JPH01230042A - Silver halide color photographic sensitive material having improved color reproducibility and color formability - Google Patents

Abstract

PURPOSE:To obtain the above photosensitive material which has high sharpness of absorption, has lesser absorption in a green region, is excellent in color reproducibility and has the excellent light resistance of a cyan dye image by incorporating a pyrazoloazole type cyan coupler and a specific high boiling org. solvent into said material. CONSTITUTION:The pyrazoloazole type cyan coupler having an electron- withdrawing group and/or hydrogen bonding group in the substitutable position except the active point of the pyrazoloazole ring and the high boiling org. solvent expressed by the formula I are incorporated into the red-sensitive silver halide emulsion layer. In the formula, R denotes an alkyl group, alkoxy carbonyl group, aryl sulfonyl amino group or alkyl sulfonyl amino group; X denotes a halogen atom. or the group which can be substd. to a benzene ring; m denotes 0-4 integer. The max. density is thereby improved and the absorption max. wavelength is increased. The absorption of the green part is decreased, the color reproducibility is improved and the light resistance of the cyan dye image is improved.

Description

Detailed Description of the Invention [Technical Field] The present invention has excellent color reproducibility and color development, and also improves the storage stability of dye images, especially the durability of dye images when exposed to light (hereinafter referred to as "
This invention relates to a silver halide photographic material with improved light resistance (referred to as "lightfastness").

[Background of the Invention] After a silver halide photographic material is exposed to light and subjected to color development processing, an oxidized aromatic primary amine color developing agent and a dye-forming coupler react to form a dye. One color image is formed.

Generally, this photographic method uses a subtractive color reproduction method to form yellow, magenta and cyan color images.

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 unnecessary absorption, that is, asymmetric absorption occurs in the edge region as well. 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 vapors, there is no means for correction, and the current situation is that the color reproducibility is considerably deteriorated.

Also, for example, the 2-acylaminophenolic cyan couplers described in U.S. Pat. No. 2,367.531 and U.S. Pat. No. 2,423,730;
No. 29 and 2 described in Specification No. 2,772,162
．． 5-diacyl aminophenol cyan coupler, 1-
Hydroxy-2-natutamidocyan coupler, U.S. Pat. No. 4,122,369 and JP-A-57-15553
8, 2,5-diacylaminophenol cyan coupler described in specifications such as JP-A No. 57-157246,
A 2,5-diacylaminophenolic cyan coupler having a doxy group in the ballast portion has been developed as described in U.S. Pat. No. 3,880,661.

However, these have not yet achieved a sufficiently satisfactory level in terms of fastness to light and heat and the occurrence of yellow stain.

Furthermore, Japanese Patent Application No. 62-85510, No. 62-8551
No. 1, No. 402-114838, No. 62-115946
It has been found that the pyrazoloazole cyan coupler described in No. 62-184554 can provide a dye image with excellent spectral absorption characteristics and good durability against heat and humidity. There was still room for improvement.

[Object of the Invention] The first object of the present invention is to provide a novel silver halide color photographic light-sensitive material containing a pyrazoloazole type cyan coupler.

A second object of the present invention is to provide a silver halide color photographic material with sharp absorption, less absorption in edge regions, and excellent color reproducibility.

A third object of the present invention is to provide a silver halide color photographic material in which cyan dye images have excellent light fastness.

[Structure of the Invention] The above-mentioned object of the present invention is to provide a silver halide color photographic photosensitive material having 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. In the material, a pyrazoloazole having at least one electron-withdrawing group and/or hydrogen-bonding group at a substitutable position other than the active site of the pyrazoloazole ring in the red-sensitive silver halide emulsion layer. at least one type cyan coupler and a high boiling point t represented by the following general formula [A]
This is achieved by using a silver halide color photographic light-sensitive material containing at least one R solvent.

General formula [A] (wherein, R represents an alkyl group, an alkoxycarbonyl group, an arylsulfonylamino group, or an alkylsulfonylamino group; each of these groups may have a substituent; X is a halogen atom or a benzene ring) represents a substitutable group, m represents an integer of 0 to 4) [Specific structure of the invention] At least one substitutable position other than the active site of the pyrazoloazole ring according to the present invention The pyrazoloazole cyan coupler having an electron-withdrawing group and/or a hydrogen-bonding group 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 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 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. It means a substituent that has a strong electron-attracting force.

