JP2000284443A - Color developing agent, silver halide photographic sensitive material and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form an image with sufficiently developed colors during development, having excellent picture quality and excellent storage property of the image by incorporating a specified color developing agent. SOLUTION: At least one hydrophilic colloidal layer formed on a supporting body contains at least one kind of color developing agent expressed by the formula. In the formula, X is a halogen atom, alkylthio group, alkylsulfinyl group, alkylsulfonyl group, arylthio group or the like, however, the substituents for X do not include hydroxy group, carboxyl group, mercapto group, aminosulfonyl group, carbonylamino sulfonyl group, sulfonylamino group or sulfonylaminocarbonyl group, Z is a carbamoyl group, acyl group, alkoxycarbonyl group or aryloxycarbonyl group, and Z is preferably a carbamoyl group with one or more hydrogen atoms coupled to the nitrogen atom on the carbamoyl group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel color developing agent, a silver halide photographic material using the same, and an image forming method. In particular, the present invention relates to a silver halide photographic material having good color development during development. The present invention relates to a photosensitive material and an image forming method.

[0002]

2. Description of the Related Art In a color photographic light-sensitive material, after the material is exposed to light and color-developed, an oxidized color-developing agent reacts with a coupler to form an image.
Color development is achieved, for example, by immersing the exposed photosensitive material in an aqueous alkaline solution (developing solution) in which a color developing agent is dissolved. However, there are many problems, such as the fact that the developer tends to deteriorate with time and the problem of waste liquid treatment of the used developer.

As a method for solving these problems, there has been proposed a method of incorporating an aromatic primary amine developing agent or a precursor thereof into a hydrophilic colloid layer of a photosensitive material.
A method has also been proposed in which a sulfonylhydrazine-type developing agent is incorporated in a hydrophilic colloid layer. Examples of these are disclosed in U.S. Pat. No. 803783, Japanese Patent Publication No. 58-14.
No. 671, etc .;
No. 1 and No. 565165A1. However, even with these methods, sufficient color formation was not obtained at the time of development, or there was a problem in storage stability.

In the field of silver halide photographic light-sensitive materials, a so-called color diffusion transfer method for forming a color image by forming a diffusible dye imagewise on the light-sensitive material, and transferring and fixing the same to an image-receiving material is known. A known technique,
Many proposals have been made in this regard. Since these methods generally use a compound (hereinafter, referred to as a coloring material) in which a pre-colored image forming dye (preformed dye) is made non-diffusible, if the coloring material is added to the same layer as the silver halide emulsion, Due to the filtering effect of the dye moieties, a reduction in sensitivity to unwanted exposure is caused. As a method for improving these disadvantages, a so-called coupling system in which a dye is formed by a coupling reaction between an oxidized developing agent and a coupler is disclosed in U.S. Pat. No. 4,469,773.
JP-B-63-36487 proposes that the color-developing agents described therein have difficulty in satisfying both storage stability and the activity of the coupling reaction, or have the effect of making both the color-developing agent and the coupler resistant to diffusion. Was difficult.

[0005] Japanese Patent Application Laid-Open No. 09-152702,
No. 9-152705 proposes a novel color developing agent. However, the methods described therein are not yet sufficient with regard to the color developing property, or are there problems with the hue and color image stability of the dye formed? No mention is made of the color image stability of the formed dye or the like.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a novel color developing agent which is capable of obtaining a sufficient color at the time of development, providing an image excellent in image quality and excellent in image storability. An object of the present invention is to provide a silver halide photographic light-sensitive material to be formed and an image forming method.

[0007]

It has been found that the object of the present invention is achieved by the following means. That is, the present invention provides (1) a color developing agent represented by the following general formula (1),

Embedded image (Wherein X is a halogen atom, an alkylthio group, an alkylsulfinyl group, an alkylsulfonyl group, an arylthio group, an arylsulfinyl group, an arylsulfonyl group,
Or a sulfamoyl group. However, the substituent that can be further substituted on X does not include a hydroxy group, a carboxyl group, a mercapto group, an aminosulfonyl group, a carbonylaminosulfonyl group, a sulfonylamino group, and a sulfonylaminocarbonyl group. Z represents a carbamoyl group, an acyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group. (2) The general formula (1), wherein Z is a carbamoyl group and is a carbamoyl group in which one or more hydrogen atoms are bonded to a nitrogen atom on the carbamoyl group. Color developing agent, (3) at least one of the color developing agents represented by the general formula (1) described in the item (1) is contained in at least one hydrophilic colloid layer provided on the support. A silver halide photographic light-sensitive material; (4) an image forming method comprising thermally developing the silver halide photographic light-sensitive material according to item (3);
(5) An image forming method, wherein the silver halide photographic light-sensitive material according to the item (3) is developed in the presence of a metal salt which is hardly soluble in water and a complexing agent for the metal salt to generate alkali. (6) An image forming method characterized in that the color diffusion transfer silver halide photographic material described in (3) is developed by developing an alkaline processing solution.

[0008]

Next, the compound represented by formula (1) used in the present invention will be described in detail. In the general formula (1), X is a halogen atom (eg, a chlorine atom, a bromine atom, etc.), an alkylthio group which may have a substituent (eg, a methylthio group, an ethylthio group, a cyanomethylthio group, etc.), a substituent Alkylsulfinyl group which may have (for example, methanesulfinyl group,
Ethanesulfinyl group, etc.), optionally substituted alkylsulfonyl group (eg, methanesulfonyl group, ethanesulfonyl group, benzylsulfonyl group, etc.), and optionally substituted arylthio group (eg, phenylthio group) , Naphthylthio group, 4-methoxyphenylthio group, etc.), optionally substituted arylsulfinyl group (eg, benzenesulfinyl group, naphthalenesulfinyl group, etc.), optionally substituted arylsulfonyl group (For example, benzenesulfonyl group, p-toluenesulfonyl group, p-methanesulfonylbenzenesulfonyl group, etc.), sulfamoyl group which may have a substituent (N, N-disubstituted sulfamoyl group, for example, N, N- Diethylsulfamoyl group, etc.)
Represents These preferably have 1 to 50 carbon atoms, and more preferably 1 to 20 carbon atoms.

Of these, a halogen atom, an alkylthio group, an alkylsulfonyl group, an arylthio group and an arylsulfonyl group are preferred. These may have a substituent.

Z represents a carbamoyl group, an acyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group. Of these, a carbamoyl group is preferable, and a carbamoyl group having one or two, more preferably one hydrogen atom on a nitrogen atom is particularly preferable. The carbamoyl group is preferably a carbamoyl group having 1 to 50 carbon atoms, more preferably 8 to 40 carbon atoms. Specific examples include a hexadecylcarbamoyl group, an octadecylcarbamoyl group, a 3- (2,4-di-tert-pentylphenoxy) propylcarbamoyl group, a 4-dodecyloxyphenylcarbamoyl group, and a 2-chloro-5-dodecyloxy group. A carbonylphenylcarbamoyl group and a naphthylcarbamoyl group.

Preferred examples of the substituent described above include:
Cyano group, carboxyl group, sulfo group, hydroxy group,
Nitro group, mercapto group, halogen atom (fluorine atom,
A chlorine atom, a bromine atom, an iodine atom, an alkyl group (an alkyl group having 30 or less carbon atoms, preferably an alkyl group having 8 or less carbon atoms, for example, a methyl group, a trifluoromethyl group, a benzyl group, a dimethylaminomethyl group) , Ethoxycarbonylmethyl group, acetylaminomethyl group, ethyl group, carboxyethyl group, allyl group, n-propyl group,
iso-propyl group, n-butyl group, t-butyl group, t
-Pentyl group, cyclopentyl group, n-hexyl group, t
-Hexyl group, cyclohexyl group, t-octyl group, n
-Decyl group, n-undecyl group, n-dodecyl group, etc.), aryl group (optionally substituted aryl group having 30 or less carbon atoms, preferably 10 or less carbon atoms, for example, phenyl group, naphthyl group, 3- Hydroxyphenyl group, 3-
Chlorophenyl group, 4-acetylaminophenyl group, 2
A methanesulfonylphenyl group, a 4-methoxyphenyl group, a 4-methanesulfonylphenyl group, a 2,4-dimethylphenyl group, etc.), a heterocyclic residue (having 30 or less carbon atoms,
An optionally substituted heterocyclic residue having preferably 10 or less carbon atoms. For example, 1-imidazolyl group, 2-furyl group, 2-
Pyridyl group, 3-pyridyl group, 3,5-dicyano-2-
Pyridyl group, 5-tetrazolyl group, 5-phenyl-1-
A tetrazolyl group, a 2-benzothiazolyl group, a 2-benzimidazolyl group, a 2-benzoxazolyl group, a 2-oxazolin-2-yl group, a morpholino group, etc., an acyl group (having 20 or less carbon atoms, preferably 8 or less carbon atoms) Which may be substituted, for example, acetyl, propionyl, butyroyl, iso-butyroyl, 2,2-dimethylpropionyl, benzoyl, 3,4-dichlorobenzoyl, 3-acetylamino-4 -Methoxybenzoyl group, 4-methylbenzoyl group, etc.), sulfonyl group (optionally substituted sulfonyl group having 20 or less carbon atoms, preferably 8 or less carbon atoms, for example, methanesulfonyl group, ethanesulfonyl group, chloromethanesulfonyl group) ,
Propanesulfonyl group, butanesulfonyl group, n-octanesulfonyl group, n-dodecanesulfonyl group, benzenesulfonyl group, 4-methylphenylsulfonyl group, etc.),

An alkoxy group (optionally substituted alkoxy group having 20 or less carbon atoms, preferably 8 or less carbon atoms; for example, methoxy group, ethoxy group, n-propyloxy group,
an iso-propyloxy group, a cyclohexylmethoxy group, etc.), an aryloxy group, or a heteroaryloxy group (an optionally substituted aryloxy group or a heteroaryloxy group having 20 or less carbon atoms, preferably 10 or less carbon atoms) For example, phenoxy, naphthyloxy, 4-acetylaminophenoxy, pyrimidine-
2-yloxy group, 2-pyridyloxy group, etc., silyloxy group (optionally substituted silyloxy group having 10 or less carbon atoms, preferably 8 or less carbon atoms, for example, trimethylsilyloxy group, tert-butyldimethylsilyloxy group) ), An alkylthio group (having 20 or less carbon atoms,
An optionally substituted alkylthio group preferably having 8 or less carbon atoms. For example, methylthio, ethylthio, n-butylthio, n-octylthio, t-octylthio,
Ethoxycarbonylmethylthio, benzylthio, 2
-Hydroxyethylthio group, etc.), arylthio group or heteroarylthio group (optionally substituted arylthio or heteroarylthio group having 20 or less carbon atoms, preferably 10 or less carbon atoms. For example, phenylthio group, 4- Chlorophenylthio group, 2-n-butoxy-5
-T-octylphenylthio group, 4-nitrophenylthio group, 2-nitrophenylthio group, 4-acetylaminophenylthio group, 1-phenyl-5-tetrazolylthio group, 5-methanesulfonylbenzothiazol-2-yl group Carbamoyl group (optionally substituted carbamoyl group having 20 or less carbon atoms, preferably 8 or less carbon atoms. For example, carbamoyl group, methylcarbamoyl group, dimethylcarbamoyl group, bis- (2-methoxyethyl) carbamoyl group, A diethylcarbamoyl group, a cyclohexylcarbamoyl group, a di-n-octylcarbamoyl group, etc., a sulfamoyl group (an optionally substituted sulfamoyl group having 20 or less carbon atoms, preferably 8 or less carbon atoms, for example, a sulfamoyl group, methylsulfamoyl) Group, dimethyl sulfamoi Group, bis- (2-methoxyethyl) sulfamoyl group, diethylsulfamoyl group, di-n-butylsulfamoyl group, methyl-n-octylsulfamoyl group, 3-ethoxypropylmethylsulfamoyl group, N -Phenyl-N-methylsulfamoyl group),

Acylamino group (optionally substituted acylamino group having 20 or less carbon atoms, preferably 8 or less carbon atoms;
For example, an acetylamino group, a 2-carboxybenzoylamino group, a 3-nitrobenzoylamino group, a 3-diethylaminopropanoylamino group, an acryloylamino group, etc., a sulfonylamino group (having 20 or less carbon atoms, preferably having 8 or less carbon atoms) A sulfonylamino group which may be substituted, for example, a methanesulfonylamino group, a benzenesulfonylamino group, a 2-methoxy-5-n-methylbenzenesulfonylamino group, an alkoxycarbonylamino group (having 20 or less carbon atoms, preferably An optionally substituted alkoxycarbonylamino group of the number 8 or less, for example, a methoxycarbonylamino group, an ethoxycarbonylamino group, a 2-methoxyethoxycarbonylamino group,
iso-butoxycarbonylamino group, benzyloxycarbonylamino group, t-butoxycarbonylamino group, 2-cyanoethoxycarbonylamino group, etc., alkoxycarbonyloxy group (having 20 or less carbon atoms, preferably having 8 or less carbon atoms) An alkoxycarbonyloxy group such as a methoxycarbonyloxy group,
An ethoxycarbonyloxy group, a methoxyethoxycarbonyloxy group, etc., an aryloxycarbonylamino group (optionally substituted aryloxycarbonylamino group having 20 or less carbon atoms, preferably 8 or less carbon atoms, for example, phenoxycarbonylamino group, 2 , 4-nitrophenoxycarbonylamino group, 4-t-butoxyphenoxycarbonylamino group, etc.), aminocarbonylamino group (optionally substituted aminocarbonylamino group having 20 or less carbon atoms, preferably 8 or less carbon atoms. Methylaminocarbonylamino group, morpholinocarbonylamino group, diethylaminocarbonylamino group, N-ethyl-N-phenylaminocarbonylamino group, 4-cyanophenylaminocarbonylamino group, 4-methanesulfonylaminocarbo Aminocarbonyloxy group (optionally substituted aminocarbonyloxy group having 20 or less carbon atoms, preferably 8 or less carbon atoms, for example, dimethylaminocarbonyloxy group, pyrrolidinocarbonyloxy group, etc.), aminosulfonyl An amino group (an optionally substituted aminosulfonylamino group having 20 or less carbon atoms, preferably 8 or less carbon atoms, such as a diethylaminosulfonylamino group, a di-n-butylaminosulfonylamino group, and a phenylaminosulfonylamino group);

An amino group (having 30 or less carbon atoms, preferably 8
The following optionally substituted amino groups. For example, an amino group,
Methylamino group, dimethylamino group, ethylamino group,
Ethyl-3-carboxypropylamino group, ethyl-2
-A sulfoethylamino group, a phenylamino group, a methylphenylamino group, a methyloctylamino group, etc., an alkoxycarbonyl group (an optionally substituted alkoxycarbonyl group having 20 or less carbon atoms, preferably 6 or less carbon atoms, for example, methoxycarbonyl Group, ethoxycarbonyl group,
A methoxyethoxycarbonyl group or the like), an aryloxycarbonyl group (an optionally substituted aryloxycarbonyl group having 20 or less carbon atoms, preferably 10 or less carbon atoms, such as a phenoxycarbonyl group or a p-methoxyphenoxycarbonyl group), or an acyloxy group (An optionally substituted acyloxy group having 20 or less carbon atoms, preferably 8 or less. For example, an acetoxy group, a benzoyloxy group, a 2-
Butenoyloxy group, 2-methylpropanoyloxy group, etc., aryloxycarbonyloxy group (C 2
0 or less, preferably 8 or less, optionally substituted aryloxycarbonyloxy groups. For example, a phenoxycarbonyloxy group, a 3-cyanophenoxycarbonyloxy group, a 4-acetoxyphenoxycarbonyloxy group,
-T-butoxycarbonylaminophenoxycarbonyloxy group, etc., sulfonyloxy group (optionally substituted sulfonyloxy group having 20 or less carbon atoms, preferably 8 or less. For example, phenylsulfonyloxy group, methanesulfonyloxy group, chloromethane Sulfonyloxy group, 4-chlorophenylsulfonyloxy group, dodecylsulfonyloxy group, etc.). However, the substituent that can be further substituted on X does not include a hydroxy group, a carboxyl group, a mercapto group, an aminosulfonyl group, a carbonylaminosulfonyl group, a sulfonylamino group, and a sulfonylaminocarbonyl group.

