JPH01224761A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To form a dye image having superior color reproducibility and shelf stability by incorporating a pyrazoloazole type cyan coupler and a specified cyan coupler into a red-sensitive silver halide emulsion layer. CONSTITUTION:A pyrazoloazole type cyan coupler having at least one electron attracting group and/or a group bonding to H at a substitutable position other than the active site and a cyan coupler represented by formula I and/or a cyan coupler represented by formula II are incorporated into a red-sensitive silver halide emulsion layer. In formula I, R21 is alkyl, R22 is a ballast group, R23 is H, etc., and Z1 is a group which can be released by a reaction with H, etc. In formula II, R24 is alkyl, etc., R25 is alkyl, etc., R26 is H, etc., and Y1 is a group which can be released by a reaction with H, etc. A dispersion liq. contg. the cyan couplers has superior shelf stability and a dye image having superior color reproducibility and shelf stability is formed.

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to a silver halide photographic material, and more particularly to a silver halide color photographic material having excellent color reproducibility and image storage stability.

[Background of the invention]

After exposing the silver halide photographic light-sensitive material to light, color development is performed, whereby the oxidized aromatic primary amine color developing agent reacts with the dye-forming coupler to generate dyes and form a two-color image. Ru. Generally, in this photographic method, a subtractive color reproduction method is used to form yellow, magenta, and cyan color images. Until now, phenols or naphthols have been widely used as cyan image-forming couplers, but the cyan images obtained from these phenols or naphthols have poor sharpness on the short wavelength side. , there is a problem in color reproduction in that the edge region also has unnecessary asymmetric absorption. Further, color images obtained from conventionally used cyan image-forming couplers of phenols and naphthols have not been able to satisfy both heat fastness and light fastness. As a means to solve the above problems, the patent application No. 62-473
The technology No. 23 has been proposed, and it is said that the use of the pyrazoloazole coupler described in the specification of this proposal has the effect of greatly improving color reproducibility and heat fastness properties. ing. However, the light fastness was not sufficient and, surprisingly, the storage stability of the coupler dispersion was found to be unsatisfactory, and improvements in this area have been awaited. As a result of various studies regarding the above-mentioned problems, the present inventors found that
The present inventors have discovered that preferable results can be obtained by using a pyrazoloazole cyan coupler and a specific phenol coupler in combination, and have completed the present invention.

[Structure of the invention]

An object of the present invention is to provide a silver halide photographic light-sensitive material having at least one blue-sensitive silver halide emulsion layer, one green-sensitive silver halide emulsion layer and one red-sensitive silver halide emulsion layer on a support. The silver oxide emulsion layer is
A pyrazoloazole-type cyan coupler having at least one electron-withdrawing group and/or hydrogen-bonding group at a substitutable position other than the active site, and the following-Fukudai [PC-I]
This was achieved using a silver halide photographic light-sensitive material containing a cyan coupler represented by and/or -Fukudai [PC-II].゛General formula [PC-1] - (In the formula, R21 represents an alkyl group having 2 to 6 carbon atoms. R2□ represents a ballast group, R23 represents a hydrogen atom, a halogen atom, or an alkyl group, Zl represents hydrogen Represents a group that can be separated by reaction with an atom or an oxidized product of a color developing agent,
) General formula [PC-II] (In the formula, R24 represents an alkyl group or an aryl group. R25 represents an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group. R2g represents a hydrogen atom, a halogen atom,
Represents an alkyl group or an alkoxy group, where R21 is R2
(Yl may form a ring in cooperation with 4; Yl represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of a color developing agent.)

