JPS62956A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance stability of a color image after development processing by incorporating a specified magenta dye image forming coupler and a carboxylic acid type compound in the same layer. CONSTITUTION:The silver halide color photographic sensitive material enhanced in color developing ability and color image stability can be obtained by incorporating its same layer the 2-equivalent magenta dye image forming coupler represented by formula I (R1 is an aromatic, aliphatic, or heterocyclic group; R2 is a substituent; and each of Za, Zb, Zc, Zd is optionally substituted methine or -N=) and the carboxylic acid type compound represented by formula II in which R' is a group giving diffusion resistance to the compound of formula II; M<n+> is one of ions of H and metals including transition metals; and n is an integer of 1-4.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a halogen compound containing a monoequivalent magenta coupler that has excellent color image stability during processing, has a small amount of silver, or has excellent storage stability of light-sensitive materials. This invention relates to silver oxide color photographic materials.

(Background Art) It is well known that after a silver halide photographic material is exposed to light, an oxidized aromatic primary amine developer and a dye-forming coupler react to form a color image. In this method, a subtractive color reproduction method is usually applied, and cyan, magenta, which are complementary colors to red, green, and blue,
and yellow color images are formed. The reaction between the coupler and the oxidized product of the color developing agent takes place at the active site of the coupler, and the couplers that have hydrogen atoms at the active sites are theoretically stoichiometric to form equivalent couplers, i.e., 1 mole of dye. This method requires q mol of silver halide having development nuclei as an oxidizing agent. On the other hand, those having an anionic leaving group at the active site are 2-equivalent couplers, i.e. couplers that require only 2 moles of silver halide with development nuclei to form 1 mole of dye; Compared to da equivalent couplers, the amount of silver halide in the photosensitive layer can generally be reduced and the film thickness can be made thinner, making it possible to shorten the processing time of the photosensitive material and further improving the sharpness of the color image formed. improves. Furthermore, -equivalent couplers can vary widely in their coupling activity with color developing agents depending on the nature of the leaving group.

Conventionally, it has been mainly used as a magenta color image forming coupler! - Attempts have been proposed to make pyrazolone type couplers two-equivalent. For example, US Patent 3. Ko/4t,
4tJ7 and 3. In No. 2a, the G position of pyrazolone is replaced by a thiocyano group, which is a U.S. patent! , 4t/
9,39/ by the aryloxy group, U.S. Patent J, 4/7. No. 7 by the 2-triazolyl group, US Pat. No. 3tjaλ, Ojλ by the halogen atom, US Pat. No. 3,227. Substitution of jjj4 with an arylthio group, an arylthio group, or a heterocyclic thio group is described in No. 4.

However, when these q-substituted pyrazolone couplers are used, significant color fogging occurs, the coupling activity is too low, or the couplers are chemically unstable and cannot develop color over time. However, it has disadvantages such as the fact that it changes into other compounds, and furthermore, there are many difficulties in synthesis.

In addition, several patents have been published for one-pyrazolone-two-magenta couplers having a heterocyclic substituent at the G position. West German patent publication tube λ, jj &.

No. 7, No. 41-/, and No. 343 contain imidazolyl groups and derivatives thereof, /, 2. g-) riazolyl group and derivatives thereof; and/or 2. J-) riazolyl group and its derivatives are described in US Pat. No. 1.310.6/9;
Same, 30/, 231, and same g#j4ri, J/λ
A coupler in which a pyrazole group or its derivative is substituted at the q-position of terpyrazolone has been proposed.

It is true that these couplers have good stability over time and show considerable color development, but some couplers may increase color image density over time after processing or interact with silver halide emulsions (for example, emulsion grains). There were still many unsatisfactory points, such as decreased sensitivity due to adsorption to

On the other hand, compounds with structures similar to the vine compounds used in the present invention have been proposed as coloring improvers. European Patent Publication No. 7//22 discloses the effect of improving color development and improving grain size of a carboxylic acid compound having an ester group.

However, the effect of the present invention is only achieved with certain two-equivalent magenta cazolers as disclosed in the present invention. Furthermore, carboxylic acids other than those claimed in the above patents can also exhibit this effect.

(Objective of the Invention) The first object of the present invention is to provide a silver halide color photographic light-sensitive material containing a dicarium magenta pyrazolone coupler that has good color image storage stability. ,
An object of the present invention is to provide a silver halide color photographic light-sensitive material containing a divalent magenta coupler that does not cause a decrease in sensitivity.

(Structure of the Invention) An object of the present invention is to provide a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support. This is achieved by a silver halide color photographic material characterized by containing the compound represented by general formula (II) in the same layer.

Here, R1 represents an aromatic group, aliphatic group or a heterocyclic group, R2 represents a substituent, and Za%zb1Zc and Z
d each represents methine, substituted methine, or -N-.

General formula (If) (R'-COO)nM''R' represents a substituent that imparts diffusion resistance to the compound of general formula (It), Mn+ represents a hydrogen ion, a metal ion or a transition metal ion, n represents an integer from / to g.

Next, details of preferred substituents will be described.

In the general formula [1], R1 represents a linear or branched alkyl group (e.g., methyl, isopropyl, tert-butyl, hexyl, dodecyl group, etc.), alkenyl group (e.g., allyl group, etc.), cyclic alkyl group (e.g., cycloantyl group, cyclohexyl group, norbornyl group, etc.), aralkyl group (e.g., benzyl, β-phenylethyl group, etc.), cyclic alkenyl group (e.g., cycloanthenyl group, cyclohexenyl group, etc.) ) represents a halogen atom, nitro group, cyano group, aryl group, alkoxy group, aryloxy group, carboxyl group, alkylthiocarbonyl group, arylthiocarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, sulfo group, sulfamoyl group. group, carbamoyl group, acylamino group, diacylamino group, ureido group, urethane group, thiourethane group, sulfonamide group, heterocyclic group, arylsulfonyl group, alkylsulfonyl group, arylthio group, alkylthio group, alkylamino group, dialkyl Amino group, anilino group, N
-arylanilino group, N-alkylanilino group, N-
It may be substituted with an acylanilino group, a hydroxy group, a mercapto group, etc.