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 of type 1 in the present invention preferably refers to 11ar
The substituent constant δp defined by uaett is +0
．． 20 or more substituents, specifically sulfonyl,
Examples include sulfinyl, sulfonyloxy, sulfamoyl, phosphoryl, carbamoyl, acyl, acyloxy, oxycarbonyl, carboxyl, cyano, halogenated alkoxy, halogenated aryloxy, pyrrolyl, tetrazolyl, and halogen atoms. .

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.

Preferred examples of the halogenated aryloxy group include tetrafluoroaryloxy and pentafluoroaryloxy.

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, heptafluoroin-10vir group, nonylfluoro(1)butyl group, tetrafluoroaryl group, pentafluoroaryl group, etc. are also preferably used.

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

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 when measured. A group having a hydrogen atom capable of forming hydrogen bonds strong enough to form a dye having 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 coupler
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 Ra Rb (4) Ra -C-NH302Rd Ra -C-NH30Rc1 Ra -C-NHCORd (In the formula, Ra, Rb, Rc, Rd and Re are hydrogen atoms or 'J1. substituents, Ftf is Represents a substituent, 1 is 0
or 1, and 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 a hydrogen atom, an alkyl group, an aryl group, a heterocyclic residue, etc. , Rc are preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic residue, a sulfonyl group, a sulfinyl group, etc. which may be substituted with an alkyl group, an aryl group, or 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. Particularly preferred are , a sulfonyl group, a sulfinyl group, and a carbonyl group which may be substituted with an alkyl group, an aryl group, or the like.

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

Moreover, each of these images 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 O2N HRc, -3ONHRc
, -CONHRc and the hydrogen-bonding group described above 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 [11].

General formula [I] (wherein, R1 represents a hydrogen atom or a substituent, R2 represents Z
At least one of R2 and R2 representing a substituent bonded to the carbon atom of the nonmetallic atom group represented by is a group selected from an electron-withdrawing group or a hydrogen-bonding group.

n indicates the number of substituents R2.

X represents a hydrogen atom or a 'J:l substituent which can be eliminated by reaction with an oxidized product of a color developing agent.

Z represents a non-metallic atomic group necessary to form an azole ring to which a benzene ring etc. may be fused) R1 and R2 above
Among the substituents represented by , there are various substituents other than electron-withdrawing groups and hydrogen-bonding groups, and there are no particular limitations, but typical examples include alkyl, aryl, anilino, Acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl,
Cycloalkyl, alkynyl, heterocycle, alkoxy, aryloxy, heterocycleoxy, siloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, hetero Examples include ring thio, thioureido, hydroxy, and mercapto groups, spiro compound residues, bridged hydrocarbon compound residues, and the like.

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

The alkyl group is preferably one having 1 to 32 carbon atoms, and may be Mg 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 sulponamide 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 polyphonic ring are preferable, for example, 3
, 4,5.6-tetrahydropyranyl-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 group, triethylsiloxy group, dimethylbutylsiloxy group, etc.; imide groups include succinimide group, 3-hegetadecylsuccinimide group , phthalimide group, glutarimide group, etc.; Spiro compound residues include spio[3,,3]hebutan-1-yl, etc.; bridged hydrocarbon compound residues include bicyclo[2°2.1
] heptan-1-yl, tricyclo[3°3.1.1'
・7] Decane-1-yl, 7,7 dimethyl-bicyclo[
2,2,1]heptane-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 [I], 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, and polycyclic Oxy, acyloxy, sulfonyloxy0, alkoxycarbonyloxy, aryloxycarbonyl, alkyl'oxalyloxy,
Alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocycle bonded with N atom, alkyloxycarbonylamino, aryloxycarbonylamino, galboxyl, ~--0 (R1' and R2' have the same meanings as R1 and R1 above, Rg and Rh represent a hydrogen atom, or an alkyl group, an aryl group, or a heterocyclic group which may have a substituent, and Z' is It has the same meaning as the above-mentioned Z.), but preferably a halogen atom. Of these, X
Especially preferred are hydrogen atoms and chlorine atoms.

