JP2003084403A - 2-amidonaphthol coupler, silver halide color photographic sensitive material using the same and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a 2-amidonaphthol coupler which achieves satisfactory coloring by an oxidative coupling reaction and is excellent in storage stability, to provide a silver halide photographic sensitive material which forms an image of high coloring density using the coupler and a color developing agent and to provide an image forming method (particularly a diffusion transfer color image forming method). SOLUTION: A specified 2-amidonaphthol coupler, a silver halide color photographic sensitive material using the coupler and an image forming method using the sensitive material are provided.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel 2-amidonaphthol coupler, a novel silver halide color photographic light-sensitive material containing the coupler, and a novel image forming method using the same. The present invention relates to a silver halide color photographic light-sensitive material excellent in color developability and having good image sharpness and storability, and an image forming method.

[0002]

2. Description of the Related Art A 2-acylaminonaphthol coupler is a dye having a long wavelength and a high image sharpness due to a reaction with a color developing agent described in JP-A Nos. 9-152694 and 9-152704. Known to form. However, it is known that the coupler has low oxidation stability and it is difficult to achieve both storage stability and coupling reaction. JP-A-8-292529 and 10-550.
The naphthol couplers described in No. 47 and No. 10-55055 are excellent in storage stability, but a coupler satisfying both storage stability and coupling reaction, such as low reactivity of coupling reaction, has been found. Not not.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a 2-amidonaphthol coupler capable of obtaining sufficient color development by an oxidative coupling reaction and having excellent storage stability. Another object of the present invention is to provide a silver halide photographic light-sensitive material and an image forming method (particularly a diffusion transfer color image forming method) for forming an image having a high color developing density by the coupler and a color developing agent.

[0004]

The objects of the present invention have been found to be achieved by the following means. That is, the present invention provides the following (1) to (7). (1) 2-amide naphthol coupler represented by the following general formula (1) general formula (1)

[0005]

[Chemical 2]

In the general formula (1), R ¹ is a hydrogen atom,
It represents an aminocarbonylamino group, an acylamino group, a benzoylamino group, a sulfonylamino group, an alkoxycarbonylamino group, or an aryloxycarbonylamino group. R ² represents a substituent having a Hammett σp value of 0.1 or more. L represents a coupling-off group having a formula weight of 250 or more. R ³ represents a substituent, and m represents an integer of 0 to 4. (2) In the general formula (1), R ² is an aryl group or a heteroaryl group (more preferably a heteroaryl group) having a Hammett's σp value of 0.2 or more. 2-amido naphthol coupler. (3) The 2-amidonaphthol coupler according to item (1) or (2), wherein L in the general formula (1) is an aryloxy group. (4) A silver halide color photographic light-sensitive material containing the 2-amidonaphthol coupler according to item (1), (2) or (3). (5) An image forming method, which comprises developing the silver halide color photographic light-sensitive material according to the item (4) with an alkali processing liquid. (6) An image forming method, which comprises thermally developing the silver halide color photographic light-sensitive material according to the item (4). (7) An image forming method, wherein the silver halide color photographic light-sensitive material according to the item (6) is subjected to heat development under the generation of an alkali by a sparingly soluble metal salt and a complexing agent of the metal salt.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the compound represented by the general formula (1) used in the present invention will be described in detail. In the general formula (1), R ¹ is a hydrogen atom, an aminocarbonylamino group (an optionally substituted aminocarbonylamino group having 12 or less carbon atoms, preferably 8 or less carbon atoms. For example, a monomethylaminocarbonylamino group or a dimethylamino group. Carbonylamino group, bis- (2-methoxyethyl) aminocarbonylamino group, monoethylaminocarbonylamino group, diethylaminocarbonylamino group, N-phenyl-N-methylaminocarbonylamino group, etc., acylamino group (C12 or less) And preferably an optionally substituted acylamido group having 8 or less carbon atoms, such as an acetylamino group, a propionylamino group, a chloroacetylamino group, or a benzoylamino group (having 12 or less carbon atoms, preferably 8 or less carbon atoms) A benzoylamino group which may be substituted. For example, a benzoylamino group, a 3-mesylaminobenzoylamino group, a 2-mesylaminobenzoylamino group, and the like, a sulfonylamino group (having 12 or less carbon atoms, preferably 8 or less carbon atoms, which may be substituted). Methanesulfonylamino group, ethanesulfonyl V group, chloromethanesulfonylamino group, propanesulfonylamino group, butanesulfonylamino group,
n-octanesulfonylamino group, n-dodecanesulfonylamino group, benzenesulfonylamino group, 3-mesylaminobenzenesulfonylamino group, 4-methylbenzenesulfonylamino group, etc., alkoxycarbonylamino group (C10 or less, preferably An optionally substituted alkoxycarbonylaminocarbonylamino group having 6 or less carbon atoms, for example, a methoxycarbonylaminocarbonylamino group, an ethoxycarbonylaminocarbonylamino group, a methoxyethoxycarbonylaminocarbonylamino group, etc., an aryloxycarbonylamino group (carbon An optionally substituted aryloxycarbonylamino group having 15 or less, preferably 10 or less carbon atoms, such as a phenoxycarbonylaminocarbonylamino group,
p-chlorophenoxycarbonylaminocarbonylamino group, etc.).

Preferably, a hydrogen atom, an acylamino group,
It is a sulfonylamino group. More preferably, it is a sulfonylamino group.

R ² represents a substituent having a Hammett σp value of 0.1 or more. Examples of this include a chloromethyl group (σp value 0.12), a fluoromethyl group (same 0.11), a bromomethyl group (same 0.14), a 4-chlorophenyl group (same 0.12), a phenylsulfonylmethyl group. (Same as 0.1
6), cyanomethyl group (same as 0.18), 1-phenyl-
2-Benzimidazolyl group (same as 0.21), 2- (5-
Cyanofuryl) group (same as 0.1), 3-nitrophenyl group (same as 0.20), 4-nitrophenyl group (same as 0.2)
6), pentachlorophenyl group (0.24), pentafluorophenyl group (0.27), 2-pyrimidyl group (0.53), 2-benzothiazolyl group (0.2)
9), 3-pyridyl group (0.25), 4-pyridyl group (0.44), 3-pyridazyl group (0.48), 5
-Pyrimidyl group (same 0.39), 2-pyridyl group (same 0.17), trifluoromethyl group (same 0.32), 2
-Benzo-thiopyrronyl group (the same as 0.35), 2-benzoxazole group (the same as 0.33), 4-pyrimidyl group (the same as 0.63) and the like.

Among these, a preferable example is a substituent having a Hammett's σ _p value of 0.2 or more, more preferably 0.3 or more. This σ _p value is preferably 0.75 or less.

R ³ represents a substituent. An example of this is R ¹
And a halogen atom, a sulfamoyl group (sulfamoyl group having 12 or less carbon atoms, preferably 8 or less carbon atoms, which may be substituted. For example, N-methylsulfamoyl group, N, N-dimethylsulfamoyl group Moyl group, N,
N-bis- (2-methoxyethyl) sulfamoyl group,
N-ethylsulfamoyl group, N, N-diethylsulfamoyl group, N-phenyl-N-methylsulfamoyl group, N, N-di-n-butylsulfamoyl group, etc.), and preferably Examples thereof include an acylamino group, a benzoylamino group, and a sulfamoyl group, more preferably an acylamino group and a sulfamoyl group.

M represents an integer of 0 to 4, preferably 2
Below, 0 is more preferable. Group represented by L (group capable of splitting off upon reaction with an oxidation product of a color developing agent)
Represents a organic group having a formula weight of 250 or more and preferably bonded to a naphthol ring by a nitrogen atom, an oxygen atom or a sulfur atom, and examples thereof include an aryloxy group, a heterocyclic oxy group, an acyloxy group, an alkoxy group and a carbamoyloxy group. Aryloxycarbonyloxy group, alkoxycarbonyloxy group, arylthio group, heterocyclic thio group,
Alkylthio group, alkylsulfonyloxy group, arylsulfonyloxy group, carbonamido group, sulfonamide group, alkylsulfonyl group, arylsulfonyl group, alkylsulfinyl group, arylsulfinyl group, nitrogen-containing heterocyclic group bonded by nitrogen atom, arylazo group , A carbamoylamino group and the like. Formula weight 250
If it is less than 1, the coupler itself becomes diffusive, resulting in low color density and poor color balance.

Preferred specific examples thereof include aryloxy groups (eg, phenoxy, 1-naphthoxy, etc.), heterocyclic oxy groups (eg, pyridyloxy, pyrazolyloxy, etc.), acyloxy groups (eg, acetoxy, benzoyloxy, etc.), Alkoxy group (eg, dodecyloxy), carbamoyloxy group (eg, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, etc.), aryloxycarbonyloxy group (eg,
Phenoxycarbonyloxy etc.), alkoxycarbonyloxy group (eg dodecyloxycarbonyloxy, ethoxycarbonyloxy etc.), arylthio group (eg phenylthio, naphthylthio etc.), heterocyclic thio group (eg tetrazolylthio, 1,3,4-) Thiadiazolylthio, 1,3,4-oxadiazolylthio, benzimidazolylthio, etc.), alkylthio group (for example,
Hexadecylthio, etc.), alkylsulfonyloxy groups (eg, hexadecanesulfonyloxy, etc.), arylsulfonyloxy groups (eg, benzenesulfonyloxy, toluenesulfonyloxy, etc.), carbonamide groups (eg, acetamide, etc.), sulfonamide groups (eg, , Hexadecansulfonamide, benzenesulfonamide, etc.) alkylsulfonyl group (eg, hexadecanesulfonyl, etc.), arylsulfonyl group (eg, benzenesulfonyl, etc.), alkylsulfinyl group (eg, hexadecanesulfinyl, etc.), arylsulfinyl group (For example, benzenesulfinyl, etc.), a nitrogen-containing heterocyclic group bonded by a nitrogen atom (nitrogen as a hetero atom,
It is a saturated or unsaturated 5- to 7-membered monocyclic or condensed ring containing at least one of oxygen, sulfur and the like, and examples thereof include succinimide, maleinimide, phthalimide,
Diglycolimide, pyrazole, imidazole, 1,
2,4-triazole, tetrazole, indole, benzopyrazole, benzimidazole, benzotriazole, imidazoline-2,4-dione, oxazolidine-2,4-dione, thiazolidine-2,4-dione, imidazolidin-2-one, Oxazolin-2-one, thiazolin-2-one, benzimidazolin-2-one,
Benzoxazolin-2-one, benzothiazoline-2
-One, 2-pyrrolin-5-one, 2-imidazoline-
5-one, indoline-2,3-dione, 2,6-dioxypurine, parabanic acid, 1,2,4-triazolidine-3,5-dione, 2-pyridone, 4-pyridone, 2-
Pyrimidone, 6-pyridazone, 2-pyrazone, 2-amino-1,3,4-thiazolidine, 2-imino-1,3
4-thiazolidin-4-one etc.), an arylazo group (eg phenylazo, naphthylazo etc.), a carbamoylamino group (eg N-hexadecylcarbamoylamino etc.) and the like. The total number of carbon atoms contained in L is preferably 6 or more and 50 or less, more preferably 8 or more and 40 or less, and most preferably 10 or more and 35 or less. X is preferably an aryloxy group, a heterocyclic oxy group, an alkoxycarbonyloxy group or a carbamoyloxy group, and more preferably an aryloxy group, a heterocyclic oxy group or an alkoxycarbonyloxy group.

Next, the novel 2-amidonaphthol couplers used in the present invention will be specifically shown, but the scope of the present invention is not limited to these specific examples.

[0015]

[Chemical 3]

[0016]

[Chemical 4]

[0017]

[Chemical 5]

[0018]

[Chemical 6]

[0019]

[Chemical 7]

[0020]

[Chemical 8]

[0021]

[Chemical 9]

[0022]

[Chemical 10]

[0023]

[Chemical 11]

[0024]

[Chemical 12]

[0025]

[Chemical 13]

[0026]

[Chemical 14]

[0027]

[Chemical 15]

[0028]

[Chemical 16]

Next, general synthetic methods for the compounds of the present invention will be described. Synthesis Example 1 Synthesis of Exemplified Compound (C-18) Exemplified Compound (C-18) was synthesized by the following synthetic route.

[0030]

[Chemical 17]

Synthesis of compound (T-2) 128.0 g of compound (T-1) and methyl octadecylamine 13
5 g was dissolved in 500 ml of methylene chloride, and 139.5 ml of triethylamine was added dropwise under ice cooling while keeping the internal temperature at 10 ° C or lower. After the dropping, the reaction was further performed for 1 hour. The reaction solution is concentrated under reduced pressure,
1000 ml of methanol was added, the mixture was stirred at room temperature for 1 hour, the crystals were collected by filtration and washed with 200 ml of methanol. Thus
222.0 g of the compound (T-2) was obtained as pale yellow crystals.

Synthesis of compound (T-4) 200.0 g of compound (T-2) and 69.0 g of compound (T-3) were mixed with N
Under 2 air streams, it was suspended in 1080 ml of N, N-dimethylformamide, and 110.0 g of potassium carbonate was added. After the addition, the internal temperature was raised to 80 ° C. and the reaction was carried out for 1 hour. After cooling the reaction solution with water and returning to room temperature, 1500 ml of ethyl acetate, 1500 of saturated saline solution
The extraction operation was performed by pouring ml. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. Thus, the compound (T-
250.0 g of 4) was obtained as a pale yellow oil.

