JPS62151849A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a color photographic sensitive material superior in color reproductivity and good in light fastness of a magenta dye image by incorporating at least each one of specified magenta dye image-forming couplers and specified compounds. CONSTITUTION:The color photographic sensitive material contains at least one of the blocket magenta dye image-forming couplers represented by formula I and at least one of the compounds represented by formula II. In these formu lae, R is H or a substituent; X is H or a coupling releasable group; Cp is a coupling blocking group to be allowed to release a colorless or alkali-soluble product by the coupling reaction with the oxidation product of a color develop ing agent; each of A, B, D and E is -N (-Cp, side chain)-, =N-, or the like in accordance with the presence of Cp or not; each of R<1>-R<3> is H, halogen, alkyl, alkenyl, aryl, aryloxy, acyl, acylamino, acyloxy, sulfonamide, cycloalkyl, alkoxycarbonyl, or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide color photographic light-sensitive material. This invention relates to silver chemical color photographic materials.

[Prior art]

Conventionally, when a silver halide color photographic light-sensitive material is imagewise exposed and subjected to color development, an oxidized product of an aromatic primary amine color developing agent and a color former undergo a force-two-pulling reaction, resulting in the production of, for example, indophenol. It is well known that dyes such as , indoaniline, ingmin, azomethine, fenoxacune, 7enadine, and similar dyes are produced and dye images are formed. In such photographic systems, a subtractive color reproduction method is usually adopted, and a color forming agent having an additional color relationship, that is, yellow A silver 10 dendenide color photographic material containing a coupler that develops magenta and cyan colors is used.

Couplers used to form the yellow dye image include, for example, acylaceto-7nilide couplers, and couplers for forming magenta images include, for example, pyrazolone, pyrazolobenzimidazole,
Pyrazolotriazole or indacylon couplers are known, and as couplers for forming cyan dye images, for example, phenol or 7-tole couplers are generally used.

It is desired that the dye image obtained in this way does not change color or fade even if it is exposed for a long time or stored under high temperature and high humidity. It is also desired that the uncolored areas of silver halide color photographic materials (hereinafter referred to as color photographic materials) do not turn yellow (hereinafter referred to as Y-stain) when exposed to light or heat.

However, in the case of magenta couplers, Y-staining due to wet heat in uncolored areas and fading due to light in dye image areas are extremely large compared to yellow couplers and cyan couplers, and often become a problem.

Couplers commonly used to form magenta dyes are 5-pyrazolones. The dye formed from this magenta coupler of 5-pyrazolones is 550nn
In addition to the main absorption near 430 nm, a major problem is that it has a sub-absorption near 430 nm, and various studies have been conducted to solve this problem.

Magenta couplers having an anilino group at the 3-position of 5-pyrazolones have small side absorption and are useful for obtaining color images for printing. Regarding these technologies, for example, U.S. Patent No. 2,343°703, British Patent No. 1,
No. 059,994, etc.

However, the above-mentioned magenta coupler has the disadvantage that the image storage property, especially the fastness of the dye image to light, is severely inferior, and the Y-stain in the uncolored area is large.

As another means for reducing the side absorption near 430nIIl of the magenta coupler, British Patent No. 1.047
, pyrazolobenzimidazoles described in U.S. Pat.
1H described in Nos. 52,418 and 1,334,515
-Pyrazolo[5,1-cl -1,2,4-) lyazole coupler, IH- described in JP-A-59-171956, Research Dischrono+-No. 24531
Pyrazolo [1°5-bl-1,2,4-triazole coupler, Research Disclosure No. 24
IH-piracyo[1,5-cJ 1,
2,3-triazole type coupler, JP-A-59-162
No. 548, Research Disclosure No. 24
IH-imidazo[1,2-bl pyrazole type coupler described in 531, JP-A-60-43659, Research.
Disclosure at--No.

IH-pyrazolo[1,5-bl pyrazole type coupler described in JP-A No. 60-33552, Research Disclosure No. 24220]
Magenta couplers such as IH-pyrazoel[1,5-d]tetrazole type couplers have been proposed. Among these, IH-piracye7[5,1-cl-1,2,4-)
Liazole coupler, IH-pyrazolo El, 5-b
l-1.

2.4-) Riazole coupler, IH-pyrazolo[1
, 5-cJ -1,2,3-triazole coupler,
IH-imidazo[1,2-bl pyrazole coupler,
The dye formed from the IH-pyrazolo[1,5-bl pyrazole type coupler and the IH-pyrazolo[1,5-dl tetrazole type coupler has an Ill absorption near 430n-, which has an anilino group at the above-mentioned 3-position. - Compared to dyes formed from pyrazolones, it is more pigmented and smaller, which is preferable in terms of color reproduction, and furthermore, it has the advantage that the occurrence of Y-stin in uncolored areas is extremely small when exposed to light, heat, and humidity.

However, the light fastness of the azomethine dyes formed from these couplers is rather low, and moreover, the dyes are easily discolored by light, impairing the performance of color photographic materials, especially printed color photographic materials. However, it has not been put to practical use in printed color photographic materials.

Furthermore, in JP-A No. 59-125732, a phenolic compound, a 7-functional diyl ether compound, a A technique has been proposed for improving the fastness to light of a magenta dye image obtained from a 1-t-pyrazolo[5,1-cl 1.2.4-) lyazole type magenta coupler by using a combination of . However, it has been recognized that even the above techniques are still not sufficient to prevent the magenta dye image from fading due to light, and moreover, it is almost impossible to prevent discoloration due to light.

On the other hand, JP-A-56-133734 and JP-A-58-1075
No. 37, No. 58-107538, No. 58-11103
No. 4, No. 58-111035, No. 58-111036
No. 58-111943, No. 58-111944, No. 58-113936, No. 58-113937,
No. 58-113938, No. 58-113939, No. 58-113940, and No. 58-115437 contain
- In the cyclic nitrogen atom of the triazole type magenta coupler,
Various magenta dye image-forming couplers have been proposed in which a blocking group is bonded at a position capable of reacting with an oxidized product of an aromatic primary amine color developing agent.

In addition, JP-A-60-191253 discloses IH-pyrazolo(1,5-b)-1,2,4-) lyazole coupler, IH-pyrazolo(1,5-c) 1,2.3 −
) lyazole coupler, IH-imidazo(1,2-b
) Piracy J Shikokugohei-1me-1+#→~lmonr1tun-k) Sealing type coupler, IH-Pirazoro (1,
5-d) Various magenta dye image-forming couplers have been disclosed in which a blocking group is bonded to a tetrazole type coupler in the same manner as described above.

The above magenta dye image-forming couplers (hereinafter referred to as magenta couplers) are all color developing agents in which the blocking group is an aromatic primary amine type (hereinafter referred to as color developing agents).
The molecular design is such that when it reacts and couples with the oxidant of , it produces a colorless reaction product or an alkali-soluble product that flows out into the developer. In other words, 11-1-pyrazolo(5,1-c
) -1,2,4-) The aforementioned azole-type blocked magenta couplers, including lyazole-type couplers, become capable of a coupling reaction with the oxide of a color developing agent only when the blocking group is removed, resulting in a non-diffusible A magenta dye image can be formed.

One of the reasons why the use of an azole-type magenta coupler having a blocking group as described above can improve the light stability of the magenta dye image produced is that the magenta dye image obtained from the azole-type magenta coupler Although the photostability of the coexisting unreacted 7zole magenta coupler is adversely affected by the photostability of the coexisting unreacted 7zole magenta coupler, the blocking of the monodissociated hydrogen atom that connects one of the cyclic nitrogen atoms of the azole magenta coupler with the blocking group-2 As a result, the photostability of the azole-type magenta coupler itself is improved, and the above-mentioned adverse effects can be reduced to as much as 1J.

