JPH11352640A - Heat developing photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a heat developable photosensitive material having excellent decolorizing property of dyes in an easy heat developing process, excellent color resolution and sharpness after the photosensitive material is stored, by preparing the photosensitive material to have a specified antidiffusive dye which decolorizes by the reaction with a decolorizing agent during heat treatment and incorporating the diffusive dye as dispersed in a binder in a coexistent state with a specified chlorinated paraffin at normal pressure. SOLUTION: This photosensitive material contains an antidiffusive dye which decolorizes by the reaction with a decolorizing agent during heat treatment, and the antidiffusive dye is expressed by A51 =L51 -(L52 =L53 )m51 -Q51 , A51 = L51 -(L52 =L53 )n51 -A52 , A51 (=L51 -L52 )p51 =B51 or (NC)2 C=C(CN)-Q51 . The antidiffusive dye is dispersed in a binder in an coexistent state with chlorinated paraffin having >175C boiling point at normal pressure. In the formula, = represents a double bond, - is a single bond, A51 and A52 are acidic rings, B51 is a basic ring, Q51 is an aryl or heterocyclic group, L51 to L53 are methine groups which may be substituted.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photothermographic material capable of rapidly forming an image. It relates to an excellent photothermographic material.

[0002]

2. Description of the Related Art Ordinary silver halide light-sensitive materials have high photosensitivity and can obtain high-definition images, but are developed with a processing solution having a complicated composition, so that environmental restrictions and complicated liquid management are required. There are difficulties. As a system that solves these problems, a heat-developable dye transfer type photosensitive material that can obtain high-quality color images easily and quickly by using a small amount of water and heating without the need for a developing solution and an image forming apparatus using the photosensitive material have been developed. (Fuji Photo Film Co., Ltd.,
Pictrography 3000, Pictrostat 200
etc). These systems obtain a print image for viewing by simple thermal development. In the past, thermal development systems similar to these were limited to similar photosensitive materials for printing,
In recent years, a method for preparing a photographic material by a heat development method has been disclosed in JP-A-9-146247.

[0003] Colloidal silver or filter dyes are usually used in silver halide photographic materials for photography, which require high image quality, for the purpose of improving color separation and sharpness. However, since colloidal silver becomes fog nuclei, it must be separated from the silver halide emulsion layer, and the effect of improving sharpness decreases with an increase in film thickness due to the addition of an intermediate layer or the like. Prior art filter dyes are eluted or bleached in a processing solution during development processing, and when used in a photothermographic material using only a small amount of water, bleaching is insufficient. Therefore, when image information is read, it remains as an unnecessary density component. Furthermore, in systems where thermal development is carried out by applying a small amount of water to photosensitive materials, the use of water-soluble dyes elutes and contaminates these small amounts of water, making it impossible to use water repeatedly. Causes inconvenience. In order to solve this problem, Japanese Patent Application Laid-Open No. 6-337,511 discloses an image forming method in which a water-insoluble organic pigment is dispersed in solid fine particles and contained in a photosensitive material, and is thermally developed in the presence of water. However, this also has a problem that it remains as an unnecessary concentration component. To solve these problems,
Japanese Patent Application Laid-Open No. 8-101,487 discloses a method using a solid dispersion dye. However, during storage of a light-sensitive material, a part of the dye is solubilized and migrates, thereby reducing the reactivity between the coupler and the color developing agent. And other problems. Further, Japanese Patent Application Laid-Open No. 9-146,247 describes a system in which a color former formed of a leuco dye and a developer is decolorized with an alkali during development processing. However, although the decoloring property is excellent, a large amount of a developer must be used, and alkali is consumed. Therefore, there is a problem that the reactivity between the coupler and the color developing agent often decreases.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an excellent dye decoloring property in simple thermal development, free of unnecessary density components when reading image information, and color separation after storage of a photosensitive material. Another object of the present invention is to provide a photothermographic material having excellent sharpness and sharpness.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for imagewise exposing a photosensitive material having at least photosensitive silver halide grains, a color developing agent (or a precursor thereof), a coupler and a binder on a support. Thereafter, in the presence of a small amount of water, the photosensitive material is used in a method for forming an image on the photosensitive material by applying one or more processes of heating the photosensitive material by overlapping the processing member with the photosensitive material. It has a diffusion-resistant dye that is decolorized by a reaction with a decoloring agent during heat treatment, and at least one of the diffusion-resistant dyes is represented by the following general formulas (I) to (IV): A dye (preferably a diffusion-resistant dye that is a yellow or magenta dye represented by the following general formula (V)), and at least one of the diffusion-resistant dyes has a boiling point of 175 ° C. or more at normal pressure. Coexisted with paraffin Was achieved by photothermographic material characterized in that it is dispersed in a binder in state. General formula _{(I) A 51 = L 51} - (L 52 = L 53) m51 -Q 51 Formula _{(II) A 51 = L 51} - (L 52 = L 53) n51 -A 52 formula (III) A ₅₁ (= L ₅₁ -L ₅₂ ) _p51 = B ₅₁ General formula (IV) (NC) ₂ C = C (CN) -Q ₅₁ General formula (V)

[0006]

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(Wherein, = represents a double bond, and-represents a single bond.)
You. A₅₁, A₅₂, A₆₁Each represents an acidic nucleus;₅₁Is
Represents a basic nucleus. Q₅₁Represents an aryl group or a heterocyclic group.
You. L ₅₁, L₅₂, L₅₃, L₆₁, L₆₂, L₆₃Is German
Represents a methine group which may be substituted. L₅₁, L₅₂
Or L₅₃Are present in the molecule,
They may be the same or different. L₆₄, L₆₅
Each independently represents an alkylene group having 1 to 4 carbon atoms
You. R₆₁Represents a substituent;₆₂, R₆₃Are independent
, A cyano group, -COOR₆₄Group, -CONR₆₅R₆₆Group,
-COR₆₄Group, -SO_TwoR₆₄Group, or -SO_TwoNR₆₅
R₆₆R represents a group₆₄Represents an alkyl group, an alkenyl group,
A loalkyl or aryl group is represented by R₆₅, R₆₆Is it
Each independently represents a hydrogen atom, an alkyl group, an alkenyl group,
Represents a loalkyl group or an aryl group. Note that R₆₅,
R₆₆May be linked to each other to form a nitrogen-containing heterocyclic ring.
No. m₅₁Represents 0, 1, 2; n₅₁, P₅₁Are each
Represents 0, 1, 2, or 3, and m₆₁Is 0 or 1 to n₆₁
Represents an integer of 0 to 4. However, in the general formulas (I) to (V),
The compound represented is a carboxyl group and / or a sulfo
Having no group and represented by the general formulas (I) to (V).
The compound to be used has a diffusion-resistant group and
The product after (decolorization) is also diffusion resistant, and is
It does not elute qualitatively. Further, general formulas (I) to
The compound represented by the formula (V):
Response, followed by a bond break,
It does not have a group that splits into molecules. )

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The dye which is decolorized by the reaction with the decolorizing agent during the heat treatment by superposing the photothermographic material of the present invention and the processing member is one which decolorizes by the reaction with the decoloring agent during the processing, and has a diffusion resistance. It has. Further, at least a part of the dye constituting the present invention has diffusion resistance even when the color is erased after the treatment. By using such a dye, it is possible to provide a photosensitive material which is excellent in storability, sharpness and granularity, and which can be processed easily and quickly. Also,
It is also preferable from an environmental point of view because unnecessary materials are not taken out of the photosensitive material. Specific examples of such dyes include cyanines, merocyanines, oxonols, arylidenes (including heteroarylidenes), anthraquinones, triphenylmethanes, azo dyes, and azomethine dyes. Can be. The dye used in the present invention does not have a carboxyl group and / or a sulfo group in the molecule. When these groups are present, the storage stability of the photosensitive material is deteriorated, and the sensitivity, granularity, sharpness, etc. are deteriorated. In addition, when the dye or its decomposition product comes out on the surface of the photosensitive material during processing, the surface property is deteriorated. It is not preferable because it causes problems such as failure of hardware and hardware.

The dye used in the present invention will be described below in detail. Here, when the substituent in the compound of the dye used in the present invention includes an alkyl moiety (moiety), an alkenyl moiety, an alkylene moiety, and a cycloalkyl moiety, unless otherwise specified, even if these moieties are linear, It may be branched, further unsubstituted or substituted. When the substituent in the compound of the dye used in the present invention includes an aryl moiety, the aryl moiety may be substituted or unsubstituted, and may be a single ring or a condensed ring, unless otherwise specified. Further, when the substituent in the compound of the dye used in the present invention includes a heterocyclic moiety, the heterocyclic moiety may be substituted or unsubstituted, unless otherwise specified, may be substituted, may be a single ring, or may be a condensed ring. Good. In the present invention, as the hetero ring, a 3- to 8-membered ring is preferably formed by a nonmetal atom,
More preferably, a member ring is formed. As the nonmetal atom, carbon, oxygen, nitrogen, sulfur and hydrogen are preferred, and carbon, hydrogen and nitrogen are more preferred. As the substituent at each of the above sites, preferably, for example, a halogen atom, an alkyl group, an alkylene group, an alkenyl group, a cycloalkyl group,
Aryl group, heterocyclic group, aliphatic oxy group, aryloxy group, acyl group, aliphatic oxycarbonyl group, aryloxycarbonyl group, carbamoyl group, acylamino group, sulfonamide group, aliphatic sulfonyl group, arylsulfonyl group, etc. No.

The "acid nucleus" in the above general formulas (I) to (IV) means an electron-withdrawing cyclic or non-cyclic atomic group. The term "basic nucleus" means an electron-donating cyclic or acyclic atomic group. For the classification and details of “acid nuclei” and “basic nuclei” in the molecular structure of dyes (dyes), see TH James, The Theory of the Photogr.
aphic Process, 4th edition, Macmillan Publishing Co., Inc.
(1977), pp. 197-200.

[0011] In the general formula (I) ~ (IV), acidic nucleus represented by A ₅₁ or A ₅₂ is preferably a compound having a methylene group sandwiched between ketomethylene compound or an electron withdrawing group of a cyclic. Examples of cyclic ketomethylene compounds include 2-pyrazolin-5-one, 1,2,3,6-tetrahydropyridine-2,6-dione, rhodanin, hydantoin, thiohydantoin, 2,4-oxazolidinedione, isoxazolone , Barbituric acid, thiobarbituric acid, indandione, dioxopyrazolopyridine, hydroxypyridine, pyrazolidinedione, 2,5
-Dihydrofuran-2-one and pyrrolin-2-one. These may have a substituent. Among these, a preferred compound is 2-pyrazolin-5.
-One, 1,2,3,6-tetrahydropyridine-2,
6-dione, isoxazolone, dioxopyrazolopyridine, hydroxypyridine, pyrazolidinedione, barbituric acid, and particularly preferably 2-pyrazolin-5
-One, 1,2,3,6-tetrahydropyridine-
2,6-dione, isoxazolone, hydroxypyridine, pyrazolidinedione and barbituric acid.

