JPS59162547A - Phenol type cyan coupler - Google Patents

Abstract

PURPOSE:To obtain a cyan coupler having superior weather resistance and favorable spectral absorption characteristics by bonding a specified substituent to a substituent at the 2- or 5-position of the benzene ring of a 2,5-diacylaminophenol type cyan coupler. CONSTITUTION:A substituent represented by formula I (where R1 is alkoxy, aryloxy, halogen or OH; R2 is halogen or a univalent org. group; n is 0-4; and when n is >=2, the substituents R2 may be identical with or different from each other) is bonded to a substituent at the 2- or 5-position of the benzene ring of a cyan coupler so as to provide a structure represented by formula II or III (where R3 is alkylene; R4 is alkyl or aryl; R5 is H or alkyl; R6 is halogen, alkyl or alkoxy; m is 0-4; J is alkylene or phenylene; and Z is H or a group which can be eliminated during a coupling reaction with the oxidized product of a color developing agent). A cyan coupler having considerably improved light resistance and superior color developing power is obtd.

Description

Detailed Description of the Invention ■ Background Technical Field of the Invention The present invention relates to a phenolic cyan coupler, and more particularly to a 2,5-diacylaminophenol cyan coupler suitable as a cyan coupler for silver halide color photographic light-sensitive materials. .

Prior art and its problems Usually in silver halide color photographic materials, exposed silver halide grains are reduced with an aromatic primary amine color developing agent, and the color developing agent produced at this time is oxidized. A dye image can be obtained by coupler tonocoupling to form yellow, magenta, and cyan dyes.

Cyan couplers widely used to form the cyan dyes are phenolic and naphtholic cyan couplers. In particular, what is desired to be improved in the phenolic cyan coupler used as the final image is that the cyan dye formed first has good spectral absorption characteristics, that is, the green region of the absorption spectrum (particularly in the 500 nm to 500 nm range). 550 nm) and the maximum absorption wavelength is long wavelength (640 nm to 660 nm); the cyan dye formed second has sufficient fastness against light, heat, and moisture; and Under these storage conditions, there should be little contamination in the uncolored areas, and thirdly, the coloring property should be good, that is, the coloring sensitivity should be sufficient. and fourth, there is little dye loss even if a bleaching bath or bleach-fixing bath containing EDTA ferric salt as a main component becomes fatigued due to long-term use.

Therefore, many proposals have been made to improve these points. As a cyan coupler that is attracting attention as having excellent characteristics particularly regarding the fourth point,
There is a 2.5-diacyl aminophenol cyan coupler. For example, U.S. Patent No. 2,772,162;
．． 895,826 A 2,5-diacylaminophenol-based cyan coupler having a fluorine-substituted aliphatic carboxylic acid amide group at the 2-position of the phenol and an acylamide 7 group at the 5-position, which is described in the Aromatic Specification etc. . The 2,5-diacylaminophenol cyan coupler, which is known as one of these specific compounds, does have excellent heat resistance and spectral absorption characteristics of the cyan dye formed, but the color forming properties of the coupler itself and the dye It has a serious drawback that its light resistance is extremely poor. Therefore, in order to improve these drawbacks, a so-called 2-equivalent coupler was proposed, in which a fluorine atom was introduced at the 4-position of the phenol ring, which undergoes a coupling reaction with the oxidized product of a color developing agent. , 758,308. Although these couplers exhibit excellent color development, they have the undesirable property of causing yellow staining when exposed to light.

In addition, 2 with a sulfonamide group at the 5-position of the phenol ring
, 5-diacylaminophenol cyan couplers have been developed, for example, JP-A-53-109630, JP-A-55-163537, JP-A-56-22235, JP-A-56.
No. -99341, No. 56-116030, No. 56-5
No. 5945 and No. 56-80054.

However, although the dyes produced from these turnips 2- are excellent in fastness, they are insufficient in spectral absorption characteristics.

Furthermore, as a 2,5-diacylaminophenol-based cyan coupler that exhibits satisfactory properties in terms of color development and pre-color staining among the above properties, a compound with an 0-sulfonamidobenzamide group at the 2-position of the phenol and a 0-sulfonamide benzamide group at the 5-position is used. Cyan couplers having an acylamino group are known and are described, for example, in JP-A-56-80045. However, this cyan coupler was not necessarily sufficient in terms of dye fastness, especially light fastness, and there remained room for improvement in this respect.

