JPS6319852B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel photographic color coupler, a color photographic light-sensitive material containing the same, or an image forming method using this type of coupler.

It is well known that when a silver halide photographic material is exposed to light and then subjected to color development, an oxidized aromatic primary amine developer reacts with a dye-forming coupler, and a color image is obtained.

This method typically applies a subtractive color reproduction method to form cyan, magenta, and yellow color images that are complementary to red, green, and blue. For example, to form a cyan image, a phenol derivative or a naphthol derivative is used as a coupler. The reaction between the coupler and the color developing agent takes place at the active site of the coupler, and a coupler having a hydrogen atom at this active site is a 4-equivalent coupler, i.e., the theoretical stoichiometry is 4 moles to form 1 mole of dye. This method requires silver halide having development nuclei of 1 as an oxidizing agent. On the other hand, those having an anionically detachable group at the active site are 2-equivalent couplers, that is, couplers that require only 2 moles of silver halide with development nuclei to form 1 mole of dye; Compared to 4-equivalent couplers, the amount of silver halide in the photosensitive layer can generally be reduced and the film thickness can be made thinner, making it possible to shorten the processing time of photosensitive materials and further improving the sharpness of the color images formed. do. Such leaving groups include a sulfonamide group in U.S. Pat. No. 3,737,316 and an imide group in U.S. Pat. No. 3,749,735.
U.S. Pat. No. 3,622,328 uses a sulfonyl group, and U.S. Pat. No. 3,476,563 uses an aryloxy group.
3311476, the acyloxy group is
No. 3214437 has a thiocyano group,
Substituted alkoxy groups are known in JP-A No. 120334, JP-A-50-117422, and JP-A-52-18315.

Furthermore, by appropriately selecting the leaving group, it can be used in a diffusion transfer method in which, for example, the leaving group contains a diffusible dye moiety and the leaving dye is used to form a dye image of the diffusible dye on the image-receiving layer. Yes, this type of coupler is called a diffusible dye-releasing coupler and is described, for example, in U.S. Pat. No. 3,227,550;
No. 3765886, US Defense Patent Application No. T900029, British Patent No. 1330524, etc. In addition, certain colored two-equivalent couplers have a masking effect for color correction of dye images, and this type of couplers are called colored couplers, and are described in, for example, JP-A-51-26034. .

Two-equivalent couplers whose separation products have the effect of inhibiting development are called development inhibitor-releasing couplers, and they suppress development in proportion to the amount of developed silver, resulting in finer grains and gradation of images. It has effects such as adjusting tone and improving color reproducibility. It can also be used in a diffusion transfer method by utilizing the effect on adjacent layers. Couplers of this type are described in U.S. Pat.

As described above, 2-equivalent couplers tend to be widely used because they are inherently superior to 4-equivalent couplers and have a variety of applicability.

However, many of the conventionally known two-equivalent cyan-forming couplers have insufficient coupling reactivity or cause significant color fog.
There are disadvantages such as poor dispersibility, which may cause coating failures, the compound being unstable and not being able to be stored for a long period of time, and the storage stability of the color image produced after color development being low. Improvements are desired.

It is a first object of the present invention to provide a new two-equivalent cyanogenic coupler in which these prior drawbacks are eliminated.

A second object of the present invention is to provide a method for forming cyan images by developing a silver halide emulsion in the presence of a novel two-equivalent coupler.

A third object of the present invention is to provide a silver halide color photographic material containing a novel coupler or a photographic processing method thereof.

As a result of various studies, the present inventors decided to use a colorless photographic cyan color-forming coupler having a group represented by the following general formula [] at the position where it couples with the oxidized product of an aromatic primary amine developer. Therefore, it has been found that the above objectives can be effectively achieved.

General formula -O-R-COOH [] R represents a straight chain alkylene group having 2 to 4 carbon atoms.

Here, a colorless coupler refers to a coupler having a molecular extinction coefficient of 5000 or less at its maximum absorption wavelength in the visible light region.

