JP2002156733A - Processing method for silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a processing method for a silver halide color photographic sensitive material, in which a bleaching solution is less liable to become turbid and to cause precipitation, even in the case of processing using a color developing solution containing phosphate ions, and to further provide a processing method which ensures few defects due to recoloring and also ensures a slight increase of stain, even after storage under high temperature and high humidity. SOLUTION: In the processing method for a silver halide color photographic sensitive material, a bleaching solution used in a bleaching step contains at least one iron (III) complex salt of a diaminopolycarboxylic acid or a diaminobis(dialkylenedicarboxylic) acid, in which the linking group between amino nitrogen atoms comprises at least three atoms, has pH in the range of 4.0-5.5 and further contains a hydroxy fatty acid having a specified structure. The effect of this invention is enhanced by having imidazoles contained in the fixing solution.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention
And more particularly to a processing method using a bleaching solution. In particular, the present invention relates to a processing method in which desilvering property, recoloring property and stain are improved and excellent development quality is exhibited.

[0002]

2. Description of the Related Art A silver halide color photographic light-sensitive material is subjected to image exposure and then processed to obtain an image. In the processing step, processing with a bleaching solution or a fixing solution is performed after development. As the bleaching agent contained in the bleaching solution, iron (III) complex salt of ethylenediaminetetraacetic acid (EDTA) has been widely used, but from the viewpoint of speeding up the development process and reducing the amount of processing waste solution, the (III) There is a demand for a powerful bleaching agent which has a faster bleaching speed and requires less use than complex salts, and various bleaching agents have been proposed. From this viewpoint, the iron (III) complex salt of 1,3-propylenediaminetetraacetic acid (1,3-PDTA) is a particularly excellent bleaching agent, and there is an example in which the iron (III) complex salt of EDTA is used instead of the iron (III) complex salt. is increasing. However, 1,
A bleaching agent having high activity, which is quick and requires a small amount of use, represented by an iron (III) complex salt of 3-PDTA, can be used as a bleaching agent in a bleaching solution for processing using a color developing solution containing phosphate ions. It has been found that while the development processing is continuously performed, the bleaching solution is liable to become dirty or sedimented, which causes a serious problem in the case of continuous operation. Further, processing using a bleaching agent having a high activity has a disadvantage that stains are easily generated when a processed photosensitive material, that is, a color print or a developed film is stored at high temperature and high humidity. In addition, even if a highly active bleaching agent is used in combination with the above-described color developing solution, if rapid bleaching is performed, poor recoloring, that is, coloration of a dye often remains in an incomplete state. There is also.

It has been found that these weaknesses are particularly noticeable in a photosensitive material in which a large amount of developed silver is generated in a developing step, such as a color reversal photographic photosensitive material, and cause deterioration in image quality. .

[0004]

Accordingly, an object of the present invention is to provide a process using a color developing solution containing phosphate ions,
In particular, it is an object of the present invention to solve the above-mentioned deficiencies in the processing of a reversal color photographic light-sensitive material. Specifically, in the processing using the above-described color developing solution, silver halide color photographic light It is to provide a method of processing the material. It is a further object of the present invention to provide a halogen, in addition to the above, in which a color is sufficiently formed at the time of processing and the color reversal failure is small, and the stain does not increase much even after being processed and stored under high temperature and high humidity. An object of the present invention is to provide a method for processing a silver halide color photographic light-sensitive material.

[0005]

Means for Achieving the Object The present inventors have conducted intensive studies on the above-mentioned problems, and as a result, have found that iron (I)
II) Iron (II
I) It was found that when the complex salt was used in a specific pH range, the above-mentioned defects did not appear even in the treatment in combination with the above-mentioned phosphate ion-containing color developing solution, and based on this finding, a condition for further increasing the effect thereof. After repeated studies, the present invention was achieved. That is, the present invention is achieved by the processing method described below.

[0006] 1. In a method for processing a silver halide color photographic light-sensitive material having at least one processing step between the color developing step and the bleaching step, the color developing solution used in the color developing step contains 0.05 to 0. 25mo
1 / L, and the bleaching solution used in the bleaching step contains at least one iron (III) complex salt of a compound represented by the following general formula (I) or (II). At least one compound represented by the general formula [A]
0.25 mol / L, and the pH of the bleaching solution was 4.0 to 4.0.
5.5. A method for processing a silver halide color photographic light-sensitive material, wherein the method is 5.5. General formula (I)

[0007]

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In the general formula (I), A ₁ , A ₂ , A ₃ and A ₄ each represent —CH ₂ OH, —PO ₃ (M ² ) ₂ or —COOM ¹ ;
Each may be the same or different. M ¹ and M ² represent a hydrogen atom, an alkali metal atom, an ammonium group or an organic ammonium group. X ₁ is a linear or branched alkylene group having 3 to 6 carbon atoms, a saturated or unsaturated 2
Valent organic group, or _{- (B 1 O) n 5} -B 2 - represents a. n ₅ is 1 to 8
And B ₁ and B ₂ may be the same or different and each represents an alkylene group having 1 to 5 carbon atoms. n ₁ , n ₂ , n ₃ and n ₄ represent an integer of 1 or more and 10 or less,
Each may be the same or different. General formula (II)

[0009]

[Formula 4]

In the general formula (II), R ₁ , R ₂ , R ₃ , R ₄ ,
R ₅ , R ₆ , R ₇ and R ₈ are each a hydrogen atom, an alkyl group,
Represents an aromatic group or a hydroxy group. W has 3 to 3 carbon atoms
And 10 represents a divalent linking group. X ₁ and X ₂ each represent a hydrogen atom, an alkyl group, a hydroxyalkyl group or an alkoxyalkyl group. M ¹ , M ² , M ³ and M ⁴ represent a hydrogen atom, an alkali metal atom, an alkaline earth metal atom or an onium group. t and u are 1 or 0.

General formula [A] A ₅ (—COOM ⁵ ) n _{51 In} general formula [A], A ₅ is an n _51- valent organic group (provided that
Excluding an unsubstituted methyl group, an unsubstituted ethyl group and an unsubstituted ethylene group>, n ₅₁ represents an integer of 1 to 6,
M ⁵ represents an ammonium group, an organic ammonium group, an alkali metal (sodium, potassium, lithium, etc.) or a hydrogen atom.

2. The processing of a silver halide color photographic light-sensitive material as described in the above item 1, wherein the fixing solution used in the fixing step following the bleaching step contains 1 to 50 g / L of a compound selected from imidazoles. Method.

[0013] One treatment method for achieving the object of the present invention is to treat the compound represented by the general formula (I) or (II) with iron.
(III) at least one complex salt is contained, and represented by the general formula (A)
Containing at least one of the compounds at the concentration described above,
Further, this is a processing method using a bleaching solution whose pH value is also set in the above-mentioned specific region. When this bleaching solution is used, the color developing solution contains 0.05 to 0.25 mol / L of phosphate ions.
Even when the bleaching solution is contained, the bleaching solution does not become turbid during the development process. In addition, poor recoloring and stain are less likely to occur. The diaminopolycarboxylic acid compound represented by the general formula (I) or (II) is characterized by the number of constituent atoms of a linking group between two amino nitrogen atoms. Usually, when the pH of the bleaching solution is lowered, an iron compound is likely to be precipitated. Therefore, the pH of the bleaching solution usually used is 6.0 to 6.0.
Although it is about 6.8, in the above-mentioned bleaching solution composition, the stability is increased, so that precipitation and turbidity do not occur even if the pH region is set to a low region of 4.0 to 5.5. It is possible to choose a pH range, which makes the stain less likely to occur, which can have a significant effect on the object of the invention. In the present invention, the compound represented by the above general formula (I) or (II)
I) A compound selected from imidazoles as a fixing solution (or a bleach-fixing solution) containing a complex salt and a carboxylic acid represented by the general formula (A) and combined with the above bleaching solution having a specific pH value. Use of a fixing solution (or a bleach-fixing solution) having a concentration of 1 to 50 g / L further enhances the effect of the present invention.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. First, the compound represented by formula (I) will be described. In the general formula (I), A _{1 to} A ₄ may be the same or different, and each represents —CH ₂ OH, —P
O ₃ (M ² ) ₂ or —COOM ¹ is represented. M ¹ and M ² represent a hydrogen atom, an alkali metal atom (eg, sodium, potassium, etc.), an ammonium group or an organic ammonium group (eg, methyl ammonium, trimethyl ammonium, etc.).

X₁Is a straight or branched chain having 3 to 6 carbon atoms.
A alkylene group, a saturated or unsaturated organic group forming a ring, or
Is-(B₁O) n_FiveB_TwoRepresents-. B₁And B_TwoAre the same but different
And each may be an alkylene group having 1 to 5 carbon atoms
(Including substituted ones). n₁~ N_FourIs an integer from 1 to 10
Represents a number, which may be the same or different, at least
One is two or more. X₁And an alkylene group represented by
For example, ethylene, trimethylene, tetramethylene, etc.
No. Also, B₁And B_TwoAnd an alkylene group represented by
Include methylene, ethylene, trimethylene and the like.
You. X₁, B₁Or B _TwoAs a substituent of the alkylene group represented by
Is a hydroxyl group, an alkyl group having 1 to 3 carbon atoms (eg,
For example, a methyl group and an ethyl group). n_FiveIs 1
Represents an integer of 8, preferably 1 to 4. Especially preferred
Or 1-2. Hereinafter, represented by the general formula (I)
Specific examples of preferred compounds are given below, but are not limited thereto.
It is not something to be done.

[0016]

[Formula 5]

[0017]

[Formula 6]

[0018]

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[0019]

[Formula 8]

The above compounds (I-11), (I-12),
(I-13), (I-14) and (I-15) include both cis- and trans-forms.

The compound represented by the general formula [I] can be synthesized by a generally known method.

Particularly preferred compounds among the specific examples are (I
-3), (I-4), (I-8), (I-11) and (I-
16).

In the present invention, the iron (III) complex salt of the compound represented by the general formula (I) is preferably a 1: 1 complex in which the stoichiometric ratio between the iron (III) ion and the general formula (I) is 1: 1. Further, an amine, a thiocyanate group, a cyanate group, or the like may be coordinated, and the valence of either positive or negative is made neutral by a water-soluble cation or anion. Further, it may be further hydrated. Examples of the iron (III) complex of the general formula (I) are shown below, but are not limited thereto.

[0024]

[Formula 9]

[0025]

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[0026]

[Formula 11]

Next, the compound of the general formula (II) will be described. In the general formula (II), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ ,
R ₆ , R ₇ and R ₈ are each a hydrogen atom, an alkyl group, an aromatic group or a hydroxy group, and when these groups represent an alkyl group, the alkyl group is linear, branched or cyclic. And those having 1 to 10 carbon atoms are preferable. More preferably, it is a linear alkyl group, still more preferably an alkyl group having 1 to 3 carbon atoms, particularly preferably a methyl group and an ethyl group.
When R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ represent an aromatic group, the aromatic group is a monocyclic or bicyclic aryl group or an aromatic heterocyclic ring A phenyl group, a naphthyl group, and a pyridyl group, and a phenyl group is more preferable.

These R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and
The alkyl group and the aromatic group represented by R ₈ may have a substituent, and when the substituent is an alkyl group, it has 1 carbon atom.
-20, preferably 1-10 carbon atoms, more preferably 1 carbon atom
To 4, linear, branched or cyclic alkyl groups such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, lauryl Group, stearyl group, cyclohexyl group and 2-ethylhexyl group. When the substituent is an aryl group,
An aryl group having 6 to 12 carbon atoms, preferably 6 to 10 carbon atoms, more preferably 6 to 8 carbon atoms, such as a phenyl group, a tolyl group, and a cresyl group. When the substituent is an amino group, the substituent is an amino group having 0 to 20 carbon atoms, preferably 0 to 10 carbon atoms, and more preferably 0 to 6 carbon atoms, such as amino group, methylamino group, and dimethylamino. Groups, a diethylamino group, a dibutylamino group, and a dioctylamino group. When the substituent is an alkoxy group, it is an alkoxy group having 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, such as a methoxy group, an ethoxy group, a butoxy group, a propoxy group,
Lauryloxy groups. When the substituent is an aryloxy group, it has 6 to 12 carbon atoms, preferably 6 to 1 carbon atoms.
0, more preferably an aryloxy group having 6 to 8 carbon atoms, such as a phenoxy group and a tolyloxy group. When the substituent is an acyl group, it is an acyl group having 2 to 12 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, such as an acetyl group and a propanoyl group. When the substituent is an alkoxycarbonyl group, it has 2 carbon atoms.
To 12, preferably 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, such as a methoxycarbonyl group.