In this way, conventional phenolic photographic cyan couplers cannot be said to be satisfactory in all of the above-mentioned characteristics 1 to 4. In the case of 2,5-diacylaminophenol cyan couplers having an 0-sulfonamide benzamide group at the 2-position and an acylamino group at the 5-position, further improvements have been made in terms of the fastness, especially light resistance, and spectral absorption characteristics of the formed dye. Object of the Invention The object of the present invention is to satisfy the above-mentioned characteristics desired for the phenolic cyan coupler, and to provide a dye that is formed in a colorant having excellent fastness, especially light resistance. The object of the present invention is to provide a phenolic cyan coupler which has good spectral absorption characteristics.

The above object of the present invention is to provide two phenolic cyan couplers.
At least the 0-position has a benzamide group substituted with a sulfonamide group, the 5th position has an acylamino group, and the at least 0-position has a benzamide group substituted with a sulfonamide group. At least one group selected from the benzene ring and sulfonamide group and the acylamino group has at least one phenoxy group represented by the following general formula [I] or a group having the phenoxy group as a substituent. This is accomplished by using a phenolic cyan coupler.

General Formula [I] [In the formula, R1 represents an alkoxy group, an aryloxy group, a halogen atom or a hydroxyl group. R2 represents a halogen atom or a monovalent organic group. n represents an integer from 0 to 4. However, when n is an integer of 2 or more, a plurality of R2's may be the same or different. [Detailed Description of the Invention] In the present invention, the alkoxy group represented by R□ in the general formula CI) is preferably an alkyloxy group having 1 to 20 carbon atoms, such as a methoxy group, an ethoxy group, a propyloxy group, etc. group, butyloxy group, pentyloxy group,
These include octyloxy group, dodecyloxy group, pentadecyloxy group, octadecyloxy group, benzyloxy group, phenethyloxy group, and the like. The aryloxy group represented by R1 is, for example, a phenoxy group or a naphthoxy group. The halogen atom represented by R1 is, for example, fluorine,
It is poisoned by chlorine, bromine, etc.

In the present invention, R1 in general formula CI) is particularly preferably an alkoxy group (particularly preferably, specifically a methoxy group, an ethoxy group, a dodecyloxy group, a benzyloxy group) and a halogen atom (particularly preferably , specifically a chlorine atom).

The nitrogen atom represented by R2 in the general formula CI) can be, for example, chlorine, fluorine, bromine, etc., and the monovalent organic group can be, for example, an alkyl group (preferably an alkyl group having 1 to 20 carbon atoms). (e.g. methyl group, t-butyl group, t-pentyl group, t-octyl group, dotecyl group, pentadecyl group, benzyl group, phenethyl group)), aryl group (e.g. phenyl group), heterocyclic group (preferably 1) alkoxy groups (preferably linear or branched alkyloxy groups having 1 to 20 carbon atoms (e.g., methoxy groups, ethoxy groups, L-butyloxy groups, octyloxy groups), decyloxy group, dodecyloxy group)), aryloxy group (e.g. phenoxy group), hydroxyl group, acyloxy group (preferably ha), alkylcarbonyloxy group (e.g. acetoxy group), arylcarbonyloxy group (e.g. benzoyloxy group) ), hydroxycarbonyl group, alkoxycarbonyl group (preferably a straight @branched alkyloxycarbonyl group having 1 to 20 carbon atoms), aryloxycarbonyl group (preferably enoxycarbonyl group), mercapto group, alkylthio group (preferably a straight-chain or branched alkylthio group having 1 to 20 carbon atoms, (e.g. methylthio group, octylthio group, dodecylthio group)), acyl group (preferably a straight-chain or branched chain having 1 to 20 carbon atoms) Straight chain or branched alkylcarboxamide group having 1 to 20 alkylcarbonyl molecules, benzenecarboxamide group), sulfonamide group (
(preferably a linear or branched alkylsulfonamide group having 1 to 20 carbon atoms, a benzenesulfonamide group)
, carnocumoyl group (preferably an alkylaminocarbonyl group having 1 to 20 carbon atoms, phenylaminocarbonyl group), sulfamoyl group (preferably having 1 carbon atom)
~20 linear or branched alkylaminesulfonyl groups, phenylaminesulfonyl groups).

