JPH01144052A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain superior color reproducibility without lowering photographic sensitivity by incorporating at least one kind of pyrazoloazole type cyan coupler and a specified compd. CONSTITUTION:At least one kind of pyrazoloazole type cyan coupler having an electron withdrawing group at a substitutable position other than the active site of the pyrazoloazole ring and at least one kind of compd. represented by formula I or II are incorporated. In formula I, RA1 is a univalent group, m is an integer of 1-6, n is 2 or 3 and QA is a group which may form a naph thalene ring together with the benzene ring. In formula II, A is -CO- or -SO2-, each of RB1 and RB2 is alkyl, aryl, etc., RB3 is a univalent group and each of land j is an integer of 0-2. Superior color reproducibility is obtd. and color stain is prevented.

Description

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

[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. A 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 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.

In addition, dye images obtained from conventionally used phenols and naphthols have some problems in their storage stability.For example, U.S. Pat.
The dye images obtained with the 2-acylaminophenolic cyan couplers described in U.S. Pat. No. 67,531 and U.S. Pat. The dye image obtained from the 2,5-diacylaminophenol cyan coupler described in No. 772,162 generally has poor light fastness, and the dye image obtained from the 1-hydroxy-2-natutamido cyan coupler , generally poor in both light and heat fastness.

Also, U.S. Patent No. 4,122,369 and Japanese Unexamined Patent Application No. 5
2,5-diacylaminophenolic cyan couplers described in specifications such as No. 7-455538 and JP-A-57-157246, and U.S. Patent No. 3,880,661.
The 2,5-diacylaminophenol cyan coupler that has a hydroxyl group in the ballast part described in the specification of the patent is also required in terms of fastness to light and heat and generation of yellow stain in order to preserve the dye image for a long time. However, 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. 461-3131155, No. 6
No. 2-53417, No. 62-47327, No. 62-4
No. 8895, No. 62-53418, No. 62-6216
No. 2, No. 62-85511, No. 62-62163,
No. 62-99950, No. 62-114838, No. 6
Various pyrazoloazole cyan couplers have been proposed in Japanese Patent No. 2-115946 and the like. It is true that the cyan image obtained from the pyrazoloazole cyan coupler has extremely excellent color reproducibility, and it is recognized that the thermal stability of the cyan image is also extremely excellent. It also has larger defects than the 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 paraphenylene diamine, the color developing agent oxide produced during development causes the adjacent images to It is well known that the phenomenon of so-called "color turbidity" (color mixing) occurs, in which undesirable pigments are formed by migration into the forming layer. It is also known that during color development, undesirable "color fog" development occurs due to oxidation of the developing agent, fog of the emulsion, etc. In the following,
This "color turbidity" and "color fog" are collectively referred to as "color pollution."

In recent years, in the field of manufacturing technology for color photographic materials, in order to obtain even higher quality color photographs, it has become possible to more efficiently prevent color contamination and improve sharpness without reducing photographic sensitivity. Significant efforts have been made to develop thin layered color photographic materials.

However, in the case of pyrazoloazole cyan couplers, especially in thin layered color photographic materials, color developing agent oxides generated in other layers during development migrate to the pyrazoloazole cyan coupler-containing layer. The disadvantage is that undesirable color staining is greater than that of conventional phenolic or naphthol cyan couplers.

[Objective of the Invention] The object of the present invention is to produce a silver halide using a pyrazoloazole cyan coupler that has excellent color reproducibility without reducing photographic sensitivity, and has extremely low color staining even in a thin film state. Our objective is to provide color photographic materials.

[Structure of the Invention] The object of the present invention is to provide at least one pyrazoloazole cyan coupler having at least one electron-withdrawing group at a substitutable position other than the active site of the pyrazoloazole ring, and a compound of the following general formula [ This is achieved by a silver halide photographic material containing at least one compound selected from [A] and [B].

General formula (A) (wherein RAl represents a monovalent group, m represents an integer of 1 to 6, when m is 2 to 6, multiple RAls may be the same or different, n is 2 or 3, and when n is 2, 2
Two -OH are at the ortho or meta position, and when n is 3-, the three -OH are bonded to each other at adjacent positions* ---
--Q A----1 represents that it may be combined with a benzene ring to form a naphthalene ring) General formula CB) (In the formula, A represents -C〇- or 15O2- , Rs+ and R112 each represent an alkyl group, an aryl group, a heterocyclic group, or an amino group, and R11m represents a monovalent group, J)
represents an integer from 0 to 2, and when 1 is 2, each NHA RI
2 may be the same or different, and j represents an integer of 0 to 2. However, the sum of 1 and j is 1 or 2.

