JPH02184848A - Silver halide photographic sensitive material having superior color reproducibility - Google Patents

Abstract

PURPOSE:To improve color reproducibility by incorporating at least one kind of specified cyan coupler into at least one of red-sensitive silver halide emulsion layers and at least one kind of specified compd. into at least one of photographic constituent layers. CONSTITUTION:At least one kind of cyan coupler represented by formula I is incorporated into at least one of red-sensitive silver halide emulsion layers and at least one kind of compd. represented by formula II and capable of releas ing a compd. which can react with the oxidized product of a developing agent to scavenge the product or a precursor thereof is incorporated into at least one of photographic constituent layers. In the formula II, Coup is a residue of a coupler capable of releasing (Time)eSc by a reaction with the oxidized product of a color developing agent, Time is a timing group capable of releasing Sc after (Time)eSc is released from Coup, Sc is a scavenger for the oxidized product of the color developing agent and l is 0 or 1. Color reproducibility is improved.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide color photographic light-sensitive material, and particularly to a color photographic light-sensitive material with excellent color reproducibility. The present invention can be suitably applied to, for example, light-sensitive materials for direct observation such as silver halide color photographic light-sensitive materials for printing.

[Background of the Invention] As is well known, in conventional silver halide color photography, a silver halide photographic light-sensitive material containing a color-forming coupler is developed using a phenylenediamine-based color developing agent or the like. As a result, the oxidized developing agent and the color-forming coupler are coupled to form a dye and a color image is obtained.

Among the processes for obtaining color images, in the current process using the subtractive color method, a negative image is obtained by photographing and recording on a photographic photosensitive material called a color negative, and then developing it using the above-mentioned color development method. , and then print it on color paper using a printer.

In color negative photosensitive materials, for example, usually 400 to
500nm, 500-800nm, Boo~
A multilayer structure is adopted in which three types of silver halide emulsion layers spectrally sensitized to each wavelength range of 700 ni contain a yellow coupler, a magenta coupler, and a cyan coupler, respectively. That is, a yellow dye is formed in the blue-exposed area, a magenta dye is formed in the green-exposed area, and a cyan dye is formed in the red-exposed area, thereby forming a so-called negative image.

After obtaining such a negative image, the color image is printed on a color paper consisting of a blue photosensitive layer also containing a yellow coupler, a green photosensitive layer containing a magenta coupler, and a red photosensitive layer containing a cyan coupler. It is common to obtain

However, the dyes used in color photography differ from the block-type dyes that are ideal in subtractive color methods, that is, those that absorb light only in a specific wavelength range, and have considerable asymmetric absorption in other regions of the spectrum. Therefore, since some of the light that is not desired to be absorbed is absorbed, sufficient color reproduction cannot be achieved as it is. For this reason, for example, in color negative films, masking using colored couplers is performed to correct this asymmetric absorption, thereby achieving good color reproducibility.

In addition, negative spectral sensitivity correction is performed based on the principle of the three primary colors of the subtractive color method and the characteristics of the human eye, and interimage effects are used to emphasize pure colors.

In this way, various color correction means are used in color negative photosensitive materials, but when the original signals recorded after various corrections as described above are printed on color vapor, conventional color paper itself has a color difference. Since there is no correction function at all, the problem remains that the color reproducibility of the entire system ends up deteriorating here.

Direct positive photosensitive materials used in color copiers and other fields are also photosensitive materials for direct observation by the user, so colored couplers used in color negative photosensitive materials, etc. Since masking techniques such as those described above cannot be used, it cannot be said that it has sufficient color reproducibility, and improvements are desired.

Furthermore, these light-sensitive materials for direct observation use materials that substantially contain silver chloride, silver chlorobromide, etc. as silver halide components, so DIR, which is conventionally used in color negative films to improve image quality, is used. Couplers are difficult to use because they slow down the development speed of the light-sensitive material or are not very effective when the development speed is rapid.

The reality is that there is no effective masking means for light-sensitive materials that substantially contain silver chloride and the like.

[Object of the Invention] An object of the present invention is to improve the above-mentioned drawbacks and provide a silver halide photographic material with excellent color reproducibility.

[Structure of the Invention] The above-mentioned object of the present invention is to provide a silver halide color photographic light-sensitive material having at least one red-sensitive silver halide emulsion layer on a support. contains at least one cyan coupler represented by the following general formula [I], and further contains at least one cyan coupler represented by the following general formula [DS-1] in at least one of the photographic constituent layers.
] A halogenated compound containing at least one of the following: a compound capable of reacting with the oxidation product of a developing agent to scavenge the oxide, or a compound capable of releasing its precursor (hereinafter referred to as "rDSR compound") This was achieved using silver 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 is eliminated by reaction with an oxidized product of a color developing agent. 2 represents a nonmetallic atom group necessary to form a nitrogen-containing 6-membered hetero ring by condensation with the pyrazole ring together with -N-, and the 6-membered ring may have a substituent; In addition to the ring, it may be fused with a benzene ring. ] General formula [DS-I] Coup-→T im e +F-S c [In the above general formula [DS-11, Coup represents (T f m e + f-5c) by reaction with an oxidized color developing agent. represents a releasable coupler residue, Time represents a timing group that can release Sc after TLme-8c is released from Coup, and Sc is a color-forming group after TLme-8c is released from Coup or Time-3c. represents a scavenger of an oxidized color developing agent that can scavenge an oxidized developing agent by a redox reaction or a coupling reaction, and I represents 0 or 1.] The photographic material of the present invention has an interimage effect brought about by the above DSR compound. As a result, it is possible to achieve excellent color reproducibility, for example, in a negative-positive system using a subtractive color method, and it can also be applied to direct positive photosensitive materials for color copying to obtain excellent color reproducibility. can.