A methylene group sandwiched between electron-withdrawing groups
Is Z₅₁-CH_Two-Z ₅₂Can be expressed as
Here, Z₅₁, Z₅₂Are -CN and -SO, respectively.
_TwoR₅₁, -COR₅₁, -COOR₅₁, -CON (R₅₂)
_Two, -SO_TwoN (R₅₂)_Two, -C [= C (CN)_Two] R
₅₁, -C [= C (CN)_Two] N (R₅₁)_TwoAnd R₅₁
Is an alkyl, alkenyl, cycloalkyl,
A heteroaryl group or a heterocyclic group;₅₂Is a hydrogen atom or R₅₁so
Represents the groups mentioned above. R₅₁, R₅₂Each has a substituent
May have multiple Rs in the molecule.₅₁Or R₅₂Where there is
If so, they can be the same or different. Z₅₁
And Z₅₂May be the same.

[0013] Examples of the basic nucleus represented by B _51, there may be mentioned pyridine, quinoline, indolenine, oxazole, imidazole, thiazole, benzoxazole, benzimidazole, benzothiazole, oxazoline, naphthoxazole, pyrrole . Each of these may have a substituent. Among these, preferred compounds are indolenine, benzoxazole, benzimidazole, benzothiazole and pyrrole, and particularly preferred are indolenine and benzoxazole. Examples of the aryl group represented by Q _51, a phenyl group, and a naphthyl group may have a substituent (preferably an electron donating group). Of these, preferably a dialkylamino group, a hydroxyl group,
A phenyl group substituted with an alkoxy group or an alkyl group, particularly preferably a phenyl group substituted with a dialkylamino group. Examples of the heterocyclic group represented by Q _51, pyrrole, indole, furan, thiophene, imidazole, pyrazole, indolizine, quinoline, carbazole, phenothiazine, phenoxazine, indoline, thiazole, pyridine, pyridazine, thiadiazine, pyran, Examples include thiopyran, oxadiazole, benzoquinoline, thiadiazole, pyrrolothiazole, pyrrolopyridazine, tetrazole, oxazole, coumarin, and chroman, each of which may have a substituent. Of these, pyrrole and indole are preferred.

The methine groups represented by L ₅₁ , L ₅₂ and L ₅₃ may have a substituent.
Alternatively, a 6-membered ring (for example, cyclopentene, cyclohexene) may be formed. Examples of the substituent which the above group may have include a sulfonamide group (eg, methanesulfonamide, benzenesulfonamide, octanesulfonamide) and a sulfamoyl group (eg, sulfamoyl, methylsulfamoyl, phenylsulfamoyl, butylsulfamoyl) Moyl), a sulfonylcarbamoyl group (eg, methanesulfonylcarbamoyl, benzenesulfonylcarbamoyl), an acylsulfamoyl group (eg, acetylsulfamoyl, pivaloylsulfamoyl, benzoylsulfamoyl), a linear or cyclic alkyl group (eg, Methyl, isopropyl, cyclopropyl, cyclohexyl, 2-ethylhexyl, dodecyl, octadecyl, 2-phenethyl, benzyl), alkenyl group (eg, vinyl, allyl), alkoxy group (eg, Carboxy,
Octyloxy, dodecyloxy, 2-methoxyethoxy), aryloxy group (eg, phenoxy), halogen atom (eg, F, Cl, Br), amino group (eg, amino, diethylamino, ethyldodecylamino), ester group (eg, ethoxycarbonyl) Octyloxycarbonyl, 2-hexyldecyloxycarbonyl), acylamino group (eg, acetylamino, pivaloylamino, benzoylamino), carbamoyl group (eg, unsubstituted carbamoyl, ethylcarbamoyl, diethylcarbamoyl, phenylethylcarbamoyl), aryl group (eg, Phenyl, naphthyl), alkylthio groups (eg, methylthio, octylthio), arylthio groups (eg, phenylthio, naphthylthio), acyl groups (eg, acetyl, benzoyl) , Pivaloyl), a sulfonyl group (eg, methanesulfonyl, benzenesulfonyl), a ureido group (eg, 3-propylureido, 3,3-dimethylureido), a urethane group (eg, methoxycarbonylamino, butoxycarbonylamino), a cyano group, a hydroxyl group, Examples thereof include a nitro group and a heterocyclic group (for example, a benzoxazole ring, a pyridine ring, a sulfolane ring, a furan ring, a pyrrole ring, a pyrrolidine ring, a morpholine ring, a piperazine ring, and a pyrimidine ring).

The dye used in the present invention is preferably represented by the general formula (I), (II) or (III), more preferably represented by the general formula (I) or (II) Things.

The dye represented by the general formula (I) is generally called an arylidene dye.
When the dye represented by the formula (1) is a yellow or magenta dye, the dye represented by the general formula (V) is preferable.

Hereinafter, the dye represented by formula (V) will be described in detail. In the compound (dye) represented by the general formula (V), m ₆₁ is 0 or 1, and when m ₆₁ is 0, it is called a benzylidene dye, often a yellow dye, and m ₆₁ is 1 In this case, it is called a cinnamylidene dye, and is often a magenta dye. In the present invention,
M ₆₁ in the general formula (V) is preferably 0, and the compound of the general formula (V) is preferably a yellow dye.

In the general formula (V), A ₆₁ represents an acidic nucleus, and is the same as A ₅₁ and A ₅₂ in the general formulas (I) to (III), and more preferably, 2-pyrazolin-5-one. , Isoxazolone, hydroxypyridine, pyrazolidinedione, barbituric acid, more preferably isoxazolone, pyrazolidinedione, barbituric acid, and most preferably pyrazolidinedione.

Examples of the methine groups represented by L ₆₁ , L ₆₂ and L ₆₃ in the formula (V) are the same as L ₅₁ , L ₅₂ and L _{53 in the} formulas (I) to (III). But L
_61, methine groups represented by L _62, L ₆₃ is preferably a = C
R _67- (R ₆₇ is the number of carbon atoms (hereinafter referred to as “C number”)
1 to 10 alkyl groups or hydrogen atoms). Further, as a combination of L ₆₁ , L ₆₂ and L ₆₃ ,
Preferably R ₆₇ of L _61, L _62, or L ₆₃ both R ₆₇ is a hydrogen atom, or L _61, L ₆₂ R ₆₇ is a hydrogen atom L ₆₃ is a methyl group, L _61, L ₆₂ , L ₆₃ and R ₆₇ are most preferably hydrogen atoms.

In the formula (V), L ₆₄ and L ₆₅ each independently represent an alkylene group having 1 to 4 carbon atoms, preferably a methylene group or an ethylene group. It is preferred that the L ₆₄ and L ₆₅ are the same.

In the general formula (V), R₆₂, R₆₃Is it
Each independently represents a cyano group, -COOR ₆₄Group, -CONR₆₅
R₆₆Group, -COR₆₄Group, -SO_TwoR₆₄Group, -SO_TwoNR
₆₅R ₆₆Represents R₆₄Is an alkyl group (eg, methyl,
Tyl, i-propyl, t-butyl, benzyl, trifur
Oromethyl, 2-chloroethyl, 2-ethoxyethyl
Alkenyl groups (eg, vinyl, allyl, oley)
), Cycloalkyl groups (eg, cyclopentyl,
Rohexyl), an aryl group (eg, phenyl, 2-naph
Tyl, 4-chlorophenyl, 2-methoxyphenyl, 3
-Dimethylaminophenyl), preferably alkyl
Group or alkenyl group, more preferably straight-chain unsubstituted
Represents an alkyl group. R₆₅, R₆₆Is independently R₆₄so
Represents a group or a hydrogen atom, preferably alkyl
Group, an aryl group, a hydrogen atom, more preferably a chain
It is an unsubstituted alkyl group or a hydrogen atom. R₆₅, R₆₆Is hydrogen
When it is other than an atom, it preferably has 1 to 20 C atoms.
More preferably, the C number is from 6 to 20, particularly preferably the C number.
8 to 16. R₆₂, R₆₃Represents a cyano group, -C
OOR₆₄Group, -CONR₆₅R₆₆Groups are more preferred,
NO group, -COOR₆₄Groups are particularly preferred, -COOR₆₄Base
Is most preferred. Note that R₆₂, R₆₃Is a cyano group
L when₆₄, L₆₅Is an ethylene group
Preferably, R₆₂, R₆₃Is COOR₆₄When it is a group
L₆₄, L₆₅Are preferably each a methylene group
No. R₆₂And R₆₃Is the same or different
However, it is preferred that they be the same.

In the general formula (V), R ₆₁ represents a substituent, preferably a group exemplified as a substituent of the methine group of L ₆₁ , L ₆₂ and L ₆₃ , more preferably an alkyl group,
It represents an alkoxy group, a dialkylamino group or an alkoxycarbonyl group, particularly preferably represents an alkyl group or an alkoxy group, and most preferably represents a methyl group or a methoxy group.

In the general formula (V), n ₆₁ represents an integer of 0 to 4, preferably 0 or 1, and more preferably 0. When n ₆₁ is 1, R ₆₁ is preferably substituted at the m-position of the amino group. Specific examples of the dye used in the present invention are shown below, but the present invention is not limited to these.

[0024]

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[0026]

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[0041]

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[0042]

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[0048]

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The dyes used in the present invention are described in International Patent WO
88/04794, European Patent EP 274,723,
276,556, 299,435, U.S. Pat. Nos. 2,527,583, 3,486,897, 3,746,539, 3,933,798, 4,130, 429, 4,040,841, JP-A-48-68,623, 52-92,716, 55-155,350, 55-155,351,
No. 61-205,934, JP-A-2-173,630
No. 2-230,135 and 2-277,044
Nos. 2-282, 244, 3-7,931, 3-167,546, 3-13,937, 3-
Nos. 206,443, 3-208,047, 3-1
Nos. 92,157, 3-216,645 and 3-27
4,043, 4-37,841, 4-45,4
No. 36, No. 4-138, 449, No. 5-197, 07
7, No. 6-332112, No. 7-206824,
The compound can be synthesized according to the method described in, for example, JP-A-8-20582 or a method analogous thereto.

