JPH02179636A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide photographic sensitive material having improved color reproducibility of Cyan picture image, preservability of picture image, and preservability of liquid dispersion of coupler by using specified two kinds of Cyan coupler in combination. CONSTITUTION:A Cyan coupler expressed by the formula I and >= one kinds of Cyan couplers expressed by the formula II or III are contained in a red- sensitive silver halide emulsion layer of the sensitive material. In the formulas, each R and Y is H or a substituent; each X, Z1 and Y1 is H or an eliminable group; Z is a nonmetal atomic group necessary for forming an N-contg. 6-membered heterocyclic ring; R21 is a 2-6C alkyl; R22 is a ballast group; R23 is H, halogen, etc.; R24 is an alkyl or aryl group; R25 is an alkyl cycloalkyl group, etc.; R26 is H, halogen, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application j] The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material having excellent color reproducibility and image storage stability.

[Background of the Invention] After exposing a silver halide photographic light-sensitive material to light, a color development process is performed, whereby an oxidized aromatic primary amine color developing agent and a dye-forming coupler react to form a dye. A color image is formed.

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

Until now, phenols or naphthols have been widely used as cyan image-forming couplers, but the cyan images obtained from these phenols or naphthols have poor sharpness on the short wavelength side. , there is a problem in color reproduction in that the edge region also has unnecessary asymmetric absorption.

Moreover, cyan images obtained from conventional cyan image-forming couplers of phenols and naphthols have not been able to satisfy both heat fastness and light fastness.

In order to solve this problem, Japanese Patent Application No. 62-203450, No. 62-203451, No. 63-7204, No. 63-
No. 32094, No. 63-36086, No. 63-379
No. 98, No. 63-237681, etc., various pyrazolopyrimidone and pyrazoloquinazolone type cyan couplers,
Proposed.

It is certainly recognized that the cyan images obtained from these cyan couplers have extremely excellent color reproducibility, and also have extremely excellent thermal stability.

However, the light fastness was not sufficient and, surprisingly, the storage stability of the coupler dispersion was found to be unsatisfactory, and improvements in this area have been awaited.

As a result of various studies regarding the above-mentioned problems, the present inventors found that
Pyrazolopyrimidone, pyrazoquinazolone type cyan coupler (hereinafter "cyan coupler represented by general formula [I]")
The present inventors have discovered that preferable results can be obtained by using a specific phenolic coupler in combination with a specific phenolic coupler, and have completed the present invention.

OBJECTS OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide color photographic light-sensitive material which has excellent color reproducibility and image storage stability, and which has improved storage stability of a coupler dispersion.

[Structure of the Invention] The object of the present invention is to provide a silver halide photographic material having at least one blue-sensitive silver halide emulsion layer, one green-sensitive silver halide emulsion layer, and one red-sensitive silver halide emulsion layer on a support. In the red-sensitive silver halide emulsion layer,
At least one type selected from a cyan coupler represented by the following general formula [I], a cyan coupler represented by the following general formula [PC-I], and a cyan coupler represented by the following general formula [PC-Ill] This was achieved by a silver halide photographic material characterized by containing a cyan coupler.

General formula [I] (wherein R and Y represent a hydrogen atom or a substituent,
X represents a hydrogen atom or a substituent that leaves by reaction with an oxidized product of a color developing agent, and Z represents a nitrogen-containing hetero 6- which is condensed with the pyrazole ring together with the general formula [PC-U] -N-.
Represents a group of nonmetallic atoms necessary to form a ring, and the 6-membered ring may have a substituent and may be fused with a benzene ring in addition to the pyrazole ring.) General formula [PC -I] H (wherein, R21 represents an alkyl group having 2 to 6 carbon atoms.

R2□ represents a ballast group, R23 represents a hydrogen atom, a halogen atom, or an alkyl group, zl represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of a color developing agent;
) Below margin H Y.

(In the formula, R24 represents an alkyl group or an aryl group.

Rzs represents an alkyl group, cycloalkyl group, aryl group or heterocyclic group, R26 is a hydrogen atom, a halogen atom,
Represents an alkyl group or an alkoxy group, where R26 is R2
(Yl may form a ring in cooperation with 4; Yl represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of a color developing agent) [Specific constitution of the invention] Silver halide photograph of the invention The photosensitive material has the general formula [
I] and the -fi formula [PC
-I] and the following general formula [PC
-II] is used in combination with at least one cyan coupler selected from cyan couplers represented by [-II].

Hereinafter, when these cyan couplers are used together, they will be referred to as the cyan coupler of the present invention.

First, the cyan coupler represented by the general formula [I] will be explained.

