JP3208694B2 - New photographic coupler - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel photographic coupler used as a color photographic material, and more particularly to a color photographic coupler which provides a dye image having excellent fastness.

[0002]

2. Description of the Related Art After exposure of a silver halide photographic light-sensitive material, color development processing is carried out, whereby an oxidized aromatic primary amine color developing agent reacts with a dye-forming coupler to form a dye, and a color image is formed. It is formed.

In general, in this photographic method, a color reproduction method based on a subtractive color method is used to form yellow, magenta, and cyan color images.

As couplers used to form the above-mentioned yellow image, there are, for example, acylacetoanilide couplers. As magenta image forming couplers, for example, pyrazolone couplers are known, and furthermore, cyano couplers are known. As color image forming couplers, for example, phenol or naphthol couplers are generally known.

It is desired that the dye image thus obtained does not discolor even if it is exposed to light for a long period of time, or if it is stored under high temperature and high humidity.

The dyes formed from 5-pyrazolone couplers which have been widely put into practical use and studied as magenta dye image forming couplers have excellent fastness to heat and light, but have a yellow component. The presence of unnecessary absorption caused color turbidity. Pyrazolobenzimidazole, indazolone,
Couplers such as pyrazolotriazole, imidazopyrazole, pyrazolopyrazole and pyrazolotetrazole have been proposed, and in fact, dyes formed from these couplers are preferable in color reproduction. However, these couplers have the disadvantage that they are extremely low in light fastness and cause discoloration.

Further, phenolic couplers which have been studied as couplers for forming cyan dyes have been improved in spectral absorption characteristics, light resistance, heat resistance and moisture resistance, respectively, by devising substituents and the like. However, a compound satisfying all of them has not been obtained yet.

[0008]

SUMMARY OF THE INVENTION Regarding the color developing property of a coupler used as a material for color photography, and the improvement of spectral absorption characteristics,
Improvements in the robustness against heat and humidity have been made, but the level has not yet reached a sufficiently satisfactory level, and the present situation is that the search for couplers is being carried out earnestly.

In particular, as for couplers forming a magenta dye image, a number of novel compounds such as pyrazolobenzimidazole and pyrazolotriazole have been proposed. They form a dye image having a yellow component and having no unnecessary absorption and having a favorable color reproduction, but have a serious disadvantage that the light fastness of the coupler is remarkably low and discoloration of the dye image is caused.

On the other hand, the 3,5-pyrazolidinedione magenta coupler described in US Pat. No. 2,427,911 has a low color-forming property and cannot satisfy the high-density color-forming property required in recent years.

Accordingly, a first object of the present invention is to provide a novel photographic coupler used as a material for color photographic.

A second object of the present invention is to provide a photographic coupler which forms a magenta dye image which is excellent in color developability and does not change its hue to heat, humidity and light.

[0013]

The above object of the present invention has been attained by a photographic coupler represented by the following general formula [I].

[0014]

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In the formula, R ₁ and R ₂ represent a hydrogen atom or a substituent, and R ₁ and R ₂ may be fused to each other to form a ring;
X represents a group capable of reacting with the oxidized form of the color developing agent and leaving.

Hereinafter, the present invention will be described more specifically.

The substituents represented by R ₁ and R ₂ in the general formula [I] are not particularly limited, but typically include alkyl, aryl, alkenyl, cycloalkyl and the like. Other cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl,
Examples include acyl, carbamoyl, sulfamoyl, cyano, alkoxycarbonyl, aryloxycarbonyl, sulfonic acid, and other groups, as well as spiro compound residues and bridged hydrocarbon compound residues.

Among the substituents represented by R ₁ and R ₂ , the alkyl group preferably has 1 to 32 carbon atoms, and may be linear or branched.