Next, examples of the color developing agent represented by the general formula (1) are shown, but the scope of the present invention is not limited to these specific examples.

[0016]

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[0017]

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[0018]

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[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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Next, a general method for synthesizing the compound of the present invention will be described. Synthesis Example 1 Synthesis of Exemplified Compound (R-1)
The synthesis was carried out by the following synthesis route according to the method described in No. 02. Further, other compounds can be synthesized in the same manner as in the above method.

[0025]

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Synthesis of Compound (T-1) 69.5 g of methyl isothiourea was added to 500 m of methylene chloride.
of perchloromethyl mercaptan 92.9
Add g. While cooling with methanol / dry ice, a solution in which 100 g of sodium hydroxide was dissolved in 200 ml of water was added dropwise while adjusting the internal temperature to 5 ° C. or lower. After the dropwise addition, the mixture was reacted at 15 ° C. or lower for 1 hour, and then an extraction operation was performed. After washing twice with 200 ml of water, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. 200 ml of tetrahydrofuran was added to the residue, and 101 g of hydrazine monohydrate was added dropwise under ice cooling. After the dropwise addition, the mixture was reacted at room temperature for 1 hour, and then 200 ml of water was added to precipitate crystals. The crystals are collected by filtration and acetonitrile 3
It was washed with 00 ml and dried. Thus, the compound (T-
1) 58.3 g (72%) were obtained as white crystals.

Synthesis of Exemplified Compound (R-1) 50.8 g of triphosgene was dissolved in 1 liter of tetrahydrofuran, and while cooling, 149. g of compound (T-2) was dissolved.
8 g was added dropwise, and 104 g of triethylamine was further added dropwise. After the dropwise addition, the reaction was carried out at room temperature for 1 hour.
-1) 64.8 g was separately added in five divided portions. After the addition, the mixture was further reacted for 2 hours. Then, 1 liter of ethyl acetate and 1 liter of water were added, and an extraction operation was performed.
After washing twice with liter, the organic layer was dried with anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was recrystallized from acetonitrile to give Exemplified Compound (R-1) 1
18.9 g (62%) were obtained as white crystals.

Synthesis of Exemplified Compounds (R-12) and (R-14)

[0029]

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Synthesis of Compound (T-3) 171.5 g of m-nitrobenzyl chloride and 80 g of thiourea were dissolved in 1 liter of isopropyl alcohol and heated under reflux for 2 hours. After the reaction, the mixture was cooled to room temperature, and the precipitated crystals were collected by filtration and washed with 300 ml of isopropyl alcohol. Thus, 237.6 g of compound (T-3) (9
6%) as white crystals.

The synthesis of the compound (T-4) is carried out by the exemplified compound (R
-1) was performed according to the synthesis method. Synthesis of Compound (T-5) 57.5 g of Compound (T-4) was suspended in 300 ml of acetic acid, and 35 ml of 35% aqueous hydrogen peroxide was added dropwise at an internal temperature of 50 ° C. One hour after the dropwise addition, the reaction system became completely homogeneous and the reaction was completed. The reaction solution was poured into 1 liter of 1N hydrochloric acid, and the precipitated crystals were collected by filtration and washed with water. The resulting crude crystals were subjected to silica gel column chromatography, and 30.9 g of compound (T-5) (4/1) was eluted with hexane / ethyl acetate = 3/1.
4%) as white crystals.

Compound (T-6), exemplified compound (R-1)
The synthesis of 2) was performed according to the synthesis method of the exemplified compound (R-1). Synthesis of Exemplified Compound (R-14) 33.2 g of Exemplified Compound (R-12) was added to ethyl acetate 500
The mixture was dissolved in 400 ml of water, 400 ml of water and 100 ml of ethanol, and 87 g of sodium hydrosulfite was further added. After reacting for 2 hours, an extraction operation is performed, and water 500
After washing twice with ml, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. DMAC to residue
Dissolve in 100 ml and 7 ml of triethylamine and add 3.8 g of acetyl chloride under ice cooling to an internal temperature of 15 ° C.
It was dropped so as not to exceed. After the dropwise addition, the mixture was further reacted for 1 hour, and the reaction mixture was poured into 500 ml of 1N hydrochloric acid. The precipitated crystals were collected by filtration, washed with water and dried to obtain crude crystals. The crude crystals were recrystallized from acetonitrile to give the exemplified compound (R-1).
4) 25.3 g (68%) were obtained as white crystals. The color developing agent of the present invention is used together with a compound (coupler) that forms a dye by an oxidative coupling reaction. This coupler is a so-called "4-equivalent coupler" even in the so-called "4-equivalent coupler" which is used in a system using a conventionally used paraphenylenediamine-based developing agent.
However, a "2-equivalent coupler" is preferable. Specific examples of couplers are described in Theory of the Photographic Process (4th. Ed., TH James).
s Editing, Macmillan, 1977) pp. 291-3
Page 34, and pages 354 to 361, JP-A-58-12
No. 353, No. 58-149046, No. 58-1490
No. 47, No. 59-11114, No. 59-124399
Nos. 59-174835 and 59-231439
No. 59-231540, No. 60-2951, No. 60-14242, No. 60-23474, No. 60-
No. 66249 and the like.

Examples of the coupler preferably used in the present invention include couplers represented by formulas (1) to (12) described in JP-A-09-152705. Preferred examples include couplers (C-1) to (C-80) described on pages 29 to 44 of JP-A-08-286340, but the present invention is not limited thereto. Furthermore, specific examples of the coupler that can be used in the present invention are shown below, but the present invention is not limited thereto.

[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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The amount of the coupler used together with the color developing agent of the present invention depends on the molar extinction coefficient (ε) of the formed dye.
However, in order to obtain an image density of 1.0 or more in reflection density, ε of a dye generated by coupling is 500
In the case of a coupler of about 0 to 500,000, the coating amount is about 0.001 to 100 mmol / m ² , preferably 0.01 to 10 mmol / m ² , and more preferably 0.1 to 100 mmol / m ² .
An appropriate amount is about 0.5 to 5 mmol / m ² . The amount of the color developing agent of the present invention to be added is generally 0.01 to 100 times, preferably 0.1 to 100 times by mole ratio to the coupler.
It is 10 times, more preferably 0.2 to 5 times. In the present invention, it is preferable to use an auxiliary developing agent. Here, the auxiliary developing agent means a substance having an action of promoting the transfer of electrons from the color developing agent to the silver halide in the development process of silver halide development, and is an electron-emitting compound according to the Kendall-Peltz rule. is there. As an example of these,
Compounds described in JP-A-09-152705 (ETA-
1) to (ETA-36), and JP-A-09-1462
No. 48, compounds D-1 to D-35.

In the present invention, a blocked photographic reagent which releases a photographically useful group during processing can be used. Examples of these are disclosed in JP-A-09-15270.
No. 5, paragraphs 0073 to 0077.

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

The 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 introduced 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 JP-A No. 5-2370. In this case, US 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, Tokuhei 3-62,
A high-boiling organic solvent as described in No. 256 or the like can be used in combination with a low-boiling organic solvent having a boiling point of 50 to 160 ° C. as necessary. These couplers, dye-donating compounds such as color developing agents, diffusion-resistant reducing agents, high-boiling organic solvents, etc. may be used alone or in combination of two or more. As the color developing agent, those represented by the above general formula (1) may be used in combination with other compounds. The amount of the high boiling organic solvent is 10 g or less, preferably 5 g or less, more preferably 1 g to 0.1 g, per 1 g of the color image forming compound used. Further, the amount is preferably 1 cc or less, more preferably 0.5 cc or less, particularly preferably 0.3 cc or less, based on 1 g of the binder. In addition, Tokubo Sho 5
Nos. 1-39,853 and JP-A-51-59,943.
No. 242, JP-A-63-271339, and the like, and a method of adding it in the form of a fine particle dispersion can also be used. In the case of a compound which is substantially insoluble in water, it can be dispersed and contained as fine particles in a binder in addition to the above method. When dispersing a hydrophobic compound in a hydrophilic colloid,
Various surfactants can be used. For example, Japanese Patent Application Laid-Open No. 59-157,636 (37) to (38)
The surfactants listed as surfactants in the RD magazine shown in the page and the list below can be used. In the light-sensitive material of the present invention, a compound for stabilizing an image simultaneously with activation of development can be used. Specific compounds preferably used are described in U.S. Pat. No. 4,500,626, columns 51-52.

In order to obtain a wide range of colors on the chromaticity diagram using the three primary colors of yellow, magenta and cyan, at least three silver halide emulsion layers having photosensitivity in different spectral regions are combined. Used. For example, there are a combination of three layers of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer, and a combination of a green-sensitive layer, a red-sensitive layer, and an infrared-sensitive layer. Each photosensitive layer can adopt various arrangement orders known for ordinary color photosensitive materials. Each of these photosensitive layers may be divided into two or more layers as necessary.

The photosensitive material may 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 can be added to improve the color separation.

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, such as silver rhodanate, silver sulfide, silver selenide, silver carbonate, silver phosphate,
Organic acid silver may be contained as separate grains or as part of silver halide grains. Development and desilvering (bleaching,
When speeding up of the fixing and bleach-fixing steps is desired, silver halide grains having a high silver chloride content are desirable. In order to appropriately suppress development, it is preferable to contain silver iodide. The preferred silver iodide content depends on the intended light-sensitive material. For example, in the case of X-ray sensitive material, 0.1
-15% by mole, and 0.1-5% by mole for graphic arts and micro-sensitive materials are preferred ranges. In the case of a photographic 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%, and particularly preferably 8 to 15 mol%.
Mol%. It is preferable that silver iodobromide grains contain silver chloride in order to reduce lattice strain.

The silver halide emulsion of the present invention preferably has a distribution or structure with respect to the halogen composition in the grains. A typical example is JP-B-43-131.
No. 62, JP-A-61-215540 and JP-A-60-2
No. 22845, JP-A-61-75337, etc. are core-shell or double-structure grains having a halogen composition in which the inside and the surface of the grains are different.
In addition, it is not a simple double structure.
Or a multilayer structure having three or more layers as disclosed in the above-mentioned publication, or a thin silver halide having a different composition can be applied to the surface of a core-shell double structure grain.

In order to provide a structure inside the particle, not only the wrapping structure as described above, but also a particle having a so-called junction structure can be produced. These examples are disclosed in
No. 133540, JP-A-58-108526, European Patent No. 199,290A2, JP-B-58-24772.
And JP-A-59-16254.
The crystal to be bonded can be formed by bonding to the edge, corner, or face of the host crystal with a composition different from that of the host crystal. Such a bonded crystal can be formed even if the host crystal is uniform in halogen composition or has a core-shell structure.

In the case of a junction structure, a combination of silver halides is naturally possible, but a silver salt compound having no rock salt structure such as silver rhodanate or silver carbonate can be combined with silver halide to form a junction structure. Further, a non-silver salt compound such as lead oxide may be used as long as the bonding structure is possible.

In the case of silver iodobromide or the like having such a structure, it is a preferred embodiment that the core portion has a higher silver iodide content than the shell portion. Conversely, grains having a low silver iodide content in the core and a high shell are sometimes preferred. Similarly, grains having a bonding structure may be grains having a high silver iodide content of the host crystal and relatively low silver iodide content of the bonding crystal, or vice versa. In addition, the boundary portions having different halogen compositions of grains having these structures may be clear boundaries or unclear boundaries. In addition, a configuration in which the composition is positively and continuously changed is also a preferable embodiment.

In the case of silver halide grains in which two or more silver halides are present as mixed crystals or with a structure, it is important to control the halogen composition distribution between the grains. A method for measuring the halogen composition distribution between grains is described in JP-A-60-254032. Uniform halogen distribution between grains is a desirable property. In particular, a highly uniform emulsion having a coefficient of variation of 20% or less is preferable.
Another preferred form is an emulsion having a correlation between the grain size and the halogen composition. For example, there is a case where the correlation is such that the iodine content increases as the size of the particles increases, whereas the iodine content decreases as the size of the particles decreases. 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 grains. Increasing the amount of silver iodide in the vicinity of the surface or increasing the content of silver chloride can be selected according to the purpose because the adsorption of the dye and the developing speed are changed. When changing the halogen composition in the vicinity of the surface, either a structure that wraps the entire grain or a structure that adheres only to a part of the grain can be selected. For example, the halogen composition may be changed only on one side of the tetrahedral grain composed of the (100) plane and the (111) plane, or one of the main plane and the side face of the tabular grain may be changed.

The silver halide grains used in the present invention may be normal crystals having no twin planes, as described in the Photographic Society of Japan, Fundamentals of the Photographic Industry, Silver Salt Photography (Corona), page 163. Examples include single twins containing one twin plane, parallel multiple twins containing two or more parallel twin planes, and non-parallel multiple twins containing two or more non-parallel twin planes according to the purpose. You can use it by choosing. An example of mixing particles having different shapes is disclosed in U.S. Pat. No. 4,865,964, but this method can be selected as necessary. In the case of a normal crystal, a cube consisting of (100) planes, (111)
Octahedral particles composed of planes, and dodecahedral particles composed of (110) planes disclosed in JP-B-55-42737 and JP-A-60-222842 can be used. Furthermore, Jo
urnal of Imaging Science, Vol. 30, p. 247 (1986
(H11) plane particles represented by (211) and (331) represented by (331) as reported in
Plane particles, (hk0) plane particles typified by the (210) plane, and (hkl) plane particles typified by the (321) plane also need to be devised in the preparation method, but can be selected and used according to the purpose. A tetrahedral particle in which (100) plane and (111) plane coexist in one particle, a particle in which (100) plane and (110) plane coexist, or a particle in which (111) plane and (110) plane coexist, Particles in which two faces or many faces 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 an 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; Photographic
Science and Engineering (Gutof, Photo
graphic Science and Engineering), Vol. 14, 248
257 (1970), U.S. Patent No. 4,434,2.
No. 26, No. 4,414,310, No. 4,433
No. 048, 4,439,520 and British Patent No. 2,112,157. When tabular grains are used, there are advantages such as an increase in covering power and an increase in color sensitization efficiency by a sensitizing dye. For example, US Pat. No. 4,434,22 cited above.
No. 6 describes this in detail. 80 of the total projected area of the grain
The average aspect ratio of 1% or more is desirably 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 the tabular grains can be selected from triangles, hexagons, and circles. A regular hexagon having almost equal lengths of six sides as described in U.S. Pat. No. 4,798,354 is a preferred form.

