JPH11223911A - Diffusion transfer color photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a diffusion transfer color photosensitive material superior in storage stability of raw stock and image discrimination. SOLUTION: This photosensitive material contains photosensitive silver halide, a binder, a nondiffusible dye donor to release or form a diffusive dye upon being reduced, and as an electron donor or electron transfer agent, an o- or p-sulfonamidophenol optionally substituted by halogen or cyano or <=4C substituent or one having an I/O value of >=1. This value is a parameter for indicating a measure of hydrophilicness to hydrophobicness of a substituent, that is, an inorganic property I/organic property O ratio, and the more the I/O value, the higher the inorganic property.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a diffusion transfer type color light-sensitive material, and more particularly to a positive diffusion transfer type color light-sensitive material exhibiting excellent raw storability and image discrimination.

[0002]

2. Description of the Related Art A photographic method using silver halide has been used most widely since it has superior photographic characteristics such as sensitivity and gradation control as compared with other photographic methods such as electrophotography and diazo photography. I have been. In particular, since the best image quality can be obtained as a color hard copy, it has been energetically studied more recently. In recent years, image formation processing methods for photosensitive materials using silver halide have been changed from conventional wet processing to instant photographic systems with a built-in developer, and dry heat development processing by heating etc. Have been developed. Photothermographic materials are described in “Basics of Photographic Engineering (Non-Silver Photography), Corona”, p.242-, but the content is black-and-white image formation such as dry silver. Stays in the law. Recently, as photothermographic color light-sensitive materials, products such as Pictrography and Pictrostat have been sold by Fuji Photo Film Co., Ltd.
In the above-described simple and rapid processing method and the color instant photographic light-sensitive material, a color image is formed by a diffusion transfer method using a redox coloring material connected to a preformed die. See Angew. Chem. Int. For the idea of the chemical reaction for forming this diffusion transfer type color photosensitive material.
Ed. Engl. 1983 (22) 191-reviews the details. The most common method for forming a color image of a photographic light-sensitive material is a method utilizing a coupling reaction between a coupler and an oxidized developing agent. A heat-developable color light-sensitive material employing this method is also disclosed in US Pat. 3,761,270
No. 4,021,240, JP-A-59-231539, JP-A-60-128
Many ideas have been filed, including 438.

[0003]

The inventors have been studying the diffusion transfer type color photosensitive material including the above-mentioned thermal development. Among them, various studies have been made on a positive type diffusion transfer type color photosensitive material such as the above-mentioned Pictrostat manufactured by Fuji Photo Film Co., Ltd. In such a positive-type photosensitive material, rapid silver development occurs in the exposed area due to the action of the electron transfer agent, thereby consuming the electron donor. Thereafter, in accordance with the pattern of the remaining electron donor, a diffusible dye is released by the reaction between the dye-donating compound and the electron donor to form a positive image. This chemical reaction is described above in An
gew. Chem. Int. Ed. Engl. 1983 (22) 191. As is well known in other literatures and the like, as an electron transfer agent, it is known in the art that a 1-phenyl-3-pyrazolidinone derivative is an effective compound. However, this review and JP-A-1-138556, 2-53049
No. 2-53050, Journal of the Photographic Society of Japan 57, (5), 1994, p340-
And the like, electron transfer agents including compounds such as 1-phenyl-3-pyrazolidinone derivatives are compounds having a disadvantage that they are easily decomposed during raw storage.
When the electron transfer agent decomposes during raw storage, a significant increase in Dmin occurs due to a delay in silver development. To overcome this,
The above-mentioned documents and patent specifications disclose techniques such as the use of a precursor that gradually releases an electron transfer agent during raw storage and a method of solid dispersion addition of an electron transfer agent. However, an electron transfer agent that is sufficiently stable alone during raw storage and has rapid silver developability has not been found so far, and development of this technique has been demanded. No. 4,021, U.S. Pat.
It has been found that sulfonamide phenols described in JP-A No. 240, JP-A-60-128438 and the like are excellent in discrimination and raw storage when incorporated in a light-sensitive material. As a result of various studies on the performance of this sulfonamide phenol as a reducing agent, this compound is a compound having sufficient raw preservability even if it increases hydrophilicity as a built-in developing agent and improves silver developability. I understand.

(Object of the Invention) It is an object of the present invention to provide a diffusion transfer type color photosensitive material excellent in image discrimination and raw preservability.

[0005]

The object of the present invention has been attained by a diffusion transfer type color photosensitive material described below.

1) A light-sensitive silver halide, a binder, a non-diffusible dye-donating compound capable of releasing or forming a diffusible dye upon reduction on a support,
A diffusion transfer type color light-sensitive material having an electron donor and an electron transfer agent, wherein the electron transfer agent is at least one compound represented by the following general formula (1) or (2). Transfer type color photosensitive material. General formula (1)

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General formula (2)

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In the formula, R _{1 to} R ₄ represent a hydrogen atom, a halogen atom, a cyano group, or an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryl group having 4 or less carbon atoms or having an I / O value of 1 or more. Oxy group, alkylthio group, arylthio group, alkylcarbonyl group, arylcarbonyl group, alkylsulfonyl group, arylsulfonyl group, alkylcarbonamide group, arylcarbonamide group,
Alkylsulfonamide group, arylsulfonamide group, alkylcarbonyloxy group, arylcarbonyloxy group, carbamoyl group, alkylcarbamoyl group,
Represents an arylcarbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfamoyl group, an alkylsulfamoyl group, an arylsulfamoyl group, a ureido group, or a urethane group. R ₅ is an alkyl group,
Represents an aryl group, a heterocyclic group, an alkylamino group, an arylamino group, or a heterocyclic amino group. 2) The diffusion transfer type color light-sensitive material according to item 1, wherein R ₅ in the general formula (1) or (2) is a group represented by the following general formula (3). General formula (3)

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In the formula, R _{6 to} R ₁₀ represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group, a heterocyclic group, an alkoxy group having 4 or less carbon atoms or an I / O value of 1 or more; Aryloxy group, alkylthio group, arylthio group, alkylcarbonyl group, arylcarbonyl group, alkylsulfonyl group, arylsulfonyl group, alkylcarbonamide group, arylcarbonamide group,
Alkylsulfonamide group, arylsulfonamide group, alkylcarbonyloxy group, arylcarbonyloxy group, carbamoyl group, alkylcarbamoyl group,
Represents an arylcarbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfamoyl group, an alkylsulfamoyl group, an arylsulfamoyl group, a ureido group, or a urethane group. R ₆ and R ₇ , R ₇ and R ₈ , R ₈ and R ₉ , R ₉ and R ₁₀ may each independently form a ring. 3) The diffusion transfer type color light-sensitive material according to item 2, wherein R ₆ and / or R _{10 in the} general formula (3) is a substituent other than a hydrogen atom. 4) In the general formula (1), R ₂ and / or R _4, the general formula (2) in R ₄ is characterized in that it is a substituent other than a hydrogen atom, of any of Claims 1-3 wherein Diffusion transfer type color photosensitive material.

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.

First, the compounds represented by formulas (1) and (2) will be described in detail.

