JPH02232650A - Novel cyan coupler - Google Patents

Abstract

PURPOSE:To obtain a dyestuff image having superior fastness to heat, moisture and light by using a coupler for photography represented by a specified formula. CONSTITUTION:A coupler represented by formula I or II is used as a coupler for photography used as a material for color photography. In the formulae I, II, R is a substituent, m is 0 or an integer of 1-4, when m is an integer of 2-4, R's may be same or different from each other, Y is a substituent having 0.3-1.5 Hammett's substituent constant sigmap and X is H or a substituent which is released by a reaction with the oxidized product of a color developing agent. A dyestuff image formed from the coupler is fast to heat, moisture and light and the coupler has high relative sensitivity and high color developing property.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a novel photographic coupler used as a color photographic material, and more specifically, it forms a dye image with excellent fastness to heat, humidity, and light. Regarding photographic couplers.

[Background of the Invention] After a silver halide photographic light-sensitive material is exposed to light and then subjected to color development processing, the oxidized aromatic primary amine color developing agent and the dye-forming coupler react in the exposed area. Pigments are produced and a color image is formed.

Generally, this photographic method uses a subtractive color reproduction method to form yellow, magenta and cyan color images.

Examples of photographic couplers used to form the above-mentioned yellow image include acylacetanilide type couplers, and examples of couplers used to form magenta images include virazolone, virazolobenzimidazole, virazolotriazole, and Indazolone couplers are known, and phenol or naphthol couplers, for example, are generally used as couplers for forming cyan images.

It is desired that the dye image obtained in this way does not change color or fade even if it is exposed to light for a long time or stored under high temperature and high humidity.

However, phenolic couplers and naphthol couplers, which have been studied as couplers for forming cyan dyes, have poor spectral absorption characteristics, heat resistance, moisture resistance, light resistance, etc. of the formed cyan dye images. This is still unsatisfactory, and various proposals have been made to improve this, including devising substituents, but a compound that satisfies all of these has so far not been obtained.

As a result of further research into the above points, the present inventors discovered a photographic coupler that can form a cyan dye image that does not change in hue due to heat, humidity, or light.
The present invention has now been completed.

[Object of the Invention] The first object of the present invention is to provide a novel photographic coupler that can be used as a color photographic material.

A second object of the present invention is to provide a photographic coupler that forms a cyan dye image that does not change in hue due to heat, humidity, or light.

[Structure of the Invention] The above object of the present invention is the following general formula [2N] or the general formula [
r1].

The following is a blank space/General formula [General formula [I1] λ [In the formula, R represents a substituent, and m represents 0 or an integer from 1 to 4. When m is an integer of 2 to 4, multiple R's may be the same or different. Y is a substituent having a Hammett's substituent constant σp of 0.3 or more and 1.5 or less, and X represents a hydrogen atom or a substituent that is separated by reaction with an oxidized product of a color developing agent. ] Hereinafter, the present invention will be explained in more detail.

The substituent represented by R in general formulas [I] and [II] is not particularly limited, but typically includes alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl, etc. In addition to these groups, halogen atoms, cycloalkenyl, alkynyl, heterocycles, sulfonyl,
Sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, sulfonyloxy, aryloxy, heterocyclicoxy, cyano, acyloxy, carbamoyloxy, amino, alkylamino,
imide, ureido, sulfamoylamino, alkoxyluponylamino, aryloxyluponylamino,
Alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, thioureido, carboxyl, hydroxy,
Examples include groups such as merkabuto, nitro, and sulfonic acid, as well as spiro compound residues, Ukahashi hydrocarbon compound residues, and the like.

Among the substituents represented by R, the alkyl group preferably has 1 to 32 carbon atoms, and may be linear or branched.

As the aryl group, a phenyl group is preferred.

Examples of the acylamino group include an alkylcarbonylamino group and an arylcarbonylamino group.

Examples of the sulfonamide group include an alkylsulfonylamino group and a ryorylsulfonylamino group.

Examples of the alkyl component and aryl component in the alkylthio group and arylthio group include the above-mentioned alkyl groups and aryl groups.

