JPH01172954A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a cyan image of a high density with high sensitivity by incorporating a specific cyan dye forming coupler into at least one layer of silver halide emulsion layers. CONSTITUTION:The cyan dye forming coupler expressed by the formula I is incorporated into at least one layer of the silver halide emulsion layers. In the formula I, A denotes a substd. or unsubstd. alkyl group or aryl group; B denotes a substd. or unsubstd. aryl group. X denotes a substd. or unsubstd. alkyl group, aryl group, alkyl amino group, aryl amino group, alkoxy group or aryl oxy group; Y denotes a substd. or unsubstd. alkyl group, aryl group, heterocyclic group. The cyan image of the high density is thereby obtd. with the high sensitivity and the loss of the dyes is decreased even if a bleaching bath or bleath-fix bath fatigued by running is used. In addition, the stable cyan image is obtd. without picking up the deviation in the performance of the emulsion.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a silver halide photographic material containing a novel cyan coupler.

[Background of the Invention] Silver halide color photographic materials generally use so-called dye-forming couplers that react with a light-sensitive silver halide emulsion and an oxidized aromatic primary amine developing agent to form a dye.

Among these, phenols or naphthols have been widely used as cyan couplers, and these include, for example, U.S. Pat.
No. 730, No. 2,474,293, No. 2,772
, No. 162, No. 2,895,826, No. 2,36
No. 7.531, No. 3,002,836, No. 3.0
No. 34.892, No. 3,041゜836, Japanese Unexamined Patent Publication No. 1973
6-65134 etc.

Naphthol-based compounds, which have been widely used as cyan couplers for color negative films, have a tendency to produce leuco dyes when processed with tired bleach or bleach-fix solutions.

However, a drawback was found that dye loss occurred.

In order to improve these drawbacks, a cyan coupler having a phenylureido group at the 2-position of the phenol was developed, and the above dye loss was dramatically improved.

However, in our research, these two
It has been found that couplers having a phenylureido group in position have significant drawbacks. In other words, these couplers were sensitive to slight fluctuations in the performance of the emulsion of the solder, and the results always varied, making them very difficult to use.

In addition, as a means of increasing the sensitivity of photographic materials, couplers with even higher color development and higher density have been desired.

[Object of the Invention] The first object of the present invention is to provide a silver halide photographic material that provides a cyan image with high sensitivity and high density.

A second object of the present invention is to provide a silver halide photographic material that can produce cyan images with little dye loss even when using a bleach solution or a bleach-fix solution that has been exhausted by running.

A third object of the present invention is to provide a silver halide photographic material that does not pick up on slight fluctuations in emulsion performance and provides stable cyan images.

[Structure of the Invention] The object of the present invention is to provide a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, in which at least one of the silver halide emulsion layers has the following -
This was achieved by providing a silver halide photographic material containing a cyan dye-forming coupler represented by [I].

The following is a blank general formula [1'] Alkyl group, aryl group,
Represents an alkylamino group, an arylamino group, an alkoxy group, or an aryloxy group.

Y is a substituted or unsubstituted alkyl group, aryl group,
Examples of substituents for A, B, X and Y include alkyl groups, aryl groups, heterocyclic groups, alkoxy groups (e.g. methoxy
2-methoxyethoxy group), aryloxy group (e.g., phenoxy group, 2.4-';-tert-amylphenoxy group, 2-chlorophenoxy group), carboxy group,
carbonyl group (e.g. acetyl group, benzoyl group), ester group (e.g. methoxycarbonyl group, phenoxycarbonyl group, acetoxy group, benzoyloxy group, butoxysulfonyl group, toluenesulfonyloxy group),
Amide group (e.g., acetylamino group, ethylcarbamoyl group, dimethylcarbamoyl group, methanesulfonamide group, butylsulfamoyl group), sulfamide group (e.g., dipropylsulfamoylamino group), imide group (e.g., succinimide group, hydantoinyl group), ureido group (e.g., phenylureido group, dimethylureido group), sulfonyl group (e.g., methanesulfonyl group), phosphoric acid amide group (e.g., diethyl phosphate monoamide group, tetramethyl phosphoric acid triamide group) ,
It is selected from a hydroxy group, a cyano group, a nitro group, a halogen atom, a thio group (eg, ethylthio group, phenylthio group), an amino group (eg, monobutylamino group, dipropylamino group, simple amino group), and the like.