Furthermore, when R1 represents an aryl group (e.g. phenyl group, α- or β-naphthyl group, etc.), the aryl group is 7
It may have one or more substituents, such as an alkyl group, an alkenyl group, a cyclic alkyl group, an aralkyl group, a cyclic alkenyl group, a halogen atom, a nitro group, a cyano group, an aryl group, an alkoxy group, and an aryloxy group. group, carboxy group, alkoxycarbonyl group, aryloxycarbonyl group, sulfo group, sulfamoyl group, carbamoyl group, acylamino group, diacylamino group, ureido group, urethane group, sulfonamide group, heterocyclic group, arylsulfonyl group, alkylsulfonyl group group, arylthio group, alkylthio group, alkylamino group, dialkylamino group, anilino group, N-alkylanilino group, N
1 (more preferably as +1, at least 7 of the ortho positions are an alkyl group, an alkoxy group, a halogen atom, etc.) Substituted phenyl is useful because the coupler remaining in the film exhibits little coloration due to light or heat.

Furthermore, R1 is a heterocyclic group (for example, a 3- or 6-membered heterocyclic group containing at least 7 nitrogen atoms, oxygen atoms, or sulfur atoms as heteroatoms, a fused heterocyclic group, a pyridyl group, a quinolyl group, a furyl group, benzothiazolyl group, oxasilyl group, imidazolyl group, naphthoxacylyl group, etc.),
A heterocyclic group, an aliphatic or aromatic acyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylcarbamoyl group, an arylcarbamoyl group, an alkylthiocarbamoyl group or an arylthiocarbamoyl group substituted with the substituents listed for the above aryl group; May be expressed.

In the formula, R2 is a hydrogen atom, carbon number 7 to 3.2, preferably a linear or branched alkyl, alkenyl, cyclic alkyl, aralkyl, cyclic alkenyl group (these groups are substituted with the substituents listed above for R1). group), an aryl group, and a heterocyclic group (these may have the above-mentioned R1
), alkoxycarbonyl groups (e.g. methoxycarbonyl group, ethoxycarbonyl group, stearyloxycarbonyl group, etc.),
Aryloxycarbonyl group (e.g., phenoxycarbonyl group, naphthoxycarbonyl group, etc.), aralkyloxycarbonyl group (e.g., benzyloxycarbonyl group, etc.), alkoxy group (e.g., methoxy group, ethoxy group, heptadecyloxy group, etc.), aryloxy group (e.g., phenoxy group, tolyloxy group, etc.), alkylthio group (e.g., ethylthio group, dodecylthio group, etc.), arylthio group (e.g., phenylthio group, α-naphthylthio group, etc.), carboxy group, acylamino group (e.g., acetylamino group, 3-t :(xt4t-G te
r t-amylphenoxy)acetamido]inzamide group, etc.), diacylamino group, N-alkyl acylamino group (e.g. N-methylpropionamide group, etc.), N
-Arylacylamino groups (e.g. N-phenylacetamido groups, etc.), ureido groups (e.g. ureido, N-arylureido, N-alkylureido groups, etc.), thiourido groups (e.g. thioureido, N-alkylthioureido groups, etc.), urethane group, thiourethane group, arylamino group (e.g., phenylamino, N-methylanilino group, diphenylamino group, N-acetylanilino group, Cochrolow!-tetradecanamideanilino group, etc.), alkylamino group (e.g., n-butylamino group). group, methylamino group, cyclohexylamino group, etc.), cycloamino group (e.g. biyridino group, pyrrolidino group, etc.),
Heterocyclic amino groups (e.g., q-pyridylamino group, -1penzoxazolylamino group, etc.), alkylcarbonyl groups (e.g., methylcarbonyl group, etc.), alkylcarbonyl groups (e.g., phenylcarbonyl group, etc.), sulfonamide groups (e.g. alkylsulfonamide group, arylsulfonamide group, etc.), carbamoyl group (e.g., ethylcarbamoyl group, dimethylcarbamoyl group, N-methyl-phenylcarbamoyl, N-phenylcarbamoyl, etc.), sulfamoyl group (e.g., N-alkylsulfamoyl, N-phenylcarbamoyl group, etc.), , N-dialkylsulfamoyl group, N-
arylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, N,N-diarylsulfamoyl group, etc.), acyloxy group (e.g. benzoyloxy group etc.), sulfonyloxy group (e.g. benzenesulfonyloxy group etc.) , cyano group, hydroxy group, mercapto group, halogen atom, nitro group and sulfo group.

In general formula (1), R2 is particularly preferably an anilino group, an acylamino group or an arylureido group,
This is when R1 is an aryl group in which at least 7 ortho-positions are substituted with chloro atoms.

When Za%zb%Zc and Zd in general formula (1) represent substituted methine, the substituent is selected from those mentioned above for R2.

The nitrogen-containing ring composed of Za%Zb, Zc, and Zd includes two adjacent λ from among roughly condensed rings (for example, Za force) and Zd! membered or six-membered ring, preferably cyclohexene, cyclo is a hydrocarbon ring such as methine, benzene, and naphthalene rings, a heterocyclic ring such as pyridine, pyrimidine ring, dihydrofuran ring, dihydrothiophene ring, in which R2 (, Z
a to Zd may be the same or different (however, benztriazolyl-/ and penztriazolyluco are excluded).

Particularly preferred couplers of the present invention include formulas (1) and (1) in which (υ substituent is methine, substituted methine, substituted methine,
It is a coupler representing a nonmetallic atomic group that represents a monocyclic nitrogen-containing aromatic heteroj-membered ring group consisting of a member selected from -N-. Substituted methine is the same as in general formula (1).

They may also have similar substituents. More concrete consisting of 2! Alternatively, the 6-membered wire mesh ring portion is the same as in the case of general formula CI).

Examples of suitable nitrogen-containing heterocyclic groups include the following. /-imidazolyl, λ-methyl-/-imidazolyl, -1methylthio-7-imidazolyl, coethylthio/-imidazolyl, 2,4t-dimethyl-/-imidazolyl, goomethyl-/-imidazolyl, goonitro-/-imidazolyl, l-chloro- /-
imidazolyl, phenyl-l-imidazolyl, 嘱-
Acetyl-/-imidazolyl, 9-tetradecanamido-/-imidazolyl, /-pyrrolyl% 3t "-dichloro-/-pyrrolyl, coisointril, /-indolyl, /-pyrazolyl, /-benzimidazolyl, zebromo/-benzimi , dazolyl, !-octadecanamide/-benzimidazolyl, λ-methyl/-benzimidazolyl, !-methyl/-benzimidazolyl, 2-purinyl, λ-indazolyl, /, 2.Q-
g-triazolyl, /, 2.3-/-triazolyl, /
-tetrazolyl group and the like.