[Specific structure of the invention]

The silver halide photographic light-sensitive material of the present invention has the formula -m [
PC-1] and the above-mentioned cyan coupler represented by [PC-1]
A birazoloazole type having at least one selected from the cyan couplers represented by PC-I[] and at least one electron-withdrawing group and/or hydrogen-bonding group at a substitutable position other than the active site. A cyan coupler is also used. Hereinafter, when these cyan couplers are used together, at least one electron-withdrawing group and/or hydrogen-bonding group is added to a substitutable position other than the active site of the pyrazoloazole ring according to the present invention. The pyrazoloazole cyan coupler having the following will be explained in more detail. A pyrazoloazole type cyan coupler is a cyan coupler having a condensed ring, that is, a pyrazoloazole ring, in which an azole ring (including one in which a benzene ring or the like is condensed) is condensed to a pyrazole ring. The pyrazoloazole ring has at least 61 electron-withdrawing groups and/or one hydrogen-bonding group at substitutable positions other than the active site, thereby forming a cyan dye by color-forming parent image. It becomes a cyan coupler. The pyrazoloazole ring may have any other substituents at substitutable positions other than the active site. The active site of the pyrazoloazole ring refers to a position to which hydrogen or a substituent that can be released by reaction with an oxidized product of a color developing agent formed as a result of color development is bonded. The electron-withdrawing group of the present invention is a pyrazoloazole cyan coupler that reacts with an oxidized developing agent to form a dye that has an absorption maximum between 580 and 700 nm when dissolved in methanol and measured. yt, which has such a strong electron-attracting force, means a substituent. Each of the electron-withdrawing groups may have the above-mentioned electron-attracting power alone, or they may have the above-mentioned electron-withdrawing power together. The electron-withdrawing group according to the present invention preferably refers to 11ann
The substituent constant δp defined by ett is 100.2
Zero or more substituents, specifically sulfonyl, sulfinyl, sulfonyloxy, sulfamoyl, phosphoryl, carbamoylacyloxy, oxycarbonyl, carboxyl, cyan, nitro, halogenated alkoxy, halogenated aryloxy, pyrrolyl, tetrazolyl, etc. Examples include each group and a halogen atom. Examples of the sulfonyl group include groups such as alkylsulfonyl, arylsulfonyl, halogenated alkylsulfonyl, and halogenated arylsulfonyl. Examples of the sulfinyl group include groups such as alkylsulfinyl and arylsulfinyl. Examples of the sulfonyloxy group include groups such as alkylsulfonyloxy and arylsulfonyloxy. Examples of the sulfamoyl group include groups such as N,N-dialkylsulfamoyl, N,N-diarylsulfamoyl, and N-alkyl-N-arylsulfamoyl. Examples of the phosphoryl group include groups such as alkoxyphosphoryl, aryloxyphosphoryl, alkylphosphoryl, and arylphosphoryl. Examples of the carbamoyl group include groups such as N,N-dialkylcarbamoyl, N,N-diarylcarbamoyl, and N-alkyl-N-arylcarbamoyl. Examples of the acyl group include groups such as alkylcarbonyl and arylcarbonyl. As the acyloxy group, alkylcarbonyloxy and the like are preferred. As the oxycarbonyl group, alkoxycarbonyl,
Examples include groups such as aryloxycarbonyl. As the halogenated alkoxy group, an α-halogenated alkoxy group is preferable. As the halogenated aryloxy group, groups such as tetrafluoroaryloxy and pentafluoroaryloxy are preferable. Examples of the pyrrolyl group include groups such as -pyrrolyl. Examples of the tetrazolyl group include groups such as 1-tetrazolyl. In addition to the above substituents, trifluoromethyl group, heptafluoroin 10-pyl group, nonylfluoro(1)butyl group, tetrafluoroaryl group, pentafluoroaryl group, etc. are preferably used. The hydrogen-bonding group of the present invention means that the pyrazoloazole cyan coupler reacts with the oxidized developing agent between the nitrogen atom on the pyrazoloazole ring, and is dissolved in methanol for measurement. A group having a hydrogen atom capable of forming hydrogen bonds of such strength as to form a dye that sometimes has an absorption maximum between 580 and 700 nm. By forming a strong hydrogen bond between the hydrogen atom and the nitrogen atom on the pyrazoloazole ring, the curler can
The dye formed by color development becomes a cyan coupler. Typical examples of substituents having a hydrogen atom that can form the above hydrogen bond with the nitrogen atom on the pyrazoloazole ring are:
Substituents represented by the following formulas can be mentioned. Ra Rb Ra Rb 4.3) Ra Rb Ra -C-NHSO,Rd Rb Ra -C-NHSORd R,b Ra -C-NHCORd Rb (wherein, Ra, Rb, Rc, Rd and Re are hydrogen atoms or substituted group, Rf represents a substituent, 1 represents O or 1, n represents an integer of 0 to 4. When n is 2 or more, each Rf may be the same or different.) In the above formula, preferred as Ra, Rb and Rd are hydrogen atom, alkyl group, aryl group, hetero yA
Residues, etc., and preferred as Re are hydrogen atoms,
These include alkyl groups, aryl groups, hetero yJ residues, and sulfonyl groups and sulfinyl groups that may be substituted with alkyl groups, aryl groups, and the like. Preferred examples of Re include hydrogen atoms, alkyl groups, aryl groups, heterocyclic residues, and sulfonyl groups, sulfinyl groups, and carbonyl groups that may be substituted with alkyl groups, aryl groups, etc., but particularly preferred are: These are sulfonyl groups, sulfinyl groups, and carbonyl groups that may be substituted with alkyl groups, aryl groups, etc. There are no particular limitations on the substituent represented by Rf. Among the above, particularly preferable hydrogen-bonding groups used in the present invention are the above formulas +1) and f2)(3).