An example of the compound represented by the general formula [I] will be shown below with specific examples.

The coupler of the present invention can be easily synthesized, for example, by the following route.

XCQC) ICONHY H XC0C) IconHY XCOCHCONHY XCoC
HCONHY Next, a synthesis example will be shown.

Synthesis of Exemplified Compound 5 1.

CH2(COOC2H!112 + C'aHsNHa
−>CHa (CONHCaHs12[11[2]
[31 Diethyl malonate 64(] and 128 g of monoethylamine 35χ aqueous solution were mixed and left overnight at room temperature.

Concentrate to dryness and dissolve the crystals in 200 ml of ethyl acetate and 8 ml of acetone.
Recrystallize from 0ml of the mixed solution. 31.50 at 50χ yield
White needle crystals [3] were obtained.

2゜CH2(CONHC2Hs)2+ Br2-+BrCH
(CONHC2Hs)2[3] [
4] Intermediate [3] 25! Dissolve I+ in 200 ml of chloroform and add 4.3 cal of bromine. After stirring for 2 hours at 40-50°C, water is added. The chloroform layer is washed with an aqueous solution of sodium carbonate and an aqueous solution of sodium sulfite, and then dried.

After concentrating the chloroform, dissolve the crystals in 150ml of acetonitrile.
1 to obtain intermediate [4] 16.9!11.

(t) CsL+ Intermediate C4] 14.90, Intermediate [5126,4a 8.3 g of potassium carbonate are mixed in 300 ml of acetone and heated to reflux with stirring. After 7.5 hours, the inorganic substances were separated by furnace and the solvent was distilled off. The crystals were recrystallized from 400 ml of acetonitrile to obtain Intermediate [6] 29.5.0.

4°OH [6118,3+1 was dissolved in 200ml of methanol, and then sodium methylate 1. Add OQ and heat under reflux for 30 minutes. After draining the reaction solution, collect the precipitated crystals. Recrystallize from 390 ml of acetonitrile.

Intermediate [7114,4G was obtained.

5°OH [7] 12t11 is dissolved in 10G of chloroform (11 times), cooled to below 5°C, and 2.6ml of concentrated nitric acid is added dropwise.5
After stirring for 2.5 hours at a temperature below 0.degree. C., water is added. Furthermore, the chloroform layer is washed with water, dried, and concentrated to obtain a yellow candy-like substance.

10.1 g of intermediate [8] was isolated by column chromatography using a developing solvent of hexane:ethyl acetate 9:1.

6゜[8110Q was dissolved in 100ml of ethyl acetate and Pd/C
Add G and 4Q to perform hydrogenation reduction.

Add Pd/C to F and 30 mg of 3.2G toimidazol as raw material [9], and heat and reflux for 2 hours. After cooling, the precipitated crystals are collected and recrystallized from a mixed solution of 100 ml of ethyl acetate and 50 ml of hexane. White exemplary compound [5
19.2 CI was obtained. All these reaction products are tHI
The structure was confirmed by n and mass spectra.

The cyan coupler of the present invention has a silver halide emulsion layer and/or
The cyan coupler of the present invention is typically blended into a silver halide emulsion, and this emulsion is coated onto a support to form a silver halide layer. It can be used as a color photographic material containing silver halide in the emulsion layer. This silver halide color photographic light-sensitive material may be monochromatic or multicolored.
In the case of multicolor, the cyan coupler of the present invention is usually contained in a red-sensitive emulsion, but it may also be contained in a non-sensitized emulsion or an emulsion layer sensitive to the three primary color regions of the spectrum other than red.

Each structural unit forming a dye image in the present invention is
It consists of a single-hole emulsion layer or a multilayer emulsion layer that is sensitive to a certain region of the spectrum.

The layers necessary for silver halide color photographic materials, including the layers of image-forming units described above, can be arranged in various orders as known in the art.