Specific examples of the synthesis of the exemplified compounds (A10), (A100) and (A134) of the present invention are shown below as typical examples. (Synthesis Example-1) Synthesis of Exemplified Compound (A10)

[0054]

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A solution of (A10-2) (0.52 mol) in acetonitrile (250 ml) was dissolved in an ice-methanol bath.
Cool to 7 ° C and add phosphorus oxychloride (0.55mo
l) was added dropwise while maintaining the temperature of the reaction solution at 15 ° C or lower. Subsequently, a solution of (A10-1) (0.5 mol) in acetonitrile (150 ml) was added dropwise while maintaining the internal temperature at 5 ° C. or lower, and then the cooling bath was removed and the mixture was further stirred for 1 hour. Then, the reaction solution was poured into ice water (1 liter), and a solution of sodium hydroxide (100 g) in water (500 ml) was added thereto. The reaction mixture was extracted twice with ethyl acetate (500 ml), and the organic layer was washed with brine and concentrated. The resulting residue was recrystallized from methanol to give (A10-
3) was obtained with a yield of 49%.

(A10-3) (0.05 mol) and (A10-3)
10-4) (0.05 mol), potassium carbonate (0.1
0 mol) with N, N-dimethylacetamide (200 m
In l), the reaction was carried out at 100 ° C. for 3 hours. After cooling to room temperature
Ethyl acetate (200 ml) was added, and the insoluble matter was removed by filtration. The filtrate was washed with 2N hydrochloric acid, water and brine, and concentrated to give (A10-5) quantitatively. (A10-5)
(0.03 mol) and (A10-6) (0.03 mol)
1) was refluxed in ethanol (80 ml) for 5 hours, after which the solvent was distilled off. The residue was subjected to silica gel column chromatography (eluent, methylene chloride / hexane = 4/1 to 1).
1/0) to give Exemplified Compound (A10)
Was obtained in a yield of 76%.

(Synthesis Example-2) Illustrative Compound (A-100)
Synthesis of

[0058]

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76.4 g (0.55 mol) of bromoacetic acid (a), 93.2 g (0.5 mol) of dodecanol (b),
1.4 g of p-toluenesulfonic acid monohydrate in toluene 2
1 ml while dissolving in water and azeotropically removing generated water.
Refluxed for hours. After washing three times with a 2% aqueous sodium carbonate solution, drying over magnesium sulfate and concentration were carried out to obtain a transparent liquid ester (c). (100% yield)

21.1 g (0.227 mol) of aniline,
0.5 mol of the above ester (c), 105 g of potassium carbonate
(0.75 mol), 11.2 g of sodium iodide (0.
075 mol) was dissolved in 300 ml of dimethylacetamide, and the mixture was heated with stirring at 80 ° C. for 4 hours under a nitrogen atmosphere. After cooling, water and ethyl acetate were added to carry out liquid separation, and the mixture was washed twice with water. Concentrate after drying with magnesium sulfate and aniline (d)
Was obtained as a main component.

Dimethylformamide (300 ml) at 10 ° C.
Stir while cooling below, and add phosphorus oxychloride 6
9.6 g (0.454 mol) was added dropwise so that the temperature did not rise to 20 ° C. or higher, and the mixture was further stirred at 20 ° C. for 30 minutes.
A solution containing aniline (d) was added thereto, and the temperature was further increased to 60 ° C.
For 1 hour. After cooling, 1 liter of water and 110 g of potassium hydroxide were carefully added in that order to adjust the pH to 8, and the mixture was extracted with ethyl acetate and washed twice with water. After drying over magnesium sulfate, the mixture was concentrated, acetonitrile was added, and the mixture was cooled to crystallize benzaldehyde (e) as light brown crystals, which was separated by filtration and washed with cold acetonitrile. Benzaldehyde (e) was obtained in a yield of 74.2 g (57% yield (from aniline)).

6.31 g of pyrazolidinedione (f)
(0.025 mol), the above-mentioned benzaldehyde (e) 1
5.8 g (0.0275 mol), 7.7 g of acetic anhydride
(0.075 mol) was dissolved in 50 ml of ethanol.
Refluxed for hours. Upon cooling, crystals were precipitated, separated by filtration and washed with cold ethanol to obtain pale yellow crystals of Exemplified Compound (A-100). The yield was 16.4 g (81.2% yield (from pyrazolidinedione (f)).

(Synthesis Example-3) Illustrative Compound (A-134)
Synthesis of

[0064]

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(A134-1) 102 in a three-necked flask
0 g, 24.3 ml of pyridine and 2 liters of N, N-dimethylacetamide were added, and 347 ml of diketene was added dropwise over 30 minutes while heating and stirring at an internal temperature of 85 ° C. After continuing to heat and stir for 3 hours, the mixture was cooled to room temperature, extracted with 4 l of ethyl acetate and 4 l of water, and the obtained ethyl acetate layer was washed 5 times with a mixed solution of 500 ml of saturated saline and 2 l of water. And dried over anhydrous sodium sulfate. This was concentrated with a rotary evaporator, and the residue obtained was added with 2.5 liters of isopropyl alcohol and the precipitated crystals were separated by filtration to obtain 944 g of compound (A134-2) (yield 74%).

The above compound (A134-
2) Add 424 g and 900 ml of isopropyl alcohol, and add 119 ml of piperidine here while stirring at room temperature.
Was added dropwise over 5 minutes. After completion of the dropwise addition, 128 ml of ethyl cyanoacetate was added dropwise thereto over 10 minutes while stirring under heating and refluxing. The mixture was stirred under heating and refluxing for 3 hours, and then cooled to room temperature. The resulting ethyl acetate layer was washed five times with a mixed solution of 300 ml of a saturated saline solution and 1 liter of water, and extracted.
It was dried over anhydrous sodium sulfate. This was concentrated by a rotary evaporator, and 1.2 liters of acetonitrile was added to the residue obtained. 129 ml of concentrated hydrochloric acid was added dropwise thereto over 20 minutes while stirring under ice-cooling, and the precipitated crystals were separated by filtration to obtain a compound ( A134-3) 393 g was obtained.
(83% yield).

The above compound (A134-
4) Put 142 g and 1.5 liter of acetonitrile,
While stirring at room temperature, 202 ml of pyridine is added to 25 ml.
After dropwise addition over a period of 94 minutes, 94 ml of acetic anhydride was continuously added dropwise over a period of 10 minutes. After stirring for 10 minutes after completion of the dropwise addition, 473 g of (A134-3) was added thereto over 20 minutes, stirring was continued for 3 hours, and the mixture was further stirred for 1 hour under ice-cooling, and the precipitated crystals were separated by filtration. Compound (A134) 3
88 g were obtained (77% yield).

The structures of these compounds were confirmed by NMR, MS spectrum and elemental analysis.

The above-mentioned dye in the present invention can be used as a decolorizable dye layer in a yellow filter layer, a magenta filter layer, and an antihalation layer. Accordingly, for example, when the photosensitive layer is provided in the order of a red photosensitive layer, a green photosensitive layer, and a blue photosensitive layer from the side closest to the support, a yellow filter layer and a green photosensitive layer are provided between the blue photosensitive layer and the green photosensitive layer. A magenta filter layer can be provided between the red photosensitive layer and the red photosensitive layer, and a cyan filter layer (antihalation layer) can be provided between the red photosensitive layer and the support. The dye is used in such an amount that the transmission density of each layer is 0.03 to 3.0, more preferably 0.1 to 2.0, for blue, green and red light, respectively. Specifically, although it depends on ε and the molecular weight of the dye, 0.005 to ² mmol / m ² may be used, and more preferably 0.05 to 1 mmol / m ² .

The light-sensitive material of the present invention may be used by mixing two or more dyes in one layer. For example, three kinds of dyes of yellow, magenta and cyan may be mixed and used in the above-mentioned antihalation layer.

Next, the chlorinated paraffin used in the present invention will be described. The chlorinated paraffin used in the present invention may be a polymer obtained from chlorinated linear, branched or cyclic paraffin, or a chlorinated unsaturated hydrocarbon such as vinyl chloride, vinylidene chloride, allyl chloride, or a monomer thereof, or another polymer. And may be a single composition or a mixture. The carbon number of the chlorinated paraffin is preferably 8 or more, and the molecular weight is preferably 250 or more and 10,000 or less. The chlorine content of the chlorinated paraffin is preferably an average of 10 by weight.
%, More preferably 30% to 80% on average. Hereinafter, specific examples of the chlorinated paraffin used in the present invention are shown by the average composition, the average molecular weight, and the average chlorine content.

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[Table 1]

The amount of the chlorinated paraffin of the present invention depends on the type of the coexisting decolorizable dye and its physicochemical properties, but can be arbitrarily changed in most cases within the range of 1 to 200% by weight. Preferably, the chlorinated paraffin and the decolorizable dye are used under such conditions that they coexist and disperse uniformly in a compatible state. The light-sensitive material of the present invention is used in a state where oil droplets in which chlorinated paraffin is dissolved together with a decolorizable dye are dispersed in a binder. An emulsification dispersion method is preferable as the preparation method, and for example, a method described in US Pat. No. 2,322,027 can be used. In this case, US Pat.
5,470, 4,536,466, 4,58
7,206, 4,555,476 and 4,59
No. 9,296, Japanese Patent Publication No. 3-62,256, etc., a high-boiling oil, if necessary, having a boiling point of 50 ° C. to 160 ° C.
It can be used in combination with an organic solvent having a low boiling point of ° C. In addition, an oil-soluble polymer can be used in combination,
Examples are described in PCT International Publication No. WO 88/00723. Further, as a method of dissolving the chlorinated paraffin and the decolorizable dye in the polymer, a latex dispersion method can be used, and the process and specific examples of the latex for impregnation are described in US Pat.
These are described in West German Patent Application (OLS) Nos. 2,541,274, 2,541,230, JP-B-53-41091 and European Patent Publication No. 029104.

In dispersing the oil droplets in the hydrophilic binder, various surfactants can be used. For example, surfactants described in JP-A-59-157,636, pp. 37-38, and publicly known technique No. 5 (March 22, 1991, published by Aztec Co., Ltd.), pp. 136-138, can be used. Also, Japanese Patent Application No. 5-204,325
No. 6-19,247, West German Published Patent No. 93
A phosphate ester type surfactant described in 2,299A can also be used. As the hydrophilic binder, a water-soluble polymer is preferable. Examples include gelatin, proteins of gelatin derivatives, or cellulose derivatives, starch, gum arabic,
Natural compounds such as polysaccharides such as dextrin and pullulan and synthetic high molecular compounds such as polyvinyl alcohol, polyvinylpyrrolidone, and acrylamide polymer are exemplified.
These water-soluble polymers can be used in combination of two or more. Particularly preferred is a combination with gelatin.
Gelatin may be selected from lime-processed gelatin, acid-processed gelatin, and so-called demineralized gelatin having a reduced content of calcium and the like according to various purposes, and may be used in combination. They can be used in combination.

