JPH01273036A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the color reproducibility and the raw preserving property of the photosensitive material by incorporating a vinylsulfone type hardening agent and a specified cyan coupler in the photosensitive material. CONSTITUTION:The photosensitive material comprises a photographic constituting layer composed of a blue, a green and a red photosensitive silver halide emulsion layers, an intermediate layer and a protective layer, and the vinylsulfone type hardening agent (for example, a compd. shown by formula I) is incorporated in one or more layers of the photographic constituting layers. And, the pyrazoloazole type cyan coupler (for example, a compd. shown by formula II) which contains one or more of electron attractive groups and/or groups capable of forming a hydrogen bond at a position capable of substituting except an active point, is incorporated in the red photosensitive layer. In the formula, R1 is hydrogen atom or a substituting group, R2 is a substituting group, X is hydrogen atom or a releasing group, Z is an atomic group capable of forming an azole ring, and one or more of groups R1 and R2 are an electron attractive group or a group capable of forming a hydrogen bond.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material, and more specifically, a silver halide photographic light-sensitive material that has excellent color reproducibility and good storage stability. Regarding.

[Background of the Invention] After a silver halide photographic material is exposed to light and then subjected to color development processing, the oxidized aromatic primary amine color developing agent reacts with the dye-forming coupler to produce a dye. An image is formed.

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

Until now, phenols or naphthols have been widely used as cyan image forming couplers.

However, cyan images obtained from conventionally used phenols and nano-ols have serious problems in terms of color reproduction. The problem is that the absorption is not sharp on the short wavelength side, and there is unnecessary absorption, that is, asymmetric absorption, in the edge region.

As a result, in the case of paper, it is necessary to correct the asymmetric absorption by masking or the like, and in the case of paper, there is no means of correction, and the current situation is that the color reproducibility is considerably deteriorated.

In addition, conventionally used phenols and nano-1
The dye images obtained from the dye-based dyes still have some problems in their storage stability. For example, U.S. Patent No.
The dyes obtained from the 2-acylaminophenolic cyan couplers described in U.S. Pat. Nos. 367.531 and 2,423,730 generally have poor heat fastness, and are No. 2.772, 16
Dye images obtained from the 2,5-diacylaminophenol cyan coupler described in No. 2 are generally poor in light fastness, and dye images obtained from the 1-hydroxy-2-natutamido cyan coupler are generally sensitive to light and heat. It is insufficient in terms of both robustness.

In addition, 2,5-diacylaminophenol cyan couplers described in U.S. Pat. 3,880,66
The 2,5-diacylaminophenol cyan coupler that has a hydroxyl group in the ballast part described in Specification No. 1 also has to have its dye side for long-term storage, such as fastness to light and heat and the occurrence of yellow stain. In this respect, a fully satisfactory level has not yet been achieved.

In order to solve this problem, Japanese Patent Application No. 61-280164, No. 61-282355, No. 61-299332, No. 6
No. 1-313458, No. 61-313455, No. 62
-53417, 62-47327, 62-48
No. 895, No. 62-53418, No. 62-62162
No. 62-85511, No. 61-62163, No. 62-99950, No. 62. -114838, same 6
Various pyrazoloazole type cyan couplers are proposed in No. 2-115946 and the like. It is true that the cyan image C image obtained from pyrazoloazole type cyan couplers has excellent color reproducibility, and the thermal stability of the cyan image is also extremely excellent. In this case, the storage stability of the photographic material before exposure (
Hereinafter, it will be referred to as raw storage stability. ) has not yet reached a sufficient level for practical use.

Conventionally, when forming photographic constituent layers such as silver halide emulsion layers, intermediate layers, and protective layers, hardening agents have been used to significantly improve the properties of the films. As a hardening agent, vinyl sulfone compounds (US Pat. No. 3,490.'911), aldehyde compounds (US Pat. No. 3,288,775), reactive ethylene compounds (US Pat. No. 3,635,718) are used. , epoxy compounds and mucochloric acid compounds (U.S. Pat. No. 3,091,5
No. 37), aziridine compounds (US Pat. No. 3,017,
No. 280) etc. are known.

As a result of extensive studies, the present inventors have found that the shelf life of a photographic light-sensitive material when using the above-mentioned pyrazoloazole cyan coupler is lower than that when a certain hardening agent is applied to the constituent layers of the above-mentioned photographic light-sensitive material. We found a phenomenon that was significantly improved. In particular, when the photographic light-sensitive material was stored under high temperature and high humidity conditions, the improvement in raw shelf life was remarkable.