However, even if these measures are taken, the photostability of magenta dye images obtained from azole type magenta couplers is still insufficient and unsatisfactory.

[Purpose of the invention]

The present invention has been made in view of the above problems, and an object of the present invention is to provide a color photographic material with excellent color reproducibility and improved light fastness of magenta dye images. .

[Structure of the invention]

The above object of the present invention is achieved by a color photographic material characterized by containing a magenta coupler represented by the following general formula [I] and a compound represented by the following general formula (XI).

General formula [1] In the formula, R represents a hydrogen atom or a substituent, X represents a hydrogen atom or a coupling-off group, and Cρ reacts with an oxidized form of a color developing agent to produce a colorless or fully soluble product. When the Cp group is not bonded, it is synonymous with -N= or the notation, but each may be the same or different), and E is the coupling block that produces the Cp group. When the Cp group is bonded, it represents -N-p, and when no Cp group is bonded, it represents -N=.

Double represents three movable double bonds, where ^, B
ID cannot be 10= at the same time, * R or X may form a dimer or more multimer (, substituents R on adjacent carbons may form a ring) .

General formula (XI[) In the formula, R1 and R4 are each a hydrogen atom, a halogen atom, a furkyl group, an alkenyl group, an alkoxy group, an alkenyloxy group, a hydroxy group, an aryl group, an aryloxy group, an acyl group, and an acylami group. R2 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, a cycloalkyl group, or a heterocyclic group; R3 represents hydrogen Represents an atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a 7-aryloxy group, a 1/2 group, an acyl group, an acyloxy group, a sulfonamide group, a cycloalkyl group, or an alfkidicarbonyl group. Further, R2 and 83 may be ring-closed with each other to form a 5-shell or 6-shell ring, and R2 and R3 may further form a methylenedioxy ring. Y represents an atomic group necessary to form a chroman or coumaran ring.

The present invention will be explained in more detail below.

First, the azole type magenta coupler having a blocking group represented by the general formula [I] according to the present invention will be described.

General formula ([) In general formula [1], R represents a hydrogen atom or a substituent, and among the substituents, preferred are a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a Schiff/group, alkoxy group, aryloxy group, heterocyclic oxy group,
7 syloxy group, carbamoyloxy group, silyloxy group, sulfonyloxy group, acylami 7 group, anilino group, ureido group, imido group, sul 7 amoyl 7 mi 7 group, carbamoyl 7 group, furkylthio group, 7 lylthio group, heterocycle These include a thio group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfonamide group, a carbamoyl group, an acyl group, a sulfonyl group, a sulfonyl group, a sulfinyl group, a flukoxycarbonyl group, and an aryloxycarbonyl group. X is a hydrogen atom, a halogen atom, a carboxyl group, an oxygen atom, a nitrogen atom,
Alternatively, it represents a group that couples with a carbon at a coupling position via a sulfur atom and is a group that is decoupled, and R or X may form a dimer or more multimer, or a substitution on an adjacent carbon. The groups R may form a ring, and the coupler group represented by the general formula [I]
It may be in the form of a polymer coupler present in the A chain, and a polymer derived from a vinyl monomer having a moiety represented by general formula [I] is particularly preferred. In this case, at least one of R and X represents a vinyl-containing group.

More preferably, a halogen atom (e.g., chlorine atom, bromine atom, etc.), a substituted or unsubstituted alkyl group (e.g.,
Methyl group, propyl group, t-butyl group, trifluoromethyl group, tridecyl group, 3-(Z,4-di-t-amylphenoxy)propyl group, allyl group, 2-dodenyloxyethyl group, 3-phenoxy propyl group, 2-hexysulfonylethyl group, cyclopentyl group, pencil group, etc.), substituted or unsubstituted 7-aryl group (e.g. phenyl group, 4-1-butyl 7-enyl group, 2,4-di- t-7 mylphenyl group, 4-tetradecane 7 midophenyl group, etc.)
, heterocyclic group (5-7 shell ring group including 0, N, S etc., for example,
2-furyl group, 2-chenyl group, 2-pyrimidinyl group,
2-benzothiazolyl group, etc.), cyano group, alkoxy group (e.g., ethoxy group, ethoxy group, 2-methoxyethoxy group, 2-dodecyloxyethoxy group, 2-methanesulfonylethoxy group, etc.), aryloxy group, (e.g., phenoxy group, 2-methylphenoxy group, 4-1-butylphenoxy group, etc.), heterocyclic oxy group (e.g., 2-methylphenoxy group, 4-1-butylphenoxy group, etc.),
penzimigzolyloxy group, etc.), acyloxy group (e.g., acetoxy group, hexadecanoyloxy group, etc.),
Carbamoyloxy group, (for example, N-phenylcarbamoyloxy group, N-ethylcarbamoyloxy group, etc.)
, silyloxy group (e.g., trimethylsilyloxy group, etc.), sulfonyloxy group (e.g., dodecylsulfonyloxy group, etc.), acylamide 7 group (e.g., 7set7)
Mido group, benz7mido group, tetradecanamide group, α-
(2,4-not-7-milphenoxy)butyramide group, γ-(3-t-butyl-4-hydroxyphenoxy)
Butyramide group, ff-(4-(4-hydroxyphenylsulfonyl)phenoxy)decaneamide group, etc.), 7
Nilino group (e.g. phenylamide 7 group, 2-chloroanilino group, 2-chloro-5-tetradecanamide ani+J/
group, 7 groups of 2-chloro-5-dodenyloxylponylanily, 7 groups of N-7 cetylanily, 2-chloro-5-If
f -(3-t-butyl-4-hydroxy72/xy)
dodecanamide) anilino group, etc.), ureido groups (e.g., phenylureido group, methylureido group, N,N-dibutylureido group, etc.), imide groups (e.g., N-succinimide group, 3-pencylhyguntoynyl group, 4-(2
-ethylhexanoyl7mino)7talimido group, etc.), sulfur77moylamide7 groups (e.g., N,N-noprobylsul77moylamide7 groups, N-methyl-N-decylsulfur77
moylamide 7 groups, etc.), alkylthio groups (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, 2-butoxy-5-t-octylphenylthio group, 3-pentadecylphenylthio group, 2-carboxyphenylthio group, 4-tetradecanamidophenylthio group, etc.), heterocyclic thio group group (e.g., 2-benzothiazolylthio group, etc.), alkoxycarbonylamino group (e.g., 7 methoxycarbonylamine group, 7 tetradecyloxycarbonylamine group, etc.), aryloxycarbonylamino group (e.g., phenoxycarbonylamino group, 7 group, etc.), 2,4-not-butylphenoxycarbonylamide group, etc.), sulfone 7mido group (e.g., methanesulfonamide group, hexadecanesulfone 7mide group, benzenesulfone 7mide group, p-toluenesulfonamide group, octadecane group) slephon 7 mido group, 2-methyloxy-5-butylbenzenesulfonamide group, etc.), carbamoyl group (e.g., N-ethylcarbamoyl i, N, N-dibutylcarbamoyl group, N-
(2-dodecyloxyethyl)carbamoyl group, N-methyl-N-dodecylcarbamoyl group, N-+3-(2,
(4-di-L-amyl7eth/xy)propyl)carbamoyl group, etc.), acyl group (e.g., acetyl group, (2,4-
di-t-7-milphenoxy)acetyl group, benzoyl group, etc.), sulfamoyl group (e.g., N-ethylsulfamoyl group, N,N-dipropylsulfamoyl group, N-
(2-dodecyloxyethyl)sulfamoyl group, N-
ethyl-N-dodecyl77moyl group, N,N-noethylsulf7amoyl group, etc.), sulfonyl group (e.g. methanesulfonyl group, octanesulfonyl group, benzenesulfonyl group, toluenesulfonyl group!!F), sulfinyl group (e.g. octanesulfinyl group, dodecanesulfinyl group, benzenesulfinyl group, etc.), alkoxycarbonyl group (e.g., methoxycarbonyl group, butyloxycarbonyl group, dodecyloxycarbonyl group, octadecyloxycarbonyl group, etc.), aryloxycarbonyl group (e.g., 7-ethyloxycarbonyl group, etc.), /oxycarbonyl group, 3-pentadecyloxycarbonyl group, etc.);
For example, acetoxy group, propanoyloxy group, benzoyloxy group, 2,4-dichlorobenzoyloxy group,
Ethoxyoxaloyloxy group, bilbinyloxy group,
Cinnamoyloxy group, phenoxy group, 4-cyanophenoxy group, 4-methanesulfone 7 mido 7 2/oxy group, 4
-methanesulfonylphenoxy group, a-su7toxy group,
3-pentadecylphenoxy group, benzyloxycarbonyloxy group, nidoxy group, 2-cyanoethoxy group, benoloxy group, 2-7enethyloxy group, 2-phenoxyethoxy group, 5-phenyltetrazolyloxy group,
(2-benzothiazolyloxy group, etc.), groups linked via nitrogen atoms (e.g., benzenesulfone 7miV group, N-ethyltoluenesulfonamide group, heptafluorobutane 7mil'i, 2,3,4, 5,6-bentafluoro E7 henz7 mido group, octane sulfonamide group, p-cyanophenylureido group, N,N-diethylsul77 moyl7
Mi7 groups, 1-piperidyl! ,5゜5-tmethyl-2,4
-dioxo-3-oxazolidinyl group, 1-benzyl-
5-ethoxy-3-hydantoynyl group, 2N-1,1-
Nooxo-3(2■)-oxo-1°2-benzointhi7zolyl group, 2-oxo-1,2-fuhydro-1-pyridinyl group, imidazolyl group, pyrazolyl group, 4-7ceto7mido-1-pyrazolyl group, 3゜5-tmethylpyrazolyl group, 4-(3-hydroxypropyl)-1-pyrazolyl group, 3.5-diethyl-1,2t4-tri7zol-1-yl, 5- or 6-promobenzotriazol-1 -yl group, 5-methyl-1゜2.3-) +77
Sol-1-yl group, penzimitazolyl group, 3-benzyl-1-hyguntoynyl group, 1-benzyl-5-hexadecyloxy-3-hydantoynyl group, 5-methyl-1-tetrazolyl group, arylazo group (e.g. 4-methoxyphenylazo group, 4-hybaloylami/-3-hydroxyphenylazo group, β-su7tyl7zo group, 4-hydroxy-3-methylphenylazo group, 4-pivaloyl7minophenylazo group, etc.), sulfur atom (e.g., 7 enylthio group, 2-carboxyphenylthio group, 2-methoxy-5-t-octylphenylthio group, 4
-methane
-t-octylphenylthio group, bennorthio group, 2-
Cyanoethylthio group, 1-ethoxycarbonyltridecylthio group, 5-phenyl-2,3,4,5-tetrazolylthio group, 2-benzothiazolylthio group, 2-dodecylthio-5-thiophenylthio group, 2-7 (enyl-3-dodecyl-1,2,4-)riazolyl-5-thio group, etc.).

