JPH01314240A - Silver halide color photographic sensitive material containing yellow coupler - Google Patents

Abstract

PURPOSE:To obtain good color development performance sufficient in development density and high image quality by incorporating a specified active site substituting type yellow dye forming coupler. CONSTITUTION:The photographic sensitive material contains the coupler represented by formula I in which each of R1 and R2 is optionally substituted alkyl, such cycloalkyl, or such aryl; L is a divalent organic bonding group; Z is a hetero atom; m is 1, 2, or 3; each of X and Y is H or a group substitutable on a benzene ring; each of B1 and B2 is a group substitutable on a benzene ring; and each of p and q is 0, 1, or 2, thus permitting sufficient dispersion stability to the silver halide emulsion to be obtained, good color development performance sufficient in color density to be obtained and a high- quality image, especially, high in sharpness to be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic material containing a yellow dye-forming coupler with active site substitution and excellent color development. This invention relates to silver color photographic materials.

BACKGROUND OF THE INVENTION In color photography, as is well known, when a silver halide color photographic light-sensitive material is color-developed, an oxidized aromatic primary amine color developing agent and a coupler are coupled to produce indophenol and indophenol. Aniline, azomethine, phenoxacin, quinone imine, phenazine and similar dyes are produced and a color image is formed. In this case, a subtractive color method is generally used for color reproduction, such as blue,
a silver halide emulsion selectively sensitive to green and red;
Couplers that form yellow, magenta, and cyan pigments, which are complementary colors, are used. For example, as a yellow coupler that forms a yellow dye, a compound having an open-chain active methylene group is generally used, and as a magenta coupler that forms a magenta dye, a pyrazolone type,
Pyrazolobenzimidazole-based, pyrazolotriazole-based, or indasilone-based compounds are used, and as cyan couplers that form cyan dyes, phenol-based or naphthol-based compounds having hydroxyl groups are used.

These color couplers usually require four atoms of silver to form one molecule of dye, but due to reasons such as a shortage of silver resources, silver-saving color couplers have been proposed.

For example, as described in Japanese Patent Publication No. 49-13576, a technique using a so-called 2-equivalent coupler in which one dye molecule is formed from two silver atoms by introducing a leaving group into the active site of a color coupler. It has been known. According to this method, it is possible to reduce the amount of silver used to half the amount of silver used when using conventional so-called 4-equivalent couplers, so in recent years, 2-equivalent couplers have come into widespread use. ing. However, although the known two-equivalent type couplers have a certain degree of performance, it has been desired to further improve the performance. In particular, color development is unsatisfactory, and a highly reactive coupler has been desired from the viewpoint of high image quality and high sensitivity, which have been strongly sought after in recent years, and from the viewpoint of shortening development processing time. That is, by increasing the reactivity of the coupler to the oxidized developing agent, it is possible to improve the sensitivity of the photosensitive material. Furthermore, by increasing the reactivity of the coupler, the amount of the coupler and silver halide used can be reduced unless particularly high sensitivity is desired. As a result, the film thickness of the photosensitive material is reduced and light scattering of incident light is reduced, resulting in improved sharpness. Furthermore, in this case, in color negatives and color reversal sensitive materials, since the blue-sensitive layer is closest to the light incident side, reducing the thickness of the blue-sensitive layer has the greatest effect on improving sharpness. The development of a highly reactive yellow coupler has been eagerly awaited.

On the other hand, in terms of development processing, benzyl alcohol has been added to conventional color developing solutions to increase the color development efficiency in photosensitive materials, but benzyl alcohol has environmental pollution problems, such as B.

It has problems such as increasing the 0, D, (biological oxygen demand) value. Therefore, it has become necessary to reduce the amount of benzyl alcohol added in color development processing. On the other hand, conventional color couplers have had the disadvantage that the color density is significantly reduced when benzyl alcohol is reduced and the development time is shortened in particular. Therefore, there has been a strong desire to develop a yellow coupler that has sufficient color development even when the amount of benzyl alcohol is reduced.

However, among the conventional 4-equivalent type and 2-equivalent type yellow couplers, no one has been found that fully satisfies both of the above problems. Among them, the 2-equivalent type yellow coupler having an aryloxy group as a leaving group is
For example, U.S. Pat.
As described in No. 174839 and No. 60-69653, it is known as a highly reactive yellow coupler. In particular, when a so-called electron-withdrawing group such as a sulfonyl group, sulfamoyl group, carbamoyl group, acyl group, formyl group, nitro group, or cyano group is introduced at the para-position of the aryloxy leaving group, coloring efficiency is significantly improved. It turns out that. However, since the electron-withdrawing group is directly bonded to the aryloxy group, these couplers have the drawbacks of low solubility in high-boiling organic solvents and low dispersion stability in silver halide emulsions. Furthermore, many of the couplers disclosed in these documents have problems such as insufficient coupling reactivity or low color density requiring an increase in the amount of the coupler applied. existing, and further improvements were desired.