In the general formula [I], examples of the nitrogen-containing heterocycle formed by Z include a pyrazole ring, an imidazole ring, a benzimidazole ring, a triazole i, t, or teI-razole ring.

Among the compounds represented by general formula [I], R1 and R1
More specifically, at least one of the groups is an electron-withdrawing group, and is represented by the following general formula [■ααcol■α].

General formula [■α] General formula [■α] General formula [IVα] General formula [Vα] In the above general formula, in [■α], at least one of R+a and Rol+, in [■α], R1 , and R4, at least one of
At least one of R11, Rst and R611 in [IVα], at least one of RIn, R7J3Jl: HiRa, Nauchino in [VcZ], R1, and R9 in [VIα] At least one of [V[[α], R+, [■α], R3, and R4°, 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 preferred substituent for Y is, for example, one which is removed from the cyan coupler before the compound of the present invention reacts with the oxidized wood developing agent. For example, JP-A-61-22
Coupling off by reaction with a group that can be separated under alkaline conditions as described in JP-A No. 8444, etc., or an oxidized product of a developed crude drug as described in JP-A-56-133734, etc. Substituents etc. can be mentioned.

Preferred Y is a hydrogen atom.

Furthermore, in the general formulas [II(2] to [■α], R1,
~R1゜, there are no particular restrictions on the substituents that are not electron-withdrawing groups. Specifically, in general formula [11]
When R1 or R2 is other than an electron-withdrawing group or a hydrogen-bonding group, the substituents represented by R1 or R2 or the aforementioned hydrogen-bonding groups may be mentioned.

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
-62163, 402-48895, 62-99
It can be easily synthesized according to the methods described in various specifications such as No. 950.

Among the compounds represented by formula 1/12 CI], those in which at least one of R1 and R2 is a hydrogen-bonding group are more specifically represented by the following general formula [■ββcol■β] .

General formula [■β General formula [■β] General formula [IVβ Co I N -N -N -Y General formula [■β Co The above general formula [■β] ~ [■ β Co, X is the above general formula It has the same meaning as X in [].

General formula [■β], “Vβko, [VIβ” and [VWβ
], - at least one of R11 and R41 in the i formula [■β], - at least one of R□ and R5J in the i formula [IVβ], R1. in the general formula [■β]. At least one of R1.1 and R1.1 is a hydrogen bonding group.

R1 in -fi formulas [■β] to [■β]. ~R1m,
Among these, there are no particular limitations on the substituents that are not hydrogen-bonding groups. Specifically, in general formula [I], when R8 or R2 is other than an electron-withdrawing group or a hydrogen-bonding group, , R1 or R2, or the electron-withdrawing group described above.

Y in the general formula [■β1 to [■β] is the general 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
x10-' mol-1 mol, preferably in the range of 1 x 10-2 mol to s x io-' mol.

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.

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

Margins below] I ]1 +1 ■ ■ NHCOC + 48211 C-13 C-16 tcaH+7 N ■ N -N -N C-31 C-32 ++ Ntlbsu21;1et137 C day H23 I tcaH+7 Bar□IT-IT NH+ υ(item H23C-48 C-49 N -N -N H Next, the high boiling point organic solvent represented by the general formula [A] will be explained.

In the general formula [A], R represents an alkyl group, an alkoxycarbonyl group, an arylsulfonylamino group, or an alkylsulfonylamino group which may have a substituent.

The alkyl group represented by R is preferably a straight chain or branched one having 1 to 32 carbon atoms, including those having a substituent. Examples of such alkyl groups include straight chain and branched butyl groups, Examples include hexyl group, decyl group, dodecyl group, and octadecyl group. Among the alkyl groups represented by R, those having 4 to 20 carbon atoms are particularly preferred, and those having 5 to 9 carbon atoms are particularly preferred.

Further, the alkoxycarbonyl group represented by R preferably has a total carbon number of 2 to 20. The alkyl moiety in these alkoxycarbonyl groups may be linear or branched, and furthermore, these alkoxycarbonyl groups may have a substituent. Including those with.

Examples of such alkoxycarbonyl groups include me-1-oxycarbonyl group, ethoxycarbonyl group, hexyloxycarbonyl group, octyloxycarbonyl group, undecyloxycarbonyl group, octadecyloxycarbonyl group, and the like.