To describe in more detail the divalent group in which R or
0-Decylene group, + CH2Cl12-0- CIl□
C1! □-, etc.), substituted or unsubstituted phenylene groups (e.g., 1.4-phenylene group, 1.3-phenylene group,
-NlIC0-R, -C0t41(- group (R, represents a substituted or unsubstituted alkyl group or phenylene group, for example -NHCOC1hCH2CONH-5 -NHCOCII2C-CII□C0NH-1Hp -S-R, -S group (R, represents a substituted or S-substituted fullkylene group, for example, + s-CI(2CH2-S-1
represents a divalent group at an appropriate location.

When what is represented by the general formula [■] is contained in the vinyl monomer, the vinyl group may have a substituent other than that represented by the general formula [I], and preferably one substituent is a hydrogen atom. , represents a chlorine atom, or a lower furkyl group having 1 to 4 carbon atoms (eg, methyl group, ethyl group).

Monomers including those represented by general formula [1] may be copolymerized with non-color-forming ethylene-like monomers that do not couple with the oxidized color developing agent.

Non-color-forming ethylene-like monomers that do not couple with the oxidized form of a color-forming developing agent include acrylic acid, α-chloroacrylic acid, a-alkyl acrylic acid (such as methacrylic acid), and esters derived from these acrylic acids. or amides, such as acrylamide, butylacrylamide, t-butylacrylamide, diacetone acrylamide, methacrylamide, methyl acrylate, ethyl acrylate, propyl acrylate, butylacrylate, t-butylacrylate, i-butylacrylate, 2-ethylhexyl acrylate , octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and β-hydroxy methacrylate), methylene dibis acrylamide, vinyl esters (e.g. vinyl acetate, vinyl propionate and vinyl laurate), 7-crylonitrile, methacrylo Nitriles, aromatic vinyl compounds (e.g. styrene and its conductors, vinyltoluene, cuvinylbenzene, vinylacetophenone and sulphostyrene), itaconic acid, citraconic acid,
Crotonic acid, vinylidene chloride, vinyl alkyl ether (e.g. vinyl ethyl ether), maleic acid,
Maleic anhydride, maleic ester, N-vinyl-2
-pyrrolidone, N-vinylpyridine and 2- and 4
-Vinylpyridine, etc. Two or more kinds of the non-color-forming ethylenically unsaturated monomers used here can also be used together. For example, butyl 7 acrylate and methyl acrylate, styrene and methacrylic acid, methacrylic acid and acrylamide, methyl 7 acrylate and diacetone acrylic 7
Mido et al.

As is well known in the polymer color coupler art, non-chromogenic ethylenically unsaturated monomers for copolymerization with solid water-insoluble monomeric couplers depend on the physical properties and/or chemistry of the copolymer formed. The photographic colloidal properties such as solubility, compatibility with the binder of the photographic colloid composition, such as gelatin, its flexibility, thermal stability, etc., can be selected to be most suitable.

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

The Cp group represents a blocking group which produces a colorless or alkali-soluble reaction product after reaction with an oxidized color developing agent and is attached at its coupling position;
More preferably, the following general formula % formula % General formula (n) where R2 is an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic oxycarbonyl group, an alkylcarbamoyl group, a 7-arylcarbamoyl group, a heterocyclic carbamoyl group, an alkyl Carbonyl group, arylcarbonyl group, heterocyclic carbonyl group, alkoxythiocarbonyl group, aryloxythiocarbonyl group, furkylsulfonyl group, arylsulfonyl group, heterocyclicsulfonyl group, alkylsulfinyl group, arylsulfinyl i, ix
R5 represents the above R2
In addition to the same groups as defined in , hydrogen atoms, halogen atoms, alkyl groups (linear, branched, cyclic), aryl groups, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, acyloxy groups, ami7 groups , represents an alkylcarbamoyl group, an arylcarbamoyl group, an acylcarbamoyl group, or a polycyclic ring. Moreover, R1 and R2 are ring-closed to each other, and -CI! - may form a 5-shell or 6-shell hydrocarbon ring or a 5-shell or 6-shell heterocycle having a carbonyl group at the 0-position.

General formula CI [I] However, R2, R, reacts with the oxidation product of the color developing agent as described in the above general formula [■], and after the -TIMEe group is released, an intramolecular nucleophilic reaction occurs. represents a group that causes charge transfer or a group that causes charge transfer along a conjugated system.

General formula [IV] ffiL, R2, and R3 have the same meanings as stated in the above general formula (V), Y represents an oxygen atom or a sulfur atom, and Z represents a carbonyl group, a thiocarbonyl group, an oxalyl group, or a sulfonyl group. group, sulfinyl group, methylene or substituted methylene group.

