JPH0629958B2 - Silver halide photographic light-sensitive material using 2-equivalent yellow coupler - Google Patents

Description

The present invention relates to a silver halide photographic light-sensitive material.

More specifically, it relates to a silver halide color photographic light-sensitive material using a novel 2-equivalent yellow coupler which is excellent in color developability, has little fog, is excellent in light resistance, and is excellent in dispersion stability.

[Background of the Invention] A photosensitive silver halide is exposed and then treated with a color developing solution containing an aromatic primary amine type color developing agent, and an oxidized developing agent generated at that time is reacted with a coupler to form a color image. Is generally known, and three kinds of couplers are used to form three dyes of yellow, magenta, and cyan to reproduce the original image.

2-pyrazolin-5-ones or pyrazolotriazoles couplers for magenta dye formation, phenols or naphthols couplers for cyan dye formation, and active methylene groups for yellow dye formation. Ketomethylene class couplers such as those having .alpha.-acylacetanilide have been used.

In general, silver halide color photographic light-sensitive materials have become the mainstream of modern color photographic methods because they give images of high photosensitivity and excellent image quality. However, since this method uses a large amount of silver, the recent shortage of silver resources and the resulting rise in market prices have become a major problem for the industry. To address this problem, methods have been proposed to obtain maximum dye density and photographic speed with as little silver as possible. In other words, conventionally, four atoms of silver were required to form one molecule of dye, whereas the coupling position (active point) of the coupler that reacts with the oxide of the developing agent.
This is a technique in which a silver atom of 2 atoms is sufficient by introducing a substituent into. The former is a 4-equivalent coupler,
The latter is called a 2-equivalent coupler.

Examples of the active site substituent of the yellow coupler include, for example, JP-A-50-87650, aryloxy group of US Pat. No. 3,408,194, oxazolyloxy group of JP-A-51-131325, and JP-A-51-139333. Chroman-4-oxy group, JP-A-52-43426, tetrazolyloxy group, JP-A-52-150
The 5-pyrazolyloxy group of 631, the nitrogen-containing heterocyclic group of JP-A-52-115219, the urazole group of JP-B-51-33410, a hydantoin group, the arylthio group of U.S. Pat. Some of these have been put to practical use.

The advantage of the 2-equivalent coupler brings about not only the resource saving point that the amount of silver can be theoretically reduced to half as compared with the case of using the 4-equivalent coupler as described above, but also other preferable result. In other words, by reducing the amount of gold halide emulsion required, it is possible to reduce the film thickness, and therefore unnecessary scattering and absorption of irradiation exposure are prevented, improving the photographic performance such as sensitivity, resolution and sharpness. give. A coupler used in a silver halide color photographic light-sensitive material is required to have many performances described below. The coupler covers the silver halide emulsion as a photoreceptor, reduces the sensitivity, and adds various other additives contained in the emulsion (for example, stabilizers, antifoggants, hardeners, sensitizers, etc.). Do not react. Must not decompose in emulsion for long periods of storage. Further, during color development, a reaction with a color developing agent occurs promptly and sufficient density is required. Color development in the unexposed area must be kept as low as possible, and the dye formed is stable against external conditions such as light, heat, and humidity, and at that time, it does not remain in the silver halide color photographic light-sensitive material. Color couplers should not cause discoloration, contamination or fading.

Although the use of the 2-equivalent coupler improved the coloring efficiency to some extent, it was still insufficient, and benzyl alcohol was added to the color developing solution to increase the coloring efficiency in the light-sensitive material. , Benzyl alcohol is an environmental pollution problem, for example, B.I. O. D. There are problems such as increasing the (biological oxygen demand) value. Japanese Examined Patent Publication No. 56-44420 discloses a 2-equivalent yellow coupler excellent in color development even when the amount of benzyl alcohol is reduced. However, these have low solubility in low boiling point solvents such as ethyl acetate used when dispersing the coupler, and a large amount of ethyl acetate must be used, and further, dispersion stability is poor and a major problem in production. , These improvements were strongly desired.

[Object of the Invention] The present invention has been made in view of the above circumstances, and a first object of the present invention is excellent in color forming property, particularly even when the amount of benzyl alcohol in a color developing solution is reduced or removed. It is to provide a silver halide photographic light-sensitive material containing a novel 2-equivalent yellow coupler excellent in color forming property.

A second object of the present invention is to provide a silver halide photographic light-sensitive material containing a novel 2-equivalent yellow coupler which has less fog, good light resistance and excellent storage stability.

A third object of the present invention is to provide a silver halide photographic light-sensitive material containing a novel 2-equivalent yellow coupler which has high solubility in a low boiling point solvent and is excellent in dispersion stability.

[Constitution of Invention] The above object of the present invention has been achieved by providing a silver halide photographic light-sensitive material containing a coupler represented by the following general formula [I].