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

The cycloalkenyl group may have 3 to 3 carbon atoms.
12, especially 5-7 are preferred. Examples of the sulfonyl group include an alkylsulfonyl group and an arylsulfonyl group; examples of the sulfinyl group include an alkylsulfinyl group and an arylsulfinyl group; and examples of the phosphonyl group include an alkylphosphonyl group, an alkoxyphosphonyl group, an aryloxyphosphonyl group, and an arylphosphonyl group. An acyl group such as an alkylcarbonyl group or an arylcarbonyl group;
As the carbamoyl group, an alkylcarbamoyl group, an arylcarbonyl group, or the like; as the sulfamoyl group, an alkylsulfamoyl group, an arylsulfamoyl group, or the like; As the heterocyclic group, a 5- to 7-membered group is preferable.
2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl, 1-pyrrolyl, 1-tetrazolyl and the like;
Spiro [3,3] heptan-1-yl and the like as spiro compound residues; bicyclo [2.2.
1] heptane-1-yl, tricyclo [3,3,1,1 ^37] decane -
1-yl, 7,7-dimethyl-bicyclo [2,2,1] heptane-1-
And the like.

The above-mentioned groups may further have a substituent such as a long-chain hydrocarbon group or a non-diffusible group such as a polymer residue.

Examples of the group capable of leaving by reaction with an oxidized form of the color developing agent represented by X include, for example, a halogen atom (a chlorine atom, a bromine atom, a fluorine atom, etc.) and alkoxy, aryloxy, heterocyclic oxy, acyloxy, sulfonyl. Oxy, alkoxycarbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocyclic ring bonded with an N atom,
Alkyloxycarbonylamino, aryloxycarbonylamino, carboxyl, and the groups shown below.

[0023]

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(R ₁ and R ₂ have the same meanings as R ₁ and R ₂ , and Ra and Rb each represent a hydrogen atom, an aryl group, an alkyl group, or a heterocyclic group).

Next, specific examples of the compound of the present invention represented by the general formula [I] are shown, but the present invention is not limited thereto.

[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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The coupler represented by the general formula [I] can be synthesized by various synthetic methods. For example, as shown in the following reaction formula, the coupler is synthesized by dehydration condensation of a malonic acid derivative and a 1,2-disubstituted hydrazine. can do.

[0037]

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Synthesis of Intermediate 1 70 ml of acetone, 9.1 g of paracresol, and 15.0 g of potassium carbonate were added to 18 g of diethyl bromomalonate, and the mixture was heated under reflux for 1 hour. The reaction solution was filtered to remove solids, the filtrate was concentrated under reduced pressure, and 50 ml of methanol was added to the resulting oil.While heating, an aqueous solution in which 9.6 g of potassium hydroxide was dissolved in 30 ml of water was slowly added. In addition, the mixture was heated at 50 ° C. for 15 minutes. Then, while the reaction mixture was cooled with ice, dilute hydrochloric acid was added to adjust the pH to about 1, and the mixture was extracted with ethyl acetate. The aqueous layer was further extracted three times with ethyl acetate. Ethyl acetate was distilled off, and the obtained solid was washed with chloroform to obtain 9.9 g of Intermediate 1 as a white solid. ^The structure was confirmed by ¹ H NMR, IR and mass spectrum.

Synthesis of Exemplified Compound No. 12 To 6.1 g of phenylhydrazine was added 10.7 g of 2-dodecanone, and the mixture was stirred at room temperature for 30 minutes. The reaction solution was extracted with ethyl acetate, and a palladium-carbon catalyst was added, followed by hydrogenation. The catalyst was removed by filtration, and the reaction solution was concentrated under reduced pressure. To an oily substance obtained, 300 ml of tetrahydrofuran and 23.5 g of dicyclohexylcarbodiimide were added, and 9.6 g of intermediate 1 was added little by little under ice cooling.

