JPH11109573A - Reversal bath composition for color reversing and color reversal treatment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To effectively prevent oxidation deterioration of a reversal bath, to maintain the fogging agility, to prevent production of precipitate and bad influences on succeeding processes by incorporating at least a lead (II) chelate and a specified hydroxylamine deriv. SOLUTION: The reversal bath contains at least a tin (II) chalate and a hydroxylamine deriv. expressed by the formula, since a hydroxylamine deriv. having a specified structure prevents oxidation with air in a reversal bath containing a lead (II) chelate as a covering agent. In the formula L is an alkylene group which may by substituted, A is a carboxyl group, sulfo group, phosphono group, phosphoric acid residue, hydroxyl group, amino group which may be replaced with an alkyl group, or ammonio group which may be replaced with an alkyl group, carbamoyl group which may be replaced with an alkyl group or sulfamoly group which may be replaced with an alkyl group, or alkylsulfonyl group which may be replaced, and R is hydrogen atom or alkyl group which may be substituted, and L and R may be connected to form a ring.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a processing solution composition for color photographic light-sensitive materials and a color reversal processing method.

[0002]

2. Description of the Related Art At present, there are two most common forms of color photography, one of which is performed by photographing on a color negative film, developing the film, and printing the resulting negative image on a color paper. A so-called negative / paper system (N / P system) for obtaining prints, and a color reversal system (R / P system) for directly photographing on a color reversal film (hereinafter referred to as a color reversal film) to obtain a positive image by reversal processing. There is).

The color reversal system has disadvantages such as limited processing quality control elements and complicated processes as compared with the N / P system, but has the advantage that a positive image can be obtained directly and that it is suitable for photolithography. For this reason, it is widely used like the N / P system.

General color reversal film processing includes first (black and white) development, washing with water, reversal bath (reversal bath), second (color development) development, adjustment bath (conditioner), bleaching, fixing, washing with water, and image stability. It consists of each step of the bath. See LFAMason's Photog
raphic Processing Chemistry (1966, Focal Press)
257-266, Modern Photographic Pro by GMHaist
cessing (1982), Vol. 2, Chapter 10 (pp. 523-527).

[0005] In order to form a positive dye image by color development, it is necessary to make it possible to develop an undeveloped part, that is, a part which has not been exposed to the image, at the stage of completing the first development. The method includes a light fogging method in which the entire surface of the film is irradiated with light and a fogging method, and a chemical fogging method in which a reversal bath containing a fogging agent for developing the silver halide is provided to process the film. is there. The chemical fogging method is easier to maintain than the light fogging method, and effectively covers a portion of the film surface having a large degree of blackening due to the first development, and furthermore, has a fogging effect. Has been widely adopted because it has a stability that is hardly affected by fluctuations in the temperature and composition of the developing solution. At the outset of the chemical fogging system, U.S. Pat.
No. 46987 discloses a method using an alkali borohydride as a fogging agent, but has a disadvantage in that the processing solution has poor temporal stability.

[0006] Thereafter, a treatment bath using a tin (II) compound, which is known as an inorganic compound having an extremely strong reducing power like an alkali borohydride, as a fogging agent was disclosed in US Pat. No. 3,617,282. The fogging agent has the advantages of the above-described chemical fogging method and also has a much better stability over time of the reversal bath than the alkali borohydride, and is currently most commonly used in the processing of color reversal films. ing. However, the reversal bath using a tin (II) compound, although significantly improved, has the drawback that it is still susceptible to air oxidation and, consequently, tends to precipitate insolubles in the form of tin hydroxide and the like. Have.

Therefore, a reversal bath containing a tin (II) compound is desired to have stability against air oxidation, and a reversal bath using a chelating agent suitable for the purpose in combination with a tin (II) compound is desired. It has been disclosed. For example, while the above-mentioned U.S. Pat. No. 3,617,282 uses an organic phosphonate as a chelating agent, British Patent No. 1,209,050 using an aminopolycarboxylate, and Japanese Patent Publication No. 56-32616 using a phosphonocarboxylate. There have been many proposals to use chelating agents for many tin (II) ions. Although reversal baths using these chelating agents have shown progress in terms of strong and uniform fogging action and stability over time of the processing solution, they have nevertheless been insufficient in stability over time.