The compounds represented by the general formulas (1) and (2) are reducing agents collectively referred to as sulfonamidophenols, and are used in the present invention as electron transfer agents. In the formula, R ₅ is most preferably an aryl group represented by the general formula (3), and R _{1 to} R ₄ and R _{6 to} R ₁₀ are each a hydrogen atom, a halogen atom, or a group having 4 or less carbon atoms or / O represents a substituent having one or more values. The I / O value is a parameter indicating a measure of the hydrophilicity / lipophilicity of a compound or a substituent, and is referred to as an “organic conceptual diagram” (by Yoshio Koda, published by Sankyo)
Has a detailed explanation. I represents inorganic, O represents organic, and the larger the I / O value, the higher the inorganicity. Here, a specific example of the I / O value will be described. Typical values of I are 200 for -NHCO- group, 240 for -NHSO ₂ -group, -COO
-The base is 60. For example, in the case of -NHCOC ₅ H _11, the number of carbon atoms is 6, O value is 20 × 6 = 120. Since I = 200, I / O ≒ 1.67 and I / O> 1. The compound of the present invention is a compound substituted with a substituent having an I / O value of 1 or more or a carbon number of 4 or less, and has a feature of being hydrophilic. Examples of specific substituents include
For example, halogen atom (for example, chloro group, bromo group), alkyl group (for example, methyl group, ethyl group, isopropyl group, n-butyl group, t-butyl group), aryl group (for example, 3-methanesulfonylaminophenyl group), alkyl group Carbonamido group (eg, acetylamino group, propionylamino group, butyroylamino group), arylcarbonamide group (eg, benzoylamino group), alkylsulfonamide group (eg, methanesulfonylamino group, ethanesulfonylamino group), arylsulfonamide Groups (eg, benzenesulfonylamino, toluenesulfonylamino), alkoxy (eg, methoxy, ethoxy), aryloxy (eg, 4-methanesulfonylaminophenoxy), alkylthio (eg, methylthio, ethylthio) O, butylthio), arylthio (eg, 4-methanesulfonylaminophenylthio), alkylcarbamoyl (eg, methylcarbamoyl, dimethylcarbamoyl, ethylcarbamoyl, diethylcarbamoyl, dibutylcarbamoyl, piperidinocarbamoyl) Group, morpholinocarbamoyl group), arylcarbamoyl group (eg, phenylcarbamoyl group, methylphenylcarbamoyl group, ethylphenylcarbamoyl group, benzylphenylcarbamoyl group), carbamoyl group, alkylsulfamoyl group (eg, methylsulfamoyl group, dimethylsulfamoyl group) Famoyl group, ethylsulfamoyl group, diethylsulfamoyl group, dibutylsulfamoyl group, piperidinosulfamoyl group, morpholinosulfamoyl group), Reelsulfamoyl group (eg, phenylsulfamoyl group, methylphenylsulfamoyl group, ethylphenylsulfamoyl group, benzylphenylsulfamoyl group), sulfamoyl group, cyano group, alkylsulfonyl group (eg, methanesulfonyl group, ethane Sulfonyl group), arylsulfonyl group (for example, phenylsulfonyl group, 4-chlorophenylsulfonyl group, p-toluenesulfonyl group), alkoxycarbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group), aryloxycarbonyl group (for example, A phenoxycarbonyl group), an alkylcarbonyl group (eg, an acetyl group, a propionyl group, a butyroyl group), an arylcarbonyl group (eg, a benzoyl group, an alkylbenzoyl group), or Represents an acyloxy group (for example, an acetyloxy group, a propionyloxy group, a butyroyloxy group). Particularly, R _{5 in the} general formulas (1) and (2) is preferably a group represented by the general formula (3). Here, the substituent R ₆ and / or R ₁₀ in the general formula (3) is preferably a substituent other than a hydrogen atom, and R ₂ and / or R ₄ in the general formula (1), and Equation (2)
R ₄ is preferably a substituent other than a hydrogen atom.
In the above general formulas, R ₁ and R ₂ , R ₃ and R ₄ , R
_{When 6} and R ₇ , R ₇ and R ₈ , R ₈ and R ₉ , and R ₉ and R ₁₀ are each a substituent other than a hydrogen atom, the range of the condition of the I / O value in the combination of each group In the above, they may be independently bonded to form a ring.

The compounds represented by the general formulas (1) and (2) can be synthesized by combining stepwise methods known widely in the field of synthetic organic chemistry. The synthesis scheme is shown below, and an example of a stepwise synthesis method is described.

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<< Synthesis of Exemplified Compound D-5 >> 1) Synthesis of Compound A In a 5-liter three-necked flask equipped with a condenser, a thermometer, a dropping funnel, and a mechanical agitator, 766 g of 6-amino-m-cresol was added. 5mol), acetonitrile 2000ml
And stirred under room temperature conditions. At this time, the solution is a non-uniform slurry. Here, 791 g of isobutyric anhydride (5 m
ol) over 30 minutes, the temperature gradually rises and finally rises to 60 ° C. until the solution becomes homogeneous. When the temperature rise subsides, product crystals begin to precipitate in the flask. After stirring for another 1 hour, the contents were reduced to 10%
The solution is poured into 15 liters of a saline solution, and the precipitated crystals are filtered under reduced pressure using a Nutsche. The crystals are further washed with 2 liters of distilled water and dried. The crystals have such a purity that they can be used as they are in the next step. Thus, 928 g of Compound A crystals were obtained (96% yield).

2) Synthesis of Compound B In a 10-liter beaker, 193 g (1 mol) of Compound A is charged, and an aqueous solution obtained by dissolving 500 ml of methanol and 120 g (3 mol) of sodium hydroxide in 500 ml of water is added. This solution is kept under 0 ° C. and stirred. On the other hand, 216 g of sulfanilic acid (1.2
(5 mol) is completely dissolved in an aqueous solution of 50 g of sodium hydroxide dissolved in 400 ml of water. 300 ml of concentrated hydrochloric acid is added to make a slurry-like solution. The solution was stirred vigorously while maintaining the temperature at 0 ° C or lower, and 93 g (1.35 mol) of sodium nitrite was added to water 20
The solution dissolved in 0 ml is gradually added to form a diazonium salt. At this time, the reaction is performed while appropriately adding ice so as to keep the temperature at 0 ° C. or lower. The diazonium salt thus produced is gradually added to the compound A solution that has been stirred earlier. Also at this time, keep the temperature below 0 ° C.
The reaction is carried out while appropriately adding ice. As it is added, the solution takes on the red color of the azo dye. After completion of the addition, the mixture was further reacted at 0 ° C. or lower for 30 minutes. When the disappearance of the raw materials was confirmed, 750 g of sodium hydrosulfite (4.5 mol
Add l) as a powder. When this solution is heated to 50 ° C., azo groups are reduced while vigorously foaming. When the bubbling stops, the solution decolorizes and becomes a yellowish transparent liquid,
When the solution is gradually cooled to 10 ° C., crystals are gradually precipitated from the time when the cooling is started. The precipitated crystals were separated by filtration, and the crude crystals were recrystallized from a mixed solvent of methanol and water to obtain 162 g of Compound B crystals (78% yield).

3) Synthesis of Compound C In a 5-liter three-necked flask equipped with a condenser, a thermometer, a dropping funnel, and a mechanical agitator, 833 g (4 mol) of Compound B and 2000 ml of acetonitrile are charged and stirred at room temperature. . At this time, the solution is a non-uniform slurry. Here, 840 g (4 mol) of trifluoroacetic anhydride is added.
Add over 30 minutes and the temperature will gradually rise. Cool in an ice bath as appropriate to raise the temperature to 45 ° C. After the addition, the solution becomes uniform. When the temperature rise subsides, product crystals begin to precipitate in the flask. After further stirring for 1 hour, the content was poured into 15 liters of 10% saline, and the precipitated crystals were filtered under reduced pressure using a Nutsche. The crystals are further washed with 2 liters of distilled water and dried. The crystals have such a purity that they can be used as they are in the next step. In this way, 1132 g of compound C crystals were obtained (yield 93).
%).