In the present invention, the DSR compound is a compound that is contained in any photographic constituent layer, preferably any emulsion layer, and thereby undergoes a coupling reaction with an oxidized developing agent in an imagewise manner during development, or a compound that is oxidized. It has the function of suppressing pigment formation in the white layer by releasing a compound that undergoes an oxidation-reduction reaction with the developing agent and reacting with the oxidized developing agent produced as a result of development in the white layer. This lowers the gamma of the white layer, and the compound that scavenges the oxidized developing agent not only has these effects in the white layer, but also diffuses to other layers and has the effect of suppressing color reactions in other layers. .

Due to this effect, for example, when a DSR compound is added to the magenta layer, when magenta develops, the development of the cyan dye can be suppressed in proportion to the magenta dye concentration in the magenta layer. It is thought that it suppresses the absorption of, for example, red light in areas other than the edge area, and performs a masking effect. Among these, it is preferable to contain a DSR compound in the magenta layer and apply an interimage effect from the magenta layer to other layers for color reproduction in the red to violet range, and is particularly effective in forming highly pure red.

It is also preferable to include a DSR compound in the cyan layer. For example, applying interimage from the cyan layer to the magenta layer in the same way is particularly effective in reproducing blue colors. Similarly, by increasing the degree of diffusion of the compound that scavenges the released oxidized developing agent,
It is also possible to interimage from the cyan layer to the yellow layer, or conversely from the yellow layer to the magenta layer and then to the cyan layer, and the present invention can be used in various embodiments.

It is also possible to use iodine-containing silver halide emulsions, DIR couplers, etc. as materials that produce interimage effects, but these release development inhibitors and therefore delay the overall development, so they are not suitable for modern processing. This goes against the request for speeding up the process.

Therefore, it is difficult to use for photosensitive materials that require rapid processing. In addition, these multilayer photosensitive materials that require rapid processing are
Since it is difficult to stop the development of each layer in a well-balanced manner, masking by releasing these development inhibitors is
Application to such photosensitive materials may require some ingenuity.

That is, the present inventors have discovered that by using a DSR compound in combination with a cyan coupler having a specific structure, a very large interimage effect can be obtained and color reproducibility is also synergistically improved. This is what led to this.

The present invention will be explained in more detail below.

First, the cyan coupler represented by the general formula [11] according to the present invention will be explained in more detail.

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 group rings; sulfinyl groups include alkylsulfinyl groups, arylsulfinyl groups, etc.; phosphonyl groups include alkylphosphonyl groups, alkoxyphosphonyl groups, and aryloxyphosphonyl groups. , arylphosphonyl group, etc.; As an 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.; as a siloxy group, a trimethylsiloxy group, a triethylsiloxy group, a dimethylbutylsiloxy group, etc.; as an imide group, a succinimide group, a 3-heptadecylsuccinimide group, a phthalimide group, a glutarimide group, etc.; As a spiro compound residue, spiro[3,3]hebutane-
1-yl, etc.; As a bridged hydrocarbon compound residue, bicyclo[2°2.1
]hebutan-1-yl, tricyclo[3°3.1.1'
-7] 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.

Examples of the group that is released by reaction with the oxidized product of the color developing agent represented by X include halogen atoms (chlorine atom, bromine atom, fluorine atom, etc.), alkoxy, aryloxy, heterocyclic oxy, acyloxy, sulfonyloxy, 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, 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.) Among them, a halogen atom is preferable. 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].

General formula [■CoY' [wherein Z' is fused with the pyrazole ring to form a nitrogen-containing compound containing a small amount of Y' (both containing 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 condensed with a benzene ring in addition to the pyrazole ring.R' and Y' represents a hydrogen atom or a substituent, and X' represents a hydrogen atom or a substituent that leaves by reaction with the oxidized product of the color developing agent.] The compound represented by the general formula [1F 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,
It contains at least one -N- and 1 to 4 nitrogen atoms, and the at least one carbonyl group contained in the six-membered ring represents a group such as >C-0 or >C-S. Also,
Specific examples containing the 6-membered ring include the following general formula [II-a
Examples include compounds represented by lC■-b, [II-c and [II-d].

Margin below represents.

In the general formula [II, Y represents a hydrogen atom or a substituent, and the preferable substituent represented by Y is, for example, one that is 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 if it were being done,
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 general formula [II, preferred are the compounds represented by the general formula [11-al [II -b] [II -c] [nd] υ υ to 3 [wherein R, , R2 and R3 have the same meaning as R in general formula [II, X has the same meaning as X in general formula [1], and Y has the same meaning as Y in general formula [11]. In the general formula [11-b], n represents an integer of 0 to 4,
When n is an integer of 2 to 4, a plurality of R2's may be the same or different. ] R2 and R1 in general formula 11-a, [II-c] and [II-d represent general formula CI
], but R2 is not a hydroxy group.

Preferred examples of R2 and R5 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.

Synthesis Example 1 [Synthesis of Compound (A-13)] [Synthesis of Compound a] 15.9 g (0.1 mol) of 5-amino -3-phenylpyrazole and 15.9 g (0.1 mol) of 2-ethoxylic acid ethyl ester
The mixture was heated and refluxed for 2 hours in 00ml of dehydrated ethanol.