Furthermore, at least one of NHA RB2 and 10H must be bonded to -NHS Ox R* + at the ortho or para position.

l( is an integer from 0 to 6, and when k is 2 to 6, R11
3 may be the same or different < , -----Q ,
---- represents that a naphthalene ring may be formed together with a benzene ring.) [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 at a substitutable position other than the active site of the pyrazoloazole ring will be specifically explained.

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.

Since the pyrazoloazole ring has at least one electron-withdrawing group at a substitutable position other than its active site, it becomes 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 the position W to which hydrogen or a substituent that can be attached by reaction with the acid form of the 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-described electron-withdrawing power alone, or may have the above-described electron-withdrawing power together.

The pyrazoloazole type cyan coupler of the present invention is represented by the following - CI).

General formula CI) In the formula, R3 represents a hydrogen atom or one substituent, and R2
represents a monovalent substituent.

m indicates the number of substituents R2; when m is O, R1 represents an electron-withdrawing group; when m is 1 or 2 or more, R1 and R
At least one of 2 represents an electron-withdrawing group When 6m is 2 or more, a plurality of R2 may be the same or different.

Z represents a nonmetallic atomic group necessary to form a nitrogen-containing heterocycle which may be fused with a benzene ring or the like.

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

The electron-withdrawing group according to the present invention is preferably trannn
The substituent constant δP defined by ett is 100.2
Zero or more substituents, specifically sulfonyl, sulfinyl, sulfonyloxy, sulfamoyl, phosphoryl, carbamoyl, acyl, acyloxy, oxycarbonyl, carboxyl, cyano, nitro, halogenated alkoxy, halogenated aryloxy, pyrrolyl, Examples include polygroups such as 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 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, polygroups such as tetrafluoroaryloxy and pentafluoroaryloxy are preferred.

Examples of biI'lyl groups include groups such as 1-pyrrolyl.

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

] - In addition to the substituent, trifluoromethyl group, heptafluoroisopropyl group, nonylfluoro (t3 butyl group, tetrafluoroaryl group, pentafluoroaryl group, etc.) are preferably used.

In the general formula [■], among the substituents represented by R or R2, various substituents other than the electron-withdrawing group can be mentioned. Although there is no particular restriction, typical examples include alkyl , aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl, cycloalkenyl, alkynyl,
heterocycle, alkoxy, aryloxy, heterocycleoxy,
Siloxy, amino, alkylamino, imido, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, thioureido, hydroxy and mercapto polygroups, and spiro compound residues , bridged hydrocarbon compound residues, and the like.

The -E alkyl group preferably has 1 to 32 carbon atoms, and may be linear or branched.

As the aryl group, a phenyl group is preferred.

Examples of the acylamino group include an alkylcarbonylamino group and an arylcarbonylamino group.

Examples of the sulfonamide group include an alkylsulfonylamino group and an arylsulfonylamino group.

Examples of the alkyl component and aryl component in the alkylthio group and arylthio group include the above-mentioned alkyl groups and aryl groups.

The alkenyl group preferably has 2 to 32 carbon atoms, and the cycloalkyl group preferably has 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms, and the alkenyl group may be linear or branched.

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

Examples of the ureido group include an alkylureido group and an arylureido group; examples of the sulfamoylamino group include an alkylsulfamoylamino group and an arylsulfamoylamino group; and the preferred heterocyclic group is a 5- to 7-membered one; Specifically, 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, etc.; as the heterocyclic oxy group, those having a 5- to 7-membered heterocycle are preferable, for example, 3
, 4,5.6-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-heptadecylsuccinimide group, Phthalimide group, glutarimide group, etc. Spiro compound residues include spiro [3,31 hebutane-
1-yl, etc.; As a bridged hydrocarbon compound residue, bicyclo[2,2゜1
]hebutan-1-yl, tricyclo[3゜3, 1.1
'.7]decane-1-yl, 7,7dimethyl-bicyclo[2,2,1]hebutan-1-yl, and the like.

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

In the general formula [I], examples of groups that can be separated by reaction with the oxidized 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, calhokiN-N.

