JPH01261639A - Silver halide color photographic sensitive material with excellent color reproducibility - Google Patents

Abstract

PURPOSE:To reduce the generation of a color fogging of the title material, and to improve the preservability of an image by incorporating a pyrazoloazole type cyan coupler having at least one of an electron attractive group and/or a group capable of forming a hydrogen bond an a specified compd., in the red-sensitive silver halide emulsion layer of the sensitive material, respectively. CONSTITUTION:The pyrazoloazole type cyan coupler which has at least one of the electron attractive group and/or the group capable of forming the hydrogen bond at a position capable of substituting except an active point, is incorporated in the red sensitive silver halide emulsion layer, and the compd. shown by formula I is incorporated in the sensitive material. In formula I, Ar is arylene or cycloalkylene group, Ra is alkyl or alkoxy group, M is hydrogen or an alkali metal atom or an ammonium group. Thus, the color image of the sensitive material which has a less tendency for generating the color fog, and excellent preservability is obtd.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, a silver halide color photograph that forms a dye image with little color cast and excellent image storage stability. Regarding photosensitive materials.

BACKGROUND OF THE INVENTION 1 After exposing a silver halide photographic light-sensitive material to light for 42 hours, it is subjected to color development treatment, whereby the oxidized aromatic primary amine photochromic agent reacts with the thread-forming agent. dye is generated and a color image is formed.

Generally, this photographic method uses a subtractive color reproduction method, which produces yellow, magenta, and cyan.
(1 is formed.

Phenols or naphthols have been widely used as cyan image forming couplers.

However, cyan images obtained from conventionally used phenols and naphthols have serious problems in color reproduction. The reason is that the absorption is not sharp on the short wavelength side, and the edge region also has unnecessary absorption, that is, asymmetric absorption. As a result, in the case of negatives, it is necessary to correct the asymmetric absorption by masking or the like, and in the case of paper, there is no means for correction, and the current situation is that the color reproducibility is considerably deteriorated.

Furthermore, dye images obtained from conventionally used phenols and naphthols still have some problems in their storage stability9, for example, U.S. Pat.
G7,531 and No. 2,423.730 Mei 4II
The dye side 1 obtained from the 2-acylaminophenol cyan coupler described in I# generally has poor heat fastness;
U.S. Patent Nos. 2,369,929 and 2,772.
Dye images obtained from the 2,5-diacylaminophenol cyan coupler described in 1f32 are generally poor in light fastness, and dye images obtained from the 1-hydroxy-2-natutamido cyan coupler are generally poor in light fastness. Both light and heat fastness are inadequate.

Furthermore, the 2,5-diacylaminophenol cyan couplers described in U.S. Pat. 1 Patent No. 3,880,
The 2,5-diacylaminophenol cyan coupler described in No. 661, which has a hydroxyl group in the ballast part, must also have fastness to light and heat and the occurrence of yellow stain in order to preserve the dye image for a long time. In terms of
A fully satisfactory level has not yet been achieved.

In order to solve this problem, Japanese Patent Application Nos. 61-280104, 01-282355, 61-299332, and G
l-313458, 61-313455, 6
No. 2-53417, No. 62-47327, No. 62-4
No. 8895, No. 02-53418, G2-6216
Various pyrazoloazole cyan couplers have been proposed in No. 2, No. 62-85511, No. 62-021+33, No. 62-99950, No. 62-114838, No. 62-115946, etc. It is true that the color reproducibility of the cyan image obtained from the pyrazoloazole cyan coupler is significantly impaired, and the thermal stability of the cyan image is also extremely impaired. It was found that it has the disadvantage of being larger than the cyan coupler. .

When a multilayer color photographic material containing a color-forming coupler in a silver halide photographic emulsion is developed using a color developing agent such as paraphenylenediamine, an inconvenient "color cast" phenomenon occurs due to fogging of the emulsion, etc. is known.

In recent years, in the field of manufacturing technology for color photographic materials, in order to obtain even higher quality color photographs, color photographic materials have been developed that more efficiently prevent color cast without reducing photographic sensitivity. Great efforts are being made to do so.