A typical multicolor silver halide color photographic light-sensitive material comprises a cyan dye image-forming unit consisting of at least one red-sensitive silver halide emulsion l- having at least one cyan dye-forming coupler, at least one magenta dye-forming coupler. a magenta dye image-forming unit consisting of at least one green-sensitive silver halide emulsion layer having at least one green-sensitive silver halide emulsion layer; It consists of things carried on the body.

This photographic material may have additional layers, such as filter layers, interlayers, subbing layers, etc.

When the cyan coupler of the present invention and each coupler according to the present invention are added to a silver halide emulsion, it is usually about o, oos to 2 mol, preferably 0.01 mol per mol of silver halide.
It is added in a range of 0.5 mol.

The silver halide used in the silver halide emulsion used in the present invention may include ordinary silver halide emulsions such as silver bromide, silver chloride, silver iodobromide, silver chlorobromide, and silver chloroiodobromide. Includes anything used.

The silver halide emulsion constituting the silver halide emulsion layer according to the present invention can be produced by various manufacturing methods including the usual manufacturing method, such as the method described in Japanese Patent Publication No. 46-7772,
That is, a so-called emulsion of silver salt grains consisting of at least some silver salts having higher solubility than silver bromide is formed, and then at least a part of these grains is converted into silver bromide or silver iodobromide. Conversion emulsion manufacturing method or 0.1
It can be produced by any production method such as the production method of a Lippmann emulsion consisting of fine-grained silver halide having an average grain size of Em or less. Furthermore, the silver halide emulsion of the present invention may contain sulfur sensitizers (for example, arylthiocarbamide, thiourea, cystine, etc.), active or inactive selenium sensitizers, reduction sensitizers (for example, stannous salts, polyamines, etc.). etc.), noble metal sensitizers (e.g. gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-oresulfobenzthiazole methyl chloride, etc.), or water-soluble salts such as ruthenium, rhodium, iridium, etc. Chemical sensitization can be carried out by using sensitizers such as ammonium chloroparadate, potassium chlorooleate, and sodium chloroparadate 1 to 1 alone or in appropriate combinations.

Furthermore, the silver halide emulsion used in the present invention can contain various known photographic additives9. For example, "Research Disclosure" December 1978,
A photographic additive such as that described in Nα17643.

The silver halide used in the present invention is spectral sensitized by selecting an appropriate sensitizing dye in order to impart photosensitivity in the required wavelength range. Various types of spectral sensitizing dyes can be used, and these can be used IN or in combination of two or more.

Spectral sensitizing dyes that are advantageously used in the present invention include, for example, U.S. Patent No. 2,269,234;
No. 270,378, No. 2,442,710, No. 2
Typical examples include cyanine dyes, merocyanine dyes, and complex cyanine dyes as described in , 454.620 and 2,776.280.

In the present invention, in addition to the coupler of the present invention, a compound that can develop color by oxidative coupling with an aromatic-grade amine developer (for example, a phenylenediamine derivative, an aminophenol derivative, etc.) in other color development processing is used in combination. Can be used.

Magenta couplers include 5-pyrazolone couplers, pyrazolopenzimidazole couplers, pyrazolotriazole couplers, cyanoacetylcoumaron couplers, open-chain acylacetonitrile couplers, etc. Yellow couplers include acylacetamide couplers (e.g. benzoylacetanilides, pivaloyl cyan couplers include naphthol couplers and phenol couplers. These couplers preferably have a hydrophobic group called a ballast group in the molecule, and the couplers may be either 4-equivalent or 2-equivalent to silver ions.

It may also be a colored coupler that has a color correction effect or a coupler that releases a development inhibitor during development (so-called DIR coupler).

In addition to DIR couplers, there are also colorless DIR couplers in which the product of the coupling reaction is colorless and releases a development inhibitor.
It may also contain a coupling compound.

In order to incorporate the cyan coupler of the present invention and each coupler according to the present invention into a silver halide photosensitive material, conventionally known methods may be followed9. After dissolving the cyan coupler of the present invention or each coupler according to the present invention in a mixture of boiling point solvents, it is mixed with an aqueous gelatin solution containing a surfactant, and then emulsified using a high-speed rotating mixer, a colloid mill, or an ultrasonic disperser. After that, it can be added to silver halide to prepare a silver halide emulsion for use in the present invention.