Other substituents include an aryloxycarbonyl group (C 7-20, preferably C 7-20)
15, particularly preferably 7 to 10 carbon atoms, for example, a phenyloxycarbonyl group), acyloxy group (2 to 12 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, for example, acetoxy group) Group), an acylamino group (2 to 10 carbon atoms, preferably 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms, for example, an acetylamino group), an alkoxycarbonylamino group (2 to 1 carbon atoms).
2, preferably 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, for example, methoxycarbonylamino group),
An aryloxycarbonylamino group (preferably having 7 to 20 carbon atoms, more preferably having 7 to 12 carbon atoms, particularly preferably having 7 to 10 carbon atoms, for example, a phenyloxycarbonylamino group), a sulfonylamino group (having 1 to 1 carbon atoms) 1
0, preferably 1 to 6 carbon atoms, more preferably 1 carbon atom
To 4, for example, a methanesulfonylamino group), a sulfamoyl group (0 to 10 carbon atoms, preferably 0 to 0 carbon atoms)
6, more preferably 0 to 4, for example, a sulfamoyl group, a methylsulfamoyl group), a carbamoyl group (1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms; For example, a carbamoyl group, a methylcarbamoyl group), an alkylthio group (having 1 to 8, preferably 1 to 6, more preferably 1 to 4 carbon atoms, such as a methylthio group, an ethylthio group, a carboxymethylthio group), an arylthio group Groups (C6-20, preferably C6-10, more preferably C6-8
For example, a phenylthio group), a sulfonyl group (1-8 carbon atoms, preferably 1-6 carbon atoms, more preferably 1-4 carbon atoms, for example, a methanesulfinyl group), and a ureido group (1-8 carbon atoms). , Preferably having 1 to 6 carbon atoms, more preferably having 1 to 4 carbon atoms, such as a ureido group,
A methylureido group), a hydroxy group, a mercapto group, a cyano group, a sulfo group, a carboxyl group, a nitro group, a hydroxamic acid group, and a heterocyclic group (eg, an imidazolyl group, a pyridyl group). Where possible, it may be a dissociated form or a salt thereof. These substituents may be further substituted with the substituents described above.

Preferably, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇
And R ₈ are a hydrogen atom or a hydroxy group. More preferably an _{R 1, R 2, R 3} , R 5, R 6, and R ₇ is a hydrogen atom, R ₄ and R ₈ is a hydrogen atom or a hydroxy group. Most preferably, all of R _{1 to} R ₈ are hydrogen atoms.

In the general formula (II), the divalent linking group represented by W can be preferably represented by the following general formula (W). Formula _{(W) - (W 1 -D} ) m- (W 2) n- In formula (W), W ₁ and W ₂ may be different even in the same, the sum of carbon atoms 3 And a preferred connecting group is a linear alkylene group having 3 to 8 carbon atoms or a branched alkylene group having 2 to 8 carbon atoms (for example, n-propylene group, i-propylene group, i-butylene group, 1,2-
Hexylene group, 3-ethylhexylene group), having 5 to 5 carbon atoms
10 cycloalkylene groups (for example, 1,2-cyclohexylene group, 1,4-cyclohexylene group), and having 6 to 6 carbon atoms.
10 arylene groups (eg, a 1,2-phenylene group,
A 1,4-o-tolylene group), an aralkylene group having 7 to 10 carbon atoms (eg, an o-xylenylene group, a 2,2-phenethylene group) or a carbonylene group.

D represents -O-, -S-, -N (Rw)-, a divalent nitrogen-containing heterocyclic group, preferably -O-, -S
-, -N (Rw)-. Rw is a hydrogen atom or -CO
OMa, -PO ₃ MbMc, -OH or -SO ₃ Md
Or an alkyl group having 1 to 8 carbon atoms (eg, a methyl group, a butyl group, a hexyl group) or a
10 aryl groups (for example, phenyl group, tolyl group, 2-
Ethylphenyl group). Preferably, Rw has 1 carbon atom
To 8 alkyl groups.

The linking group represented by W has a total carbon number of W of 1
It may have a substituent within the range of 0, and examples of the substituent include the above-mentioned substituents which may be substituted by the alkyl group or the aromatic group represented by R _{1 to} R ₈ . The divalent nitrogen-containing heterocyclic group is preferably a 5- or 6-membered ring in which the hetero atom is nitrogen, and those linked to W ₁ and W ₂ at adjacent carbon atoms such as an imidazolyl group are preferable. More preferred. Preferred W ₁ and W ₂ include an alkylene group having 2 to 4 carbon atoms.

Ma, Mb, Mc and Md each represent a hydrogen atom, an alkali metal atom, an alkaline earth metal atom or an onium group. Alkali metal atoms include metal atoms such as lithium, sodium and potassium, alkaline earth metal atoms include metal atoms such as calcium and magnesium, and onium groups include ammonium groups (eg, ammonium and tetraethylammonium) and pyridinium. And the like.

M represents an integer of 0 to 3, and when m is 2 or 3, W ₁ -D may be the same or different.
m is preferably 0 to 2, more preferably 0 or 1, and particularly preferably 0. n represents an integer of 1 to 3, and n is 2 or 3
In this case, W ₂ may be the same or different. n is preferably 1 or 2, and 1 is particularly preferred. Specific examples of W include, for example, the following.

[0036]

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[0037]

[Formula 13]

The alkyl group (unsubstituted) represented by X ₁ and X ₂ represents a linear or branched alkyl having 1 to 5 carbon atoms.
More preferred ₂ °, preferably a linear alkyl group, more preferably a methyl group or an ethyl group. The alkoxyalkyl group represented by X ₁ and X ₂ preferably has 1 to 6 carbon atoms in the alkoxy group and 1 to 6 carbon atoms in the alkyl group. More preferably, the alkoxy group has 1 to 3 carbon atoms and the alkyl group has 1 to 3 carbon atoms. Specific examples include a methoxymethyl group, a methoxyethyl group, and an ethoxyethyl group. The hydroxyalkyl group represented by X ₁ and X ₂ preferably has 1 to 5 carbon atoms, more preferably a hydroxyethyl group. Preferred X ₁ and X ₂ are a hydrogen atom, a methyl group, an ethyl group, a hydroxyethyl group, a methoxymethyl group, a methoxyethyl group and an ethoxyethyl group, more preferably a hydrogen atom and a methyl group, most preferably It is a hydrogen atom.

Preferred cations represented by M ¹ , M ² , M ³ and M ⁴ may be the same or different in the molecule. Examples of the onium group include an ammonium group (for example, ammonium group, tetraethylammonium). Group), alkali metal atoms include metal atoms such as lithium, sodium and potassium), and alkaline earth metal atoms include metal atoms such as calcium, magnesium and barium, and pyridinium. More preferably, it is an alkali metal atom.

Of the integers 0 to 5 represented by t and u,
Preferably it is 0 or 1, more preferably 0. When t and u are 2 or more, a plurality of R ₂ may be the same or different, and a plurality of R ₆ may be the same. The compound represented by the general formula (II) is preferably a compound represented by the following general formula (III), and more preferably a compound represented by the general formula (IV). Most preferably, it is a compound represented by the general formula (V).

Formula (III)

[Formula 14]

In the general formula (III), R ₁ , R ₂ , R ₃ , R ₄ , R
_{5, R 6, R 7,} M 1, M 2, M 3, M 4, X 1, X 2, W, t and u
Have the same meanings as those of formula (II), respectively, and the preferred range is also the same. * Indicates that the absolute configuration of the asymmetric carbon is S
It represents that.

General formula (IV)

[Formula 15]

In the general formula (IV), R ₁ , R ₂ , R ₃ , R ₄ ,
R ₅ , R ₆ , R ₇ , M ¹ , M ² , M ³ , M ⁴ , t and u have the same meanings as those of formula (II), and the preferred ranges are also the same. W ₃ represents a trimethylene group or a hydroxytrimethylene group. * Represents that the absolute configuration of the asymmetric carbon is S.

General formula (V)

Embedded image

In the general formula (V), M ¹ , M ² , M ³ and M ⁴ have the same meanings as those in the general formula (II), and the preferred ranges are also the same. W ₃ represents a trimethylene group or a hydroxytrimethylene group. * Represents that the absolute configuration of the asymmetric carbon is S. Since the compound of the general formula (II) has two asymmetric carbons, three compounds of the SS form, SR form and RR form are available.
There are species of isomers. Preferably, they are SS-form and SR-form, more preferably SS-form. However, synthesis of ligand,
In some cases, the racemate may be racemized with the passage of time or in the preparation of a liquid. The optical purity of the SS body is preferably 90% ee,
It is more preferably at least 95% ee, still more preferably at least 99% ee. In the present invention, specific examples of the compound represented by the above general formula (II) are shown, but the present invention is not limited thereto.

[0047]

[Formula 17]

[0048]

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[0049]

Embedded image

[0050]

Embedded image

Compounds represented by the general formula (II) are described in Chelate Chemistry (5), edited by Ueno Keihei, Nankodo, p. 311 (Synthesis of ethylenediamine-N, N'-disuccinic acid), Inorgnic C
hemistry, 7,2405 (1968), Chm.Zvesti., 20,414 (1966), Z
hurnal Obshchei Khinii, 49, 659 (1978), etc.
12570, WO96 / 01802, WO96 / 01803, WO96 / 01804, WO96 / 35
662, US5466867, EP0694528, EP0731171, WO96 / 32371,
Compounds can also be synthesized with reference to the methods described in each gazette such as GB2299809, WO96 / 35662, and DE19518150.

The iron complex salt of the compound represented by the general formula (II) according to the present invention (hereinafter sometimes simply referred to as the iron complex salt or the iron chelate compound according to the present invention) is represented by the general formula (MI) Can be. Of the general formula (MI), a compound represented by the general formula (M-II) is preferred, a compound represented by the general formula (M-III) is more preferred, and a compound represented by the general formula (M-III) is most preferred. A compound represented by IV).
General formula (M-1)

[0053]

[Formula 21]

In the general formula (M-1), R ₁ , R ₂ , R ₃ ,
R ₄ , R ₅ , R ₆ , R ₇ , M ¹ , M ² , M ³ , M ⁴ , X ₁ , X ₂ , W, t and u have the same meanings as those of the general formula (I),
The preferred range is also the same. M _1a , M2a, M _3a and M _4a are
Represents a hydrogen atom, a cation, or a carboxylate anion. M represents a counter cation. p is 1 /
Represents an integer or decimal number from 3 to 6. Y represents a monodentate or bidentate ligand. r represents an integer of 0 to 2. q
Represents an integer of 0 to 10 or a decimal number.

General formula (M-II)

Embedded image In the general formula (M-2), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ ,
R ₆ , R ₇ , X ₁ , X ₂ , W, t and u have the same meanings as those of formula (I), and the preferred ranges are also the same. M ^1a , M ^2a , M ^3a and M ^4a represent a hydrogen atom, a cation, or a carboxylate anion. M represents a counter cation. p represents an integer or decimal number from 1/3 to 6. Y represents a monodentate or bidentate ligand.
r represents an integer of 0 to 2. q represents an integer of 0 to 10 or a decimal number. * Represents that the absolute configuration of the asymmetric carbon is S.

General formula (M-III)

Embedded image

In the general formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ ,
R ₆ , R ₇ , t and u have the same meanings as those of formula (II), and the preferred ranges are also the same. W ₃ represents an ethylene or trimethylene group. M ^1a , M ^2a , M ^3a and M ^4a
Represents a hydrogen atom, a cation, or an anion of a carboxylate group. M represents a counter cation. p
Represents an integer or a decimal number from 1/3 to 6. Y represents a monodentate or bidentate ligand. r represents an integer of 0 to 2. q represents an integer of 0 to 10 or a decimal number. * Represents that the absolute configuration of the asymmetric carbon is S.

General formula (M-IV)

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In the general formula (M-IV), W ₃ represents an ethylene or trimethylene group. M represents a counter cation. p represents 1/3, 1/2 or 1. r is 0
Represents an integer of 10 to 10 or a decimal number. * Represents that the absolute configuration of the asymmetric carbon is S.

M^1a, M^2a, M^3aAnd M^4aCation represented by
Is M of the general formula (II)¹, M^Two, M^ThreeAnd M^FourKatio represented by
The ones listed above can be applied. Also M^1a, M^2a, M^3a
And M ^4aAnd an anion of a carboxylate group represented by
Is -CO_TwoM^1aIs -CO_Two ^-Finger to represent
Then M^2a, M^3aAnd M^4aThe same applies to. M^1a,
M^2a, M^3aAnd M^4aPreferably as few of them
At least two are anions of carboxylate groups
And more preferably three or more carboxylates.
And most preferably all.
Is a carboxylate group anion.

The counter cation represented by M can be a metal atom or an onium group ion represented by M ¹ , M ² , M ³ and M ⁴ in the general formula (II). Preferred are ammonium, sodium and potassium ions, more preferred are ammonium and sodium ions, and most preferred are ammonium ions. p is 1
Represents an integer or decimal number from / 3 to 6, and requires a number sufficient to neutralize the charge of the entire complex. However, when the cation represented by M has two or more valences, the cation may be a decimal number. p is preferably 1/3, 1/2 or 1, and more preferably 1.

