JPS62180365A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a cyan color image causing little secondary absorption of magenta, not lowering the density or contrast even in a bleach-fixing bath of a low pH and having satisfactory shelf stability by incorporating two kinds of specified couplers into photosensitive layers having different color sensitivities. CONSTITUTION:This silver halide color photographic sensitive material having red-, green- and blue-sensitive photosensitive layers on the support contains a coupler represented by formula I and a coupler represented by formula II in photosensitive layers having different color sensitivities. In the formula I, R1 is -CONR3R4, -NHCOR3, -NHCOOR5, -NHSO2R5, -NHCONR3R4 or -NHSO2NR3R4, R2 is a group substitutable on the naphthol ring, m is an integer of 0-3, X is >O, >S or R6N< and Y1 is H or a group (atom) eliminable by a coupling reaction with the oxidized product of an aromatic primary amine developing agent. In the formula II, R10 is H or a substituent (atom), Y2 is H or a group (atom) eliminable by a coupling reaction with the oxidized product of an aromatic primary amine developing agent and each of Za-Zc is methine, substituted methine, =N- or -NH-. The coupler represented by the formula I, the coupler represented by the formula II and an arbitrarily selected yellow coupler are combined with silver halide emulsion layers having different color sensitivities and the couplers may be used in combination with a fading inhibitor or an antioxidant.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, it has improved color reproducibility, reduced variation in development processing, and shortened development time. This invention relates to silver halide color photographic materials.

(Background technology) Silver halide color photosensitive materials (hereinafter referred to as photosensitive materials) are -
A photosensitive layer consisting of three types of silver halide emulsion layers selectively sensitized to be sensitive to evening light, green light, and red light is coated on a support in a multilayer configuration. for example,
With color photographic paper, red sensitivity, red sensitivity,
Green-sensitive and blue-sensitive emulsion layers are coated, and furthermore, an intermediate layer or protective layer having color mixing prevention properties or ultraviolet absorbing property is provided between the emulsion layers having different color sensitivities. The general layer arrangement of a color negative film consists of blue-sensitive, green-sensitive, and red-sensitive emulsion layers coated in order from the exposed side, followed by a bleachable yellow filter layer or antihalation layer, an intermediate layer, and a protective layer. Layers etc. are added according to various aspects. In high-sensitivity photographic materials, it is common practice to provide two or three silver halide emulsion layers with the same color sensitivity and different sensitivities in order to improve sensitivity and graininess. However, the specific layer arrangement can be freely changed.

Force 2 - In order to form photographic images, the additive color method and the subtractive color method can be broadly classified, and the latter method usually produces yellow,
A photographic coupler that develops three colors, magenta and cyan, is contained in the photosensitive layer, and the image-exposed photosensitive material is subjected to color development processing using a color developing agent.

During color development, an oxidative coupling reaction occurs between the aromatic primary amine of the color developing agent and the photographic coupler, and as a result, an indophenol-based or azomethine-based chromophore is produced. In this case, it is preferable that the coupling rate be as high as possible, that is, a photographic coupler with good color forming properties that can provide high color density within a limited development time is preferable. Furthermore, in order to obtain a color photographic image with good color reproducibility, it is essential that the chromophore be a bright cyan, magenta, or yellow dye with little side absorption. In particular, efforts have been made to reduce the magenta or yellow unnecessary absorption of colored cyan dyes, or the yellow unnecessary absorption of magenta dyes, but the results have been limited, and colored couplers, such as magenta coloring, have been unavoidable to offset the side absorption. In reality, a cyan coloring coupler or a yellow colored magenta coloring coupler is used in combination. Since this so-called color masking method has the disadvantage of long exposure times when printing negative film onto color photographic paper, there is a need for new combinations of cyan and magenta couplers that can reduce or eliminate color masking.゛In order to achieve even better color reproduction, it is essential to vividly reproduce the primary colors on color photographic paper, and for this purpose development inhibitor release (hereinafter the commonly used abbreviation "DIR") is used. It takes advantage of the coupler's glabellar layering effect. In other words, primary color objects such as blue, green, red or yellow, magenta, and cyan are different from gray objects, and the sensitivity of the blue, green, and red layers is not the same in the three layers, and DIR occurs during color development. The development inhibitor released from the coupler strongly inhibits the development of the less developed emulsion layer, and as a result, the primary colors are finally reproduced vividly on the color print.

The trade-off for improved color reproduction with DIR couplers is development lag due to the action of development inhibitors. Therefore, there is a need for a novel combination of Kircian and magenta couplers that reduces the amount of DIR couplers so that the development process can be shortened and uneven development does not occur even during short processing times.

Nowadays, there is a strong desire to improve the storage stability of negative films, and conventional naphthol-based cyan couplers, which have little side absorption but low fastness, have the disadvantage of decreasing density and softening in the fixing whitening bath, but have the advantage of high color development. This is the opposite. Cyan couplers based on 5-diacyl amino can be preferably used because they do not exhibit the above-mentioned drawbacks in fixing and bleaching baths; however, couplers with this structure have a large amount of magenta side absorption, and an improved cyan coupler is desired.

(Problems to be Solved by the Invention) The present invention attempts to solve the above-mentioned problems of silver halide color photographic light-sensitive materials.

The first object of the present invention is to provide a silver halide color photosensitive material that exhibits little magenta side absorption and provides a cyan image that has good storage stability and does not deteriorate in density or soften even in a fixing bleaching bath with a low pH. Second, the purpose is to provide a silver halide color sensitive material that can improve the color reproducibility of colorants due to the small side absorption of cyan and magenta color pigments, and thirdly, the DIR
To provide a color photosensitive material having a novel combination of cyan and magenta, which can improve color reproduction by using only a small amount of coupler, shorten development time, and reduce variation in development.

(Means for Solving the Problems) The present invention has been made for the purpose of solving the above problems, and the means for this purpose is to provide a silver halide color photographic light-sensitive material as described below. A silver halide color photographic light-sensitive material having red-sensitive, green-sensitive and blue-sensitive photosensitive layers on a support, comprising a coupler represented by the following general formula (I) and a coupler represented by the general formula (n). A silver halide color photographic light-sensitive material, characterized in that silver halide is contained in photosensitive layers having mutually different color sensitivities.

In general formula (I), R□ is -CONR3R4, -1c
OR-NI(COOR-NH8O2R5,315l-NHCONRRtTach-NH8O2R3R4L,
R2 represents a group that can be substituted on the naphthol ring, m represents an integer from 0 to 3, and X represents /"s/St or R6N,
, Y□ is a hydrogen atom or a group (including a removable atom) that can be separated by a coupling reaction with an oxidized aromatic primary amine developer; 'f: represents. However, R3 and R4 may be the same or different, and independently represent a hydrogen atom,
It represents an aliphatic group, an aromatic group or a heterocyclic group, R5 represents an aliphatic group, an aromatic group or a heterocyclic group, and R6 represents a hydrogen atom or a monovalent organic group. When m is 2 or 3, R2 may be the same or different, or may be bonded to each other to form a ring. R2 and Xl or X and Y
D and may be combined with each other to form a ring.

Furthermore, R1, R2, X or Y□ may form a dimer or higher multimer.

In general formula (I[), Ro. represents a hydrogen atom or a substituent (including substituent atoms), and Y2 includes a hydrogen atom or a coupling-off group <m deatomization. The same applies hereinafter), and Za, Zb and Zc are methine.

Represents substituted methine, =N- or -NH-. Za-Z
One of the b bond and the Zb-Zc bond is a double bond,
The other is a single bond. When Z b -Z c is a carbon-carbon double bond, it includes the case where it is a part of an aromatic ring. further KRlo, Y2 and Za representing substituted methine;
Dimers or higher multimers may be entirely formed by one group in the group Zb or Zc.

Here, the aliphatic group refers to a linear, branched, or cyclic alkyl group, alkenyl group, or alkynyl group, and may be substituted or unsubstituted. The aromatic group refers to a substituted or unsubstituted aryl group, and may be a condensed ring. The term "heterocycle" refers to a substituted or unsubstituted, monocyclic or fused ring heterocyclic group.

General formula [I] will be described in detail below.

The photographic coupler represented by the general formula (I) is a cyan dye-forming coupler, and may be used alone or in combination of two or more.

R is -CONR3R4, -[ICOR3, -N)ICO
OR5, -NH8O2R5, -NHCONR3R4 or -NH3O2 dish 3R4 is shown. Examples of RR and R5 include aliphatic groups having 1 to 30 carbon atoms, aromatic groups having 6 to 30 carbon atoms, and heterocyclic groups having 2 to 30 carbon atoms. R
3 and R4 may each be a hydrogen atom.

R2 represents a group (including an atom, the same applies hereinafter) that can be substituted on the naphthol ring, and typical examples include a halogen atom, a hydroxy group, an amino group, a carboxyl group, a sulfonic acid group, a cyano group, an aliphatic group, an aromatic group, Heterocyclic group, carbonamide group, sulfonamide 9 groups, carbamoyl group, sulfamoyl group, ureido 9 groups, acyl group, acyloxy group, aliphatic oxy group, aromatic oxy group, aliphatic thio group, aromatic thio group, aliphatic Examples include a group sulfonyl group, an aromatic sulfonyl group, a sulfamoylamino group, a nitro group, and an imide 9 group, and the number of carbon atoms contained in R2 is 0-30, and groups having a hydrogen atom include these. may be substituted with a substituent. An example of cyclic R2 when m=2 is a dioxymethylene group.

X represents >0, 'X/S or R,N<, and R6 represents a hydrogen atom or a monovalent organic group. The organic group of 11i11i is preferably R7(Y
3) 1- (In) where Y3 is 〉l,
] indicates CO or SO□, l indicates zero or one gold,
R7 is a hydrogen atom, an aliphatic group having 1 to 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms, a heterocyclic group having 2 to 30 carbon atoms, -0
R3, R3 and R4 represent the groups defined above and may be present.