General formula (V) General formula (Vl) -' However, in general formulas (V) and [VI], ゛~eye' represents a cyan image-forming coupler residue, - is a phenyl nucleus and a 7-toll nucleus condensed with R represents the same meaning as defined above, n represents an integer from 1 to 4 when the cyan image forming coupler has a phenol nucleus, and 1 when the cyan image forming coupler has a naphthol nucleus. represents an integer of ~6,
For TIME, in the general formula CI[[], + Y−z
- represents the same meaning as explained in general formula (N). Here, when n=2 or more, R may be the same or different.

Next, the substituent represented by the general formula (If), [I[I], (IV], (V) or (Vl) will be described in more detail.

R2 is an alkoxycarbonyl group (e.g., methoxycarbonyl group, dodecyloxycarbonyl group, benoloxycarbonyl group, cyclohexyloxycarbonyl group, etc.), aryloxycarbonyl group (e.g., 7E/xycarbonyl group, etc.), heterocyclic oxycarbonyl group groups (e.g., 3-pyridyloxycarbonyl group, 2-tetrahydropyranyloxycarbonyl group, 2-chenyloxycarbonyl group, etc.), alkylcarbamoyl groups (e.g., N-
methylcarbamoyl group, N-methyl-N-(4-carboxyphenyl)carbamoyl group, N,N-noethylcarbamoyl group, N-cyclohexylcarbamoyl group, etc.),
Arylcart(moyl group (Example 11rN-phenylcarbamoyl group, N-(4-carboxyphenyl)carbamoyl group, N-(3,5-dicarboxyphenyl)carbamoyl group, N-(2-chloro-5-7cetamido) phenyl)carbamoyl group, 2-N-7tylcarbamoyl group, N-4-ethoxycarbonylphenyl)carbamoyl i, etc.), monocyclic carbamoyl group (e.g. N-(2-pyrinol)carbamoyl group, N-ethyl- N-(4-pyrimidinyl)carbamoyl group, etc.), furkylcarbonyl group (e.g., acetyl group, pivaloyl group, i-butyroyl group, cyclohexanoyl group, 3-butynoyl group, cyclopropanecarbonyl group, phenyl 7-cetyl group) , arylcarbonyl group (e.g., benzoyl group, 4-7toxybenzoyl group, 2-chlorobenzoyl group, β-7toyl group, 4-t-butylbenzoyl group, etc.), heterocyclic carbonyl group (e.g., 2-pyrybenzoyl group, etc.) noncarbonyl group, etc.), alkoxythiocarbonyl group (e.g., benyloxythiocarbonyl group, ethoxythiocarbonyl group, etc.), arylthiocarbonyl group (e.g., phenoxythiocarbonyl group, etc.), alkylsulfonyl group (e.g., methanesulfonyl group) , octanesulfonyl group, dodecanesulfonyl group, 2-ethylhexanesulfonyl group, etc.), arylsulfonyl group (e.g. benzenesulfonyl group, p-)
luenesulfonyl group, p-7cetamidophenylsulfonyl group, etc.), heterocyclic sulfonyl group (e.g. 2-pyrinonesulfonyl group, 2-thio7enesulfonyl group, etc.), alkylsulfinyl i+ (e.g. methanesulfinyl group, octane sulfinyl Ml), arylsulfinyl group (e.g., 4-benzenesulfinyl group, etc.), bicyclic sulfinyl group (e.g., 4-pyridine sulfinyl group, 5-ky7rinsulfinyl group?), alkylsulfamoyl group (e.g., N- Ethylsulfamoyl group, N-
benzylsulfamoyl group l), 7lylsul7amoyl group (example L+!, N-phenylsulfamoyl group, N-ethyl-N7!nylsulfamoyl group, N-(4
-methoxycarbonyl7enyl)sul77moyl group, N
-(2-chlorophenyl)sulf77 moyl group $), heterocyclic sulfT moyl group (e.g., N-(2-pyridyl)
sulfamoyl group, N-(2-quinolyl)sulfamoyl group, etc.), nitro group, cyano group, carboxyl group.

In addition to the same group as defined in R2 above, R3 is
Hydrogen atoms, halogen atoms (e.g., chlorine atoms, bromine atoms, etc.), alkyl groups (e.g., methyl groups, t-butyl groups,
i-propyl group, cyclohexyl group, allyl group), aryl group (e.g. phenyl group, 4-nitrophenyl group, 2-nitro-4-Schiff/phenyl group, 4-cyanophenyl group, 4-methanesulfonylphenyl group) etc.), alkoxy groups (e.g., methoxy, ethoxy, benzyloxy??), 7-aryloxy groups (e.g., phenoxy, 4-nitrophenoxy), alkylthio groups (e.g., ethylthio, benzylthio group, 2-cyclohexanone-1-thio group, etc.), 7-arylthio group (e.g., phenylthio group, 4-chlorophenylthio group, 4-methoxyphenylthio group, 4-cyanophenylthio group, 2
-chloro-4-tetradecanorphenylthio group, etc.), 7
siloxy group (e.g., acetoxy group, benzoyloxy group, 2-pyrinonecarbonyloxy group, hexanoyloxy group, etc.), ami7 group (e.g., ami7 group, 7nilino group, 2-chloroanili7 group, cyclopentylamino group) ,
a-ethoxycarbonyltridecylamine 7 groups, N-piperidi 7 groups, N-morpholino groups, etc.), alkylcarbamoyl groups (e.g., ethylcarbamoyl groups, etc.), arylcarbamoyl groups (e.g., phenylcarbamoyl groups, 4-
methoxycarbamoyl group, 2-chloro-4-7tansulfonylcarbamoyl group, etc.), acylcarbamoyl group (e.g., N-7 cetylcarpamoyl group, N-benzoylcarbamoyl group, etc.), or heterocyclic group (e.g., 2-pyridyl group, 2-pyrimidyl group, 2-chenyl group, 2-furyl group, etc.). In addition, R2 and R3 are ring-closed with each other, and -C
A 5-shell or 6-shell hydrocarbon ring having a carbonyl group at the α-position relative to H= (for example, the following margin υ, etc., where R, R1 is a hydrogen atom, or an alkyl group, aryl group, alkoxy group defined as R1) group, aryloxy group, alkylthio group, arylthio group, ami7 group,
Acylamide 7 groups, carbamoyl group, sul 77 moyl group,
Represents a sulfonamide group, sulfonyl group, sulfinyl group, and acyl group. ) may be formed.

TIME represented by the general formula [■] is U.S. Patent No. 4,248
゜962, JP-A-56-114946, JP-A No. 57-5
No. 6837, No. 57-154234, No. 57-188
635 and 58-98728, which are already known.

Y in the general formula (IV) represents an oxygen atom or a sulfur atom, and 2 represents a carbonyl group, thiocarbonyl group, oxalyl group, sulfonyl group, sulfinyl group, methylene group or substituted methylene group (for example, methylmethylene group, Ethylmethylene group, phenylmethylene group, chloromethylene group, isopropylmethylene group, 2-pyrinnormethylene group, 1
-imigzolylmethylene group, etc.).

To explain general formula [1] in more detail, general formula [■], [
■] or CIM).

In the following margin general formula [■] General formula [■] General formula (IX) General formula [■], [■] and (IX), R1
X5Cp, ^, B and HiDba general formula (r) Nio (f
'l R, X5Cp, A, B and D, respectively, are synonymous.

Among the magenta couplers according to the present invention represented by general formulas [■], [■] and (IX), [IX] is particularly preferred, and couplers represented by general formulas (X] and (XI) are most preferred. It is.

General formula (X) General formula [XI] In general formula [X] and (XI), R,
ρ has the same meaning as R, X and cp in general formula [1].

Typical specific examples of the magenta coupler according to the present invention are shown below, but the magenta coupler used in the present invention is not limited thereby.