The ligand represented by Y represents a monodentate or bidentate ligand. For example, oxalate ion, aquo ion, hydroxo ion, malonate ion and tartrate ion.
Even when the ligand has three or more coordinating groups, all that coordinate to the iron ion as a bidentate ligand are included. r is 0
Represents an integer of 2 to 2, preferably 0 or 1, and more preferably 0. q represents an integer or decimal number of 0 to 10, preferably 0 to 3, more preferably 0
Or 1, most preferably 0.

The iron chelate compound of the compound represented by the general formula (II) (ie, the general formula (MI)) is not only isolated in a solid state (for example, powdery, granular, solid) but also not isolated. It may be in a solution state (for example, an aqueous solution). Regarding the iron chelate compound represented by the general formula (MI), JP-A-11-130741, JP-A-10-279544,
It can be synthesized with reference to JP-A-8-34764, JP-A-7-291984, JP-A-7-2745, U.S. Pat. No. 5,717,123, and U.S. Pat. No. 5,763,634.

The iron chelate compound can be synthesized by reacting the compound represented by the general formula (I) or (II) with an iron salt in a solution, and represented by the general formula (I) or (II). As the compound to be used, an ammonium salt or an alkali metal salt (for example, a lithium salt, a sodium salt, or a potassium salt) may be used. When the iron chelate compound is used in a solution state in which it is not isolated, it is preferable to remove excess salts in the solution generated by the reaction. In the present invention, examples of the method for removing salts include ultrafiltration and electrodialysis, salt filtration by solvent concentration, salt filtration by addition of a poor solvent, and the like, but electrodialysis is preferred. . When the solvent is water, the solution of the iron chelate compound of the compound represented by formula (I) or (II) preferably has a pH of 4 to 9, more preferably 5 to 8, and particularly preferably 6 to 6. ８8. The concentration of the iron chelate compound is 1 to 80% by mass.
Is more preferably 1 to 50% by mass, and still more preferably 3 to 35% by mass. As a solvent for the iron chelate compound solution that is not isolated, water is preferable. The ratio of the compound represented by the general formula (I) or (II) to the iron ion is preferably 1.0 or more in terms of molar ratio. It is more preferably 1.05 or more and 2 or less, and particularly preferably 1.
It is 1 or more and 1.2 or less.

The general formula (I) or (II) according to the present invention
When synthesizing an iron chelate compound of the compound represented by
As the raw material of the component (III), any salt or a simple substance may be used, but as the inorganic salt, ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate, Ferrous sulfate, ferrous chloride, ferrous nitrate, ferrous ammonium sulfate, ferrous phosphate, ferric oxide, iron sesquioxide, iron hydroxide, organic salts of iron acetate, In addition, iron powder and steel wool can be used alone. These iron (III) component raw materials may be used alone or as a mixture of two or more kinds at an arbitrary ratio. As a solvent that can be used for the synthesis of the iron chelate compound, any compound may be used as long as it does not participate in the reaction, but water is most preferable.

In the present invention, the compound represented by the general formula (I) or (II)
The supply form of the compound is one in which an iron (III) complex salt has been formed in advance, and the amount of the salt other than the iron (III) complex salt in the supply form is 0 to 10% by weight based on the iron (III) complex salt. Is more preferably 0 to 7% by weight, and particularly preferably 0 to 5% by weight. More specifically, an iron complex salt-containing compound obtained by reacting a compound represented by the general formula (I) with iron sesquioxide, or a compound of the general formula (I) or (II) and iron (III) chloride After the reaction, it is preferable to use an iron complex salt-containing compound that has been desalted to a desired state. Iron here
(III) The salt other than the complex salt is a by-product formed by reacting the compound represented by the general formula (I) or (II) with an iron salt. In some cases, it refers to a salt other than the compound represented by the general formula (M-1).

In the present invention, the above-mentioned general formula (MI)
Specific examples of the compound represented by are shown below, but the present invention is not limited thereto.

[0068]

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[0069]

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[0070]

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The iron (II) used in the bleaching solution in the present invention
I) complex salt is a complex forming compound of the general formula (I) or (II) and an iron (III) compound (for example, iron oxide (III), ferric sulfate, ferric chloride, ferric bromide, Iron (III) nitrate, etc.), and may be added and dissolved as a complexed iron complex salt,
Further, a complex-forming compound and an iron (III) salt (for example, ferric sulfate,
Ferric chloride, ferric bromide, iron (III) nitrate, etc.) may be added to the bleaching solution to form a complex in the bleaching solution to obtain an aqueous iron complex salt solution. When performing complex salt formation in the bleaching solution, the complex-forming compound may be slightly excessive in an amount required for complex formation of iron (III) ions, and when added in excess, usually
The excess is preferably in the range of 0.01 to 20%.

The compound forming an iron (III) complex salt in the bleaching solution of the present invention is preferably a compound represented by the above-mentioned general formula (I) or (II), more preferably 50 mol% or more of which is more preferable. Should account for at least 80 mol%. In the present invention, as the compound forming the iron (III) complex salt in the bleaching solution, the compound represented by the above general formula (I) or (II) may be used alone or in combination of two or more. You may. Further, within the scope of the present invention, as the compound forming an iron (III) complex salt in the bleaching solution, the compound represented by the aforementioned general formula (I) or (I)
Compounds other than the compound represented by I) may be used in combination. Such compounds include EDTA, diethylenetriaminepentaacetic acid, iminodiacetic acid, methyliminoniacetic acid, N- (2-acetamido) iminoniacetic acid, nitrilotriacetic acid, N- (2-carboxyethyl) iminodiacetic acid,
Examples include, but are not limited to, ethylenediaminetetrakismethylenephosphonic acid, nitrilotrismethylenephosphonic acid, diethylenetriaminepentakismethylenephosphonic acid, N- (2-carboxylateethyl) -L-aspartic acid, and the like.

In the present invention, the bleaching agent in the bleaching solution includes the complex-forming compound represented by the above-mentioned general formula (I) or (II) and optionally the above-mentioned iron (III) of another chelating agent. ) In addition to the complex salt, an inorganic oxidizing agent may be used in combination as a bleaching agent. Such inorganic oxidizing agents include hydrogen peroxide,
Alternatively, examples include, but are not limited to, hypochlorite, persulfate, and bromate (the form of the salt is an alkali metal flame or an alkaline earth metal salt).
The concentration of the bleaching agent in the bleaching solution of the present invention is suitably in the range of 0.003 to 3.0 mol / l, preferably in the range of 0.02 to 1.50 mol / l, and more preferably in the range of 0.05 to 0.50 mol / l. However, when the inorganic oxidizing agent as described above is used in combination, the iron (III) concentration is 0.005 to 0.03.
A mole / liter range is preferred.

In the present invention, the bleaching solution contains chloride, bromide, or chloride as a rehalogenating agent for accelerating the oxidation of silver.
It is preferred to add a halide such as iodide. Further, an organic ligand which forms a sparingly soluble silver salt may be added instead of the halide. The halide is preferably added as an alkali metal salt or an ammonium salt, and the organic ligand is preferably added as a salt of guanidine, amine or the like. Specific examples include sodium bromide, potassium bromide, ammonium bromide, potassium chloride, and guanidine hydrochloride. Of these, ammonium bromide is particularly preferred. The bromide ion concentration in the bleaching solution is preferably 0.05 to
2.0 mol / liter, and more preferably in the range of 0.5 to 1.5 mol / liter. When an inorganic oxidizing agent as described above is used in combination, the bromide ion concentration is preferably in the range of 0.05 to 0.1 mol / liter.

The bleaching solution according to the present invention preferably contains a compound represented by the following general formula [A].

General Formula [A] A ₅ (—COOM ⁵ ) n _{51 In the} general formula [A], A ₅ represents an n _51- valent organic group;
n ₅₁ represents an integer of 1 to 6, and M ⁵ represents an ammonium group, an organic ammonium group, an alkali metal (eg, sodium, potassium, lithium) or a hydrogen atom. However, A ₅ is not an unsubstituted methyl group, an unsubstituted ethyl group or an unsubstituted ethylene group.

In the general formula [A], n represented by A ₅
Examples of the _51- valent organic group include an alkylene group (eg, a methylene group, a trimethylene group, a tetramethylene group), an alkenylene group (eg, an ethenylene group), an alkynylene group (eg, an ethynylene group), a cycloalkylene group (eg,
4-cyclohexanediyl group, etc.), arylene group (for example,
o-phenylene group, p-phenylene group, etc.), alkanetriyl group (eg, 1,2,3-propanetriyl group etc.), arenetriyl group (eg, 1,2,4-benzenetriyl group etc.), Alkyl group (for example, propyl group, butyl group, octyl group,
Cyclohexyl group).

The n ₅₁ -valent group represented by A ₅ includes those having a substituent (eg, a hydroxy group, an alkyl group, a halogen atom, etc.) (eg, 1,2-dihydroxyethylene, hydroxyethylene, -Hydroxy-1,2,3-propanetriyl, methyl-p-phenylene, 1-hydroxy-2-
Chloroethylene, chloromethylene, chlorethenylene, etc.). Preferred specific examples of the compound represented by the formula [A] are shown below.

(A-1) HOOCCH ₂ C (OH)
_{(COOH) CH 2 COOH (A} -2) HOOC (CHOH) 2 COOH (A-3) HOOCCH (OH) CH 2 COOH (A-4) HOOCCH = CHCOOH (A-5) Propylene glycol acid (A-6) Butylene glycolic acid (A-7) Phthalic acid (A-8) Terephthalic acid (A-9) Cyclohexane-1,4-dicarboxylic acid (A-10) Acetin-1,2-dicarboxylic acid (A-11) 2-methyl Luterephthalic acid (A-12) 1,1,2,2-tetracarboxyethylene (A-13) 1,1,2,2-tetracarboxyethane (A-14) Aspartic acid (A-15) Glutaric acid (A-16) HOOCCH ₂ COOH

Of the above exemplified compounds, particularly preferred are the exemplified compounds (A-3), (A-4), (A-15) and (A-1).
6), and particularly preferred are (A-3) and (A-
16). The addition of the organic acid of the general formula (A) improves the stability of the bleaching solution and suppresses the precipitation of the iron (III) compound.
It is considered that the (III) complex is further weakly coordinated to contribute to the stabilization, and that it is further considered that the interference effect described later also contributes to the stabilization. Therefore, in a bleaching solution in which the compound of the general formula (A) is present, the stability is maintained even when the pH is lowered. Can be.

The above-mentioned organic acids may be used as their metal salts (eg, sodium salts and potassium salts) and ammonium salts. The compound represented by the general formula [A] is preferably contained in an amount of 0.01 to 0.25 mol per liter of the treatment tank liquid, more preferably 0.02 to 0.15 mol.

In the present invention, the preferable pH of the bleaching solution is 4.0 to 5.5 when the compound of the general formula (A) is not contained.
And particularly preferably 4.2 to 5.2. In order to adjust the bleaching solution to the above pH range, known inorganic acids and organic acids can be used alone or in combination. Organic acids having a pKa of 2.0 to 5.5, especially 0.1 to 2
It may contain moles / liter. This pKa value is the absolute value of the reciprocal of the acid dissociation constant, and has an ionic strength of 0.1 mol / liter, 25
It shows the value determined under the condition of ° C. PKa used in the present invention
The organic acid of 2.0 to 5.5 does not necessarily have to be the compound of the above general formula (A), and other monobasic acids or polybasic acids can be used, and their metal salts (eg, sodium salts and potassium salts) And ammonium salts.
Preferred examples of the organic acid include formic acid, acetic acid, monochloroacetic acid, including those listed as the general formula (A).
Aliphatic monobasic acids such as monobromoacetic acid, glycolic acid, propionic acid, monochloropropionic acid, lactic acid, pyruvic acid, acrylic acid, butyric acid, isobutyric acid, pivalic acid, aminobutyric acid, valeric acid, isovaleric acid; asparagine; Alanine, arginine, ethionine, glycine, glutamine,
Amino acid compounds such as cysteine, serine, methionine and leucine; benzoic acid and monosubstituted benzoic acids such as chloro and hydroxy; aromatic monobasic acids such as nicotinic acid; oxalic acid, malonic acid, tartaric acid, malic acid, maleic acid, Aliphatic dibasic acids such as fumaric acid, oxaloacetic acid, glutaric acid and adipic acid; amino acid-based dibasic acids such as aspartic acid, glutamic acid, cystine and ascorbic acid; aromatic dibasic acids such as phthalic acid and terephthalic acid Acids: Various organic acids such as citric acid and other basic acids can be listed. In the present invention, among these, acetic acid and glycolic acid are particularly preferred. In the present invention, these pKa
It is preferable to add 1 to 50 g / L of a compound selected from imidazoles in addition to the organic acid having a value of 2.0 to 5.5. As imidazoles, C 1 -C 1-, 2-, 4- or 5-positions
6 alkyl groups, 2-6 alkenyl groups, 2 carbon atoms
One to six hydroxyalkyl groups, carboxyalkyl groups, or carboxyl groups may be substituted. Preferred imidazoles are imidazole, 2-methylimidazole, 4-methylimidazole, 4-methyl-5- (hydroxymethyl) imidazole, imidazole-4,5-
In the present invention, particularly, imidazole, 2-methylimidazole, imidazole-
4,5-dicarboxylic acid is preferred, and imidazole is particularly preferred. These imidazoles are present in the bleaching solution at 1.0 to 3
It is preferably contained in the range of 0.0 g / L, and more preferably 1.5 to 5.0 g / L.

