JPH01287564A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the light durability of the title material by incorporating at least one kind of a specified magenta coupler and at least one kind of a specified compd. in the photosensitive material. CONSTITUTION:At least one kind of the magenta coupler shown by formula I and at least one kind of the compd. shown by formula II are incorporated in the photosensitive material. In formula I, X0 is hydrogen atom or a substituting group, Z1 is hydrogen atom or a group capable of being released by coupling, W is hydrogen atom or acyl group, etc., Za and Zb are each methine or a substd. methine group or -N= group. In formula II, R is -(Y)n-R' group, Y is -O- or -S- group, etc., (n) is 0 or 1, R' is a residual group of phosphoric acid, Q is a divalent group. Thus, the durability of an image against light, heat and humidity is improved, the generation of a stain is prevented, and especially, the excellent anti-discoloring effect of the photosensitive material against the light is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a color photographic material containing a magenta image-forming coupler. More specifically, the magenta image formed has excellent fastness against light, heat, and humidity;
The present invention also relates to a silver halide color photographic light-sensitive material that causes less staining.

(Prior Art and its Problems) Known examples of magenta couplers include 5-pyrazolones, indacilones, cyanoacetyls, and pyrazoloazoles. Among them, 5-pyrazolones and pyrazoloazoles have been widely studied as skeletons with practical performance, and many improvements have been proposed.

Silver halide color photographic light-sensitive materials generally have silver halide emulsion layers that are sensitive to each of the three primary colors of blue, green, and red, and each color develops yellow, magenta, and cyan, using the so-called subtractive color method. Reproduce color images. Therefore, the reproduced color image largely depends on the color reduction characteristics of each layer and the spectral absorption characteristics of color development. In general, these properties are not necessarily the best theoretically possible due to restrictions such as color development properties of the compounds used. In particular, the color development hue of magenta couplers is important for color reproduction, and various improvements have been made. Among them, pyrazoloazole-based magenta couplers have particularly excellent spectral absorption characteristics of the coloring hue.For example, in order to improve the coloring hue of magenta couplers, 5-pyrazolone-based magenta couplers have particularly excellent spectral absorption characteristics than the ureido type and acylamino type. Excellent anilino-type magenta couplers (JP-A-49-74027, JP-A-49-111631, etc.) have been developed. Furthermore, a pyrazoloazole macenta coupler with less unnecessary radiation absorption (U.S. Pat. No. 3,725)
, No. 067, No. 3,369,897, No. 4,500,
No. 630, No. 4,540,654, JP-A-60-33
No. 552, No. 60-43659, etc.) have been developed. This type of coupler has less unnecessary absorption in the blue light region and red light region than the color image obtained from the 5-pyrazolone type magenta coupler, and is advantageous in terms of color reproduction.

However, magenta images formed from these couplers have extremely low fastness to light and are easily discolored by light.

Furthermore, fastness to heat and humidity and discoloration of uncolored areas (so-called stain) are not necessarily sufficient, and further improvements are required.

Numerous proposals have been made to eliminate these drawbacks. Among these, the most effective method is the use of anti-fading agents.

For example, hydroquinones, hindered phenols, tocopherols, chromans, coumarans, compounds obtained by etherifying the phenolic hydroxyl group of these compounds, amines, metal complexes, etc. (U.S. Pat. No. 4,559,29
No. 7, No. 4.588.679, No. 4,590.1
No. 53, No. 4,623.617, No. 4. 639
．． 415, 4.713.317, European Patent Publication No. 164.130, 255,722, JP 61-177454, 61-282840, 6
No. 1-282845, No. 62-69266, No. 62-
No. 92945, No. 62-244045, No. 62-24
No. 4046, No. 62-273531, No. 63-389
No. 36, Japanese Patent Application No. 62-158342, etc.) are known.

Although these compounds have been recognized to be effective as agents to prevent color fading and changes in dye images, they are insufficient to meet the demands of customers who are increasingly demanding high image quality, and they do not change the hue or change the color. However, it has not been able to exhibit an overall excellent effect for color photography because it causes fog, poor dispersion, or the formation of microcrystals after emulsion coating.

On the other hand, from the perspective of environmental conservation, waste liquid from developing processes is viewed as a problem and reduction is desired. When the amount of washing water or stabilizing solution is reduced (for example, the method described in JP-A No. 57-8543), the storage stability of such images is significantly deteriorated, and in this sense, magenta image hardening technology is is strongly desired.

(Problems to be Solved by the Invention) As described above, compared to the 5-pyrazolone magenta coupler, the pyrazoloazole magenta coupler, which has excellent spectral absorption characteristics in the color development hue, is The shelf life was not sufficient, and it was necessary to further improve the shelf life.

Therefore, a first object of the present invention is to provide a color photographic material with significantly improved light fastness.

A second object of the present invention is to provide a color photographic material having a magenta image that is less discolored by light.

A third object of the present invention is to provide a color photographic material in which the occurrence of yellow stain on the white background in uncolored areas is significantly prevented from occurring when exposed to light, heat, and humidity.

The fourth object of the present invention is to use water for washing in the development process.

Another object of the present invention is to provide a color photographic material whose storage stability is not impaired even when the amount of a stabilizing solution is reduced.

A fifth object of the present invention is to provide a color photographic material in which the color balance of the three colors of yellow, magenta and cyan dyes is maintained even during long-term storage, and the coloring of the white background is significantly reduced.

(Means for Solving the Problem) As a result of various studies, the inventors of the present invention have unexpectedly discovered that there are a small number of magenta couplers represented by the following general formula (I) (both one type and the following general formula [A-I]). It has been found that the above object can be achieved by incorporating a small amount (or at least one kind) of the compound represented by into a silver halide color photographic light-sensitive material.

Za===zb In the formula, X represents a hydrogen atom or a substituent, Z represents a hydrogen atom or a coupling-off group, W represents a hydrogen atom, acyl i, or an aliphatic or aromatic sulfonyl group * Z a 1Z b is methine, substituted methine,
Alternatively, a dimer or more multimer may be formed with substituted methine of Xo, ZI, Za, or Zb representing -N-.

General formula [A-13 In the formula, R represents -(Y)TR', Y represents H, and n represents O or 1. Rr and R# may be the same or different, and each is a phosphoric acid residue. , Q represents a divalent group represented by the general formula [A-1-I].

General formula [A-1-13 In the formula, A represents an atomic group forming a substituted or unsubstituted benzene ring, and X is a single bond, a substituted or unsubstituted methylene group, -5-1-〇-1-C -1 RIII is a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group,
Represents an aryl group, a heterocyclic group, an acyl group, and a sulfonyl group.

The free bond in the formula indicates the bond position with 0 in Q of general formula [A-1].

Next is the general ceremony [! The pyrazoloazole coupler represented by ] will be explained in detail.

In the general formula (1), a multimer means one having two or more groups represented by the general formula (I) in one molecule, and includes bis forms and polymer couplers. Here, the polymer coupler may be a homopolymer consisting only of a monomer having a moiety represented by general formula (I) (preferably one having a vinyl group, hereinafter referred to as vinyl monomer), or an aromatic primary amine A copolymer may be prepared with a non-color-forming ethylene-like monomer that does not couple with the oxidized developer.

Among the pyrazoloazole type couplers represented by the general formula (I), preferred ones are the following general formula % Formula %) Among the couplers represented by the general formulas (Ila) to (Ice), preferred ones for the purpose of the present invention is the general formula %Formula % Preferred compounds are those represented by the general formula (Ilc).

In general formulas (I[a) to (ne), Xl5Xs and X may be the same or different from each other, and each represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, Aryloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, silyloxy group, sulfonyloxy group, acylamino group, anilino group, ureido group, imido group, sulfamoylamino group, carbamoylamino group, alkylthio group, alkylthio group , heterocyclic thio group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide group, carbamoyl group, acyl group, sulfamoyl group, sulfonyl group, sulfinyl group, alkoxycarbonyl group, aryloxycarbonyl group, and these groups is used to include those further substituted with substituents. The same applies below. x
, , xt , xs or Z□ may serve as a divalent group to form a bis body.

It may also be in the form of a polymer coupler in which the coupler residues represented by general formulas (IIa) to (Ice) are present in the main chain or side chain of the polymer, and in particular derived from a vinyl monomer having a moiety represented by the general formula. Polymers are preferred;
In this case, XI, Xt, Xs or Z8 represents a vinyl group or a linking group.

