JPH01172953A - 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, A denotes a substd. or unsubstd. aryl group; B denotes a substd. or unsubstd. alkyl group or aryl group; Z is expressed by the formula II; X denotes a hydrogen atom., halogen atom., -OR<1>, -SR<1>, etc.; R denotes a hydrogen atom., substd. or unsubstd. alkyl group, substd. or unsubstd. aryl 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 J.

Silver halide color photographic materials generally use so-called dye-forming couplers, which form dyes by reacting with a light-sensitive silver halide emulsion and an oxidized aromatic primary amine developing agent.

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, JP-A-5
6-65134 etc.

Naphthol-based compounds, which have been widely used as cyan couplers for color negative films, have the disadvantage that when processed with a tired bleach or bleach-fix solution, the dye once formed returns to the leuco form, causing dye loss. discovered.

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 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 general formula [ This was achieved by providing a silver halide photographic material containing a cyan dye-forming coupler represented by II.

General formula [II (wherein A represents a substituted or unsubstituted aryl group,
B represents a substituted or unsubstituted alkyl group or aryl group.

Child, -〇R1, -8RI, -8OR', -8OaR
', -COORl, -NR'R--COR', -NH
8O2R', -CN, -N09, represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or, R is a hydrogen atom, a substituted or unsubstituted alkyl group group, substituted or unsubstituted aryl group.

R1 and Rz are groups selected from a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, and an acyl group, and R1 and R2
may be the same or different, and R1, R2
When is other than a hydrogen atom, these may have a substituent,
) Substituents for A, B, R, R1 and R2 include alkyl groups, aryl groups, heterocyclic groups, alkoxy groups (e.g. methoxy group, 2-methoxyethoxy group), aryloxy groups (e.g. phenoxy group, 2-methoxyethoxy group), 4-di-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) group, butoxysulfonyl group, toluenesulfonyloxy group), amide group (e.g., acetylamino group, ethylcarbamoyl group, dimethylcarbamoyl group, methanesulfonamide group, butylsulfamoyl group), sulfamide group (e.g., dipropylsulfamoyl group) amino group),
imide groups (e.g., succinimide group, hydantoinyl group), ureido groups (e.g., phenylureido group, dimethylureido group), sulfonyl groups (e.g., methanesulfonyl group), phosphoric acid amide groups (e.g., diethyl phosphate monoamide group, (tetramethylphosphate triamide group), hydroxyl group, cyano group, nitro group, halogen atom, thio group (e.g., ethylthio group, phenylthio group)
, an amino group (eg, a monobutylamino group, a dipropylamino group, a 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 cyan coupler of the present invention is synthesized by a known method, for example, in the following steps.

El] [2] [31 [4] N [51] Alternatively, compounds with various substituents introduced can be derived from [5].

Synthesis Example-1 (Synthesis of Exemplary Compound 1) Next, a synthesis example is shown: 5.8 g of paraformaltehyde and 16.8 g of morpholine
Mix and heat on a hot water bath until uniform. Add 2-(3-cyano-4-chlorophenyl)ureido to this solution.
A solution of 121 t of 5-[2-(2',4'-di-t-amylphenoxy)hexanoylaminocophenol in 200 ml of acetone is added. After refluxing for 2 hours,
Crystals are obtained by distilling off the solvent under reduced pressure. Recrystallization from acetonitrile gave white prismatic crystals in a yield of 6'3x. It was confirmed from NMR and mass spectra that it was the desired product.

Synthesis Example-2 (Synthesis of Exemplified Compound 26) 164 g of the Exemplified Compound synthesized in Synthesis Example-1 was dissolved in acetic anhydride 9
The reaction mixture was refluxed for 19 hours with 0 ml of tIk. Acetic acid and acetic anhydride were thoroughly distilled off to obtain a candy-like substance. Dissolve this candy in 200ml of methanol and add 4.7f of CHsON to this.
After the reaction, the mixture was cooled and the WI medium was distilled off. The contents were recrystallized from hexane to obtain white crystals. The yield was 98%. It was confirmed by NMR1Mass spectrum that it was the desired product.

Synthesis Example 3 (Synthesis of Exemplified Compound 25) The Exemplified Compound 26 was dissolved in 140 ml of methylene chloride, then 45 g of HBr 3% acetic acid solution was added, and after standing overnight at room temperature, the solvent was distilled off under reduced pressure to precipitate crystals. is recrystallized from hexane. The target product was obtained with a yield of 79%. NMR,M
Confirmed by ASS spectrum.