General formula [I] [In the formula, R ₁ represents a group capable of substituting on the benzene ring;
₂ represents a hydrogen atom, an alkyl group, an aralkyl group, or an aryl group, R ₃ represents an alkyl group having 2 to 8 carbon atoms, and R ₄ represents a group capable of substituting on the benzene ring. X
Represents an alkylene group, an arylene group, an aralkylene group or a divalent organic group represented by the following general formula [II], and Y represents an alkyl group, a cycloalkyl group or an aryl group. m represents 0 or 1, and n represents an integer of 0 to 5. When n is 2 or more, R ₄ may be selected from the same group or different groups. General formula [II] -A-V-B- [In the formula, A and B each represent an alkylene group, an arylene group or an aralkylene group, and V represents a divalent linking group. [Specific Configuration of the Invention] Examples of the group capable of substituting the benzene ring represented by R ₁ in the general formula [I] include, for example, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acyloxy group, an acylamino group, Examples thereof include a carbamoyl group, an alkylsulfonamide group, an arylsulfonamide group, a sulfamoyl group and an imide group.

Examples of the halogen atom capable of substituting the benzene ring represented by R ₁ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and examples of the alkyl group include methyl, ethyl, t-butyl and n-. Examples thereof include a propyl group and the like, examples of the alkoxy group include a methoxy group, ethoxy group, and a propoxy group. Examples of the aryloxy group include a phenyloxy group and the like, and examples of the acyloxy group include an alkylcarbonyloxy group ( Examples thereof include a methylcarbonyloxy group, etc.) and an arylcarbonyloxy group (eg, benzoyloxy group, etc.). Examples of the acylamino group include an alkylcarbonylamino group (eg, acetamide group etc.), an arylcarbonylamino group (eg, phenylcarbonylamino group). Etc.), Further, the carbamoyl group capable of substituting on the benzene ring represented by R ₁ includes those substituted with an alkyl group, an aryl group (preferably a phenyl group) and the like, for example, an N-methylcarbamoyl group and an N-phenylcarbamoyl group. And the like. Examples of the alkylsulfonamide group include a methylsulfonylamino group and an ethylsulfonylamino group, and examples of the arylsulfonamide include a phenylsulfonylamino group.

Further, the sulfamoyl group which can be substituted on the benzene ring represented by R ₁ includes those substituted with an alkyl group, an aryl group (preferably a phenyl group) or the like, for example, N-
Examples thereof include a propylsulfamoyl group and an N-phenylsulfamoyl group.

The imide group which can be substituted on the benzene ring represented by R ₁ may be an open chain or cyclic imide group, and further includes those having a substituent, for example, a succinimide group,
3-heptadecyl succinimide group, phthalimide group,
Examples thereof include a glutarimide group.

In the general formula [I], examples of the alkyl group represented by R ₂ include a methyl group, an ethyl group, an isopropyl group, a t-butyl group and a dodecyl group. Also,
Examples of the aralkyl group represented by R ² include a benzyl group and the like. Examples of the aryl group represented by R ₂ include a phenyl group and a naphthyl group.

The alkyl group, aralkyl group, or aryl group represented by R ₂ also includes those having a substituent. The substituent is not particularly limited, but as a typical example, a halogen atom, for example, a fluorine atom, a chlorine atom,
Examples thereof include bromine atom and iodine atom, alkyl group such as methyl group, ethyl group, t-butyl group and dodecyl group, and aryl group such as phenyl group, p-chlorophenyl group and p-methoxyphenyl group. p-dodecylphenyl group, naphthyl group and the like, alkoxy group such as methoxy group, ethoxy group, t-butoxy group, benzyloxy group, dodecyloxy group and the like, aryloxy group such as phenoxy group and the like. , An alkylthio group such as an ethylthio group and a hexylthio group, an arylthio group such as a phenylthio group, and an alkylsulfonyl group such as a β-hydroxyethylsulfonyl group and a dodecylsulfonyl group.
An arylsulfonyl group, for example, a phenylsulfonyl group, etc., an acylamino group, for example, an alkylcarbonylamino group (acetamido group, etc.), an arylcarbonylamino group (for example, phenylcarbonylamino group, etc.), a carbamoyl group, for example, an alkyl group. , Aryl groups (preferably phenyl groups) and the like are substituted, and specific examples thereof include N-methylcarbamoyl group and N-phenylcarbamoyl group. Acyl group, for example, alkylcarbonyl group such as acetyl group. Examples include arylcarbonyl groups such as benzoyl group and the like, sulfonamide groups such as alkylsulfonylamino group and arylsulfonylamino group, specifically, methylsulfonylamino group, benzenesulfonamide group and the like,
Including those substituted with a sulfamoyl group such as an alkyl group or an aryl group (preferably a phenyl group),
Specific examples include an N-methylsulfamoyl group, an N-phenylsulfamoyl group, and the like, and further a hydroxyl group, a nitrile group, and the like.