As the grain size of tabular grains, the circle equivalent diameter of the projected area is often used, but US Pat.
No. 8,106 has an average diameter of 0.6.
Submicron particles are preferred for high image quality. Also preferred are emulsions having a narrow grain size distribution as described in U.S. Pat. No. 4,775,617. It is preferable to limit the grain thickness of the tabular grains to 0.5 μm or less, more preferably 0.3 μm or less, in order to increase sharpness. Further, an emulsion having a highly uniform thickness having a variation coefficient of grain thickness of 30% or less is also preferable. Further, particles described in JP-A-63-163451, in which the thickness of the particles and the distance between twin planes are specified, 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 particle containing no dislocation line, a particle containing several dislocations, or a particle containing many dislocations according to the purpose. Also, it is possible to select dislocations introduced linearly or distorted dislocations in a specific direction of the crystal orientation of the grains, to introduce them throughout the grains, or to introduce them only to a specific portion of the grains, For example, dislocations can be introduced only in the fringe portion of the particles. The introduction of dislocation lines is preferable not only in the case of tabular grains but also in the case of normal grains or irregular grains typified by potato grains. Also in this case, it is a preferable embodiment to limit the particle to a specific portion such as a vertex or a ridge.

The silver halide emulsion used in the present invention may be prepared by subjecting a grain to a roundness as disclosed in European Patent No. 96,412B1 or the like, or by a method described in West German Patent No. 2,30.
The surface may be modified as disclosed in JP-A-6-447C2 and JP-A-60-221320.

A structure having a flat particle surface is generally used.
It is preferable in some cases to form irregularities intentionally. JP-A-58-106532, JP-A-60-221
For example, a method of making a hole in a part of the crystal described in No. 320, for example, a vertex or a center of a plane, or a raffle particle described in US Pat. No. 4,643,966.

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

The emulsion used in the present invention may be a polydisperse emulsion having a wide grain size distribution, or a monodisperse emulsion having a narrow size distribution. The coefficient of variation of the projected area equivalent circle diameter or sphere equivalent diameter of a particle 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 variation coefficient of 25% or less, more preferably 20% or less, and still more preferably 15% or less.

In some cases, the monodisperse emulsion is defined as an average particle size distribution by the number or weight of particles. In order to satisfy the target gradation of the light-sensitive material, two or more monodispersed silver halide emulsions having different grain sizes are mixed in the same layer or different layers in an emulsion layer having substantially the same color sensitivity. Can be applied in layers. Further, two or more kinds of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion may be mixed or layered. As the emulsion used in the present invention, an emulsion containing the above-mentioned grains is used. Here, as one of the embodiments for carrying out the present invention, the active ingredient of the present invention and a silver chloride content of 50 mol% are used.
An embodiment in which the above-described emulsion composed of tabular grains is not used in combination can also be adopted.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Grafkid, published by Paul Monte (P. Glaf).
kides, Chemie et Phisique Photographique, Paul Mon
tel, 1967), Duffin, "Photographic Emulsion Chemistry", Focal Press (GF Duffin, Photographic Emulsion Chem)
istry, Focal Press, 1966), “Production and Coating of Photographic Emulsions” by Zelikuman et al., Published by Focal Press (VLZelikm)
an, et al., Makingand Coating Photographic Emulsio
n, Focal Press, 1964), etc., 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 a method of reacting a soluble silver salt and a soluble halide may be any of a one-side mixing method, a double-mixing method, a combination thereof, and the like. . A method of forming grains in the presence of excess silver ions (a so-called reverse mixing method) can also be used. A method of maintaining a constant pAg in a liquid phase in which silver halide is formed as one type of the double jet method;
That is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.

No. 4,334,012, US Pat. No. 4,301,241, US Pat. No. 4,150,994, in which silver halide grains which have been previously precipitated are added to a reaction vessel for preparing an emulsion. Is optionally preferred. These can be used as seed crystals, and are also effective when supplied as silver halide for growth. In the latter case, it is preferable to add an emulsion having a small grain size, and the addition method can be selected from a total amount addition at once, an addition in a plurality of times, or a continuous addition. It is also effective in some cases to add particles having various halogen compositions to modify the surface.

A method for converting a large part of the halogen composition of silver halide grains by a halogen conversion method is disclosed in US Pat. Nos. 3,477,852 and 4,142,142.
No. 900, European Patent Nos. 273,429 and 273,
No. 430, West German Patent No. 3,819,241, etc., which are effective particle forming methods. A solution of a soluble halogen or silver halide grains can be added to convert the silver salt into a hardly soluble silver salt. The method can be selected from a method of converting at once, a method of converting into a plurality of times, and a method of performing continuous conversion.

In addition to the method of adding a soluble silver salt and a 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;
The particle forming method of changing the concentration or changing the flow rate as described in the above-mentioned 4,242,445 is a preferable method. By changing the concentration or increasing the flow rate, the amount of silver halide to be supplied can be changed by a linear function, a quadratic function, or a more complicated function of the addition time. If necessary, it is more preferable to reduce the amount of silver halide supplied. Further, when adding a plurality of soluble silver salts having different solution compositions or adding a plurality of soluble halide salts having different solution compositions, an addition method of increasing one and decreasing the other is also an effective method. It is.

A mixer for reacting a solution of a soluble silver salt and a soluble halide salt is disclosed in US Pat. No. 2,996,287.
No. 3,342,605, No. 3,415,65
No. 0, No. 3,785,777, West German Patent No. 2,
556,885 and 2,555,364.

A silver halide solvent is useful for the purpose of accelerating ripening. For example, it is known to have an excess of halogen ions in the reactor to promote ripening. Other ripening agents can also be used. These ripening agents can be incorporated in their entirety in a dispersion medium in a reactor before silver and halide salts are added,
A halide salt, silver salt or deflocculant can be added and introduced into the reactor. As another variant,
The ripening agent can also be introduced independently at the stage of halide and silver salt addition.

Ammonia, thiocyanates (rhodancali, rhodanammonium, etc.), organic thioether compounds (for example, US Pat. Nos. 3,574,628 and 3,
Nos. 021, 215, 3,057,724, 3,038,805, 4,276,374, 4,297,439, 3,704,130,
No. 4,782,013, JP-A-57-104926
And the like, and thione compounds (for example, tetra-substituted thioureas described in JP-A-53-82408 and JP-A-55-77737, U.S. Pat. No. 144319), mercapto compounds capable of promoting the growth of silver halide grains described in JP-A-57-202531, and amine compounds (for example, JP-A-54-1007).
No. 17, etc.).

It is advantageous to use gelatin as a protective colloid used in preparing 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 and cellulose sulfate, sodium alginate, starch derivatives, gum arabic , Dextran, sugar derivatives such as natural compounds such as polysaccharides such as pullulan, polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. And various kinds of synthetic hydrophilic high-molecular substances such as a single or copolymer. Also, vinyl having U.S. Patent No. 4,960,681, superabsorbent polymers described in JP-A-62-245,260, etc., i.e. -COOM or -SO ₃ M a (M is a hydrogen atom or an alkali metal) Copolymers with monomers or copolymers of these vinyl monomers or 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 kinds. Combinations of gelatin and the above binders are also preferred.

As gelatin, in addition to lime-processed gelatin,
It may be selected from acid-treated gelatin and so-called demineralized gelatin having a reduced content of calcium and the like, and it is also preferable to use them in combination. Bull.Soc.Sci.Photo.Japan.N
o.16.p30 (1966), an enzyme-treated gelatin may be used, and a hydrolyzate or enzymatic degradation product of gelatin may also be used. The use of low molecular weight gelatin described in JP-A-1-158426 is preferred for preparing 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. There are benzotriazoles, fatty acids and other compounds described in column Nos. 52 to 53 of 500,626. The acetylene silver described in U.S. Pat. No. 4,775,613 is also useful. Two or more organic silver salts may be used in combination.
The above organic silver salt is used per mole of photosensitive silver halide,
0.01 to 10 mol, preferably 0.01 to 1 mol, can be used in combination. Total coating amount of light-sensitive silver halide emulsion and the organic silver salt is 0.05 to 10 g / m ² in terms of silver, and preferably from 0.1-4 g / m ^2.

The emulsion of the present invention is preferably washed with water for desalting and dispersed in a newly prepared protective colloid. The temperature of water washing can be selected according to the purpose, but is preferably selected in the range of 5 to 20 ° C. The pH at the time of washing can be selected depending on the purpose, but is preferably selected from 2 to 10. More preferably, it is in the range of 3 to 8. The pAg at the time of washing can be selected according to the purpose, but is preferably selected from 5 to 10. The method for washing can be selected from noodle washing, dialysis using a semipermeable membrane, centrifugal separation, coagulation sedimentation, and ion exchange. In the case of the coagulation sedimentation method, 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 can be selected.

When preparing the emulsion of the present invention, for example, during grain formation,
In the desalting step, at the time of chemical sensitization, the presence of a metal ion salt before coating is preferable depending on the purpose. When doping the grains, it is preferable to add them at the time of grain formation, when modifying the grain surface or when using as a chemical sensitizer, after grain formation and before the end of chemical sensitization. The case of doping the whole grain and the method of doping only the core portion, only the shell portion, only the epitaxial portion, or only the base grain of the 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 or the like can be used. These metals can be added in the form of salts which can be dissolved at the time of particle formation, such as ammonium salts, acetates, nitrates, sulfates, phosphates, hydroxides, six-coordinate complex salts, and four-coordinate complex salts. 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
Cl ₆ , (NH ₄ ) ₃ RhCl ₆ , K ₄ Ru (CN) _{6 and the} like. Halo, aquo, and ligands for coordination compounds
It can be selected from cyano, cyanate, thiocyanate, nitrosyl, thionitrosyl, oxo, and carbonyl. These may use only one type of metal compound, or may use two or more types in combination.

A method of adding a chalcogen compound during preparation of an emulsion as described in US Pat. No. 3,772,031 is sometimes useful. In addition to S, Se, and Te, cyanide, 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 are collectively referred to as chalcogen sensitization), noble metal sensitization, or reduction sensitization may be applied in any step of the production process of a silver halide emulsion. it can. It is preferable to combine two or more sensitization methods. Various types of emulsions can be prepared depending on the step of chemical sensitization. There are a type in which a chemical sensitizing nucleus is embedded inside the grain, a type in which the chemical sensitizing nucleus is embedded at a position shallow from the grain surface, and a type in which a chemical sensitizing nucleus is formed on the surface. In the emulsion of the present invention, the location of the chemical sensitization nucleus can be selected according to the purpose. Generally, the case where at least one type of chemical sensitization nucleus is formed near the surface is preferred.

The chemical sensitization which can be preferably carried out in the present invention is chalcogen sensitization and noble metal sensitization alone or in combination, and is described in THJames, The Photographic Process, 4th Edition, published by Macmillan. , 1
977 (THJames, The Photographic Process, 4th
ed. Macmillan, 1977), pages 67-76, and can be performed using active gelatin, as well as Research Disclosure Item 12008 (1977).
April 974), Item 13452 (June 1975)
), 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
No. 6,018, and 3,904,415 and British Patent 1,315,755, sulfur, selenium, tellurium, at pAg 5-10, pH 5-8 and temperature 30-80 ° C. Gold, platinum, palladium, iridium or a combination of a plurality of these sensitizers can be used.

In the sulfur sensitization, an unstable sulfur compound is used. 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 US Patent Nos. 3,857,711 and 4,2
Known sulfur-containing compounds described in US Pat. Nos. 66,018 and 4,054,457 can be used. Sulfur sensitization is often used in combination with noble metal sensitization.

The preferred amount of the sulfur sensitizer used for the silver halide grains of the present invention is 1 × 10 ⁻⁷ to 10 ⁻³ mol per mol of silver halide, more preferably 5 × 10 ⁻⁷ to 10 ⁻³ mol.
It is ^10-7 to ^1-10-4 mol.

In selenium sensitization, a known unstable selenium compound is used, for example, as described in US Pat. No. 3,297,44.
No. 6,297,447 and the like, and specifically, colloidal metal selenium, selenoureas (for example, N, N-dimethylselenourea, tetramethylselenourea) Urea, etc.), selenoketones (eg, selenoacetone), selenoamides (eg, selenoacetamide), selenocarboxylic acids and esters, isoselenocyanates, selenides (eg, diethyl selenide, triphenylphosphine selenide), Selenophosphates (eg, tri-p
-Tolyl selenophosphate) and the like. It may be preferable to use selenium sensitization in combination with sulfur sensitization and / or noble metal sensitization.

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

The tellurium sensitizers used in the present invention include Canadian Patent No. 800,958 and British Patent Nos. 1,2.
No. 95,462, No. 1,396,696, Japanese Patent Application No. 2
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, tetramethyltellurourea, N-carboxyethyl-N ', N'
-Dimethyltellurourea, N, N'-dimethylethylenetellurourea), isotellurocyanates, telluroketones, telluramides, tellurohydrazides, telluroesters, phosphine tellurides (eg, tributylphosphine telluride, butyldiisopropylphosphine) Telluride), other tellurium compounds (eg, potassium tellurocyanate, sodium telluropentathionate)
And the like.

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

In the noble metal sensitization, noble metal salts such as platinum, gold, palladium, and iridium can be used. Among them, gold sensitization, palladium sensitization, and a combination of both are 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 palladium salt or a tetravalent salt. Preferred palladium compounds are 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 is preferred. The gold compound and the palladium compound are preferably used in combination with a thiocyanate or a selenocyanate.

The emulsion of the present invention is preferably used in combination with gold sensitization.
Good. The preferred amount of the gold sensitizer is 1 mole of silver halide.
1 × 10 per le^-7~ 1 × 10^-3Mole, more preferred
Is 5 × 10^-7~ 5 × 10^-FourIs a mole. Palladium compound
The preferred range of the product is 5 × 10 ^-7~ 1 × 10^-3In mole
You. Preferred are thiocyan compounds and selenocyan compounds.
A good range is 1 × 10^-6~ 5 × 10^-2Is a mole.