In R□ or R7, R3 and R of -NR3R4
4 may be bonded to each other to form a nitrogen-containing heterocycle (morpholine ring, piperidine ring, pyrrolidine ring, etc.).

Y□ represents a hydrogen atom or a coupling-off group (including a leaving atom; the same applies hereinafter). Typical examples of coupling-off groups include a halogen atom, an aromatic azo group of -0R8,6-30, and an atomyl ring group having 1 to 30 carbon atoms and linked to the coupling active position of the coupler with a nitrogen atom. Ugly imide group, phthalimide; r, , l-hydantoinyl group, 1-pyrazolyl group, 2-benzotriazolyl group, etc.). Here, R8 has 1- carbon atoms.
It represents an aliphatic group having 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms, or a heterocyclic group having 2 to 30 carbon atoms.

In the present invention, the aliphatic group may be saturated or unsaturated, substituted or unsubstituted, linear, branched, or cyclic,
Typical examples include methyl group, ethyl group, methyl group, cyclohexyl group, allyl group, propargyl group, methoxyethyl group, n-f group, n-dovucyl group, n-hexadecyl group, trifluoromethyl group. , hezotafluoropropyl group, bidecyloxypropyl group, 2.4-di-tθrt-amylphenoxypropyl group, 2.4-di-t-1rt-amylphenoxybutyl group, and the like.

Further, the aromatic group may be substituted or unsubstituted,
Typical examples include phenyl group, tolyl group, 2-tetradecyloxyphenyl group, and hantafluorophore! ,
2-chloro-5-)"r' syloxycarbonylphenyl, M, 4-chlorophenyl group, 4-cyanophenyl group, 4-hydroxyphenyl group, and the like.

In addition, the heterocyclic group may be substituted or unsubstituted,
Typical examples include 2-pyridyl group, 4-pyridyl group, 2-furyl group, 4-chenyl group, yanolinyl group, and the like.

When the aliphatic/aromatic or heterocyclic group has one or more 112 substituents, the substituent may further have one or more substituents.

All preferred substitution methods in the present invention will be explained below. R
-CONR3R4 is preferred for engineering, especially R3 and 1,
It is preferable that one of them is a hydrogen atom.

Specific examples include carbamoyl group, ethylcarno dimoyl group, morpholinocarbonyl group, todecylcarnomoyl group, hexadecylcarbamoyl group, decyloxypropylcarbamoyl group, dobutyloxypropylcarbamoylmilphenoxypropylcarbamoyl group, 2.4-cypropylcarbamoyl group, 18rt-Amylphenoxybutylcarbamoyl group etc. are removed for 2 hours.

For R, , m, m=Q, that is, unsubstituted −
The most preferred substituent is R2, and relatively preferred substituents include a halogen atom, an aliphatic group, a carbonamide group, and a sulfonamide group.

A favorable X is R6<, where R6 is -CO
R7 (formyl group, acetyl group, trifluoroacetyl group, chloroacetyl group, benzoyl group, hantafluorobenzoyl group, p-chlorobenzoyl group, etc.), -G
OOR3 (methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, decyloxycarbonyl group, methoxyethoxycarbonyl group, phenoxycarbonyl group), -So2R7 (methanesulfonyl group, ethanesulfonyl group, butanesulfonyl group, hexatecanesulfonyl group) , henzenesulfonyl group, toluenesulfonyl, JJ, p-10robenzenesulfonyl group, etc.), -
CONR3R4 (N, N-dimethylcarbamoyl group, N*N-diethylcarbamoyl group, LN-dibutylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group, 4-cyanophenylcarbamoyl group,
'54=)chlorophenylcarbamoyl group, 4-methanesulfonylphenylcarbamoyl group, etc.), -SO2N
R3R4 (N, N-dimethycncor7 and)
It is NSO2R7. Here, R3 and R4 have the same meanings as before.

Preferred examples of Y include hydrogen atom, )-rogen atom (e.g., chlorine atom, fluorine atom, bromine atom, iodine atom, etc.)
, aliphatic oxy group (e.g. 2-hydroxyethoxy group,
2-chloroethoxy group, carboxymethyloxy group, 1
-carboxyethoxy group, 2-methanesulfonylethoxy group, 3-levoxypropyloxy group, 2-methoxyethoxycarbazoylmethyloxy group, 1-carboxytritecyloxy group, 2-(1-carboxytridecyl thio)ethyloxy group, 2-carboxymethylthioethyloxy group, 2-methanesulfonamidoethyloxy group, etc.), aromatic oxy group (e.g. 4-acetamido9
Phenoxy group, 2-acetamidophenoxy group, 4-(
3-carboxypropanamide 4) Phenoxy group, 4-
mesylphenoxy group, etc.), and heterocyclic thio groups (e.g., 1-phenyltetrazol-5-ylthio group, -ethyltetrazol-5-ylthio group, 1-phenylimidazol-2-ylthio group, 4-pyridylthio group, etc.). .

The coupler represented by general formula (1) has substituents R1, R2
. In this case, the carbon number range shown in each of the above-mentioned substituents may be outside the specified range.

When the coupler represented by general formula (1) forms a multimer, a typical example is a single or copolymer of an addition-polymerizable ethylenically unsaturated compound (cyan color-forming monomer) containing a cyan dye-forming coupler residue. . In this case, the multimer contains a repeating unit of the general formula (IV), and the multimer contains a repeat unit of the general formula (IV).
) may contain one or more types of cyan color-forming repeating units in the polymer, even if the copolymer contains one or more non-color-forming ethylene-like monomers as a copolymerization component. good.

In the formula, R0 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a chlorine atom, A represents 100Nkl-1-COO- or a substituted or unsubstituted 7-enylene group, and B represents a substituted or unsubstituted 7-enylene group. Substituted alkyl q, phenylene group or aralkylene group, Z is -CONri-, -NHCO
Nll-, -NhCOO-1-NHCO-1-(JC
ONfi-1-1'1i(-,-COO-1-t)CO
-, -Co-.

=-, -8Q2-, -tqH8o2- or -SO28H-. Indicates 0% bs ctj, o or 1. Q is a hydrous cyan coupler residue in which a hydrogen atom other than the hydrogen atom of the hydroxyl group at position 91 is removed from the compound represented by the general formula (1), and preferably substituents R1, R2, and X in the compound represented by the general formula (1). Or a cyan coupler residue containing water with one hydrogen atom removed from Yl.

As the multimer, a copolymer of a cyan color-forming monomer providing a coupler unit of the general formula (IV) and a non-color-forming ethylene-like monomer shown below is preferred.

Examples of non-chromogenic ethylene-like monomers that do not couple with the oxidation products of aromatic-grade amine developers include acrylic acid,
α-chloroacrylic acid, α-alkylacrylic acid (e.g. methacrylic acid, etc.) Esters or amides derived from these acrylic acids (e.g. acrylamide, methacrylamide a, n-butylacrylamide, diacetone acrylamide, methylene Bisacrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate), 1so-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate , n-butyl methacrylate and β-hydroxy methacrylate), vinyl esters (e.g. vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylateryl, aromatic vinyl compounds (e.g. styrene and its derivatives, e.g. vinyltoluene, cyhinylbenzene) , vinylacetophenone and sulphostyrene), itaconic acid, citraconic acid, croton ν, vinylidene chloride, vinyl alkyl ethers (e.g. vinyl ethyl ether), maleic acid esters, N-vinyl-2-pyrrolido-9, N-vinylpyridine and −
and 4-vinylpyridine.

Particularly preferred are acrylic esters, methacrylic esters, and maleic acid esters. Two or more of the non-color-forming ethylene pigments used here can also be used together. For example, methyl acrylate and butyl acrylate, butyl acrylate and styrene, butyl methacrylate and methacrylic acid, methyl acrylate and diacetone acrylamide, etc. can be used.

As is well known in the field of polymer additives, the ethylenically unsaturated monomer to be copolymerized with the vinyl monomer corresponding to the above general formula [■] depends on the physical properties and/or chemical properties of the copolymer to be formed. physical properties, such as solubility, compatibility with the binder of the photographic colloid composition, such as gelatin, its flexibility,
It can be selected so that thermal stability etc. are favorably influenced.

Cyan polymer coupler used in the present invention (oleophilic polymer coupler obtained by polymerizing a vinyl monomer to provide a coupler unit represented by the above general formula (IV))
It may be made by dissolving it in an organic solvent and emulsifying and dispersing it in the form of latex in an aqueous gelatin solution, or it may be made directly by emulsion polymerization.

U.S. Patent No. 34S describes a method for emulsifying and dispersing lipophilic polymer couplers in an aqueous gelatin solution in the form of latex.
No. L820, and U.S. Patent No. 408Q for emulsion polymerization.
The method described in No. 211 and A37Q952 can be used.

Next, the general formula [dragon] will be explained in detail.

General formula (It) represents a magenta dye-forming coupler having a pyrazoloazole skeleton.

In the general formula (II), Rlo represents any group that can be substituted at the 3-position of the pyrazole ring, and includes a hydrogen atom or any group described below.

The optional substituents are as follows, and these substituents may be further substituted with one or more groups selected from this group of substituents.