4) Synthesis of Compound D Compound 5 was placed in a 5-liter three-necked flask equipped with a condenser, a thermometer, a dropping funnel, and a mechanical agitator.
913 g (3 mol) of C and 2500 ml of dichloromethane are charged and stirred at room temperature. At this time, the solution is a non-uniform slurry. Here, 540 g (4 mol) of sulfuryl chloride
When added over 30 minutes, the temperature gradually rises and gas begins to evolve and reflux begins. After completion of the dropwise addition, under reflux conditions,
After a further 2 hours of reaction, gas evolution subsides. At this time, the solution also remains in a non-uniform state. After stirring for an additional hour, the internal temperature is lowered to room temperature, and the contents are poured into 10 liters of n-hexane. The precipitated crystals are filtered under reduced pressure using a Nutsche, further washed with 2 liters of n-hexane, and dried. The crystals have such a purity that they can be used as they are in the next step. Thus, 904 g of compound D crystals
Was obtained (89% yield).

5) Synthesis of Compound E In a 3-liter three-necked flask equipped with a condenser, a thermometer, a dropping funnel, a nitrogen inlet tube, and a mechanical agitator, 224 g of potassium hydroxide and 1200 ml of water are charged and completely dissolved. . While passing nitrogen here, 678 g of compound D
(2 mol) as powder, gradually add
Increase to ° C. At this time, the solution changes from a non-uniform slurry state to a uniform solution. After continuing stirring for 2 hours, the internal temperature is lowered to room temperature, and 200 ml of acetic acid is added thereto to precipitate crystals. The precipitated crystals are filtered under reduced pressure using a Nutsche. The crystals were further washed with cold distilled water, and then recrystallized from a mixed solvent of methanol and water to give Compound E.
(403 g) was obtained (yield 83%).

6) Synthesis of Exemplified Compound D-5 The compound was placed in a 5-liter three-necked flask equipped with a condenser, a thermometer, a dropping funnel, and a mechanical agitator.
E971 g (4 mol) and acetonitrile (2800 ml) are charged and stirred at room temperature. At this time, the solution is a non-uniform slurry. Here, 875 g of mesitylenesulfonyl chloride
(4mol) is added as a powder over 10 minutes, the temperature gradually rises. Cool in an ice bath as needed to raise the temperature to 30 ° C. After completion of the addition, the mixture is cooled in an ice bath so that the internal temperature becomes 15 ° C. or lower, and 324 ml (4 mol) of pyridine is added dropwise thereto over 10 minutes. After completion of the dropwise addition, the mixture is further stirred at room temperature for 2 hours.
Let react for hours. After some time, product crystals begin to precipitate in the flask. After completion of the reaction, the contents are poured into 20 liters of 3% hydrochloric acid, and the precipitated crystals are filtered under reduced pressure using a Nutsche. After the crystals were further washed with 4 liters of distilled water, the crystals were recrystallized from a mixed solvent of acetonitrile and water to obtain 1564 g of crystals of Exemplified Compound D-5 (yield 9).
2%).

<< Synthesis of Exemplified Compound D-9 >> 1) Synthesis of Compound F In a 5-liter three-necked flask equipped with a condenser, a thermometer, a dropping funnel, and a mechanical agitator, 153 g of 4-nitro-m-cresol ( 1 mol) and 1000 ml of methanol, and the mixture is stirred at room temperature. At this time, the solution is a non-uniform slurry. Here, 2 liters of an aqueous solution of sodium hypochlorite (effective chlorine amount: 5%) is dropped while paying attention so that the internal temperature does not exceed 50 ° C. Upon addition, the color of the solution changes to reddish brown. After the completion of the dropping, 500 g (3 mol) of sodium hydrosulfite is gradually added thereto in powder form, and the nitro group is reduced while vigorously foaming. At this time, care should be taken that the internal temperature does not exceed 60 ° C and that the foaming does not become excessive. When foaming stops and the solution decolorizes and turns into a yellowish transparent liquid, slowly add this solution to 10
When cooled to ° C., crystals are gradually precipitated from the beginning of cooling. The precipitated crystals are separated by filtration, and the crude crystals are recrystallized from a mixed solvent of methanol and water to obtain a compound F crystal.
142 g were obtained (74% yield).

2) Synthesis of Exemplified Compound D-9 Compound 5 was placed in a 5-liter three-necked flask equipped with a condenser, a thermometer, a dropping funnel, and a mechanical agitator.
F768 g (4 mol), acetonitrile 1500 ml and N, N-dimethylacetamide (DMAc) 1100 ml are charged and stirred at room temperature. At this time, the solution becomes uniform. When 1212 g (4 mol) of triisopropylbenzenesulfonyl chloride is added as a powder over 10 minutes, the temperature gradually rises.
Cool in an ice bath as needed to raise the temperature to 30 ° C.
After completion of the addition, the mixture is cooled in an ice bath so that the internal temperature becomes 15 ° C. or lower, and 324 ml (4 mol) of pyridine is added dropwise thereto over 10 minutes. After completion of the dropwise addition, the reaction is further continued for 2 hours while stirring at room temperature. After completion of the reaction, the contents are poured into 20 liters of 3% hydrochloric acid, and the precipitated crystals are filtered under reduced pressure using a Nutsche.
After the crystals were further washed with 4 liters of distilled water, the crystals were recrystallized from a mixed solvent of methanol and water to obtain 1669 g of crystals of Exemplified Compound D-9 (yield: 91%).

Specific examples of the compounds represented by formulas (1) and (2) are listed below, but the present invention is of course not limited thereto.

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[0034]

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[0035]

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[0036]

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In the present invention, in order to form a color image, a non-diffusible dye-donating compound capable of releasing a diffusible dye upon reduction is used. Various dye donating compounds have been known so far, but the following compounds can be used as examples of the compounds usable in the present invention.

1) A compound in which the diffusivity of a dye is lost by oxidization and thus discrimination is imparted to the diffusivity of a dye. For example, a dye developing agent,
Examples of this include U.S. Patent Nos. 3,134,764 and 3,362,
No. 819, No. 3,597,200, No. 3,544,545, No. 3,
No. 482,972.

2) A compound capable of diffusing a dye by the action of silver ions. For example, thiazolidine compounds and the like,
An example of this is described in J. Image. Tech. 15, (3), 1989, p114-.

3) A compound that releases a diffusible dye when reduced. Examples of this include U.S. Pat.
No. 290, No. 4,783,396, European Patent No. 220,746A2,
Published Technical Report No. 87-6199, U.S. Pat.Nos. 4,139,389,
139,379, JP-A-59-185333, JP-A-57-84453, U.S. Patent No. 4,232,107, JP-A-59-101649, JP-A-61-88257
No., West German Patent No. 3,008,588A, JP-A-56-142530,
U.S. Pat.Nos. 4,343,893, 4,619,884, U.S. Pat.Nos. 4,450,223, 4,609,610, European Patent 220,74
6A2, U.S. Pat.No. 4,783,396, JP-A-63-201654
And U.S. Pat. No. 4,840,887, JP-A-63-271344, JP-A-63-271341, and JP-B-8-20695.

Among the above-mentioned compounds, particularly preferred are those described in US Pat. No. 4,783,396 and Japanese Patent Publication No. 5-73221, in which the NO bond is cleaved by reduction, Compounds that release dyes can be mentioned as triggers. Among these, examples of the compounds that can be used for the purpose of the present invention include compounds described in U.S. Pat. No. 4,783,396 which release a dye, and two or more diffusible compounds in one redox nucleus. Dyes are bound, EP 620,490A, those releasing dyes among the compounds described in JP-A-6-347968 and the like, and as novel dye-bound compounds, JP-A-3-48247, JP 63
-261738 and the like.

In the present invention, an electron donor is used for reducing the coloring material and forming an image. As this compound, a reducing agent substituted with an oil-solubilizing group is preferably used. Preferably, JP-A-2-35451, JP-A-2-32338,
Compounds described in JP-A-2-48659, JP-A-2-64633, JP-A-2-234158 and the like can be used, and particularly preferred is JP-A-2-32338.
The hydroquinone derivatives described in (1) are preferably used.