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

Here, reduction sensitization refers to a method in which a reduction sensitizer is added to a silver halide emulsion, or pAg1 to silver ripening.
7, a method of growing or ripening in a low pAg atmosphere, or a method of growing or ripening in a high pH atmosphere of pH 8 to 11, which is called high pH ripening. Further, two or more methods can be used in combination.

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

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

Chemical sensitization can be carried out in the presence of a so-called chemical sensitization aid. Useful chemical sensitization aids include compounds known as azaindene, azapyridazine, azapyrimidine, which suppress fog during chemical sensitization and increase sensitivity. Examples of chemical sensitization aid modifiers are described in U.S. Pat.
Nos. 411,914 and 3,554,757, JP-A-58-126526 and the aforementioned "Emulsion Chemistry" by Duffin, pp. 138-143.

It is preferable to use an oxidizing agent for silver during the production process of the emulsion of the present invention. The oxidizing agent for silver is
A compound that acts on metallic silver to convert it into silver ions. In particular, extremely fine silver grains by-produced during the formation process and chemical sensitization process of silver halide grains,
Compounds that can be converted to silver ions are effective. The silver ions generated here may form a silver salt that is hardly soluble in water such as silver halide, silver sulfide, silver selenide, or a silver salt that is easily soluble in water such as silver nitrate. good. The oxidizing agent for silver may be inorganic or organic. Examples of the inorganic oxidizing agent include ozone, hydrogen peroxide and adducts thereof (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 (for example,
KMnO ₄ ), oxyacid salts such as chromate (eg, K ₂ CrO ₇ ), halogen elements such as iodine and bromine, perhalates (eg, potassium periodate), salts of high valent metals ( For example, potassium hexacyanoferrate) and thiosulfonate.

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

Preferred oxidizing agents of the present invention are ozone, hydrogen peroxide and its adducts, halogen elements, inorganic oxidizing agents of thiosulfonates and organic oxidizing agents of quinones.
It is a preferred embodiment to use the above-described reduction sensitization and an oxidizing agent for silver in combination. After the use of the oxidizing agent, the method can be selected from a method of performing reduction sensitization, a reverse method thereof, or a method of coexisting both methods. These methods can be selectively used in both the grain formation 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, storage or photographic processing of the photographic material, or stabilizing photographic performance. . That is, thiazoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, amino Triazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (particularly 1-phenyl-5-mercaptotetrazole), mercaptopyrimidine, mercaptotriazine,
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. Patent Nos. 3,954,474 and 3,982,94
No. 7 and JP-B No. 52-28660 can be used. One of the preferred compounds is Japanese Patent Application No. Sho 62
No. 47225. Antifoggants and stabilizers can be used at various times before, during, or after particle formation, during the rinsing step, during dispersion after rinsing, before chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. It can be added according to the purpose. Besides controlling the crystal wall of the grains, reducing the grain size, reducing the solubility of grains, and controlling the chemical sensitization, in addition to exhibiting the original fogging prevention and stabilizing effect when added during emulsion preparation. It can be used for various purposes such as controlling the arrangement of dyes.

In the case where the photosensitive silver halide used in the present invention has green, red, and infrared sensitivity, the photosensitive silver halide emulsion is spectrally sensitized with methine dyes or the like. . If necessary, the blue-sensitive emulsion may be subjected to spectral sensitization 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 nuclei usually used for cyanine dyes as base heterocyclic nuclei can be applied to these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus,
Nuclei in which an alicyclic hydrocarbon ring is fused to these nuclei, such as an imidazole nucleus, a tetrazole nucleus, and a pyridine nucleus, and a nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, that is, an indolenine nucleus, a benzindolenine nucleus, 5 to 6-membered heterocyclic nucleus such as indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, rhodanine nucleus, thiobarbituric acid nucleus, etc. Can be. These nuclei may be substituted on carbon atoms. Specifically, U.S. Pat. No. 4,617,257, JP-A-59-180,550, JP-A-64-13,546,
Sensitizing dyes described in JP-A-5-45,828 and JP-A-5-45,834 are exemplified.

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

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

Along with the sensitizing dye, a dye which does not itself have a spectral sensitizing effect or a compound which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (for example, US Pat. No. 3,615,641 and those described in JP-A-63-23,145).

These sensitizing dyes may be added to the emulsion at any stage in the preparation of the emulsion which has been known to be useful.

Most commonly, it is performed after completion of chemical sensitization but before coating, but US Pat. No. 3,628,96.
As described in JP-A-58-113 and JP-A-4225666, spectral sensitization may be carried out simultaneously with chemical sensitization by simultaneous addition with a chemical sensitizer. , 92
As described in No. 8, it can be carried out prior to chemical sensitization. Further, it may be added before completion of precipitation of silver halide grains to start spectral sensitization. Nos. 4,183,756 and 4,225,666.
The addition may be performed before or after the nucleation of silver halide grains according to the above method, or divided additions in which a part of the compound is added before chemical sensitization and the remainder is added after chemical sensitization.

These sensitizing dyes and supersensitizers may be added as a solution of an organic solvent such as methanol, a dispersion of gelatin or the like, 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. 10 ^{-5 to} 2 × 10 ^-3 mol is more effective.

The above-mentioned various additives are used in the light-sensitive material according to the present technology, but other various additives can be used according to the purpose.

These additives are described in more detail in Research Disclosure Item 17643 (December 1978) and Item 18176 (November 1979).
And Item 307105 (November 1989), and the relevant portions are summarized in the table below.

Type of Additive RD17643 RD18716 RD307105 1. Chemical sensitizer page 23 page 648 right column page 996 2. Sensitivity increasing agent, page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column 996 to 998 Super sensitizer, page 649, right column Brightener 24 page 647 page right column 998 5. 5. Light absorber, page 25-26, page 649, right column, page 1003, filter-page 650, left column, dye, ultraviolet absorber. Binder 26 pages 651 pages 1003 to 1004 7. 7. Plasticizer, page 27 page 650 page 1006 Lubricant 8. Coating aid, pages 26 to 27, page 650, page 1005 left to surface active agent, page 1006 right Static page 27 page 650 right column 1006 to inhibitor 1007 page 10. Antifoggants 24 to 25 pages 649 pages 998 to 1000 and stabilizers 11. Stain 25 page right column 650 page left to right inhibitor 12. 12. Dye image stabilizer page 25 Hardener 26 pages 651 left column 1004 right to 1005 left

As hardening agents, in addition to those described above, US Pat. No. 4,678,739, column 41 and 4,791,04.
No. 2, JP-A-59-116,655 and JP-A-62-24
5,261, 61-18,942, JP-A-4-24-2
18,044 and the like. More specifically, aldehyde hardeners (such as formaldehyde), aziridine hardeners, epoxy hardeners, and vinyl sulfone hardeners (N, N'-ethylene-bis (vinylsulfonylacetamide)) Ethane, etc.), N-methylol hardeners (dimethylolurea, 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 gelatin applied.
5 g to 0.5 g are used. The layer to be added may be any of 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 or an image-receiving element). Is also 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 giving a non-glossy surface. Matting agents such as silicon dioxide, polyolefin or polymethacrylate are disclosed in
8,256 (page 29), benzoguanamine resin beads, polycarbonate resin beads, A
There are compounds such as S resin beads described in JP-A-63-274,944 and JP-A-63-274,952. In addition, the compounds described in the aforementioned 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 as needed.

In addition, the constituent layers of the photothermographic material may contain a thermal solvent, an antifoaming agent, an antibacterial agent, a fungicide, colloidal silica, and the like. Specific examples of these additives are disclosed in
No. 88-256, pp. 26-32, JP-A-3-1
No. 1,338, and Japanese Patent Publication No. 2-51-51,496.

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 releasability, improvement of lubricity, prevention of electrification, acceleration of development and the like. Specific examples of the surfactant are described in the above-mentioned RD Magazine and JP-A-62-173,464.
No. 63, 62-183, 457 and the like. In the case of a photothermographic material, it is also preferable to include an organic fluoro compound in the constituent layers for the purpose of improving slipperiness, preventing static charge, improving releasability, and the like. Representative examples of organic fluoro compounds include fluorine-based surfactants described in JP-B-57-9,053, columns 8-17, JP-A-61-20,944, and JP-A-62-135,836. And a hydrophobic fluorine compound such as an oily fluorine compound such as fluorine oil or a solid fluorine compound resin such as ethylene tetrafluoride resin.

A known anti-fading agent can be used in the light-sensitive material of the present invention. Organic anti-fading agents include hydroquinones, 5-hydroxychromans, 5-hydroxycoumarins, paraalkoxyphenols, hindered phenols mainly including bisphenols, gallic acid derivatives, methylenedioxybenzenes, amino Representative examples include phenols, hindered amines, and ether or ester derivatives in which the phenolic hydroxyl group of each of these compounds is silylated or alkylated.
Further, metal complexes represented by (bissalicylaldoximato) nickel complex and (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used. Compounds having both a hindered amine and a hindered phenol partial structure in the same molecule as described in U.S. Pat. No. 4,268,593 are effective in preventing deterioration of a yellow dye image due to heat, humidity and light. give. Further, in order to prevent the deterioration of the magenta dye image, particularly the deterioration due to light, spiroindanes described in JP-A-56-159,644 and hydroquinone diethers described in JP-A-55-89,835 can be used. Monoether-substituted chromans give favorable results.

In the constituent layers of the light-sensitive material of the present invention, various antifoggants or photographic stabilizers and precursors thereof can be used. Specific examples of the above R
Magazine D, US Patent Nos. 5,089,378 and 4,50
0,627, 4,614,702, JP-A-64
-13,546 pages (7) to (9), (57) to (7)
1) and (81)-(97), U.S. Pat.
No. 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 available in 5 moles per silver mole.
X 10 ^-6 to 1 x 10 ^-1 mol is preferable, and 1 x 10
^-5 to 1 × 10 ^-2 is preferably used.

Suitable supports that can be used in the present invention include synthetic plastic films such as polyolefins such as polyethylene and polypropylene, polycarbonates, cellulose acetate, polyethylene terephthalate, polyethylene naphthalate, and polyvinyl chloride; photographic base paper; Paper supports such as paper, baryta paper, and resin-coated paper, and supports in which a reflective layer is provided on the plastic film described above;
To 31) as a support. The RD. No. 17643, page 28; 1
8716, right column from page 647 to left column, page 648, and N
o. Those described on page 879 of 307105 can also be preferably used. These supports include U.S. Pat.
By performing a heat treatment of Tg or less as in 1,735,
It is possible to use a material having a hard curl. The surface of these supports may be subjected to surface treatment for the purpose of improving the adhesion between the support and the emulsion undercoat layer. In the present invention, a glow discharge treatment, an ultraviolet irradiation treatment, a corona treatment, and a flame treatment can be used as the surface treatment. Further, the support described in the publicly known technique No. 5 (issued by Aztec Co., Ltd. on March 22, 1991) at pages 44 to 149 can also be used. A transparent support such as polyethylene naphthalene dicarboxylate or a support obtained by coating a transparent magnetic substance thereon can also be used.

In the photothermographic material, various development terminators can be used for the purpose of always obtaining a constant image with respect to fluctuations in processing temperature and processing time during development. As used herein, the term "development terminator" means that after appropriate development, the base is immediately neutralized or reacted with the base to lower the base concentration in the film, and interacts with a compound or silver and silver salt which stops the development to effect development. It is a compound that suppresses. Specific examples include an acid precursor that releases an acid when heated, an electrophilic compound that undergoes a substitution reaction with a coexisting base when heated, or a nitrogen-containing heterocyclic compound, a mercapto compound, and a precursor thereof. For further details, see JP-A-62-253159 (3.
It is described on pages 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. Examples of the base precursor used in the present invention include a salt of an organic acid and a base that is decarboxylated by heat, a compound that decomposes by a reaction such as an intramolecular nucleophilic substitution reaction, a Rossen rearrangement or a Beckmann rearrangement, and releases amines. A compound which causes a certain reaction to release a base and a compound which generates a base by an electrolysis or a complex formation reaction are preferably used. Examples of the former base precursors that generate a base by heating include salts of trichloroacetic acid described in British Patent No. 998,959 and the like, and those described in US Pat. No. 4,060,420 as those having improved stability. Α-sulfonylacetic acid salt, propiolic acid salt described in Japanese Patent Application No. 58-55,700, 2-carboxycarbamide derivative described in U.S. Pat. No. 4,088,496, and an organic base as a base component. Besides, salts with thermally decomposable acids using alkali metals or alkaline earth metals (Japanese Patent Application No. 58-69,597), and hydroxam carbamates described in Japanese Patent Application No. 58-43,860 utilizing Rossen rearrangement And aldoxime carbamates described in Japanese Patent Application No. 58-31,614 which produces a nitrile upon heating. In addition, UK Patent No. 9
Nos. 98,945 and 2,079,480;
No. 0-226,225, U.S. Pat. No. 3,220,846.
No. 4,514,493 and 4,657,84
No. 8 and Known Technique No. 5 (March 22, 1991, Aztec Co., Ltd.), pp. 55-86, etc., are also useful.

The method of exposing and recording an image on the light-sensitive material of the present invention includes, for example, 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 a enlarger. Scanning, exposing the original image through slits, etc. using an exposure device of a copying machine, and scanning by emitting light emitting diodes and various lasers (laser diodes, gas lasers, etc.) via image information and electric signals. Exposure method (Japanese Patent Application Laid-Open No. 2-129625, Japanese Patent Application No. 3-338,
No. 182, No. 4-9,388, No. 4-281, 442
And a method of outputting image information to an image display device such as a CRT, a liquid crystal display, an electroluminescence display, and a plasma display, and exposing directly or via an optical system.

As a light source for recording an image on a photosensitive material,
As described above, U.S. Pat. No.4, such as natural light, tungsten lamp, light emitting diode, laser light source, CRT light source, etc.
No. 500,626, column 56, JP-A-2-53,378.
And the light source and the exposure method described in JP-A-2-54,672. Also, image exposure can 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 nonlinearity between localization and an 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 and the} like, urea derivatives, nitroaniline derivatives, for example, 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 Nippon Television Signal Standard (NTSC), or an original image into a plurality of pixels such as a scanner. Image signal,
Images created using a computer represented by CG and CAD can be used.

The color developing agent of the present invention is used for all silver halide photosensitive materials such as color negatives, color papers, color instant photographs and X-ray photographic materials for color reversal or for forming color images and photographic materials for plate making. be able to. Further, the color developing agent of the present invention can be added to a silver halide photosensitive material, and can also be added to a processing solution. When used in a silver halide photosensitive material,
The color developing agent of the present invention is contained in at least one hydrophilic colloid layer provided on a support. The silver halide light-sensitive material containing the color developing agent of the present invention is preferably a color diffusion transfer silver halide photographic light-sensitive material.

When the color developing agent of the present invention is added to a silver halide photosensitive material, development can be carried out by heat treatment or activator treatment.