The reaction solution was further stirred for 1 hour under ice cooling.
The reaction solution was filtered to remove solids, and the filtrate was concentrated under reduced pressure.
Purification by silica gel column chromatography gave 14.5 g of Exemplified Compound 12. ^The structure was confirmed by ¹ H NMR, IR and mass spectrum.

The coupler of the present invention can be used in an amount of usually 1 × 10 ^-3 mol to 1 mol, preferably 1 × 10 ^-2 mol to 8 × 10 ^-1 mol, per mol of silver halide.

The coupler of the present invention can be used in combination with another type of magenta coupler.

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

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

When the coupler of the present invention is used as a material for forming a color photograph by an internal color developing method, the coupler of the present invention is contained in a photographic light-sensitive material.

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

The light-sensitive material using the coupler of the present invention such as the color photographic paper may be of a single color or a multicolor. In the multicolor light-sensitive material, the coupler of the present invention may be contained in any layer, but is usually contained in a green-sensitive silver halide emulsion layer. The multicolor light-sensitive material has dye image-forming constituent units each having photosensitivity in three primary color regions of the spectrum. Each structural unit can be composed of a single layer or multiple emulsion layers sensitive to certain regions of the spectrum. The constituent layers of the light-sensitive material, including the layers of the image forming constituent units, can be arranged in various orders as known in the art. A typical multicolor light-sensitive material is a cyan dye image-forming unit composed of at least one red-sensitive silver halide emulsion layer containing at least one cyan coupler, and at least one green color containing at least one magenta coupler. At least one blue-sensitive silver halide containing at least one magenta dye image-forming structural unit comprising a light-sensitive silver halide emulsion layer (at least one of the magenta couplers is the magenta coupler of the present invention) and at least one yellow coupler It comprises a yellow dye image forming structural unit composed of an emulsion layer supported on a support.

The light-sensitive material can have additional layers such as a filter layer, an intermediate layer, a protective layer, an undercoat layer and the like. The coupler of the present invention may be incorporated into an emulsion according to a conventionally known method. For example, tricresyl phosphate, dibutyl phthalate or the like, a high boiling point organic solvent having a boiling point of 175 ° C. or more or a low boiling point solvent such as butyl acetate or butyl propionate alone or, if necessary, a mixture thereof may be used as a coupler of the present invention. Is dissolved alone or in combination, and then mixed with a gelatin aqueous solution containing a surfactant,
Next, after emulsifying with a high-speed rotary mixer or a colloid mill, the emulsion can be added to silver halide to prepare a silver halide emulsion used in the present invention.

The silver halide composition preferably used in the light-sensitive material using the coupler of the present invention includes silver chloride, silver chlorobromide or silver chloroiodobromide. Further, 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. Therefore, the silver halide preferably contains a chlorine atom as a halogen composition and contains at least 1% of silver chloride. Particularly preferred is silver, silver chlorobromide or silver chloroiodobromide.

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

The silver halide emulsion contains an antifoggant or a stabilizer in the photographic industry for the purpose of preventing fog during the production process, storage, or photographic processing of a light-sensitive material and / or stably maintaining photographic performance. Compounds known as can be added.

The color light-sensitive material using the coupler of the present invention includes a color fogging inhibitor, a dye image stabilizer, an ultraviolet ray inhibitor, an antistatic agent, a matting agent, which are usually used in light-sensitive materials.
Surfactants and the like can be used.

These are described, for example, in Research Disclosure Vol. 176, 22-31.
Page (December 1978) can be referred to.

The color photographic light-sensitive material using the coupler of the present invention can form an image by performing a color development process known in the art.

The color photographic light-sensitive material using the coupler according to the present invention contains a color developing agent in the hydrophilic colloid layer as the color developing agent itself or as a precursor thereof, and can be processed by an alkaline activation bath. it can.

The color photographic light-sensitive material using the coupler of the present invention is subjected to bleaching and fixing after color development.
The bleaching process may be performed simultaneously with the fixing process.

