JPH08304977A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE: To improve desilverability and to obtain stable photographic characteristics even if a crossover time is shortened by incorporating a specified silver halide solvent and the like in a color developing solution and specifying the crossover time between the color developing solution and a bleach fixing solution. CONSTITUTION: The color developing solution contains a thiosulfate or methanethiosulfonate or thiocyanate and the silver halide solvent represented by formula I or II or III, and the crossover time between the color developing solution and the bleach fixing solution is regulated to <=10sec. In formulae I-III, Qa1 is a nonmetallic atomic group necessary to form a 5- or 6-membered hetero ring; La1 is a simple bond or a divalent aliphatic group; Ra1 is a carboxylic acid or its salt: Qb1 is a mesoionic ring comprising C and Se atoms and the like; Xb1 is a -O<-> or -S<-> anion or the like; Rb1 is an aliphatic or aromatic hydrocarbon group or the like; each of Xd and Yd is an aliphatic or aromatic hydrocarbon group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and more specifically, in a method of desilvering with a bleach-fixing solution immediately after color development processing, the desilvering property is improved. Stable photographic performance can be obtained even if the crossover time is shortened for improvement and speedup.
In particular, the present invention relates to a method for processing a silver halide color photographic light-sensitive material, which has a small photographic property variation with respect to the incorporation of a bleach-fixing solution into a color developing solution.

[0002]

2. Description of the Related Art Generally, a process for processing a color light-sensitive material comprises a color development process and a desilvering process. In the color developing step, the silver halide exposed by the color developing agent is reduced to produce silver, and the oxidized color developing agent reacts with the color developing agent (coupler) to form a dye image. In the next desilvering step, the silver generated in the color development step is oxidized by an oxidizing agent called a bleaching agent into silver ions, which are then dissolved by a silver ion complexing agent called a fixing agent to remove from the light-sensitive material. To be removed.

The above desilvering process is carried out using a bleaching solution containing a bleaching agent and a fixing solution containing a fixing agent, and a bleaching fixing solution in which a bleaching agent and a fixing agent are allowed to coexist. There is. From the viewpoint of reducing the number of desilvering baths, simplifying the processing steps, and speeding up, it is preferable to use a bleach-fixing solution.
In particular, a silver iodobromide emulsion composed of 1 mol% or more of silver iodide was hardly dissolved and a desilvering failure occurred.

In the method of desilvering with a bleach-fixing solution immediately after color development processing, the desilvering property is improved by processing with a continuous bleach-fixing solution of at least two baths in which a replenisher is replenished in a countercurrent system. The method is disclosed in JP-A-5-49094. However, the method described in the patent is insufficient in rapidity and the replenishment amount is reduced, but the number of baths for desilvering treatment is required to be two or more, and further improvement has been desired.

As means for accelerating the treatment, reduction of the number of treatment baths, reduction of residence time in each treatment bath, reduction of air time (crossover time) between the treatment baths have been studied. To shorten the residence time of the color developing bath, it is effective to increase the temperature of the color developing solution or increase the concentration of the color developing agent. However, if the temperature of the color developing solution is raised, during the crossover time before entering the next desilvering bath,
There is a problem that air fog occurs due to oxygen in the air.
With respect to this problem, Japanese Patent Application Laid-Open No. 2-3038 discloses a method of reducing the crossover time to 10 seconds or less. However, a method of lowering the partition between the liquids and a method of crossing over the photosensitive material below the liquid surface of the tank (Japanese Patent Laid-Open No. 2-3)
(Disclosed in No. 038), etc., the cross-over time is shortened, so that the processing solutions of both are likely to be mixed. In that case, the bleach-fixing solution is more problematic than the bleaching solution because the fluctuation of the photographic properties when mixed in the color developing solution is significantly increased.

At present, it is becoming possible to easily change the installation location due to the miniaturization of processing equipment, but the probability that liquid will mix between adjacent baths during the movement of processing equipment will increase, and an earthquake will also occur. Mixing of the liquid between the baths also occurs due to such a natural disaster as described above or a conveyance trouble of the photosensitive material in the processing equipment. In particular, when the color developing bath and the bleach-fixing bath are adjacent to each other, as described above, the mixing of the bleach-fixing solution into the color developing is very problematic.

[0007]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to improve the desilvering property in a method of desilvering with a bleach-fixing solution immediately after color development for rapid processing.
To provide a method for processing a silver halide color photographic light-sensitive material, which can obtain stable photographic properties even if the crossover time is shortened, and in particular, has little fluctuation in photographic properties when a bleach-fixing solution is mixed with a color developing solution. It is in.

[0008]

The above objects of the present invention have been achieved by the following method. That is, (1) a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer containing a silver halide emulsion having a silver iodide content of 1 to 30 mol% on a transparent support, In the method of desilvering with a bleach-fixing solution immediately after color development processing with a color developing solution, the color developing solution contains thiosulfate, methanethiosulfonate, thiocyanate and the following general formulas (A) to ( E) containing at least one silver halide solvent and having a crossover time of 10 between the color developing solution and the bleach-fixing solution.
A method for processing a silver halide color photographic light-sensitive material, which is characterized by being less than a second. General formula (A)

[0009]

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In the formula, Q _a1 represents a nonmetallic atom group necessary for forming a 5- or 6-membered heterocycle. The heterocycle may be condensed with a carbon aromatic ring or a heteroaromatic ring.
L _a1 represents a single bond, a divalent aliphatic group, a divalent aromatic hydrocarbon group, a divalent heterocyclic group, or a connecting group in which these are combined. R _a1 represents a carboxylic acid or a salt thereof, a sulfonic acid or a salt thereof, a phosphonic acid or a salt thereof, an amino group or an ammonium salt. q represents an integer of 1 to 3, M _a1 represents a hydrogen atom or a cation. General formula (B)

[0011]

[Chemical 6]

In the formula, Q _b1 represents a 5- or 6-membered mesoionic ring composed of a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a selenium atom, and X _b1 ^- is -O ^- ,-.
Represents S ^- or -N ^- R _b1 . R _b1 represents an aliphatic group, an aromatic hydrocarbon group or a heterocyclic group. Formula (C) L _C1- (A _C1 -L _C2 ) _r -A _C2 -L _{C3 In the} formula, L _C1 and L _C3 may be the same or different and each is an aliphatic group, an aromatic hydrocarbon group or a heterocyclic group. Represents a cyclic group, and L _C2 represents a divalent aliphatic group, a divalent aromatic hydrocarbon group, a divalent heterocyclic linking group, or a linking group combining them. A
_C1 and A _C2 are respectively -S-, _-O- , -NR _C20- ,
-CO -, - it represents a or group composed of a combination of them - SO _2. r represents an integer of 1 to 10. However, L _C1 and L
_C3 at least one -SO ₃ M _C1, -PO ₃ M
_{C2 M C3, -NR C1 (R} C2), - N + R C3 (R C4)
^{_{(R C5) · X C1 -}} , -SO 2 NR C6 (R C7), - NR C8
_{SO 2 R C9, -CONR C10 (} R C11), - NR C12 C
_{OR C13, -SO 2 R C14,} -PO (-NR C15 (R
_C16 )) ₂ , -NR _C17 CONR _C18 ( _RC19 ), -C
It is assumed to be substituted with OOM _C4 or a heterocyclic group.
M _C1 , M _C2 , M _C3 and M _C4 may be the same or different and each represents a hydrogen atom or a counter cation. M _C1 ~ M _C20
May be the same or different and each represents a hydrogen atom, an aliphatic group or an aromatic hydrocarbon group, and X _C1 ⁻ represents a counter anion. Provided that at least one of A _C1 and A _C2 represent -S-. General formula (D)

[0013]

[Chemical 7]

In the formula, X _d and Y _d are an aliphatic group, an aromatic hydrocarbon group, a heterocyclic group, -N (R _d1 ) R _d2 , -N (R _d3 ).
N (R _d4) R _d5, represent -OR _d6, or -SR _d7.
Incidentally, X _d and Y _d may form a ring, but they do not undergo enolization. However, at least one of X _d and Y _d is substituted with at least one of a carboxylic acid or a salt thereof, a sulfonic acid or a salt thereof, a phosphonic acid or a salt thereof, an amino group or an ammonium group, and a hydroxyl group. . R _d1 , R _d2 , R _d3 , R _d4 and R _d5 represent a hydrogen atom, an aliphatic group, an aromatic hydrocarbon group or a heterocyclic group, and R _d6 and R _d7 represent a hydrogen atom, a cation, an aliphatic group, an aromatic group. It represents a group hydrocarbon group or a heterocyclic group. General formula (E)

[0015]

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In the above general formula (E), R _e1 , R _e2 ,
R _e3 and R _e4 each represent a hydrogen atom, an alkyl group or an alkenyl group.

In the present specification, the aliphatic group, aromatic hydrocarbon group and heterocyclic group are as follows unless otherwise specified. An aliphatic group is a substituted or unsubstituted,
It represents a linear, branched or cyclic alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted alkynyl group. The divalent aliphatic group is a divalent group of these aliphatic groups, and is a substituted or unsubstituted linear, branched or cyclic alkylene group, a substituted or unsubstituted alkenylene group, a substituted or unsubstituted alkynylene. Represents a group. Examples of the aliphatic group include methyl group, ethyl group, propyl group, butyl group, isopropyl group, 2-hydroxypropyl group, hexyl group, octyl group, vinyl group, propenyl group, butenyl group, benzyl group and phenethyl group. To be The aromatic hydrocarbon group is a substituted or unsubstituted,
It represents an aryl group which may be monocyclic or may be condensed with an aromatic ring or a heterocycle. What is a divalent aromatic hydrocarbon group?
It represents a substituted or unsubstituted arylene group which may be monocyclic or may be condensed with an aromatic ring or a heterocycle. Examples of the aromatic hydrocarbon group include a phenyl group, a 2-chlorophenyl group, a 3-methoxyphenyl group and a naphthyl group. The heterocyclic group means a nitrogen atom as a hetero atom,
3 to 3 having at least one oxygen atom or sulfur atom
It represents a 10-membered, saturated or unsaturated, substituted or unsubstituted, monocyclic ring, which may be further condensed with an aromatic ring or a heterocycle. Examples of the heterocycle include a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a triazole ring, a thiadiazole ring, an oxadiazole ring, a quinoxaline ring, a tetrazole ring, a thiazole ring and an oxazole ring.

Further, each group in the present specification may be substituted unless otherwise specified, and examples of the substituent which they may have include an alkyl group, an aralkyl group, an alkenyl group and an alkynyl group. , Alkoxy group, aryl group, amino group, acylamino group, sulfonamide group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, acyl group, hydroxy group , Halogen atom, cyano group, sulfo group, carboxy group, phosphono group, aryloxycarbonyl group, alkoxycarbonyl group, acyloxy group, nitro group, hydroxamic acid group, heterocyclic group and the like. (2) The method for processing a silver halide color photographic light-sensitive material according to (1), wherein the bleach-fixing solution contains thiosulfate in an amount of 1.0 to 2.0 mol / liter. (3) The silver halide color photograph as described in (1) or (2), which has a magnetic recording layer containing magnetic grains on the side opposite to the silver halide emulsion layer with the transparent support interposed therebetween. Method of processing photosensitive material.

Next, the compound represented by formula (A) of the present invention will be described in detail. In the general formula (A), Q _a1 is preferably a non-atom which is necessary for forming a 5- or 6-membered heterocycle composed of at least one atom of carbon atom, nitrogen atom, oxygen atom, sulfur atom and selenium atom. Represents a group of metal atoms. The heterocycle may be condensed with a carbon aromatic ring or a heteroaromatic ring. Examples of the heterocycle include a tetrazole ring, a triazole ring, an imidazole ring, a thiadiazole ring, an oxadiazole ring, a selenadiazole ring, an oxazole ring, a thiazole ring, a benzoxazole ring, a benzthiazole ring, a benzimidazole ring, a pyrimidine ring, and triazain. Examples thereof include a den ring, a tetraazaindene ring and a pentaazaindene ring. R _a1 is carboxylic acid or a salt thereof (eg sodium salt, potassium salt, ammonium salt, calcium salt), sulfonic acid or a salt thereof (eg sodium salt, potassium salt, ammonium salt,
Magnesium salt, calcium salt), phosphonic acid or salts thereof (eg sodium salt, potassium salt, ammonium salt), substituted or unsubstituted amino group (eg unsubstituted amino, dimethylamino, diethylamino, methylamino, bismethoxyethylamino) Represents a substituted or unsubstituted ammonium group (eg, trimethylammonium, triethylammonium, dimethylbenzylammonium). L _a1 represents a single bond, a divalent aliphatic group, a divalent aromatic hydrocarbon group, a divalent heterocyclic group, or a connecting group in which these are combined. L _a1 is preferably an alkylene group having 1 to 10 carbon atoms (eg, methylene, ethylene, propylene, butylene, isopropylene, 2-hydroxypropylene, hexylene, octylene), an alkenylene group having 2 to 10 carbon atoms (eg, vinylene, propenylene, Butenylene), aralkylene group having 7 to 12 carbon atoms (for example, phenethylene), arylene group having 6 to 12 carbon atoms (for example, phenylene, 2-chlorophenylene, 3-methoxyphenylene, naphthylene), heterocyclic group having 1 to 10 carbon atoms. It may be a divalent one (for example, pyridyl, thienyl, furyl, triazolyl, imidazolyl), a single bond and a group in which these groups are arbitrarily combined, or -CO- or -SO.
_{2 -, - NR 202 -,} - O- or -S- and may be one arbitrarily combined. Here, R ₂₀₂ is a hydrogen atom and has 1 carbon atom
Represents an alkyl group having 6 to 6 (eg, methyl, ethyl, butyl, hexyl), an aralkyl group having 7 to 10 carbon atoms (eg, benzyl, phenethyl), and an aryl group having 6 to 10 carbon atoms (eg, phenyl, 4-methylphenyl). .

M _a1 is a hydrogen atom or a cation (eg,
And an alkali metal atom such as sodium atom and potassium atom, an alkaline earth metal atom such as magnesium atom and calcium atom, an ammonium group, and an ammonium group such as triethylammonium group). Further, the heterocycle represented by the general formula (A) and R _a1 are a nitro group, a halogen atom (eg, chlorine atom, bromine atom), a mercapto group, a cyano group, and a substituted or unsubstituted alkyl group (eg, methyl, ethyl, Propyl, t-butyl,
Cyanoethyl), aryl groups (eg phenyl, 4-methanesulfonamidophenyl, 4-methylphenyl,
3,4-dichlorophenyl, naphthyl), alkenyl group (eg allyl), aralkyl group (eg benzyl, 4
-Methylbenzyl, phenethyl), a sulfonyl group (for example, methanesulfonyl, ethanesulfonyl, p-toluenesulfonyl), a carbamoyl group (for example, unsubstituted carbamoyl, methylcarbamoyl, phenylcarbamoyl),
Sulfamoyl group (eg, unsubstituted sulfamoyl, methylsulfamoyl, phenylsulfamoyl), carbonamide group (eg, acetamide, benzamide), sulfonamide group (eg, methanesulfonamide, benzenesulfonamide, p-toluenesulfonamide), acyloxy Group (eg acetyloxy, benzoyloxy), sulfonyloxy group (eg methanesulfonyloxy), ureido group (eg unsubstituted ureido, methylureido, ethylureido, phenylureido), acyl group (eg acetyl, benzoyl), oxycarbonyl group (Eg methoxycarbonyl, phenoxycarbonyl), oxycarbonylamino group (eg methoxycarbonylamino, phenoxycarbonylamino, 2-ethylhexyloxycarboxyl) Boniruamino), it may be substituted with hydroxyl group and the like.

