JPS5941181B2 - Silver halide color photographic material containing phenolic cyan coupler - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a silver halide color photographic light-sensitive material containing a novel cyan dye image-forming coupler.

Normally, color images are produced by an aromatic primary amine color developing agent reducing exposed silver halide grains.
It is formed by oxidative coupling between the resulting oxidation product of the color development main ingredient and couplers forming yellow, magenta and yellow dyes in a silver halide emulsion. Couplers typically used to form cyan dyes are phenols and naphthols. Considering the photographic performance of conventional couplers, especially for phenols, the basic properties required are that the dye has good spectral absorption characteristics, that is, it has no absorption in the green region of the spectrum and is sharp, and the dye formed has sufficient fastness to light, heat, moisture, etc.; has good color development, that is, has sufficient color development sensitivity and color density; It is required that there is no dye loss even when the bath or bleach-fix bath is fatigued by running.

Furthermore, from the viewpoint of depollution, the removal of benzyl alcohol added to color developing solutions has been taken up as a major problem.

However, the current situation is that sufficient color development cannot generally be obtained unless benzyl alcohol is added. The decrease in color development due to the removal of benzyl alcohol is particularly noticeable in phenolic cyan couplers, and from this point of view as well, there is a demand for phenolic cyan couplers that exhibit high color development even without benzyl alcohol. Research has been carried out to satisfy the above-mentioned requirements, but to the best of the present inventor's knowledge, a cyan coupler that satisfies all of the above-mentioned required properties has not yet been found.

For example, 6-[α-(2,4-di-amylphenoxy)butanamide]-2,4-dichloro-3-methylphenol described in U.S. Patent No. 2,801,171 has good light resistance but poor heat resistance. In addition to having disadvantages in terms of performance, there is also a large loss of dye in a tired bleach-fix solution.

Further, the color development is highly dependent on benzyl alcohol, and it is difficult to remove penzyl alcohol from the color developing solution. The 2-heptafluorobutanamide-5-[α-(2,4-di-t-amylphenoxy)hexanamide] phenol described in U.S. Pat. Although it is excellent, it is inferior in terms of light resistance and color development. Also, JP-A-53-
The coupler described in Japanese Patent No. 109630 also has problems in terms of removal of benzyl alcohol and light resistance. Furthermore, U.S. Patent No. 3839044, Japanese Patent Application Publication No. 4
7-37425, JP 48-36894, JP 50-10135, JP 50-117422, JP 50-130441, JP 50-108841,
The phenolic cyan couplers described in Publication No. 50-120334 are also unsatisfactory in terms of heat resistance and removal of benzyl alcohol.

Phenol couplers having a ureido group at the 2-position are disclosed in British Patent No. 1011940 and US Patent Nos. 3446622, 3996253, 3758308 and 38
No. 80661, etc., the cyan dyes formed by these couplers have broad spectral absorption, and furthermore, the absorption maximum is in the relatively short wave region of the red region, so there is considerable absorption in the green region of the spectrum. This is unfavorable in terms of color reproduction.

Although the phenol coupler having a ureido group at the 2-position described in JP-A-56-65134 has considerably improved green absorption in the spectral region, other properties are still insufficient. As a result of extensive research into these conventional techniques, the present inventors have discovered that the coupler described below fully satisfies the various characteristics required of the above-mentioned phenolic cyan coupler. That is, 2
Substituted or fused 4-cyanophenyl ureido group in the 4-position by a coupler having a hydrogen atom or a group that can be separated by coupling with an oxidation product of a color developing agent and a ballasted acylamino group in the 5-position. was able to achieve this. The substituent of the substituted-4-cyanophenylureido group is of course located on the phenyl group, but preferably has the following general formula.

In the formula, Y is an alkyl group, preferably a C1 to C5 branched or linear alkyl group, a halogen such as chlorine or bromine, a hydroxyl group, a nitro group, an acyloxy group (preferably an aromatic acyloxy group), an alkoxy group (preferably a C1 ~C5 alkoxy group), an acyl group (aromatic acyl group, aliphatic acyl group), and m represents an integer of 1 to 4.