The alkenyl group preferably has 2 to 32 carbon atoms, and the cycloalkyl group preferably has 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms, and the alkenyl group may be linear or branched.

The cycloalkenyl group has 3 to 12 carbon atoms, especially 5
-7 is preferred.

Sulfonyl groups include alkylsulfonyl groups, arylsulfonyl groups, etc.; sulfinyl groups include alkylsulfinyl groups, arylsulfinyl groups, etc.; phosphonyl groups include alkylphosphonyl groups, alkoxyphosphonyl groups, aryloxyphosphonyl groups, and arylphosphonyl groups. Acyl groups include alkylcarbonyl groups, arylcarbonyl groups, etc.; carbamoyl groups include alkylcarbamoyl groups, arylcarbamoyl groups, etc.; sulfamoyl groups include alkylsulfamoyl groups,
Arylsulfamoyl groups, etc.; Acyloxy groups include alkylcarbonyloxy groups, arylcarbonyloxy groups, etc.; carbamoyloxy groups include alkylcarbamoyloxy groups, arylcarbamoyloxy groups, etc.; ureido groups include alkylureido groups, arylureido groups, etc. ; As the sulfamoylamino group, an alkylsulfamoylamino group, an arylsulfamoylamino group, etc.; As the heterocyclic group, a 5- to 7-membered one is preferable, and specifically, a 2-furyl group, a 2- Chenyl group, 2-pyrimidinyl group, 2-penzothiazolyl group, 1-virolyl group, 1-tetrazolyl group, etc.; As the heterocyclic oxy group, those having a 5- to 7-membered heterocycle are preferable, such as 3-, 4-, 5-membered heterocycles, etc. 6-tetrahydrocyranyl-2-oxy group, 1-phenyltetrazole-5-
Oxy group, etc.; As the heterocyclic thio group, a 5- to 7-membered heterocyclic thio group is preferable, such as 2-biridylthio group, 2-penzothiazolylthio group, 2,4-diphenoxy-1,3.5-triazole- 6-thio group, etc.; Siloxy group includes trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc.; imide group includes succinimide group, 3-hebutadecylsuccinimide group, phthalimide group, glutarimide group, etc. ; As a spiro compound residue, SubiroC3.3]hebutane-
1-yl, etc.; as a bridged hydrocarbon compound residue, bicyclo[2,2.1
]hebutan-1-yl, tricyclo[3.3.1.1'
-']decane-1-yl, 7,7-dimethyl-bicyclo[2.2.1]hebutan-1-yl, and the like.

Among the above substituents, R is an alkyl group, an aryl group, a carboxyl group, an oxycarboxyl group, a cyano group, a hydroxy group, an alkoxy group, an aryloxy group, an amino group, an amide group, a sulfonamide group, etc. Each group and a halogen atom are preferred.

m represents 0 or an integer of 1 to 4; however, when m is 2 to 4, the plurality of R's may be the same or different.

Moreover, a plurality of R may be combined with each other to form a ring,
The ring is preferably a saturated or unsaturated 5-, 6-, 7-, or 8-membered ring, and specific examples thereof include a pyridine ring and a quinoline ring.

The above group may further have a substituent such as a long-chain hydrocarbon group or a diffusion-resistant group such as a polymer residue.

Examples of the group represented by X that separates upon reaction with the oxidized product of the color developing agent include halogen atoms (chlorine atom, bromine atom, fluorine atom, etc.), alkoxy, aryloxy,
Heterocyclicoxy, acyloxy, sulfonyloxy, alkoxylponyloxy, aryloxycarbonyl,
Alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, argyloxythiocarbonylthio, azilamino, sulfonamide, nitrogen-containing heterocycle bonded with N atom, alkyloxyluponylamino, aryloxyluponylamino,
Examples include various groups such as carboxyl.