The bleaching solution of the present invention can be reused after collecting the overflow solution after the treatment, correcting the composition by adding components, and then reusing it. Such a method of use is usually called "reproduction", and this reproduction method is described in Japanese Patent Laid-Open No. 5-3031.
No. 86, paragraph [0033] to [0034].

The temperature of the bleaching solution is preferably from 20 to 50 ° C., but is preferably from 25 to 45 ° C. Further, various fluorescent whitening agents, defoaming agents or surfactants can be contained. In the present invention, the replenishment amount of the bleaching solution is preferably 200 ml or less, more preferably 100 ml or less, and most preferably 5 ml or less per m ^{2 of} silver halide color photographic light-sensitive material.
0 ml or less, and the lower the replenishment amount, the more remarkable the effect of the present invention.

In the present invention, air or oxygen may be blown in the processing bath and the processing replenisher storage tank as required to increase the activity of the bleaching solution, or a suitable oxidizing agent such as peroxide Hydrogen oxide, bromate, persulfate, or the like may be appropriately added.

Following the description of the bleaching solution used in the present invention, the overall color reversal process of the present invention will be described below. First, black-and-white development (first development), which is the first step, will be described. Conventionally known developing agents can be used for the black and white developer. As a developing agent, dihydroxybenzenes (for example, hydroquinone, hydroquinone monosulfonate), 3-pyrazolidones (for example, 1-phenyl-3-pyrazolidone, 1-phenyl-4)
-Methyl-4-hydroxymethyl-3-pyrazolidone), aminophenols (eg, N-methyl-p-
Aminophenol, N-methyl-3-methyl-p-aminophenol), ascorbic acid and isomers and derivatives thereof can be used alone or in combination. Preferred developing agents are potassium hydroquinone monosulfonate or sodium hydroquinone monosulfonate. The addition amount of these developing agents is 1 × 10 ^-5 to 2 mol / l per liter of developer.

In the black and white developer used in the present invention, a preservative can be used if necessary. Sulfites and bisulfites are generally used as preservatives. The amount of these additives is 0.01 to 1 mol / l, preferably 0.1 to 1 mol / l.
0.5 mol / l. In addition, ascorbic acid is also an effective preservative, and the preferable addition amount is 0.01 mol / liter to 0.5 mol / liter. In addition, JP 3
Hydroxylamines, saccharides, o-hydroxyketones, hydrazines and the like described in the general formula (I) of JP-A-144446 can also be used. In this case, the amount of addition is 0.1 mol / liter or less.

The pH of the black-and-white developer of the present invention is preferably in the range of 8 to 12, most preferably in the range of 9 to 11.
Range. Various buffering agents can be used to maintain the pH. Preferred buffering agents are carbonates, phosphates, borates, 5-sulfosalicylates, hydroxybenzoates, glycines, N, N-dimethylglycines,
Leucine salt, norleucine salt, guanine salt, 3,4-dihydroxyphenylalanine salt, alanine salt, aminobutyrate, valine salt, lysine salt and the like. In particular, the use of carbonate, borate, and 5-sulfosalicylate is preferred in that the pH range is maintained and the cost is low. These buffering agents may be used alone or in combination of two or more. Further, an acid and / or an alkali may be added to obtain a desired pH. As the acid agent, an inorganic or organic water-soluble acid can be used.
For example, sulfuric acid, nitric acid, hydrochloric acid, acetic acid, propionic acid, ascorbic acid and the like are preferable. Various hydroxides and ammonium salts can be added as the alkali agent.
For example, preferred examples include potassium hydroxide, sodium hydroxide, aqueous ammonia, triethanolamine, diethanolamine and the like.

The black-and-white developer used in the present invention preferably contains a silver halide solvent as a development accelerator. For example, thiocyanate, sulfite, thiosulfate, 2-methylimidazole, thioether compounds described in JP-A-57-63580, and the like are preferable. The addition amount of these compounds is preferably from 0.005 to 0.5 mol / l. In addition, various quaternary amines, polyethylene oxides, 1-phenyl-3-pyrazolidones as development accelerators,
Primary amines, N, N, N ', N'-tetramethyl-p
-Phenylenediamine and the like.

In the black and white developer used in the present invention, diethylene glycol, propylene glycol, other amines such as polyethylene glycols, diethanolamine and triethanolamine are used as solubilizers, and quaternary ammonium salts are used as sensitizers. Further, various surfactants and hardeners can be used.

In the black and white development step used in the present invention, various antifoggants may be added for the purpose of preventing development fog. As antifoggants, alkali metal halides such as sodium chloride, potassium chloride, potassium bromide, sodium bromide and potassium iodide and organic antifoggants are preferred. Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole,
-Nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2-
Nitrogen-containing heterocyclic compounds such as thiazolylmethyl-benzimidazole and hydroxyazaindolizine; mercapto-substituted heterocyclic compounds such as 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole and 2-mercaptobenzothiazole; and thiosalicylic acid Mercapto-substituted aromatic compounds can be used. These antifoggants include those which elute from the color reversal photosensitive material during processing and accumulate in these developers. Of these, the concentration of iodide added is 5
It is about × 10 ^{−6 to} 5 × 10 ⁻⁴ mol / l. Bromide is also preferred for preventing fog, and the preferred concentration is 0.0
It is from 0.01 mol / l to 0.1 mol / l, and more preferably from 0.01 to 0.05 mol / l.

Further, the black-and-white developer used in the present invention may contain a swelling inhibitor (for example, an inorganic salt such as sodium sulfate and potassium sulfate) and a water softener. Examples of water softeners include aminopolycarboxylic acids, aminopolyphosphonic acids, phosphonocarboxylic acids, organic and inorganic phosphonic acids,
Those having various structures such as the compound of the general formula (I) according to the present invention described above can be used. Specific examples are shown below, but the present invention is not limited thereto. Ethylenediaminetetraacetic acid, nitrilotriacetic acid, hydroxyethyliminodiacetic acid, propylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ' N′-tetramethylene phosphonic acid,
1-hydroxyethylidene-1,1-diphosphonic acid. Two or more of these water softeners may be used in combination. The preferred addition amount of these water softeners is 0.1 g to 20 g / l, more preferably 0.5 g to 10 g / l.

The standard processing time for black-and-white development is usually about 4 to 8 minutes, especially about 6 minutes. However, by appropriately changing the processing time for a photosensitive material having inappropriate shooting conditions, The sensitivity can be increased or decreased (both are collectively referred to as increase / decrease feeling processing). Usually 2 minutes ~
The sensitivity can be adjusted by changing the processing time within 18 minutes. The processing temperature is 20-50 ° C, preferably 33-45.
° C. The replenishment amount of the black and white developer is 1 per m ² of the photosensitive material.
00 ml to 5000 ml, preferably 200 ml to 2500 ml
It is.

In the processing of the present invention, after black-and-white development, washing and / or rinsing are performed, if necessary, and then a reversal process is performed, followed by color development. One washing or rinsing bath may be used, but it is more preferable to adopt a multistage countercurrent system of two or more tanks for the purpose of reducing the replenishment amount. Here, rinsing refers to a system in which a relatively large amount of water is replenished, whereas rinsing refers to a system in which the replenishment amount is reduced to another treatment bath level. The replenishing amount of the washing water is preferably about 3 to 20 liters per square meter of the photosensitive material. The replenishing amount of the rinsing bath is about 50 ml to 2 liters, more preferably about 100 ml to 500 ml, and the amount of water used is greatly reduced as compared with the washing step. In the rinse bath of the present invention, if necessary, an oxidizing agent, a chelating agent, a buffer,
A bactericide, a fluorescent whitening agent and the like can be added.

Subsequently, a reversal bath or a light fogging step is started. In the reversal bath, a fogging agent known as a chemical fogging agent, that is, stannous ion-organic phosphoric acid complex salt (U.S. Pat. No. 3,617,282), stannous ion organic phosphonocarboxylic acid complex salt (Japanese Patent Publication No. Sho 56) No. 32616), stannous ion complex salts such as stannous ion-aminopolycarboxylic acid complex salt (U.S. Pat. No. 1,209,050), and general formula (II) or general formula (III) described in JP-A-11-109573. ), And borohydride compounds (US Pat. No. 2,982).
No. 4,567) and a boron compound such as a heterocyclic amine borane compound (UK Patent No. 1,011,000). The pH of the reversal bath ranges from an acidic side to an alkaline side depending on the type of the fogging agent.
H2 to 12, most preferably in the range of 2.5 to 10, especially 3 to 9.

The concentration of tin (II) ions in the reversal bath was 1 × 10
^{-3 to 5} x 10-2 mol / liter, preferably ² x ^10-3
１．５1.5 × 10 ⁻² mol / l. When a boron-based fogging agent is used in the reversal bath, its concentration is
1 × 10 ^{−3 to} 5 × 10 ⁻² mol / liter, preferably 2
x10 ^{-3 to} 1.5x10 ^-2 mol / l.

Further, the reversal bath is used to increase the solubility of the tin (II) chelate, by using propionic acid, acetic acid or
It is preferable to contain an alkylenedicarboxylic acid compound described in General Formula (I) of JP-A-109572. Further, as a bactericide, sorbate, US Pat.
It is preferable to contain a quaternary ammonium compound described in No. 1,225.

The time of the reversal bath is 10 seconds to 3 minutes, preferably 20 seconds to 2 minutes, more preferably 30 seconds to 90 seconds. The temperature of the reversal bath is preferably in the range of the first development, followed by rinsing or rinsing and color development, or within the temperature range of each of these baths. The replenishing amount of the reversal bath is 10 to 2000 ml per square meter of the light-sensitive material, preferably 200 to 2000 ml.
1500 ml is appropriate.

The tin (II) chelate and the boron-based fogging agent in the reversal bath are effective over a wide pH range, so that there is no need to add a pH buffer, but organic acids such as citric acid and malic acid can be used. It does not prevent the addition of inorganic acids such as acids, boric acid, sulfuric acid and hydrochloric acid, and acids, alkalis and salts for imparting pH buffering properties such as alkali carbonate, caustic alkali, borax and potassium metaborate. If necessary, a water softener such as aminopolycarboxylic acid, a swelling inhibitor such as sodium sulfate, or an antioxidant such as p-aminophenol may be added.

The light-sensitive material processed in the reversal bath enters a color development step. The color developing solution used in the color developing process of the present invention is an alkaline aqueous solution mainly containing an aromatic primary amine type color developing agent. As the color developing agent, a p-phenylenediamine compound is preferably used. Representative examples of p-phenylenediamine compounds include 3-methyl-4-amino-N, N-diethylaniline,
3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline,
3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides, phosphates or p-toluenesulfonates, tetraphenylborates, p- (t- Octyl) benzenesulfonate and the like. If necessary, these developing agents
Two or more kinds may be used in combination. Preferred developer concentrations are
It is 0.005 mol / l to 0.1 mol / l, preferably 0.01 mol / l to 0.05 mol / l.

The pH of the color developing solution of the present invention is preferably in the range of 8 to 13, more preferably 10.0 to 12.
5 In order to maintain this pH, the present invention contains a phosphate as an essential alkaline agent. The phosphate may be in any form of third, second and first phosphate, and may be an alkali metal salt such as a sodium salt, a potassium salt, a lithium salt or an ammonium salt, or an organic onium salt. Can be added. Preferred are sodium and potassium salts. The concentration of the phosphate is 0.05 to 0.25 mol / L, preferably 0.05 to 0.15 mol / L, as phosphate ions. Further, an alkaline agent and a buffer other than the phosphate may be used in combination. Alkaline agents and buffering agents having a buffer region at pH 8.0 or higher that may be used together with phosphates in the present invention include carbonates, borates, 5-sulfosalicylates, tetraborates,
Hydroxybenzoate, glycine, N, N-dimethylglycine, leucine, norleucine, guanine,
3,4-dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-methyl-1,3-
Propanediol salt, valine salt, proline salt, trishydroxyaminomethane salt, lysine salt and the like can be used. In particular, carbonate and 5-sulfosalicylate are excellent in solubility and buffer capacity in a high pH region of pH 10.0 or more,
The pH buffer region of phosphate ions is further expanded to suppress pH fluctuation.