Further, the compound represented by the general formula [I] is R11 (M-#
)) L8 (M-/ri.

(M-#) a (M-/ri) (M-10), (M-23) (M-2g) (,M-λri) ((M-J, 2) ~ (M-2? ) represents weight %) These compounds are described in Japanese Patent Application Laid-Open No. 2012-20126, Ibid. ! −
-//rOJ4t, same j4-jr04tJ, same j≦-3
It can be synthesized by the method described in r0 (Hedo j j-10rko!, Dodo!7-9Q7jJ, etc.).

The group represented by R' that imparts diffusion resistance to the compound of general formula [1] has a total carbon number r to 4t0, preferably /J to 3-2, and has a straight or branched alkyl group (for example, hexyl , octyl, dodecyl, interdecyl groups, etc.)
, alkenyl groups (e.g. allyl group), cyclic alkyl groups (e.g. cyclointyl group, cyclohexyl group, melbonyl group, etc.), aralkyl groups (benzyl group, β-phenethyl group, etc.), cyclic alkenyl groups (e.g. cyclo means enthenyl group, cyclohexenyl group) etc.), and these represent HA"7'7Jl, nitro group, cyano group, ary-714
, alkoxy group, aryloxy group, carboxy group, alkylthiocarbonyl group, arylthiocarbonyl group,
Alkylsulfonyl group, aryloxycarbonyl group,
Sulfo group, sulfamoyl group, carbamoyl group, acylamino group, diacylamino group, ureido group, urethane group, thiourethane group, sulfonamide group, heterocyclic group, arylsulfonyl group, alkylsulfonyl group, arylthio group, alkylthio group, alkyl Amino group, dialkylamino group, anilino group, N-arylanilino group, N-
It may be substituted with an alkylanilino group, an N-acylanilino group, a hydroxy group, a mercapto group, or the like.

Furthermore, when R' represents an aryl group (e.g. phenyl group, α- or β-naphthyl group, etc.), the aryl group is 7
It may have one or more substituents, such as an alkyl group, an alkenyl group, a cyclic alkyl group, an aralkyl group, a cyclic alkenyl group, a halogen atom, a nitro group, a cyano group, an aryl group, an alkoxy group, and an aryloxy group. group, carboxy group, alkoxycarbonyl group, aryloxycarbonyl group, sulfo group, sulfamoyl group, carbamoyl group, acylamino group, diacylamino group, ureido group, urethane group, sulfonamide group, heterocyclic group, arylsulfonyl group, alkylsulfonyl group group, arylthio group, alkylthio group, alkylamino group, dialkylamino group, anilino group, N-alkylanilino group, N
-It may have an arylanilino group, an N-acylanilino group, a hydroxy group, a mercapto group, etc.

Furthermore, R' is a heterocyclic group (for example, a !- or 6-membered heterocyclic group containing at least 7 nitrogen atoms, oxygen atoms, or sulfur atoms as heteroatoms, or a fused heterocyclic group, such as a pyridyl group, a quinolyl group, or a furyl group). , benzothiazolyl group, oxasilyl group, imidazolyl group, naphthoxacylyl group, etc.),
A heterocyclic group, an aliphatic or aromatic acyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylcarbamoyl group, an arylcarbamoyl group, an alkylthiocarbamoyl group or an alkylthiocarpa group substituted with the substituents listed for the above aryl group. It may also represent a moyl group.

Mn+ is an ion in group 1 of the periodic table (e.g. H+, Na
”, K+, Cs+, etc.), group II ions (for example, M
g2+, Ca", Ba2+) and group 1 ions (e.g. Fe", I+'e", C02+, Co", N
i2+, etc.), but preferably the first
They are ions of groups 1 and 2.

Particularly preferred are H+, Na+ and Na+, most preferred is H+.

Preferred specific examples of the compounds represented by general (II) will be shown below, but the invention is not limited to the following.

(tlcsHu (sc, Hll (t)Ca Ni3 (A-4') C13H27COOH (A-,?) C17H3,C00H (A-bu) α (A-7) (A-,1') C16H3,C00H ( A-#) (t) C5H1l (A-//) (A-/ko) (A-/J) (A-/4t) (A-/j) CH2-COOH (A-#) α (A- /ri) C5Hll (t) (A-#) (A-/ri) The magenta coupler represented by the general formula (1) used in the present invention is a photosensitive silver halide emulsion layer in a silver halide color photographic light-sensitive material. It is added to the adjacent layer or the same layer, preferably the same layer.

The magenta coupler is preferably used per mole of halogenated fs in the same or adjacent layer! x10-1 mol, particularly preferably jX/0=-0.4 tmol.

The compound represented by the general formula (If) used in the present invention is added to the same layer as the magenta coupler, and the amount added is less than 1 mol of the magenta coupler, preferably 0.0/~! mol, more preferably 0. Oj,
, -1 mole.

The mechanism by which the compound represented by the general formula (1) used in the present invention suppresses the increase in magenta density of the magenta coupler represented by the general formula [I] after color development processing is not clear, but it can be considered as follows. I can do it too. for example,
If the coupling-off group of the magenta coupler does not have a compound, it will couple with the oxidized form of the aromatic 7th-class amino developing agent to form a leuco form, but this will become a compound and will continue to exist even after the development process and drying process. exists in this form and gradually releases the coupling-off group over time,
It becomes a magenta dye (R in the above formula represents a hydrogen atom or a substituent, and may be different from each other). Therefore, the magenta density increases over time. (Here, R is a substituent defined in the present invention and may be the same or different.) However, when the compound represented by the general formula [I] of the present invention is present, it donates protons to the above intermediate and forms an intermediate. It may be thought that the magenta dye is produced from an early point due to the effect of increasing the stability of the production system by destabilizing the molecule and/or protonating the detached coupling-off group.

In addition, the magenta coupler of the present invention has a mechanism for reducing the sensitivity of silver halide during aging of a light-sensitive material, and a mechanism of the general formula (I
Although the mechanism of prevention by the compound f) is not clear, the present inventors believe as follows.

For example, a magenta coupler coupling off during reading and/or storage. p.

As shown, the coupler forms a heptacomplex of Ag+ ions in gelatin or adsorbs to silver halide emulsion grains, thereby exhibiting a desensitizing effect.

However, if the compound represented by the general formula (1) is present at the same time, it is presumed that the following compound is formed, which hinders the interaction with silver ions and/or silver halide grains.