R ₂ is preferably a hydrogen atom.

In the general formula [I], the number of carbon atoms represented by R ₃ is 2
Examples of the alkyl group of to 8 are ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, n-amyl group, iso-amyl group, 1-methylbutyl group. , 1-ethylpropyl group, n-
Hexyl group, 1-methylamyl group, 1-ethylamyl group, n-heptyl group, 1-methylhexyl group, n-octyl group, 2-ethylhexyl group and the like can be mentioned. Preferably, it has 3 to 8 carbon atoms, and more preferably a linear alkyl group.

In the general formula [I], the group capable of substituting on the benzene ring represented by R ₄ has the same meaning as R ₁ .

In the above general formula [I], X represents an alkylene group, an arylene group, an aralkylene group or a divalent organic group represented by the following general formula [II], and the general formula [II] -AVB- [ In the formula, A and B each represent an alkylene group, an arylene group or an aralkylene group, and V represents a divalent linking group. Examples of the alkylene group represented by X include a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and the like, and those having a substituent are further included,
Substituted with an alkyl group such as methyl-methylene group, ethyl-methylene group, propyl-methylene group, 1-
Methyl-ethylene group, 2-ethyl-ethylene group, 1,1
-Dimethyl-ethylene group, 1-methyl-2-ethyl-ethylene group, 1-hexyl-ethylene group, 2-decyl-ethylene group, 1-ethyl-propylene group, 2-methyl-propylene group, 3-hexyl-propylene group. Group, 1,2-diethyl-3-methyl-propylene group and the like substituted with an aralkyl group, for example, 1-benzyl-ethylene group, 2
-Benzyl-propylene group and the like, and those substituted with an aryl group, for example, 2-phenyl-ethylene group, 3-naphthyl-propylene group and the like.

Examples of the arylene group include a phenylene group and a naphthylene group.

Examples of the aralkylene group include a methylenephenylene group and the like.

The alkylene group, arylene group or aralkylene group represented by A and B represented by the above general formula [II] has the same meaning as the alkylene group, arylene group and aralkylene group represented by X in the above general formula [I], Examples of the divalent linking group represented by V include, for example, -O- and -S.
-, - CONH -, - NHCO -, - SO 2 NH -, -
Examples include groups such as NHSO ₂ —.

Among the alkylene group represented by X, the arylene group, the aralkylene group and the divalent organic group represented by the above formula [II], the alkylene group is particularly preferable.

In the general formula [I], examples of the alkyl group represented by Y include an ethyl group, a butyl group, a hexyl group, an octyl group, a dodecyl group, a hexadecyl group, and an octadecyl group. It may be a branch. Examples of the cycloalkyl group include a cyclohexyl group and the like. Examples of the aryl group include a phenyl group and a naphthyl group. The alkyl group, cycloalkyl group and aryl group represented by Y include those having a substituent. Examples of the substituent include the same groups as the above-mentioned substituents of R ₂ .

In the general formula [I], As the part shown by, the preferable one is Is.

Typical examples of the two-equivalent yellow coupler represented by the above general formula [I] are shown below, but the invention is not limited thereto.

(1) (2) (3) (Four) (Five) (6) (7) (8) (9) (Ten) (11) (12) (13) (14) (15) (16) (17) (18) (19) (20) (twenty one) (twenty two) (twenty three) (twenty four) (twenty five) (26) (27) (28) (29) (30) (31) (32) (33) (34) (35) (36) (37) (38) (39) (40) The coupler of the present invention can be easily synthesized by a usual method.

Examples of the leaving group component include those of R. F. Brunel and S. F. Acree described in American Chemical Journal 43, 505 (1910). It can be synthesized by a method. Further, the carboxylic acid component having a sulfone group,
For example, it can be synthesized by the method described in JP-A-47-24321 and JP-B-56-44420.

These 2-equivalent yellow couplers are disclosed, for example, in the above-mentioned JP-A-
47-24321, JP-B-51-33410 and JP-B-56-44420 can be used for the synthesis.

Next, typical synthetic examples of the coupler of the present invention will be shown.

Synthesis Example 1 (Synthesis of Exemplified Coupler (1)) Synthesis of 1-phenyl-2-n-propylurazole 35.4 g of 1-phenylurazole and 49.2 g of n-propylbromide were added to 180 m of dimethylformamide to give 7
The mixture was heated to 0 ° C., and an aqueous solution prepared by dissolving 8.0 g of sodium hydroxide in 16 m of water was added dropwise over 1 hour. After reacting at 80 ° C for 1 hour, the reaction solution was poured into 900 m of water, and the aqueous solution was adjusted to pH 10
Adjusted to. The side reaction product was extracted with ethyl acetate, the aqueous solution was adjusted to pH 7.5, and the precipitated crystals were filtered. Reconcentration from ethanol gave the desired product. The structure was confirmed by NMR, IR and Mass spectra.