In the present invention, the dye is used for the reaction with the decoloring agent.
Color is erased during processing. Alcohol is also used as a decolorizer
Or phenols (R₅₁OH), amine or ani
Phosphorus ((R₅₂)_ThreeN), hydroxylamines ((R
₅₂)_TwoNOR₅₂), Sulfinic acids (R₅₁SO_TwoH) also
Or its salt, sulfurous acid or its salt, thiosulfuric acid or
Is a salt thereof, a carboxylic acid (R₅₁CO_TwoH) or that
Salts, hydrazines ((R₅₂)_TwoNN (R₅₂)_Two), Gua
Niidines ([(R₅₂)_TwoN]_TwoC = NH), amino gua
Niidines ((R₅₂)_TwoNR₅₂N (R₅₂N) C = NH),
Amidines, thiols (R₅₁SH, where R₅₁, R₅₂
Is the same as that of the above general formulas (I) to (IV)),
Cyclic or chain active methylene compound (Z₅₃-CH _Two−
Z₅₄, Where Z₅₃, Z₅₄Is a compound of the above general formulas (I) to (IV)
Z₅₁, Z₅₂Is synonymous with Z₅₃And Z₅₄Are combined
May form a ring), cyclic or chain active methination
Compound (Z₅₃-CH (R₅₁) -Z₅₄Or Z₅₃-CH (Z
₅₄) -Z₅₅, Where Z₅₅Is Z₅₃Is synonymous with Z₅₃, Z
₅₄, Z₅₅(Or R₅₁) Are linked together to form a ring
And anionic species generated from these compounds
And the like. Of these, hydroxy is preferred.
Luamines, sulfinic acids, sulfurous acid, guanidines,
Aminoguanidines, heterocyclic thiols, cyclic or
Active methylene chain, active methine compounds, especially
Preferred are guanidines and aminoguanidines.
Even if these decolorizing agents are added to the photosensitive material from the beginning,
Good, and added to photosensitive material in some way during processing
May be added to the processing member, and
A method of transferring to a photosensitive material is preferred. When adding
Add a precursor as a decolorizer form
May be.

The above-described decoloring agent comes into contact with the dye during the treatment and decolorizes the dye by nucleophilic addition to the dye molecule.
Preferably, after imagewise exposure or simultaneously with imagewise exposure of the silver halide photosensitive material containing a dye, the film surfaces are superimposed on each other in the presence of water and a processing material containing a decolorant or a decolorant precursor. By heating and then peeling off both, a colored image is obtained on the silver halide light-sensitive material and the dye is decolorized. In this case, the density of the dye after decoloring is 1/3 or less, preferably 1/5 or less of the original density. The amount of the decoloring agent used is 0.1 to 200 times, preferably 0.5 to 100 times the mol of the dye.

In the present invention, at least the photosensitive silver halide particles, the color developing agent, the coupler and the binder are contained on the transparent support, and the photosensitive wavelength region and the absorption wavelength of the dye formed from the color developing agent and the coupler are included. Using a photosensitive material having at least three types of photosensitive layers having different regions and a processing material having at least a base and / or a base precursor on a support, and excluding the back layer of both the photosensitive material and the processing material In the presence of water equivalent to 0.1 to 1 times the amount required for maximally swelling the coating film, the photosensitive material and the processing material are overlapped with the photosensitive layer and the processing layer facing each other. C. for 5 to 60 seconds to form an image based on at least three non-diffusible dyes on the light-sensitive material. It is preferred to obtain a color image on the recording material.

The silver halide which can be used in the present invention may be any of silver iodobromide, silver bromide, silver chlorobromide, silver iodochloride, silver chloride and silver iodochlorobromide. The size of the silver halide grains is 0.1 to 2 μm, particularly 0.2
~ 1.5 µm is preferred. The shape of the silver halide grains may be those having a shape composed of normal crystals such as cubic, octahedral or tetradecahedral, and those having a hexagonal or rectangular tabular shape.
Preferably, the tabular grains have a grain size of 8 or more, more preferably 20 or more, and 50% or more, preferably 80% or more, more preferably 90% or more of the projected area of all the grains in such tabular grains.
% Of the emulsion is preferably used. U.S. Patent Nos. 5,494,789 and 5,503,970
No. 5,503,971, No. 5,536,632, etc., particles having a smaller thickness than 0.07 μm and a higher aspect ratio can also be preferably used. U.S. Patent Nos. 4,400,463 and 4,7,
High silver chloride tabular grains having a (111) plane as a main plane described in US Pat. Nos. 13,323 and 5,217,858, and the like, and US Pat. Nos. 5,264,337, 5,2.
High silver chloride tabular grains having a (100) plane as a main plane described in JP-A Nos. 92,632 and 5,310,635 can also be preferably used. Examples of actually using these silver halide grains are described in JP-A-9-274295, JP-A-9-319047, Japanese Patent Application No. 8-238672, and the like. It is preferable that the emulsion of the present invention is usually subjected to chemical sensitization and spectral sensitization. As chemical sensitization,
Reducing silver nuclei are introduced using chalcogen sensitization using sulfur, selenium or tellurium compounds, noble metal sensitization using gold, platinum, iridium, etc., or using a compound that has an appropriate reducing property during grain formation. Thus, a so-called reduction sensitization method that obtains high sensitivity can be used alone or in various combinations. As the spectral sensitization, cyanine dye, merocyanine dye, complex cyanine dye, complex merocyanine dye, holopolar dye, hemicyanine dye, styryl dye or A so-called spectral sensitizing dye such as a hemioxonol dye is used alone or in combination, and is preferably used together with a supersensitizer. In the silver halide emulsion of the present invention, nitrogen-containing heterocyclic compounds such as azaindenes, triazoles, tetrazoles, and purines, mercaptotetrazole, and mercapto for the purpose of preventing fog and increasing the stability during storage. It is preferable to add various stabilizers such as mercapto compounds such as triazoles, mercaptoimidazoles, and mercaptothiadiazoles. Photographic additives for silver halide emulsions are available from Research Disclosure No. 1764
No. 3 (December 1978) and No. 18716 (197
November 2009), No. 307105 (November 1989)
) And No. 38957 (September 1996) can be preferably used. The coating amount of the photosensitive silver halide is generally 0.05 to 2 in terms of silver.
0 g / m ^2, preferably from 0.1 to 10 g / m ^2.

As the binder for the light-sensitive material, hydrophilic binders are preferable.
Disclosure and those described on pages 71 to 75 of JP-A-64-13546. Among them, gelatin and a combination of gelatin with another water-soluble binder such as polyvinyl alcohol, modified polyvinyl alcohol, cellulose derivative, acrylamide polymer and the like are preferable. The coating amount of the binder is generally from 1 to 20 g / m ^2, preferably from 2 to 15 g / m ^2, more preferably suitably 3~12g / m ^2. Among them, gelatin is generally 50% to 100%, preferably 70%.
% To 100%.

As the color developing agent (or a precursor thereof), p-phenylenediamines or p-aminophenols are preferable, and a compound represented by the general formula (a) or (b) is more preferable. . In the general formulas (a) and (b), R _{501 to} R ₅₀₄ represent a hydrogen atom or a substituent, and examples of the substituent include a halogen atom (for example, a chloro group and a bromo group) and an alkyl group (for example, Methyl group, ethyl group, isopropyl group, n-butyl group, t
-Butyl group), an aryl group (for example, phenyl group, tolyl group, xylyl group), a carbonamide group (for example, acetylamino group, propionylamino group, butyroylamino group, benzoylamino group), a sulfonamide group (for example, methanesulfonylamino group) Group, ethanesulfonylamino group, benzenesulfonylamino group, toluenesulfonylamino group), alkoxy group (eg, methoxy group, ethoxy group), aryloxy group (eg, phenoxy group), alkylthio group (eg, methylthio group, ethylthio group, butylthio group) Group), arylthio group (for example, phenylthio group, tolylthio group), carbamoyl group (for example, methylcarbamoyl group, dimethylcarbamoyl group, ethylcarbamoyl group, diethylcarbamoyl group, dibutylcarbamoyl group, piperidinocar Moyl group, morpholinocarbamoyl group, phenylcarbamoyl group, methylphenylcarbamoyl group, ethylphenylcarbamoyl group, benzylphenylcarbamoyl group), sulfamoyl group (for example, methylsulfamoyl group, dimethylsulfamoyl group, ethylsulfamoyl group, diethyl Sulfamoyl, dibutylsulfamoyl, piperidinosulfamoyl, morpholinosulfamoyl, phenylsulfamoyl, methylphenylsulfamoyl, ethylphenylsulfamoyl, benzylphenylsulfamoyl Group), cyano group, sulfonyl group (for example, methanesulfonyl group, ethanesulfonyl group, phenylsulfonyl group, 4-chlorophenylsulfonyl group, p-toluenesulfonyl group), alkoxycarbonyl group (example) If a methoxycarbonyl group, an ethoxycarbonyl group, butoxycarbonyl group), an aryloxycarbonyl group (e.g. phenoxycarbonyl group), an acyl group (e.g. acetyl group,
A propionyl group, a butyroyl group, a benzoyl group, an alkylbenzoyl group), a ureido group (eg, a methylaminocarbonamide group, a diethylaminocarbonamide group),
Examples thereof include a urethane group (for example, a methoxycarbonamide group and a butoxycarbonamide group), and an acyloxy group (for example, an acetyloxy group, a propionyloxy group, and a butyroyloxy group). Among R _{501 to} R ₅₀₄ , R ₅₀₂ and / or R ₅₀₄ are preferably a hydrogen atom. Also,
When A ₁₀₁ is a hydroxyl group, the sum of Hammett constants σp values of R _{501 to} R ₅₀₄ is preferably 0 or more, and when A ₁₀₁ is a substituted amino group, the Hammett constant σ of R _{501 to} R ₅₀₄ is σ.
It is preferable that the sum of the p values is 0 or less.

A₁₀₁Is a hydroxyl group or a substituted amino group (eg,
For example, dimethylamino group, diethylamino group, ethylhydro
A hydroxy group), and a hydroxyl group is preferable. General
In the formula (a), X₁₀₁Is -CO-, -SO-,-
SO_Two-And-(Q₁₀₁) P (= O)-(Q₁₀₁Is
Represents a monovalent group substituted for P, and specifically,₅₀₁~
R₅₀₄And-(Y_k1= Z
_k1)_k1-D ₁₀₁including. O is linked to P by a double bond
I do. ) Represents a divalent or higher valent linking group selected from Y_k1
And Z_k1Is a nitrogen atom or -CR₅₀₅= (R₅₀₅Is the water
Represents an atom or a substituent. ) Represents a group represented by here
In R₅₀₅As the R₅₀₁~ R₅₀₄As a substituent of
Examples are given. k1 represents an integer of 0 or more
However, 0, 1 and 3 are preferable, and any of 0 and 1 is preferable.
Is more preferable, and 0 is particularly preferable.