As is clear from the above mechanism, only the combination of the present invention is effective, and there is no necessity for the combination described in Yorotsu e Patent No. 771 Coco.

The silver halide photographic material used in the present invention may be a monochromatic color photographic material having one light-sensitive silver halide emulsion layer on a support, or a multilayer color photographic material having at least λ different spectral sensitivities on a support. It can also be applied to materials.

Multilayer color photographic materials usually have at least one each of a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer on a support. The order of these layers can be arbitrarily selected as required. Usually, the red-sensitive emulsion layer 6C contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case.

The same or other photographic emulsion 1iI or non-light-sensitive layer of the photographic light-sensitive material prepared using the present invention has the general formula σ (
The coupler represented by 1) and other color couplers, i.e., colors are developed by oxidative coupling with an aromatic 7th class amine developer (for example, phenylenediamine derivatives, aminophenol derivatives, etc.) during color development processing. Vine compounds may also be used.

The silver halide multilayer color photographic light-sensitive material using the present invention usually uses yellow, magenta, and cyan color-forming couplers, but the couplers of the present invention can also be used for all three colors, and if necessary, Some of the couplers of the present invention can also be replaced with conventionally known color couplers.

Useful color couplers are cyan, magenta and yellow colored couplers, typical examples of which are naphthol or phenolic compounds, pyrazolone or pyrazoloazole compounds and open chain or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers that may be used in the present invention are provided in Research Disclosure.
It is described in the patents cited in December 1-D (December 2010) and December 7, 2013 (/Taku 2015//).

The color coupler incorporated in the light-sensitive material is preferably diffusion-resistant by having a pallast group or being made into a polymer. A two-equivalent color coupler substituted with a leaving group can reduce the amount of coated silver and provide higher sensitivity than an equivalent color coupler whose coupling active position is a hydrogen atom. Couplers in which the color-forming dye has adequate diffusivity, non-color-forming couplers, or DIR couplers that release a development inhibitor or couplers that release a development accelerator upon coupling reaction can also be used.

Typical examples of yellow couplers that can be used in combination with the present invention include oil-protected acylacetamide couplers. A specific example is U.S. Patent No. 4t.
No. 07,210, same No. 2. ♂7! ,O! No. 7 and No. 3 of the same. λ≦j, as described in issue j05, etc. As a second yellow coupler, U.S. Patent No. 3, 4t0
? , /Tada issue, same No. J, &4t ri, No. 922, same No. 3. Ri3! , jO1, and the oxygen atom separation type yellow couplers described in the same Nos. g, 0J, 4, etc. ♂-/θ73, U.S. Patent No. t, 4
to"/, rij'λ issue, same number da, 3 kot, 0 kog issue, R
D/r(VjJ(/ri7ri), British Patent No. 1゜4
t=1,020, Tori German Application Publication No. 2. -/ri.

No. 72, No. 2, 21a/, No. 36/, Ko.

! 29. j? Typical examples include the nitrogen atom separation type yellow couplers described in No. 2 and No. 2,41JJ, No. 112. α-piparoylacetanilide couplers have excellent color fastness, particularly light fastness, while α-benzoylacetanilide couplers provide high color density.

The magenta coupler that can be used in combination with the present invention is preferably an oil-protected indacylon or -cyanoacetyl coupler! - Pyrazoloazole couplers such as pyrazolone and pyrazolotriazoles are mentioned. ! Among the -pyrazolone couplers, couplers in which the 3-position is substituted with an arylamino group or an acylamino group are preferable from the viewpoint of the hue and color density of the coloring dye, and representative examples thereof include U.S. Pat. J//, No. 01, No. 2 J413.203, No. λ, too, No. 22, No. 2,90jr, No. 173, No. 3.06, ≦
! No. 3, same No. 3. /j co, /tie issue and the same No. 3゜rii
t, No. 0/j, etc. Two equivalents! - As a leaving group for pyrazolone couplers, U.S. Pat.
θ, 479 or the nitrogen atom leaving group described in U.S. Patent No. 4t, 3! The arylthio group described in No. 227 is particularly preferred.

It also has a pallast group as described in European Patent No. 73,434! - Pyrazolone couplers provide high color density.

As a pyrazoloazole coupler, U.S. Patent No. 3,
Pyrazolobenzimidazoles as described in U.S. Patent No. 36, No. 279, preferably U.S. Pat. Wolf! , No. 067: This described pyrazolo (, t, /-c) (' * 2s ”
) Pyrazolotetrazoles and Research Disclosure λ4t described in t' Soriazoles Research Disclosure 2μ22θ (/t4 June 2013)
Examples include pyrazolopyrazoles described in 2JO (April/9♂DA). European Patent No. 1 in terms of low yellow side absorption and light fastness of the coloring dye. The imidazo(/,-2-b)pyrazoles described in EP 1/260 are preferred, as are the pyrazolo[/, -2-b) pyrazoles described in EP 1/260.

j-b)(/,λt'')-)'lyazole is particularly preferred.

Cyan couplers that can be used in combination with the present invention include oil-protected naphthol-based and phenol-based couplers, as described in US Patent No. 2. Kukuda.

No. 223, preferably the naphthol couplers described in U.S. Patent No. G, 0! λ, No. 2/-, No. q.

/4tb, No. 396, No. 221.2JJ and No. 4t, 2ri6. A typical example is the oxygen atom separation type naphthol coupler described in No.-00. Further, specific examples of phenolic couplers include U.S. Pat.
Same No. 27 Cuco, No. 742, Same No. 2. r9j, 2.24
It is written in the number etc. Cyan couplers that are stable against humidity and temperature are preferably used in the present invention, and a typical example thereof is as described in U.S. Pat. Phenolic Cyan Couplers Having Alkyl Groups, U.S. Pat. No. 2,772. /1. Ko No. 3. the law of nature! ? , 3θr issue, same issue, /24. Jri No. 5, same No. 5, J34t, 0/
/ issue, same No. 3, 32nd issue.

3, West German Patent Publication No. 3, 32, Kukota No., and patent application Shojt-e-2t No. 7, etc. −
Diacylamino-substituted phenolic couplers and US Pat.
! ! ,? 99th issue, same issue evening, 4tj/, j1ri issue and same issue g, 4t! It has a phenylureido group at the λ-position as described in No. 7,747, and! These include phenolic couplers having an acylamino group at the - position.