The cyan coupler represented by the general formula [I] has a structure in which it is fused with a pyrazole ring to form a 6-membered hetero ring, and there are no particular restrictions on the substituent represented by R, but representative Examples include alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl, etc., but this includes halogen atoms and cycloalkyl, alkynyl,
heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, sulfonyloxy, aryloxy, heterocycleoxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, Polygroups such as alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, thioureido, carboxyl, hydroxy, mercapto, nitro, sulfonic acid, spiro compound residues, bridged hydrocarbon compound residues etc. can also be mentioned.

The alkyl group represented by R preferably has 1 to 32 carbon atoms, and may be linear or branched.

The aryl group represented by R is preferably a phenyl group.

Examples of the acylamino group represented by R include an alkylcarbonylamino group and an arylcarbonylamino group.

Examples of the sulfonamide group represented by R include an alkylsulfonylamino group and an arylsulfonylamino group.

Examples of the alkyl component and aryl component in the alkylthio group and arylthio group represented by R include the alkyl group and aryl group represented by R above.

The alknyl group represented by R preferably has 2 to 32 carbon atoms, and the cycloalkyl group preferably has 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms, and the alknyl group may be straight or branched.

The cycloalkenyl group represented by R has 3 to 3 carbon atoms.
12, especially those of 5 to 7 are preferred.

Sulfonyl groups represented by R include alkylsulfonyl groups, arylsulfonyl groups, etc.; sulfinyl groups include alkylsulfinyl groups, arylsulfinyl groups, etc.; phosphonyl groups include alkylphosphonyl groups, alkoxyphosphonyl groups, and aryloxyphosphonyl groups. , arylphosphonyl group ring; As the acyl group, an alkylcarbonyl group, an arylcarbonyl group, etc.; As a carbamoyl group, an alkylcarbamoyl group, an arylcarbamoyl group, etc.; As a sulfamoyl group, an alkylsulfamoyl group,
Arylsulfamoyl groups, etc.; Acyloxy groups include alkylcarbonyloxy groups, arylcarbonyloxy groups, etc.; carbamoyloxy groups include alkylcarbamoyloxy groups, arylcarbamoyloxy groups, etc.; ureido groups include alkylureido groups, arylureido groups, etc. ; As the sulfamoylamino group, an alkylsulfamoylamino group, an arylsulfamoylamino group, etc.; as a heterocyclic group, a 5- to 7-membered one is preferable, and specifically, a 2-furyl group, a 2-thienyl group , 2-pyrimidinyl group, 2-benzothiazolyl group, 1-pyrrolyl group, 1-tetrazolyl group, etc.; As the heterocyclic oxy group, one having a 5- to 7-membered heterocycle is preferable, for example, 3.4.5.6- Tetrahydropyranyl-2-oxy group, 1-phenyltetrazole-5-
Oxy group, etc.; The heterocyclic thio group is preferably a 5- to 7-membered heterocyclic thio group, such as 2-pyridylthio group, 2-benzothiazolylthio group, 2,4-diphenoxy-1,3,5-triazole- 6-thio group, etc.: Siloxy group includes trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc. Imide group includes succinimide group, 3-hairtadecylsuccinimide group, phthalimide group, glutarimide group, etc. ; As a spiro compound residue, spiroE3.3]hebutane-
1-yl, etc.: As a bridged hydrocarbon compound residue, bicyclo[2゜2.1
] to 1-tan-1-yl, tricyclo[3,3,1,1'
-7] Decane-1-yl, 7,7-dimethyl-bicyclo[2,2,11-hebutan-1-yl, etc. are mentioned.

The above group may further have a substituent such as a long-chain hydrocarbon group or a diffusion-resistant group such as a polymer residue. For example, halogen atoms (chlorine atom, bromine atom, fluorine atom, etc.) and alkoxy, aryloxy, heterocyclicoxy, acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio , arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocycle bonded by N atom, alkyloxycarbonylamino, aryloxycarbonylamino, carboxyl, (R' is the same as the above R Z′ has the same meaning as Z, and Ra and Rb represent a hydrogen atom, an aryl group, an alkyl group, or a heterocyclic group.
Preferably it is a halogen atom. Among these, particularly preferred ones represented by X are hydrogen atoms and chlorine atoms.

A preferred specific example of the compound represented by the general formula [I] is represented by the following general formula [II].

The general formula [II Represents a group of nonmetallic atoms necessary to form a 6-membered nitrogen heterocycle, and the 6-membered ring may have an f substituent and may be condensed with a benzene ring in addition to the pyrazole ring. R'' and Y'' represent a hydrogen atom or a substituent, and X'' represents a hydrogen atom or a substituent that is eliminated by reaction with an oxidized product of a color developing agent. More detailed explanation of the compound represented by the general formula [II] do.

