JPS5997143A - Silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To enhance resistance to light, heat, and humidity, granularity, color sharpness, etc. by incorporating a specified cyan coupler in a silver halide emulsion layer on a support. CONSTITUTION:A silver halide emulsion layer formed on a support contains 2,5-diacylaminophenol type cyan coupler represented by formula I in which R is a group for giving sufficient diffusion resistance in the silver halide emulsion, and Z is H or a group releasable when the coupler reacts with the oxidized product of a color developing agent. These cyan couplers are superior in solubility, dispersion stability, light absorbance, light stability, etc., and hence the cyan color image obtained after the color development is superior in image storage stability, and it is not deteriorated in image density even by processing it with a bleaching agent weak fatigued in oxidation force.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a silver halide photographic material containing a novel 2,5-diacylaminophenol type cyan coupler. More specifically, it contains a cyan coupler with excellent properties such as solubility, dispersion stability, spectral absorption characteristics, and photostability, and has excellent image storage stability of the cyan dye image obtained after color development, and has low oxidizing power. The present invention relates to a silver halide color photographic light-sensitive material in which image density does not decrease even when processed with a weak or exhausted target liquid.

As is well known, subtractive color photography uses the oxidation products of a color developer produced when an aromatic primary amine color developer reduces exposed silver halide grains, and yellow, cyan, and magenta dyes. A color image is formed by oxidative coupling of the couplers formed in a halogenated emulsion. As a yellow coupler that forms a yellow dye, a compound having an open chain methylene group is generally used, and as a magenta coupler that forms a magenta dye, compounds such as pyrazolone, pyrazolinobenzimidazole, and imidasilone are used. . As a cyan coupler that forms a cyan dye, a compound having a phenol or naphtholic hydroxyl group is used.

Each coupler is dissolved in a substantially water-insoluble high-boiling organic solvent or in combination with an auxiliary solvent if necessary, and added to the silver halide emulsion, or dissolved in an aqueous alkaline solution and added to the emulsion. added to. The former is an oil drop dispersion method, and the latter is an alkali dispersion method, but the former is generally considered to be superior to the latter in terms of light resistance, heat resistance, moisture resistance, granularity, and color sharpness. .

The basic properties required of each coupler include not only the ability to simply form a dye, but also high solubility in high-boiling organic solvents or alkaline solutions, and dispersibility in silver halide photographic emulsions. and have good stability, the dye formed has fastness to light, heat, moisture, etc., good spectral absorption characteristics, good transparency, high color density, and It is desired that the resulting images have various characteristics such as clarity. In particular, cyan couplers are required to have improved image storage properties such as heat resistance, moisture resistance, and light resistance.

Conventionally known cyan couplers include the following compounds. , that is, in the US patent publication:
A coupler consisting of 6-[α-(2,4-di-tert-aminophenoxy)-butanamido]-2,4-dichloro-3-methylphenol has been reported. This coupler has good light resistance but poor heat resistance. JP-A-50-112038 reports a cyan coupler in which the 2- and 5-positions of phenol are substituted with an acylamino group, and the acylamino group at the 2-position is substituted with an alkyl group substituted with a fluorine atom. has been done. This coupler has features such as good heat resistance and little loss of density when treated with a bleaching solution with weak oxidizing power or a bleaching solution that is tired, but it has poor light resistance. Furthermore, the cyan coupler described in JP-A-53-110963.0 is the second and fifth phenolic cyan coupler.
It is a phenolic cyan coupler in which the acylamino group at position 5 is substituted with an acylamino group, and the terminal of the acylamino group at the 5th position is substituted with a sulfonamide group or a sulfamoyl group. However, the light resistance was still insufficient.

Therefore, while maintaining the above-mentioned characteristics of the phenolic cyan coupler at a sufficiently high level, the light resistance has been further improved. A 2,5-diacylaminophenol type cyan coupler, which is a chloro-substituted pennzamide group such as -chloropenzamide group, has been proposed, and is described as a specific compound in, for example, JP-A-56-99341.

However, these cyan couplers still cannot be said to exhibit sufficient light resistance.

The present invention has been developed through extensive research in order to solve the above-mentioned disadvantages of conventional cyan couplers, and has been developed in a patent application filed in 1983.
No. 172386 proposes a 2,5-diacylaminophenol type cyan coupler in which the substituent at the 2-position is a 2,6-dichlorobenzamide group.