After the fixing process, a washing process is usually performed. Further, a stabilization treatment may be performed as an alternative to the water washing treatment, or both may be used in combination.

[0058]

EXAMPLES Next, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.

Example 1 The following layers were sequentially coated on a paper support laminated on both sides with polyethylene from the support side, to prepare a green photosensitive color photosensitive material sample 1. In the following examples, the amount of the compound added is represented per 1 m ² unless otherwise specified (silver halide is a silver equivalent value).

First layer: emulsion layer 1.4 g of gelatin, green-sensitive silver chlorobromide emulsion (85 mol% of silver bromide)
A green light-sensitive emulsion layer comprising 5.4 × 10 ^-4 mol of the following comparative coupler dissolved in 0.35 g of dioctyl phthalate and 1.35 g of dioctyl phthalate.

[0061]

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Second layer: protective layer A protective layer containing 0.50 g of gelatin. In addition, 2,4-dichloro-6-hydroxy-s-triazine sodium salt was added as a hardening agent in an amount of 0.017 g per 1 g of gelatin.

Next, a sample of the present invention was prepared in exactly the same manner except that the comparative coupler a used in Sample 1 was replaced with the coupler according to the present invention shown in Table 1 (the amount of addition was the same as that of the comparative coupler a). 2-13 were created.

[0064]

[Table 1]

To each sample, a hardener, an activator, and a fungicide (a mixture of 2-methylisothiazol-3-one and 5-chloro-2-methylisothiazol-3-one) were added.

Each of the samples 1 to 13 obtained above was subjected to wedge exposure according to a conventional method, and then subjected to development processing in the following step.

(Development processing step) Color development 38 ° C. 3 minutes 30 seconds Bleaching and fixing 38 ° C. 1 minute 30 seconds Stabilization processing / or water washing processing 25 ° C. to 30 ° C. 3 minutes Drying 75 ° C. to 80 ° C. 2 minutes Each processing step The composition of the processing solution used in the above is as follows.

(Color developing solution) Benzyl alcohol 15 ml Ethylene glycol 15 ml Potassium sulfite 2.0 g Potassium bromide 0.7 g Sodium chloride 0.2 g Potassium carbonate 30.0 g Hydroxylamine sulfate 3.0 g Polyphosphoric acid (TPPS) 2.5 g 3-Methyl-4- Amino-N-ethyl-N-β-methanesulfonamidoethyl aniline sulfate 5.5 g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 1.0 g Potassium hydroxide 2.0 g Add water to make 1 liter. , PH adjusted to 10.20.

(Bleaching-fixing solution) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% solution) 100 ml Ammonium sulfite (40% solution) 27.5 ml Water was added to make a total volume of 1 l. With potassium or glacial acetic acid
Adjust to pH 7.1.

(Stabilizing solution) 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g ethylene glycol 10 g Water was added to make 1 liter.

The concentrations of the samples 1 to 13 thus treated were measured using a densitometer (model KD-7R manufactured by Konica Corporation). In addition, heat and treat each of the above treated samples at
RH) The sample was allowed to stand for 14 days in an atmosphere, and the heat resistance and humidity resistance of the dye image were examined. Table 1 shows the obtained results. However, the heat and humidity resistance of the dye image is represented by the percentage of the dye remaining after the heat and humidity test with respect to the initial density of 1.0.

Each sample was measured with a xenon fade meter for 10 minutes.
After irradiation for 0 hours, the density was measured, and the light resistance of the dye image was examined from the dye remaining rate after the light resistance test with respect to the initial density of 1.0. The results are also shown in Table 1.

As is clear from the results shown in Table 1, the sample N using the coupler represented by the general formula [I] according to the present invention was used.
In o.2 to 13, the light resistance was greatly improved and the heat and humidity resistance was excellent compared to Sample No. 1 using Comparative Coupler a, so that a robust dye image was formed. I understand.