(R1' and R2' have the same meanings as R1 and R2 above, RQ and Rh represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and Z' has the same meaning as Z above.

), preferably a halogen atom. Among these, particularly preferred ones represented by X are:
They are hydrogen atoms and chlorine atoms.

In general formula [I], examples of the nitrogen-containing heterocycle formed by Z include a pyrazole ring, an imidazole ring, a benzimidazole ring, a triazole ring, and a tetrazole ring.

- More specifically, the compound represented by the formula [11] is represented by the following formulas [■1 to [■]].

Below is a blank general formula [■ General formula [11[] General formula [IV] General formula [Vl General formula [Vl ] -f Reverse formula しV[ll Vl General formula [■] Y In the above-formula, [I[ ], at least one of R1 and R3, [■], at least one of R1 and R1, [IV], R,, R5 and R
at least one of [Vl, R,, R, and ns, [v1], at least one of R1 and R9, [Vn ], R1
, [■], at least one of R1 and R+o 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 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. For example, JP-A-61-22
8444, etc., which can undergo 1IifJBA under alkaline conditions, and JP-A-56-13373.
Examples include substituents which are coupled off by reaction with the oxidized developing agent, as described in No. 4 and the like. Preferred Y is a hydrogen atom.

Also, in - formulas [I[] to [■], R8 to RIG
Among them, those that are not electron-withdrawing groups represent hydrogen atoms or substituents, and among RIO, those that are not electron-absorbing groups are not particularly limited as substituents, and specifically, one formula CI] In the above, when R1 or R2 is other than an electron-withdrawing group, the substituents represented by R1 or R2 include those mentioned above.

The cyan coupler having an electron-withdrawing group according to the present invention is
Patent Application No. 62-47323, No. 62-53417, No. 62-62162, No. 62-53418, No. 62-
No. 62163, No. 62-48895, No. 62-999
It can be easily synthesized according to the methods described in various specifications such as No. 50.

The couplers of the present invention typically have tx per mole of silver halide.
io-'mol to 1 mol, preferably 1XIQ-'mol to
It can be used in a 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-I ■ ■ NHCOC14H21 ■ C-13 C-15 C7HI S N N N
tcJ+7N -N -N ■ * NHCOCI2 ) 125 I N N -N -N C-30 0-3I One of the color stain inhibitors that can be used in combination with the pyrazoloazole cyan coupler of the present invention has the general formula (A ) is a compound selected from pyrogallol compounds, resorcinol compounds, and catechol compounds.

In general formula (A), monovalent groups represented by RAl include, for example, halogen atoms, aliphatic groups, cycloalkyl groups, aromatic groups,
Alkylthio group, carbamoyl group, cyano group, formyl group, aryloxy group, acyloxy group, carboxyl group or its salt, sulfo group or its salt, alkoxycarbonyl group, cycloalkoxycarbonyl group, aryloxycarbonyl group, CORA2, S O2R
As, -CONHRA, and -NHCORAs are mentioned, and RAl, RAM, RA4 and RAS each represent an aliphatic group, an aromatic group or a heterocyclic group.

m represents an integer of 1 to 6, and when m represents an integer of 2 to 6, the plurality of RA l may be the same or different.

n is 2 or 3; when n is 2, two -OI ( are in the ortho or meta position; when n is 3, three -O
H's are bonded adjacent to each other.

------Q----E represents that a naphthalene ring may be formed together with a benzene ring.

Next, as representative examples of specific compounds represented by general formula (A), the following are listed as a table.

The following margins describe the aforementioned pyrogallol compounds, catechol compounds, and resorcinol compounds in Berly Patent No. 868,44.
No. 1, JP-A-58-156993, etc. However, the above-mentioned cited documents and patents state that color staining is significantly improved by using the pyrogallol compound, catechol compound, and resorcinol compound described in -F in combination with the pyrazoloazole cyan coupler of the present invention. There is no mention of.

Furthermore, another type of rapid staining aid 1L that can be used in combination with the pyrazoloazole cyan coupler of the present invention
The agent is a sulfonylamino compound represented by formula [8].

In the general formula [B], A represents -Co- or -5O2-, Ro and RI12 each represent an alkyl group, an aryl group, a heterocyclic group, or an amino group, and R and 3 represent a monovalent group.

In general formula CB), the alkyl group represented by Rel and R112 may be linear or branched, and preferably has 1 to 30 carbon atoms.