The first object of the present invention is to provide a silver oxide compound containing a cyan coupler which further improves the light resistance of the conventional 2,5-diacylaminophenol type cyan coupler in which the substituent at the 2-position is a chloro-substituted penzamide group. Our objective is to provide photographic materials.

The second object of the present invention is image storage stability, that is, heat resistance,
An object of the present invention is to provide a silver halide photographic material containing a cyan coupler having excellent light resistance and moisture resistance.

A third object of the present invention is to provide a silver halide photographic material containing a cyan coupler that has excellent spectral absorption characteristics and light stability, and has excellent dispersibility and dispersion stability in silver halide color photographic emulsions. It's about doing.

'A fourth object of the present invention is to provide a silver oxide photographic material containing a cyan coupler that is highly soluble in high-boiling organic solvents or alkaline solutions.

The fifth object of the present invention is to reduce the density loss even when processed with a bleaching solution with weak oxidizing power or a bleaching solution with a weak oxidizing power (containing cyan coupler) in the marking process after color development processing. - To provide silver halide photographic materials.

The above objects and other objects mentioned below of the present invention are:
In a silver halogenide photographic light-sensitive material having at least one silver halogenide emulsion layer on a support, the silver halogenide emulsion layer is represented by the following general formula [I] 2,
This can be achieved by using a silver halide photographic material characterized by containing a 5-diacyl aminophenol type cyan coupler.

Represents a group sufficient to impart dispersion. Z is a hydrogen atom or a group that can be separated in a coupling reaction with an oxidation product of a color developing agent. ] In the cyan coupler represented by general formula [I], the coupling-off group represented by Z is well known to those skilled in the art, and it modifies the reactivity of the coupler or separates from the coupler to form a halogen In the coating layer or other layers containing the coupler in the silver oxide color photographic light-sensitive material, it acts advantageously by performing functions such as development inhibition, bleaching inhibition, and color correction. Typical examples of coupling-off groups include chlorogen atoms such as chlorine and fluorine, alkoxyl groups,
Examples include aryloxy groups, arylazo groups, thioethers, and heterocyclic groups such as oxasilyl, diazolyl, triazolyl, and tetrazolyl. A particularly preferred example of Z is a hydrogen atom or a chlorine atom.

In the cyan coupler represented by general formula [I], R
Examples of the diffusion-resistant group represented by include an alkyl group or an aryl group. These alkyl groups or aryl groups may have one or more substituents, and preferred substituents for the alkyl groups include:
Examples include acylamino group, sulfonamide group, sulfamoyl group, ester group, sulfonyl group, and ether group. Preferred substituents for the aryl group include a group, an ether group, a sulfonyl group, and the like.

In the cyan coupler represented by general formula [I], R
The diffusion-resistant group represented by is preferably one represented by the following general formula [11] [wherein R2 represents an alkylene group]. Crow represents a group that can be substituted on the benzene ring. Y represents a 10- or -8- group. n is θ~5
An integer number. ] In the general formula [(), R represents preferably a linear or branched alkylene group having 1 to 20 carbon atoms. Examples of groups that can be substituted on the benzene ring prohibited by the rules include halogen atoms (e.g., chlorine, fluorine, etc.), hydroxyl, hydroxycarbonyl, alkyl groups (e.g., methyl, ethyl, 5ec-9 = monobutyl, 5ec-9), amyl, t-amyl, n-octyl, t-octyl, n-dodecyl, etc.), alkoxy groups (e.g. methoxy, ethoxy, 1-propylsulfonamide groups (e.g. methanesulfonamide, ethanesulfonamide, n-butanesulfonamide) , ethoxyethanesulfonamide, 1-butanesulfonamide, dodecanesulfonamide, hexadecanesulfonamide, etc.), arylsulfonamide groups (e.g. benzenesulfonamide,
p-) Rue/sulfonamide, p-promohenzenesulfonamide, m-methoxybenzenesulfonamide, O
- methoxybenzenesulfonamide, dodecylbenzenesulfonamide, tetradecyloxybenzenesulfonamide, etc.), alkylaminosulfonamide groups (e.g. dimethylaminosulfonamide, diethylaminosulfonamide, butylaminosulfonamide, dodecylaminosulfonamide, oleylaminosulfonamide) amide, etc.), alkylsulfamoyl groups (e.g., i-propylsulfamoyl, butylsulfamoyl, t-amylsulfamoyl, dodecylsulfamoyl, etc.), arylsulfamoyl groups (e.g., benzenesulfamoyl, moyl, p-)luenesulfamoyl, p-methoxybenzenesulfamoyl, dodecylbenzenesulfamoyl, etc.)
, and alkoxycarbonyl groups (eg, ethoxycarbonyl, t-butoxycarbonyl, 5ec-amyloxycarbonyl, t-octyloxycarbonyl, dodecyloxycarbonyl, benzyloxycarbonyl, etc.). Preferably halogen atoms, alkyl groups, hydroxyl, alkylsulfonamide groups,
They are an alkylsulfamoyl group and an alkoxycarbonyl group.