R□. Examples of optional substituents permissible in basis,
It has the same meaning as "aromatic group, heterocyclic group". ), aliphatic oxy groups (e.g. methoxy, 2-methoxyethoxy, 2-propenyloxy), 1 aromatic oxy groups (e.g. z4-dite
rt-amylphenoxy, 2-chlorophenoxy, 4-
cyanophenoxy), acyl groups (e.g. acetyl, benzoyl), ester groups (e.g. butoxycarbonyl, phenoxycarbonyl, benzoyloxy, phenylsulfonyl, toluenesulfonyloxy), amide groups (e.g. acetylamino, methanesulfonamide, ethylcarbamoyl) , diethylcarbamoyl, butylsulfamoyl), imide (e.g.

basuccinimit 9, hydantoinyl), ureido (e.g. phenylureido, dimethylureide 9), sulfamoylamino groups (e.g. dipropylsulfamoylamino), aliphatic, aromatic or heterocyclic sulfonyl groups (
(e.g. methanesulfonyl, phenylsulfonyl), aliphatic, aromatic or heterocyclic thio groups (e.g. ethylthio, phenylthio), aliphatic/aromatic or heterocyclic thiooxy groups, aliphatic/aromatic or heterocyclic oxyamide groups, substituted Amino group (e.g. diethylamino, anilino)
, silyl group (eg, trimethylsilyl), hydroxyl group, cyano group, carboxyl group, sulfonic acid group, nitro group, thiocyanato group, halogen atom (fluorine, chlorine, bromine, iodine), and the like. Note that two or more substituents further substituting these substituents may form one or more cyclic structures (eg, R4-dimethyleneoxyphenyl, L2λ4-tetrahydronaphthyl, etc.).

In the general formula (II), when Y2 is not a hydrogen atom and represents a coupling-off group, the leaving group can be coupled to an active carbon via oxygen, nitrogen, sulfur or a carbon atom, an aliphatic group, an aromatic group, Heterocyclic group, aliphatic/aromatic or heterocyclic sulfonyl group, aliphatic/aromatic or heterocyclic carbonyl group, aliphatic/aromatic or heterocyclic oxycarbonyl group, aliphatic/aromatic or heterocyclic carbamoyl group A bonding group, a halogen atom, an aromatic azo group, etc., and the aliphatic, aromatic or heterocyclic group contained in these leaving groups may be substituted with a substituent allowed by Rlo, When there are two or more of these substituents, they may be the same or different.

Specific examples of leaving groups include halogen atoms (e.g. fluorine atoms, chlorine atoms, bromine atoms, etc.), a! −? Syl groups (e.g. ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy, carboxylpropyloxy, methylsulfonylethoxy, etc.), aryloxy groups (e.g. 4-chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy, etc.), acyloxy groups (e.g. acetoxy, tetrazokayloxy, benzoyloxy, aliphatic or aromatic sulfonyloxy groups (e.g. methanesulfonyloxy, toluenesulfonyloxy, etc.), acylamino groups (e.g. dichloroacetylamino, heptafluorobutyrylamino, etc.)
, aliphatic or aromatic sulfonamido groups (e.g., methanesulfonamino, p-k f k honylaminoto), alkoxycarbonyloxy groups (e.g., ethoxycarbonyloxy, benzyloxycarbonyloxy, etc.), aryloxycarbonyloxy groups (e.g. phenoxycarbonyloxy, etc.), aliphatic/aromatic or heterocyclic thio groups (e.g. ethylthio, phenylthio, tetrazolylthio, etc.), carbamoylamino groups (e.g. N-methylcarbamoylamino, N-phenylcarbamoylamino, etc.), 5-membered or 6-membered nitrogen-containing heterocyclic groups (e.g. imidazolyl, pyrazolyl, triazolyl, tetrazolyl, L2-dihyto10-2-oxo-1-pyridyl, etc.), imide groups (e.g. succinimide, hydantoinyl, etc.), aromatic azo groups (e.g. phenylazo, etc.), and these groups are further similar to the above-mentioned R. It may be substituted with any group represented by.

As the leaving group bonded via the tfc1 carbon atom, there is a bis-type coupler obtained by condensing a positive equivalent coupler with aldehibis or ketones.

The leaving groups of the present invention may include photographically useful agents such as development inhibitors and development accelerators.

In the present invention, the aliphatic group may be saturated or unsaturated, substituted or unsubstituted, vertical or branched, or cyclic, and typical examples include methyl, ethyl, and butyl groups. ,
7 chlorohexyl group, allyl group, propargyl group, methoxyethyl lli, n-decyl group, n-dogucyl 4, Q-
Hexadecyl group, trifluoromethyl group, heptafluoropropyl group, bidecyloxyglobyl group, 2.4-:
)-tert-amylphenoxypropyl group, 44-
Di-tert-amylphenoxyphthyl group, etc. are included.

Further, the aromatic group may be substituted or unsubstituted,
Typical examples include phenyl group, tolyl group, 2-tetradecyloxyphenyl group, pentafluorophenyl group,
2-chloro-5-)”decyloxycarbonylphenyl i, 4-10 lophenyl group, 4-cyanophenyl group, 4
-Hydroxyphenyl group, etc.

In addition, the heterocyclic group may be substituted or unsubstituted,
Typical examples include 2-pyridyl group, 4-pyridyl group,
Included are 2-furyl group, 4-chenyl group, quinolinyl group, and the like.

When the aliphatic/aromatic or heterocyclic group has one or more substituents, that substituent may further have one or more substituents.

Among the pyrazoloazole compounds represented by the general formula (II), preferable photographic turnips 2- are IH-imidazo(L2-b) pyrazoles represented by the following general formula (v),
IH-pyrazolo(1,5-
b) Pyrazole, 1ki- represented by the general formula (■)
Pyrano0(!51-(ri(124)triazoles, IH-pyrazolo I represented by the general formula (■): 1,5-
b) (1,24) l-lyazoles, general formula (IX
) IH-pyrazolo (L5-d) tetrazoles represented by formula (X) and IH-pyrazolo (L5-d) represented by general formula (X)
1,5-a) Indimigusols.

(V) (Vl) (νU)
, ('v111)(K)
(X) The substituents in the general formulas from (V) to (X) will be explained in detail. R11, R12 and R13 represent an aliphatic group, an aromatic group or a heterocyclic group, and these groups may be substituted with at least one of the permissible substitutions for R10 (the above A group of substituents (ie, substituted or unsubstituted aliphatic/aromatic and heterocyclic groups) is represented by R). R11, R12 and R13 may be a hydrogen atom, a halogen atom, a cyano group, or an imide group. R11, R12 and R13 are
Furthermore, it may be a carbamoyl group, a sulfamoyl group, a ureido group, or a sulfamoylamino group, and these groups may be substituted with permissible substituents for Rlo. X□ is synonymous with Y2, and R11, R
Either 12, R13 or Xl is a divalent group and 2
It may form a 'ffk body, or it may serve as a divalent group that connects the polymer main chain and the coupler chromophore.

Preferred R11, R12 and R13 are a hydrogen atom, a halogen atom, a substituent defined by R, RO-1RCOI-
, R802NH-1RNH-, R8- or 1(OC
It is an ONH group. Preferred X groups include a hydrogen atom, a halogen atom, an acylamino group, an imide group, an aliphatic or aromatic sulfonamide group, a 5M or 6i nitrogen-containing heterocyclic group bonded to the coupling active position with a nitrogen atom, an aryloxy group, and It is an alkoxy group.

The coupler of general formula (n) may be a dimer, a multimer or a polymer.

(V) to (X) R11, R12, R in the general formula at t
Any group selected from the groups 13 and Alternatively, it may be contained in the main chain of the polymer. Polymer couplers allow the coupler-containing layer to be made thinner and improve sharpness.

It is generally desirable that the cyan coupler represented by the general formula (I) or the magenta coupler represented by the general formula (II), preferably represented by the general formulas (V) to (X), have all ballast groups that make the coupler itself diffusion resistant. It is also possible to improve graininess by designing the chromophore formed from a coupler whose leaving group is a ballast group to have appropriate diffusivity.

Synthetic methods or compound examples of couplers represented by the general formulas (V) to (X) are described in the following documents. The compound of general formula (V) is disclosed in Japanese Patent Application No. 58-23434 and 58-145331, etc., the compound of general formula (M) is disclosed in Japanese Patent Application No. 58-151354, etc., and the compound of general formula (■) is disclosed in Japanese Patent Application Publication No. 58-151354, etc. 47-27411 and patent application 1982-103
336, etc., the compound of general formula (■) is
5512, 59-27745, 59-45601,
59-53443 and 59-70146, etc.
The compound of general formula (K) is disclosed in Japanese Patent Application No. 58-142801, etc., and the compound of general formula (X) is disclosed in U.S. Patent No. 3,061,43.
There are detailed descriptions in 2 etc.

Further, as a cyan or magenta ballast group of the present invention, Japanese Patent Application Laid-Open No. 58-402045, Japanese Patent Application No. 58-8894
0. 58-52923, 58-52924 and 5
8-52927 and the like, high color density or high color development rate can be obtained.

Examples of cyan and magenta couplers according to the present invention are shown below (C-1) and CM-1, respectively.

(C-1) C11' 3UUΔh (C-2) (C-3) (c-4) (C-6) (C-8) (C-9) (C-1O) (C-11) (C-13) (C-14) (C-15) (C-16) (C-17) flood (C-18) (C-19) C top’3So2flJH (C-21) (C-22) 12H25 (C-23) (c-24) NfiCOCH2CH2COOH (C-26) (C-27) (C-29) (C-30) (C-3t) (C-32) (C-33) (C-34) H 2H5 (C-35) (c-36) (C-37) (C-38) (C-39) (C-40) (C-41) C1i3S02NH (C-42) (C-43) (C-44) (C-46) (C-47) H (C-48) OH x:y=80:20 (molar ratio) (C-49) e4kiq(+XXJNHnaWn, n9(M-1) CM-2) CM-3) (M-4) CM-5) (M-6) n-CaH13 (M-13) CM-14) (M-15) H3CH3 \-LHs.

00O-ca-uNHO(CH2)3hal""
C12H2S Be Nu, J (M-16) (M-17) (M-18) (M-19) (M-20) (M-21) C10) 121 (M-22) (M-23) CM- 24) (M-25) H x/y=40/60 (weight) (M-27) x/7=55/45 (weight) Preferred petero ring of pyrazoloazole coupler represented by general formula (n) The skeleton structure is general formula (V) or X
), among which formulas (V), (VI), (■) and (■) are particularly excellent in terms of hue, and the hue improves in this order. General formula (Vll),
! =(X)! 4 General formulas (V), (■), (Vllll)
The compound of (IX) has higher chromophore fastness,
In particular, it has excellent fastness against light. Especially general formula (■)
The compound is excellent in both hue and fastness.