Q represents an integer of 1 to 3, but when q represents 2 or 3, each R _a1 may be the same or different. In formula (A), preferably Q _a1 represents a tetrazole ring, a triazole ring, an imidazole ring, an oxadiazole ring, a triazaindene ring, a tetraazaindene ring, a pentaazaindene ring, and R _a1 represents a carboxylic acid or a carboxylic acid thereof. It represents an alkyl group having 1 to 6 carbon atoms, which is substituted with one or two groups selected from a salt, a sulfonic acid or a salt thereof, and q represents 1 or 2. Among the compounds represented by the general formula (A), more preferable compounds include the compounds represented by the general formula (A-1). General formula (A-1)

[0022]

[Chemical 9]

In the formula, M _a1 and R _a1 have the same _{meanings as} in the general formula (A). T and U represent C—R _a2 or N, and R _a2 represents a hydrogen atom, a halogen atom, a hydroxy group, a nitro group, an alkyl group, an alkenyl group, an aralkyl group, an aryl group, a carbonamido group, a sulfonamide group or a ureido group. Or R _a1 . However, when R _a2 represents R _a1 , it may be the same as or different from R _{a1 in the} general formula (A). Next, general formula (A-1) will be described in detail. T and U represent C—R _a2 or N, and R _a2 is a hydrogen atom, a halogen atom (eg chlorine atom, bromine atom), a hydroxy group, a nitro group, an alkyl group (eg methyl, ethyl, methoxyethyl, n-butyl). , 2-ethylhexyl), alkenyl groups (eg allyl), aralkyl groups (eg benzyl, 4-methylbenzyl, phenethyl, 4-methoxybenzyl), aryl groups (eg phenyl, naphthyl, 4-methanesulfonamidophenyl, 4) -Methylphenyl), carbonamido group (eg, acetylamino, benzoylamino, methoxypropionylamino), sulfonamide group (eg, methanesulfonamide, benzenesulfonamide, p-toluenesulfonamide), ureido group (eg, unsubstituted) Ureido, Methyl Ureido, Fe Ruureido), or represents a R _a1. However, when R _a2 represents R _a1 , it may be the same as or different from R _{a1 in the} general formula (A).
In the general formula (A-1), preferably T = U = N and R
_a1 is a carbon number 1 substituted with one or two groups selected from carboxylic acids or salts thereof, sulfonic acids or salts thereof
Represents an alkyl group of ~ 4. Specific examples of the compound represented by formula (A) of the present invention are shown below, but the present invention is not limited thereto.

[0024]

[Chemical 10]

[0025]

[Chemical 11]

The compound of the general formula (A) used in the present invention is Berichte der Deutschen Chemischen Ge
sellschaft) 28, 77 (1895), JP-A-60-6
No. 1749, No. 60-147735, Berichte der Germany Chen Hemitschen Gesellschaft (Beri
chte der Deutschen Chemischen Gesellschaft) 22,
568 (1889), 29, 2483 (1896),
Journal of Chemical Society (J. Che
m.Soc.) 1932, 1806, Journal of the
American Chemical Society (J. Am. Chem. So
c.) 71, 4000 (1949), Advances in Heterocyclic Chemistry (Advances in H)
eterocyclic Chemistry) 9, 165 (1968), Organic Synthesis IV, 569
(1963), Journal of the American Chemical Society (J. Am. Chem. Soc.) 45, 23.
90 (1923), Chemische Berichte
richte) 9, 465 (1876).

Next, the general formula (B) will be described in detail. In the general formula (B), Q _b1 is composed of a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a selenium atom.
Or a 6-membered mesoionic ring, wherein X _b1 ⁻ is —O ⁻ ,
-S ^- or -N ^- represents a R _b1. R _b1 represents an aliphatic group, an aromatic hydrocarbon group, or a heterocyclic group. The mesoionic compound represented by the general formula (B) of the present invention refers to W. Bake
r and W. D. Ollis has a quarterly review (Ouart.R
ev.) 11, 15 (1957), Advanced in
Heterocyclic Chemistry (Advances in Heter
ocyclic Chemistry) 19, 1 (1976), which is a group of compounds defined as “5- or 6-membered heterocyclic compound,
A compound that cannot be satisfactorily represented by a single covalent bond structure or polar structure, and that has a π-electron sextant associated with every atom that makes up the ring, has a partially positive charge on the ring, "Balances the same negative charge on the exocyclic atom or group." The mesoionic ring represented by Q _b1 includes an imidazolium ring, a pyrazolium ring, an oxazolium ring, a thiazolium ring, a triazolium ring, a tetrazolium ring, a thiadiazolium ring, an oxadiazolium ring, a thiatriazolium ring, and an oxatriazolium ring. And so on.

R _b1 is a substituted or unsubstituted aliphatic group (for example, methyl, ethyl, n-propyl, n-butyl, isopropyl, n-octyl, carboxymethyl, dimethylaminoethyl, cyclohexyl, 4-methylcyclohexyl, cyclopentyl, Propenyl, 2-methylpropenyl, propargyl, butynyl, 1-methylpropargyl, benzyl, 4-methoxybenzyl), a substituted or unsubstituted aromatic group (for example, phenyl, naphthyl, 4-methylphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 4-methoxybenzyl) Ethoxycarbonylphenyl) and a substituted or unsubstituted heterocyclic group (eg pyridyl, imidazolyl, morpholino, triazolyl, tetrazolyl, thienyl). Further, the mesoionic ring represented by M may be substituted with the substituent described in formula (A). Further, the compound represented by the general formula (B) may form a salt (for example, acetate, nitrate, salicylate, hydrochloride, iodate, bromate). In the general formula (B), preferably X _b1 ⁻ represents —S ⁻ . Among the mesoionic compounds of the general formula (B) used in the present invention, the following general formula (B-1) is more preferable. General formula (B-1)

[0029]

[Chemical 12]

In the formula, X _b2 represents N or C—R _b3 ,
Y _b1 represents O, S, N or N—R _b4 , Z _b1 represents N,
It represents N-R _b5 or C-R _b6 . R _b2 , R _b3 , R _b4 ,
R _b5 and R _b6 represent an aliphatic group, an aromatic group, a heterocyclic group, an amino group, an acylamino group, a sulfonamide group, a ureido group, a sulfamoylamino group, an acyl group or a carbamoyl group. However, R _b3 and R _b6 may be hydrogen atoms. R _b2 and R _b3 , R _b2 and R _b5 , R _b2 and R _b6 , R _b4 and R _b5, and R _b4 and R _b6 may form a ring. The compound represented by formula (B-1) will be described in detail. Aliphatic group, aromatic group, heterocyclic group, amino group, acylamino group, sulfonamide group, ureido group, sulfamoylamino group, acyl group and carbamoyl of R _b2 , R _b3 , R _b4 , R _b5 and R _b6 The group may be substituted. In general formula (B-1), X _b2 is preferably N, C-
R _b3 , Y _b1 represents N—R _b4 or S, O,
Z _b1 represents N or C—R _b6 , R _b2 , R _b3 or R
_b6 represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted heterocyclic group. However, R _b3 and R _b6 may be hydrogen atoms. R
_b4 is preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted amino group. In formula (B-1), more preferably X _b2 represents N, Y _b1 represents N—R _b4 , and Z _b1 represents C—R _b6 . R _b2 and R _b4 represent an alkyl group having 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, R _b6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and more preferably a hydrogen atom or carbon number. It represents an alkyl group of 1 to 3. However, it is more preferable that at least one alkyl group of R _b2 , R _b4 and R _b6 is substituted with at least one carboxylic acid group, sulfonic acid group, amino group or phosphono group, and particularly carboxylic acid group or sulfonic acid group. Those substituted with a group are preferred.

Further, the following general formula (B-2) can be mentioned as a similar compound of the general formula (B-1). General formula (B-2)

[0032]

[Chemical 13]

In the formula, X _b2 , Y _b1 and Z _b1 are represented by the general formula (B
It is exactly the same as -1). The general formula (B) of the present invention is described below.
Specific examples of the compound are shown below, but the present invention is not limited thereto.

[0034]

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[0035]

[Chemical 15]

[0036]

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[0037]

[Chemical 17]

[0038]

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[0039]

[Chemical 19]

The compounds represented by the general formula (B) of the present invention are disclosed in JP-A-1-201659 and JP-A-4-14375.
It can be synthesized by the method described in No. 5 or the like. Next, general formula (C) will be described in detail. L _C1 and L _C3 are substituted or unsubstituted aliphatic groups having 1 to 10 carbon atoms (eg, methyl, ethyl, propyl, hexyl, isopropyl, carboxyethyl, benzyl, phenethyl, vinyl, propenyl,
1-methyl vinyl), substituted or unsubstituted carbon number 6 to
12 aromatic groups (eg, phenyl, 4-methylphenyl, 3-methoxyphenyl), or substituted or unsubstituted heterocyclic groups having 1 to 10 carbon atoms (eg, pyridyl, furyl, thienyl, imidazolyl), L _C2 is a substituted or unsubstituted divalent aliphatic group having 1 to 12 carbon atoms (for example, methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, 1-methylethylene, 1-hydroxytrimethylene, 1 , 2-Xylylene), a substituted or unsubstituted divalent aromatic group having 6 to 12 carbon atoms (for example, phenylene, naphthylene), a substituted or unsubstituted divalent heterocyclic linking group having 1 to 10 carbon atoms ( For example

[0041]

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A _C1 and B _C1 are --S--, --O--, --NR
_{C20 -, - CO -, -} CS -, - SO 2 - or they represent any combination groups, the groups in any combination example _{-CONR C21 -, - NR C22 CO} -, - NR
_C23 CONR _C24- , -COO-, _-OCO- , -SO
_{2 NR C25 -, - NR C26} SO 2 -, - NR C27 CON
R _C28- and the like. r represents an integer of 1 to 10. However, at least one of L _C1 and L _C3 is —SO ₃
M _C1 , -PO ₃ M _C2 M _C3 , -NR _C1 (R _C2 ) (hydrochloride,
It may also be in the form of a salt such as acetate, for example, unsubstituted amino, methylamino, dimethylamino, N-methyl-N-hydroxyethylamino, N-ethyl-N-carboxyethylamino), -N ⁺ R _C3 (R _{C4 ) (R C5) · X C1} - ( e.g., trimethylammonio chloride), - SO ₂ NR _C6
(R _C7) (e.g., unsubstituted sulfamoyl, _{dimethylsulfamoyl), - NR C8 SO 2 R} C9 ( e.g., methanesulfonamido, benzenesulfonamide), - CON
R _C10 (R _C11 ) (eg, unsubstituted carbamoyl, N-
Methylcarbamoyl, N, N-bis (hydroxyethyl) carbamoyl), -NR _C12 COR _C13 (for example,
Formamide, acetamide, 4-methyl-benzoylamino), - SO ₂ R ₁₄ (e.g., methanesulfonyl, 4
-Chlorophenylsulfonyl), -PO (-NR
_C15 (R _C16 ) ₂ (for example, unsubstituted phosphonamide, tetramethylphosphonamide), -NR _C17 CONR _C18
(R _C19 ) (eg, unsubstituted ureido, N, N-dimethylureido), heterocyclic group (eg, pyridyl, imidazolyl, thienyl, tetrahydrofuranyl) -COOM _C4
Be replaced with.

M _C1 , M _C2 , M _C3 and M _C4 are hydrogen atoms or counter cations (eg, alkali metal atoms such as sodium atom, potassium atom, magnesium atom, alkaline earth metal atoms such as calcium atom, ammonium). , Ammonium groups such as triethylammonium)
Represents R _{C1 to} R _C28 are a hydrogen atom, a substituted or unsubstituted aliphatic group having 1 to 12 carbon atoms (for example, methyl, ethyl, propyl, hexyl, isopropyl, benzyl, phenethyl, vinyl, propenyl, 1-methylvinyl),
Represents a substituted or unsubstituted aromatic group having 6 to 12 carbon atoms (eg, phenyl, 4-methylphenyl, 3-methoxyphenyl), and X ⁻ represents a counter anion (eg, halogen ion such as chlorine ion, bromide ion). , Nitrate ion,
Sulfate ion, acetate ion, p-toluenesulfonate ion). When each of L _C1 , L _C2 , L _C3 , and R _{C1 to} R _C28 has a substituent, the substituent has 1 to 10 carbon atoms.
4 lower alkyl groups (eg methyl, ethyl), aryl groups having 6 to 10 carbon atoms (eg phenyl, 4-methylphenyl), aralkyl groups having 7 to 10 carbon atoms (benzyl), 2 to 4 carbon atoms Alkenyl group (eg, propenyl), alkoxy group having 1 to 4 carbon atoms (eg, methoxy group, ethoxy group), halogen atom (eg, chlorine atom, bromine atom), cyano group, nitro group, carboxylic acid group (of salt) Form may be used), a hydroxy group and the like.
When r is 2 or more, A _C1 and L _C2 may be any combination of the groups mentioned above. Also, at least one of A _C1 and B _C1
Represents -S-.

In the general formula (C), preferably at least one of L _C1 and L _C3 is —SO ₃ M _C1 , —PO ₃ M _C2 M _C3 , —
NR _C1 ( _RC2 ), -N ⁺ _RC3 ( _RC4 ) ( _RC5 )
X _C1 ^-, carbon atoms substituted by a heterocyclic group -COOM _C4. 1 to
6 represents an alkyl group, and L _C2 represents an alkylene group having 1 to 6 carbon atoms. A _C1 and B _C1 represent —S—, —O— or —NR _C20 —, and R _C1 , R _C2 , R _C3 , R _C4 and R _C5.
And R _C20 represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and r represents an integer of 1 to 6. General formula (C)
And more preferably L _C1 and L _C3 are —SO ₃ M _C1 , —P.
O ₃ M _C2 M _C3, carbon atoms substituted with -COOM _C4 1 to 4
Is an alkyl group of A _C1 and B _C1 represent -S-,
r represents an integer of 1 to 3. Specific examples of the compound represented by formula (C) of the present invention are shown below, but the present invention is not limited thereto.