U.S. Patent No. 4,401.752, Japanese Patent Publication No. 59-228
No. 649 and No. 62-250446 describe that color development can be further improved by introducing an electron-withdrawing group, especially a so-called "polarizable group", to the ortho position of the aryloxy group. . However, even with the couplers disclosed in these documents, the problems of low solubility in high-boiling organic solvents and low dispersion stability remain unsolved.

On the other hand, in JP-A No. 62-204259, a technique was disclosed for the first time that it is possible to improve color development by introducing a so-called electron-donating group such as an alkoxy group or a thioalkyl group into the ortho position. . However, many of the couplers disclosed in this publication have a heteroatom directly bonded to the ortho position, which has a large effect on the structure and physical properties of the compound, so they have low solubility in high-boiling organic solvents. It was not possible to escape from the drawback of being defective.

Therefore, the present inventors have continued to research these conventional problems, and in particular have conducted research to obtain a yellow coupler that has good color development and sufficient solubility in high-boiling organic solvents, that is, sufficient dispersion stability. As a result of continued efforts, I was able to complete an invention that I was satisfied with on this point.

Purpose of the Invention The purpose of the present invention is to provide a silver halide emulsion with sufficient dispersion stability and high reactivity, by containing an active site-substituted yellow dye-forming coupler, which provides good coloring properties and sufficient coloring. The object of the present invention is to provide a silver halide color photographic light-sensitive material that provides high density, high image quality, and high sensitivity.

Structure of the Invention The above object of the present invention has been achieved by a silver halide color photographic light-sensitive material containing a coupler shown in Funatsuri [I] below.

General formula (1) (wherein R1 and R2 represent a substituted or unsubstituted alkyl group, cycloalkyl group, and °7 lyl group.L
represents a divalent organic linking group, and Z represents a heteroatom. m
represents 1 to 3. X and Y represent a hydrogen atom or a group that can be substituted on the benzene ring. B and B2 represent groups that can be substituted on the benzene ring, and p and q represent 0-2. )
Next, the coupler represented by the general formula [I] will be explained in detail.

In general formula (I), the alkyl group represented by R and R2 is a linear or branched alkyl group having 1 to 3 carbon atoms, such as a methyl group, an isopropyl group, or
Examples include butyl group, t-octyl group, and n-dodecyl group. Further, the cycloalkyl group represented by R+ and R2 includes a cycloalkyl group having 3 to 30 carbon atoms, such as a cyclopropyl group and a cyclohexyl group. The alkyl group and cycloalkyl group represented by R1 and R2 can further have a substituent, and examples of the substituent include a halogen atom, an aryl group, an aryloxy group, a thioalkyl group, an alkylsulfonyl group, an acylamino group, Examples include carbamoyl group, anilino group, alkoxy group, and hydroxy group. Furthermore, the aryl group represented by R1 and R2 in general formula (1) includes an aryl group having 6 to 30 carbon atoms, such as a phenyl group, and this aryl group may further have a substituent. can. Examples of this substituent include an alkyl group, a halogen atom, an alkoxy group, a nitro group, a cyano group, and an amide group.

Examples of the divalent organic linking group represented by the general formula (4) include an alkylene group, an alkenylene group,
or an arylene group, and an alkylene group or an alkenylene group is preferable.

More preferably, an alkylene group or alkenylene group having 1 to 6 carbon atoms, such as a methylene group, an ethylene group,
These include ethynylene group, isopropylene group, cyclopropylene group, 1,3-butadienylene group, and n-butylene group.

Further, L is bonded to the ortho, meta and para positions with respect to the oxygen atom of the aryloxy group bonded to the active site.

In the general formula (I), examples of the atom atom represented by Z include -0-1-N-1 and -S-. R1 represents a hydrogen atom or a substituent having the same meaning as R2 in the general formula (1).

In the general formula (1), m represents an integer from 1 to 3.

When m is 2 or 3, the substituents represented by -(L-Z-R2) may be the same or different.

In the general formula (1), R2 is preferably an alkyl group. More preferably, R2 is represented by the following general formula (I
It is a substituted alkyl group represented by I).

General formula (I I) -(C,H!, Zl)! -IR4 In the formula, Zl represents the same heteroatom as the heteroatom represented by Z in the general formula CI). R4 represents a hydrogen atom or a substituent having the same meaning as R2 in the general formula (1). r represents an integer from 1 to 4, and S represents an integer from 1 to 3.