In the general formula [II, the nitrogen-containing 6-membered heterocycle formed by 2 is preferably a 6π electron system or an 8π electron system,
It contains at least one -N- and 1 to 4 nitrogen atoms, and the at least one carbonyl group contained in the 6ji ring represents a group such as >C=0 or >C=S, or , the 6-membered ring represents inclusion.

In the general formula CI], Y represents a hydrogen atom or a substituent, and the preferable substituent represented by Y is, for example, when the compound represented by the general formula CI] is reacted with an oxidized developing agent, For example, Y
The substituent represented by is a group that can be separated under alkaline conditions as described in JP-A No. 61-228444, etc., or a group that can be separated under alkaline conditions as described in JP-A No. 56-133734, etc. , a substituent that couples off by reaction with the oxidized developing agent, etc., but preferably Y
is a hydrogen atom.

-i Among the compounds represented by the formula [II, preferred specific examples include the following general formula CII-a], [■-b], [I
Examples include compounds represented by I-cl and [1l-dl.

Below is the margin general formula [! I-a3 General formula [II-bl General formula [II-cl s General formula [■-d] [Wherein, R,, R2 and R3 are synonymous with R in general formula [II, and X is general formula [ It has the same meaning as X in 11, and Y has the same meaning as Y in general formula [II. In the general formula []I-b], n represents an integer of 0 to 4,
When n is an integer from 2 to 4, R2 may be the same or different. R2 and R3 in the general numerals II-al, [ff-c] and [II-d are represented by the general formula [I
It has the same meaning as R in I, except that R2 is not a hydroxy group.

Preferred examples of R2 and Rj include polygroups such as alkyl groups, aryl groups, carboxyl groups, oxycarbonyl groups, cyano groups, alkoxy groups, aryloxy groups, amino groups, amide groups, and sulfonamide groups, and hydrogen atoms; Such as halogen atoms.

Next, typical examples of compounds represented by the general formula [II are shown below, but the present invention is not limited thereto.

Next, a typical synthesis example of a compound represented by the general formula [eco] is shown below. Synthesis Example 1 [Synthesis of compound (A-13)] Compound (A-13) [Synthesis of compound restraint] 15.9 g (0.1 mol) of 5-amino-3-phenylpyrazole and 15.9f (0.1 mol) of 2-ethoxycarbonylacetimidic acid ethyl ester in 20
After heating and refluxing the 9 reaction solution in 0 ml of dehydrated ethanol for 2 hours and filtering it while hot, the R solution was cooled, and the generated precipitate was collected as P. After washing with cold ethanol, a mixed solvent of dimethylformamide and water was added. Recrystallization was performed to obtain 17.8 g (0,079 mol) of white needle-like crystals of compound a.

(Compound a) Melting point: 300°C or higher NMR spectrum and mass spectrum show that Compound a
The structure of was confirmed.

[Synthesis of compound (A-13) from compound a] Compound a
17. og (0,075 mol) in ethyl acetate 60
31.2 g (0,075 mol) of compound b in 0 ml
Add 100ml of ethyl acetate solution, and add 7.81r
of triethylamine was added thereto, and the mixture was stirred at room temperature for 2 hours, and the precipitated crystals were collected. This was washed with water and further recrystallized with acetonitrile to give white needle-like crystals of compound (A-13) 23. Or (0,038 mol) was obtained.

The compound (
The structure of A-13) was confirmed.

Synthesis Example 2 [Synthesis of compound (B-1>)] [Synthesis of compound] 16.2 g (0.1 mol) of the above compound and 34.8. (0.1 mol) of the above compound d were dissolved in 40 ml of methanol. After stirring for 2 hours at room temperature and then adding 9.8 g of sodium carbonate and then stirring for 2 hours at 50° C., the reaction solution was poured into 300 ml of water and then neutralized using hydrochloric acid, thereby The precipitated solid was recrystallized from a mixed solvent of toluene and acetonitrile to obtain 12.8° (0.03 mol) of the above compound in the form of white crystals.

[Synthesis of compound (B-1) from compound e] Next, this compound e 10. Og (0,023 mol) to 100
ml of #acid, and 35 ml of 35% hydrogen peroxide solution was slowly added dropwise to the resulting solution, followed by stirring at 50° C. for 3 hours. Add 300ml of water to this solution and
Neutralize with an aqueous sodium hydroxide solution at a temperature below ℃, extract the resulting solution with ethyl acetate, distill off the ethyl acetate from the extract, and recrystallize the formed precipitate using acetonitrile. and 8.5 g of compound (B-1) crystallized as a white powder ((1, (118
mole) obtained.