For this reason, p-aminophenol is used as an antioxidant for the tin (II) chelate in the reversal bath, but its effect is not sufficient. Also, ascorbic acid and the like are effective in preventing oxidation, but when brought into the color development step following the reversal bath, they act as black-and-white developing agents, resulting in impaired color image quality. Hydroxylamine also has similar defects and cannot be used practically.

[0009] From such a background, oxidative deterioration of the reversal bath containing tin (II) chelate is effectively prevented over a long period of use, the fogging ability of the reversal bath should be maintained, and the insoluble matter will be removed over time. There is a strong demand for the development of a stabilizing means which does not cause the formation of precipitates and does not adversely affect the subsequent steps.

[0010]

The problem to be solved by the present invention is to solve the above-mentioned drawbacks of the reversal bath for color reversal film processing. Specifically, tin (II) A reversal bath which does not impair the fogging action of the compound, has stability against air oxidation, does not cause precipitation, and has no adverse effect on development characteristics even when the reversal bath liquid is brought into the color developing tank together with the developing film. And a method for processing a color reversal film using the same.

[0011]

Means for Solving the Problems In order to achieve the above object, the present inventors have conducted intensive studies and as a result, have found that a hydroxylamine derivative having a specific structure contains a tin (II) chelate as a fogging agent. Found the fact of preventing air oxidation, and conducted further research based on it, leading to the present invention. That is, the present invention is as follows.

1. A reversal bath composition for color reversal, comprising at least a tin (II) chelate and a hydroxylamine derivative represented by the following general formula [I]. General formula [I]

[0013]

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(In the formula [I], L represents an alkylene group which may be substituted, A represents a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid residue, a hydroxyl group, an amino group which may be substituted with an alkyl group, Represents an ammonio group which may be alkyl-substituted, a carbamoyl group which may be alkyl-substituted, a sulfamoyl group which may be alkyl-substituted or an alkylsulfonyl group which may be substituted, and R is a hydrogen atom or an alkyl group which may be substituted And L and R may combine to form a ring.)

2. The reversal bath composition according to claim 1, wherein the tin (II) chelate is a chelate comprising tin (II) ions and a chelating agent represented by the following formula [II] or [III]. General formula (II)

[0016]

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(Wherein, M ₁ , M ₂ and M ₃ represent a hydrogen atom, an alkali metal atom or an ammonium atom group).
m and n each represent an integer of 1 or 2, and X represents a hydrogen atom or a substituent. ) General formula [III]

[0018]

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(Wherein, M ⁴ , M ⁵ , M ⁶ and M ⁷ represent a hydrogen atom, an alkali metal atom or an ammonium atom group. 1 represents an integer of 1 to 4, and Y and Z represent hydrogen. Represents an atom or a substituent.)

3. Take the color photographic light-sensitive material
Or a color reversal treatment method, wherein the treatment is performed using the reversal bath composition according to 2.

[0021]

Embodiments of the present invention will be described below in detail. In the color inversion processing of the present invention,
As described above, the reversal bath is provided after the completion of the first development and before entering the color development step, and covers the unexposed part, that is, the non-image part of the silver halide which has not been developed in the first development. This is a processing bath that enables development. The reversal bath used in the present invention is characterized by containing at least one of a hydroxylamine derivative represented by the general formula [I], a tin (II) compound and a chelating agent thereof as essential components. II) The compound and its chelating agent may contain a tin (II) chelate previously synthesized from both instead of using each.

The compound of the formula (I) will be described.
In the formula [I], L represents a linear or branched alkylene group having 1 to 10 carbon atoms which may be substituted, and preferably has 1 to 5 carbon atoms. Specifically, methylene, ethylene, trimethylene, and propylene are preferred examples. As the substituent, a carboxyl group, a sulfo group, a phosphono group,
A phosphinic acid residue, a hydroxyl group, an amino group which may be substituted with alkyl (preferably having 1 to 5 carbon atoms)
Preferred examples include a carboxyl group, a sulfo group, a phosphono group, and a hydroxyl group.

