JPH02135442A - Silver halide color photographic sensitive material having improved color reproducibility - Google Patents

Abstract

PURPOSE:To obtain a silver halide color photographic sensitive material having a sharp spectral absorption and improved color reproducibility by incorporating a cyan coupler having a specified compsn. and an org. solvent having a high b.p. into a red sensitive silver halide emulsion layer. CONSTITUTION:Each at least one cyan coupler expressed by the general formula [I] and an org. solvent having high b.p. expressed by the general formula [II] are contained in a red sensitive silver halide emulsion layer. Thus, a photosensitive material having superior color reproducibility, providing a cyan dye picture having a sharp spectral absorption and scarce auxiliary absorption is obtd. In the general formula [I], X is an H atom or a substituent eliminable by a reaction with an oxidized body of a color developing agent. Z is a group of nonmetal atoms necessary for forming an N-contg. 6-membered heterocyclic ring by condensing with a pyrazole ring. In the general formula [II], each R1-R3 is an alkyl group, cycloalkyl group, or an aryl group.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a silver halide photographic material which has excellent color reproducibility and image storage stability and which can provide a high maximum density.

[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 vapors, 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.
67.531, 2.3f39.929 and 2.423.730, the dye images obtained from the 2-acylaminophenolic cyan couplers generally have poor heat fastness and are Patent No. 2.772.1
Dye images obtained from the 2,5-diacylaminophenol cyan coupler described in No. 62 generally have poor light fastness, and dye images obtained from the 1-hydroxy-2-natutamido cyan coupler are generally sensitive to light and heat. It is insufficient in terms of both robustness.

Also, US Pat.
2,5-diacylaminophenol cyan coupler described in Japanese Patent Publication No. 3,880,66, etc.
Regarding the 2,5-diacylaminophenol cyan coupler described in Specification No. 1, which has a hydroxyl group in the ballast part, in order to preserve the dye image for a long time, the fastness to light and heat and the occurrence of yellow stain must be considered. However, a satisfactory level has not yet been achieved.

[Object of the Invention] The present invention has been made in view of the above-mentioned circumstances, and the first object of the present invention is to provide a cyan dye image with sharp spectral absorption, little side absorption, and excellent color reproducibility. An object of the present invention is to provide a silver halide color photographic material.

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

A third object of the present invention is to provide a silver halide color photographic light-sensitive material that has high color density and can provide a sufficient maximum density.

[Structure of the Invention] The above-mentioned object of the present invention is to provide a silver halide color photographic photosensitive material having a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support. In the material, the red-sensitive halogenated emulsion layer contains at least one cyan coupler represented by the following general formula [I] and at least one high-boiling point organic solvent represented by the following general formula [ff]. This can be achieved using silver halide color photographic materials.

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 nonmetal necessary to form a nitrogen-containing 6-membered heterocycle by condensing with -N- with the pyrazole ring. Represents an atomic group, the 6-membered ring may have a substituent, and may be condensed with a benzene ring in addition to the pyrazole ring.] - Formula [n] R・-〇＼ R2-OP =0°, -8/ [In the formula, R1, R2 and R3 represent an alkyl group, a cycloalkyl group or an aryl group] [Specific constitution of the invention] Contained in the red-sensitive silver halide emulsion layer according to the present invention The cyan coupler represented by the general formula [11] will be explained.

The cyan coupler of the present invention is fused with a pyrazole ring,
It has a structure in which a 6-membered hetero ring is formed, and the substituent represented by R is not particularly limited, but typically includes alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, and cyclo. Examples include multiple groups such as alkyl, but also include halogen atoms and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, sulfonyloxy, aryloxy, heterocycleoxy, Shiroxy,
Acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, thioureido, carboxyl, hydroxy, mercapto, nitro, sulfone Also included are polygroups such as acids, spiro compound residues, bridged hydrocarbon compound residues, and the like.