In the present invention, usable dye-donating compounds and electron donors are precursors in which active sites are blocked by protecting groups during raw preservation, and the protecting groups are removed during processing so that they can react. May be added. Examples thereof include JP-A-3-31848, 3-16
There is a description in 0444 and the like.

When the compounds represented by the general formulas (1) and (2) are used in a light-sensitive material, the coating amount can be selected from a wide range. The amount of addition may vary depending on the relationship. First, the dye-donating compound used for image formation depends on the molar extinction coefficient of the dye to be formed or released, but usually, a compound having a molar extinction coefficient of 500 to 500,000 is preferable.
0.001 ~1000mmol / m ^2, more preferably 0.05～50Mmol /
a m ^2. On the other hand, the electron donor is used in an amount of 0.01 to 100 times, preferably 0.05 to 50 times, more preferably 0.1 to 10 times the mole of the dye-providing compound. At this time, general formula (1) used as an electron transfer agent,
The compound represented by (2) is added to the electron donor in an amount of 0.
It is appropriate to add 001 to 1000 mole times, preferably 0.01 to 100 mole times, more preferably 0.05 to 10 mole times.

As a method for adding the compounds represented by the general formulas (1) and (2), first, an oil-soluble compound used other than a dye-donating compound and the like, and a high-boiling organic solvent (for example, alkyl phosphate, Phthalic acid alkyl ester, etc.), dissolve in a low boiling point organic solvent (eg, ethyl acetate, methyl ethyl ketone, etc.), disperse in water using an emulsification dispersion method known in the art, and then add. Also,
Addition by the solid dispersion method described in JP-A-63-271339 is also possible. Of the compounds represented by the general formulas (1) and (2),
There is no limitation on the method of addition and the coating layer to be added, and it can be added to the same coating layer together with the dye-donating compound and the electron donor, or can be added to separate coating layers.

The color light-sensitive material of the present invention basically has a light-sensitive silver halide, a dye-donating compound and a binder on a support. These components are often added to the same layer, but they can be added separately in separate layers if they can react. For example, if a coloring dye-providing compound is present in the lower layer of the silver halide emulsion, the sensitivity can be prevented from lowering.

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 used in combination. . For example, there are 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 can be provided with various auxiliary layers such as a protective layer, an undercoat layer, an intermediate layer, an antihalation layer, and a back layer. Further, various filter dyes can be added to improve color separation.

The silver halide which can be used in the present invention may be any of silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide and silver chloroiodobromide. The silver halide emulsion used in the present invention may be a surface latent image type emulsion or an internal latent image type emulsion. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent or light fogging. Further, a so-called core-shell emulsion having a different phase between the inside of the grain and the grain surface layer may be used. The silver halide emulsion may be monodispersed or polydispersed, or a mixture of monodispersed emulsions may be used. The particle size is preferably from 0.1 to 2 μm, particularly preferably from 0.2 to 1.5 μm. The crystal habit of silver halide grains is cubic, octahedral, 1
It may be a tetrahedron, a flat plate with a high aspect ratio, or any other.

Specific examples include US Pat. No. 4,500,62.
No. 6, Column 50, No. 4,628,021, Research Disclosure Magazine (RD) 1702
9 (1978), any of the silver halide emulsions described in JP-A-62-253159 and the like can be used. Although the silver halide emulsion may be used as it is after unripe, it is usually used after chemical sensitization. Known sulfur sensitization, reduction sensitization, noble metal sensitization, and the like can be used singly or in combination for emulsions for conventional light-sensitive materials. These chemical sensitizations can be carried out in the presence of a nitrogen-containing heterocyclic compound (Japanese Patent Application Laid-Open No. 62-253159).

The coating amount of the photosensitive silver halide used in the present invention is in the range of 1 mg to 10 g / m ² in terms of silver. The silver halide used in the present invention may be spectrally sensitized with methine dyes or the like. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.

Specifically, US Pat. No. 4,617,25
7, JP-A-59-180550, JP-A-60-1403
No. 35, RD17029 (1978), pp. 12-13, and the like. These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for supersensitization.

Along with the sensitizing dye, a dye which has no 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. Patent No. 3,615,641) described in JP-A-63-23145). These sensitizing dyes may be added to the emulsion at or before or after chemical ripening, or according to U.S. Pat. Nos. 4,183,756 and 4,225,666 before and after nucleation of silver halide grains. Good. The addition amount is generally about 10 ^-8 to 10 ^-2 mol per mol of silver halide.

In the present invention, an organic metal salt can be used as an oxidizing agent together with the photosensitive silver halide. Particularly, in a photothermographic element, use of an organic metal salt is preferable. Among such organic metal salts, an organic silver salt is particularly preferably used. Organic compounds that can be used to form the above organic silver salt oxidizing agents include U.S. Pat.
There are benzotriazoles, fatty acids and other compounds described in columns Nos. 52 to 53 of 500,626. Also useful are silver salts of carboxylic acids having an alkynyl group such as silver phenylpropiolate described in JP-A-60-113235 and acetylene silver described in JP-A-61-249044. Two or more organic silver salts may be used in combination.

The above-mentioned organic silver salt is a photosensitive silver halide 1
0.01 to 10 mol, preferably 0.1 to 10 mol, per mol.
01 to 1 mol can be used in combination. The total coating amount of the photosensitive silver halide and the organic silver salt is suitably from 50 mg to 10 g / m ² in terms of silver. In the present invention, various antifoggants or photographic stabilizers can be used.
Examples are RD17643 (1978) 24-
Azoles and azaindenes described on page 25;
Carboxylic acids and phosphoric acids containing nitrogen described in JP-A-9-168442, or mercapto compounds and metal salts thereof described in JP-A-59-111636, JP-A-62-8
Acetylene compounds described in No. 7957 can be used.

In the present invention, a compound for stabilizing an image simultaneously with activation of development can be used in the light-sensitive material. Specific compounds preferably used are described in U.S. Pat. No. 4,500,626, columns 51 to 52. As in the present invention, a dye fixing material is used together with a photosensitive material in a system for forming an image by diffusion transfer of a dye. The dye-fixing material may be in the form of being separately coated on a support separate from the photosensitive material, or may be in the form of being coated on the same support as the photosensitive material. As for the relationship between the photosensitive material and the dye fixing material, the relationship with the support, and the relationship with the white reflective layer, the relationship described in column 57 of US Pat. No. 4,500,626 can be applied to the present invention.

The dye fixing material preferably used in the present invention has at least one layer containing a mordant and a binder. As the mordant, those known in the field of photography can be used, and specific examples thereof are described in US Pat. No. 4,500,626.
Nos. 58-59 and JP-A-61-88256 (32)-
(34) mordant described on page 34, JP-A-62-244043,
Nos. 62-244036 and the like. Further, a dye-receiving polymer compound as described in U.S. Pat. No. 4,463,079 may be used.

Auxiliary layers such as a protective layer, a release layer and an anti-curl layer can be provided on the dye fixing material as required.
It is particularly useful to provide a protective layer. As the binder for the constituent layers of the photosensitive material and the dye fixing material, hydrophilic binders are preferably used. An example thereof is disclosed in JP-A-62-25315.
No. 9 on pages (26) to (28).
Specifically, transparent or translucent hydrophilic binders are preferable, for example, gelatin, proteins or cellulose derivatives such as gelatin derivatives, starch, gum arabic, dextran, natural compounds such as polysaccharides such as pullulan,
Examples include polyvinyl alcohol, polyvinylpyrrolidone, acrylamide polymers, and other synthetic high molecular compounds. Furthermore, superabsorbent polymers described in JP-A-62-245260, i.e. -COOM or -SO ₃ M
(M is a hydrogen atom or an alkali metal) homopolymer of a vinyl monomer or a copolymer of the vinyl monomers or other vinyl monomers (eg, sodium methacrylate, ammonium methacrylate, Sumikagel manufactured by Sumitomo Chemical Co., Ltd.) L-5H) are also used. These binders can be used in combination of two or more kinds.