Among the alkoxycarbonyl groups represented by R, those having a total of 2 to 14 carbon atoms are particularly preferred, and those having 5 to 13 carbon atoms are particularly preferred.

Examples of the arylsulfonylamino group represented by R include a benzenesulfonylamino group and a naphthalenesulfonylamino group, including those having substituents.

Specific examples of such arylsulfonylamino groups include:
p-toluenesulfonylamino group, p-dodecylbenzenesulfonylamino group, p-dodecyloxybenzenesulfonylamino group, p-chlorobenzenesulfonylamino group, ρ-octylbenzenesulfonylamino group, 1-
Examples include naphthalenesulfonylamino group and 4-dodecyloxynaphthalenesulfonylamino group.

The alkylsulfonylamino group represented by R is preferably one having a straight or branched alkyl group having 1 to 32 carbon atoms, and these alkyl groups include those having substituents. Examples of rubonylamino groups include methylsulfonylamino groups, ethylsulfonylamino groups, straight-chain and branched butylsulfonylamino groups,
Examples include dodecylsulfonylamino group and hexadecylsulfonylamino group.

In general formula [A], the halogen atom represented by X is particularly preferably a chlorine atom.

Furthermore, the groups that can be substituted on the benzene ring represented by group, aryloxy group represents an aryl group), cyano group, acyl group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group, nitro group, carboxyl group, sulfo group, alkylthio group, acylamino group, sulfonamido group, arylthio group group, hydroxy group, etc.

Each of these images may have a substituent.

Specific examples of the high boiling point organic solvent of the present invention are shown below.

The following margins (A-1) (A-2) (
A-3) (A-4) (A-
9) (A-10) (A-11) (A-12) (A-13) Ce8 mouth ([) (A'-14) (A-1
5) (A-16) (A-1
7>0 CF3
CN (A-20) (A
-21) (A-24) (A-25) (A-32) (A-33) (A-
36> FF (A-37) FF (A-38) (A-39>
(A-40) (A-4
1)<A-42) (A-43
) (A-44) (A-45)
(A-46) (A-47)
(A-48) NH3O2C+5Hii (A-49) (A-50) (A-51) (A-52) (A-53) (A-54) (A-55) (A-56) j (A- 57) CQH17C8M+7 The high boiling point organic solvent of the present invention can be easily synthesized by a conventionally known method.
, No. 579 and the like. In addition, there are many commercially available compounds,
For example, the exemplified compounds (A-3), (A-5), <A-
7>, (A-16), (A-21), etc. are commercially available.

The amount of the high-boiling organic solvent used in the present invention is preferably 5 to 500 mol%, more preferably 10 to 300 mol%, based on the pyrazoloazole cyan coupler.

In addition, the high boiling point organic solvent of the present invention may be used alone or in combination, or may be used in combination with other high boiling point organic solvents, and if necessary, low boiling point organic solvents, water-soluble organic solvents, etc. etc. may be used in combination.

Specifically, the cyan coupler of the present invention is used together with other compounds as necessary, the high boiling point organic solvent of the present invention is used, other high boiling point organic solvents are used as necessary, and low boiling point is further used as necessary. Simultaneously dissolve using a boiling point and/or water-soluble organic solvent, emulsify and disperse in a hydrophilic binder such as an aqueous gelatin solution using a surfactant, and then add to the desired red-sensitive silver halide emulsion layer. It is preferable to do so.

Examples of the high-boiling organic solvent used in combination with the high-boiling organic solvent of the present invention include phosphoric acid esters, phthalic acid esters, citric acid esters, benzoic acid esters, alkylamides, fatty acid esters, Preferred solvents have a boiling point of 150° C. or higher, such as trimesic acid ester.

Further, as the low boiling point organic solvent used in combination with the high boiling point organic solvent of the present invention. Examples include ethyl acetate, cyclohexanol, methyl ethyl getone, and the like.

The coupler solvent of the present invention, when used in combination with the pyrazoloazole type cyan coupler, lengthens the maximum spectral absorption wavelength of the cyan dye image formed from these cyan couplers, improves light resistance, and improves color density. This has the effect of improving the

The silver halide emulsion used in the present invention includes:
Any silver halide emulsion may be used, such as silver chloride emulsion, silver chlorobromide emulsion, silver chloroiodromide emulsion, etc., but there are no particular limitations.
Silver halide emulsions having high chloride silver halide grains are preferred.