and (7), among which more preferable ones are -3Ox N HRc, -3ONHR
c, -CONHRc and the above hydrogen bonding group are long chain hydrocarbon groups and polymer l! It may contain a diffusion-resistant substituent such as a U group. A pyrazoloazole-type cyan coupler is one in which an azole ring is fused to a pyrazole ring, and specifically, preferably, it can be represented by the following general formula [I]. General formula [1] (wherein, R1 represents a hydrogen atom or a substituent, and R2 represents Z
At least one of Rr and μ2 is a group selected from an electron-withdrawing group or a hydrogen-bonding group, representing a substituent bonded to a carbon atom of the nonmetallic atom group represented by: n indicates the number of substituents R2. X represents a hydrogen atom or a substituent capable of eliminating St by reaction with an oxidized product of a color developing agent. Z represents a nonmetallic atom group necessary to form an azole ring to which a benzene ring etc. may be fused;) R2 and R7 above;
Among the substituents represented by, various substituents other than electron-withdrawing groups and hydrogen-bonding groups can be mentioned,
There are no particular restrictions, but typical examples include alkyl, aryl,
Anilino, acylamino, sulponamide, alkylthio, arylthio, alkenyl, cycloalkyl, cycloalkenyl, alkynyl, heterocycle, alkoxy, aryloxy, heterocycleoxy, siloxy, amine, alkylamino, imide, ureido, sulfamoylamino,
Examples include alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, thioureido, hydroxy, and mercapto groups, spiro compound residues, bridged hydrocarbon compound residues, and the like. The above alkyl group preferably has 1 to 32 carbon atoms, and may be linear or branched. As the aryl group, a phenyl group is preferred. Examples of the acylamino group include an alkylcarbonylamino group and an arylcarbonylamino group. Examples of the sulfonamide group include an alkylsulfonylamino group and an arylsulfonylamino group. Examples of the alkyl component and aryl component in the alkylthio group and arylthio group include the above-mentioned alkyl groups and aryl groups. The alkenyl group preferably has 2 to 32 carbon atoms, and the cycloalkyl group preferably has 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms, and the alkenyl group may be linear or branched. The cycloalkenyl group has 3 to 12 carbon atoms, especially 5
-7 is preferred. The ureido group includes an alkylureido group, an arylureido group, etc.; the sulfamoylamino group includes an alkylsulfamoylamino group, an arylsulfamoylamino group, etc.; the heterocyclic group is preferably a 5- to 7-membered one; Specifically, 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, etc.; as the heterocyclic oxy group, those having a 5- to 7-membered heterocycle are preferable, for example, 3
, 4,5.6-tetrahydrobilanyl-2-oxy group,
1-phenyltetrazole-5-oxy group, etc.; As the heterocyclic thio group, a 5- to 7-membered heterocyclic thio group is preferable, such as 2-pyridylthio group, 2-benzothiazolylthio group, 2,4-diphenoxy- 1,3,5-triazole-6 monothio group, etc.; Siloxy groups include trimethylsiloxy, triethylsiloxy, dimethylbutylsiloxy, etc.; imide groups include succinimide, 23-heptadecylsuccinimide, phthalimide group, glutarimide group, etc.; as a spiro compound residue, spiro[3,3]hebutane-
1-yl, etc.; As a bridged hydrocarbon compound residue, bicyclo[2°2.1
] heptan-1-yl, tricyclo[3°3.1.1'
・7] Decan-1-yl, 7.7 dimethyl-bicyclo[
2,2,1]hebutan-1-yl and the like. These groups may further contain substituents such as long-chain hydrocarbon groups and diffusion-resistant groups such as polymer residues. In the general formula [1], examples of groups that can be separated by reaction with the oxidized product of the color developing agent represented by X include halogen atoms (chlorine atom, bromine atom, fluorine atom, etc.), alkoxy, aryloxy, heterocyclic oxy , acyloxy, sulfonyloxy, alkoxycarbonyloxybonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclicthio, alkyloxythiocarbonylthio, acylamino,
sulfonamide, nitrogen-containing heterocycle bonded with N atom, alkyloxycarbonylamino, aryloxycarbonylamino, carphoki (R,' and R2' are synonymous with R1 and R, above, Ra and R11 are hydrogen atoms,
It represents an alkyl group, an aryl group or a heterocyclic group, and Z' has the same meaning as Z above. ), preferably a halogen atom. Among these, particularly preferred ones represented by X are hydrogen atoms and chlorine atoms. In formula [I], examples of the nitrogen-containing heterocycle formed by Z include a pyrazole ring, an imidazole ring, a benzimidazole ring, a triazole ring, and a tetrazole ring. , -Among the compounds represented by formula [I], those in which at least one of R and R2 is an electron-withdrawing group are more specifically described as follows - formula [■α] to general formula [■α] General formula [■α] General formula [IVα] - Numerical formula [VIα] General formula [■α] Y In the above - mathematical formula, at least one of R8 and Rst in [■α]
In [■α], at least one of R□ and R4g, in [IV(Z], R1,, Rs # OJ: U R6
# f) Uchino a little short I:Jl, [V(Z] middle, R1,, Rt-o and Ra-(')
At least one of [■α] medium, R1, and R9m
At least one of R1, in [■α1, RIa and R2° in [■α], is an electron-withdrawing group. X has the same meaning as X in general formula [I], and P is 0 to 4
Y represents a hydrogen atom or a substituent, and the preferable substituent represented by Y is, for example, one that separates from the cyan coupler before the compound of the present invention reacts with the oxidized developing agent. For example, JP-A-61-228