Synthesis of Compound (T-5) 222.6 g of reduced iron, 10.6 g of ammonium chloride and 180.0 ml of water were mixed and stirred at 100 ° C. for 30 minutes. Then, 1260 ml of isopropyl alcohol was added, and 245.0 g of compound (T-4) N, N
-Dissolved in 500 ml of dimethylacetamide and added dropwise over 30 minutes. After reacting for 30 minutes under reflux condition, reduced iron was removed by suction filtration with Celite. The filtrate was concentrated under reduced pressure, 704.40 ml of N, N-dimethylacetamide was added to the residue to dissolve it, and 30.0 ml of acetyl chloride was added dropwise at room temperature. At this time, the reaction temperature rose from 24 ° C to 36 ° C. After the dropping, the reaction was performed at room temperature for 30 minutes, and the mixture was poured into 5000 ml of ice water.
The precipitated crystals were collected by filtration and washed with 1000 ml of water. The crystals collected by filtration were added to 1500 ml of methanol, and the mixture was stirred at room temperature for 1 hour. The crystals were collected by filtration and washed with 200 ml of methanol. Thus, the compound (T-5) was obtained as white crystals 210.
0 g was obtained.

Synthesis of compound (T-6) 200 g of compound (T-5) was mixed with 1400 ml of acetic acid and methylene chloride.
It was dissolved in 00 ml and the reaction system was heated to 40 ° C. 70% nitric acid 24
ml was added dropwise over 0 minutes. At this time, the reaction system generated heat up to 45 ° C. Further, the reaction system was heated to 50 ° C. and reacted for 2 hours. After cooling with water and returning to room temperature, 1,500 ml of ethyl acetate and 1,500 ml of saturated saline were poured to carry out an extraction operation. The organic layer was neutralized with an aqueous sodium hydrogen carbonate solution, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue is ethyl acetate / n
-Heat-dissolved in 100 ml / 300 ml of hexane and slowly returned to room temperature. The precipitated crystals were collected by filtration and ethyl acetate / n-
It was washed with 30 ml / 90 ml of hexane. Thus, 132.1 g of the compound (T-6) was obtained as pale yellow crystals.

Synthesis of Compound (T-7) 110.9 g of reduced iron, 5.1 g of ammonium chloride and 92.0 ml of water were mixed and stirred at 100 ° C. for 30 minutes. Then, 920 ml of isopropyl alcohol was added, and 132.0 g of the compound (T-4) was added in 8 batches. After reacting for 30 minutes under reflux condition, reduced iron was removed by suction filtration with Celite. The filtrate is concentrated under reduced pressure,
The residue was extracted with 1000 ml of ethyl acetate and 1000 ml of saturated saline. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. To the residue, 704.40 ml of N, N-dimethylacetamide was added and dissolved, and 37.0 g of isonicotinic acid chloride hydrochloride was added at room temperature. At this time, the reaction temperature rose from 24 ° C to 33 ° C. After the dropping, the reaction was carried out at room temperature for 30 minutes, 1000 ml of ethyl acetate and 1000 ml of saturated saline were poured, and an extraction operation was performed. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. Thus, 145.0 g of the compound (T-7) was obtained as a light brown oily matter.

Synthesis of Exemplified Compound (C-18) 14.0 g of compound (T-7) was dissolved in 2200 ml of methylene chloride, and boron tribromide (80.0 m) was cooled with ice / MeOH.
1 was added dropwise while maintaining the internal temperature at 0 ° C or lower. It took one hour for the dropping. After reacting under ice cooling for 1 hour, ice water, 1500 ml
The reaction solution was carefully poured into and the extraction operation was performed. The organic layer was neutralized with an aqueous sodium hydrogen carbonate solution, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was put on a silica gel column chromatograph and the ethyl acetate / n-hexane 2/1 effluent was concentrated under reduced pressure. 1000 ml of the residue is acetonitrile
It was dissolved by heating at room temperature and slowly returned to room temperature. The precipitated crystals were collected by filtration and washed with 300 ml of acetonitrile. Thus, 100.0 g of the exemplified compound (C-18) was obtained as white crystals.

Synthesis Example 2 Synthesis of Exemplified Compound (C-53) Exemplified compound (C-53) was synthesized by the following synthetic route.

[0038]

[Chemical 18]

Synthesis of Compound (T-8) 66.5 g of reduced iron, 3.1 g of ammonium chloride and 55.0 ml of water were mixed and stirred at 100 ° C. for 30 minutes. Then, 550 ml of isopropyl alcohol was added, and 79.2 g of the compound (T-4) was added in 8 batches. After reacting for 30 minutes under reflux condition, reduced iron was removed by suction filtration with Celite. The filtrate is concentrated under reduced pressure,
600 ml of ethyl acetate and 600 ml of saturated saline were poured into the residue for extraction. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. To the residue, 422.4 ml of N, N-dimethylacetamide was added and dissolved, and 28.8 g of pentafluorobenzoyl chloride was added at room temperature. At this time, the reaction temperature rose from 24 ° C to 35 ° C. After dropping, at room temperature for 30 minutes,
The reaction was carried out, and 500 ml of ethyl acetate and 500 ml of saturated saline were poured to perform an extraction operation. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. 500 ml of acetonitrile in the residue
Was dissolved by heating, and the mixture was slowly returned to room temperature. The precipitated crystals were collected by filtration and washed with 150 ml of acetonitrile. Thus, 95.0 g of the compound (T-8) was obtained as white crystals.

Synthesis of Exemplified Compound (C-53) 90.0 g of compound (T-8) was dissolved in 1400 ml of methylene chloride, and 44.4 ml of boron tribromide under cooling with ice / MeOH.
Was maintained at an internal temperature of 0 ° C or lower and added dropwise. It took one hour for the dropping. After reacting for 1 hour under ice cooling, the reaction solution was carefully poured into 1000 ml of ice water, and extraction operation was performed. The organic layer was neutralized with an aqueous sodium hydrogen carbonate solution, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was put on a silica gel column chromatograph and the ethyl acetate / n-hexane 2/1 effluent was concentrated under reduced pressure. The residue was dissolved by heating in 400 ml of acetonitrile and slowly returned to room temperature. The precipitated crystals were collected by filtration and washed with 100 ml of acetonitrile. Thus, 75.0 g of the exemplified compound (C-53) was obtained as white crystals.

The naphthol coupler of the present invention is used together with a compound (color developing agent) which forms a dye by an oxidative coupling reaction. Specific examples of this color developing agent are JP-A 8-286340, 9-152694, 9-152704, 9-
152705, 9-152700, 9-152703, 12-284438
No. 12-284443, and so on.

Further, (R-1) to (R-10) are also mentioned as examples of preferable color developing agents, but the present invention is not limited thereto.

[0043]

[Chemical 19]

[0044]

[Chemical 20]

The coupler of the present invention is preferably one which forms a diffusible dye by coupling with the above-mentioned oxidized product of the color developing agent, and can be effectively utilized in the diffusion transfer color image forming method. The coupler represented by formula (1) of the present invention is preferably used as a magenta dye-forming coupler. The addition amount of the coupler used in the present invention depends on its molar absorption coefficient (ε), but in order to obtain an image density of 1.0 or more in reflection density, ε of the dye produced by coupling is about 5000 to 500000. In case of the coupler of
0.01 to 10 mmol / m ² , more preferably 0.05 to 5 mmol / m ² is suitable.

When a color developing agent is contained in the light-sensitive material, any layer (eg emulsion layer, intermediate layer, etc.) may be used. It is preferably contained in the emulsion layer. Also, when there are a plurality of emulsion layers, it is preferable to include them in all layers. The amount of the color developing agent added is 0.01 to 100 times, preferably 0.2 to 5 times the molar ratio of the corresponding coupler. Further, the color developing agent may be contained in the processing solution instead of being contained in the light-sensitive material. In this case, the amount is preferably 0.1 g to 100 g, and more preferably 1 g to 20 g per liter.

In the present invention, an auxiliary developing agent can be used. Here, the auxiliary developing agent means a substance having an action of promoting electron transfer from the color developing agent to silver halide in the development process of silver halide development, and follows the Kendall-Pertz rule. The auxiliary developing agent in the invention is preferably a compound represented by the general formula (B-1) or the general formula (B-2) described in JP-A 08-286340, and examples thereof are JP-A 08-286. -286340 and the like. Further, the compound represented by the general formula (1) described in JP-A 09-146248 is also preferable. Examples of these include compound examples D-1 to D-35 described in JP-A 09-146248.

Blocked photographic reagents which release photographically useful groups upon processing can be used in the present invention. These are disclosed in JP-A 09-152704, pages 41 to 42.
See page for details.

The light-sensitive material of the present invention preferably has on a support a light-sensitive silver halide, at least one of the couplers represented by the general formula (1), a color developing agent and a binder. If necessary, an organic metal salt oxidizing agent and the like can be included. These components are often added to the same layer, but if they are in a reactive state, they can be added separately to separate layers.

Hydrophobic additives such as couplers and color developing agents used in the present invention are described in US Pat. No. 2,322,027.
It can be incorporated into a layer of a light-sensitive material (a photographic constituent layer such as a hydrophilic colloid layer) by a known method such as the method described in No. In this case U.S. Pat. No. 4,555,470
No. 4,536,466, No. 4,536,46
No. 7, No. 4,587, 206, No. 4, 555, 4
No. 76, No. 4,599,296, Japanese Patent Publication No. 3-62,
A high-boiling organic solvent such as that described in No. 256 can be used in combination with a low-boiling organic solvent having a boiling point of 50 to 160 ° C., if necessary. Each of these couplers, color developing agents, diffusion resistant reducing agents, high boiling organic solvents, etc.
Seeds may be used, or two or more types may be used in combination. The amount of the high boiling point organic solvent is 10 g or less, preferably 5 g or less, and more preferably 1 g to 0.1 g, relative to 1 g of the compound to be emulsified and dispersed. In addition, 1 ml or less, further 0.5 ml or less, especially 0.3 m per 1 g of binder
It is preferably 1 or less. Also, Japanese Examined Patent Publication No. 51-39,853
And a dispersion method using a polymer described in JP-A-51-59943 and a fine particle dispersion described in JP-A-62-30,242 and JP-A-63-271339. A method of adding can also be used. In the case of a compound which is substantially insoluble in water, fine particles can be dispersed and contained in a binder in addition to the above method. When dispersing the hydrophobic compound in the hydrophilic colloid, various surfactants can be used. For example, JP-A-59-157,
The compounds listed as the surfactants in Research Disclosure magazines, which are listed in the following tables, pages (37) to (38) of No. 636, can be used. For the light-sensitive material of the present invention, a compound that activates development and stabilizes an image at the same time can be used. Specific compounds preferably used are described in US Pat. No. 4,500,626, columns 51 to 52.

In order to obtain a wide range of colors on the chromaticity diagram by using the three primary colors of yellow, magenta, and cyan, at least three silver halide emulsion layers having different spectral regions, which are sensitive to each other, are combined. To use. For example, there are combinations of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer, a green-sensitive layer, a red-sensitive layer and an infrared-sensitive layer. Each of the light-sensitive layers can take various arrangement orders known in ordinary color light-sensitive materials. Further, each of these photosensitive layers may be divided into two or more layers if necessary.

The photosensitive material can be provided with various auxiliary layers such as a protective layer, an undercoat layer, an intermediate layer, an antihalation layer and a back layer. Further, various filter dyes may be added to improve the color separation property.

The silver halide grains used in the present invention include silver bromide, silver chloride, silver chlorobromide, silver chloroiodide, silver iodobromide and silver chloroiodobromide. Other silver salts, for example, silver rhodan, silver sulfide, silver selenide, silver carbonate, silver phosphate,
The organic acid silver salt may be contained as a separate grain or as a part of the silver halide grain. Development and desilvering (bleaching,
When it is desired to accelerate the fixing and bleach-fixing steps, silver halide grains having a high silver chloride content are desirable. Further, in the case of suppressing development appropriately, it is preferable to contain silver iodide. The preferable silver iodide content depends on the intended light-sensitive material. For example, 0.1 for X-ray sensitive material.
.About.15 mol%, and for graphic arts and micro sensitive materials, 0.1 to 5 mol% is a preferable range. In the case of a photographic light-sensitive material represented by a color negative, preferably 1 to 3
A silver halide containing 0 mol% of silver iodide, more preferably 5 to 20 mol%, particularly preferably 8 to 15 mol%.
Mol%. The inclusion of silver chloride in the silver iodobromide grains is preferred for alleviating lattice distortion.

The silver halide emulsion of the present invention preferably has a distribution or structure with respect to the halogen composition in its grains. The typical one is Japanese Patent Publication No. 43-131.
62, JP-A-61-215540, and JP-A-60-2.
No. 22845, JP-A No. 61-75337, and the like, which are core-shell type or double-type particles having a halogen composition in which the inside and the surface layer of the particles are different.
Further, it is not a simple double structure, but is disclosed in JP-A-60-222844.
It is possible to form a triple structure as disclosed in JP-A No. 2000-242242 or more, or to form a multilayer structure having more than that, or to thinly coat a silver halide having a different composition on the surface of a core-shell double structure grain.