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 alkenyl 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 alkenyl group may be linear 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, etc.; Acyl group includes alkylcarbonyl group, arylcarbonyl group, etc.; carbamoyl group includes alkylcarbamoyl group, arylcarbamoyl group, etc.; sulfamoyl group includes 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 ring; The heterocyclic oxy group preferably has a 5- to 7-membered heterocycle, for example, 3.4.5.6- Tetrahydropyranyl-2-oxy group, 1-phenylnatrazole-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- 6-1000 group, etc.; Siloxy group includes trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc.; imide group includes succinimide group, 3-1-tadecylsuccinimide group, phthalimide group, glutarimide group, etc. ; As a spiro compound residue, 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'
・? ] Decane-1-yl, 7,7-dimethyl-bicyclo[2,2,1]hebutan-1-yl, and the like.

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.

Groups that can be separated by reaction with the oxidized product of the color developing agent represented by X include, for example, halogen atoms (chlorine atom, bromine atom, fluorine atom, etc.), alkoxy, aryloxy, heterocyclic oxy, acyloxy, sulfonyloxy, alkoxy Carbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocycle bonded via N atom, alkyloxycarbonylamino , aryloxycarboniamino, carboxyl, (R' has the same meaning as R, 2' has the same meaning as 2, and Ra and Rb represent a hydrogen atom, an aryl group, an alkyl group, or a heterocyclic group) There are many groups such as,
Preferably it is a halogen atom. Among these, particularly preferred ones represented by X are hydrogen atoms and chlorine atoms.

- Preferred specific examples of the compound represented by the formula [I] are shown by the following formula [■].

- Formula [II] Y# [wherein Z'' is fused with the pyrazole ring to form a nitrogen-containing compound containing at least one -N- and at least one carbonyl group or at least one sulfonyl group. Represents a group of nonmetallic atoms necessary to form a 6-membered hetero ring, and the 6-membered ring may have a substituent and may be fused with a benzene ring in addition to the pyrazole ring. and Y″ represents 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.] The compound represented by the general formula [I] will be explained in more detail. .

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

In the general formula [I], Y represents a hydrogen atom or a substituent, and preferred examples of the substituent represented by Y include those that are eliminated from the compound of the present invention after the compound reacts with the oxidized developing agent. However, for example, the substituent represented by Y may be 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. As described,
Examples include substituents that are coupled off by reaction with the oxidized developing agent, and preferably Y is a hydrogen atom.

- Among the compounds represented by the formula [II, preferred specific examples include the following formulas [II-al, [■-b], [n
-C] and [II-d].

In the following margins General formula [1-al General formula [II-bl General formula [II-C] General formula [II-d] [In the formula, FLl, R2 and Rs are synonymous with R in the general formula [II, is the same as X in the general formula [II, and Y is the same as Y in the general formula [II]. −
In the mathematical formula [n-bl, n represents an integer from 0 to 4,
When n is an integer from 2 to 4, multiple R'a may be the same or different,] general number total 1r-al, [II-cl
and R2 and R3 in [II-d] are represented by the general formula [
It has the same meaning as R in II, except that R2 is not a hydroxy group.

Preferred examples of R2 and R3 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 compound examples of the present invention are shown below, but the present invention is not limited thereto.

Below are the margins.Next, typical synthesis examples of the compounds of the present invention are shown below. Synthesis Example 1 [Synthesis of Compound (A-13)] I [Synthesis of Compound A] 15.9. (0.1 mol) of 5-amino-3-phenylpyrazole and 15.9 g (0.1 mol) of 2-ethoxycarbonylacetimidic acid ethyl ester in 20
After heating and refluxing the 0 reaction solution in 0 ml of dehydrated ethanol for 2 hours, the lachrymal fluid was cooled and the resulting precipitate was collected, washed with cold ethanol, and then mixed with dimethylformamide and water. Recrystallization from a solvent yielded 17.8 g (0,079 mol) of white needle-like crystals representing the compound.

(Compound observation) Melting point: 300°C or higher The structure of the compound was confirmed by NMFL spectrum and mass spectrum.

