as citric acid, tartaric acid, and malic acid; persulfates;
Permanganate; nitrosophenol, etc. can be used. Of these, potassium ferricyanide, sodium ferric ethylenediaminetetraacetate, and ammonium ferric ethylenediaminetetraacetate are particularly useful. Ethylenediaminetetraacetic acid iron() complex salts are useful in both stand-alone bleach solutions and single bath bleach-fix solutions. As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used. The fixing solution may contain a water-soluble aluminum salt as a hardening agent. (Examples) The present invention will be explained in more detail by Examples below, but the present invention is not limited thereto. <Example> As described in Table 1, the first layer (lowest layer) to the seventh layer (top layer) were coated on double-sided polyethylene laminated paper to prepare a color photographic material. (Sample A
~M) The coating solution for the first layer was prepared as follows. That is, 100 g of yellow coupler (1) (sample A) or 115 g of yellow coupler (2) (sample B) was dissolved in a mixture of 100 ml of dibutyl phthalate (DBP) and 200 ml of ethyl acetate, and this solution was
% sodium dodecylbenzenesulfonate aqueous solution
This emulsified dispersion was then mixed with 1450 g of a blue-sensitive silver chlorobromide emulsion (80% Br) (containing 66.7 g of Ag) to prepare a coating solution. Coating solutions for the other layers were prepared in the same manner. The hardening agent for each layer is 2,4-
Dichloro-6-hydroxy-s-triazine sodium salt was used. The following spectral sensitizers were used for each emulsion. Blue-sensitive emulsion layer: 3,3'-di-(γ-sulfopropyl)-selenacyanine sodium salt (2×10 ^-4 mol per mol of silver halide) Green-sensitive emulsion layer: 3,3'-di-( γ-sulfopropyl)-5,5'-diphenyl-9-ethyloxacarbocyanine sodium salt (2.5 x 10 ^-4 mol per 1 mol of silver halide) Red-sensitive emulsion layer; sulfopropyl)-9-methyl-thiadicarbocyanine sodium salt (2.5x per mole of silver halide)
(10 ^-4 mol) The following dyes were used as anti-irradiation dyes in each emulsion layer. Green-sensitive emulsion layer; red-sensitive emulsion layer; In Table 1, TOP represents tri(n-octyl phosphate), DBP represents dibutyl phthalate, and the chemical structures of the compounds a to c and the yellow coupler are as follows. a; Cyan coupler b for comparison; Cyan coupler c for comparison;

[Formula] Comparison magenta coupler yellow coupler (1) Yellow coupler (2) After both the green and red layers of these samples were subjected to gradation exposure, the following development process was carried out. Developer solution Nitrilotriacetic acid/3Na 2.0g Benzyl alcohol 15ml Diethylene glycol 10ml Na ₂ SO ₃ 2.0g KBr 0.5g Hydroxylamine sulfate 3.0g 4-amino-3-methyl-N-ethyl-N-
[β-(methanesulfonamido)ethyl]-p-
Phenylenediamine/sulfate 5.0g Na ₃ CO ₃ (monohydrate) 30g Add water to make 1 (PH10.1) Bleach-fix ammonium thiosulfate (70wt%) 150ml Na ₂ SO ₃ 15g NH ₄ [Fe( 55g EDTA・2Na 4g Add water to make 1 (PH6.9) Processing process Temperature Time Developing solution 33℃ 3 minutes 30 seconds Bleach-fix solution 33℃ 1 minute 30 seconds Water Washing 28-35℃ Dry for 3 minutes. For each sample developed in this manner, the reflection density at 420 nm was measured when the magenta density and cyan density were each 1.0. A fading test was also conducted in which each sample was exposed to direct sunlight. The magenta and cyan concentrations were measured using a Macbeth densitometer model RD-514 under green light and red light, and Table 2 shows the concentrations at an initial concentration of 1.0 after the samples were exposed to light for 4 and 8 weeks. The following can be seen from Table 2. It can be seen that when the magenta and cyan couplers of the present invention are used, the reflection spectrum density at 420 nm is significantly reduced. As a result, the saturation of blue color improved, making it less desirable in terms of color reproduction. On the other hand, the photobleaching test of the magenta and cyan layers (respectively
It can be seen that the D _G and D _R values (expressed as D G and D R values) have been improved, and that the combination of both has achieved a balance (the closer the D _G /D _R value is to 1.00, the better). Furthermore, the magenta and cyan dye images of Samples C to F of the present invention hardly change even under high temperature and high humidity.
It was extremely stable.

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Claims (1)

[Scope of Claims] 1. In a multilayer silver halide color photographic material having red-sensitive and green-sensitive photosensitive layers on a support, a cyan coupler represented by the following general formula () is added to the red-sensitive photosensitive layer and the general formula A multilayer silver halide color photographic light-sensitive material, characterized in that a magenta coupler represented by ( ) is contained in a green-sensitive light-sensitive layer. [Formula] General formula () In the formula, R represents a substituted or unsubstituted aliphatic, aromatic, heterocyclic group, or amino group, and W represents at least one hetero atom forming a 5- to 6-membered ring. Z represents a hydrogen atom, a halogen atom, or a coupling-off group. [Formula] General formula () In the formula, X represents a hydrogen atom or a coupling-off group, and R ¹ represents a hydrogen atom or a substituent.
Za, Zb and Zc represent methine, substituted methine, methylene, substituted methylene, =N- or -NH-, and one of the Za-Zb bond and Zb-Zc bond is a double bond, and the other is a single bond. be. Furthermore, R ¹
Alternatively, X may form a dimer. Also, Za,
When Zb or Zc is a substituted methine, the substituted methine may form a dimer.