In order to give a structure to the inside of the particle, not only the wrapping structure as described above but also a so-called bonded structure can be produced. Examples of these are JP-A-59-
133540, JP-A-58-108526, European Patent 199,290A2, and JP-B-58-24772.
And JP-A-59-16254.
The crystal to be bonded can have a composition different from that of the crystal serving as the host and can be generated by bonding to the edge, corner, or surface of the host crystal. Such a junction crystal can be formed even if the host crystal has a uniform halogen composition or has a core-shell type structure.

In the case of a junction structure, it is naturally possible to combine silver halides with each other, but a silver salt compound not having a rock salt structure such as silver rhodan or silver carbonate may be combined with silver halide to form a junction structure. Further, a non-silver salt compound such as lead oxide may also be used as long as a joint structure is possible.

In the case of grains such as silver iodobromide having these structures, it is a preferred embodiment that the core portion has a higher silver iodide content than the shell portion. On the contrary, in some cases, grains having a low silver iodide content in the core portion and a high shell portion are preferable. Similarly, with respect to the grains having a junction structure, the grains having a high silver iodide content in the host crystal and having a relatively low silver iodide content in the junction crystal may be used, or vice versa. Further, the boundary portion having different halogen compositions of grains having these structures may be a clear boundary or an unclear boundary. In addition, a positive embodiment in which the composition is positively and continuously changed is also a preferred embodiment.

In the case of silver halide grains in which two or more silver halides exist as a mixed crystal or with a structure, it is important to control the halogen composition distribution between grains. The method for measuring the halogen composition distribution between grains is described in JP-A-60-254032. A uniform halogen distribution between grains is a desirable property. In particular, a highly uniform emulsion having a variation coefficient of 20% or less is preferable.
Another preferred form is an emulsion where there is a correlation between grain size and halogen composition. For example, there is a correlation in which larger size particles have a higher iodine content, while smaller particles have a lower iodine content. Depending on the purpose, an inverse correlation or a correlation with another halogen composition can be selected. For this purpose, it is preferable to mix two or more emulsions having different compositions.

It is important to control the silver halide composition near the surface of the grain. Increasing the amount of silver iodide in the vicinity of the surface or increasing the content of silver chloride changes the adsorbability of the dye and the developing rate, and can be selected according to the purpose. When changing the halogen composition in the vicinity of the surface, it is possible to select either a structure that encloses the entire grain or a structure that adheres only to a part of the grain. For example, the halogen composition may be changed only on one side of a tetrahedral grain composed of (100) planes and (111) planes, or the halogen composition on one of the main plane and side planes of a tabular grain may be changed.

Even if the silver halide grains used in the present invention are normal crystals that do not contain twin planes, they are as described on page 163, edited by The Photographic Society of Japan, Fundamentals of The Photographic Industry, Silver Salt Photography (Corona Publishing Co.). Examples include, for example, single twin containing one twin plane, parallel multiple twin containing two or more parallel twin planes, non-parallel multiple twin containing two or more non-parallel twin planes, depending on the purpose. Can be selected and used. An example of mixing particles having different shapes is disclosed in US Pat. No. 4,865,964, but this method can be selected as necessary. In the case of normal crystal, a cube consisting of (100) plane, (111)
An octahedron having a plane, a dodecahedral grain having a (110) plane disclosed in JP-B-55-42737 and JP-A-60-222842 can be used. In addition, Jo
urnal of Imaging Science, Vol. 30, 247 (1986)
(H11) plane particles represented by (211) and (331) represented by (hh1).
Plane grains, (hk0) plane grains typified by the (210) plane, and (hkl) plane grains typified by the (321) plane also require devising an adjusting method, but can be selected and used according to the purpose. A tetrahedral particle in which the (100) plane and the (111) plane coexist in one particle, a particle in which the (100) plane and the (110) plane coexist, or a particle in which the (111) plane and the (110) plane coexist. Particles in which two surfaces or a large number of surfaces coexist can be selected and used according to the purpose.

The value obtained by dividing the circle-equivalent diameter of the projected area by the grain thickness is called the aspect ratio, and defines the shape of tabular grains. Tabular grains having an aspect ratio of greater than 1 can be used in the present invention. Tabular grains are described in Cleav, Photography Theory and Practice.
(1930)), p. 131; Gatov, Photographic
Science and Engineering (Gutof, Photo
graphic Science and Engineering), Volume 14, 248
~ 257 (1970), U.S. Pat. No. 4,434,2
No. 26, No. 4,414, 310, No. 4,433.
It can be prepared by the method described in, for example, 048, 4,439,520 and British Patent 2,112,157. When the tabular grains are used, there are advantages such as an increase in covering power and an increase in color sensitization efficiency by the sensitizing dye, and the above-cited US Pat. No. 4,434,22.
It is described in detail in No. 6. 80 of the total projected area of the grain
It is desirable that the average aspect ratio of 1% or more is 1 or more and less than 100. It is more preferably 2 or more and less than 20, and particularly preferably 3 or more and less than 10. The shape of tabular grains can be selected from triangles, hexagons, circles, and the like. A regular hexagon with six sides of approximately equal length, as described in U.S. Pat. No. 4,798,354, is the preferred form.

As the grain size of tabular grains, a circle-equivalent diameter of the projected area is often used, and US Pat.
The average diameter as described in No. 8,106 is 0.6
Particles of micron or smaller are preferable for improving image quality. An emulsion having a narrow grain size distribution as described in U.S. Pat. No. 4,775,617 is also preferable. It is preferable to increase the sharpness by limiting the grain thickness of the tabular grains to 0.5 μm or less, more preferably 0.3 μm or less. Further, an emulsion having a highly uniform thickness having a variation coefficient of grain thickness of 30% or less is also preferable. Further, grains described in JP-A-63-163451, in which the grain thickness and the interplanar distance between twin planes are defined, are also preferable.

In the case of tabular grains, dislocation lines can be observed with a transmission electron microscope. It is preferable to select a grain containing no dislocation lines, a grain containing several dislocations or a grain containing many dislocations according to the purpose. Further, it is also possible to select a dislocation or a curved dislocation linearly introduced with respect to a specific direction of the crystal orientation of the particle, introduced over the entire particle, or introduced only in a specific part of the particle, For example, dislocations can be introduced only in the fringe portion of the grain. The introduction of dislocation lines is preferable not only in the case of tabular grains but also in the case of regular grains or amorphous grains typified by potato grains. In this case as well, it is a preferable form to limit the particles to specific portions such as vertices and edges.

The silver halide emulsion used in the present invention is a treatment for rounding grains as disclosed in European Patent No. 96,412B1 or the like, or West German Patent No. 2,30.
The surface may be modified as disclosed in No. 6,447C2 and JP-A No. 60-221320.

A structure having a flat particle surface is generally used.
It is sometimes preferable to intentionally form the unevenness. JP-A-58-106532, JP-A-60-221
Examples are the part of the crystals described in U.S. Pat. No. 320, for example the method of drilling holes in the centers of vertices or planes, or the ruffled particles described in U.S. Pat. No. 4,643,966.

The grain size of the emulsion used in the present invention depends on the circle equivalent diameter of the projected area using an electron microscope, the sphere equivalent diameter of the grain volume calculated from the projected area and grain thickness, or the sphere equivalent diameter of the volume determined by the Coulter counter method. Can be evaluated. It can be selected from ultrafine particles having a sphere-equivalent diameter of 0.05 micron or less, and coarse particles having a sphere-equivalent diameter of more than 10 microns. Preferably, grains having a size of 0.1 micron or more and 3 microns or less are used as the photosensitive silver halide grains.

The emulsion used in the present invention may be a so-called polydisperse emulsion having a wide grain size distribution or a monodisperse emulsion having a narrow size distribution, and can be selected and used according to the purpose. The variation coefficient of the projected area circle diameter of particles or the equivalent sphere diameter of particles may be used as a scale representing the size distribution. When a monodisperse emulsion is used, it is preferable to use an emulsion having a size distribution with a coefficient of variation of 25% or less, more preferably 20% or less, still more preferably 15% or less.

The monodisperse emulsion may be defined as the average grain size distribution in terms of grain number or mass. In order to satisfy the target gradation of the light-sensitive material, two or more kinds of monodisperse silver halide emulsions having different grain sizes in an emulsion layer having substantially the same color sensitivity are mixed in the same layer or different layers. Can be applied in multiple layers. Further, two or more kinds of polydisperse silver halide emulsions or a combination of monodisperse emulsions and polydisperse emulsions can be mixed or laminated and used. As the emulsion used in the present invention, the emulsion containing the above-mentioned grains is used. Here, as one of the modes for carrying out the present invention, the main ingredient of the present invention and the silver chloride content of 50 mol%
It is also possible to adopt a mode in which the above-mentioned emulsion comprising tabular grains is not used in combination.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Graphide, published by P. Montela (P.Glaf).
kides, Chemie et Phisique Photographique, Paul Mon
Tel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photographic Emulsion Chem)
istry, Focal Press, 1966), "Production and coating of photographic emulsions" by Zelikmann et al., published by Focal Press (VLZelikm).
an, et al., Makingand Coating Photographic Emulsio
n, Focal Press, 1964) and the like, any of which can be used. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and as a method of reacting a soluble silver salt and a soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used. . A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one form of the simultaneous mixing method, a method of keeping pAg constant in a liquid phase in which silver halide is produced,
That is, the so-called controlled double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

A method of adding silver halide grains which have been preliminarily formed in a reaction vessel for preparing an emulsion, US Pat. Nos. 4,334,012, 4,301,241 and 4,150,994. Are optionally preferred. These can be used as seed crystals, and are effectively supplied as silver halide for growth. In the latter case, it is preferable to add an emulsion having a small grain size. As an addition method, the whole amount can be added at once, divided into a plurality of times or added continuously, or the like. It is also effective in some cases to add particles having various halogen compositions in order to modify the surface.

Most of the halogen composition of silver halide grains is converted by a halogen conversion method, and a method for converting the halogen composition is described in US Pat. Nos. 3,477,852 and 4,142.
900, European Patent Nos. 273,429 and 273.
No. 430 and West German Laid-Open Patent No. 3,819,241 and the like, which is an effective particle forming method. A solution of soluble halogen or silver halide grains can be added to convert it to a more sparingly soluble silver salt. It is possible to select from a method such as conversion at once, conversion by dividing into plural times, or continuous conversion.

Besides the method of adding soluble silver salt and halogen salt at a constant concentration and a constant flow rate for grain growth, British Patent No. 1,
469,480, U.S. Pat. No. 3,650,757,
A particle forming method in which the concentration is changed or the flow rate is changed as described in the above-mentioned No. 4,242,445 is a preferable method. By changing the concentration or increasing the flow rate, the amount of silver halide supplied can be changed by a linear function, a quadratic function, or a more complicated function of the addition time. It is also preferable in some cases to reduce the amount of silver halide supplied if necessary. Furthermore, when adding a plurality of soluble silver salts having different solution compositions, or when adding a plurality of soluble halogen salts having different solution compositions, an addition method in which one is increased and the other is decreased is also an effective method. Is.

A mixer for reacting a solution of a soluble silver salt and a soluble halogen salt is described in US Pat. No. 2,996,287.
No. 3, ibid. 3,342, 605, ibid. 3, 415, 65
No. 0, No. 3,785,777, West German Published Patent No. 2,
It can be selected and used from the methods described in Nos. 556,885 and 2,555,364.

Silver halide solvents are useful for the purpose of promoting ripening. For example, it is known to have excess halogen ions present in the reactor to accelerate aging. Other ripening agents can also be used. All of these ripening agents can be added to the dispersion medium in the reactor before adding the silver and halide salts,
It is also possible to add halide salts, silver salts or peptizers and to introduce them into the reactor. As another modification,
The ripening agent can also be introduced independently at the halide salt and silver salt addition stages.

Ammonia, thiocyanates (Rhodan potassium, Rhodan ammonium, etc.), organic thioether compounds (for example, US Pat. Nos. 3,574,628 and 3,3,628).
No. 021,215, No. 3,057,724, No. 3,038,805, No. 4,276,374, No. 4,297,439, No. 3,704,130,
No. 4,782,013, JP-A-57-104926.
Compounds and thione compounds (for example, tetrasubstituted thioureas described in JP-A Nos. 53-82408 and 55-77737, U.S. Pat. No. 4,221,863, etc. and JP-A-53- No. 144319), mercapto compounds and amine compounds described in JP-A-57-202531, which can promote the growth of silver halide grains (for example, JP-A-54-1007).
No. 17, etc.) and the like.

Gelatin is advantageously used as a protective colloid used in the preparation of the emulsion of the present invention and as a binder for other hydrophilic colloid layers, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxycellulose, carboxymethylcellulose, cellulose sulfate, sodium alginate, starch derivatives and gum arabic. , Sugar derivatives such as natural compounds such as polysaccharides such as dextran and pullulan, polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. A variety of synthetic hydrophilic polymeric substances such as homo- or copolymers of the above can be used. Further, super absorbent polymers described in U.S. Pat. No. 4,960,681, JP-A-62-245,260, etc., that is, vinyl having --COOM or --SO ₃ M (M is hydrogen atom or alkali metal). Copolymers with monomers or copolymers of these vinyl monomers, or copolymers with other vinyl monomers (for example, sodium methacrylate, ammonium methacrylate, Sumikagel L-5H manufactured by Sumitomo Chemical Co., Ltd.) are also used. These binders can be used in combination of two or more. A combination of gelatin and the above binder is also preferable.