A is a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid residue, a hydroxyl group, an amino group (preferably having 1 to 5 carbon atoms) which may be substituted, an alkyl group (preferably having 1 to 5 carbon atoms) An optionally substituted ammonium group, an alkyl (preferably having 1 to 5 carbon atoms), an optionally substituted carbamoyl group, an alkyl (preferably having 1 carbon atom)
~ 5) represents a sulfamoyl group which may be substituted, an alkylsulfonyl group which may be substituted, and preferred examples thereof include a carboxyl group, a sulfo group, a hydroxyl group, a phosphono group, and a carbamoyl group which may be alkyl-substituted. When A represents an ammonium group, the compound of the general formula [I] has a sulfate ion, p-type as a counter ion of the ammonium group.
It may be accompanied by toluenesulfonic acid ion, chlorine ion, sulfite ion and the like. When L and A have a substituent having an acid group such as a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid residue, or a hydroxyl group, the hydrogen may be replaced with an alkali metal atom or an ammonium atom group. Good. Preferred examples of -LA include a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, a sulfoethyl group, a sulfopropyl group, a sulfobutyl group, a phosphonomethyl group, a phosphonoethyl group, and a hydroxyethyl group. Groups, carboxyethyl groups, sulfoethyl groups, sulfopropyl groups, phosphonomethyl groups, and phosphonoethyl groups can be mentioned as particularly preferred examples.

R represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms which may be substituted, and preferably has 1 to 5 carbon atoms. As the substituent, a carboxyl group,
Sulfo group, phosphono group, phosphinic acid residue, hydroxyl group, amino group which may be substituted with alkyl, carbamoyl group which may be substituted with alkyl, sulfamoyl group which may be substituted with alkyl, alkylsulfonyl group which may be substituted, Acylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkoxycarbonyl group,
It represents an amino group, an arylsulfonyl group, a nitro group, a cyano group, or a halogen atom which may be substituted by alkyl. There may be two or more substituents. Among them, preferred R includes a hydrogen atom, a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, a sulfoethyl group, a sulfopropyl group, a sulfobutyl group, a phosphonomethyl group, a phosphonoethyl group, and a hydroxyethyl group. Particularly preferred examples include a hydrogen atom. Carboxymethyl group, carboxyethyl group, sulfoethyl group, sulfopropyl group, phosphonomethyl group and phosphonoethyl group.

L and R may be linked to form a ring. L
When R and R form a ring, L and R directly form a ring to have A as a substituent, or A represents an amino group which may be alkyl-substituted, and L represents a nitrogen atom of the amino group. And R can also form a ring (eg, a piperazine ring). Next, specific compounds of the present invention are described, but are not limited thereto.

[0026]

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[0027]

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[0028]

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The compound represented by the general formula [I] can be synthesized by subjecting commercially available hydroxylamines to an alkylation reaction (nucleophilic substitution reaction, addition reaction, Mannich reaction, etc.). West German Patent 1159634, `` Inorganica Chemica Acta '' (Inorganica
Chimica Acta), 93, (1984) 101-108, and the like. A more specific method for synthesizing a compound is described in JP-A-3-266837.

These hydroxylamine derivatives prevent the tin (II) chelate from deteriorating by air oxidation, maintain the fogging action of the reversal bath, and continue development processing for a long period of time without replacing the solution in the reversal bath treatment tank. be able to. Further, even if the solution in the reversal bath adheres to the film and is carried into the next color developing tank, it does not affect the color developing characteristics. The amount of the hydroxylamine derivative of the general formula [I] added to the reversal bath of the present invention is 0.1 g to 20 g, preferably 0.5 g to 10 g per liter as the composition of the treatment tank liquid.
And the amount of addition to the replenisher is 1.0 to 1.8 times, preferably 1.0 to 1.3 times.