[0045]

[Chemical 21]

[0046]

[Chemical formula 22]

The compounds represented by the above general formula (C) of the present invention are disclosed in JP-A-2-44355 and European Patent Publication 458.
It can be synthesized by the method described in No. 277 and the like. Next, the general formula (D) will be described in detail. In the general formula (D),
Examples of the aliphatic group, aromatic group and heterocyclic group represented by X _d , Y _d , R _d1 , R _d2 , R _d3 , R _d4 , R _d5 , R _d6 and R _d7 are as follows. . That is, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms (eg, methyl, ethyl, propyl, hexyl, isopropyl, carboxyethyl, sulfoethyl, aminoethyl, dimethylaminoethyl, phosphonopropyl, carboxymethyl, hydroxyethyl). A substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms (eg vinyl, propenyl, 1-methylvinyl), a substituted or unsubstituted aralkyl group having 7 to 12 carbon atoms (eg benzyl, phenethyl, 3-carboxy) Phenylmethyl, 4-sulfophenylethyl), a substituted or unsubstituted aryl group having 6 to 12 carbon atoms (for example, phenyl, naphthyl, 4-carboxyphenyl, 3-sulfophenyl), substituted or unsubstituted 1 to carbon atoms 10 heterocyclic groups (eg pyridyl, free Represents thienyl, imidazolyl, pyrrolyl, pyrazolyl, pyrimidinyl, quinolyl, piperidyl, a 5 or 6-membered rings are preferred), such as pyrrolidyl.

The alkyl group, alkenyl group, aralkyl group, aryl group and heterocyclic group may be substituted. Examples of the substituent include an alkyl group, aralkyl group, alkenyl group, alkynyl group, aryl group, alkoxy group, aryloxy group, acylamino group, ureido group, urethane group, sulfonylamino group, sulfamoyl group, carbamoyl group, sulfonyl group, sulfinyl group. Base,
Examples thereof include an alkyloxycarbonyl group, an aryloxycarbonyl group, an acyl group, an acyloxy group, a halogen atom, a cyano group and a nitro group. These groups may be further substituted. When there are two or more substituents, they may be the same or different. In the general formula (D), X _d and Y _d may form a ring, but they do not undergo enolization. As the ring formed by X _d and Y _d ,
For example, 4-imidazoline-2-thione ring, imidazolidine-2-thione ring, thiazoline-2-thione ring, 4-thiazolidine-2-thione ring, 4-oxazoline-2-thione ring, oxazolidine-2-thione ring, Pyrrolidine-
A 2-thione ring, or each benzo condensed ring body is mentioned.

However, in the general formula (D), X _d and Y
_At least one of _d is carboxylic acid or a salt thereof (eg, alkali metal salt, ammonium salt), sulfonic acid or a salt thereof (eg, alkali metal salt, ammonium salt), phosphonic acid or a salt thereof (eg, alkali metal salt). , Ammonium salts), amino groups (eg unsubstituted amino, dimethylamino, methylamino, dimethylamino hydrochloride) or ammonium (eg trimethylammonium, dimethylbenzylammonium),
It is assumed that it is substituted with at least one of the hydroxyl groups.
In the general formula (D), the cations represented by R _d6 and R _d7 are
Represents a hydrogen atom, an alkali metal, ammonium and the like. In formula (D), preferably X _d and Y in the present invention.
_d is preferably a carboxylic acid or a salt thereof, a sulfonic acid or a salt thereof, a phosphonic acid or a salt thereof, an amino group or an ammonium group, and a carbon number 1 to 10 substituted with at least one group selected from a hydroxyl group. Alkyl group, C 1-10 heterocyclic group, C 0-10-
N (R _d1 ) R _d2 , -N (R _d3 ) N (R having 0 to 10 carbon atoms
_d4 ) R _d5 represents _C0 to C10 -OR _d6 . R _d1 , R
_d2 , R _d3 , R _d4 , R _d5 and R _d6 represent a hydrogen atom or an alkyl group. In the general formula (D), more preferably X _d and Y _d
Is an alkyl group having 1 to 6 carbon atoms substituted with at least one or two groups selected from carboxylic acids or salts thereof, sulfonic acid or salts thereof, and -N having 0 to 6 carbon atoms.
(R _d1 ) R _d2 , -N (R _d3 ) N (R _d4 ), which has 0 to 6 carbon atoms.
R _d5 represents —OR _d6 having 0 to 6 carbon atoms. R _d1 , R _d2 , R
_d3 , R _d4 , R _d5 and R _d6 represent a hydrogen atom or an alkyl group. Specific examples of the compound represented by formula (D) of the present invention are shown below, but the present invention is not limited thereto.

[0050]

[Chemical formula 23]

[0051]

[Chemical formula 24]

[0052]

[Chemical 25]

[0053]

[Chemical formula 26]

The compound represented by the general formula (D) of the present invention can be prepared by a known method, for example, Journal of Organic
Chemistry (J. Org. Chem.) 24, 470
-473 (1959), Journal of Heterocyclic Chemistry (J. Heterocycle.
Chem. ) 4,605-609 (1967), "Pharmaceutical magazine" 82, 36-45 (1962), Japanese Patent Publication No. 39-26.
203, JP-A-63-229449, OLS-2,
It can be synthesized with reference to 043,944.

The general formula (E) will be described in detail below. In formula (E), R _e1 , R _e2 , R _e3 and R _e4 each represent a hydrogen atom, an alkyl group or an alkenyl group. As the alkyl group, a hydroxy group,
It may have a substituent such as a carboxyl group, a sulfo group, an amino group and a nitro group, and preferably has 1 to 5 carbon atoms, and particularly preferably 1 to 2 carbon atoms.

The alkenyl group may have the above-mentioned substituents, and preferably has 2 to 5 carbon atoms, and particularly preferably 2 to 3 carbon atoms.

Among the above, in the present invention, R _e1 to
R _e4 is preferably a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 2 carbon atoms, and R _e1 is particularly preferably a substituted alkyl group. As the substituent, a hydroxy group, a carboxyl group and a sulfo group are preferable, and a carboxyl group and a sulfo group are particularly preferable. Specific examples of the compound represented by formula (E) are shown below, but the invention is not limited thereto.

(E-1) Imidazole (E-2) 1-Methylimidazole (E-3) 2-Methylimidazole (E-4) 4-Methylimidazole (E-5) 4-Hydroxymethylimidazole (E-6) ) 1-Ethylimidazole (E-7) 1-Vinylimidazole (E-8) 4-Aminomethylimidazole (E-9) 2,4-Dimethylimidazole (E-10) 2,4,5-Trimethylimidazole (E -11) 2-Aminoethylimidazole (E-12) 2-Nitroethylimidazole

(E-13) 1-carboxymethyl-2-
Methyl-imidazole (E-14) 1-carboxymethyl-2,4-dimethyl-imidazole (E-15) 1-carboxyethyl-2-methyl-4-
β-Hydroxyethyl-imidazole (E-16) 1-sulfoethyl-2-methyl-imidazole (E-17) 1-sulfoethyl-2,4-dimethyl-imidazole (E-18) 1-sulfomethyl-4,5-dimethyl -Imidazole (E-19) 1-sulfomethyl-2,5-dimethyl-imidazole (E-20) 1-sulfoethyl-imidazole

Among the silver halide solvents of the present invention, sodium thiosulfate, sodium methanethiosulfonate,
A-1, A-2, A-3, A-4, A-9, A-10,
B-3, B-8, B-9, B-11, B-12, D-
2, D-3 are preferable, and especially A-1, A-2, A-
3, A-4, B-3, B-8, B-9, B-11, B-
12 is preferred.

The addition amount of the silver halide solvent of the present invention is preferably 0.1 to 50 mmol, more preferably 0.1 to 10 mmol, and 0.5 per liter of the color developing solution.
~ 5.0 mmol is most preferred. If it is less than 0.1 mmol / liter, the effect of the present invention becomes very small,
If it exceeds 50 mmol, the fog density in the unexposed area remarkably increases. Further, the silver halide solvent of the present invention can be used in combination of two or more kinds depending on the purpose.

In the present invention, the light-sensitive material is subjected to color development processing and immediately thereafter subjected to desilvering processing with a bleach-fixing solution. Specifically, the following are mentioned. 1. (Color development)-(Bleach fixing)-(Stable) 2. 〃 − 〃 − (Washing) − (Stable) 3. 〃 − 〃 − (Bleach fixing) − (Stable) 4. 〃 − 〃 − 〃 − (Washing) − (Stable) 5. 〃 − 〃 − (Fixing) − (Stable) 6. 〃-〃-〃- (Washing)-(Stable) From the viewpoints of reducing the number of processing baths, speeding up and simplifying the processing steps, which are the objects of the present invention, the above steps 1 and 2 are preferable,
1. Is particularly preferred.

The crossover time between the color developing step and the bleach-fixing step of the present invention is 10 seconds or less, and the shorter the crossover time, the more preferable. , And most preferably 3 to 5 seconds.

When the crossover time exceeds 10 seconds,
Fog generation in the air increases, and it is not preferable from the viewpoint of rapid processing. In addition, in 10 seconds or less, the probability of mixing of the liquid between two adjacent baths remarkably increases, and the effect of the present invention is remarkably observed.

In the present invention, the effect is more remarkable than in the case of rapid processing, but in particular, the total time from the immersion of the light-sensitive material in the color developing solution to the exit of the bleach-fixing solution is 1 to 3.
It becomes noticeable in minutes.

The color developing process of the present invention will be described below. The color development time of the color development processing of the present invention is 25 seconds or more and 90 seconds or less, preferably 35 seconds or more and 75 seconds or less, and most preferably 45 seconds or more and 65 seconds or less. The color development time of the present invention is a time including the crossover time (time from the exit of the color developer to the entrance of the processing solution of the next step).

The developing agent in the color developing process of the present invention is p-
Phenylenediamine derivatives, preferable representative examples of which are shown below. (DA-1) 2-methyl-4- [N-ethyl-N-
(Β-Hydroxyethyl) amino] aniline (DA-2) 2-methyl-4- [N-ethyl-N-
(3-Hydroxypropyl) amino] aniline (DA-3) 2-methyl-4- [N-ethyl-N-
(4-Hydroxybutyl) amino] aniline (DA-4) 2-methyl-N, N-diethyl-p-phenylenediamine (DA-5) 2-methyl-4- [N-ethyl-N-
(Β-Methanesulfonamidoethyl) amino] aniline (DA-6) 2-methoxy-4- [N-ethyl-N-
(Β-Hydroxyethyl) amino] aniline (DA-7) 4-amino-3-methoxy-N, N-bis (3-hydroxypropyl) aniline (DA-8) 4-amino-3-isopropoxy-
N, N-bis (β-hydroxyethyl) aniline (DA-9) 1- (β-hydroxyethyl) -5-amino-6-methyl-indoline (DA-10) 1,2,3,4-tetrahydro- 1-
(3,4-Dihydroxybutyl) -2,2,4,7-tetramethyl-6-amino-quinoline (DA-11) 1,2,3,4-tetrahydro-1-
(Β-hydroxyethyl) -4-hydroxymethyl-6
-Amino-7-methyl-quinoline

In the color development processing of the present invention, DA-
1, DA-2, DA-3, DA-6, DA-7, DA-
8, DA-10 and DA-11 are particularly preferable, and DA-
1, DA-2 and DA-3 are more preferable, and DA-1 is the most preferable.

The concentration of the developing agent is 25 to 80 mmol, preferably 25 to 60 mmol, more preferably 27 to 50 mmol, and most preferably 30 to 45 per liter of the processing solution. It is below millimolar. Within the developing agent concentration range, two or more developing agents may be used in combination.

[0070] bromide ion in the color developer of the present invention (Br ^-) is particularly important as an antifoggant, B
The r ⁻ concentration is 13 mmol or more and 60 mmol or less, preferably 15 mmol or more and 42 mmol per liter of the treatment liquid.
It is not more than 16 mmol, particularly preferably not less than 16 mmol and not more than 35 mmol. If necessary, I ⁻ or Cl ⁻ may be contained as a halogen ion other than Br ⁻ .

The temperature of the color developing solution is 40 ° C. or higher and 60 ° C. or lower, preferably 42 ° C. or higher and 55 ° C. or lower, and particularly preferably 43 ° C. or higher and 50 ° C. or lower. The pH of the color developing solution is 9.9 or more and 11.0 or less, preferably 1
It is 0.0 or more and 10.5 or less.

In the color developing solution of the present invention, as a compound which directly preserves the aromatic primary amine color developing agent,
Various hydroxylamines described in JP-A-63-5341, 63-106655 or JP-A-4-144446, hydroxamic acids described in JP-A-63-43138, and hydrazine described in JP-A-63-146041. And hydrazides, 63-44657 and 63
The phenols described in JP-A-58443, 63-446;
[Alpha] -hydroxyketones and [alpha] -aminoketones described in No. 56, various sugars described in No. 63-36244, and the like can be contained. Further, in combination with the above compound, JP-A Nos. 63-4235, 63-24254 and 63
-21647, 63-146040, 63-2
7841 and 63-25654 and the like, monoamines, 63-30845 and 63-14640.
Nos. 63-43139 and the like, diamines, 6
3-21647, 63-26655 and 63
Nos. 44655, 63-535.
Nitroxy radicals described in No. 51, 63-431
Alcohols described in Nos. 40 and 63-53549, oximes described in No. 63-56654, and tertiary amines described in No. 63-239447 can be used. Other preservatives include JP-A-57-44
148 and 57-53749, various metals, 59-180588, salicylic acids, 54-3582, alkanolamines, 5
The polyethyleneimine described in 6-94349, the aromatic polyhydroxy compound described in U.S. Pat. No. 3,746,544, and the like may be contained as necessary. Particularly preferable preservatives are hydroxylamines represented by the general formula (I) of JP-A-3-144446, and among them, compounds having a sulfo group or a carboxy group are preferable.
The most preferable examples include N, N-bis (sulfonate ethyl) hydroxylamine and monosulfonate ethylhydroxylamine.

Others Various additives described in JP-A-3-144446 can be used in the color developing solution of the present invention. For example, examples of buffers for maintaining pH include carbonic acid, phosphoric acid, boric acid, hydroxybenzoic acid and the like on page 6 of the publication (9), upper right column, line 6 to lower left column, line 1. Examples of the chelating agent include various aminopolycarboxylic acids, phosphonic acids, and sulfonic acids from the lower left column, line 2 to the lower right column, line 18 on the same page, preferably ethylenediaminetetraacetic acid, triethylenetetraminehexaacetic acid, and 1,3-diaminopropanoltetraacetic acid. , 1-hydroxyethylidene-1,1-diphosphonic acid, 4,5-dihydroxybenzene-1,3-disulfonic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N, N, N ', N'-tetrakis (methylenephosphonic acid), Catechol-3,5-disulfonic acid is preferred.
Examples of the development accelerator include various additives described on page 9, lower left column, line 19 to page 10, upper right column, line 7 of the same publication. Examples of the antifoggants include halide ions and organic antifoggants described in the same publication, page (10), upper right column, line 8 to lower left column, line 5. If necessary, various surfactants such as alkyl sulfonic acid, aryl sulfonic acid, aliphatic carboxylic acid, aromatic carboxylic acid may be added.