D ₁₀₁ represents a proton-dissociable group or a group capable of becoming a cation, and an oxidized product of the compound represented by the general formula (a) produced by an oxidation-reduction reaction with silver halide is converted into a coupler. after coupling and has a function of forming a dye by elimination of the substituents attached to the electron transfer and triggers the coupling site of cleavage and coupler N-X ₁₀₁ coupling from D _101. Specifically, the unshared electron pair of obtaining atom which results in a proton dissociated anions or cations on the coupling reaction after D _101, electron transfer occurs towards the coupling site, between X _101, Y _{k1 (k1} = When it is 0, a double bond is generated between X ₁₀₁ and D ₁₀₁ ), thereby causing cleavage of the NX ₁₀₁ bond, and further generating a double bond between the coupling site of the coupler and the N atom. At the same time, the substituent on the coupler side is released as an anion. This series of electron transfer mechanisms results in the formation of a dye and the elimination of a substituent. As an atom having such a function, as a proton dissociable atom, an oxygen atom,
Examples include a sulfur atom, a selenium atom, and a nitrogen atom or carbon atom substituted by an electron-withdrawing group or an electron-rich aromatic group (for example, an aryl group or a heteroaromatic ring group). In addition, examples of atoms that can be cations include a nitrogen atom and a sulfur atom.

D ₁₀₁ is a substituent containing an atom that can trigger electron transfer as described above, and this atom can be substituted with various substituents. Examples of the substituent to be substituted on the atom include an alkyl group (for example, a methyl group, an ethyl group, an isopropyl group, an n-butyl group, a t-butyl group),
Aryl group (eg, phenyl group, tolyl group, xylyl group), carbonamido group (eg, acetylamino group, propionylamino group, butyroylamino group, benzoylamino group), sulfonamide group (eg, methanesulfonylamino group, ethanesulfonylamino) Group, benzenesulfonylamino group, toluenesulfonylamino group), alkoxy group (eg, methoxy group, ethoxy group), aryloxy group (eg, phenoxy group), alkylthio group (eg, methylthio group, ethylthio group, butylthio group), arylthio group (For example, phenylthio group, tolylthio group), carbamoyl group (for example, methylcarbamoyl group,
Dimethylcarbamoyl group, ethylcarbamoyl group, diethylcarbamoyl group, dibutylcarbamoyl group, piperidinocarbamoyl group, morpholinocarbamoyl group, phenylcarbamoyl group, methylphenylcarbamoyl group,
Ethylphenylcarbamoyl group, benzylphenylcarbamoyl group), sulfamoyl group (for example, methylsulfamoyl group, dimethylsulfamoyl group, ethylsulfamoyl group, diethylsulfamoyl group, dibutylsulfamoyl group, piperidinosulfamoyl) Group, morpholinosulfamoyl group, phenylsulfamoyl group, methylphenylsulfamoyl group, ethylphenylsulfamoyl group, benzylphenylsulfamoyl group), cyano group, sulfonyl group (for example, methanesulfonyl group, ethanesulfonyl group) Group, phenylsulfonyl group, 4-chlorophenylsulfonyl group, p-toluenesulfonyl group), alkoxycarbonyl group (for example, methoxycarbonyl group,
Ethoxycarbonyl group, butoxycarbonyl group), aryloxycarbonyl group (for example, phenoxycarbonyl group), acyl group (for example, acetyl group, propionyl group,
Butyroyl group, benzoyl group, alkylbenzoyl group), or acyloxy group (for example, acetyloxy group,
A propionyloxy group, a butyroyloxy group), a ureido group, a urethane group, a heterocyclic group (eg, a pyridyl group, a furyl group, a quinolyl group). The D _101, an aralkyl group (especially benzyl), an anilino group, a heterocyclic group, or a methylene group or a methine group substituted with an electron withdrawing group is particularly preferable. These groups may be substituted, and in this case, examples of the substituent include a hydroxy group and the substituents described for R _{501 to} R ₅₀₄ . At least two types of atoms or substituents selected from Y _k1 , Z _k1 and D ₁₀₁ may be bonded to each other to form a ring.

In the general formula (b), X ₂₀₁ represents —CO
-, - SO -, - SO 2 -, and represents a -P (= O) <2 divalent or more linking group selected from. Z represents a nucleophilic group, after the compound represented by the general formula (b) has the oxidant coupler and coupling occurs after the reduction of the silver halide, the nucleophilic groups X _{20 1} Represents a group having a function of forming a dye by nucleophilic attack on a carbon atom, a sulfur atom or a phosphorus atom. In the nucleophilic group, nucleophilicity is expressed by an atom having an unshared electron pair (for example, a nitrogen atom, a phosphorus atom, an oxygen atom, a sulfur atom, a selenium atom), as is common in the field of organic chemistry. Etc.) and anionic species (eg, nitrogen anion, oxygen anion, carbon anion, sulfur anion). Examples of the nucleophilic group include groups having a partial structure or a dissociated form thereof as shown in the following specific examples.

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Y represents a divalent linking group. The term "linking group" refers to a group that links Z to a position at which X ₂₀₁ can be conveniently subjected to intramolecular nucleophilic attack via Y. In practice, it is preferable that the atoms are connected so that the transition state when the nucleophilic group attacks X ₂₀₁ by nucleophilicity can form a 5- to 6-membered ring by the number of atoms. Preferred as Y is, for example, 1,
2- or 1,3-alkylene group, 1,2-cycloalkylene group, Z-vinylene group, 1,2-arylene group, 1,
8-naphthylene group and the like.

R ₅₀₁ and R ₅₀₂ may be bonded to each other to form a ring. The R ₅₀₃ and R _{50 4,} may be bonded to each other to form a ring. 5 to 5
A 6-membered carbocyclic or heterocyclic ring is preferred.

In the present invention, the above-mentioned general formula (a)
The compound represented by (b) is preferably an oil-soluble compound. In other words, the compounds represented by the general formulas (a) and (b) preferably include at least one group having ballast property. Here, the ballast group represents an oil-solubilizing group and is a group containing an oil-soluble partial structure having 8 to 80 carbon atoms, preferably 10 to 40 carbon atoms. Therefore, R _{501 to} R ₅₀₄ , a ballast group having 8 or more carbon atoms is substituted for Y _k1 , Z _k1 and D _{101 in} the general formula (a), or X ₂₀₁ Y or Z in the general formula (b). Is preferred.

As a method for adding the developing agents represented by the general formulas (a) and (b) to a silver halide photographic light-sensitive material, first, a coupler, a developing agent and a high-boiling organic solvent (for example, an alkyl phosphate ester) , Phthalic acid alkyl ester, etc.) to mix with a low boiling organic solvent (eg, ethyl acetate,
Dissolved in water using a known emulsification dispersion method in the art, and then added. Further, addition by the solid dispersion method described in JP-A-63-271339 is also possible.

The amount of the developing agent represented by the above general formulas (a) and (b) has a wide range, but is preferably 0.01 to 100 times, preferably 0.1 to 10 times, based on the coupler. Double is more preferred. The color developing agent is used alone or in combination of a plurality thereof, and the total amount thereof is generally 0.05 to 20 mmol / m ² , preferably 0.1 to 20 mmol / m ² .
10 mmol / m ² are suitable.

The specific examples of the compounds represented by formulas (a) and (b) (developing agents D-1 to D-115) are shown below, but the present invention is not limited by these specific examples. Not something.

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As the light-sensitive material, a coupler which forms a dye by a coupling reaction with an oxidized form of the color developing agent is used. Preferred examples thereof include active methylene, 5-pyrazolone, pyrazoloazole, phenol, naphthol,
A compound generically referred to as pyrrolotriazole is included.
A specific example is Research Disclosure No. 38
No. 957 (September 1996), pages 616 to 624 can be preferably used. Particularly preferred examples include pyrazoloazole couplers described in JP-A-8-110608 and JP-A-8-110608.
And pyrrolotriazole couplers described in Japanese Patent Application No. 8-45564. These couplers are generally 0.05 to 10 mm for each color
ol / m ² , preferably 0.1 to 5 mmol / m ² . Use of colored couplers for correcting unnecessary absorption of coloring dyes, residues of photographically useful compounds that react with oxidized developing agents, such as compounds (including couplers) that release development inhibitors, etc. Can be.

The light-sensitive material is usually composed of three or more kinds of light-sensitive layers having different color sensitivity. Each photosensitive layer has at least one
Including a silver halide emulsion layer, a typical example comprises a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. The photosensitive layer is blue light,
A unit photosensitive layer having color sensitivity to either green light or red light. In a multilayer silver halide color photographic light-sensitive material, the arrangement of the unit photosensitive layers is generally arranged in order from the support side to red color sensitivity. Layer, a green color sensitive layer, and a blue color sensitive layer in this order. However, even if the above installation order is reversed according to the purpose,
Further, the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers. The total thickness of the photosensitive layer is generally 1 to 20 .mu.m, preferably 3 to 15 .mu.m.

The silver halide, the color developing agent and the coupler may be contained in the same photosensitive layer or in different layers. Further, in addition to the photosensitive layer, a protective layer, an undercoat layer, an intermediate layer, and a non-photosensitive layer such as the above-described yellow filter layer and antihalation layer may be provided, and a back layer may be provided on the back side of the support. . The thickness of the entire coating film on the photosensitive layer side is generally 3 to 25.
μm, preferably 5 to 20 μm. In photosensitive materials,
For various purposes, hardeners, surfactants, photographic stabilizers, antistatic agents, slip agents, matting agents, latex, formalin scavengers, dyes, UV absorbers and the like can be used. Specific examples of these are described in the above-mentioned Research Disclosure and JP-A-9-202031. Examples of particularly preferred antistatic agents are ZnO, TiO ₂ ,
SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO, MoO ₃ , V ₂ O ₅
And the like.

As a support for the photographic material, a photographic support described in "Basics of Photographic Engineering-Silver salt photography", edited by The Photographic Society of Japan, Corona Co., Ltd. (1979), pages 223 to 240, is preferred. Specific examples include polyethylene terephthalate, polyethylene naphthalate, polycarbonate, syndiotactic polystyrene, and celluloses (for example, triacetyl cellulose). These supports can be subjected to heat treatment (crystallinity and orientation control), uniaxial and biaxial stretching (orientation control), blending of various polymers, surface treatment, etc. to improve optical and physical properties. it can. Further, as a support, for example,
No. 124645, No. 5-40321, No. 6-3509
It is preferable to record photographic information and the like using a support having a magnetic recording layer described in JP-A Nos. 2 and 6-31875. It is also preferable to coat a water-resistant polymer as described in JP-A-8-292514 on the back surface of the support of the photosensitive material. The polyester support particularly preferably used for the light-sensitive material having the magnetic recording layer is described in detail in Published Technical Report 94-6023 (Invention Association; 1994. 3.15). The thickness of the support is generally 5 to
It is 200 μm, preferably 40 to 120 μm.