[Object of the Invention] Accordingly, an object of the present invention is to provide a silver halide photographic material which has excellent color reproducibility and improved storage stability.

[Structure of the invention] = 5-1 4- The present invention comprises a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide 1L emulsion layer, a red-sensitive silver halide emulsion layer, an intermediate layer and In a silver halide photographic light-sensitive material having a photographic constituent layer including a protective layer, at least one of the photographic constituent layers contains a vinyl sulfone hardener, and
The red-sensitive silver halide emulsion layer contains a pyrazoloazole cyan coupler having at least one electron-withdrawing group and/or hydrogen-bonding group at a substitutable position other than the active site. This is achieved by using a silver halide photographic light-sensitive material.

[Specific structure of the invention] Next, the present invention will be specifically explained.

The pyrazoloazole cyan coupler according to the present invention having at least one electron-withdrawing group and/or hydrogen-bonding group at a substitutable position other than the active site will be specifically explained.

A pyrazoloazole type cyan coupler is a cyan coupler having a pyrazole ring and an azole ring (including those fused with a benzene ring, etc.) or a condensed ring, that is, a pyranloazole ring.

By 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, it becomes a cyan coupler that forms a cyan dye by color development6. 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. Each of the four electron-withdrawing groups, which means a substituent having a strong electron-withdrawing force, may have the above-mentioned electron-withdrawing force alone, or may jointly have the above-mentioned electron-withdrawing force. It may have.

The electron-withdrawing group according to the present invention is preferably 11a+u
The substituent constant δp defined by net is +0□
20 or more substituents, specifically sulfonyl, sulfinyl, sulfonyloxy, sulfamoyl, phosphoryl, carbamoyl, acyl, acyloxy, oxycarbonyl, carboxyl, cyano, 21-, halogenated alkoxy, halogenated aryloxy , pyrrolyl, tetrazolyl, and a halogen atom.

Examples of the sulfonyl group include alkylsulfonyl, arylsulfonyl, halogenated alkylsulfonyl,
Examples include groups such as 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-sialkylsulfamoyl, 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-diarylsulfmoyl, and N-alkyl-N-arylcarbamoyl.

Examples of the acyl group include groups such as alkylcarbonyl and aryl sulfonyl.

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, tetra-8
- Groups such as fluoroaryloxy and pentafluoroaryloxy are preferred.

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, heptafluoroisopropyl, nonylfluoro(1)butyl, tetrafluoroaryl, pentafluoroaryl, and the like are also preferably used.

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

The hydrogen-bonding group of the present invention is a group that reacts with the pyrazoloazole cyan coupler or the oxidized developing agent between the nitrogen atom on the pyrazoloazole ring, and when measured after being dissolved in methanol. 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 formula may be mentioned.

Ra Ruichi→C-)S O2N HRc Giant, 2) R” Ra Rb Ra Ra -C-NH302Rd Rb Ra --C--NH30Rd Ra Rb Ra -C--NHCORd Rb (In the formula, Ra, Rb, Rc , Rd and Re represent a hydrogen atom or a substituent, Rf represents a substituent, p 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. ) = 12- In the above formula, preferred as Ra, Rb and Rd are a hydrogen atom, an alkyl group, an aryl group, a heterocyclic residue, etc., and preferred as Rc are a hydrogen atom, an alkyl group, an aryl group, These include a sulfonyl group, a sulfinyl group, and the like, which may be substituted with a heterocyclic residue, an alkyl group, an aryl group, or the like. Preferred examples of Re include a hydrogen atom, an alkyl group, an aryl group, a heterocyclic residue, and a sulfonyl group, a sulfinyl group, and a carbonyl group which may be substituted with an alkyl group or an aryl group. is 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 groups may further have a substituent.

Among the above, particularly preferable hydrogen-bonding groups for use in the present invention are the above-mentioned 2(1), (2)(3).
and (7), among which more preferable ones are SO2N HRc, -5ONHR
c, -CONHRc 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 type cyan coupler is one in which an azole ring is condensed with a pyrazole ring, and specifically, preferably, it can be represented by the following general formula [I].

General formula [I] (wherein, R1 represents a hydrogen atom or a substituent, R2 represents Z
represents a substituent bonded to the carbon atom of the nonmetallic atom group represented by At least one of R1 and R2 is an electron-withdrawing group or a group having hydrogen bond=14=.

n indicates the number of substituents R2.