Example 2 On a transparent polyethylene terephthalate film support,
The photothermographic layer comprising the following components support 1 m ² per was prepared photothermographic material by coating.

Silver benztriazole 0.6 g gelatin 3.0 g reducing agent * 1 0.97 g coupler (29) 1.0 g silver iodobromide (in terms of silver) 0.45 g polyvinylpyrrolidone 1.0 g benztriazole 0.02 g inhibitor * 2 0.05 g hot solvent * 3 4.5g

[0076]

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After imagewise exposure of the above photosensitive material, the photosensitive material was overlaid with an image receiving material obtained by coating polyvinyl chloride on photographic baryta paper and thermally developed at 150 ° C. for 1 minute. A magenta transfer image was obtained.

Example 3 One Side (Surface) of Triacetyl Cellulose Film Support
Was subjected to an undercoating process, and then each layer having the following composition was sequentially formed on the surface (back surface) opposite to the surface on which the undercoating process was performed with the support interposed therebetween.

Back surface first layer Alumina sol AS-100 (aluminum oxide) (manufactured by Nissan Chemical Industries, Ltd.) 0.8 g Back surface second layer Diacetyl cellulose 100 mg Stearic acid 10 mg Silica fine particles (average particle size 0.2 μm) 50 mg On the surface of the acetylcellulose film support, each layer having the composition shown below was formed sequentially from the support side to prepare a multilayer color photographic light-sensitive material 14.