[Synthesis of compound (A-13) from compound viewpoint] Compound a1
7.0 g (0,075 mol) of ethyl acetate solution 600
ml was added with 100 ml of an ethyl acetate solution containing 31.2 t (0,075 mol) of the compound, and further added with 1.8 g of triethylamine. 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 obtain 23.0 g (0,038 mol) of white needle-like crystals of compound (A-13).

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 c and 34.8 t (0.1 mol) of the above compound were dissolved in 40 ml of methanol. After stirring at room temperature for 2 hours, 9.8 g
of sodium carbonate and stirred at 50°C for 2 hours. The reaction solution of 9 was poured into 300 ml of water and then neutralized using hydrochloric acid. The solid thus precipitated was recrystallized from a mixed solvent of toluene and acetonitrile. In this way, 12.8 g <0.03 mol) of the above compound e in the form of white crystals was obtained.

[Synthesis of compound (B-1) from the viewpoint of compounds] Next, this compound e 10. Og (0,023 mol) to 100
After slowly adding 35ml of 35% hydrogen peroxide solution to the resulting solution, 35ml of 35% hydrogen peroxide solution was dissolved at 50℃.
Stir for hours. Add 300ml of water to this solution and
Neutralize with an aqueous sodium hydroxide solution at the following temperature,
After extracting the solution obtained thereby with ethyl acetate,
Ethyl acetate was distilled off from the extract, and the resulting precipitate was recrystallized using acetonitrile, yielding 8-5 g (0,018 mol) of gold compound (B-1) crystallized as a white powder. .

The compound (
The structure of B-1) was confirmed.

Synthesis Example 3 [Synthesis of Compound (C-5)] Compound (C-5) [Synthesis of Compound 3 Ethyl-3,5-diaminopyrazole-4-carboxylic acid 17.0 g (0.1 mol), p- 36.1 tr (0.1 mol) of dodecaoxyphenylsulfonyl chloride and 15.2 g (0.15 mol) of triethylamine were
Add to 00ml of ethyl acetate and heat under reflux for 1 hour.

After cooling, the precipitated crystals were collected and washed with water to give 29.6 g (0.
, 06 moles).

[Synthesis of compound leg from compound crab 29.1 g (0,059 mol) of compound crab and 14
．． 6 g (0,089 mol) of α-chloroacetoacetic acid ethyl ester was heated in 600a+I toluene for 6 hours.
The mixture was refluxed to perform a hydrophilic 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.
(0,027-1 nyl) was obtained.

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

[Synthesis of compound (C-5) from compound foot] Compound! 15
．． 4 g (0,026 mol) was dissolved in 130 ml (100:25:5) of a mixed solvent of acetic acid, sulfuric acid, and water, and heated under reflux for 1 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 give white needle-like crystals of compound (C-5) 7゜3t (0,01
4 mol) was obtained.

The compound (
Check the structure of C-5).

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 1 J of chloroform and further 1
2 g (0.12 mol) of triethylamine was added, heated and refluxed for 5 hours, then cooled, the reaction solution was washed twice with diluted hydrochloric acid, chloroform was distilled off under reduced pressure, and the compound was recrystallized twice from methanol. 30g of white powder crystals (0
,045 mol) was obtained.

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

[Synthesis on compound from compound] 2G, (0.03 mol) of compound 140-16
After heating at 0°C for 11 hours, it was cooled, and the precipitated crystals were recrystallized with ethanol to obtain off-white powder crystals of the compound 9.
8 g (0,015 mol) were obtained.

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

[Synthesis of compound (D-5) from above the compound] Compound (D-5) was synthesized from 6°3 g (0°01 mol) of the compound in exactly the same manner as the method for obtaining compound (C-5) from the compound in Synthesis Example 3. -5) white powder crystals 2.9g (0,00
5 mol) was obtained.

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

The cyan couplers of the invention are usually used per mole of silver halide to 1x10-' mole, preferably 1x10-' mole.
It can be used in the range of 2 mol - 8 x 10 -' mol.