After filtering the reaction solution while hot, the filtrate was cooled, and the formed precipitate was collected by filtration, washed with cold ethanol, and recrystallized with a mixed solvent of dimethylformamide and water to obtain white needle-like crystals of compound a. 17.8g (0,079 mol) was obtained.

(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 6
Q Oml, compound b81.2g (0, (175
Add 100 ml of ethyl acetate solution of 7.
8 g of triethylamine was added, and the mixture was stirred at room temperature for 2 hours, and the precipitated crystals were collected by filtration. This was washed with water, further recrystallized with acetonitrile, and the compound (A-13
) white needle-like crystals 23.0g (0,038 mol)
I got it.

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

Synthesis Example 2 [Synthesis of Compound (B-1)] ■ [Synthesis of Compound e] The above compound c 1B, 2g: (0.1 mol) and the above compound d 34.8 g (0.1 mol) were added to 40 ml of After dissolving in methanol, stir at room temperature for 2 hours, then 9.
Add 8g of sodium carbonate and then add 2g at 50°C.
Stir for hours. After pouring the reaction solution into 300 ml of water, it was neutralized using hydrochloric acid, and the solid precipitated thereby was recrystallized from a mixed solvent of toluene and acetonitrile to obtain 12.8 g of the above compound e in the form of white crystals ( 0.03 mol) was obtained.

[Synthesis of compound (B-1) from compound e] Next, this compound e LO,Or (0,023 mol) was added to 10
The mixture was dissolved in 0 ml of acetic 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 300 ml of water to this solution, neutralize with an aqueous sodium hydroxide solution at a temperature below 5°C, extract the resulting solution with ethyl acetate, and then distill off the ethyl acetate from the extract to remove the product. When the precipitate was recrystallized using acetonitrile, 8.5 g (0,01
8 mol) was obtained.

Compound C by NMR spectrum and mass spectrum
The structure of B-1) was confirmed.

Synthesis Example 3 [Synthesis of compound (C-5)] Compound (C-5) [Synthesis of compound f] Ethyl-3,5-diaminopyrazole-4-carboxylic acid 17.0sr (0, 1 mol ), 36.1i (0.1 mol) of p-dodecaoxyphenylsulfonyl chloride and 15.2 g (0.15 mol) of triethylamine were added to 500 ml of ethyl acetate and heated under reflux for 1 hour.

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

[Synthesis of compound g from compound f] 29.1 g (0,059 mol) of compound f and 14
．． [ig (0,089 mol) of α-chloroacetoacetic acid ethyl ester was heated and refluxed in BOOml 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 from ethanol to obtain 16.1 g of white needle-like crystals of compound g.
(0,027 mol) was obtained.

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

[Synthesis of compound '(C-5) from compound g] Compound g
15.4 g (0,028 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)] [Synthesis of Compound R] 45sr (0.1 mol) of compound f (used in Synthesis Example 3) and 22 g (0.1 mol) of ω-acetophenonesulfonyl The chloride was added to 11 chloroform, and 12 g (0.12 mol) of triethylamine was added. After heating and refluxing for 5 hours, the reaction solution was diluted with dilute hydrochloric acid.
After washing twice, chloroform was distilled off under reduced pressure, and recrystallized twice from methanol to obtain 30 g of white powder crystals, which is the compound
(0,045 mol) was obtained.

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

[Synthesis of compound i from compound RI] 20g (0.03 mol) of compound RI 140-160
After heating at ℃ for 1 hour and cooling, the precipitated crystals were recrystallized with ethanol to obtain 9.8 g of off-white powder crystals of Compound I.
(0,015 mol) was obtained.

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

[Synthesis of compound (D-5) from compound i] Compound (D-5) was synthesized from 8.3 g (0.01 mol) of compound i in exactly the same manner as in the method for obtaining compound (C-5) from compound g in Synthesis Example 3. 2.9g of white powder crystals (0,0
05 mol) was obtained.

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

The cyan coupler of the present invention usually has a content of 1 x 10 -3 mol to 1 mol, preferably I x 1 per mol of silver halide.
It can be used in the range of 0-2 mol-8X 1 G-' 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.

The DSR compound in the present invention is represented by the general formula [DS-1].

General formula [DS-1] Coup - (Time + f-3c In the above general formula [DS-II, Coup releases (Time-+-f-8C) by reaction with an oxidized color developing agent. Time represents a timing group capable of releasing Sc after Time-3c is released from Coup, and Sc is capable of color development after being released from Coup or Time-Sc. It represents a scavenger of an oxidized color developing agent that can scavenge an oxidized main agent by a redox reaction or a coupling reaction, and g represents 0 or 1.

Furthermore, to specifically explain the compound represented by the general formula [DS-11, the coupler residue represented by Coup is generally a yellow coupler residue, a magenta coupler residue, a cyan coupler residue, or a substantially image-based coupler residue. It is a coupler residue that does not form a color forming dye, and is preferably represented by the following general formula [D
These are coupler residues represented by S-Ia] to [DS-1hl.

Below are the blank spaces General formula [DS-Ia] General formula [DS-1b] General formula [DS-IO3 One-drug suspension [DS-Id general formula [DS-Ie] General formula [DS-If] General formula [DS- 1f] General formula [DS-1h
]H In the above general formula [DS-Ia], R1 represents an alkyl group, an aryl group, or an arylamino group, and R2 represents an aryl group or an alkyl group.

In the above general formula [DS-1bl, R5 represents an alkyl group or an aryl group, and R4 represents an alkyl group, an acylamino group, an arylamino group, an arylureido group, or an alkylureido group.