First layer: Anti-halation layer (HC) Black colloidal silver 0.15 g UV absorber (UV-1) 0.20 g Colored cyan coupler (CC-1) 0.02 g High boiling solvent (Oil-1) 0.20 g High boiling point Solvent (Oil-2) 0.20 g Gelatin 1.6 g Second layer; Intermediate layer (IL-1) Gelatin 1.3 g Third layer; Low-sensitivity red-sensitive emulsion layer (RL) Silver iodobromide emulsion (average grain size 0.3 μm) (average iodine content 2.0 mol%) 0.4 g silver iodobromide emulsion (average particle size 0.4 μm) (average iodine content 8.0 mol%) 0.3 g sensitizing dye (S-1) 3.2 × 10 ^-4 ( Mol / silver 1 mol) Sensitizing dye (S-2) 3.2 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-3) 0.2 × 10 ^-4 (mol / silver 1 mol) Cyan coupler (C -1) 0.50 g Cyan coupler (C-2) 290.13 g Colored cyan coupler (CC-1) 0.07 g DIR compound (D-1) 0.006 g DIR compound (D-2) 0.01 g High boiling point solvent (Oil-1) 0.55 g Gelatin 1.0 g Fourth layer; high-sensitivity red-sensitive emulsion layer (R-H) Silver iodobromide emulsion (average particle size 0.7 μm ) (Average iodine content 7.5 mol%) 0.9 g Sensitizing dye (S-1) 1.7 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-2) 1.6 × 10 ^-4 (mol / silver 1 mol) Mol) Sensitizing dye (S-3) 0.1 × 10 ^-4 (mol / silver 1 mol) Cyan coupler (C-2) 0.23 g Colored cyan coupler (CC-1) 0.03 g DIR compound (D-2) 0.02 g High boiling solvent (Oil-1) 0.25 g Gelatin 1.0 g Fifth layer; Intermediate layer (IL-2) Gelatin 0.8 g Sixth layer; Low sensitivity green-sensitive emulsion layer (GL) Silver iodobromide emulsion (average grain Diameter 0.4 μm) (Average iodine content 8.0 mol%) 0.6 g Silver iodobromide emulsion (average particle size 0.3 μm) (Average iodine content 2.0 mol%) 0.2 g Sensitizing dye (S- ) 6.7 × 10 ^-4 (mol / mole of silver) Sensitizing dye (S-5) 0.8 × 10 -4 ( mol / mole of silver) Magenta coupler (M-1) 0.45 g Colored magenta coupler (CM-1) 0.10 g DIR compound (D-3) 0.02 g High boiling solvent (Oil-2) 0.7 g Gelatin 1.0 g Seventh layer; high-sensitivity green-sensitive emulsion layer (GH) Silver iodobromide emulsion (average particle size 0.7 μm ) (Average iodine content 7.5 mol%) 0.9 g Sensitizing dye (S-6) 1.1 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-7) 2.0 × 10 ^-4 (mol / silver 1 mol) Mol) Sensitizing dye (S-8) 0.3 × 10 ^-4 (mol / silver 1 mol) Magenta coupler (M-1) 0.35 g Colored magenta coupler (CM-1) 0.04 g DIR compound (D-3) 0.004 g High boiling solvent (Oil-2) 0.35 g Gelatin 1.0 g Eighth layer; Yellow filter layer (YC) Yellow colloidal silver 0.1 g Additive (HS- 1) 0.07 g Additive (HS-2) 0.07 g Additive (SC-1) 0.12 g High boiling solvent (Oil-2) 0.15 g Gelatin 1.0 g Ninth layer; low-sensitivity blue-sensitive emulsion layer (BL) Silver iodobromide emulsion (average particle size 0.3 μm) (average iodine content 2.0 mol%) 0.25 g Silver iodobromide emulsion (average particle size 0.4 μm) (average iodine content 8.0 mol%) 0.25 g sensitizing dye ( S-9) 5.8 × 10 ^-4 (mol / silver 1 mol) Yellow coupler (Y-1) 0.6 g Yellow coupler (Y-2) 0.32 g DIR compound (D-1) 0.003 g DIR compound (D-2) 0.006 g High boiling point solvent (Oil-2) 0.18 g Gelatin 1.3 g 10th layer; high-sensitivity blue-sensitive emulsion layer (B-H) Silver iodobromide emulsion (average particle size 0.8 μm) (average iodine content 8.5 mol% ) 0.5 g sensitizing dye (S-10) 3 × 10 -4 ( mol / mole of silver) sensitizing dye (S-11) 1.2 × 10 -4 ( mol / mole of silver) yellow Coupler (Y-1) 0.18 g Yellow coupler (Y-2) 0.10 g High boiling solvent (Oil-2) 0.05 g Gelatin 1.0 g 11th layer; 1st protective layer (PRO-1) Silver iodobromide (average grain Diameter 0.08μm) 0.3g UV absorber (UV-1) 0.07g UV absorber (UV-2) 0.10g Additive (HS-1) 0.2g Additive (HS-2) 0.1g High boiling solvent (Oil- 1) 0.07 g High boiling solvent (Oil-3) 0.07 g Gelatin 0.8 g 12th layer; 2nd protective layer (PRO-2) Compound A 0.04 g Compound B 0.004 g Polymethyl methacrylate (average particle size 3 μm) 0.02 g Methyl Methacrylate: ethyl methacrylate: methacrylic acid = 3: 3: 4 (weight ratio) copolymer (average particle size: 3 μm) 0.13 g The above-mentioned photosensitive material 14 further includes compounds SU-1 and SU
-2, viscosity modifier, hardener H-1, H-2, stabilizer ST
-1, antifoggants AF-1, AF-2 (weight average molecular weight of 10,000 and 1,100,000), dye AI-
1, AI-2 and DI-1 (9.4 g / m ² ).

The silver iodobromide emulsion of the tenth layer was prepared by the following method.

A silver iodobromide emulsion was prepared by a double jet method using monodispersed silver iodobromide grains having an average grain size of 0.33 μm (silver iodide content: 2 mol%) as seed crystals.

Solution <G-1> was heated at a temperature of 70 ° C., pAg 7.8, p
The seed emulsion equivalent to 0.34 mol was added while maintaining the pH at 7.0 and stirring well.