Examples of gelatin include lime-processed gelatin,
It suffices to select from acid-treated gelatin and so-called demineralized gelatin with a reduced content of calcium and the like, and it is also preferable to use them in combination. Bull.Soc.Sci.Photo.Japan.N
An enzyme-treated gelatin as described in o.16.p30 (1966) may be used, and a hydrolyzed product or an enzymatically decomposed product of gelatin may also be used. It is preferable to use the low molecular weight gelatin described in JP-A-1-158426 for the preparation of tabular grains.

In the case of a photothermographic material, an organic silver salt oxidizing agent may be used together with the photosensitive silver halide emulsion, and as an organic compound which can be used for forming the same, US Pat. There are benzotriazoles, fatty acids and other compounds described in Columns 52 to 53 of No. 500,626. The acetylene silver described in U.S. Pat. No. 4,775,613 is also useful. Further, silver salts of mercaptotetrazoles and silver salts of mercaptotriazoles are also useful. Two or more kinds of organic silver salts may be used in combination. The above organic silver salt is 0.01 to 10 moles per 1 mole of photosensitive silver halide,
Preferably, 0.01 to 1 mol can be used in combination.
The total coating amount of the photosensitive silver halide emulsion and the organic silver salt is 0.05 to 10 g / m ^{2 in} terms of silver, preferably 0.1 to 4 g.
/ M ² is suitable.

The emulsion of the present invention is preferably washed with water for desalting and dispersed in a newly prepared protective colloid. The temperature for washing with water can be selected according to the purpose, but it is preferably selected within the range of 5 to 20 ° C. The pH at the time of washing with water can also be selected according to the purpose, but it is preferably selected between 2 and 10. More preferably, it is in the range of 3-8. The pAg at the time of washing with water can also be selected according to the purpose, but it is preferably selected between 5 and 10. As a method of washing with water, a noodle washing method, a dialysis method using a semipermeable membrane, a centrifugation method, a coagulation sedimentation method, or an ion exchange method can be selected and used. In the case of the coagulation sedimentation method, it can be selected from a method using a sulfate, a method using an organic solvent, a method using a water-soluble polymer, a method using a gelatin derivative and the like.

During preparation of the emulsion of the present invention, for example, during grain formation,
In the desalting step, during chemical sensitization, it is preferable to allow a salt of a metal ion to exist before coating, depending on the purpose. When the grains are doped, they are preferably added at the time of grain formation, when the grains are modified, or when used as a chemical sensitizer, after grain formation and before the end of chemical sensitization. A method of doping the entire grain, a method of doping only the core portion of the grain, only the shell portion, only the epitaxial portion, or only the base grain can be selected. Mg, Ca, Sr, B
a, Al, Sc, Y, La, Cr, Mn, Fe, Co,
Ni, Cu, Zn, Ga, Ru, Rh, Pd, Re, O
s, Ir, Pt, Au, Cd, Hg, Tl, In, S
n, Pb, Bi, etc. can be used. These metals can be added in the form of salts such as ammonium salts, acetates, nitrates, sulfates, phosphates, hydrates, hexacoordinated complex salts and tetracoordinated complex salts which can be dissolved at the time of grain formation. For example, CdBr ₂ , CdCl ₂ , Cd (NO ₃ ) ₂ ,
Pd (NO ₃ ) ₂ , Pb (CH ₃ COO) ₂ , K ₃ [Fe
(CN) ₆ ], (NH ₄ ) ₄ [Fe (CN) ₆ ], K ₃ Ir
Examples thereof include Cl ₆ , (NH ₄ ) ₃ RhCl ₆ , and K ₄ Ru (CN) ₆ . Halo, aco, as ligands of coordination compounds,
It can be selected from cyano, cyanate, thiocyanate, nitrosyl, thionitrosyl, oxo and carbonyl. These may use only one type of metal compound, but may use two types or three or more types in combination.

The method of adding a chalcogen compound as described in US Pat. No. 3,772,031 during emulsion preparation may be useful in some cases. In addition to S, Se and Te, cyanate, thiocyanate, selenocyanate, carbonate, phosphate and acetate may be present.

The silver halide grains of the present invention are sulfur sensitized,
At least one of selenium sensitization, tellurium sensitization (these three types are collectively referred to as chalcogen sensitization), noble metal sensitization, or reduction sensitization may be performed at any step in the silver halide emulsion production process. it can. It is preferable to combine two or more sensitizing methods. Various types of emulsions can be prepared depending on which step is chemically sensitized. There are types that embed chemically sensitized nuclei inside grains, types that are embedded at a shallow position from the grain surface, and types that form chemically sensitized nuclei on the surface. In the emulsion of the present invention, the location of the chemically sensitized nuclei can be selected depending on the purpose, but generally preferred is the case where at least one chemically sensitized nucleus is formed near the surface.

The chemical sensitization that can be preferably carried out in the present invention is a chalcogen sensitization and a noble metal sensitization alone or in combination thereof, and is written by TH James in The Photographic Process, 4th edition, published by Macmillan. 1
977 (TH James, The Photographic Process, 4th
ed. Macmillan, 1977) 67-76 and using active gelatin, or Research Disclosure Item 12008 (1).
April 974), Item 13452 (6 June 1975).
Month), Item 307105 (November 1989),
U.S. Pat. Nos. 2,642,361 and 3,297,4
No. 46, No. 3,772,031, No. 3,857,
No. 711, No. 3,901,714, No. 4,26
6,018, and 3,904,415 and British Patent 1,315,755, pAg 5-10, pH 5-8 and temperature 30-80 ° C. with sulfur, selenium, tellurium, It can be performed by combining gold, platinum, palladium, iridium or a plurality of these sensitizers.

In sulfur sensitization, an unstable sulfur compound is used, and specifically, thiosulfates (eg, hypo), thioureas (eg, diphenylthiourea, triethylthiourea, allylthiourea, etc.), rhodanine. Kind,
Mercaptos, thioamides, thiohydantoins, 4
-Oxooxazolidine-2-thiones, di- or polysulfides, polythionates and elemental sulfur,
And U.S. Pat. Nos. 3,857,711 and 4,2.
Known sulfur-containing compounds described in Nos. 66,018 and 4,054,457 can be used. Sulfur sensitization is often used in combination with precious metal sensitization.

A preferable amount of the sulfur sensitizer used for the silver halide grains of the present invention is 1 × 10 ^-7 to 10 ^-3 mol, and more preferably 5 mol / mol of the silver halide.
It is x10 ^-7 to 1 x 10 ^-4 mol.

In the selenium sensitization, known unstable selenium compounds are used, for example, US Pat. No. 3,297,44.
No. 6, No. 3,297,447 and the like can be used, and specifically, colloidal metal selenium and selenoureas (for example, N, N-dimethylselenourea and tetramethylseleno) are used. Urea, etc.), selenoketones (eg, selenoacetone), selenoamides (eg, selenoacetamide), selenocarboxylic acids and esters, isoselenocyanates, selenides (eg, diethylselenide, triphenylphosphine selenide), Selenophosphates (eg tri-p
-Selenium compounds such as tolylselenophosphate) can be used. Selenium sensitization may be preferably used in combination with sulfur sensitization, precious metal sensitization, or both.

The amount of the selenium sensitizer used varies depending on the selenium compound used, silver halide grains, chemical ripening conditions, etc., but generally it is 10 ^-8 to 10 ^-4 per mol of silver halide.
A molar amount, preferably about 10 ⁻⁷ to 10 ⁻⁵ mol, is used.

The tellurium sensitizers used in the present invention include Canadian Patent 800,958 and British Patents 1,2.
No. 95,462, No. 1,396,696, Japanese Patent Application No. 2
The compounds described in JP-A-333819 and JP-A-3-131598 can be used, and specific tellurium sensitizers include colloidal tellurium and telluroureas (for example, tetramethyl tellurourea, N-carboxyethyl-N). ', N'
-Dimethyl tellurourea, N, N'-dimethylethylene tellurourea), isotellurocyanates, telluroketones, telluroamides, tellurohydrazides, telluroesters, phosphine tellurides (for example, tributylphosphine telluride, butyldiisopropylphosphine) Telluride), other tellurium compounds (eg potassium tellurocyanate, telluropentathionate sodium salt)
Etc.

The amount of tellurium sensitizer used is 1 silver halide.
10 ^{-7 to} 5 × 10 ^-2 mol, preferably 5 × 1
It is about 0 ^-7 to 10 ^-3 mol.

Noble metal salts such as platinum, gold, palladium and iridium can be used in the noble metal sensitization, and gold sensitization, palladium sensitization and a combination of both are particularly preferable. In the case of gold sensitization, chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide,
Known compounds such as gold selenide can be used.
The palladium compound means a divalent or tetravalent palladium salt. A preferred palladium compound is represented by R ₂ PdX ₆ or R ₂ PdX ₄ . Here, R represents a hydrogen atom, an alkali metal atom or an ammonium group. X represents a halogen atom and represents a chlorine, bromine or iodine atom.

Specifically, K ₂ PdCl ₄ , (NH ₄ ) ₂ P
dCl ₆ , NaPdCl ₄ , (NH ₄ ) ₂ PdCl ₄ , Li ₂
PdCl ₄ , Na ₂ PdCl ₆ or K ₂ PdBr ₄ are preferred. The gold compound and the palladium compound are preferably used in combination with thiocyanate or selenocyanate.

The emulsion of the present invention is preferably combined with gold sensitization.
Good The preferred amount of gold sensitizer is 1 mol of silver halide.
1 x 10 per le^-7~ 1 x 10^-3Mol, more preferably
Is 5 × 10^-7~ 5 x 10^-FourIt is a mole. Palladium compound
The preferable range of the product is 5 × 10 ^-7~ 1 x 10^-3In moles
It A thiocyan compound or selenocyan compound is preferred.
The preferred range is 1 x 10^-6~ 5 x 10^-2It is a mole.

During grain formation of the silver halide emulsion of the present invention,
It is preferable to carry out reduction sensitization after grain formation and before or during chemical sensitization or after chemical sensitization.

Here, the reduction sensitization is a method of adding a reduction sensitizer to a silver halide emulsion, pAg1 called silver ripening.
No. 7, a method of growing or aging in a low pAg atmosphere, or a method of growing or aging in a high pH atmosphere of pH 8 to 11 called high pH aging can be selected. Also, two or more methods can be used in combination.

The method of adding a reduction sensitizer is a preferable method because the level of reduction sensitization can be finely adjusted.

As the reduction sensitizer, known reduction sensitizers such as stannous salt, ascorbic acid and its derivatives, amines and polyamines, hydrazine and its derivatives, formamidinesulfinic acid, silane compounds and borane compounds are selected. And two or more compounds can be used in combination. Stannous chloride as a reduction sensitizer,
Aminoiminomethanesulfinic acid (commonly known as thiourea dioxide), dimethylamineborane, ascorbic acid and its derivatives are preferred compounds. The addition amount of the reduction sensitizer depends on the emulsion production conditions, so it is necessary to select the addition amount, but the range of 10 ^-7 to 10 ^-3 mol per mol of silver halide is suitable.

The chemical sensitization can be carried out in the presence of a so-called chemical sensitization aid. Useful chemical sensitization aids include compounds such as azaindene, azapyridazine, and azapyrimidine which are known to suppress fog and increase sensitivity during the chemical sensitization process. Examples of the chemical sensitization aid modifier are described in US Pat. Nos. 2,131,038 and 3,311.
411, 914, 3,554, 757, JP-A-58-126526 and Duffin, "Photographic Emulsion Chemistry", pages 138-143.

It is preferable to use an oxidizing agent for silver during the process of producing the emulsion of the present invention. What is an oxidizing agent for silver?
It refers to a compound that acts on metallic silver to convert it into silver ions. In particular, the extremely fine silver particles produced as a by-product in the process of forming silver halide grains and the chemical sensitization process,
Compounds that give silver ions are effective. The silver ions produced here may form a water-insoluble silver salt such as silver halide, silver sulfide, or silver selenide, or may form a water-soluble silver salt such as silver nitrate. good. The oxidizing agent for silver may be an inorganic substance or an organic substance. Examples of the inorganic oxidant include ozone, hydrogen peroxide and its adducts (for example, NaBO ₂ , H ₂ O ₂ · H ₂ O, 2NaCO ₃ · H).
₂ O ₂ , Na ₄ P ₂ O ₇ · H ₂ O ₂ , 2NaSO ₄ · H ₂ O ₂ · 2
H ₂ O), peroxy acid salts (eg, K ₂ S ₂ O ₈ , K ₂ C ₂
O ₆ , K ₂ P ₂ O ₈ ) peroxy complex compound (for example, K ₂
[Ti (O ₂ ) C ₂ O ₄ ] / 3H ₂ O, 4K ₂ SO ₄ · Ti
(O ₂ ) OH ・ SO ₄・ 2H ₂ O, Na ₃ [VO (O ₂ )
(C ₂ O ₄ ) ₂ ] .6H ₂ O), permanganate (eg,
KMnO ₄ ), chromates (eg, K ₂ CrO ₇ ) and other oxyacid salts, iodine and bromine and other halogen elements, perhalogenates (eg, potassium periodate), and high valent metal salts ( For example, potassium hexacyanoferrate) and thiosulfonate.

Examples of the organic oxidant include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogen (for example, N-bromosuccinimide and chloramine). T, chloramine B) are mentioned as examples.