The colorless two-equivalent cyan color-forming coupler of the present invention forms a dye faster due to the bonding group than conventional couplers having an alkoxy group, and therefore provides high sensitivity, gradation, and maximum density. This makes it suitable not only for normal processing but also for rapid processing. Further, it does not cause fogging, color staining, etc. to the photosensitive layer, and has good dispersibility in the constituent layers of the photographic light-sensitive material such as the photosensitive layer, and can be dispersed at a high concentration. The dye obtained from this cyan coupler has excellent durability against light, heat, and temperature, and also exhibits sharp absorption without unnecessary light absorption, and has excellent light absorption characteristics. .

It also has the advantage of being useful as a coupler for imaging in conventional systems.

Among the couplers of the present invention, particularly useful couplers are represented by the following general formula [].

General formula R ₁ -A ₁ -O-R-COOH [] where A ₁ represents a cyan dye-forming coupler residue having a phenol nucleus or a cyan dye-forming coupler residue having an α-naphthol nucleus.

-O-R-COOH is a group that binds to the active site of the coupler residue and is released when a dye is formed through oxidative coupling with an aromatic primary amine developer. R has the same meaning as R above.

R ₁ is a hydrogen atom, an aliphatic group with up to 30 carbon atoms (e.g., an alkyl group such as methyl, isopropyl, pentadecyl, and eicosyl), an alkoxy group with up to 30 carbon atoms (e.g., methoxy, isopropoxy,
pentadecyloxy, icosyloxy group), aryloxy group (e.g. phenoxy, p-tert-butylphenoxy group), acylamido group shown in the following formulas () to (), sulfonamide group, phosphoric acid amide group, ureido group, or the following formula ()or()
represents a carbamyl group shown in

In the formula, B and B' may be the same or different,
Aliphatic groups having 1 to 32 carbon atoms, preferably linear or branched alkyl groups or cyclic alkyl groups having 1 to 20 carbon atoms (e.g. cyclopropyl, cyclohexyl, norbornyl, etc.), or aryl groups (e.g. phenyl, naphthyl, etc.) represents. Here, the above alkyl group and aryl group are halogen atoms (e.g. fluorine, chlorine, etc.), nitro group, cyano group, hydroxyl group,
Carboxy group, amino group (e.g. amino, alkylamino, dialkylamino, anilino, N-
alkylanilino), alkyl groups (e.g. R ₁
aliphatic groups), aryl groups (e.g., phenyl, acetylaminophenyl, etc.), alkoxycarbonyl groups (e.g., tetradecyloxycarbonyl, etc.), acyloxycarbonyl groups, amide groups (e.g., acetamide, methanesulfonamide, etc.) , imide group (e.g. succinimide etc.), carbamoyl group (e.g. N,
N-dihexylcarbamoyl, etc.), sulfamoyl groups (e.g., N,N-diethylsulfamoyl, etc.), alkoxy groups (e.g., ethoxy, tetradecyloxy, octadecyloxy, etc.) or aryloxy groups (e.g., phenoxy, p-
tert-butylphenoxy, 2,4-diamylphenoxy, 4-hydroxy-3-tert-butylphenoxy, etc.). C and C' represent B, -OB, -NH-B or _-NB2 ,
B is as described above. In addition to the above substituents, R ₁ may contain commonly used substituents.

Among the compounds represented by the above general formula (), particularly preferred are those represented by the general formula () and ().
Indicated by

R and R ₁ have the same meanings as R and R ₁ in general formula ().
R ₂ is a hydrogen atom, an aliphatic group having 30 or less carbon atoms, especially an alkyl group having 1 to 20 carbon atoms, or a carbamoyl group represented by () or () shown for R ₁ in the general formula (). represent _R3 , _R4 , _R5 ,
R ₆ and R ₇ each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an alkylthio group, a heterocyclic group, an amino group, a carbonamide group, a sulfonamide group, a sulfamyl group, or a carbamyl group. For example, R ₃ represents any of the following groups:

Hydrogen atoms, halogen atoms (e.g. chloro, bromine, etc.), primary with 1 to 22 carbon atoms,
Secondary or tertiary alkyl groups (e.g. methyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, hexyl, dodecyl, 2-chlorobutyl, 2-hydroxyethyl, 2-phenylethyl, 2-(2,4 ,6-trichlorophenyl)
ethyl, 2-aminoethyl, etc.), alkylthio groups (e.g. hexadecylthio, etc.), aryl groups (e.g. phenyl, 4-methylphenyl, 2,4,
6-trichlorophenyl, 3,5-dibromophenyl, 4-trifluoromethylphenyl, 2-trifluoromethylphenyl, 3-trifluoromethylphenyl, naphthyl, 2-chloronaphthyl,
3-ethylnaphthyl, etc.), heterocyclic groups (e.g.
benzofuranyl group, furanyl group, thiazolyl group,
benzothiazolyl group, naphthothiazolyl group, oxazolyl group, benzoxazolyl group, naphthoxazolyl group, pyridyl group, quinolinyl group, etc.), amino group (e.g. amino, methylamino, diethylamino, dodecylamino, phenylamino, tolylamino, 4-( 3-sulfobenzamide) anilino, 4-cyanophenylamino, 2-trifluoromethylphenylamino, benzothiazolamino, etc.}, carbonamide groups {for example, ethylcarbonamide, decylcarbonamide, phenylcarbonamide, etc. Alkylcarbonamide group, phenylethylcarbonamide,
2,4,6-trichlorophenylcarbonamide, 4-methylphenylcarbonamide, 2-ethoxyphenylcarbonamide, 3-[α-(2,
4-di-tert-amylphenoxy)acetamide] benzamide or arylcarbonamide such as naphthylcarbonamide or thiazolylcarbonamide, benzothiazolylcarbonamide, naphthothiazolylcarbonamide, oxazolylcarbonamide, benzoxa Heterocyclic carbonamide groups such as zolylcarbonamide, imidazolylcarbonamide or benzimidazolylcarbonamide}, sulfonamide groups {e.g. alkylsulfonamide groups such as butylsulfonamide, dodecylsulfonamide or phenylethylsulfonamide, etc. , phenylsulfonamide, 2,4,6-trichlorophenylsulfonamide, 2-methoxyphenylsulfonamide, 3-carboxyphenylsulfonamide or naphthylsulfonamide, or arylsulfonamide group or thiazolylsulfonamide. , heterocyclic sulfonamide groups such as benzothiazolylsulfonamide, imidazolylsulfonamide, benzimidazolisulfonamide or pyridylsulfonamide}, sulfamyl groups {e.g. propylsulfamyl, octylsulfamyl, pentadecylsulfamyl Alkylsulfamyl groups such as amyl or octadecylsulfamyl, phenylsulfamyl, 2,4,6-
Arylsulfamyl groups such as trichlorophenylsulfamyl, 2-methoxyphenylsulfamyl or naphthylphamyl, or thiazolylsulfamyl, benzothiazolylsulfamyl,
Heterocyclic sulfamyl groups such as oxazolylsulfamyl, benzimidazolylsulfamyl or pyridylsulfamyl groups} and carbamyl groups {such as ethylcarbamyl, octylcarbamyl, pentadecylcarbamyl or octadecylcarbamyl, etc. Alkylcarbamyl group;
Arylcarbamyl groups such as phenylcarbamyl or 2,4,6-trichlorophenylcarbamyl, or thiazolylcarbamyl, benzothiazolylcarbamyl, oxazolylcarbamyl, imidazolylcarbamyl or benzimidazolyl Heterocyclic carbamyl group such as carbamyl group}
It is. Examples of R ₄ , R ₅ , R ₆ and R ₇ include those exemplified for R ₃ . W represents a nonmetallic atom necessary to form a 5- or 6-membered ring as described above. That is, benzene ring, cyclohexene ring, cyclopentene ring, thiazole ring, oxazole ring, imidazole ring,
Pyridine rings, pyrrole rings, etc. Among these, a benzene ring is preferred.