Examples of high boiling point solvents include phthalic acid alkyl esters (e.g. dibutyl phthalate, dioctyl phthalate), phosphoric acid esters (e.g. diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid Esters (eg acetyl tributyl citrate), benzoic acid esters (eg octyl benzoate), alkylamides (eg diethyl laurylamide), fatty acid esters (eg dibutoxyethyl succinate, dioctyl azelate), phenols (eg 2. (4-ditertiary-amylphenol), trimesic acid esters (eg, tributyl trimesate), and the like can be used.

Also, Japanese Patent Publication No. 51-39853, Japanese Patent Publication No. 51-5994
The dispersion method using a polymer described in No. 3 can also be used, or if the coupler has an acid group such as carboxylic acid or sulfonic acid, it can be introduced into the hydrophilic colloid as an alkaline aqueous solution. be done.

Typical color developing agents include those based on p-phenylenediamine, such as diethyl-p-phenylenediamine hydrochloride, monomethyl-p-phenylenediamine hydrochloride, dimethyl-p-phenylenediamine hydrochloride,
-Amino-5-diethylaminotoluene hydrochloride, 2-amino-5-(N-ethyl-N-β-hydroxylethylamino)-toluene, 2-amino-5-(N-ethyl-N-β-methane) sulfonamidoethyl)aminotoluene sulfate, 2-amino-5-(N-ethyl-N-β-methanesulfonamidoethylamino)toluene, 4-(N
-ethyl-N-β-hydroxyethylamino)aniline, 2-amino-5-(N-ethyl-β-methoxyethyl)aminotoluene, and the like.

These color developing agents may be used alone or in combination of two or more, and if necessary, in combination with a black and white developing agent such as hydroquinone.

Furthermore, the color developer generally contains an alkaline agent such as sodium hydroxide, ammonium hydroxide, sodium carbonate, sodium sulfite, etc., and various additives such as an alkali metal halide such as potassium bromide, or a development regulator. , for example, citradinic acid.

The silver halide color photographic light-sensitive material of the present invention is usually subjected to bleaching and fixing, bleach-fixing, and water washing after color development. Many compounds are used as bleaching agents, among them iron (M) and cobalt (I).
f),! Polyvalent metal compounds such as I (If), especially complex salts of these polyvalent metal cations and organic acids, such as aminopolycarbonates such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, N-hydroxyethylenecyaroxy7diacetic acid Acids, metal complex salts such as malonic acid, tartaric acid, malic acid, diglycolic acid, dithioglycolic acid, ferricyanates, dichromates, etc. are used alone or in appropriate combinations.

The present invention will be specifically described below with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example 1 Weigh out 0.1 mol of each of the sheaf colors of the present invention shown in Table 1 per 1 mol of silver, and add 3 times the same weight of phthalic acid dibutyl ester (as a high boiling point solvent) as the coupler. of ethyl acetate and heated to 60°C to completely dissolve. For comparison, 0.1 mol of each of the conventionally known comparative couplers shown in Table 1 was weighed per 1 mol of silver, and dibutyl 7-talate of the same weight as the coupler weight was mixed with ethyl acetate of 3 times the amount. The mixture was added and heated to 60°C to completely dissolve. This solution was mixed with 120% aqueous solution of Alkanol B (alkylnaphthalene sulfonate: manufactured by DuPont).
The mixture was mixed with 1,200 aj of a 5% aqueous gelatin solution containing mj and dispersed using an ultrasonic disperser to obtain an emulsion. Thereafter, this dispersion was mixed into a red-sensitive silver iodobromide emulsion (silver iodide 7 mol %).
(containing) 4ksr and as a hardening agent, 2% solution of 1,2-bis(vinylsulfonyl)ethane (water: methanol = 1:1) 120+al was added and coated on the subbed transparent polyester base. A sample was dried and had a stable coating film (coated silver amount 15μ/100a).
a).

The sample thus obtained was subjected to wedge exposure according to a conventional method, and then subjected to the following development treatment.

The results are shown in Table 1.

In addition, the sensitivity and maximum color density are for PDA manufactured by Konica Corporation.
-Measurement was made using a densitometer type 65.