Preferred oxidizing agents of the present invention are ozone, hydrogen peroxide and its adducts, halogen elements, thiosulfonic acid inorganic oxidizing agents and quinone type organic oxidizing agents.
It is a preferable embodiment to use the reduction sensitization and the oxidizing agent for silver in combination. It is possible to select and use the method of performing reduction sensitization after using an oxidizing agent, the reverse method thereof, or the method of coexisting both of them. These methods can be selectively used in the grain forming step and the chemical sensitization step.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, during storage or during photographic processing, or stabilizing photographic performance. . That is, thiazoles, for example, benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, amino Triazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines, mercaptotriazines,
Thioketo compounds such as oxazolinethione, azaindenes such as triazaindenes, tetraazaindenes (especially 4-hydroxy-6-methyl-1,
Many compounds known as antifoggants or stabilizers can be added such as 3,3a, 7-tetraazaindene), pentaazaindenes and the like. For example, U.S. Pat. Nos. 3,954,474 and 3,982,94
No. 7 and Japanese Patent Publication No. 52-28660 can be used. JP-A-63-63 is one of the preferred compounds.
There are compounds described in No. 212932. Antifoggants and stabilizers are used at various times before particle formation, during particle formation, after particle formation, during the water washing step, during dispersion after water washing, before chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. It can be added depending on the purpose. Addition during emulsion preparation to prevent the original fog and to exert a stabilizing effect, in addition to controlling the crystal wall of the grain, reducing the grain size, reducing the solubility of the grain, controlling chemical sensitization It can be used for various purposes such as controlling the arrangement of dyes.

When the photosensitive silver halide used in the present invention is provided with green-sensitive, red-sensitive and infrared-sensitive color sensitivity, the photosensitive silver halide emulsion is spectrally sensitized with a methine dye or the like. . Further, if necessary, the blue-sensitive emulsion may be spectrally sensitized in the blue region.

The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.
Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei normally used for cyanine dyes as a base heterocyclic nucleus can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus,
Imidazole nuclei, tetrazole nuclei, pyridine nuclei, etc. fused with alicyclic hydrocarbon rings on these nuclei, and nuclei fused with aromatic hydrocarbon rings on these nuclei, that is, indolenine nuclei, benzindolenine nuclei, Applying a 5- or 6-membered heterocyclic nucleus such as indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, rhodanin nucleus and thiobarbituric acid nucleus You can These nuclei may be substituted on carbon atoms. Specifically, U.S. Pat. No. 4,617,257, JP-A-59-180,550, and JP-A-64-13,546,
Sensitizing dyes described in JP-A Nos. 5-45,828 and 5-45,834 can be used.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidine-2,4-dione nucleus, a thiazolidine-2,4-
5 such as dione nucleus, rhodanine nucleus, thiobarbituric acid nucleus
~ 6-membered heterocyclic nuclei can be applied.

These dyes may be used alone or in combination, and the combination of sensitizing dyes is often used for the purpose of supersensitization or wavelength adjustment of spectral sensitivity. A typical example thereof is US Pat. No. 2,688,5.
No. 45, No. 3,397,060, No. 2,977,
No. 229, No. 3,522,052, No. 3,52
7,64, 3,617,293, 3,62
No. 8,964, No. 3,672,898, No. 3,6
79,428, 3,703,377, and 3,
769,301, 3,814,609, 3,837,862, 4,026,707, British Patents 1,344,281, 1,507,80.
No. 3, Japanese Patent Publication No. 43-4,936, No. 53-12, 37
No. 5, JP-A Nos. 52-110,618 and 52-10.
No. 9,925.

Along with the sensitizing dye, a dye having no spectral sensitizing effect by itself or a compound which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (eg, US Pat. Nos. 3,615,641 and JP-A-63-23,145).

The timing of adding these sensitizing dyes to the emulsion may be at any stage in the emulsion preparation which has heretofore been known to be useful.

Most commonly, it is carried out after the completion of chemical sensitization and before coating, but it is described in US Pat. No. 3,628,96.
No. 9 and No. 4,225,666, the spectral sensitization may be carried out simultaneously with the chemical sensitization by adding the chemical sensitizer at the same time. , 92
It can also be performed prior to chemical sensitization as described in No. 8. It is also possible to start the spectral sensitization by adding the silver halide grains before completion of precipitation formation. Further, U.S. Pat. Nos. 4,183,756 and 4,225,666.
It may be added before or after the nucleation of silver halide grains according to the above-mentioned publication, and a part of the compound may be added before chemical sensitization and the rest may be added after chemical sensitization.

These sensitizing dyes and supersensitizers may be added in a solution of an organic solvent such as methanol, a dispersion of gelatin or a solution of a surfactant.

The addition amount is generally about 4 × 10 ⁻⁶ to 8 × 10 ⁻³ mol per mol of silver halide, but about 5 × for a more preferable silver halide grain size of 0.2 to 1.2 μm. 10 ^{-5 to} 2 × 10 ^-3 mol is more effective.

The above-mentioned various additives are used in the light-sensitive material of the present technology, but various additives other than the above can be used depending on the purpose.

More specifically, these additives are described in Research Disclosure Item 17643 (December 1978) and Item 18176 (November 1979).
And Item 307105 (November 1989), and the relevant parts are summarized in the table below.

[0114]   Types of additives RD17643 RD18716 RD307105 1. Chemical sensitizer page 23 page 648 right column page 996 2. Sensitivity enhancer page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column, pages 996 to 998     Supersensitizer: page 649, right column 4. Whitening agent Page 24 Page 647 Right column Page 998 5. Light absorber, pages 25-26, page 649, right column, page 1003     Filter: page 650, left column     Dye, ultraviolet     Line absorber 6. Binder 26 pages 651 pages 1003-1004 7. Plasticizer, page 27 page 650 page 1006     lubricant 8. Coating aid, pages 26-27 pages 650 pages 1005 left-     Surfactant 1006 page right 9. Static page 27 page 650 page right column 1006-     Inhibitor 1007 pages 10. Antifoggant page 24-25 page 649 page 998-1000     And stabilizers 11. Stain 25 pages right column 650 pages left to right       Preventive agent 12. Dye image stabilizer, page 25 13. Hardener page 26 page 651 left column 1004 right ...                                                             1005 left

In addition to the above, hardeners include US Pat. No. 4,678,739, column 41, and US Pat. No. 4,791,04.
No. 2, JP-A-59-116,655 and JP-A-62-24.
5,261, 61-18,942, JP-A 4-2.
Examples include hardeners described in No. 18,044. More specifically, aldehyde type hardeners (formaldehyde etc.), aziridine type hardeners, epoxy type hardeners, vinyl sulfone type hardeners (N, N'-ethylene-bis (vinylsulfonylacetamide)) Ethane, etc.), N-methylol type hardeners (dimethylol urea, etc.), or polymer hardeners (compounds described in JP-A-62-234157). These hardeners are used in an amount of 0.001 to 1 g, preferably 0.001 g per 1 g of coated gelatin.
5g to 0.5g is used. The layer to be added may be any of the constituent layers such as a light-sensitive material (also referred to as a light-sensitive element) and a dye-fixing material (also referred to as a dye-fixing element and an image-receiving element), or may be divided into two or more layers and added. Good.

A matting agent can be used in the light-sensitive material of the present invention for the purpose of preventing adhesion, improving slipperiness, and providing a non-glossy surface. Matting agents such as silicon dioxide, polyolefins and polymethacrylates are disclosed in JP-A-61-8.
No. 8,256 (29) page, benzoguanamine resin beads, polycarbonate resin beads, A
There are compounds described in JP-A-63-274,944 and JP-A-63-274,952, such as S resin beads. In addition, the compounds described in the above RD magazine can be used. These matting agents can be added not only to the uppermost layer (protective layer) but also to the lower layer if necessary.

In addition, the constituent layers of the photothermographic material may contain a thermal solvent, a defoaming agent, an antibacterial agent, an antifungal agent, colloidal silica and the like. Specific examples of these additives are described in JP-A-61 / 1986.
-88,256 (26) to (32), JP-A 3-1
No. 1,338, Japanese Patent Publication No. 2-51-51,496 and the like.

In the constituent layers of the light-sensitive material of the present invention, various surfactants can be used for the purpose of coating aid, improvement of peeling property, improvement of slipperiness, antistatic property, acceleration of development and the like. Specific examples of the surfactant are described in RD magazine, JP-A-62-173,4.
63, 62-183, 457 and the like. In the case of a photothermographic material, it is also preferable that the constituent layer contains an organic fluoro compound for the purpose of improving slipperiness, preventing static electricity, improving peelability and the like. Typical examples of organic fluoro compounds include fluorine-based surface active agents described in JP-B No. 57-9,053, columns 8 to 17, JP-A Nos. 61-20,944 and 62-135,836. Agent, or an oily fluorine-based compound such as fluorine oil or a hydrophobic fluorine compound such as a solid fluorine compound resin such as tetrafluoroethylene resin.

A known anti-fading agent can be used in the light-sensitive material of the present invention. As the organic anti-fading agent, hydroquinones, 5-hydroxychromans, 5-hydroxycoumarans, paraalkoxyphenols, hindered phenols centering on bisphenols, gallic acid derivatives, methylenedioxybenzenes, amino Typical examples thereof include phenols, hindered amines, and ether or ester derivatives obtained by silylating and alkylating the phenolic hydroxyl groups of these compounds.
Further, a metal complex typified by (bissalicylaldoximato) nickel complex and (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used. In order to prevent deterioration of the yellow dye image by heat, humidity and light, a compound having both partial structures of hindered amine and hindered phenol in the same molecule as described in US Pat. No. 4,268,593 gives good results. give. Further, in order to prevent the deterioration of the magenta dye image, especially the deterioration by light, spiroindanes described in JP-A-56-159,644, and hydroquinone diethers described in JP-A-55-89,835 or Monoether substituted chromans give favorable results.

Various antifoggants or photographic stabilizers and their precursors can be used in the constituent layers of the light-sensitive material of the present invention. Specific examples thereof include the above R
D magazine, US Pat. Nos. 5,089,378 and 4,50.
0,627, 4,614,702, JP-A-64
-13,546 (7) to (9), (57) to (7)
1) and (81)-(97), U.S. Pat.
75,610, No. 4,626,500, No. 4,
983,494, JP-A-62-174,747, JP-A-62-239,148, JP-A-63-264,747,
JP-A-1-150,135, 2-110,557
No. 2-178,650, RD. No. 17,64
No. 3 (1978), pages (24) to (25), and the like. These compounds are 5 per mol of silver
X10 ^-6 to 1 x 10 ^-1 mol is preferable, and further 1 x 10
^-5 to 1 × 10 ^-2 is preferably used.

Suitable supports usable in the present invention are polyolefins such as polyethylene and polypropylene, polycarbonates, cellulose acetate, polyethylene terephthalate, polyethylene naphthalate, synthetic plastic films such as polyvinyl chloride, photographic base paper and printing. Paper supports such as paper, baryta paper, and resin-coated paper, and supports having the above-mentioned plastic film provided with a reflective layer, JP-A-62-253,159 (29).
Up to page 31). The RD. No. 17643, page 28, No. 17643. 1
8716, page 647, right column to page 648, left column, and ibid.
o. Those described on page 879 of 307105 can also be preferably used. These supports include US Pat.
By applying heat treatment below Tg like No. 1,735,
It is possible to use a material that has less curling tendency. Further, the surface of these supports may be surface-treated for the purpose of improving the adhesion between the support and the emulsion undercoat layer. In the present invention, glow discharge treatment, ultraviolet irradiation treatment, corona treatment and flame treatment can be used as the surface treatment. Further, the support described on pages 44 to 149 of Known Technology No. 5 (published by Aztec Co., Ltd. on March 22, 1991) can also be used. A transparent support such as polyethylene naphthalene dicarboxylate or a support having a transparent magnetic material coated thereon can also be used.

In the photothermographic material, various development stoppers can be used for the purpose of always obtaining a constant image with respect to variations in processing temperature and processing time during development. The term "development terminating agent" as used herein means that after proper development, a base is promptly neutralized or reacted with a base to lower the concentration of the base in the film, and the development is stopped by interacting with a compound or silver and a silver salt which stop the development. It is a compound that suppresses. Specific examples thereof include an acid precursor that releases an acid when heated, an electrophilic compound that causes a substitution reaction with a coexisting base when heated, or a nitrogen-containing heterocyclic compound, a mercapto compound and a precursor thereof. More specifically, JP-A-62-253,159 (3
1) to (32).

When the light-sensitive material of the present invention is used as a heat-developable light-sensitive material, the method of supplying a base is preferably a method of generating a base from a base precursor. As the base precursor used in the present invention, a salt of an organic acid and a base that is decarboxylated by heat, a compound that decomposes by a reaction such as intramolecular nucleophilic substitution reaction, Rossen rearrangement or Beckmann rearrangement to release amines, and the like. A compound that causes a reaction to release a base and a compound that generates a base by electrolysis or a complex formation reaction are preferably used. As the former type of base precursor that generates a base by heating, a salt of trichloroacetic acid described in British Patent No. 998,959 and the like, and further improved stability are described in US Pat. No. 4,060,420. A-Sulfonyl acetic acid salt, a propiolic acid salt described in JP-A-59-180537, a 2-carboxycarbamide derivative described in US Pat. No. 4,088,496, and an organic base as a base component. Salts with thermally decomposable acids using alkali metals and alkaline earth metals (JP-A-59-195237), hydroxamum carbamates described in JP-A-59-168440 using Rossen rearrangement, and nitriles by heating. The aldoxime carbamates described in JP-A-59-157637 can be used. Others, British Patent No. 9
98,945, 2,079,480, JP-A-5
0-226,225, U.S. Pat. No. 3,220,846.
No. 4,4,514,493, 4,657,84
The base precursors described in Nos. 8 and 5 (known by Aztec Co., Ltd., March 22, 1991), pages 55-86, etc. are also useful.