Examples of groups that can be substituted on the benzene ring represented by X in the general formula (1) include halogen atoms, alkoxy groups, aryloxy groups, acyloxy groups, alkylamino groups, anilino groups, and acylamino groups. , preferably a halogen atom or an alkylene group, particularly a chlorine atom or a methoxy group.

In the general formula (I), the groups that can be substituted on the benzene ring represented by Y include a hydrogen atom, a halogen atom, an alkylcarbonylamino group, an alkylsulfonylamino group, an alkyloxycarbonyl group, an alkylsulfamoyl group, and an arylsulfamoyl group, and particularly preferred are an alkylcarbonylamino group, an alkylsulfonylamino group, and an alkyloxycarbonyl group.

In the general formula (1), examples of the group that can be substituted on the benzene ring represented by B+ include a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, an alkylamino group, an anilino group, an acylamino group, etc. It will be done. Further, p is an integer from 0 to 2.

In the general formula (1), examples of groups that can be substituted on the benzene ring represented by B2 include a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, an alkylamino group, an anilino group, an acylamino group, and a carboxyl group. , alkyloxycarbonyl group, aryloxycarbonyl group, alkylcarbonylamino group, arylcarbonylamino group, alkylcarbonyl group, arylcarbonyl group, formyl group, cyano group, nitro group, carbamoyl group, alkylcarbamoyl group, arylcarbamoyl group, sulfamoyl group, an alkylsulfamoyl group, an arylsulfamoyl group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, an alkylsulfonylamine group, an arylsulfonylamino group, and the like. Further, q is an integer from 0 to 2.

The coupler represented by the general formula CI) has substituents R,,
Any of L, Z, R2, Also good. In this case, the range of carbon atoms shown in each of the above-mentioned substituents may be outside the specified range.

In the present invention, the aryloxy leaving group in general formula (1) represents the following, and specific representative examples of the aryloxy leaving group are shown below. However, the present invention is not limited thereto.

-0<3-CI=CIINHCIl□CIl□OCR,
, Next, specific representative examples of the yellow coupler used in the present invention represented by the general formula (() are shown below, but the present invention is not limited thereto.

(Margin below) Examples of synthesis of the above couplers are shown below.

Synthesis Example-1 (Synthesis of Exemplary Coupler (1)) α-Chloro-
11.8 g of α-pivaloyl-2-chloro-5-heptadecylsulfonylaminoacetanilide, 3.6 g of α-(2-methoxyethoxy)-p-cresol and 2.2 g of triethylamine were dissolved in 10 d of acetonitrile and heated under reflux for 6 hours. I let it happen. After refluxing, acetonitrile was distilled off under reduced pressure. The obtained dry matter was dissolved in 200ml of ethyl acetate.
1 and washed three times with 3N hydrochloric acid 100%.

After washing with water, the organic layer was separated, dried over magnesium sulfate, ethyl acetate was distilled off under reduced pressure, and separated and purified by column chromatography, yielding 10.2 g of the desired example coupler (1). (yield 72%). The structure of the exemplary coupler (1) is shown in the NMR spectrum, I
Confirmed by R spectrum and mass spectrum.

Synthesis Example-2 (Synthesis of Exemplary Coupler 23) α-Chloro-α
-(4-methoxybenzoyl)-2-chloro-5-dodecyloxycarbonylacetanilide 8.5 g, α-(
2-methoxyethylamino)-p-cresol 2.7g
and 1.8 g of triethylamine in 15 g of acetonitrile.
0d and heated under reflux for 8 hours. After refluxing, post-treatment was carried out in the same manner as in Synthesis Example 1, and separation and purification by column chromatography yielded 6.9 g of the desired exemplary coupler (23) (yield: 65%).

The structure of the exemplary coupler (23) was confirmed by NMR spectrum, IR spectrum, and mass spectrum.

Other couplers of the present invention were also synthesized starting from the corresponding starting materials and following the procedures described in Synthesis Examples 1 and 2.

The above yellow couplers of the present invention can be used alone or in combination of two or more. It may also be used in combination with any known pivaloylacetanilide or benzoylacetanilide yellow coupler.

The yellow coupler of the present invention includes, for example, dibutyl phthalate,
It is useful as a so-called protected dispersion type coupler which is used by dissolving it in a high boiling point organic solvent such as tricresyl phosphate, which has a boiling point of 175°C or higher and is difficult to miscible with water. Use only by dissolving it in substantially water-insoluble low-boiling organic solvents such as ethyl acetate and butyl acetate, or water-soluble low-boiling organic solvents such as methanol, ethanol, methyl cellosolve, and methyl isobutyl ketone. You can also do that.

The yellow coupler of the present invention can also be used as a coupler for the so-called diffusion transfer method, in which a photosensitive element having a photosensitive layer is brought into contact with a processing sheet for the purpose of blocking light, etc. to form a transferred image on the image receiving layer of the image receiving element. It can also be used.