More specifically, XI, XI and Methyl group, tridecyl group, 3-(2゜4-')-t-amylphenoxy)propyl group, 2-(2-octyloxy-5-tar)
t-octylbenzenesulfonamide) ethyl group, allyl group, 2-dodecyloxyethyl group, 3-phenoxyprobyl group, 2-hexylsulfonyl-ethyl group, cyclopentyl group, benzyl group, etc.), aryl group (e.g.
phenyl group, 4-t-butylphenyl group, 2.4-di-amylphenyl group, 4-tetradecanamidophenyl group, etc.), heterocyclic group (e.g., 2-furyl group, 2-
thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, etc.), cyano group, alkoxy group (e.g. methoxy group, ethoxy group, 2-methoxyethoxy group, isopropoxy group, 2-dodecyloxyethoxy group, 2-methane group) sulfonylethoxy group, etc.), aryloxy group (e.g., phenoxy group, 2-methylphenoxy group, 4-t-
butylphenoxy group, etc.), heterocyclic oxy group (e.g., 2-benzimidazolyloxy group, etc.), acyloxy group (e.g., acetoxy group, hexadecanoyloxy group, etc.), carbamoyloxy group (e.g., N-phenyl group, etc.), carbamoyloxy group, N-ethylcarbamoyloxy group, etc.), silyloxy group (e.g., trimethylsilyloxy group, etc.), sulfonyloxy group (e.g., dodecylsulfonyloxy group, etc.), acylamino group (e.g., acetamide group, benzamide group) , tetradecanamide group, α-(2゜4-di-t-amylphenoxy)butyramide group, T-(3-t-butyl-4-hydroxyphenoxy)butyramide group, α-(4-(4-hydroxyphenylsulfonyl) ) phenoxy 1 decanamide group, etc.), anilino group (e.g. phenylamino group, 2-
Chloroanilino group, 2-chloro-5-tetradecanamideanilino group, 2-chloro-5-dodecyloxycarbonylaniline L N-acetylaniline L2-70 Rho 5-(α-(3-t-butyl-4-hydroxyphenoxy ) dodecanamide) anilino group, etc.), ureido group (
For example, phenylureido group, methylureido group, N,
N-dibutylureido group, etc.), imide group (e.g. N-dibutylureido group, etc.), imide group (e.g.
-succinimide group, 3-penzylhydantoynyl group,
4-(2-ethylhexanoylamino)phthalimide group, etc.), sulfamoylamino group (e.g., N,N-dipropylsulfamoylamino group, N-methyl-N-decylsulfamoylamino group, etc.) , alkylthio group (
For example, 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 (e.g., 2-benzo thiazolylthio group, etc.), alkoxycarbonylamino group (
For example, methoxycarbonylamino group, tetradecyloxycarbonylamino group, etc.), aryloxycarbonylamino group (for example, phenoxycarbonylamino group, 2,4-di-tert-butylphenoxycarbonylamino group, etc.), sulfonamide group ( For example, methanesulfonamide group, hexadecanesulfonamide group, benzenesulfonamide group, P-toluenesulfonamide group, octadecanesulfonamide group, 2-methyloxy-5-t-butylbenzenesulfonamide group, etc.), carbamoyl group ( M, for example, N-ethylcarbamoyl group, N
, N-dibutylcarbamoyl group, N-(2-dodecyloxyethyl)carbamoyl group, N-methyl-N-dodecylcarbamoyl group, N-(3-(2,4-di-tart)
-amylphenoxy)propyl)carbamoyl group, etc.)
, acyl group (e.g. acetyl group, (2,4-te
r t-amylphenoxy)acetyl group, benzoyl group, etc.), sulfamoyl group (e.g., N-ethylsulfamoyl group, N,N-dipropylsulfamoyl group, N
-(2-dodecyloxyethyl)sulfamoyl group, N
-ethyl-N-dodecylsulfamoyl group, N,N-diethylsulfamoyl group, etc.), sulfonyl group (e.g. methanesulfonyl group, octanesulfonyl group, benzenesulfonyl group, toluenesulfonyl group, etc.), sulfinyl group (e.g., octane sulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, etc.), alkoxycarbonyl group (e.g., methoxycarbonyl group,
Z8
is a hydrogen atom, a halogen atom (e.g., chlorine atom, bromine atom, iodine atom, etc.), a carboxy group, or a group linked with an oxygen atom (e.g., acetoxy group, propanoyloxy group, benzoyloxy group, 2.4- dichlorobenzoyloxy group, ethoxyoxaroyloxy group, pyruvinyloxy group, cinnamoyloxy group, phenoxy group,
4-cyanophenoxy group, 4-methanesulfonamidophenoxy group, 4-methanesulfonylphenoxy group, α-
Naphthoxy group, 3-pentadecylphenoxy group, benzyloxycarbonyloxy group, ethoxy group, 2-cyanoethoxy group, benzyloxy group, 2-phenethyloxy group, 2-phenoxyethoxyhydantoinyl group, 5-methyl- 1-tetrazolyl group, etc.), arylazo group (e.g., 4-methoxyphenylazo group, 4-pivaloylaminophenylazo group, 2-naphthylazo group, 3-methyl-4-hydroxyphenylazo group, etc.), sulfur Groups connected by atoms (e.g., phenylthio group, 2-carboxyphenylthio group, 2-methoxy-5-t-octylphenylthio group, 4-methanesulfonylphenylthio group, 4
-Octanesulfonamidophenylthio group, 2-butoxyphenylthio group, 2-(2-hegisansulfonylethyl) -5-tert-octylphenylthio group, benzylthio group, 2-cyanoethylthio group, 1-ethoxycarbonyl Tridecylthio group, 5-phenyl-2,3,
4,5-tetrazolylthio group, 2-benzothiazolylthio group, 2-dodecylthio-5-thiophenylthio group, 2-
phenyl-3-dodecyl-1,2,4-1-riazolyl-5-thio group, etc.).

In the coupler of general formula ([Ia), X! and Xs may be combined to form a 5- to 7-membered ring.

X+, Xa, Xs or Z! becomes a divalent group to form a bis body, preferably X+, Xs, and X are substituted or unsubstituted alkylene groups (e.g., methylene group, ethylene group, 1.10-decylene group, CHgCHt
0-CHzCHt-1, etc.), substituted or unsubstituted phenylene groups (e.g., 1,4-phenylene group, 1,3-phenylene group, etc.).

NHCOXa-CONH- group (Xa represents a substituted or unsubstituted alkylene group or phenylene group, for example,
NHCOCH*CHzCONtl-1Hs etc.), -3-Xa-5- group (Xa represents a substituted or unsubstituted alkylene group, for example, F13 5 CHgCHt S-1-3-CLCCOx
S, etc.) represents Hs; 2. The divalent group represented by the above-mentioned monovalent group for Z is made into a divalent group at an appropriate location.

General formulas (Ila), (Ilb), (Ilc), (lid
) and (me) are included in the vinyl monomer, the linking group represented by x, , x, , xs or 21 is an alkylene group (substituted or unsubstituted alkylene group, e.g. , methylene group, ethylene group, 1
．． 10-Decylene group -CHgCHtOCH*CHm-1
etc.) Phenylene group (substituted or unsubstituted phenylene group, for example, 1.4-phenylene group, 1.3-phenylene group, -NHCO-5-C0Nfl =, -o -, -o
co -, and aralkylene groups (for example, groups formed in combination with shiL).

Preferred linking groups include the following.

-NHCO-1-CHICIlg-1゜C0NHCH*
CHtNIICO-1CHICHIOCHtCHi
The vinyl group of NHCO-1 has the general formula (Ila), (Il
Substituents other than those represented by b), (Ilc), (lid) or (Ile) may be used, and preferred substituents include a chlorine atom and a lower alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group). ).

Monomers containing those of general formulas (na), (Ilb), (nc), (■d) and (I[e) do not couple with oxidation products of aromatic-grade amine developers. Copolymers may also be made with non-chromogenic ethylene-like monomers.

The group represented by the general formula [A-I] will be explained in more detail.

The phosphoric acid residues referred to in R' and R' represent the residues of phosphoric esters constituting the compound of the general formula [A-■), such as alkyl groups, alkenyl groups, cycloalkyl groups, aryl groups, etc. , represents a heterocyclic group.

Among the compounds represented by the general formula [A-I], the case where n is 1 and Y is 10- is preferred from the viewpoint of the effects of the present invention.

Next, the group represented by the general formula [A-1-I] will be explained in more detail.

The group represented by general formula [A-1-13] is preferably a group represented by general formula [A-1-2).

In the general formula [A-1-23], the free bond and X have the same meanings as in the general formula [A-1-1]. Also, R', R'', Rtsu and R・
each represents a hydrogen atom or a substituent.

Next, R1, R', R in general formula [A-1-1)
', R''X will be explained in detail.

&NrR'%R'', R7 and R1 each represent a hydrogen atom or one substituent in the general formula [A-1-2),
Preferred substituents include aliphatic groups, aromatic groups (e.g., phenyl, naphthyl), heterocycles (e.g., 2-pyridyl, 2-natrahydrobilanyl), halogen atoms (e.g., fluorine, chlorine, bromine), Aliphatic oxy groups (e.g.
methoxy, butoxy), acyloxy groups (e.g. acetoxy, benzoyloxy), sulfonyloxy (e.g. benzenesulfonyloxy), acylamino groups (e.g. acetylamino, benzoylamino), sulfonamide groups (e.g. methanesulfonamide), amino groups ,
Examples include aliphatic and aromatic oxycarbonyl groups (eg, phenoxycarbonyl, butoxycarbonyl), carbamoyl groups (eg, dimethylcarbamoyl, phenylcarbamoyl), hydroxy groups, and the like.

Moreover, X is preferably a substituent or an unsubstituted methylene group (
For example, methylene, isopropylidene), acyl bonds,
Examples include an oxygen atom, a sulfur atom, a sulfonyl bond, and a substituted or unsubstituted nitrogen atom.