The coupler represented by the general formula (n) has less yellow unnecessary absorption in the coloring magenta dye than the conventionally known 5-pyrazolone couplers, and in particular, the compounds of the general formulas (V) to (■) have longer wavelengths. There is little absorption on the side.

Furthermore, compared to conventionally known 35-diacylaminophenol couplers or phenolic cyan couplers in which ureide is present at the 2nd position, general formula (I) exhibits less unnecessary absorption of magenta.
cyan couplers to finally achieve good color reproduction on color prints.

The coupler represented by general formula (I), the coupler represented by general formula (n) and an arbitrarily selected yellow coupler are combined with silver halide emulsion layers having mutually different color sensitivities. A coupler represented by the general formula (I) is preferably contained in the red-sensitive emulsion layer, a coupler represented by the general formula (II) is preferably contained in the green-sensitive emulsion layer, and preferably a coupler represented by the general formulas (V) to (X). Furthermore, a yellow coupler is added to the blue-sensitive emulsion layer. The combination of color sensitivities of the coupler and the photosensitive layer can also be changed to other combinations than those mentioned above.

Two or more couplers of the same hue represented by general formulas (I), (It), and (V) to (X) can be selected and used together, and co-emulsification can also be used to circumcise. It is also possible to use sb in combination with an anti-fading agent or an antioxidant.

A cyan hue t-vP4 may be obtained by using a short-wave absorbing cyan coupler having a chromophore having a maximum absorption wavelength of 680 nm or less and a coupler of general formula (I).

Further, couplers of general formulas (n) and (V) to (X) may be used in combination with known magenta couplers, such as 5-pyrazolone couplers. However, since the known cyan or magenta couplers increase unnecessary absorption other than the main absorption, the same hue is used in combination with the cyan coupler of general formula CI) or the magenta couplers of general formulas (n) and (V) to (X). The amount of known couplers used is 50
It is preferably less than molti, and preferably less than 30 molti.

When a shortwave absorption type cyan coupler is used in combination, 2-acylamino-5-
Ethylphenols, such as 45-diacylaminophenols described in JP-A-56-80045, JP-A-58-42671 and JP-A-58-70604, are preferred because they have good fastness to light and heat.

A 2-equivalent or 4-equivalent yellow coupler is used in the color photosensitive material of the present invention. Preferably, open-chain ketomethylene compounds of acylacetanilides are used, which are broadly classified into benzoylacetanilide and pinochoylacetanilide. A specific example of a yellow coupler is shown in U.S. Patent No. 2.87.
ao No. 57, No. 2407, No. 210, No. 3,265
, No. 506, No. 229a443, No. 3.04a194
No. 3447.928, etc.

The couplers of general formula (I) and general formula (II) of the present invention include those having 4 equivalents or 2 equivalents.

In order to increase the sensitivity of the photosensitive material of the present invention and to reduce the coated silver amount et-, 2-equivalent couplers are preferable to 4-equivalent couplers. When the red-sensitive or green-sensitive light-sensitive layer has two or more layers with different sensitivities, it is preferable to use the 2-equivalent coupler of the present invention in one of the emulsion layers with different sensitivities, and particularly preferably in each emulsion layer with different sensitivities. The two-equivalent coupler of the present invention is fully used in the highest sensitivity layer. In a preferred embodiment, all couplers including the yellow coupler to be combined have t-2 equivalents.

The coupler represented by the general formula (I) or (II) is contained in the silver halide emulsion layer constituting the photosensitive layer in an amount of J of 0.01 to 1.0 mol, preferably 0.1 to 1 mol of silver halide. ~0.5 mol is contained. Further, in order to preferably set the strain ratio between the double force pullers represented by the general formulas CI) and (II) in a molar ratio of about 1:0.2 to 1.5, various known techniques can be used. can be applied. Usually, it can be added by the oil-in-water dispersion method known as the oil protection method. Esters are used as preferred high boiling organic solvents;
Usually, it is dissolved in a mixed solvent with a low-boiling organic solvent such as ethyl acetate, and then emulsified and dissolved in an aqueous gelatin solution containing a surfactant. Alternatively, water or an aqueous gelatin solution may be added to a coupler solution containing a surfactant to form an oil-in-water partial covering with phase inversion. Alkali-soluble couplers can also be dispersed by the so-called Fischer dispersion method.

After completely removing the low-boiling organic solvent from the coupler dispersion by distillation, noodle washing, or ultrafiltration,
May be mixed with photographic emulsion.

The tu of the high boiling point solvent used in combination with the Shiman and magenta couplers according to the present invention is preferably within the range of 10 to 300% by weight, and is optimized from the viewpoint of the solubility of the coupler, the developability of the photosensitive material, etc. .

The photosensitive material of the present invention may contain a special coupler 'fr other than the coupler of the present invention represented by the above general formula, if necessary. For example, in the green-sensitive emulsion layer,
By containing all the colored magenta couplers, it is possible to obtain a good masking effect. In addition, in each color-sensitive emulsion layer or in its adjacent layer, there is a development inhibitor releasing power shifter (DI).
R Kazler) A development inhibitor releasing agent such as hydroquinone can also be used in combination. The development inhibitor released from these compounds during development brings about interlayer effects such as improving the sharpness of the lj image, making the image finer, or improving monochromaticity.

In the present invention, by combining the couplers represented by general formulas (I) and (n), it is possible to reduce the use of DIR couplers and improve the color reproducibility of objects. Therefore, it is possible to improve color reproducibility, increase the amount of development progress, shorten development time, reduce variation in development, and produce a uniform finish with excellent color reproducibility, especially even with a tired developer. becomes possible.

D-engine R couplers that can be used in the present invention will be described below.

As a DIR coupler, for example, US 1% permit No. 3227,
Those that release heterocyclic mercapto-based development inhibitors as described in No. 554, etc.; Those that release benzotriazole derivatives as development inhibitors, as described in Japanese Patent Publication No. 58-9942, etc.;
So-called colorless DI described in Japanese Patent Publication No. 51-16141 etc.
R coupler; described in JP-A-52-90932, which releases a nitrogen-containing heterocyclic development inhibitor with decomposition of methylol after separation; described in U.S. Pat. No. 4,248,962 and JP-A-57-56,837; All intramolecular nucleophilic reactions release all of the development inhibitor after separation; JP-A-56-11
4946, 57-154234, 57-18803
5, 5B-98728, 58-209736, 5
8-209737, 58-209738 and 58
JP-A-57-151944, JP-A-58-2179, which releases a development inhibitor by electron transfer via a conjugated system after separation, as described in JP-A-209739, JP-A-58-209740, etc.
32, etc., which releases a diffusible development inhibitor whose development inhibitory ability is deactivated in the developer solution; Japanese Patent Application No. 59-38263,
releasing the reactive compound described in 59-39653 etc.,
All examples include those that generate a development inhibitor or completely deactivate the development inhibitor by a reaction in the film during development. Among the above-mentioned DIR couplers, the one more preferable in combination with the present invention is disclosed in Japanese Patent Application Laid-open No. 57-15194.
Developer deactivated type represented by 4; U.S. Patent No. 148,
962 and Japanese Patent Application No. 57-154234; reaction type as represented by Japanese Patent Application No. 59-39653, and particularly preferred among them are the
7-151944 and the like, and a reactive type D-engine R coupler described in Japanese Patent Application No. 59-39653 and the like.

Preferred specific examples of DIR couplers for use in combination with the present invention are shown below.

IA D-6 l c'. n ト(J112)2U-kA;f12Uf12LJL. ;
l-13D-13 D-14 (J D-21 D-22 O2 Q D-29 D-30 H H H In the present invention, a development accelerator or caplace agent (referred to as rl'AJ) is formed during silver development. (hereinafter referred to as “
By using the F'R compound (referred to as "F'R compound"), it is possible to obtain effects such as improving the sensitivity, improving graininess, and increasing contrast of the color sensitive material of the present invention. General formulas (I) and (I[) of the present invention
When all 1'R compounds are used together with the above coupler combination, the above-mentioned effects can be obtained more markedly than with other sensitive materials. In particular, when the amount of DIR coupler is completely reduced to lower the degree of inhibition of silver development as a whole, the original performance of the F'R compound can be more significantly obtained.

In addition, in color photosensitive materials that do not contain DIR Kazler gold, F'
By using the R compound, it is possible to achieve good color reproducibility, high sensitivity, and improved graininess.

F'R compounds that can be used in the present invention include the following.

(1) A coupler that releases all of F'A or its precursor upon coupling with an oxidation product of an aromatic primary amine developing agent.

(11) coupling with an oxidation product of an aromatic primary amine developing agent to produce a broadening coupling product;
A coupler in which the coupling product functions as F''A or a precursor thereof.

(FA may be used for the coordination reduction reaction with the oxidation product of the 1111 aromatic primary amine developing agent or for the subsequent reaction of the reaction.
or redox compounds releasing their precursors.

As for the PRR compound to be used in combination with the present invention, the type (1) is the most preferred, and the preference decreases in the order of the type (1[) and the types (...).

Exemplary compounds and synthetic methods of PR compounds of type (1) above are disclosed in Japanese Patent Application Laid-open No. 57-150845 and Japanese Patent Application No. 57-161.
515, 58-91610. It is described in 58-31611 and 58-146097.

The general formula of the PRR compound can be expressed as A, where A□ is a residue with one hydrogen removed from the active position of the compound that can undergo a coupling reaction with the oxidized product of an aromatic primary amine developer. In all the expressions, Bo represents a group which exhibits a fogging effect in a developer after being separated by a coupling reaction. Specific examples of these compounds include the aforementioned Japanese Patent Application No. 58-47601.
There are 39 compounds listed in , but preferred is a compound in which a formylhydrazine invasion group having an adsorption group is bonded to the active position of the inzoyl fJi or hapivaloyl type yellow coupler mother nucleus. Here, the adsorption group is preferably a phenylmercaptotetrazole residue or an zotriazole residue.

