JPH0450835A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the photosensitive material which is high in color development and sensitivity and has good graininess by combining a yellow coupler of a benzoyl acetanilide system and a specific DIR compd. CONSTITUTION:This photosensitive material has at least one layer of silver halide emulsion layers on a base and the yellow coupler of the benzoyl acetanilide system expressed by formula I is incorporated into the emulsion layers. Further, at least one kind of the compds. which release a development inhibitor or the precursor thereof by reacting with the oxidant of the developing agent expressed by formula II, etc., are incorporated into the same layers and/or the same color sensitive layers. In the formula I, II, R<1>, R<2> respectively denote a hydrogen atom or substituent; m, n respectively denote 0 to 5 integer; X denotes the group which is eliminated by reaction with the oxidant of the developing agent. Cp denotes the residual coupler group which makes coupling reaction with the oxidant of the color developing agent; TIME denotes a timing group bonded in the coupling position of Cp; J denotes a combination group; Y denotes a group which can be hydrolyzed; m', n' respectively denote 0 or 1. The silver halide photographic sensitive material which is high in the color development and high sensitivity and has the good graininess is obtd. in this way.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a silver halide photographic material, and more specifically, a silver halide color photographic material with high sensitivity and improved graininess, color reproducibility, and processing stability. Regarding materials.

[Background of the invention]

In recent years, there has been a strong desire to develop color photosensitive materials that have high sensitivity, excellent sharpness, and color reproducibility.

As a means for improving sharpness, a DIR compound is known that reacts with an oxidized product of a color developing agent to release a development inhibitor. It is well known that by including this in an emulsion, the sharpness of a color image is enhanced by the edge effect, graininess is improved, and color reproduction is further improved by the multilayer effect. However, these DIR compounds have the disadvantage that the development inhibitor released during color development diffuses into the processing solution from the light-sensitive material and accumulates therein, resulting in the processing solution exhibiting development inhibiting properties.

On the other hand, it is known that benzoylacetanilide yellow couplers have good coloring properties and can provide high-density images with short development times.

However, benzoylacetanilide yellow couplers have large fluctuations in photographic performance due to variations in the pH of the color developing solution, and their graininess is also inferior to that of pivaloylacetanilide yellow couplers.

In order to solve these problems, the present inventors have conducted extensive research and found that a benzoylacetanilide yellow coupler and a specific D
When an IR compound is combined, it is possible to significantly improve the graininess while maintaining the high sensitivity and high color development of the benzoylacetanilide yellow coupler, and to reduce fluctuations in photographic performance due to pH variations. This discovery led to the present invention. In this DIR compound, the released development inhibitor decomposes in the developer and no longer exhibits an inhibitory effect, so that it is possible to assemble a photosensitive material with less contamination of the developer even if continuous processing is performed.

[Purpose of the invention]

Therefore, an object of the present invention is to provide a silver halide photographic light-sensitive material that eliminates the problems of the benzoylacetanilide yellow couplers described above and takes advantage of the feature of high color development.

That is, the first object of the present invention is to provide a silver halide photographic light-sensitive material that exhibits high color development, but has small fluctuations in photographic performance due to variations in the pH of a color developing solution, and has good graininess. be.

A second object of the present invention is to provide a silver halide photographic material with good color reproducibility.

A third object of the present invention is to provide a silver halide photographic material in which the developing solution exhibits little deterioration even after continuous processing.

[Structure of the invention]

The above object of the present invention is to have at least one photosensitive silver halide emulsion layer on a support, and the silver halide emulsion layer contains a benzoylacetanilide yellow coupler represented by the following general formula CI). , and in the same layer and/or the same color-sensitive layer, reacts with an oxidized form of a developing agent represented by the following general formulas (I[) to [■] to form a development inhibitor or a precursor of a development inhibitor. This was achieved using a silver halide photographic material containing at least one compound that can be released.

General formula CI) λ In the formula, R1 and R1 each represent a hydrogen atom or a substituent,
m and n each represent an integer of 0 to 5. When m and n are 2 or more, a plurality of R1 and R2 may be the same or different.

X represents a group that can be separated by reaction with the oxidized form of the developing agent.

General formula (I[) represents a coupler residue capable of a coupling reaction, TIME represents a timing group bonded at the coupling position of Cp, J represents a linking group, and Y represents a hydrolyzable group. m', n'
each represents 0 or 1.