In the general formulas [I] and [IN, the substituent represented by Y is a substituent having a Hammett's substituent constant σp of 0.3 or more and 1.5 or less, and typically includes a cyano group, a nitro group,
Sulfonyl groups (e.g. octylsulfonyl group, phenylsulfonyl group, trifluoromethylsulfonyl group, pentafluorophenylsulfonyl group, etc.), β-carboxyvinyl group, sulfinyl group (e.g. t-butylsulfinyl group, tolylsulfinyl group, trifluoro methylsulfinyl group, pentafluorophenylsulfinyl group, etc.), β,β-dicyanovinyl group, halogenated alkyl group (e.g. trifluoromethyl group, barfluorooctyl group, ω-hydroborfluorododecyl group, etc.), formyl group, carboxyl group, carbonyl group (e.g. acetyl group, bivaloyl group, benzoyl group, trifluoroacetyl group, etc.), alkyl and aryloxycarbonyl group (
For example, ethoxycarbonyl group, phenoxycarbonyl group, etc.), 1-tetrazolyl group, 5-chloro-1-tetrazolyl group, carbamoyl group (e.g. dodenylcarbonyl group, phenylcarbamoyl group, etc.), sulfamoyl group (
Examples include trifluoromethylsulfamoyl group, phenylsulfamoyl group, ethylsulfamoyl group, etc.).

Preferred among these substituents are a cyano group, a sulfonyl group, and a sulfamoyl group.

Typical specific examples of compounds used in the present invention are shown below.

The following margins These couplers of the present invention are based on organic synthesis.
Collective Volume 4 (Organ1c Synthese
sCollectlve Volume 4) 1 8
It can be synthesized by referring to the method described on pages 0 and 172.

The method for synthesizing the coupler of the present invention will be specifically shown below.

Synthesis method of compound ■-2 Synthesis of intermediate 2 1,5-diaminonaphthalene 47.5, water 300m
1, and then add 55 ml of 12N hydrochloric acid to dissolve it. In this solution ammonium thiocyanate 2
5. Add and heat and stir at 80-90°C for 1 hour.

After slowly concentrating the reaction solution, the obtained solid is finely ground with a mortar and heated at 150 to 200°C for 5 hours. Add 300 ml of water to the obtained solid,
The mixture was heated to 0°C, then cooled to room temperature, and the precipitated solid was filtered, dried, and further recrystallized with a mixed solvent of toluene and ethanol. 23.1 g of Intermediate 2 was obtained as white crystals.
I got it.

(Confirmed to be Intermediate 2 by 1HNMR, FD mass spectrum, and IR.) Synthesis of Intermediate 3 Intermediate 2 22.9. was suspended in 100 ml of boiling water, and then 49.9% of potassium hydroxide was added. ! Add a hot solution of B in 60 ml of water and immediately add lead diacetate trihydrate 37.7. After adding a hot saturated aqueous solution of and boiling for 10 minutes,
The black insoluble material was filtered while hot, and when the resulting filtrate was cooled to room temperature, white crystals were precipitated. Filter this crystal,
Furthermore, it was washed with water and dried to obtain 14.3 g of an intermediate product.

(It was confirmed to be intermediate 3 by IHNMR, FD mass spectrum, and IR.) Synthetic intermediate 314.0 of compound n-2 was suspended in 300 ml of ethyl acetate, and 7.5 g of sodium acetate was further added to 50 ml of water. Add the solution dissolved in and cool with water to form a suspension at 5°C.

Add to this mixture a solution of 21.9 g of pentadecanoyl chloride in ethyl acetate. was added dropwise over about 30 minutes, and then stirred at 5°C for 4 hours. The reaction solution was separated, washed three times with 200 ml of water, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. When the obtained solid was recrystallized from acetonitrile, white crystals of compound 1-2 were obtained, 22.1. I got it.

(It was confirmed to be compound I1-2 by IHNMR, FD mass spectrometry, and IR.) The coupler of the present invention usually contains I x 10-' mol to 1 mol per mol of silver halide.
moles, preferably I x 10-2 moles to 8 x tG
It can be used in the range of −' molar.

The coupler of the present invention can also be used in combination with other types of cyan couplers.

The methods and techniques used in conventional dye-forming couplers apply similarly to the couplers of the present invention.

The coupler of the present invention can be used as a material for forming color photographs by any coloring method, and specific examples include external coloring method and internal coloring method. When used as an external coloring method, the coupler of the present invention can be dissolved in an alkaline aqueous solution or an organic solvent (eg, alcohol) and added to a developing solution.