[Processing process] (38℃) Processing time Color development 3 minutes 30 seconds Bleach fixing
Wash with water for 1 minute and 30 seconds
The composition of the treatment liquid used in the 3 minute 15 second treatment step was as follows.

[Color developer composition] 4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl) monoaniline sulfate 4.75 g anhydrous sodium anhydride 4.25 g hydroxylamine 1/2 sulfate 2. 0 g anhydrous potassium carbonate 37.5 g sodium bromide
1.3g nitrilotriacetic acid trisodium salt (monohydrate) 2.5g potassium hydroxide 1.0g Add water to 1j
and adjust the pH to 1 (1.0) using potassium hydroxide.

[Bleach-fix solution composition J Ethylenediaminetetraacetate iron ammonium salt so, og ethylenediaminetetraacetate #M2 Ammonium salt 10.0g ThioP
Ammonium L acid (50x aqueous solution) 170aj Anhydrous sodium F7X acid 12.5g Add water to make 1j.

Below is the margin Table 1 Comparison coupler (A)
Compound described in No. 72245) From Table 1, it can be seen that Samples Nos. 4 to 8 using the couplers of the present invention all exhibit extremely high sensitivity and high maximum color density compared to the comparative couplers.

Example-2 After performing wedge exposure on the sample obtained in Example-1,
The development process of Example-1 (referred to as "new bleach-fix solution process")
) was carried out. On the other hand, the bleach-fix solution was changed to the following composition corresponding to a fatigued bleach-fix solution, and the fading property of the cyan dye due to the fatigue bleach-fix solution was investigated after processing (referred to as ``fatigue bleach-fix solution treatment'').

[Bleach-fix solution composition] Ethylenediaminetetraacetic acid iron ammonium salt so g ammonium sulfite <40% solution) 50aj ammonium thiosulfate (70% solution) 140at aqueous ammonia (28% solution) 20ml ethylenediaminetetraacetic acid 4g hydrosulfide
Add 5g water to make up to 1Il.

The maximum color density of the obtained sample was measured. The results are shown in Table 2. The dye residual rate at the maximum density was determined as follows.

According to Table 2, the sample using the naphthol coupler (comparative coupler A) showed significantly greater fading of the cyan dye when treated with a fatigue bleach-fix solution, but the sample using the coupler according to the present invention It will be understood that the fading of the cyan dye is less in the samples using comparative couplers (B) and (C).

Example 3 The couplers shown in Table 3 were used in the same manner as in Example 1, except that the red-sensitive silver iodobromide emulsions were (A) aged the day before coating, (B) aged for 2 months. A sample was prepared using the previously aged sample and treated in the same manner as in Example-1. The results are shown in Table 3.

Table 3 From Table 3, compared to naphthol-based couplers, the conventionally known phenylureido group-containing couplers are very sensitive to slight changes in the emulsion, and their effects are However, it can be seen that the coupler of the present invention is an easy-to-use coupler that is not affected by subtle changes in the emulsion.

From the above Examples 1) and 3, by using the coupler of the present invention, an excellent light-sensitive material can be obtained which has high sensitivity, can obtain high density even with a tired bleach-fix solution, and maintains stable performance even with small changes in the emulsion. You can see what you can get.

[Effects of the Invention] According to the present invention, a cyan image with high sensitivity and high density can be obtained, and there is little dye loss even when using a bleach solution or a bleach-fix solution that is tired from running, and there is no fluctuation in emulsion performance. This has the effect that a stable cyan image can be obtained without picking up.

Claims (1)

[Scope of Claims] In a silver halide photographic material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers contains a cyan compound represented by the following general formula [I]. A silver halide photographic material containing a dye-forming coupler. General formula [I] ▲ Numerical formula, chemical formula, table, etc.▼ (In the formula, A represents a substituted or unsubstituted alkyl group or aryl group, B represents a substituted or unsubstituted aryl group. X is substituted or unsubstituted alkyl group, aryl group,
Represents an alkylamino group, an arylamino group, an alkoxy group, or an aryloxy group. Y represents a substituted or unsubstituted alkyl group, aryl group or heterocyclic group. )