General formula [■] In the formula, cp represents a coupler residue capable of a coupling reaction with an oxidized color developing agent, and TIME represents a timing group bonded at the coupling position of Cp. R3 is -J'
-Y or a substituent; When R3 is -J'-Y, R4 represents a hydrogen atom or a substituent, and when R3 is a substituent, R4 represents -J'-Y. Jl represents a linking group, and Y represents a hydrolyzable group.

m' represents 0 or l.

General formula [IV] In the formula, cp is an oxidized product of a color developing agent and in the Kabli formula, c
p represents a coupler residue capable of a coupling reaction with an oxidized color developing agent, TIME represents a timing group bonded at the coupling position of Cp, and R' represents an unsubstituted alkyl group. m' represents 0 or l.

General formula [v] In the formula, Cp represents a coupler residue capable of a coupling reaction with an oxidized color developing agent, TIME represents a timing group bonded at the coupling position of Cp, and J" has a carbon number of 1
-3 represents an alkylene group, and Y represents a hydrolyzable group. m' represents O or l.

The present invention will be described in detail below.

Among the benzoylacetanilide yellow couplers represented by the general formula CI), preferred are the following general formulas (CI):
This is a compound represented by YB-1).

General formula (YB-1) In the formula, R1-R2 and W are hydrogen atoms or substituents,
Preferably, R, , R, and R1 include both the same and different ones, and each represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an acylamino group, a carbamoyl group, an alkoxycarbonyl group, and a sulfonamide group. Or represents a sulfamoyl group.

R, , R, , R and R2 include both the same and different ones, and each preferably represents a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group or a sulfonamide group.

W preferably represents a halogen atom, an alkyl group, an alkoxy group, an aryloxy group or a dialkylamino group.

xL represents a hydrogen atom or a releasable group, and examples of the releasable group include a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, and saturated or unsaturated 5 or 6 members of
Examples include nitrogen-containing heterocyclic groups, and particularly preferred groups are represented by general formulas (YB-n) and (YB-111).

General formula (YB-11:1 Y.' Y represents a nonmetallic atom group necessary to form a 5- to 6-membered ring, and the nonmetallic atom group includes those having substituents.

General formula (YB-In) -O-A r Ar represents an aryl group, and the aryl group includes those having a substituent.

Specific examples of benzoylacetanilide yellow couplers are listed below, but the present invention is not limited thereto.

C, I (3A CH3 NHCOC17)+15 C○0C121 (2S COOCHCOOCI 2 H21 CH1 NHCOCHCt(2sO2c1+)I2iH3 -3O2N(CHI)2 COOCHCH: 5OzC+zH2i CH1 CH.

Oh.

OS02C+sH3 co 10CHC,H.

B3 -SO□NHCl, Hxs -COOC2H.

These benzoylacetanilide yellow couplers according to the present invention are disclosed in U.S. Pat. No. 3,725,072, U.S. Pat. P15
No. 1-102636, No. 52-115219, No. 54
-21448, 56-95237, 59-15
No. 9163, No. 59-174838, No. 59-206
No. 835, Japanese Patent Application Publication No. 1187560, 1-20774
No. 8, No. 1-207749, No. 1214848, No. 1-227152, No. 1-231050, No. 1-2
No. 95256, No. 1-309057, No. 1-3142
40, No. 1-316744, No. 1-316745, etc., and are synthesized by the methods described.

Two or more types of benzoylacetanilide yellow couplers according to the present invention may be used, or they may be used in combination with other yellow couplers.

To add a yellow coupler to a light-sensitive material, depending on the physical properties (e.g. solubility) of the yellow coupler, there are two methods: an oil-in-water emulsion dispersion method using a water-insoluble high-boiling organic solvent, and an alkaline dispersion method where it is added as an alkaline solution. , latex dispersion method, solid dispersion method where fine solids are added directly, etc.
Various methods can be used.

The total amount of yellow coupler added is usually 1 silver halide.
1. per mole. OX 10-n mol - 1,0 mol, preferably 5. The range is from 10-'' mol of OX to 8.10-t mol of Ox.

The benzoylacetanilide yellow coupler according to the present invention is normally contained in a blue-sensitive silver halide emulsion layer, but depending on the purpose, halogens having color sensitivity other than blue, such as green sensitivity or red sensitivity, may be added. It may be contained in the silver emulsion layer.

Next, general formulas (n) to -general formula V] will be explained.