In order to correct unnecessary absorption in the short wavelength range of dyes generated from magenta and cyan couplers, it is preferable to use colored couplers in combination with color sensitive materials for photographing. U.S. Patent No. 'l,/43. ≦7θ and yellow-colored magenta couplers described in Japanese Patent Publication No. 3-4T/3 or US Pat. No. 9,00<1. Data No., No. G, /3♂2.2-2 and British Patent No. 1. /4t4
Typical examples include the magenta-colored cyan coupler described in , No. 341, etc.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Such blur couplers are described in US Patent No. g,j <4,2j2 and British Patent No. 2. A specific example of a magenta coupler is given in No. 170 and European Patent No. Otsu.

No. 170 and West German Application No. 3. Specific examples of yellow, magenta or cyan couplers are described in No.-34t and j33.

The dye-forming couplers and the special couplers described above may form dimers or more polymers. Typical examples of polymerized dye-forming couplers are U.S. Pat. No. 3,4t! /, 2
No. 20 and No. 20, oro.

, No. 211. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102,123 and US Patent No. 1,36, Co/λ.

These couplers may be either g-equivalent or di-equivalent to silver ions. It may also be a colored coupler that has a color correction effect or a coupler that releases a development inhibitor during development (so-called DIR coupler).

In addition to DIR couplers, there are also colorless DIs in which the coupling-reactive product is colorless and releases a development inhibitor.
It may also contain an R coupling compound. In addition to the DIR coupler, the light-sensitive material may contain a compound that releases a development inhibitor during development.

In order to satisfy the characteristics required for a photosensitive material, two or more of the above-mentioned couplers can be used in the same layer of the photosensitive layer, or the same compound can be introduced into two or more different layers. You can also do that.

The coupler represented by the general formula (1) of the present invention, the general formula (n
) and the coupler that can be used in combination with the compound can be introduced into the silver halide emulsion layer by a known method, such as the method described in US Pat. No. 2.32.2, 0.27. For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate) , benzoic acid ester (
(e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, diethyl azelate),
Trimesic acid esters (e.g. tributyl trimesate), etc., or boiling points of 30°C to /! After dissolving in an organic solvent of σ0C, such as lower alkyl acetate such as ethyl acetate or butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc., it is dispersed in a hydrophilic colloid. be done. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be used in combination.

Also, Tokko Akira! l-3ri No. 13-3, Tokukai Shoj/-! It is also possible to use the dispersion method using polymers described in No. 9-4tJ.

When the coupler has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use claritine, but other hydrophilic colloids can also be used alone or together with gelatin. can.

In the present invention, the gelatin may be either lime-treated or acid-treated. For details on how to make gelatin, see Arthur Vuis.
Wei ss), The Macromole 1/The Macromole
cular Chemistry of Gelatin
), (Academic Press (Academcare)
ss), /ri 44 published in 2010).

The photographic emulsion layer of the photographic light-sensitive material used in the present invention contains silver bromide as silver halide. Any of silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride may be used. The preferred silver halide is l! It is silver iodobromide containing silver iodide less than molti. Particularly preferred is silver iodobromide containing silver iodide from 2 molti to /λ molti.

The average grain size of the silver halide grains in the photographic emulsion (expressed as the grain diameter for spherical or approximately spherical grains, and the ridged grain size for cubic grains, expressed as an average calculated by the projected area) is Although not particularly limited, it is preferably 3μ or less.

The particle size may be narrow or wide.

Silver halide grains in photographic emulsions may have regular crystal bodies such as cubic or octahedral, or may have spherical,
It may have an irregular crystalline shape such as a plate shape, or it may have a composite shape of these crystalline shapes. It may also consist of a mixture of particles of various crystalline forms.

Also, the diameter of the particle is the same as its thickness! It is also possible to use an emulsion in which silver halide grains with a hypertabular size of at least twice the size of the total projected area occupy 10@4 or more of the total projected area.

The silver halide grains may have different phases inside and on the surface. Further, the particles may be particles in which a latent image is mainly formed on the surface, or may be particles in which a latent image is mainly formed inside the particles.

The photographic emulsion used in the present invention is P.
, Glafkides), 'ChimieetPhysi Photographic'
que Photographique)' (Po/L
/-%nte/L/(Paul Montel), /
ri6≦year), W.L.Zerikman (V,L.

'Making and Coating Photographic Emulsion (Making and Coating Photographic Emulsion)
King and Coat ing Photogr
aphicEmulsion) (published by The Focal Press (The Focal Pre8s, 1996)). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the methods for reacting the soluble silver salt and soluble halogen salt include the one-sided mixing method, the simultaneous mixing method,
Any combination thereof may be used.

It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).

As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald double jet method can also be used.

According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

One or more silver halide emulsions formed separately may be used in combination.

In the process of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be allowed to coexist.

Silver halide emulsions are usually chemically sensitized.

For chemical sensitization, for example, an etch fuser (H
, Fieser) ed.
Silver Halogen Die (DieGrundlage)
der PhotographischenPro
zesse mit 8i1ber Haloge
niden)” (Akademische Verlagsgesellschaft)
Gesellschaft), /ri6♂), No. 67!
The method described on page 34 can be used.

That is, a sulfur sensitization method using sulfur-containing compounds that can react with active gelatin and silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines); reducing substances (e.g., stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds); noble metal compounds (e.g., total complex salts, Pt, I
A noble metal sensitization method using complex salts of metals of group 1 of the periodic table such as r, Pd, etc. can be used alone or in combination.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. Namely, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. , benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles 1 to 7-phenyl-! -mercaptotetrazole); mercaptopyrimidines; mercaptotriazines; thioketo compounds, such as oxadorinthione; azaindenes,
For example, triazaindenes, tetraazaindenes (
In particular, antifoggants such as dihydroxy-substituted (/, J, Ja, ]) tetraazaindenes), tetraazaindenes; henzenethiosulfonic acid, inzenesulfonic acid, inzenesulfonic acid amide, etc. Alternatively, a number of compounds known as stabilizers can be added.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared using the present invention may contain coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and photographic property improvement (e.g.
Various surfactants may be included for various purposes such as development acceleration, high contrast, and sensitization.

The photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, quaternary ammonium salt compounds, urethane derivatives,
It may also contain urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like.