X represents a hydrogen atom or a substituent which is eliminated 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. ) 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, sulponamide, alkylthio, arylthio, alkenyl, cycloalkyl,
cycloalkenyl, alkynyl, heterocycle, alkoxy,
Aryloxy, heterocyclicoxy, siloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, thioureido, hydroxy and mercapto groups, as well as spiro compound residues, bridged hydrocarbon compound residues, and the like.

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

The alkyl group is preferably one having 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.

A ureido group is an aryl ureido group, an arylureido group, etc.

Examples of the sulfamoylamino group include an alkylsulfamoylamino group and an arylsulfamoylamino group.

The compound ring group is preferably a 5- to 7-membered group, and specifically, a 2-furyl group, a 2-dienyl group, a 2-pyrimidinyl group, a 2-benzothiazolyl group, etc.; a 5- to 7-membered heterocyclic group is preferable. Preferably, those having a heterocyclic ring having a member of 3. /I, 5.6-te1-rahido IV pyranyl-2-oAsi group, 1-phenylde1-razole-5-oxy group, etc.: As a heterocyclic thio group, a 5- to 7-membered heterocyclic ring-) -O group is preferred, such as 2-pyridylthio group, 2-penzdeazolylthio group, 2,4-diphenoxy-1,3,5-
1 to lyazole-6 monothio group etc. 1
~limethylsiloxy group, 1~ethylsiloxy group, dimedylbutylcyIT7xy group, etc., 17--116-imide group includes succinimide group, 3-heptadecylsuccinimide group, 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゜3.1.13
7] Decan-1-yl, 7,7 dimethyl-bicyclo[2
,2,1]butan-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 general formula CI], 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, alkoxycarbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclicthio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing bonded by N atom heterocycle, alkyloxycarbonylamino, aryloxycarbonylamino, carboxyl, (R1' and R2' have the same meanings as R1 and R2 above, Rg and Rh are hydrogen atoms, or alkyl which may have a substituent) group, aryl group, or heterocyclic group, and Z' has the same meaning as the above-mentioned Z.), preferably a halogen atom. Of these, X
Especially preferred are hydrogen atoms and chlorine atoms.

In general formula [I], examples of the nitrogen-containing heterocycle formed by Z include a pyrazole ring, an imitazole ring, a penzimitazole ring, a triazole ring, and a te-razole ring.

Among the compounds represented by general formula [I], R1 and R2
More specifically, those in which at least one of the groups is an electron-withdrawing group are represented by the following general formulas [■α] to [■α].

General formula [■α] General formula [■α] General formula [IVα] -2〇 - General formula [■α ko Y l General formula [■α] Y In the above general formula, in [■α], R+a and R311 at least one of R1l+ and R4t in [■α], at least one of lR+a, Rs- and °R611 in [IVα], R+ in [vα], v, R7,, at least one of Rs, in [Vlα], at least one of R+- and R,, in [■■α], in R1,,, in [■α] , R+, and R1oe is an electron-withdrawing group.

X has the same meaning as X in general formula [I], and ρ is 0 to 4
represents an integer. Y represents a hydrogen atom or a substituent, and preferred examples of the substituent represented by Y include those that separate from the cyan coupler before the compound of the present invention reacts with the oxidized developing agent; Kaisho 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.

In addition, in the general formula [■α] to [■α, R+- to R
Among +oe, there are no particular limitations on the substituents that are not electron-withdrawing groups. Specifically, in general formula [I], R7
Alternatively, when R2 is a group other than an electron-withdrawing group or a hydrogen-bonding group, R1 or R2 may be a substituent or a group 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
-62163, 62-48895, 62-99
It can be easily synthesized according to the methods described in various specifications such as No. 950.

Among the compounds represented by general formula [I], R1 and R2
More specifically, at least one of the groups is a hydrogen-bonding group, and is represented by the following general formula [■β]h - "■β".

General formula "■β" y) General formula [■β] General formula [IVβ] General formula [■β] Y In the above general formulas [■β] to [■β], X is X in the above general formula [I] is synonymous with

General formula [■β], [Vβ], [Vlβ] and [Vnβ
], R1/l in the general formula [■β], at least one of R+a and R4 in the general formula [■β], at least one of R11 and R95 in the general formula [IVβ], R11 and R+os in the general formula [■β] At least one of them is a hydrogen-bonding group.