Yield 17.5 g (40%) Melting point 127-179 ° C Synthesis of Exemplified coupler (1) α-chloro-α-pivaloyl-2-chloro-5- (α-
Methyl-β-dodecylsulfonylpropanamide) acetanilide (25.1 g), 1-phenyl-2-n-propylurazole (10.0 g) and acetone (150 m) were refluxed with 6.6 g of potassium carbonate for 6 hours. The insoluble material was filtered off, the acetone was distilled off, ethyl acetate was added, the organic layer was washed with an aqueous solution of potassium carbonate, washed with water, and then neutralized with dilute hydrochloric acid. After drying over magnesium sulfate, ethyl acetate was concentrated under reduced pressure, and the residue was 120 m.
Was recrystallized from methanol to obtain the desired product. The structure is NM
Confirmed by R, IR and Mass spectra.

Yield 22.5 g (69%) Melting point 127-129 ° C. Synthesis Example 2 (Synthesis of Exemplified Coupler (5)) Synthesis of 1-phenyl-2-n-butylurazole 50.0 g of 1-phenylurazole and 77 g of n-butyl bromide Was added to a mixed solution of 200 m of ethanol and 100 m of water. After further adding 14.7 g of sodium hydroxide, the mixture was heated under reflux for 6 hours. After ethanol was distilled off under reduced pressure, 15.0 g of sodium hydroxide and 30 m of toluene were added. The aqueous layer was separated and neutralized with concentrated hydrochloric acid to pH 6.5. The precipitated crystals were filtered, washed with water, dried, and then reconcentrated from toluene to obtain the desired product. The structure was confirmed by NMR, IR and Mass spectra.

Yield 35.3g (54%) Melting point 129-130 ° C Synthesis of Exemplified coupler (5) α-chloro-α-pivaloyl-2-chloro-5- (α-
Methyl-β-dodecylsulfonylpropanamide) acetanilide (60.6 g), 1-phenyl-2-n-butylurazole (25.7 g) and ethyl acetate (400 m) were refluxed with potassium carbonate (15.9 g) for 3 hours. After the reaction, the ethyl acetate solution was washed with water and neutralized with diluted hydrochloric acid. After drying with magnesium sulfate,
Ethyl acetate was concentrated under reduced pressure, and the residue was recrystallized from 300 m of methanol to obtain the desired product. The structure was confirmed by NMR, IR and Mass spectra.

Yield 50.6 g (63%) Melting point 130-132 ° C. Synthesis Example 3 (Synthesis of Exemplified Coupler (10)) Synthesis of 1-phenyl-2-n-hexylurazole 10.0 g of 1-phenylurazole and 18.6 of n-hexyl bromide From g, the same procedure as in Synthesis Example 1 was carried out, and the product was separated by silica gel column chromatography to obtain an oily target product. The structure was confirmed by NMR, IR and Mass spectra.

Yield 8.4 g (56%) Synthesis of exemplified coupler (10) α-chloro-α-pivaloyl-2-chloro-5- (α,
α-Dimethyl-β-octadecylsulfonylpropanamide) acetanilide 14.1 g and 1-phenyl-2-n-
The desired product was obtained from 5.7 g of hexylurazole in the same manner as in Synthesis Example 1. The structure was confirmed by NMR, IR and Mass spectra.

Yield 12.3 g (66%) Melting point 103 to 105 ° C. The yellow coupler of the present invention can be used alone or in combination of two or more kinds.

The yellow coupler of the present invention is useful as a so-called protect dispersion type coupler of a type having a boiling point of 175 ° C. or higher such as dibutyl cotalate, tricresyl phosphate, etc., and used by being dissolved in a high boiling point organic solvent which is difficult to mix with water. Further, without using the high-boiling point organic solvent, a substantially water-insoluble low-boiling point organic solvent such as ethyl acetate and butyl acetate, or a water-soluble solvent such as methanol, ethanol, methyl cellosolve, and methyl isobutyl ketone. It can also be used by dissolving it only in an organic solvent having a low boiling point. Also,
The yellow coupler of the present invention can also be used as a coupler used in a so-called diffusion transfer method in which a photosensitive element having a photosensitive layer and a processing sheet for the purpose of shielding light are brought into contact with each other to form a transfer image on the image receiving layer of the image receiving element. You can also

The yellow coupler of the present invention is disclosed in Japanese Examined Patent Publication No. 49-26585, U.S. Pat. No. 3,486,890, Research Disclosure 12044 and 12
It can also be used in the dye image forming method described in No. 840 and the like.

That is, the yellow coupler of the present invention and the aromatic primary amine developing agent are both contained in a light-sensitive material, and after imagewise exposure, color development is carried out by treatment with an alkali bath black and white developer or heat treatment. A dye image with good gradation can be obtained.