The photographic light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability. For example, alkyl acrylate, alkyl methacrylate, alkoxyalkyl acrylate, alkoxyalkyl methacrylate, glycidyl acrylate, glycidyl methacrylate, acrylamide, methacrylamide, vinyl ester (e.g. vinyl acetate), acrylonitrile, olefin, styrene, etc. alone or in combination, or these and acrylic acid. , methacrylic acid, α,
Polymers containing a combination of β-unsaturated dicarboxylic acid, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, sulfoalkyl acrylate, sulfoalkyl methacrylate, styrene sulfonic acid, etc. as monomer components can be used.

The photographic emulsions used in the present invention may be spectrally sensitized with methine dyes and others. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopholarianine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, viroline nucleus, oxazoline nucleus, thiazoline nucleus, virol nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus,
Pyridine nuclei, etc.: Nuclei in which an alicyclic hydrocarbon ring is fused to these nuclei; and nuclei in which aromatic hydrocarbon rings are fused to these nuclei, i.e., indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxane nucleus, etc. Dole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. are applicable. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes contain pyrazoline-! as a core having a ketomethylene structure. It is possible to apply s- to d-membered heterocyclic nuclei such as -on nucleus, thiohydantoin nucleus, corchioxazolidine nucleus, 4t-dione nucleus, thiazolidine-,2,g-dione nucleus, rhodanine nucleus, and thiobarbic acid nucleus. can.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion. for example,
Aminostyl compounds substituted with nitrogen-containing heterocyclic groups (for example, those described in U.S. Pat. For example, those described in U.S. Pat.

The photographic material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer.

For example, chromium salts (chromium alum, chromium acetate, etc.)
, aldehydes, (formaldehyde, glyoxal, geltaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), activated vinyl compounds (/, 'J , J-) lyacryloyl-hexahydro-s-triazine, /,!
-vinylsulfonyl-coprononol, etc.), active halogen compounds ('t''-dichloro-6-hydroxy-s-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), etc. alone or in combination. You can use it the most.

In the photosensitive material produced using the present invention, when dyes, ultraviolet absorbers, etc. are contained in the hydrophilic colloid layer, they may be mordanted with a cationic polymer or the like.

The light-sensitive material produced using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color anti-capri agent.

The photosensitive material produced using the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, benzotriazole compounds substituted with aryl groups (e.g. those described in U.S. Pat. !'2.

4t! benzophenone compounds (e.g., those described in JP-A No. 2003-2013), silicon acid ester compounds (e.g., those described in U.S. Patent No. 3.
J, 707.37j), dutadiene compounds (for example, those described in U.S. Pat. No. 707.37j);

04tJ-, 2 Cobb), or benzoxazole compounds (for example, those described in U.S. Patent No. 3.0θ, 4
tJ-1) can be used. An ultraviolet absorbing coupler (for example, an α-naphthol cyan dye-forming coupler) or an ultraviolet absorbing polymer may be used. These ultraviolet absorbers may be mordanted in specific layers.

The photosensitive material produced using the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include oxonol dyes, hemioxonol dyes 1. Included are styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful.

In carrying out the present invention, the following known anti-fading agents may be used in combination, and the color fade stabilizers used in the present invention may be used alone or in combination of one or more. Known antifading agents include hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenols, p-oxyphenol derivatives, and bisphenols.

Photographic processing of layers comprising photographic emulsions made using the present invention may include, for example, Research Disclosure/Research Disclosure No. 6 whistles,
Any of the known methods and known treatment liquids as described on pages 2/-30 can be applied. The processing temperature is usually chosen between /r0c and jooC, but i
The temperature may be lower than r"c or higher than !0°C.

Color developers generally consist of an alkaline aqueous solution containing a color developing agent. The color developing agent is a known primary aromatic amine developer, such as phenylenediamines (e.g., guamino-N, N-diethylaniline, 3-methyl-scarred-
Amino-N, N-diethylaniline, Guamino-N-
Ethi JL/-N-β-hydroxyethylaniline,
3-Methyl-gu'7 minnow N-ethyl-N-β-hydroxyethylaniline, 3-methyl-guamino-N-
ethyl-N-β-methanesulfamide ethylaniline,
kuamino-3-methyl-N-ethyl-N-β-methoxyethylaniline, etc.) can be used.

In addition, F.N. Mason (F, A.

Mason), 'Photographic Processing Chemistry'
ssing Chemistry)' (Focal Press, /D4
), pp. 224-Kokota, U.S. Patent 2. /ri3,0
1! No., same co,! ? Ko, evening issue on 3rd, Tokukai Showa 4tr-ta
Those described in RI No. 33 may also be used.

Color developers may also contain pH buffering agents such as alkali metal sulfites, carbonates, borates, and phosphates, development inhibitors or antifoggants such as bromides, iodides, and organic antifoggants. can include. Also, if necessary, water softeners, preservatives such as hydroxylamine,
Organic solvents such as benzyl alcohol, diethylene glycol, polyethylene glycol, quaternary ammonium salts,
Development accelerators such as amines, dye-forming couplers, competitive couplers, fogging agents such as sodium poron hydride, auxiliary developers such as /-phenyl-3-pyrazolidone, viscosity-imparting agents, polycarboxylic acid chelating agents, antioxidants. It may also contain agents.

After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. Examples of bleaching agents include iron (1),
Compounds of polyvalent metals such as cobalt (1), chromium (VI), and copper (II), peracids, quinones, nitroso compounds, and the like are used.

For example, ferricyanide, dichromate, organic complex salts of iron(1) or cobalt(I), such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, /.

Aminopolycarboxylic acids such as 3-diamino-pronoqnoltetraacetic acid; complex salts of organic acids such as citric acid, tartaric acid, and malic acid; persulfates, permanganates; nitrosophenols, and the like can be used. Of these, potassium ferricyanide, iron ethylenediaminetetraacetate (1
) Sodium and iron(1) ammonium ethylenediaminetetraacetate are particularly useful. Ethylenediaminetetraacetic acid iron(1) complexes are useful both in stand-alone bleach solutions and in -bath bleach-fix solutions.

As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used. The fixing solution may contain a water-soluble aluminum salt as a hardening agent.

Here, after the fixing step or bleach-fixing step, washing with water,
It is common practice to perform treatment processes such as stabilization, but it is also possible to perform only a water washing process or, conversely, to perform only a stabilization process without any substantial water washing process (l! #Kaisho!? -rj4t3) can also be used.