Among [+ and ~R13] in the general formula [■ββcol■β], there are no particular limitations on the substituents that are not hydrogen-bonding groups. Specifically, in general formula [I], when R1 or R2 is a substituent other than an electron-withdrawing group or a hydrogen-bonding group, the substituent represented by Ro or R2, or the above-mentioned electron-withdrawing group. It may be mentioned as a sexual group.

Y in the general formula [■β] 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. 62-11594f3, No. 62-184554, etc.

The couplers of the present invention typically contain I/mole of silver halide.
X 10-3 mol to 1 mol, preferably 1 x 10-2
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 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.

Below margin ceH17 CI OH2+ ■ ■ ■ C-13 C-14 ■ tcaH+ヮ] I * tc6H++ N ■ ■ N -□ N □ N C-31 C-32 I 0 mouth) 123 〇-43 N □N --□ N NHI; Rishill'123
C-48 C-49 〇-61 Next, the vinyl sulfone hardener according to the present invention will be explained.

Vinyl sulfone hardeners used in the present invention include, for example, German Patent No. 1,100,942 and U.S. Pat.
, 490,911 etc., Japanese Patent Publication Nos. 44-29622 and 47-25373.
No. 47-24259, etc., alkyl compounds bonded with hedero atoms, Japanese Patent Publication No. 47-87
Sulfonamides and ester compounds such as those described in No. 36, etc., JP-A No. 4! 1,3,5-tris[β-(vinylsulfonyl)-propionyl]-hexahydro-S-triazine as described in IJ-24435 etc. or Japanese Patent Publication No. 50-35807, Japanese Patent Application Laid-Open No. 51-4
It includes alkyl compounds such as those described in JP-A-59-18944 and the like, and compounds described in JP-A-59-18944 and the like.

The vinyl sulfone hardener preferably used in the present invention is represented by the following general formula [H-I].

General formula [H-I] L→S02-X)m In the above general formula [H-I], L is an m-valent linking group and may be substituted, and X is -CH-CH2 or -CR2CR2Y Y is substituted with a nucleophilic group or represents a group that can be eliminated in the form of HY with a base (eg, a halogen atom, a sulfonyloxy group, a sulfuric acid monoester, etc.).

m represents an integer of 2 to 10.

The m-valent linking group is, for example, an alkylene group, an arylene group, or these groups and -0-1-N-1-CO-1-SO
-1-8O2-1S O3-1-3O2N-1-COO
-1-CON-1 (I RI R' RI RI R1 -NCON-1-N C02- is an m-valent group formed by combining one or more bonds. R' is a hydrogen atom, or represents an alkyl group or an aralkyl group having 1 to 15 carbon atoms.Also, -N-
1. When two or more RI R'R' SO2N-1-CON-1-N CO2- are included, R1's thereof may be bonded together to form a ring. Furthermore, L may have a substituent, and examples of the substituent include a hydroxy group, an alkoxy group, a carbamoyl group, a sulfamoyl group, an alkyl group, and an aryl group. Moreover, the substituent may be further substituted with one or more groups represented by X35O2-. X3 is the same as X mentioned above! It is righteousness.

Typical examples of L include the following. However, a to ■ in the steel are integers of 1 to 6, and only d may be 0. Among these, d, l(, p and p are 1
-3 is preferable, and it is preferable that 1st is 2 for the above-mentioned d, u and p of a to V. Furthermore, R1 is preferably a hydrogen atom or an alkyl group having a valence of 1 to 6 carbon atoms, and particularly preferably a hydrogen atom, a methyl group, and an ethyl group.

(C1-[2)a O(CH2)b-1R'
R' - (CH2) C-CON (CH2) d
NCO(C)[2) e -5~(CH2)
f 802 (CH2) g-1] (CH2) h-N (CH2) i -5R'
R' (CI(2) n CO2(CH2) P
OCO (CH2) Q -5Co (CH2
) t-8o. X3, I can do it.

-CH=CH2, -CH=CH2Cl, CI2 CI2
B r, CI2 CI20 S Oe CI3, -CH2CH2
0803Na, CI2 CI20 S 03 K, CH2CH20
H1CH2CH20COCIh, CH,! CH20COCF3, CHe CHR0COCHCj2, Among these, especially CH= CHe, CHp CHe Cj, -CH2
CH2Br, CHe CHe OS H2CI3 and -CHe CH
20SO3Na is preferred.