Specific examples of these alkaline agents and buffers include phosphates such as trisodium phosphate, tripotassium phosphate, disodium phosphate and dipotassium phosphate, and alkaline agents which may be used in combination. Is sodium carbonate,
Potassium carbonate, sodium bicarbonate, potassium bicarbonate, 5
-Dipotassium sulfosalicylate, sodium borate, potassium borate, sodium tetraborate (borax), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, 5-sulfo- Sodium 2-hydroxybenzoate (sodium 5-sulfosalicylate), 5-sulfo-2
And potassium-hydroxybenzoate (potassium 5-sulfosalicylate), preferably trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, dipotassium 5-sulfosalicylate, Disodium sulfosalicylate. These buffers may be added alone to the developing solution of the phosphate, or two or more of them may be used in combination, and the pH can be adjusted to a desired pH by an alkali agent or an acid. The amount of the buffer to be added to the color developer is preferably 0.05 mol / L or more (when used in combination), and more preferably 0.05 mol / L to 0.4 mol / L. It is particularly preferred that there is.

In the present invention, various development accelerators may be used in combination, if necessary. Further, examples of the development accelerator include U.S. Pat. No. 2,648,604 and JP-B-44-95.
No. 03, U.S. Pat. No. 3,171,247, various pyridinium compounds and other cationic compounds, cationic dyes such as phenosafranine, neutral salts such as thallium nitrate and potassium nitrate, and the like.
No. 9304, U.S. Pat.
No. 1832, No. 2950970, No. 257712
7, nonionic compounds such as polyethylene glycol and derivatives thereof, polythioethers, and thioether compounds described in U.S. Pat. No. 3,201,242 may be used. If necessary, benzyl alcohol and its solvent such as diethylene glycol, triethanolamine and diethanolamine can be used. However, in consideration of the environmental load, the solubility of the liquid, the generation of tar, and the like, it is preferable to use these as little as possible. Further, it may contain the same silver halide solvent as in the black and white developer. For example, alkali metal salts of thiocyanic acid, 2-methylimidazole, JP-A-57-63
And thioether compounds described in each gazette such as 580. Particularly preferred is 3,6-dithiaoctane-1,8-diol. The preferred range of the addition amount of these silver halide solvents also applies to the preferred ranges described in the section on black-and-white (first) development.

In the color development process of the present invention, it is not necessary to prevent development fog, but when the color film is replenished and processed constantly, that is, when running, the composition and performance of the developer are kept constant. For the purpose, various antifoggants may be contained. As the antifoggant in these developing steps, alkali metal halides such as potassium chloride, sodium chloride, potassium bromide, sodium bromide and potassium iodide, and organic antifoggants are preferable. Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole,
-Nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2-
Nitrogen-containing heterocyclic compounds such as thiazolylmethyl-benzimidazole and hydroxyazaindolizine; mercapto-substituted heterocyclic compounds such as 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole and 2-mercaptobenzothiazole; and thiosalicylic acid Mercapto-substituted aromatic compounds can be used. These antifoggants include those which elute from the color reversal photosensitive material during processing and accumulate in these developers. In the case of color reversal development, the concentration of these antifoggants does not affect the photographic performance, and it is not usually necessary to control the concentration.

Various preservatives can be used in the color developing solution according to the present invention. As typical preservatives, hydroxylamines and sulfites can be used, and sulfites are preferable. These addition amounts are 0 to 0.1.
Mol / l. The color developer used in the present invention may contain an organic preservative in place of the hydroxylamine or sulfite ion.

Here, the organic preservative refers to any organic compound that reduces the deterioration rate of an aromatic primary amine color developing agent by being added to a processing solution for a color photographic light-sensitive material.
That is, organic compounds having a function of preventing oxidation of a color developing agent by air or the like, among which hydroxylamine derivatives (excluding hydroxylamine), hydroxamic acids, hydrazines, hydrazides, phenols, α-hydroxy Ketones, α-aminoketones,
Sugars, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, condensed amines, and the like are particularly effective organic preservatives. These are Tokubyo Sho 4
8-30496, JP-A-52-143020, 6
No. 3-4235, No. 63-30845, No. 63-21
No. 647, No. 63-44655, No. 63-53551
No. 63-43140, No. 63-56654, No. 63-58346, No. 63-43138, No. 63-
No. 146041, No. 63-44657, No. 63-44
No. 656, U.S. Pat. Nos. 3,615,503 and 24,949.
No. 03, JP-A-1-97953 and JP-A-1-186939.
Nos. 1,186,940, 1-187557, 2-306244 and the like. Other preservatives include JP-A-57-44148 and JP-A-5-44148.
Various metals described in JP-A-7-53749;
Salicylic acids described in 80588, JP-A-63-239
447, JP-A-63-128340, JP-A-1-1-1
Amines as described in JP 86939 and 1-187557, alkanolamines described in JP-A-54-3532, polyethyleneimines described in JP-A-56-94349, U.S. Pat. No. 3,746. An aromatic polyhydroxy compound described in No. 544 or the like may be used as necessary. Particularly, alkanolamines such as triethanolamine, dialkylhydroxylamines such as N, N-diethylhydroxylamine and N, N-di (sulfoethyl) hydroxylamine, and hydrazines such as N, N-bis (carboxymethyl) hydrazine. Derivatives (excluding hydrazine) or catechol-3,5-
Addition of an aromatic polyhydroxy compound represented by sodium disulfonate is preferred.

The addition amount of these organic preservatives is preferably about 0.02 mol / l to 0.5 mol / l, more preferably about 0.05 mol / l to 0.2 mol / l. Two or more kinds may be used together.

In addition, the color developing solution according to the present invention includes organic solvents such as diethylene glycol and triethylene glycol; dye-forming couplers; citrazic acid, J acid, H
Competitive couplers such as acids; nucleating agents such as sodium boron hydride; auxiliary developing agents such as 1-phenyl-3-pyrazolidone; viscosity-imparting agents; ethylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid;
Hydroxyethyl iminodiacetic acid, iminodiacetic acid, N-hydroxymethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, and aminopolycarboxylic acids represented by the compounds described in JP-A-58-195845; -Hydroxyethylidene-1,1'-diphosphonic acid, organic phosphonic acid described in Research Disclosure No. 18170 (May 1979), aminotris (methylene phosphonic acid), ethylenediamine-N, N, N ', N'- Aminophosphonic acids such as tetramethylenephosphonic acid;
No. 2726, No. 53-42730, No. 54-1211
No. 27, No. 55-4024, No. 55-4025, No. 55-126241, No. 55-65555, No. 55
-65556 and Research Disclosure
A chelating agent such as phosphonocarboxylic acid described in No. 18170 (May 1979) can be contained. The addition amount of these chelating agents is 0.05 g / liter to 2 g.
0 g / liter, preferably about 0.1 g to 5 g / liter, and if necessary, two or more kinds may be used in combination.

If necessary, various surfactants such as alkyl sulfonic acid, aryl sulfonic acid, aliphatic carboxylic acid and aromatic carboxylic acid polyalkylenimine may be added. The processing temperature of the color developing solution applicable to the present invention is from 20 to 50C, preferably from 33 to 45C. The processing time is 20 seconds to 5 minutes, preferably 20 seconds to 4 minutes. Replenishment rate is desirably small as possible remain active, but the photosensitive material 1 m ² per 100~2500ml are suitable,
Preferably it is 400 ml to 1200 ml.

The color reversal photosensitive material after the color development is
Subsequently, a desilvering process is performed. The desilvering step is usually performed by the following steps. 1. (Color development) -adjustment-bleaching-fixing (Color development) -washing-bleaching-fixing 3. (Color development) -bleaching-fixing4. (Color development)-washing with water-bleaching-washing with water-fixing5. (Color development)-bleaching-washing-fixing 6. (Color development)-water washing-bleach-fixing7. (Color development)-Adjustment-Bleaching and fixing (Color development) -Bleaching and fixing9. (Color development)-washing-bleaching-bleach-fixing 10. (Color development) -Bleaching-Bleaching-fixing 11. (Color development) -Washing-Bleaching-Bleaching-Fixing-Fixing The "adjustment" step is also called a "pre-bleaching" step.

Of the above steps, the steps shown as 1 and 3 are particularly preferred. The replenishing method in the above-mentioned processing step may be such that the replenisher of each bath may be individually replenished to the corresponding processing bath, as in the prior art, or in steps 9 and 10, the overflow of the bleaching solution is added to the bleach-fix bath. And the bleach-fix bath may be replenished with only the fixer composition. Step 1
In the method 1, the overflow solution of the bleaching solution may be introduced into the bleach-fixing solution, the overflow solution of the fixing solution may be introduced into the bleach-fixing solution in a countercurrent manner, and the two may overflow from the bleach-fixing bath. .

Various bleach-fixing accelerators can be added to the bleaching bath, the bleach-fixing bath, or the conditioning bath as a prebath thereof. Examples of such bleaching accelerators include, for example, U.S. Patent No. 3,893,858, British Patent No. 1,138,842, and JP-A-53-141623.
And various compounds having a disulfide bond described in JP-A-53-95630, and JP-B-53-9854.
Thiazolidine derivative described in JP-A-5
Isothiourea derivatives described in JP-A-3-94927, JP-B-45-8506, JP-B-49-26
Thiourea derivatives described in JP-A-586, thioamide compounds described in JP-A-49-42349, dithiocarbamate salts described in JP-A-55-26506, and the like. Further examples of the bleaching accelerator include an alkyl mercapto compound which is unsubstituted or substituted with a hydroxyl group, a carboxyl group, a sulfonic acid group, or an amino group (which may have a substituent such as an alkyl group or an acetoxyalkyl group). Can be used. For example, trithioglycerin, α, α′-thiodipropionic acid, δ-mercaptobutyric acid and the like can be mentioned. Further, compounds described in U.S. Pat. No. 4,552,834 can also be used.

The amount of the compound having a mercapto group or a disulfide bond in the molecule, the thiazoline derivative or the isothiourea derivative in the preparation or bleaching solution depends on the type of photographic material to be processed, the processing temperature and the purpose. Depending on the time required for the treatment, etc., 1 × 10 ⁻⁵ to 10 ⁻¹ mol per liter of treatment liquid is appropriate
Preferably it is 1 × 10 ^{-4 to} 5 × 10 ^-2 mol.

The adjusting solution preferably contains an image stabilizer described below. In the present invention, it is particularly preferable to contain a formaldehyde bisulfite adduct described in US Pat. No. 5,037,725. It can also contain a secondary amine described in U.S. Pat. No. 5,523,195. The pH of the adjusting solution is usually used in the range of 3 to 11, preferably 4 to 9, and more preferably 4.
5-7. The processing time with the adjustment liquid is preferably from 20 seconds to 3 minutes, more preferably from 20 seconds to 2 minutes, and most preferably from 30 seconds to 60 seconds. The replenishing amount of the adjusting solution is preferably 30 ml to 2000 ml per 1 m ^{2 of the} light-sensitive material, and particularly preferably 50 ml to 1500 ml. The treatment temperature of the conditioning liquid is preferably from 20C to 50C, and particularly preferably from 30C to 40C.

In the bleach-fixing solution, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate, ammonium thiocyanate and potassium thiocyanate; ethylene bisthioglycolic acid; 6-dithia-1,8-
It is a water-soluble silver halide dissolving agent such as thioether compounds such as octanediol and thioureas, and these can be used alone or in combination of two or more.
Further, a special bleach-fixing solution comprising 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. The amount of these fixing agents is from 0.1 mol to 3 mol, preferably from 0.2 mol to 2 mol, per liter of a bath having a fixing ability.

In the present invention, the bleaching solution contains an iron (III) complex salt of a compound represented by the above general formula (I) or (II) and a carboxylic acid represented by the general formula (A), In addition to using a bleaching solution having a specific pH value and using a fixing solution or a bleach-fixing solution containing a compound selected from imidazoles at a concentration of 1 to 50 g / L as a fixing solution or a bleach-fixing solution. The effects of the present invention, such as prevention of color defects, reduction of stains, and prevention of contamination of compound materials, are further increased. Preferred imidazoles include unsubstituted imidazole and C 1 -C 1, 2, 4 or 5 positions.
6 alkyl groups, 2-6 alkenyl groups, 2 carbon atoms
An imidazole derivative substituted with 1 to 6 hydroxyalkyl groups, carboxyalkyl groups, or carboxyl groups. Particularly preferred imidazoles include imidazole, 2-methylimidazole, 4-methylimidazole, 4-methyl-5- (hydroxymethyl) imidazole, imidazole-4,5-dicarboxylic acid and the like, and in the present invention, particularly imidazole, 2-Methylimidazole and imidazole-4,5-dicarboxylic acid are preferred, and imidazole is also preferred. The preferable addition amount of these imidazoles is 1 to 25 g / L.
And more preferably 1.5 to 10 g / L.