[Object of the Invention] An object of the present invention is to provide a silver halide color photographic material that uses a pyrazoloazole cyan coupler to form a dye image with little color cast and excellent image storage stability. .

[Configuration of the Invention 1 The object of the present invention is to provide a halogenated support 1 having photographic constituent layers including a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer. In a silver photographic light-sensitive material, a pyramid having at least one electron-withdrawing group and/or a hydrogen-bonding group at a substitutable position other than the active site is added to the red-sensitive silver halide pore agent layer. A silver halide color photographic light-sensitive material containing a zoroazole type cyan coupler and further containing a compound represented by the following general formula [S].

General formula [S] Ar RA In the formula, Ar represents an arylene group or a cycloalkylene group, and RA is an alkyl group, an alkoxy group, a carboxyl group or a salt thereof, a sulfo group or a salt thereof, a hydroxyl group, an amino group, an acyl R'' and R'' each represent a hydrogen atom, an alkyl group or an aryl group, and M does not represent a hydrogen atom, an alkali metal atom or an ammonium group.

[Specific structure of the invention] The present invention will be explained in more detail below.

In the silver halide color photographic material of the present invention,
The red-sensitive silver halide emulsion layer contains 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. I will explain the cyan coupler in 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 one electron-withdrawing group and/or hydrogen-bonding group at a substitutable position other than its active site, thereby becoming a cyan coupler that forms a cyan dye through color development. .

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 refers to a pyrazoloazole cyan coupler that reacts with an oxidized developing agent to produce a dye that has an absorption maximum between 580 and 700 n1 when dissolved in methanol and measured. It means a substituent that has a strong electron-attracting force such that it forms.

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 11 anl
The substituent constant δp defined by ajt is +0.
20 or more substituents, specifically sulfonyl, sulfinyl, sulfonyloxy, sulfamoyl, phosphoryl, carbamoyl, acyl, acyloxy, oxycarbonyl, carboxyl, cyanide, halogenated alkoxy, halogenated aryloxy , pyrrolyl, tetrazolyl, and halogen atoms.

Examples of the sulfonyl group include groups such as alkylsulfonyl, arylsulfonyl, halogenated arylsulfonyl, 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 posboryl group include groups such as alkoxyphosphoryl, aryloxyphosphoryl, alkylbosboryl, 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, various groups such as tetrafluoroaryloxy and pentafluoroaryloxy are preferable.

Examples of the pyrrolyl group include groups such as 1-pyrrolyl.

Examples of the tetrazolyl group include groups such as 1-tetrazolyl.

In addition to the above substituents, trifluoromethyl group, heptafluoroisopropyl group, nonylfluoro([)butyl group, tetrafluoroaryl group, pentafluoroaryl group, etc. are also preferably used.

Moreover, each of these stations may further have a substituent.

The hydrogen-bonding group of the present invention means that the Biracy 7 azole-type cyankadaler reacts with an oxidized developing agent and dissolves in methanol to give a 580% hydrogen bond between the nitrogen atom on the pyrazoloazole ring A group containing a hydrogen atom capable of forming a strong hydrogen bond to form a dye having an absorption maximum between 7001n1 and 7001n1.

By forming a strong hydrogen bond between the hydrogen atom and the nitrogen atom of the pyrazoloazole ring -E, the coupler becomes a cyan coupler in which the dye formed by color development becomes a cyan dye.

A typical example of a substituent having a hydrogen atom capable of forming the hydrogen bond with the nitrogen atom of the pyrazoloazole ring is an if substituent represented by the following formula.

R, a b Ra R1) Ra b Ra Goose-C-Nll5O□Rd b Ra -C-Nf[5ORd b Ra! --C-NHCORd b In the formula, Ra, Rh, RC, Rd and Re represent a hydrogen atom or a substituent, Rf represents no substituent, p represents 0 or 1, and n represents an integer of 0 to 4. represent.

When l is 2 or more, each Rf may be the same or different.