When the color developing solution of the present invention is used for processing in an automatic developing machine, it is preferable that the area (opening area) in which the color developing solution comes into contact with air is as small as possible. For example, when the aperture ratio is a value obtained by dividing the opening area (cm ² ) by the volume of the developer (cm ³ ), the aperture ratio is preferably 0.01 cm ^-1 or less, and
It is more preferably 005 cm ^-1 or less. The color developing solution can be regenerated and used. Regeneration of the color developing solution means that the used color developing solution is subjected to anion exchange resin or electrodialysis, or a processing chemical called a regenerant is added to increase the activity of the color developing solution and use it again as a color developing solution. It is to be. In this case, the regeneration rate (ratio of the overflow solution in the replenisher) is preferably 50% or more, particularly preferably 70% or more. As a process using the regenerating of the color developing solution, the overflow solution of the color developing solution is regenerated and then used as a replenishing solution. As a method of regenerating the color developing solution, an anion exchange resin is preferably used. Particularly preferred anion exchange resin compositions and resin regeneration methods are described in DIAION MANUAL (I) (1) issued by Mitsubishi Kasei Co., Ltd.
986, 14th edition). Further, among the anion exchange resins, JP-A-2-95
Resins having the compositions described in JP-A No. 2-281152 and JP-A No. 1-281152 are preferable.

It is preferable that the processing solution in the replenishing tank of the color developing solution or the processing tank is shielded with a liquid agent such as a high boiling point organic solvent to reduce the contact area with air. Liquid paraffin is most preferable as the liquid shield agent. It is particularly preferable to use it as a replenisher. In addition, the replenishment amount is 1
30-800 ml per square meter, preferably 50-
It is about 500 ml.

The bleach-fixing solution of the present invention will be described below. As the bleaching agent used in the present invention, aminopolycarboxylic acid iron (III) complex, persulfate, bromate, hydrogen peroxide, red blood salt and the like can be used, but aminopolycarboxylic acid (III) complex Can be most preferably used. The ferric iron complex salt used in the present invention may be added and dissolved as a complexed iron complex salt in advance, and the complex forming compound and the ferric iron salt (for example, ferric sulfate, ferric chloride) may be added. Iron, ferric bromide, iron (III) nitrate, iron (III) sulfate ammonium, etc.)
It is also possible to coexist with and form a complex salt in a liquid having a bleaching ability. The complex-forming compound may be slightly in excess of the amount required for complex formation with ferric ion, and when it is added in excess, it is usually preferably in the range of 0.01 to 10%.

In the present invention, as the compound forming the ferric complex salt in the liquid having bleaching ability, ethylenediaminetetraacetic acid (EDTA), 1,3-propanediaminetetraacetic acid (1,3-PDTA), Diethylenetriaminepentaacetic acid, 1,2-cyclohexanediaminetetraacetic acid, iminodiacetic acid, methyliminodiacetic acid, N- (2-acetamido) iminodiacetic acid, nitrilotriacetic acid, N- (2-carboxyethyl) iminodiacetic acid, N- (2-Carboxymethyl) iminodipropionic acid, β-alanine diacetic acid, 1,
4-diaminobutane tetraacetic acid, glycol ether diamine tetraacetic acid, N- (2-carboxyphenyl) iminodiacetic acid, ethylenediamine-N- (2-carboxyphenyl) -N, N ', N'-triacetic acid, ethylenediamine-
N, N'-disuccinic acid, 1,3-diaminopropane-
N, N'-disuccinic acid, ethylenediamine-N, N'-
Examples thereof include dimaleonic acid and 1,3-diaminopropane-N, N′-dimalonic acid, but are not particularly limited thereto.

The concentration of the ferric complex salt in the bleach-fixing solution of the present invention is appropriately in the range of 0.005 to 1.0 mol / l, preferably 0.01 to 0.50 mol / l. , And more preferably 0.02 to 0.30
It is in the range of mol / liter. The concentration of the ferric complex salt in the replenisher for the bleach-fixing solution of the present invention is preferably
0.005 to 2 mol / liter, more preferably 0.0
It is 1 to 1.0 mol / liter.

In addition, in the bleach-fixing solution of the present invention, bromide (eg, potassium bromide, sodium bromide, ammonium bromide) or chloride (eg, potassium chloride, sodium chloride, ammonium chloride) or iodide (eg, potassium chloride). ,
A rehalogenating agent such as ammonium iodide) may be included. If necessary, pH buffering capacity of borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, malonic acid, succinic acid, glutaric acid, etc. It is possible to add one or more kinds of inorganic acid or organic acid having the above, an alkali metal or ammonium salt thereof, or a corrosion inhibitor such as ammonium nitrate or guanidine. Further, other various fluorescent whitening agents, antifoaming agents or surfactants, polyvinylpyrrolidone, organic solvents such as methanol and the like can be contained.

The fixing agent component in the bleach-fixing solution of the present invention is a known fixing agent, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; ethylenebisthio. Glycolic acid, thioether compounds such as 3,6-dithia-1,8-octanediol, water-soluble silver halide solubilizers such as mesoionic compounds and thioureas, which may be used alone or in admixture of two or more. Can be used. Further, a special bleach-fixing solution containing a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can be used. In the present invention, it is preferable to use thiosulfates, particularly ammonium thiosulfate and sodium thiosulfate.

The concentration of thiosulfate in the bleach-fixing solution of the present invention is 0.6 to 2.5 mol / liter, preferably 1.0 to 2.0 mol / liter, particularly preferably 1. 2 to 1.6 mol / liter. If it is less than 0.6 mol / liter, defective desilvering due to poor fixing occurs.
If the amount exceeds 5 mol / liter, the desilvering defect is also increased due to a fixing solution failure (the silver ion complex formed is difficult to be dissolved in the solution and remains in the light-sensitive material) due to the salt concentration effect.

For the bleach-fixing solution of the present invention, it is preferable to use the silver halide solvent of the present invention used in the color developing solution of the present invention together with thiosulfate. The addition amount is 0.0
1 to 0.5 mol / liter is preferable, and 0.05 to 0.
4 mol / l is more preferable, and 0.1 to 0.3 mol / l is particularly preferable. It is preferable to add the silver halide solvent of the present invention to the bleach-fixing solution of the present invention from the viewpoint of improving desilvering property and speeding up. The bleach-fixing solution of the present invention preferably contains a sulfite (or bisulfite or metabisulfite) as a preservative, but is preferably 0.08-
0.4 mol / liter, more preferably 0.1 to 0.3
It is preferable that the content is mol / liter. The bleach-fixing solution of the present invention comprises a sulfite salt (for example, sodium sulfite, potassium sulfite, ammonium sulfite), a bisulfite salt (for example, ammonium bisulfite, sodium bisulfite, potassium bisulfite), a metabisulfite as a preservative. In addition to containing sulfite ion-releasing compounds such as sulfites (eg, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite), aldehydes (benzaldexide, acetaldehyde, etc.), ketones (acetone, etc.), ascorbic acids, etc. , Hydroxylamines and the like can be added as required.

Further, a buffering agent, a fluorescent brightening agent, a chelating agent, a defoaming agent, an antifungal agent and the like may be added as required. In the bleach-fixing solution of the present invention, the pH range is preferably 4.5 to 6.2, more preferably 5 to 6.
In some cases, the magnetic recording performance may not be sufficiently exhibited even if the pH is higher or lower than the normal pH.

The replenishing amount of the bleach-fixing solution used in the present invention is 50 to 2000 ml per 1 m ² of the light-sensitive material. Particularly preferably, it is 100 to 1000 ml. Further, after-wash water such as washing water or overflow solution of the stabilizing bath may be replenished if necessary. The processing temperature of the bleach-fixing solution is 20 to 50 ° C, preferably 30 to 45 ° C.
Is. The processing time is 25 seconds to 3 minutes. In terms of speeding up, it is preferably 25 seconds to 90 seconds, more preferably 35 seconds.
~ 75 seconds, most preferably 45-65 seconds. The shorter the desilvering time, the more remarkable the effect of the present invention.

In the bleach-fixing solution of the present invention, it is particularly preferable to carry out aeration during processing because the photographic performance is kept extremely stable. Means known in the art can be used for the aeration, and blowing of air into the processing liquid having a bleaching ability or absorption of air using an ejector can be performed. At the time of blowing air, it is preferable to discharge the air into the liquid through an air diffusing tube having fine pores. Such an air diffuser is widely used as an aeration tank in activated sludge treatment. Regarding aeration, Z-1 issued by Eastman Kodak Company
21, Youth Process C-41 3rd Edition (198)
2 years), and the matters described on pages BL-1 to BL-2 can be used. In the processing using the bleach-fixing solution of the present invention, it is preferable that the agitation is intensified. , The contents described in the second line can be used as they are.

In the desilvering process, it is preferable that the stirring is strengthened as much as possible. Specific examples of the method for strengthening stirring include a method in which a jet of a processing solution is made to collide with the emulsion surface of a light-sensitive material described in JP-A-62-183460, and JP-A-62-1834.
A method of increasing the stirring effect using the rotating means of No. 61, and further moving the light-sensitive material while bringing the emulsion surface into contact with the wiper blade provided in the liquid to make the emulsion surface turbulent, thereby further improving the stirring effect. Examples thereof include a method for improving the method and a method for increasing the circulation flow rate of the entire processing solution. Such a stirring improving means is also effective in the bleach-fixing solution of the present invention. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently the desilvering rate.
Further, the above-mentioned means for improving the stirring is more effective when a bleaching accelerator is used, and can significantly increase the accelerating effect or eliminate the fixing inhibiting effect of the bleaching accelerator.

After the treatment step with the fixer and / or the bleach-fixer, a washing treatment step is usually performed. It is also possible to use a simple processing method in which after the treatment with the treatment liquid having the fixing ability, the stabilizing treatment using the stabilizing liquid is carried out without substantially washing with water. The washing water used in the washing step and the stabilizing solution used in the stabilizing step may contain various surfactants in order to prevent water droplet unevenness during drying of the processed photosensitive material. Among these, it is preferable to use a nonionic surfactant, and an alkylphenol ethylene oxide adduct is particularly preferable. Octyl, nonyl, dodecyl and dinonylphenol are particularly preferable as the alkylphenol, and 8 to 14 are particularly preferable as the number of moles of ethylene oxide added. Further, it is also preferable to use a silicon-based surfactant having a high defoaming effect.

The washing water and the stabilizing solution may contain various antibacterial agents and antifungal agents in order to prevent the generation of water stains and the mold generated in the processed light-sensitive material. Further, it is preferable to add various chelating agents to the wash water and the stabilizing solution. Preferred chelating agents include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, and diethylenetriamine-N, N, N ', N'-tetramethylenephosphonic acid. Organic phosphonic acid or European Patent 345172A
The hydrolyzate of the maleic anhydride polymer described in 1 and the like can be mentioned. It is also preferable that the preservative that can be contained in the fixing solution or the bleach-fixing solution is contained in the washing water and the stabilizing solution.

The stabilizing solution used in the stabilizing step is a processing solution for stabilizing the dye image, such as an organic acid or pH 3 to
6, a solution containing an aldehyde (for example, formalin or glutaraldehyde), or the like. The stabilizing solution may contain all compounds that can be added to the washing water, and in addition, if necessary, ammonium compounds such as ammonium chloride and ammonium sulfite, metal compounds such as Bi and Al, optical brighteners and hardeners. Agents such as alkanolamines described in US Pat. No. 4,786,583 can be used.

In the present invention, it is preferable that the stabilizer does not substantially contain formaldehyde as a stabilizer for the dye image. The term "substantially free of formaldehyde" means that the total amount of free formaldehyde and its hydrate is 0.003 mol or less per liter of the stabilizing solution. By using such a stabilizing solution, it is possible to suppress the scattering of formaldehyde vapor during processing. In this case, for the purpose of stabilizing the magenta dye, it is preferable that the formaldehyde substitute compound is present in the stabilizing solution, the bleaching solution or its prebath (for example, a preparation bath).

Preferred compounds as the formaldehyde substitute compound are hexamethylenetetramine and its derivatives, formaldehyde bisulfite adduct, N-methylol compound and azolylmethylamine compound. In addition to stabilizing the magenta dye, these preferable compounds suppress the generation of yellow stain over time.

Examples of hexamethylenetetramine and its derivatives include “Beilsteins Handbook Der.
Organischen Chemie (Beilsteins Handbuch der
Organishen Chemie) Volume II Supplement 26, P.200-P.
The compounds described in 212 can be used, but in particular:
Hexamethylenetetramine is preferred. Further, as the formaldehyde bisulfite addition product, sodium formaldehyde bisulfite is preferable.

As the N-methylol compound, an N-methylol compound of pyrazole and its derivative, an N-methylol compound of triazole and its derivative, and an N-methylol compound of urazole and its derivative are particularly preferable. Specific examples of these N-methylol compounds include 1-hydroxymethylpyrazole, 1-hydroxymethyl-2-methylpyrazole, 1-hydroxymethyl-2,4-dimethylpyrazole, 1-hydroxymethyl-1,2,4. -Triazole, 1-hydroxymethylurazole and the like can be mentioned. Of these, particularly preferred are 1-hydroxymethylpyrazole and 1-hydroxymethyl-1,2,4-triazole. N above
The methylol compound can be easily synthesized by reacting an amine compound having no methylol group with formaldehyde or paraformaldehyde. When the above N-methylol compound is used, it is preferable that an amine compound not having a methylol group is allowed to coexist in the treatment liquid, and it is preferable that the N-methylol compound is present in a molar concentration of 0.2 to 10 times.

As the azolylmethylamine compound,
1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine and 1,4-bis (pyrazol-1-ylmethyl) piperazine are mentioned, and azo-like 1,2,4-triazole and pyrazole are mentioned. In combination with the
No. 359249), the image stability is high and the formaldehyde vapor pressure is small, and thus it is particularly preferable. The addition amount of the above formaldehyde substitute compound is preferably 0.003 to 0.2 mol, and more preferably 0.005 to 0.5 mol, per liter of the treatment liquid. Two or more of these formaldehyde substitute compounds may be used in combination in the bath.

The pH of the stabilizing solution is preferably 3 to 9, more preferably 4 to 7. The washing process and stabilization process are
A multi-stage countercurrent system is preferable, and the number of stages is preferably 2 to 4. The amount of replenishment is 1 to 50 times, preferably 1 to 30 times, more preferably 1 times the amount carried in from the previous bath per unit area.
10 times. Regarding the washing and stabilizing steps carried out in the present invention, the contents described in JP-A-3-33847, page 11, lower right column, line 9 to page 12, upper right column, line 19 can be preferably carried out. .