The aryl group represented by Rel, R, and □ preferably has 6 to 30 carbon atoms.

The heterocyclic group represented by Rel and R8□ preferably has 5 to 30 carbon atoms and at least one of 0 and N as a heteroatom.

The amino groups represented by Rs + and RB2 include those substituted with an alkyl group or an aryl group.

The groups represented by Re r and RB2 include those having substituents.

For R113, the same group as RAl shown in general formula (A) is used.

1 represents an integer from O to 2, and when 1 is 2, each -NH-A
R! 12 may be the same or different.

j represents an integer from 0 to 2, provided that the sum of 1 and j is 1 or 2.

In addition, at least one of NH'A FtmxO and -OH<7) is for -NHS Ox Rsr,
It must be bound in the ortho or para position.

l( is an integer from 0 to 6, and when k is 2 to 6, RIl
l may be the same or different.

------Q and ------ represent that a naphthalene ring may be formed together with a benzene ring.

- The compound represented by the formula CB) can be synthesized by a known method, and the synthesis method is described in Japanese Patent Application Laid-Open No. 59-5247.
No. 59-192247, No. 59-195239, No. 59-204040, No. 60-108843,
6G-118836 etc. can be referred to.

However, these publications do not disclose that color staining is significantly improved by using a sulfonylamino color staining inhibitor in combination with the cyan coupler of the present invention.

Next, specific compound examples of the sulfonylamino color stain inhibitor will be shown.

1;41e(tJ 0 ■ I3 B-11 B-120I 0 ■ I NH Shishir3 The color stain inhibitor according to the present invention may be contained in the same layer as the cyan coupler according to the present invention, and the color stain preventive agent according to the present invention may be contained in the same layer as the cyan coupler according to the present invention. It may be contained in a so-called intermediate layer that is adjacent to the layer containing the cyan coupler and does not contain a photosensitive silver halide emulsion, or in a non-photosensitive layer called a protective layer.

In the present invention, the color stain prevention according to the present invention is added to the intermediate layer adjacent to the layer containing the cyan coupler according to the present invention and between the layer containing the magenta coupler or the layer containing the yellow coupler. It is most preferred to include an agent. In the present invention, the amount of color stain inhibitor used for the cyan coupler of the present invention is 1 mole of coupler.
It ranges from x10-' mol to 1 mol, preferably from lX10-2 mol to 5 x 10-1 mol.

The color stain preventive agent is contained in the emulsion layer containing the pyrazoloazole cyan coupler of the present invention or in a non-photosensitive layer adjacent to the emulsion layer, and migrates from other emulsion layers other than the emulsion layer. It plays an important role by reacting with and removing undesirable oxidized color-forming developing agents, thereby preventing the formation of undesirable cyan images in the emulsion layer and causing color contamination. .

When the above-mentioned color stain inhibitor is used in combination with the pyrazoloazole type cyan coupler of the present invention, the oxidized form of the color developing agent is more difficult to predict at first than when used in combination with the conventional phenol type and naphthol type cyan couplers. It was discovered that the reaction can be removed with such high efficiency.

In particular, the pyrazoloazole cyan coupler of the present invention,
By using the color stain preventive agent of the present invention in combination, it has become possible to provide a thin multilayer color photographic material with significantly less color stain.

The coupler and color stain inhibitor of the present invention can be added using various methods such as solid dispersion method, latex dispersion method, oil-in-water emulsion dispersion method, etc., as well as the method of adding numerically hydrophobic compounds. This 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 a hydrophobic compound such as a coupler, and is usually mixed with a high boiling point organic solvent with a boiling point of about 150°C or higher, and if necessary with a low boiling point and/or water-soluble organic solvent. After emulsifying and dispersing in a hydrophilic binder such as an aqueous gelatin solution using a surfactant using a dispersion means such as a stirrer, homogenizer, colloid mill, flow jet mixer, or ultrasonic device, A step of removing the low-boiling organic solvent at the same time as the dispersion or dispersion may be added to the hydrophilic colloid layer.

Examples of high-boiling organic solvents include phenol derivatives, phthalate esters, phosphate esters, citrate esters, benzoate esters, alkylamides, fatty acid esters, trimesate esters, etc. that do not react with the oxidized form of the developing agent. Organic solvents are used.