In the above formula, preferable examples of Ra, Rh and I' (d are a hydrogen atom, an alkyl group, an aryl group, a polycyclic ring residue, etc.), and preferable examples of R□ are a hydrogen atom, an alkyl group, an aryl group. , a polycyclic ring residue, a sulfonyl group which may be substituted with an alkyl group, an aryl group, etc., a sulfinyl group, etc. Preferred as Re are a hydrogen atom, an alkyl group, an aryl group, a heterocyclic residue, and an alkyl group. sulfonyl groups, sulfinyl groups, carbonyl groups, etc. which may be substituted with alkyl groups, aryl groups, etc. are particularly preferred. It is the basis.

There are no particular limitations on the substituent represented by Rf.

Moreover, each of these stations may further have a substituent.

Among the above, those represented by the above formulas (1), (2), (3) and (7) are particularly preferable as hydrogen-bonding groups used in the present invention, and among them, more preferable are the hydrogen-bonding groups used in the present invention. The thing is S Ox N HRc, -S ON
l-f Rc , CON HRc and the above-mentioned hydrogen-bonding group may contain a diffusion-resistant substituent such as a long-chain hydrocarbon group or a polymer residue.

A pyrazoloazole 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 [ffl].

General formula [[11 In the formula, R3 represents a hydrogen atom or a substituent, R2 represents a substituent bonded to a carbon atom of the nonmetallic atom group represented by Z, and at least one of R1 and R2 is a group selected from an electron-withdrawing group or a hydrogen-bonding group.

n indicates the number of substituents R□.

X represents a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent.

Z represents a group of nonmetallic atoms necessary to form an azole ring to which a benzene ring or the like may be fused.

Among the Wl substituents in which R1 and R2 above are represented, various substituents other than electron-withdrawing groups and hydrogen-bonding groups can be mentioned, and although there are no particular limitations, typically alkyl , aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl, cycloalkyl, alkynyl, heterocycle, alkoxy, aryloxy, heterocycleoxy, siloxy, amino, alkylamino, imide, ureido,
Sulfamoylamino, alkoxycarbonylamino,
Examples include aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, thioureido, hydroxy, and mercapto stations, spiro compound residues, bridged hydrocarbon compound residues, and the like.

Moreover, each of these stations may further have a substituent.

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 alknyl 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 alknyl group may be linear or branched.

The cycloalkyl group has 3 to 12 carbon atoms, especially 5 to 12 carbon atoms.
7 is preferred.

Examples of ureido groups include alkylureido groups and arylureido groups; examples of sulfamoylamino groups include arylsulfamoylamino groups and arylsulfamoylamino groups; and preferred heterocyclic groups include 5- to 7-membered ones; Specifically, a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, a 2-benzothiazolyl group; as a heterocyclic oxy group, those having a 5- to 7-membered heterocycle are preferable, for example, 3
．． /1,5.6-te1-lahydropyranyl-2-oxy group, ■-phenyltetrazole-5-oxy group, etc.; As the heterocyclic thio group, a 5- to 7-membered heterocyclic thio group is preferable, for example, 2- Pyridylthio group, 2-benzothiazolylthio group, 2,4-diphenoxy-1,3,5-1-riazole-6-thio group, etc.; Siloxy group includes trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc. ; Imide groups include succinimide group, 3-heptadecylsuccinimide group, phthalimide group, glutarimide group, etc.; Spiro compound residues include spiro[3,31hebutane-
1-yl, etc.; As a bridged hydrocarbon compound residue, bicyclo[2°2.1
]hebutan-1-yl, tricyclo[3°3.1.1'
・7] Decan-1-yl, 7.7 dimethyl-bicyclo[
Examples include 2,2,11-butan-1-yl.

These groups may further contain substituents such as long-chain hydrocarbon groups and diffusion-resistant groups such as polymer residues.