In the present invention, a processing member different from the photosensitive material is used for developing the photographed photosensitive material. The treatment member preferably contains at least a base and / or a base precursor. The most preferred is EP21
No. 0,660 and U.S. Pat. No. 4,740,445, which are capable of forming a complex with a poorly water-soluble basic metal compound and a metal ion constituting the basic metal compound using water as a medium. In this method, a base is generated by a combination of compounds. In this case, it is preferred that the basic compound which is hardly soluble in water is added to the photosensitive material and the complex forming compound is added to the processing member, but the reverse is also possible. A preferred combination of the compounds is a system in which zinc hydroxide fine particles are used as a photosensitive material and a picolinic acid salt such as guanidine picolinate is used as a processing member. A mordant may be used for the processing member, and in this case, a polymer mordant is preferable. The processing member contains a physical development nucleus such as colloidal silver or palladium sulfide and a silver halide solvent such as hydantoin as described in JP-A-9-146246, and simultaneously develops the photosensitive material. May be solubilized and fixed to the processing member. Processing members also include a development stopper,
A printout inhibitor may be included. The processing member may have a protective layer, an undercoat layer, a back layer, and other auxiliary layers in addition to the processing layer. The processing member is preferably provided with a processing layer on a continuous web, and after being supplied from a delivery roll and used for processing, it is preferably wound up on another roll without being cut. An example is described in JP-A-9-127670. The support for the processing member is not limited, and a plastic film or paper as described for the photosensitive material is used. The thickness is from 4 μm to 120 μm, preferably from 6 to 70 μm. A film on which aluminum is deposited, as described in JP-A-9-222690, can also be preferably used.

In the present invention, as a method of developing a photosensitive material photographed by a camera or the like, the amount of 0.1% of the amount required for maximizing the swelling of all the coating films except for the back layer of both the photosensitive material and the processing member.
In the presence of water equivalent to 1 to 1 times, the photosensitive material and the processing member are overlapped so that the photosensitive layer and the processing layer face each other.
Heat for 5 to 60 seconds at a temperature of 100C to 100C. As a method for applying water, there is a method of immersing the photosensitive material or the processing member in water and removing excess water with a squeeze roller. Also, as described in JP-A-10-26817, a plurality of nozzle holes for injecting water are linearly arranged at regular intervals along a direction intersecting with the conveying direction of the photosensitive material or the processing member. A method of spraying water by a water application device having a nozzle and an actuator for displacing the nozzle toward a photosensitive material or a processing member on a transport path is also preferable. A method of applying water with a sponge or the like is also preferable. As a heating method in the development step, a heated block or plate may be brought into contact, or a heat roller, a heat drum, an infrared or far-infrared lamp, or the like may be used. In the present invention, another bleach-fixing step for further removing silver halide and developed silver remaining in the light-sensitive material after development is not essential. However, a fixing step and / or a bleaching step may be provided in order to reduce the load of reading image information and to enhance image storability. In that case, ordinary liquid treatment may be used.
It is preferable to perform a heat treatment together with another sheet coated with a treatment agent as described in JP-A-8402.

In the present invention, after obtaining an image on a photosensitive material, it is preferable to obtain a color image on another recording material based on the image information. As a method, a photosensitive material such as color paper may be used, and normal projection exposure may be used. It is preferable to output to another recording material.
The material to be output may be a sublimation type thermosensitive recording material, a full color direct thermosensitive recording material, an ink jet material, an electrophotographic material, or the like, in addition to a photosensitive material using silver halide.

[0105]

EXAMPLES Hereinafter, the effects of the present invention will be described in detail with reference to examples. Example 1 <Preparation of Support> A support used in the present invention was prepared by the following method. 100% by weight of polyethylene-2,6-naphthalate (PEN) polymer and Tinuvin P. After drying 2 parts by weight of 326 (manufactured by Ciba-Geigy Co.), it was melted at 300 ° C., extruded from a T-die, and stretched longitudinally 3.3 times at 140 ° C.
The film was transversely stretched 3.3 times at 30 degrees and heat-set at 250 degrees for 6 seconds to obtain a PEN film having a thickness of 92 μm. The PEN film has a blue dye, a magenta dye,
Yellow dye (public technical report: I-1, I-4, I-6, I-24, I-26, I-26 described in Kogi No. 94-6023)
-27, II-5) were added so that the yellow density was 0.01, the magenta density was 0.08, and the cyan density was 0.09.
Furthermore, wrap it around a stainless steel core with a diameter of 20 cm,
A heat history of 113 ° C. for 30 hours was given to make the support hard to curl. <Coating of Undercoat Layer> The support was subjected to a corona discharge treatment, a UV irradiation treatment, and a glow discharge treatment on both surfaces thereof, and then gelatin (0.1 g / m ² ) and sodium α-sulfodiamine were applied to each surface. 2-ethylhexyl succinate (0.01 g / m ² ), salicylic acid (0.025 g /
^{m 2), PQ-1 (} 0.005g / m 2), PQ-2 (0.
006 g / m ² ) (10 cc / m ² )
m ² , using a bar coater), and an undercoat layer was provided on the high temperature side during stretching. Drying was performed at 115 degrees for 6 minutes (all rollers and conveying devices in the drying zone were at 115 degrees).

<Coating of Back Layer> 1) Coating of Antistatic Layer Dispersion of fine powder of tin oxide-antimony oxide composite having an average particle diameter of 0.005 μm and a specific resistance of 5 Ω · cm (secondary aggregate particle diameter about 0.08μ; 0.027g / m ^2), gelatin (0.03g / m ^2),
(CH ₂ = CHSO ₂ CH ₂ CH ₂ NHCO) ₂ CH ₂ (0.02 g / m ² ), poly (degree of polymerization
10) Oxyethylene-p-nonylphenol (0.005 g /
m ² ), PQ-3 (0.008 g / m ² ) and resorcin. 2) Coating of magnetic recording layer 3-Cobalt-γ-iron oxide coated with poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (15% by weight) (specific surface area 43 m ² / g, major axis 0.14μ, short axis 0.03μ, saturation magnetization 89 emu / g, Fe ^{+ 2} / Fe ⁺³ = 6/94, the surface is treated with silicon oxide aluminum oxide with 2% by weight of iron oxide) 0.06 g / m ² To diacetyl cellulose 1.15 g / m ² (dispersion of iron oxide was carried out with an open kneader and a sand mill), PQ-4 (0.075 g / m ² ) as a curing agent, PQ-5
(0.004 g / m ² ) was applied with a bar coater using acetone, methyl ethyl ketone, cyclohexanone, and dibutyl phthalate as solvents to obtain a 1.2 μm-thick magnetic recording layer. As a slipping agent _{C 6 H 13 CH (OH)} C 10 H 2 0 COOC 40 H 81 (50g /
m ² ), silica particles (average particle size 1.0μ) as a matting agent and aluminum oxide (Reynolds Metal Reynolds Meta) as an abrasive
lmg ERC-DBM; average particle size 0.44μm)
/ M ² and 15 mg / m ² . 115 dry
For 6 minutes (115 ° C. for all rollers and conveyors in the drying zone). X- write saturation magnetization moment 4.2 emu / g to about 0.1, and the magnetic recording layer color density increment of D ^B of the magnetic recording layer in the (blue filter), the coercive force 7.3 × 10
⁴ A / m and the squareness ratio were 65%. 3) Adjustment of sliding layer Hydroxyethyl cellulose (25 mg / m ² ), PQ-6 (7.
5mg / m ^2), was applied to ^{PQ-7 (1.5mg / m 2} ) polydimethylsiloxane 1.5 mg / m ^2. This mixture was prepared in xylene / propylene glycol monomethyl ether (1/1).
Melted at 105 ° C and propylene monomethyl ether at room temperature
(10 times the volume), and the mixture was dispersed in acetone (average particle size: 0.01 μm) and then added. 11 for drying
The test was performed at 5 ° C. for 6 minutes (115 ° C. for all rollers and transport devices in the drying zone). The sliding layer has excellent dynamic friction coefficient of 0.10 (stainless steel hard ball of 5mmφ, load of 100g, speed of 6cm / min), static friction coefficient of 0.09 (clip method), and the above-mentioned dynamic friction coefficient of 0.18 between the emulsion surface and the sliding layer. Was.

[0107]

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<Method for Preparing Photosensitive Silver Halide Emulsion> The method for preparing the blue photosensitive silver halide emulsion (1) is described below. 1191 ml of distilled water containing 0.96 g of gelatin having an average molecular weight of 12000 and 0.9 g of potassium bromide was placed in a reaction vessel, and the temperature was raised to 40 ° C. An aqueous solution (A) containing 0.5 g of sodium silver nitrate while vigorously stirring this solution
10.5 ml and 10 ml of an aqueous solution (B) containing 0.35 g of potassium bromide were added over 150 seconds. After addition 3
After 0 second, 12 ml of a 10% aqueous solution of potassium bromide was added, and after 30 seconds, the temperature of the reaction solution was raised to 75 ° C. After adding 35.0 g of lime-processed gelatin together with 250 ml of distilled water, an aqueous solution (C) 3 containing 10.0 g of silver nitrate was added.
Aqueous solution (D) 30 containing 9 ml and 6.7 g of potassium bromide
ml was added over a period of 3 minutes and 15 seconds while accelerating the addition flow rate. Next, 302 ml of an aqueous solution (E) containing 96.7 g of silver nitrate and an aqueous solution (F) (potassium bromide concentration: 26%) containing potassium iodide at a molar ratio of 7:93 to potassium bromide were added while increasing the flow rate. The reaction solution was added for 20 minutes so that the silver potential of the reaction solution became -20 mV with respect to the saturated calomel electrode. Further, 97 ml of an aqueous solution (G) containing 24.1 g of silver nitrate and a 21.9% aqueous solution of potassium bromide (H) were added over 3 minutes so that the silver potential of the reaction solution became 25 mV with respect to the saturated calomel electrode. . After maintaining the temperature at 75 ° C. for 1 minute after the completion of the addition, the temperature of the reaction solution was set to 55
The temperature was lowered to ° C. Then, 1N sodium hydroxide 1
5 ml was added. Two minutes later, 100 ml of an aqueous solution (I) containing 5 g of silver nitrate and 200.5 ml of an aqueous solution (J) containing 4.7 g of potassium iodide were added over 5 minutes. After the addition was completed, 7.11 g of potassium bromide was added, and the mixture was added at 55 ° C.
, And 248 ml of an aqueous solution (K) containing 62 g of silver nitrate and 231 ml of an aqueous solution (L) containing 48.1 g of potassium bromide were further added over 8 minutes. 30 seconds later, 0.03 g of sodium ethylthiosulfonate
Was added. The temperature was lowered, and the emulsion particles were coagulated and settled using Kao's Demol to desalinate.
Dispersion was performed by adding sodium benzenethiosulfonate, phenoxyethanol, a water-soluble polymer (10), and lime-processed gelatin. Chemical sensitization was performed at 60 ° C.
After adding the sensitizing dye (12) as a gelatin dispersion before chemical sensitization, a mixed solution of potassium thiocyanate and chloroauric acid was added, and then sodium thiosulfate and a selenium sensitizer were added. The termination of sensitization was performed with a mercapto compound. The amounts of the sensitizing dye, the chemical sensitizer, and the mercapto compound were optimized by sensitivity and fog. In the obtained grains, tabular grains account for more than 99% of the total projected area of all grains,
The average equivalent sphere diameter was 1.07 μm, the average thickness was 0.38 μm, the equivalent circular diameter was 1.47 μm, and the aspect ratio was 3.9.