When the coupler of the present invention is used as a material for forming a color photograph by the internal coloring method, the coupler of the present invention is incorporated into the photographic light-sensitive material.

Typically, a method is preferably used in which the coupler of the present invention is blended into a silver halide emulsion and this emulsion is coated on a support to form a color light-sensitive material. The coupler of the present invention is used, for example, in color photographic materials such as color negative and positive films and color photographic paper.

This color photographic paper and other light-sensitive materials using the coupler of the present invention may be monochromatic or multicolor. In a multicolor light-sensitive material, the coupler of the present invention may be contained in any layer, but it is usually contained in a red-sensitive silver halide emulsion layer.

Multicolor light-sensitive materials have dye image-forming constituent units that are sensitive to each of the three primary color regions of the spectrum. Each building block can consist of a single or multiple emulsion layer sensitive to a certain region of the spectrum. The constituent layers of the light-sensitive material, including the layers of image-forming units, can be arranged in various orders as known in the art. a cyan dye image-forming unit consisting of at least one red-sensitive silver monohalide emulsion layer containing two cyan couplers (at least one of the cyan couplers being a cyan coupler of the invention); at least one magenta coupler; a magenta dye image-forming unit consisting of at least one green-sensitive silver halide emulsion layer containing at least one green-sensitive silver halide emulsion layer; a yellow dye image-forming unit consisting of at least one blue-sensitive silver halide emulsion layer containing at least one yellow coupler; is supported on a support.

The photosensitive material may contain additional layers such as filter layers, interlayers,
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 coupler of the present invention may be added to a high boiling point organic solvent having a boiling point of 175°C or higher such as tricresyl phosphate or dibutyl phthalate, or a low boiling point solvent such as butyl acetate or butyl brobionate, or a mixture thereof as necessary. alone or in combination, mixed with an aqueous gelatin solution containing a surfactant, then emulsified in a high-speed rotary mixer or colloid mill, and then added to silver halide to obtain the halogenated compound used in the present invention. Silver emulsions can be prepared.

Silver halide compositions preferably used in the photographic material using the coupler of the present invention include silver chloride, silver chlorobromide, and silver chloroiobromide. Furthermore, a combination mixture such as a mixture of silver chloride and silver bromide may be used. That is, when a silver halide emulsion is used for color photographic paper, particularly fast developability is required, so it is preferable that the halogen composition of the silver halide contains chlorine atoms, and at least 1%.
It is particularly preferable to use silver chloride, silver chlorobromide or silver chloroiodobromide containing silver chloride.

The silver halide emulsion is chemically sensitized by conventional methods. Furthermore, it can be optically sensitized to a desired wavelength range.

Silver halide emulsions are used during the manufacturing process of photosensitive materials, during storage,
Alternatively, compounds known as anti-fog agents or stabilizers in the photographic industry may be added for the purpose of preventing fog during photographic processing and/or keeping photographic performance stable.

Color photosensitive materials using the coupler of the present invention can contain color antifoggants, dye image stabilizers, ultraviolet inhibitors, antistatic agents, matting agents, surfactants, etc. that are commonly used in photosensitive materials. .

Regarding these, for example, Research Disclosure
The description in Vol. 178, pp. 22-31 (December 197!l) may be referred to.

An image can be formed on the color photographic material using the coupler of the present invention by subjecting it to a color development treatment known in the art.

The color photographic material using the coupler according to the present invention is
A color developing agent is contained in the hydrophilic colloid layer as the color developing agent itself or as a precursor thereof,
Treatment can also be carried out using an alkaline activation bath.

A color photographic material using the coupler of the present invention is subjected to a bleaching treatment and a fixing treatment after color development.

Bleaching treatment may be performed simultaneously with fixing treatment.

After the fixing process, a washing process is usually performed.

Furthermore, stabilization treatment may be performed as an alternative to pilot treatment, or both may be used in combination.