As used herein, the term "aliphatic group" refers to a straight 1*41', branched or cyclic aliphatic hydrocarbon group, and includes saturated and unsaturated groups such as alkyl, alkenyl and alkynyl groups. Representative examples include methyl group, ethyl group, butyl group, dodecyl group, octadecyl group, alkynyl group, iso-propyl group, tert-butyl group, tert-octyl group, tert-dodecyl group, cyclohexyl group, cyclopentyl group. , allyl group, vinyl group, 2-hexadecenyl group, propargyl group, etc.

Among the substituents mentioned above, substitutable groups include alkyl groups, aryl groups, heterocyclic groups, and alkoxy groups (
For example, methoxy group, 2-methoxyethoxy group, etc.)
Aryloxy groups (e.g., 2,4-di-tart-amylphenoxy group, 2-chlorophenoxy group, 4-cyanophenoxy group, etc.), alkenyloxy groups (e.g.,
2-propenyloxy group, etc.), acyl group (e.g.,
acetyl group, benzoyl group, etc.), ester group (e.g., butoxycarbonyl group, phenoxycarbonyl group, acetoxy group, benzoyloxy group, butoxysulfonyl group, toluenesulfonyloxy group, etc.), amide group (e.g., acetylamino group, ethylcarbamoyl group, etc.) group, dimethylcarbamoyl group, methanesulfonamide group, butylsulfamoyl group, etc.), sulfamide group (e.g., dipropylsulfamoylamino group, etc.), imide group (e.g., succinimide group, hydantoinyl group, etc.), ureido group (e.g. , phenylureido group, dimethylureido group, etc.), aliphatic or aromatic sulfonyl group (e.g., methanesulfonyl group, phenylsulfonyl group, etc.), aliphatic or aromatic thio group (e.g., ethylthio group, phenylthio group, etc.), hydroxy group, cyano group,
It may be substituted with a group selected from a carboxy group, a nitro group, a sulfo group, a halogen atom, etc.

Specific examples of magenta couplers represented by general formula [I] are shown below, but the present invention is not limited thereto.

M-9 M-10 Hs! CHs COOCHsM-30 CH3C00C4119C0OH x/y=45155 (wt ratio) x/y/z=50/4515 (wt ratio) Ils ■ x/y/z-4515015 (wt ratio) x/y-501
50 (wt ratio) C)+! x/y=45155 (wt ratio) The magenta coupler of the present invention is disclosed in Japanese Patent Application Laid-Open No. 59-162548.
No. 59-171956, No. 60-33552,
It can be easily synthesized by methods such as US Pat. No. 3,725,067.

Next, specific examples of compounds represented by the general formula [A-I] will be illustrated, but the present invention is not limited thereto.

The compound represented by the general formula [A-I] of the present invention can be prepared by the method described in U.S. Patent No. 2,735,765, U.S. Pat. You can get these from rorgano
phoaphorus Co+5pounds”, Jo
hn Wily L 5ons, Inc, + New
Work, 1950, p. 266, p. 22B,
U.S. Patent No. 3,209°021, U.S. Patent No. 4,278,7
It can be easily synthesized by reacting with phosphorus oxychloride, phosphoric acid, or phosphorous dichloride according to the method described in No. 57.

The coupler represented by general formula (I) is preferably added to the emulsion layer at a ratio of 1X10-' mol-1 mol per 11 mol of halogen present in the same layer, more preferably 5
The proportion is from X10-' moles to 5X10-' moles.

The compound of general formula [A-1] may be added in an amount of 1 mol % to 200 mol %, particularly preferably in a range of 2 mol % to 30 mol %, based on the coupler represented by general formula (I).

In carrying out the present invention, it is preferable that the lipophilic coupler represented by the general formula (I) and the compound represented by the general formula [An] be dissolved or impregnated in the lipophilic fine particles. In addition to the above-mentioned compounds, if desired, additives such as couplers, oil-based solvents (including those fixed in greenhouses such as wax), polymers, couplers, color mixing inhibitors, and ultraviolet absorbers may be used. agents, etc.
The additive itself is a substance that also serves as an oily solvent.

Here, the lipophilic fine particles mean fine particles that are not substantially dissolved in the gelatin aqueous solution and exist as a separate layer in the gelatin aqueous solution.

The lipophilic fine particles according to the present invention are usually prepared by combining a coupler of the general formula ([) and a compound of the general formula [A-1] with a boiling point of 1 in the atmosphere.
Dissolve a high boiling point solvent (oil) alone at 70°C or higher, a low boiling point solvent alone (if no oil is needed as mentioned above), or a mixed solvent with the above oil low boiling point solvent, and add this solution to gelatin, etc. It is prepared by emulsifying and dispersing it in a hydrophilic colloid aqueous solution. There is no particular restriction on the particle size of lipophilic particles, but
0.05μ to 0.5μ is preferable, particularly 0.1μ to 0.0μ.
3μ is preferred.

Furthermore, the oil/coupler ratio is 0.0 by weight.
It is preferable that it is 01-4.0.

Specific examples of the oil include phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, diisodecyl phthalate, dimethoxyethyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl). phosphonate, monophenyl-p-t-butylphenyl phosphate, trioctyl phosphate, trinonyl phosphate),
Citrate esters (e.g. acetyl tributyl citrate), benzoate esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide, dibutyl laurylamide), fatty acid esters II (e.g. dibutoxyethyl succinate, diethyl azelate), Trimesic acid ester! ! (for example, tributyl trimesate).

Examples of polymers include acrylic and methacrylic acid and their esters (e.g., methyl acrylate, ethyl acrylate, butyl methacrylate, etc.), acrylamide, ivy acrylamide, vinyl esters (e.g., vinyl acetate, vinyl propionate, etc.), acrylonitrile, styrene, Divinylbenzene, vinyl alkyl ethers (e.g. vinyl ethyl ether), maleic acid esters (e.g. evaporated maleic acid methyl ester), N
-vinyl-2-pyrrolidone, N-vinylpyridine, 2-
A latex polymer or a water-insoluble organic solvent-soluble polymer manufactured using one or more monomers such as 4-vinylpyridine and the like is used.

Further, as the low boiling point solvent used to prepare the lipophilic fine particles according to the present invention, organic solvents having a boiling point of 30°C to 150°C at atmospheric pressure, such as lower alkyl acetate such as ethyl acetate, isopropyl acetate, butyl acetate, Ethyl propionate, methanol, ethanol, secondary butyl alcohol, cyclohexanol, fluorinated alcohol,
Examples include methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, acetone, methyl acetone, acetonitrile, dioxane, dimethyl formamide, dimethyl sulfoxide, chloroform, and cyclohexane.

In addition, the compound of the present invention can be used with various other known materials, such as halogenated am, magenta, and cyan couplers, to form photonic materials.

Magenta couplers that can be used in the present invention include oil-protected indacylon or cyanoacetyl couplers, preferably 5-pyrazolone couplers. A 5-pyrazolone coupler is a coupler in which the 3-position is substituted with an arylamino group or an acylamino group.
It is preferable from the viewpoint of the hue and coloring density of the coloring dye, and representative examples thereof include U.S. Patent Nos. 2,311.082 and 2,34.
3゜703, same No. 2,600,788, same No. 2゜9
No. 08,573, No. 3,062,653, No. 3.
No. 152.896 and No. 3,936°015, etc. As the leaving group for the two-equivalent 5-pyrazolone coupler, the nitrogen atom leaving group described in U.S. Pat. No. 4,310,619 or the leaving group in U.S. Pat. ．． 351
．． The 5-pyrazolone couplers having the arylthio group described in European Patent No. 897 are preferred, and the 5-pyrazolone couplers having a ballast group described in European Patent No. 73,636 provide high color density.

Cyan couplers that can be used in the present invention include oil-protected naphthol-based and phenol-based couplers, preferably the naphthol-based couplers described in U.S. Pat.
, No. 212, No. 4゜146.396, No. 4.22
Typical examples include two-equivalent naphthol couplers of the oxygen atom elimination type described in No. 8,233 and No. 4,296,200. Further, specific examples of phenolic couplers include U.S. Patent Nos. 2,369,929 and 2,8
No. 01.171, No. 2.772,162, No. 2,
No. 895,826, etc. Cyan couplers that are robust to humidity and temperature are preferably used in the present invention and are typically described in U.S. Pat. No. 3,772.
, 002, a phenolic cyan coupler having an alkyl group greater than or equal to an ethyl group at the meta-position of the phenol nucleus, U.S. Pat.
No. 8,308, No. 4,126.396, No. 4,3
No. 34,011, No. 4,327゜173, West German Patent Publication No. 3.329.729 and Japanese Patent Application No. 1983-426
2,5-diacylamino-substituted phenolic couplers described in US Pat. No. 71, etc. and U.S. Pat.
No. 2, No. 4.333.999, No. 4,451,5
These include phenolic couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position, as described in No. 59 and No. 4,427,767.

In addition, antioxidants, color enhancers, ultraviolet absorbers, cyan, magenta and/or yellow dye image fading inhibitors, color mixing inhibitors, stain inhibitors, capri inhibitors, spectral sensitizers, dyes, and hardening agents. , a surfactant, an antistatic agent, a development accelerator, a desilvering accelerator, and the like can be added.