Typical examples of the vinyl sulfone hardener according to the present invention are shown below.

A-1) 12e-C) 1802CI (2S02C) I=
CHzA 2 H2c=cH802(CI(2)
2sO2cH=cH2A 3 H2cmcH8O
p(Ch)3SkCH=CH2A-4H2c=cH! 1
o2cH20cHdo2cfl=chA 5 h
c=cH8O2(CL)20(CL)d02cH=cH
2A-6H2C=CHH2C=CH80aCH2CHC
H2SO■ OH A-7kC=CH8O2ChCHChCHCH2SO2
CI(=C)I20)1 0H A 8 H2C=C)ISO2CH2CONIC
)12NI(COCI(eso.CI(=C)12A
9H2c=cH802cH2cONH(CL)2NH
COChSO2CH=fj12A 10 kC=C
H8OpCH2CONHCH2ChCHJt(COCH
2SO2CH=CH2A 12
C0ChSO2CH=CH2I2(:=CH8O2CH
2CO-N N-C0CHqSO2CH=CH2A-
14H2C=CH502(CH2)2CONH-C)+
2H2C=CH8O2(Ch) 2CONH-CH2A
-15C)13 QuantityOH3 H2C=CH8O2CH2CHCH2SO2C)I=C
H25O2CH=CH2 SO3CH=CH2 82C=C)ISO2CH2CH25OH=CH2H2
C=CH8O8CH2-C-CH2-0-CH2-C-
CH2SOH=C)+2)12c=c)lsO2cH2
C) I2SO) I=eH2A −20[()12c=c
H3O2) 3CC) 12802 (Ch) 28C)
+2120OA~22 (H2C=CH8O2CH
2) 4CA 24 (H2C=CH8O2CH2
)3cc2HsSO2CH=CH2 H3 A -28'5O2CI(=CH2 A-30H2C=CH302(CH2)2sO2(CH
2) d02cH=cH2H2C=CH8O2[CH3I
20 (CH2I 2NHONH(CH2) 20
(CH2) 2sO2cH=cH2A 32
Co(CH2)2SO2CH=CH2A
-35(H2C=CH8O2NH12CkA-36H2
C=CH802(CH2)2NH(CH2+2NH(C
)+2+2sO2cH=c)12A-37[H2C=C
H302(C)12)2cONcH2)20h■ C)I3 A-38C1(C1(2)2s02cHc00(CH2
)20cOcH8O2(CH2)2c1C2H5C2H
! 5 A-41C8H+7C[CH25O2CH=CH2hH
2C=CH3O25O2CH=CH2A 44
C) 12[C0NI(CH2SO2CH=CH2)2A
-46C(Co(CH2)2SO2CH=CH214A
48 NH[[CH2)2sOecH=cH2
]2A 49 CH2O(ChOC)I2SOp
C1(=Ck)3A 50 C(CH20CH2
SO2CH=CI2+4A -51N [[Ck)20c
)IdO2CH=CH213A -52(CHe=CH
8OQCH2) 3ccH8O2(CH2) 2cl or less Margin -52 = These vinyl sulfone hardeners are dissolved in water or organic solvent, and contain 0.005 to 20% by weight based on gelatin.
Preferably, it is used in an amount of 0.02 to 10% by weight.

For addition to the photographic layer, a batch method or an in-line addition method is adopted.

The layer to which these hardeners are added to the photographic layer is not particularly limited; for example, the object of the present invention can be achieved even if the hardener is added to the top layer, the bottom layer, or all layers. can.

The above-mentioned hardener is highly diffusible in the photographic constituent layers, so when all the photographic constituent layers are coated at the same time, even if it is added to any of the constituent layers that are coated at the same time, it will not be able to exhibit its hardening properties. Alternatively, it is possible for the photographic constituent layers that are coated simultaneously while exhibiting hardening properties to spread over almost the entire layer, and finally to harden the entire layer almost uniformly.

In addition, when coating all the photographic constituent layers in several coats, the present invention may be applied to the red-sensitive silver halide emulsion layer containing the pyrazoloazole cyan coupler of the present invention or to the constituent layers above the emulsion layer. Preferably, the vinyl sulfone hardener of the invention is added.