The compounds represented by the general formulas CI to [■] exhibit development inhibiting properties when released from the coupling position of the coupler mentioned above, but after they flow out into the processing solution, It is an old R coupler with an inhibitor component that decomposes into compounds that do not affect photographic properties.

First, the coupler residue cp and timing group TIME common to general formulas (U) to [V] will be explained.

Coupler residues represented by Cp include residues that produce yellow magenta or cyan dyes and residues that produce substantially colorless products.

Among the coupler residues represented by Cp, typical yellow coupler residues are disclosed in U.S. Patent No. 2゜29L443.
No. 2,407,210, No. 2, 875, 05
No. 7, 3°048, No. 194, 3,265.50
No. 6, No. 3,447.928 and “7 Albkuppler Eine Literateursicht Agfa Mittelung (Band ■)” (Farbkuppler
5ine Literatuversiecht
Agfa11itteilung (Band I
[)) pages 112-129 (1961). Among these, acylacetanilides, such as benzoylacetanilide and pivaloylacetanilide, are preferred.

Typical magenta coupler residues are U.S. Patent Nos. 2,369.489, 2,343.703, and 2
, 311° 182, 2,600.788, 2,
No. 908.573, 3, 062.

No. 653, No. 3,152.896, No. 3,519.4
No. 29, No. 3,725゜067, No. 4,540.65
No. 4, JP-A No. 59-162548 and the above-mentioned Agfa
Mitteilung (Bandl[) 126~
156 (1961), etc. Among these, pyrazolone or pyrazoloazole (e.g., pyrazoloimidazole, pyrazolotriazole, etc.)
Preferably.

Typical cyan coupler residues are U.S. Patent 2
, 367.531, 2,423.73 (1, 2,
No. 474,293, No. 2,772.162, No. 2, 3
No. 95.826, No. 3,002.836, No. 3,03
No. 4.892, No. 3,041,236, No. 4,666
No. 999 and the above-mentioned Agfa Mitteilung.
(Band II) pp. 156-175 (1961). Among these, phenols or naphthols are better.

Representative coupler residues that form substantially colorless products include, for example, British Patent No. 861,138, U.S. Pat. No. 3,632.345, U.S. Pat. No. 993 and No. 3,961.959, etc. Among these, cyclic carbonyl compounds are preferred.

Typical timing groups represented by TIME include, for example, U.S. Pat.
No. 6837, which releases a photographically useful group through an intramolecular nucleophilic substitution reaction, and JP-A-56-114.
Examples thereof include those that release photographically useful groups through an electron transfer reaction along a conjugated chain, as disclosed in Japanese Patent No. 946 and No. 57-154234.

Others: JP-A-57-188035, JP-A No. 58-987
No. 28, No. 59-206834, No. 60-7429, No. 60-214358, No. 50-225844,
Also included are the timing groups disclosed in No. 60-229030, No. 60-233649, No. 60-237446, and No. 60-237447.

As the yellow coupler residue represented by cp in the general formulas (I[) to -general formula v], those represented by the following general formulas [A] and CB) are preferable.

General formula (A) General formula CB) In the above general formulas (A) and CB), R@ and R1 represent, for example, alkyl, cycloalkyl, aryl, heterocycle, or a halogen atom, and the alkyl, cycloalkyl,
Aryl and heterocycles may be bonded via an oxygen atom, nitrogen atom, or sulfur atom.

Furthermore, the alkyl, cycloalkyl, aryl, and heterocycle may be bonded via the bonding groups listed below. That is, acylamino, carbamoyl, sulfonamide, sulfamoyl, sulfamoylcarbonyl, carbonyloxy, oxycarbonyl, ureido, thioureido, thioamide, sulfone, sulfonyloxy, and the like.

Furthermore, the alkyl, cycloalkyl, aryl, and heterocycle may further have a substituent as described below. That is, halogen atom, nitro, cyano, alkyl, alkenyl, cycloalkyl, aryl, alkoxy, aryloxy, alkoxycarbonyl, aryloxycarbonyl, carboxyl, sulfo, sulfamoyl, carbamoyl, acylamino, ureido, urethane, sulfonamide, heterocycle, Arylsulfonyl, alkylsulfonyl, arylthio, alkylthio, alkylamino, anilino, hydroxyl, imide, acyl, etc.

When there are two or more R1 and R7, they may be the same or different.

The magenta coupler residues represented by cp in general formulas (II) to -general formula V) include the following general formulas (C), (
Those represented by D), (E) and CF) are preferred.