[Example] Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

Example 1 A red-sensitive color photosensitive material sample 1 was prepared by sequentially coating the following layers on a paper support laminated on both sides with polyethylene from the support side. Note that the amount of the compound added is per lrri” unless otherwise specified (silver halide is a silver equivalent value). 1st layer: Emulsion layer 1.2 g of gelatin, red-sensitive silver chlorobromide emulsion ( Contains 96 mol% silver chloride) 0.30g and dioctylbosphene
i. Comparative Cyan Cabler 39.1× dissolved in ASR
Red-sensitive emulsion layer consisting of 1Q-4 moles.

2nd layer: Security layer gelatin 0.50. A protective layer containing. In addition, as a hardening agent, 2
．． 4-dichloro-6-hydroxy-s-triazine sodium salt per gram of gelatin Q. (Added to 117 [.

Next, Samples 2 to 8 of the present invention were prepared in exactly the same manner except that Comparative Coupler a in Sample 1 was replaced with the coupler shown in Table 1 (the amount added was the same molar amount as Comparative Coupler a).

Samples 1 to 8 obtained above were each subjected to wedge exposure according to a conventional method, and then developed in the next step.

(Development processing process) Color development 38°C 3 minutes 30 seconds Bleach fixing 38°C 1 minute 30 seconds Stabilization processing 25°C to 30"C 3 minutes drying
Drying: 75°C to IIO''C for 2 minutes The composition of the processing liquid used in each processing step is as follows.

(Color developer) Benzyl alcohol 15m j) Ethylene glycol 15m! ) Potassium sulfite 2.0 g Potassium bromide
0.7g sodium chloride
0.2 g potassium carbonate
30. OK hydroxylamine sulfate
3.0g polyphosphoric acid (TPPS) 2.5
g3-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)aniline sulfate 5.5 g Optical brightener (4,4'-diaminostilbendisulfonic acid conductor) 1.0 g Potassium hydroxide・Add 2.01 water to bring the total amount to 1 g, and adjust the pH IQ. Adjust to 20.

(Bleach-fix solution) Ferric ammonium ethylenediaminetetraacetic acid dihydrate 60, ethylenediaminetetraacetic acid 3g ammonium thiosulfate (70% solution) 100ml2 ammonium sulfite (40% solution) 27.5mJ7 Adjust to pH 7.1 with potassium carbonate or glacial acetic acid Then, add water and bring the total volume to IN.
shall be.

(Stabilizing liquid) 5-chloro-2-methyl-4-isothiazolin-3-one L. O i ethylene glycol to g Add water and IM
shall be.

The concentrations of Samples 1 to 8 treated above were measured using a densitometer (Model KD-7 manufactured by Konica Corporation), and each of the above-treated samples was measured at high temperature and high humidity (60°C, 80% RH).
) The dye image was left in an atmosphere for 14 days, and the heat resistance and moisture resistance of the dye image were examined.

Further, each sample was irradiated with a xenon fade meter for 10 days, and then the density was measured to examine light resistance. The results are shown in Table-1. However, the heat resistance, moisture resistance, and light resistance of the dye image are expressed as percentages of dye remaining after heat, moisture resistance, and light resistance tests with respect to an initial density of 1.0.

Table 1 Comparative coupler a As is clear from the results in Margin Table 1 below, the samples using the coupler of the present invention had a higher dye residual rate than the samples using the comparative coupler, and were heat resistant and moisture resistant. It can be seen that it has excellent durability and light resistance, and is robust.

Example 2 A red-sensitive color photosensitive material (sample 9) was prepared by coating each of the following layers sequentially from the support side onto an undercoated triacetate film. Note that the amount of the compound added is per 1M unless otherwise specified (silver halide is 1i! in terms of silver).
).

1st layer: Emulsion layer gelatin L. Comparative cyan coupler b8.4f, red-sensitive silver iodobromide emulsion (containing 4 mol% silver iodide) dissolved in 1.5r and tricresyl phosphate 1.1g. O
Red-sensitive emulsion layer consisting of XIQ-' moles.

, 2nd layer: protective layer protective layer containing 1.5 g of gelatin. In addition, as a hardening agent, 2,
4-dichloro-6-hydroxy-S-triazine sodium salt was added in an amount of 0.017 g per 1 g of gelatin.