At least one compound represented by the following general formula (B), (C) or (D) is effective for preventing magentastin, and (1) the following general formula (E) is effective for fading magenta color images. or (2) an organometallic complex having at least one organic ligand having a central metal of copper, cobalt, nickel, palladium, or platinum and having a bidentate or more conformation. The use of the magenta coupler of the general formula (1) according to the present invention in combination with the compound of the formula [A-1] is even more effective in terms of image storage stability.

General formula (B) R5-←A+-rX General formula (C) 1-C-Y In the formula, R1 and R1 each represent an aliphatic group, an aromatic group, or a heterocyclic group, and X has a pH of 8 or less. Represents a group that reacts with an aromatic amine developer and leaves, A represents a group that reacts with an aromatic amine developer to form a chemical bond, n is l
or 0, B is a hydrogen atom, an aliphatic group, an aromatic group,
It represents a heterocyclic group, an acyl group or a sulfonyl group, and Y represents a group that promotes addition of an aromatic amine developer to the compound of general formula (C).

Here, R, X%Y, and R2 or B may be bonded to each other to form a cyclic structure.

General formula (D) -Z In the formula, R represents an aliphatic group, an aromatic group, or a -terocyclic group, and is a ZH nucleophilic group or a nucleophilic group that is decomposed in a photosensitive material to release a nucleophilic group. represents a group.

General formula (E) R1°-W-R,.

In the formula, R3 represents an aliphatic group, aromatic group or heterocyclic group 6 R11 is a hydrogen atom, an aliphatic group, an aromatic group where R
3ts Ro and R84 may be the same or different and each represents an alkyl group, alkenyl group, aryl group, alkoxy group, alkenoxy group, or aryloxy group, W is R□ is a hydrogen atom, an aliphatic group, an aromatic group represents a group group, a heterocyclic group, an acyl group, a sulfonyl group, a sulfinyl group, an oxy radical group, or a hydroxyl group.

R1 and R31 may be bonded to each other to form a 5- to 7-membered ring, or R1% and R31 or R31 may be bonded to each other to form a 5- to 7-membered ring.

The color developer of the present invention will be explained below.

The color developer used in the present invention contains a known aromatic primary amine color developing agent.

Preferred examples are p-phenylenediamine derivatives, representative examples of which are shown below, but are not limited thereto.

D-IN, N-diethyl-p-phenylenediamine D-22-amino-5-diethylaminotoluene D-32-amino-5-(N-ethyl-N-laurylamino)toluene D-44-(N-ethyl- N-(β-hydroxyethyl)aminocoaniline D-52-methyl-4-[N-ethyl-N-(β-hydroxyethyl)aminocoaniline D-64-amino-3-methyl-N-ethyl-N −(β
-(methanesulfonamido)ethyl]-aniline D-7N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide-D-8N,N-dimethyl-p-phenylenediamine D-94-amino-3-methyl -N-ethyl-N-methoxyethylaniline D-104-amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline D-114-amino-3-methyl-N-ethyl-N-β
-Butoxyethylaniline Among the above p-phenylenediamine derivatives, 4-amino-3-methyl-N-ethyl-N-[β-(
methanesulfonamido)ethyl]-aniline (exemplified compound D-6).

Furthermore, these p-phenylenediamine derivatives may be salts such as sulfates, hydrochlorides, sulfites, and p-)luenesulfonates. Preferably about 0.1g to about 20g per 11
More preferred is a concentration of about 0.5 g to about 10 g.

In addition, sulfites such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, and carbonyl sulfite adducts are added to the color developer as preservatives as necessary. be able to.

In addition, as compounds that directly preserve the color developing agent, various hydroxylamines, 'tllllll
No. 86559 E17) HiFC)-1tMucal! ,
Hydrazines and hydrazides described in No. 61-170756, No. 61-188742 and No. 61-2032
It is preferable to add phenols described in No. 53, α-hydroxyketones and α-7 minoketones described in No. 61-188741, and/or each [[1] described in No. 61-180616, and In combination with the above compounds, Japanese Patent Application Nos. 61-147823, 61-166674, 61-165621, 61-164515, 6
Monoamines described in No. 1-170789 and No. 61-168159, No. 61-173595, No. 61
-164515, diamines described in No. 61-186560, etc., No. 61-165621, and No. 61-1
Polyamines described in No. 69789, No. 61-18861
Polyamines described in No. 9, nitroxy radicals described in No. 61-197760, alcohols described in No. 61-186561 and No. 61-197419, No. 61-197419;
Oximes listed in 18874 and 61-2651
It is preferable to use the tertiary amines described in No. 49.

Other preservatives include various metals described in JP-A-57-44148 and JP-A-57-53749;
180588 tlJf le fil
Alkanolamines described in No.-3532, JP-A-56
-94349, aromatic polyhydroxy compounds described in U.S. Pat. No. 3,746,544, etc. may be added before meals as necessary, especially addition of aromatic polyhydroxy compounds and triethanolamine. is preferred.

The color developer used in the present invention preferably has a pH of 9
-12, more preferably 9-11.0, and the color developer may contain other known developer component compounds.

In order to maintain the above pH, it is preferable to use various buffering agents. Specific examples of buffering agents include sodium carbonate,
Potassium carbonate, sodium bicarbonate,! Potassium carbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borax), potassium tetraborate, 〇-hydroxybenzoic acid Sodium (sodium salicylate), O-hydroxybenzoic acid, potassium, 5-
Sodium sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate)
etc. can be mentioned. However, the present invention is not limited to these compounds.

The amount of the buffer added to the color developer is 0.1 mol/1
It is preferably at least 0.1 mol/l-00
, 4 mol/1 or more is particularly preferred.

In addition, various chelating agents can be used in the color developer as an anti-settling agent for calcium or magnesium or to improve the stability of the color developer.

Specific examples are shown below, but the invention is not limited to these.

Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N,N,N-1 rimethylenephosphonic acid, ethylenediamine-N,N,N'.

N'-tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine orthohydroxyphenyl rlp acid, 2-phosphonobutane-1,2,4-)licarboxylic acid, 1-Hydroxyethylidene-1,1-diphosphonic acid, N,N”-bis(2
-Hydroxybenzyl)ethylenediamine-N,N''-
Diacetic acid Two or more of these chelating agents may be used in combination, if necessary.

The amount of these chelating agents added may be sufficient as long as the amount is sufficient to sequester metal ions in the color developer. For example, 11
It is about 0.1g to log per unit.

Any development accelerator can be added to the color developer if necessary.

The above-mentioned compounds used in the present invention have particularly remarkable effects in the case of color developers which do not contain benzyl alcohol in practice. The amount of benzyl alcohol is 0
．． 5mj/j! The following are preferred, and most preferred is the total (
This is the case where it is not included.

Other development accelerators include Japanese Patent Publications No. 37-16088, No. 37-5987, No. 38-7826, No. 44-
No. 12380, No. 45-9019 and U.S. Patent No. 3,
813.247, p-phenylenediamine compounds shown in JP-A-52-49829 and JP-A-50-15554, JP-A-50-137726, JP-B-Sho 44-30074, JP-A-56-156826 and JP-A No. 52-43429,
Quaternary ammonium salts represented by U.S. Patent No. 2.
No. 494.903, No. 3,128゜182, No. 4,2
No. 30゜796, No. 3,253.919, Special Publication No. 1977
-11431, U.S. Patent No. 2,482.546, 2. Amine compounds described in No. 596.926 and No. 3.582.346, etc., Japanese Patent Publication No. 37-16088,
No. 42-25201, U.S. Patent No. 3. 128. 1
No. 83, Special Publication No. 41-11431, No. 42-2388
3 and U.S. Pat. No. 3,532,501, etc., and other 1-phenyl-3
-Pyrazolidones, imidazoles, etc. can be added as necessary.

In the present invention, any antifoggant can be added if necessary. As antifoggants, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide, and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobesizotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, Representative examples include nitrogen-containing heterocyclic compounds such as 2-thiazolylmethyl-benzimidazole, imidazole, hydroxyazaindolizine, and adenine.

The color developer used in the present invention preferably contains a fluorescent whitening agent.
-Diamino-2,2f-disulfostilbene compounds are preferred, the amount added is 0 to 5 g/l, preferably 0.1 g
~4g/l.

Furthermore, various surfactants such as alkyl sulfonic acid, aliphosphonic acid, aliphatic carboxylic acid, and aromatic carboxylic acid may be added as required.

The processing temperature of the color developer of the present invention is 20 to 50°C, preferably 30 to 40°C. Processing time is 20 seconds to 5 minutes.
Preferably it is 30 seconds to 2 minutes.

The smaller the amount of replenishment, the better, but the photosensitive material 1rI? 20 to 600 mj, preferably 50 to 300 mj. More preferably, it is 100 mj to 200 m1.

Next, the derailment step in the present invention will be explained.

The derailing process of the present invention uses a bleach-fix solution. In the present invention, the process time of the derailing process is short (then the effect of the present invention becomes more pronounced. That is, 6 minutes or less, more preferably 30 seconds to 4 minutes). minutes, more preferably 30 seconds to 60 seconds.