The coupler of the present invention can also be used in combination with other types of cyan couplers.

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

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 the coupler in the form of fine particles, and add it to the silver halide emulsion according to the present invention.

At this time, if necessary, a hydroquinone derivative, an ultraviolet absorber, an anti-fading agent, etc. may be used in combination.

Next, the high boiling point organic solvent represented by formula [II] will be explained.

In the general formula [1[], Rr, R2 and R1 each represent an alkyl group, a cycloalkyl group or an aryl group.

Such an alkyl group is preferably a straight chain or branched alkyl group having 1 to 32 carbon atoms, and these alkyl groups also include those having a substituent. Butyl group, hexyl group, octyl group, dodecyl group, octadecyl group, etc. can be mentioned. Among such alkyl groups, those having 4 to 18 carbon atoms are particularly preferred, and those having 6 to 12 carbon atoms are particularly preferred.

Examples of the cycloalkyl group include a cyclopentyl group,
Examples include cyclohexyl group and cycloheptyl group.

These cycloalkyl groups include those having substituents, and among these cycloalkyl groups, a particularly preferred one is a cyclohexyl group.

Examples of the aryl group include phenyl group, naphthyl group, etc., including those having substituents. Specific examples of such aryl group include phenyl group, P-cresyl group, m-cresyl group, O- Cresyl group, P-chlorophenyl group, pt-butyluphenyl group, etc. can be mentioned.

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

The high boiling point organic solvent of the present invention can be used, for example, in Japanese Patent Publication No. 48-327
No. 27, JP-A-53-13923, JP-A No. 54-1192
No. 35, No. 54-119921, No. 59-11992
No. 2, No. 55-25057, No. 55-36869,
It includes phosphoric acid ester compounds described in various publications such as No. 56-81836, and can be synthesized by the methods described in these publications.

The high boiling point organic solvent of the present invention is used when a hydrophobic compound such as a cyan coupler represented by formula [I] is contained in the red-sensitive silver halide emulsion layer of the silver halide photographic light-sensitive material of the present invention. It is used as a solvent for dissolving or dispersing such hydrophobic compounds.

The amount of the high boiling point organic solvent used in the present invention is not particularly limited, but it is preferably used within the range of IOQ to 50 hours per 100 g of the cyan coupler represented by formula [I].

When dissolving or dispersing the cyan coupler represented by formula [I] in the high boiling point organic solvent of the present invention, the high boiling point organic solvent of the present invention may be used alone, or the high boiling point organic solvent of the present invention may be used alone. A solvent may be used in combination, and if necessary, a low boiling point organic solvent, a water-soluble organic solvent, an organic solvent-soluble polymer, etc. may be used in combination.

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

Other high-boiling organic solvents used in combination with the high-boiling organic solvent of the present invention include phenol derivatives that do not react with oxidized developing agents, phthalates, citric esters, benzoic esters, alkylamides, fatty acid esters, and trimesine. Organic solvents having a boiling point of 150° C. or higher, such as acid esters, are preferred.

Examples of the low-boiling organic solvent used in combination with the high-boiling organic solvent of the present invention include ethyl acetate, cyclohexanol, and methyl ethyl ketone.

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. As the magenta coupler and the yellow coupler at this time, there are no particular restrictions and known ones can be used.

As the magenta coupler, for example, a 5-pyrazolone coupler, a vilalopenzimidazole coupler, or an open-chain acylacetonitrile coupler can be used.

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

The silver halide color photographic light-sensitive material of the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation.

The silver halide color photographic material of the present invention may contain various other photographic additives, such as antifoggants, development accelerators, development retardants, bleaching accelerators, stabilizers, and ultraviolet absorbers. , a color stain inhibitor, a fluorescent whitening agent, a color image fading inhibitor, an antistatic agent, a hardening agent, a surfactant, a plasticizer, a wetting agent, etc. can be used. (Refer to Research Disclosure No. 17643.) Furthermore, by coupling with competing couplers and oxidized forms of developing agents, development accelerators, bleach accelerators, developing agents, silver halide solvents, toning agents, hardeners, fogging agents, etc. Compounds that release photographically useful fragments such as agents, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers can be used.