Next, typical examples of the coupler of the present invention will be described.
It is not limited to this.

These compounds according to the present invention can be synthesized by the following method.

One of the hydroxyl groups of the 1,4-dihydroxybenzene derivative may be protected in advance by, for example, pyranyl etherification, or
1 in advance by the method described in 69572.
After forming an oxazole ring with the hydroxyl group at the 2-position and the acetylamino group at the 2-position, a base-catalyzed reaction is carried out with the corresponding ester-substituted alkyl halide to alkoxylate the hydroxyl group at the 4-position. Next, the oxazole ring is cleaved with an acid, the corresponding acid chloride is reacted in the presence of a dehydrochlorination agent, and the ester is then hydrolyzed to synthesize the corresponding coupler.

Next, typical synthesis examples of couplers according to the present invention will be specifically shown below.

Synthesis Example 1 1-Hydroxy-4-(γ-carboxypropyloxy)-N-[γ-(2,4-di-tert-amylphenoxy)propyl]-2-naphthamide; Synthesis of Exemplary Coupler (1) 41 g (0.2 mol) of 1,4-dihydroxynaphthoic acid was dissolved in 200 ml of DMF, 80 g (0.4 mol) of a 28% methanol solution of sodium methoxide was added dropwise under nitrogen at room temperature, and the reaction temperature was then raised to 35-40°C. 25 g (0.18 mol) of γ-ethoxycarbonylpropyl chloride was added while maintaining the temperature at 100 ml, and the mixture was stirred for 1 hour, then poured into 50 ml of concentrated hydrochloric acid and 1 part of water, and the precipitated crystals were filtered out. The obtained crystals were washed with acetonitrile to obtain 35.8 g (56.3%) of 1-hydroxy-4-(γ-ethoxycarbonylpropyloxy)-2-naphthoic acid. Then, 31.8 g (0.1 mol) of the obtained carboxylic acid and 14.1 g of phenol
(0.15 mol) was added dropwise to 24.0 g (0.2 mol) of thionyl chloride while stirring while heating in 500 ml of acetonitrile.
After heating and stirring for 3 hours, add acetonitrile to approx.
After distilling off ml, the reaction temperature was cooled to room temperature (20℃) and the precipitated crystals were filtered out to form the phenyl ester compound.
31.8g (80.7%) was obtained. Next, 30 g (0.076 mol) of the obtained 1-hydroxy-4-(γ-ethoxycarbonylpropyloxy)-2-phenoxycarbonylnaphthalene was dissolved in 300 ml of acetonitrile while heating and stirring. amylphenoxy)propylamine 26.5g (0.091mol)
added. After 3 hours, the acetonitrile was distilled off under reduced pressure and the precipitated crystals were filtered out to give 1-hydroxy-4-
(γ-ethoxycarbonylmethoxy)-N-[γ-
32.5 g (72.3%) of (2,4-di-tert-amylphenoxy)propyl]-2-naphthamide was obtained.
Next, 30 g (0.05 mol) of the obtained naphthamide was added dropwise to 500 ml of ethanol at room temperature with 600 ml of an aqueous solution in which 40 g of sodium hydroxide had been previously dissolved.
After stirring for an hour, the mixture was acidified with 83 ml of concentrated hydrochloric acid and the precipitated crystals were filtered out.

Recrystallized from ethanol to give example coupler (1) at 23.4
g (83.0%) was obtained.