Moreover, the yellow coupler of the present invention is disclosed in Japanese Patent Publication No. 49-2658.
No. 5, U.S. Patent Section 3.486.890, Research Disclosure
12044, 12840, 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,
By processing with an alkali bath black and white developer or by heat treatment, color development can be carried out and a dye image with good gradation properties can be obtained.

The color developing agent used in the present invention is an aromatic primary amine compound, and is a p-aminophenol or p-aminophenol compound.
Typical examples are phenylene diamines, such as 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)]
Examples include ethyl)-3-methyl-4-aminoaniline, p-)luenesulfonate, and the like.

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

The color developing agents mentioned above may be used alone or in combination of two or more, and in the present invention, various components normally added to color developing solutions, such as alkaline agents such as sodium hydroxide, sodium carbonate, and potassium carbonate; Metal sulfites, alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, thickening agents such as water softeners, and development regulators such as hydrazine acid may optionally be included. The pH value of this color developing solution is usually 7 or more, most preferably about 10 to about 13.

The color developer used in the present invention can be used in combination with a black and white developer. The black-and-white developer is a so-called black-and-white first developer used in the processing of silver halide color photographic light-sensitive materials, or a black-and-white developer used in the processing of black-and-white photographic light-sensitive materials. Various well-known additives can be included. A typical additive is 1-phenyl-
Developing agents such as 3-pyrazolidones, methol and hydroquinone, preservatives such as sulfites, accelerators consisting of alkalis such as sodium hydroxide, sodium carbonate, potassium carbonate, potassium bromide, 2-methylbenzimidazole, methyl Examples include inorganic or organic inhibitors such as benzthiazole, water softeners such as polyphosphates, and surface overdevelopment inhibitors consisting of trace amounts of iodides and mercapto compounds.

In the present invention, after development with a color developing solution, any desired treatment can be carried out, including bleaching, fixing, bleach-fixing, stabilization, washing with water, and stopping.

Bleach agents added to bleach or bleach-fix solutions include:
Metal complex salts of aminopolycarboxylic acids and/or metal complex salts of polycarboxylic acids such as iron(n) complex salts of ethylenediaminetetraacetic acid are preferred.

Further, the color development treatment may be performed two or more times, such as the first and second times.

Conventionally known methods can be used to incorporate the yellow coupler of the present invention into a silver halide photographic emulsion of a color photographic light-sensitive material. For example, when using the protect dispersion method as described above, a high boiling point organic solvent with a boiling point of 175°C or higher such as tricresyl phosphate or dibutyl phthalate or a low boiling point organic solvent such as ethyl acetate or butyl propionate may be used alone or in combination. After dissolving in a silver halide photographic emulsion, it is mixed with an aqueous gelatin solution containing a surfactant, then emulsified and dispersed in a high-speed rotating mixer or colloid mill, and then directly added to a silver halide photographic emulsion, coated on a support and dried, or Alternatively, after the emulsified dispersion is set, it may be cut into pieces, the low boiling point solvent may be removed by means such as washing with water, and then this may be added to the emulsion, which may be applied to a support and dried.

In this case, it is generally preferable to add 10 to 300 g of the yellow coupler of the present invention per mole of silver halide, but of course this may be varied depending on the purpose of application.

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

These silver halides include active gelatin: sulfur sensitizers, such as allylthiocarbamide, 1,000 urea, cystine, etc.; selenium sensitizers: reduction sensitizers, such as stannous salts, polyamines, etc.; noble metal sensitizers, such as Gold sensitizers specifically potassium aurithiocyanate, potassium chloroaurate, 2
- Sensitizers such as aurosulfobenzothiazole methochloride or water-soluble salts such as ruthenium, rhodium 1, iridium, etc., specifically ammonium chloroparadate, potassium chlorooleate, sodium chloroparamaid, etc. The seeds act as sensitizers, fog suppressants, etc. depending on the amount.

): may be chemically sensitized either alone or in appropriate combination (for example, a combination of a gold sensitizer and a sulfur sensitizer, a combination of a gold sensitizer and a selenium sensitizer, etc.). .

Furthermore, this silver halide can be optically sensitized to a desired wavelength range, such as zeromethine dye, monomethine dye,
Optical sensitization can be carried out using optical sensitizers such as cyanine dyes such as dimethine dyes and trimethine dyes or merocyanine dyes alone or in combination (for example, supercolor sensitization).