Coupling-off occurs by reaction with a group that can be separated under alkaline conditions as described in No. 444, etc., or with an oxidized developing agent as described in JP-A-56-133734, etc. Substituents etc. can be mentioned. Preferred Y is a hydrogen atom. Also, in - formula [■α], ~ [■α], R,, ~
Among R1゜, substituents that are not electron-withdrawing groups are:
There is no particular restriction. Specifically, in general formula [I], R
When o or R2 is other than an electron-withdrawing group or a hydrogen-bonding group, examples of R1 or R1 include those mentioned as a substituent or those mentioned above as a hydrogen-bonding group. . The cyan coupler having an electron-withdrawing group according to the present invention is
Patent Application No. 62-47323, No. 62-53417, No. 62-62162, No. 62-53418, No. 62-
No. 62163, No. 62-48895, No. 62-999
It can be easily synthesized according to the methods described in various specifications such as No. 50. Among the compounds represented by general formula [1], RI and R2
More specifically, at least one of the groups is a hydrogen-bonding group: In [■βJ to [■β], X has the same meaning as X in formula [I] above. - Formulas [■β], [Vβ], [VIβ] and [■Jβ
RIJ in -i formula [■β], at least one of R, 4J in formula [■β], at least one of R□ and R5I in general formula [IVβ], general formula [■β] R13. and R1 (at least one of 11 is a hydrogen-bonding group. Among R□ to R3□ in the general formulas [■β] to [■β], substituents that are not hydrogen-bonding groups are , there is no particular restriction, specifically, in general formula [I], R3 or R2
is other than an electron-withdrawing group or a hydrogen-bonding group, the substituents represented by R8 or R2 or those mentioned above as the electron-withdrawing group can be mentioned. Y in general formulas [■β] to [■β] is -i formula [■α
] to [■α] is synonymous with Y. The cyan coupler having a hydrogen-bonding group according to the present invention is disclosed in Japanese Patent Application No. 62-85510 and No. 62-85511. It can be easily synthesized according to the methods described in the specifications of No. 62-114838, No. 62-115946, and No. 62-184554. The couplers of the invention usually contain 1
It can be used in the range of x1 o-' moles to 1 mole, preferably 1 x 10-2 moles to 8 x 10-' moles. Moreover, the coupler of the present invention can also be used in combination with other types of cyan couplers. The methods and techniques used for conventional cyan dye-forming couplers are similarly applicable to the cyan couplers of the present invention. Typically, the cyan coupler of the present invention is blended into a silver halide emulsion, and this emulsion is coated on a support to form the color light-sensitive material of the present invention. Below, pyrazoloazole-type shea IOH2 according to the present invention
1 C-7 N) ICOC+J2s 1, bottom margin NHCOC+ 212s jcgH+7 N -N -N C-22 C-23 [I N I ■ IJ Q1
1'Q
Q(+)
'J U+1-N
-N l l C-56 C-57 It 5O2NlIC++H2s If 5O2NHC+2Hes Next, the compound represented by the general formula [PC-II according to the present invention will be explained. General formula [PC-1] ll Zl (wherein, R21 represents an alkyl group having 2 to 6 carbon atoms, R22 represents a ballast group, R23 represents a hydrogen atom, a halogen atom, or an alkyl group, Zl represents a hydrogen atom or represents an atom or group that can be separated by reaction with an oxidized product of a color developing agent.) The alkyl group represented by R21 may be linear or branched,
It also includes those having substituents. The ballast group represented by R22 is an organic group having a size and shape that imparts sufficient bulk to the coupler molecule to substantially prevent the coupler from diffusing from the layer to which it is applied to other layers. . Preferred ballast groups are as follows - clothing cost % formula % R2? represents an alkyl group having 1 to 12 carbon atoms, and ^r represents an aryl group such as a phenyl group, and this aryl group includes those having a substituent. Particularly desirable as R23 is a halogen atom, especially C
It is 1. Zl has the same meaning as Yl in the general formula [PC-If]. Next, specific examples of the coupler represented by the general formula [PC-1] will be shown, but the invention is not limited thereto. PC-I-10 0II Specific examples of cyan couplers that can be used in the present invention including these include Japanese Patent Publication No. 49-11572, Japanese Patent Application Publication No. 61-3142, Japanese Patent Application Publication No. 61-9652,
Publication No. 61-9653, Publication No. 61-39045,
It is described in 61-50136, 61-99141, 61-105545, etc. The cyan dye-forming coupler of the present invention represented by the above-mentioned PC-1 is *? 4 lXl per mole of silver halide
0-' mole to 1 mole, preferably lXl0-" mole to 8
It can be used in the range of X10-' moles. Next, the compound represented by the above-mentioned -Fukudai [PC-[1] according to the present invention will be explained. General formula [PC-[[coIJ (wherein, R24 represents an alkyl group or an aryl group. R25 represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group, and R26 represents a hydrogen atom, a halogen atom,
Represents an alkyl group or an alkoxy group, where R26 is R2
(Yl represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of a color developing agent) In the coupler, the alkyl group represented by R24 has 1 to 1 carbon atoms.