Although tap water can be used as the water used in the washing step and the stabilizing step, water, halogen, and ultraviolet rays deionized to have Ca and Mg ion concentrations of 5 mg / liter or less by an ion exchange resin or the like. It is preferable to use water that has been sterilized by a germicidal lamp or the like. Further, by using a method in which the overflow solution of the washing step or the stabilizing step is caused to flow into a bath having a fixing ability as a pre-bath,
It is preferable because the amount of waste liquid can be reduced.

In the treatment of the present invention, in order to correct the concentration due to evaporation, it is preferable to replenish an appropriate amount of water or a correction solution or a processing replenishing solution. The specific method for replenishing water is not particularly limited, but among them, JP-A 1-2
A monitor water tank different from the bleaching tank described in Nos. 54959 and 1-254960 is installed, the evaporation amount of water in the monitor water tank is obtained, and the evaporation amount of water in the bleaching tank is calculated from the evaporation amount of this water. However, a method of replenishing the bleaching tank with water in proportion to the amount of evaporation and JP-A-3-248155 and 3-24
No. 9644, No. 3-249645, No. 3-24864
The evaporation correction method using a liquid level sensor or an overflow sensor described in JP-A No. 6 and JP-A No. 4-14042 is preferable. Also, the water for correcting the evaporation of each processing liquid is
Although tap water may be used, it is preferable to use deionized water or sterilized water that is preferably used in the above washing step.

Automatic developing machines used in the light-sensitive material of the present invention are disclosed in JP-A-60-191257, JP-A-60-191258 and JP-A-60-191258.
It is preferable to have the photosensitive material conveying means described in No. 191259. As described in the above-mentioned JP-A-60-191257,
Such a conveying means can significantly reduce the carry-in of the treatment liquid from the front bath to the rear bath, and is highly effective in preventing the performance deterioration of the treatment liquid. Such an effect is particularly effective for reducing the processing time in each step and reducing the replenishing amount of the processing solution.

The supply form of the treating agent used in the present invention is as follows:
It may be in any form such as a concentrated or concentrated liquid preparation, a granule, a powder, a tablet, a paste or an emulsion. As an example of such a treating agent, JP-A-63-1
7453 is a liquid agent stored in a container with low oxygen permeability,
19655 and 4-230748 are vacuum packed powders or granules, and 4-21951 are granules containing a water-soluble polymer,
JP-A-51-61837 and JP-A-6-102628 have tablets and special tables
00485 discloses a paste-like treatment agent, and any of them can be preferably used, but from the viewpoint of ease of use,
It is preferable to use a liquid which has been prepared in advance in a concentration at the state of use. Polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, nylon and the like are used alone or as a composite material in a container for containing these treatment agents. These are selected according to the level of oxygen permeability required. For a liquid such as a color developing solution which is easily oxidized, a material having low oxygen permeability is preferable, and specifically, polyethylene terephthalate or a composite material of polyethylene and nylon is preferable. These materials have a thickness of 500 to 1500 μm, are used for a container, and preferably have an oxygen permeability of 20 ml / m ² · 24 hrs · atm or less.

The light-sensitive material of the present invention may have at least one light-sensitive layer provided on a support. As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. Is. The photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light, and in a multilayer silver halide color photographic light-sensitive material, the arrangement of the unit photosensitive layers is generally The red color-sensitive layer, the green color-sensitive layer and the blue color-sensitive layer are arranged in this order from the support side. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers. A non-photosensitive layer may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer. These may contain a coupler, a DIR compound, a color mixing inhibitor, etc. described later. A plurality of silver halide emulsion layers constituting each unit light-sensitive layer are formed by sequentially exposing two layers, a high-speed emulsion layer and a low-speed emulsion layer, to a support as described in DE 1,121,470 or GB 923,045. It is preferable to arrange them so that the degree is low. In addition, JP-A-57-112751, 62-200350, 62-2
As described in 06541 and 62-206543, a low-sensitivity emulsion layer may be provided on the side farther from the support and a high-sensitivity emulsion layer may be provided on the side closer to the support. As a specific example, from the side farthest from the support, low-sensitivity blue photosensitive layer (BL) / high-sensitivity blue photosensitive layer (BH) / high-sensitivity green photosensitive layer (GH) / low-sensitivity green photosensitive layer (GL) / High-sensitivity red photosensitive layer (RH) / Low-sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH / RL, or BH / BL / GH / GL / RL / RH It can be installed in the order of. Further, as described in JP-B-55-34932, from the side farthest from the support, the blue-sensitive layer / GH / RH / GL
It can also be arranged in the order of / RL. In addition, JP-A-56-2573
8 and 62-63936, the blue-sensitive layer / GL / RL / GH / RH may be arranged in this order from the side farthest from the support. Further, as described in JP-B-49-15495, the upper layer is the silver halide emulsion layer having the highest sensitivity, the middle layer is the silver halide emulsion layer having a lower sensitivity, and the lower layer is a silver halide emulsion layer having a higher sensitivity than the middle layer. An example is an arrangement in which low silver halide emulsion layers are arranged and three layers having different sensitivities are sequentially lowered toward the support. Even when it is composed of such three layers having different sensitivities, as described in JP-A-59-202464, in the same color-sensitive layer, the medium-sensitivity emulsion layer / high-sensitivity layer is separated from the side distant from the support. You may arrange in order of a speed emulsion layer / a low speed emulsion layer. In addition, the layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. Also, in case of 4 layers or more,
The arrangement may be changed as described above. In order to improve color reproducibility, BL, GL, described in US 4,663,271, 4,705,744, 4,707,436, JP-A-62-160448, and 63-89850.
It is preferable to dispose a donor layer (CL) having a multilayer effect, which has a spectral sensitivity distribution different from that of the main photosensitive layer such as RL, adjacent to or close to the main photosensitive layer.

The preferred silver halide used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide, which contains about 30 mol% or less of silver iodide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide. Silver halide grains in photographic emulsions have regular crystals such as cubes, octahedra and tetradecahedrons, grains having irregular crystal forms such as spheres and plates, twin planes, etc. It may have a crystal defect of, or a composite form thereof. The grain size of silver halide is about 0.2 μm or less
It may be large-sized grains up to 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion. The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (hereinafter abbreviated as RD) No. 17643 (December 1978), 22-.
Page 23, "I. Emulsion preparation and typ
es) ”and ibid. No. 18716 (November 1979), p.648,
Id. No. 307105 (November 1989), pages 863-865, and Graphide, Physics and Chemistry of Photography, published by Paul Montel (P.Glafkides, Chemie et PhisiquePhotographique, P.
aul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photographic Emul
sion Chemistry, Focal Press, 1966), "Production and coating of photographic emulsions" by Zelikmann et al., published by Focal Press (V.
L. Zelikman, et al., Making and Coating Photograph
ic Emulsion, Focal Press, 1964) and the like.

US 3,574,628, US 3,655,394 and GB 1,4
The monodisperse emulsions described in 13,748 are also preferred. Further, tabular grains having an aspect ratio of about 3 or more can be used in the present invention. Tabular grains are described in Gutof, Photographic Science and Engineering (Gutof
f, Photographic Science and Engineering), Volume 14
248-257 (1970); US 4,434,226, US 4,414,310,
It can be easily prepared by the method described in 4,433,048, 4,439,520 and GB 2,112,157. The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. Silver halides having different compositions may be joined by epitaxial joining, and may be joined with a compound other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used. The above emulsion is a surface latent image type that forms a latent image mainly on the surface,
Either an internal latent image type formed inside the grain or a type having a latent image both on the surface and inside may be used, but it is necessary that the emulsion is a negative type. Of the internal latent image types, JP-A-6
The core / shell type internal latent image type emulsion described in 3-264740 may be used, and its preparation method is described in JP-A-59-133542. The thickness of the shell of this emulsion varies depending on development processing and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. Additives used in such processes are RD No.17643 and RD No.187.
16 and No. 307105, and the relevant parts are summarized in the table below. In the light-sensitive material of the present invention, two or more kinds of emulsions having different characteristics of at least one of the grain size, grain size distribution, halogen composition, grain shape, and sensitivity of the photosensitive silver halide emulsion are mixed in the same layer. Can be used. US Pat. No. 4,082,553, the surface of which is covered with silver halide grains, US Pat. No. 4,626,498, and JP-A-59-21.
4852, a silver halide grain in which the inside of the grain is fogged,
It is preferred to apply colloidal silver to the light-sensitive silver halide emulsion layer and / or the substantially light-insensitive hydrophilic colloid layer. The fogged silver halide grain inside or on the surface means a silver halide grain which enables uniform (non-imagewise) development regardless of the unexposed area and exposed area of the light-sensitive material. , Its preparation method is described in US 4,626,498 and JP-A-59-214852. The silver halide forming the inner core of a core / shell type silver halide grain having a fogged inside may have a different halogen composition.
As the silver halide whose inside or surface is fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The average grain size of these fogged silver halide grains is 0.01 to 0.75 μm,
It is particularly preferably 0.05 to 0.6 μm. The grain shape may be regular grains or polydisperse emulsions, but monodisperse grains (weight of silver halide grains or grain number of at least 95
% Having a particle size within ± 40% of the average particle size).

In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. Non-photosensitive fine grain silver halide is silver halide fine grains that are not exposed during imagewise exposure to obtain a dye image and are not substantially developed in the developing process, and are preferably not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may contain silver chloride and / or silver iodide, if necessary. Preferred is one containing 0.5 to 10 mol% of silver iodide. Fine grain silver halide has an average grain size (average value of circle equivalent diameter of projected area)
Is preferably 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm. Fine grain silver halide can be prepared by the same method as that for ordinary photosensitive silver halide. The surface of the silver halide grain does not need to be optically sensitized nor spectrally sensitized. However, prior to adding this to the coating liquid, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, mercapto-based compound or zinc compound in advance. Colloidal silver can be contained in the fine silver halide grain-containing layer. Coated silver amount of the light-sensitive material of the present invention is preferably 6.0 g / m ² or less, 4.5 g / m ² or less is most preferred.

The photographic additives that can be used in the present invention are also described in RD, and the relevant portions are shown in the table below. Types of additives RD17643 RD18716 RD307105 1. Chemical sensitizer page 23 page 648 page right column page 866 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column 866 to 868, supersensitizer, page 649, right column 4. Whitening agent, page 24, 647, right column, page 868, 5 Light absorber, pages 25 to 26, page 649, right column, page 873, filter, page 650, left column, dye, ultraviolet absorber 6. Binder, page 26, page 651, left column 873 to 874, page 7. Plasticizer, page 27, page 650, right Column 876 Lubricants 8. Coating aids, 26-27 Pages 650 Right column 875-876 Pages Surfactants 9. Static 27 pages 650 Page right columns 876-877 Inhibitors 10. Matting agents 878-879

Although various dye-forming couplers can be used in the light-sensitive material of the present invention, the following couplers are particularly preferable. Yellow couplers: couplers represented by formulas (I) and (II) of EP 502,424A; couplers represented by formulas (1) and (2) of EP 513,496A (particularly Y-28 on page 18); EP 568,037A Claim 1
A coupler represented by formula (I) in US Pat. No. 5,066,576, column 1, lines 45 to 55; a coupler represented by formula (I) in paragraph 0008 of JP-A-4-274425; Couplers according to claim 1 of page 4 of EP 498,381A1 (especially D-35 on page 18); couplers of formula (Y) on page 4 of EP 447,969A1 (especially Y-1 (page 17), Y- 54 (p. 41)); US
Couplers represented by formulas (II) to (IV) at 4,476,219, column 7, lines 36 to 58 (especially II-17,19 (column 17), II-24 (column 19)). Magenta coupler; JP-A-3-39737 (L-57 (bottom right of page 11), L-68 (bottom right of page 12), L-77 (bottom right of page 13); EP 456,257
A-4 -63 (page 134), A-4 -73, -75 (page 139); EP 486,965.
M-4, -6 (page 26), M-7 (page 27); EP 571,959A M-45 (19
Page); (M-1) of JP-A-5-204106 (page 6); M-22 of paragraph 0237 of JP-A-4-362631. Cyan coupler: CX-1,3,4,5,11,12,1 of JP-A-4-204843
4,15 (pages 14 to 16); C-7,10 (page 35) of JP-A-4-43345, 3
4,35 (page 37), (I-1), (I-17) (pages 42 to 43); JP-A-6-67385
A coupler represented by the general formula (Ia) or (Ib) according to claim 1. Polymer coupler: JP-A-2-44345, P-1, P-5 (page 11).

Examples of couplers in which the color forming dye has an appropriate diffusibility include US 4,366,237, GB 2,125,570, EP 96,873B,
Those described in DE 3,234,533 are preferred. The coupler for correcting the unwanted absorption of the color forming dye is a yellow-colored cyan coupler represented by the formulas (CI), (CII), (CIII) and (CIV) described on page 5 of EP 456,257A1 (especially on page 84). YC-86), the EP
Yellow colored magenta coupler ExM-7 (202
Page), EX-1 (page 249), EX-7 (page 251), US 4,833,069
Magenta colored cyan coupler CC-9 (column
8), CC-13 (column 10), US 4,837,136 (2) (column 8),
The colorless masking couplers represented by formula (A) in claim 1 of WO92 / 11575 (in particular, the exemplified compounds on pages 36 to 45) are preferred. Examples of the compound (including a coupler) which reacts with an oxidized product of a developing agent to release a photographically useful compound residue include the following. Development inhibitor releasing compound: EP 37
Compounds represented by formulas (I), (II), (III) and (IV) described on page 11 of 8,236A1 (particularly T-101 (page 30), T-104 (page 31), T-113 ( 36
Page), T-131 (page 45), T-144 (page 51), T-158 (page 58)), EP436, 93
Compounds represented by formula (I) on page 7 of 8A2 (especially D-4
9 (page 51)), compounds represented by formula (1) of EP 568,037A (particularly (23) (page 11)), formulas (I), (II), and EP 440,195A2 on pages 5 to 6, Compounds represented by (III) (especially I- on page 29)
(1)); Bleach accelerator releasing compounds: compounds represented by formulas (I) and (I ′) on page 5 of EP 310,125A2 (particularly (60) and (6 on page 61)
1)) and a compound represented by the formula (I) of claim 1 of JP-A-6-59411 (particularly (7) (page 7); Ligand releasing compound: US
Compound represented by LIG-X described in claim 1 of 4,555,478 (especially compound on lines 21 to 41 of column 12); Leuco dye-releasing compound: compound 1 of columns 3 to 8 of US 4,749,641
~ 6; Fluorescent dye-releasing compound: C in claim 1 of US 4,774,181
Compounds represented by OUP-DYE (particularly compounds 1 to 11 in columns 7 to 10); development accelerator or fogging agent releasing compound: US
Compounds represented by formulas (1), (2), and (3) in 4,656,123, column 3 (particularly (I-22) in column 25) and EP 450,637A2
ExZK-2, lines 75-36, page 75; Compounds that release dye groups only upon elimination: Formula (I) of claim 1 of US 4,857,447
Compounds represented by (especially Y-1 to Y-19 in columns 25 to 36)
.