The bleach-fix solution used in the present invention will be explained below.

As the bleaching agent used in the bleach-fix solution used in the present invention, tan salts of iron, cobalt, nickel, manganese, and chromium can be used, but especially iron (If
f) Ionic acid complex salts (for example, complex salts of aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, and organic phosphonic acid) or citric acid, tartaric acid, malic acid, etc. Acid and the like are preferred.

Among these, aminopolycarboxylic acid salts of iron (Ill) are particularly preferred from the viewpoint of rapid processing and prevention of environmental pollution.
Aminobolycarboxylic acids useful for forming organic complex salts include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-diaminopropanetetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, and methyliminodiacetic acid. , iminodiacetic acid, glycol ether diamine tetraacetic acid, and the like.

These compounds may be sodium, potassium, lithium or ammonium salts; among these compounds, ethylenediamine salts are diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, methyliminodiacetic acid iron salts. (I[I)
i! Salt is preferred because of its high bleaching properties.

These ferric ion complex salts may be used in the form of complex salts, or ferric salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, and ferric phosphate. etc. and an aminopolycarboxylic acid chelating agent in a solution.
Iron ion salts may be formed, and the chelating agent may be used in excess of the amount required to form the second VK ion salts; the amount added is 0.601 to 1.0 mol/1, preferably 0. 05 to 0.50 mol/1. Various compounds can be used as bleach accelerators in the bleach-fix solutions and/or their pre-baths. For example, U.S. Pat. No. 3.8
93.858, German Patent No. 1.290.81
2 specification, JP-A-53-95630, Research Disclosure No. 17129 (July 1978 issue), compounds having a mercapto group or disulfide bond, and JP-A-45-8506, JP-A-Sho. 52-
No. 20832, No. 53-32735, U.S. Patent No. 3,7
Thiourea compounds described in No. 06.561, etc., or halides such as iodine and bromide ions are preferable because they have excellent bleaching blades.

In addition, the bleach-fix solution used in the present invention contains bromide (
Rehalogenating agents such as potassium bromide, sodium bromide, ammonium bromide) or chlorides (e.g. potassium chloride, sodium chloride, ammonium chloride) or iodides (e.g. ammonium iodide) may be included. . Boric acid, borax, sodium metatmate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, as required
pH of sulfurous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc. 3) One or more kinds of inorganic acids, organic acids, and their alkali metal or ammonium salts, or ammonium nitrate, guanidine, etc. Corrosion inhibitors and the like can be added.

The fixing agent used in the bleach-fixing solution according to the present invention is preferably a known fixing agent, that is, a thiosulfate such as sodium thiosulfate or ammonium thiosulfate.
A special bleach-fixing solution consisting of a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can also be used. 11
The amount of fixing agent per mol is preferably from 0.3 to 2 mol, more preferably from 0.5 to 1.0 mol.

The pH of the bleach-fix solution of the present invention is 3.5 to 6.5, more preferably 4 to 6. Various organic and inorganic acids, bases and buffers can be used to adjust these pHs. Examples of acids include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid,
Examples of the alkali include acetic acid, propionic acid, phenic acid, etc., and sodium hydroxide, potassium hydroxide, aqueous ammonia, various amines, etc., but are not limited to these.

If the pH is higher than that of the present invention, the derailment property and image stability will be poor, and if it is lower, the liquid stability will deteriorate and the leucoization of the cyan dye will become noticeable.

Further, the bleach-fix solution may contain various other fluorescent brighteners, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol.

The bleach-fix solution and fixing agent used in the present invention contain sulfites (e.g., sodium sulfite, potassium sulfite,
ammonium sulfite, etc.), bisulfites (e.g. ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.), metabisulfites (e.g. potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.) ) and other sulfite ion-releasing compounds. These compounds have approximately 0.0% in terms of sulfite ion.
The content is preferably 02 to 0.50 mol/j, more preferably 0.04 to 0.40 mol/j.

Generally, sulfites are added to the balm, but other additives include ascorbic acid, carbonyl bisulfite adducts,
Alternatively, a carbonyl compound or the like may be added.

Furthermore, buffering agents, fluorescent brighteners, chelating agents, antifoaming agents, antifungal agents, and the like may be added as necessary.

Next, the water washing step and/or stabilization step used in the present invention will be explained in detail below.

The amount of replenishment in the water washing and/or stabilization step in the present invention is from the amount brought in from the previous bath to O1S ~94°18-&,
More preferably, it is set to 5 times to 30 times.

Here, the amount brought in from the pre-bath differs depending on the film properties of the photosensitive material, squeegee strength, processing speed, etc., but in practical terms it is about 20 m1 to 100 mj per 100 mJ of water washing and/or stabilization of the present invention. As for the processing method of the process, it is preferable to use a multiple countercurrent method for the purpose of reducing the amount of replenishment, especially in 2-stage to 6-stage processing.
A multi-stage countercurrent system is preferred. In this case, the particularly preferred replenishment amount is 50 mj per 1 d of photosensitive material! ~500mj! To some extent.

According to the multistage countercurrent method, the effect of the present invention is remarkable, but
As the time for clearing water in the tank increases, problems such as bacteria propagation and floating matter adhering to the photosensitive material occur. As such, the method for reducing calcium and magnesium described in Japanese Patent Application No. 131632/1988 can be used very effectively. In addition, JP-A-57
Isothiazolone compounds and thiabendazoles described in No. 8542, chlorine-based disinfectants such as chlorinated sodium isocyanurate described in No. 61-120145, benzotriazole and copper ions described in Japanese Patent Application No. 105487-1987 Other disinfectants described in Hiroshi Horiguchi's "Chemistry of Antibacterial and Antifungal Agents," Sanitation Technology Society Akebono's "Sterilization of Microorganisms, Disinfection, and Antifungal Technology," and "Encyclopedia of Antibacterial and Antifungal Agents" edited by Japan Society of Antifungal and Surface Protection. It is also possible to use

Further, in the washing water, a surfactant as a draining agent and a chelating agent typified by EDTA as a water softener can be used.

The above-mentioned water washing step can be followed or the stabilizing solution can be directly treated without going through the water washing step. A compound having an image stabilizing function is added to the stabilizing solution, such as an aldehyde compound such as formalin, or a film that stabilizes the dye.
Examples include buffering agents and ammonium compounds for adjusting to H. Further, in order to prevent the proliferation of bacteria in the liquid and to apply a fungicide to the photographic material after processing, the various fungicides and fungicides described above can be used.

Furthermore, a surfactant, a fluorescent brightener, and a hardening agent may also be added. In the processing of the photosensitive material of the present invention, when stabilization is performed directly without going through a water washing step, JP-A-57-
No. 8543, No. 58-14834, No. 60-2203
All known methods described in No. 45 and the like can be used.

In addition, it is also a preferable embodiment to use chelating agents such as 1-hydroxyethylidene-1,1-diphosphonic acid and ethylenediaminetemethylenephosphonic acid, and magnesium and bismuth compounds.

The pH of the water washing step or stabilization step of the present invention is 4 to 10, preferably 5 to 8. Temperature depends on the use of photosensitive materials.
Although it can be set variously depending on the characteristics, etc., the temperature is generally 15 to 45°C, preferably 20 to 40°C. The zero time can be set arbitrarily, but the effect of the present invention is more pronounced as it is shorter, and is preferably 30 seconds. ~4 minutes, more preferably 30 seconds ~ 2 minutes.

The smaller the amount of replenishment, the better in terms of running costs and reduction in emissions.

If the method of the present invention uses a color developer,
Can be used in any processing process, such as color paper, color reversal paper, color direct positive photosensitive material, color positive film, color negative film, color reversal film, etc., but especially color paper and color reversal paper. It is preferable to apply

The silver halide emulsion of the light-sensitive material used in the present invention can be of any halogen composition, such as silver iodobromide, primate bromide, chlorobromide, or silver chloride. When processing, add 60% silver chloride.
A silver chlorobromide emulsion or a silver chloride emulsion containing mol% or more is preferable, and a content of chloride rays is preferably 80 or more,
90 to 100 mol% is particularly preferable, and when high sensitivity is required and fog during production, storage, and/or processing needs to be kept particularly low, 50 mol of silver bromide may be used. Silver chlorobromide emulsions containing at least 3 mol % of silver iodide are preferred, and more preferably 70 mol % or less of silver iodide is preferred.
It is preferably mol% or more.

Silver iodobromide and silver chloroiodobromide are preferable for color light-sensitive materials for photography, and the silver iodide content is preferably 0.1 to 15 mol %.

The silver halide grains used in the present invention may have different phases inside and on the surface, may have a multiphase structure such as a bonded structure, or may consist of a uniform phase throughout the grain, or may have They may be mixed.

The average grain size distribution of the silver halide grains used in the present invention may be narrow or wide, but the value obtained by dividing the standard deviation value in the grain size distribution curve of the silver halide emulsion by the average grain size (variation ratio) is within 20%, particularly preferably 1
It is preferable to use a so-called monodisperse silver halide emulsion of 5% or less in the present invention, and in order to satisfy the target gradation of the light-sensitive material, a layer having the same color sensitivity as that of the conventional light-sensitive material is preferably used. Two or more types of monodispersed silver halide emulsions having different grain sizes (preferably those having the above-mentioned fluctuation rate as monodispersity) can be mixed in the same layer or coated in separate layers. Furthermore, two or more types of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion may be used in a mixed or layered manner.