Synthesis Example-4 (Synthesis of Exemplified Compound 27) 3.9 g of Na salt of p-nitrothiophenol and Synthesis Example-
Exemplary compound 25 synthesized in step 3 14.5g t-DMF
200 ml of water after 1 reaction stirring at room temperature for 3 hours in 50 ml
The precipitated crystals were scooped out, washed with water, and then recrystallized from acetonitrile to obtain yellow needle-shaped target product in a yield of 45%.

Confirmed by NMR and Mass spectrum.

Synthesis Example-5 (Synthesis of Exemplified Compound 23) 2-(3-cyano-4-chlorophenyl)ureido-5
-[2-(2',4'-di-t-amylphenoxy)
Hexanoylaminocophenol 24, at was dissolved in 50 ml of benzene, 1.62 g of 37% formalin, 0.5 ml of concentrated hydrochloric acid, and a drop of thioglycolic acid were added, and the mixture was heated to room temperature for 4 hours.
Stir for 1 hour and then reflux for 2 hours. After cooling, water is added to wash the organic layer. The organic layer is dried and then distilled off. The resulting candy-like substance is purified by column chromatography. A caramel-like target product was obtained in a yield of 35%. Confirmed by NMR and Mass spectrum.

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 a silver halide color photographic light-sensitive material containing silver halide in an emulsion layer. This silver halide color photographic light-sensitive material may be monochromatic or multicolor. In the case of multicolor, the cyan coupler of the present invention is usually contained in a red-sensitive emulsion; It may be contained in an emulsion layer that is sensitive to the three primary color regions of the spectrum.

Each structural unit forming a dye image in the present invention is
It consists of a single emulsion layer or multiple emulsion layers that are 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 building block consisting of at least one red-sensitive silver halide emulsion layer having at least one cyan dye-forming coupler, at least one magenta dye-forming coupler. a magenta dye image-forming ellipsoidal unit consisting of at least one green-sensitive silver halide emulsion layer, and a yellow dye image-forming unit consisting of at least one blue-sensitive silver halide emulsion layer containing at least one yellow dye-forming coupler. is supported on a support.

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 0.005 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 Lippmann emulsion consisting of fine grain silver halide having an average grain size of .mu.m or less. Furthermore, the silver halide emulsion of the present invention may contain sulfur sensitizers (such as arylthiocarbamide, thiourea, cystine, etc.), active or inactive selenium sensitizers, reduction sensitizers such as stannous salts, polyamines, etc. etc.), noble metal sensitizers (e.g. gold sensitizers, specifically potassium aurithiocyanate-1 to potassium chloroaurate, 2-
aurosulfobenzthiazole methyl chloride, etc.), or sensitizers of water-soluble salts such as ruthenium, rhodium, iridium, ammonium chloroparadate,
Chemical sensitization can be carried out using sensitizers such as potassium chlorooleate and sodium chlorovaladite alone or in combination as appropriate.

Furthermore, the silver halide emulsion used in the present invention may contain various known photographic additives.For example, [Research Disclosure], December 1978,
Photographic additives such as those described in No. 17643.

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 spectral sensitizing dyes are used, and these may be used alone or in combination of two or more.

Spectral sensitizing dyes advantageously used in the present invention include, for example, U.S. Pat.
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, pyrazolobenzimidazole couplers, pyrazolotriazole couplers, cyanoacetyl coumaron 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 followed. 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 (e.g. diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, dioctyl azelate), phenols (e.g. 2,4- ditertiary-amylphenol), trimesic acid esters (eg, tributyl trimesate), and the like.

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. .

Typical color developing agents are those based on p-phenylenediamine, such as diethyl-p-phenylenediamine hydrochloride, monomethyl-p-phenylenediamine hydrochloride, dimethyl-p-phenylenediamine hydrochloride, and dimethyl-p-phenylenediamine hydrochloride. Dilene diamine hydrochloride, 2
-Amino-5-diethylaminotoluene hydrochloride, 2-amino-5-(N-ethyl-N-β-hydroxylethylamino)-toluene, 2-amino-5-(N-ethyl-
N-β-methanesulfonamidoethyl)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)
Examples include aminotoluene.