The tin (II) compound to be added to the reversal bath of the present invention is preferably a water-soluble tin (II) salt, particularly stannous chloride, stannous bromide, or stannous iodide. Tin and their tin halide dihydrates, stannous nitrate, stannous sulfate and its dihydrate, stannous acetate, tin (II) citrate, tin tartrate (I)
I) is preferable, and stannous chloride, stannous bromide, stannous nitrate, and stannous sulfate are particularly preferable.

Next, the chelating agent added to the reversal bath of the present invention will be described. The chelating agent used is tin (I
I) Any of the known compounds that complex with ions to form a water-soluble tin (II) chelate can be used, but preferred chelating agents are the organic phosphonates disclosed in U.S. Pat. No. 3,617,282; Aminopolycarboxylates disclosed in Japanese Patent No. 1209050, JP-B-56-326
No. 16, the phosphonocarboxylate disclosed in JP-B-46
-Aminopolycarboxylates disclosed in US Pat.
Compounds of the general formulas (II) and (III), of which the compounds of the general formulas (II) and (III) do not contain phosphorus, have biodegradability, and have high fogging It has excellent properties such as maintaining its function.

The compounds of the general formulas [II] and [III] will be described. In the general formula [II], M ₁ , M ₂ and M ₃ represent a hydrogen atom, an alkali metal atom such as lithium, sodium or potassium, or an ammonium atom group such as an ammonium group or a tetraethylammonium group.
Further, m and n are integers of 1 or 2.

X is a hydrogen atom or a substituent. When the substituent represented by X is described in detail, an alkyl group (eg, a methyl group, an ethyl group, an isopropyl group, an n-propyl group, an n-octyl group) , T-octyl group), aralkyl group (eg, phenylmethyl group, tolylmethyl group, phenethyl group), alkenyl group (eg, allyl group, butenyl group), alkynyl group (eg, ethynyl group), alkoxy group (eg, methoxy group, ethoxy group) , T-pentyl group), aryl group (for example, phenyl group, p-tolyl group,
p-butylphenyl group), amino group (for example, dimethylamino group), acylamino group (for example, acetylamino group), sulfonylamino group (for example, alkylsulfonylamino group having 1 to 5 carbon atoms such as methanesulfonylamino group), ureido group , Urethane group, aryloxy group (eg, phenyloxy group), sulfamoyl group (eg, methylsulfamoyl group), carbamoyl group (eg, carbamoyl group, methylcarbamoyl group), alkylthio group (eg, methylthio), arylthio group (eg, phenylthio group) ), A sulfonyl group (eg, a methanesulfonyl group), a sulfinyl group (eg, a methanesulfinyl group), a hydroxy group, a halogen atom (eg, a chlorine atom,
A bromine atom, a fluorine atom, a cyano group, a sulfo group (for example, an alkylsulfo group having 1 to 5 carbon atoms), a carboxy group, a phosphono group, an aryloxycarbonyl group (for example, a phenyloxycarbonyl group), an acyl group (for example, an acetyl group, Benzoyl group), alkoxycarbonyl group (eg, methoxycarbonyl group), acyloxy group (eg, acetoxy group, butyryl group), carbonamide group (alkylamide group having 1 to 9 carbon atoms such as acetamide group, propionamide group), nitro And a hydroxamic acid group, and if possible, a dissociated product or a salt thereof (an ammonium salt or an alkali metal salt) may be used. X above
When has a carbon atom, it preferably has 1 to 1 carbon atoms.
4 things. Preferred X is a hydrogen atom, an alkyl group,
An alkoxy group, a sulfinyl group, a hydroxyl group, a halogen atom, a cyano group, a sulfo group, a carboxy group, a phosphono group, an acyl group, and a nitro group, particularly a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and a carbon atom of 1 ~ 5 alkoxy and carboxy groups are preferred. Specific examples of the compound represented by the general formula [II] are shown below, but the present invention is not limited thereto.