32 are preferable, and these may be linear or branched, and include those having substituents. The aryl group represented by R24 is preferably a phenyl group, including those having substituents. The alkyl group represented by R25 preferably has 1 to 3 carbon atoms, and these alkyl groups may be linear or branched, and also include those having substituents. The cycloalkyl group represented by R25 has 3 to 3 carbon atoms.
12 are preferred, and these cycloalkyl groups also include those having substituents. The aryl group represented by R25 is preferably a phenyl group, including those having substituents. The heterocyclic group represented by R25 is preferably a 5- to 7-membered ring, including those having substituents, and may be fused. R2 represents a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group, and the alkyl group and the alkoxy group include those having a substituent, but 82& is preferably a hydrogen atom. Further, the ring formed jointly by R24 and R2 is preferably a 5- or 6-membered ring, and examples thereof include the following. Groups that can be separated by reaction with the oxidized product of the color developing agent represented by Y in the general formula [PC-I[] include a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, a sulfonyloxy group, and an acylamino group. group, a sulfonylamino group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, and an imide group (including those each having a substituent), but preferably a halogen atom, an aryloxy group, and an alkoxy group. Among the above-mentioned cyan couplers, particularly preferred are those represented by the following formula [PC-11-A]. General Formula [PC-11-A] In the formula, R2g represents a phenyl group substituted with at least one halogen atom, and these phenyl groups also include those having substituents other than the halogen atom. R29 has the same meaning as R)I in the above-mentioned formula [PC-It]. Y2 represents a halogen atom, an aryloxy group, or an alkoxy group, including those having a substituent. Typical specific examples of cyan couplers represented by the general formula [PC-It] are shown below. To 0■! IIS. Specific examples of the above-mentioned cyan couplers include Japanese Patent Application No. 61-21853, pages 26 to 35, JP-A-60-225155, lower left column on page 7 to lower right column on page 10, 2, 5- described in JP-A No. 60-222853, page 6, upper left i to page 8, lower right column, and JP-A-59-185335, page 6, lower left column to page 9, lower left column. It contains a diacylamino cyan coupler and can be synthesized according to the methods described in these specifications and publications. This cyan coupler is used in the red-sensitive silver halide emulsion layer, and the amount added is lXl0 per mole of silver halide.
-' to 1 mol, preferably 1 x to -2 to 8 x 10 -'
It is in the molar range. In order to incorporate the cyan coupler of the present invention into the color photosensitive material of the invention, known techniques used for ordinary cyan couplers can be applied. For example, it is preferable to dissolve the coupler in a high boiling point solvent and, if necessary, in combination with a low boiling point solvent, disperse it in the form of fine particles, and add it to the silver halide emulsion according to the present invention. Hydroquinone derivatives, ultraviolet absorbers, anti-fading agents, etc. may be used in combination. Examples of the silver halide used in the silver halide emulsion layer of the sensitive material of the present invention include silver chloride, silver bromide, silver iodide,
Any material used in ordinary silver halide photographic emulsions such as silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc. can be used. These silver halide grains may be coarse or fine, and the grain size distribution may be narrow or wide. Further, the crystals of these silver halide grains may be normal crystals or twin crystals, and any ratio of [100] planes to [111] planes can be used. Furthermore, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may have a layered structure with different inside and outside. It may be of a type that forms a latent image mainly on the surface or of a type that forms a latent image inside the particle. These silver halide grains can be prepared by known methods commonly used in the art. It is preferable that soluble salts be removed from the silver halide emulsions used in the light-sensitive materials of the present invention, but those in which soluble salts have not been removed can also be used. It is also possible to use a mixture of two or more silver halide emulsions prepared separately. The silver halide emulsion used in the present invention includes:
Any silver halide emulsion may be used, such as a silver chloride emulsion, a silver chlorobromide emulsion, a silver chloroiodromide emulsion, etc., and there are no particular limitations.