As a result of intensive studies, the inventors of the present invention have investigated the shelf life of photographic light-sensitive materials when using the pyrazoloazole cyan coupler of the present invention, and applied a vinyl sulfone-based hardener to the constituent layers of the photographic light-sensitive materials. In this case, they discovered a phenomenon that was significantly improved, and recognized that this improvement could not be achieved with any other type of hardening agent.

The coupler of the present invention can be added by various methods such as solid dispersion method, latex dispersion method, oil-in-water emulsion dispersion method, etc. in the same way as the addition method for general hydrophobic compounds. can be appropriately selected depending on the chemical structure of the hydrophobic compound such as the coupler. The oil-in-water emulsion dispersion method can be applied to a method of dispersing hydrophobic compounds such as couplers, and is usually applied to a high-boiling organic solvent with a boiling point of about 150°C or higher, and if necessary, a low-boiling point and/or water-soluble organic solvent. After dissolving with a solvent and emulsifying and dispersing it using a surfactant in a hydrophilic painter such as an aqueous gelatin solution using a dispersion means such as a stirrer, homogenizer, colloid mill, flow jet mixer, or ultrasonic device. , may be added to the desired hydrophilic colloid layer. A step of removing the low boiling point organic solvent may be included after or simultaneously with the dispersion.

Examples of high-boiling organic solvents include phenol derivatives, phthalate esters, phosphate esters, citric acid esters, benzoic esters, alkylamides, fatty acid esters, trimesic esters, etc., which have a boiling point of 150°C or higher and do not react with the oxidized form of the developing agent. of organic solvents are used.

The high boiling point organic solvent that can be preferably used in the present invention is a compound with a dielectric constant of 6.0 or less, such as esters such as phthalates and phosphates with a dielectric constant of 6.0 or less, organic Acid amides, carboxylates,
Hydrocarbon compounds, etc.

Preferably dielectric constant is 6.0 or less and 1.9 or more and 100'C
It is a high boiling point organic solvent with a vapor pressure of 0.5 mm l-I G or less. Furthermore, the high boiling point organic solvent may be a mixture of two or more kinds.

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, silver chloroiodobromide, etc., may be included.

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 the ratio of the (100) plane to the (111] plane may be arbitrary. Furthermore, the crystal structure of these silver halide grains may be The silver halide may be uniform from the inside to the outside, or it may have a layered structure with different interior and exterior layers. It may be of the type formed inside the particle.

These silver halide grains can be prepared by known methods commonly used in the art.

Heroes used in the photosensitive material of the present invention 5
6 - Is it preferable to remove soluble salts from the silver germide emulsion?
Unremoved ones can also be used. It is also possible to mix two or more types of silver halide emulsions that have been prepared separately and use them as one emulsion.

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.
Preferably, the emulsion is a silver halide emulsion having high chloride silver halide grains.

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. More preferred is silver chlorobromide having 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 the 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. Further, when the composition inside and outside the particle is different, the composition may change continuously or discontinuously.

There is no particular limit to the grain size of the high chloride silver halide grains, but considering 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.
It is in the range of 25 to 1.2 μm. In addition, the above particle diameter is
It can be measured by various methods commonly used in the technical field.

A typical method is Loveland's [Particle Size Analysis Method 1]
(A, S, T, M, Symposium on Rye I...
Microscopy, 1955, pp. 194-122) or Theory of the Photographic Process (co-authored by Mies and Georges, 3rd edition, published by Macmillan, 1966), 2nd edition.
chapter).

The particle size can be measured using the projected area of the particle or an approximate diameter. If the particles are of substantially uniform shape, the particle size distribution can be described fairly accurately as diameter or projected area.

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 variation coefficient 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.
It may be obtained by either the neutral method or the ammonia method. The particles may be grown all at once, or may be grown after seed particles are produced.

The method of creating and growing the seed particles may be the same or different.

Further, the soluble silver salt and the soluble halogen salt may be reacted by 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. Furthermore, as a type of simultaneous mixing method, the IIA (]-controlled dosing double jet) method described in JP-A-54-48521 and the like can also be used.

Furthermore, if necessary, a silver halide solvent such as thioether may be used. Further, a compound such as a mercapto group-containing compound, a nitrogen-containing heterocyclic compound, or a sensitizing dye may be added during the formation of silver halide grains or after the completion of grain 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.