Preferably, the coupler of the present invention is a compound represented by the following general formula (III or general formula [■]). and general formula Cm), R1, R
2 and n have the meanings given above. R3 is an alkylene group, preferably a linear or branched alkylene group having 1 to 20 carbon atoms (e.g., methylene group, ethylene group, propylene group, trimethylene group, methylmethylene group, ethylmethylene group, n-7" propylmethylene group) , i-propylmethylene group, n-butylmethylene group, t-butylmethylene group, decylmethylene group, dodecylmethylene group).R4 represents an alkyl group, preferably an alkyl group having 1 to 22 carbon atoms (for example, methyl R5 represents a hydrogen atom or an alkyl group, preferably an alkyl group having 1 to 22 carbon atoms (such as a methyl group, an ethyl group) or an aryl group (e.g., phenyl group, naphthyl group). group, propyl group, butyl group, octyl group, dodecyl group, pentadecyl group, octadecyl group).When these alkyl groups and aryl groups represented by R4 and R5 have a substituent,
Examples of this substituent include halogen atoms (e.g. fluorine, fluorine, bromine, etc.), nitro groups, amine groups, cyano groups,
Hydroxyl group, hydroxycarbonyl group, alkyl group having 1 to 20 carbon atoms (e.g. methyl group, ethyl group,
propyl group, isopropyl group, t-butyl group, octyl group, benzyl group, phenethyl group, etc.), alkoxy group (e.g. methoxy group, ethoxy group, benzyloxy group, etc.)
, aryloxy groups (e.g., phenoxy group, p-nitrophenoxy, etc.), acylamino groups (e.g., acetylamino group, propionylamino group, benzoylamino group, phenoxyacetylamino group, etc.), carbamoyl groups (e.g., methylcarbamoyl group) , dimethylcarbamoyl group, phenylcarbamoyl group, diphenylcarbamoyl group, etc.)
, sulfonamide group (e.g. methanesulfonamide group,
butanesulfonamide group, benzenesulfonamide group,
P-toluenesulfonamide, l), sulfamoyl group (e.g. methylsulfamoyl group, dimethylsulfamoyl group, phenylsulfamoyl group, etc.), alkylcarbonyl group (e.g. methylcarbonyl group, propylcarbonyl group, octylcarbonyl group, etc.) ), arylcarbonyl group (e.g. ephenylcarbonyl group, etc.), alkyloxycarbonyl group (e.g. methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, 7-butyloxycarbonyl group, etc.), aryloxycarbonyl group (e.g. phenyloxycarbonyl group, methoxyphenyloxycarbonyl group, etc.), 7 # Ki #
x * = M (eg, methanesulfonyl group, butanesulfonyl group, etc.), arylsulfonyl group (eg, benzenesulfonyl group, etc.).

R6 is a halogen atom (e.g. fluorine, fluorine, bromine, etc.),
Alkyl group Preferably an alkyl group having 1 to 22 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, octyl group, dodecyl group, pentadecyl group, octadecyl group, benzyl group, phenethyl group, etc.), or alkoxy represents a group (preferably an alkyloxy group having 1 to 20 carbon atoms (e.g., methoxy group, ethoxy group, t-butyloxy group, octyloxy group, decyloxy group, dodecyloxy group, etc.); In is an integer of 0 to 4; represents,
When m is 2 or more, multiple pupils R6 may be the same or different.

J is an alkylene group, preferably a linear or branched alkylene group having 1 to 20 carbon atoms (e.g., methylene group, ethylene group, propylene group, trimethylene group, methylmethylene group, ethylmethylene group, n-propylmethylene group,
i-propylmethylene group, n-butylmethylene group, t-
represents a butyl (4 ethylene group, decyl methylene group, dodecyl methylene group), or a phenylene group. In addition, a divalent group formed by connecting an alkylene group and a phenylene group directly or via a bonding group, or a divalent group formed by connecting an alkylene group or a phenylene group to a bonding group. May also represent a group. The bonding group is -〇-1-s-1-so2-1-NHCO-1-CONH-
1-CO-1-COO-1-OCO-1-NH8O2-
1-8O2NH- and the like. However, general formula CI
In II), when J represents a divalent group formed by linking the alkylene group or phenylene group with a bonding group, the alkylene group or phenylene group is bonded to the sulfonamide group.