In the case of employing a system in which a small amount of water is supplied to carry out thermal development, the use of the above superabsorbent polymer makes it possible to rapidly absorb water. Further, when the superabsorbent polymer is used for the dye fixing layer and its protective layer, it is possible to prevent the dye from being re-transferred from the dye fixing element to another after transfer. In the present invention,
The coating amount of the binder is preferably 20 g or less per 1 m ² , particularly preferably 10 g or less, and more preferably 7 g or less.

As the hardener used in the constituent layers of the photosensitive material and the dye fixing material, US Pat. No. 4,678,739 No. 4
Column 1, JP-A-59-116655, JP-A-62-2452
No. 61, No. 61-18942 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-based hardeners (such as dimethylol urea) and polymer hardeners (compounds described in JP-A-62-234157). In the present invention, an image formation accelerator can be used in the light-sensitive material and / or the dye-fixing material. Examples of the image formation accelerator include a redox reaction between a silver salt oxidizing agent and a reducing agent, promotion of a reaction such as formation of a dye from a dye-providing compound or decomposition of the dye or release of a diffusible dye, and a photosensitive material layer. From the physicochemical function to bases or base precursors, nucleophilic compounds, high-boiling organic solvents (oils), thermal solvents, surfactants, silver Or, it is classified into a compound having an interaction with silver ions. However,
These substance groups generally have multiple functions and usually have some of the above-mentioned promoting effects. For details of these, see US Pat. No. 4,678,739, No. 3,
It is described in columns 8-48.

Examples of the base precursor include salts of an organic acid and a base which are decarboxylated by heat, compounds which release amines by an intramolecular nucleophilic substitution reaction, Lossen rearrangement or Beckmann rearrangement, and the like. A specific example is described in U.S. Pat.
1,493, and JP-A-62-65038. In a system in which thermal development and transfer of a dye are carried out simultaneously in the presence of a small amount of water, it is preferable to include a base and / or a base precursor in the dye-fixing material from the viewpoint of improving the storability of the photosensitive material.

In addition to the above, European Patent Publication 210,660
No. 4,740,445, a combination of a compound (hereinafter referred to as a complex-forming compound) capable of forming a complex with a metal ion constituting the hardly-soluble metal compound, Compounds that generate a base by electrolysis described in JP-A-61-232451 can also be used as the base precursor. In particular, the former method is effective. This poorly soluble metal compound and complex forming compound
It is advantageous to separately add the light-sensitive material and the dye-fixing material.

In the present invention, various development stopping agents can be used in the light-sensitive material and / or the dye-fixing material 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" refers to a compound that neutralizes a base or reacts with a base immediately after appropriate development to reduce the concentration of base in the film and to react with a compound or silver and silver salt that stops development, thereby suppressing development. Compound. Specific examples include an acid precursor that releases an acid when heated, an electrophilic compound that causes a substitution reaction with a coexisting base when heated, or a nitrogen-containing heterocyclic compound, a mercapto compound, and a precursor thereof. For further details, see JP-A-62-2
No. 53159, pages (31) to (32).

The constituent layers (including the back layer) of the light-sensitive material or the dye-fixing material are used for the purpose of improving film physical properties such as dimensional stability, curl prevention, adhesion prevention, crack prevention of the film and pressure sensation. Various polymer latexes can be included. Specifically, any of the polymer latexes described in JP-A Nos. 62-245258, 62-136648, and 62-110066 can be used. Especially,
When a polymer latex having a low glass transition point (40 ° C. or less) is used for the mordant layer, cracking of the mordant layer can be prevented, and when a polymer latex having a high glass transition point is used for the back layer, a curl preventing effect can be obtained. .

In the constituent layers of the light-sensitive material and the dye-fixing material, a plasticizer, a sliding agent, or a high-boiling organic solvent can be used as a releasability improving agent for the light-sensitive material and the dye-fixing material. Specifically, JP-A-62-253159 (25)
Page, pp. 62-245253, and the like. Further, for the above purpose, various silicone oils (all silicone oils from dimethyl silicone oil to modified silicone oil obtained by introducing various organic groups into dimethyl siloxane) can be used. For example, see “Modified Silicone Oil” published by Shin-Etsu Silicone Co., Ltd., p. Various modified silicone oils, especially carboxy-modified silicones described in 6 to 18B (trade name X-
22-3710) are effective.

Also, JP-A-62-215953 and JP-A-62-15953
No. 46449 is also effective. An anti-fading agent may be used in the light-sensitive material and the dye-fixing material. Anti-fading agents include, for example, antioxidants, ultraviolet absorbers, or certain metal complexes. Examples of the antioxidant include chroman compounds, coumaran compounds, phenol compounds (eg, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. Also, Japanese Unexamined Patent Publication No.
The compound described in -159644 is also effective.

Examples of the ultraviolet absorber include benzotriazole compounds (US Pat. No. 3,533,794),
4-thiazolidone compounds (US Pat. No. 3,352,6)
No. 81), benzophenone-based compounds (JP-A-46-
2784, etc.), and JP-A-54-48535,
There are compounds described in JP-A-62-136641 and JP-A-61-88256. Further, ultraviolet absorbing polymers described in JP-A-62-260152 are also effective.

As the metal complex, US Pat. No. 4,24
No. 1,155, No. 4,245,018, columns 3 to 36,
No. 4,254,195, columns 3-8, JP-A-62-17
Nos. 4741, 61-88256, (27)-(29), 6
3-199248, JP-A-1-75568, 1-
74272 and the like.

Examples of useful discoloration inhibitors are described in JP-A-62-21.
No. 5272, pages (125) to (137). An anti-fading agent for preventing fading of the dye transferred to the dye-fixing material may be previously contained in the dye-fixing material,
The dye fixing material may be supplied from outside such as a photosensitive material.

The above antioxidants, ultraviolet absorbers and metal complexes may be used in combination with each other. A fluorescent whitening agent may be used for the photosensitive material and the dye fixing material. In particular, it is preferable to incorporate a fluorescent whitening agent into the dye-fixing material or to supply it from outside such as a photosensitive material. For example, K. Veenkataraman ed., "The Chemistry of Synthetic
Dyes ", Vol. V, Chapter 8, and JP-A-61-143752. More specifically, stilbene compounds, coumarin compounds,
Biphenyl compounds, benzoxazolyl compounds, naphthalimide compounds, pyrazolidone compounds, carbostyryl compounds and the like can be mentioned.

The fluorescent whitening agent can be used in combination with a fading inhibitor. The constituent layers of the light-sensitive material and the dye fixing material include coating aids, improved releasability, improved slipperiness, antistatic,
Various surfactants can be used for the purpose of accelerating development and the like. Specific examples of the surfactant are described in JP-A-62-17346.
No. 3, No. 62-183457 and the like.

The constituent layers of the light-sensitive material and the dye-fixing material may contain an organic fluoro compound for the purpose of improving sliding property, preventing static charge, improving releasability, and the like. Representative examples of organic fluoro compounds include JP-B-57-9053, columns 8 to 17,
JP-A-61-20944, JP-A-62-135826, etc., such as fluorine-based surfactants, or oil-like fluorine-based compounds such as fluorine oil or solid fluorine compound resins such as tetrafluoroethylene resin, etc. And hydrophobic fluorine compounds.

A matting agent can be used for the light-sensitive material and the dye fixing material. Examples of the matting agent include silicon dioxide, polyolefin and polymethacrylate.
In addition to the compounds described on page 1-88256 (29), benzoguanamine resin beads, polycarbonate resin beads, A
JP-A Nos. 63-274944 and 6
There is a compound described in 3-274952.