The compound (
Check the structure of 8-1).

Synthesis Example 3 [Synthesis of Compound (C-5>)] [Synthesis on Compound Coethyl-3,5-diaminopyrazole-4-carboxylic acid 17.0. (0.1 mol), P-dodecaoxyphenylsulfonyl chloride 36 .1 g (0.1 mol) and 15.2 g (0.15 mol) of triethylamine in 5
00 all of ethyl acetate and heated under reflux for 1 hour.

After cooling, the precipitated crystals were collected with P and washed with water to give 29.6 g (0
, 06 mol) of compound f was obtained.

[Synthesis of compound foot from above compound J 29.1t (0,059 mol) on compound and 14
．． 6 g (0,089 mol) of α-taloloacetoacetic acid ethyl ester was heated and refluxed in 600 ml of toluene for 6 hours to perform a dehydration reaction.

The reaction solution was concentrated under reduced pressure to obtain crude crystals, which were recrystallized with ethanol to obtain 16.1 g of white needle-like crystals, which are the legs of the compound.
Obtain (0,027 mol).

The structure of the compound foot was confirmed by NMR spectrum and mass spectrum.

[Synthesis of compound (C-5) from compound foot] Compound z15
．． 4+r (0,026 mol) was dissolved in 130 ml (100:25:5) of a mixed solvent of acetic acid, sulfuric acid, and water, and 1
The mixture was heated to reflux for an hour. After adjusting the pH to 5 with an aqueous sodium hydroxide solution, extraction was performed with ethyl acetate, the solvent was dried over magnesium sulfate, and then evaporated. The residue was recrystallized from acetonitrile to obtain 7.3 g (0,0
14 mol) was obtained.

The compound (
The structure of C-5) was confirmed.

Synthesis Example 4 [Synthesis of Compound (D-5)] Compound (D-5) [Synthesis of Compound] 45 g (0.1 mol) of the compound (used in Synthesis Example 3)
and 22 g (0.1 mol) of ω-acetophenonesulfonyl chloride were added to 1j of chloroform and further 1
Add 2t (0.12 mol) of triethylamine,
After heating and refluxing for an hour, it was cooled, and the reaction solution was washed twice with diluted hydrochloric acid, and then chloroform was distilled off under reduced pressure.
White powder crystal 30f (
0,045 mol) was obtained.

The structure of the compound was confirmed by NMR spectrum and mass spectrum.

[Synthesis on the compound from the compound 1 20 g (0.03 mol) of the compound 140-16
After heating at 0°C for 1 hour and cooling, the precipitated crystals were recrystallized with ethanol to give compound i, gray-white powder crystals 9.8
g (0,015 mol) was obtained.

Compound I by NMR spectrum and mass spectrum
The structure of was confirmed.

[Synthesis of compound (D-5') from above compound] 6.3. (0.01 mol) of compound 1 to 2.9f (Q
, 005 mol) was obtained.

The compound (
The structure of D-5) was confirmed.

Next, the compound represented by the general formula [PC-11] according to the present invention will be explained.

General formula [PC-I] 0H z+ (In the formula, R21 represents an alkyl group having 2 to 6 carbon atoms.

R22 represents a ballast group, R23 represents a hydrogen atom, a halogen atom, or an alkyl group; Zr represents a hydrogen atom or a group capable of being separated by reaction with an oxidized product of a color developing agent;
) The alkyl group represented by R21 may be linear or branched,
It includes those having substituents.

The ballast group represented by R22 is an organic group having a size and shape that imparts sufficient bulk to the coupler molecule to substantially prevent the rapple from diffusing from the layer to which the coupler is applied to other layers. .

Preferred examples of the ballast group include the following general formula: % R2 represents an alkyl group having 1 to 12 carbon atoms, Ar represents an aryl group such as a phenyl group, and this aryl group also includes those having a substituent. .

Particularly desirable R2M is a halogen atom, especially chlorine.

Groups that can be separated by reaction with the oxidized product of the color developing agent represented by Zl include halogen atoms, alkoxy groups,
Examples include an aryloxy group, an acyloxy group, a sulfonyloxy group, an acylamino group, a sulfonylamino group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, and an imide group (including those having a recombinant, respectively!), but are preferred. is a halogen atom, an aryloxy group, or an alkoxy group.

Next, specific examples of the coupler represented by the -fi formula [PC-I] will be shown, but the invention is not limited thereto.