(Formation of Internal High Iodine Phase-Core Phase-) Thereafter, the flow rate was gradually increased while maintaining the flow ratio of <H-1> and <S-1> at 1: 1 (at the end of the process). (A flow rate of 3.6 times the initial flow rate) was added in 86 minutes.

(Formation of External Low Iodine Phase-Shell Phase-) Subsequently, while maintaining pAg 10.1 and pH 6.0, <H-2> and <S
-2> was added at a flow ratio of 1: 1 while gradually increasing the flow rate (the flow rate at the end was 5.2 times the initial flow rate) and required 65 minutes.

The pAg and pH during particle formation were controlled using an aqueous potassium bromide solution and a 56% acetic acid aqueous solution. After the particles were formed, the particles were subjected to a water washing treatment by a conventional flocculation method, and then gelatin was added for redispersion, and the pH and pAg were adjusted to 5.8 and 8.06 at 40 ° C., respectively.

The resulting emulsion was a monodisperse emulsion containing octahedral silver iodobromide grains having an average grain size of 0.80 μm, a grain size distribution of 12.4% and a silver iodide content of 8.5 mol%.

<G-1> Ossein gelatin 100.0 g 10% by weight methanol solution of compound-I 25.0 ml 28% ammonia aqueous solution 440.0 ml 56% acetic acid aqueous solution 660.0 ml Finish with water 5000.0 ml <H-1> ossein gelatin 82.4 g Potassium bromide 151.6 g Potassium iodide 90.6 g Finished with water 1030.5 ml <S-1> Silver nitrate 309.2 g 28% ammonia aqueous solution Equivalent finished with water 1030.5 ml <H-2> Ossein gelatin 302.1 g Potassium bromide 770.0 g Iodine Potassium iodide 33.2g Finished with water 3776.8ml <S-2> Silver nitrate 1133.0g 28% ammonia aqueous solution equivalent Finished with water 3776.8ml In the same way, average particle size of seed crystal, temperature, pAg, pH,
The above emulsions having different average grain sizes and silver iodide contents were prepared by changing the flow rate, addition time and halide composition. All were core / shell monodisperse emulsions having a variation coefficient of particle size distribution of 20% or less.

Each emulsion was subjected to optimal chemical ripening in the presence of sodium thiosulfate, chloroauric acid and ammonium thiocyanate to give a sensitizing dye, 4-hydroxy-6-methyl-1,3,3
a, 7-Tetrazaindene, 1-phenyl-5-mercaptotetrazole were added.

[0090]

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[0091]

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[0092]

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[0093]

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[0094]

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[0095]

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[0096]

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[0097]

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Samples 15 to 28 were prepared in the same manner as in Sample 14, except that the magenta couplers in the sixth and seventh layers of Sample 14 were changed to equimolar magenta couplers as shown in Table 3. The light-sensitive materials 14 to 28 produced as described above were exposed to white light through a sensitometric step wedge, and processed according to the following development processing [I].

Development [I]

[0100]

[Table 2]

The following color developing solutions, bleaching solutions, fixing solutions, stabilizing solutions and replenishers were used.

Color developer water 800 ml Potassium carbonate 30 g Sodium hydrogen carbonate 2.5 g Potassium sulfite 3.0 g Sodium bromide 1.3 g Potassium iodide 1.2 g Hydroxylamine sulfate 2.5 g Sodium chloride 0.6 g 4-Amino-3-methyl-N- Ethyl-N- (β-hydroxyethyl) aniline sulfate 4.5 g Diethylenetriaminepentaacetic acid 3.0 g Potassium hydroxide 1.2 g Add water to make up to 1 liter, add potassium hydroxide or 20
The pH is adjusted to 10.06 with% sulfuric acid.