Two or more PR compounds may be used in combination. The amount of PR compound added is 0.2 mol or less per mol of silver in the same layer10
The amount is 1 mole or more, preferably 0.02 mol or less and 10 mol or more. The F'R compound is used alone or together with a coupler for color image formation to achieve the desired purpose by introducing it into the silver halide emulsion layer by an oil-in-water dispersion method known as the oil protection method. can do.

Representative examples of FR compounds are listed below.

B'R-t R-2 R-3 R-4 IJUI-12CM2Nii+, ;111 0℃-NOPR-sFR FR-6FR FR-9 F'R-10 H3 FR-11 FR-12 1i'R-13 FR-16 FR-17 1'R-18 F'R-19 1'R-20 FR-21 FR-22 FR-23 The photographic emulsion used in the present invention includes the following: Various compounds can be contained for the purpose of preventing fogging during processing or for the purpose of stabilizing the overall photographic performance. Representative compounds are listed in order of preference: heterocyclic mercapto compounds (e.g. mercaptothiazoles, mercaptobenzothiazoles,
mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles, mercaptopyrimidines, etc.), the above-mentioned heterocyclic mercapto compounds having a water-soluble group such as a carboxyl group or a sulfo group, azoles (such as benzothiazolium salts, Examples include nitroindazoles, triazoles, benzol-IJ azoles, preferably nitro- or halogen-substituted pe/zimidazoles, etc.), thioketones (for example, oxazolinthione, etc.), and quaternary salt type compounds.

Furthermore, azaindenes are particularly preferably used as anti-capri and stabilizers for photographic performance.

A typical example is 4-hydroxy-(L3.3a.

7) There are tetrazaindenes.

The preferred antifoggant heterocyclic mercapto compounds described above are represented by the general formula Z□-8-M.

In the formula, M represents a hydrogen atom, a cation (e.g. an alkali metal ion, an ammonium ion, etc.), or -5-z6,
Z represents a heterocyclic residue containing at least one nitrogen atom.

The heterocyclic residue represented by Z□ may be further fused, and specifically includes imidazole, triazole, tetrazole, thiazole, oxazole, selenazole,
Benzimidazole, benzoxazole, benzthiazole, thiadiazole, oxadiazole, benzselenazole, pyrazole, pyrimidine, triazine, pyridine, naphthothiazole, naphthoimidazole, naphthoxazole, azabenzimidazole, purine, azainthene (e.g. triazaindene, tetra zyinden, zyintazainden, etc.) are preferred.

Further, these heterocyclic residues and condensed rings may be substituted with any suitable substituent. Examples of substituents include alkyl groups (e.g. methyl group, ethyl group, human 10-oxyethyl group, trifluoromethyl group, sulfopropyl group, di-
propylaminoethyl group, adamantane group, etc.), alkenyl group (e.g. allyl group, etc.), aralkyl group (e.g. benzyl group, p-chlorophenethyl group, etc.), aryl group (
For example, phenyl group, naphthyl group, p-carboxyphenyl group, 35-di-carboxyphenyl as m-sulfophenyl group, p-acetamidophenyl group, 3-casramidophenyl group, p-sulfamoyl 7xnyl group,
m-human 90xyphenyl group, p-nitrophenyl group,
3.5-dichlorophenyl group, 2-methoxyphenyl group, etc.), heterocyclic residues (e.g. pyridine, furan, thiophene, etc.), /%rogen atoms (e.g. chlorine atom, bromine atom '4), mercapto group, cyano group , carboxyl group,
Sulfo group, hydroxyl group, carbamoyl group, sulfamoyl group, amine group, nitron group, alkoxy group (e.g. methoxy group 44), aryloxy group (e.g. phenoxy group etc.), acyl group (e.g. acetyl group etc.), acylamino group (e.g., acetylamino group, capramide group, methylsulfonylamino group, etc.), substituted amino group (e.g., diethylamino group, hydroxyamino group, etc.), alkyl or arylthio group (e.g., methylthio group, carboxyethylthio group, sulfobutylthio group, etc.) ), alkoxycarbonyl groups (eg, ehamethoxycarbonyl group, etc.), aryloxycarbonyl groups (eg, phenoxycarbonyl group, etc.), and the like.

The compound represented by the above general formula Z, -5-M is E,
J, B1rr ``5tabilization of
Photographic Silver f(alld
e EEmul-sions ""(1'ocax P
(Res Publishing, 1974), C.G. Bar'low
et a1 ``Rep.

Prog, Appl, Chem, '''Volume 59, 15
9 pages (1974), Re5earch Diθclo
Sure No. 17643 (1978), etc. can be referred to for synthesis.

Specific examples of mercapto-type anti-capri agents that can be used in the present invention are described in Japanese Patent Application No. 59-8100.

In the light-sensitive material of the present invention, a compound capable of deactivating the oxidized form of a color developing agent may be used in the intermediate layer as a color cast preventive agent. Typical compounds include compounds that can deactivate the oxidized color developing agent by redox reaction, and typical examples include hydroquinone derivatives, aminophenol derivatives, gallic acid derivatives, and ascorbic acid derivatives.

The color fog preventive agent used in the photographic material of the present invention is a compound having at least one substituted or unsubstituted sulfonylamino group on a phenol or naphthol ring, and this compound can be a mono-form, a bis-form, or a polymer. Yet another type of color fog inhibitor is monoalkylhydroquinones having a sulfonic acid group (including salt, hereinafter the same) as a substituent.

Specific examples of compounds having a sulfonylamino group include z4-disulfonamidophenols described in Japanese Patent Application Laid-Open No. 59-5247.
66629, 58-60630, 58-68877
, 58-78666, 58-78607, 58-
No. 78608 and No. 58-81523, representative compounds thereof will be described following typical examples of monoalkylhydroquinones substituted with phenyl nucleosulfonic acid groups.

H H H H Q-8 H In the present invention, an ultraviolet absorber can be added to any layer. Preferably, an ultraviolet absorber is contained in the compound-containing layer represented by general formula (I) or in an adjacent layer.

The ultraviolet absorber that can be used in the present invention is a group of compounds listed in Item 0 of Research Disclosure 17643, preferably benzotriazole derivatives represented by the following two compounds.

The color photographic material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic organic colloid layer. Examples include chromium salts (chromium acetate, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, geltaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (Z3-dihydroxydioxane, etc.) ), activated vinyl compound (Lλ5-
triacryloyl-hexahydro-θ-t')1:y
, 1,3-vinylsulfonyl-2-pronoξnor, etc.), active halogen compounds (24-dichloro-6-bitroxy-6-triazine, etc.), mucohalogen [i (mucochloric acid, mucophenoxychloroic acid, etc.), etc. can be used alone or in combination.

The curing agent that can be preferably used in the present invention is a curing agent containing an active vinyl group, for example, JP-A No. 53-41
No. 221, JP-A-53-57257, JP-A-51-1
No. 26124, Japanese Patent Publication No. 49-13563, Japanese Patent Publication No. 1973
-44164, JP-A-52-21059, U.S. Pat. No. 3,490,911, U.S. Pat.
6, Special Publication No. 50-35807, Japanese Patent Publication No. 54-300
No. 22, Japanese Patent Publication No. 53-66960, Special Publication No. 52-46
No. 495, Japanese Patent Publication No. 47-8736, U.S. Patent No. 363
No. 5718, No. 3040720, West German Patent No. 8721
Curing agents described in No. 53 can be used. Among the vinyl sulfone curing agents, compounds represented by the following general formula are particularly preferred.

(2) (CH2=CH-802-CH2-CO-N+2A2 In the formula, A2 represents a divalent organic residue or a single bond.

R represents a hydrogen atom or a hydrocarbon having 1 to 4 carbon atoms, but two R14s in one molecule are not necessarily the same.

The amount of gelatin hardening agent used in the present invention can be selected arbitrarily depending on the purpose. Typically, it can be used in proportions ranging from 0.01 to 20 weight percent based on dry gelatin. Particular preference is given to using proportions ranging from 0.1 to 10% by weight.

Specific examples of compounds that can be used in the present invention include the following.

Compound example (CH2=Ckl-8020M2COMkl+2CM2
G) 12c CH2=CH-, 30□0H2CONH-
) 2CH2C) i2CH2 In order to correct unnecessary absorption tubes on the shortwave side of magenta and cyan generated in negative films and obtain correct color reproduction on prints, a masking method using colored couplers is used, PSA Journal, Vol. 13. , page 94, 1947, etc. In order to correct the yellow unnecessary absorption of the magenta coupler, a yellow-colored magenta coupler in which an arylazo group is substituted at the 4-position of the 5-pyrazolone is used; Group-substituted colored couplers have been used. These force 2-de couplers are described in Research Disclosure 17643 (1978).
Exemplary compounds are listed in the specification described in Section 1-G of February).

The cyan coupler of the general formula (1) of the present invention and the general formula (II)
) magenta couplers have little unnecessary absorption, so
The amount of magenta-colored cyan coupler and yellow-colored magenta coupler required for correction can be greatly reduced, and it is also possible to reproduce colors with good clarity without using these colored couplers. In the present invention, the minimum image density is cyan,
It is preferable that the amount of the colored coupler added be 0.30 or less for both magenta and yellow. Preferred colored couplers for use in this case are: (1) yellow-colored magenta couplers as described in Japanese Patent Publication No. 57-39413 and U.S. Pat.
4004929 and Research Disclosure 1
A magenta-colored cyan coupler containing a sulfonic acid group as described in US Pat. No. 6,560.

A representative example of this is Co1or-Cheker, which is a color checker that is obtained by actually photographing and printing all color samples to evaluate the color reproducibility of silver halide photosensitive materials. When black is reproduced on color photographic paper, how accurately it can be reproduced on the remaining 18 colored/ξ latte color photographic papers was subjected to a full sensory test and quantitatively evaluated by measuring with an instrument. Quantitative testing methods for this color difference are reviewed, for example, in Chapter 7 of "Industrial Color Studies" by Yoshinobu Naya, Chokai Shoten (published in 1980). Many researchers have proposed various color expression values and color difference formulas that are calculated from the tristimulus values obtained by measuring both colors of photographic samples and reproduced prints with an instrument under the same lighting conditions.