In addition, the constituent layers of the light-sensitive material and the dye-fixing material may contain a heat solvent, an antifoaming agent, an antibacterial and antibacterial agent, colloidal silica, and the like. Specific examples of these additives are described in JP-A-61-88256, pages (26) to (32). In the present invention, as the support of the photosensitive material or the dye fixing material, a support that can withstand the processing temperature is used. Generally, paper and synthetic polymers (films) are used. Specifically, polyethylene terephthalate (P
ET), polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetyl cellulose), or films containing pigments such as titanium oxide, and film-processed synthetic paper made from polypropylene. Mixed paper, Yankee paper, baryta paper, coated paper (especially cast-coated paper), metal, cloth, glass, etc., made from synthetic resin pulp such as polyethylene and natural pulp are used.

These can be used alone,
It can also be used as a support laminated on one or both sides with a synthetic polymer such as polyethylene. In addition, the supports described in JP-A-62-253159, pages (29) to (31) can be used. A hydrophilic binder, a semiconductor metal oxide such as alumina sol or tin oxide, carbon black, or another antistatic agent may be applied to the surface of these supports.

The light source used for exposing the color light-sensitive material of the present invention is a light emitting diode or a semiconductor laser. As the light emitting diode in the present invention,
GaAsP (red), GaP (red, green), GaAsP: N
(Red, yellow), GaAs (infrared), GaAlAs (infrared,
Various types such as red), GaP: N (red, green, yellow), GaAsSi (infrared), GaN (blue), and SiC (blue) can be used.

As described above, the infrared light emitting diode
Infrared-visible conversion element that converts external light into visible light with phosphor
Can also be used. Such a phosphor is rarely used.
Phosphors activated by earth are preferably used, and are rare earths.
And Er³⁺, Tm³⁺, Yb ³⁺Etc. can be used
You. Semiconductor laser that can be used in the present invention
As a specific example, In as a light emitting material, In_1-xGa_xP
(~ 700 nm), GaAs_1-xP_x(610-900n
m), Ga_1-xAl_xAs (690-900 nm), In
GaAsP (100-1670 nm), AlGaAsSb
(1250-1400 nm)
Users. To the color light-sensitive material in the present invention
Light irradiation is performed by N
d: YAG crystal is GaAs_xP_(1-X)For light emitting diodes
Even with a more exciting YAG laser (1064 nm)
Good.

In the present invention, the second harmonic generation element (SHG element) converts the wavelength of a laser beam to one half by applying a nonlinear optical effect. Examples include those using CD ^* A and KD ^* P (Laser Handbook, edited by The Laser Society of Japan, published December 15, 1982, pages 122 to 1).
See page 39). Also, Li ⁺ is converted into H ⁺ in LiNbO ₃ crystal.
A LiNbO ₃ optical waveguide device having an optical waveguide ion-exchanged with the above [NIKKEI ELECTRONICS, 1
986.7.14 (No. 399) pp. 89-90].

As other light sources, light sources such as natural light, a tungsten lamp, and a CRT light source can be used. In some cases, for example, a method of directly photographing a landscape or a person using a camera or the like, or a method of exposing through a reversal film or a color negative film using a printer or a enlarger may be used.

Further, the image information is a video camera,
Image signals obtained from electronic still cameras, television signals represented by the Nippon Television Signal Standards (NTSC),
An image signal obtained by dividing an original image into a large number of pixels such as a scanner, and an image signal created using a computer represented by CG and CAD can be used. When the present invention is used as a heat-developable color light-sensitive material and heat development is performed, the heating temperature in the heat development step can be developed at about 50 ° C. to about 250 ° C., and particularly about 80 ° C. to about 180 ° C. Useful. The dye diffusion transfer step may be performed simultaneously with the heat development, or may be performed after the heat development step. In the latter case, the heating temperature in the transfer step can be transferred within the range from the temperature in the heat development step to room temperature, but is more preferably from 50 ° C. or higher to about 10 ° C. lower than the temperature in the heat development step. In such a heat-developable color light-sensitive material, the total film thickness of each layer coated on the support is 15 μm or less in terms of a dry film thickness. With such a film thickness, dye transfer is promoted, and an effect of forming an image having excellent sharpness can be obtained.

In the present invention, a solvent may be used to promote dye transfer. Also, Japanese Patent Application Laid-Open No. Sho 59-2184
As described in detail in JP-A Nos. 43 and 61-238056, for a photothermographic material, a method in which development and transfer are performed simultaneously or continuously by heating in the presence of a small amount of a solvent (particularly water) is also useful. It is. In this method, the heating temperature is 50
It is preferable that the temperature is not lower than the boiling point of the solvent at a temperature of not less than ° C. For example, when the solvent is water, the temperature is preferably 50 ° C. or more and 100 ° C. or less.

Examples of the solvent used for accelerating the development and / or transferring the diffusible dye to the dye-fixing layer include water or a basic aqueous solution containing an inorganic alkali metal salt or an organic base (these bases). Examples thereof include those described in the section of the image formation accelerator). In addition, a low-boiling solvent or a mixed solution of a low-boiling solvent and water or a basic aqueous solution can also be used. Further, a surfactant, an antifoggant, a sparingly soluble metal salt and a complex forming compound may be contained in the solvent.

These solvents can be used by a method for imparting them to a dye fixing material, a photosensitive material, or both.
The amount used may be as small as the weight of the solvent corresponding to the maximum swelling volume of the entire coating film (especially, the weight of the solvent corresponding to the maximum swelling volume of the entire coating film minus the weight of the total coating film). As a method for applying a solvent to the photosensitive layer or the dye fixing layer, for example, JP-A-61-147244 (2)
There is a method described on page 6). Further, the solvent can be used by being incorporated in a photosensitive material or a dye-fixing material or both in advance, for example, by enclosing a solvent in a microcapsule.

In order to promote dye transfer, a method in which a hydrophilic heat solvent which is solid at normal temperature and dissolves at high temperature is incorporated in the light-sensitive material or the dye-fixing material can be adopted. The hydrophilic thermal solvent may be incorporated in either the photosensitive material or the dye fixing material, 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, but is preferably incorporated in the dye-fixing layer and / or an adjacent layer.

Examples of the hydrophilic heat solvent include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes and other heterocycles. Also,
In order to promote dye transfer, a high-boiling organic solvent may be contained in the light-sensitive material and / or the dye-fixing material. As a heating method in the development and / or transfer step,
Contacting heated blocks or plates, hot plates,
Examples include contact with a hot presser, a heat roller, a halogen lamp heater, infrared and far-infrared lamp heaters, and passage through a high-temperature atmosphere. Further, a resistive heating element layer may be provided on the photosensitive material or the dye fixing material, and the layer may be heated by being energized. The heating element layer is disclosed in
What is described in 1-1147244 etc. can be used.

The photosensitive element and the dye-fixing material are overlapped,
Japanese Patent Application Laid-Open No. Sho 6
The method described in page 1-127244 (27) can be applied.
Any of a variety of thermal development equipment can be used to process the photographic elements of the present invention. For processing of heat-developable color light-sensitive materials, for example, JP-A-59-75147 and JP-A-59-17754.
No. 7, No. 59-181353, No. 60-18951
And the devices described in JP-A-62-259944 are preferably used.

[0087]

【Example】

 Example 1 A method for preparing a dispersion of zinc hydroxide will be described.

12.5 g of zinc hydroxide having an average particle size of 0.2 μm, 1 g of carboxymethylcellulose as a dispersant, and 0.1 g of sodium polyacrylate were added to 100 ml of a 4% aqueous gelatin solution, and milled to give an average particle size of 0.75 mm. Grinding was performed using glass beads for 30 minutes. The glass beads were separated to obtain a dispersion of zinc hydroxide.