Next, typical examples of the cyankazoler according to the present invention represented by the general formula [I] are shown below, but the invention is not limited thereto.

Typical synthesis examples of cyan couplers according to the present invention are shown below in the margins 11-12- below. According to these synthesis examples, the 2,5 diacylaminophenol type cyan coupler of the general formula [I] can be easily obtained by the reaction route shown below [In the formula and in the reaction route, R and X have the above-mentioned meanings] . ] 37.8 g of 2-amino-4-chloro-5-nitrophenol-15-l [IIJ] 50 gv of Oyohi 3,4-dichlorobenzoyl chloride [IV] were added to 500 cc of acetonitrile, and the mixture was boiled for 5 hours. After the reaction solution was allowed to cool to room temperature, the crystals were separated, washed with a small amount of methanol, and air-dried to give 2-(3,4-dichloro)penzami).
65 g of yellow crystals of -4-chloro-5-ditrophenol [V] (7) were obtained.

Next, 7154 g of this compound and 5 g of a palladium-carbon catalyst were added to 500 mJ of ethanol and hydrogenated at atmospheric pressure. After consuming the theoretical amount of hydrogen, the palladium-carbon catalyst f! :
F was separated, and the P solution was concentrated under reduced pressure to obtain pale yellow crystals of 2-(3,4-dichloro)be/cyamido-4-chloro-5-aminephenol (intermediate [VI).The structure was MASS
5 g of the intermediate obtained in Synthesis Example [1] determined and confirmed by spectroscopy and 6.1 g of α17-16-(2,4-di-t-amylphenokidine hexanoyl chloride) were added to 250 cc of acetonitrile. , and boiled for 3 hours. After cooling the reaction solution to room temperature, crystal YF was separated, and the obtained crude crystals were recrystallized using ethanol to obtain 3.5 g of white powder of the target compound [I]. m, p, 190-191° C. The structure was determined and confirmed by NMR and MASS spectra.

Combined, the result is ℃ - ~ λ: Zuko 1 (-Miorigami) Ligojii 7L to = = 1 = - Glower =, -5 = L (X
-(,,p-=Schiff(Tenocore 10g of the intermediate obtained in Synthesis Example 1 [■
00 cc, and 16.7 g'g of α-(p-dimethylaminosulfonamidophenoxy)tetradecamyl chloride was added at room temperature. After 1 hour, the reaction solution was added to water, and the precipitated crystals were filtered, washed with water, and dried.

The obtained crude crystals were recrystallized using a mixed solution of acetonitrile and ethyl acetate to obtain 60 g of a white 18-color powder of the target compound [I]. m, p, 164-165°C. The structure was determined and confirmed by SOFT and MASS spectra.

For the cyan coupler used in the present invention, the method techniques used for conventional cyan couplers can be similarly applied. Typically, the coupler is incorporated into a silver halide emulsion and the emulsion is inseparated onto a paste to form a photographic element.