The above-mentioned high chloride silver halide grains refer to those having a silver chloride content of 90 mol% or more.In the 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 proportion of high chloride silver halide grains in the total silver halide grains contained in the emulsion layer is 60% by weight or more. The amount is preferably 80% 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 between the inside and outside of the grain may be different, or the composition between the inside and outside of the grain may be different. , the composition may change continuously or discontinuously.

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 creating and growing the seed particles 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 the mixing method, the back mixing method, the simultaneous mixing method, or a combination thereof, but those obtained by the simultaneous mixing method are preferable. Furthermore, as a type of simultaneous mixing method, pA is described in JP-A-54-48521, etc.
The g-chondrold-double jet method can also be used.

The emulsion of the present invention is chemically sensitized by a sulfur sensitization method, a selenium sensitization method, a reduction sensitization method, a noble metal sensitization method, 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 and sufficient maximum density can be obtained. You will be able to do this.

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 material of the present invention further includes an ultraviolet absorber, an antistain agent, an irradiation inhibitor,
Additives such as hardeners, color clouding inhibitors, image stabilizers, plasticizers, latex, surfactants, matting agents, lubricants, antistatic agents and the like can be used as necessary.

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.

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 color developer usually has a DH value of 7 or higher, most commonly about 10 to 13.

Color development temperature is usually 15°C or higher, generally 20°C.
It is in the range of °C to 50 °C. 30°C for quick development
It is preferable to carry out the above process, and although the conventional processing is 3 to 4 minutes, the color development time for the purpose of rapid processing is generally preferably carried out in the range of 20 seconds to 60 seconds. More preferably, it is in the range of 30 seconds to 50 seconds.

The silver halide photographic 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 ml or less of benzyl alcohol per 11 used for rapid development. .

After color development, bleaching and fixing are performed.

The bleaching process may be performed simultaneously with the fixing process, and 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.

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 pyrazolotriazole magenta couplers are preferred.

As the yellow coupler, for example, acylacetanilide couplers can be used, including benzacetanilide and pivaloylacetanilide compounds.

[Example] Specific examples of the present invention will be described below, but the present invention is not limited thereto.

Example 1 On a paper support laminated with polyethylene (titanium oxide content: 2.7 g/rrf), the following layers were sequentially coated from the support side, and a silver halide color photographic light-sensitive material (N
o1-15) were produced.

Layer 1...1.20/rrr gelatin, 0.3
Blue-sensitive silver chlorobromide emulsion (silver chloride content: 99.3 mol%), 0.5
0g/rr? Q,8 dissolved in dioctyl phthalate of
Layer containing 0g/rrr of yellow coupler (Y-1).

Layer 2: Intermediate layer consisting of gelatin of 0.7 (J/d).

Layer 3--1,25 CI/rrr of gelatin, 0
．． A green-sensitive silver chlorobromide emulsion (silver chloride content 99.5 mol%) of 22 (1#+?), a magenta coupler (M-1) of 0.62Q/d dissolved in dioctyl phthalate of 0.30Qlrd. Containing layer.

[4...1.20/rrf gelatin and 12■
An intermediate layer consisting of (AIC-1) of /d.

Layer 5...1.40 (J/rrf gelatin, 0
．． A layer containing a red-sensitive silver chlorobromide emulsion (silver chloride content 99.7 mol %) of 20 g/a and a cyan coupler shown in Table 1 dissolved in a high boiling point organic solvent shown in Table 1.

Layer 6...1. OIJ/i gelatin and 0.2
(0,3 dissolved in J/rrr of dioctyl phthalate)
A layer containing an ultraviolet absorber (UV-1) of 0/rrr.

Layer 7: A layer containing gelatin of 0°5 (1/r&).

As a hardening agent, sodium 2,4-dichloro-6-hydroxy-s-triazine was added to HI2.4 and HI7 in an amount of 0.017 g per 1 g of gelatin, respectively.

Margin below (Y-1) C (CC-1) <AlC-1) NaO+5HaCNHO0ff (UV-1) Margin below Each of the above photosensitive materials Nα1 to N015 was exposed through an optical wedge and then processed in the next step.