[0109]

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[0110]

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The method for preparing the blue-sensitive silver halide emulsion (2) is described below. Gelatin having an average molecular weight of 12,000
Distilled water 119 containing 96 g and 0.9 g of potassium bromide
1 ml was placed in a reaction vessel and heated to 40 ° C. To this solution, 37.5 ml of an aqueous solution (A) containing 1.5 g of silver nitrate and 37.5 ml of an aqueous solution (B) containing 1.051 g of potassium bromide were added over 90 seconds with vigorous stirring. Thirty seconds after the completion of the addition, 12 m
After 30 seconds, the temperature of the reaction solution was raised to 75 ° C. 35.0 g of lime-processed gelatin is added to 250 parts of distilled water.
Then, 116 ml of an aqueous solution (C) containing 29.0 g of silver nitrate and 91 ml of an aqueous solution (D) containing 20 g of potassium bromide were added for 11 minutes 35 while increasing the addition flow rate.
Added over seconds. Next, while adding 302 ml of an aqueous solution (E) containing 96.7 g of silver nitrate and an aqueous solution (F) (potassium bromide concentration: 26%) containing potassium iodide at a molar ratio of 3.3: 96.7 to potassium bromide, the addition flow rate was accelerated. And the silver potential of the reaction solution was adjusted to 2 mV with respect to the saturated calomel electrode for 20 minutes. 24.1g of silver nitrate
97 g of an aqueous solution (G) containing potassium bromide and 21.9 of potassium bromide
% Aqueous solution (H) was added over 3 minutes so that the silver potential of the reaction solution became 0 mV with respect to the saturated calomel electrode. After maintaining the temperature at 75 ° C. for 1 minute after the completion of the addition, the temperature of the reaction solution was lowered to 55 ° C. Then, 15 ml of 1N sodium hydroxide was added. Two minutes later, silver nitrate 1
153 ml of an aqueous solution (I) containing 0.4 g and 414.5 ml of an aqueous solution (J) containing 9.35 g of potassium iodide were added over 5 minutes. After completion of addition, potassium bromide 7.1
1 g, and kept at 55 ° C. for 1 minute.
228 ml of an aqueous solution (K) containing 7.1 g and 201 ml of an aqueous solution (L) containing 43.9 g of potassium bromide were added over 8 minutes. Thirty seconds later, an aqueous solution containing 0.04 g of sodium ethylthiosulfonate was added. The temperature was lowered, and desalting and dispersion were carried out in the same manner as in the blue-sensitive silver halide emulsion (1). Chemical sensitization was carried out except that blue-sensitive silver halide emulsion (1) and selenium sensitization were not added.
Performed similarly. The sensitizing dye and the mercapto compound whose chemical sensitization was stopped were substantially proportional to the surface area of the emulsion grains. In the obtained grains, tabular grains account for more than 99% of the total projected area of all grains, have an average equivalent sphere diameter of 0.66 μm, and have an average thickness.
The equivalent circular diameter was 0.15 μm and the aspect ratio was 6.3.

The method for preparing the blue-sensitive silver halide emulsion (3) is described below. 1345 ml of distilled water containing 17.8 g of lime-processed gelatin, 6.2 g of potassium bromide and 0.46 g of potassium iodide was placed in a reaction vessel, and the temperature was raised to 45 ° C. To this solution, 70 ml (A) of an aqueous solution containing 11.8 g of silver nitrate and 70 ml (B) of an aqueous solution containing 3.8 g of potassium bromide were added over 45 seconds with vigorous stirring. After maintaining at 45 ° C. for 4 minutes, the temperature of the reaction solution was raised to 63 ° C. After adding 24 g of lime-processed gelatin together with 185 ml of distilled water, 208 ml of an aqueous solution containing 73 g of silver nitrate (C)
And a 24.8% aqueous solution of potassium bromide (D) were added over a period of 13 minutes while accelerating the addition flow rate so that the silver potential of the reaction solution became 0 mV with respect to the saturated calomel electrode. After maintaining at 63 ° C. for 2 minutes after completion of the addition, the temperature of the reaction solution was lowered to 45 ° C. Then, 15 ml of 1N sodium hydroxide was added. Two minutes later, silver nitrate 8.
60 ml of an aqueous solution containing 4 g (E) and 8.3 potassium iodide
g of an aqueous solution containing 461 ml (F) was added over 5 minutes. Further, an aqueous solution 49 containing 148.8 g of silver nitrate 49
6 ml (G) and a 25% aqueous solution of potassium bromide (H) were added over 47 minutes so that the silver potential of the reaction solution became 90 mV with respect to the saturated calomel electrode. End of addition 30
After 2 seconds, an aqueous solution containing 2 g of potassium bromide and 0.06 g of sodium ethylthiosulfonate was added. Lower the temperature,
Desalting, dispersion, and chemical sensitization were performed in the same manner as in the blue-sensitive silver halide emulsion (2). The resulting emulsion had an average grain size of 0.44 μm and an average thickness of 0.2 expressed as a sphere-equivalent diameter.
It was a hexagonal tabular grain having a μm equivalent circular diameter of 0.53 μm and an average grain aspect ratio of 2.6.

The method for preparing the green photosensitive silver halide emulsion (4) is described below. Gelatin having an average molecular weight of 12,000
Distilled water 119 containing 96 g and 0.9 g of potassium bromide
1 ml was placed in a reaction vessel and heated to 40 ° C. To this solution, 17.5 ml of an aqueous solution (A) containing 0.7 g of silver nitrate and 17.5 ml of an aqueous solution (B) containing 1.051 g of potassium bromide were added over 120 seconds with vigorous stirring. Thirty seconds after the completion of the addition, 12 m
After 30 seconds, the temperature of the reaction solution was raised to 75 ° C. 35.0 g of lime-processed gelatin is added to 250 parts of distilled water.
Then, 56 ml of an aqueous solution (C) containing 19.0 g of silver nitrate and 461 ml of an aqueous solution (D) containing 10 g of potassium bromide were added for 7 minutes 35 while increasing the addition flow rate.
Added over seconds. Next, while adding 302 ml of an aqueous solution (E) containing 96.7 g of silver nitrate and an aqueous solution (F) (potassium bromide concentration: 26%) containing potassium iodide at a molar ratio of 3.3: 96.7 to potassium bromide, the addition flow rate was accelerated. The reaction solution was added for 20 minutes so that the silver potential of the reaction solution became 0 mV with respect to the saturated calomel electrode. 24.1g of silver nitrate
97 g of an aqueous solution (G) containing potassium bromide and 21.9 of potassium bromide
% Aqueous solution (H) was added over 3 minutes so that the silver potential of the reaction solution became 0 mV with respect to the saturated calomel electrode. After maintaining the temperature at 75 ° C. for 1 minute after the completion of the addition, the temperature of the reaction solution was lowered to 55 ° C. Then, 122 ml of an aqueous solution (I) containing 8.3 g of silver nitrate and 7.48 g of potassium iodide
And an aqueous solution (J) containing 332 ml were added over 5 minutes. After the addition was completed, 7.11 g of potassium bromide was added, and 5
After keeping at 5 ° C. for 1 minute, 228 ml of an aqueous solution (K) containing 62.8 g of silver nitrate and 201 ml of an aqueous solution (L) containing 48.3 g of potassium bromide were added over 8 minutes. The temperature was lowered, and desalting and dispersion were carried out in the same manner as in the blue-sensitive silver halide emulsion (1). Chemical sensitization was carried out except that a gelatin dispersion of a mixture of sensitizing dyes (13), (14) and (15) was added instead of sensitizing dye (12). Was performed in the same manner as described above. In the obtained grains, tabular grains account for more than 99% of the total projected area of all grains, have an average equivalent sphere diameter of 0.85 μm, and have an average thickness.
The equivalent circular diameter was 0.26 μm and the aspect ratio was 4.8.

[0114]

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The method for preparing the green photosensitive silver halide emulsion (5) is described below. Desalting and dispersion are performed in the same manner as for the blue-sensitive silver halide emulsion except that sodium hydroxide and sodium ethylthiosulfonate are not added during grain formation, and the chemical sensitization is performed using the green-sensitive silver halide emulsion. Same as (4). In the obtained grains, tabular grains account for more than 99% of the total projected area of all grains, have an average equivalent sphere diameter of 0.66 μm, and an average thickness of 0.17 μm.
The thickness was 05 μm and the aspect ratio was 6.3.

The preparation method of the green photosensitive silver halide emulsion (6) is described below. Grain formation, desalting and dispersion were carried out in the same manner as in the blue-sensitive silver halide emulsion (3), except that sodium ethylthiosulfonate was changed to 4 mg without adding sodium hydroxide during grain formation. Chemical sensitization was carried out in the same manner as for the green light-sensitive silver halide emulsion (4), except that no selenium sensitizer was added.
The resulting emulsion has an average grain size of 0, expressed as a sphere equivalent diameter.
Hexagonal tabular grains having a diameter of 44 μm, an average thickness of 0.2 μm, an equivalent circular diameter of 0.53 μm, and an average grain aspect ratio of 2.6.

The method for preparing the red-sensitive silver halide emulsion (7) is described below. The sensitizing dye at the time of chemical sensitization is replaced with a sensitizing dye (1
It was prepared in the same manner as the green light-sensitive silver halide emulsion (4), except that the gelatin dispersion of 6) and the gelatin dispersion of a mixture of the sensitizing dyes (17) and (18) were added. The resulting grains had tabular grains of 99% of the total projected area of all grains.
Occupies a ratio exceeding 0.85 μm
The average thickness was 0.26 μm, the equivalent circular diameter was 1.25 μm, and the aspect ratio was 4.8.