[0035]

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The compound of the present invention can be prepared by the method described in "Bulletin of
The Chemical Society of Japan, Vol. 42, pp. 2835-2840 (1969) (BULLETIN OF TH
ECHEMICAL SOCIETY OF JAPAN VOL. 42 2835-2
840 (1969)), Aspartic-N, N-diacetic acid.
Acid), Inorgani Chemistry (Inorgani
c Chemistry) 34 (1974), West German Patent 373961.
No. 0, JP-A-63-267751, and a method analogous thereto.

Next, the chelating agent represented by the general formula [III] will be described. In the general formula [III], M ₄ , M ₅ , M
₆ and M ₇ have the same meanings as M _{1 to} M ₃ in the general formula [III], l is an integer of 1 to 4, preferably 2 or 3,
Particularly, 2 is most preferable. Y and Z are a hydrogen atom or a substituent, and the substituent is an alkyl group (for example, a methyl group, an ethyl group, an isopropyl group, an n-propyl group, an n-
Octyl group, t-octyl group), aralkyl group (for example, phenylmethyl group, tolylmethyl group, phenethyl group),
Alkenyl group (eg, allyl group, butenyl group, pentenyl group), alkynyl group (eg, ethynyl group), alkoxy group (eg, methoxy group, ethoxy group, t-pentyl group), aryl group (eg, phenyl group, p-tolyl group) , A p-butylphenyl group), a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom), and when Y and Z have a carbon atom, the number thereof is preferably 1 to 1
4. Preferred Y and Z are a hydrogen atom and an alkyl group having 1 to 5 carbon atoms. Specific examples of the compound represented by the general formula [III] are shown below, but the present invention is not limited thereto.

[0038]

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The compounds represented by the general formula [III] of the present invention are described in JP-A-63-199295 and JP-A-3-17.
It can be synthesized according to the description in, for example, 3857 gazette. As described in these documents, the compounds represented by the general formula [III] of the present invention include optical isomers ([R, R], [S, S], [S, R]). , [R, S])
(However, depending on the compound, the [S, R] form and the [R, S] form may be structurally identical.) For example, the exemplary compound (III-1) of the compound represented by the general formula [III] of the present invention has three optical isomers ([R,
R], [S, S], [S, R] = [R, S]), which can be synthesized individually or as a mixture. It goes without saying that the present invention includes these individual optical isomers and mixtures thereof. Optical isomers [R, R], [S,
[S], [S, R] and [R, S] are each a mixture of about 25%. In addition, among the optical isomers [S,
It is preferable to selectively use the [S] form, and from this point, it is preferable to use mainly the [S, S] form as an optical isomer.
Compounds synthesized from human amino acids are preferred. In order to selectively obtain the [S, S] form, a method of synthesizing the L-form amino acid corresponding to the product as a raw material as described above, or a method of preparing a mixture of optical isomers using a commercially available column by a conventional method Separation method and the like can be mentioned. The method is preferably a synthesis method, and this method is also preferable in terms of cost.

The [S, S] compound is easily biodegradable when discharged to the environment, and is a preferable compound for environmental pollution. Here, the meaning of "selectively" or "mainly" means that the compound is present in a larger amount than other optical isomers, for example, 50% or more is [S, S] isomer. Preferably, at least 70% of the mixture of optical isomers is [S, S]
It is preferably a body, and more preferably 90% or more is a [S, S] body. Mostly, for example, 1
00% may be the [S, S] body. These compounds are available from Springer and Cobeca Chem. Zvesti.
(6): It can be synthesized based on the method described in 414-422 (1966) or the method described in JP-A-3-173857. Also,
The selective synthesis of the [S, S] form is described by UMEZAWA et al. In THE JOURNAL OFANTIBIOTICS, Vol. 37, No. 4,
It can be synthesized by the method described on page 426 (APR. 1984) and the like.

In the present invention, a particularly preferred general formula [II]
Alternatively, a reversal bath using a tin (II) chelate using the compound of the general formula [III] or both as a chelating agent has excellent characteristics over the conventionally known reversal bath, particularly in the following points. That is, as shown later, there is little decrease in the fogging action due to the aging of the reversal bath, there is no phenomenon that insoluble precipitates increase over time, and it is not a phosphorus compound as is clear from the above structure. Not restricted by wastewater regulations for phosphorus, and the biodegradability of discharged wastewater is improved. Especially, the use of the [S, S] body for optical activity reduces the burden on the environment. It becomes a reversal bath.