−ゝ、 Margin below 0OH N-N-N (13) CI.

O H C26) CH.

1:J* C8゜ shstl,, NHL:0CHCONIC,H,.

O CH.

Nυ2 These couplers are disclosed in Japanese Patent Application Laid-open Nos. 56-133734, 58-107537, 58-107538, and 5
No. 8-111034, No. 58-111035, No. 58
-111036, 5B-111943, 58-
No. 111944, No. 58-113938, No. 58-1
No. 13937, No. 58-113938, No. 58-11
No. 3939, No. 58-113940, No. 58-115
It can be synthesized with reference to No. 437, No. 60-191253, and the like.

The couplers of the invention typically have IX per mole of silver halide.
1G-3 to 1 mole preferably lX10-2 to 8X 1
It can be used in a 0-' molar range.

The couplers of the present invention can also be used in combination with other types of magenta couplers.

The magenta dye image stabilizer (hereinafter referred to as dye image stabilizer) used in conjunction with the magenta coupler of the present invention is a coumaran or chroman compound represented by the following general formula [■].

The following is a blank general formula [■] In the formula, R1 and R4 are each a hydrogen atom, a) lodene atom, an alkyl group, an alkenyl group, an alkoxy group, an alkenyloxy group, a human mixy group, an aryl group, an aryloxy group, a 7-syl group, represents a 7syl7mino group, a 7syloxy group, a sulfonamide group, a cycloalkyl group, or an alphkidicarbonyl group, and R2 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, a dichlorofurkyl group, or a heterocyclic group. , R3 is a hydrogen atom, a halogen atom,
It represents an alkyl group, an alkenyl group, an aryl group, an aryloxy group, an acyl group, an acylamide group, an acyloxy group, a sulfonamide group, a dichlorofurkyl group, or an alkoxycarbonyl group.

Each of the groups listed above may be substituted with other substituents. Examples of substituents include alkyl groups, alkenyl groups, alkoxy groups, aryloxy groups, hydroxy groups,
Examples include an alphkidicarbonyl group, an aryloxycarbonyl group, an acylamide group, a carneumoyl group, a sulfonamide group, a sulfamoyl group, and the like.

Further, R2 and R5 may be ring-closed with each other to form a 5-shell or 6-shell ring. Further, R2 and R3 may be ring-closed to form a methylenezoxy ring.

Yl represents an atomic group necessary to form a chroman or coumaran ring.

This chroman or coumaran ring may be substituted with a /S loden atom, an alkyl group, a dichlorofurkyl group, an alkoxy group, an alkenyl group, a flukenyloxy group, a hydroxy group, an aryl group, a 7-aryloxy group, or a heterocyclic group, and may further be substituted with a spiro ring. may be formed.

Among the compounds represented by the general formula [■], the compounds particularly useful in the present invention are the general formulas [■a] and [■b].

It is included in the compounds represented by (XI c), (XI d) and [■e].

General formula Cffa) General formula (Xlb) General formula [■C] General formula (X[d) General formula (Xl[e) General formula [■a) t(■b], [■e), (XI[d ]
and R', R2, R3 and R4 in [X[e] have the same meanings as in the above-mentioned formula [■], and R5, R
6, R7R", R9 and lR10 each represent a hydrogen atom, a halogen atom, a furkyl group, a dichlorofurkyl group, an alkoxy group, a hydroxy group, an alkenyl group, a flukenyloxy group, an aryl group, a 7-aryloxy group, or a heterocyclic group.

Further, Rs and R6, R6 and R', R7 and R', R' and R'', and R9 [10] bond to each other to form a hydrocarbon ring (furthermore, the hydrocarbon ring is an alkyl group). May be replaced with

The general formula (X[al-(■b), (Xll eat■
d] and [■e], R1 and R4 are hydrogen atoms, furkyl groups, alkoxy groups, hydroxy groups, or cycloalkyl groups [2 and R3 are hydrogen atoms, alkyl groups, cycloalkyl groups, R5, R', R) Re , R9 and RIG hydrogen atoms, alkyl groups, or cycloalkyl groups are particularly useful.

Typical specific examples of these compounds are shown below, but these are not intended to limit the compounds used in the present invention.

Below margins C11-1) C11-2) l3 CI-3) CH3 C11-4) CI-5) CH-6) CI-7) CI-8) C11-9) CI-10) CI-11) II CH -12) CI-13) CI-14) C11-15) CI-16) -= Tomiro.
Q-υ CH-22) C11-23) ell-24) CI-25) C11-26) CI-27) CI-28) CI-29) CI-30) Cl-31) C11-32) C11-33 ) CI+-34) C11-35) CI! -36) CH-37) CH-38) CI-39) CM-40) CI-41) C11-42) CI-43) CI-44) CH-45) CI-46) C11-47) H CI! -48> CH-49) CH-50) CH-51) C11-52) H CH-53) C5H7 CI-54) The magenta dye image stabilizer represented by the general formula [■] is tetraheto o7 (Teraherdron)
.

1970, vol 26, pages 4743-4751, Journal of the Chemical Society of Japan, 19f2, No. 10, 198
pp. 7-1990, Chemical Letters (Chess,
Lett), 1972 (4), 315 ~
It includes the compounds described in JP-A-55-139383, page 316, and can be synthesized according to the methods described therein.

The amount of the dye image stabilizer represented by the general formula [■] of the present invention to be used is preferably 5 to 300 mol%, and more preferably Preferably it is 10 to 200 mol%.

In the color photographic material of the present invention, in addition to the magenta dye image stabilizer of the present invention, other magenta dye image stabilizers, such as U.S. Pat.
, 982.944, 4,254.216, JP-A-55-21004, JP-A-54-145530, British Patent Publication 2, 077.

No. 455, No. 2,062,888, U.S. Patent No. 3,76
No. 4,337, No. 3.432,300, No. 3,57
No. 4,627, No. 3,573,050, Japanese Unexamined Patent Publication No. 1973
-152225, 53-20327, 53-1
No. 7729, No. 55-6321, No. 54-485
No. 38, No. 56-159644, British Patent No. 1,34
Phenol compounds or phenyl ether compounds described in No. 7.556, Fine 1fi Z, No. 066°975, Japanese Patent Publication No. 54-12337, No. 48-31625, U.S. Patent No. 3,700,455, etc. are also used together. You can also.

Although it is preferred that the magenta couplers of the invention and the dye image stabilizers of the invention are used in the same layer, the stabilizers may be used in layers adjacent to the layer in which the couplers are present.

The color photographic material of the present invention can be, for example, color negative and positive films, color photographic paper, etc., but the method of the present invention is especially effective when using color photographic paper that is intended for direct viewing. is effectively demonstrated.

The silver dendecide photographic materials of the present invention, including this color photographic paper, may be for monochromatic use or for multicolor use. In the case of 7% silver lodenide photographic material for multicolor use,
In order to perform subtractive color reproduction, a /10 silver denride emulsion layer containing magenta, yellow and cyan couplers as photographic couplers and a non-photosensitive layer are formed on the support in an appropriate number and layer. It has a structure in which layers are laminated in order (although the number and order of layers may be changed as appropriate depending on the important performance and purpose of use).

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention includes silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloride, etc. as I\silver halide. Any of those used in conventional silver halide emulsions can be used.

The silver halide grains used in the silver halide 7L polishing of the present invention may be obtained by any one of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are created. The method for seeding and growing the seed particles may be the same or different.

In the silver halide emulsion, halide ions and silver ions may be mixed simultaneously, or one may be mixed in the presence of the other. In addition, while considering the critical growth rate of silver halide crystals, we added halide ions and silver ions to
Growth may be performed by controlling and sequentially adding H+pA g. The silver halide composition of the grains may be changed using the Comperbutane method after growth.

When producing the silver halide of the present invention, the grain size, grain shape, grain size distribution, and grain growth rate of silver halide grains can be controlled by using a silver halide solvent as necessary.