The following additives are preferable as additives other than the coupler. Dispersion medium of oil-soluble organic compound: P-3,5 of JP-A-62-215272
16,19,25,30,42,49,54,55,66,81,85,86,93 (140〜144
Page); Latex for impregnation of oil-soluble organic compounds: US 4,199,
Latex described in 363; Oxidized developer scavenger: a compound represented by the formula (I) in column 2, lines 54 to 62 of US Pat. ) (Column 4-
5), US Pat. No. 4,923,787, column 2, lines 5-10 (especially compound 1 (column 3); stain inhibitor: EP 298321A, 4).
Formulas (I)-(III) on pages 30-33, especially I-47, 72, III-1, 27 (24
~ Page 48); Anti-fading agent: A-6,7,20,21,23,2 of EP 298321A
4,25,26,30,37,40,42,48,63,90,92,94,164 (69〜118
Pp.), US 5,122,444, columns 25-38, II-1 to III-23, especially
III-10, EP 471347A, pages 8-12, I-1 to III-4, especially II-
2, US 5,139,931 columns 32-40 A-1 to 48, especially A-39,
42; Materials that reduce the use of color-enhancing agents or color-mixing inhibitors: I-1 to II-15 on pages 5 to 24 of EP 411324A, especially I-4
6; Formalin scavenger: EP 477932A, pages 24 to 29, SCV-1 to 28, especially SCV-8; Hardener: JP-A 1-214845
Formulas in columns 13-23 of H-1,4,6,8,14, US 4,618,573 on page 17
Compounds (H-1 to 54) represented by (VII) to (XII), JP-A-2-
214852, page 8, lower right, compound represented by formula (6) (H-1 to 7
6), especially the compound described in claim 1 of H-14, US 3,325,287; Development inhibitor precursor: P-2 of JP-A-62-168139
4,37,39 (pages 6-7); compounds as claimed in claim 1 of US 5,019,492, in particular column 7, 28,29; preservatives, fungicides: US
4,923,790 columns 3 to 15 I-1 to III-43, especially II-1,
9,10,18, III-25; Stabilizers, antifoggants: US 4,923,79
I-1 to (14) in columns 6 to 16 of 3, especially I-1,60, (2), (13), U
S 4,952,483 columns 25-32 compounds 1-65, especially 36:
Chemical sensitizer: triphenylphosphine selenide, compound 50 of JP-A-5-40324; dye: 15-18 of JP-A-3-156450
A-1 to b-20, especially a-1,12,18,27,35,36, b-5,27 to 29
Pages V-1 to 23, especially V-1, EP 445627A pages 33 to 55 FI-
1 to F-II-43, especially FI-11, F-II-8, EP 457153A 17 to 28
Pages III-1 to 36, especially III-1,3, WO 88/04794 8-26
Microcrystalline dispersion of Dye-1 to 124, compounds 1 to 22 of EP 319999A, pages 6 to 11, especially compound 1, compounds D-1 to 87 (3) represented by formulas (1) to (3) of EP 519306A. ~ Page 28), US 4,26
Compounds 1-22 represented by formula (I) of 8,622 (columns 3-1
0), a compound (1) represented by the formula (I) of US 4,923,788 ~
(31) (Columns 2 to 9); UV absorber: Formula of JP-A-46-3335
Compounds (18b) to (18r), 101 to 427 (6 to
(Page 9), compounds (3) to (6 represented by formula (I) of EP 520938A.
6) (pages 10 to 44) and the compound HBT-1 represented by the formula (III).
~ 10 (page 14), compounds represented by formula (1) of EP 521823A
(1) to (31) (columns 2 to 9).

The present invention can be applied to various color light-sensitive materials such as general or movie color negative films, slide or television color reversal films, color papers, color positive films and color reversal papers. In addition, Japanese Patent Publication No.
Suitable for the lens-fitted film unit described in 3-39784. Suitable supports that can be used in the present invention include
For example, the RD. No. 17643, page 28, No. 18716
Page 647, right column to page 648, left column, and No. 307105, 879
Page. In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, more preferably 23 μm or less,
It is more preferably not more than μm, particularly preferably not more than 16 μm.
The film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. T _1/2 is a color developer at 30 ° C for 3 minutes 15
When 90% of the maximum swollen film thickness reached at the time of second treatment is taken as the saturated film thickness, it is defined as the time until the film thickness reaches 1/2. The film thickness means the film thickness measured under a humidity condition of 25 ° C. and 55% relative humidity (2 days), and T _1/2 is A Green (A.
Green) et al. Photographic Science and
Engineering (Photogr.Sci.Eng.), 19 squares, 2,124
It can be measured by using a swellometer of the type described on page 129. T _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or changing the aging condition after coating.
The swelling rate is preferably 150 to 400%. What is swelling rate?
It can be calculated from the maximum swollen film thickness under the conditions described above by the formula: (maximum swollen film thickness-film thickness) / film thickness. The photographic material of the present invention is preferably provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer. This back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, and surface active agent. The swelling ratio of this back layer is preferably 150 to 500%.

Next, the magnetic recording layer used in the present invention will be described. The magnetic recording layer used in the present invention is one in which an aqueous or organic solvent-based coating liquid in which magnetic particles are dispersed in a binder is coated on a support. Magnetic particles used in the present invention include ferromagnetic iron oxide such as γFe ₂ O _3, Co deposited γFe ₂ O _3, Co coated magnetite ,, Co-containing magnetite, ferromagnetic chromium dioxide, ferromagnetic metal, ferromagnetic Alloys, hexagonal Ba ferrite, Sr ferrite, Pb ferrite, Ca ferrite, etc. can be used. Co deposition γFe ₂ O
Co-coated ferromagnetic iron oxides such as ₃ are preferred. The shape may be needle-like, rice grain-like, spherical, cubic, plate-like or the like. The specific surface area of S _BET is preferably 20 m ² / g or more, 30 m ²
/ g or more is particularly preferable. The saturation magnetization (σs) of a ferromagnet is
It is preferably 3.0 × 10 ⁴ to 3.0 × 10 ⁵ A / m, and particularly preferably 4.0 × 10 ^{4 to} 2.5 × 10 ⁵ A / m. The ferromagnetic particles may be surface-treated with silica and / or alumina or an organic material. Further, magnetic particles are disclosed in JP-A-6-
The surface may be treated with a silane coupling agent or a titanium coupling agent as described in 161032. Further, magnetic particles having a surface coated with an inorganic or organic material described in JP-A-4-259911 and 5-81652 can also be used.

Next, the binder used for the magnetic particles is
Thermoplastic resin described in JP-A-4-219569, thermosetting resin,
Radiation curable resins, reactive resins, acids, alkalis or biodegradable polymers, natural polymers (cellulose derivatives, sugar derivatives, etc.) and mixtures thereof can be used. The Tg of the above resin is -40 ℃ ~ 300 ℃, the weight average molecular weight is
It is 20,000 to 1 million. Examples thereof include vinyl copolymers, cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose tripropionate, and other cellulose derivatives, acrylic resins, polyvinyl acetal resins, and gelatin is also preferable. Cellulose di (tri) acetate is particularly preferable. The binder can be hardened by adding an epoxy-based, aziridine-based, or isocyanate-based crosslinking agent. As the isocyanate-based cross-linking agent, tolylene diisocyanate,
Isocyanates such as 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate, and reaction products of these isocyanates and polyalcohols (for example, a reaction product of 3 mol of tolylene diisocyanate and 1 mol of trimethylolpropane). ), And polyisocyanates produced by condensation of these isocyanates, and are described in, for example, JP-A-6-59357.

As a method for dispersing the above-mentioned magnetic material in the binder, a kneader, a pin type mill, an annular type mill, etc. are preferable and a combination thereof is also preferable, as in the method described in JP-A-6-35092. The dispersant described in JP-A-5-088283 and other known dispersants can be used. The thickness of the magnetic recording layer is 0.1 μm to 10 μm, preferably 0.2 μm to 5 μm
m, more preferably 0.3 μm to 3 μm. The weight ratio of the magnetic particles and the binder is preferably 0.5: 100 to 60: 100.
And more preferably 1: 100 to 30: 100. The coating amount of magnetic particles is 0.005 to 3 g / m ² , preferably 0.01 to 2
g / m ² , more preferably 0.02 to 0.5 g / m ² . The magnetic recording layer used in the present invention can be provided on the back surface of the photographic support by coating or printing and provided in the entire surface or in a stripe shape. As a method of applying the magnetic recording layer, an air doctor, a blade, an air knife, a squeeze, an impregnation, a reverse roll, a transfer roll, a gravure, a kiss,
Cast, spray, dip, bar, extrusion and the like can be used, and the coating liquid described in JP-A-5-341436 is preferable.

The magnetic recording layer has improved lubricity, curl adjustment,
It may have functions such as antistatic, anti-adhesion and head polishing, or may be provided with another functional layer to impart these functions, and at least one kind of particles has a Mohs hardness of 5 or more. The above-mentioned non-spherical inorganic particle abrasives are preferable. As the composition of the non-spherical inorganic particles, oxides such as aluminum oxide, chromium oxide, silicon dioxide, titanium dioxide, and silicon carbide, carbides such as silicon carbide and titanium carbide, and fine powders such as diamond are preferable. The surface of these abrasives may be treated with a silane coupling agent or a titanium coupling agent. These particles may be added to the magnetic recording layer, or may be overcoated (for example, a protective layer, a lubricant layer, etc.) on the magnetic recording layer. As the binder used at this time, the above-mentioned binders can be used, and preferably the same binder as that of the magnetic recording layer is used. US Pat. No. 5,336,589, US Pat. No. 5,250,404, US Pat.
5,229,259, 5,215,874 and EP 466,130.

Next, the polyester support used in the present invention will be described. For details, including the light-sensitive material, processing, cartridges and examples described later, open technical report, official technique number 94-6023 (Invention Society; 1994.3). .15.).
The polyester used in the present invention is formed by using a diol and an aromatic dicarboxylic acid as essential components, and the aromatic dicarboxylic acid is 2,6-, 1,5-, 1,4-, and 2,7.
-Naphthalenedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, diethylene glycol as diol,
Examples include triethylene glycol, cyclohexanedimethanol, bisphenol A, and bisphenol.
Examples of the polymerized polymer include homopolymers such as polyethylene terephthalate, polyethylene naphthalate, and polycyclohexanedimethanol terephthalate. Particularly preferred is a polyester containing 50 to 100 mol% of 2,6-naphthalenedicarboxylic acid. Among them, polyethylene 2,6-naphthalate is particularly preferable. Average molecular weight ranges from about 5,000 to
It is 200,000. The polyester of the present invention has a Tg of 50 ° C or higher, preferably 90 ° C or higher.

Next, the polyester support is subjected to a heat treatment at a heat treatment temperature of 40 ° C. or higher and lower than Tg, more preferably Tg−20 ° C. or higher and lower than Tg in order to prevent the curling tendency. The heat treatment may be performed at a constant temperature within this temperature range, or the heat treatment may be performed while cooling. The heat treatment time is 0.1 hour or more and 1500 hours or less, and more preferably 0.5 hour or more and 200 hours or less. The heat treatment of the support may be carried out in the form of a roll or may be carried out while being conveyed in the form of a web.
Irregularity may be imparted to the surface (for example, conductive inorganic fine particles such as SnO ₂ or Sb ₂ O ₅ may be applied) to improve the surface state. Further, it is desirable to devise a technique such as giving a knurl to the end and slightly raising only the end to prevent the cut end of the winding core from being exposed. These heat treatments are after the support film formation, the surface treatment,
It may be carried out at any stage after coating the back layer (antistatic agent, slip agent, etc.) and after coating the undercoat layer. Preferred is after the antistatic agent is applied. An ultraviolet absorber may be kneaded into this polyester. Also, to prevent light piping,
The purpose can be achieved by kneading a commercially available dye or pigment for polyester such as Diaresin manufactured by Mitsubishi Kasei or Kayaset manufactured by Nippon Kayaku.

Next, in the present invention, it is preferable to carry out a surface treatment in order to bond the support and the light-sensitive material constituting layer. Chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment,
Surface activation treatments such as laser treatment, mixed acid treatment and ozone oxidation treatment can be mentioned. Among the surface treatments, ultraviolet irradiation treatment, flame treatment, corona treatment and glow treatment are preferable. Next, the undercoating method may be a single layer or two or more layers. As the binder for the undercoat layer, vinyl chloride, vinylidene chloride, butadiene, methacrylic acid,
Starting with copolymers starting from monomers selected from acrylic acid, itaconic acid, maleic anhydride and the like, polyethyleneimine, epoxy resins, grafted gelatin, nitrocellulose and gelatin are listed. Compounds that swell the support include resorcin and p-chlorophenol. As a gelatin hardening agent for the undercoat layer, chromium salts (chrome alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, active halogen compounds (2,4-dichloro-6-) are used.
(Hydroxy-S-triazine, etc.), epichlorohydrin resin, active vinyl sulfone compound and the like. SiO ₂ , TiO ₂ , inorganic fine particles or polymethylmethacrylate copolymer fine particles (0.01 to 10 μm) may be contained as a matting agent.

In the present invention, an antistatic agent is preferably used. Examples of these antistatic agents include carboxylic acids and carboxylates, polymers containing sulfonates, cationic polymers, and ionic surfactant compounds. The most preferred antistatic agent is Z
nO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO,
At least one selected from MoO ₃ and V ₂ O ₅ has a volume resistivity of 10 ⁷ Ω · cm or less, more preferably 10 ⁵ Ω · cm or less, and a particle size of 0.001 to 1.0 μm crystalline metal. Fine particles of oxides or their complex oxides (Sb, P, B, In, S, Si, C, etc.), and further sol-like metal oxides or fine particles of these complex oxides. The content in the sensitive material is 5 to
500 mg / m ² are preferred and particularly preferably 10 to 350 mg / m ^2. The ratio of the conductive crystalline oxide or its composite oxide to the binder is preferably 1/300 to 100/1, more preferably 1/100 to 100/5.

The light-sensitive material of the present invention preferably has a slip property. The slip agent-containing layer is preferably used on both the photosensitive layer surface and the back surface. The preferred sliding property is a dynamic friction coefficient of 0.
25 or less and 0.01 or more. The measurement at this time represents the value when the stainless steel ball with a diameter of 5 mm is transported at 60 cm / min (25
℃, 60% RH). In this evaluation, even if the photosensitive material surface is replaced as the mating material, the values are almost the same. Examples of slip agents that can be used in the present invention include polyorganosiloxanes, higher fatty acid amides, higher fatty acid metal salts, and esters of higher fatty acids and higher alcohols. Polyorganosiloxanes include polydimethylsiloxane, polydiethylsiloxane, and polydiethylsiloxane. Styrylmethyl siloxane, polymethylphenyl siloxane, etc. can be used. The addition layer is preferably the outermost layer of the emulsion layer or the back layer. Particularly, polydimethylsiloxane and ester having a long chain alkyl group are preferable.