The color-developing agent used in the present invention is an aromatic primary amine compound, which is a p-aminophenol compound or a p-aminophenol compound.
Phenylenediamine-based compounds are typical, and specifically, for example, p-aminophenol, diethyl-p-phenylenediamine hydrochloride, monomethyl-p-phenylenediamine hydrochloride, dimethyl-p-phenylenediamine hydrochloride, 2- Amino-5-diethylaminotoluene hydrochloride,
2-amino-5- (N-ethyl-N-dodecylamino)
-Toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N
-Ethyl-N-β-methanesulfonamidoethyl-4-
Aminoaniline, 4-N-ethyl-N-β-hydroxyethylaminoaniline, N-ethyl-N-β-methoxyethyl-3-methyl-4-aminoaniline, p-toluenesulfonate, N-ethyl-N -[2- (2-Methoxyethoxy) ethyl] -3-methyl-4-aminoaniline, p-toluenesulfonate, N-ethyl-N- {2
-[2 [(2-methoxyethoxy) ethoxy] ethyl}
Examples thereof include -3-methyl-4-aminoaniline and p-toluenesulfonate.

The present invention is also applicable to various color photographic light-sensitive materials, for example, silver halide color photographic light-sensitive materials sensitive to electromagnetic wave energy such as ultraviolet rays, visible light, infrared rays, X-rays, γ-rays and microwaves.

The above color developing agents may be used alone or in combination of two or more, and in the present invention, various components usually added to the color developing solution, for example, alkali agents such as sodium hydroxide, sodium carbonate and potassium carbonate, alkali A metal sulfite, an alkali metal bisulfite, an alkali metal thiocyanate, an alkali metal halide, benzyl alcohol, a thickening agent such as a water softener, a development regulator such as hydrazinic acid, and the like can be optionally contained. The pH value of this color developing solution is usually 7 or more, and most commonly about 10 to about 13.

The color developing solution used in the present invention can be used in combination with a black and white developing solution. The black-and-white developing solution is what is called a black-and-white first developing solution which is generally used for processing a silver halide color photographic light-sensitive material, or one which is used for processing a black-and-white photographic light-sensitive material. Various well-known additives to be added can be contained. A typical additive is 1-phenyl-
3-pyrazolidone, developing agents such as metol and hydroquinone, preservatives such as sulfurous acid, accelerators consisting of alkalis such as sodium hydroxide, sodium carbonate, potassium carbonate, potassium bromide, 2-methylbenzimidazole and methylbenz. Examples thereof include an inorganic or organic inhibitor such as thiazole, a water softener such as polyphosphate, and a surface development inhibitor composed of a trace amount of iodide or mercapto compound.

In the present invention, after the development treatment with the color developing solution, any treatment can be carried out, such as bleaching, fixing or bleach-fixing, stabilizing, washing with water and stopping.

As the bleaching agent added to the bleaching solution or the bleach-fixing solution,
A metal complex salt of an aminopolycarboxylic acid such as an iron (II) complex salt of ethylenediaminetetraacetic acid and / or a metal complex salt of a polycarboxylic acid is preferable. Further, the color development processing may be performed twice or more like the first and the second.

In order to incorporate the yellow coupler of the present invention into a silver halide photographic emulsion of a color photographic light-sensitive material, a conventionally known method can be used. For example, as described above, when using the protect dispersion method, tricresyl phosphate, dibutyl phthalate or the like having a high boiling point of 175 ° C. or higher or a low boiling point organic solvent such as ethyl acetate or butyl propionate may be used alone or in combination. And then mixed with an aqueous gelatin solution containing a surfactant, then emulsified and dispersed by a high-speed rotating mixer or colloid mill, directly added to a silver halide photographic emulsion, coated on a support and dried, or the above emulsion. After the chemical dispersion has been set, it is finely chopped, the low boiling point solvent is removed by a means such as washing with water, this is added to the emulsion, and the support is coated and dried.
In this case, it is generally preferable to add 10 to 300 g of the yellow coupler of the present invention per mol of silver halide, but it goes without saying that various changes may be made depending on the purpose of application.

The silver halide photographic light-sensitive material to which the present invention is applied may be of any kind regardless of type and use. For example, it can be particularly advantageously used for a multilayer negative type color photographic light-sensitive material or a color print photographic light-sensitive material, or a color photographic light-sensitive material for reversal color processing. And
The silver halide used at this time is, for example, silver chloride, silver bromide, silver iodide silver chlorobromide, silver iodobromide, silver chloroiodobromide, or the like.
These silver halide emulsions are prepared by any known method. The silver halide emulsion may be, for example, a so-called conversion emulsion, Lippmann emulsion, covered grain emulsion, or one which is previously fogged optically or chemically, depending on the kind and use of the photographic light-sensitive material. Is appropriately selected. Further, the type of silver halide, the content and mixing ratio of silver halide, the average grain size, the size distribution, etc. are also appropriately selected according to the type and use of the photographic light-sensitive material.