Next, for sample 9, the comparison cyan coupler b is shown in Table-2.
The coupler shown in (the amount added is the same molar amount as comparative coupler b)
The samples of the present invention were prepared in exactly the same manner except that
1B was produced.

The obtained film samples 9 to 16 were each subjected to wedge exposure according to a conventional method, and color development was performed according to the following color processing steps.

Comparative coupler b [Processing process] Processing time Color development/development 38°C 3 minutes 15 seconds Bleaching
Wash at 38℃ for 6 minutes and 30 seconds.
25-30℃ 3 minutes 15 seconds fixation 38℃ 6 minutes 30 seconds water
Washing 25-30℃ Stabilization 3 minutes 15 seconds Drying 25-30℃ 1 minute 30 seconds
75-80°C The composition of the treatment liquid used in each treatment step is as follows.

[Color developer]

4-Amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)aniline sulfate 4.75g Anhydrous sodium sulfite 4.25K? Doxamine 1/2 sulfate 2.0, anhydrous potassium carbonate
87.5 ■ Sodium bromide
1.3 g trisodium nitrilotriacetic acid (monohydrate) 2.5 g potassium hydroxide 1.0 g Add water to 1
g and adjust the pH to 10.6 using sodium hydroxide.

[Bleach solution] Ethylenediaminetetraacetic acid iron ammonium salt 100.0 [Ethylenediaminetetraacetic acid diammonium salt 10.0g Ammonium bromide 150.0g Glacial acetic acid
Add 10·Og water to make 1 g, and adjust the pH to 8.0 using ammonia water.

[Fixer] Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.8 g Sodium metasulfite 2 to 3 g Add water to make 1 g, and adjust to pH 6.0 using acetic acid.

[Stabilizer] Formalin (37% by weight) 1.5mft
Konidax (manufactured by Konica Corporation) Add 7.5 ml of water to make 11.

For the samples 9 to 16 treated above, the transmission density was measured using a densitometer (model KD-7 manufactured by Konica Corporation),
Furthermore, each of the above-mentioned treated samples was left in a high temperature and high humidity (60°C, 8% RH) atmosphere for 14 days to improve the heat resistance of the dye image.
We investigated moisture resistance.

In addition, each sample was irradiated with a xenon fade meter for 10 days to examine light resistance. The results are shown in Table-2. However, the heat resistance, moisture resistance, and light resistance of the dye image are at an initial density of 1. It is expressed as the percentage of dye remaining after heat resistance, humidity resistance and light resistance tests against O.

Margin Table 2 Below: As is clear from the results in Table 2, the samples using the coupler of the present invention had a higher dye residual rate than the samples using the comparative coupler, and had better heat resistance, moisture resistance, and light resistance. It can be seen that it has excellent properties and is robust.

Example 3 The following layers were sequentially coated on a triacetyl cellulose film support from the support side to prepare red-sensitive color reversal photographic materials 17 to 22 containing the couplers shown in Table 3.

1st layer: emulsion layer gelatin 1.4. , red-sensitive silver chlorobromide emulsion (silver chloride 9B
mol%) 0.5g and dibutyl phthalate 1
．． Coupler shown in Table 3 dissolved in 5g 9.1 x 10
- a red-sensitive emulsion layer consisting of 4 moles;

2nd layer: protective layer protective layer containing 0.5 g of gelatin. In addition, as a hardening agent, 2,
4-dichloro-6-hydroxy-S-triazine sodium salt was added in an amount of 0.017 g per 1 g of gelatin.

The samples obtained above were each subjected to wedge exposure according to a conventional method, and then developed in the next step.

[Reversal process] Process Time Temperature first development 6 minutes 38℃ water washing
2 minutes 38℃ inversion ・Inversion
2 minutes 38℃ color development 6 minutes 38℃ adjustment 2 minutes
38℃ bleaching 6
Minutes 38℃ fixation
Wash with water at 38℃ for 4 minutes
Stable at 38℃ for 4 minutes
Dry at 38℃ for 1 minute
The following composition is used for the room temperature treatment liquid.