Note that when m≧2, Y may be the same or different. The fused-4-cyanophenylureido group forms a ring at the 2- and 3-positions of the phenyl moiety, and is preferably expressed by the following general formula. In the formula, Y is the same as defined above and may be present in the phenyl moiety or the Z moiety. n represents an integer from 0 to 4. Z represents a group of nonmetallic atoms that together with the benzene ring form a 5- or 6-membered condensed ring. Examples of the condensed ring formed with z include naphthalene, quinoline, benzothiophene, benzofuran, and isocoumaran. Specific examples of groups that can be separated in a coupling reaction include... rogene atoms (e.g., chlorine, bromine, fluorine, etc. atoms), aryloxy groups in which an oxygen atom or nitrogen atom is directly bonded to the coupling position. , carbamoyloxy group,
Examples include carbamoylmethoxy group, acyloxy group, sulfonamide group, co-citric acid imide group, etc. More specific examples include U.S. Pat.
7-37425, JP 48-36894, JP 50-10135, JP 50-117422, JP 50
-130441, 51-108841, 50-
No. 120334, No. 52-18315, No. 53-52
Those described in various publications such as No. 423 and No. 53-105226 are useful. Ballasted acylamino group ballasts act as weights in multilayer color photographic elements, retaining the coupler in a particular layer and substantially preventing diffusion to other layers; , 1 bulk is required. Specific examples of acylamino include aromatic acylamino and aliphatic acylamino, but in the case of aromatic acylamino, the aromatic ring contains C
Substituents with alkyl chains from 5 to Cl8 are required.
Examples of the substituent having a C5 to Cl8 alkyl chain include an alkyl group, an acyloxy group, an acylamino group, a sulfonylamino group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, an alkylamino group, and a dialkylamino group. In the case of aliphatic acylamino, typical examples of the aliphatic group include C5 to Cl8 long chain alkyl groups, furthermore, phenoxyalkyl groups and phenylthioalkyl groups. In the case of phenoxyalkyl groups and phenylthioalkyl groups, there are cases where the phenoxy moiety has a substituent having an alkyl chain of C5 to Cl8, and cases where the alkyl moiety itself has a C5 to C18 alkyl chain.
It may have 5 to Cl8 carbon.

As the ballasted acylamino group of the present invention, particularly a phenoxyalkyl group or a phenylthioalkyl group gives preferable results. Specific examples of acylamino ballasting phenoxyalkyl groups include the following. α-(3-pentadecylphenoxy)butanamide
*: α-(2,4-di-t-amylphenoxy)hexanamide γ-(2,4-di-t-amylphenoxy)
Butanamide α-(2,4-di-t-amylphenoxy)tetradecanamide α-(4-butylsulfonylaminophenoxy)tetradecanamide α-(4-butylsulfamoylphenoxy)tetradecanamide α-(4
-acetoxyphenoxy)dodecanamide α-{p-[
α-(4-hydroxyphenyl)-α・α-dimethyl]
tolyloxy}dodecanamide α-(4-carboxyphenoxy)dodecanamide α-(2-chloro-4-butylsulfonylaminophenoxy)tetradecanamide α
-(4-dimethylaminosulfonylaminophenoxy)
Tetradecanamide α-(3-dodecyloxyphenoxy)butanamide α-(4-dodecyloxyphenoxy)butanamide α-(4-hydroxyphenylthio)dodecanamide α-(4-acetylaminophenylthio)
Dodecanamide Couplers included within the scope of the present invention are exemplified below, but are not limited thereto.

The couplers used in this invention combine a substituted -p-cyanophenyl isocyanate with a suitable aminophenol, such as 2-amino-5-nitrophenol or 2-amino-
By reacting with 4-chloro-5-nitrophenol, 2-
It can be produced by producing a (substituted-p-cyanophenyl)ureido compound. It can then be obtained by reducing the nitro group to an amine by a conventional method and bonding the ballast group to the amine. Typical synthesis examples of the couplers of the present invention are shown below.

Synthesis Example 1 (Exemplary Coupler 2) C7) Synthesis of 2-(p-cyano-m-methoxyphenyl)ureido-5-nitrophenol 15.41 2-
Amino-5-nitrophenol is suspended in 300 d of toluene and brought to reflux.

A solution prepared by dissolving 17.4 ml of p-cyano-m-methoxyphenyl isocyanate in 150 ml of toluene was added dropwise to this while stirring. After the dropwise addition, the reaction solution was heated under reflux for 1 hour, and then cooled. The precipitate was filtered and washed with hot toluene and alcohol for 1.22r to obtain the desired product. (a) Synthesis of Exemplary Coupler 2 6.6? 2-(p-cyano-m-methoxyphenyl)
A hydrogenation reaction was carried out in 200 ml of alcohol at room temperature and pressure using ureido-5-nitrophenol and a palladium-on-carbon catalyst.