In the general formula [nl, groups that can be separated by reaction with the oxidized product of the color developing agent represented by X include, for example, halogen atoms (chlorine atoms, bromine atoms, fluorine atoms, etc.), alkoxy, aryloxy, polycyclic , acyloxy, sulfoninyloxy, alkoxycarbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkylthio, arylthio, polycyclic thio, alkyloxydithiocarbonylthio, acylamino, sulponamide, with N atom A bonded nitrogen-containing heterocycle, alkyloxycarbonylamino, aryloxycarbonylamino, carphoki (R1' and R
2' has the same meaning as the above RI and R2, Rg and R
h represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group which may have a substituent, and 2' 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 general formula [11], examples of the nitrogen-containing heterocycle formed by 2 include a pyrazole ring, an imidazole ring, a benzimidazole ring, a triazole ring, and a tetrazole ring.

- clothing [[[Among the compounds represented by 1, RI and R
More specifically, those in which at least one of □ is an electron-withdrawing group are represented by the following - clothing cost [■αJ to [■α].

The following margin general formula [■αJ General formula [■α] General formula [, IVα1 N-N-N-Y --・Formula rVIα] − "In the two general formulas, [■α1, RIg and R1, at least 1
In [■α], at least one of R11 and R4,
NVα], at least one of R11, Rs, and R6m; [vα1, at least one of RIf, R71, and R111; [v1α], Rt, and R91; , [VIα1, RIf, [■α], at least one of R1, and R3° is an electron-withdrawing group.

X has the same meaning as X in the general formula [ff], and ρ is 0 to
represents an integer of 4, Y represents a hydrogen atom or a substituent, Y
Preferred substituents represented by are those which separate from the cyan coupler before the compound of the present invention reacts with the oxidized developing agent;
Coupling-off occurs by reaction with a group that can be separated under alkaline conditions, as described in Japanese Patent Application Laid-Open No. 5FT-133734, etc. Substituents etc. can be mentioned. Preferred Y is a hydrogen atom.

In addition, in the general formula [■α] to [■α], R, , ~R
There are no particular restrictions on the substituents that are not electron-withdrawing groups among + o e, specifically, when R3 or R2 is other than an electron-withdrawing group or a hydrogen-bonding group in the general formula [ill] Examples include those mentioned as the substituent represented by Rt or R2, or those mentioned above as the 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 method described in each specification, such as No. 50.

Among the compounds represented by the general formula [I[1, R3 and R
More specifically, those in which at least one of 1 is a hydrogen-bonding group are represented by the following general formulas [■β] to [■β].

Below is the margin - Mathematical formula [■β] General formula [■β1 General formula [lvβ] N-N-N-Y - Clothing cost [VIβ] J1 - Clothes cost [■β] ~ [■β], where X is Said-
It has the same meaning as X in Clothing fee [11].

- Clothes cost “■β”, [Vβ], [Vlβ] and ・[vI
RIJ in β1, at least one of R, Is and R4t in general formula [111β1, - at least one of Rla and R5 in GJ in β1, RIJ in general formula [■β] and At least one of Rlas is a hydrogen bonding group.

-・Clothing cost [II 13] ~ [VI B] Nit3
Among HR R1p to R31, there are no particular restrictions on the substituents that are not hydrogen-bonding groups.
111, when R1 or R2 is other than an electron-withdrawing group or a hydrogen-bonding group, the substituents represented by RI or R2, or the above-mentioned electron-withdrawing groups are listed. It will be done.

Y in the general formula [■β1 to [■β] is - clothing cost [■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. G2-184554.

The couplers of the present invention typically contain I/mole of silver halide.
X 10-” mol-1 mol, preferably 1×10-1
It can be used in the range of -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 1L emulsion is coated on a support to form the color photosensitive material t1 of the present invention.

Typical specific examples of the pyrazoloazole cyan coupler according to the present invention are shown below.

Below margin II ]I C+OK+ C-7 I C-10 ]I ■ I C-22 C-23 N C-34 N11) υ*Cl5lla7 I Cl1l+23 C-39 ■ n N N NHCIJC1+H23C
-56 C-59 Margin below Next, the compound represented by -Fukudai [Sl] will be explained.

In the silver halide photographic material of the present invention, the red-sensitive silver halide emulsion layer contains a compound represented by the general formula [Sl].