These silver halides are active gelatin: sulfur sensitizers such as allylthiocarbamide, thiourea, cystine, etc .: selenium sensitizers: reduction sensitizers, such as stannous salt, polyamines: noble metal sensitizers, such as gold. Sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate,
2-Aurosulfobenzothiazolemethochloride and the like or water-soluble sensitizers such as ruthenium, rhodium and iridium, specifically ammonium chloroparadate, potassium chloroplatinate and sodium chloroparamaid, etc. Acts as a sensitizer or fog inhibitor depending on the amount.):
Etc., and may be chemically sensitized alone or in appropriate combination (for example, a gold sensitizer and a sulfur sensitizer are used, a gold sensitizer and a selenium sensitizer are used in combination).

Further, this silver halide can be optically sensitized to a desired wavelength range, and for example, a zero methine dye, a monomethine dye,
Optical sensitization can be carried out alone or in combination (for example, supersensitization) with an optical sensitizer such as a cyanine dye such as a dimethine dye or a trimethine dye or a merocyanine dye.

This silver halide is dispersed in a suitable protective colloid to form a photosensitive layer, and as a protective colloid used for the layer structure of the photosensitive layer and other constituent layers such as an intermediate layer, a protective layer and a filter layer. Alkali-processed gelatin is generally used, and other acid-processed gelatin, derivative gelatin, colloidal albumin, cellulose derivatives or synthetic resins such as polyvinyl compounds (for example, polyvinyl alcohol) are used. These can be used alone or in combination. However, acetyl cellulose having an acetyl content of about 19 to 26%, water-soluble ethanolamine cellulose acetate and the like can also be used in combination.

The silver halide photographic light-sensitive material according to the present invention may contain other color couplers in addition to the yellow coupler of the present invention for forming a multicolor image. Other useful couplers include, for example, 5-pyrazolone type magenta couplers, phenol type or naphthol type cyan couplers, and the like. It is also possible to use an azo type colored coupler for automasking, an osazone type compound, a development diffusible dye releasing type coupler and the like in combination with these couplers. At this time, it is desirable to use the desired colorless coupler, which is colorless before color development, in combination with the masking coupler. Further, various couplers for improving photographic characteristics, for example, so-called computing couplers, DIR couplers, BAR (Bleach Accelerator Releasing) couplers and the like can be included.

In the present invention, examples of the magenta coupler that can be used in combination with the yellow coupler of the present invention include pyrazolone-based, pyrazolotriazole-based, pyrazolinobenzimidazole-based and indazolone-based compounds.

Examples of cyan couplers that can be used in combination with the yellow coupler of the present invention include phenol compounds and active sites -o-
Examples thereof include aryl-substituted naphthol compounds and naphthol compounds.

The silver halide emulsion containing the yellow coupler of the present invention prepared as described above is provided on a support together with an undercoat layer, an intermediate layer, a filter layer, an anti-curl layer, a protective layer, etc., if necessary. Thus, a silver halide photographic light-sensitive material applicable to the present invention is produced. The support that can be used at this time is a film of a substrate such as paper, laminated paper (for example, a laminate of polyethylene and paper), glass, cellulose, acetate, cellulose nitrate, polyester, polycarbonate, polyamide, polystyrene, or polyolefin. The shape can be a sheet or a sheet. These supports can be subjected to surface treatments such as various hydrophilic treatments for the purpose of improving the adhesion to each constituent layer. For example, saponification treatment, corona discharge treatment, undercoating treatment, and setting treatment. And so on.

The silver halide photographic light-sensitive material according to the present invention is basically composed of at least a support and a light-sensitive layer provided on the support, but as described above, it is a layer suitable for various positions depending on the purpose. In general, it is composed of several layers or more. Further, the photosensitive layer itself is a multi-layer comprising a layer containing a relatively high-sensitivity silver halide and a layer containing a relatively low-sensitivity silver halide, which are sensitized in the same wavelength range or different wavelength ranges. It may be configured.

Further, the silver halide photographic light-sensitive material according to the present invention has a photographic layer and / or other constituent layers (for example, an intermediate layer, an undercoat layer, a filter layer, a protective layer, an image-receiving layer, etc.) for various photographic purposes depending on the purpose. Additives can be included. Examples of such photographic additives include stabilizers (mercury compounds, triazoles, azaindenes, quaternary benzothiazolium, zinc or cadmium salts, etc.): quaternary ammonium salts, sensitizers such as polyethylene glycols. : Physical property improving agents such as glycerin, dihydroxyalkanes such as 1,5-pentanediol, esters of ethylenebisglycolic acid,
Bisethoxydiethylene glycol succinate, acrylic acid amide, polymer emulsion dispersion, etc .: Hardeners such as formaldehyde, mucochromic acid, halogen-substituted fatty acids such as mucobromic acid, compounds having an acid anhydride group, dicarboxylic acid Chloride, disulfonic acid chloride, methanesulfonic acid biester, aldehyde group 2
Sodium bisulfite derivatives of dialdehydes, bisaziridines, ethyleneimines, etc. separated by ~ 3 carbon atoms: Spreading agents such as saponins, lauryl or oleyl monoethers of polyethylene glycol, sulfated and alkylated polyethylene glycol salts Etc .: Coating aid such as sulfosuccinate etc .: Organic solvent such as coupler solvent (high boiling organic solvent and / or low boiling organic solvent, specifically dibutyl phthalate, tricresyl phosphate, acetone, methanol, ethanol, etc.
Ethylene cell solve etc. ): A so-called DIR compound that releases a color development inhibitor during color development and forms a substantially colorless compound, other antistatic agents, defoamers, ultraviolet absorbers, optical brighteners, anti-slip agents, mats Various agents such as agents, antihalation agents and anti-irradiation agents are used alone or in combination.