2 is a hydrogen atom or a group that can be eliminated during the coupling reaction with the oxidation product of the color developing crude drug (e.g., a halogen atom (e.g., chlorine, bromine, fluorine, etc.), an oxygen atom or a nitrogen atom at the direct coupling position); Examples include bonded aryloxy groups, carbamoyloxy groups, carbamoylmethoxy groups, acyloxy groups, sulfonamide groups, succinimide groups, and more specific examples include U.S. Pat. No. 3,476,563. Specification, JP-A-47-374
No. 25, Japanese Patent Publication No. 1983-36894, Japanese Patent Publication No. 1984-10
No. 135, No. 50-117422, No. 50-1304
No. 41, No. 51-108841, No. 50-12033
No. 4, No. 52-18315, No. 53-52423,
It represents what is described in each publication such as No. 53-105226.

Typical specific examples of couplers of the present invention are described below,
The present invention is not limited to this. 10) (11) (12) 5 (14) (15) OT( (16) H QC)t, CuH2s (17) (18) H (19) H (20) H (21) The coupler of the present invention is As detailed in the specific synthesis examples shown below, it can be easily synthesized, for example, according to the following reaction formula.

That is, in the coupler of the present invention, a benzamide group substituted with a sulfonamide group at least at the 0-position of the phenol is replaced by -NHCOR.

When the acylamino group at the 5-position is abbreviated as R'CONH-, and the above-mentioned 2 is bonded to the 4-position of the phenol, the coupler (IX) of the present invention can be obtained based on the following reaction formula. .

Reaction formula: OH (IV) (V) Synthesis example 1゜2-(2-benzenesulfonamide benzamide)-4
-Synthesis of chloro-5-(2-(3-dodecyloxyphenoxy)propanamide)phenol [Exemplary coupler (1)] 1. Synthesis of 2-benzenesulfonamide benzoyl chloride (V) Methyl 0-amine benzoate 15F Acetonitrile 50
tnl and pyridine, 10.5 M of benzenesulfonyl chloride was added dropwise, and the mixture was stirred at room temperature for 3 hours. The reaction solution was poured into ice water, and a large amount of precipitated crystals was collected.

Yield: 162°. Of the crystals obtained, 15F was converted into potassium hydrate with 8.7% of the obtained crystals. , added to a solution of 20-1 alcohol and 30-1 water, and stirred at room temperature for 1 hour. Thereafter, the mixture was acidified with hydrochloric acid, and the precipitated crystals were collected. Yield 12.1'. 1° of the obtained carboxylic acid was added to 10-benzene and 16-thionyl chloride, and after heating and refluxing for 2 hours, the solvent and thionyl chloride were distilled off under reduced pressure, and the residue was recrystallized from acetonitrile.

Yield: 1 tlO.

2. Synthesis of Exemplary Coupler (1) 2-7mi/-4-chloro-5-ditrophenol (IV
:15.7f was added to 1oo- of acetonitrile, the above carboxylic acid chloride (V) 10F was added, and heating under reflux was continued for 4 hours. The reaction solution was added to ice water, and the precipitated crystals were collected by F to obtain 12.2F crystals [■].

Add this crystal [VI) 10f to alcohol 270-,
Atmospheric pressure catalytic hydrogenation was carried out using palladium-carbon catalyst 1'f as a catalyst. After the reaction was completed, the catalyst was separated and the solvent was distilled off under reduced pressure to obtain the amine compound [■]. Add 3.6 F of this amine [■] with a yield of 82 F and 0.85 F of sodium acetate to 50 tnt of acetic acid, and add 2-(3-dodecyloxyphenoxy)butanoic acid monorolide (■1I) st to 100 tnt of acetic acid.
A solution dissolved in - was added dropwise, and after stirring at room temperature for 30 minutes, the reaction stream was added to ice water, and the precipitated crystals were collected. The crystals were purified by silica gel column chromatography using a mixed solvent of toluene and acetone as a developing solvent to obtain the target product (IX) 3.4F as a waxy solid with a melting point of 65 to 70°. The structure of the target product was confirmed by mass spectroscopy and nuclear magnetic resonance spectroscopy.