Examples of the method for exposing and recording an image on the light-sensitive material of the present invention include a method of directly photographing a landscape or a person using a camera or the like, and a method of exposing through a reversal film or a negative film using a printer or an enlarger. Method, a method of scanning and exposing the original image through a slit, etc. using an exposure device of a copying machine, and scanning by emitting light from a light emitting diode, various lasers (laser diode, gas laser, etc.) via image information and electric signals. Method of exposure (Japanese Patent Application Laid-Open No. 2-129,625, Japanese Patent Application No. 3-338,
182, 4-9,388, 4-281,442
No.), image information is output to an image display device such as a CRT, a liquid crystal display, an electroluminescence display, and a plasma display, and exposed directly or through an optical system.

As a light source for recording an image on a photosensitive material,
As described above, the natural light, tungsten lamp, light emitting diode, laser light source, CRT light source, etc.
500,626, column 56, JP-A-2-53,378.
The light source and the exposure method described in No. 2-54,672 can be used. Image exposure can also be performed using a wavelength conversion element in which a non-linear optical material and a coherent light source such as laser light are combined. Here, the non-linear optical material is a material capable of expressing the non-linearity between the electric field and the electric field that appears when a strong optical electric field such as laser light is applied,
Lithium niobate, potassium dihydrogen phosphate (KDP),
Inorganic compounds represented by lithium iodate, BaB ₂ O _4, etc., urea derivatives, nitroaniline derivatives such as 3
-Methyl-4-nitropyridine-N-oxide (PO
Nitropyridine-N-oxide derivatives such as M) and the compounds described in JP-A Nos. 61-53,462 and 62-210,432 can be preferably used. As a form of the wavelength conversion element, a single crystal optical waveguide type, a fiber type and the like are known, and any of them is useful.

The image information is obtained by dividing an image signal obtained from a video camera, an electronic still camera or the like, a television signal represented by the Japanese Television Signal Standard (NTSC), or an original image into a large number of pixels such as a scanner. Image signal,
An image created by using a computer represented by CG or CAD can be used.

The couplers of the present invention can be used as couplers for hair dyes, but in particular, color negatives, color papers, color instant photographic films, photosensitive materials, photothermographic materials, color reversals or for forming color images. X
It can be preferably used for all silver halide light-sensitive materials such as a ray-sensitive material and a plate-making photosensitive material. The silver halide light-sensitive material containing the coupler of the present invention is preferably used as a color diffusion transfer silver halide photographic light-sensitive material.

When the coupler of the present invention and a color developing agent are added to a silver halide light-sensitive material, development can be carried out by heat treatment or activator treatment.

The heat treatment of a light-sensitive material is known in the art.
For example, the basics of photographic engineering (Published by Corona Publishing Company in 1979)
553 to 555, issued April 1978 Video Information 4
Page 0, Nebletts Handbook of P
photography and Reprograph
y 7th Ed. (Van No Strand an
32-33 of d Reinhold Company)
Page, U.S. Pat. Nos. 3,152,904 and 3,30.
No. 1,678, No. 3,392,020, No. 3,4
57,075, British Patents 1,131,108, 1,167,777 and Research Disclosure, June 1978, pages 9-15 (RD-1702).
9).

The activator processing is a processing method in which a color developing agent is incorporated in a light-sensitive material, and development processing is performed with a processing solution containing no color developing agent. The processing liquid in this case is characterized in that it does not contain the color developing agent contained in the usual developing processing liquid components, and may contain other components (for example, alkali, auxiliary developing agent, etc.). Regarding the activator treatment, European Patent No. 545,491A
No. 1 and No. 565,165A1 and the like. In the present invention, the "alkaline processing solution" means a processing solution containing a color developing agent and a processing solution not containing a color developing agent (activator processing solution).

Next, the processing material and processing method used in the case of the activator processing in the present invention will be described in detail. In the present invention, the light-sensitive material is subjected to development (silver development / cross oxidation of built-in color developing agent), desilvering and washing or stabilization. Also, after washing or stabilizing treatment,
In some cases, a treatment for enhancing color development such as application of alkali is also performed.

In the present invention, when a light-sensitive material is developed using an alkaline processing solution, the developer functions as a developing agent for silver halide and / or an oxidized product of a developing agent generated during silver development is incorporated into the photosensitive material. Compound that has the function of cross-oxidizing the built-in color developing agent (auxiliary developing agent)
Is preferably used. Preferably pyrazolidones,
Dihydroxybenzenes, reductones and aminophenols are used, particularly preferably pyrazolidones.

As the pyrazolidones, 1-phenyl-3
-Pyrazolidones are preferable, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4. , 4-dihydroxydimethyl-3-pyrazolidone, 1-phenyl-
5-methyl-3-pyrazolidone, 1-phenyl-5-phenyl-3-pyrazolidone, 1-p-tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-p
-Chlorophenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-2-hydroxymethyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-2-acetyl-3-pyrazolidone, 1-phenyl 2-hydroxymethyl-5-phenyl-3-pyrazolidone, 1- (2-chlorophenyl) -4-hydroxymethyl-4-methyl-3-pyrazolidone and the like.

Examples of dihydroxybenzenes include hydroquinone, chlorohydroquinone, bromhydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,5-dimethylhydroquinone,
Examples include potassium hydroquinone monosulfonate.

As the reductones, N-methyl-p-
Aminophenol, N- (a-hydroxyethyl) -p
-Aminophenol, N- (4-hydroxyphenyl)
Glycine, 2-methyl-p-aminophenol, and the like.

These compounds are usually used alone, but it is also preferable to use two or more kinds in combination in order to enhance the development and cross-oxidation activities. The amount of these compounds used in the developer is 2.5 × 10 ⁻⁴ mol / liter to 0.2 mol / l.
Liter, preferably 0.0025 mol / liter
The amount is 0.1 mol / liter, more preferably 0.001 mol / liter to 0.05 mol / liter.

In a system for forming an image by diffusion transfer of a dye using the light-sensitive material of the present invention, the light-sensitive material has a light-sensitive element and an image-receiving element (dye fixing element) which are separately coated on two supports. The form is roughly divided into a form coated on the same support. For the relationship between the light-sensitive element and the dye fixing element, the relationship with the support, and the relationship with the white reflective layer, see JP-A-61.
The relationships described in pages 58 to 59 of the specification of -147244 and column 57 of US Pat. No. 4,500,626 can be applied to the light-sensitive material of the present invention.

A typical form of a film unit in which the light-sensitive element and the image-receiving element (dye fixing element) are provided on the same support is that the image-receiving element and the light-sensitive element are laminated on one transparent support. However, the photosensitive element does not need to be peeled from the image receiving element after the transfer image is completed. More specifically, the image-receiving element is composed of at least one mordant layer (also referred to as an image-receiving layer or a dye fixing layer), and in a preferred embodiment of the light-sensitive element, a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer. A combination of emulsion layers, or a combination of green-sensitive emulsion layers, red-sensitive emulsion layers, and infrared-sensitive emulsion layers, or a combination of blue-sensitive emulsion layers, red-sensitive emulsion layers, and infrared-sensitive emulsion layers, and the above In each emulsion layer, a yellow dye image-forming compound (a dye image-forming compound containing a color developing agent of the present invention and a coupler), a magenta dye image-forming compound (a dye image-forming compound containing a color developing agent of the present invention and a coupler), and a cyan dye. An image-forming compound (a color image-forming compound of the present invention and a dye image-forming compound containing a coupler) is formed in combination. (Here, the "infrared light-sensitive emulsion layer" means 700 nm or more, especially 740 n.
An emulsion layer having photosensitivity to light of m or more. ) Each of these photosensitive emulsion layers may be divided into two or more layers if necessary. Then, between the mordant layer and the photosensitive layer or the layer containing the dye image forming compound (the dye image forming compound containing the color developing agent of the present invention and the coupler) of the present invention, titanium oxide is provided so that the transferred image can be viewed through a transparent support. A white reflective layer containing a solid pigment such as A light shielding layer may be further provided between the white reflective layer and the photosensitive layer so that the development processing can be completed in a bright place. If desired, a peeling layer may be provided at an appropriate position so that all or part of the light-sensitive element can be peeled from the image-receiving element (for example, such an embodiment is disclosed in JP-A-56-67840 and Canada). No. 674,082).

In another form in which peeling is not required, the above-mentioned photosensitive element is coated on one transparent support, a white reflective layer is coated thereon, and an image receiving layer is further laminated thereon.
An image receiving element, a white reflective layer, a peeling layer, and a photosensitive element are laminated on the same support, and as for a mode in which the photosensitive element is intentionally peeled from the image receiving element, US Pat. No. 3,730,7 is disclosed.
18 is described. On the other hand, there are roughly two representative forms in which a light-sensitive element and an image-receiving element are separately coated on two supports, one is a peeling type and the other is a peeling-free type. These will be described in detail. In a preferable embodiment of the release film unit, the support has a light-reflective layer on the back surface, and at least one image-receiving layer is coated on the surface. The photosensitive element is coated on a support having a light-shielding layer, and the photosensitive layer coating surface and the mordant layer coating surface do not face each other before the exposure is completed, but after the exposure is completed (for example, during development processing), the photosensitive layer coating is applied. It is designed so that the surface is turned over and overlaps with the coated surface of the image receiving layer.
After the transfer image is completed on the mordant layer, the light-sensitive element is rapidly separated from the image-receiving element. In a preferred embodiment of the peel-free type film unit, at least one mordant layer is coated on a transparent support, and a photosensitive element is coated on a support having a transparent or light-shielding layer. The layer coated surface and the mordant layer coated surface face each other and are superposed.

Any of the above-mentioned forms can be applied to both a method of developing with an alkali processing solution by developing an alkali processing solution and a heat development method. In the former case, however, an alkali processing solution is further contained and pressure is applied. A rupturable container (processing element) may be combined. Among others, in a peel-free type film unit in which an image receiving element and a photosensitive element are laminated on one support, this processing element is preferably arranged between the photosensitive element and a cover sheet overlaid thereon. Further, in the form in which the light-sensitive element and the image-receiving element are separately coated on the two supports, it is preferable that the processing element is disposed between the light-sensitive element and the image-receiving element at the latest during the development processing. The processing element preferably contains a light-shielding agent (such as carbon black or a dye whose color changes with pH) and / or a white pigment (such as titanium oxide) depending on the form of the film unit. Further, in a film unit of the type that develops with an alkaline processing liquid, a neutralization timing mechanism composed of a combination of a neutralization layer and a neutralization timing layer is incorporated in a cover sheet, an image receiving element, or a photosensitive element. Is preferred. A polymer mordant is preferable as the mordant used in the image receiving element and the dye fixing element described later. Here, the polymer mordant is
Examples thereof include polymers containing a tertiary amino group, polymers having a nitrogen-containing heterocyclic moiety, and polymers containing a quaternary cation group. A concrete example of this is described in JP-A-61-147244.
No. 98-100 and U.S. Pat. No. 4,500,626, columns 57-60.

The photosensitive element used in the present invention contains various additives known for use in a photothermographic element, if necessary, and layers other than the photosensitive layer, such as a protective layer, an intermediate layer, an antistatic layer and an antihalation layer. It may have a layer, a peeling layer for facilitating peeling from the dye fixing element, a matte layer and the like. As various additives, Research Disclosure, June 1978, pp. 9-15, JP-A-61-8825.
No. 6, etc., plasticizer, matting agent, sharpness improving dye, antihalation dye, surfactant, fluorescent whitening agent, anti-slip agent, antioxidant, anti-fading agent, diffusible dye trapping agent. There are additives such as. In particular, the protective layer usually contains an organic or inorganic matting agent to prevent adhesion. Further, this protective layer may contain a mordant and an ultraviolet absorber. The protective layer and the intermediate layer may each be composed of two or more layers. Further, the intermediate layer may contain a reducing agent for preventing discoloration or color mixture, an ultraviolet absorber, or a white pigment such as titanium dioxide. The white pigment may be added to the emulsion layer as well as the intermediate layer for the purpose of improving the sensitivity.

If necessary, the dye-fixing element may have a protective layer,
Auxiliary layers such as a peeling layer and a curl preventing layer can be provided. In particular, it is useful to provide a protective layer. One or more of the above layers may include a hydrophilic thermal solvent, a plasticizer, an anti-fading agent, an ultraviolet absorber, a slip agent, a matting agent, an antioxidant,
A dispersed vinyl compound for increasing dimensional stability, a surfactant, an optical brightener and the like may be included. Further, particularly in a system in which heat development and dye diffusion transfer are simultaneously carried out in the presence of a small amount of water, it is preferable that the dye-fixing element contains a base and / or a base precursor described later in order to enhance the storage stability of the light-sensitive element. Specific examples of these additives are described on pages 101 to 120 of JP-A No. 61-88256.