In the present invention, the color reproducibility formula proposed by David Eastwood in the paper published in F'arbe, Vol. 24, No. 1, p. 97 et seq. Tested quantitatively.

The present invention can be used in general silver halide color light-sensitive materials such as color negative film, color paper, color positive film, remedial film for slides, color reversal film for movies, and color reversal film for TV. In particular, when used in color negative films and various color reversal films that require high sensitivity and high image quality, a remarkable effect on color reproducibility can be obtained.

Various silver halides can be used in the silver halide emulsion layer according to the present invention. Examples include silver chloride, silver bromide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide.

Silver iodobromide containing 2 to 20 moles of silver iodide and silver chlorobromide containing 10 to 50 moles of silver bromide are preferred. There are no limitations on the crystal form, crystal structure, grain size, grain size distribution, etc. of the silver halide grains. Silver halide crystals may be normal crystals or twin crystals, and may be hexahedral, octahedral, or tetradecahedral. The grains may be tabular grains having a thickness of 0.5 micron or less, a diameter of at least 0.6 micron, and an average aspect ratio of 5 or more, as described in Research Disclosure 22534.

The crystal structure may be uniform, the inside and outside may have different compositions, it may have an entirely layered structure, or silver halide of different compositions may be joined by epitaxial bonding, It may also consist of a mixture of particles of various crystalline forms. Further, the latent image may be formed mainly on the surface of the particle or may be formed inside the particle.

The grain size of silver halide may be fine grains of 0.1 micron or less or large grains with a projected area diameter of up to 3 microns, and may be a monodisperse emulsion with a narrow distribution or a polydisperse emulsion with a wide distribution. good.

These silver halide grains can be produced by known methods commonly used in the art.

The silver halide emulsion can be sensitized by conventional chemical sensitization, such as sulfur sensitization, noble metal sensitization, or a combination thereof. Furthermore, the silver halide emulsion according to the present invention can be imparted with color sensitivity in a desired wavelength range by using a sensitizing dye. Dyes that can be advantageously used in the present invention include methine dyes and styryl dyes such as cyanine, hemicyanine, logcyanine, merocyanine, oxonol, and hemioxonol, and they can be used alone or in combination of two or more. .

Along with the sensitizing dye, it is a dye that does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may be included in the entire emulsion.

Useful sensitizing dyes, dye combinations exhibiting supersensitization, and substances exhibiting supersensitization are disclosed in Research Disclosure (Res.
176 volume 176
43 (published December 1978), page 23, item 7.

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

Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful.

The photographic emulsion layer of the photographic light-sensitive material of the present invention contains fll, u, for the purpose of increasing sensitivity, increasing contrast, or promoting development.
may contain gold, such as polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, quaternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, and 3-pyrazolidones. For example, US Patent 240Q5
No. 32, No. 2423549, No. 2.71 & 062,
Same No. a617,280, No. 3772.021, Same: a
80 &003, British Patent No. 1,488,991, etc.

In carrying out the present invention, all of 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-oxy7phenol derivatives, and bisphenols.

Gelatin is advantageously used as a binder or protective colloid in photographic emulsions, but other hydrophilic colloids can also be used.

Further, depending on the case, a fine-grain silver halide emulsion having substantially no photosensitivity (for example, silver chloride, silver bromide, chloride odor with an average grain size of less than 020 μm) may be included in the silver halide emulsion layer or other hydrophilic colloid layer. A silver oxide emulsion) may also be added.

Research Disclosure 17643
The additives described in may also be used.

The color developing solution that can be used in the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. As a color developing agent, 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-human"oxyethylaniline, 3-methyl-4-amino-N-ethyl-N-
β-methanesulfamide ethylaniline, 4-amino-
Representative examples include 3-methyl-N-ethyl-N-β-methoxyethylani 177.

The color developer contains p)I buffers such as alkali metal sulfites, carbonates, borates, and phosphates, development inhibitors or anticapri agents such as bromides, iodides, and organic anticapri agents. etc. can be included. Also, if necessary,
Water softeners, preservatives such as hydroxylamine, organic solvents such as benzyl alcohol and diethylene glycol,
Development accelerators such as polyethylene glycols, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers, fogging agents such as sodium boron hydride, 1
- Auxiliary developers such as phenyl-3-pyrazolidone, tackifying agents, polycarboxylic acid chelating agents as described in US Pat. No. 4,083,723, OLS 1,622,950
It may also contain antioxidants as described in the above.

Bleaching may be carried out simultaneously with fixing or separately. Bleaching agents include polyvalent metals such as iron (Ill), cobalt (If), chromium (Vl), and copper (II). Compounds, peracids, quinones, nitroso compounds, etc. are used. For example, ferricyanide, dichromate, organic complex salts of iron (In) or cobalt (■), such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, L3
-Diamino-2-propatol 7-minopolycarboxylic acids such as tetraacetic acid; complex salts of organic acids such as citric acid, tartaric acid, and malic acid; persulfates, permanganates; nitrosophenols, and the like can be used. Among these, potassium ferricyanide, ethylenediaminetetraacetic acid (11)
Sodium and iron([)ammonium ethylenediaminetetraacetate are particularly useful. Ethylenediaminetetraacetic acid iron(III) complex salts are useful in both stand-alone bleach solutions and -bath bleach-fix solutions.

For bleaching and Fi bleach-fixing solutions, U.S. Patent No. 3,042,520
In addition to the thiol compound described in JP-A-53-65732, and the thiol compound described in JP-A-53-65732, various additives may be added. You can also do it.

Since ferric ion complex salts have a relatively small whitening power and insufficient whitening properties, the ones used as t-m whitening agents are, for example, low-sensitivity halogenated color photographs based entirely on silver chlorobromide emulsions. When bleaching or bleach-fixing a light-sensitive material, it is possible to reach the desired goal, but it is possible to achieve the desired goal by bleaching or bleach-fixing a photosensitive material. When fully processing silver oxide color photographic materials, especially color reversal photographic materials and color negative photographic materials that use high-silver emulsions, the bleaching effect may be insufficient and desilvering may be insufficient, or the bleaching may fail. It tends to last for a long time, and if bleaching or bleaching is carried out using all the bleaching accelerators mentioned below, it can be processed in the conventional process time.

Persulfates are known as bleaching agents other than ferric ion complex salts, and persulfates are usually used as a bleaching solution in the form of a complete chloride content. However, the disadvantage of bleach solutions using persulfates is that they have a weak bleaching blade compared to ferric ion complex salts, and it takes a long time to bleach. Bleaching ability can be increased.

Examples of the bleach accelerator include compounds having a mercapto group or a disulfite group bond, thiazolidine derivatives and inthiourea derivatives, and at least one kg of these compounds is allowed to coexist in the white bath or bleach-fixing bath. Furthermore, for the purpose of preventing precipitation during continuous treatment, 2-mercapto-5-sulfonate alkylenethio-La4-thiadiazoles or the like may be allowed to coexist. Specific examples and amounts of these bleach accelerators or anti-settling agents are described in detail in Japanese Patent Application No. 58-233844.

Processing of color sensitive materials consists of steps such as color development, zero-whitening, fixing or color development, and bleach-fixing, and washing or stabilization steps may be added as necessary. After the fixing step or bleach-fixing, the entire stabilization treatment may be performed without substantially washing with water.

The final bath of the process, ie the bath at the end of the process, is usually located just before drying. The final bath is generally a washing bath or a stabilizing bath, but is not limited to these.

When the final bath is a water washing bath, the washing step needs to be a multistage countercurrent washing of 2 m or more, and 3 to 9 tanks are particularly preferable.

In some cases, known compounds may be added to this washing water. For example, water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphoric acid, disinfectants that prevent the growth of various bacteria and algae, hardening agents such as magnesium salts and aluminum salts, and drying loads,
A surfactant for preventing unevenness can be added as necessary. Or L, E, West, Wat
erQuality Cr1teria-Photo,
Sal, ana Eng.

Compounds described in 1 7019, Ya 6 (1965), etc. may be added.

When the final bath is a stabilizing bath, the pre-bath may be a water washing process of one or more tanks, or a multi-stage countercurrent stabilization process without a water washing process as described in JP-A-57-8543. It can also be a process. In the case of a multistage countercurrent stabilization treatment process, 2 to 9 tanks are required.

Various compounds tm can be added to the stabilizing bath. For example, as buffering agents, borates, metaborate salts,
Borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid,
Polycarboxylic acids, etc. can be mentioned.

Examples of water softeners include inorganic phosphoric acid, aminopolycarphonic acid, organic phosphoric acid, aminopolyphosphonic acid, and phosphonocarboxylic acid.

Other commonly known additives include antifungal agents such as Proxel and 4-thiazolylbenzimidazole, hardening agents such as formalin, aluminum salts, and magnesium salts, and surfactants. be able to.

In addition, ammonium chloride,
Various ammonium salts such as ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate can also be added.

The final bath as shown above may contain at least 1 x 10 mol of oJ soluble iron salt.

The above-mentioned soluble iron salt may be added to the final bath, or it may be included in the bleach solution or white fixer solution in the pre-bath. For example, the above concentration may be due to the introduction of ethylenediamine iron complex during processing. - For example, when the final bath is a multi-stage countercurrent type water washing process, in order to maintain the above concentration, it is possible to reduce the amount of washing water from several tenths to several hundredths.

The preferred final bath pH is f13-9. Outside this range, the ability of the cyan dye to prevent fading will be impaired.

The temperature of the final bath is 5@~40℃, preferably 10℃~35℃
It is ℃.