PC-l-5 PC-l-6 PC-l-3 I PC-I-8 PC-I-9 PC-I-10 PC-I-12 PC-I-17 PC-I-18 PC-I- 13 PC-I-14 PC-I-15 PC-I-16 C@)I+3 OCkCkSOaC)I3 2H8 Specific examples of cyan couplers that can be used in the present invention, including these, are disclosed in Japanese Patent Publication No. 11572/1983, Publication No. 61-3142, Publication No. 61-9652,
Publication No. 61-9653, Publication No. 61-39045,
It is described in 61-50136, 61-99141, 61-105545, etc.

Next, the compound represented by the general formula [PC-n] according to the present invention will be explained.

General formula [PC-R1 H Margin below (In the formula, R24 represents an alkyl group or an aryl group.

R2S represents an alkyl group, cycloalkyl crystal, aryl group or heterocyclic group, R1& is a hydrogen atom, a halogen atom,
Represents an alkyl group or an alkoxy group, where R1, is R2
In the cyan coupler represented by the general formula [PC-III] , the alkyl group represented by R24 has 1 carbon number
-32 are preferable, and these may be linear or branched, and include those having substituents.

The aryl group represented by R24 is preferably a phenyl group, including those having substituents.

The alkyl group represented by R2S preferably has 1 to 32 carbon atoms, and these alkyl groups may be linear or branched, and also include those having two substituents.

The cycloalkyl group represented by R25 has 3 to 3 carbon atoms.
12 are preferred, and these cycloalkyl groups also include those having substituents.

The aryl group represented by Rzs is preferably a phenyl group, including those having a substituent.

The heterocyclic group represented by Ris is preferably a 5- to 7-membered ring, including those having a substituent, and may be fused.

[24 represents a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group, and the alkyl group and the alkoxy group include those having a substituent, but R24 is preferably a hydrogen atom.

Further, the ring formed jointly by R24 and R26 is preferably a 5- or 6-membered ring, and examples thereof include the following.

Yl has the same meaning as 21 in the general formula [PC-I].

Among the cyan couplers represented by the general formula [PC-III, particularly preferred ones are those represented by the following general formula [PC-II-AI
It is expressed as .

General formula [PC-■-A] H In the formula, Ro represents a phenyl group substituted with at least one halogen atom, and these phenyl groups also include those having substituents other than the halogen atom.

R29 has the same meaning as R24 in the general formula [PC-III].

Y2 represents a halogen atom, an aryloxy group, or an alkoxy group, including those having a substituent.

Typical specific examples of cyan couplers represented by the general formula [PC-III] are shown below.

Below margin C-n-1 C4H@C387(il H Js PC-1f-5 pc-4-6 PC-1-7 PC-II-8 C6H13 PC-ff-13 CI21(2m PC-ff-14 C+tHas PC -ff-15 PC-IF-16 F PC PC-II-10 C,tH part PC-1-17 PC-II-18 C+ aH2g PC-II-19 PC-II-20 C3H7 (11 PC- II-21 CL2H2! pc-...-22 PC-II-23 PC-II-24 C@H13 PC-If-29 PC-II-30 PC-ff-31 Below margin PC-n-25 1sH7 (1) PC -n-27 H PC-II-28 HC, HS Specific examples of the above-mentioned cyan couplers include those described in Japanese Patent Application No. 1983-21853, pages 26 to 35, and Japanese Patent Application Laid-Open No. 1983-225155. Publication No. 7, bottom left corner (capital) ~ 1
Column at the bottom right of page 0, JP-A No. 60-222853, upper left print on page 6 to Jun at the bottom right of page 8, and JP-A-59-18533
It includes the 2°5-diacylamino cyan couplers described in the lower left column on page 6 of Publication No. 5 to the lower left column on page 9, and can be synthesized according to the methods described in these specifications and publications.

The cyan coupler of the present invention is used in the red-sensitive silver halide emulsion layer, and the amount added is not particularly limited, but the total amount is 1 x 10-1 mol to 1 mol, preferably 1 x 10-2 per mol of silver halide. It ranges from 8×10-' moles to 8×10-' moles.

Further, the addition amount of the cyan coupler represented by the general formula [II] and at least one cyan coupler selected from the cyan couplers represented by the general formula [PC-II and the general formula [PC-II]] Although the ratio is not particularly limited, the molar ratio is in the range of 1:10 to 10:1, preferably 1:3 to 3:1.

In addition, when using [PC-I and [PC-n] together, [
There is no restriction on the ratio of [PC-I] and [PC-It].

In order to incorporate the cyan coupler of the present invention into the color brightening material of the present invention, known techniques used for ordinary cyan couplers can be applied.