The photosensitive material of the present invention preferably contains a matting agent. The matting agent may be either on the emulsion side or the back side, but it is particularly preferable to add it to the outermost layer on the emulsion side.
The matting agent may be soluble in the treatment liquid or insoluble in the treatment liquid, and preferably both are used in combination. For example, polymethylmethacrylate, poly (methylmethacrylate / methacrylic acid = 9/1 or 5/5 (molar ratio)), polystyrene particles and the like are preferable. The particle size is preferably 0.8 to 10 μm, and the particle size distribution is preferably narrow, and the average particle size is 0.9 to 1.
It is preferable that 90% or more of the total number of particles be contained in one time. It is also preferable to add fine particles of 0.8 μm or less at the same time in order to enhance the matting property. For example, polymethylmethacrylate (0.2 μm), poly (methylmethacrylate /
Methacrylic acid = 9/1 (molar ratio), 0.3 μm)), polystyrene particles (0.25 μm), and colloidal silica (0.03 μm).

Next, the film cartridge used in the present invention will be described. The main material of the cartridge used in the present invention may be metal or synthetic plastic. Preferred plastic materials are polystyrene, polyethylene, polypropylene, polyphenyl ether and the like. Further, the cartridge of the present invention may contain various antistatic agents, and carbon black, metal oxide particles, nonions, anions, cations and betaine-based surfactants or polymers can be preferably used. These antistatic patrones are described in JP-A 1-312537 and 1-312538. Particularly, the resistance at 25 ° C. and 25% RH is preferably 10 ¹² Ω or less. Usually, a plastic patrone is manufactured by using a plastic in which carbon black, a pigment and the like are kneaded in order to impart a light shielding property. The size of the Patrone can be left at 135 at the moment, or to make the camera smaller,
It is also effective to reduce the diameter of the current 135 size 25 mm cartridge to 22 mm or less. The volume of the case of the cartridge is 30 cm ³ or less, preferably 25 cm ³ or less. The weight of the plastic used in the cartridge and cartridge case is preferably 5 to 15 g.

Further, the cartridge used in the present invention may be one that rotates the spool to feed the film. Further, the structure may be such that the leading end of the film is housed in the cartridge body and the leading end of the film is fed to the outside from the port portion of the cartridge by rotating the spool shaft in the feeding direction of the film. These are disclosed in US 4,834,306 and 5,226,613. The photographic film used in the present invention may be a so-called raw film before development, or may be a photographic film subjected to development processing. The raw film and the developed photographic film may be stored in the same new cartridge,
Different patrones may be used.

[0122]

EXAMPLES The present invention will be described in more detail with reference to specific examples, but the invention is not limited to the examples as long as the gist of the invention is not exceeded. Example 1 1) Support The support used in this example was prepared by the following method. Polyethylene-2,6-naphthalate polymer 100
After drying 3 parts by weight and 2 parts by weight of Tinuvin P.326 (manufactured by Ciba-Geigy Co., Ltd.) as an ultraviolet absorber, 300 ° C.
After melting at T, it is extruded from a T-die, longitudinally stretched 3.3 times at 140 ° C, then transversely stretched 3.3 times at 130 ° C, and heat-set at 250 ° C for 6 seconds to form a PEN with a thickness of 90μm.
I got a film. This PEN film contains blue dye, magenta dye, and yellow dye (I-1, I-4, I-6, I-24, I-26, I- in Public Technical Report No. 94-6023). 27, II-5)
Was added in an appropriate amount. Furthermore, it was wound on a stainless steel core having a diameter of 20 cm and subjected to a heat history of 110 ° C. for 48 hours to obtain a support with less curling tendency.

2) Coating of undercoat layer The above-mentioned support was subjected to corona discharge treatment, UV discharge treatment and glow discharge treatment on both surfaces thereof, and then gelatin 0.1 g / m ² and sodium α-sulfodione were formed on each surface. -2-ethylhexyl succinate 0.01 g / m ² , salicylic acid 0.04 g / m ² , p
-Chlorophenol 0.2 g / m ² , (CH ₂ = CHSO ₂ CH ₂ CH ₂ NHCO) ₂
CH ₂ 0.012 g / m ² , a polyamide-epichlorohydrin polycondensate 0.02 g / m ² undercoat liquid was applied (10 cc / m ² , using a bar coater), and an undercoat layer was provided on the high temperature surface side during stretching. Dry 1
The test was carried out at 15 ° C for 6 minutes (the temperature of the rollers and the conveying device in the drying zone are 115 ° C). 3) Coating of back layer After the undercoating, an antistatic layer having the following composition, a magnetic recording layer and a sliding layer were coated as back layers on one surface of the support.

3-1) Coating of antistatic layer A tin oxide-antimony oxide composite having an average particle diameter of 0.005 μm has a specific resistance of 5 Ω · cm and is a dispersion of fine particle powder (secondary agglomerated particle diameter of about 0.08 μm). 0.2 g / m ^2, gelatin 0.05g / m ^2, (C
H ₂ = CHSO ₂ CH ₂ CH ₂ NHCO) ₂ CH ₂ 0.02g / m ² , poly (degree of polymerization 1
0) Oxyethylene-p-nonylphenol 0.005g / m ²
And Resorcin. 3-2) Coating of magnetic recording layer 3-Poly (degree of polymerization 15) Cobalt-γ-iron oxide coated with oxyethylene-propyloxytrimethoxysilane (15% by weight) (specific surface area 43 m ² / g, Long axis 0.14μm, uniaxial 0.03μm, saturation magnetization 89emu / g, Fe ^{+ 2} / Fe ⁺³ = 6/94, surface is treated with aluminum oxide silicon oxide at 2% by weight of iron oxide) 0.06g / m ² is diacetyl cellulose 1.2 g / m ² (iron oxide was dispersed in an open kneader and a sand mill), C ₂ H ₅ C (CH ₂ OCONH-C ₆ H ₃ (CH ₃ ) NCO) ₃ as a curing agent
0.3 g / m ² was applied with a bar coater using acetone, methyl ethyl ketone, and cyclohexanone as a solvent,
A magnetic recording layer having a thickness of 1.2 μm was obtained. As a matting agent, silica particles (0.3 μm) and abrasive aluminum oxide (0.15 μm) coated with 3-poly (polymerization degree 15) oxyethylene-propyloxytrimethoxysilane (15% by weight) were coated, respectively.
It was added at 10 mg / m ² . Drying was carried out at 115 ° C for 6 minutes (all rollers and conveyors in the drying zone are 115
° C). The color density increase of D ^B of the magnetic recording layer by the X-light (blue filter) is about 0.1, the saturation magnetization moment of the magnetic recording layer is 4.2 emu / g, the coercive force is 7.3 × 10 ⁴ A / m, and the squareness ratio is Was 65%.

3-3) Preparation of sliding layer Diacetyl cellulose (25 mg / m ² ), C ₆ H ₁₃ CH (OH) C ₁₀ H ₂₀ C
OOC ₄₀ H ₈₁ (Compound a, 6 mg / m ² ) / C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₆ H
The (compound b, 9 mg / m ² ) mixture was applied. This mixture is xylene / propylene monomethyl ether (1/1)
It was melted at 105 ° C. in water, poured into and dispersed in propylene monomethyl ether (10 times amount) at room temperature to prepare a dispersion (average particle diameter 0.01 μm) in acetone, and then added. Silica particles (0.3 μm) as a matting agent and 3-poly (polymerization degree 15) oxyethylene-propyloxytrimethoxysilane (aluminum oxide coated with 15% by weight (0.15 μm) as an abrasive were 15 mg / m ² and The amount of drying was 115
C., 6 minutes (115 ° C. for all rollers and conveyors in the drying zone). The sliding layer had an excellent dynamic friction coefficient of 0.06 (stainless steel ball of 5 mmφ, load 100 g, speed of 6 cm / min), static friction coefficient of 0.07 (clip method), and the dynamic friction coefficient of the emulsion surface, which will be described later, was 0.12. .

4) Coating of Photosensitive Layer Next, on the opposite side of the back layer obtained above, each layer having the following composition was multilayer coated to form a color negative film.
This is designated as Sample 101.

(Photosensitive layer composition) The main materials used for each layer are classified as follows: ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling organic solvent ExY: Yellow coupler H: Gelatin hardening agent ExS: Sensitizing dye The numeral corresponding to each component indicates the coating amount expressed in g / m ² , and for silver halide, the coating amount in terms of silver. However, for the sensitizing dye, the coating amount is shown in mol units with respect to 1 mol of silver halide in the same layer.

First layer (antihalation layer) Black colloidal silver Silver 0.09 Gelatin 1.60 ExM-1 0.12 ExF-1 2.0 × 10 ^-3 Solid disperse dye ExF-2 0.030 Solid disperse dye ExF-3 0.040 HBS-1 0.15 HBS- 2 0.02

Second layer (intermediate layer) Silver iodobromide emulsion M Silver 0.065 ExC-2 0.04 Polyethyl acrylate latex 0.20 Gelatin 1.04

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Silver Iodobromide Emulsion A Silver 0.25 Silver Iodobromide Emulsion B Silver 0.25 ExS-1 6.9 × 10 ^-5 ExS-2 1.8 × 10 ^-5 ExS-3 3.1 × 10 ^-4 ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-6 0.010 Cpd-2 0.025 HBS-1 0.10 Gelatin 0.87

Fourth Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Silver Iodobromide Emulsion C Silver 0.70 ExS-1 3.5 × 10 ^-4 ExS-2 1.6 × 10 ^-5 ExS-3 5.1 × 10 ^-4 ExC-1 0.13 ExC-2 0.060 ExC-3 0.0070 ExC-4 0.085 ExC-5 0.015 ExC-6 0.0070 Cpd-2 0.023 HBS-1 0.10 Gelatin 0.74

Fifth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion D Silver 1.40 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-4 ExS-3 3.4 × 10 ^-4 ExC-1 0.10 ExC-3 0.045 ExC-6 0.020 ExC-7 0.010 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.050 Gelatin 1.10

Sixth layer (intermediate layer) Cpd-1 0.090 Solid disperse dye ExF-4 0.030 HBS-1 0.050 Polyethyl acrylate latex 0.15 Gelatin 1.10

Seventh Layer (Low Sensitivity Green Sensitive Emulsion Layer) Silver iodobromide emulsion E Silver 0.15 Silver iodobromide emulsion F Silver 0.10 Silver iodobromide emulsion G Silver 0.10 ExS-4 3.0 × 10 ^-5 ExS-5 2.1 × 10 ^-4 ExS-6 8.0 × 10 ^-4 ExM-2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73

Eighth Layer (Medium-Sensitivity Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion H Silver 0.80 ExS-4 3.2 × 10 ^-5 ExS-5 2.2 × 10 ^-4 ExS-6 8.4 × 10 ^-4 ExC-8 0.010 ExM-2 0.10 ExM-3 0.025 ExY-1 0.018 ExY-4 0.010 ExY-5 0.040 HBS-1 0.13 HBS-3 4.0 × 10 ^-3 Gelatin 0.80

Ninth layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion I Silver 1.25 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3.2 × 10 ^-4 ExC-1 0.010 ExM-1 0.020 ExM-4 0.025 ExM-5 0.040 Cpd-3 0.040 HBS-1 0.25 Polyethyl acrylate latex 0.15 Gelatin 1.33

10th layer (yellow filter layer) Yellow colloidal silver Silver 0.015 Cpd-1 0.16 Solid disperse dye ExF-5 0.060 Solid disperse dye ExF-6 0.060 Oil-soluble dye ExF-7 0.010 HBS-1 0.60 Gelatin 0.60

11th layer (low-sensitivity blue emulsion layer) Silver iodobromide emulsion J Silver 0.09 Silver iodobromide emulsion K Silver 0.09 ExS-7 8.6 × 10 ^-4 ExC-8 7.0 × 10 ^-3 ExY-1 0.050 ExY-2 0.22 ExY-3 0.50 ExY-4 0.020 Cpd-2 0.10 Cpd-3 4.0 × 10 ^-3 HBS-1 0.28 Gelatin 1.20

12th layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion L Silver 1.00 ExS-7 4.0 × 10 ^-4 ExY-2 0.10 ExY-3 0.10 ExY-4 0.010 Cpd-2 0.10 Cpd-3 1.0 × 10 ^-3 HBS-1 0.070 Gelatin 0.70

Thirteenth layer (first protective layer) UV-1 0.19 UV-2 0.075 UV-3 0.065 HBS-1 5.0 × 10 ^-2 HBS-4 5.0 × 10 ^-2 gelatin 1.8

14th layer (second protective layer) Silver iodobromide emulsion M Silver 0.10 H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.15 B-3 0.05 S-1 0.20 Gelatin 0.80

Further, in order to improve the storability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property of each layer, W-1 to W-3, B-4 to B- may be used. 6, F
-1 to F-17 and iron salt, lead salt, gold salt, platinum salt,
It contains a palladium salt, an iridium salt, and a rhodium salt.

[0143]

[Table 1]

In Table 1, (1) Emulsions J to L were reduction-sensitized at the time of grain preparation using thiourea dioxide and thiosulfonic acid in accordance with the examples of JP-A-2-91938. (2) Emulsions A to I were subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the examples of JP-A-3-237450. ing. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the example of JP-A 1-158426. (4) Dislocation lines as described in JP-A-3-237450 are observed in the tabular grains using a high voltage electron microscope. (5) Emulsion L is a double-structured grain containing an internal high iodine core described in JP-A-60-143331.

Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 shown below was dispersed by the following method. That is, water 21.7
3 ml of 5% aqueous solution of p-octylphenoxyethoxyethoxyethaneethanesulfonate and 5 g of 5% aqueous solution of p-octylphenoxypolyoxyethylene ether (polymerization degree: 10) (0.5 g) were put in a 700 ml pot mill, and the dye was added. 5.0 g of ExF-2 and 500 ml of zirconium oxide beads (diameter 1 mm) were added and the contents were dispersed for 2 hours. A BO type vibrating ball mill manufactured by Chuo Koki was used for this dispersion. After the dispersion, the contents were taken out, added to 8 g of a 12.5% gelatin aqueous solution, and the beads were removed by filtration to obtain a gelatin dispersion of the dye. The average particle size of the dye fine particles was 0.44 μm.

Similarly, solid dispersions of ExF-3, ExF-4 and ExF-6 were obtained. The average particle diameters of the dye fine particles were 0.24 μm, 0.45 μm and 0.52 μm, respectively.
ExF-5 was dispersed by the microprecipitation dispersion method described in Example 1 of EP549,489A. The average particle size was 0.06 μm.