Melting point 80-82℃ Synthesis example 2 Synthesis of exemplified coupler (3) 1 Synthesis of compound B Hydroquinone 660g, acetonitrile 1300g
ml, 1205 ml of ethyl chloroformate was slowly added to a suspension of 1030 ml of pyrrolidine under ice cooling, and after addition 15 ml of ethyl chloroformate was added.
Stirring was continued for a minute. Next, the reaction solution was poured into 5 portions of water, filtered and washed with water to obtain 1465 g of Compound B.
(mp97~8℃) 2 Synthesis of compounds C~ and D~ 762g of compound B~ was slowly added to 150ml of concentrated sulfuric acid with stirring under ice cooling, and then the internal temperature was 15~20℃.
210 ml of concentrated nitric acid (d=1.42) was added dropwise while maintaining the temperature, and stirring was continued for 1 hour after the addition. The reaction solution was poured into ice water 5, and the precipitated crystals were collected and washed with water to obtain Compound C~.

Furthermore, compound C was added to 1500 ml of ethanol and water.
1500ml, added to a solution of 150g of sodium carbonate,
The mixture was heated under reflux for 2 hours.

After the reaction is complete, cool to room temperature and add 1N hydrochloric acid (3000 g)
ml was added, and the precipitated crystals were collected and washed with water to obtain ~648 g of Compound D. (mp63~64℃) 3 Synthesis of compounds E~, F~, G~ Add 159 g of compound D~, 150 g of ethyl γ-bromo-n-butyrate, and 140 g of potassium carbonate to 350 ml of dimethylformamide, and heat and stir on a steam bath. It lasted 6 hours. After the reaction was completed, the mixture was extracted with ethyl acetate, washed twice with water, and concentrated under reduced pressure to obtain an oily compound E~.

Dissolve the above compound E ~ in 700 ml of ethyl acetate,
Catalytic reduction was carried out using a carbon-supported palladium catalyst under 40 kg/cm ² of hydrogen. After the theoretical amount of hydrogen has been consumed, the solution without the catalyst is concentrated under reduced pressure,
The resulting oil was dissolved in 750 ml of acetonitrile, and 237 g of 2-(2,4-di-t-pentylphenoxy)butyryl chloride was added with stirring. The mixture was then heated to reflux for 1.5 hours,
After the reaction was completed, the mixture was concentrated under reduced pressure to obtain an oily compound F.

The above compound F and 20 g of sodium hydroxide were added to a solution of 700 ml of methanol and 150 ml of water, and stirring was continued at room temperature for 6 hours. After the reaction was completed, the mixture was acidified with hydrochloric acid, extracted with ethyl acetate, washed twice with water, concentrated under reduced pressure, and recrystallized with 600 ml of acetonitrile to obtain 292 g of compound G. (mp119-120℃) 4 Synthesis of Compounds H~ and I~ Dissolve 40.6 g of Compound G~ in 300 ml of chloroform, slowly dropwise add 7 ml of concentrated nitric acid (d=1.42) under ice cooling, and stir for 15 minutes after the dropwise addition. continued. After washing three times with water, the chloroform solution is concentrated under reduced pressure to obtain an oily compound H~.

Dissolve the above compound H in 200 ml of ethyl acetate,
Catalytic reduction was carried out using a carbon-supported palladium catalyst under 40 kg/cm ² of hydrogen. After the theoretical amount of hydrogen was consumed, 22.5 g of heptafluorobutyryl chloride was added to the solution without the catalyst under ice cooling.
Next, 14 ml of triethylamine was added dropwise, and stirring was continued for 1 hour after the addition. After washing with water three times,
The residue was concentrated under reduced pressure and crystallized with 150 ml of acetonitrile to obtain 45 g of Compound I. (mp160-162℃) 5 Synthesis of coupler (3) Add ~15.2g of compound I and 1.8g of sodium hydroxide to a solution of 50ml of methanol and 30ml of water, and after standing overnight at room temperature, dilute the reaction solution with 300ml of 0.2N hydrochloric acid. The precipitated crystals were collected and washed with water. Recrystallization was performed using a mixed solvent of ethyl acetate and n-hexane to obtain 12.3 g of coupler (3). (mp173-175°C) In order to produce a silver halide color photographic light-sensitive material using the coupler of the present invention, the coupler of the present invention may be used alone or in combination of two or more. You may. The couplers described below can be used in color photographic materials containing the couplers of the present invention. For example, U.S. Pat.
No. 2474293, No. 3034892, No. 3591383, No. 3591383, No. 3034892, No. 3591383, No.
Cyan dye-forming couplers described in US Pat. No. 3,311,476, US Pat.
It is described in No. 3227554, No. 3379529, etc. )
Yellow dye-forming couplers (e.g. those described in OLS 2213461, U.S. Pat. No. 3,510,306, etc.) and magenta dye-forming couplers (e.g. U.S. Pat.
No. 2, published in West German patent application (OLS) No. 2418959).