Whitening and whitening fixing can be carried out at any temperature from 18°C to 50°C, but preferably 30°C or higher. When the temperature is 35° C. or higher, the processing time can be reduced to 1 minute or less, and the amount of liquid replenishment can be reduced. The time required for washing with water after color development or white fixation is usually within 3 minutes, and can be substantially omitted by using a stabilizing bath.

Colored pigments not only deteriorate due to light, heat, or temperature, but also deteriorate and fade due to mold during storage. Cyan images are particularly susceptible to severe deterioration due to mold, so it is preferable to use a mold preventive agent. Specific examples of antifungal agents are disclosed in JP-A-57-15724.
2-thiazolylbenzimidazoles as described in 4.

The antifungal agent may be incorporated into the photosensitive material, or may be cooled from the outside during the development process, or may be added at any step if it coexists with the processed photosensitive material.

The chemical structures of the compounds used in Examples 1-5 are shown below.

V-1 v-2 Cpa-6 Ul Cpa-7 Cpa -B 0 base Cpa -g CI) (1-IQ OH pd-11 pd-12 pa-13 pd-14 pd-15 pa-16 ° knee 1. °9 N2N pa-19 CDd-20 n:m:ρ=2:1:1 (weight ratio) Average molecular weight 4000 Cpa-21 Cpa-22 H Cpa-23 ShiU Average molecular weight 40,000 Cpa -24 Cpa -2S W-1 tcH2=CM-8o2CH2CONHCH2-)7〈
Example 1 Comparative multilayer color photosensitive material 10 consisting of each layer having the composition shown below on a cellulose triacetate film support.
1 was produced.

1st Jf4: Antihalation layer black colloidal silver Silver coating amount 0.2 g/m' Gelatin 1.3 97W? UV-
1 (ultraviolet gland M411J) 0.1 9/? UV-
2 (same as above) 0.2 9/n1
011-1 (UV-1, UV-2 dispersion oil) 0.029 fi 011
-2 (UV-1, UV-2 dispersion oil) 0.019/m" 2nd
Layer: Intermediate layer fine grain silver halide (AgBr with average grain size 0.07 μm) Silver coating amount 0.189/m" Gelatin 1.297'cpa-
1 (colored coupler) 0.1 9/dc
pa-2 (colored coupler) 0.019/
m”01x-1 (Cp(1-1, 2O dispersion oil)
0.1 9/2F? Third No. 1 = First red-sensitive emulsion layer Silver iodobromide emulsion (average grain size 0.8 μm).

Uniform distribution of iodine within the grain, 4 moles of silver iodide> Silver coating amount 0.6’j/d Silver iodobromide emulsion (average grain size 0.3 μm.

Natural distribution is uniform within the grain, silver iodide 3 mol%) Silver coating amount 0.2 9/? Fl' Gelatin 2.4 9/I P-1
(Sensitizing dye) 4.2 x 10 moles per mole of silver P-2 (sensitizing dye) 1.4 x 10 moles per mole of silver Cpd-3 (coupler) 0.69/G Cpa-4 (DIR coupler > 0 .029/
dcpa-2 (colored coupler) 0.13
g/i01'l-1 (Qpd-S'a4 dispersion oil) 0.2 97?011-2
(cpa-2, aA O dispersion oil>
0.2 97w? 4th layer: 2nd red-sensitive emulsion layer Silver iodobromide emulsion (average grain size 1.2 μm1, grains with uneven iodine distribution within and between grains by single-jet method, 10 moles of silver iodide) Silver Coating f 1.4 9/rP? Gelatin 1.6 'j/? P-
1 (sensitizing dye) 3.3 x 10 mol per mol of silver P-2 (sensitizing dye) 1, I x 10 mol Cpd-3 (coupler) 0.259 per mol of silver
/Icpa-2 (colored coupler) 0.0
49/m'011-i (cpa-23 dispersion oil) 0.1 9/d (hl
-2 (Cpd-23 dispersion oil) 0゜1 9/n? 51st
Layer: Third red-sensitive emulsion layer Silver iodobromide emulsion (average grain size 18 μm, spherical grains used in forming all ammonia grains, silver iodide 7 mol) Trowel coating t 1.8 g/W? Gelatin 2 9/r? P-1(
Sensitizing dye) 2 × 10 mol per mol of silver P-2 (sensitizing dye) 0.8 × 10 mol per mol of silver Cpd-3 (coupler) 0.2 9/
v&Cpd-2 (colored coupler) 0.0
59/ff10, tx-1 (Cpa-2,3 dispersion oil>0.1597m'011
-2 (Cpa-23 dispersion oil) 0.149/ff? 6th Nj: Intermediate layer gelatin 1.1 9/dCpd
-5 (color mixing prevention agent) 0.2 g/ze (hx
-1<cpd-s dispersion oil> 0.159/1011
-2 (Cpa -5 dispersion oil> 0.159/i 7th layer: 1st green-sensitive emulsion layer Silver iodobromide emulsion (average grain size 0.7 μm, uniform distribution of iodine within the grains, iodide) Silver coating amount 0.3 g/lrI Silver iodobromide emulsion (average grain size 0.3 μm, iodine distribution uniform within grains, silver iodide 3 mol%) Silver coating amount 0.1 97 m ” Gelatin 0.7 9/rr?0
-1 (sensitizing dye) 5 x 10 mol per mol of silver 0-2 (sensitizing dye) 2 x 10 mol per mol of silver cpa-6 (coupler) 0.25 g/
m”cpd-7 (DIR coupler) 0.05
9/rr? Cpd-8 (colored coupler)
0.069/1Qi1-1 (Cpd-7.8 dispersion oil) 0.2 9/lr/8th
Layer: 2nd green-sensitive emulsion layer Silver iodobromide emulsion (average grain size 1.0 μm, grains with uneven distribution of iodine within and between grains by single jet method, silver iodide 10 mol%) Silver coating to , 99/Igelatin 1 g/-〇-1(
Sensitizing dye) 3.8X10 mole per mole of silver 0-2 (sensitizing dye) 1.5X10 mole per mole of silver cpa-6 (coupler) 0.25g/
1Cpa-8 (colored coupler) 0.06
g/l & (hl-1 (oil for dispersing 8 into CpcL-) 0.159/i 9th layer: 3rd green-sensitive emulsion layer silver iodobromide emulsion (average grain size 2.L μm, ammonia grain size Spherical particles using L'i I'ζ, 7 moles of silver iodide) Silver coating amount 2.2 97?gelatin 1.9 min/n?0-1 (
Sensitizing dye) 2.2 x 10 mol o-2 per mol of silver (sensitizing dye) 0.9 x 10 mol per mol of silver Cpd-6 (coupler) 0.13 g/
Zecpa-8 (colored coupler) 0.03
g/i0i1-1 (Qpd -6,8 dispersion oil) 0.159/i 10th layer: Yellow filter, more yellow colloidal silver Silver coating amount 0.049/rn
``Gelachi 7 1.2 9/rr?
epd-5 (color mixing prevention agent) o, 2 9#n
'Ch1-1 (EPA-5 dispersion oil) 0.1 g/lr?
oi1-2 (Oil for dispersion of Upd-5) 0.1 'j/nl
Eleventh layer: First back-sensitive emulsion layer Silver iodobromide emulsion (average grain size 0.8 μm).

Iodine distribution is uniform within the grain, silver iodide is 3 molar) Silver coating amount 0.4 9In? Silver iodobromide emulsion (average grain size 0.3 μm1, uniform distribution of iodine within grains, 3 molar silver iodide) Pan coating i-0,8';j/lr? Gelatin 1.2 9/rr?
0-3 (sensitizing dye) 2.8 x 10 moles per mole of silver Cpd-9 (coupler) 0.7 9/
dQpa-7 (D engineering R coupler) 0.029
/FF10il 1 (Cpa -7,9 dispersion oil) 0.4 97W? 12th
Layer: 2nd blue-sensitive emulsion layer Silver iodobromide emulsion (average grain size 1.2 μm, grains with uniform distribution of iodine within and between grains by single-jet method, silver iodide coating weight 10 mmoles) 0 .3 'ij/rrl gelatin
0.697m'0-3 (sensitizing dye)
1.8 x 10 moles per mole of silver Cpd-9 (coupler) 0.39/ze011-1 < cpa -9 dispersion oil)
0.259/rr? 13th layer: Third blue-sensitive emulsion layer Silver iodobromide emulsion (average grain size 2.0 μm).

Spherical particles using ammonia during particle formation, silver iodide 7 mol%) Silver coating amount 1 9/zegelatin
0.99/-〇-3 (sensitizing dye)
1.6 x 10 moles per mole of silver (Cpd-9L cuffler) 0.2
97n10il-1 (Cpd-9 dispersion oil) 0.129/m” 1st
4th layer: Happy 1st membrane layer gelatin 1.4 9/lt? t
rv-1 (ultraviolet absorber > 0.1 9/n?U
V-2 (same as above) 0.2 9/
d011-1 (UV-L 2ty) Dispersion oil>
0.019/m"Oll-2(
U V -L 2) Oil for molecule i)
0.019/m' 15th layer: 2nd protective layer Fine grain silver halide (AgBr with average grain size 0.07 μm) Silver coating amount 0.5 9/m' Zera f: / 1.1 9/i
Polymethyl methacrylate particles (diameter approx. 1.5 μm) 0.2 9/m”
W-1 (charge control agent) 0.029/m”H
-1 (hardener) 0.4 9/m"5-
1 (formaldehyde scavenger) 1 9/d sample 1
02 (Comparative example) Sample 102 was obtained by making the following changes to sample 10'l.
And so.

(1) Remove the colored coupler cpa-2 in the 2nd to 5th layers and replace each with an equimolar amount of Cpa-a and tefl and replace each with an equimolar amount of Cpa-6. Sample 103 (comparative example) The changed sample is sample 103.
And so.

(1) 2nd to 5th layer cyan coupler cpd -3'fr
Sample 104 (comparative example) substituted with equivalent mole of C-40 of the present invention All samples 104 were obtained by making the following changes to sample 102.