[0118]

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The method for preparing the red-sensitive silver halide emulsion (8) is described below. The sensitizing dye during chemical sensitization is replaced with a sensitizing dye (1
It was prepared in the same manner as the green light-sensitive silver halide emulsion (5) except that the gelatin dispersion of 6) and the gelatin dispersion of a mixture of the sensitizing dyes (17) and (18) were added. In the obtained grains, tabular grains account for more than 99% of the total projected area of all grains, have an average equivalent sphere diameter of 0.66 μm, an average thickness of 0.17 μm, an equivalent circular diameter of 1.05 μm, and an aspect ratio of 6.3.
Met.

The method for preparing the red-sensitive silver halide emulsion (9) is described below. The sensitizing dye during chemical sensitization is replaced with a sensitizing dye (1
It was prepared in the same manner as the green light-sensitive silver halide emulsion (6) except that the gelatin dispersion of 6) and the gelatin dispersion of a mixture of the sensitizing dyes (17) and (18) were added. The resulting emulsion has an average particle size of 0.44μ expressed in sphere equivalent diameter.
m, average thickness 0.2 μm, equivalent circular diameter 0.53 μm, and average particle aspect ratio 2.6.

<Preparation method of zinc hydroxide dispersion> 31 g of zinc hydroxide powder having a primary particle size of 0.2 μm,
1.6 g of carboxymethylcellulose, 0.4 g of sodium polyacrylate, 8.5 g of lime-treated ossein gelatin, and 158.5 ml of water were mixed as a dispersant, and the mixture was dispersed for 1 hour by a mill using glass beads. After the dispersion, the glass beads were filtered off, and a dispersion 188 of zinc hydroxide was obtained.
g was obtained.

<Method for Preparing Emulsified Dispersion of Color Developing Agent and Coupler> The oil phase component and the aqueous phase component having the compositions shown in Table 1 are each dissolved to form a uniform solution at 60 ° C. Combine the oil phase component and the water phase component in a 1 liter stainless steel container,
The mixture was dispersed at 10,000 rpm for 20 minutes by a dissolver equipped with a 5 cm diameter disperser. To this, warm water in the amount shown in Table 2 was added as post-water and mixed at 2000 rpm for 10 minutes. Thus, an emulsified dispersion of couplers of three colors of cyan, magenta and yellow was prepared.

[0123]

[Table 2]

[0124]

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<Preparation of Dye Composition for Yellow Filter, Magenta Filter, and Antihalation Layer> The decolorizable dye composition was prepared and added as an emulsified dispersion as follows. 7.1 g of a yellow dye (A-100) was added to chlorinated paraffin (1) (trade name: Empara K-6, manufactured by Ajinomoto Co., Inc.).
5) 7.8% gelatin aqueous solution 1 dissolved in 6.6 g, 30 cc of ethyl acetate and 30 cc of cyclohexanone and containing 0.75 g of sodium dodecylbenzenesulfonate
35 g and 100 g using a dissolver stirrer.
The mixture was stirred at 00 rpm for 20 minutes, and emulsified and dispersed. After the dispersion, distilled water was added so that the total amount became 260 g, and the mixture was mixed at 2,000 rpm for 10 minutes to prepare a dye dispersion for a yellow filter layer. Similarly, the dye was magenta dye (A-4) 6.
The amount was changed to 1 g to prepare a dye dispersion for a magenta filter layer, and the dye was changed to 8.9 g for a cyan dye (A-74) to prepare a dye dispersion for an antihalation layer.

Using the above bases and materials, a photosensitive material 101 having a multilayer structure shown in Table 3 was produced.

[0127]

[Table 3]

[0128]

[Table 4]

[0129]

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Further, the first processing member R-
1 and a second processing member R-2 having the contents shown in Table 6.

[0131]

[Table 5]

[0132]

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[0133]

[Table 6]

[0134]

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Examples 2 to 9 and Comparative Examples 1 and 2 Further, the decolorizable dye and the high boiling point solvent of the yellow filter, the magenta filter, and the dye composition for the antihalation layer were changed as shown in Table 7, and The photosensitive materials 102 to 109 of Examples 2 to 9 and Comparative Examples 1 and 2 and H-1 and H-2 were prepared.

[0136]

[Table 7]

Comparative Example 3 To 4 g of the following yellow, magenta and cyan dyes, 4 g of a 25% aqueous solution of surfactant (30) and 92 ml of water were added, and the mixture was dispersed with glass beads having an average particle size of 0.75 mm for 24 hours using a Dynomill. did. The glass beads were separated to obtain a solid dispersion dye of each dye. A light-sensitive material H-3 was prepared using the above solid disperse dye in place of the yellow filter, magenta filter, and dye composition for an antihalation layer of Example 1.

[0138]

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The light-sensitive material 101 prepared without exposure
After applying 15 cc / m ² (equivalent to 45% of the maximum swelling) of water at 40 ° C. to H-1 to H-3, the photosensitive member was backed up with a heat drum at 83 ° C. The surface was heated for 17 seconds. The first processing member R-1 is changed to the photosensitive member 10
1 and water was again applied to the photosensitive member at 40 ° C. at 15 cc / m ^2.
After the application, it was overlapped with the second processing member R-2 and heated at 83 ° C. for 10 seconds. The second processing member R-2 was peeled from the photosensitive member, and the obtained photosensitive material was measured by the transmission density of the status filter A. Table 8 shows the average of the values measured at three points. As is apparent from Table 8, since the density of the Dmin part of the photosensitive material is lower than that of the photosensitive material H-1 (Comparative Example 1) having no dye, the decolorizable dye and the paraffin chloride constituting the present invention are included. Has excellent decolorability during processing and is completely decolored by processing. In addition, as a result of analyzing the processing members after processing,
There was no adduct of the decolorizable dye of the present invention with the decolorant.

Further, the prepared photosensitive material was cut into an APS format, punched, packed in a cartridge, loaded into an APS camera, and photographed a person and a Macbeth chart. This photographed photosensitive material was subjected to the same processing as described above to obtain a negative image on the photosensitive material. This image is read by a digital image reader Frontier SP-1000 (manufactured by Fuji Photo Film), processed on a workstation, and then subjected to a heat development printer (PICTROGRAPHY4000, manufactured by Fuji Photo Film).
And output the print image. Table 8 shows the case where the output print image was clear and excellent in color reproducibility, and the case where the clearness and color reproducibility were inferior or caused halation or the like. Further, after the photosensitive material of the present invention was left for 3 days in an environment of 45 ° C. and 80% humidity, the same treatment and evaluation were carried out.

[0141]

[Table 8]

The following can be seen from the results in the table. In Comparative Example H-1, the fresh and stored print images were not particularly sharp at the edges of the images. Comparative Example H
In the case of -2, the printed image after storage caused halation or the like and became unclear. Comparative Example H-3 was inferior in decoloration property,
Unnecessary density components during reading remained. However, the light-sensitive materials 101 to 109 of the present invention did not have an unnecessary residual density and provided clear images.

[0143]

According to the photothermographic material of the present invention in which a decolorizable dye is dispersed using chlorinated paraffin and the decolorizable dye is contained in a hydrophilic organic colloid layer, color separation and sharpness after storage can be improved. It is possible to provide a photothermographic material which is excellent, has excellent decoloring properties, and has a small amount of unnecessary density components at the time of reading.

Claims (2)

[Claims] 1. The method according to claim 1, wherein at least a photosensitive halogen is provided on the support.
Silver halide particles, color developing agents (or their precursors), couplers
After imagewise exposing a photosensitive material having a binder and a binder,
In the presence of a large amount of water, the photosensitive material and the processing member are stacked and heated.
To form an image on photosensitive material
In the photothermographic material to be used, the photothermographic material is
Diffusion resistant dye that decolorizes by reaction with decolorant during heat treatment
Wherein at least one of the diffusion-resistant dyes is
Represented by any one of the general formulas (I) to (IV), and
At least one of the diffusible dyes has a boiling point of 175 ° C at normal pressure.
In the binder with the above chlorinated paraffin
A photothermographic material characterized by being dispersed in General formula (I) A₅₁= L₅₁− (L₅₂= L₅₃)_m51−Q₅₁ General formula (II) A₅₁= L₅₁− (L₅₂= L₅₃)_n51-A₅₂ General formula (III) A₅₁(= L₅₁-L₅₂)_p51= B₅₁ General formula (IV) (NC)_TwoC = C (CN) -Q₅₁ (Wherein, = represents a double bond and-represents a single bond.₅₁, A
₅₂Each represents an acidic nucleus;₅₁Represents a basic nucleus. Q
₅₁Represents an aryl group or a heterocyclic group. L₅₁, L ₅₂, L
₅₃Represents a methine group which may be independently substituted.
You. m₅₁Represents 0, 1, or 2. n₅₁, P₅₁Is it
Represents 0, 1, 2, or 3, respectively. L₅₁, L₅₂Or L
₅₃Are present in the molecule,
It may be the same or different. However, the general formula (I)
The compounds represented by the formulas (IV) to (IV) have a carboxyl group and / or
Or a sulfo group and has no general formula (I)
The compound represented by (IV) has a diffusion-resistant group.
The product after the development process (decolorization) is also diffusion resistant,
It does not substantially elute from the material. More general formula
The compounds represented by (I) to (IV) are referred to as “acids during development processing”.
Redox reaction, followed by bond cleavage.
And has no group that splits into multiple molecules. ) 2. The photothermographic material according to claim 1, wherein the diffusion-resistant dye is a yellow or magenta dye represented by the following general formula (V). Embedded image (Wherein A ₆₁ represents an acidic nucleus, L ₆₁ , L ₆₂ and L ₆₃ each independently represent a methine group which may be substituted,
L ₆₄ and L ₆₅ each independently represent an alkylene group having 1 to 4 carbon atoms. R ₆₂ and R ₆₃ are each independently a cyano group, a —COOR ₆₄ group, a —CONR ₆₅ R ₆₆ group, a —COR ₆₄
A —SO ₂ R ₆₄ group or —SO ₂ NR ₆₅ R ₆₆ group, wherein R ₆₄ represents an alkyl group, an alkenyl group, a cycloalkyl group, or an aryl group, and R ₆₅ and R ₆₆ each independently represent a hydrogen atom , An alkyl group, an alkenyl group, a cycloalkyl group, or an aryl group. R ₆₁ represents a substituent, m
₆₁ represents 0 or 1 and n ₆₁ represents an integer of 0 to 4. Note that R
₆₅ and R ₆₆ may be linked together to form a nitrogen-containing heterocycle. )