In the present invention, an image formation accelerator can be used in the light-sensitive element and / or the dye-fixing element.
The image-forming accelerator includes a redox reaction between a silver salt oxidizing agent and a reducing agent, formation of a dye from a dye image-forming compound containing a color developing agent of the present invention and a coupler, or decomposition of the dye or release of a diffusible dye. And the like, and the function of accelerating the transfer of the dye from the constituent layer of the light-sensitive element to the dye fixing layer.From the physicochemical function, a base or a base precursor, a nucleophilic compound, a high-boiling organic solvent, etc. It is classified into (oil), thermal solvent, surfactant, compound having interaction with silver or silver ion, and the like. However, these substance groups generally have a composite function, and usually have some of the above-mentioned accelerating effects together. Details thereof are described on pages 67 to 71 of JP-A No. 61-93451.

There are various methods for generating a base, and all the compounds used in the method are useful as a base precursor. For example, European Patent No. 0210660A2
By mixing a water-insoluble metal compound (for example, a metal salt) and a compound capable of forming a complex with a metal ion constituting the sparingly-soluble metal compound (referred to as a complex-forming compound or a complexing agent), The method of generating the light and
There is a method of generating a base by electrolysis described in No. 1-2232451. The former method is particularly effective. As the sparingly soluble metal compound, zinc, aluminum,
Examples thereof include carbonates such as calcium and barium, hydroxides and oxides. Further, regarding the complex-forming compound, for example, A. E. Martell and R. M. Smith (A.
E. Martell, RM Smith), "Critical Stability Const
ants) ", Volumes 4 and 5, Plenum Press
Press). Specifically, aminocarboxylic acids, iminodiacetic acids, pyridinecarboxylic acids, aminophosphoric acids, carboxylic acids (mono, di, tri, tetracarboxylic acids and further phosphono, hydroxy, oxo,
Compounds having substituents such as ester, amide, alkoxy, mercapto, alkylthio, phosphino), hydroxamic acids, polyacrylates, polyphosphoric acids, etc., and salts with alkali metals, guanidines, amidines, quaternary ammonium salts, etc. To be

The poorly soluble metal compound and complex-forming compound are advantageously added separately to the light-sensitive element and the dye-fixing element. In the light-sensitive element and / or the dye-fixing element of the present invention, various development terminators can be used for the purpose of always obtaining a constant image against variations in processing temperature and processing time during development. The term "development terminating agent" as used herein means that after proper development, a base is promptly neutralized or reacted with a base to lower the concentration of the base in the film, and the development is stopped by interacting with a compound or silver and a silver salt which stop the development. It is a compound that suppresses. Specific examples thereof include acid precursors that release an acid upon heating, electrophilic compounds that undergo a substitution reaction with a coexisting base upon heating, or nitrogen-containing heterocyclic compounds, mercapto compounds and precursors thereof (for example, JP-A- 60-108837, 60-192939, 60-230133 or 60-230134, etc.). Also,
A compound which releases a mercapto compound when heated is also useful, and for example, JP-A-61-167851 and JP-A-61-14.
No. 7244, No. 61-124941, No. 61-185.
No. 743, No. 61-182039, No. 61-1857.
No. 44, No. 61-184539, No. 61-18854.
There are compounds described in No. 0 and No. 61-53632.

A hydrophilic binder can be used as the binder of the photosensitive element and / or the dye fixing element of the present invention. Typical hydrophilic binders are transparent or translucent hydrophilic binders, and examples thereof include proteins such as gelatin and gelatin derivatives, natural substances such as cellulose derivatives and starch, and polysaccharides such as gum arabic, and polyvinylpyrrolidone. , Synthetic polymer materials such as water-soluble polyvinyl compounds such as acrylamide polymers. It is also possible to use a dispersed vinyl compound which is used in the form of a latex and which increases the dimensional stability of the photographic material. These binders can be used alone or in combination.
In the present invention, the binder is applied in an amount of 20 g or less per 1 m ² , preferably 10 g or less, and more preferably 7 g or less. The ratio of the high-boiling organic solvent dispersed in the binder together with the color developing agent of the present invention and a hydrophobic compound such as a coupler to the binder is 1
The solvent is suitably 1 ml or less, preferably 0.5 ml or less, and more preferably 0.3 ml or less. The constituent layers (photographic emulsion layer, dye fixing layer, etc.) of the light-sensitive element and / or dye fixing element of the present invention may contain an inorganic or organic hardener. Specific examples of the hardener are disclosed in JP-A-61-161.
No. 147244, pages 94 to 95 and Japanese Patent Laid-Open No. Sho 5
No. 9-157636, page 38,
These can be used alone or in combination.

In order to promote dye transfer, a hydrophilic thermal solvent that is solid at room temperature and dissolves at high temperature may be incorporated in the photosensitive element or the dye fixing element. The hydrophilic thermal solvent may be incorporated in either the photosensitive element or the dye fixing element, or may be incorporated in both. The layer to be incorporated may be any of an emulsion layer, an intermediate layer, a protective layer and a dye fixing layer,
It is preferably incorporated in the dye fixing layer and / or the adjacent layer. Examples of hydrophilic thermal solvents include ureas, pyridines, amides, sulfonamides, benzamides,
There are imides, alcohols, oximes and other heterocycles. Phenolic hot solvents are also useful. Also,
A high-boiling organic solvent may be contained in the light-sensitive element and / or the dye-fixing element in order to promote dye transfer. The support used in the light-sensitive element and / or the dye-fixing element of the present invention can withstand the processing temperature. As a general support, not only glass, paper, polymer film, metal and its analogs are used, but also 95 to 9 of JP-A-61-147244.
What is described as a support on page 6 can be used.
The light-sensitive element and / or the dye-fixing element may be in a form having a conductive heating element layer as a heating means for heat development or dye transfer. In this case, the transparent or opaque heating element can be manufactured by using a conventionally known technique as a resistance heating element. As the resistance heating element, there are a method of using a thin film of a semiconductive inorganic material and a method of using an organic thin film in which conductive fine particles are dispersed in a binder. Materials usable in these methods are disclosed in JP-A-61 / 1986.
-29835 specification etc. can be utilized.

In the present invention, the photothermographic layer, the protective layer,
The coating method of the intermediate layer, undercoat layer, back layer, dye fixing layer and other layers is described in US Pat. No. 4,500,626, Nos. 55-5.
The method described in column 6 can be applied. Radiation containing visible light can be used as a light source for image exposure for recording an image on the photosensitive element. In general, light sources used for ordinary color printing, such as tungsten lamps, mercury lamps, halogen lamps such as iodine lamps, xenon lamps, laser light sources, CRT light sources, light emitting diodes (L
ED) and the like, the light sources described on page 100 of JP-A-61-147244 and column 56 of US Pat. No. 4,500,626 can be used. In the image forming method having the heating step to which the present invention is applied, for example, the steps of heat development and dye transfer may be independent or simultaneous. Further, it may be continuous in the sense that development is followed by transfer in one step. For example, (1) a method in which a photosensitive element is imagewise exposed and heated, and then a dye fixing element is overlaid, and when necessary, a movable dye is transferred to the dye fixing element, and (2) a photosensitive element is imagewise exposed. However, there is a method in which the dye fixing elements are stacked and heated. Above (1), (2)
The method (1) can be carried out in the substantial absence of water, or can be carried out in the presence of a trace amount of water. The heating temperature in the heat development step is about 50 ° C. to about 250 ° C., and development is possible, but 70 ° C. to 180 ° C. is particularly useful and 75 ° C.
~ 150 ° C is particularly useful. When heating in the presence of a trace amount of water, the upper limit of the heating temperature is the boiling point or lower. When the transfer step is performed after the heat development step, the heating temperature in the transfer step can be transferred in the range from the temperature in the heat development step to room temperature, but it is lower than the temperature in the heat development step by about 10 ° C. especially at 50 ° C. or higher. Up to temperature is more preferred.

[0149]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. Example 1 First, a method for preparing silver halide will be described.

Preparation of Emulsion-T (Hexagonal tabular internal latent image type direct positive emulsion): 0.05 M potassium bromide in 1.2 liter gelatin aqueous solution containing 0.7% by weight of gelatin having an average molecular weight of 100,000 or less. In addition, 1.4 containing the above gelatin
33 ml of each was simultaneously mixed by the double jet method for 1 minute while vigorously stirring the M silver nitrate aqueous solution and the 2M potassium bromide aqueous solution. During this period, the gelatin aqueous solution was kept at 30 ° C. Furthermore, 300 ml of a gelatin solution containing 10% by mass of deionized gelatin having a Ca content of 100 ppm or less was added, and the temperature was raised to 75 ° C. Next, 40 ml of 0.9 M silver nitrate aqueous solution
Was added over 3 minutes, 25% by mass aqueous ammonia solution was added, and aging was performed at 75 ° C. After completion of aging, after neutralizing ammonia, 5 mg of lead acetate (added in an aqueous solution) was added, and a 1 M silver nitrate aqueous solution and a 1 M potassium bromide aqueous solution were accelerated while maintaining a pBr of 2.5 (at the time of completion). (6 times the flow rate at the start) was added by the double jet method (the amount of silver nitrate aqueous solution used was 500 ml).

The particles thus formed (hereinafter referred to as core particles) were washed with water by a conventional flocculation method, and gelatin, 2-phenoxyethanol and methyl p-hydroxybenzoate were added thereto to obtain 750 g of hexagonal tabular form. Core particles were obtained. The obtained hexagonal tabular core particles have an average projected area circle-equivalent diameter of 0.9 μm and an average thickness of 0.20.
The hexagonal tabular grains accounted for 95% of the total projected area of the silver halide grains in the emulsion.

The core chemical sensitization was carried out under the following conditions. 1. Tank: Teflon (registered trademark) -coated hemispherical bottom shape with a metal surface coated with a fluororesin material FEP (trade name) developed by Du Pont with a thickness of 120 μm. 2. Stirrer: A seamless propeller type with a Teflon coated metal surface.

200 g of the above hexagonal tabular core emulsion was mixed with 13 parts of water.
00 ml, potassium bromide 0.11M and deionized gelatin 4
After adding 0 g and raising the temperature to 75 ° C., 3,6-dithia-
0.3 g of 1,8-octanediol, 10 mg of sodium benzenethiosulfate, 2.4 ml of an aqueous solution prepared by dissolving 90 mg of potassium tetrachloroaurate and 1.2 g of potassium bromide in 1000 ml of water, and 15 mg of lead acetate (added as an aqueous solution) Was added and the mixture was heated at 75 ° C. for 180 minutes for chemical sensitization. In the same manner as when the core particles were prepared, the core particles thus chemically sensitized were mixed with a 2M silver nitrate aqueous solution and 2.
Double jet of 5M aqueous potassium bromide solution at an accelerated flow rate (flow rate at the end is 3 times the flow rate at the start) while adjusting the addition rate of the aqueous potassium bromide solution so that the pBr is 2.2. Method (the amount of silver nitrate aqueous solution used was 810 ml).

After adding 0.3 M potassium bromide, this emulsion was washed with water by a conventional flocculation method and gelatin was added. Thus, a hexagonal tabular internal latent image type core / shell emulsion was obtained. The obtained hexagonal tabular grains had an average projected area circle-equivalent diameter of 2.0 μm, an average thickness of 0.38 μm, and an average volume size of 1.3 μm ³ , and had a total projected area of silver halide grains in the emulsion. 88% was occupied by hexagonal tabular grains. Next, 10 parts of sodium thiosulfate was added to the hexagonal tabular internal latent image type core / shell emulsion.
Add 15 mg of an aqueous solution of 0 mg and 40 mg of sodium tetraborate in 1000 ml of water, and further add 20 mg of poly (N-vinylpyrrolidone), and chemically sensitize the surface of the grain by heating at 70 ° C for 100 minutes. Internal latent image type direct positive emulsion was prepared.

Using this emulsion T, a comparative photosensitive element (Sample 101) having the constitution shown in Tables 1 and 2 below was prepared. The sensitizing dyes are shown in Table 3 below at the end of the shell chemical sensitization.
The pigment type, dispersion form, addition temperature, and amount shown in 1 were added.

[0156]

[Table 1]

[0157]

[Table 2]

[0158]

[Table 3]

[0159]

[Chemical 21]

[0160]

[Chemical formula 22]

[0161]

[Chemical formula 23]

[0162]

[Chemical formula 24]

[0163]

[Chemical 25]

[0164]

[Chemical formula 26]

[0165]

[Chemical 27]

[0166]

[Chemical 28]

[0167]

[Chemical 29]

[0168]

[Chemical 30]

[0169]

[Chemical 31]

[0170]

[Chemical 32]

Preparation of cover sheet A cover sheet was prepared by coating a transparent support having a thickness of 75 μm in a layer structure as shown in Table 4.

[0172]

[Table 4]

The chemical structural formulas and the like of the compounds used in the cover sheet are shown below.