Two or more types of the above-mentioned couplers and the like can be used together in the same layer in order to satisfy the characteristics required of a photosensitive material, and the same compound can of course be added to two or more different layers.

The phenolic or α-
Naphthol couplers are dissolved in an aqueous medium or an organic solvent and then dispersed in a photographic emulsion.

Among the couplers of the present invention, the oil-soluble diffusion-resistant couplers used in the internal mold method are once dissolved in an organic solvent, and then dispersed into fine colloidal particles in a photographic emulsion and incorporated into a photographic material.

Specific examples of coupler dispersion methods suitable for practicing the present invention are described in detail in US Pat. No. 3,676,131. Organic solvents used to dissolve couplers are sparingly soluble in water and have a high boiling point, and those that coexist with couplers in color light-sensitive materials include substituted hydrocarbons, carboxylic acid esters, carboxylic acid amides, There are compounds such as phosphoric acid esters and ethers, and specific examples include di-
n-Butyl phthalate, di-isooctyl acetate, di-n-butyl sebacate, tricresyl phosphate, tri-n-hexyl phosphate, N,N-diethyl caprylamide, butyl-n-pentadecyl phenyl ether , chlorinated paraffin, butyl benzoate, pentyl-o-
These include methylbenzoate and propyl-2,4-dichlorobenzoate. In addition to these high-boiling solvents, it is advantageous to use auxiliary solvents which can be removed during the production of the light-sensitive material to aid in the dissolution of the coupler. Examples include propylene carbonate, ethyl acetate, butyl acetate, cyclohexanol, tetrahydrofuran, cyclohexanone, and the like.

It is advantageous to use surfactants to help finely disperse these oil-soluble internal couplers in the hydrophilic polymeric materials used in photographic emulsions. In particular, anionic surfactants such as sodium cetyl sulfate, sodium p-dodecylbenzenesulfonate, sodium nonylnaphthalenesulfonate, di(2-ethylhexyl)-α-sulfosuccinate, sodium salt, and sorbitan sesquioleate. , sorbitan monolaurate, and other nonionic surfactants are suitable.

Emulsion homogenizers, colloid mills, ultrasonic emulsifiers, etc. are useful for dispersing oil-soluble couplers. Diffusion-resistant couplers having a ballast group and a carboxylic acid group or a sulfonic acid group in one molecule are soluble in neutral to weakly alkaline aqueous solutions. Couplers can be incorporated into photographic emulsions by adding their aqueous solutions to the photographic emulsion. It is believed that couplers become diffusion resistant by forming micelles within hydrophilic polymers.

Examples of silver halide light-sensitive materials in which the coupler used in the present invention can be used include various color light-sensitive materials including general color light-sensitive materials such as color negative films, color positive films, color reversal films, and color papers. In addition, there are various other materials such as color direct positive light-sensitive materials, monochrome light-sensitive materials, color radiography, instant color light-sensitive materials using color diffusion transfer methods, and the like.

The coupler of the present invention can be used using known multilayer construction methods for multilayer color photosensitive materials (for example, U.S. Pat. No. 3,726,681,
No. 3516831, British Patent No. 818687, British Patent
923045 etc.) or the method described in Japanese Patent Application Laid-open No. 50-5179, or the method described in West German Patent Application (OLS) No. 2322165 or the U.S. Pat.
It can also be applied in combination with the DIR compound described in No. 3703375.