Next, the palladium on carbon was separated, the liquid ▲ was concentrated, and the residue was dissolved in 200 ml of acetonitrile. This IICl
．． Add 6V of pyridine, and then add 2-( of 9.5V at room temperature).
4-Butylsulfonylaminophenoxy)tetradecanoyl chloride was added with stirring. After stirring at room temperature for 5 hours, the mixture was poured into water and extracted with ethyl acetate.

Ethyl acetate was distilled off, and the residue was recrystallized from methanol and further from acetonitrile to obtain the desired product 7.2f. The target product was confirmed using mass spectra and nuclear magnetic resonance vectors. Synthesis Example 2 (Exemplary Coupler 1) (7) Synthesis of 2-(0-chloro-p-cyanophenyl)ureido-4-chloro-5-nitrophenol 18.
87 of 2-amino-4-chloro-5-nitrophenol 27.37 of phenyl O-chloro-p-cyanophenyl carbamate and 0.687 of imidazole were dissolved in 400 m
The mixture was heated under reflux for 5 hours in xylene.

After cooling, the precipitate was separated and washed with xylene and a small amount of alcohol to obtain 23.57 of the desired product. (a) Synthesis of Exemplary Coupler 1 Using 2-(0-chloro-p-cyanophenyl)ureido-4-chloro-5-nitrophenol of 117 and a palladium-on-carbon catalyst, in 300 ml of alcohol at room temperature and pressure. Catalytic reduction with hydrogen was carried out.

After the reaction, the catalyst was separated (▲), the liquid (▲) was concentrated, and 250 ml of acetonitrile was added to the residue. 2.4 for this? of pyridine was added thereto, and 12.37 g of 2-(3-pentadecylphenoxy)butanoyl chloride was added at room temperature with stirring.
After stirring at room temperature for 6 hours, the mixture was poured into water and extracted with ethyl acetate.

The residue obtained by distilling off ethyl acetate was subjected to chromatography using silica gel as a carrier and benzene-ethyl acetate as an eluent. The target product fractions were combined and the solvent was distilled off. The residue was recrystallized from methanol to obtain the desired product with a voltage of 5.8V. The target product was confirmed using mass spectra and nuclear magnetic resonance spectra. The cyan dye-forming couplers used in this invention are similarly applicable to the process techniques used for conventional cyan dye-forming couplers.

Typically, the coupler is incorporated into a silver halide emulsion and the emulsion is coated onto a base to form the photographic element. Photographic elements can be single color or multicolor elements.

In multicolor elements, the cyan dye-forming couplers of this invention are normally included in red-sensitive emulsions, but have unsensitized emulsions or dye image-forming units sensitive to each of the three primary regions of the spectrum. Each structural unit can consist of a single emulsion layer or multiple emulsion layers that are sensitive to a certain region of the spectrum. The layers of the element, including the layers of imaging units, can be arranged in various orders as is known in the art. A typical multicolor photographic element comprises a cyan dye image-forming unit comprising at least one red-sensitive silver halide emulsion layer having at least one cyan dye-forming coupler (at least one of the cyan dye-forming couplers being a coupler of the invention). ), a magenta dye image-forming unit consisting of at least one green-sensitive silver halide emulsion layer having at least one magenta dye-forming coupler and at least one blue-sensitive silver halide emulsion having at least one yellow dye-forming coupler. It consists of a layer of yellow dye image-forming structural units supported on a base. The element can have additional layers such as a filter layer, an interlayer protective layer, a subbing layer, etc. In order to incorporate the coupler of the present invention into an emulsion, a conventionally known method may be followed. For example, the coupler of the present invention may be added to a high boiling point organic solvent having a boiling point of 175° C. or higher such as tricresyl phosphate or dibutyl phthalate, or a low boiling point solvent such as butyl acetate or butyl propionate, or a mixture thereof as necessary. alone or in combination, mixed with an aqueous gelatin solution containing a surfactant, then emulsified in a high-speed rotary mixer or colloid mill, and then added to silver halide to obtain the halogenated compound used in the present invention. Silver emulsions can be prepared. When the coupler of the present invention is added to the silver halide emulsion of the present invention, it is usually about 0.07 to 0.7 per mole of silver halide.
The couplers of the invention are added in moles, preferably in the range from 0.1 mole to 0.4 mole. The silver halide used in the silver halide emulsion of the present invention includes silver bromide, silver chloride, silver iodobromide, silver chlorobromide, silver chloroiodobromide, etc., which are commonly used in silver halide emulsions. Any of the above is included.