For example, it is preferable to dissolve the coupler in a high boiling point solvent and, if necessary, in combination with a low boiling point solvent, disperse it in the form of fine particles, and add it to the silver halide emulsion according to the present invention. Hydroquinone derivatives, ultraviolet absorbers, anti-fading agents, etc. may be used in combination.

Examples of the silver halide used in the silver halide emulsion layer of the sensitive material of the present invention include silver chloride, silver bromide, silver iodide,
Any of those used in conventional silver halide photographic emulsions, such as silver chlorobromide, silver iodobromide, and silver chloroiodobromide, are included.

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

Further, the crystals of these silver halide grains may be normal crystals or twin crystals, and any ratio of [100 co-plane to [11N plane] can be used. Furthermore, even though the crystal structure of these silver halide grains is uniform from the inside to the outside,
It may have a layered structure in which the inside and outside are different. Further, these silver halides 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 grain.

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

It is preferable that soluble salts be removed from the silver halide emulsions used in the light-sensitive materials of the present invention, but those in which soluble salts have not been removed can also be used. It is also possible to use a mixture of two or more silver halide emulsions prepared separately.

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

The above-mentioned high chloride silver halide grains 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 the high chloride silver halide grains may be uniform from the inside to the outside of the grain, or the composition between the inside and outside of the grain may be different. If the composition inside and outside of the particle is different, the composition may change continuously,
It may be discontinuous.

There is no particular restriction on the grain size of the high chloride silver halide grains, but in consideration of rapid processing properties, sensitivity, and other photographic performance, 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 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'' (by Mies and James, 3rd edition, published by Macmillan, 1966), 2nd edition.
There is a method described in Chapter).

This particle size can be measured using either the projected area of the particle or an approximation to its diameter.6 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 may be obtained by either the neutral method or the ammonia method, and the particles may be grown all at once, or may be grown after forming seed particles. They may be the same or different.

Further, the method of reacting the soluble silver salt and the soluble halogen salt may be any method such as a forward mixing method, a back mixing method, a simultaneous mixing method, or a combination thereof, but those obtained by a simultaneous mixing method are preferable. Furthermore, as a type of simultaneous mixing method, p is described in Japanese Patent Application Laid-Open No. 54-48521, etc.
It is also possible to use a single controlled double jet method.

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

The silver halide grains used in the present invention may have any shape. One preferable example is (100)
It is a cube with planes as crystal surfaces.

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 interior of the particles and/or on the surface of the particles by using iron salts or lead salts, and reduction sensitization can be achieved within the particles and/or on the surface of the particles by placing them in an appropriate reducing atmosphere. Can give a nucleus.

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 has finished, or may contain unnecessary salts. However, if the salts are removed, please refer to Research, Disclosure 17643.
It can be carried out based on the method described in No.

The silver halide grains used in the emulsion of the present invention are preferably grains on which a latent image is mainly formed, but
It may also be a particle in which a latent image is formed inside the particle.

In the present invention, chalcogen sensitizers can be used.

The chalcogen sensitizer is a general term for sulfur sensitizers, selenium sensitizers, and tellurium sensitizers, and sulfur sensitizers and selenium sensitizers are preferred.

Examples of the sulfur sensitizer include thiosulfate, allylthiocarbazide, thiourea, allyl isothiocyanate, cystine, ρ-toluenethiosulfonate, and rhodanine. Others, U.S. Patent No. 1.574,944, U.S. Patent No. 2
．． No. 410.889, No. 2,278,947, No. 2,
No. 728,668, No. 3,501,313, No. 3.6
No. 58.955, West German Publication (OLS) 1,
No. 422,869, JP-A-56-24937, JP-A No. 55
Sulfur sensitizers described in JP-A-45016 and the like can also be used.

The amount of sulfur sensitizer added varies over a considerable range depending on various conditions such as 1) H1 temperature and the size of silver halide grains, but as a guideline, it is 1/1 mole of halide.
The amount is preferably about 0-7 mol to 10-1 mol.

The emulsion of the present invention can be produced by a reduction sensitization method using a reducing substance, a noble metal sensitization method using a noble metal compound, or the like.

By including the high chloride silver halide emulsion layer in the photographic constituent layer containing the cyan coupler of the present invention,
Faithful color reproducibility and sufficient maximum density can be obtained.

The silver halide emulsion used in the present invention can be optically sensitized to a desired wavelength range using a dye known as a sensitizing dye in the photographic industry.