(11 2nd layer, 7th to 9th layer magenta coupler cpa -6
was replaced with M-1 equimole of the present invention Sample 105 (present invention) Sample 105 was obtained by making the following changes to Sample 102.

(11 Replacement of the cyan coupler cpa-3' in the 2nd to 5th layers with an equimolar amount of C-40 of the present invention (2) Magenta coupler cpa-6 in the 747th to 9th layers
Samples 106 to 115 in which cyan coupler and magenta coupler were replaced with those shown in Table 1 in the same manner as sample 105 were used as samples 106 to 115.
And so.

The obtained E materials 101 to 115 were subjected to gradation exposure using 4800'K O white light and subjected to the development process described later, and then subjected to sensitometry using a densitometer used with a Status M filter.
' went. As a result, almost the same sensitivity gradations were obtained, except that the density of the unexposed area by the front and green Status M filters was higher in sample 101 by 0.5.03 than in the other samples.

The following experiments were further conducted on these unexposed samples from the viewpoint of color reproduction. After performing wedge exposure through green and red color filters and performing the same processing, the yellow density at the point where the difference between the unexposed area and the magenta density developed by green exposure is 1.0, as shown in Parts 1 and 2. The difference between the yellow density of the unexposed area (ΔY) and the difference between the cyan density of the unexposed area and the cyan density developed by red exposure is the difference between the magenta density of the unexposed area and the magenta density of the unexposed area ( ΔM) was measured. It is known that the higher the value, the worse the reproduction of green and red when printed on color paper. These results are shown in Table 1.

As is clear from Table 1, the combination of the cyan coupler and magenta coupler of the present invention has little sub-absorption, and is preferred in terms of color reproduction.

The development treatment used here was carried out at 38° C. in the following manner.

l, Color development...3 minutes 15 seconds 2, Meng Bai...
6 minutes 30 seconds 3, wash with water...
・3 minutes 15 seconds 4, fixed river... old... 6
Minute 30 seconds 5, Wash with water・・・・・・・・・・・・・・・
3 minutes 15 seconds 6, stable...
・3 minutes 15 seconds The composition of the treatment liquid used in each step is as follows.

Color developer Sodium nitrilotriacetate 1.09 Sodium sulfite 4.0g Sodium carbonate 30.09 Potassium bromide
1.4g Hydroxylamine sulfate 2.494-(N-Ethyl-N-β-human-oxyethelamino)-2-methylaniline sulfate 4.5g Add water IJ2 Bleach Ammonium Bromide 160.09 Ammonia Water (28%) 25.0 CC Ethylenediamine-tetraacetic acid sodium iron salt 130.09 Glacial acetic acid
14. Add OCe water
IQ fixer Sodium tetrapolyphosphate 2.0g Sodium sulfite 4.09 Ammonium thiosulfate (70g) 175. OCC Sodium Bisulfite 4.69 Add water
1st base stabilizer formalin 8. Q Add Ce water 11 <Example 2> Sample 201 N215 Photosensitive material with the same composition as Samples 101 to 115 to 175 μm
The gelatin layer 'k159/- was coated on the back layer to prevent curling. This was processed into a disc film with a diameter of 70 mm. These were designated as samples 201 to 215.

For these films, all of the Macbeth charts were photographed in daylight under the same conditions, and under the conditions in which they are normally photographed.
For example, 15 photos were taken, including scenes shot indoors with a strobe light. These samples were processed as described below and printed on color paper (cabinet size) using an auto printer.
printed on. The average exposure time during printing was checked and recorded.

In addition, Macbeth's Char) 1 - I made a hand-printed print to match the gray from the photographed negative to Color Eaper, and played around with the 18 colors of the resulting print using the U*v*W* color system ( Postscript). In order to express how far each of these points deviates from the original chromaticity point of the Macbeth chart, an average color difference ΔEuv k defined by the following equation was calculated.

These results are shown in Table 2.

Table 2 From this table, it is clear that Samples 205 to 215 of the present invention have a printing time reduced by half compared to Sample 201, and also have excellent color reproducibility.

The disc film of the present invention was subjected to the following rotary development treatment 2.

Color development 38℃ 3 minutes 15 seconds 200 bleaching 6 minutes 30 seconds Washing with water
Fixed for 3 minutes and 15 seconds
Wash with water for 6 minutes and 30 seconds 3
Stable for 15 seconds 1 minute 5 seconds Rotating water 9 30℃ 30 seconds 2000 The liquid composition used in the color development, bleaching, fixing, and stabilization steps used here was the same as the liquid used in Example 1. .

<Example 3> Sample 301 All samples 301 were obtained by making the following changes to sample 201.

(1) 3rd to 5th layer cyan coupler Cpd-3t
1) Replacement with an equivalent mole of C-40 of the present invention (2) Replacement of the magenta coupler pd-5 in the 7th to 9th layers with 2 times the mole of M-11 of the present invention (3) Yellow coupler in the 11th to 13th layers Cpd
-9 was increased to 1.2 times the mole.For this sample, a Macbeth chart print was created using the same procedure as in Example 2.G, R, C, M, Y JEuv was calculated for six colors.

The results are shown in Table 3 together with the results for all samples 201.

As is clear from this result, if all colored couplers are used in the coupler combination of the present invention, all photosensitive materials with vivid reproduction of primary colors can be prepared, and the effects of the present invention are clear.

<Example 4> Sample 401 (present invention) Sample 401 was obtained by making the following changes to sample 201.

(+1 3rd to 5th layer cyan coupler cpa -3'
! Substitute 7 times the mole of C-230 of the present invention f2 + Substitute the magenta coupler cpa -6' of the 7th to 9th layers with an equivalent mole of M-7 of the present invention (3) Furthermore, DIR coupler Cpd -7 of the 7th layer
halved to 0.0259/- Sample 402 (comparative example) The following changes to sample 201? The sample obtained was designated as sample 402.

(1) Cyan coupler cpa-3't in the 3rd to 5th layers was substituted with 100.7 times the mole of Cpd outside the present invention (21 7th layer)
1) IR coupler Cpd-7 of layer 0. O259/
lr? Samples 403 to 405 reduced by half to 50% Same as sample 401, replaced with a coupler as shown in Table 4, and the DIR coupler in the 7th layer Cpd -7'10.0259
/lr? Samples that were reduced in half to 403 to 405 were designated as 403-405.

The above sample was wedge exposed using white light at 4800', and the standard processing and development time described below was halved (1'4
0") treatment and bleaching solution pHt-6.0 to 5.0
The process was lowered to . Further, as in Example 3, B, G, and R in standard treatment.

ΔEuv k of six colors of C, M, and Y was calculated. The results are shown in Table 4.

As is clear from this table, the magenta coupler of the present invention,
The combination of 0 cyan couplers is D due to a little side absorption.
The deterioration of color reproducibility due to the reduction in the interlayer effect that occurs when the number of IR couplers is reduced or when a second grade cypress coupler having high coupling activity is used as a coupler can be effectively prevented. Therefore, it is possible to improve the progress of development without impairing color reproducibility.
It is possible to reduce variations in sensitivity due to development time. Furthermore, it is clear that in the samples of the present invention, even with a bleaching solution having a low pH, the sensitivity of the red-sensitive layer does not decrease, demonstrating the stability of photographic properties due to processing variations in the present invention.

<Example 5> Sample 501 All samples 501 with the changes shown in Table 5 relative to sample 201
~505.

Samples 501 to 505 of the present invention were tested in the same manner as in Example 3, and almost the same effects were obtained.

[Brief explanation of drawings]

Figures 1 and 2 show the results of schematic sensitometry of color photosensitive materials containing water. FIG. 1 shows the magnitude t of unnecessary yellow sub-absorption in the magenta coloring area, and FIG. 2 shows the magnitude of unnecessary magenta sub-absorption in the cyan coloring area. Both figures show the increase Δ in the sub-absorption density corresponding to the exposure amount that gives a density of (fog density + 1.0) of the characteristic curve edge corresponding to gradation exposure. In Figure 1, 1% L'' is shown in Figure 2.

Claims (1)

[Scope of Claims] A silver halide color photographic material having red-sensitive, green-sensitive and blue-sensitive photosensitive layers on a support, comprising a coupler represented by the following general formula (I) and a general formula (II). A silver halide color photographic light-sensitive material characterized in that couplers represented by the following are contained in photosensitive layers having mutually different color sensitivities. (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ In the general formula (I), R_1 is -CONR_3R_4
, -NHCOOR_3, -NHCOOR_5, -NHSO
_2R_5, -NHCONR_3R_4 or -NHS
O_2NR_3R_4, R_2 represents a group that can be substituted on the naphthol ring, m represents an integer from 0 to 3, and X
represents >O, >S, or R_6N<, and Y_1 is a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized aromatic primary amine developer (including an atom that can be separated)
shows. However, R_3 and R_4 may be the same or different and independently represent a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group, and R_5 represents an aliphatic group, an aromatic group, or a heterocyclic group, R_6 represents a hydrogen atom or a monovalent organic group. When m is 2 or 3, R_2 may be the same or different, or may be bonded to each other to form a ring. R_2 and X, or X and Y_1 may be bonded to each other to form a ring. Furthermore, R_1, R_2, X, or Y_1 may form a dimer or more. In general formula (II), R_1_0 represents a hydrogen atom or a substituent (including substituent atoms), and Y_2 represents a hydrogen atom or a group that can be separated (eliminated) by a coupling reaction with an oxidized aromatic primary amine developer. (including possible atoms), and Za, Zb and Zc are methine, substituted methine, =
Represents N- or -NH-. Za-Zb bond and Zb-Z
One of the C bonds is a double bond and the other is a single bond. The case where Zb-Zc is a carbon-carbon double bond includes the case where it is a part of an aromatic ring. Furthermore, R_1_0, Y_
2 and one group in the group consisting of Za, Zb or Zc representing substituted methine may form a dimer or more multimer.