The high boiling point organic solvent that can be preferably used in the present invention is a compound having a dielectric constant of 6.0 or less, such as esters such as heptatarate and phosphoric acid ester having a dielectric constant of 6.0 or less; These include lit acid amides, ketones, hydrocarbon compounds, and the like.

Preferably, it is a high boiling point organic solvent with a dielectric constant of 6.0 or below and 1.9 or above and a vapor pressure at 100° C. of 0.5 wH (1 or below). More preferably, it is a phosphoric acid ester. The solvent may be a mixture of two or more.

One of the preferable high-boiling point organic solvents used in the present invention is a phosphoric acid ester compound represented by formula (C).

- Formula (C)'0 Rcso -P -ORat 01'tct (In the formula, Rat, Ra2 and RCI each represent an alkyl group, an alkenyl group, a cycloalkyl group, or an aryl group.) In the present invention, the - formula In the phosphoric acid ester compound represented by [C], Rc l, Rc * and R
CI represents an alkyl group, an alkenyl group, a cycloalkyl group or an aryl group, respectively, but especially Rcl
The total number of carbon atoms of the groups represented by , RCI and Rcj is preferably 24 to 48.

If it is less than 24, the improvement effect aimed at by the present invention is small, and if it exceeds 48, its function as a coupler solvent tends to be somewhat weakened.

The alkyl group represented by Rcl, Ra2 or Rcs is, for example, an ethyl group, a propyl group, a butyl group, a hexyl group, a heptyl group, a 1so-octyl group, a 5ec-nonyl group, a dodecyl group, a 1so-pentadecyl group, Examples include hexadecyl group, heptadecyl group, octadecyl group, etc., aryl groups include phenyl group, naphthyl group, etc., and alkenyl groups include butenyl group, pentenyl group, octadecenyl group, etc. These alkyl groups, alkenyl groups, and aryl groups may have single or multiple substituents, and examples of substituents for alkyl groups and alkenyl groups include halogen atoms, alkoxy groups, aryl groups, aryloxy groups, Examples of substituents for aryl groups include alkenyl groups, alkoxycarbonyl groups, etc., and examples of substituents for aryl groups include halogen atoms, alkyl groups, alkoxy groups, aryl groups,
Examples include an aryloxy group, an alkenyl group, and an alkoxycarbonyl group. Two or more of these substituents may be introduced into the alkyl group, alkenyl group or aryl group, preferably Rc +, RCI and Ft
cs is an alkyl group, such as 2-ethylhexyl group, n-octyl group, 3.5.5-trimethylhexyl group, n-nonyl group, n-decyl group, 5ec-decyl group, 5
Examples include ec-dodecyl and t-octyl groups.

In the present invention, the high boiling point organic solvent represented by formula (C) preferably has a boiling point of 175° C. or higher at 1 atm.

Typical specific examples of the high boiling point organic solvent represented by the general formula (C) are shown below, but the invention is not limited thereto.

The silver halide used in the silver halide emulsion layer of the sensitive material of the present invention includes silver chloride, silver bromide, silver iodide,
These include silver chlorobromide, silver iodobromide, silver chloroiodobromide, and other materials used in ordinary silver halide photographic emulsions.

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

Further, the crystals of these silver halide grains may be normal crystals or twin crystals, and any ratio of [100] planes to (111) planes can be used. Furthermore, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may have a layered structure with different inside and outside, and - these halogenated grains Silver may be of a type that forms a latent image mainly on the surface or of a type that forms a latent image inside the particles.

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

It is preferable to remove soluble salts from the silver halide emulsions used in the photosensitive materials of the present invention, but those without removal can be used. It is also possible to use a mixture of two or more silver halide emulsions prepared separately.

The silver halide emulsion used in the present invention includes:
Any silver halide emulsion may be used, such as 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 of 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 inside and outside the grain may be different, or the composition inside and outside the grain may be different. In this case, the composition may change continuously or discontinuously.

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. In addition, the above particle diameter is
It can be measured by various methods commonly used in the art.

A typical method is Loveland's [Particle Size Analysis Method J
(A, S, T, M, Symposium on Light Microscopy, 1955, pp. 94-122) or "The Theory of the Photographic Process" (co-authored by Mies and James, 3rd edition, Macmillan Publishing Co., Ltd. (1966)) Chapter 2).

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 creating and growing the seed particles may be the same or 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 one type of method, the ICAO-Condroald double-jet method described in JP-A No. 54-48521 and the like can also be used.