When a fixing solution is used in the present invention, the fixing agent may be a known fixing agent, that is, a thiosulfate such as sodium thiosulfate or ammonium thiosulfate, or a thiocyanate such as sodium thiocyanate, ammonium thiocyanate or potassium thiocyanate. Thioether compounds such as ethylenebisthioglycolic acid, 3,6-dithia-1,8-octanediol, and water-soluble silver halide solubilizers such as thioureas. Can be used. The concentration of the fixing agent is 0.1 mol to 3 mol, preferably 0.1 mol per liter of fixing solution.
It is 2 mol to 2 mol. In the solution having a fixing ability, in addition to the above-mentioned additives, preservatives such as sulfites (eg, sodium sulfite, potassium sulfite, and ammonium sulfite), bisulfite, hydroxylamine, hydrazine, and bisulfite adducts of aldehyde compounds ( For example, sodium acetaldehyde bisulfite) can be contained.
Sulfinic acids (such as benzenesulfinic acid) and ascorbic acid are also effective preservatives. Further, various fluorescent whitening agents, defoaming agents or surfactants, polyvinylpyrrolidone, antibacterial and antibacterial agents, and organic solvents such as methanol can be contained.

[0118] Bleaching solution in the present invention, the fixing solution replenishment amount of such bleach-fixing solution, can be respectively arbitrarily set as long as satisfying the function of each processing bath, preferably the light-sensitive material 1 m ²
30 ml to 2000 ml per unit. More preferably 50 ml
~ 1000 ml. The processing temperature is preferably 20
C. to 50C, more preferably 33C to 45C. The processing time is 10 seconds to 10 minutes, preferably 20 seconds to 6 minutes.

After desilvering such as fixing or bleach-fixing, washing with water and / or processing with a stabilizing solution are generally performed. The stabilizer generally contains an image stabilizer, but may not contain an image stabilizer.In this case, the stabilizer may be referred to as a washing alternative stabilizer to be distinguished from a stabilizer containing a wing stabilizer, In addition, it can be said that the washing substitute bath in that sense has almost the same function as the rinsing liquid (cleaning liquid). Therefore, in the following description, each step or liquid will be described collectively except for the image stabilizer. The amount of rinsing water in the rinsing step can be set in a wide range depending on the characteristics of the photosensitive material (for example, depending on the material used such as a coupler), the use, the rinsing water temperature, the number of rinsing tanks (the number of stages), and various other conditions. Of these, the relationship between the number of washing tanks and water volume in the multi-stage counter-current method is described in Journal of the Society of Motion Picture and Television Engineers (Journal of the Soc).
(iety of Motion Pictureand Television Engineers)
Volume 4, p.248-253 (May 1955)
You can ask. Usually, the number of stages in the multistage countercurrent system is preferably 2 to 15, and particularly preferably 2 to 10.

According to the multi-stage countercurrent method, the amount of washing water can be greatly reduced, and bacteria increase due to an increase in the residence time of water in the tank. Occurs. As a solution to such a problem, the method for reducing calcium and magnesium described in JP-A-62-288838 can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8542,
Chlorinated fungicides such as chlorinated sodium isocyanurate described in JP-A-120145;
No. benzotriazole, copper ion, and others, written by Hiroshi Horiguchi, "The Chemistry of Bactericidal and Fungicide Protection" (1986), edited by Sankyo Shuppan, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982)
Year) The Fungicide described in "Encyclopedia of Bacterial and Fungicide" (ed. 1986), edited by the Japan Society of Industrial Technology, Japan Society of Bacteria and Fungi.

Aldehydes such as formaldehyde, acetaldehyde and pyruvaldehyde for inactivating the remaining magenta coupler to prevent fading of the dye and generation of stain; methylol compounds and hexamethylenetetramine described in US Pat. No. 4,786,583; Hexahydrotriazines described in JP-A-2-153348, formaldehyde bisulfite adduct described in U.S. Pat. No. 4,921,779, EP-A-504609
And azolylmethylamines described in JP-A Nos. 519190 and 519190 can be added. US 496
0687, US4975356, US503772
As described in No. 5, an image stabilizer and a precursor thereof are added to the adjusting solution, and the stabilizer solution (rinse solution) does not contain these image stabilizers, which occurs on the film surface after processing. It is preferable to reduce dirt and unevenness.

Further, the washing water, the stabilizing solution or the rinsing solution may contain a surfactant as a draining agent or E as a hard water softener.
DTA or a chelating agent represented by the general formula (II) of the present invention described above can be used. Examples of the surfactant include a polyethylene glycol type nonionic surfactant, a polyhydric alcohol type nonionic surfactant, an alkylbenzene sulfonate type anionic surfactant, and a higher alcohol sulfate ester salt type anionic surfactant. Surfactant, alkyl naphthalene sulfonate type anionic surfactant, quaternary ammonium salt type cationic surfactant, amine salt type cationic surfactant, amino salt type amphoteric surfactant, betaine type amphoteric surfactant And two or more of these surfactants may be used in combination. Further, a fluorine-based surfactant or a siloxane-based surfactant described in US Pat. No. 5,716,765 can also be used.
Among the nonionic surfactants, nonionic surfactants such as alkyl polyethylene oxides, alkyl phenoxy polyethylene oxides and alkyl phenoxy polyhydroxypropylene oxides are preferred, and alkyl-poly (oxyethylene having 8 to 15 carbon atoms is particularly preferred. ) (5-12) alcohol. In order to improve the solubility of the surfactant, it is also preferable to include a solubilizing agent for amines such as diethanolamine and triethanolamine, and glycols such as diethylene glycol and propylene glycol.

It is preferable to add a chelating agent for collecting heavy metals to the stabilizing solution or the rinsing solution in order to improve the stability of the solution and reduce the generation of dirt. As the chelating agent, the same compounds as those added to the developer and the bleaching solution can be used. The stabilizer or rinse solution of the present invention is preferably added with an antibacterial / antifungal agent for the purpose of preventing the generation of bacteria and fungi, and commercially available products can be used. Further, a surfactant, a fluorescent whitening agent and a hardening agent may be added.

The pH of the stabilizing or rinsing solution of the present invention and the washing water is 4 to 9, preferably 5 to 8.
The processing temperature and the processing time can also be variously set depending on the characteristics of the light-sensitive material, the application, and the like.
Preferably, it is 30 seconds to 2 minutes at 25 to 40 ° C. Furthermore,
When the stabilizing solution or the rinsing solution of the present invention is treated directly with the stabilizing solution or the rinsing solution after desilvering without washing with water, the effect of preventing contamination is remarkably exhibited.

The replenishing amount of the stabilizing solution or the rinsing solution of the present invention is preferably 200 to 2000 ml per 1 m ^{2 of the} light-sensitive material. The overflow solution resulting from the washing and / or replenishment of the stabilizing solution can be reused in another step such as a desilvering step.

In order to reduce the amount of washing water used, ion exchange, reverse osmosis or ultrafiltration may be used, and ultrafiltration is particularly preferable. Various treatment liquids in the present invention are used at 10 ° C to 50 ° C. Usually 33
Although the temperature is typically in the range of ℃ to 38 ° C, it is possible to increase the temperature to accelerate the processing and shorten the processing time, or to lower the temperature to improve the image quality and the stability of the processing solution. .

In the processing of the light-sensitive material according to the present invention, when the stabilization is directly performed without going through a washing step, JP-A-57-8543, JP-A-58-14834,
Any of the known methods described in JP-A-60-220345 and the like can be used. In addition, it is also a preferable embodiment to use a chelating agent such as 1-hydroxyethylidene-1,1-diphosphonic acid or ethylenediaminetetramethylenephosphonic acid, or a magnesium or bismuth compound.

Following the washing and / or stabilizing step, drying is performed. From the viewpoint of reducing the amount of water carried into the image film, it is possible to speed up drying by absorbing water with a squeeze roller or cloth immediately after leaving the washing bath. As a means of improvement from the dryer side, as a matter of course, it is possible to speed up the drying by increasing the temperature or changing the shape of the spray nozzle to increase the drying air. Further, as described in Japanese Patent Application Laid-Open No. 3-157650, it is possible to adjust the blowing angle of the dry air to the photosensitive material,
Drying can also be accelerated by the method of removing the discharged air.

Next, the color light-sensitive material used in the present invention will be described. The amount of developed silver in the present invention is the total amount of developed silver generated in each of color development and black-and-white development, and the total amount of developed silver is 3.0 to 7.0 g / m ² substantially. Is a reversal color photosensitive material such as a reversal color film. Currently available color negative photosensitive materials and reflective color photosensitive materials (e.g., color paper photosensitive materials, color reversal paper photosensitive materials) are developed only in the exposed portions, and thus the developed silver amount is almost 2 g / m ² or less. On the other hand, in a reversal color photosensitive material, since the exposed portion is developed in the first development and the remaining silver halide is developed in the color development, 90% or more of the applied silver halide on the photosensitive material is substantially reduced. , Since almost 100% is developed, the amount of developed silver is large, and therefore, the bleaching load is much larger than that of a color negative film or color paper, and bleaching is likely to be incomplete. In the present invention, the effect is particularly remarkably exerted in the processing of a color reversal film.

The color reversal film is usually composed of a red-sensitive unit, a green-sensitive unit,
The photosensitive units are arranged in the order of the blue-sensitive unit, and have one or more non-color-forming intermediate layers between the red-sensitive unit and the green-sensitive unit, and / or between the green-sensitive unit and the blue completed unit. Silver halide color photographic light-sensitive material.

A photosensitive material having a three-layered photosensitive unit is as follows:
It is preferable that the low-speed emulsion layer, the medium-speed emulsion layer, and the high-speed emulsion layer are coated in this order from the side close to the support. (Which may contain a neutral silver halide emulsion). The photosensitive unit is preferably blue-sensitive, green-sensitive, and red-sensitive all have a three-layer structure, but the blue-sensitive layer has a structure of two layers or less, and the green-sensitive and red-sensitive layers have a three-layer structure. Good. The blue-sensitive layer contains a yellow coupler, the green-sensitive layer contains a magenta coupler, and the red-sensitive layer contains a cyan coupler. For the purpose of adjusting color reproducibility, other combinations of couplers may be mixed.

Among the three-layer units, the coating amount of the silver halide emulsion is 10 to 60% for the high-sensitivity layer, 10 to 50% for the intermediate layer, and low for the silver halide emulsion coating weight of the whole unit. It is preferable that 30 to 70% is allocated to the sensitivity layer,
The silver / coupler ratio in each photosensitive layer is preferably such that the low-sensitivity layer is maximized.

A non-color-forming intermediate layer is preferably provided between units having different photosensitivity. The non-chromogenic intermediate layer may contain a light-sensitive, non-light-sensitive, or pre-fogged silver halide emulsion. The intermediate layer may be composed of a single layer or a composite structure of two or more layers and five layers or less.In the latter case, the layer located farther from the support has colloidal silver particles, It preferably contains a silver halide emulsion in which the inside of the grains is fogged. When a silver halide emulsion is contained in the intermediate layer, it is preferable to add a color mixture inhibitor to the intermediate layer or an adjacent layer.

More preferred embodiments of the color reversal film according to the present invention include the following. A red-sensitive unit, a green-sensitive unit, and a blue-sensitive unit are coated from the side close to the support, and at least the red-sensitive unit and the green-sensitive unit are composed of three photosensitive emulsion layers, which are closer to the support side. Low sensitivity,
It is applied in the order of medium sensitivity and high sensitivity. For this reason, the silver / coupler ratio in each photosensitive layer is preferably from 25 to 150. In this case, the silver / coupler ratio of the middle-speed layer is preferably 5 to 30, and the silver / coupler ratio of the high-speed layer is preferably 2 to 20.

Further, between the red-sensitive unit and the green-sensitive unit, and between the green-sensitive unit and the blue-sensitive unit, there are two or more and five or less intermediate layers, and a layer adjacent to the former green-sensitive layer, The layer adjacent to the latter blue-sensitive layer may contain colloidal silver grains or a previously fogged silver halide emulsion. The thickness of the intermediate layer (total thickness of the composite constituent layer) is 0.5 to 5 μm, more preferably 1.0 to 3.0 μm.
m. This film thickness can be theoretically easily determined by the specific gravity of the additive, and the actual coated material can be easily measured by observing the cross section with an electron microscope. The side closer to the support than the red-sensitive unit has an antihalation layer, and the side farther from the support than the blue-sensitive layer unit has at least one protective layer, and at least one of the protective layers has silver halide. It is also preferred to include an emulsion.

Regarding various techniques and inorganic and organic materials which can be used for the silver halide emulsion of the present invention and the silver halide photographic light-sensitive material using the same, see European Patent 4369.
38A2 at the following places and in the patents cited below.