The shape of the silver halide grains used in the present invention is regular (cubic, octahedral, rhombidodecahedral, dodecahedral, etc.).
r ) crystals or coexistence of these crystals, or irregular (ir) crystals such as spherical ones.
It may have a regular) crystal form,
They may also have a composite form of these crystal forms, or they may be tabular grains, especially those with a length/thickness ratio of 5 to 8.
or 8 or more tabular grains account for 50% of the total projected area of the grains.
An emulsion comprising a mixture of these moderate crystal forms may be used.

These various emulsions may be either a surface latent image type in which a latent image is mainly formed on the surface or an internal latent image type in which a latent image is formed inside the grains.

The photographic emulsion used in the present invention is Re5searchDi
sclosur@vo1.170 summer tem&17643
(1, n, I[[) (December 1978).

The emulsion used in the present invention is usually one that has been subjected to physical ripening, chemical ripening, and spectral enhancement.

Additives used in such processes are described in Research Disclosure Vol. 176, Arashi 17643 (1978, 1
February) and Volume 187, Yang 18716 (1979
, November), and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also listed in the above two IJ Search Disclosures, and the locations listed are shown in the table below.

Additive type! @If RD 17643
RD 187161 Chemical sensitizer 23 pages 648
Page right column 2 Sensitivity enhancer Same as above 3 Spectral sensitizer Page 23-24 Page 648 Right column - Superchromic multiplier Page 649 Right column 4 Brightening agent Page 24 5 Anti-fogging agent Page 24-25 Page 649 Right column and stabilizer 6 Kabura - page 25 7 organic solvent page 25 8 light absorption, fu pages 25-26 page 649 right column ~
Ilter Dye Page 650 Left Column Ultraviolet Absorber 9 Stain Inhibitor Page 25 Right Ill 650
Page left ~ 'fTWIlO dye image stabilizer page 25 11 Hardener page 26 651
Page left column Additive type g RD17643 R
DI day 71612 Binder page 26 Same as above 13 Plasticizer, lubricant page 27 650
Page right column 14 Coating aid, pages 26-27
Same as above Surfactant 15 Static Page 27 Same as above
Stopper Example 1 A multilayer halogenated U1 photosensitive material having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

(First layer coating liquid preparation) Yellow coupler CI! cY-1) and (ExY-2
) Ethyl acetate 27.2cc to 10.2g and 9.1g respectively
and high boiling point solvent (So 1 v-1)? .

7ee (8.0 g) was added and dissolved, and this solution was mixed with 10% sodium dodecylbenzenesulfonate (8 cc).
% gelatin aqueous solution (185 cc). This emulsified dispersion and emulsions EMI and EM2 were mixed and melted, and the gelatin concentration was adjusted to 111 to prepare a coating solution for the first layer so as to have the following composition. The coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer. For the gelatin hardening side of each layer, 1-oxy-3,5-dichloro-3-) riazine sodium salt was used.

Moreover, (Cpd-2) was used as a thickener.

(Layer structure) The composition of each layer is shown below. The numbers represent the coating amount (g/d). For halogen emulsions, the coating amount is expressed in terms of silver.

Support polyethylene laminated paper (the polyethylene on the first layer side contains a white pigment (TiOx) and a bluish dye) Layer - (blue sensitive layer) Monodispersed salt spectrally sensitized with an enhancing dye (ExS-I) Silver bromide emulsion (EMI)...0.13 sensitizing dye (E
A monodisperse silver chlorobromide emulsion (EM
2) ...0.13 gelatin
...1.86 yellow coupler (ExY-1)
--0,44 Yellow coupler (EXY-2)...0
．． 39 Solvent (Solv-1)...0.35
Second layer (color mixing prevention layer) Gelatin...0.99 Color mixing prevention agent (Cpd-3)...0.08 Third layer (green sensitive layer) Spectral enhancement with sensitizing dye (ExS-2,3) Sensitized monodisperse silver chlorobromide emulsion (EM3)... Monodisperse silver chlorobromide emulsion (EM4) spectrally sensitized with 0.05 sensitizing dye (ExS-2,3)... ...0.11 Gelatin ...1.80 Magenta coupler (ExM-1) ...0.39 Color image stabilizer (Cpd
-4) ...0.20 color image stabilizer (Cpd-10
0) ...0.02 color image stabilizer (CPd-101)
...0.03 Solvent (Solv-2) --0,1
2 Solvent (Solv-3)...0.25 Fourth layer (ultraviolet absorption layer) Gelatin...1.60 Ultraviolet absorber (Cp a-7/Cpd-8/Cpd-9=3 /2 to 6: Weight ratio)...0.70 Color mixing inhibitor (Cpd-IQ)...0.05 Solvent (SoIv
-4) ...0.27 Fifth layer (red-sensitive layer) Monodisperse silver chlorobromide emulsion (EMS) spectrally sensitized with sensitizing dye (ExS-4, 5) ... 0.07 Monodisperse silver chlorobromide emulsion spectrally sensitized with sensitizing dyes (ExS-4, 5)...0.16 Gelatin...0.92 Cyan coupler (ExC-1) ...0.32 color image stabilizer (
Cpd-8/Cpd-9/Cpd-12=3/4/2: Weight ratio)...0.17 Polymer for dispersion (Cpd-11)...0.28 Solvent (Sol
v-2) -...0.20 Sixth layer (ultraviolet absorption layer) Gelatin...0.54 Ultraviolet absorber (Cpd-7/Cpd-9/Cpd-12-115/3: weight ratio) ...0.21 solvent (So
lv-2) ...0.08 Seventh layer (protective layer) Gelatin ...1.33 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) ...0.17 Liquid paraffin ...0.03 At this time, as the irradiation prevention dye, Cod-13, Cpd
-14 was used. Further, in each layer, Alkanol xC (manufactured by Oupont), sodium alkylbenzenesulfonate, succinic acid ester, and Megafac F 120 (manufactured by Dainippon Ink) were used as emulsifying and dispersing agent coating aids. Cpd-1 as a silver halide stabilizer
, 5, Cpd-16 was used.

Details of the emulsion used are as follows.

Emulsion name Shape Particle size Br content Coefficient of variation (■o
lχ) EMI Cube 1.0 800.08EM2
Cube 0.75 80 0.07EM3 Cube 0.5 830.09EM4 Cube 0.
4 830.1OEM5 Cube 0.5
730.09EM6 Cube 0.4 730.
10 The structural formula of the compound used is as follows.

xY-1 rθ xY-2 xM-1 Cρ Shi L ExC-1 H Shi! ExS-1 5OJN(CJs)s 6X10-' mol/Ag mol xS-2 SOsNH(CJs)i 4X10-' mol/Ag mol 5OsHN(CJs)s 8X10-' mol/Ag mol 1.8 X 10-' mol /Ag mole Solv-1 dibutyl phthalate 5olv-2) licresyl phosphate 5olv-3)
Lioctyl phosphate 5OIV-4) Linonyl phosphate Cpd-13 1100H pd-14 HO01l l It 111H Cpd-16 cpct-to.

Next, in the third layer of the light-sensitive material, the magenta coupler is replaced with the coupler of the present invention in an equimolar amount as ExM-1, or an additional 50 moles of the compound represented by the general formula [A-I] of the present invention is added to the coupler. Similar photosensitive materials were prepared using the combinations shown in Table 1, except that % was added.

After imagewise exposure of the above photosensitive material, Fuji Color Paper processing 1
Continuous processing (running test) was performed using IPP600 until twice the tank capacity for color development was replenished in the following processing steps.

2 color development 38°ci min 40 seconds 290IIi17I! .

Bleach fixing 33°C 60 seconds 150d 9f rinse ■ 30-34°C 20 seconds □ 41 rinse ■ 30-34°C 20 seconds □ 41 rinse ■ 30-34°C 20 seconds 364d 4ffi
Drying: 70 to 80'C, 50 seconds *per photosensitive material (3-tank countercurrent force type for rinsing from ■ to ■) The composition of each processing solution is as follows.

left standing two hiki l hill LヱL hill filtration water
800af 5
ooIi diethylenetriaminepentaacetic acid 1.0g
1.0g nitrilotriacetic acid 2.0g 2
．． 0g 1-Hydroxyethylidene-1,1-diphosphonic acid 2-0g 2.0g Benzyl alcohol 16d 22af Diethylene glycol 10d 101d Sodium sulfite 2.0g 2.5g Potassium bromide 0.5g - Potassium carbonate 30g 30g N-ethyl-N-(β -Methanesulfonamidoethyl) -3-methyl-4-amino) Aniline sulfate 5.5g 7.5g Hydroxylamine sulfate 2.0g 2.5g Optical brightener (WHITEX4B -〇Add water 1000d 1000
afpH (25℃) 10.20 10
．． 1 plate of 60 yen page LIL filtration water 400d
40 (ld ammonium thiosulfate (70χ) 20
0g 300g Sodium sulfite 20
g 40g ethylenediaminetetraacetic acid iron (ill) ammonium 60 g 120
g Ethylenediaminetetraacetic acid dilam 5 l〇-Add water 1000d 1000mfp10
0O°C) 6.70 6.30
Yurego 1 mourning ion exchange water (calcium, magnesium each 3GIP
- Below) Photographic properties are minimum density (Dmin), maximum density (Ds+a
It is expressed by two points x).