The silver halide grains used in the silver halide emulsion of the present invention are prepared in the process of forming and/or growing the grains such as cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or complex salt, rhodium salt or complex salt. , iron salts or complex salts,
Metal ions can be added to the inside of the particles and/or included on the particle surfaces, and by placing them in an appropriate reducing atmosphere, reduction sensitizing nuclei can be provided inside the particles and/or on the particle surfaces. .

Silver halide of the present invention? In the L agent, ineffective soluble salts may be removed after the growth of silver halide grains is completed, or the L agent may be left in the L agent. When removing the salts, the method described in Research Disclosure No. 17643 can be followed.

The silver halide grains used in the silver halide emulsion of the present invention may consist of a uniform layer inside and on the surface, or
It may also consist of different debris.

The silver halide grains used in the silver halide emulsion of the present invention may be grains in which a latent image is mainly formed on the surface, or grains in which a latent image is mainly formed inside the grains.

The silver halide grains used in the silver halide emulsion of the present invention may have a regular crystal shape or may have an irregular crystal shape such as a spherical or plate shape. In these particles, any ratio between the (too1 plane and the (1111 plane) can be used. Also, they may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.

The silver halide emulsion of the present invention may be a mixture of two or more silver halide emulsions that have been separately formed.

The silver halide emulsion of the present invention is T-sensitized by a conventional method. That is, compounds containing sulfur that react with silver ions,
A sulfur sensitization method using activated gelatin, a selenium sensitization method using a selenium compound, a reduction sensitization method using a reducing substance, a noble metal sensitization method using a Ta metal compound, etc. can be used alone or in combination. can.

The silver halide emulsion of the present invention can be optically sensitized to a desired wavelength range using a dye known as a sensitizing dye in the photographic industry. As the sensitizing dye, +11 may be used alone, but 2Ni or more may be used in combination. Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect, or a compound that does not substantially absorb visible light! A supersensitizer that enhances the sensitization of 4'rE with an intensification angle of 1 and 6 may be included in the emulsion.

The silver halide emulsion of the present invention includes steps for producing light-sensitive materials,
During chemical ripening for the purpose of preventing capri during storage or photo processing and/or maintaining stable photographic performance,
and/or at the end of the chemical ripening, and/or after the end of the chemical ripening and before coating the silver halide emulsion, compounds known in the photographic industry as capri anti+L cutters or stabilizers can be added.

Gelatin is advantageously used as a binder (or protective colloid) for the silver halide emulsion of the present invention, but
In addition, hydrophilic colloids such as gelatin derivatives, graft polymers of gelatin and other polymers, proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as single or co-RP aggregates can also be used.

The photographic emulsion layer of the light-sensitive material using the silver halide emulsion of the present invention, the hydrophilic colloid (hydrophilic colloid) C4 is used alone or in combination with a hardening agent that crosslinks binder (or protective colloid) molecules and increases film strength. It is hardened by this. Before the dura mater, go to JI! ! It is desirable to add the photosensitive material in an amount that can harden the solution so that there is no need to add a hardener to the solution.
It is also possible to add a hardening agent to the processing solution.

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

A dispersion of a water-insoluble or poorly soluble synthetic polymer (
latex).

In the emulsion layer of the silver halide color photographic light-sensitive material of the present invention, an aromatic primary amine developer (
For example, a dye-forming coupler is used that forms a dye by performing a camping reaction with an oxidized product of p-phenylenediamine derivatives, aminophenol derivatives, etc.). The dye-forming couplers are typically selected for each emulsion layer to form a dye that absorbs light in the light sensitive spectrum of the emulsion layer, with a yellow dye forming layer for the blue light sensitive 7L agent layer. A magenta dye-forming coupler is used in the green light-sensitive emulsion layer, and a cyan dye-forming coupler is used in the red light-sensitive emulsion layer. However, depending on the purpose, silver halide color photographic materials may be produced using different combinations from the above.

Examples of yellow dye-forming couplers include acylacetamide couplers (e.g., benzoylaceto 7nilides, pivaloylaceto 7nilides), and magenta dye-forming couplers include, in addition to the couplers of the present invention, 5-pyrazolone couplers, pyrazolobenzimidazole couplers, and pyrazolobenzimidazole couplers. Examples include zolotriazole, open-chain acylacetamide couplers, and cyan dye-forming couplers such as lotus 7 toll couplers and phenol couplers.

These dye-synthesizing couplers preferably have a group called a pallast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. In addition, even if these dye-forming couplers are 4-equivalent, in which 4 molecules of silver ions need to be reduced in order to form 1 molecule of dye, only 2 molecules of silver ions need to be reduced. It doesn't matter what's current.

For hydrophobic compounds such as dye-forming couplers that do not need to be adsorbed onto the surface of silver herodenide crystals, various methods can be used, such as solid dispersion, latex dispersion, and oil-in-water emulsion dispersion. It can be appropriately selected depending on the chemical structure of the hydrophobic compound such as the coupler. For the oil-in-water emulsion dispersion method, conventionally known methods for dispersing hydrophobic additives such as couplers can be applied. Usually, a high boiling point organic solvent with a boiling point of about 150°C or higher is used, and if necessary, a low boiling point, α and/or a water-soluble organic solvent are used together to dissolve and disperse in a hydrophilic binder such as an aqueous gelatin solution using a surfactant using a stirrer, homogenizer, colloid mill, 70-noet mixer, ultrasonic device, etc. After emulsifying and dispersing using a means,
It may be added to the desired hydrophilic colloid layer. A step of removing the low boiling point organic solvent may be included simultaneously with the dispersion or dispersion.

High-boiling point oils and L (↑: 1: core acids and non-spreading phenol derivatives, 7-talic acid esters, phosphoric acid esters, citric acid esters, benzene varnishes, alkylamides, fatty acid esters, An organic solvent having a boiling point of 150''C or higher, such as trimesic acid ester, is used.

Anionic surfactants, nonionic surfactants, and cationic surfactants are used as dispersion aids when hydrophobic compounds are dissolved in a low boiling point solvent alone or in combination with a high boiling point solvent and dispersed in water using machines or ultrasound. Surfactants can be used.

The oxidized form of the developing agent or the electron transfer agent may migrate between the emulsion layers (between the same color-sensitive layers and/or between different color-sensitive layers) of the color photosensitive material of the present invention, causing color turbidity. Color antifogging agents are used to prevent deterioration of sharpness and noticeable graininess.

What is the color antifoggant? One L agent layer itself may be used,
An intermediate layer may be provided between adjacent emulsions Jtd and used as the intermediate layer.

Anti-fogging 11-1 IF prevents deterioration of images due to UV exposure due to discharge caused by charging of the photosensitive material due to friction, etc. in hydrophilic colloid layers such as protective layers and intermediate layers of the photosensitive material of the present invention.
It may contain an ultraviolet absorber in order to

A color light-sensitive material using the silver halide emulsion of the present invention can be provided with auxiliary layers such as a filter layer, an antihalation layer, and/or an ylanobin prevention layer.

These layers and/or the emulsion layer may contain dyes that are washed out or bleached from the color light-sensitive material during development.

The silver halide emulsion j (II) of the silver halide photosensitive material using the silver halide emulsion of the present invention, and/or the hydrophilic colloid layer of the silver halide emulsion reduces the gloss of the photosensitive material and increases the additivity. A matting agent can be added to prevent sticking.

A lubricant may be added to reduce the sliding friction of the light-sensitive material using the silver halide emulsion of the present invention.

An antistatic agent for the purpose of preventing static electricity is added to a light-sensitive material using the silver halide emulsion of the present invention.

・Total anti-W coating is sometimes used for the antistatic layer on the side of the support on which the emulsion is not laminated, or when the 7L agent layer is laminated on the emulsion layer and/or the support. For use in protective colloid layers other than the emulsion layer (1).