As the binder (or protective colloid) used in the silver halide photographic material of the present invention, gelatin is advantageously used, but gelatin derivatives, graft polymers of gelatin and other polymers, proteins, sugars, etc. Hydrophilic colloids such as derivatives, cellulose derivatives, synthetic hydrophilic polymeric substances such as single or copolymers can also be used.

The silver halide photographic light-sensitive material of the present invention having the above structure can be, for example, a color negative film, a positive film, or a color photographic paper, but especially when a color photographic paper intended for direct viewing is used. The effects of the present invention are effectively exhibited.

When the silver halide color photographic 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 magenta couplers and yellow couplers, and known ones can be used.

As the magenta coupler, 5-pyrazolone type, pyrazolobenzimidazole type, pyrazoloazole type, open chain acylacetonitrile type coupler etc.
-Pyrazolone and pyrazolotriazole magenta couplers are preferred.

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

The silver halide photographic material of the present invention further includes a hardening agent, an anti-irradiation agent, an anti-color clouding agent, an image stabilizer, a plasticizer, a latex, a surfactant, a matting agent, a lubricant, a band'! Additives such as No. 4 inhibitors can be used as necessary.

An image can be formed on the silver halide photographic material of the present invention by subjecting it to color development treatment known in the art.

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

The color development temperature is usually 15°C or higher, numerically -20°C.
It is in the range of °C to 50 °C. For rapid development, it is preferable to carry out the process at 30°C or higher, and in conventional processing, it takes 3 to 4 minutes.
However, the color development time of the present invention for the purpose of rapid processing is generally preferably carried out in the range of 20 seconds to 60 seconds, more preferably in the range of 30 seconds to 50 seconds.

The silver halide photographic light-sensitive material of the present invention can be rapidly developed without decreasing the maximum density of the characteristic curve even when a color developing solution containing benzyl alcohol used for rapid development is 2 ml or less per IIl. .

After color development, bleaching and fixing are performed.

Note that the bleaching treatment may be performed simultaneously with the 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. ! ! You 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 mt.

Layer 1...1.2g/I gelatin, 0.32g
/rr? Blue-sensitive silver halide emulsion (silver chloride content: 97 mol%), 0.50 g/
0.80 g dissolved in dioctyl phthalate of rrl/
A layer containing a yellow coupler (YA) of rrr.

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

Layer 3: 1.25 g/rrr of gelatin, 0.
A layer containing 22 g/rrr of green-sensitive silver halide emulsion (silver chloride content 100 mol%), 0.62 g/rd magenta coupler (M-A) dissolved in 0.30 g/rrr dioctyl phthalate.

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

Layer 5...--1,40g/rr? gelatin, 0.
20 g/r# red-sensitive silver halide emulsion (silver chloride content 100 mol%), 0.20 g/rrr trin-
0.45g/rr dissolved in octyl phosphate? (9,1xlO-'mol/rr?)
A layer containing a cyan coupler (A-13).

Layer 6: Intermediate layer consisting of 1.2 g/d gelatin.

Layer 7: Layer containing 0.5 g/m of gelatin.

In addition, as a hardening agent, 2,4-dichloro-6-hydroxy-5-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.

This was designated as sample 1.

Next, Samples 2 to 18 were prepared in the same manner as Sample 1 except that the cyan coupler shown in Table 1 was used instead of the cyan coupler (A-13) for layer 5 (addition of two types of cyan couplers). The amounts were 4.55 x 10-' moles/rrl each, for a total of 9. I x 10-' moles/co).

-A -A l-1 C# I-2 Margin below The above photosensitive material samples NQ1 to NQ18 were exposed to light through a light wedge in a conventional manner and then processed in the following steps.

Processing process> Temperature Time color development 34.7±0.3℃ 45 seconds bleach-fixing 34.7±0.5℃ 50 seconds stabilization 30-34℃ drying for 90 seconds
Color developer for 60 seconds at 60-80°C Pure water 800mj Triethanolamine 8gN, N
-diethylhydroxyamine 5g potassium chloride 2gN-ethyl-N-β
-Methanesulfonamidoethyl-3-methyl-4- Aminoaniline sulfate 5g Sodium tetrapolyphosphate 2g Potassium carbonate 30g Potassium sulfite
0.2g optical brightener (4,4'
-diaminostilbendisulfonic acid derivative) 1g Add pure water to bring the total amount to 11, and adjust the pH to 10.2.

Bleach-fix solution> Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60g Ethylenediaminetetraacetic acid M 3g Ammonium thiosulfate (70% solution) 100＠j Ammonium sulfite (40% solution) 27.5ajj Potassium carbonate or glacial acetic acid to pH 5.7 and add water to make a total volume of 1j.