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 grains used in the present invention are produced by using a cadmium salt, a zinc salt, a complex salt, a thallium salt, an iridium salt or a complex salt, a codium salt or a complex salt, an iron salt or a complex salt during the grain formation process and/or growth process. Ions can be added and included inside the particles and/or on the particle surfaces, and reduction sensitizing nuclei can be provided inside the particles and/or on the particle surfaces by placing them in a suitable reducing atmosphere.

The emulsion containing silver halide grains used in the present invention (hereinafter referred to as "the emulsion of the present invention") may have unnecessary soluble salts removed after the growth of the silver halide grains is completed.
Alternatively, it may be left as is. In the case of 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 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. The chalcogen sensitizer is a general term for sulfur sensitizers, selenium sensitizers, and tellurium sensitizers, and preferably sulfur sensitizers and selenium sensitizers. Examples of the sulfur sensitizer include thiosulfate, allylthiocarbazide, thiourea, allylisothiocyanate, cystine, p-toluenethiosulfonate,
Examples include rhodanine. That song, U.S. Patent No. 1,574
, No. 944, No. 2,410,689, No. 2,2711
．． No. 947, No. 2,728,668, No. 3,501,
No. 313, No. 3,656,955, West German Application Publication (O
L S ) L422,869, JP-A-56-24
Sulfur sensitizers described in No. 937, No. 55-45016, etc. can also be used. The amount of sulfur sensitizer added varies over a considerable range depending on various conditions such as pH, temperature, and size of silver halide grains, but as a guide, it is 10"7 mol to 10 mol per mol of silver halide.
-1 mol 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 emulsion layer in the photographic constituent layer containing the pyrazoloazole cyan coupler of the present invention, faithful color reproducibility can be obtained, and sufficient maximum density can be obtained. You will be able to get things done.

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 light-sensitive material of the present invention, it is preferable to use gelatin, or alternatively gelatin derivatives, graft polymers of gelatin and other polymers, proteins, and sugar derivatives. Hydrophilic colloids such as cellulose derivatives, synthetic hydrophilic polymeric substances such as monopolymers or copolymers can also be used.

The silver halide photographic light-sensitive material of the present invention having the structure described above can be, for example, color negative and positive films, color photographic paper, etc., but it is especially suitable for color photographic paper used for direct viewing. When used, 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. Any known magenta coupler or yellow coupler can be used without any particular restriction.

As the magenta coupler, 5-pyrazolone type, virazolobensimidazole type, pyrazoloazole type, open-chain acylacetate 1-nitrile type couplers, etc. are used, and among them, 5-pyrazolone type and pyrazolo 1-lyazole type magenta couplers are preferred.

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

The silver halide photographic light-sensitive material of the present invention further includes a pre-hardening agent, an irradiation inhibitor, a color clouding prevention agent, an image stabilizer, a plasticizer, a latex, a surfactant, a matting agent, a lubricant, and an antistatic agent. Additives such as agents may be used as necessary.

The silver halide photographic material of the present invention can form an image by subjecting it to a color development process known in the art.

The pH value of the color developer is usually above 7, most commonly about 10-13.

The temperature at which color development occurs is usually 15°C or higher, and generally 2°C.
It is in the range of 0°C to 50°C. 3 for quick development
It is preferable to carry out the reaction at a temperature of 0°C or higher. In addition, it is preferable that the color development time of the present invention for the purpose of rapid processing is generally carried out in the range of 20 seconds to 60 seconds, more preferably 30 seconds to 4 minutes in conventional processing. It ranges from seconds to 50 seconds.

The silver halide photographic light-sensitive material of the present invention can be used for rapid color development without decreasing the maximum density of the characteristic curve even when using a color development method in which benzyl alcohol used for rapid development is 2 m/p or less. It can be developed into

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] Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited to these.

Example-1 Here, the present invention was applied to color paper.

That is, silver halide color photographic materials No. 1 to No. 18 were prepared by sequentially coating the following layers from the support side onto a paper support laminated on both sides with polyethylene.

Layer 1- = -1,2 g/rrl' of gelatin, 0.3
Blue-sensitive silver chlorobromide emulsion (silver chloride content: 99.3 mol%), 0.5 g/rrf' (in terms of silver, the same applies hereinafter)
0.80 g dissolved in 0 g/d dioctyl phthalate
A layer containing yellow coupler (Y-1) of /rrr.

Layer 2--0.70 g/rr? ’ gelatin, 12m
f/r+ anti-irradiation dye (AI-1), 6
Intermediate layer consisting of 40 mg/rd of color turbidity inhibitor (AS-1) dissolved in dioctyl phthalate (AI-2) of ■/d and 40 mg/rd of dioctyl phthalate of 40 ■/rI'i'.