Item Applicable section 1) Layer structure, page 146, line 34 to page 147, line 2) Silver halide emulsion, page 147, line 26 to page 148, line 3) Yellow coupler page 137, page 35 From line 146 to line 33 on page 146, line 21 to line 23 on page 149 4) Magenta coupler, line 24 to line 149, page 149; line 3 to line 5 of EP 421,453A1 Page 25 line 55 5) Cyan coupler page 149 line 29 to line 33; EP 432,804A2 page 3 line 28 to page 40 line 2 6) Polymer coupler page 149 Lines from line 38 to line 38: EP 113,334A1, page 113, line 39 to page 123, line 7) Colored coupler page 53, line 42 to page 137, line 34, page 149, 39 Lines 45 to 45 8) Other functional couplers, page 7, line 1 to page 53, line 41, page 149, line 46 to page 150, line 3; EP 435,334A2 Page 3, line 1 to page 29, line 50 9) Antiseptic and fungicide page 150, lines 25 to 28

10) Formalin, page 149, lines 15-17 Scavenger 11) Other additives, page 153, lines 38-47; EP 421,453A1, page 75, lines 21-84. Page 56 line, page 27 line 40 to page 37 line 40 12) Dispersion method page 150 line 4 to line 13 13) Support page 150 line 32 to line 34 14) film thickness • Film physical properties, page 150, lines 35 to 49 15) Color development, black and white development, page 150, line 50 to page 151, line 47; fogging step of EP 442,323A2 page 34, page 11 Lines 54 to 54, page 27, line 40 to page 37, line 40 16) Desilvering process page 151, line 48 to page 152, line 53 17) Automatic developing machine, page 152, line 54 to Page 153, line 2 18) Washing and stabilization process Page 153, line 3 to page 153, line 37

(Example 1) The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. (1) Preparation of Photosensitive Material Preparation of Sample 101 A multilayer color photosensitive material comprising the following layers was prepared on an undercoated cellulose triacetate film support having a thickness of 127 μm to prepare Sample 101. The numbers represent the amount added per m ² .

First layer: Antihalation layer Black colloidal silver 0.25 g Gelatin 2.40 g Ultraviolet absorber U-1 0.10 g Ultraviolet absorber U-3 0.10 g Ultraviolet absorber U-4 0.10 g High boiling organic solvent Oil-1 0.050 g High-boiling organic solvent Oil-2 0.050 g High-boiling organic solvent Oil-5 0.010 g Dye D-4 1.0 mg Dye D-8 2.5 mg Fine crystalline solid dispersion of Dye E-1 0.05 g

Second layer: Intermediate layer Gelatin 0.40 g Compound Cpd-A 0.2 mg Compound Cpd-J 1.0 mg Compound Cpd-K 3.0 mg Compound Cpd-M 0.030 g Ultraviolet absorber U-6 6.0 mg High boiling organic solvent Oil- 3 0.010 g High boiling organic solvent Oil-4 0.010 g High boiling organic solvent Oil-7 2.0 mg High boiling organic solvent Oil-8 4.0 mg Dye D-7 4.0 mg

Third layer: Intermediate layer Yellow colloidal silver 0.010 g Gelatin 0.50 g Compound Cpd-M 0.010 g High boiling organic solvent Oil-3 0.010 g

Fourth layer: low-sensitivity red-sensitive emulsion layer Emulsion A silver amount 0.20 g Emulsion B silver amount 0.20 g Emulsion C silver amount 0.15 g gelatin 0.70 g Coupler C-1 0.050 g Coupler C-2 0.080 g Coupler C-3 0.010 g Coupler C-6 6.0 mg Coupler C-9 5.0 mg Coupler C-11 0.030 g Ultraviolet absorber U-1 0.010 g Ultraviolet absorber U-2 0.010 g Compound Cpd-A 1.0 mg Compound Cpd-I 0.020 g Compound Cpd -J 2.0mg High boiling organic solvent Oil-2 0.10g High boiling organic solvent Oil-5 0.010g Additive P-1 0.020g

Fifth layer: middle-sensitivity red-sensitive emulsion layer Emulsion C silver amount 0.25 g Emulsion D silver amount 0.25 g gelatin 0.60 g coupler C-1 0.040 g coupler C-2 0.10 g coupler C-3 0.020 g coupler C-6 7.0mg Coupler C-11 0.050g UV absorber U-1 0.010g UV absorber U-2 0.010g High boiling organic solvent Oil-2 0.10g Additive P-1 0.020g

Sixth layer: High-sensitivity red-sensitive emulsion layer Emulsion E silver amount 0.25 g Emulsion F silver amount 0.35 g gelatin 1.50 g Coupler C-1 0.10 g Coupler C-3 0.60 g Coupler C-6 0.010 g Coupler C-11 0.20 g UV absorber U-1 0.010 g UV absorber U-2 0.010 g High boiling organic solvent Oil-2 0.10 g High boiling organic solvent Oil-9 0.010 g Compound Cpd-K 1.0 mg Compound Cpd-L 1.0 mg Compound Cpd -F 0.050g Additive P-1 0.10g

Seventh layer: Intermediate layer Gelatin 0.70 g P-2 added 0.10 g Compound Cpd-I 0.010 g Dye D-5 0.020 g Dye D-9 6.0 mg Compound Cpd-M 0.040 g Compound Cpd-O 3.0 mg Compound Cpd -P 5.0mg High boiling organic solvent Oil-6 0.050g

Eighth layer: Intermediate layer Yellow colloidal silver Silver amount 0.010 g Gelatin 1.00 g Additive P-2 0.05 g Ultraviolet absorber U-1 0.010 g Ultraviolet absorber U-3 0.010 g Compound Cpd-A 0.050 g Compound Cpd -M 0.050 g High boiling organic solvent Oil-3 0.010 g High boiling organic solvent Oil-6 0.050 g

Ninth layer: low-sensitivity green-sensitive emulsion layer Emulsion G silver amount 0.20 g Emulsion H silver amount 0.35 g Emulsion I silver amount 0.30 g gelatin 1.50 g Coupler C-4 0.020 g Coupler C-7 0.070 g Coupler C-8 0.070 g Coupler C-12 0.020 g Coupler C-13 0.010 g Compound Cpd-B 0.030 g Compound Cpd-D 5.0 mg Compound Cpd-E 5.0 mg Compound Cpd-G 2.5 mg Compound Cpd-F 0.010 g Compound Cpd-K 2.0 mg Ultraviolet absorber U-6 5.0mg High boiling organic solvent Oil-2 0.15g High boiling organic solvent Oil-6 0.030g High boiling organic solvent Oil-4 8.0mg Additive P-1 5.0mg

Tenth Layer: Medium-Sensitive Green-Sensitive Emulsion Layer Emulsion I Silver content 0.30 g Emulsion J Silver content 0.30 g Silver bromide emulsion (cubic, sphere-equivalent mean particle size 0.11 μm) silver content 5.0 mg Gelatin 0.70 g Coupler C-4 0.30 g Coupler C-8 0.020 g Coupler C-12 0.020 g Coupler C-13 0.010 g Compound Cpd-B 0.030 g Compound Cpd-F 0.010 g Compound Cpd-G 2.0 mg High boiling organic solvent Oil-2 0.050g High boiling organic solvent Oil-5 6.0mg

Eleventh layer: High-sensitivity green-sensitive emulsion layer Emulsion K Silver content 0.55 g Gelatin 0.70 g Coupler C-3 5.0 mg Coupler C-4 0.35 g Coupler C-8 0.010 g Coupler C-12 0.020 g Compound Cpd-B 0.050 g Compound Cpd-F 0.010 g Compound Cpd-K 2.0 mg High boiling organic solvent Oil-2 0.050 g

Twelfth layer: Intermediate layer Gelatin 0.30 g Compound Cpd-M 0.05 g High boiling organic solvent Oil-3 0.025 g High boiling organic solvent Oil-6 0.025 g Dye D-6 5.0 mg

13th layer: Yellow filter layer Yellow colloidal silver Amount of silver 0.050 g Gelatin 0.70 g Compound Cpd-C 0.010 g Compound Cpd-M 0.030 g High boiling organic solvent Oil-1 0.020 g High boiling organic solvent Oil-6 0.030 g 0.030 g of microcrystalline solid dispersion of dye E-2

Fourteenth layer: Intermediate layer Gelatin 0.30 g Compound Cpd-Q 0.20 g

Fifteenth layer: low-sensitivity blue-sensitive emulsion layer Emulsion L Silver content 0.20 g Emulsion M Silver content 0.20 g Gelatin 0.80 g Coupler C-5 0.30 g Coupler C-6 0.010 g Coupler C-10 0.030 g Compound Cpd-I 8.0 mg Compound Cpd-K 1.0 mg Compound Cpd-M 5.0 mg Ultraviolet absorber U-6 0.010 g High boiling organic solvent Oil-2 0.010 g High boiling organic solvent Oil-3 0.010 g

Sixteenth layer: Medium-sensitivity blue-sensitive emulsion layer Emulsion N Silver amount 0.20 g Emulsion O Silver amount 0.20 g Silver bromide emulsion (cubic, sphere-equivalent mean particle size 0.11 μm) silver covered 0.010 g Gelatin 0.90 g Coupler C-5 0.50 g Coupler C-6 0.020 g Coupler C-10 0.060 g Compound Cpd-N 2.0 mg High boiling organic solvent Oil-2 0.080 g

17th layer: High-sensitivity blue-sensitive emulsion layer Emulsion O silver amount 0.20 g Emulsion P silver amount 0.25 g gelatin 2.00 g Coupler C-3 5.0 mg Coupler C-5 0.20 g Coupler C-6 0.020 g Coupler C-10 1.00 g High boiling organic solvent Oil-2 0.10 g High boiling organic solvent Oil-6 0.020 g Ultraviolet absorber U-6 0.10 g Compound Cpd-B 0.20 g Compound Cpd-N 5.0 mg

Eighteenth layer: First protective layer Gelatin 0.80 g Ultraviolet absorber U-1 0.10 g Ultraviolet absorber U-2 0.050 g Ultraviolet absorber U-5 0.20 g Compound Cpd-O 5.0 mg Compound Cpd-A 0.030 g Compound Cpd-H 0.20 g Dye D-1 8.0 mg Dye D-2 0.010 g Dye D-3 0.010 g High boiling organic solvent Oil-3 0.10 g

Nineteenth layer: Second protective layer Colloidal silver amount of silver 0.11 mg Fine grain silver iodobromide emulsion (average particle size 0.06 μm, AgI content 1
(Mol%) silver amount 0.10 g gelatin 0.70 g UV absorber U-1 0.010 g UV absorber U-6 0.010 g High boiling organic solvent Oil-3 0.010 g

Twentieth layer: Third protective layer Gelatin 1.00 g Polymethyl methacrylate (average particle size 1.5 μm) 0.10 g Copolymer of methyl methacrylate and methacrylic acid 6: 4 (average particle size 1.5 μm) 0.10 g Silicone oil SO-1 0.10 g Surfactant W-1 3.0 mg Surfactant W-2 8.0 mg Surfactant W-3 0.040 g Surfactant W-7 0.015 g

Further, additives F-1 to F-8 were added to all emulsion layers in addition to the above composition. Further, in addition to the above composition, gelatin hardener H-1 and surfactants W-3, W-4, W-5 and W-6 for coating and emulsification were added to each layer. Further, phenol, 1,2-benzisothiazolin-3-one, 2-phenoxyethanol, phenethyl alcohol, and butyl p-benzoate were added as preservatives and fungicides.

[0161]

[Table 1]

[0162]

[Table 2]

[0163]

[Table 3]

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[0180]

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Preparation of Dispersion of Organic Solid Disperse Dye Dye E-1 was dispersed by the following method. That is, water and 200 g of Pluronic F88 (ethylene oxide-propylene oxide block copolymer) manufactured by BASF were added to 1430 g of a wet cake of a dye containing 30% of methanol, followed by stirring to obtain a slurry having a dye concentration of 6%. Next, 1700 ml of zirconia beads having an average particle size of 0.5 mm was filled in Ultra Viscomil (UVM-2) manufactured by Imex Co., Ltd.
A peripheral speed of about 10 m / sec through the slurry and a discharge rate of 0.51
/ Min for 8 hours. The beads were removed by filtration and diluted with water to a dye concentration of 3% by adding water.
Heated at ° C for 10 hours. The average particle size of the obtained fine dye particles was 0.60 μm, and the width of the particle size distribution (standard deviation of particle size × 100 / average particle size) was 18%. Similarly, a solid dispersion of Dye E-2 was obtained. Average particle size is 0.5
It was 4 μm.

(2) Exposure and development treatment The photosensitive material obtained above was treated with a CIE D50 light source and a light wedge for photosensitive material for photography (neutral color, density gradient 0.4 / cm, density range 4.8). After the exposure, the film was subjected to a developing process (developing process A) shown below. Processing time Time Temperature Tank capacity Replenishment amount First development 6 minutes 38 ° C 165 liters 2200ml / m ² First water wash 2 minutes 38 ° C 50 liters 7500ml / m ² Inversion 2 minutes 38 ° C 86 liters 1100ml / m ² Color development 6 minutes 38 ° C. 165 liters 2200 ml / m ² before bleaching 2 min 38 ° C. 65 liters 1100 ml / m ² bleaching 4 min 38 ° C. 0.99 liters 220 ml / m ² Fixing 4 min 38 ° C. 108 liters 1100 ml / m ² second water washing 4 minutes 38 55 ° C 7500ml / m ² Final rinse 1 minute 25 ° C 44L 1100ml / m ² The composition of each treatment solution was as follows.