The heat treatment of the photosensitive material is known in the art. For the photothermographic material and the process,
For example, the basics of photo engineering (Corona, 1979)
Pages 553-555, published April 1978, video information 4
Page 0, Nebbetts Handbook of P
photography and Reprograph
y 7th Ed. (Van Nostrand an
d Reinhold Company) 32-33
, U.S. Patent Nos. 3,152,904 and 3,30
Nos. 1,678, 3,392,020, 3,4
57,075, British Patent Nos. 1,131,108 and 1,167,777, and Research Disclosure, June 1978, pp. 9-15 (RD-1702).
9).

Activator processing refers to a processing method in which a color developing agent is incorporated in a photosensitive material and development is performed using a processing solution containing no color developing agent. The processing solution in this case is characterized in that it does not contain a color developing agent contained in a normal developing solution component, and may contain other components (for example, an alkali, an auxiliary developing agent, etc.). Regarding the activator treatment, European Patent No. 545,
No. 491A1, No. 565, 165A1, and the like. In the present invention, the “developer” refers to a processing solution containing a color developing agent or a processing solution containing no main agent (for an activator).

Next, a processing material and a 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 a built-in color developing agent), desilvering, and washing or stabilization. After washing or stabilizing,
In some cases, a treatment (alkali treatment) for enhancing color development, such as alkali addition, is also performed.

In the present invention, when the photosensitive material is subjected to development processing using a developer, the developer functions as a silver halide developing agent and / or an oxidized developing agent generated in silver development is incorporated in the photosensitive material. It is preferable to use a compound having a function of cross-oxidizing the color developing agent (auxiliary developing agent). Preferred are pyrazolidones, dihydroxybenzenes, reductones and aminophenols, and particularly preferred are pyrazolidones.

The pyrazolidones include 1-phenyl-3
-Pyrazolidones are preferred, and 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, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,5-dimethylhydroquinone,
And potassium hydroquinone monosulfonate.

As the reductones, N-methyl-p-
Aminophenol, N- (β-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 of them in combination to enhance the development and cross-oxidation activities. The amount of these compounds used in the developer is from 2.5 × 10 ⁻⁴ mol / l to 0.2 mol / l, preferably from 0.0025 mol / l to 0.1 mol / l.
1 mol / l, more preferably 0.001 mol / l
Liter to 0.05 mol / liter.

The preservatives used in the developer of the present invention include sodium sulfite, potassium sulfite, lithium sulfite, sodium formaldehyde sodium bisulfite, and hydroxylamine / sulfate.
Liter or less, preferably 0.001 to 0.02 mol /
May be used in the liter range. When a high silver chloride emulsion is used for the light-sensitive material,
It may not be contained at 1 mol / l or less, preferably at all.

In the present invention, an organic preservative is preferably contained in place of the above-mentioned hydroxylamine and sulfite ions. Here, the term "organic preservative" refers to all organic compounds that reduce the rate of deterioration of the developing agent by being added to a developer.
That is, organic compounds having a function of preventing the developing agent from being oxidized by air or the like, among which hydroxylamine derivatives (excluding hydroxylamine), hydroxamic acids, hydrazines, phenols, α-hydroxyketones, α- Aminoketones, sugars, monoamines, diamines, polyamines, quaternary ammoniums,
Nitroxy radicals, alcohols, oximes, diamide compounds, condensed amines and the like are particularly effective organic preservatives. These are disclosed in JP-A-63-4235 and JP-A-63-4235.
No.-5341, No.63-30845, No.63-216
No. 47, No. 63-44655, No. 63-46454
No. 63-53551, No. 63-43140, No. 63-56654, No. 63-58346, No. 63-
No. 43138, No. 63-146041, No. 63-44
657, 63-44656, U.S. Pat.
No. 5,503, No. 2,494,903, Tokubo Sho48
-30496 and the like. Other preservatives include JP-A-57-44148 and JP-A-57-537.
Various metals described in JP-A No. 49-180588
Salicylic acids, alkanolamines described in JP-A-54-3532, polyethyleneimines described in JP-A-56-94349, U.S. Pat. No. 3,746,54
An aromatic polyhydroxy compound described in No. 4 or the like may be contained as necessary. It is particularly preferable to contain alkanolamines described in JP-A-4-97355, pp. 631-632, and dialkylhydroxylamine described in JP-A 627-630. Further, a dialkylhydroxylamine and / or a hydrazine derivative may be used in combination with an alkanolamine, or α such as dialkylhydroxylamine and glycine described in EP 530,921 A1.
-It is also preferable to use amino acids in combination.

The use amount of these compounds is preferably 1 × 10 ^{−35 to} 5 × 10 ⁻¹ mol, more preferably 1 × 10 ⁻² to 2 × 10 ⁻¹ per liter of the developer.

In the present invention, the developer contains halogen ions such as chlorine ions, bromine ions and iodine ions. In particular, when a high silver chloride emulsion is used, it preferably contains 3.5 × 10 ^{-3 to} 3.0 × 10 ^-1 mol / l of chloride ions, more preferably 1 × 10 ^-2 to 2 × 2.
× 10 ^-1 mol / l, and / or preferably contains bromide ions in an amount of 0.5 × 10 ^{-5 to} 1.0 × 10 ^-3 mol / l, more preferably 3.0 × 10 ^-3 mol / l.
^{-5 to} 5 × 10 ^-4 mol / liter. Here, the halide may be directly added to the developer or may be eluted from the photosensitive material into the developer during the development processing.

When added to the developing solution, the supply materials include the respective sodium, potassium, ammonium, lithium and magnesium salts.

When eluted from the light-sensitive material, it is mainly supplied from a silver halide emulsion, but may be supplied from other sources.

The developing solution used in the present invention preferably has a pH of 8 to 13, more preferably 9 to 12. The above p
In order to retain H, it is preferable to use various buffers. Buffers include carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycine salt, N, N
-Dimethylglycine salt, leucine salt, norleucine salt,
Guanine salts, 3,4-dihydroxyphenylalanine salts, alanine salts, aminobutyrate salts, 2-amino-2-methyl-1,3-propanediol salts, valine salts, proline salts, trishydroxylaminomethane salts, lysine salts, etc. Can be used. In particular, carbonate, phosphate, tetraborate, and hydroxybenzoic acid have solubility and pH 9.0 or higher.
It is preferable to use these buffers because they have excellent buffering capacity in the H region and do not adversely affect photographic performance even when added to a developer.

Specific examples of these buffers include lithium carbonate, sodium carbonate, potassium carbonate, potassium bicarbonate, tripotassium phosphate, trisodium phosphate, dipotassium phosphate, disodium phosphate, potassium borate, and borate. Examples include sodium, sodium tetraborate, potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), and the like. The amount of the buffer added to the developer is preferably at least 0.05 mol / l, particularly preferably from 0.1 mol to 0.4 mol / l.

In addition, various chelating agents can be used in the developer as a precipitation inhibitor for calcium or magnesium, or for improving the stability of the developer. For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid,
Ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylenesulfonic acid, 1,2-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine orthohydroxy Phenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 1,2-dihydroxybenzene-4,6-disulfonic acid and alkali metal salts thereof. . These chelating agents may be used in combination of two or more as necessary. The addition amount of these chelating agents may be an amount sufficient to mask metal ions in the developer, for example, 0.1 g to 10 g per liter.
g.

In the present invention, an optional antifoggant can be added as required. As the antifoggant, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide and nitrogen-containing heterocyclic compounds are used. Examples of the nitrogen-containing heterocyclic compound include, for example,
Benzotriazole, 5-nitrobenzotriazole,
5-methylbenzotriazole, 5-nitrobenzimidazole, 5-nitroindazole, 2-thiazolylbenzimidazole, indazole, hydroxyazaindolizine, adenine, 1-phenyl-5-mercaptotetrazole or derivatives thereof are mentioned as typical examples. be able to. The addition amount of the nitrogen-containing heterocycle is 1 × 10 ⁻⁵ to 1
× 10 ^-2 mol / liter, preferably 2.5 to 10 ^-5
It is 1 × 10 ⁻³ mol / l.

An optional development accelerator can be added to the developer if necessary. As development accelerators, JP-B-37-16
No. 088, No. 37-5987, No. 38-7826,
Thioether compounds described in JP-A Nos. 44-12380 and 45-9019 and U.S. Pat. No. 3,813,247;
P-phenylenediamine compound represented by JP-A-5-554, JP-A-50-137726, JP-B-44-300
No. 74, JP-A-56-156826 and JP-A-52-4
Quaternary ammonium salts described in US Pat. Nos. 2,494,903, 3,128,182, 4,230,796, and 3,253,919; No. 11431, U.S. Pat. No. 2,482,546
Nos. 2,596,926 and 3,582,34
No. 6, etc., and the amine compounds described in JP-B-37-1608.
No. 8, No. 42-25201, U.S. Pat.
No. 501, etc., polyalkylene oxides and imidazoles can be added as necessary.

The developer preferably contains a fluorescent whitening agent. In particular, it is preferable to use a 4,4-diamino-2,2'-disulfostilbene compound. Specifically, commercially available optical brighteners, for example, "Stained Note 19th Edition"
Compounds described on pages 165 to 168 and JP-A No. 4-24
The compounds described on page 3 to page 7 of 2943 can be used. The addition amount is 0.1 g to 10 g / l, preferably 0.5 g to 5 g / l.

The processing temperature of the developing solution applied to the present invention is 2
The temperature is 0 to 50 ° C, preferably 30 to 45 ° C. The processing time is 5 seconds to 2 minutes, preferably 10 seconds to 1 minute. While replenishing amount is desirably small, the photosensitive material 1 m ² per 15
The volume is 600 ml, preferably 25 to 200 ml, and more preferably 35 to 100 ml.

The light-sensitive material of the present invention may have a form having a conductive heating element layer as a heating means for heat development. The heat generating element in this case is described in JP-A-61-145,
No. 544 can be used. The heating temperature in the thermal development step is about 65 ° C to 180 ° C, preferably about 70 ° C to 180 ° C, and more preferably about 75 ° C to 1 ° C.
It is 80 degreeC, Especially preferably, it is 80 degreeC-150 degreeC, More preferably, it is 80 degreeC-135 degreeC. The heating time is preferably 0.1 seconds to 120 seconds, more preferably 0.1 seconds to 60 seconds, and particularly preferably 0.1 seconds to 30 seconds.

As a heating method in the developing step, the film is brought into contact with a heated block or plate, or brought into contact with a hot plate, hot presser, heat roller, heat drum, halogen lamp heater, infrared or far-infrared lamp heater, or the like. Or passing through a high-temperature atmosphere. A method of superposing a heat-developable photosensitive material and a dye fixing material is described in JP-A-62-253,159 and 61-147,2.
The method described on page 44 (27) can be applied.

After the development, a desilvering treatment can be performed.
The desilvering process includes a fixing process and a bleaching and fixing process. When bleaching and fixing are performed, the bleaching process and the fixing process may be performed separately or simultaneously (bleach-fixing process). Further, processing in two continuous bleach-fixing baths, fixing before bleach-fixing, or bleach-fixing after bleach-fixing can be arbitrarily performed according to the purpose. In some cases, it is also preferable to carry out a stabilization treatment without performing a desilvering treatment after the development to stabilize a silver salt or a color image.

Examples of the bleaching agent used in the bleaching solution or the bleach-fixing solution include compounds of polyvalent metals such as iron (III), cobalt (III), chromium (IV) and copper (II), peracids and quinones. And nitro compounds. Representative compounds include iron chloride, ferricyanide compounds, dichromates, and organic complex salts of iron (III) (eg, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid). , Methyliminodiacetic acid and JP-A-4-365036
Nos. 5 to 17 and aminopolycarboxylic acids and metal salts), persulfates, permanganates, bromates, hydrogen peroxide and its releasing compounds (such as percarbonate and perboric acid), nitrobenzenes and the like Can be mentioned. Of these, iron (III) complex salts of aminopolycarboxylic acid such as iron (III) complex salt of ethylenediaminetetraacetate and iron (III) complex of 1,3-diaminopropanetetraacetate, hydrogen peroxide, persulfate and the like are rapidly treated and subjected to environmental treatment. It is preferable from the viewpoint of preventing contamination.
The pH of the bleaching solution or the bleach-fixing solution using the iron (III) aminopolycarboxylate is used at 3 to 8, preferably 5 to 7. The pH of the bleaching solution using a persulfate or hydrogen peroxide is 4 to 11, preferably 5 to 10.
It is.

In the bleaching solution, the bleach-fixing solution and the prebath thereof, a bleaching accelerator can be used if necessary.
Specific examples of useful bleach accelerators include US Pat.
No. 93,856, West German Patent No. 1,290,812, JP-A-53-95630, Research Disclosure No. Compounds having a mercapto group or a disulfide bond described in No. 17129 (July, 1978);
Thiazolidine derivatives described in JP-A-50-140129, thiourea derivatives described in U.S. Pat. No. 3,706,561, iodide salts described in JP-A-58-16235, West German Patent 2,748, No. 430, polyamine compounds described in JP-B-45-9936, bromide ions and the like can be used. Among them, compounds having a mercapto group or a disulfide group are preferred because they have a large accelerating effect. These bleaching accelerators are particularly effective in desilvering color photographic materials for photography.

With respect to the persulfate bleaching accelerator, see
-214365 (European Patent No. 602600A1)
A complex salt of the described iron (III) ion with 2-pyridinecarboxylic acid or 2,6-pyridinedicarboxylic acid is effective. Regarding the accelerator for hydrogen peroxide bleaching,
The metal salts of organic acids described in 1-116067 and 61-19024 are effective.

The bleaching solution, bleach-fixing solution and fixing solution include a rehalogenating agent such as ammonium bromide and ammonium chloride, ammonium nitrate, acetic acid, boric acid, citric acid or a salt thereof, tartaric acid or a salt thereof, succinic acid or a salt thereof. salt,
Known additives such as a pH buffer such as imidazole and the like, and a metal corrosion inhibitor such as ammonium sulfate can be used. In particular, it is preferable to contain an organic acid in order to prevent bleaching stain. The organic acid is a compound having an acid dissociation constant (pKa) of 2 to 7, specifically, acetic acid, succinic acid, citric acid, propionic acid and the like.

Examples of the fixing agent used in the fixing solution or the bleach-fixing solution include thiosulfates, thiocyanates, thioureas, large amounts of iodides, and JP-A-4-365037, pp. 11-21 and 5-66540. No. 1088-1092, a nitrogen-containing heterocyclic compound having a sulfide group,
Mesoionic compounds and thioether compounds can be mentioned. Of these, thiosulfates are generally used, and ammonium thiosulfate is most widely used.
It is also preferable to use a combination of a thiosulfate with a thiocyanate, a thioether compound, a thiourea, a mesoionic compound, or the like.