The amount of coupler used is generally 10 to 1,500 g per mole of silver halide, but it can be changed depending on various application purposes.

The silver halide photosensitive material used in the present invention includes an emulsion layer, an intermediate layer, an antihalation layer, a protective layer, a yellow filter layer, a back layer, a mordant polymer layer,
A photographic element consisting of various layers such as a developer stain prevention layer is coated on a support. The color silver halide emulsion layer includes a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer, but the order of these layers is not particularly limited, and each layer can be further divided into two or more layers.

It is advantageous for the light-sensitive material used in the present invention to contain a p-substituted phenol derivative in the emulsion layer or a layer adjacent thereto in order to increase the stability of color photography. Particularly effective p-substituted phenol derivatives include U.S. Pat.
No. 2675314, No. 2701197, No. 2704713, No. 2710801,
Hydroquinone derivatives as described in Nos. 2728659, 2732300, 2735765, and 2816028: Gallic acid derivatives as described in U.S. Pat.
p-alkoxyphenols as described in US Pat. No. 2735765 and JP-A-47-4738;
It can be selected from p-oxyphenol derivatives such as those described in No. 3764337.

The light-sensitive material used in the present invention advantageously contains an ultraviolet absorber, such as those described in US Pat. Nos. 3,250,617 and 3,253,921, for image stabilization in the emulsion layer or adjacent layer.

After exposure, the color photographic material of the present invention can be subjected to known processing methods that basically include color development, bleaching, and fixing steps. Each of these steps may be completed in a single treatment using a treatment liquid that has the functions of two or more steps.
An example is a one-bath bleach-fix solution.

In addition to the above, the development process includes a pre-hardening bath, a neutralization bath, a first development (black and white development), an image stabilization bath, and various steps after washing, if necessary. The processing temperature is set within a preferable range depending on the photosensitive material and processing prescription, and may be lower than 18°C, but is often 18°C or higher.

The coupler according to the present invention can also be used in light-sensitive materials with a low silver content, where the amount of silver halide in the emulsion is a fraction to one-hundredth of that in conventional light-sensitive materials. . For these color photosensitive materials with a reduced amount of silver halide, image forming methods that increase the amount of dye produced by utilizing color intensification using peroxide or cobalt complex salts (for example,
West German Patent Publication (OLS) No. 2357694, U.S. Patent
No. 3674490, No. 3761265, West German Patent Publication (OLS)
No. 2044833, No. 2056359, No. 2056360, No.
2226770, JP-A No. 48-9728, JP-A No. 48-9729, etc.)
etc., it was possible to obtain a sufficient color image.

EXAMPLES The present invention will be specifically described below with reference to Examples, but the present invention is not limited thereto.

Example 1 The exemplary coupler (1), i.e. 1-hydroxy-
4-(γ-carboxypropyloxy)-N-[γ
-(2,4-di-tert-amylphenoxy)propyl]-2-naphthamide 42.2 g, dioctylbutyl phosphate 80 ml, ethyl acetate 80 ml and 20% methanol solution of sorbitan monolaurate 8
ml of gelatin, 3.0 g of di-2-ethylhexylsulfonodium succinate, and 2.8 g of phenol.
The mixture was added to 400 ml of an aqueous solution at 60° C. containing the following, and the solution was vigorously mechanically stirred using a homogenizer to emulsify and disperse.

The emulsion used is 1.0 kg of silver chlorobromide emulsion containing 50 mol% of bromide, 0.3 mol of silver and 70 g of gelatin, and a red-sensitive photosensitive dye.
200ml of 0.01% methanol solution of compound-6 described in No.-22189 was added, and then 5-methyl-7-
It was prepared by adding 50 ml of a 1% methanol solution of hydroxy-1,3,4,7a-tetrazaindene.

To this emulsion, add the entire amount of the emulsified dispersion described above, add 30 ml of a 3% acetone solution of triethylene phosphamide as a hardening agent, and finally add the PH.
The emulsion was adjusted to 6.5 to obtain a red-sensitive silver halide emulsion.