In the general formula [Sl, examples of the arylene group represented by Ar include a phenylene group and a naphthylene group, and examples of the cycloalkylene group include a cyclohexylene group.

Examples of the alkyl group represented by R include methyl group,
Examples of the alkoxy group include methoxy group and propoxy group. Examples of the acylamino group include acetylamino group, hexanoylamino group, benzoylamino group, N-methylcarbamoyl group, and N-
Examples include phenylcarbamoyl group, N)tsOe
Examples of R' include methylsulfonylamino group, benzenesulfonamide group, etc., N-methylureido group, N-ethylureido group, N,N
-dimethylureido group, N,N-dimethylureido group,
Examples include N-phenylureido group. Each station represented by RA also includes a substituent.

As the alkali metal atom represented by M, for example,
-Rium atom, potassium atom, etc.

Below, examples of compounds 11 and 11, represented by -Fukudai [Sl] are shown, but the present invention is not limited thereto.

The following margin r-RA Compounds represented by the above general formula [Sl are, for example, U.S. Pat.
No. 57-167023, No. 58-95728,
It can be synthesized according to the method described in No. 59-68732.゛In order to incorporate the compound represented by the general formula [Sl (hereinafter referred to as r compound IS] J) according to the present invention into the silver halide emulsion layer according to the present invention, water or water and 11: The compound [Sl may be used alone, or it may be added after being dissolved in a miscible organic solvent (for example, methanol, ethanol, etc.)
It may be used in combination with a compound represented by 1, or a stabilizer other than the compound represented by the general formula [Sl, or a flash suppressor.

Compounds [Sl is added before the formation of silver halide grains, during the formation of silver halide grains, after the completion of silver halide grain formation and before the start of chemical ripening, during chemical ripening, at the end of chemical ripening, and during chemical ripening. It may be added at any time between the end of ripening and the time of coating, preferably during chemical ripening, at the end of chemical ripening, or from the end of chemical ripening until the time of coating. The entire amount may be added at a certain time, or it may be added in multiple portions.

It can be added directly to the silver halide emulsion or silver halide emulsion coating solution, or it can be added to the coating solution for the adjacent non-photosensitive hydrophilic colloid layer, and it can be added to the main layer by diffusion during multilayer coating. It may be contained in the silver halide emulsion layer according to the invention.

There is no particular restriction on the amount added, but it is usually I x 10-' mol to I x 10-' mol per mol of silver halide.
'mole, preferably 1X10-5 mole to IX10
- It is added in a range of 2 moles.

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 of those used in conventional silver halide photographic emulsions, such as silver chlorobromide, silver iodobromide, and silver chloroiodobromide, are included.

These silver halide grains may be coarse or fine, and the grain size distribution may be narrow or wide.

In addition, the crystals of these silver halide grains are usually normal crystals and twin crystals, and the ratio of (100) and (11,1) planes is (
k and t 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. may be of the type that forms the latent image primarily on the surface or may be of the type that forms the 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 may also be used. It is also possible to use two or more types of silver halide emulsions that have been separately adjusted in tll and mixed together.

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 chloride emulsion, a silver chloride iodobromide emulsion, etc., and there is no particular limitation, but a silver halide emulsion having high chloride silver halide grains may be used. It is preferable that there be.

The above-mentioned high chloride silver halide grains are those having a silver chloride content of 90 mol % or more. In the high chloride silver halide grains, it is preferable that the silver bromide &fJ'' ratio is 10 mol% or less, and the silver iodide content is 0.5 mol% or less, and more preferably, the silver bromide content is 0. .1 to 2 mol% silver chlorobromide.

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 proportion of high chloride silver halide grains in the total silver halide grains contained in the emulsion layer is 60% by weight or more. Preferably, it is 80% by weight or more.”
It is more preferable that the number is 2.

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,
It may be discontinuous.

There is no particular restriction on the grain size of the high chloride silver halide grains, but in consideration of other photographic performance such as rapid processing and sensitivity, it is preferably 0.2 to 1.6 μm, more preferably 0.2 μm to 1.6 μm, more preferably 0.2 to 1.6 μm.
It is in the range of 25 to 1.2 μm. Note that the -h distribution particle size can be measured by various methods commonly used in the technical field.