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

The silver halide grains used in the present invention may have any shape. One preferable example is (1001
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 may contain cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or lead salts, rhodium salts or complex salts,
Metal ions can be added to the inside of the particles and/or on the surface of the particles by using iron salts or complex salts, and reduction-sensitized nuclei can be formed inside the particles and/or on the surface of the particles by placing them in an appropriate reducing atmosphere. can be granted.

In the emulsion containing silver halide grains used in the present invention (hereinafter referred to as the emulsion of the present invention), unnecessary soluble salts may be removed after the growth of the silver halide grains, or unnecessary soluble salts may be added to the emulsion containing silver halide grains. Even good.

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. 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 100sulfate, Allylthiocarbazide, 1,000 urea, allyl isothiocyanate, cystine, p-toluenethiosulfonate,
Examples include rhodanine. Other US patents 1,574
, No. 944, No. 2,410,689, No. 2,278,
No. 947, No. 2,728,668, No. 3,501,3
No. 13, No. 3,656,055, West German Application Publication (OL
S) No. 1,422,869, 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 I) H1 temperature and the 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 according to the present invention, faithful color reproducibility and sufficient maximum density can be obtained. You will be able to do this.

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.

Typical specific examples of magenta couplers are shown below.

Margin below I M-2 I C# t CI282! I C1. [21 CH.

M-13 M-14 N -N -N These are, for example, disclosed in JP-A-49-111631 and JP-A-56.
-133734, f30-143337, f61
-90155, 61-158329, 61-1
No. 89540, No. 62-38463, No. 62-599
No. 53, U.S. Patent No. 3,519,429, U.S. Patent No. 3,684
．． It is described in No. 514.

Among the magenta couplers described in 1., using pyrazoloazole type magenta couplers such as those shown in M-7 to M-16 not only makes it possible to save silver, but also suppresses the generation of capri, and also allows for raw storage. This is preferable because it also improves image quality and image storage stability.

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

Also, reducing the processing time of photographic materials is an important issue for the photographic industry. In other words, photographic elements are processed on a running basis using automatic processing machines installed in each laboratory, but as part of our efforts to improve our services to our users, photographic elements are processed on the same day they are received. It is required to return the money to the user, and recently,
It has become necessary to return items within a few hours or even tens of minutes from the time they are received, and there is a strong demand for short processing times from the perspective of shortening delivery times.

Conventionally, benzyl alcohol has been used in the color developing solution to achieve rapid processing.If the color developing solution does not substantially contain benzyl alcohol, the maximum density of the characteristic curve will decrease and the current ('A time will be extended). This makes it necessary, and promptness is impaired.

Therefore, in order to save money and reduce environmental pollution, the color developing solution does not substantially contain benzyl alcohol, and even with low replenishment, rapid processing is possible, photographic performance is maintained constant, and At present, there is a strong desire for a method for processing photographic elements with excellent color reproducibility.

The silver halide photographic light-sensitive material of the present invention can satisfy the above-mentioned requirements even when it is developed using a color developer (fA solution) that does not substantially contain benzyl alcohol.

The term "substantially free of benzyl alcohol" means that the amount of benzyl alcohol is 2 mj or less per 1j of the color developing solution, and if it is 2 ml or less, there is almost no problem in terms of environmental pollution.

The color developing agent used in the color developing solution in the present invention includes known color developing agents that are widely used in various color photographic processes.

These developers include aminophenol and p-phenylenediamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, since they are more stable than in the free state. Further, these compounds are generally used in a concentration of about 0.1 g to about 30 t per color developer solution 1, preferably about 1 tr to about 1 t per color developer solution 11.
Use at a concentration of 5ir.

Examples of aminophenol-based developers include 0-aminophenol, p-aminophenol, and 5-amino-2-
Oxytoluene, 2-amino-3-oxytoluene, 2
-oxy-3-amino-1°4-dimethylbenzene and the like.

Particularly useful primary aromatic amine color developers include N, N
'-Dialkyl-p-phinidinediamine type compound, the alkyl group and phenyl group may be substituted with any substituent.Among them, particularly useful examples include N,N'-diethyl -p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N,
N'-dimethyl-p-phenylenediamine hydrochloride, 2-
Amino-5-(N-ethyl-N-dodecylamino)-toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N-β-hydroxy Ethylaminoaniline, 4-
Amino-3-methyl-N.

N'-diethylaniline, 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-p-
Examples include toluene sulfonate.