In the above general formula [DS-1c], R4 is the general formula [D
R9 represents an acylamino group, a sulfonamide group, an alkyl group, an alkoxy group, or a halogen atom.

In the above general formulas [DS-1d] and [DS-16], R7 is an alkyl group, an aryl group, an acylamino group,
It represents an arylamino group, an alkoxy group, an arylureido group, or an alkylureido group, and R6 represents an alkyl group or an aryl group.

In the above general formula [DS-If], R7 represents an acylamino group, a carbamoyl group, or an arylureido group, and R
8 represents a halogen atom, an alkyl group, an alkoxy group, an acylamino group, or a sulfonamide group.

In the above general formula [DS-Ig], R7 is the general formula [D
S-If], and Rlo represents an amino group, a carbonate amide group, a sulfonamide group, or a hydroxyl group.

In the above general formula [DS-1h], R1 represents a nitro group, an acylamino group, a succinimide group, a sulfonamide group, an alkoxy group, an alkyl group, a halogen atom, or a cyano group.

In the above general formula, 2 in [DS-1c] is O to 3, n in [DS-1f] and [DS-Ih] is 0 to 2, and m in [DS-1f] is an integer of 0 to 1. represents the sentence, when n is 2 or more, each R,, R8
and R1 may be the same or different.

The above-mentioned polygroups include those having a substituent, and preferred substituents include a halogen atom, a nitro group, a cyano group, a sulfonamide group, a hydroxyl group, a carboxyl group, an alkyl group, an alkoxy group, a carbonyloxy group, and an acylamino group. , aryl groups, etc., as well as so-called bis-type couplers.
Examples include those containing a coupler portion constituting a polymer coupler.

The lipophilicity exhibited by R1 to R11 in each of the above general formulas can be arbitrarily selected depending on the purpose.

In the case of conventional image-forming couplers, the total number of carbon atoms in R1 to R1° is preferably from 10 to 60, more preferably from 15 to 30. Further, in order to allow the dye produced by color development to move appropriately in the light-sensitive material, the total number of carbon atoms in R1 to R2° is preferably 15 or less.

Couplers that do not substantially generate image-forming coloring dyes include those that do not generate coloring dyes, so-called run-off dye-forming couplers in which the coloring dye flows out from the light-sensitive material into the processing solution, and those that react with components in the processing solution. This refers to so-called bleaching dye-forming couplers that do not leave a color image after development, and in the case of run-off dye-forming couplers,
The total number of carbon atoms in R1 to R2° is preferably 15 or less, and it is further preferred that R1 to Rlo have at least one carboxyl group, arylsulfonamide group, or alkylsulfonamide group as a substituent.

In the general formula [DS-I], the timing group represented by Time is preferably a timing group represented by the following general formula % general formula [DS-1i], where B is necessary to complete the benzene ring or naphthalene ring. represents an atomic group, Y is 10--8- or -N-
and binds to the active site of Coup (coupling component) of the general formula [DS-1]. R12, R1 and R14 represent a hydrogen atom, an alkyl group or an aryl group.

death.

The above -C- group is substituted at the ortho position or rose position with respect to Y, and the other is substituted with the general formula [Sc of the general formula [Ds-r]
is combined with

General formula [DS-Ij] In the formula, Y, R, 2, R1, each represent the general formula [DS-Ij]
i], and RI5 is a hydrogen atom, an alkyl group,
represents an aryl group, an acyl group, a sulfone group, an alkoxycarbonyl group, or a heterocyclic residue; R16 is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic residue, an alkoxy group, an amino group, an acid amide group, a sulfonamide group; Represents a carboxy group, alkoxycarbonyl group, carbamoyl group or cyano group.

Further, in the timing group represented by the above general formula [DS-1j], as in the above general formula [DS-It], Y is the active point of the Coup (Force R02 Tubbling component) of the above general formula [DS-IF]. Additionally, a -C- group is bonded to Sc.

Next, Time releases Sc by an intramolecular nucleophilic substitution reaction.
Examples of the group include those represented by the following general formula [DS-1k].

Coup of the general formula [DS-13] where Nu represents a nucleophilic group having an electron-rich oxygen, sulfur or nitrogen atom, etc. It binds to the active site of (coupling component). E represents an electrophilic group having an electron-poor carbonyl group, thiocarbonyl group, phosphinyl group, or thiophosphinyl group. This electrophilic group E is bonded to the heteroatom of Sc, D sterically relates Nu and E, and Coup (coupling component) to Nu
After the release of Sc
represents a binding group capable of releasing .

Further, scavengers for the oxidized color developing agent represented by Sc include redox type scavengers and coupling type scavengers.

In the general formula [DS-I], when Sc scavenges the oxidized color developing agent by a redox reaction, the Sc is a group capable of reducing the oxidized color developing agent, such as Angew, Chew.

[nt, Ed, 17 875-886 (197
8), The Theory of the PhO
tOgraphie Process 4th Edition (Mac
illan1977) Chapter 11, JP-A-59-524
Reducing agents described in No. 7 and the like are preferred, and Sc may be a precursor that can release these reducing agents during development.

Specifically represents a cycloalkyl, alkenyl, and aryl group. ) is preferable, and an aryl group or a heterocyclic group having at least two of them is preferable, an aryl group is especially preferable, and a phenyl group is more preferable. The lipophilicity of Sc is determined by the general formula [DS
-18] to [DS-1h Coupler may be arbitrarily selected depending on the purpose, but in order to maximize the effect of the present invention, the total number of carbon atoms in Sc should be 6 to 50.
, preferably 6-30, more preferably 6-20.