The photographic element may be a single color element or a multicolor element; in multicolor elements, the cyan couplers of this invention are usually included in the red-sensitive emulsion, but not in an unsensitized emulsion or in each of the three primary regions of the spectrum. It has a dye image-forming structural unit that is photosensitive to . Each structural unit can consist of a single pore emulsion layer or a multilayer emulsion layer that is 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 consists of a cyan dye image-forming unit consisting of a red-sensitive silver halide emulsion layer having at least one cyan coupler. The element consists of a yellow dye image-forming unit maintained at the base consisting of at least one blue-sensitive silver halide emulsion layer with one magenta coupler) and a small number (with one magenta coupler). It can have a filter layer, an intermediate protective layer, an undercoat 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 with a boiling point of 175°C or higher such as tricresyl phosphate or dibutyl phthanate, or a low boiling point solvent such as butyl acetate or butyl propylonate, either alone or in a mixture thereof as necessary. The silver halide used in the present invention is added to the silver halide after being dissolved alone or in combination, mixed with an aqueous gelatin solution containing a surfactant, and then emulsified in a high-speed rotary mixer or colloid mill. Emulsions can be adjusted. When the coupler of the present invention is added to the silver halide emulsion used in the present invention, 5
Usually about 0.07 to 0.7 mol per mol of silver halide,
Preferably, the coupler of the present invention is added in an amount in the range of 0.1 to 0.4 mol.

The silver halide used in the silver halide emulsion used in the present invention includes silver bromide, silver chloride, silver iodobromide, silver chlorobromide, silver chloroiodobromide, etc., which are commonly used in silver halide emulsions. is included.

The silver halide emulsion constituting the silver halide emulsion used in the present invention can be manufactured by various manufacturing methods including the usual manufacturing method, for example, the method described in Japanese Patent Publication No. 46-7772, i.e., the solubility is lower than that of bromide. The so-called convergence H7 process involves forming an emulsion of silver salt grains that are thicker than silver and consisting of a small amount (some of them), and then converting at least a part of these grains to silver bromide or silver iodobromide salt. It can be prepared by any manufacturing method such as an emulsion manufacturing method or a Lippmann emulsion manufacturing method consisting of fine grain silver halide having an average grain size of 0.1 μm or less.

Furthermore, the silver halide emulsion used in the present invention contains sulfur sensitizers such as allylthiocarbamide, thiourea, cystine, etc., active or inactive selenium sensitizers, and reduction sensitizers such as stannous salts. , polyamines, etc., noble metal sensitizers, such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-sulosulfopensthiazole methyl chelolide, etc., or water-soluble materials such as ruthenium, rhodium, iridium, etc. Chemical sensitization can be carried out by using a salt sensitizer, specifically ammonium chlorovaladate, potassium chloroaurate, sodium chlorovaladite, etc. alone or in combination as appropriate.

Furthermore, the silver halide emulsion used in the present invention may contain various known photographic additives, such as Re.
Photographic additives such as those described in Research Disclosure, December 1978, Item 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 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. 378, No. 2,442,710, No. 2゜45
Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in the specifications of No. 4.620 and No. 2,776,280.

The color developing solution that can be used in the present invention is preferably
The main component is an aromatic primary amine color developing agent. Typical examples of this color developing agent include those based on p-phenylenediamine, such as diethyl-p-phenylenediamine hydrochloride, monomethyl-p-phenylenediamine hydrochloride, dimethyl-p-phenylenediamine hydrochloride, 2-Amino-5-diethylaminotoluene hydrochloride, 2-amino-5-(N-ethyl-N-dotecylamino)-toluene, 2-amino-5-(N-neej
-ruN-β-methanesulfonamidoethyl)aminotoluene sulfate, 4-(N-ethyl-N-β-methanesulfonamidoethylamino)aniline, 4-(N-ethyl-N-β-hydroxyethylamino) Examples include aniline, 2-amino-5-(N-ethyl-N-β-methoxyethyl)aminotoluene, and the like.

After development, bleach to remove silver and silver halides,
The usual steps of fixing or bleaching, washing and drying are carried out.

The 2,5-diacylamino cyan coupler of the present invention is
It has desirable properties required as a cyan coupler, such as spectral absorption characteristics. Moreover, it has excellent solubility in alkali or high-boiling organic solvents, and has excellent dispersibility and dispersion stability in silver halide color photographic emulsions. In addition, the cyan dye image obtained after color development has better light resistance, humidity resistance, heat resistance, etc. than the conventional 2.5-
It has superior properties such as better image preservation than when diacylamino cyan couplers are used, and less loss of image density even when processed with weak oxidizing or tired bleaching solutions. The present invention will be specifically described below with reference to Examples, which are silver halide color photographic light-sensitive materials, but the embodiments of the present invention are not limited thereto.