The cyan coupler residues represented by Cp in the general formulas [CD, thick general formula [■]] to CV'l are preferably those represented by the following general formulas CG), (H), and [J].

General formula CG) General formula CD'l General formula [H) General formula CJ) General formula CF] In the above general formulas (C) to [F], R' and R are general formula (A), I:B) is synonymous with R@ and R7.

In the above CG) to [J], R6 and R7 are represented by the general formula [A
), 1:B) are synonymous with RB and RT.

As the coupler residues forming the substantially colorless product represented by Cp in the general formulas [■] to [■], those represented by the general formulas (K] to [N) are preferred.

General Formula (K) In the formula, R8 represents, for example, a hydrogen atom, an alkyl group, an aryl group, a halogen atom, an alkoxy group, an acyloxy group, or a heterocyclic group, and X represents an oxygen atom or -NR'. R″ represents an alkyl group, an aryl group, a hydroxyl group, an alkoxy group, or a sulfonyl group. 2 represents a 5- to 7-membered carbon ring (e.g., indanone, cyclopentanone, cyclohexanone, etc.) or a heterocycle (e.g., piperidone, pyrrolidone,
Represents a group of nonmetallic atoms necessary to form hydrocarbostyryl, etc.).

General formula (L) aryl group, heterocyclic group, cyano group, hydroxyl group,
alkoxy group, aryloxy group, heterocyclic oxy group,
Represents an alkylamino group, dialkylamino group or anilino group.

General formula (M) R"-CH-R" 1* In the formula, R" and RI2 may be the same or different, for example, an alkoxycarbonyl group, a carbamoyl group, an acyl group, a cyan group, a formyl group, Represents a sulfonyl group, sulfinyl group, sulfamoyl group, ammonium mil group, or - to.

A represents a group of nonmetallic atoms necessary to form a 5- to 7-membered heterocycle (eg, 7-talimide, triazole, tetrazole, etc.) together with the nitrogen atom.

General formula [N] ψ * In the formula, Ra and X have the same meanings as R8 and X in the general formula [K], R10 is an alkyl group, B represents an amino group or an alkoxy group, and B represents an oxygen atom, a sulfur atom or a nitrogen atom.

TIMEs useful in the present invention include the following general formulas CP), C
It includes, but is not limited to, those represented by Q) and (R).

General formula [P] Substituted and bonded to the sulfur atom of the development inhibitor group.

General Formula (Q) In the formula, X represents an atomic group necessary to complete a benzene ring or a naphthalene ring which may have a substituent.

Y l; represents 1-0-, -S-, -N-, and has the general formula (
I[)-(V) is bonded to the coupling position of the coupler residue represented by Cp, and R'', R1s and R''
each represents a hydrogen atom, an alkyl group or an aryl group.

In the formula R, y, R14, and RIs each have the same meaning as in the general formula [P]. R'' is, for example, a hydrogen atom, an alkyl group, an aryl group, an acyl group, a sulfonyl group, an alkoxycarbonyl group, or a heterocyclic group, and R1 is, for example, a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, or an alkoxy group. , amino group, acid amide group, sulfonamide group, carboxyl group, alkoxycarbonyl group, carbamoyl group, and cyano group.

In addition, this timing group is represented by Y in the same way as in general formula [P], and in the general formulas (If) to CV), at the coupling position of the coupler residue represented by Cp, the -C- group IS is and bonds to the sulfur atom of the development inhibitor group.

Next, an example of a timing group that releases a development inhibitor group by an intramolecular nucleophilic substitution reaction is shown by the general formula (R).

General formula [R] Nu -E- In the formula, Nu is a nucleophilic group having an electron-rich oxygen, sulfur or nitrogen atom, and is represented by Cp in general formulas (II) to (V). It is attached to the coupling position of the coupler residue. E is an electrophilic group having an electron-poor carbonyl, thiocarbonyl, bosphinyl or thiophosphinyl group and is bonded to the sulfur atom to the development inhibitor group. X has Nu and E in a steric relationship, and after Nu is released from the coupler residue represented by cp in general formula (II) ~ [v], the three-membered ring ~
It is a linking group that can undergo an intramolecular nucleophilic reaction with the formation of a 7-membered ring and thereby release a development inhibitor.

Next, for each of the general formulas (It) to [v], the parts other than Cp and TIME will be explained in detail.