When the Sc scavenges the oxidized color developing agent through a coupling reaction, the Sc can be a variety of coupler residues, but is preferably a coupler residue that does not substantially produce an image-forming color dye. The above-mentioned run-off dye-forming couplers, bleaching dye-forming couplers, and Weiss couplers that have a non-reactive substituent at the reaction active site and do not form dyes can be used.

Specific compounds represented by the general formula [DS-ICoup-→TimefSc include, for example, British Patent No. 1546837.
No. specification, JP-A No. 52-150631, JP-A No. 57-11
No. 1538, No. 57-111537, No. 57-138
No. 636, No. 60-1115950, No. 60-203
No. 943, No. 80-213944, No. 80-2143
No. 58, No. 61-53843, No. 61-84646, No. 61-86751, No. 81-102846, et-i.

No. 2647, No. 61-107245, et-113
No. 060, No. 61-231553, No. 61-2337
No. 41, No. 61-236550, No. 81-23655
No. 1, No. 61-238057, No. 61-240240
No. 81-249052, No. 62-81838,
There are those described in 82-205346, 82-287249, and the like.

As Sc, a redox type scavenger can be preferably used, and in this case, the color developing agent can be reused by reducing the oxidized product of the color developing agent.

Next, DSR compounds represented by the above general formula [DS-I] will be illustrated, but the present invention is not limited to the exemplified compounds below.

The following margins DSR-1 CO 5R-2 CO 5R-3 CO 5R-7 CO DSR CO Shili3 5R-9 CO 5R-4 CO 5R-6 C0 5R-10 Ci! 5R-11 5R-12 αηH Q 5) to (1) DSR-13 0H 5R-14 5R-15 5R-18 H 5R-20 5R-16 H 5R-17 H DSR-21 H DSR H DSR-23 DSR -24 5R-27 5R-28 O H 0 ■ 5R-25 5R-26 5R-29 H DSR H H DSR-31 DSR-32 5R-35 5R-36 H H H 5R-33 5R-34 H 5R-37 H 5R-38 H The DSR compound of the present invention can be added to a light-sensitive silver halide emulsion layer and/or a non-light-sensitive photographic constituent layer, but it is preferably added to a light-sensitive silver halide emulsion layer. .

Two or more types of DSR compounds of the present invention can be contained in the same layer. The same DSR compound may also be included in two or more different layers.

These DSR compounds are generally preferably used in an amount of 2 x 10-' to 5 x 10-1 mol, more preferably I x 10-' to I x 10-', per mol of silver in the emulsion layer.
Use moles.

In order to incorporate these DSR compounds into the silver halide emulsion or other photographic constituent layer coating solution according to the present invention,
If the DSR compound is alkali-soluble, it may be added as an alkaline solution; if it is oil-soluble, it may be added, for example, in U.S. Patent No. 2,322.027;
No. 801.170, No. 2.801゜171, No. 2
．． 272,191 and 2,304.940, the DSR compound is dissolved in a high boiling point solvent, if necessary in combination with a low boiling point solvent, and dispersed in the form of fine particles. Preferably, it is added to the silver halide emulsion.

The above DSR compounds are disclosed in JP-A-57-1+38688, JP-A-57-155537, JP-A-57-171334,
No. 58-111941, No. 61-53643, No. 8
No. 1-84846, No. 61-86751, No. 81-1
No. 02646, No. 81-102847, No. 61-10
It can be synthesized by the method described in No. 7245, No. 81-113080, etc.

The compound or its precursor that undergoes a coupling reaction or redox reaction with the oxidized developing agent released from the DSR compound of the present invention in accordance with the density of the image during development is as follows:
Within the light-sensitive emulsion layer, the dye-forming reaction (coupling reaction) is suppressed in accordance with the image density, producing so-called intra-image effects such as improving image sharpness, and on the other hand, in other layers where it has diffused. It is possible to obtain two types of image effects, such as a so-called inter-image effect, such as a masking effect that inhibits the dye-forming reaction of that layer in accordance with the density of the image of the layer of the diffusion source.

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 the (100) plane to the (111) plane can be used. Further, 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. 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 chloroiodobromide emulsion, etc., and there is no particular limitation, but a silver halide emulsion having high chloride silver halide grains may be used. It is preferable that there be.

The above-mentioned high chloride silver halide grains are those having a silver chloride content of 90 mol % or more. In high chloride silver halide grains, the silver bromide content is 10 mol% or less,
The silver iodide content is preferably 0.5 mol% or less. More preferred is silver chlorobromide having a silver bromide content of 0.1 to 2 mol%.

High chloride silver halide grains do not have to be used alone, but can also be used in combination with other silver halide grains having different compositions.

For example, it may be mixed with silver halide grains having a silver chloride content of 10 mol % or less.

In addition, in a silver halide emulsion layer containing high chloride silver halide grains, the proportion of high chloride silver halide grains in the total silver halide grains contained in the emulsion layer is 60% by weight or more. The amount is preferably 80% by weight or more, and more preferably 80% by weight or more.

The composition of the high chloride silver halide grains may be uniform from the inside to the outside of the grain, or the composition inside and outside the grain may be different. Further, when the composition inside and outside the particle is different, the composition may change continuously or discontinuously.

There is no particular restriction on the particle size of the high chloride silver halide grains, but in consideration of other photographic performance such as rapid processability and sensitivity, it is preferably 0.2 to 1.6 μm1, and 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 ψ Microscopy, 1955, pp. 94-122)
or "The Theory of Photographic Processes" (Chapter 2, co-authored by Mies and James, 3rd edition, published by Macmillan Publishing Co., Ltd. (1968)).