This silver halide is dispersed in a suitable protective colloid to constitute a photosensitive layer, and is used as a protective colloid to be used in the composition of the photosensitive layer and other constituent layers such as an intermediate layer, a protective layer, and a filter layer. Alkali-processed gelatin is common, and other types include acid-processed gelatin, derivative gelatin,
There are synthetic resins such as colloidal albumin, cellulose derivatives, and polyvinyl compounds (e.g., polyvinyl alcohol), which are used alone or in combination7, but in addition, acetyl cellulose with an acetyl content of about 19 to 26%, water-soluble It is also possible to use ethanolamine cellulose acetate or the like in combination.

The silver halide photographic material according to the present invention may contain other color couplers together with the yellow coupler of the present invention in order to form a multicolor image. Other useful couplers include, for example, 5-pyrazolone magenta couplers, phenolic or naphthol cyan couplers, and the like. In combination with these couplers, it is also possible to use azo-type colored couplers, osazone-type compounds, development-diffusible dye-releasing couplers, etc. for auto-masking. Further, at this time, it is desirable to use a desired colorless coupler, which is colorless before color development, together with the above-mentioned masking coupler. Furthermore, various couplers such as so-called competing couplers, DIR couplers,
BAR (Bleach Accelerator R
It may also include a coupler called a leasing coupler or the like.

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 indasilone-based compounds.

Examples of cyan couplers that can be used in combination with the yellow coupler of the present invention include phenol compounds, naphthol compounds substituted with -0-aryl at the active site, and naphthol compounds.

The silver halide emulsion containing the yellow coupler of the present invention prepared as described above is applied to a subbing layer, an intermediate layer,
A silver halide photographic light-sensitive material applicable to the present invention is prepared by forming the silver halide photosensitive material on a support together with a filter layer, an anti-curl layer, a protective layer and the like. Supports that can be used at this time include paper, laminated paper (for example, a laminate of polyethylene and paper), glass, films of substrates such as cellulose, acetate, cellulose nitrate, polyester, polycarbonate, polyamide, polystyrene, and polyolefin. It can be in the form of a shape or a sheet. These supports can be subjected to various surface treatments such as hydrophilic treatment for the purpose of improving adhesion to each constituent layer, such as saponification treatment, corona discharge treatment, subbing treatment, and setting treatment. Processing such as the following is performed.

The silver halide photographic material according to the present invention basically consists of at least a support and a photosensitive layer provided thereon, but as described above, suitable layers may be placed at various positions depending on the purpose. It is generally composed of several layers or more. In addition, the photosensitive layer itself is composed of a layer containing silver halide with relatively high sensitivity and a layer containing silver halide with relatively low sensitivity, which are sensitized to the same wavelength range or different wavelength ranges. It may be configured as follows.

Furthermore, the silver halide photographic light-sensitive material according to the present invention can be used for various photographic purposes depending on the purpose of the photosensitive layer and/or other constituent layers (for example, intermediate layer, subbing layer, filter layer, protective layer, image-receiving layer, etc.). Additives may 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 improvers such as glycerin, dihydroxyalkanes such as 1,5-pentadiol, esters of ethylene bisglycolic acid, bisethoxydiethylene glycol succinate, amides of acrylic acids, and polymers. Emulsified dispersion ring: Hardeners such as formaldehyde, halogen-substituted fatty acids such as mucochloric acid, mucobromic acid, compounds with acid anhydride groups, dicarboxylic acid chlorides, disulfonic acid chlorides, vinylesters of methanesulfonic acid, aldehyde groups with 2
Sodium bisulfite derivatives of dialdehydes separated by ~3 carbon atoms, bisaziridines, ethyleneimines, etc.: extending agents such as saponins, lauryl or oleyl monoethers of polyethylene glycol, sulfated and alkylated polyethylene glycol salts Ring: Coating aid such as sulfosuccinate Ring: Organic solvent such as coupler solvent (high boiling organic solvent and/or low boiling organic solvent, specifically dibutyl phthalate, tricresyl phosphate, acetone, methanol, ethanol,
Ethylene Molsolve etc. ): So-called DIR compounds that release color development inhibitors and produce substantially colorless compounds during color development, antistatic agents, antifoaming agents, ultraviolet absorbers, optical brighteners, and anti-slip agents. , matting agents, halation or irradiation inhibitors, etc., may be used alone or in combination.

The durability of the yellow image can be further improved by containing an ultraviolet absorber in the silver halide photographic material containing the yellow coupler of the present invention.

EXAMPLES Next, the present invention will be explained in more detail with reference to Examples, but the embodiments of the present invention are not limited to these.

Example-1 As shown in Table 1, the yellow coupler (
10 g of each of the above-mentioned exemplary couplers (indicated by numbers) and the following comparative couplers were added to a mixture of 2.0 ml of dibutyl phthalate and 20 d of ethyl acetate, and dissolved by heating to 50°C.