Tin (I) other than the compound represented by the above general formula (II) or (III) can be used in the reversal bath of the present invention.
As the chelating agent for the ion (I), any chelating agent capable of forming a water-soluble chelate with the tin (II) ion as described above can be used. Among them, the general formulas (IV), (V) and (VI) Compounds are preferred.

The general formula [IV] is a phosphonocarboxylic acid compound, the details of which will be described below. General formula (IV)

[0044]

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In the formula, R ₁ is COOM ₈ , PO (OM ₉ )
_And R ₂ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, (CH ₂ ) _n COOM _{8 or} a phenyl group, preferably a hydrogen atom, a methyl group or a carboxymethyl group. R ₃ represents a hydrogen atom, COOM ₈ . M ₈
And M ₉ represent a hydrogen atom, an alkali metal atom, or an ammonium atom group. m represents 0 or 1, and n represents an integer of 1 to 4, respectively. Specific examples of the compound represented by the general formula [IV] include the following, and a phosphonocarboxylic acid compound useful for producing a tin (II) phosphonocarboxylate chelate used in the present invention. Is not limited to this.

IV-1 1-phosphonopropane-1,2,3-tricarboxylic acid IV-2 21-phosphonobutane-2,3,4-tricarboxylic acid IV-3 1,1-diphosphonopropane-2,3 -Dicarboxylic acid IV-4 2-phosphonobutane-2,3,4-tricarboxylic acid IV-5 2,2-diphosphonobutane-3,4-dicarboxylic acid IV-6 2-phosphonobutane-1,2,4-tricarboxylic acid

These compounds are described for other uses in JP-A-49-49887, and their synthesis is described in West German Patent Publication No. 2015068.

The compound represented by the general formula [V] is a (poly) amino- (poly) carboxylic acid compound, and the details thereof will be described below. General formula [V]

[0049]

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In the formula, L ₁ represents a lower alkylene group, a hydroxy-substituted lower alkylene group, a cycloalkylene group including a substituted cycloalkylene group, or an alkylene group interrupted by an oxygen atom, and x represents 0, 1 or 2 And R
Represents a lower alkylene group including a lower alkylene group substituted with an aryl group (for example, a methylene and ethylene group), each of R ₄ and R ₅ may be the same or different and includes hydrogen, substituted lower alkyl, Represents an aralkyl group including a lower alkyl group and a substituted aralkyl group;
Examples of the substituted lower alkyl group for ₄ and R ₅ include a hydroxyl group, a halogen, an amino group, a substituted amino group (eg, a dihydroxyalkylamino group), a carboxyl group, a sulfo group, a phosphono group, a mercapto group, and a pyridyl group. Lower alkyl groups. Examples of the substituted aralkyl group for R ₄ and / or R ₅ include a hydroxyl group, a halogen, an alkyl group, an alkoxy group,
There are aralkyl groups substituted by nitro, carboxyl and sulfo groups. M ₁₀ represents a hydrogen atom, an alkali metal atom, an ammonium group of atoms. The following are examples of (poly) amino- (poly) carboxylic acid corresponding to the above general formula [V], but the invention is not limited thereto.