The 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 be described fairly accurately as diameter or projected area.

The grain size distribution of the high chloride silver halide grains may be polydisperse or monodisperse.

Preferably, the silver halide grains are monodisperse silver halide grains having a 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.
It may be obtained by either the neutral method or the ammonia method. The particles may be grown all at once, or may be grown after seed particles are produced.

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

Further, the soluble silver salt and the soluble halogen salt may be reacted by any method such as a forward mixing method, a back mixing method, a simultaneous mixing method, or a combination thereof, but those obtained by a simultaneous mixing method are preferable. Further, as a type of simultaneous mixing method, it is also possible to use the pAg-chondral double jet method described in JP-A-54-48521 and the like.

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

The silver halide grains used in the present invention may have any shape. One preferable example is (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 complex 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.

The emulsion containing silver halide grains used in the present invention (hereinafter referred to as the "emulsion of the present invention") may have unnecessary soluble salts removed after the growth of the silver halide grains is completed, or
Alternatively, it may be left as is. In the case of removing the salts, it can be carried out based on the method described in Research Disclosure No. 17643.

The silver halide grains used in the emulsion used in the present invention are:
Preferably, the particles are particles in which the latent image is mainly formed on the surface, but particles in which the latent image is formed inside the particles may also be used.

In the present invention, a chalcogen sensitizer can be used. 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 thiosulfates and aliphatic sensitizers. ruthiocarbazide, thiourea, allyl isothiocyanate, cystine, p-toluenethiosulfonate,
Examples include rhodanine. Other US patents 1,574
．． No. 944, No. 2,410.1389, No. 2,278
, No. 947, No. 2,728,688, No. 3,501,
No. 313, No. 3.658,955, West German Application Publication (O
L S ) L, No. 422,869, JP-A-56-2
Sulfur sensitizers described in JP-A No. 4937 and JP-A No. 55-45016 can also be used. The amount of sulfur sensitizer added varies over a considerable range depending on various conditions such as pH, temperature, and size of silver halide grains, but as a guide, it is lo-7 mol-10 per mol of silver halide.
−' molar level is preferable.

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.

In the photographic constituent layer containing the cyan coupler according to the present invention,
By including the high chloride silver halide emulsion layer, faithful color reproduction can be obtained 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, color negative and positive films, color photographic paper, etc., but in particular color photographic paper used for direct viewing can be used. In such cases, the effects of the method of the present invention are effectively exhibited.

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 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-based, pyrazolobenzimidazole-based, pyrazoloazole-based, open-chain acylacetonitrile-based couplers, etc. are used, and among them, 5-pyrazolone-based and pyrazolotriazole-based 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, and an antistatic agent. Additives such as the following 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, and -20°C for boat fishing.
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. In addition, conventional processing takes 3 minutes or more.
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 using a color developing solution containing 2 m2 or less of benzyl alcohol per 1 fl, which is used for rapid development. can.

After color development, bleaching and fixing are performed.

Bleaching treatment may be performed simultaneously with fixing treatment.

After the fixing process, a washing process is usually performed.

Further, as an alternative to the water washing treatment, a stabilization treatment may be performed, or both may be used in combination.

〔Example〕

Although specific examples of the present invention are described above, the embodiments of the present invention are not limited to these.

Example 1 Three types of silver halide emulsions shown in Table 1 were prepared by a neutral method and a simultaneous mixing method.

*2 Addition of 0.9 mmol per mol of silver halide *3
Addition of 0.7 mmol per mole of silver halide*4 Addition of 0.2 mmol per mole of silver halide The spectral sensitizing dyes used are as follows.

(SD-1) Table-1 (SD-2) SO3NH(C2H5)3 *1 Addition of 1 g of 2II per mol of silver halide (SD-
3) C,H.

After chemical sensitization, each silver halide emulsion was prepared by adding (STB-1) shown below as an emulsion stabilizer to silver halide 1.
5 X to-3 moles were added per mole.

(STB-1) (Preparation of silver halide color photographic light-sensitive material sample) Next, the following layers 1 to 7 were sequentially coated (simultaneously coated) on a paper support coated with polyethylene on both sides, and silver halide color A photographic material (comparative sample No. 1) was produced. (
In the following examples, the amount added is expressed per 1M of light-sensitive material. ) Layer 1: 1.2 g of gelatin, 0.29 g (in terms of silver, the same applies hereinafter) of blue-sensitive silver halide emulsion (Em-1), and 0.75 g of yellow coupler (Y-1), 0.3g light stabilizer (ST-1)
and 0.015gno2.

A layer containing 0.3 g of dinonyl phthalate (DNP) in which 5-dioctylhydroquinone (HQ-1) was dissolved.

Layer 2...Gelatin 0.9g and 0.04g HQ
0.2 g of dioctyl phthalate (DO
A layer containing P).

Layer 3: 1.4 g of gelatin, 0.2 g of green-sensitive silver halide emulsion (Em-2), 0.9 mmol of magenta coupler (M-1), and 0.01 g of HQ-1 A layer containing 0.5 g of dioctyl phthalate (DOP) and 6 mg of the following filter dye (AI-1) in solution.

Layer 4: 1.2g of gelatin and 0.6g of the following
of ultraviolet absorber (UV-1) and 0.05 g of (HQ
- A layer containing 0.3 g of DNP dissolved in 1).

Layer 5: 1.4 g of gelatin, 0.20 g of red-sensitive silver halide emulsion (Em-3), and 0.39 g
A comparison of coupler C with 0.01 g of (HQ-1) and 0
．． ! Layer containing 0.3 g DOP in which 3 g (ST-1) was dissolved.