The rinsing water used in the rinsing step can contain known additives, if necessary. For example, chelating agents such as inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid,
Bactericidal agents and antifungal agents to prevent the growth of various bacteria and algae, hardening agents such as magnesium salts and aluminum salts, and surfactants to prevent drying load and unevenness can be used. Or L.E. West (L, E.

West), “Water Quality Flyteri 7
(Water Quality Cr1teria
)'Photographic Science and Engineering (Photo, 8ci, and -Eng
), Vol, ta 166 page J <ta
Compounds described in 3j ri (/ri 4j) etc. can also be used.

Further, the washing step may be carried out using more than one tank if necessary, and the washing water may be saved by performing multi-stage countercurrent washing (for example, two stages).

As the stabilizing solution used in the stabilization step, a processing solution that can stabilize the dye image is used. For example, a solution having a buffering capacity of pH 3 to O, a solution containing an aldehyde (for example, formalin), etc. can be used. Optical brighteners, chelating agents, bactericidal agents, fungicides, hardeners, surfactants, and the like can be used in the stabilizing liquid as necessary.

In addition, the stabilization process may be carried out using two or more tanks if necessary, and the stabilizing liquid can be saved by performing multi-stage countercurrent stabilization (for example, - to three stages), and furthermore, the water washing process can be omitted. can.

(Example) The present invention will be described in detail below with reference to Examples, but the present invention is not limited thereto.

Example: A silver halide emulsion and a coupler Cp-/ were dissolved in tricresyl phosphate, emulsified and dispersed, and added to coat a transparent cellulose triacetate film support to form an emulsion layer as shown below. /It was created.

(Sample 10/) (1) Emulsion layer negative silver iodobromide turnip-7Cp-/ 0.4tJ1p/m
"Tricresyl phosphate o, ttrp7m gelatin /, zF/m" (2) Protective layer - 94t-dichloro-≦-hydroxy-3-triazine sodium 0, / Op/m gelatin,! y/m" (Sample/θ=~10) Instead of coupler Cp-/ of sample 10/, comparative couplers Cp-co, Cp-3 and coupler M-J of the present invention
Sample 1 except that M−/2 was replaced by equimolar
10 samples to IO! in the same manner as 0/! - Created each.

(Sample 10≦~l10) Sample 10/~10J- except that the compound A-10 of the present invention was added at a coating amount of 0.0♂F/m to each of the emulsion layers of Sample 10/~10J-. 10! Samples 104 to 10 were prepared in the same manner as above.

(Samples///~//ri Samples 10/~10! A coating amount of the compound A-/j of the present invention was 0, 0/f/tri on each of the emulsion layers of samples 10/-10!
Sample 10/~101 except that it was added so that
Similarly, sample ///~//! were created respectively.

These samples were exposed to light for sensitometry, subjected to the following color development process, and then subjected to density measurement through a green filter (Fuji Film Co., Ltd. g BPN-13) (A condition). Furthermore, the treated sample was heated to a relative humidity of 7.
After 24 was left to stand for an hour under 0.01% conditions, the concentration was measured again (B conditions). These results are summarized in Table 1.

In addition, these samples were exposed to light for sensitometry, (immediately after (q), (o) 4tt'c relative humidity? After being left for 3 days, the above color development process was performed, and the same density measurements were performed. The relative sensitivity was defined as the logarithm of the exposure amount giving the density of Cub9+Q,-, and Table 1 shows the sensitivity of each sample under the D condition with respect to the C condition.

The color development process used here is 3/'C as shown below.
I went there.

1 Color development ---7 minutes 11 seconds 2 Bleaching ---4 minutes 30 seconds 3 Washing ---3 minutes/! 4 seconds Fixing ------- for 30 seconds 5 Washing with water---7
Minutes 73 seconds 6 Stable ----3 minutes/j seconds The composition of the treatment liquid used in each step was as follows.

Color liquid diethylenetriaminepentaacetic acid 7.0P/-Hydroxyethylidene-/,/-diphosphonic acid Co, op Sodium sulfite G, O p Potassium carbonate
30.09 Potassium Bromide
/, 4tp potassium iodide /
, Jq hydroxylamine sulfate 2. If Dag-N-ethyl-N-β-hydroxyethylamino)-1-methylaniline sulfate,! ! Add water /, 0L pH 10.0 Bleach solution Ethylenediaminetetraacetic acid ferric ammonium salt 100.07 Ethylenediaminetetraacetic acid disodium salt 10.09 Ammonium bromide /10. Of ammonium nitrate
10.07 Add water
/,04pHt,.

Fixer Ethylenediaminetetraacetic acid disodium salt /, Of sodium sulfite, 07 Thiosulfuric ammonium aqueous solution (to%) /yz, Oft Sodium bisulfite, 45j Add water
/, 01° pH 4,4 Stable liquid formalin (da<71) Co 1.0d polyoxyethylene-p-monononylphenyl ether (average degree of polymerization! 10) 0,3! Add water /, 01° From Table 1, sample 1041 using the two-monomer magenta coupler of the present invention alone
and/Q! Although it has high color development performance, it causes a significant increase in magenta density after processing, but the test IO? used in conjunction with the compound of the present invention? , 110% //1 and /
/! It can be seen that the coloring performance is high and the color image density after development is also stable. It is also clear that, even with the -2 equivalent magenta coupler, the color image cannot be stabilized with the magenta coupler Cp-3, which is outside the scope of the present invention, demonstrating the effectiveness of the combination of the present invention.

From Table 1, when the coupler of the present invention is used alone (samples 104t and 106), the forced deterioration condition after exposure (D condition)
However, it is clear that this reduction in sensitivity can be prevented by the combination of the present invention.

(Cp-co) x : y--/ : / wt/wt average molecular weight /
j, 000 Example λ A multilayer color photosensitive material sample 20/ was prepared on a transparent cellulose triacetate film support, each layer having the composition shown below.

The amount of emulsion coated was expressed as the amount of silver coated.