The durability of a yellow image can be further improved by incorporating an ultraviolet absorber into the silver halide photographic light-sensitive material containing the yellow coupler of the present invention.

[Specific effects of the invention] The silver halide photographic light-sensitive material containing the 2-equivalent yellow coupler provided by the present invention has excellent color forming property, and particularly, the amount of benzyl alcohol in the color developing solution is reduced or removed. Even in this case, the color development is excellent, and in addition, it has less fog, good light resistance, and excellent storage stability.

Further, the 2-equivalent yellow coupler of the present invention has high solubility in a low boiling point solvent and excellent dispersion stability.

EXAMPLES Next, the present invention will be described in more detail by way of examples, but the embodiments of the present invention are not limited to these.

Example-1 As shown in Table 1, 3.0 × 10 ⁻² mol of each of the yellow coupler of the present invention (shown by the number of the exemplified coupler) and the following comparative coupler was used as 1/0 of each yellow coupler.
A dibutyl phthalate corresponding to the weight of 4 and a phenol compound corresponding to the weight of 1/4 of the yellow coupler were added to a mixed solution of 40 m of ethyl acetate, heated to 50 ° C and dissolved.

This solution was mixed with 10 m of a 10% aqueous solution of alkanol-B (alkylnaphthalene sulfonate, manufactured by DuPont) and 200 m of a 5% aqueous solution of gelatin, and the mixture was passed through a colloid mill several times to emulsify the dispersion (A), and then a Poic integrating sphere. The turbidity was measured with a turbidimeter (made by Nippon Seimitsu Optical KK). At 40 ° C., a half amount of the above dispersion liquid (A) was added to 8
What was kept for a while was used as a dispersion liquid (B), and the turbidity was measured in the same manner.

These dispersions (A) and (B) were used as a gelatin silver chlorobromide emulsion.
It was added to 500 m, and silver chlorobromide was coated on polyethylene laminated paper so as to be 0.25 g / m ^2, and dried to prepare samples 1 to 11 of silver halide photographic light-sensitive materials. This sample was subjected to wedge exposure by a usual method, and processed according to the following steps and processing solution formulation.

Color development 3 minutes 30 seconds Bleaching fixing 1 minute 30 seconds Washing with water 2 minutes 0 seconds Stabilization 1 minute 0 seconds [Color developer (A)] Benzyl alcohol 15m Sodium hexametaphosphate 3.00g Anhydrous sodium sulfite 1.85g Sodium bromide 1.40 g Potassium bromide 0.50 g Boric acid (Na ₂ B ₄ O ₇ · 10H ₂ O) 39.10 g N-ethyl-N- [2- (methanesulfonamidoethyl)]-3-methyl-4-aminoaniline sulfate 4.50
g Water was added to make 1 and the pH was adjusted to 10.3 with sodium hydroxide.

[Bleaching fixer] Ethylenediaminetetraacetic acid ammonium ammonium 61.0 g Ethylenediaminetetraacetic acid-2-ammonium
0 g Ammonium thiosulfate 124.5 g Sodium metabisulfite 13.3 g Sodium bisulfite 2.7 g Water was added to make 1 and the pH was adjusted to 6.5.

[Stabilizing liquid] Glacial acetic acid (trihydrate) 20m Add pure water 800m, and use sodium acetate trihydrate to p
After adjusting to H3.5-4.0, it was finished to 1.

A color photographic developer (B) was prepared in the same manner except that the amount of benzyl alcohol in the color photographic developer (A) was reduced to 1.0 m.

Table 1 shows the turbidity of the dispersion and the result of the dye image obtained by the development treatment.