Color developing replenisher 800 ml Potassium carbonate 35 g Sodium hydrogen carbonate 3 g Potassium sulfite 5 g Sodium bromide 0.4 g Hydroxylamine sulfate 3.1 g 4-Amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) Aniline sulfate 6.3 g Potassium hydroxide 2 g Diethylenetriaminepentaacetic acid 3.0 g Add water to make 1 liter, and add potassium hydroxide or 20
The pH is adjusted to 10.18 with% sulfuric acid.

Bleaching solution water 700 ml 1,3-dianopropanetetraacetic acid iron (III) ammonium 125 g ethylenediaminetetraacetic acid 2 g sodium nitrate 40 g ammonium bromide 150 g glacial acetic acid 40 g Add water to make 1 liter, and use ammonia water or glacial acetic acid. Adjust to pH 4.4.

Bleach replenisher water 700 ml 1,3-dianopropanetetraammonium iron (III) ammonium 175 g ethylenediaminetetraacetic acid 2 g sodium nitrate 50 g ammonium bromide 200 g glacial acetic acid 56 g After adjusting the pH to 4.0 using ammonia water or glacial acetic acid.
Add water to make 1 liter.

Fixer solution water 800 ml Ammonium thiocyanate 120 g Ammonium thiosulfate 150 g Sodium sulfite 15 g Ethylenediaminetetraacetic acid 2 g After adjusting the pH to 6.2 using aqueous ammonia or glacial acetic acid,
Add water to make 1 liter.

Fixing replenisher water 800 ml Ammonium thiocyanate 150 g Ammonium thiosulfate 180 g Sodium sulfite 20 g Ethylenediaminetetraacetic acid 2 g After adjusting the pH to 6.5 using ammonia water or glacial acetic acid,
Add water to make 1 liter.

Stabilizing solution and stabilizing replenishing solution Water 900 ml 25 25 g

[0109]

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Dimethylolurea 0.5 g Hexamethylenetetramine 0.2 g 1,2-benzisothiazolin-3-one 0.1 g Siloxane (L-77 manufactured by UCC) 0.1 g Aqueous ammonia 0.5 ml Add water to make 1 liter, and add ammonia water or 50 %
Adjust to pH 8.5 with sulfuric acid.

Samples 14 to 28 were subjected to a development process (development process [II]) in the same manner as the development process [I] except that the pH of the color developing solution in the development process [I] was 9.90.

For each of the developed samples, the maximum density of the magenta color development was measured with green light using an optical densitometer PDA-65 (manufactured by Konica Corporation).

Table 3 shows specific sensitivity and pH variability.

[0114]

[Table 3]

The specific sensitivities in Table 3 are relative values of the reciprocal of the exposure amount that gives fog density + 0.10 density. The specific sensitivity and the maximum density are measured values in the development process [I].

The pH variability was determined by the following equation.

[0117]

(Equation 1)

As is clear from Table 3, Samples 16 to 28 using the magenta coupler of the present invention are remarkably superior in the maximum density, sensitivity and pH variability as compared with Comparative Sample 14 using the known coupler. I understand.

[0119]

Embedded image

[0120]

According to the present invention, firstly, a novel photographic coupler used as a material for color photographic can be provided.

Secondly, the color developing property is excellent, the fluctuation of the color developing property is small with respect to the change in the conditions of the color developing solution, especially the fluctuation of the pH, the color developing property is excellent, and the hue is not affected by heat, humidity and light. A photographic coupler that forms a magenta dye image that does not change can be provided. This coupler is also effective as a dye-providing substance for a photothermographic material.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-4-204732 (JP, A) JP-A-51-147320 (JP, A) JP-A-4-188136 (JP, A) JP-A-58-58 125038 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) G03C 7/38

Claims (1)

(57) [Claims] 1. A photographic coupler represented by the general formula [I]. Embedded image Wherein, R ₁ and R ₂ represents a hydrogen atom or a substituent, R ₁
And R ₂ may be condensed with each other to form a ring, and X represents a group capable of reacting with an oxidized form of a color developing agent and leaving. ]