V-1 Ethylenediamine-N, N, N ', N'-tetraacetic acid V-2 1,2-propylenediamine-N, N, N',
N'-tetraacetic acid V-3 ethylenediamine-N, N, N ', N'-tetrapropionic acid V-4 N- (2-hydroxyethyl) -ethylenediamine-N, N, N',-triacetic acid V-5 N- (2-hydroxypropyl) -ethylenediamine-N, N ', N'-triacetic acid V-6 N- (2,3-dihydroxypropyl) -ethylenediamine-N, N, N', N'-triacetic acid V -7 N, N'-di (2-hydroxyethyl) -ethylenediamine-N, N'-diacetate V-8 diethylenetriamine-N, N, N ', N',
N'-pentaacetic acid V-9 nitriloacetic acid V-10 ethylenediamine-N, N'-di- (o-hydroxyphenylacetic acid) V-11 di- (2-hydroxyethyl) -aminoacetic acid V-12 2-hydroxyethyl -Aminoacetic acid V-13 1,2-aminocyclohexane-N, N,
N ', N'-tetraacetic acid V-14 2,3-dihydroxypropyl-aminodiacetic acid V-15 Ethylene glycol-bis (2-aminoethyl) -N, N, N', N'-tetraacetic acid V-16N , N'-Di [3-di (2-hydroxyethyl) -amino-2-hydroxypropyl] -ethylenediamine-N, N'-diacetate V-17 N- (2-hydroxyethyl) -N '-(α −
Pyridinomethyl) -ethylene-diamine-N, N'-diacetate V-18 N- (2-hydroxyethyl) -N'-phosphonomethyl-ethylenediamine-N, N'-diacetate V-19 N- (2,3- Dihydroxypropyl) -N '
-(2-sulfoethyl) -ethylenediamine-N, N '
-Diacetic acid V-20 N, N'-di (2-hydroxyethyl) -ethylenetriamine-N, N ', N'-triacetic acid V-21 N- (2-mercapto-1-carboxy-ethyl) -N '-(2-Hydroxyethyl) -ethylenediamine-N, N'-diacetate V-22 N- (3,5-dichloro-4-hydroxy-benzyl) -N'-(2-hydroxyethyl) -ethylenediamine-N , N'-Diacetic acid V-23 2-hydroxy-propylenediamine-N,
N ', N'-tetraacetic acid

Next, the details of the phosphonic acid compound which is a tin (II) chelating agent represented by the general formula [VI] will be described. General formula (VI)

[0053]

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In the formula [VI], R ⁰ represents 1 carbon atom.
C6 to C8 aralkyl, cyclohexyl, cyclopentyl, hydroxypentyl, hydroxy, C6 to C8 aryl, C6 to C8 aryl, phenyl, tolyl, carboxyphenyl, etc. pyrrolidyl alkyl group having the number of atoms of 6-9, acetamide benzyl group, or a PO ₃ M _'2 group or CH ₂ PO
₃ M 'shows the ₂ groups. M ′ has the same meaning as M _{1 to} M ₁₁ in formulas [I] to [V].

Specific examples of the compound represented by the general formula [VI] are shown below. VI-1 Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid VI-2 Nitrilo-N, N, N- Trimethylenephosphonic acid VI-3 1,2 cyclohexanediamine-N, N, N ', N'-tetramethylenephosphonic acid VI-4 o-carboxyanilino-N, N-dimethylenephosphonic acid VI-5 propylene-N , N-dimethylenephosphonic acid VI-6 propylamino-N, N-dimethylenephosphonic acid VI-7 4- (N-pyrrolidino) butylamino-N, N-bismethylenephosphonic acid VI-8 1,3-diamino Lopanol-N, N, N ', N'-tetramethylenephosphonic acid VI-9 1,3-propanediamine-N, N, N', N'-tetramethylenephosphonic acid VI-10 1,6- Hexanediamine-N, N, N ', N'-tetramethylenephosphonic acid VI-11 o-acetamidobenzylamino-N, N-dimethylenephosphonic acid VI-12 o-toluidine-N, N-dimethylenephosphonic Acid above Chelating agents of the general formula [II] ~ [VI] may be used in combination of two or more.

As is clear from the above description, the reversal bath composition of the present invention is a treating agent composition used for color reversal treatment, and may be solid or liquid. Further, it may be in the form of a paste or a suspension.

Hereinafter, the color reversal process using the reversal bath of the present invention will be described. 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) and 3-pyrazolidones (for example, 1-phenyl-3)
-Pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone), aminophenols (for example, N-methyl-p-aminophenol, N-
Methyl-3-methyl-p-aminophenols), ascorbic acid and its isomers and derivatives can be used alone or in combination. The addition amount of these developing agents is about 1 × 10 ⁻⁵ to 2 mol / l per liter of developer.