In addition to the above-mentioned primary aromatic amine color developer, known developer component compounds can be added to the color developer applied to the processing of the silver halide photographic material of the present invention.

For example, alkaline agents such as sodium hydroxide, sodium carbonate, and potassium carbonate, alkali metal periocyanates, alkali metal halides, water softeners, and thickeners may optionally be contained.

VRite salts and droxylamine compounds are used as preservatives in the color developing solution.

As the droxylamine compound, a sulfate of a compound represented by formula (V) is preferable.

(In the formula, RSt and Rsz represent hydrogen or an alkyl group having 1 to 5 carbon atoms which may have a substituent, however, Rs+ and R52 do not have hydrogen at the same time.) As a substituent, sulfonic acid group, hydroxy group, alkoxy group (methoxy group, ethoxy group, glopyloxy group, etc.), carboxyl group, amine group, etc., and these include, for example, U.S. Pat.
Examples include hydroxylamines described in No. 3,287.124 of the same.

Preferred specific compounds represented by formula (V) are shown below.

(V-1) CHI-NH-OH (V-2) C2Hs NH0
H(V-3) 1so-CsHt-NH-OH(V
-4) CsH, -NH-oH (V-5) ) [0-CH2-NH-OH (V-6)
Cl-l5-0-C,H,-NH-OH(
V-7) )[0-C,H,-NH-OH(V-8)
HOOC-C2H4-NH-OH(V-9) H
O3S-C2H, -NH-OH (V-10)
HN 2-C, H, -NH-OH (V-11)
CH, -0-C2H, -NH-OH (V-12)
HO-C284-0-C*H4-NH-OH The PH value of the color developer is usually 7 or higher, most commonly about 10-13.

The color development treatment in the present invention is carried out at 30°C or higher and 90 seconds or less, preferably at 33°C or higher and 80 seconds or less, most preferably at 35°C or higher and 70 seconds or less, and at 30°C or higher. When processing is carried out for more than 90 seconds, the fog density is not satisfactory and the processing stability is also poor. The processing temperature is raised to finish the current (tl) in a short period of time, and is 30°C or higher, 55°C or higher.
If the temperature is below 0℃, the higher the temperature, the shorter the processing time.
Particularly preferably the temperature is 33°C or higher and 48°C or lower, most preferably 35°C or higher and 43°C or lower.

〔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 silver halide color photographic light-sensitive material sample NQI.

Layer 1...1.2g/I gelatin, 0.32g
Blue-sensitive silver halide emulsion (silver chloride content 97 mol%) of /rrr (in terms of silver, the same applies hereinafter), 0.50 g/
0.80 g dissolved in dioctyl phthalate of rrl'
/rtf yellow coupler (YA) layer.

Layer 2...0.7g/d gelatin, 10■/d
An intermediate layer consisting of an irradiation dye (AI-1>, 5/d (AI-2)).

Layer 3--1,25g/rd gelatin, 0.22g/
A layer containing a green-sensitive silver halide emulsion (silver chloride content 100 mole %) of r#, 0.62 g/rrl' of magenta coupler (M-A>) dissolved in 0.30 g/ba of dioctyl phthalate.

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

Layer 5...---1,40g/rr? gelatin, 0.20g/rr? red-sensitive silver halide emulsion (silver chloride content 100 mol%), 0.20 g/rr+' g(n
)-0.45 g/r dissolved in lactyl phosphate-I.
Layer containing rF cyan coupler (C-A).

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

In addition, as a hardening agent, 2,4-dichloro-6-hydroxy-S-triazine sodium was added in layers 2.4 and 6.
Each was added in an amount of 0.017 g per 1 g of gelatin.

In addition, gelatin in layer 4 was added at a rate of 0.9g/rri", 0.6g1
Sample 2 was prepared in the same manner as sample 1 except that rd was replaced.
, No. 3 was created. Sample order 1. Color stain prevention WiA-6, B-1 dissolved in dibutyl phthalate h (DBP) in the amounts shown in Table 1 in each layer 4 of NQ2 and Hatch 3
Samples NQ4 to NQ9 were prepared.

Furthermore, as shown in Table 1 for each of Samples No. 1 to N119, the cyan coupler C-
Sample No. 10 was prepared in the same manner as the above samples NQI to 1IQ9 except that A was replaced with cyan coupler C-2 of the present invention.
18 was created in ~.