Next, a method for preparing a dispersion of the electron transfer agent will be described.

The following electron transfer agent A (10 g) was used as a dispersant, carboxymethyl cellulose (manufactured by Daiichi Kogyo Co., Ltd.
0.4 g of trade name Cellogen 6A) and 0.2 g of the following anionic surfactant were added to a 5% aqueous gelatin solution, and pulverized with a mill using glass beads having an average particle diameter of 0.75 mm for 60 minutes. Separate glass beads, average particle size 0.35μ
m of electron transfer agent dispersion was obtained.

[0091]

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Next, a method for preparing the dye trapping agent dispersion will be described.

The following polymer latex (solid content 13
%) 108 ml, the following surfactant 20 g, water 1232 ml
While stirring this mixture, 600 ml of a 5% aqueous solution of the following anionic surfactant was added over 10 minutes. Using the ultrafiltration module, the dispersion made in this way is
It was concentrated and desalted to 500 ml. Next, 1500 ml of water was added and the same operation was repeated once again to obtain 500 g of a dye trapping agent dispersion.

[0094]

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

The cyan, magenta, and yellow dye-donating compounds and the gelatin dispersion of the electron donor were adjusted according to the formulations shown in Table 1, respectively. That is, each oil phase component was heated and dissolved at about 60 ° C. to form a uniform solution. This solution and the aqueous phase component heated at about 60 ° C. were added, mixed with stirring, and dispersed with a homogenizer for 13 minutes at 12,000 rpm. Add water to this,
Stirring yielded a uniform dispersion. Further, regarding a gelatin dispersion of a magenta or cyan dye-donating compound, an ultrafiltration module (Asahi Kasei's ultrafiltration module ACV) is used.
-3050) using water to repeat dilution and concentration,
Ethyl acetate and methyl ethyl ketone in Table 1 were reduced to 1/6.

[0097]

[Table 1]

[0098]

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[0099]

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[0100]

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[0101]

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[0102]

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Next, a method of preparing a photosensitive silver halide emulsion will be described.

Photosensitive silver halide emulsion (1) [for red-sensitive emulsion layer] A well-stirred gelatin aqueous solution (20 g of gelatin, 0.5 g of potassium bromide, 2.5 g of sodium chloride and 700 g of the following chemicals in 700 ml of water) (A) Add 15mg and 42 ℃
Solution (I) and solution (II) in Table 2 were simultaneously added at a constant flow rate for 8 minutes. Then, 8 minutes after the completion of the addition of the liquids (I) and (II), an aqueous solution of a gelatin dispersion of a dye (water 1) was added.
1.9 g of gelatin in 60 ml, the following pigment (a) 127
mg, the following pigment (b) 253 mg, the following pigment (c) 8 mg
Containing 35 ° C. and kept at 35 ° C.). Two minutes later, solution (III) and solution (IV) shown in Table 2 were simultaneously added at the same flow rate for 32 minutes.

After washing with water and desalting in a conventional manner, 22 g of lime-processed ossein gelatin and 50 mg of the following chemical (B) were added to adjust the pH to 6.2 and the pAg to 7.8, and the 4-hydroxy-6 was added. Methyl-1,3,3a, 7-tetrazaindene was added, and then sodium thiosulfate and chloroauric acid were added for optimal chemical sensitization at 68 ° C. Then, the following antifoggant (1) and chemical (C) ) 80 mg and 3 g of the chemical (D) were added and the mixture was cooled. Thus, the average particle size is 0.21 μm
635 g of a monodispersed cubic silver chlorobromide emulsion was obtained.

[0106]

[Table 2]

[0107]

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[0108]

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Photosensitive silver halide emulsion (2) [for red-sensitive emulsion layer] A well-stirred aqueous gelatin solution (20 g of gelatin, 0.3 g of potassium bromide, 9 g of sodium chloride in 700 ml of water)
g) and 15 mg of the above-mentioned chemical (A) were added thereto, and the mixture was kept at 53 ° C.). Solution (I) and solution (II) in Table 3 were simultaneously added at an equal flow rate for 10 minutes. Then, 6 minutes after the completion of the addition of the liquids (I) and (II), an aqueous solution of a gelatin dispersion of the dye (115 ml of water) was added.
Including 1.2 g of gelatin, 77 mg of the above dye (a), 153 mg of the above dye (b), and 5 mg of the above dye (c).
(Preserved at 5 ° C.). After 4 minutes, Solution (III) and Solution (IV) in Table 2 were simultaneously added at an equal flow rate for 30 minutes.

After washing with water and desalting by a conventional method, 33 g of lime-treated ossein gelatin and 50 mg of the above-mentioned chemical (B) were added to adjust the pH to 6.2 and the pAg to 7.8, and to adjust 4-hydroxy-6. Methyl-1,3,3a, 7-tetrazaindene was added, and then sodium thiosulfate and chloroauric acid were added for optimal chemical sensitization at 68 ° C. Then, the antifoggant (1) and the chemical (C) ) 80 mg and 3 g of the chemical (D) were added and the mixture was cooled. Thus, the average particle size is 0.45 μm
635 g of a monodispersed cubic silver chlorobromide emulsion was obtained.

[0111]

[Table 3]

Photosensitive silver halide emulsion (3) [for green-sensitive emulsion layer] A well-stirred aqueous gelatin solution (20 g of gelatin, 0.5 g of potassium bromide, 5 g of sodium chloride in 690 ml of water)
g) and 15 mg of the above-mentioned chemical (A) were added thereto, and the mixture was kept at 41 ° C.). Solution (I) and solution (II) in Table 4 were simultaneously added at a constant flow rate for 8 minutes. After 10 minutes, solutions (III) and (IV) shown in Table 4 were simultaneously added at the same flow rate for 32 minutes. (II
One minute after completion of the addition of the liquids (I) and (IV), a methanol solution of the dye (containing 280 mg of the following dye (d) in 47 ml of methanol and kept at 30 ° C.) was added all at once.

After washing with water and desalting in a conventional manner, 22 g of lime-treated ossein gelatin, 50 mg of the above-mentioned chemical (B) and 3 g of chemical (D) were added to adjust the pH to 6.0 and the pAg to 7.1. 4-hydroxy-6-methyl-1,3,3a, 7
-Tetrazaindene was added, then sodium thiosulfate was added for optimal chemical sensitization at 60 ° C, and then the antifoggant (1) was added, followed by cooling. Thus, a monodisperse cubic silver chlorobromide emulsion 63 having an average grain size of 0.23 μm was prepared.
5 g were obtained.

[0114]

[Table 4]

[0115]

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Photosensitive silver halide emulsion (4) [for green-sensitive emulsion layer] A well-stirred aqueous gelatin solution (20 g of gelatin, 0.3 g of potassium bromide, 9 g of sodium chloride in 710 ml of water)
g) and 7.5 mg of the above-mentioned chemical (A) were added, and the mixture was kept at 63 ° C.).
It was added at an equal flow rate for 0 minutes. After 10 minutes, (III) in Table 5
The solution and the solution (IV) were simultaneously added at an equal flow rate for 20 minutes. Also
One minute after the completion of the addition of the liquids (III) and (IV), a methanol solution of the dye (170 mg of the above-mentioned dye (d) in 35 ml of methanol)
Which was kept at 46 ° C.).

After washing with water and desalting in a conventional manner, 33 g of lime-treated ossein gelatin, 50 mg of the above-mentioned chemical (B) and 3 g of chemical (D) were added to adjust the pH to 6.0 and the pAg to 7.2. 4-hydroxy-6-methyl-1,3,3a, 7
-Tetrazaindene was added, then sodium thiosulfate and chloroauric acid were added for optimal chemical sensitization at 60 ° C, and then the antifoggant (1) was added, followed by cooling. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.45 μm was obtained.