Synthesis example 2 2-(2-benzenesulfonamidobenzamide)-4
-chloro-5-(2-(2,4,6-)lichlorophenoxy)dodecanamide] Synthesis of phenol [exemplified coupler (9)] Zensulfonamide benzamide)-4-chloro-5-aminephenol [■ ) 21f and sodium acetate 0.52 to acetic acid 10
In addition to 0-, 2-(2,4゜6-drichlorophenoxy)dodecanoic acid chloride 232 [■] was added to 1001n
The solution was added dropwise to the solution in dewatered water under stirring at room temperature for 1 hour, and the precipitated crystals were recrystallized from acetonitrile after PIIR. 291 of the desired product (IX) was obtained as white crystals with a melting point of 123-125°. The structure of the target product was confirmed by mass spectrometry and nuclear magnetic resonance spectroscopy.

IV Specific Uses of the Invention The couplers of the invention are generally used as cyan dye-forming couplers, in which case the methods and techniques used for conventional cyan dye-forming couplers are similarly applicable. Typically, the coupler of the present invention is blended into a silver halide emulsion, and this emulsion is coated on a support to form a silver halide photographic material (hereinafter referred to as the silver halide photographic material thus formed). is referred to as the silver halide photographic material according to the present invention).

The silver halide photographic material according to the present invention can be a monochrome or multicolor silver halide photographic material. In a multicolor silver halide photographic light-sensitive material, the coupler of the present invention is usually contained in a red-sensitive silver halide emulsion layer, but it is also used in non-sensitized emulsions or those sensitive to the three primary color regions of the spectrum other than red-sensitivity. It may also be contained in the emulsion layer.

Each of these emulsion layers may be composed of either a single emulsion layer or a multilayer emulsion layer that is sensitive to a certain region of the spectrum. The constituent layers of the silver-oxide photographic material can be arranged in various orders as is known in the art. A typical multicolor silver halide photographic material comprises at least one red-sensitive silver halide emulsion layer containing at least one cyan dye-forming coupler (at least one of the cyan dye-forming couplers being a coupler of the present invention). be.

), at least one green-sensitive silver halide emulsion layer containing at least one maze/red dye-forming coupler, at least one blue-sensitive silver halide photographic material containing at least one magenta dye-forming coupler. is supported on a support. A silver halide photographic light-sensitive material consists of a filter layer, an intermediate layer,
It can have a 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 present invention may be applied 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 organic solvent such as butyl acetate or butyl propionate, or a mixture thereof as necessary. After dissolving the couplers alone or in combination, they are mixed with an aqueous gelatin solution containing a surfactant, then emulsified in a high-speed rotating mixer or colloid mill, and then added to silver halide to form a silver halide emulsion. can be prepared. When the coupler of the present invention is added to a silver halide emulsion, it is usually k) per mole of silver halide.
It is added in an amount of 0.07 to 0.7 mole, preferably 0.1 to 0.4 mole.

The silver halide used in the silver halide emulsion in the present invention includes silver bromide, silver chloride, silver iodobromide, silver chlorobromide, silver chloroiodobromide, etc. Any of the above is included.

The silver halide emulsion in the present invention can be produced by various manufacturing methods including the usual manufacturing method, for example, Japanese Patent Publication No. 46-77.
72, or the method described in U.S. Pat. No. 2,592,250, i.e., silver salt particles consisting of at least a portion of a silver salt having a higher solubility than silver bromide. A process for producing a so-called conversion emulsion, in which an emulsion is formed, and then at least a portion of the grains are converted into silver bromide or silver iodobromide salt, or fine-grain silver halide having an average grain size of 0.1 μm or less. It can be produced by any manufacturing method such as the method of manufacturing Lippmann emulsion consisting of.

Furthermore, the silver halide emulsion described above may contain sulfur sensitizers such as allylthiocarbamide, thiourea, cystine, etc., active or inactive selenium sensitizers, and reduction sensitizers.
For example, stannous salts, polyamines, etc., noble metal sensitizers, such as gold sensitizers, specifically potassium aurithiocyanate, potassium chlorate, 2-ourosulfobenzthiazole methyl chloride, etc., or, for example, ruthenium, Chemical sensitization can be carried out using water-soluble salt sensitizers such as rhodium and iridium, specifically ammonium chloroparadate, potassium chloroplatinate, and sodium chlorovaladite, alone or in combination as appropriate.

Further, the above-mentioned silver halide emulsion can contain various known photographic additives. For example, Re5earc
h L)iscrosure A photographic additive as described in December 1978 Item 17643.