This solution was mixed with alkanol-sulfonate solution 5d and gelatin 5% aqueous solution 100a+f, and passed through a colloid mill several times to emulsify. After emulsification, 20
The samples were stored at °C for 48 hours, and then observed with the naked eye using a 20x magnifying glass.

The results are shown in Table 1.

The following couplers were used for comparison.

(Coupler described in U.S. Patent No. 4,401,752) (Coupler described in JP-A-60-69653) (Coupler described in U.S. Patent No. 4,401,752)
．． 4.81.752) (Coupler described in JP-A-62-153954) (Coupler described in JP-A-55-142340) Y-6 (Coupler described in U.S. Pat. No. 3.933.501) ( Coupler described in JP-A-59-1°74839)
2-204259 (Coupler described in No. 2-204259) (hereafter blank) Table 1 As is clear from Table 1 above, none of the yellow couplers of the present invention precipitates, and the dispersion of the emulsion over time is more stable than the comparative couplers. It turned out that he has excellent sex.

Example 2 After corona discharge was applied to a paper support coated with polyethylene on both sides, the following seven layers were sequentially applied from the support side,
Multilayer color photographic paper sample 13 was produced.

1st layer: 1.5 g of gelatin, 0.33 g (in terms of silver) of blue-sensitive silver chlorobromide emulsion (silver bromide 85 mol%, average grain size 0.65 μm), 1. 1 x 10-'' moles of exemplary yellow coupler (1) and 0.015 g of H as shown below.
Layer 2 containing 0.25 g of dioctyl phthalate dissolved in Q-1...1.0 g of gelatin, and 0.09 g
Layer 3 contains 0.06 g of dioctyl phthalate dissolved in HQ-1 of 50 mol % silveride, average particle size 0.45 µm), 0.59 x 10-'' mol of magenta coupler M-1 below and 5 g of O,Ol HQ
-1 dissolved in 0.2 g of dioctyl phthalate, 0.
Layer 4 containing 15 g of the following anti-irradiation dye AID-1: 1.5 g gelatin, 0.8 g ultraviolet absorbing layer UV-1 and 0.04 g HQ-1. Melted 0,
Layer 5 containing 6 g of dioctyl phthalate: 1.3 g of gelatin, 0.3 g (in terms of silver) of red-sensitive silver chlorobromide emulsion (silver bromide 50 mol%, average grain size 0) .3
Layer 6 containing 0.2 g of dioctyl phthalate dissolved in 5 μm), 0.75 , Og of gelatin, 0.4g of ultraviolet absorption layer UV-2 and O,Olg of HQ-1 dissolved in 0,0
A layer containing 15 g of dioctyl phthalate Seventh layer: A layer containing 1.0 g of gelatin and 0.015 g of the following filter dye AID-2. Those kept at 40°C for 8 hours were used.

I! HQ-1 0 ID-1 ID-2 V-1 V-2 Next, Samples 14 to 23 were prepared by changing the coupler of the first layer of Sample 13 as shown in Table 2. Obtained sample 13-2
3 was wedge-exposed in a conventional manner and processed according to the following steps and processing solution formulation.

Color development 3 minutes 30 seconds Bleach fixing 1 minute 30 seconds Washing with water 2 minutes 0 seconds Stabilization
1 minute 0 seconds [Color photographic developer (A)] Benzyl alcohol 15ml Sodium hexametaphosphate 3.00g Anhydrous sodium sulfite 1.85g Sodium bromide 1.40g Potassium bromide
0.50 g boric acid CNazB, O, r-10H20) 39.1
0 g N-ethyl-N-(2-(methanesulfonamidoethyl))-3-methyl-4-aminoaniline sulfate 4.50 g Water was added to make the solution 12, and the pH was adjusted to 10 with sodium hydroxide.
Adjusted to 3.

[Bleach-fix solution]

Iron ammonium ethylenediaminetetraacetate 61.0 g Ethylenediaminetetraacetate-2-ammonium 5.0 g Ammonium thousand sulfate 124.5 g Sodium metabisulfite 13.3 g Sodium bisulfite 2.7 g Add water to adjust the pH to 12. Adjusted to 6.5.

[Stabilizing liquid]

20 d of glacial acetic acid (trihydrate) and 800 mft of pure water were added, the pH was adjusted to 3.5 to 4.0 using sodium acetate trihydrate, and the pH was adjusted to 11.

A color photographic developer (B) was prepared in the same manner as the above color photographic developer (A) except that benzyl alcohol was omitted.

Table 2 shows the results of the dye images obtained after the development process.

(The following is a blank space) As is clear from Table 2, the yellow coupler of the present invention can be developed with a developer (A) containing benzyl alcohol as well as with a developer (A) from which benzyl alcohol has been removed.
Even when developed with B), there was little decrease in maximum density, and the color balance was better than that of the comparative couplers.