In the general formula (n), J is a simple bond, alkylene, cycloalkylene, phenylene, Al II kenylene, -N -, -0-, -3- (R'' is, for example, a hydrogen atom, an alkyl group, a cycloalkyl group , represents an aryl group) and a combination thereof.

Preferred among these are alkylene, general formula (I
In I), CDI) and (V), the hydrolyzable group represented by Y is, for example, -COOR"°, -0
COR", -OSO□R"', -0COOR
20.

Among these, -COOR''° is preferred.

Examples of the group represented by R'' include alkyl groups (methyl, ethyl, propyl, isopropyl, butyl, 5ec-
butyl, hexyl, etc.), cycloalkyl groups (cyclopentyl, cyclohexyl, etc.), aryl groups (phenyl, naphthyl, etc.), and heterocyclic groups (pyridinyl, imidazolyl, pyrrolyl, etc.). These groups may further have a substituent, such as a halogen atom, nitro, cyano, alkyl, alkenyl, cycloalkyl, aryl, alkoxy, aryloxy, alkoxycarbonyl, aryloxycarbonyl, carboxyl, sulfo,
These are sulfamoyl, carbamoyl, acylamino, ureido, urethane, sulfonamide, heterocycle, arylsulfonyl, alkylsulfonyl, arylthio, alkylthio, alkylamino, anilino, hydroxyl, imide, and acyl groups.

Preferred among R'' are an alkyl group and an aryl group. More preferred is an aryl group.

Compound of the present invention represented by general formula (II) below ■-18 1[-19 H t-14 Shinko I-15 H ■-16 ■ ■-21 H Then the general formula I will explain about it.

In the general formula [■], the substituents represented by R3 and R4 include, for example, hydrogen atom, halogen atom, nitro, cyan, alkyl, alkenyl, cycloalkyl, aryl, alkoxy, aryloxy, alkoxycarbonyl, aryl Oxycarbonyl, carboxyl, sulfo, sulfamoyl, carbamoyl, acylamino,
ureido, urethane, sulfonamide, heterocycle, arylsulfonyl, alkylsulfonyl, arylthio,
These are alkylthio, alkylamino, anilino, hydroxyl, imide, and acyl groups.

Among these, preferred are hydrogen atoms, alkyl groups,
It is an aryl group.

In the general formula [■], J and Y are interlaced with X and Y in the general formula [■].

Preferred compounds in the general formula (I [[)] are represented by the following general formula [■'].

General formula [■′] x-cooC! .

In the formula, Cp, TIME, X, m, R', R''
represents a group similar to the general formula [■]. More preferred among these is R20 or an unsubstituted alkyl group.

Typical exemplified compounds of the present invention represented by the general formula Cn1) are shown below, but the invention is not limited thereto.

To 8 □ This is a compound in which the unsubstituted alkyl group represented by has 1 to 10 carbon atoms. The alkyl group may be linear or branched. -〇〇OR' may be attached to any position of the benzene nucleus, but it is most preferably attached to the para position.

Specific examples of the compound represented by general formula (IV) are listed below.

IV-3 IV-10 IV-19 mV-21 Next, the compound represented by general formula (V) will be explained.

In the general formula (V), the alkylene group represented by J preferably has 1 to 3 carbon atoms.Among the alkylene groups represented by J, methylene, ethylene, and trimethylene are more preferable.

Among the compounds represented by the general formula (V), more preferred are those represented by the following general formula [V'].

[V′]

In the general formula [v'], Cp, TIME, m are -
It has the same meaning as in general formula (V). n is 1 to 3
represents an integer. R'' represents an alkyl group.

Specific examples of the compound represented by general formula [v] are shown below.

CHt C00C4Fi * CH2C1 (ICOOC2Hs CH2CHzCOOCHs CH2COOC, H* The present invention can be applied to any of the red-sensitive silver halide emulsion layer, the green-sensitive silver halide layer, and the blue-sensitive silver halide layer, Preferably, it is applied to a blue-sensitive silver halide layer.

Further, the benzoylacetanilide yellow coupler according to the present invention and the DIR compound according to the present invention do not necessarily need to be added to the same light-sensitive layer if they are the same color-sensitive layer, but it is better to add them to the same layer. preferable.

There are no particular restrictions on the method of incorporating these yellow couplers and DIR compounds into the hydrophilic colloid layer of a color photosensitive material, but for example, a high boiling point organic solvent such as tricresyl phosphate or dioctyl phthalate is mixed with a low boiling point solvent such as ethyl acetate. It is advantageous to dissolve and emulsify the gelatin in an aqueous gelatin solution.