[0147]

[Chemical 27]

[0148]

[Chemical 28]

[0149]

[Chemical 29]

[0150]

Embedded image

[0151]

[Chemical 31]

[0152]

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[0153]

[Chemical 33]

[0154]

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[0155]

Embedded image

[0156]

Embedded image

[0157]

Embedded image

[0158]

[Chemical 38]

[0159]

[Chemical Formula 39]

[0160]

[Chemical 40]

[0161]

Embedded image

[0162]

Embedded image

The light-sensitive material prepared as described above is used in a 24 mm width,
Cut it to 160 cm, and add a 2 mm square perforation 0.7 mm from the width of one side of the photosensitive material.
Two are provided at 5.8 mm intervals. We have made a set of these two sets at intervals of 32 mm, and are shown in FIGS. 1 to 7 of US 5,296,887.
It was placed in the plastic film cartridge described in. An FM signal was recorded on this sample at a feed rate of 1,000 / s during the above-mentioned perforation of the photosensitive material by using a head gap of 2,000 turns and a head gap of 5 μm from the coated surface side of the magnetic recording layer.

After recording the FM signal, the color temperature was changed from the photosensitive layer side to 4
Wedge exposure was performed with 800 K white light, and the development processing described below was performed. After the treatment, the absorption density of magenta was measured to obtain a characteristic curve, and the absorption density (D) of magenta at an exposure dose of 0.20 cms was calculated. Development process and processing liquid composition Processing process Temperature Time Color development 45 ℃ 60 seconds Bleach fixing 40 ℃ 50 seconds Stable (1) 40 ℃ 15 seconds Stable (2) 40 ℃ 15 seconds Stable (3) 40 ℃ 15 seconds Stabilization 40 ℃ 15 seconds Dry 80 ℃ 60 seconds (Stabilization was a 3 tank counter current system from (3) to (1).) Crossover time of each process is 5 seconds, this time is the previous process Included in the processing time.

Liquid composition (color developer) Tank liquid (g) Diethylenetriaminepentaacetic acid 2.0 1-Hydroxyethylidene-1,1 diphosphonic acid 3.3 Sodium sulfite 3.9 Potassium carbonate 37.5 Potassium bromide 2.5 Potassium iodide 1.3 mg Disodium N, N -Bis (sulfonate ethyl) hydroxylamine 15.0 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 12.0 (0.041M) Water was added to 1.0 liter pH (potassium hydroxide 10.05 (bleach-fixing solution) (unit mol) ethylenediamine- (2-carboxyphenyl) -N, N ', N'-triacetic acid 0.17 ferric nitrate nonahydrate 0.15 ammonium thiosulfate 1.25 ammonium sulfite 0.10 Metacarboxybenzenesulfinic acid 0.05 Add water 1.0 liter pH (with acetic acid and ammonia Preparation) 5.8

(Stabilizing Solution) (Unit: g) Sodium p-toluenesulfinate 0.03 1,2-benzisothiazolin-3-one 0.05 Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization 10) 0.2 Succinic acid 1.0 Chlorine Sodium isocyanurate 0.02 1000 ml pH (with ammonia / sulfuric acid) 6.5

The present inventor set the mixing amount to be guaranteed as follows, based on the crossover time and the probability of mixing the liquid between adjacent baths. That is, the crossover time is 1
When 0 seconds, the mixture of the after-bath is 0.2 ml per liter of the previous bath, and when 7 seconds is 0.4 ml, 5
It was concluded that the product could not be put on the market if it was not guaranteed against the mixture of 0.7 ml per second, 1.2 ml per second, and 2.0 ml per second. Therefore, a bleach-fixing solution was added to the color developing solution as shown in Table 2 to determine the increase value (ΔD) of the magenta absorption density at an exposure amount of 0.20 cms. Next, the silver halide (AgX) solvent (B-3) of the present invention was added to the color developing solution in an amount of 1.
Except for the addition of 0 mmol / l,
A bleach-fixing solution was added to the color developing solution as shown in Table 2, and ΔD was similarly determined. The results obtained are summarized in Table 2.

[0168]

[Table 2]

The smaller the ΔD, the smaller the fluctuation of the photographic property even if the bleach-fix solution is mixed. From the results of Table 2, the AgX solvent (B-3) of the present invention was added to the color developing solution.
It can be seen that the addition of is significantly reduced in the fluctuation of photographic properties due to the incorporation of the bleach-fixing solution. The effect of the present invention becomes more prominent when mixing is easier, that is, when the crossover time is shorter.

Example 2 In Experiment 09 of Example 1, the AgX solvent of the present invention (B
-3) was changed as shown in Table 3 in exactly the same manner, and the increase value (ΔD) of the magenta density with respect to the time when the bleach-fixing solution was not added was determined. Table 3 shows the obtained results.

[0171]

[Table 3]

Similarly, for the AgX solvents other than (B-3) of the present invention, the effect of remarkably reducing the fluctuation of photographic properties due to the incorporation of the bleach-fix solution was observed.

Example 3 Sample 101 of Example 1 was exposed to white light having a color temperature of 4800K from the photosensitive layer uniformly over the entire surface for 1000 cms, and then the amount of ammonium thiosulfate added to the bleach-fixing solution of Example 1 was changed. Development processing was performed in exactly the same manner except that the changes were made as shown in Table 4. After the processing, the amount of silver remaining in the light-sensitive material was measured by a fluorescent X-ray analysis method to determine the amount of residual silver. Further, as shown in Table 4, 1.2 ml (each liter of color developing solution) of the bleach-fixing solution in which the addition amount of thiosulfate was changed was added to each color developing solution,
The magenta density increase value (ΔD) was obtained in the same manner as in Example 1 except that desilvering was performed with each bleach-fixing solution. The results obtained are summarized in Table 4.

[0174]

[Table 4]

From the results shown in Table 4, it is understood that the processing method of the present invention markedly reduces the amount of residual silver and also makes little change in photographic properties when the bleach-fixing solution is mixed. The effect of the present invention is remarkably observed when the thiosulfate concentration of the bleach-fixing solution is 1.0 to 2.0 mmol / l, and particularly remarkably when it is 1.2 to 1.6 mmol / l. .

Example 4 With respect to the AgX solvent of the present invention used in Example 2, the desilvering property and the change in photographic property upon incorporation of a bleach-fixing solution were examined in the same manner as in Example 3, and AgX of the present invention was found. Similar to the solvent (B-3), the effect of the present invention was remarkably observed.

Example 5 Sample 101 of Example 1 was subjected to FM signal recording, and then uniformly exposed to 1000 cms over the entire surface with white light having a color temperature of 4800K from the photosensitive layer side in the same manner as in Example 3 and then The running process (until the cumulative replenishment amount of the color developing solution becomes 3 times the tank capacity) was developed by a cine type automatic processor.

(Processing process) Processing process Temperature Time Replenishment amount * Color development 45 ° C 55 sec 10 ml Bleach fixing 45 ° C 55 sec 10 ml Stability (1) 45 ° C 13 sec --Stability (2) 45 ° C 13 sec --Stability (3) 10 seconds at 45 ℃, 30 milliliters Drying at 75 ℃ for 30 seconds-(Stability is 3 tank countercurrent method from (3) to (1).) * 24mm × 160cm per bottle

The composition of each processing liquid is as follows. (Color developer) (Unit: g) Tank solution Replenisher Diethylenetriaminepentaacetic acid 4.0 4.0 4,5-Dihydroxybenzene-1,3-disulfonic acid disodium salt 0.5 0.5 Sodium sulfite 4.0 8.0 Potassium carbonate 38.0 38.0 Potassium bromide 2.0- Potassium iodide 1.3 mg-Disodium N, N-bis (sulfonate ethyl) hydroxylamine 15.0 20.0 2-Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 11.0 ( 0.038M) 14.5 Add water 1.0 liter 1.0 liter pH (adjust with potassium hydroxide and sulfuric acid) 10.05 10.40

(Bleaching Fixing Solution) (Unit: g) Tank Solution Replenishing Solution 2-{[1- (carboxyethyl) -carboxymethylamino] ethyl} -carboxymethylaminoiron (III) ammonium benzoate monohydrate 0.08 mol 0.10 Ammonium iron (III) tetraacetate diammonium dihydrate 0.10 mol 0.12 mol Ammonium thiosulfate 0.50 mol 0.60 mol Ammonium iodide 1.0 ---- Ammonium sulfite 20.0 50.0 Ammonium methanethiosulfinate 5.0 7.0 Succinic acid 12.0 12.0 Add water 1.0 Liter 1.0 liter pH (adjusted with nitric acid and ammonia water) 6.0 5.5

(Stabilizing Solution) The tank solution and the replenishing solution have the same formulation (unit: g) sodium p-toluenesulfinate 0.03 1,2-benzisothiazolin-3-one 0.05 polyoxyethylene-p-monononylphenyl ether (average polymerization 10) 0.2 Sodium chlorinated isocyanurate 0.02 1000 ml pH 7.5 to 8.5

After the processing, the residual silver amount was obtained in the same manner as in Example 3, and the signal was read out at the same speed as when the signal was recorded by the head before the processing. Ratio (error rate) was calculated (Experiment 4
4). Further, as shown in Table 5, the addition amounts of the bleach-fixing solution tank solution and the replenishing solution ammonium thiosulfate were changed (Experiments 45 to 51), and the AgX solvent (B- 3.0 mmol / l of 3) and 3.6 of (B-3) of the present invention as a replenisher for the color developing solution.
The amount of ammonium thiosulfate added to the bleach-fix solution was changed in the same manner as in the bleach-fixing solution, except that the amount was added in millimoles / liter. The amount of residual silver and the error rate were determined (Experiments 52 to 59). It is preferable that both the residual silver amount and the error rate are small. The results obtained are shown in Table 5.

[0183]

[Table 5]

The effects of the present invention are remarkably observed even during the running process, and especially when the amount of ammonium thiosulfate added in the bleach-fixing solution (in the tank solution) is 1.0 to 2.0 mmol / liter. The amount of silver and the error rate were significantly reduced.

Example 6 In the experiment 38 of Example 3, the bleach-fix solution was mixed with A of the present invention.
An experiment was conducted in exactly the same manner except that 0.1 mol / liter of gX solvent (D-2) was added, and the residual silver amount was 2
μg / cm ^2, variation in cyan density was 0.02. From this result, the bleach-fixing solution of the present invention was added to the Ag of the present invention.
It can be seen that the addition of the X solvent further improves the desilvering property, and that the photographic property does not fluctuate little even when the bleach-fixing solution is mixed in the color developing solution.

Example 7 In Example 1 of the present application, 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate, which is a color developing agent, was used as DA-3, DA-7, DA-1
When an experiment was conducted in exactly the same manner except that the equimolar amount was changed to 0, the effect of the present invention was remarkably observed as in Example 1.

Claims (3)

[Claims] 1. A silver halide color photographic light-sensitive material having, on a transparent support, at least one silver halide emulsion layer containing a silver halide emulsion having a silver iodide content of 1 to 30 mol%. After color development processing with color developing solution,
In the method of immediately desilvering with a bleach-fix solution,
The color developer contains thiosulfate, methanethiosulfonate, thiocyanate and at least one silver halide solvent selected from the following general formulas (A) to (E), and the color developer and A method for processing a silver halide color photographic light-sensitive material, characterized in that a crossover time with a bleach-fixing solution is 10 seconds or less. General formula (A): In the formula, Q _a1 represents a nonmetallic atom group necessary for forming a 5- or 6-membered heterocycle. The heterocycle may be condensed with a carbon aromatic ring or a heteroaromatic ring. L _a1 represents a single bond, a divalent aliphatic group, a divalent aromatic hydrocarbon group, a divalent heterocyclic group, or a connecting group in which these are combined. R _a1 represents a carboxylic acid or a salt thereof, a sulfonic acid or a salt thereof, a phosphonic acid or a salt thereof, an amino group or an ammonium salt. q represents an integer of 1 to 3, M _a1 represents a hydrogen atom or a cation. General formula (B): In the formula, Q _b1 represents a 5- or 6-membered mesoionic ring composed of a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a selenium atom, and X _b1 ^— represents —O ^— , —S ^— or —N.
^- representing the R _b1. R _b1 represents an aliphatic group, an aromatic hydrocarbon group or a heterocyclic group. Formula (C) L _C1- (A _C1 -L _C2 ) _r -A _C2 -L _{C3 In the} formula, L _C1 and L _C3 may be the same or different and each is an aliphatic group, an aromatic hydrocarbon group or a heterocyclic group. Represents a cyclic group, and L _C2 represents a divalent aliphatic group, a divalent aromatic hydrocarbon group, a divalent heterocyclic linking group, or a linking group combining them. A
_C1 and A _C2 are respectively -S-, _-O- , -NR _C20- ,
-CO -, - it represents a or group composed of a combination of them - SO _2. r represents an integer of 1 to 10. However, L _C1 and L
_C3 at least one -SO ₃ M _C1, -PO ₃ M
_{C2 M C3, -NR C1 (R} C2), - N + R C3 (R C4)
^{_{(R C5) · X C1 -}} , -SO 2 NR C6 (R C7), - NR C8
_{SO 2 R C9, -CONR C10 (} R C11), - NR C12 C
_{OR C13, -SO 2 R C14,} -PO (-NR C15 (R
_C16 )) ₂ , -NR _C17 CONR _C18 ( _RC19 ), -C
It is assumed to be substituted with OOM _C4 or a heterocyclic group.
M _C1 , M _C2 , M _C3 and M _C4 may be the same or different and each represents a hydrogen atom or a counter cation. M _C1 ~ M _C20
May be the same or different and each represents a hydrogen atom, an aliphatic group or an aromatic hydrocarbon group, and X _C1 ⁻ represents a counter anion. Provided that at least one of A _C1 and A _C2 represent -S-. General formula (D) In the formula, X _d and Y _d are an aliphatic group, an aromatic hydrocarbon group, a heterocyclic group, —N (R _d1 ) R _d2 , —N (R _d3 ) N (R _d4 ) R
represents _d5 , -OR _d6 , or -SR _d7 . Note that X _d and Y _d
May form a ring but does not enolize.
However, at least one of X _d and Y _d is a carboxylic acid or a salt thereof, a sulfonic acid or a salt thereof, a phosphonic acid or a salt thereof, an amino group or an ammonium group,
It is assumed that it is substituted with at least one of the hydroxyl groups.
R _d1 , R _d2 , R _d3 , R _d4 and R _d5 represent a hydrogen atom, an aliphatic group, an aromatic hydrocarbon group or a heterocyclic group, and R _d6 and R _d6
d7 represents a hydrogen atom, a cation, an aliphatic group, an aromatic hydrocarbon group or a heterocyclic group. General formula (E) In the general formula (E), R _e1 , R _e2 , R _e3 and R _e
e4 represents a hydrogen atom, an alkyl group or an alkenyl group, respectively. 2. The bleach-fixing agent contains thiosulfate in an amount of 1.0 to
2. The method for processing a silver halide color photographic light-sensitive material according to claim 1, wherein the content is 2.0 mol / liter. 3. A silver halide color photograph according to claim 1, which has a magnetic recording layer containing magnetic grains on the side opposite to the silver halide emulsion layer with the transparent support interposed therebetween. Method of processing photosensitive material.