Layer 3...1.25g/resistant gelatin, 0.25
g/rrf green-sensitive silver chlorobromide emulsion (silver chloride content 99.
0.74 g/r& of magenta coupler (M
-1) A layer containing.

Layer 4 - 1.20 g/rrI+ gelatin and 1
Intermediate layer consisting of 40 mg/n of anti-tarnishing agent (As-1) dissolved in 40 mg/n of dioctyl phthalate.

Layer 5 =...1.20g/J gelatin, 0.
30g/rrI? A layer containing a red-sensitive silver chlorobromide emulsion (silver chloride content 99.7 mol %), 0.9 mmol of the cyan coupler shown in Table 1 dissolved in 0.20 g/rd dioctyl phthalate.

Layer 6...1.00g 7'rrr gelatin and 0
．． 20g/rr? 0 dissolved in dioctyl phthalate of
, 30 g/rrf of ultraviolet absorber (UV-1).

Layer 7: Layer containing 0.50 g/rrr of gelatin.

-I C-t I l-1 AI-2 As-1 UV-1 H C5H1t (t) C,0 H-2 In addition, the hardening agent shown in Table-1 was added to layers 2.4 and 7. Each was added in an amount of 0.1 mmol per gram of seratin.

Each sample obtained was left to stand for 3 days and at 55℃80%
After storage for 36 hours under a relative humidity of
After wedge exposure using Type 7 (manufactured by Konica Corporation),
After processing according to the following color development process, the maximum density (Dla×), sensitivity (S) and fog (Fog) of the red-sensitive emulsion layer were measured using an optical densitometer (PDA-65 model manufactured by Konica Corporation). ) were measured and shown in Table-1.

[Processing process]

Temperature Time Development color development 34.7±0.3°C 45 seconds bleach fixing
34.7±0.5℃ Stabilized for 50 seconds 30
Dry at ~34°C for 90 seconds 60-80°C for 60 seconds Color developer> Pure water 800mj Triethanolamine 8gN,N
-Diethylhydroxylamine 5g Potassium chloride
2gN-ethyl-N-β-
Methanesulfonamide ethyl-3-methyl-4 = amine aniline sulfate 5g Te1~
Labori sodium phosphate 2g Potassium carbonate 30g Potassium sulfite 0.2g Optical brightener (4,4
'-diaminostilbendisulfonic acid derivative) 1g Add pure water to make the total amount into one layer, and adjust to I) Hlo, 2.

Bleach-fix solution> Ethylenediaminetetraacetate iron ([[) ammonium 2
Water salt 60g ethylenediaminetetraacetic acid 3g ammonium thiosulfate (70%
? Capacity: a) 100ml ammonium sulfite (4
0% solution) Adjust the pH to 5.7 with 27.5mj potassium carbonate or glacial acetic acid, and add water to bring the total volume to 1.

Stabilizing liquid> 5-chloro-2-methyl-4-inchazolin-3-one 1g 1-droxyethylidene-1゜1-diphosphone #2g Add water to make 1fJ, and add sulfuric acid or potassium hydroxide to II
Adjust H to 7.0.

The following margins (S is the relative sensitivity when Sample No. 1 and S of 1 are taken as 100.) From Table 1, the combination of the cyan coupler and hardener according to the present invention can be used at a high temperature of 55°C 180%. It can be seen that a sample with excellent shelf life can be obtained without much deterioration in photographic performance even if left under high humidity for 3 days.

Example-2 With the combination of couplers and hardeners shown in Table-2, Example-
Samples were prepared and treated in exactly the same manner as in Example 1, and the results shown in Table 2 were obtained.

It can be seen from this that the raw storage stability of the samples according to the present invention is improved.

Below is a margin table-2 [Effects of the invention - Silver halide of the present invention! True light-sensitive materials have excellent color reproducibility and have the advantage of improved shelf life.

Claims (1)

[Claims] In 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, a red-sensitive silver halide emulsion layer, an intermediate layer and a protective layer on a support. , at least one of the photographic constituent layers contains a vinyl sulfone hardener, and the red-sensitive silver halide emulsion layer contains at least one electron-withdrawing agent at a substitutable position other than the active site. A silver halide photographic material comprising a pyrazoloazole cyan coupler having a group and/or a hydrogen-bonding group.