Example 3 On a triacetyl cellulose film support, each layer having the composition shown below was sequentially formed from the support side to prepare a single-layer color photographic element sample 24.

1st layer: Gelatin layer containing antihalation black colloidal silver 2nd layer: Intermediate gelatin layer 3rd layer: Blue-sensitive emulsion layer Silver iodobromide emulsion Coated silver amount: 0.12 g/m"
Exemplary coupler (1)...0.0% per mole of silver.
15 mole tricresyl phosphate...0.3g/m"
Fourth layer: protective layer gelatin layer Samples 25 to 34 were prepared by changing the coupler of the first layer of sample 24 as shown in Table 3. This sample was wedge exposed according to conventional methods and processed according to the following steps and developer formulation.

Processing process (38°C) Color development 3 minutes 15 seconds bleaching
Rinse with water for 6 minutes and 30 seconds, set for 3 minutes and 15 seconds
Arrive: Wash for 6 minutes and 30 seconds
Stabilized for 3 minutes and 15 seconds
Drying for 1 minute and 30 seconds The composition of the treatment liquid used in each treatment step is as follows.

[Color developer] 4-Amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline sulfate 4.75g Anhydrous sodium sulfite 4.25g Hydroxylamine 1/2 sulfate 2.0g Anhydrous potassium carbonate
37.5 g sodium bromide
1.3 g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Add water to make 11.

[Bleach solution] Ethylenediaminetetraacetic acid iron ammonium salt 100.0g Ethylenediaminetetraacetic acid diammonium salt 10.0g Ammonium bromide 150.0g Glacial acetic acid 10.0ml Add water and add 1! and using ammonium water, pH=
Adjust 8 times to 6.0.

[Fixer]

Ammonium thiosulfate 175.0 g
Anhydrous sodium sulfite 865g Sodium metasulfite 2.3g Add water to make If, and adjust to pH=6.0 using acetic acid.

[Stabilizing liquid]

Formalin (37% aqueous solution) 1, 5
ml Konidax (Konica H)? ,
5 Add rtdl water to make 11.

After processing, the results of the dye images obtained are shown in Table 3.

(Margins below) Table 3 *Sensitivity is expressed as a relative sensitivity with the sensitivity of sample 24 as 100.

As is clear from Table 3, compared to the comparative couplers, the yellow coupler of the present invention was found to provide higher sensitivity and maximum density without increasing fog.

Example 4 Multilayer color photographic element sample 35 was prepared by sequentially forming layers having the compositions shown below on a triacetyl cellulose film support from the support side.

First layer: antihalation layer (HC-1) Gelatin layer containing black colloidal silver.

2nd layer: middle layer (1, L,) 2.5-di-t-octyl hydroxide A gelatin layer containing an emulsified dispersion of non-alcoholic acid.

3rd layer: low-sensitivity red-sensitive silver halide emulsion layer (RL-1) average grain size (r) 0.30 am, monodisperse emulsion (emulsion I) consisting of AgBr1 containing 6 mol% of Ag I...・・Silver coating amount 1.8g1
0f sensitizing dye I... 6 x 10-s mol per mol of silver Sensitizing dye ■... 1.0 x 10-' mol cyan coupler (C-2) per 1 mol of silver ...0.06 mole colored cyan coupler (CC-1) for 1 mole of silver...1 silver
0.0 per mole. OO3 mol DIR compound (D-1)... 0.0015 mol per mol of silver DIR compound (D-2)... 0.0015 mol per mol of silver. OO2 mole 4th layer: High sensitivity red-sensitive silver halide emulsion layer (RH-1) Average grain size (r) 0.5 am, monodispersed emulsion (emulsion ■) consisting of AgBr1 containing 17.0 mol% Ag. ... Silver coating amount 1.3g/
rd sensitizing dye ■... 3 x 10-S mols per 1 mol of silver sensitizing dye ■... 1.0 x 10-'Morsian coupler' (C- 2)...0.02 per mole of silver
Mol colored cyan coupler (CC-1)・・・Silver 1
0.0015 mol to mol DIR compound (D-2)... 0.001 mol to 1 mol of silver 5th layer: Intermediate layer (1,L,) Same as 2nd layer, gelatin layer·.