Silver halide emulsions having high chloride silver halide grains are preferred. The above-mentioned high chloride silver halide grains are those having a silver chloride content of 90 mol % or more. In high chloride silver halide grains, the silver bromide content is 10 mol% or less,
The silver iodide content is preferably 0.5 mol% or less, and more preferably silver chlorobromide has a silver bromide content of 0.1 to 2 mol%. High chloride silver halide grains do not have to be used alone, but can also be used in combination with other silver halide grains having different compositions. For example, it may be mixed with silver halide grains having a silver chloride content of 10 mol % or less. In addition, in a silver halide emulsion layer containing high chloride silver halide grains, the ratio of high chloride silver halide grains to the total silver halide grains contained in the emulsion layer is 6.
It is preferably 0% by weight or more, and more preferably 80% by weight or more. The composition of high chloride silver halide grains may be uniform from the inside to the outside of the grain, or the composition inside and outside the grain may be different, or the composition inside and outside the grain may be different. In this case, the composition may change continuously or discontinuously. The grain size of the high chloride silver halide grains is not particularly limited, but in consideration of rapid processing efficiency and photographic performance such as sensitivity, it is preferably 0.2 to 1.6 μm, and more preferably 0.2 μm to 1.6 μm.
It is in the range of 25 to 1.2 μm. The above particle size can be measured by various methods commonly used in the technical field. One representative method is Loveland's "Particle Size Analysis Method J (A, S, T, M , Symposium on Light Microscopy, 1955,
94-122) or ``Theory of the Photographic Process'' (co-authored by Mies and Ginimes, 3rd edition, published by McLamin Publishing Co., Ltd. (1999))
There is a method described in Chapter 2) of 1966). This particle size can be measured using either the projected area of the particle or an approximation to its diameter.If the particles are of substantially uniform shape, the particle size distribution will measure this fairly accurately as the diameter is the projected area. can be expressed. The grain size distribution of the high chloride silver halide grains may be polydisperse or monodisperse. Preferably, the silver halide grains are monodisperse silver halide grains having a coefficient of variation of 0.22 or less, more preferably 0.15 or less in the grain size distribution. The silver halide grains used in the emulsion of the present invention can be prepared by acidic method.
The particles may be obtained by either the neutral method or the ammonia method, and the particles may be grown all at once, or may be grown after forming seed particles. They may be the same or different. Further, the method of reacting the soluble silver salt and the soluble halogen salt may be any method such as a forward mixing method, a back mixing method, a simultaneous mixing method, or a combination thereof, but those obtained by a simultaneous mixing method are preferable. pAg described in JP-A-54-48521 etc. as a form of simultaneous mixing method
-Chondrold-double jet method can also be used. Furthermore, if necessary, a silver halide solvent such as a thioether may be used, and a compound such as a mercapto group-containing compound, a nitrogen-containing heterocyclic compound, or a sensitizing dye may be used during the formation of silver halide grains or It may be added and used after the completion of formation. The silver halide grains used in the present invention may have any shape. One preferable example is (100)
It is a cube with planes as crystal surfaces. Furthermore, particles having shapes such as octahedron, tetradecahedron, dodecahedron, etc. can also be used. Furthermore, particles having twin planes may be used. The silver halide grains used in the present invention may be of a single shape or may be a mixture of grains of various shapes. The silver halide grains used in the present invention may contain cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts, rhodium salts or complex salts,
Metal ions can be added to the inside of the particles and/or on the surface of the particles using iron salts or complex salts, and reduction sensitization can be achieved inside the particles and/or on the surface of the particles by placing them in an appropriate reducing atmosphere. can be granted. In the emulsion containing silver halide grains used in the present invention (hereinafter referred to as the emulsion of the present invention), unnecessary soluble salts may be removed after the growth of the silver halide grains is completed, or unnecessary soluble salts may be left in the emulsion. In addition, when removing the salts, it can be carried out based on the method described in Research Disclosure No. 17643. The silver halide grains used in the emulsion of the present invention are preferably grains in which a latent image is mainly formed on the surface, but may also be grains in which a latent image is formed inside the grain. In the present invention, a chalcogen sensitizer can be used. The chalcogen sensitizer is a general term for sulfur sensitizers, selenium sensitizers, and tellurium sensitizers, and sulfur sensitizers and selenium sensitizers are preferred. Examples of the sulfur sensitizer include 1,000 sulfur salts, allylthiocarbazide, thiourea, allyl isothiocyanate, cystine, p-toluenethiosulfonate, and rhodanine. Other U.S. Patents No. 1,574,944, U.S. Patent No. 2,410,689, U.S. Patent No. 2,278,947, U.S. Patent No. 2
, No. 728,668, No. 3,501,313, No. 3,
No. 656,955, West German Application Publication (OL S H, 42
No. 2,869, JP-A-56-24937, JP-A No. 55-4
Sulfur sensitizers described in Publication No. 5016 and the like can also be used. The amount of sulfur sensitizer added varies over a considerable range depending on various conditions such as pH and temperature, and the size of silver halide grains, but as a guide, 10-
The amount is preferably about 7 to 10-1 mol. The emulsion of the present invention can be produced by a reduction sensitization method using a reducing substance, a noble metal sensitization method using a noble metal compound, or the like. By including the high chloride silver halide emulsion layer in the photographic constituent layer containing the pyrazoloazole cyan coupler according to the present invention, faithful color reproducibility can be obtained;
It becomes possible to obtain a sufficient maximum concentration. The silver halide emulsion used in the present invention can be optically sensitized to a desired wavelength range using a dye known as a sensitizing dye in the photographic industry. As the binder (or protective colloid) used in the silver halide photographic material of the present invention, gelatin is advantageously used, but gelatin derivatives, graft polymers of gelatin and other polymers, proteins, sugars, etc. Hydrophilic colloids such as derivatives, cellulose derivatives, synthetic hydrophilic polymeric substances such as single or copolymers can also be used. The silver halide photographic light-sensitive material of the present invention having the above structure can be, for example, a color negative film, a positive film, or a color photographic paper, but especially when a color photographic paper intended for direct viewing is used. The effects of the present invention are effectively exhibited. When the silver halide color photographic material of the present invention is used as a full-color light-sensitive material, a magenta coupler and a yellow coupler are used in addition to the cyan coupler of the present invention. There are no particular restrictions on magenta couplers and yellow couplers, and known ones can be used. As the magenta coupler, 5-pyrazolone type, pyrazolobenzimidazole type, pyrazoloazole type, open chain acylacetonitrile type coupler etc.