Layer 6--Zeran 1. Lg and 0.2g (tJ
A layer containing 0.2 g of DOP in which V-1) was dissolved and 5 mg of the following filter dye (AI-2).

Layer 7... Gelatin 1.0g and 0.05g 2
．． Layer containing sodium 4-dichloro-6-hydroxy-s-triazine.

Also, in layer 5, instead of 0.39 g of comparative coupler C, 0.5
Comparative Sample No. 2 was prepared in the same manner as Comparative Sample No. 1 above, except that 4 g of the cyan coupler (A-13) of the present invention was used.

In addition, in the same manner as the above comparative sample No. 2, except that 0.14 g of DSR-29 of the present invention was added to layer 5,
Inventive sample N11L1 was prepared, and inventive samples Nos. 2 to 13 were further prepared using the inventive cyan coupler and the inventive DSR compound as shown in Table 2.

Each compound used for sample preparation is as shown below.

(ST-1) (UV-1) (AI-1) (AI-2) Comparative coupler C (Y-1) C (M-1) C, Ill I The obtained sample was passed through a photosensitive needle KS-7 type ( Wedge exposure was performed using monochromatic light of blue, green, and red using a lens (manufactured by Konica ■), and processing was performed according to the following color development processing steps.

Using an optical densitometer (Konica ■ PDA-85 model),
The reflection density of the red-sensitive emulsion layer was measured, and the dye image was examined for heat resistance and humidity resistance by being left in a high temperature and high humidity (65° C., 80% RH) atmosphere for 14 days. The obtained results are also shown in Table-2. However, the heat resistance and humidity resistance of the dye image is expressed as the percentage of dye remaining after the heat and humidity resistance test with respect to the initial density of 1.0.

In addition, the negative film obtained by photographing and developing the color checker (manufactured by Macbeth) with Konica Color GX-100 (manufactured by Konica ■) was adjusted to match some of the gray tones.
The samples obtained above were printed and the color reproducibility of each hue was evaluated.

The results are shown in Table-2.

[Color developer]

Pure water
800 ml triethanolamine
8g N,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 fluorescent brightener (4,4'-diaminostilbendisulfonic acid derivative) 1g Add pure water to bring the total amount to Ig, and adjust the pH to 10.2.

[Bleach-fix solution]

1 g of bleach-fix solution contains 80 g of ferric ammonium ethylenediaminetetraacetic acid dihydrate, 3 g of ammonium thiosulfate (70% solution), 100 ml of ammonium sulfite (40% solution), and 27.5 ml of ammonium sulfite (40% solution). Adjust to I) H5,7 with potassium carbonate or glacial acetic acid.

[Stabilizing liquid]

1 g of stabilizing liquid contains 1 g of 5-chloro-2-methyl-4-isothiazolin-3-one and 2 g of 1-hydroxyethylidene-1°1-diphosphonic acid. Adjust the pH to 7.0 with sulfuric acid or potassium hydroxide.

[Processing process]

Color development bleach fixing stabilization drying temperature 34.7±0.3℃ 34.7±0.5℃ 30~34℃ 60~80℃ Time 45 seconds 50 seconds 90 seconds 60 seconds Table-2 xl Red sensitivity Emulsion layer! 20: Good color reproducibility (hue, saturation) △: Color reproducibility (
Slightly poor hue and saturation ×: poor color reproducibility (hue, saturation) As is clear from Table 2, comparative sample Nα1 using comparative coupler C has poor heat resistance, moisture resistance, and color reproduction. Bad sex. In addition, a comparative sample Nα using the coupler of the present invention
In No. 2, the heat resistance and humidity resistance are considerably improved, but the color reproducibility is still not sufficiently good.

It can be seen that samples Nos. 1 to 13 of the present invention using the coupler and DSR compound of the present invention are excellent in both heat resistance, moisture resistance, and color reproducibility, and exhibit the effects of the present invention.

Example 2 In this example, the present invention was directly applied to a positive silver halide photographic material. In this example, an internal latent image type silver halide emulsion was first prepared as follows.

(Preparation of Emulsion S) 750 ml of a 2.0% inert gelatin solution was kept at 50°C, and the following solutions A1 and B were simultaneously injected over a period of 3 minutes while stirring. After aging for 25 minutes, excess salt was removed by precipitation and washing, followed by redispersion, and liquid C1 and liquid D1 were added. 10
After a few minutes, the excess water-soluble salt was removed again, and a small amount of gelatin was added to disperse the silver halide grains.

(Preparation of emulsion) 750 ml of a 1.5% inert gelatin solution was kept at 60° C., and while stirring, solutions A2 and B were simultaneously injected over 15 minutes. After aging for 40 minutes, excess salt was removed by precipitation and washing, followed by redispersion, hypolomg was added, and then liquid C2 and liquid D2 were added. After 10 minutes, excess water-soluble salt was removed again, and a small amount of gelatin was added to disperse the silver halide grains.

(Preparation of Emulsion M) 750 ml of a 2.0% inert gelatin solution was kept at 50°C, and the following solutions A3 and B were simultaneously injected over 5 minutes while stirring. After aging for 25 minutes, excess salt was removed by precipitation and washing, followed by redispersion, and liquid C1 and liquid D2 were added. lO
After a few minutes, the excess water-soluble salt was removed again, and a small amount of gelatin was added to disperse the silver halide grains.