As a preservative of the fixing solution or the bleach-fixing solution, a sulfite, a bisulfite, a carbonyl bisulfite adduct or a sulfinic acid compound described in European Patent No. 294,769A is preferable. Furthermore, various aminopolycarboxylic acids and organic phosphonic acids (for example, 1-hydroxyethylidene-1, 1-hydroxyethylidene-1, etc.) are added to the fixing solution, the bleaching solution and the bleach-fixing solution for the purpose of stabilizing the solution.
1-diphosphonic acid, N, N, N ', N'-ethylenediaminetetraphosphonic acid, 2-phosphonobutane-1,2,2
Addition of sodium tristannate (4-tricarboxylic acid) is preferred.

The fixing solution and the bleach-fixing solution may further contain various fluorescent whitening agents, antifoaming agents, surfactants, polyvinylpyrrolidone, methanol and the like.

The processing temperature in the desilvering step is from 20 to 50 ° C., preferably from 30 to 45 ° C. The processing time is 5 seconds to 2 minutes, preferably 5 seconds to 1 minute. The replenishment amount is preferably smaller, but is preferably 15 to 600 ml, preferably 25 to 200 ml, more preferably 35 to 100 ml per m ^{2 of} the light-sensitive material.
ml. It is also preferable to perform the treatment without replenishment, to the extent that the evaporation amount is supplemented with water.

The light-sensitive material of the present invention generally undergoes a washing step after desilvering. When the stabilization treatment is performed, the washing step may be omitted. In such a stabilization process, JP-A-57-8543 and JP-A-58-1483 are used.
Nos. 4 and 60-220345, and JP-A-5-220345.
8-127926, 58-13837, 58
All known methods described in JP-A-140741 can be used. Further, a washing-stabilizing step may be carried out in which a stabilizing bath containing a dye stabilizer and a surfactant, typified by processing of a color light-sensitive material for photography, is used as a final bath.

The washing solution and the stabilizing solution include hard water softeners such as sulfite, inorganic phosphoric acid, polyaminocarboxylic acid and organic aminophosphonic acid, metal salts such as Mg salt, Al salt and Bi salt, and surfactants. Agents, hardeners, pH buffers, optical brighteners, silver salt-forming agents such as nitrogen-containing heterocyclic compounds, and the like can be used. Examples of the dye stabilizer of the stabilizing solution include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine and aldehyde sulfite adducts.

The pH of the washing or stabilizing solution is 4 to 9, preferably 5 to 8. The processing temperature is from 15 to 45C, preferably from 25 to 40C. Processing time is 5 seconds ~
2 minutes, preferably 5 to 40 seconds. The overflow solution accompanying the washing and / or replenishment of the stabilizing solution can be reused in other steps such as a desilvering step.

The amount of washing water and / or stabilizing solution can be set in a wide range depending on various conditions, but the replenishing amount is preferably 15 to 360 ml per 1 m ² of the photographic material, and is preferably 25 to 12 ml.
0 ml is more preferred. In order to reduce the amount of replenishment water, it is preferable to use a plurality of tanks and carry out a multi-stage countercurrent system. In particular, it is preferable to use 2 to 5 tanks. In order to prevent the propagation of bacteria which occur when the amount of water is reduced and the contamination of the resulting suspended matter to the photosensitive material, isothiazolone compounds, siapentazoles, and chlorinated compounds described in JP-A-57-8542 are used. Fungicides such as sodium isocyanurate, and other benzotriazoles, etc., written by Hiroshi Horiguchi, "Chemistry of Fungicides and Fungicides" (1986)
(Published by Sankyo Publishing Co., Ltd.), "Sterilization, Sterilization, and Fungus Control Techniques of Microorganisms" edited by the Society of Sanitary and Fungicides (1982, Industrial Technology Association), edited by the Japan Society of Antibacterial and Fungicides, "Encyclopedia of Antifungal and Fungicides" (1986) Can be used. Also, JP-A-62-28
The method of reducing Mg and Ca ions described in No. 8838 is also particularly preferably used.

In the present invention, water obtained by treating an overflow liquid or a liquid in a tank with a reverse osmosis membrane to save water can be used. For example, the treatment by reverse osmosis is preferably performed on water in the second and subsequent tanks for multi-stage countercurrent washing and / or stabilization. Specifically, in the case of a two-tank configuration, the water in the second or fourth tank is treated with a reverse osmosis membrane in the case of a four-tank configuration, and the permeated water is treated in the first tank (reverse osmosis membrane treatment). (A tank from which water has been collected) or a subsequent washing and / or stabilizing tank. One solution is to return the concentrated liquid to a tank upstream of the same tank and return to a desilvering bath.

As the material of the reverse osmosis membrane, cellulose acetate,
Crosslinked polyamide, polyether, polysulfone, polyacrylic acid, polyvinylene carbonate and the like can be used.
The liquid sending pressure in the use of these membranes is preferably 2 to
10 kg / cm ^2, particularly preferably 3~7Kg / cm ^2.

In the present invention, it is preferable that the stirring is strengthened as much as possible. Specific methods of strengthening the stirring are described in JP-A-62-183460 and JP-A-62-183.
No. 461, a method in which a jet jet of a processing liquid impinges on an emulsion surface of a light-sensitive material, a method described in JP-A-62-183461, in which stirring efficiency is increased by using a rotating means, and a wiper provided in a liquid. A method of improving the stirring effect by moving the light-sensitive material while bringing the blade and the emulsion surface into contact with each other to make the emulsion surface turbulent, and a method of increasing the circulating flow rate of the entire processing solution. Such stirring improving means include a developing solution, a bleaching solution, a bleach-fixing solution, a stabilizing solution,
It is useful in any washing. These methods are effective in that the supply of the effective component in the liquid into the photosensitive material and the diffusion of the unnecessary component in the photosensitive material are promoted.

In the present invention, the liquid opening ratio [air contact area (cm ² ) / liquid volume (cm ³ )] of any bath shows excellent performance in any state, but from the viewpoint of stability of liquid components. The liquid aperture ratio is preferably from ⁰ to 0.1 cm ^-1 . In a continuous process, 0.001 cm ^{-1 to} 0.0
5 cm ^-1 is preferable, and more preferably 0.002 to
0.03 cm ^-1 .

The automatic developing machine used for the light-sensitive material of the present invention is described in JP-A-60-191257 and JP-A-60-19125.
No. 8, No. 60-191259. Such a transport means can significantly reduce the carry-in of the processing solution from the pre-bath to the post-bath,
The effect of preventing performance deterioration of the processing liquid is high. Such an effect is effective in shortening the processing time of each step and in reducing the amount of processing replenishment. In order to shorten the processing time, it is preferable to shorten the crossover time (air time). For example, FIGS. 4, 5 and 6 of JP-A-4-86659 and FIGS. 4 and 6 of JP-A-5-66540. The method of transporting between the processes described in 5 through a blade having a shielding effect is preferable. Further, when the respective processing liquids are concentrated by evaporation in the continuous processing, it is preferable to correct the concentration by adding water.

The processing time of the step in the present invention means the time required from the start of processing of the photosensitive material in one step to the start of processing in the next step. The actual processing time in an automatic developing machine is usually determined by the linear velocity and the capacity of the processing bath.
000 mm / min. In particular, in the case of a small developing machine, the speed is preferably 500 to 2500 mm / min. The entire processing step, that is, the processing time from the developing step to the drying step is preferably 360 seconds or less, more preferably 120 seconds or less, and particularly preferably 9 seconds or less.
Preferably, it is used for 0 to 30 seconds. Here, the processing time is the time from when the photosensitive material is immersed in the developing solution to when it comes out of the drying unit of the processor. Further, the color developing agent and the coupler of the present invention can be used in combination in the same photographic element with known dye donating compounds such as a dye developing agent described later and a compound which releases a diffusible dye by a redox reaction. For example, a method of forming an image of yellow and cyan with the color developing agent of the present invention and a coupler, and forming an image of magenta with another dye image forming compound can be used. Examples of the dye image forming compound that can be used in the present invention include a combination of a known developing agent and a coupler that can react therewith. The method using the coupler is a method in which an oxidized form of a developing agent generated by an oxidation-reduction reaction between a silver salt and a developing agent reacts with the coupler to form a dye, and is described in many documents. The coupler may be a 4-equivalent coupler or a 2-equivalent coupler. Also, having a non-diffusible group in the leaving group,
Produces a diffusible dye by reaction with an oxidized form of developer 2
Equivalent couplers are also preferred. Specific examples of developing agents and couplers can be found in James The Theory of the Photographic Process, 4th Edition (TH James “The Theory
of the Photographic Process, pp. 291-334 and 354-361, JP-A-58-123533, JP-A-58-149046, JP-A-58-149047, and JP-A-58-14947.
Nos. 9-111148, 59-124399, 59
No. 174835, No. 59-231439, No. 59-
No. 231540, No. 60-2950, No. 60-295
No. 1, No. 60-14242, No. 60-23474,
No. 60-66249, and the like.

Dye silver compounds in which an organic silver salt is combined with a dye can also be mentioned as examples of the dye image forming compound.
Specific examples of the dye silver compounds are described in Research Disclosure, May 1978, pages 54 to 58 (RD-1696).
6) and the like.

The azo dyes used in the heat-developed silver dye bleaching method can also be mentioned as examples of the dye image forming compound. Specific examples of azo dyes and the method of bleaching are described in U.S. Pat. No. 4,235,957, Research Disclosure, April 1976, pp. 30-32 (RD-14433).
And so on. No. 3,985,5.
The leuco dyes described in Nos. 65, 4,022,617 and the like can also be mentioned as examples of the dye-providing substance.

Further, as another example of the dye image forming compound, a compound having a function of releasing or diffusing a diffusible dye imagewise can be mentioned. This type of compound can be represented by the following general formula [LI]. (Dye-X) _n -Y [LI] Dye represents a known dye group or a temporarily shortened dye group or dye precursor, X represents a simple bond or linking group, and Y represents an image-like latent group. A difference is caused in the diffusivity of the compound represented by (Dye-X) _n -Y corresponding to or opposite to the photosensitive silver salt having an image, or Dye is released, and the released Dye and (Dye) -X) represents a group having a property that causes a difference in diffusibility with _n- Y. n represents 1 or 2, and when n is 2, two Dy
eX may be the same or different.

Specific examples of the dye-providing substance represented by the general formula [LI] include, for example, a dye developing agent obtained by linking a hydroquinone-based developing agent and a dye component with US Pat.
No. 4,764, No. 3,362,819, No. 3,5
No. 97,200, No. 3,544,545, No. 3,
No. 482,972. A substance capable of releasing a diffusible dye by an intramolecular nucleophilic substitution reaction is disclosed in JP-A-51-63618, and a substance capable of releasing a diffusible dye by an intramolecular reversal reaction of an isoxazolone ring is disclosed in JP-A-49-636. No. 111628 and the like. Each of these systems releases or diffuses a diffusible dye at a portion where development has not occurred, and the dye does not release or diffuse at a portion where development has occurred. As another method, the dye-releasing compound is converted into an oxidized form having no dye-releasing ability and coexists with a reducing agent or a precursor thereof.After development, the diffusing dye is reduced by the remaining non-oxidized reducing agent to form a diffusible dye. A release system has also been devised, and specific examples of the dye image-forming compound used therein are disclosed in JP-A-53-110,827.
Nos. 54-130,927 and 56-164,34
2, No. 53-35, 533.

On the other hand, as a substance capable of releasing a dye at a portion where development has occurred, a substance capable of releasing a diffusible dye by a reaction between a coupler having a leaving group for a diffusible dye and an oxidized developer is disclosed in British Patent No. 1 , 330, 524, Tokiko Sho48-
39,165 and U.S. Pat. No. 3,443,940. Also, in the method using these color developing agents, the contamination of the image by the oxidized and decomposed products of the developing agent becomes a serious problem. Therefore, in order to solve this problem, the developing agent is not required. Dye-releasing compounds having such compounds have also been devised. Representative examples are, for example, U.S. Pat. Nos. 3,928,312, 4,053,312, 4,055,428, and 4,336,322.
JP-A-59-65839, JP-A-59-69839, JP-A-51-104,343, Research Disclosure No. 17465, U.S. Pat. No. 3,725,062,
Nos. 3,728,113 and 3,443,939
No., JP-A-58-11637 and 57-179840.
And dye image forming compounds described in U.S. Pat. No. 4,500,626.

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 comprises a light-sensitive element and an image-receiving element (dye-fixing element) separately coated on two supports. It is roughly classified into a form and a form coated on the same support. The relationship between the photosensitive element and the dye-fixing element, the relationship with the support, and the relationship with the white reflective layer are described in
The relationships described on pages 58-59 of the specification of JP-147244 and column 57 of U.S. Pat. No. 4,500,626 are also applicable to the photosensitive material of the present invention.

A typical form of a film unit in which a photosensitive element and an image receiving element (dye fixing element) are provided on the same support is such that an image receiving element and a photosensitive element are laminated on one transparent support. This is a mode in which it is not necessary to peel off the photosensitive element from the image receiving element after the transfer image is completed. More specifically, the image-receiving element comprises at least one phase mordant layer (also referred to as an image-receiving layer or a dye-fixing layer). 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 are provided. A combination of an emulsion layer, or a combination of a green-sensitive emulsion layer, a red-sensitive emulsion layer, and an infrared-sensitive emulsion layer, or a combination of a blue-sensitive emulsion layer, a red-sensitive emulsion layer, and an infrared-sensitive emulsion layer, In each of the emulsion layers, 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 The image forming compound (the color developing agent of the present invention and a dye image forming compound containing a coupler) are each combined. (Here, the “infrared light-sensitive emulsion layer” is 700 nm or more, especially 740 n
m means an emulsion layer having photosensitivity to light of not less than m. ) Each of these photosensitive emulsion layers may be divided into two or more layers as necessary. Titanium oxide is provided 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 a coupler) so that the transferred image can be viewed through a transparent support. And 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 light place. If desired, a release layer may be provided at an appropriate position so that all or part of the photosensitive element can be released from the image receiving element (for example, JP-A-56-67840 and Canada). Patent No. 674,082).

In another mode in which no peeling is required, the above-described 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 release layer, and a photosensitive element are laminated on the same support, and a method of intentionally separating the photosensitive element from the image receiving element is described in US Pat. No. 3,730,7.
No.18. On the other hand, there are roughly two typical forms in which a photosensitive element and an image receiving element are separately coated on two supports, respectively, one of which is a peeling type and the other is a peeling-free type. More specifically, in a preferred embodiment of the release film unit, a light reflecting layer is provided on the back surface of the support, 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. Before the exposure, the photosensitive layer-coated surface and the mordant layer-coated surface do not face each other, but after the exposure (for example, during the developing process), the photosensitive layer is coated. The surface is turned upside down so as to overlap with the image receiving layer coating surface.
After the transfer image is completed in the mordant layer, the photosensitive element is immediately separated from the image receiving element. In a preferred embodiment of the peeling-free 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 application surface and the mordant layer application surface face each other and are overlaid.