As a support, baryta paper resin-treated with polyethylene on both sides was used, and the first layer was a coupler (h), that is, α-(5,5-dimethyl-2,4-
dioxooxazolidin-3-yl)-α-bivaloyl-2-chloro-5-[α-(2′,4′-di-
A blue-sensitive silver halide emulsion containing tert-amylphenoxy)butylamide]acetanilide was coated to a dry film thickness of 4.0 microns, and a gelatin solution was applied as a second layer on top of this to a dry film thickness of 4.0 microns.
The third layer was coated with coupler (i), 1-(2,4,6-trichlorophenyl)-3-[(2-chloro-5-n-
A green-sensitive silver halide emulsion containing tetradecaneamide)anilino]-5-pyrazolone was coated to a dry film thickness of 2.5 microns. The fourth layer is 2-(2'-benzotriazolyl)-4,6
- A gelatin solution containing dibutylphenol as an ultraviolet absorber was applied to a dry film thickness of 2.5 microns.

As the fifth layer, the previously described red-sensitive silver halide emulsion was coated to a dry film thickness of 3.5 microns. Further, a gelatin solution was applied as the top layer to a dry film thickness of 0.5 microns to prepare color photographic paper.

A color negative was optically printed on this color photographic paper and subjected to the following processing.

Treatment process Temperature (℃) Time (minutes) 1 Coloring phenomenon 30 6 2 Stop 〃 2 3 Wash with water 2 4 Bleach fixing 〃 2 5 Wash with water 2 6 Stable bath 〃 2 The treatment liquid used had the following composition.

Color developer Benzyl alcohol 12ml Diethylene glycol 3.5ml Sodium hydroxide 2.0g Sodium sulfite 2.0g Potassium bromide 0.4g Sodium chloride 1.0g Borax 4.0g Hydroxyamine sulfate 2.0g Ethylenediaminetetraacetic acid disodium dihydrate
2.0g 4-amino-3-methyl-N-ethyl-N-
(Add β-methanesulfonamidoethylaniline sesquisulfate monohydrate water to make a total volume of 1000ml Stop solution Sodium thiosulfate 10g Ammonium thiosulfate (70%) 30ml Sodium acetate 5g Acetic acid 30ml Potassium alum 15g Add water to make a total volume of 1000ml Bleach Fixer ferric sulfate 20g Ethylenediaminetetraacetic acid disodium dihydrate
36g Sodium carbonate monohydrate 17g Sodium sulfite 5g Ammonium thiosulfate (70%) 100ml Boric acid 5g Adjust the pH to 6.8 and add water to make a total volume of 1000ml Stable liquid boric acid 5g Sodium citrate 5g Sodium metaborate tetrahydrate 3g Potassium Alum ban 15g Add water to make a total volume of 1000ml The color prints obtained showed excellent color reproduction ability with vivid colors. This cyan dye image had an absorption maximum at 710 millimicrons.

Furthermore, this color print was printed under white fluorescent light at an illumination level of 3.
When irradiated for 20 days under 10,000 lux conditions, the cyan dye image had a density decrease of 0.02 in the area with an initial reflection density of 1.0. After being left for several days, the density drop at the initial reflection density of 1.0 was 0.08, showing good color image stability.

In addition, one side of the unexposed coated sample was placed at 40℃ and relative humidity.
One sample was left under 80% conditions for 3 days, and the other was stored at 25℃ and 60% relative humidity for the same period of time. After exposing the sample to stepwise exposure for sensitometry, the above treatments were applied at the same time. Despite being left under harsh conditions, there was no change in photographic properties such as maximum density, fog, or gamma, and it was found to be a stable photosensitive material.

Claims (1)

[Scope of Claims] 1. A colorless photographic cyan color-forming coupler having a group represented by the following general formula [] at the position coupling with the oxidized product of an aromatic primary amine developer General formula [] -O-R-COOH R represents a straight chain alkylene group having 2 to 4 carbon atoms.