[0174]

[Chemical 33]

[0175]

[Chemical 34]

The formulation of the alkaline treatment composition is shown below.   Silver nitrate 0.10g   Carbon black (manufactured by Dainichiseika Co., Ltd.) 160 g   Additive (27) 8.60g   Carboxymethyl cellulose Na salt 58.0 g   Benzyl alcohol 2.50g   Additive (28) 2.10g   1.90 g of potassium sulfite (anhydrous)   2.50 g of 5-methylbenzotriazole   1-p-tolyl-4-hydroxymethyl-4-methyl     -3-pyrazolidone 7.00 g   Potassium hydroxide 56.0 g   Aluminum nitrate 0.60g   Zinc nitrate 0.60g   Additive (29) 6.60g   Additive (14) 1.80g   1,2-benzisothiazolin-3-one 0.003 g

[0177]

[Chemical 35]

Preparation of Photosensitive Materials 102 to 111 The same procedure was followed except that the coupler (EXCp-1) and color developing agent (R-6) in the seventh layer of Photosensitive Material 101 were replaced with the compounds shown in Table 5 in equimolar amounts. Photosensitive materials 102 to 111 were prepared. Then, after exposing the light-sensitive elements 101 to 111 from the emulsion layer side through a continuous gray wedge, they are superposed on the cover sheet, and a pressure roller is applied between the both materials so that the alkali treatment composition has a thickness of 55 μm. Deployed using. The treatment was carried out at 25 ° C., and after 2 hours, the transfer density was measured with a full-color densitometer to measure the maximum image density of magenta. Further, the photosensitive materials 101 to 111 are 6
After leaving for 1 week under a thermo condition of 0 ° C. and 55%, the same processing was performed, the transfer density was measured by a full color densitometer, and the maximum image density of magenta was measured. The measurement results are shown in Table 5.

[0179]

[Table 5]

As is clear from Table 5, the coupler of the present invention has a high maximum image density and is excellent in color development. Further, the maximum image density after storage is also high, which shows that the compound of the present invention is excellent in storage stability.

Example 2 First, a method for preparing a silver halide emulsion will be described. The following eight kinds of silver halide emulsion grains (Emulsion-A to Emulsion-F) and Emulsion-T are prepared by the following emulsion grain preparation methods.
U was prepared.

Preparation of Emulsion-A (octahedral internal latent image type direct positive emulsion): 0.05M potassium bromide, 1 g of 3,6-dithia-1,8-octanediol, 0.034 mg of lead acetate.
And deionized gelatin with Ca content of 100ppm or less
In 1000 ml of gelatin aqueous solution containing g, the temperature is adjusted to 7
While maintaining the temperature at 5 ° C., a 0.4 M silver nitrate aqueous solution and a 0.4 M potassium bromide aqueous solution are controlled by a double jet method while controlling the addition rate of the potassium bromide aqueous solution so that the pBr becomes 1.60, and the silver nitrate aqueous solution 300 ml Was added over 40 minutes. When the addition was completed, octahedral silver bromide crystals (hereinafter referred to as core particles) having a uniform particle size with an average particle size (sphere equivalent diameter) of about 0.7 μm were produced.

Next, the core chemical sensitization was carried out under the following conditions. 1. Tank: Teflon coated with a thickness of 120 μm on the metal surface of the fluororesin material FEP developed by Du Pont. 2. Stirrer: A seamless propeller type with a Teflon coated metal surface.

Sodium thiosulfate 1 was added to the preparation liquid of Emulsion-A.
mg, and 90 mg of potassium tetrachloroaurate and potassium bromide 1.
Add 3 ml of an aqueous solution prepared by dissolving 2 g in 1000 ml of water, and add 75
The chemical sensitization treatment was performed by heating at 80 ° C. for 80 minutes. 0.1 to the emulsion solution chemically sensitized in this way
After adding 5M potassium bromide, 0.9M silver nitrate aqueous solution and 0.9M potassium bromide aqueous solution were controlled to have a pBr of 1. While adjusting the addition rate of the potassium bromide aqueous solution so as to be 30, the silver nitrate aqueous solution 6
70 ml was added over 70 minutes. This emulsion was washed with water by a conventional flocculation method, and the above-mentioned gelatin, 2-phenoxyethanol and methyl p-hydroxybenzoate were added to obtain a uniform particle size with an average particle size (sphere equivalent diameter) of about 1.2 μm. Further, octahedral silver bromide crystals (hereinafter referred to as internal latent image type core / shell grains) were obtained.

Next, 100 mg of sodium thiosulfate and 40 mg of sodium tetraborate were added to this internal latent image type core / shell emulsion.
Was added to 1000 ml of water, and 3 ml of an aqueous solution was added.
An octahedral internal latent image type direct positive emulsion was prepared by adding mg of poly (N-vinylpyrrolidone), heating and ripening at 60 ° C., and then adding 0.005M potassium bromide.

Preparation of Emulsions B to F (octahedral internal latent image type direct positive emulsion): In the preparation method of Emulsion A, the addition time of the aqueous solution of silver nitrate and the aqueous solution of potassium bromide was changed, and further the amount of chemicals added was changed. This was carried out to obtain an octahedral internal latent image type direct positive silver halide emulsion having an average grain size (equivalent sphere diameter) shown in Table 6 with a uniform grain size.

[0187]

[Table 6]

Preparation of emulsion-T (hexagonal tabular internal latent image type direct positive emulsion): 0.05M potassium bromide in 1.2 liters of gelatin aqueous solution containing 0.7% by weight of gelatin having an average molecular weight of 100,000 or less. In addition, 1.4 containing the above gelatin
33 ml of each was simultaneously mixed by the double jet method for 1 minute while vigorously stirring the M silver nitrate aqueous solution and the 2M potassium bromide aqueous solution. During this period, the gelatin aqueous solution was kept at 30 ° C. Furthermore, 300 ml of a gelatin solution containing 10% by mass of deionized gelatin having a Ca content of 100 ppm or less was added, and the temperature was raised to 75 ° C. Next, 40 ml of 0.9 M silver nitrate aqueous solution
Was added over 3 minutes, 25% by mass aqueous ammonia solution was added, and aging was performed at 75 ° C. After completion of aging, after neutralizing ammonia, 5 mg of lead acetate (added in an aqueous solution) was added, and a 1 M silver nitrate aqueous solution and a 1 M potassium bromide aqueous solution were accelerated while maintaining a pBr of 2.5 (at the time of completion). (6 times the flow rate at the start) was added by the double jet method (the amount of silver nitrate aqueous solution used was 500 ml).

The particles thus formed (hereinafter referred to as core particles) were washed with water by a conventional flocculation method, and gelatin, 2-phenoxyethanol and methyl p-hydroxybenzoate were added thereto to obtain 750 g of hexagonal tabular form. Core particles were obtained. The obtained hexagonal tabular core particles have an average projected area circle-equivalent diameter of 0.9 μm and an average thickness of 0.20.
.mu.m, and 95% of the total projected area was occupied by hexagonal tabular grains.

Next, the core chemical sensitization was performed under the following conditions. 1. Tank: Teflon coated with a thickness of 120 μm on the metal surface of the fluororesin material FEP developed by Du Pont. 2. Stirrer: A seamless propeller type with a Teflon coated metal surface.

200 g of the hexagonal tabular core emulsion was mixed with 13 parts of water.
00 ml, potassium bromide 0.11M and deionized gelatin 4
After adding 0 g and raising the temperature to 75 ° C., 3,6-dithia-
0.3 g of 1,8-octanediol, 10 mg of sodium benzenethiosulfate, 2.4 ml of an aqueous solution prepared by dissolving 90 mg of potassium tetrachloroaurate and 1.2 g of potassium bromide in 1000 ml of water, and 15 mg of lead acetate (added as an aqueous solution) Was added and the mixture was heated at 75 ° C. for 180 minutes for chemical sensitization. In the same manner as when the core particles were prepared, the core particles thus chemically sensitized were mixed with a 2M silver nitrate aqueous solution and 2.
Double jet of 5M aqueous potassium bromide solution at an accelerated flow rate (flow rate at the end is 3 times the flow rate at the start) while adjusting the addition rate of the aqueous potassium bromide solution so that the pBr is 2.2. Method (the amount of silver nitrate aqueous solution used was 810 ml).

After adding 0.3 M potassium bromide, this emulsion was washed with water by a conventional flocculation method and gelatin was added. Thus, a hexagonal tabular internal latent image type core / shell emulsion was obtained. The obtained hexagonal tabular grains had an average projected area circle-equivalent diameter of 2.0 μm, an average thickness of 0.38 μm, and an average volume size of 1.3 μm ³ , and had a total projected area of silver halide grains in the emulsion. 88% was occupied by hexagonal tabular grains. Next, 10 parts of sodium thiosulfate was added to the hexagonal tabular internal latent image type core / shell emulsion.
Add 15 mg of an aqueous solution of 0 mg and 40 mg of sodium tetraborate in 1000 ml of water, and further add 20 mg of poly (N-vinylpyrrolidone), and chemically sensitize the surface of the grain by heating at 70 ° C for 100 minutes. Internal latent image type direct positive emulsion was prepared.

Preparation of Emulsion-U (Hexagonal tabular internal latent image type direct positive emulsion): When the outer shell of Emulsion-T was formed, 0.15 mol% of iodine was uniformly added, and the outer shell formation amount was further increased. By increasing, a hexagonal tabular core / shell emulsion was obtained. The hexagonal tabular grains have an average projected area circle equivalent diameter of 2.5.
The average grain size was 0.45 μm, the average volume size was 1.7 μm ³ , and 88% of the total projected area of the silver halide grains in the emulsion was occupied by hexagonal tabular grains. Next, this hexagonal tabular internal latent image type core / shell emulsion had a silver content of 0.
After adding AgI fine grain emulsion-X corresponding to 04 mol%, the same shell chemical sensitization as in Emulsion-T was performed to prepare a hexagonal tabular internal latent image type direct positive emulsion.

Preparation of emulsion-X (AgI fine grain emulsion) 0.5 g of potassium iodide and 26 g of gelatin were added to water and stirred into a solution kept at 35 ° C., while stirring, 80 ml of a silver nitrate aqueous solution containing 40 g of silver nitrate and 39 g of iodine. 80 ml of an aqueous solution containing potassium iodide was added over 5 minutes. At this time, the addition flow rates of the aqueous silver nitrate solution and the potassium iodide solution were each 8 ml / min at the start of the addition, and the addition flow rates were linearly accelerated so that the addition of 80 ml was completed in 5 minutes. After the formation of particles was completed in this way, soluble salts were removed by a precipitation method at 35 ° C. Next, the temperature was raised to 40 ° C., 10.5 g of gelatin and 2.56 g of phenoxyethanol were added, and the pH was adjusted to 6.8 with a caustic soda. The resulting emulsion has a finished amount of 73
It was a monodisperse AgI fine particle having an average diameter of 0.015 μm at 0 g.

The following emulsions AF, T, and U were used to prepare photosensitive elements (Sample 2) having the constitutions shown in Tables 7 to 10 below.
01) was created. Incidentally, the sensitizing dyes, when the shell chemical sensitization is completed, the dye species, dispersion form, addition temperature,
Added in quantity.

[0196]

[Table 7]

[0197]

[Table 8]

[0198]

[Table 9]

[0199]

[Table 10]

[0200]

[Table 11]

[0201]

[Chemical 36]

[0202]

[Chemical 37]

[0203]

[Chemical 38]

[0204]

[Chemical Formula 39]

[0205]

[Chemical 40]

[0206]

[Chemical 41]

[0207]

[Chemical 42]

[0208]

[Chemical 43]

[0209]

[Chemical 44]

[0210]

[Chemical formula 45]

Using the same cover sheet and alkaline composition as used in Example 1, the same treatment as in Example 1 was performed, and then the concentration was measured. As a result, it was found that even in the above light-sensitive element, the coupler of the present invention was excellent in color forming property and high maximum image density after storage.

Example 3 2-Amidonaphthol Coupler of the Present Invention (Exemplified Compound C
-30, C-32, C-37, C-24, C-37) was used in place of the compound (4) in the method described in JP-A 13-42485 and Example 1, Good results were obtained as in Nos. 1 and 2.

[0213]

The 2-amide naphthol coupler of the present invention has a high maximum image density and is excellent in color development. Further, the storage stability is excellent, and a high maximum image density can be obtained even after the light-sensitive material containing the coupler is stored at a high temperature for a long time.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Nobutaka Fukagawa             Fuji Photo, 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture             Within Film Co., Ltd. F term (reference) 2H016 BF00 BK00 BK02 BK03                 4C055 AA01 BA01 CA01 DA58 DB04                       DB08                 4H006 AA01 AB84 AB99

Claims (7)

[Claims] 1. A 2-amidonaphthol coupler represented by the following general formula (1). [Chemical 1] In the general formula (1), R ¹ is a hydrogen atom, an aminocarbonylamino group, an acylamino group, a benzoylamino group,
Sulfonylamino group, alkoxycarbonylamino group,
Alternatively, it represents an aryloxycarbonylamino group. R ²
Represents a substituent having a Hammett's σp value of 0.1 or more. L
Represents a coupling-off group having a formula weight of 250 or more. R ³ represents a substituent, and m represents an integer of 0 to 4. 2. The 2-amidonaphthol coupler according to claim 1, wherein R ² in the general formula (1) is an aryl group or a heteroaryl group having a Hammett's σp value of 0.2 or more. 3. The 2-amidonaphthol coupler according to claim 1 or 2, wherein L in the general formula (1) is an aryloxy group. 4. A silver halide color photographic light-sensitive material containing the 2-amidonaphthol coupler according to claim 1. 5. An image forming method, which comprises developing the silver halide color photographic light-sensitive material according to claim 4 with an alkali processing liquid. 6. An image forming method, comprising thermally developing the silver halide color photographic light-sensitive material according to claim 4. 7. An image forming method, wherein the silver halide color photographic light-sensitive material according to claim 6 is subjected to heat development under the generation of an alkali by a sparingly soluble metal salt and a complexing agent of the metal salt.