The support for the silver halide color photographic light-sensitive material of the present invention is
Examples include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plates, polyester films such as cellulose acetate, cellulose nitrate, and polyethylene terephthalate, polyamide films, polycarbonate films, and polystyrene films. In the case of transparent supports, reflective layers are used. May be used together.

These supports are appropriately selected depending on the intended use of the photosensitive material.

Various coating methods such as dipping coating, air doctor coating, curtain coating, and hopper coating can be used to coat the emulsion layer and other constituent layers used in the present invention. Also, U.S. Patent No. 2.781,791;
It is also possible to use a simultaneous coating method of two or more layers by the method described in No. 941,898.

In the present invention, the coating position of each emulsion layer can be arbitrarily determined. It is preferable to do so.

In the photosensitive material of the present invention, it is optional to provide an intermediate layer with an appropriate thickness depending on the purpose, and a filter layer,
Various layers such as an anti-curl layer, a protective layer, and an antihalation layer can be used in appropriate combinations as constituent layers. Hydrophilic colloids can be used as binders in these constituent layers, and gelatin is preferably used. In addition, the various photographic additives mentioned in the explanation of the emulsion layer can be contained in the layer.

There are no particular restrictions on the method of processing photographic materials using the silver halide emulsion of the present invention, and all commonly known processing methods can be applied. A method in which a fixing treatment is carried out, followed by further washing with water and/or a stabilizing treatment if necessary, or a method in which bleaching and fixing are carried out separately after color development, followed by further washing with water and/or a stabilizing treatment if necessary. The silver halide color photographic light-sensitive material of the present invention may be processed by various methods, such as color development, bleach-fixing, and water washing (or stabilization).
Suitable for rapid processing.

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

Example 1 On a polyethylene-laminated paper support (titanium oxide content: 2.7 g/d), the following layers were sequentially coated from the support side to prepare a silver halide color photographic light-sensitive material (Titanium oxide content: 2.7 g/d).
7) was produced.

Layer 1...1.2g/rrf gelatin, 0.3
2 g/rrf (in terms of !N, the same applies hereinafter) blue-sensitive silver chlorobromide emulsion (silver chloride content 20 mol%), 0.50 g
0.80 g dissolved in /d dioctyl phthalate
Layer containing yellow coupler (Y-1') of lcd.

Layer 2: Intermediate layer consisting of 0.7 g/d gelatin.

Layer 3---1.25 g/trr gelatin, 0.22 g/r+f green sensitive silver chlorobromide emulsion (silver chloride content 50 mol%) dissolved in 0.30 g/rrf dioctyl phthalate. Layer containing 0.62 g/rrr magenta coupler (M-1>).

Layer 4: Intermediate layer consisting of 1.2g1rd gelatin.

Layer 5...1.40g/rrl' gelatin, 0
．． 20 g/r& red-sensitive silver chlorobromide emulsion (silver chloride content 5
0 mol%) Table dissolved in the high boiling point organic solvent shown in Table 1-
A layer containing the cyan coupler shown in 1.

Layer 6: A layer consisting of gelatin of 1.1 g/rrf.

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.

Margins below (Y-1) (M-1) (CC-1) Each of the above photosensitive material samples Nos. 1 to 17 was passed through an optical wedge and processed in a post-exposure process.

Processing steps (38°C) Color development 3 minutes 30 seconds Bleach-fixing 1 minute 30 seconds Washing with water 1 minute Drying @eo~80°C 2 minutes The composition of each processing solution is as follows.