Comparative coupler (A) (a coupler of the same kind as described in JP-A-48-29432) (B) (Coupler of the same kind as described in JP-A-48-66834) (C) (Coupler described in Japanese Patent Publication No. 56-44420) (D) (Coupler of the same type as described in Japanese Patent Publication No. 56-44420) Phenolic compound As is clear from Table 1 above, in Comparative Samples 8 to 11, Sample 8 has good dispersion stability of the yellow coupler, but its sensitivity and maximum density are still sufficient in the developing process using benzyl alcohol as usual. Furthermore, when the developing solution (B) in which benzyl alcohol was further reduced was used, the sensitivity was lowered and the maximum density was remarkably lowered. Further, in sample 9, the dispersion stability of the yellow coupler is poor, and the maximum density is significantly reduced. Samples 10 and 11
, The initial dispersibility was good, but the dispersion stability over time was poor, and sufficient sensitivity and maximum density could not be obtained in Developers (A) and (B).

On the other hand, Sample 1 using the yellow coupler of the present invention
In Nos. 7 to 7, the dispersion stability was good, there was almost no decrease in the concentration of the dispersion liquid (B) using the developing liquid (A), and the sensitivity and maximum density were sufficiently high, and the yellow couplers were excellent. Further, even when the developing solution (B) in which the amount of benzyl alcohol was reduced was used, the color developing property was better than that of the comparative coupler, and the decrease in the maximum density was small.

Example 2 After corona discharge was applied on a paper support coated on both sides with polyethylene, the following seven layers were sequentially coated from the support side,
Two types of multi-layer color photographic paper sample 12 were prepared.

Layer 1 ... 1.5 g gelatin, 0.33 g (silver equivalent) blue-sensitive silver chlorobromide emulsion (85 mol% silver bromide, average grain size 0.65 μ
m), a layer containing 1.1 × 10 ⁻³ mol of the exemplified yellow coupler (1) and 0.25 g of dioctyl phthalate dissolved in 0.015 g of HQ-1 shown below Layer 2 ... 1.0 g of gelatin, and 0.09 Layer containing 0.06 g of dioctyl phthalate in which 1 g of HQ-1 was dissolved Layer 3 ... 1.3 g of gelatin, 0.27 g (in terms of silver) of green-sensitive silver chlorobromide emulsion (50 mol% of silver bromide, Average particle size 0.45μ
m) and 0.59 × 10 ⁻³ mol of the following magenta coupler M-1
0.2 g of dioctyl phthalate in which 0.015 g of HQ-1 was dissolved, 0.15 g of the following anti-irradiation dye AID
-1 containing layer 4 ... 1.5 g gelatin, 0.8 g UV absorber UV-1
And a layer containing 0.6 g of dioctyl phthalate in which 0.04 g of HQ-1 was dissolved Layer 5: 1.3 g of gelatin, 0.3 g (in terms of silver) of red-sensitive silver chlorobromide emulsion (50 mol of silver bromide) %, Average particle size 0.35 μm),
0.75 × 10 ^-3 mol of the following cyan coupler C-1 and 0.005
Layer containing 0.2 g of dioctyl phthalate in which 1 g of HQ-1 was dissolved Layer 6 ... 1.0 g of gelatin, 0.4 g of UV absorber UV-2
And a layer containing 0.01 g of HQ-1 dissolved in 0.015 g of dioctyl phthalate Layer 7 ... a layer containing 1.0 g of gelatin and 0.015 g of the following filter dye AID-2. The dispersion used was kept at 40 ° C. for 8 hours after dispersion.

M-1 C-1 HQ-1 AID-1 AID-2 UV-1 UV-2 The coupler of Layer 1 of Sample 12 was changed as shown in Table 2 to obtain Sample 1
3-22 were created.

Each sample was exposed to blue light, green light, and red light through a continuous wedge, and then developed in the same processing steps as in Example 1. However, as the developing solution, [color developing solution (A)] and [color developing solution (C)] from which benzyl alcohol was removed were used. The results are shown in Table 2.

From the results shown in Table 2, the yellow coupler of the present invention showed less decrease in maximum density even when developed with the developer (C) from which benzyl alcohol was removed, and had a good color balance as compared with the comparative coupler.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Satoshi Nakagawa 1 Sakura-cho, Hino-shi, Tokyo Konishi Roku Photo Industry Co., Ltd. (56) Reference JP-A-55-70841 (JP, A)

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material containing a coupler represented by the following general formula [I]. General formula [I] [In the formula, R ₁ represents a group capable of substituting on the benzene ring;
₂ represents a hydrogen atom, an alkyl group, an aralkyl group, or an aryl group, R ₃ represents an alkyl group having 2 to 8 carbon atoms, and R ₄ represents a group capable of substituting on the benzene ring. X
Represents an alkylene group, an arylene group, an aralkylene group or a divalent organic group represented by the following general formula [II], and Y represents an alkyl group, a cycloalkyl group or an aryl group. m represents 0 or 1, and n represents an integer of 0 to 5. When n is 2 or more, R ₄ may be selected from the same group or different groups. General formula [II] -A-V-B- [In the formula, A and B each represent an alkylene group, an arylene group or an aralkylene group, and V represents a divalent linking group. ]