The emulsion containing sensitizing dyes, couplers, etc. as shown below is added to the three types of emulsions in the second margin below, and the first to ninth layers are simultaneously coated onto surface-treated polyethylene laminate paper, dried, and then directly coated. A positive multilayer color photosensitive material was created.

Red-sensitive emulsion layer (first layer) Sensitizing dye (D-3),
(D-4), stabilizers (T-1), (T-2), surfactant (S-2), further dibutyl phthalate, ethyl acetate,
A protected dispersed coupler solution containing surfactant (S-2), 2°5-dioctylhydroquinone, and Comparative Coupler C described above was added.

Gelatin was added and the mixing ratio of each emulsion was changed so that the resulting emulsion had a gamma value of 1.5.

First intermediate layer (second layer) A gelatin solution containing a protect-dispersed solution containing dioctyl phthalate, 2,5-dioctylhydroquinone, the ultraviolet absorber Tinuvin 328 (manufactured by Ciba Geigy), and a surfactant (S-1). Prepared tinuvin application amount 0.15
It was coated so that it became g/rd.

Green-sensitive emulsion layer (third layer) Sensitizing dye (D-2) and stabilizer (
T-1), (T-2), a protectant containing a surfactant (S2), dibutyl phthalate, ethyl acetate, 2゜5-dioctylhydroquinone, a surfactant (S-1), and a magenta coupler (M-1) The dispersed coupler solution was added.

Gelatin was added, and a hardening agent (H-1) was further added, and the resulting emulsion was coated so that the gamma value was 1.5.

2nd intermediate layer (4th layer) The same formulation as the 1st intermediate layer with a coating amount of Chikubin 328 of 0.2
g/rr? It was applied so that

Yellow filter layer (5th layer) Yellow colloidal silver made by oxidation in an alkaline weak reducing agent (the weak reducing agent was removed by the noodle water washing method after neutralization), dioctyl phthalate, ethyl acetate, surfactant (S- 1) A 2,5-dioctylhydroquinone solution, a surfactant (S-2), and a hardener (H-1) were added and coated to give a colloidal silver coating amount of 0.15 g/rrf.

3rd middle layer (6th layer) Same as the first middle layer.

Blue-sensitive emulsion layer (7th layer) Sensitizing dye (D
-1), stabilizers (T-1) (T-3), surfactants (S
-2) Furthermore, dibutyl phthalate, ethyl acetate, 2.5
- A protected dispersed coupler solution containing dioctyl hydroquinone, surfactant (S-1) and yellow coupler (Y-1) was added.

Gelatin was added and a hardening agent (H-1) was added, and the resulting emulsion was mixed and coated so that the gamma value was 1.5.

4th intermediate layer (8th layer) Tinuvin 328 coating amount 0.3 with the same formulation as the 1st intermediate layer
5g/rr? It was applied so that

Protective layer (9th layer) Colloidal silica, surfactant (S-2), hardening agent (
Using a gelatin solution containing H-2) and (H-3), apply the gelatin at a coating amount of 1.0 g/rrr.

The sample prepared as above was designated as comparative sample N3,
Furthermore, comparative sample No. 4 was prepared in the same manner as comparative sample No. 3, except that comparative coupler C in the first red-sensitive emulsion layer of comparative sample Nα3 was changed to the coupler (A-13) of the present invention. did.

In addition, an inventive sample was prepared in the same manner as Comparative Sample No. 4, except that DSR-29 was further added in an amount of 20 mol % of the inventive coupler (A-13) in the first layer in Comparative Sample No. 4. N (L14 was created.

In addition, as shown in Table 3, inventive samples Nα15 to Nα22 were created by changing the DSR compound and cyan coupler.

Each compound used in this example is as shown below.

(D-1) (H-1) (D-2) (H-2) (D-3) (H-3) So2CH””CH2 (D-4) (T-1) (T-2) Next Next, each sample obtained above was subjected to photographic processing of exposure, development, and fixing using Konica Color 7 (manufactured by Konica ■), and a copy of a color checker manufactured by Macbeth was prepared.

In addition, for each sample, the balance of the γ value of the image sensitivity after the above-mentioned photographic processing was adjusted using a filter set in advance in the copying machine so that neutral reproduction could be completely achieved.

Regarding copies, color reproducibility was evaluated.

The evaluation results are shown in Table-3.

Margin below 2H5 CH2-COO-CH2CH-(CH2)3-CH3I 03Na C2H.

Table-3 It can be seen that the effects of the present invention are exhibited.

[Effects of the Invention] The silver halide color photographic light-sensitive material of the present invention has excellent color reproducibility.

Claims (1)

[Scope of Claims] A silver halide color photographic light-sensitive material having at least one red-sensitive silver halide emulsion layer on a support,
At least one layer of the red-sensitive silver halide emulsion layer,
It contains at least one cyan coupler represented by the following general formula [I], and further contains an oxidation product of a developing agent represented by the following general formula [DS-I] in at least one of the photographic constituent layers. A silver halide photographic material containing at least one compound capable of reacting to scavenge the oxide or releasing a precursor thereof. ▲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 [DS-I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the above general formula [DS-I], Coup is due to the reaction with the oxidized color developing agent.▲There are mathematical formulas, chemical formulas, tables, etc. ▼ represents a coupler residue capable of releasing
Sc represents a timing group capable of releasing Sc after being released from Coup or Time-Sc, and Sc is a coloring group capable of scavenging an oxidized color developing agent by a redox reaction or a coupling reaction after being released from Coup or Time-Sc. It represents a scavenger of an oxidized developing agent, and l represents 0 or 1. ]