Color developer> Pure water 80
0ml benzyl alcohol 15m
IIvl & acidified droxyamine 2.0
g Potassium bromide 1.0 g Sodium chloride 1.0 g Potassium sulfite 2.0 g Triethanolamine 2.0 g Toethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 4.581-Hydroxyethylidene- 1,1-diphosphonic acid (60% aqueous solution)
1.5m I! potassium carbonate
32g Whitex 8B (50% aqueous solution) 2ml (fluorescent whitening, manufactured by Sumitomo Chemical Co., Ltd.) Add pure water to make 11 and 20% potassium hydroxide or 10%
Adjust pH to 10.1 with dilute sulfuric acid.

Bleach-fix solution> Pure water 55
0m I! Iron III ethylenediaminetetratrisoxide) Ammonium 65g Ammonium thiosulfate 85g Sodium bisulfite 10g Sodium metabisulfite
2g ethylenediaminetetraacetic acid-disodium 20g sodium bromide 1
Add 0g of pure water to make the solution 11, and adjust the pH to 7.0 with aqueous ammonia or dilute sulfuric acid.

Maximum density and λ1 of dye image obtained through development processing
IaX and Da are shown in Table 1, however, λiax is
It is the maximum wavelength (ni) of the visible absorption spectrum when the density of the cyan dye image after development is 1°0, and Do is λWaX
The R large concentration, which indicates the ratio of absorption at 550++ m when the absorption at
5 and was measured using red light. The results are shown in Table-1.

Margin Table-1 Below: As is clear from the results in Table-1, the comparative coupler CC
-1 and the comparative sample Nα1 containing the high boiling point solvent dioctyl phthalate, and the comparative samples NQ6 and 11 containing the comparative coupler CC-1 and the high boiling point solvent I-6 or I-7 of the present invention have a high maximum concentration, Although λl1aX has a sufficiently long wavelength as a cyan image, Do is high and the color reproducibility is very poor.

In addition, the comparative samples Nα2, 3.4 and 5, which contain the high boiling point solvent dioctyl phthalate compared to the couplers A-13, B-1, C-5 or D-5 of the present invention, have a maximum concentration of λ1laX is insufficient.

In contrast, couplers A-13, B-1°C-
Sample NG7.8.9. consisting of a combination of 5 or D-5 and the high boiling point solvent 1-6 or I-7 of the present invention.
It can be seen that Samples Nos. 10, 12, 13, 14, 15, 16 and 17 have high maximum density, long wavelength λlaX, low Do, and excellent color reproducibility.

After developing the above samples NQ1 to NQ17 in the same manner as above,
Light irradiation was performed for 50 hours to examine the durability of the dye image. The results obtained are shown in Table 2.The results are shown in Table 2, where the initial concentration is D.
The value of r, expressed as the dye residual rate r at the point of nin +1.0, was determined by the following formula.

r = (Concentration after 150 hours - Dln after 150 hours)
xloo [%] As is clear from the results in Margin Table 2 below, the comparative coupler and the comparative high-boiling point solvent, the coupler of the present invention and the comparative high-boiling point solvent, or the comparative coupler and the high-boiling point solvent of the present invention It can be seen that the sample of the present invention containing the coupler of the present invention and the high boiling point solvent of the present invention has a higher dye residual rate after light irradiation and is superior in the durability of the cyan dye image than the comparative samples containing the respective couplers.

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

Applicant: Konica Corporation Yoshihiro Iwama Yoshihiro - 2

Claims (1)

[Scope of Claims] A silver halide color photographic light-sensitive material having a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support. The silver halide emulsion layer contains at least one cyan coupler represented by the following general formula [I] and at least one high boiling point organic solvent represented by the following general formula [II]. Silver halide color photographic material. General formula [I] ▲There are 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 is eliminated by reaction with an oxidized product of a color developing agent. Z represents a group of nonmetallic atoms necessary to form a nitrogen-containing 6-membered hetero ring by condensing with the pyrazole ring, and the 6-membered ring has a substituent. The pyrazole ring may be fused with a benzene ring in addition to the pyrazole ring. ] General formula [II] ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ [In the formula, R_, R_2 and R_3 represent an alkyl group, a cycloalkyl group or an aryl group. ]