[0118]

[Table 5]

Photosensitive silver halide (5) [for blue-sensitive emulsion layer] A well-stirred aqueous gelatin solution (20 g of gelatin, 0.5 g of potassium bromide, 5 g of sodium chloride in 690 ml of water)
g) and 15 mg of the above-mentioned chemical (A) were added thereto, and the mixture was kept at 46 ° C.). Solution (I) and solution (II) in Table 6 were simultaneously added at the same flow rate for 8 minutes. After 10 minutes, solutions (III) and (IV) shown in Table 6 were simultaneously added at the same flow rate for 18 minutes. (II
One minute after the completion of the addition of the liquids (I) and (IV), an aqueous solution of the dye (water 9
225 mg of the following dye (e) in 5 ml and 5 ml of methanol
And the following dye (f) containing 225 mg and kept at 30 ° C.) were added all at once.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin, 50 mg of the above-mentioned chemical (B) and 3 g of chemical (D) were added to adjust the pH to 6.0 and the pAg to 7.7. 4-hydroxy-6-methyl-1,3,3a, 7
-Tetrazaindene was added, then sodium thiosulfate was added for optimal chemical sensitization at 65 ° C, and then the antifoggant (1) was added, followed by cooling. Thus, a monodisperse cubic silver chlorobromide emulsion 63 having an average grain size of 0.27 μm was prepared.
5 g were obtained.

[0121]

[Table 6]

[0122]

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Photosensitive silver halide emulsion (6) [for blue-sensitive emulsion layer] A well-stirred aqueous gelatin solution (20 g of gelatin, 0.3 g of potassium bromide, 9 g of sodium chloride in 710 ml of water)
g) and 15 mg of the above-mentioned chemical (A) were added thereto, and the mixture was kept at 59 ° C.). Liquids (I) and (II) in Table 7 were simultaneously added at a constant flow rate for 8 minutes. After 10 minutes, solutions (III) and (IV) in Table 7 were simultaneously added at the same flow rate for 18 minutes. (II
One minute after the completion of the addition of the liquids (I) and (IV), an aqueous solution of the dye (water 8
113 mg of the above dye (e) in 2 ml and 6 ml of methanol
And the above-mentioned dye (f) containing 113 mg and kept at 40 ° C.) were added all at once.

After washing with water and desalting in a conventional manner, 33 g of lime-treated ossein gelatin, 50 mg of the above-mentioned chemical (B) and 3 g of chemical (D) were added to adjust the pH to 6.0 and the pAg to 7.7. 4-hydroxy-6-methyl-1,3,3a, 7
Tetrazaindene was added, then sodium thiosulfate and chloroauric acid were added to optimally sensitize at 65 ° C, and then the antifoggant (1) was added, followed by cooling. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.47 μm was obtained.

[0125]

[Table 7]

Using the above materials, photosensitive materials 101 shown in Tables 8 to 10 were prepared.

[0127]

[Table 8]

[0128]

[Table 9]

[0129]

[Table 10]

[0130]

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[0131]

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[0132]

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Next, a method for producing the image receiving material will be described. Image receiving materials R101 having the structures shown in Tables 11 and 12 were produced.

[0134]

[Table 11]

[0135]

[Table 12]

[0136]

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[0137]

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[0138]

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Next, as shown in Table 13, photosensitive material 1 having exactly the same composition as 101 except that the electron transfer agent was changed.
02 to 110 were produced. At this time,
In 10, the electron transfer agent precursor used in 101 is
The electron transfer agent was removed from all the coating layers, and 0.1 mmol / m ² was added to the first layer and 0.1 mmol / m ² to the third layer for each coating layer.
1 mmol / m ² and 0.12 mmol / m ² were distributed to the fifth layer so that the total amount of the electron transfer agent was the same as that of the electron transfer agent A. Photosensitive materials 101 to 110 thus produced
For 0.1 second at 4000 lux through B, G, R, and gray filters of continuously varying densities. 15 ml / m ² of 40 ° C. warm water was applied to the exposed light-sensitive material surface, and the image receiving sheet R101 and each other were superposed on each other, and then heat-developed at 80 ° C. for 17 seconds using a heat drum. When the image receiving sheet R101 was peeled off after the processing, a clear image was obtained corresponding to the filter exposed on the image receiving sheet.
Immediately after the processing, the reflection density of Dmax of the exposed portion and the reflection density of Dmin of the white portion of this sample were measured with an X-rite densitometer, and the results are shown in Table 14. Table 15 shows the results of similar processing after storing each photosensitive material for 7 days at 45 ° C. and a relative humidity of 80%.

[0140]

[Table 13]

[0141]

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[0142]

[Table 14]

[0143]

[Table 15]

The results of Tables 14 and 15 are summarized. First, in Comparative Samples 102 to 104, 1- as the electron transfer agent was used.
A phenyl-3-pyrazolidinone derivative is used. In these samples, since no electron transfer agent precursor was used, as described in JP-A-1-138556,
The photographic properties after storage have deteriorated. On the other hand, it can be seen that the photographic materials 106 to 110 of the present invention show photographic properties equal to or higher than that of 101 immediately after sample preparation and after storage.

Claims (4)

[Claims] 1. A support comprising at least a photosensitive silver halide, a binder, a non-diffusible dye-donating compound capable of releasing or forming a diffusible dye upon reduction, an electron donor, and an electron transfer agent. In a diffusion transfer type color photographic material, the electron transfer agent is at least one compound represented by the following general formula (1) or (2). General formula (1) General formula (2) In the formula, R _{1 to} R ₄ are a hydrogen atom, a halogen atom, a cyano group, or a compound having 4 or less carbon atoms or an I / O value of 1 or more,
Alkyl group, aryl group, heterocyclic group, alkoxy group,
Aryloxy group, alkylthio group, arylthio group,
Alkylcarbonyl group, arylcarbonyl group, alkylsulfonyl group, arylsulfonyl group, alkylcarbonamide group, arylcarbonamide group, alkylsulfonamide group, arylsulfonamide group, alkylcarbonyloxy group, arylcarbonyloxy group, carbamoyl group, alkyl Represents a carbamoyl group, an arylcarbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfamoyl group, an alkylsulfamoyl group, an arylsulfamoyl group, a ureido group, or a urethane group. R ₅ is an alkyl group, an aryl group,
Represents a heterocyclic group, an alkylamino group, an arylamino group, or a heterocyclic amino group. 2. R ₅ in the general formula (1) or (2) is
The diffusion transfer type color light-sensitive material according to claim 1, which is a group represented by the following general formula (3). General formula (3) In the formula, R _{6 to} R ₁₀ represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, or a compound having 4 or less carbon atoms or an I / O value of 1
Above, alkyl group, heterocyclic group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylcarbonyl group, arylcarbonyl group, alkylsulfonyl group, arylsulfonyl group, alkylcarbonamide group, arylcarbonamide group, alkyl Sulfonamide group, arylsulfonamide group, alkylcarbonyloxy group, arylcarbonyloxy group, carbamoyl group, alkylcarbamoyl group, arylcarbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, sulfamoyl group, alkylsulfamoyl group, arylsulfo Represents a famoyl group, a ureido group, or a urethane group. R ₆ and R ₇ , R ₇ and R ₈ , R ₈ and R ₉ , R ₉ and R ₁₀ may each independently form a ring. 3. R ₆ and / or R in the general formula (3)
₁₀ is a substituent other than a hydrogen atom,
3. A diffusion transfer type color photosensitive material according to claim 2. 4. R ₂ and / or R in the general formula (1)
_4. The diffusion transfer type color photosensitive material according to claim 1, wherein R ₄ in the general formula (2) is a substituent other than a hydrogen atom.