[First developer] Sodium tetrabolyphosphate 2. Sodium sulfite 20. Hydroquinone・
Monosulfonate 90g Sodium carbonate (monohydrate)
30 g 1-phenyl-4-methyl-4-hydroxymethyl-3-virazolidone 2 g Potassium bromide 2.5K Potassium thiocyanate 1.2 g Potassium iodide (0.1% solution) 2 ml Add water
1000m fl [Reverse solution] Nitrilotrimethylenephosphonic acid hexasodium salt 3g Stannous chloride (dihydrate) Igp-aminophenol 0.1g Sodium hydroxide
5t glacial acetic acid 1
5mj! 1000m with water
1 [Color developer] Sodium tetrabolyphosphate 2f Sodium sulfite 7g Sodium tertiary phosphate (12 hydrate) 38g Potassium bromide
1g potassium iodide (0.1% solution)
90mN sodium hydroxide
3g Citrazic acid 1.5g N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 11. Add ethylenediamine 3g water
[OOromI [Adjustment solution] Sodium sulfite Sodium ethylenediaminetetraacetate (dihydrate) Add thioglycerin glacial acetic acid water [fX white liquor] Sodium ethylenediaminetetraacetate (dihydrate) Iron (III) ethylenediaminetetraacetate Ammonium ( dihydrate) Add potassium bromide water [Stabilizing solution] Add ammonium thiosulfate sodium sulfite and sodium bisulfite water [Stabilizing solution] g 0.4 l000 g rnl m1 m1 2.0 g 120.0 ioo. o g g 1000 m1 80.0 5.0 5.0 Formalin (37% by weight) 5.0 m
1 Konidax (manufactured by Konica Corporation) 1000 mg with addition of 5.0 mM water For each sample treated above, the heat resistance, moisture resistance, and light resistance of the dye image were examined in the same manner as in Example 2. Table 3 shows the results.
Shown below.

Table 3 As is clear from Table 3, the samples using the coupler of the present invention all had higher dye residual rates and superior heat resistance, moisture resistance, and light resistance compared to the samples using comparative coupler a. It can be seen that it is very sturdy.

Example-4 Multilayer color film trial 423 with the layer configuration shown below
was prepared by forming a layer on a support coated with an antihalation layer.

Layer configuration - Pro layer, BH layer, BL layer, YF layer, G
H layer, GL layer, IL layer, RH layer, RL layer, support, then RL layer, RH layer, GL layer, GH layer, BL layer, B H
The following describes the layers, IL layer, YF layer, and Pro layer.

RL layer (low-sensitivity red-sensitive silver halide emulsion layer) average diameter (r) 0.47 μm 1 coefficient of variation (s/r) 04
12, an emulsion consisting of AgBrl containing 8 mol% of average Agl (emulsion ■) was color sensitized to red sensitivity, 1.0 g, 1.0 g, uniform diameter 0.81 μm, coefficient of variation 0. 1.
Emulsion (emulsion ■) Og consisting of 8 gl) rl containing on average 8 g1 8 mol % and 0.07 g of 1-hydroxy-4-[4(1-hydroxy-8-acetamide 3
．． 6disulfo-2-naphthylazo)monophenoxy]N-
[δ-(2,4-di-t-amylphenoquine)butyl]
-2-nafamide disodium (referred to as CC-A) and 0.4 g of 1-hydroxy-2-[δ-(2,4-di-t-amylphenoxy)n-butyl]naphthamide (
C-A) and 0.08H of the DIR compound (exemplary compound D-1) were dissolved in 1.0 g of tricresyl phosphate (TCP) and emulsified in an aqueous solution containing 2.4 g of gelatin. A layer containing a dispersed dispersion.

RH layer (high sensitivity red-sensitive silver halide emulsion layer) average grain size 0.1 μm, coefficient of variation 0.12, average Ag 16 mol%
An emulsion (emulsion ■) consisting of AgBrl containing 2.0 g of red sensitization, 0.20 g of cyan coupler (C-A) and 0.03 g of a cyan coupler (C-A). colored cyan coupler (C
C-A) was dissolved in 0.23, TCP, and this was dissolved in 1.
A layer containing a dispersion of 2i emulsified and dispersed in an aqueous solution containing gelatin.