The photographic emulsion layer and/or the hydrophilic colloid layer of the light-sensitive material using the silver halide emulsion of the present invention may include improved coating properties,
Antistatic, improved slipperiness, and emulsification! Various surfactants are used for the purpose of preventing adhesion, improving photographic properties (such as accelerating development, increasing contrast, and increasing sensitization).

The photographic emulsion layer of the photosensitive material using the silver halide emulsion of the present invention, the other layers are a flexible reflective support such as paper or synthetic paper laminated with baryta or a-olefin polymer, cellulose acetate, Cellulose nitrate, polystyrene,
It can be applied to films made of semi-synthetic or synthetic polymers such as polyvinyl chloride, polyethylene terephthalate, polycarbonate, and polyamide, as well as rigid bodies such as lath, metal, and ceramics.

The silver halide photosensitive material of the present invention is prepared by subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc. as necessary.
Direct or support surface adhesion, antistatic properties, dimensional stability, abrasion resistance, hardness, antihalation properties, friction 5ffa
It may be coated via one or more subbing layers to improve properties such as , and V/or other properties.

When coating a photographic light-sensitive material using the silver halide emulsion of the present invention, a thickener may be used to improve coating properties. Particularly useful are roof coatings and curtain coatings.

The light-sensitive material of the present invention can be exposed using electromagnetic waves in the spectral range to which the emulsion layer constituting the light-sensitive material of the present invention is sensitive. Examples of the light source include a natural likelihood (zero likelihood), tungsten SLL lamp, Fluorescent lamps, mercury lamps, xenon lamps, carbon arc lamps, xenon lamps, cathode m'rl flying spots, 8 types of laser lamps, light emitting diode lamps,
Any known light source can be used, such as electron beam, XIQ, gamma ray, light, etc.

Exposure times include not only exposure times of 1 millisecond to 1 second commonly used in cameras, but also exposures shorter than 1 microsecond, such as 100 microseconds to 1 microsecond using cathode ray tubes and xenon flashlights.
Microsecond exposures can be used, or longer exposures of 1 second or more are possible. The exposure may be performed continuously or intermittently.

An image can be formed using the silver halide photographic material of the present invention by color development as known in the art.

The aromatic primary m-amine color developing agents used in the color developing solution of the present invention include known ones that are widely used in various color photographic processes. These developers include aminophenol and p-phenylenediamine derivatives. These compounds are 'i! L
Because it is more stable than the GL state, it is generally used in the salt form, and the side salts are in the form of hydrochloride or sulfate. Approximately 0.1 for color development tLIQ
g to about 30 g, preferably about 1 g to about 1.5 g per color developer.

Examples of the ami/7 em/-el based developer include -7 mi/7 phenol, -7 mi/phenol, and 5-7 mi/-2-.
Oxytoluene, 2-7-7-3-oxytoluene, 2
-Oxy-3-7 minnow 1°4-tmethylbenzene and the like are included.

Particularly useful primary aromatic amino color developers are N , N
It is a '-noalkyl-11-phenylenenoamine compound, and the alkyl group and phenyl group may be substituted with any substituent. Among them, an example of a particularly useful compound is N,N'-diethyl-p-phenylenenoamine [
Acid tM, N/+ p-phenylenediamine hydrochloride, N,N'-dimethyl-p-phenylenediamine hydrochloride, 2-7mi/-5-(N-ethyl-N-)'
f-zylamine/)-toluene, N-ethyl-N-β-methanesulfone 7midoethyl-3-methyl-4-7minoaniline sulfate, N-ethyl-N-β-7hydroxyethylaminoaniline t-7 minnow 3 -Methyl-N,N'
-Noethylreaniline, 4-ami/-N-(2-methynethyl)-N-ethyl-3-methylani'Jn-)
Examples include luenesulfonate.

In the present invention, after color development processing, processing is performed with a processing liquid having a fixing ability, but if the processing liquid having a fixing ability is a fixing liquid, a bleaching treatment is performed before that. A metal complex salt of an organic acid is used as the bleaching agent used in the bleaching process, and the metal complex salt converts the metallic silver produced by development into silver halide by converting it into silver halide, and at the same time colors the uncolored part of the color former. It has a composition in which metal ions such as iron, cobalt, and G14 are coordinated with amide/polycarboxylic acid or organic acids such as oxalic acid and citric acid. The most preferred organic acids used to form such organic acid metal complexes include polycarboxylic acids or aminopolycarboxylic acids. These polycarboxylic acids or heptadminoboricarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

Specific representative examples of these include the following.

[1] Ethylenediaminetetraacetic acid [2] Nitrilotriacetic acid [3] Iminodiacetic acid [4] Ethylenedi7minetetraacetic acid nonodium salt [5] Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt [6] Ethylenediaminetetra Tetrasodium acetate [7] Sodium nitrilotriacetate The bleaching agent used contains the above-mentioned metal complex salt of an organic acid as a bleaching agent, and may also contain various additives. As additives, it is particularly desirable to include re-halogenation agents such as alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, and ammonium bromide, metal salts, and chelating agents.

Ki t- 硼醆憔 异气冔 acetic acid 电 廿
Those known to be added to ordinary bleaching solutions, such as pH 1l buffering agents, alkylamines, and polyethylene oxides, can be appropriately added.

Furthermore, the fixer and bleach-fixer contain ammonium sulfite,
Potassium sulfite, ammonium bisulfite, potassium sulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, metabisulfite), sulfites such as +7um, boric acid, borax, sodium hydroxide, potassium hydroxide, carbonic acid Sodium, potassium carbonate, sodium bisulfite, sodium bicarbonate, potassium bicarbonate, acetic acid,
It may contain one or more types of pHtIt salts made of various salts such as sodium acetate and ammonium hydroxide.

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

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

〔Effect of the invention〕

According to the color photographic material containing the magenta coupler of the present invention and the magenta dye image stabilizer represented by the general formula [■], conventionally, magenta dye images that have low fastness particularly to light, heat, and humidity can be stabilized. Fastness, specifically, good prevention of discoloration and fading when exposed to light, and generation of Y-stain in uncolored areas when exposed to light, heat, and humidity.

〔Example〕

The present invention will be specifically explained below with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example 1 On a paper support laminated on both sides with polyethylene, the following layers were sequentially coated from the support side.

First layer: Emulsion layer 8. Magenta coupler 26 of the present invention is added. Oyy/100z
2. Silver chlorobromide emulsion (containing 85 mol% silver bromide) converted to silver is 3.5zg/100cv2, butyl 7 tallate is 6. 15. Oy/100cJ2 and gelatin. Ozg/
The coating was applied so that the coating amount was 100 cz".

2nd F @: Intermediate layer (ultraviolet absorber-containing layer) 2-(2-hydroxy-3-8ee-butyl-5) as an ultraviolet absorber
-tert-butylphenyl)benzotriazole 3
．． Ozg/1oocz2, dibutyl 7 talate 3.0
II19/100cz2 and gelatin 10.0J11
? The coating was applied so that the coating amount was /100cj2.

3rd layer: protective layer gelatin 8. The coating was applied so that the coating amount was Oig/100a2.

The sample obtained as described above was designated as Sample 1.

Exemplary compounds of the present invention C11-2, CH-24, CH-35, C were added to Sample 1 as a magenta dye image stabilizer.
Samples 2.3.4.5.6.7.8 and 9 were obtained by adding I(-36, C1+-38, C11-47, and comparative compounds a and b shown below in equal moles to the magenta coupler.

In addition, Sample 10 was prepared in exactly the same manner as the above sample except that an equimolar amount of comparative magenta coupler A shown below was added in place of magenta coupler 26 of the present invention as a magenta coupler.