Example Among the above-mentioned exemplified compounds, 0113 moles of each of the cyan couplers related to the present invention having the numbers shown in Table 1 and the cyan couplers having the structural formula shown below as a comparative example were weighed, and the same weight of phthalic acid was weighed. It was added to a mixture of dibutyl and 3 times the amount of ethyl acetate and heated to 60°C to completely dissolve. The obtained solution was added to Alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont) and an aqueous gelatin solution, and emulsified using a colloid mill to prepare a coupler dispersion. This coupler dispersion was then added to a silver chlorobromide emulsion containing 0'' moles of silver (containing 20 mole percent silver bromide) and applied to a polyethylene laminate paper.
A silver halogenide color photographic light-sensitive material having a stable coating film was obtained.

Comparative coupler [A] (U.S. Patent Publication No. 2,801,17
Compound described in No. 1) Comparison coupler [B] (JP-A-50-112038 Comparison Kagler [C] (JP-A-53-109630 Comparison Kagler [E] (JP-A-56-99341) Next, the silver halide color photographic materials of Examples and Comparative Examples thus obtained were wedge exposed in a conventional manner.
The following processing was performed.

[process] Processing process (30℃) Processing time The composition of the treatment liquid is as follows.

[Color developer composition] [Ginger silver fixer composition] The light fastness, heat resistance, and moisture resistance of the dye image thus obtained were evaluated by the following methods. The results are shown in the first column.

[Evaluation of light resistance] The residual density after exposing the image to a xenon fade meter for 300 hours was expressed as 1% (%), with the density before exposure being 100.

[Evaluation of Moisture Resistance] The residual density of the image after storage for 3 weeks at a temperature of 60° C. and a relative humidity of 70% was expressed as a percentage (%) with the density before the test as 100.

[Evaluation of Heat Resistance] The residual concentration after storing the image at a temperature of 77° C. for 3 weeks was expressed as a percentage (%) with the concentration before the test as 100. (However, the initial density is 1.0°) or less. It has its drawbacks. That is, those using comparative coupler [A] have excellent light resistance, but extremely low moisture resistance and heat resistance.

Those using comparative coupler [B] had high moisture resistance and heat resistance, but extremely low light resistance. Compared to this, those using comparative coupler [C] had a 2.
The substituent at position [D] is a chloro-substituted pentzamide group,
The light resistance of the cyan coupler [E] is also not sufficiently improved.

On the other hand, the silver halide color photographic light-sensitive material containing the cyan coupler of the present invention has uniformly high properties in terms of light resistance, moisture resistance, and heat resistance, and has excellent image stability. I can say that.

Example 2 Eleven types of silver halide color photographic light-sensitive materials of Examples and Comparative Examples obtained using the same raw materials and methods as Example 1 were subjected to wedge exposure, and then the same materials and methods as used in Example 1 were applied. Processed with a developer of the same composition. The image was then processed with a fatigue bleach-fix solution having the following composition, and the maximum reflection density of the cyan dye in the resulting image was measured to examine the fading properties of the cyan dye. In addition, the dye residual rate in the maximum density part was calculated|required using the following formula. The results are shown in Table 2.

Table 2 33 - As is clear from the second coating, the 710 silver oxide color photographic light-sensitive material of the present invention has a uniformly higher color density after cool-white fixing treatment than that of the conventional material. In addition, it can be said that the degree of defective restoration of cyan dye is small even when used with a tired nickel liquor, and the image density is less likely to deteriorate.

34- Procedural amendment (voluntary) 1. Indication of the case 1982 Patent Application No. 206983 2, Title of the invention Silver halide photographic light-sensitive material 3, Person making the amendment Relationship to the case Patent applicant name (name) (127) Representative of Roku Konishi Photo Industry Co., Ltd. Director Nobuhiko Kawamoto 4, Agent 5, Date of amendment order Voluntary 6, Number of inventions increased by amendment None 7, In the area enclosed by the frame on page 12 of the specification subject to amendment, at the bottom edge of said page. In the section defined by the second and third vertical lines from the side and the second and third horizontal lines from the bottom edge of the page, 2-

Claims (1)

[Scope of Claims] In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, in the silver halide emulsion layer 2 represented by the following general formula [I], A silver halide photographic light-sensitive material characterized in that it contains a 5-diacylaminophenol type cyan coupler. .Z represents a hydrogen atom or a group that can be separated in a coupling reaction with an oxidation product of a color developing agent.]