In the silver halide color photographic light-sensitive material according to the present invention, the hydrophilic colloids used to prepare the emulsion include gelatin, derivative gelatin, graft polymers of gelatin and other polymers, proteins such as albumin and casein, The present invention includes any single or copolymer synthetic hydrophilic polymers such as cellulose derivatives such as hydroxyethyl cellulose derivatives and carboxymethyl cellulose, starch derivatives, polyvinyl alcohol, polyvinyl alcohol, and polyacrylamide. Such a silver halide photographic light-sensitive material may be subjected to a corona discharge treatment, a fire treatment, or an ultraviolet irradiation treatment along with an emulsion layer containing various photographic additives as described above, as well as other constituent layers, as necessary. It is produced by coating on a support or by coating it on a support via a subbing layer or an intermediate layer. Advantageously used supports include, for example, baryta paper, polyethylene-coated paper, polyglobin/synthetic paper, transparent supports with a reflective layer or with a reflector, such as glass plates, cellulose acetate,
Examples include polyester films such as cellulose nitrate or polyethylene terephthalate, polyamide films, polycarbonate films, and polystyrene films, and these supports are appropriately selected depending on the intended use of the silver halide photographic light-sensitive material.

Various coating methods such as dipping coating, air doctor coating, curtain coating, and hopper coating can be used to coat the emulsion layer and other constituent layers used in the present invention. U.S. Patent No. 2,761,791, No. 2
It is also possible to use simultaneous coating of two or more layers by the method described in No. 941,898.

In the silver halide photographic light-sensitive material according to the present invention, it is optional to provide an intermediate layer of an appropriate thickness depending on the purpose, and various layers such as a filter layer, an anti-curl layer, a protective layer, an antihalation layer, etc. The layers can be used in appropriate combination as constituent layers. Hydrophilic colloids that can be used in the emulsion as described above can be used as binders in these constituent layers, and various types of colloids that can be contained in the emulsion layers as described above can be used in these layers. Photographic additives may be included as well.

The silver halide photographic material according to the present invention is used for various purposes and exhibits excellent properties depending on the purpose. It can be used for photosensitive materials (for X-ray, high resolution), but is particularly suitable for color photographic paper.

The silver halogenide used in the present invention is subjected to spectral sensitization by selecting an appropriate sensitizing dye in order to impart photosensitivity to 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. 4,629 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-7
Enylenediamine hydrochloride, dimethyl-p-phenylenediamine hydrochloride, 2-amino-5-dimethylaminotoluene hydrochloride, 2-amino-5-(N-ethyl-N-totecylamino)-)toluene, 2-amino- 5-(N-ethyl-N-β-methanesulfonamidoethyl)amine toluene sulfate, 4-(N-ethyl-N-β-methanesulfonamidoethylamino)aniline, 4-(N-ethyl-N
-β-hydroxyethylamino)aniline, 2-amino-5-(N-ethyl-N-β-methoxyethyl)amine toluene, and the like.

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

Color developing solutions containing the above-mentioned developing agents generally contain alkaline agents such as hydroxide, ammonium hydroxide, sodium carbonate, sodium sulfate, sodium sulfite, etc., and additives for the glaze, such as halogens. It may contain an alkali metal (such as potassium bromide) or a development regulator such as citradinic acid.

■Specific effects of the invention In the silver halide photographic material using the coupler of the invention, the spectral absorption characteristics, sensitivity, and sensitivity of the cyan dye formed are improved.
It exhibits excellent characteristics in terms of color density, color staining, and image storage stability such as light resistance, heat resistance, and moisture resistance, and provides cyan dye images with good color development. Especially in second place. -Sulfonamido It has a benzamide group and shows a remarkable improvement effect on the light resistance that was a problem in the conventionally known 2.5-U acylaminophenol cyan coupler which has an acylamino group at the 5-position. At the same time, the spectral absorption characteristics have also been favorably improved.

As described above, the coupler of the present invention is a photographic coupler that exhibits excellent properties in the use of photographic elements such as silver halide color photographic light-sensitive materials. The present invention will be described in more detail with reference to the following figures, but the embodiments of the present invention are not limited thereby.

Example 1 Using a coupler of the present invention and a comparative coupler as shown in Table 1 below, 1 (l) of each was added to a mixture of 5tn! of di-n-butyl phthalate and 3o7! of ethyl acetate, and the mixture was heated to 60°C. It was completely dissolved by heating.