The yellow coupler and DIR compound of the present invention may be present in the same oil droplets prepared by the above method or in separate oil droplets.

The amount of the yellow coupler according to the present invention to be added is preferably 5 x 1 O-S to 2 x 1 O-s mol/-2, more preferably I x 10-' to 2 x 10-'' mol/■
3, particularly preferably 2 x 10-' to 2 x 10-'' mol/12.

The amount of the DIR coupler added according to the present invention is preferably from 5 x 10-2 to 1.0 mol per mol of silver halide, particularly preferably from 5 x 10-' to I x 10-' mol.

The silver halide emulsion of the present invention may contain any silver halide used in conventional silver halide emulsions, such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. Can be used.

The silver halide grains used in silver halide emulsions may have a uniform silver halide composition distribution within the grain, or they may be core/shell grains in which the silver halide composition differs between the inside and surface layer of the grain. good.

The silver halide grains may be grains in which a latent image is mainly formed on the surface, or grains in which a latent image is mainly formed inside the grain.

Silver halide emulsions having any grain size distribution may be used. An emulsion with a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion with a narrow grain size distribution (referred to as a monodisperse emulsion) may be used alone or in combination. Further, a mixture of a polydisperse emulsion and a monodisperse emulsion may be used.

The silver halide emulsion may be a mixture of two or more separately formed silver halide emulsions.

The emulsion can be chemically sensitized by conventional methods, or optically sensitized to a desired wavelength range using a sensitizing dye.

Antifoggants, stabilizers, etc. can be added to the silver halide emulsion. Gelatin is advantageously used as binder for the emulsion.

The emulsion layer and other hydrophilic colloid layers may be hardened or may contain a plasticizer or a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer.

When producing a color photographic light-sensitive material, a coupler is generally used in the emulsion layer. Furthermore, by coupling with a competing coupler having a color correction effect and an oxidized form of a developing agent, a development accelerator, a bleach accelerator, a developer, a silver halide solvent, a toning agent, a hardening agent, a fogging agent, antifoggant,
Compounds that release photographically useful 7-ragments such as chemical sensitizers, spectral sensitizers and desensitizers can be used.

A benzoylacetanilide compound is used as the yellow dye-forming coupler, but other yellow dye-forming couplers may be used in combination. Couplers used in combination include pivaloylacetanilide compounds and acetoacetanilide compounds.

The amount of yellow dye-forming couplers other than benzoylacetanilide couplers used is preferably 60% or less of the total amount of yellow dye-forming couplers in terms of mol%, and 10
% or less is more preferable.

As the magenta dye-forming coupler, 5-pyrazolone couplers, pyrazoloazole couplers, vilazolopenine imidazole couplers, open-chain acylacetonitrile couplers, indacylon couplers, and the like can be used.

Phenol or naphthol couplers are commonly used as cyan dye-forming couplers.

The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and an antiirradiation layer. These layers and/or the emulsion layers may contain dyes that are leached from the light-sensitive material or bleached during the development process.

A matting agent, a lubricant, an image stabilizer, an ultraviolet absorber, an optical brightener, a surfactant, a development accelerator, a development retardant, and a bleach accelerator can be added to the photosensitive material.

As a support, paper laminated with polyethylene, etc.
Polyethylene terephthalate film, baryta paper, cellulose triacetate, etc. can be used.

Any means can be used to develop the photosensitive material of the present invention, including known methods. The processing temperature is preferably between 18 DEG and 50 DEG C., and depending on the purpose, black and white photographic processing, lithographic development processing, or color photographic processing to form a dye image can be applied. Further, photosensitive materials for heat development are preferably processed at a temperature of 100° C. or higher.

〔Example〕

The present invention will be explained in more detail with reference to Examples below.
The embodiments of the present invention are not limited to these.

Prior to specific explanation of each example, the production of silver halide emulsions used in the examples will be explained.

Preparation of monodispersed emulsion A gelatin aqueous solution is charged into a reaction vessel, and the p in the reaction vessel is
While controlling Ag and pH, silver nitrate aqueous solution,
After adding an aqueous potassium iodide solution and an aqueous potassium bromide solution at the opening time without controlling the addition time, precipitation and desalination were performed using pH-coagulating gelatin, and gelatin was added to form the seed emulsion N.
Prepare E-1.

The average grain size of seed emulsion NE-1 was 0.09 ha.