[First developer] [Tank solution] [Replenisher] Nitrilo-N, N, N-trimethylenephosphonic acid pentasodium salt 1.5 g 1.5 g Diethylenetriaminepentaacetic acid pentasodium salt 2.0 g 2.0 g Sodium sulfite 28 g 30 g Potassium hydroquinone monosulfonate 18 g 20 g Potassium carbonate 20 g 20 g Potassium bicarbonate 15 g 15 g 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 1.5 g 2.0 g Potassium bromide 2.5 g 1.4 g Potassium thiocyanate 1.2 g 1.2 g Potassium iodide 4.0 mg 1.5 mg Diethylene glycol 15 g 15 g Water was added to 1000 ml 1000 ml pH 9.65 9.70 pH was adjusted with sulfuric acid or potassium hydroxide.

[Reversal solution] [Tank solution] [Replenishment solution] Nitrilo-N, N, N-trimethylenephosphonic acid tank solution ・ Same as 3.0 g of pentasodium salt Stannous chloride ・ dihydrate 2.0 g p-amino acid Phenol 0.001 g Sodium hydroxide 8 g Propionic acid 15 ml Water was added to 1000 ml pH 6.00 The pH was adjusted with acetic acid or sodium hydroxide.

[Color developing solution] [Tank solution] [Replenisher] Nitrilo-N, N, N-trimethylenephosphonic acid pentasodium salt 2.0 g 2.0 g Sodium sulfite 7.0 g 7.0 g Trisodium phosphate / 12 hydrate 36 g 36 g Potassium bromide 0.7 g-Potassium iodide 40 mg-Sodium hydroxide 3.0 g 3.0 g Citradic acid 0.5 g 0.5 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4- Aminoaniline / 3/2 sulfuric acid monohydrate 11 g 11 g 3,6-dithiaoctane-1,8-diol 1.0 g 1.0 g Water was added to 1000 ml 1000 ml pH 11.90 12.10 The pH was adjusted with sulfuric acid or potassium hydroxide.

[Pre-bleaching] [Tank liquid] [Replenisher] Ethylenediaminetetraacetic acid disodium salt dihydrate 8.0 g 8.0 g Sodium sulfite 5.0 g 6.0 g 1-thioglycerol 0.4 g 0.5 g Sodium formaldehyde sodium bisulfite adduct 20g 25g Water was added to 1000ml 1000ml pH 6.30 6.10 pH was adjusted with acetic acid or sodium hydroxide.

[Bleach] [Tank solution] [Replenisher] Bleach (described in Table 4) 0.3 mol 0.6 mol Compound (A) described in Table 4 Potassium bromide 100 g 200 g Ammonium nitrate 10 g 20 g Water was added to 1000 ml 1000 ml pH described in Table 4 The pH was adjusted with nitric acid or ammonium hydroxide. The bleaching agent was supplied as an iron complex salt in which a complex-forming compound and an iron compound were complexed in advance, and the amount of ammonium nitrate was adjusted so as to obtain the composition shown in Table 4. Further, the pH value in Table 4 is the pH value of the tank solution, and the pH value of the replenisher was set to be 0.3 lower than that.

[Fixing solution] [Tank solution] [Replenisher] Ammonium thiosulfate 80 g Same as sodium sulfite 5.0 g ナ ト リ ウ ム Sodium bisulfite 5.0 g 〃 Add water to 1000 ml 〃 pH 6.60 Adjust pH with acetic acid or aqueous ammonia did. [Stabilizing solution] [Tank solution] [Replenisher] 1,6-Benzoisothiazolin-3-one 0.06 g Same as the tank solution Dipropylene glycol 0.3 g Polyoxyethylene-tridecyl ether (average degree of polymerization 10) 0.3 g Water In addition 1000ml pH 7.0

(3) Evaluation With respect to each sample obtained by the above treatment, the residual silver amount, the precipitation of the iron (III) compound, stain, and poor recoloring were determined by the following methods.

Residual silver amount: The amount of silver remaining in the photosensitive material was measured by X-ray fluorescence analysis. Further, the amount of silver in the sample not subjected to the treatment with the bleaching solution was measured, and the amount of developed silver was determined by subtracting the amount of colloidal silver, and the result was 4.5 g / m ² .

Decoloring failure: The photosensitive material processed by the above method was subjected to density measurement using a transmission densitometer having a measuring optical system in conformity with the international standard ISO5. The maximum density (Dmax (R)) measured in (light) was read, respectively. In addition, a bleaching solution was replaced with the following standard bleaching solution having sufficiently strong bleaching activity, and a bleaching time was also changed to 6 minutes. To the highest concentration (Dmax
(R)) was obtained and used as a reference Dmax (R). The poor recoloring was defined as the following formula and evaluated.

Decoloring failure (%) = each Dmax (R) / reference Dmax (R) × 100

[Standard bleaching solution] [Tank solution] [Replenisher] Ethylenediaminetetraacetate disodium dihydrate 2.0 g 4.0 g Iron (III) ammonium diaminetetraacetate dihydrate 120 g 240 g Potassium bromide 100 g 200 g Ammonium nitrate 10 g 20 g Water was added to 1000 ml 1000 ml pH 5.70 5.50 The pH was adjusted with nitric acid or ammonium hydroxide.

Stain: After obtaining the minimum density (Dmin (G)) with green light (G light) from the characteristic curve, the sample was heated at 60 ° C. and 70%
After aging for 2 weeks in a constant temperature and humidity chamber of RH,
(G) was measured, and magenta stain was defined as follows from the difference in Dmin (G) between before and after aging, and evaluated. Stain (ΔDmin (G)) = Dmin (G) after aging-initial Dmin
(G)

Precipitation of iron (III) compound: Two rounds (the processing amount when the accumulated replenishment amount reaches the tank capacity is called one round) Each bleaching tank solution after the treatment is placed in a beaker, and the solution is turbid. Was visually observed with transmitted light, and the presence or absence of a precipitate at the bottom of the beaker was observed. The evaluation scale is as follows. 〇: No turbidity was observed in the bleaching solution, and no precipitation was generated. Δ: Slight turbidity was observed in the bleaching solution, but no precipitation was generated within an allowable range. ×: Clear turbidity was observed in the bleaching solution. XX: no clear turbidity was observed in the bleaching solution, and precipitation was also observed.

Table 4 shows the test results obtained by the above evaluation methods. In Table 4, the evaluation item of liquid turbidity is used synonymously with the precipitation property.

[0197]

[Table 4]

From the above Table 4, it can be seen that in the present invention, iron (III) PDTA (compound 1-
3) When the complex salt does not contain the compound (A) in any of the pH ranges under the bleaching conditions of the present invention, the precipitate has a large sedimentation-precipitation property and stains easily occur. <Test I-1> to <Test I- 3>. Further, even in the preferable pH range of the iron (III) complex salt, the liquid turbidity still occurs.
-4>. Even if the bleach is replaced with the iron (III) complex salt of the general formula (II) according to the present invention, if the compound (A) is not contained,
When the pH is 4.0, the precipitation property is poor <Test I-6>, p
When H is 6.0, the stain tends to increase <Test I-
7> Also, when the compound of the general formula (A) is added to the iron (III) complex salt of the general formula (II), <Test I-5> and <Test I-
8> Under these pH conditions, improvement is observed, but still insufficient. On the other hand, the bleaching agent is an iron (III) complex salt of the general formula (I) or (II) according to the present invention,
When the pH range is set to the condition of the present invention after adding the compound of the above, <Tests 2-2 to 3, 3-2 to 3, and 4-1 to 4-1>
4, 5-1-4, 6-1-4, 7-1-5>, no precipitation, no generation of stains, very little poor recoloring, and sufficient desilvering is maintained. The result was obtained. Even if the bleaching agent and the pH conditions satisfy the requirements of the present invention and the compound (A) is added, the effect of the present invention is reduced if the amount of the compound (A) is too large (Test 2-3).

(Example-2) The formulation of the fixing solution is shown in Table 5 below.
The pH of the bleaching solution and the bleaching agent were changed as shown in Table 5, and the bleaching solution containing 0.15 mol / L of A-3 as the compound (A) was used. The following evaluation methods were used for the evaluation of the photosensitive material stain and adhesion, which are important evaluation items, and the following tests were conducted by the same method as in Example 1 for other photosensitive materials, processing steps, processing and evaluation methods.

[Fixing solution] [Tank solution] [Replenisher] Ammonium thiosulfate 80 g Same as the tank solution Sodium sulfite 5.0 g ナ ト リ ウ ム Sodium bisulfite 5.0 g 〃 Imidazoles (described in Table 5) 5.0 g 〃 Add water to 1000 ml ＰＨ pH 6.60 pH was adjusted with acetic acid or aqueous ammonia.

[0201]

[Table 5]

Evaluation method of "sensitive material stain": The stain on the processed photosensitive material was visually observed, and the degree was evaluated by the following three grades.汚 れ No dirt is observed with the naked eye. 縁 Dirt is observed at the edges, but tolerance is not acceptable. × Dirt is observed at various places on the surface of the photosensitive material. Evaluation method of "adhesiveness": the processed light-sensitive materials were overlapped so that the emulsion surfaces were in contact with each other, and 30 g / cm ² was placed thereon.
, And left at 35 ° C. and 80% RH for 4 days. Thereafter, the photosensitive material was peeled off, the degree of adhesion of the emulsion surface was observed, and the degree was evaluated in the following three steps.跡 No trace of adhesion is observed. △ Although slight trace of adhesion is observed, peeling of allowable area × emulsion surface is observed.

Table 5 shows the results obtained by the processing method of the present invention. The addition of a compound of imidazoles to the fixing solution can further improve the poor recoloring and the stain, though slightly, and further improve the color of the present invention. Although not intended, it was shown that the photosensitive material was improved with respect to stain and adhesion resistance.

[0204]

EFFECT OF THE INVENTION Phosphate ion is 0.05-0.25mo
Even when a color developing solution containing 1 / L is used, general formula (I) or
At least one iron (III) complex salt of the compound represented by formula (II)
In the method for processing a color photographic light-sensitive material of the present invention using a bleaching solution containing a seed, having a pH of 4.0 to 5.5, and further containing an organic acid represented by the general formula (A), the amount of developed silver Even in a reversal color photosensitive material having a large amount, precipitation from the aged bleaching solution is less likely to occur, stains are less likely to be generated, and poor recoloring is less likely to occur. . In particular, by using a fixing solution (or a bleach-fixing solution) containing an imidazole compound in combination with the above-mentioned bleaching solution, the effect of the above invention is increased.

Claims (2)

[Claims] 1. A method for processing a silver halide color photographic light-sensitive material having at least one processing step between a color developing step and a bleaching step, wherein the color developing solution used in the color developing step has a phosphate ion of 0 or less. 0.05 to 0.25 mol
/ L, and the bleaching solution used in the bleaching step contains at least one iron (III) complex salt of a compound represented by the following general formula (I) or (II). At least one compound represented by the formula (A) is used
0.25 mol / L, and the pH of the bleaching solution was 4.0 to 4.0.
5.5. A method for processing a silver halide color photographic light-sensitive material, wherein the method is 5.5. General formula (I) Wherein A ₁ , A ₂ , A ₃ and A ₄ are each —CH ₂ OH, —PO ₃ (M
² ) ₂ or -COOM ^1, which may be the same or different. M ¹ and M ² are a hydrogen atom, an alkali metal atom,
Represents an ammonium group or an organic ammonium group. X ₁ is a linear or branched alkylene group having 3 to 6 carbon atoms, a saturated or unsaturated divalent organic group forming a ring, or — (B ₁ O) n ₅ —B
Represents _2- . n ₅ represents an integer of 1 to 8, and B ₁ and B ₂ may be the same or different and each have 1 carbon atom.
To 5 alkylene groups. n ₁ , n ₂ , n ₃ and n ₄ represent integers of 1 or more and 10 or less, and may be the same or different. General formula (II) (Wherein, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ each represent a hydrogen atom, an alkyl group, an aromatic group or a hydroxy group. .M ¹ but representing the respective .X ₁ and X ₂ represents a divalent linking group which is 3 to 10 hydrogen atom, an alkyl group, hydroxyalkyl group or alkoxyalkyl group,
M ² , M ³ and M ⁴ represent a hydrogen atom, an alkali metal atom, an alkaline earth metal atom or an onium group. t and u are 1 or 0. General formula [A] A ₅ (—COOM ⁵ ) n ₅₁ (where A ₅ is an n _51- valent organic group (however, excluding unsubstituted methyl group, unsubstituted ethyl group and unsubstituted ethylene group) , N ₅₁ represents an integer of 1 to 6, and M ⁵ represents an ammonium group, an organic ammonium group, an alkali metal (such as sodium, potassium, lithium) or a hydrogen atom.) 2. The silver halide according to claim 1, wherein the fixing solution used in the fixing step following the bleaching step contains 1 to 50 g / L of a compound selected from imidazoles. Processing method for color photographic light-sensitive materials.