A typical method is Loveland's "Particle Size Analysis Method J.
(A, S, T, M, Symposium on Light
Microscopy, 1955, pp. 94-122) or 1. Theory of Photographic Processes (by Mies and James, 3rd edition, Chapter 2, published by Macmillan, 1960).

This particle size can be measured using the particle's projected area or diameter approximation. If the particles are of substantially uniform shape, the particle size distribution can fairly accurately measure this as a diameter or 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, which may be obtained by either the neutral method or the ammonia method, may be grown all at once, or may be grown after forming seed particles.

The method of making and growing the seed particles may be the same; they may be different.

In addition, the method for reacting the soluble silver salt with 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 it is preferable to use a method obtained by a simultaneous mixing method. As a method, the pAg-chondrold double-jet method described in JP-A-54-48521 etc. can 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 a crystal surface.

Further, particles having shapes such as an octahedron, a tetradecahedron, a 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 solvent used in the present invention contains cadmium salt, zinc salt, 311 salt, thallium salt, iridium salt or complex salt, 17dium salt or complex salt, iron salt or complex salt during the grain formation process and/or growth process. can be used to add metal ions and include them inside the particles and/or on the surface of the particles,
Further, by placing the particles in an appropriate reducing atmosphere, reduction sensitizing nuclei can be provided inside the particles and/or on the particle surfaces.

In the emulsion containing silver halide grains used in the present invention (hereinafter referred to as "emulsion of the present invention"), unnecessary soluble salts may be removed after the growth of the silver halide grains is completed, or
Alternatively, when removing the salts, which may remain contained, the method described in Research Disclosure No. 17643 can be used.

The silver halide grains used in the emulsion used in the present invention are:
Preferably, the particles are particles in which the latent image is mainly formed on the surface, but particles in which the latent image is formed inside the particles may also be used.

In the present invention, a chalcogen sensitizer can be used. Chalcogen sensitizer is a general term for sulfur sensitizers, selenium sensitizers, and tellurium sensitizers, and sulfur sensitizers and selenium sensitizers are preferable. Examples of sulfur sensitizers include thiosulfates and aliphatic sensitizers. ruthiocarbazide, 1,000 urea, allyl isothiocyanate, cystine, p-toluenethiosulponate,
Rhoda Nin can be mentioned. That song, US IJIJ special edition 1.
No. 574.944, No. 2,410.089, No. 2,2
No. 78,947, No. 2.728.008, No. 3,50
1,313S, 3.05G, No. 955, West German Publication (OLS) No. 1,422.8139, JP+
1. '35G-24937''-1, 55-45016
It is also possible to use sulfur sensitizers described in Japanese Patent Publication No. The addition rate of the sulfur sensitizer varies over a considerable range depending on the seed material conditions such as temperature and silver halide grain size. A molar to 10 molar culm is preferred.

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 grains in the photographic constituent layer containing the pyrazoloazole cyan coupler according to the present invention, faithful color reproducibility can be obtained, and
It becomes possible to obtain a sufficient maximum concentration.

Is the silver halide grain used in the present invention suitable for photography? 1 can be optically sensitized to a desired wavelength range using a dye known as a sensitizing dye.

As the binder (or protective colloid) used in the silver halide photographic light-sensitive material of the present invention, it is advantageous to use gelatin, but gelatin derivatives, gelatin and Ike's polymer graph 1 heborimers, proteins, Hydrophilic colloids such as M derivatives, cellulose derivatives, and 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, color negative and positive films, color photographic paper, etc., but in particular color photographic paper used for direct viewing can be used. In such cases, the effects of the method of the present invention are effectively exhibited.

When the silver halide color photographic light-sensitive 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 the magenta coupler and the yellow coupler, 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 pyrazo IV l.lyazole magenta couplers are preferred.

As the 17-coupler, acylacetanilide couplers can be used, including benzacetanilide and bivaloylacetanilide compounds.