GL layer (low-sensitivity green-sensitive silver halide emulsion layer) Emulsion ■ is color-enhanced to green-sensitivity. 1.5 g of the abbreviated product, 1.5 g of the emulsion (1) omitted with a green-sensitive color increase, and 0.35 g of the 1-
(2,4.6-triclophuninyl)-3[3 - (
p-dodecyloxybenzenesulfonamide)penzamide]-5-vilazolone (referred to as M-8), O. L.O.
g of 1-(2,4.6-triclosophenyl)-4-
(1-naphthylazo)-3(2-chloro-5-octadecenylsuccinimidoanilino)-5-vilazolone (C
M-A) and 0.04. DIR compound (D-1
) dissolved in 0. A layer containing a dispersion of TCP of Hg emulsified in an aqueous solution containing 2.4 g of gelatin.

GH layer (high-sensitivity green-sensitive silver halide emulsion layer) 2.0 g of emulsion 2, which is color sensitized to greenishness, and 0.14. 0.27g of magenta coupler (M-A) and 0.045g of colored magenta coupler (CM-A) dissolved
A layer containing a dispersion obtained by emulsifying and dispersing TCP in an aqueous solution containing 2.4 g of gelatin.

BL layer (low sensitivity blue-sensitive silver halide emulsion layer) 0.5 g of Emulsion I color sensitized to blue sensitivity, 0.5 g of Emulsion II color sensitized to blue sensitivity, and 0.7 g. α-Vivaloyl α-(1-benzyl-2-phenyl-3,5-dioxyimidazolidin-4-yl)-2-chloro-5-[α
-dodecyloxycarbonyl)ethoxycarbonyl]acetanilide (referred to as Y-A) and 0.02 g of DIR
0.88 in which compound (D-1) was dissolved. TCP of 1
．． 8. A layer containing a dispersion emulsified and dispersed in an aqueous solution containing gelatin.

BH layer (high-sensitivity blue-sensitive silver halide emulsion layer) 0.9 g of an emulsion consisting of ^girl, which has an average grain size of 0.80 μm, a coefficient of variation of 0.14, and an average Agl content of 6 mol %, is sensitized to blue sensitivity. Emulsion and 0.25g of yellow cobbler (Y
-A) dissolved in 0.25. A layer containing a dispersion obtained by emulsifying and dispersing 2.0% TCP in an aqueous solution containing 2.0% gelatin.

IL layer (intermediate layer) 0.07% of 2.5-di-1t-octylhydroquinone (referred to as IQ-1) was dissolved. (Layer containing 17 g of dibutyl phthalate (referred to as DBP).

YF layer (yellow filter layer) 0.157 yellow colloidal silver and 0.2 g HQ-1
(Color stain prevention 181) dissolved in o. tig's DBP
and a layer containing 1.0 g of gelatin.

Pro layer (protective layer) A layer consisting of 2.3 g of gelatin.

Regarding Sample 23 prepared in this way, the C-A of the low-sensitivity and high-sensitivity red-sensitive silver halide emulsion layers is shown in Table 1.
Samples 24 to 33, which were exactly the same as sample 23, were prepared except that the coupler of the present invention shown in No. 4 was used in an equimolar amount.

Each of the wipes Nα23 to Nα38 produced in this manner was subjected to wedge exposure using white light, and then subjected to the same treatment as in Example 2 above. The color density of the sample after development was measured using a red filter to obtain photographic data.

Exemplary Compound D-1 OR Table 4 The dye image formed from the coupler of the present invention is robust to heat, humidity and light, and furthermore, the coupler of the present invention has a relative sensitivity compared to conventional cyan couplers. It is highly pigmented and has high color development.

Claims (1)

[Claims] A photographic coupler represented by general formula [I] or general formula [II]. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R represents a substituent, and m is 0 or an integer from 1 to 4 represents. When m is an integer of 2 to 4, the plurality of R's may be the same or different. Y is a substituent having a Hammett's substituent constant σp of 0.3 or more and 1.5 or less, and X represents a hydrogen atom or a substituent that is separated by reaction with an oxidized product of a color developing agent. ]