Each of the above-mentioned embodiments can be applied to a method of developing with an alkali processing solution by developing an alkali processing solution and to a heat development method. In the former case, in particular, an alkali processing solution is further contained and the pressure is reduced. A rupturable container (processing element) may be combined. In particular, in a peeling-free film unit in which an image receiving element and a photosensitive element are laminated on one support, it is preferable that this processing element is disposed between the photosensitive element and a cover sheet overlaid thereon. In the case where the photosensitive element and the image receiving element are separately coated on the two supports, it is preferable that the processing element is arranged between the photosensitive element and the image receiving element at the latest at the time of development processing. The processing element preferably contains a light-shielding agent (such as carbon black or a dye whose color changes depending on pH) and / or a white pigment (such as titanium oxide) depending on the form of the film unit. Further, in a film unit developed with an alkali processing solution, a neutralization timing mechanism comprising 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. The mordant used in the image receiving element and the dye fixing element described below is preferably a polymer mordant. Here, the polymer mordant is
Examples include a polymer containing a tertiary amino group, a polymer containing a nitrogen-containing heterocyclic moiety, and a polymer containing a quaternary cationic group. This specific example 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 may contain, if necessary, various additives known for photothermographic elements and layers other than the photosensitive layer, for example, a protective layer, an intermediate layer, an antistatic layer, and an antihalation layer. It can have a layer, a release layer for facilitating release from the dye fixing element, a mat layer, and the like. Examples of various additives include Research Disclosure Magazine, June 1978, pp. 9-15, JP-A-61-8825.
No. 6, etc., plasticizers, matting agents, dyes for improving sharpness, antihalation dyes, surfactants, optical brighteners, antislip agents, antioxidants, antifading agents, and diffusible dye trapping agents And other additives. In particular, the protective layer usually contains an organic or inorganic matting agent for preventing adhesion. The 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 and color mixing, an ultraviolet absorber, and 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.

The dye-fixing element may optionally have a protective layer,
An auxiliary layer such as a release layer and an anti-curl layer can be provided. It is particularly 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 sliding agent, a matting agent, an antioxidant,
A dispersion vinyl compound for increasing dimensional stability, a surfactant, an optical brightener, and the like may be included. In particular, in a system in which thermal development and dye diffusion transfer are simultaneously performed 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, which will be described later, in order to enhance the storage stability of the photosensitive element. Specific examples of these additives are described in JP-A-61-88256, pp. 101-120.

In the present invention, an image formation accelerator can be used in the light-sensitive element and / or the dye-fixing element.
Examples of the image formation accelerator include the promotion of a redox reaction between a silver salt oxidizing agent and a reducing agent, the formation of a dye from a dye image-forming compound containing a color developing agent and a coupler of the present invention, or the decomposition or release of a diffusible dye. And the transfer of the dye from the constituent layers of the photosensitive element to the dye-fixing layer.The physicochemical functions include a base or a base precursor, a nucleophilic compound, and a high-boiling organic solvent. (Oils), thermal solvents, surfactants, compounds having an interaction with silver or silver ions, and the like. However, these substance groups generally have a composite function and usually have some of the above-mentioned promoting effects. Details of these are described in JP-A-61-93451, pp. 67-71.

There are various methods for generating a base, and any compound used in the method is useful as a base precursor. For example, European Patent No. 0210660A2
By mixing a hardly water-soluble metal compound (eg, a metal salt) and a compound capable of forming a complex with a metal ion constituting the hardly-soluble metal compound (referred to as a complex-forming compound or complexing agent) described in The method of generating
There is a method of generating a base by electrolysis described in 1-223251. In particular, the former method is effective. As the hardly soluble metal compound, zinc, aluminum,
Carbonates such as calcium and barium, hydroxides, oxides and the like. As for the complex-forming compound, for example, A.E.Martel, 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 esters, amides, alkoxy, mercapto, alkylthio, phosphino), hydroxamic acids, polyacrylates, polyphosphoric acids and the like, and salts with alkali metals, guanidines, amidines or quaternary ammonium salts. Can be

The sparingly soluble metal compound and the complex forming compound are advantageously added separately to the light-sensitive element and the dye-fixing element. In the light-sensitive element and / or dye-fixing element of the present invention, various development terminators can be used for the purpose of always obtaining a constant image with respect to fluctuations in processing temperature and processing time during development. As used herein, the term "development terminator" means that after appropriate development, the base is immediately neutralized or reacted with the base to lower the base concentration in the film, and interacts with a compound or silver and silver salt which stops the development to effect development. It is a compound that suppresses. Specific examples thereof include an acid precursor that releases an acid when heated, an electrophilic compound that undergoes a substitution reaction with a coexisting base when heated, or a nitrogen-containing heterocyclic compound, a mercapto compound, and a precursor thereof (for example, Nos. 60-10887, 60-192939, 60-230133 and 60-230134). Also,
Compounds which release a mercapto compound upon heating are also useful, for example, JP-A-61-67851 and JP-A-61-14.
Nos. 7244, 61-124941, 61-185
Nos. 743, 61-182039 and 61-1857
No. 44, No. 61-184439, No. 61-18854
No. 0 and 61-53632.

As the binder for the light-sensitive element and / or dye-fixing element of the present invention, a hydrophilic binder can be used. Representative examples of the hydrophilic binder include transparent or translucent hydrophilic binders, for example, natural substances such as gelatin, proteins such as gelatin derivatives, polysaccharides such as cellulose derivatives, starch, and gum arabic, and polyvinylpyrrolidone. And synthetic polymer substances such as water-soluble polyvinyl compounds such as acrylamide polymers. Also, dispersed vinyl compounds which are used in the form of a latex and increase the dimensional stability of the photographic material can be used. These binders can be used alone or in combination.
In the present invention, the amount of the binder to be applied is 20 g or less per 1 m ² , preferably 10 g or less, more preferably 7 g or less. The ratio of the high boiling organic solvent and the binder dispersed together with the color developing agent of the present invention and a hydrophobic compound such as a coupler in the binder is as follows.
The solvent is suitably 1 cc or less, preferably 0.5 cc or less, more preferably 0.3 cc or less, based on g. 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 hardeners are disclosed in
No. 147244, pages 94 to 95, and
9-157636, page 38, and the like.
These can be used alone or in combination.

Further, in order to promote the dye transfer, a hydrophilic heat solvent which is solid at normal temperature and dissolves at a 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 preferable to incorporate the dye in the dye fixing layer and / or the layer adjacent thereto. Examples of hydrophilic thermal solvents include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes, and other heterocycles. Further, in order to promote dye transfer, a high boiling organic solvent may be contained in the photosensitive element and / or the dye fixing element.
The support used in the light-sensitive element and / or 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 described in JP-A-61-147244, pages 95 to 96, as the support. Things can be used. The photosensitive 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 made 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 an inorganic material exhibiting semiconductivity 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 described in JP-A-61-2.
No. 9835 can be used.

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

In the present invention, a preferable image forming method is as follows.
Heating in the presence of a trace amount of water and a base and / or base precursor at the same time as the image exposure and / or
Simultaneously with the development, the diffusible dye formed in the portion corresponding to or opposite to the silver image is transferred to the dye fixing layer.
According to this method, the generation or release reaction of the diffusible dye proceeds extremely quickly, and the transfer of the diffusible dye to the dye fixing layer also proceeds rapidly, so that a high-density color image can be obtained in a short time. The amount of water used in this embodiment is at least 0.1 times, preferably 0.1 times or more, the weight of the entire coating film of the photosensitive element and the dye-fixing layer, of the solvent corresponding to the maximum swelling volume of the entire coating film. The weight may be as small as not more than the weight (in particular, not more than the weight of the solvent corresponding to the maximum swelling volume of the entire coating film minus the weight of the entire coating film). The state of the film at the time of swelling is unstable, and depending on the conditions, local bleeding may occur. To avoid this, it corresponds to the maximum swelling volume of the total coating thickness of the photosensitive element and the dye fixing element. The amount of water or less is preferred. Specifically, the total amount of the photosensitive element and the dye fixing element is 1 to 50 g, preferably 2 to 35 g, and more preferably 3 to 50 g per square meter.
A range of ２５25 g is preferred. The base and / or base precursor used in this embodiment can be incorporated in the photosensitive element as well as in the dye-fixing element. Alternatively, it can be supplied after being dissolved in water. In the above embodiment, a metal compound that is hardly soluble in water (for example, a basic compound that is hardly soluble in water) and a metal ion that forms the hardly soluble metal compound and water are used as a base precursor in the image forming reaction system. A compound capable of forming reaction (complexing agent) is contained, and the reaction of these two compounds at the time of heating generates an alkali to increase the pH of the system.
Is preferably increased. Here, the image reaction system means a region where an image forming reaction occurs. Specific examples include layers belonging to both the photosensitive element and the dye fixing element. When there are two or more layers, any of the layers may be used.

The hardly soluble metal compound and the complex forming compound need to be added to at least another layer in order to prevent a reaction before the development processing. For example, in the case of a so-called monosheet material in which a photosensitive element and a dye fixing element are provided on the same support, it is preferable that the above-mentioned two additional layers be separate layers and one or more layers be interposed therebetween. In a more preferred embodiment, the hardly soluble metal compound and the complex-forming compound are contained in layers provided on different supports, respectively. For example, it is preferable that the poorly soluble metal compound is contained in the photosensitive element, and the complex forming compound is contained in the dye fixing element having a support different from the photosensitive element. The complex-forming compound may be supplied after being dissolved in coexisting water. Poorly soluble metal compounds are disclosed in
It is desirable that the fine particles are contained as a fine particle dispersion prepared by the method described in JP-A-6-17480, JP-A-53-102733, etc., and the average particle size is 50 μm or less, particularly 5 μm or less.
μm or less is preferred. The poorly soluble metal compound may be added to any layer such as a photosensitive layer, an intermediate layer, and a protective layer of the photosensitive element.
It may be added in two or more layers. When the hardly soluble metal compound or the complex-forming compound is contained in the layer on the support, the amount added is the compound type, the particle size of the hardly soluble metal compound,
Although it depends on the complexation reaction rate, etc., it is appropriate to use each coating film at 50% by weight or less in terms of weight, more preferably 0.01% by weight to 40% by weight.
A weight percent range is useful. When the complex-forming compound is supplied after being dissolved in water, the concentration is preferably from 0.005 mol to 5 mol, particularly from 0.05 mol to 2 mol, per liter. Further, in the present invention, the content of the complex-forming compound in the reaction system is 1/100 to 100 times, particularly 1/1, in molar ratio to the content of the hardly soluble compound.
It is preferably from 0 to 20 times.

As a method for applying water to the photosensitive layer or the dye fixing layer, for example, Japanese Patent Application Laid-Open No. 61-147244
There is a method described on page 01, line 9 to page 102, line 4. As a heating means in the development and / or transfer step, a heating plate, an iron, a heating roller, etc. are disclosed in JP-A-61-14724.
No. 4, page 102, line 14 to page 103, line 11 is available. Also, in the photosensitive element and / or the dye fixing element,
A layer of a conductive material such as graphite, carbon black, metal, or the like may be applied in an overlapping manner, and the conductive layer may be directly heated by passing an electric current. The method described in pages 61 to 104 of JP-A-61-147244 can be applied as a pressure condition and a method of applying pressure when the photosensitive element and the dye fixing element are overlapped and brought into close contact with each other. Any of a variety of thermal development equipment can be used to process the photographic elements of the present invention. For example, JP-A-59-75247 and JP-A-59-17
Nos. 7547, 59-181353, 60-189
Nos. 51 and 62-25594 are preferably used.

[0193]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto. Example 1 An image receiving element R101 having the configuration shown in Tables 1 and 2 was produced.

[0194]

[Table 1]

[0195]

[Table 2]

[0196]

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[0197]

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[0198]

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[0199]

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[0200]

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[0201]

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[0202]

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Next, a method for manufacturing the photosensitive element will be described. First, a method for preparing a photosensitive silver halide emulsion will be described. Photosensitive silver halide emulsion (1) (for red-sensitive emulsion layer) Solution (I) having the composition shown in Table 4 was added to a well-stirred aqueous solution having the composition shown in Table 3 at an equal flow rate for 9 minutes. (II)
The solution was added at an equal flow rate for 9 minutes and 10 seconds from 10 seconds before the addition of solution (I). 36 minutes later, (II) having the composition shown in Table 4
The solution (I) was added at a constant flow rate for 24 minutes, and the solution (IV) was added at the same flow rate as the solution (III) for 25 minutes. After washing with water and desalting (using a precipitant a at pH 4.0) using a conventional method, 880 g of lime-treated ossein gelatin was added to adjust the pH to 6.0, and then 12.8 g of ribonucleic acid hydrolyzate trimethylthiourea After adding 32 mg and performing optimal chemical sensitization at 60 ° C. for 71 minutes, 2.6 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, 3.2 g of dye (a) and 5.1 g of KBr Then, 2.6 g of a stabilizer was sequentially added, and the mixture was cooled. In this way the average particle size is 0.35
As a result, 28.1 kg of a monodisperse cubic silver chlorobromide emulsion having a thickness of μm was obtained.

[0204]

[Table 3]

[0205]

[Table 4]

[0206]

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Photosensitive silver halide emulsion (2) (for green-sensitive emulsion layer) Solution (I) and solution (II) having the composition shown in Table 6 were simultaneously added to a well-stirred aqueous solution having the composition shown in Table 5. Add at an equal flow rate for minutes. Five minutes later, the solution (III) having the composition shown in Table 6 and the solution (I)
V) The solution was added simultaneously at an equal flow rate for 32 minutes. Also, (I
After addition of solution V) and solution (III), methanol solution of dye
60 ml (360 mg of pigment (b1) and 73.4 mg of pigment (b2)
) Were added all at once. After washing with water and desalting (using a precipitant a at a pH of 4.0) according to a conventional method, 22 g of lime-treated ossein gelatin was added to adjust the pH to 6.0 and pAg.
After adjusting to 7.6, add 1.8 mg of sodium thiosulfate and 180 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene and optimally sensitize at 60 ° C. 1) After adding 90 mg, the mixture was cooled. Thus, a monodispersed cubic silver chlorobromide emulsion having an average grain size of 0.30 μm 63
5 g were obtained.

[0208]

[Table 5]

[0209]

[Table 6]

[0210]

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Photosensitive Silver Halide Emulsion (3) (for Blue Sensitive Emulsion Layer) Ten seconds after adding the solution (II) having the composition shown in Table 8 to the well-stirred aqueous solution having the composition shown in Table 7, I) The liquids were each added over 30 minutes. Also, 2 minutes after the addition of the (I) solution, the (V) solution was added, 5 minutes after the addition of the (II) solution, the (IV) solution was added, and 10 seconds later, the (III) solution was added for 27 minutes and 50 seconds.
V) Solution was added over 28 minutes. After washing with water and desalting (using a precipitant b at a pH of 3.9) according to a conventional method, 1230 g of lime-treated ossein gelatin and 2.8 mg of the compound (b) were added to adjust the pH to 6.1 and the pAg to 8.4. Thereafter, 24.9 mg of sodium thiosulfate was added and the mixture was optimally sensitized at 60 ° C., and 13.1 g of the dye (c) and 118 ml of the compound (c) were sequentially added, followed by cooling. The silver halide grains of the emulsion thus obtained are potato-like grains and have an average grain size of 0.53 μm.
m, the yield was 30700 g.