Put the above seed emulsion and gelatin aqueous solution into a reaction pot.
While controlling pAg and pH in the reaction vessel, add ammoniacal silver nitrate aqueous solution, potassium iodide aqueous solution, and potassium bromide aqueous solution in proportion to the surface area during particle growth, and add potassium bromide solution at appropriate particle size. Change it to
Continued addition. As with the seed emulsion, precipitation and desalting are carried out.
Add gelatin and redisperse, pA g7.8. pH6
, 0 emulsion was obtained.

In this way, silver iodobromide emulsion E with a high iodine content inside the grains
M-1 to EM-2 were prepared.

Each emulsion and its contents are shown below.

Example 1 Preparation of Sample 1 (Comparative) A multilayer color photosensitive material sample 1 having a multilayer structure having the following composition was prepared on a subbed cellulose acetate support.

The coating amount is the amount expressed in units of g/rtr2 for silver halide and colloidal silver, and the amount expressed in units of g/m2 for additives and gelatin.
The sensitizing dye, coupler, and DIR compound are expressed in moles per mole of silver halide in the same layer.

The emulsion contained in each color-sensitive emulsion layer was optimally sensitized using sodium thiosulfate and chloroauric acid, and examples will now be described in detail.

Sensitizing dye V CM Q Shi1lis Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ Sensitizing dye I Sensitizing dye■ UV 02) I5 s-1 0M ■Hereinafter, each layer of the above composition is made of the above-mentioned HC, IL-1, R
-1, R-2, IL-2, G-1, G-2゜YC, B-
1, B-2, Pro-1, and Pro-2.

In addition to the above components, a surfactant was added to each layer as a coating aid.

(Preparation of Samples 2 to 26) Samples 2 to 26 were prepared in the same manner as Sample 1 except that the couplers and DIR compounds of B-1 and B-2 were changed as shown in Table 1.
I made it.

Each sample was cut, subjected to wedge exposure according to a conventional method, and subjected to the following development treatment.

Processing process (38°C) Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds water washing 3 minutes 15 seconds Fixation 6 minutes 30 seconds water washing 3 minutes 15 seconds Stabilization 1 minute 30 seconds Drying Used in each processing step The composition of the treatment solution was as follows.

Color developer 4-amino-3-methyl-N-ethyl-N-β-hydroxyethyl-aniline sulfate 4.75g anhydrous sodium sulfite 4.25g hydroxylamine 1/2WL salt anhydrous potassium carbonate potassium bromide 2 .0 g 37.5 g 1.3 g Nitrilotriacetic acid trisodium salt (monohydrate) Potassium hydroxide 2.5 g 1.0 g Add water to make Tela (pH = 10.02). It is referred to as color developer-1.

Bleach solution ethylenediaminetetraacetic acid iron (I
Add 10.0g water and
C and adjust the pH to 6.0 using aqueous ammonia.

Fixer Ammonium thiosulfate 175.0g Anhydrous ammonium sulfite 8.68 Sodium metasulfite 2.3g Add water
ff and adjusted to pH 6.0 using acetic acid.

Stabilizing liquid formalin (37% aqueous solution) 1.51 g Konidax (manufactured by Konica Corporation) 7.5 m + 2 water added
Let it be Q.

Sulfuric acid was added to the above color developing solution to adjust the pH to 9.87 to obtain color developing solution-2.

Each sample was exposed and developed in the same manner except that color developer-2 was used.

<Evaluation of photographic performance and fluctuations in photographic performance due to changes in pH of color developing solution> The density of each processed sample was measured to determine photographic performance. Table 1 shows the sensitivity at the culprit concentration and the maximum concentration. However, the sensitivity is the sensitivity of sample 6 (comparison sample)
It is expressed as relative sensitivity.

The column for Color Developer-1 shows the photographic performance of each sample when subjected to standard processing, and the column for Color Developer-2 shows the photographic performance when processed with a developer having a pH lower than the standard.

Table 1 It can be seen that the samples of the present invention maintain the high color development and high sensitivity properties of the benzoylacetanilide yellow coupler, while reducing performance fluctuations due to changes in the pH of the color developer.

Example 2 Evaluation of Graininess> Samples 1 to 26 in Example 1 were printed through a blue filter to evaluate graininess. Since a difference in graininess was observed between Sample 1, a pivaloylacetanilide coupler, and Sample 4, a benzoylacetanilide coupler, they were ranked on a scale of 10, with Sample 1 being 3 and Sample 4 being 1.