The silver halide emulsion constituting the silver halide emulsion of the present invention can be manufactured by various manufacturing methods including the usual manufacturing method, such as the method described in Japanese Patent Publication No. 46-J Kamo V2. So-called conversion, such as forming an emulsion of silver salt grains that are larger than silver bromide and consisting of at least some silver salts, and then converting at least a part of these grains to silver bromide or silver iodobromide salts. Emulsion manufacturing method or 0.
It can be produced by any production method such as the production method of Lipman emulsion consisting of fine-grained silver halide having an average grain size of 1 μm or less.

Furthermore, the silver halide emulsion of the present invention may contain sulfur sensitizers such as allylthiocarbamide, thiourea, cystine, etc., active or inactive selenium sensitizers, and reduction sensitizers such as stannous salts, polyamines, etc. etc., noble metal sensitizers, such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-olosulfobenzthiazole methyl chloride, etc., or water-soluble salts such as rutinium, rhodium, iridium, etc. Sensitizing agents, specifically ammonium chloroparadate, potassium chloroplatinate, sodium chloroplatinate, etc. alone. Chemical sensitization can be carried out with or in combination as appropriate.

Furthermore, the silver halide emulsion of the present invention can contain various known photographic additives.

For example, ResearchDisclOsure. l97
Photographic additives such as those described in December 8, Item 17643. The silver halide of the present invention is spectral sensitized by selecting an appropriate sensitizing dye in order to impart photosensitivity in the wavelength range required for red-sensitive emulsions.

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. 8, No. 2442710, No. 2454629,
Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in the specifications of No. 2776280. The color developing solution that can be used in the present invention preferably has an aromatic primary amine color developing agent as a main component.

Typical examples of this color developing agent include those based on p-phenylenediamine, such as diethyl-p-phenylenediamine hydrochloride, monomethyl-p-phenylenediamine hydrochloride, and dimethyl-p-phenylenediamine hydrochloride. Diamine hydrochloride, 2-amino-5-diethylaminotoluene hydrochloride, 2-amino-5-(N-ethyl-N-dodecylamino)-toluene, 2-amino-5-(N-ethyl-N-β)
-methanesulfonamidoethyl)aminotoluene sulfate, 4-(N-ethyl-N-β-methanesulfonamidoethylamino)aniline, 4-(N-ethyl-N-β-hydroxyethylamino)aniline, 2-amino- 5-(
Examples include N-ethyl-N-β-methoxyethyl)aminotoluene. After development, the usual steps of bleaching, fixing or bleach-fixing, washing and drying are carried out to remove silver and silver halide.

Next, preferred embodiments of the present invention will be listed.

(1) A silver halide color photographic light-sensitive material according to the claims, wherein the substituted-4-cyanophenylureido group has the following general formula. (In the formula, Y represents an alkyl group, halogen, hydroxyl group, nitro group, acyloxy group, alkoxy group, or acyl group, and m represents an integer of 1 to 4.

Note that when m≧2, Y may be the same or different. )(2) A silver halide color photographic light-sensitive material according to the claims, wherein the condensed-4-cyanophenylureido group has the following general formula.

(In the formula, Y is the same as the above definition and may be in the phenyl moiety or the z moiety. n represents an integer of O to 4. z is a 5- or 6-membered (Represents a group of nonmetallic atoms forming a condensed ring of members.) 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 0.03 mol each of the couplers of the present invention as shown in Table 1 and comparative couplers 4, 8, and 0 below were taken and mixed with an amount of dibutyl phthalate equal to their weight and 3 times the amount of ethyl acetate. was added to the mixed solution and heated to 60°C to completely dissolve.