Next, as an image fastness test, a fluorescent lamp tester (illuminance 1.
50,000 lux) for 4 months.

On the other hand, each sample was subjected to a discoloration test for 15 days under a high temperature and high humidity atmosphere of 60° C. and 180% RH.

In each of the fading tests, the solidity of the image was evaluated by taking the percentage of the remaining density after the fading test with respect to the initial density Do=l,O. On the other hand, staining was evaluated based on the density value (Dm) measured in the uncolored area using blue light.

The degree of discoloration is evaluated by subtracting (yellow density)/(magenta density) before the light fastness test from (yellow density)/(magenta density) after the light fastness test at an initial density of 1.0. This means that the color tends to change from yellow to yellowish.

The results are shown in Table 1.

As is clear from Table 1, when the magenta coupler of the present invention is used in combination with the compound of general formula [A-13] of the present invention, image fastness is significantly improved. In particular, it can be seen that the effect of improving the degree of discoloration in the light fastness test is excellent.

(R-1) Cσ E Example 2 A multilayer silver halide photosensitive material A having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

(Preparation of first layer coating solution) 19.1 g each of yellow coupler (ExY-1), 27.2 cc of ethyl acetate and high boiling point solvent (Solv-1)
7. 7 cc (8,0) was added and dissolved, and this solution was emulsified and dispersed in 185 cc of a 10% gelatin aqueous solution containing 8 cc of 10% sodium dodecylbenzenesulfonate. Mix and dissolve this emulsified dispersion and emulsions EM7 and EM8, and adjust the gelatin concentration to have the following composition! 11, and a coating solution for the first layer was prepared. The coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer. The gelatin hardening agent for each layer is l-oxy-3,5-dichloro-S-
Triazine sodium salt was used.

Moreover, (Cpd-2) was used as a thickener.

(Layer structure) The composition of each layer is shown below. The numbers represent the coating amount (g/po). The silver halide emulsion represents the coating amount in terms of silver.

Support polyethylene laminate paper (the polyethylene on the first layer side contains a white pigment (TiOz) and a bluish dye) Layer - (blue sensitive layer) Monodispersed salt spectrally sensitized with an aggravating dye (ExS-I) Silver bromide emulsion (EM7) ・0.15 sensitizing dye (ExS-I
Monodisperse silver chlorobromide emulsion (EMS) spectrally sensitized with
・0.15 Gelatin ・・・1.8
6 Yellow coupler (ExY-1)...0.82 Solvent (S01v-1)...0.35 Second layer (color mixing prevention layer) Gelatin...0.99 Color mixing prevention agent (Cpd- 3) ...0.08 Third JW (green sensitive layer) Monodisperse silver chlorobromide emulsion (2M9) spectrally sensitized with sensitizing dyes (ExS-2, 3) ...0 .12 Monodisperse silver chlorobromide emulsion (E M 10) spectrally sensitized with sensitizing dyes (ExS-2, 3) ...0.24
Gelatin...1.24 Magenta coupler (ExM-1)...0.39 Color image stabilizer (
Cpd-4) ...0.25 color image stabilizer (Cp
d-5) ...0.12 color image stabilizer (Cp d
-100)...0.02 color image stabilizer (Cpd-1
01)・・・0.03 Solvent (Sol Sea 2)
...0.25 Fourth layer (ultraviolet absorption layer) Gelatin ...1.60 Ultraviolet absorber (Cpd-6/Cpd-7/Cpd-8-3/2/6: Weight ratio )
...0.70 Color mixing prevention agent (Cp
d-9) ...0.05 solvent (Solv-3)
...0.42 Fifth layer (red-sensitive layer) Monodisperse silver chlorobromide emulsion (E Mll) spectrally sensitized with sensitizing dye (ExS-4,5) ...0.07 increase Monodispersed silver chlorobromide emulsion (E112) spectrally sensitized with a sensitive dye (ExS-4,5)...0.16 gelatin
...0.92 cyan coupler (ExC-1
)...0.15 cyan coupler (ExC-2)
...l), 18-color image stabilizer (Cpd-7/Cpd-8
/Cpd-10-3/4/2: weight ratio)...0.
17 Polymer for dispersion (Cp d-11)...0
．． 14 Solvent (Solv-1)...0.2
0 Sixth layer (ultraviolet absorbing layer) Gelatin...0.54 ultraviolet absorber (cpa-6/Cpd-8/Cpd-10-115
/3: weight ratio)...0.21 solvent (So 1v-
4) ...0.08 Seventh layer (protective layer) Gelatin ...1.33 Acrylic modified copolymer of polyvinyl alcohol (denaturation degree 17%)
...0.17 liquid paraffin
...0.03 Also, at this time, Cpd-12 and Cpd-13 were used as the anti-irradiation dyes. Furthermore, each layer contains Alkanol XC (Dupont), sodium alkylbenzene sulfonate, succinate ester, and Ma
gefacx F-120 (manufactured by Dainippon Ink Co., Ltd.) was used. As a stabilizer for silver halide, cpa-14,
Cpd-15 was used.

Details of the emulsion used are as follows.

EM7 Cube 1.0 1. OQ, 1OEM8
Cube 0.8 1.00.10EM9
Cube 0.45 1.5 0.09EMIO Cube
0.34 1.5 0.09EMII Cube 0.
45 1.5 0.09EM12 Cube 0.34
1.6 0.10 Coefficient of variation - standard deviation/average size xY-1 xM-1 Cj! Cpd-2 Cpd-3 H υH Cpd-4 Cpd-5 CH3 xS-1 ! 5OsHN(CJs)s 6 X 10-' mol/Ag mol 5OsHN(CJs)s 4X 10-' mol/Ag mol x S-3 1,8 -7 H Cpd-9 H Cpd-10 Cpd-11 1←C11ffi -C8→= (n -100
~1000) CQNIIC411s(t) Molecular weight 100,000 pd-12 Cpd-13 SOsK 50s) [cpd~1
4H Cpd-15 Solv-1 dibutyl phthalate 5olv-2) lyoctyl phosphate 5olv-3)
Linyl phosphate 5olv-4) Lyclesyl phosphate Cpd-100 Next, in the 3N of the above light-sensitive material, replace the magenta coupler with the coupler shown in Table 2-1 of etc., or use the general method of the present invention. Other light-sensitive materials were prepared in the same manner, except that 50+*o1% of the compound represented by formula [A-I] was further added to the coupler.

After exposing the above photosensitive material through an optical wedge, it was processed in the following steps.

Single open color development Bleach fixing at 35°C for 45 seconds Stable at 30-36°C for 45 seconds ■ Stable at 30-37°C for 20 seconds ■
Stable at 30-37°C for 20 seconds ■ Stable at 30-37°C for 20 seconds ■
30~37℃ Dry for 30 seconds 70~
85"C for 60 seconds (tank countercurrent flow from stable ■ to ■). The composition of each treatment solution is as follows.

Water sprinkled on the statue of Niri Tomodachi 80
0Id Ethylenediaminetetraacetic acid 2.0g Triethanolamine 8.0g Sodium chloride 1.4g Potassium carbonate
25gN-ethyl-N-(β
-Methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 5.0g N,N-diethylhydroxyamine 4.2g 5,-dihydroxybenzene-1°2.4-)lysulfonic acid 0.3g Fluorescent whitening agent (4,4'-diaminostilbene＼20 Add water
1000dpH (25°C)
10.10 Water 40
0d ammonium thiosulfate (70X) 10
0 d Sodium sulfite lag
Iron ethylenediaminetetraacetate (Iff) Ammonium 55g Disodium ethylenediaminetetraacetate 3g
8 Add water
1000dpH (25°C)
5. 5 stable strict formalin (37χ) 0.1g formalin-sulfite adduct 0.7g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02g 2-methyl-4-isothiazoline-3-off 0.01g6ka
.

Add water to 1000dpH (2
5℃)4. After the O 2 treatment, the same fastness evaluation as in Example 1 was performed.

The results are shown in Table 1-1.

As is clear from Table 2-1, it can be seen that the photosensitive material of the present invention, like Example 1, has a remarkable effect of improving fastness.

Further, after imagewise exposure of photosensitive material B, continuous processing (running test) was performed using a paper processing machine until twice the tank capacity for color development was replenished in the following processing steps.

NuJL i degree poetry plate filtration IL - Σ autopsy hair color development 35℃ 45 seconds 161m11M bleach fixing to bleach 36℃ 45 seconds 161d 17
f Rinse ■ 30-37°C 20 seconds □ 1ON
Rinse ■ 30-37°C 20 seconds □ 1 ON rinse ■ 30-37°C 20 seconds □ 101 rinse ■ 30-37°C 30 seconds 220d 10
ffi drying at 70 to 80° C. for 60 seconds per 1 rrr of photosensitive material (a 4-tank countercurrent method was used for rinsing (from ■ to ■). The composition of each processing solution was as follows.