(Poor 1←→10 Good) The results are shown in Table-2.

There is a difference in graininess between Sample 1 and Sample 4 when no DIR compound is used, but the difference almost disappears when the DIR compound used in the present invention is added. That is, in the combination of the present invention, the improvement in graininess is greater than in the combination with the pivaloylacetanilide coupler.

Evaluation of color reproducibility> Multilayer effect was evaluated as an evaluation measure of color reproducibility.

In order to examine the suppression effect from the blue-sensitive layer to the adjacent green-sensitive layer, the above reference sample (white exposure/standard treatment) and a sample exposed to green monochromatic light and subjected to the standard treatment were prepared. The green density (density of magenta image) of both was measured, and the gamma ratio (γ0/γN) of both was determined. The larger the gamma ratio, the greater the multilayer effect and the better the color reproducibility.

Gamma is the slope of the characteristic curve from the point where the density is +0.3 to the point where the exposure range (QogE) is 1.0.

The gamma of the sample exposed to green light is γ. , the gamma of the sample exposed to white light is 18.

The results are shown in Table-2.

As is clear from Table 2, the combination of the present invention reduces the contamination of the cleaning solution (accumulation of development inhibitory substances) during continuous running processing compared to the combination with pivaloylacetanilide. For evaluation, running processing was performed.

Regarding the samples shown in Table 3, photographed samples were developed under the following conditions.

The composition of the color developer replenisher is shown below.

Color developer replenisher 4-amino-3-methyl-N-ethyl-N-β hydroxyethylaniline sulfate 6.0 g anhydrous sodium sulfite 5.0 g hydroxylamine 1/2 sulfate 2.35 g anhydrous potassium carbonate 44. 0g nitrilotriacetic acid trisodium salt (l hydrate) 2.9g potassium hydroxide 1.2g Add water to make 112. (pH 10,08) After developing the wedge exposure method sample of sample 4 with the developer before running treatment and the developer after 4-hour running treatment, the density was measured, and the blue color of the sample treated with the developer before running treatment was determined. The blue density of samples developed with the developer after running and drying at an exposure dose of 2.00 was compared. The concentration is 2.
The closer it is to 00, the less contamination there is.

The results are shown in Table-3.

As is clear from Table 3, Samples 9, 12, 14, 19, and 23 using the DIR couplers of the present invention were more contaminated with color developing solution than Samples 5 and 6 using DIRs other than the present invention. are significantly less.

Table 3 [Effects of the Invention] By the combination of the present invention, a photosensitive material with high color development, high sensitivity, and good graininess can be obtained.

Furthermore, the light-sensitive material of the present invention causes less contamination of the color developing solution during continuous processing.

Claims (1)

[Scope of Claims] It has at least one photosensitive silver halide emulsion layer on a support, and the silver halide emulsion layer contains a benzoylacetanilide yellow coupler represented by the following general formula [I]. , and can react with an oxidized form of a developing agent represented by the following general formulas [II] to [V] in the same layer and/or the same color-sensitive layer, and release a development inhibitor or a precursor of a development inhibitor. A silver halide photographic material containing at least one compound. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R^1 and R^2 each represent a hydrogen atom or a substituent, and m and n each represent an integer from 0 to 5. . m and n are 2
In the above case, the plurality of R^1 and R^2 may be the same or different. X represents a group that can be separated by reaction with the oxidized form of the developing agent. ] General formula [II] ▲ Numerical formulas, chemical formulas, tables, etc. It represents a timing group, J represents a linking group, and Y represents a hydrolyzable group. m' and n' each represent 0 or 1. ] General formula [III] ▲ Numerical formulas, chemical formulas, tables, etc. are included. Represents a timing group. R^3 is -J
'-Y or a substituent; when R^3 is -J'-Y, R
^4 represents a hydrogen atom or a substituent, and when R^3 is a substituent, R^4 represents -J'-Y. J′ represents a linking group, Y
represents a hydrolyzable group. m' represents 0 or 1. ] General Formula [IV] ▲ Numerical formulas, chemical formulas, tables, etc. It represents a timing group, and R^5 represents an unsubstituted alkyl group. m' represents 0 or 1. ] General formula [V] ▲ Numerical formulas, chemical formulas, tables, etc. It represents a timing group, J″ represents an alkylene group having 1 to 3 carbon atoms, Y represents a hydrolyzable group, and m′ represents 0 or 1.]