This solution was mixed with a 10% aqueous solution of Alkanol B (alkylnaphthalene/sulfonate, manufactured by DuPont) and a 5%
The mixture was mixed with 200ml of gelatin aqueous solution and emulsified using a colloid mill to prepare respective coupler dispersions. Next, this coupler dispersion was added to 500 tons of gelatin silver chlorobromide emulsion, coated on polyethylene-coated paper, and dried to prepare a total of six types of silver halide color photosensitive materials.

After performing wedge exposure on these samples according to the conventional method,
It was processed as follows.

Processing process (30℃) Processing time Color development 3 minutes 30 seconds Bleach fixing 1 minute 30 seconds Wash with water 2 minutes The composition of each treatment is shown below.

[Color developer composition 1] [Bleach-fix solution composition] The photographic properties of the samples obtained by the above processing were measured. For the measurement, a PDA-60 type densitometer (manufactured by Konishiroku Photo Industry @) was used.

The results obtained are shown in Table 1 below.

The sensitivity values in the table are expressed as relative sensitivities, with the value of the sample having the maximum sensitivity set as 100.

(Table 1) (Comparative force dollar) (A) (described in U.S. Patent No. 2,801,171) (B) H (described in JP-A-53-109630) (C) R As is clear from the above table. Samples using comparative couplers, especially Sample 5, had problems in sensitivity, maximum density, and spectral absorption characteristics, but all samples using couplers of the present invention had excellent performance in sensitivity, maximum density, and spectral absorption characteristics. As a result, the coupler of the present invention was found to be a coupler with good color development.

Example 2 A sample having a cyan dye image was prepared in exactly the same manner as in Example 1 using the couplers of the present invention and comparative couplers as shown in Table 2 below. Using this sample, experiments and studies were conducted on the light resistance, heat resistance, moisture resistance, and occurrence of staining of the dye.

The results obtained are listed in Table 2 below.

In the table, light resistance is measured after exposing each dye image to a xenon fade meter for 200 hours, heat resistance is measured after storage at 77°C for 2 weeks, and humidity resistance is measured at 60°C and relative humidity of 80%.
The residual rate at each initial concentration of 1.0 after two weeks of storage is expressed as a percentage. Stine also expressed the rate of increase in blue density in the unexposed area of the sample subjected to the dramatic light test as a percentage.

(Table 2) (Comparative coupler) (D) H As is clear from the results in the table above, the comparative coupler (A), which had good color development in Table 1, had significantly poor heat resistance and moisture resistance. ing.

Similarly, in Table 1, it can be seen that the comparative coupler (C) having an 0-sulfonamidobenzamide group at the 2-position of the phenol, which was almost satisfactory in sensitivity and absorption maximum, was significantly inferior in light resistance.

As can be seen from Tables 1 and 2, there was room for improvement in all of the properties required of the comparative Kaflaha phenolic cyan couplers. On the other hand, the uninvented coupler not only has excellent sensitivity and image quality as shown in Table 1, but also has excellent physical properties such as image preservation and stability as shown in Table 2. It was found that this product has excellent performance in terms of both gender and performance.

Procedural Sleeve Letter (spontaneous) Mr. Kazuo Wakasugi, Commissioner of the Patent Office ~h-12-・1 Indication of the case 1984 Patent Application No. 37140 3 Relationship with the person making the amendment Patent applicant address Shinjuku, Tokyo Nishi-Shinjuku 1-26-2 Trap 9” 1 (Name) (127) Konishiroku Photo Industry Co., Ltd. 6 Number of inventions increased by amendment None 1) Lines 5-6 of page 17 of the specification are changed to “ (3) (2) Page 18 of the specification, lines 1-2, “(5) I-I [(5-R).

(3) Lines 7-8 of page 18 of the specification "(8) r (17)

Claims (1)

[Claims] The second position of the phenolic cyan coupler is at least 〇-
The benzamide group has a benzamide group substituted with a sulfonamide group at the 5-position, and an acylamino group at the 5-position, and the benzamide group has a benzene ring and a sulfonamide group substituted with a sulfonamide group at the 0-position. At least one group selected from the amide group and the acylamino group has at least one phenoxy group represented by the following general formula [I] or a group having the phenoxy group as a substituent. Phenolic cyan coupler. ~General Formula [I] [In the formula, R1 represents an alkoxy group, an aryloxy group, a halogen atom, or a hydroxyl group. R2 represents a halogen atom or a monovalent organic group. n represents an integer from 0 to 4. However, when n is an integer of 2 or more, a plurality of R'2's may be the same or different. ]