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, color developing solutions generally contain alkaline agents such as sodium hydroxide, ammonium hydroxide, sodium carbonate, g.
f! , sodium vILate, etc., and may further contain various additives, such as alkali metal halides, such as potassium bromide, or current modifiers, such as 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 (■) and cobalt (■
), polyvalent metal compounds such as tin (I[), in particular complex salts of these polyvalent metal cations with organic acids, e.g. aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, N-hydroxyethylenediaminediacetic acid , metal complex salts or ferricyanates such as malonic acid, tartaric acid, malic acid, diglycolic acid, dithioglycolic acid,
Dichromate and the like 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 Each of the cyan couplers of the present invention shown in Table 1 was weighed in an amount of 0.1 mol per 1 mol of silver, and 3 times the amount of dibutyl phthalate (as a high boiling point solvent) of the same weight as the coupler was weighed. 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 added to dibutyl phthalate of the same weight as the coupler weight and 3 times the amount of ethyl acetate. , completely dissolved by heating to 60°C. This solution was mixed with a 5% aqueous solution of Alkanol B (alkylnaphthalene sulfonate: manufactured by DuPont).
5% gelatin water solution containing 0aj? +! 1, 200+
After that, this dispersion was added to 4 kg of red-sensitive silver iodobromide emulsion (containing 7 mol% silver iodide) and hardened. As a membrane agent, 1
．． Add 120 ij of a 2% solution of 2-bis(vinylsulfonyl)ethane (water:methanol-1:1), coat on the subbed transparent polyester base, dry, and coat to obtain a sample with a stable coating film. Silver amount 15. /10
0aa).

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 sulfite 4.25 g droxylamine 1/2 [acid acid] 2.0 g anhydrous potassium carbonate 37.5 g sodium bromide
1.3 g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Water is added to make IJ, and the pH is adjusted to 10.0 using potassium hydroxide.

[Bleach-fix solution composition: Coethylenediaminetetraacetic acid iron ammonium salt 50.0g Ethylenediaminetetraacetic acid diammonium salt 10.0g Thioacid ammonium (50% aqueous solution) 170a+j Anhydrous sodium sulfite 12.5g Water was added and 1. Let it be Il.

Table 1 Comparative power, puller (A) (compound described in JP-A-61-72245) (JP-A-61-72245)
Compound described in No. 0-91355) From Table 1, it can be seen that samples NQ4 to NQ8 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,
Development processing of Example-1 (referred to as “New Bleach-Fixer Processing J”)
) was carried out. On the other hand, the bleach-fix solution was treated with the following composition corresponding to a fatigued bleach-fix solution (referred to as "fatigue bleach-fix solution treatment"), and the fading property of the cyan dye due to the fatigue bleach-fix solution was investigated.

[Bleach-fix solution composition] Ethylenediaminetetraacetic acid iron ammonium salt 50g Ammonium sulfite (40χ solution) 50a+j Ammonium thiosulfate (70χ solution) 140aj Ammonia water (28χ solution, liquid) 6.20s+1 Ethylenediaminetetraacetic acid 4g Hydrosulfide 5g Add water Let it be tIl.

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

Table 2 Table 2 shows that the sample using the naphthol coupler (comparative coupler A) showed remarkable fading of the cyan dye when treated with a fatigue bleach-fix solution, but the sample using the coupler according to the present invention showed that the sample using the comparative coupler (comparative coupler A) It will be understood that, like the samples using B) and (C), there is little fading of the cyan dye.

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

From Table 3 in the margin below, compared to naphthol couplers, conventionally known couplers with a 7-enylureido group at the 2-position are very sensitive to subtle changes in the emulsion and are not affected by them. 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.

As can be seen from Examples 1 to 3 above, by using the coupler of the present invention, a crushed photosensitive material with high sensitivity and high density can be obtained even with a tired bleach-fix solution, and which 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 cyanide represented by the following general formula [I]. A silver halide photographic material containing a dye-forming coupler. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, A represents a substituted or unsubstituted aryl group,
B represents a substituted or unsubstituted alkyl group or aryl group. Z represents ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and X is a hydrogen atom, a halogen atom, -OR^1, -SR^1, -
SOR^1, -SO_2R^1, -COOR^1, -N
R^1R^2, -COR^1, -NHSO_2R^1,
-CN, -NO_2, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted heterocyclic group, or ▲Numerical formula, chemical formula, table, etc.▼, where R is a hydrogen atom, Represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. R^1 and R^2 are hydrogen atoms, alkyl groups, aryl groups,
A group selected from a heterocyclic group and an acyl group, R^1
, R^2 may be the same or different. Also, R
When ^1 and R^2 are other than hydrogen atoms, they may have a substituent. )