-Pyrazolone and pyrazolotriazole magenta couplers are preferred. As the yellow coupler, for example, acylacetate, aniline, and do type couplers can be used, and these include benzacetanilide type and pivaloylacetanilide type compounds. The silver halide photographic material of the present invention further includes a hardening agent, an anti-irradiation agent, an anti-color clouding agent, an image stabilizer, a plasticizer, a latex, a surfactant, a matting agent, a lubricant, and an antistatic agent. Additives such as the following can be used as necessary. An image can be formed on the silver halide photographic material of the present invention by subjecting it to color development treatment known in the art. The pH value of the color developer is usually above 7, most commonly about 10-13. The color development temperature is usually 15°C or higher, numerically -20°C.
It is in the range of °C to 50 °C. For rapid development, it is preferable to carry out the process at 30°C or higher. Further, in conventional processing, the color development time is 3 to 4 minutes, but the color development time of the present invention for the purpose of rapid processing is generally preferably carried out in the range of 20 seconds to 60 seconds, more preferably 30 seconds. It ranges from seconds to 50 seconds. The silver halide photographic light-sensitive material of the present invention can be rapidly developed without decreasing the maximum density of the characteristic curve even when using a color developing solution containing 2 mN of benzyl alcohol per 11 or less, which is used for rapid development. . After color development, bleaching and fixing are performed. Incidentally, the bleaching treatment may be performed simultaneously with the fixing treatment. After the fixing process, a washing process is usually performed. Furthermore, a stabilization treatment may be performed as a substitute for the water washing treatment, or both may be used in combination.

[Example 1] Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto. Example 1 On a paper support laminated with polyethylene, the following layers were sequentially coated from the support side to prepare a silver halide color photographic light-sensitive material sample No. 011. Layer 1...1.28/m2 gelatin, 0.32. Blue-sensitive silver halide emulsion (silver chloride content: 97 mol%) of 0.80 g/m2 of yellow coupler (Y-A) dissolved in 0.50 g/m2 of dioctyl phthalate. ). Layer 2...0.7H/m2 gelatin, 10mH
/m2 of irradiation dye (AI-1), 5 mg/ra2 of (AI-2). M3...1.2511/TI" gelatin, 0
．． 22 g/m2 green-sensitive silver halide emulsion (silver chloride content 100 mol%), 0.624/m'' magenta coupler (0.624/m'' dissolved in 0.30 H/m2 dioctyl phthalate).
A layer containing M-A). Layer 4: Intermediate layer consisting of gelatin of 1.217/m2. N5...Bow, 40g/n+' gelatin, 0.2
0 g/m2 red-sensitive silver halide emulsion (silver chloride content 100 mol%), 0.45 g (9,1,1 O
Layer containing cyan coupler (C-2>-' mole/I2). Layer 6: Intermediate layer consisting of gelatin at 4.2 g/II2. Layer 7: 0.5 g/ A layer containing gelatin of 2,4-dichloro-6-hydroxy as a hardening agent.
Sodium s-triazine was added to layers 2.4 and 6 at 0.017 g/g gelatin, respectively. This was designated as sample 1. Next, Samples 2 to 18 were prepared in the same manner as Sample 1 except that the cyan coupler shown in Table 1 was used instead of the cyan coupler (C-2) for N5 (the amounts of the two types of cyan couplers were 4.55X 10-” moles/end 2 each, total 9.