6th layer: Low-sensitivity green-sensitive silver halide emulsion layer (GL-1) Emulsion - ■... Coated iI amount 1.5 g/po Sensitizing dye ■... Per mole of silver 2.5 x 10-' molar sensitizing dye...
... 1.2 x 10-' moles per mole of silver Magenta coupler (M-2) ...0.050 per mole of silver
Mol colored magenta coupler (CM-1)...0.009 mol DIR compound (D-1)...0.0010 mol DIR compound per 1 mol silver (D-3)...0.0030 mol per 1 mol of silver 7th layer: High-frequency glaucophobic silver halide emulsion layer (OH-1) Emulsion - ■... Coating amount of silver: 1.4g/sensitizing dye ■
・・・・・・ 1.5×10-' mol sensitizing dye for 1 mol of silver...
... 1.0 x 10-' mole magenta coupler (M-2) for 1 mole of silver...0.020 for 1 mole of silver
Mol Colored Magenta Coupler (CM-1> ・・・・・・
0.002 mol per 1 mol of DIR compound (D-3) 1! 0.0010 mol per 1 mol 8th layer: Yellow filter layer (YC-1) Yellow colloidal silver and an emulsified dispersion of 2,5-di-t-octylhydroquinone.

9th layer: low-speed blue-sensitive silver halide emulsion layer (BL-1) A containing 6 mol% of average grain size 0.48 umSAg I
Monodispersed emulsion (emulsion ■) consisting of gBr1... Silver coating amount o, 9 g/
Sensitizing dye V... 1.3 x 10-' mol per 1 mol of Sl Comparative coupler (Y-1)... 0.29 mol to 1 mol of silver tricresyl phos Fate...0.7d/r
RF 10th layer: High sensitivity blue sensitive emulsion layer (BH-1) Average grain size 0.8 um AgBr containing 15 mol% SAg I
Monodisperse emulsion (emulsion ■) consisting of 1... Silver coating amount 0.5 g/
Sensitizing dye V... 1.0 x 10-5 mol per 1 mol of SIJ Comparative coupler (Y-1)... 0.08 mol per mol of silver DIR compound (I )-2)...0.0% per mole of silver. OO15 mol tricresyl phosphate...0.2d/r
d 11th layer: First protective layer (Pro-1) Silver iodobromide (Ag 11 mol% average grain size 0.07 μm) 1! Coating amount: 0.5 g/rrf Gelatin layer containing ultraviolet absorbers UV-1 and UV-2.

12th layer: Second protective layer (Pro-2) Gelatin layer containing polymethyl methacrylate particles (diameter 1.5 μm) and formalin scavenger (H3-1) In addition to the above composition, each layer also contains hardened gelatin. agent (H-1
) and surfactants were added.

The compounds contained in each layer of Sample 1 are as follows.

Sensitizing dye I: Anhydro 5,5'-dichloro-9-ethyl-3,3'-di(3-sulfopropyl)thiacarbocyanine hydroxide Sensitizing dye ■: Anhydro 9-ethyl-3,3'-° Di(3-sulfopropyl)-4,5,4',5'-dibenzothiacarbocyanine hydroxide sensitizing dye ■: Anhydro 5,5'-diphenyl-9-ethyl-3,3'-di(3- sulfopropyl) oxalubocyanine hydroxide sensitizing dye ■: Anhydro 9-ethyl-3,3'-di(
3-sulfopropyl)-5,6,5',6'-dibenzoxacarbocyanine hydroxide sensitizing dye V: anhydro3,3'-di(3-sulfopropyl)-4,5-benzo-5'- Methoxythiacyanine (blank below) C-1 -I D-2 0 M-1 M-1 M-2; Js S-1 Furthermore, comparative coupler Y-1 in the 9th layer and 10th layer of sample 35 was changed as shown in Table 4, and samples 36-4
0 was created. In this case, the amounts of the coupler and tricresyl phosphate were adjusted so that the yellow color density was the same while keeping the ratio of both amounts constant.

The obtained sample was exposed to light through a pattern for MTF measurement using the tip of the mouth, and developed in the same manner as in Example 3.

After development, in order to evaluate the sharpness of each sample, the MTF value at a spatial frequency of 20 cycles/mm was measured using blue light.

The results are shown in Table 4.

The IMTF values in Table 4 are shown as relative values with the MTF of Sample 35 as 100.

As is clear from Table 4, the yellow coupler of the present invention was found to be more effective in improving sharpness than the comparative couplers.

Effects of the Invention The present invention provides a silver halide emulsion with sufficient dispersion stability by using a yellow dye-forming coupler represented by the general formula [I] in a silver halide color photographic light-sensitive material. Moreover, the coloring property is good and sufficient coloring density can be obtained.

Moreover, even if the silver halide color photographic material is not damaged, high-quality images, especially images with excellent sharpness, and high sensitivity can be obtained.

Sender: Konica Corporation Agent Patent Attorney Mikio Nakajima 1 other person

Claims (1)

[Scope of Claims] A silver halide color photographic material characterized by containing a coupler represented by the general formula [I] in at least one layer. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. , Z represents a heteroatom. m represents 1 to 3. X and Y represent a hydrogen atom or a group substitutable to the benzene ring. B_1 and B_2 represent a group substitutable to the benzene ring, and q represents 0 to 2.)