Stabilizing liquid> 5-chloro-2-methyl-4-isothiazolin-3-one 1g 1-hydroxyethylidene-1゜1-diphosphonic acid 2g Add water to make 1j, KFi solution with potassium hydroxide I)H
FIJll to 7.0.

After the treatment, the concentration of each sample was measured using a densitometer (Konica Corporation KO-7 model), and the treated sample was placed in a high temperature and high humidity (60°C, 80% RH) atmosphere. The dye image was left to stand for 14 days, and the heat resistance and moisture resistance of the dye image were examined.

In addition, after each sample was irradiated for 10 days with a xenon fade meter, the density was measured to examine light resistance.

The results are shown in Table 1. However, the heat resistance, humidity resistance, and light resistance of the dye image are expressed as the percentage of dye remaining after the heat resistance, humidity resistance, and light resistance tests with respect to the initial density of 1.0.

Margin Table 1 Below: As is clear from Table 1, Comparative Samples 1 and 2 using couplers A-13 and B-1 individually have fairly good heat resistance and moisture resistance, but have poor light resistance. Inferior.

Comparative sample 3 using PC-I-4 alone has good light resistance, but poor heat resistance and moisture resistance.
Comparative sample 4 using -II-2 alone has good light resistance, but is slightly inferior in heat resistance and moisture resistance.

However, Samples 5 to 18 of the present invention, in which specific couplers were used in combination, were found to be excellent in both heat resistance, moisture resistance, and light resistance, and to be robust.

Example 2 Coupler A-132xlO-' moles of dioctyl phthalate 3.0. After heating a mixed solution consisting of 3.0 t of ethyl acetate to 60°C, this was mixed with alkanol B (
Alkylnaphthalene sulfonate (manufactured by DuPont) 5
1.7 ml of 5% aqueous gelatin solution containing 1.7 ml of % aqueous solution
were mixed and emulsified and dispersed using an ultrasonic dispersion machine to prepare a dispersion liquid.

Ethyl acetate was distilled off under reduced pressure from these dispersions to obtain Dispersion Sample 1.

In order to observe the dispersion stability of the cyan coupler, the dispersion was stored in a refrigerator (5°C) for 10 days, then kept warm in a 40°C hot water bath, and the state of crystal precipitation was observed with an optical microscope immediately after incubation. , 10 hours later, and 20 hours later.

Furthermore, using the couplers shown in Table 2, dispersion sample 2
~10 were prepared and the dispersion stability of the couplers was investigated.

The results are shown in Table-2.

Margin below Table-2 ; The evaluation of precipitation properties in the table is as follows.

0: No precipitation △D Some precipitation occurs, but there are few problems in use.

x: Precipitation occurs and there is a problem in use.

As is clear from Table 2, the dispersion samples 5 to 10 of the present invention, in which specific couplers were used in combination, were less likely to cause precipitation and were therefore extremely dispersed, compared to comparative dispersion samples 1.2 in which a coupler was used alone. It was found that the dispersion liquid had good stability.

[Effects of the Invention] The silver halide color photographic light-sensitive material of the present invention has the effects that the obtained dye image has excellent color reproducibility and storage stability, and the cyan coupler dispersion has excellent storage stability. .

Sender: Konica Corporation

Claims (1)

[Scope of Claims] A silver halide photographic light-sensitive material having at least one blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer on a support, wherein the red-sensitive halogen The following general formula [ I
] and the following general formula [PC-
I ] and the cyan coupler represented by the following general formula [PC-
A silver halide photographic material comprising at least one cyan coupler selected from among the cyan couplers represented by II]. General formula [I] ▲Mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R and Y represent hydrogen atoms or substituents,
X represents a hydrogen atom or a substituent that leaves by reaction with an oxidized product of a color developing agent, and Z represents a nitrogen-containing 6-membered heterocyclic ring that is condensed with the pyrazole ring together with ▲Numerical formula, chemical formula, table, etc. The six-membered ring may have a substituent and may be condensed with a benzene ring in addition to the pyrazole ring. ) General formula [PC-I] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ (In the formula, R_2_1 represents an alkyl group having 2 to 6 carbon atoms. R_2_2 represents a ballast group. R_2_3 represents a hydrogen atom, a halogen atom, or Z_1, which represents an alkyl group, represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of a color developing agent.) General formula [PC-II] ▲There are numerical formulas, chemical formulas, tables, etc.▼ (In the formula, R_2_4 represents an alkyl group or an aryl group.R_2_5 represents an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group.R_2_6 represents a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group;
_2_6 may cooperate with R_2_4 to form a ring. Y_1 represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of a color developing agent. )