(Sample-07) 7th layer; antihalation layer black colloidal silver 0, /
j 77m” ultraviolet absorber U-i ・・・O1θ
♂y/m ”Same U -2-0,/-
Gelatin layer containing 27/m" λth layer: Intermediate layer 2, !-G-t-pentadecylhydroquinone...0./?f/m" coupler C-/...・0. //p/rn
Gelatin layer 3rd layer containing ``7th red-sensitive emulsion layer.../, 2P/m thick sensitizing dye ■....../ per mole of silver/
, 4tX/θ molar same ■−・・・
...0.4tX/θ mole for 1 mole of silver Sensitizing dye■......For 1 mole of silver! , 6 / θ mole same ■・・・・・・・・・0x for 1 mole of silver
lO molar coupler C-u-・-・・・・0.4t! p/
m" coupler C-5-...-o, o3jy/m" coupler C-a...0. θλz p
/ m Gelatin layer qth layer containing t: -th red-sensitive emulsion layer ...... /, θy / m 2 sensitizing dye I
For 1 mole of silver! , x10 mole same ■ For 1 mole of silver / , j × 10 mole same ■ ・・・・・・・・・λ for 1 mole of silver, /
x/θ mole same ■ ・・・・・・・・・For 1 mole of silver/, Z
Xlo molar coupler C-λ-・-・・・・o, o r o
y7m Tomi coupler c-t ・・・・・・・・・ 0
．． 02OP/m” coupler Cj −= −0, Oj j
Gelatin layer 1st layer containing 517m''; middle layer 2, !-G-t-pentadecylhydroquinone...0.0♂1p/m''
6th layer of gelatin layer containing; 1st green-sensitive emulsion layer --- = 57, / Op / rn" sensitizing dye V --- ... 1 mole of silver, Ox 10
Molar sensitizing dye■・・・・・・J per mole of silver,
0x10 mol■ ・・・・・・・・・For 1 mol of silver/, 0x10
Mol coupler〇-6=・・−=・=・0, 4tj j!
/ m” coupler C-7・・・・・・・・・-o, /
3y/m coupler C-r-・・・・・・・・・・・・
o, o coy/m! Coupler C-a --------・-・
7th layer of gelatin layer containing -...-0, o 4ty/m"; first green-sensitive emulsion layer 0, o 4ty/ml sensitizing dye V......for 1 mole of silver Leverage,
Fxio-'mole Vl ・・・・・・・・・For 1 mole of silver /
, rXlo”'-5 mole ■ ・・・・・・・・・7, j for 1 mole of silver
Xlo”””Mole coupler C-4・-・-・・・・0,0?jp
/m” coupler C-7--= 0, 0/j P
/m'' gelatin layer layer; yellow filter one layer of yellow colloidal silver ・-・・-・-o、o rri/m
Yukiko! -G-t-inkdecylhydroquinone------0, 0? 9th layer of gelatin layer containing Op/m; 1st blue-sensitive emulsion layer ---0, y/m "sensitizing dye"
・・・・・・-For 7 moles of silver, 41X10
Molar coupler C-? −・−・−−−−−0, '7 /ri/m Tomi coupler C-4t−・・・・−, Q , Q7
7m" 10th layer; 1st blue-sensitive emulsion layer...-0,1117m" Sensitizing dye ■-1...j, 0 per mole of silver
X10 molar coupler C-ta......,, o, λ
Gelatin layer 1/layer containing 3p/m2; 1st protective layer ultraviolet absorber U-10,/17m2 same U
Gelatin layer 1st λ layer containing -2o, 2 col/m"; protective layer -...0,2!7m" polymethacrylate particles (diameter/, 3μ) = 0, /Op/m In addition to the above-mentioned composition, a gelatin hardening agent H-1 and an external image activator were applied to each layer of the gelatin layer.

(Sample -〇) Sample 2 except that the coupler C-4 in the 6th layer of sample 20/ was replaced with the coupler of the present invention (M-Jj) in an equimolar amount.
Sample-0- was prepared in the same manner as 01 equimolar.

(Sample 03, λ04t) Compound A-? Samples 203 and 204t were prepared in the same manner as Samples 0 and 20, except that 0.0 mm and 17 m'' of each were added.

Immediately after exposing these samples to light for sensitometry (a), (o) #0'CtrO%, after being allowed to stand for 7 days, the following color development process was carried out using JROC.

The photographic properties of the treated strips measured using a green filter are shown in Table 1.

Table 2 shows that the combination of the present invention clearly maintains the characteristic of high sensitivity and improves the storage stability of latent images.

Color development 3 minutes/j seconds Bleach White 4 minutes 30 seconds Water wash 2 minutes 10 seconds Fixed arrival time: minutes - 0 seconds Wash with water for 3 minutes/! seconds Stability 1 minute Oj seconds The composition of the treatment liquid used in each step was as follows.

Color liquid diethylenetriaminepentaacetic acid /,0771-Hydroxyethylidene-7,/-diphosphonic acid λ,oy Sodium sulfite, op Potassium carbonate
30, Of potassium bromide
/,q! Potassium iodide／・
j Cape hydroxylamine sulfate, 30gP<t
-(N-Ethyl-N-β- Hydroxyethylaminoto 2-methylaniline sulfate! Add water.
/, θ2 pH 10,0 Bleach solution Ethylenediaminetetraacetic acid ferric ammonium salt 100.0 Taethylenediaminetetraacetic acid disodium salt io, op Ammonium bromide /Jθ, 0! ammonium nitrate
10. Add water
/, 01 pH 4,0 Fixer ethylenediaminetetraacetic acid disodium salt /, Of sodium sulfite, op ammonium thiosulfate aqueous solution (RIO) /, Od Sodium bisulfite, 4F Add water
/, 01 pH 4,4 Stable liquid formalin (4t0q6) Co, Od polyoxyethylene-p-monononylphenyl ether (average degree of polymerization -4-/l!7) 0.39 Add water /, 011 Table 1 The condition (a) for sample-20/ was set to /θθ with the relative value of the exposure amount giving a density of 90.2.

Structure of compounds used in examples U-/ (The suffix indicates the weight ratio) C-/ l −1 〇-J sensitizing dye I (CH2)3803 Na 2H5 ■ Patent Applicant: Fuji Photo Film Co., Ltd. Procedural Amendment June 2, 1986≦day

Claims (1)

[Scope of Claims] A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support has the following general formula [
1. A silver halide color photographic material comprising a magenta image-forming coupler represented by [I] and a compound represented by the following general formula [II] in the same layer. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Here, R_1 represents an aromatic group, aliphatic group, or a heterocyclic group, R_2 represents a substituent, and Za, Zb, Zc, and Zd each represent methine. , substituted methine, or -N-. General formula [II] (R'-CO@O@)_nM^n^+ R' represents a substituent that provides diffusion resistance to the compound of general formula [II], and M^n^+ is a hydrogen ion. It represents a metal, ion or transition metal ion, and n represents an integer of 1 to 4.