The silver halide photographic light-sensitive material of the present invention further includes a hardening agent, an irradiation inhibitor, a color clouding prevention agent, an image stabilizer, a plasticizer, a latex, a surfactant,
Additives such as lubricants and antistatic agents 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, which is -numerically 2
It is in the range of 0°C to 50°C. 30℃ for quick development
The color development time of the present invention, which aims at rapid processing, is generally 20 seconds to 60 seconds, whereas conventional processing takes 3 to 4 minutes. is preferable, and more preferably in the range of 30 seconds to 50 seconds.

The silver halide photographic light-sensitive material of the present invention is capable of color development in which benzyl alcohol used for rapid development is 2 ml or less per 1β (even if T4 liquid is used, rapid development is possible without decreasing the maximum density of the characteristic curve). I can do it.

After color development, bleaching and fixing are performed.

Bleaching treatment may be performed simultaneously with fixing treatment.

After the fixing process, a washing process is usually performed.

Further, as an alternative to the water washing treatment, a stabilization treatment may be performed, or both may be used in combination.

〔Example〕

Although specific examples of the present invention are described above, the embodiments of the present invention are not limited to these.

Example 1 On a paper support laminated with polyethylene, the following layers were sequentially coated from the support side to prepare a comparison sample Nαl of a silver halide color photographic light-sensitive material.

Layer l...1.2g/rf gelatin, 0.32
g/rrr (in terms of silver, the same applies hereinafter) blue-sensitive silver halide emulsion (silver chloride content 97 mol%, chemical sensitizers: sodium thiosulfate 2 / silver halide 1 mol, and spectral sensitizers: 5D- 10.9 mmol/1 mole of silver halide), 0.50 g/r
0,80 g/r dissolved in rr of dioctyl phthalate
A layer containing yellow coupler (Y-A) of rr.

1M 2 ・-・-0, 7g/rd gelatin, 10
+w/rrf of irradiation dye (AI-1), 5.mu./M (AI-2);

Layer 3...1.258/+1? gelatin, 0.
22 g/nf green-sensitive silver halide emulsion (silver chloride content 100 mol%, chemical sensitizers: 100 FIL 2 chloride/silver halide 1 mol and spectral sensitizers: 5D-2 0,7 Contains mmol/1 mole of silver halide.)
, 0.62 g/rrr of magenta coupler (M-A
).

Layer 4: Intermediate layer consisting of 1.2 g/d gelatin.

Layer 5...1.40g/rf gelatin, 0.2
Red-sensitive silver halide emulsion of 0 g/r& (silver chloride content 100 mol%, sodium thio[acid 2Ilf/1 mol of silver halide as chemical sensitizer and 5D-3 0.2 mmol/halogen as spectral sensitizer) Contains 1 mole of silver oxide.)
, 0.45 g/rrr of cyan coupler (C-A) dissolved in 0.20 g/cd of tri-n-octyl phosphate.

Layer 6: Layer containing 0.5 g/cd of gelatin.

As a hardening agent, sodium 2,4-dichloro-6-hydroxy-s-triazine was added to layers 2.11 and 6 in an amount of 0.017 g per 1 g of gelatin, respectively.

Next, when preparing the red-sensitive silver halide emulsion used in layer 5, 1xlO per mole of silver halide is added after chemical sensitization.
Comparative sample NQ 2 was prepared in the same manner as comparative sample NQI except that −' mol of comparative compound-8 was added.

Next, in place of comparative compound-S, compound S-6 of the present invention
Comparative sample NQ 3 was prepared in the same manner as comparative sample NQ2 except that .

Furthermore, 0.45g of cyan coupler used in layer 5
/rd instead of (C-A), 0.63 g/r
Comparative sample Nα4 was prepared in the same manner as comparative sample NQ1, except that coupler C-2 of the present invention of d (Q, QQ09 mol/+rr) was used.

Below, the cyan couplers shown in Table 1 (0,0009 mol/
rd) and comparative compound-8 or the compound represented by the general formula [31 (IXlo-' mol/silver halide 1 mol)
5 and the present invention sample amounts 1 to 11 were prepared by adding it to the It, IF9 samples.