1y10-'mol/mJl, t. -A Il The above photosensitive material samples No. 1 to No. 18 were exposed to light according to a conventional method and then processed in the following steps. <Processing process> Temperature Time color development 34.7±0.3℃ 45 seconds bleach fixing 34.7±0.5℃ 50 seconds stabilization 30-3
Dry at 4℃ for 90 seconds 60-80℃ for 60 seconds Color developer> Pure water
800ml triethanolamine 8g
N,N-diethylhydroxyamine 5g Potassium chloride 2gN=ethylut β-methanesulfonamidoethyl-methyl-4-aminoaniline sulfate 5g Sodium tetrapolyphosphate
2Fi potassium carbonate 30g Potassium sulfite 02g Optical brightener (4
, 4'-diaminostilbendisulfonic acid derivative)
Add IFI pure water to make the total volume 1p,
p I+ 10 , adjusted to 2. <Bleach-fix solution> Ethylenediaminetetraacetate ferric ammonium dihydrate 60g ethylenediaminetetra#
8 3g ammonium 1000sulfate (70% solution)
100mN ammonium sulfite (40% solution)
27.5+++1 Potassium carbonate or glacial acetic acid to pH 5.7
and add water to bring the total volume to 11. Stabilizing liquid> 5-chloro-2-methyl-4-isobutiazoline-3-
1 g 1-hydroxyethylidene-1,1-diphosphonic acid g Add water to bring the pH to 11 and adjust the pH with sulfuric acid or potassium hydroxide.
After the treatment, the concentration of each sample was measured using a densitometer (model KD-7, manufactured by Konica Corporation), and each of the treated samples was heated to a high temperature (60℃). C, 80% RH) atmosphere for 14 days, and the heat resistance and moisture resistance of the dye image were examined. Further, each sample was irradiated with a xenon fade meter for 10 days, and then the density was measured to examine light resistance. The results are shown in Table 1. However, the heat resistance, humidity, and light resistance of the dye image are as follows:
Comparative samples 1 and 2, in which each of Comparative Examples 8 and 8 were used alone, had fairly good heat resistance and moisture resistance, but poor light resistance. Comparative sample 3 using PC-1-4 alone had good light resistance but poor heat resistance and moisture resistance.
Comparative sample 4 using If-2 alone has good light resistance, but is slightly inferior in heat resistance and moisture resistance. However, Samples 5 to 18 of the present invention, in which a specific coupler was used in combination, were excellent in both heat resistance, moisture resistance, and light resistance, and were found to be robust. Example 2 A mixed solution containing C-22xlO-' mol of the cyan coupler of the present invention, 3.0 g of dioctyl phthalate, and 3.0 g of ethyl acetate was heated to 60°C, and then mixed with alkanol B (alkylnaphthalene sulfonate, DuPont Co., Ltd.). made)
17 ml of a 5% aqueous gelatin solution containing 17 ml of a 5% aqueous solution of
1 and emulsified and dispersed using an ultrasonic disperser to prepare a dispersion liquid. Ethyl acetate was distilled off under reduced pressure from these dispersions to obtain Dispersion Sample 1. In order to observe the dispersion stability of the cyan coupler, the dispersion was stored in a refrigerator (5°C) for 10 days, then kept warm in a 40°C water bath, and the state of crystal precipitation was observed with an optical microscope immediately after the incubation.
Observations were made after 10 hours and 20 hours. Furthermore, dispersion sample 2 was prepared in the same manner using the couplers shown in Table 2.
~10 were prepared and the dispersion stability of the coupler was investigated. Table 2 The evaluation of precipitation properties in this table is as follows. ○: No precipitation. △D Some precipitation occurs, but there are few problems in use. x: Precipitation occurs and there is a problem in use. As is clear from Table 2, the dispersion samples 5 to 10 of the present invention, in which a specific coupler was used in combination, were less likely to cause precipitation than the comparative dispersion samples 1.2 in which a coupler was used alone, so they were extremely dispersed. It was found that the dispersion liquid had good stability. Effects of the Invention The cyan coupler dispersion used in the present invention has excellent storage stability.1. In addition, the obtained dye image has excellent color reproducibility and storage stability.

Claims (1)

[Scope of Claims] A silver halide photographic light-sensitive material having at least one blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer on a support, wherein the red-sensitive halogen A pyrazoloazole-type cyan coupler having at least one electron-withdrawing group and/or hydrogen-bonding group at a substitutable position other than the active site in the silver emulsion layer, and the following general formula [PC-I] and/or a cyan coupler represented by the general formula [PC-II]. General formula [PC-I] ▲ Numerical formulas, chemical formulas, tables, etc. represents a group. Z_1 represents a group that can be separated by reaction with a hydrogen atom or an oxidized product of a color developing agent.) General formula [PC-II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_2_4 is Represents an alkyl group or an aryl group. R_2_5 represents an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group. R_2_6 represents a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group. In addition, R_
2_6 may form a ring together with R_2_4. Y
_1 represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of a color developing agent. )