[0212]

[Table 7]

[0213]

[Table 8]

[0214]

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Next, a method for preparing a gelatin dispersion of a hydrophobic additive will be described.

A gelatin dispersion of each of the yellow coupler, magenta coupler and cyan coupler and a developing agent was prepared according to the formulation shown in Table 9. That is, each oil phase component is heated and dissolved at about 70 ° C. to form a uniform solution.
The aqueous layer component heated to 0 ° C. was added, and the mixture was stirred and mixed, and then dispersed with a homogenizer for 10 minutes at 10,000 rpm. Water was added thereto and stirred to obtain a uniform dispersion.

[0219]

[Table 9]

Gelatin dispersions of an antifoggant and a reducing agent were prepared as shown in Table 10. That is, each oil layer component is heated and dissolved at about 60 ° C. to form a uniform solution, and the aqueous layer component heated to about 60 ° C. is added to this solution, and the mixture is stirred and mixed. I got something.

[0219]

[Table 10]

Table 1 shows the dispersion of the polymer latex (a).
Prepared as per 1 formulation. That is, while stirring the mixture of the polymer latex (a), the surfactant and the water, the anionic surfactant was added over 10 minutes to obtain a uniform dispersion. Further, the obtained dispersion is subjected to an ultrafiltration module (Asahi Kasei ultrafiltration module: ACV-3050).
(Trade name)), dilution with water and concentration were repeated so that the salt concentration in the dispersion became 1/9.

[0221]

[Table 11]

A gelatin dispersion of zinc hydroxide was prepared as shown in Table 12. That is, after mixing and dissolving each component, the mixture was dispersed in a mill for 30 minutes using glass beads having an average particle size of 0.75 mm. Further, the glass beads were separated and removed to obtain a uniform dispersion.

[0223]

[Table 12]

Next, a method for preparing a gelatin dispersion of a matting agent added to the protective layer will be described. A solution obtained by dissolving PMMA in methylene chloride was added to gelatin together with a small amount of a surfactant to obtain a uniform dispersion having an average particle size of 4.3 μm.

Using the above, photosensitive element 101 shown in Table 13 was prepared.

[0226]

[Table 13]

[0227]

[Table 14]

[0228]

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[0229]

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[0230]

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[0231]

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[0232]

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Next, the first layer, the third layer
The photosensitive element 103 was prepared in the same manner except that the developing agent represented by the general formula (1) of the present invention and the coupler shown in Table 15 were used instead of the developing agent and the coupler used in the layer and the fifth layer.
~ 108 were created. Table 15 shows the developing agents and couplers used here. Also, Japanese Patent Application Laid-Open No. 09-152702
The light-sensitive element 102 was prepared using the compounds described in the above item.
Then, using the photosensitive material and the image receiving element R101 obtained as described above, the heating conditions were set to 83 using a Pictrostat 330 (trade name) manufactured by Fuji Photo Film Co., Ltd.
Image output was performed at 20 ° C. for 20 seconds. Photosensitive elements 103-108
The output image was a clear color image, and when the compound of the present invention was used, the sharpness of the image was excellent. The maximum density and the minimum density of these obtained images are defined as X-ri
The measurement was performed using a reflection densitometer X-rite304 manufactured by te. The results are shown in Table 16. As is clear from Table 16, when the compound of the present invention was used, good color development could be obtained even with a short development time, and the obtained image was stable under conditions such as light, heat, and humidity. Met.

[0234]

[Table 15]

[0235]

[Table 16]

Example 2 A photosensitive element 201 was prepared by the following method. First, a method for preparing a photosensitive silver halide emulsion will be described.

Photosensitive Silver Halide Emulsion (4) (for Fifth Layer (680 nm Photosensitive Layer)) A well-stirred aqueous solution of the composition shown in Table 17 was mixed with the solution (I) and the solution (II) having the composition shown in Table 18. The liquid was simultaneously added dropwise over 13 minutes, and 10 minutes later, (II) having the composition shown in Table 18
Solution I) and solution (IV) were added over 33 minutes.

[0238]

[Table 17]

[0239]

[Table 18]

[0240]

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Also, an aqueous solution containing 0.35% of a sensitizing dye was added over a period of 27 minutes from 13 minutes after the start of the addition of the solution (III).
0 cc was added.

After washing with water and desalting (using a precipitant a at a pH of 4.1), lime-treated ossein gelatin 22 was used.
g and the pH and pAg were adjusted to 6.0 and 7.9, respectively.
Chemical sensitization at 0 ° C. The compounds used for chemical sensitization are shown in Table 1.
9. In this way the average particle size is 0.
Monodisperse cubic silver chlorobromide emulsion with a coefficient of variation of 20 μm and 10.2% 63
0 g was obtained.

[0243]

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[0244]

[Table 19]

[0245]

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[0246]

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Photosensitive silver halide emulsion (5) (for the third layer (750 nm photosensitive layer)) A well-stirred aqueous solution having the composition shown in Table 20 was mixed with the solution (I) and the solution (II) having the composition shown in Table 21. The liquids were added simultaneously over 18 minutes. Ten minutes later, solution (III) and solution (IV) having the composition shown in Table 21 were added simultaneously over 24 minutes.

[0248]

[Table 20]

[0249]

[Table 21]

After washing with water and desalting (using a precipitant b at a pH of 3.9) according to a conventional method, 22 g of decalcified lime-treated ossein gelatin (calcium content: 150 ppm or less) was added, and the mixture was added at 40 ° C. Redisperse, 4-hydroxy-6
Add 0.39 g of -methyl-1,3,3a, 7-tetrazaindene and add p
H was adjusted to 6.9 and pAg to 7.8. Thereafter, chemical sensitization was performed at 70 ° C. using the chemicals shown in Table 22. At the end of the chemical sensitization, the sensitizing dye was added as a methanol solution (a solution having a composition shown in Table 23). Furthermore, after chemical sensitization, 40
The temperature was lowered to 0 ° C., and a gelatin dispersion 20 of a stabilizer described later was prepared.
After adding 0 g and stirring well, 938 g of a monodispersed cubic silver chlorobromide emulsion having an average grain size of 0.25 μm and a variation coefficient of 12.6% was obtained in this way. The emulsion for the 750 nm photosensitive layer had a J-band type spectral sensitivity.

[0251]

[Table 22]

[0252]

[Table 23]

[0253]

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Photosensitive Silver Halide Emulsion (6) (for First Layer (810 nm Photosensitive Layer)) A well-stirred aqueous solution having the composition shown in Table 24 was mixed with the solution (I) and the solution (II) having the composition shown in Table 25. The liquid was added simultaneously over 18 minutes. After 10 minutes, the composition (II
Solution I) and solution (IV) were added over 24 minutes.

[0255]

[Table 24]

[0256]

[Table 25]

After washing with water and desalting (using a precipitant a at pH 3.8), lime-treated ossein gelatin 22 was used.
g was added to adjust the pH to 7.4 and the pAg to 7.8, followed by chemical sensitization. The compounds used for chemical sensitization are as shown in Table 26. At the end of the chemical sensitization, the sensitizing dye was added as a methanol solution (similar to the sensitizing dye shown in Table 23). Thus, the average particle size is 0.32 μm
680 g of a monodispersed cubic silver chlorobromide emulsion having a coefficient of variation of 9.7%.

[0258]

[Table 26]

[0259]

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Next, a method for preparing a gelatin dispersion of colloidal silver will be described.

To a well-stirred aqueous solution having the composition shown in Table 27, a liquid having the composition shown in Table 28 was added over 24 minutes. Then, after washing with water using the sedimentation agent a, 43 g of lime-treated ossein gelatin was added to adjust the pH to 6.3. In this way, 512 g of a dispersion containing 2% of silver and 6.8% of gelatin having an average particle size of 0.02 μm was obtained.

[0262]

[Table 27]

[0263]

[Table 28]

Next, a method for preparing a gelatin dispersion of a hydrophobic additive will be described.

A gelatin dispersion of each of the yellow coupler, magenta coupler and cyan coupler and a developing agent was prepared according to the formulation shown in Table 29. That is, each oil phase component was heated and dissolved at about 70 ° C. to form a uniform solution, and the aqueous phase component heated to about 60 ° C. was added to this solution, followed by stirring and mixing, and then dispersed with a homogenizer for 10 minutes at 10,000 rpm.
Water was added thereto and stirred to obtain a uniform dispersion.

[0266]

[Table 29]

Gelatin dispersions of an antifoggant and a reducing agent were prepared as shown in Table 30. That is, each oil phase component was heated and dissolved at about 60 ° C. to form a uniform solution, and the aqueous phase component heated to about 60 ° C. was added to this solution, followed by stirring and mixing, and then dispersed with a homogenizer for 10 minutes at 10,000 rpm to obtain a uniform solution. A dispersion was obtained.

[0268]

[Table 30]

A gelatin dispersion of the reducing agent was prepared as shown in Table 31. That is, each oil phase component was heated and dissolved at about 60 ° C. to form a uniform solution, and the aqueous phase component heated to about 60 ° C. was added to this solution, followed by stirring and mixing, and then dispersed with a homogenizer for 10 minutes at 10,000 rpm to obtain a uniform solution. A dispersion was obtained. Further, ethyl acetate was removed from the obtained dispersion using an organic solvent removal device under reduced pressure.

[0270]

[Table 31]

Table 3 shows the dispersion of the polymer latex (a).
Prepared according to Formulation 2. That is, an anionic surfactant was added over 10 minutes while stirring a mixture of the polymer latex (a), surfactant and water in the amounts shown in Table 32 to obtain a uniform dispersion. Further, the obtained dispersion is subjected to an ultrafiltration module (Ultrafiltration module manufactured by Asahi Kasei Corporation: AC
V-3050), dilution with water and concentration were repeated so that the salt concentration during dispersion was reduced to 1/9.

[0272]

[Table 32]

A gelatin dispersion of the stabilizer was prepared as per the formulation in Table 33. That is, the oil phase component is dissolved at room temperature to form a uniform solution, the aqueous phase component heated to about 40 ° C. is added to this solution, and the mixture is stirred and mixed, and then mixed with a homogenizer for 10 minutes.
Dispersed at 00 rpm. Water was added thereto to obtain a uniform dispersion.

[0274]

[Table 33]

A gelatin dispersion of zinc hydroxide was prepared as shown in Table 34. That is, after mixing and dissolving each component, the mixture was dispersed in a mill for 30 minutes using glass beads having an average particle size of 0.75 mm. Further, the glass beads were separated and removed to obtain a uniform dispersion.

[0276]

[Table 34]

Next, a method for preparing a gelatin dispersion of a matting agent added to the protective layer will be described. A solution obtained by dissolving PMMA in methylene chloride was added to gelatin together with a small amount of a surfactant to obtain a uniform dispersion having an average particle size of 4.3 μm.

Using the above, photosensitive elements 201 shown in Table 35 were prepared.

[0279]

[Table 35]

[0280]

[Table 36]

[0281]

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[0282]

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[0283]

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[0284]

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[0285]

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[0286]

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[0287]

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[0288]

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[0289]

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[0290]

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[0291]

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Next, the first layer, the third layer
The photosensitive element 203 was manufactured in the same manner except that the developing agent represented by the general formula (1) of the present invention and the coupler shown in Table 37 were used in place of the developing agent and the coupler used in the layer and the fifth layer.
~ 208 were created. Table 37 shows the developing agents and couplers used here. In addition, Japanese Patent Application Laid-Open No. 09-152702
The light-sensitive element 202 was prepared using the compounds described in No.
Next, using the photosensitive materials obtained as described above and the image receiving element R101 produced in the same manner as in Example 1, the heating conditions were changed to PG-3000 (trade name) manufactured by Fuji Photo Film Co., Ltd. Image output was performed at 83 ° C. for 17 seconds. The images output from the photosensitive elements 203 to 208 were clear color images, and when the compounds of the present invention were used, the sharpness of the images was excellent. The maximum density and the minimum density of these obtained images were determined by a reflection densitometer X-rite manufactured by X-rite.
It was measured using write304. The results are shown in Table 38. As is clear from Table 38, when the compound of the present invention was used, good color development could be obtained even with a short development time, and the obtained image was stable under conditions such as light, heat, and humidity. Met.

[0293]

[Table 37]

[0294]

[Table 38]

Example 3 The developing agents of the present invention (exemplified compounds R-1, R-2, R-
6, R-7, R-11 and R-14) are described in JP-A-09-15.
In the method described in Example 1 of No. 2702, when used in place of Compound Example D-7 and developed using an alkaline processing solution, the color development was excellent as in Examples 1 and 2, An image having good storage stability was obtained.

[0296]

By using the color developing agent of the present invention, good color developability can be obtained even with a short development time, and color development excellent in stability against light, heat, humidity and the like can be obtained.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Yasushi Katsumata 210 Nakanakanuma, Minamiashigara, Kanagawa Prefecture Inside Fuji Photo Film Co., Ltd. (72) Inventor Kiyoshi Takeuchi 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Inside Fuji Photo Film Co., Ltd. (72) Inventor Takashi Nakamura 210 Nakanuma, Minamiashigara, Kanagawa Prefecture Fuji Photo Film Co., Ltd.

Claims (6)

[Claims] 1. A color developing agent represented by the following general formula (1). Embedded image (Wherein X is a halogen atom, an alkylthio group, an alkylsulfinyl group, an alkylsulfonyl group, an arylthio group, an arylsulfinyl group, an arylsulfonyl group,
Or a sulfamoyl group. However, the substituent that can be further substituted on X does not include a hydroxy group, a carboxyl group, a mercapto group, an aminosulfonyl group, a carbonylaminosulfonyl group, a sulfonylamino group, and a sulfonylaminocarbonyl group. Z represents a carbamoyl group, an acyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group. ) 2. The method according to claim 1, wherein in the general formula (1), Z is a carbamoyl group, and is a carbamoyl group in which one or more hydrogen atoms are bonded to a nitrogen atom on the carbamoyl group. Color developing agent. 3. The method according to claim 1, wherein at least one hydrophilic colloid layer provided on the support contains at least one color developing agent represented by the formula (1) according to claim 1. Silver halide photographic material. 4. An image forming method, comprising thermally developing the silver halide photographic light-sensitive material according to claim 3. 5. An image forming method comprising developing the silver halide photographic light-sensitive material according to claim 3 in the presence of a metal salt which is hardly soluble in water and a complexing agent for the metal salt to generate an alkali. 6. An image forming method, wherein the color diffusion transfer silver halide photographic material according to claim 3 is developed by developing an alkaline processing solution.