This solution was added to an aqueous solution of Alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont) and gelatin, and emulsified using a colloid mill to prepare respective coupler dispersions. Next, this coupler dispersion was made into silver and 04
1 mole of silver halide bromide emulsion (20 mole% silver bromide) was added to a silver halide emulsion containing 20 mole % of silver bromide, coated on polyethylene laminate paper and dried to produce six types of silver halide color photographic light-sensitive materials (samples) with stable coating films. Numbers [1] to (6)) were obtained. Comparative coupler A Comparative coupler 8 Comparative coupler ◎ These samples were subjected to wedge exposure according to a conventional method, and then subjected to the following processing.

However, in the color development process, benzyl alcohol is added (color development [1]) and without benzyl alcohol (color development 2).
Two types of compositions were investigated. [Treatment] The composition of each treatment is shown below.

Photographic properties were measured for each of the obtained samples.

The results are shown in Table 1. The relative sensitivity values in the table are expressed with the maximum sensitivity value when processed with color developer (1) being 100. As is clear from Table 1, the samples obtained using the coupler according to the present invention are excellent in that good sensitivity and maximum density can be obtained regardless of the presence or absence of benzyl alcohol.

In addition, as a result of measuring the color spectrum, it was found that the dye using the coupler of this invention has the maximum absorption in a relatively long part of the red region, and shows excellent color purity with little absorption on the short wavelength side. Ivy.

Example 2 Using samples obtained in the same manner as in Example 1, the light fastness, moisture fastness, and humidity resistance of dye images were investigated.

The results obtained are shown in Table 2.

Note that the light resistance in the table is expressed as the residual density after exposing each obtained image to a xenon fademeter for 300 hours, with the density before exposure being 100.

Moisture resistance was expressed as the residual concentration after storage for 3 weeks at 60° C. and 70% relative humidity, with the concentration before the test being 100. Furthermore, the heat resistance was expressed as the residual concentration after storage for 3 weeks at 77° C., with the concentration before the test being 100. (However, the initial concentration is 1.0) As is clear from Table 2, comparative coupler A has excellent light resistance, but has problems in heat and humidity resistance, and comparative couplers B, . C has excellent heat and humidity resistance, but has a problem with light resistance in color development (2). On the other hand, exemplary couplers (6), (8) and 1 according to the present invention
It can be seen that No. 7) is a coupler with excellent performance in all respects. Example 3 Take 0.01 mole each of the coupler of the present invention, the above comparative coupler, and the following comparative coupler as shown in Table 3, and add tricresyl phosphate in an amount equal to the weight thereof and 3 times the amount of tricresyl phosphate. of ethyl acetate at 60°C.
It was heated to completely dissolve.

This solution was added to an aqueous solution of Alkanol B and gelatin and emulsified using a colloid mill to prepare respective coupler dispersions. Next, a silver iodobromide emulsion containing 0.1 mol of silver (6 mol % is silver iodide) of this coupler dispersion is prepared.
and coated on a cellulose acetate film base, and dried to obtain six types of silver halide color photographic materials (sample number 1) having a stable coating film.

Comparative coupler D These samples were subjected to wedge exposure according to a conventional method and then subjected to the following processing.

〔process〕

Photographic characteristics of the obtained cyan colored image were measured.

The results are shown in Table 3. As is clear from Table 3, the samples using the coupler according to the present invention were found to be excellent in sensitivity and color development.

Furthermore, as a result of spectroscopic measurement, the sample according to the present invention has a maximum absorption wavelength in the long wavelength region of the red region, and shows a sharp cut in the short wavelength region, which is preferable in terms of color reproduction in the green region compared to comparative couplers. It was found to give a pigmented image.

Example 4 Samples (1) to (6) obtained in the color development of Example 1 were subjected to wedge exposure and then subjected to the development treatment of Example 1 (1).

On the other hand, development was carried out using a bleach-fix solution with the composition shown below, and the discoloration of the cyan dye by the fatigued bleach-fix solution was investigated. [Bleach-fix solution composition] The maximum reflection density of the cyan dye of the sample obtained by development was measured.

The results are shown in Table 4. The dye residual rate in the maximum density area was determined as follows. Table 4 shows that the samples using the coupler according to the present invention show less fading of the cyan dye when treated with a fatigue bleach-fix solution. It is understood that there is no.

Claims (1)

[Claims] 1 Has a substituted or condensed 4-cyanophenylureido group at the 2nd position, a hydrogen atom or a group that can be separated by coupling with an oxidation product of a color developing agent at the 4th position, and a ballasted acylamino group at the 5th position A silver halide color photographic material containing a phenolic cyan coupler.