The following margins (Y-A) (M-A) (AI-1) (AI-2) Table 1 The above photosensitive material samples NG 1 to No. 018 were subjected to color separation exposure using a colored filter, and the green-sensitive emulsion layer was was exposed and processed in the next step.

Processing process (35℃) Color development 45 seconds and bleach fixing for 1 minute 15 seconds
Stabilization for 45 seconds, Drying for 1 minute and 30 seconds, 60 to 80°C for 2 minutes. The composition of each treatment solution is as follows.

Color developer (per 1j) Pure water 800ajj Ethylene glycol 10ml,
N-diethylhydroxylamine 2ml Potassium chloride 2g Potassium sulfite
0.28N-ethyl-N-β-
Methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 5g Sodium tetrapolyphosphate 2g Potassium carbonate 30g Add pure water and P
IIM to H=10.08.

Bleach-fix pure water 800aj Iron ethylenediaminetetraacetate (1) Ammonium 65g Sodium ethylenediaminetetraacetate 5g Ammonium 100sulfate 85g Sodium bisulfite iog Sodium metabisulfite 2g Sodium chloride
10g hydroxylamine sulfate
Add 2g of pure water to make IJI, and dilute with dilute sulfuric acid.
l(adjust to =7.0.

Stabilizing liquid 5-chloro-2-methyl-4-inthiazolin-3-one 1g 1-Hydroxylic acid 1.1-diphosponic acid 2g Water was added to make 1M, and the pH was adjusted to 7.0 with sulfuric acid or potassium hydroxide.
Adjust to 0.

For each sample after the above treatment, sensitometry was performed to determine the maximum magenta density (M Diax ) and the maximum cyan density (CDlax), and the color turbidity due to cyan coloring that affects magenta coloring, CDrlax / MDn
ax, was calculated and Table 2 was obtained.

Margin Table 2 Test flNa1-3 below. and Nα10-12, it can be seen that the smaller the amount of gelatin in layer 4 and the thinner the layer, the more turbidity the color becomes. Furthermore, the cyan coupler of the present invention has greater color turbidity than the comparative cyan coupler.

In particular, as the layer 4 becomes thinner, the color turbidity caused by the cyan coupler of the present invention increases.

On the other hand, sample Nos. 7 to 9 and NG13 to 18, which were prepared by adding the color stain preventive agent of the present invention to layer 4, certainly have less color turbidity, but especially the cyan coupler of the present invention and the color of the present invention. NG13-1 created in combination with anti-fouling agent
It can be seen that color turbidity is smaller in No. 8, and layer 4 is a thinner film, so that the effect of preventing color turbidity is greater even if the amount of the color stain preventing agent added is small.

Example 2 Samples NG19 to NG30 were prepared using the combinations shown in Table 3 and treated in exactly the same manner as in Example 1.

From Table 3 in Table 3 below, it can be seen that color turbidity can be greatly reduced by the cyan coupler of the present invention and the color stain preventive agent of the present invention.

[Effects of the Invention] The present invention has an effect that color reproducibility is excellent and color staining is prevented.

Claims (1)

[Scope of Claims] At least one pyrazoloazole cyan coupler having at least one electron-withdrawing group at a substitutable position other than the active site of the pyrazoloazole ring, and the following general formulas [A] and [B] A silver halide photographic material containing at least one compound selected from the following. General formula [A] ▲ Numerical formulas, chemical formulas, tables, etc. n is 2 or 3, and when n is 2, the two -OHs are in ortho or meta positions, and when n is 3, the three -OHs are bonded to adjacent positions. −−−−−Q_A−−−−− indicates that it may be combined with a benzene ring to form a naphthalene ring.) General formula [B] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, A represents -CO- or -SO_2-, R_B
_1 and R_B_2 are each an alkyl group, an aryl group,
represents a heterocyclic group or an amino group, R_B_3 represents a monovalent group, l represents an integer of 0 to 2, and when l is 2, each -NH
-A-R_B_2 may be the same or different, and j represents an integer from 0 to 2. However, the sum of l and j is 1 or 2. Furthermore, at least one of -NH-A-R_B_2 and -OH must be bonded to -NHSO_2R_B_1 at the ortho or para position. k is an integer from 0 to 6, and when k is 2 to 6, R_B_
3 may be the same or different, ----Q_B-
--- represents that a naphthalene ring may be formed together with a benzene ring. )