(Y-A) <M-A) (ALI) (AI 2) Comparative compound-8 (SI)・-1) (SD-2) 5O3H・N (C2Hs 13 (SD-3> I Hs obtained Two sets each of the above-mentioned photosensitive materials Comparative Samples Ha 1 to 5 and Invention Samples Nos. 1 to 11 were prepared.

Immediately, after wedge exposure using a sensitometer KS-7 (manufactured by Konica Corporation), the following color development process was performed according to the following steps. The fog density of the red-sensitive emulsion layer was measured using a PDA-65 model), and the color fog was evaluated.

In addition, each of the above-mentioned treated samples was heated at a high temperature (60°C, 180°C).
%R) () The heat resistance and humidity resistance of each dye image is determined by the dye residual rate expressed as 6 parts of the initial density, which is the density measured for the dye remaining after leaving it for 10 minutes in an atmosphere. was evaluated.

Furthermore, two of the two sets of the obtained photosensitive materials were added.
To assemble, the resulting dye image ('A Four fog boundaries of the red-sensitive emulsion layer were measured and the color fog over time was evaluated.

For W+, evaluation results of heat resistance/humidity, immediate fogging, and color fogging over time are shown.

Processing process> Temperature Time color development 34.7 ± 0.3°C 45 seconds self-fixing 34.7 above 0.5°C 50 seconds stabilization 30
~34"C Dry for 90 seconds 60-80°C for 60 seconds Color developer> Pure water 8001 Triethanolamine 8gN, N
-diethylhydroxyamine 5g potassium chloride 2gN-ethyl-N-β
-Methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 5g Sodium tetrapolyphosphate 2g Potassium carbonate 30g Potassium fiLite 0.2g Optical brightener (4,
4'-Diaminostilbendisulfone ili* derivative) Add 1 g of pure water to make total 1 to 1j, and adjust ptrlo to 2.

Ferric ammonium ethylene diamine tetanoate dihydrate 60 g Ethylene diamine tetanoate 3 g Ammonium nitrate (70% solution) 100 sj Ammonium sulfite (40% solution) 27.5 m 7 Potassium carbonate or glacial acetic acid p) [Adjust to 5,1 and add water to make the total amount IJ.

Stabilizing liquid> 1g of 5-chloro-2-methyl-4-inthiazolin-3-one 1g of 1-diphosphonic acid (loxhetylidene-1゜l-diphosphonic acid) Add 2g of water to make 1j, and add 1ζp to sulfuric acid or potassium hydroxide. tr
Adjust to 7.0.

Below is the margin table 1. The following can be seen from the fit results. When the comparative cyan coupler (C-A) was used, the heat and humidity resistance of the dye surface 1 image produced was quite poor, and even when the compound of the present invention (SJ) was used in combination, no significant improvement in color cast was observed.

However, when the cyan coupler of the present invention is used, the heat and humidity resistance of the generated dye image is very good, and the color cast, which was a drawback, can be reduced by using the compound Tl5I of the present invention [] It was found that this can be improved to 1.

[Effects of the Invention] The silver halide color photographic material of the present invention reduces color cast and realizes a dye image with excellent image storage stability.

Claims (1)

[Scope of Claims] A silver halide photographic light-sensitive material having photographic constituent layers including a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support. , the red-sensitive silver halide emulsion layer has at least one electron-withdrawing group and/or at a substitutable position other than the active site.
Or, a silver halide color photographic light-sensitive material, which contains a pyrazoloazole-type cyan coupler having a hydrogen-bonding group, and further contains a compound represented by the following general formula [S]. General formula [S] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, Ar represents an arylene group or a cycloalkylene group, and R_A represents an alkyl group, an alkoxy group, a carboxyl group or a salt thereof, a sulfo group or a salt thereof, or a hydroxyl group. Represents a group, an amino group, an acylamino group, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -NHSO_2R' or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. R' and R'' each represent a hydrogen atom, an alkyl group or an aryl group. M represents a hydrogen atom, an alkali metal atom or an ammonium group.