Treatment process temperature Time color development 34.7±0.3°C 45 seconds Bleach fixing 34.7±0.5'C 50 seconds stabilization 30~
Dry at 34°C for 90 seconds. Dry at 60-80°C for 60 seconds. The composition of each treatment solution is as follows.

[Color developer] Pure water 800ml 1 Triethanolamine 8gN, N-
Diethylhydroxyamine 5g Potassium chloride
2g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 5g sodium tetrapolyphosphate 2g potassium carbonate
30g potassium sulfite
0.2g optical brightener (4,4'-
Diaminostilbendisulfonic acid derivative) Add 1g of pure water to bring the total amount to 1p, and EM to pH 10.2.

[Bleach-fix solution] Pure water 800 ro
f ethylenediaminetetraacetic acid ferric ammonium 'dihydrate sog ethylenediaminetetraacetic acid 3g ammonium 1000sulfate (70X solution) 10 (1ml ammonium sulfite (40% solution) 27.5
Add ml water to bring the total volume to 1 p, and adjust the pH to 5.7 with potassium carbonate or glacial acetic acid.

[Stabilizing liquid] Pure water 800 ml
5-chloro-2-methyl-4-inchazolin-3-one 1g 1-hydroxyethylidene-1゜1-diphosphonic acid 2g Add water to make 1p, and adjust the pH to 7 with sulfuric acid or potassium hydroxide.
．． Adjust to 0.

Maximum density and λ1 of dye image obtained through development processing
1a×, D, 3 are shown in Table-1, however, λl1aX is
It is the maximum wavelength (nl) of the visible absorption spectrum of the cyan dye image after development, and Do indicates the absorption ratio at 550 nm when the absorption at λ1aX is taken as 1. The maximum density is measured using a densitometer PDA-65 manufactured by Konica Corporation. It was measured using red light.

Margin Table-1 Below: As is clear from the results in Table-1, the comparative coupler CC
-1 and a comparative sample NQ 1 containing a high boiling point solvent dioctyl phthalate, and a comparative sample Na 4 containing a comparative coupler CC-1 and a high boiling point solvent A-7 or A-9 of the present invention.
．． Samples No. 8 and No. 12 have a high maximum density, and the input nax has a sufficiently long wavelength as a cyan image, but the Do is high and the color reproducibility is very poor.

Comparative sample N containing coupler C-2 or C-10 of the present invention and a comparative high boiling point solvent dioctyl phthalate
o, beams in 2 and 3. The maximum concentration and λ1 for which
1ax is not enough.

In contrast, couplers C-2, C-10, C-
13. Sample Nα5.6.7.9 consisting of a combination of C-39 and the high boiling point solvent A-7 or A-9 of the present invention
．． 10.11.13.14 and 15 have high maximum concentrations, and λ1naX has a long wavelength.

It can be seen that the color reproducibility is low and the color reproducibility is also excellent.

After developing the above samples Nα1 to Nα15 in the same manner as above,
The durability of the dye image was examined by time-light irradiation.The obtained results are shown in Table 2.The results show that the initial density is D1i.
The value of r, expressed as the dye residual rate r at the point n+1.0, was determined by the following formula.

r= (Concentration after 150 hours - Dn+i after 150 hours
n) Compared to comparative samples containing boiling point solvents, the inventive sample containing the coupler of the present invention and the high boiling point solvent of the present invention has a higher dye residual rate after light irradiation, indicating that the durability of the cyan dye image is inferior. .

[Effects of the Invention] In the present invention, the maximum concentration is improved, the maximum absorption wavelength becomes longer, the absorption in the green part becomes smaller,
This has the effect of increasing the light fastness of the cyan dye image.

Sender: Konica Corporation

Claims (1)

[Scope of Claims] A silver halide color photographic light-sensitive material having 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. At least one pyrazoloazole cyan coupler having at least one electron-withdrawing group and/or hydrogen-bonding group at a substitutable position other than the active site of the pyrazoloazole ring is added to the silver halide emulsion layer. and at least one high-boiling point organic solvent represented by the following general formula [A]. General formula [A] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R represents an alkyl group, an alkoxycarbonyl group, an arylsulfonylamino group, or an alkylsulfonylamino group. (X represents a halogen atom or a group capable of substituting a benzene ring, and m represents an integer of 0 to 4.)