Sadatachi Niri 1 Hill
800jd 8
00d Ethylenediamine-N,N,N.

N-tetramethylenephosphonic acid 1.5g 1
．． 5g Triethanolamine 5.0g
5.0g Sodium chloride 1.4g
-Potassium carbonate 25g 25
gN-ethyl-N-(β-methanesulfonamidoethyl)-3 monomethyl-4-aminoaniline sulfate 5.0g 7.0gN,
N-bis(carboxymethyl)hydrazine 4.2g 6.0g Fluorescent brightener (4,4'-diaminosuben-2,0 Add water 1000d 1000
dpH (25χ) 10.15 10.
451n complete 1 coat (tank fluid and refill fluid are the same) water
400d Ammonium 1000sulfate (70X) 100d
Sodium sulfite I7eIron(III) ethylenediaminetetraacetate Ammonium 55g Ethylenediaminetetraacetic acid disodium 5g Ammonium bromide 40g Add water
10007pH (25℃)
5.40 Yum (tank fluid and refill fluid are the same) Ion exchange water (calcium, magnesium each 3GIP)
- below) Next, the photosensitive material B ``'' B +- was exposed to light through an optical wedge and then processed using the fatigue treatment solution used in the running test.

After the treatment, the same fastness evaluation as in Example 1 was performed. The results are shown in Table 2-2.

As is clear from Tables 2 and 2, it can be seen that even in the treatment in which the amount of washing water replenisher was reduced, the effect of improving image hardness was excellent.

Example 3 A photosensitive material was prepared by coating a first layer (top layer) to a seventh layer (top layer) in sequence on a double-sided polyethylene laminated paper that had been subjected to corona brush electrolysis treatment. The coating liquid for each layer was prepared as follows. The details of the structural formulas of the couplers, color image stabilizers, etc. used in the coating solution will be described later.

The coating liquid for the first layer was prepared as follows. i.e. yellow coupler 200 g, anti-fade side 93.3
g, 10 g of high boiling point solvent (p) and 5 g of solvent (q),
After heating and dissolving a mixture to which 600 mA of ethyl acetate was added as an auxiliary solvent at 60°C, a 5% aqueous solution of Alkanol B (trade name, alkylnaphthalene sulfonate, manufactured by DuPont) was prepared. 5% gelatin aqueous solution containing 330ml3,300
This liquid was then emulsified using a colloid mill to prepare a coupler dispersion. Ethyl acetate was distilled off under reduced pressure from this dispersion, and the sensitizing dye for the blue-sensitive emulsion layer and 1-methyl-2-mercapto-5-acetylamino-1
, 1,400 g of emulsion containing 3,4-triazole [
96.7g as Ag.

(containing 170 g of gelatin) and further added 2,600 g of a 10% aqueous gelatin solution to prepare a coating solution.

Support Paper support laminated on both sides with polyethylene 1st layer (blue sensitive layer) Silver chlorobromide emulsion (bromide 1180■o1%) ・ ・ ・
290 Yellow coupler... 600 Anti-fading agent D)... 280 Solvent'' (
p) ... 30 melt (q)
... 15 gelatin
...1800 2nd layer (color mixing prevention layer) Silver bromide emulsion (unheated grain size 0.05 micron) Silver...
・ 10 Color mixing prevention agent (S) ... 55 Solvent
(p) ... 30 solvent
(q) ... 15 gelatin
... 800 3rd layer (green-sensitive layer) Silver chlorobromide emulsion (silver bromide 70+O1%) 305 Magenta coupler 670 Anti-fading agent (1) 150 Anti-fading agent (
u) ... 1° solvent (p)
... 200 solvent (q)
... 1゜gelatin
... 1400 4th layer (color mixing prevention layer) Color mixing prevention agent (S), ... 65 Ultraviolet absorber (n) ... 450 Ultraviolet absorber (o) ... 230 Solvent (p
)...5゜Solvent (q)
... 5゜gelatin
...1700 5th layer (red-sensitive layer) Silver chlorobromide emulsion (silver bromide 70■o1%) 210 Cyan coupler anti-fade agent (r) 250 Solvent (p) 160 solvent
(9) ... 100 gelatin
...1800 6th layer (ultraviolet absorption layer) Ultraviolet absorber (n) ...260 Ultraviolet absorber (o) ...7° solvent
(p) ... 300 solvent (
q) ... io.

Gelatin... 700 7th layer (
Protective layer) Gelatin...620ns2-
(2-Hydroxy-3,5-di-tert-amylphenyl)benzotriazole 0: 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazoleanidi(2-ethylhexyl)phthalate q8 dibutyl phthalate r: 2. s-Tart-amylphenyl-3゜5-
di-tert-butylhydroxybenzoate a: 2,5-di-tert-octylhydroquinone t: l, 4-di-tert-amyl-2,5-dioctyloxybenzene ul, 2'-methylenebis-(4-methyl-5-tar
t-Butylphenol Also, the following were used as aggravating dyes for each emulsion layer.

Blue-sensitive emulsion layer: Anhydro-5-methoxy-5'-methyl-3,31-disulfoprobyl selenocyanine hydroxide Green-sensitive emulsion layer: Anhydro-9-ethyl-5,5'-diphenyl-3,3'-dis Rufoethyl oxacarbocyanine hydroxide Red-sensitive emulsion layer: 3,3'-diethyl-5-methoxy9.9-(2,2-dimethyl-1,3-propano)thiadicarbocyanine iodide The following substances were used as stabilizers for each emulsion layer.

1-Methyl-2-mercapto-5-acetylamino-1
, 3,4-) Riazole The following dye was also used as an irradiation-preventing dye.

4-(3-hydroxy-5-hydroxy-4-(3-(
3-Carboxy-5-oxo-1-(4-sulfonatophenyl)-2-pyrazolin-4-ylidene)-1-propenyl)-1-pyrazolyl)benzenesulfonate dipotassium salt N,N'-(4, 8-dihydroxy-9,10-dioxo-3,7-cissulfonatoanthracene-1,5-diyl)bis(aminomethanesulfonate)-tetrasodium salt Also used as a hardening agent: 1. 2-bis(vinylsulfonyl)ethane was used.

The couplers used are as follows.

Yellow coupler magenta coupler cyan coupler 260■/d J 120■/d (molar ratio 1:1) The 34th compound of the present invention [A-7], [
A-9), [A-25i, and A-53) were each added to the coupler in an additional 30 mo1% to prepare four types of photosensitive materials, and then the same treatments and operations as in Example 2 were carried out. The same effect as in the example was obtained.

(Advantages and Effects of the Invention) The combination of the magenta coupler of general formula (1) and the compound of general formula [A-1] according to the present invention significantly improves the fastness of images to light, heat, and humidity, and causes staining. It is also suppressed to a large extent. It is particularly effective in preventing discoloration against light. Furthermore, even in treatments where the amount of washing water replenisher is reduced, the effect of improving fastness is significant.
By using in combination with at least one of the compounds represented by D) and/or with an organic antifading agent of formula (E) or at least one of the organometallic complexes mentioned above, magentastin and magenta can be further enhanced. Fading of color images can be prevented.

Patent Applicant: Fuji Photo Film Co., Ltd. Procedural Amendment 1. Indication of the Case: 1971 Patent Application No. 1/7 t-
No. 2 No. 2, Name of the invention Silver halide power 2 - Photographic light-sensitive material 3, Relationship with the case of the person making the amendment Patent applicant Address 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Contact address 2-chome Nishiazabu, Minato-ku, Tokyo 106 [ No. 121430 Fuji Photo Film Co., Ltd. Tokyo Head Office Telephone: (406) 2537 4. Date of amendment order, 1945, r/dρ (shipment date) 5. Subject of amendment: Specification 6. Contents of amendment (No changes) will be submitted.

1930/Night Day

Claims (1)

[Scope of Claims] A silver halide color characterized by containing at least one magenta coupler represented by the following general formula [I] and at least one compound represented by the following general formula [A-I] Photographic material. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, X_0 represents a hydrogen atom or a substituent, and Z_1
represents a hydrogen atom or a coupling-off group. W represents a hydrogen atom, an acyl group, or an aliphatic or aromatic sulfonyl group. Za and Zb represent methine, substituted methine, or -N=. A dimer or more multimer may be formed with X_0Z_1 or Za, Zb substituted methine. General formula [A-I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R represents -(Y)_n-R'. Y is -O-,
-S-, -NH-, and ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and n represents 0 or 1. R′, R″
may be the same or different and each represents a phosphoric acid residue. Q represents a divalent group represented by the general formula [A-I-1]. General formula [A-I-1] ▲ Numerical formulas, chemical formulas, tables, etc. are included▼ In the formula, A represents a group of atoms forming a substituted or unsubstituted benzene ring, and X is a single bond, a substituted or unsubstituted methylene group , -S-, -O-, ▲Mathematical formulas, chemical formulas, tables, etc.▼
, -NH-, ▲Mathematical formulas, chemical formulas, tables, etc.▼, -S
Represents O_2- and -SO-. R'' is a hydrogen atom,
It represents an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a heterocyclic group, an acyl group, and a sulfonyl group.