Exemplary compounds of the present invention C11-2, CH-24, CI-35, C1 were added to Sample 10 as a magenta dye image stabilizer.
1-36° CI-38, C11-47 and comparative compound a
Sample 11, in which the same moles of and b as the magenta coupler were added,
12.13, 14, 15, 16.17 and V18 were obtained.

Comparative compound a (compound described in JP-A No. 54-43538) Comparative compound b (compound described in JP-A-56-159644) Comparative coupler^ After exposing the sample obtained above through an optical wedge in a conventional manner,
The treatment was carried out in the following steps.

[Processing step 1 Processing temperature Processing time Color development
Bleach fixing at 33°C for 3 minutes and 30 seconds 33°C
Wash with water for 1 minute and 30 seconds at 33℃
Dry for 3 minutes 50-80℃
The ingredients for each 2-minute treatment are as follows.

[Color development Ml Benzyl alcohol 12-ethylene glycol 10zN potassium carbonate
259 Sodium bromide
0.6g anhydrous sodium sulfite
2.0g Hydroxylamine sulfate 2.5g
N-Ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 4.5g Water was added to bring the solution to 11, and the pH was adjusted to 2 with sodium hydroxide.

[Bleach-fix solution 1 Ammonium 1000 sulfate tzog Sodium metabisulfite 15g Anhydrous sodium sulfite 3g EDTA ferric ammonium salt 65g Add water to bring the pH to 11 and adjust the pH to 6.7~
Adjusted to 6.8.

The concentrations of Samples 1 to 29 treated above were measured using a densitometer (model KD-7R, manufactured by Konishiroku Photo Industry Co., Ltd.) under the following conditions.

Each of the above-mentioned processed samples was irradiated with a xenon fade meter for 14 days to examine the light resistance of the dye image. However, the evaluation of the light fastness of the dye image is as follows.

[Residual rate] Percentage of dye remaining after exposure to light and moisture resistance test at initial density of 1.0.

The results are shown in Table 1.

As is clear from Table 1 below, although the coupler of the present invention in which Comparative Coupler 8 was blocked has improved light resistance compared to Comparative Coupler 8, the level of improvement is still low and unsatisfactory. However, samples prepared by adding the dye image stabilizer of the present invention to the coupler of the present invention (Nos. 2 to 7)
), it can be seen that the light resistance is significantly improved. This level of improvement was demonstrated by the combination of the coupler of the present invention and a conventionally known dye image stabilizer (Samples No. 8 and 9) and the combination of the comparative coupler and the dye image stabilizer of the present invention (Sample No.
o, 11-16).

Example 2 The combinations of magenta coupler and magenta dye image stabilizer shown in Table 2 were applied exactly as in Example 1, and
Samples 19 to 45 were created.

Samples 19-45 were treated as described in Example 1,
Furthermore, the treated sample was subjected to a light emission test in the same manner as in Example 1.
:jSZ The results shown in the table were obtained.

Margin Comparison Coupler B Below Table 2 Table 2 shows that the combination of the coupler of the present invention and the dye image stabilizer of the present invention significantly improves the light fastness of the magenta dye image.

Example 3 On a paper support laminated on both sides with polyethylene, the following layers were sequentially coated from the support side to prepare a multicolor silver halide photographic light-sensitive material, and sample 46 was obtained.

tA1 layer: Blue-sensitive silver halide emulsion layer a-pivaloyl-α-(2,4-)oxo-1 as yellow coupler
-pencylimidazolidin-3-yl)-2-chloro-
5-[γ-(2,4-di-1-amylphenoxy)butyramide 1 acetanilide at 6.8 mF1/100c
m2, blue-sensitive silver chlorobromide emulsion (containing 85 mol% bromide) converted to silver is 3.2 B/100 cm2, dibutyl 7-thalet is 3.5 mg/100 cm2, and gelatin is 1
3.5+ag/100c! The coating was applied so that the coating amount was n2.

2nd layer: Middle layer theory g/100c+a2, dibutyl 7 tallate 0.5
mH/100cm2 and gelatin at 9. Omg/1
The coating was applied so that the area was 0.00 cm2.

Third layer: green-sensitive silver halide emulsion layer containing the magenta coupler 31 at 4.5 mg/100 cm
2. Green-sensitive silver chlorobromide emulsion (containing 80 mol% silver bromide) converted to silver: 2.0 mg / 100 cm 2
, dibutyl 7 talate 3, O+og/100cm2
and gelatin at 12.0 mg/1. OOcm
It was painted so that it became 2.

4th layer: Intermediate layer UV absorber 2-(2-hydroxy-3-5ee-phthyl-5-t-butylphenyl)benztrimezole at 5%, 0 tn R/100 c +a at 2, dibutyl 7-talate at 4%. 0mg/100cm2.2.5-
No L-octylno1hydroquine7 0.5mB/1
00cm2 and gelatin at 12.0mH/100cm2
It was painted so that

Fifth scrap: red-sensitive silver halide emulsion layer 2-(α-(211-no-1-bentylphenoxy)butanamide l-4,6-' polyester as cyan coupler)
ri n -ζ -d 1- ru 7
, no - le fy 4') + na
/ I nQ0cI112, red-sensitive silver chlorobromide hole side (containing 80 mol% silver bromide) converted to silver: 3.0 mg/
100cm2, 3.5m of tricresyl phosphate
g/100c+a2 and gelatin 11.5mg/
It was coated so that the area was 100cm2.

6th layer: middle layer A layer composed of exactly the same composition as the fourth layer.

7th layer: Protective layer gelatin 8.0 + a g / 100 cm 2
It was painted so that

In the above sample 46, the dye image stabilizer of the present invention was added to the third layer in the proportions shown in Table #113 to prepare multilayer samples 47 to 55, which were exposed and processed in the same manner as in Example 1. Afterwards, a one-light test (16 days of irradiation on a xenon fade meter) was conducted. The results are also shown in Table 3.

Margin below ttTable S3 From the results, it can be seen that the dye image stabilizer of the present invention is effective in stabilizing the dye image of the magenta coupler of the present invention, and the results become thicker as the amount added increases.

Claims (1)

[Scope of Claims] It is characterized by containing at least one blocked magenta dye image-forming coupler represented by the following general formula [I] and at least one compound represented by the following general formula [XII] A silver halide color photographic light-sensitive material. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. Represents a coupling blocking group that reacts to produce a colorless or alkali-soluble product. A, D are C
When the p group is bonded, it represents ▲There is a mathematical formula, chemical formula, table, etc.▼, and when the Cp group is not bonded, it represents -N= or ▲There is a mathematical formula, chemical formula, table, etc.▼, and B represents - N=
Or ▲ represents a mathematical formula, chemical formula, table, etc. (R has the same meaning as above, but each may be the same or different), and E is a ▲ mathematical formula when a Cp group is bonded. ,
There are chemical formulas, tables, etc. ▼ is used, and -N= is used when no Cp group is bonded. ■ represents three movable double bonds. However, A, B, and D cannot simultaneously be ▲There are mathematical formulas, chemical formulas, tables, etc.▼. Further, R or X may form a dimer or more multimer, and substituents R on adjacent carbon atoms may form a ring. ] General formula [XII] ▲ Numerical formulas, chemical formulas, tables, etc. group, aryl group, aryloxy group, acyl group, acylamino group, acyloxy group, sulfonamide group, cycloalkyl group or alkoxycarbonyl group, and R^2 is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group. , represents a cycloalkyl group or a heterocyclic group, and R^3 is a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, an aryloxy group, an acyl group, an acylamino group, an acyloxy group, a sulfonamide group, a cycloalkyl group Or represents an alkoxycarbonyl group. Further, R^2 and R^3 may be ring-closed with each other to form a 5- or 6-membered ring. Furthermore, R^2 and R^3 may form a methylenedioxy ring. Y_1 represents an atomic group necessary to form a chroman or coumaran ring. ]