In the black and white developer of the present invention, a preservative can be used if necessary. Sulfites and bisulfites are generally used as preservatives. The amount of these additives
0.01 to 1 mol / liter, preferably 0.1 to 0.5 m
ol / liter. In addition, ascorbic acid is also an effective preservative, and a preferable addition amount is 0.01 mol / liter to 0.5 m.
ol / liter. In addition, hydroxylamines, sugars, o-hydroxyketones, hydrazines and the like 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 from 8 to 12, and most preferably from 9 to 11. Various buffering agents can be used to maintain the pH. Preferred buffering agents are carbonates, phosphates, borates, 5-sulfosalicylates, hydroxybenzoates, glycines,
N, N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3,4-dihydroxyphenylalanine salt, alanine salt, aminobutyrate, valine, lysine, and the like. Particularly carbonates, borates, 5
-Use of a sulfosalicylic acid salt is preferable in that it keeps the above pH range and is inexpensive. 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, 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. As the alkali, various hydroxides and ammonium salts can be added. For example, potassium hydroxide,
Examples include 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 about 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 development step of 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, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, Nitrogen-containing heterocyclic compounds such as -thiazolylmethyl-benzimidazole and hydroxyazaindolizine; and mercapto-substituted heterocyclic compounds such as 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole and 2-mercaptobenzothiazole, and thiosalicylic acid. Such 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. Among them, the concentration of iodide added is 5 × 1
It is about 0 ^{-6 to} 5 × 10 ^-4 mol / l. Bromides are also preferred for preventing fog, and the preferred concentration is 0.001 mol / L to 0.1 mol / L, and more preferably 0.01 to 0.1 mol / L.
It is about 0.05 mol / liter.

Further, a swelling inhibitor (for example, an inorganic salt such as sodium sulfate or potassium sulfate) is added to the black and white developer of the present invention.
Alternatively, a water softener can be contained. As the water softener, those having various structures such as aminopolycarboxylic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, and organic inorganic phosphonic acid can be used. Specific examples are shown below, but the present invention is not limited to these. Ethylenediaminetetraacetic acid, nitrilotriacetic acid, hydroxyethyliminodiacetic acid, propylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, nitrilo-
N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N'N'-tetramethylenephosphonic acid,
-Hydroxyethylidene-1,1-diphosphonic acid. Two or more of these water softeners may be used in combination. A preferable addition amount is 0.1 g to 20 g / liter, more preferably 0.1 g to 20 g / l.
5 g to 10 g / liter.

The processing time of black-and-white development is 20 seconds to 10 minutes, preferably 60 seconds to 6 minutes. Processing temperature is 20 ° -50
° C, preferably 33 ° to 45 ° C. The replenishment amount of the black-and-white developer is from 100 ml to 5000 ml, preferably from 200 ml to 2000 ml, per m ² of the light-sensitive material.

In the processing of the present invention, after black-and-white development, washing and / or rinsing are performed, and then processing is performed in a reversal bath processing step, followed by color development processing.
One washing or rinsing bath may be used, but it is more preferable to adopt a multi-stage 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 washing water is preferably from 3 liters of about 20 liters per photosensitive material 1 m ^2. The replenishing amount of the rinsing bath is 50 ml to 2 liters, more preferably 100 ml to 50 liters.
It is about 0 ml, and the amount of water used is greatly reduced as compared with the washing step. Further, an oxidizing agent, a chelating agent, a buffering agent, a bactericide, a fluorescent whitening agent, and the like can be added to the rinse bath of the present invention, if necessary.

Subsequently, a reversal bath process is started. In the present invention, the reversal bath contains the above-mentioned stannous ion and a chelating agent for stannous ion as a chemical fogging agent, or a stannous chelate in which both are combined, and has a general formula as an air oxidation inhibitor. It contains the hydroxylamine of [I] as an essential component. As the chelating agent, any known compound capable of forming a water-soluble chelate with stannous ion can be used. Particularly, the compound represented by the general formula [II] or [III]
Chelating agents are preferred. In addition, the general formulas (IV) to (VI)
Is a preferred example in which a chelating agent of the formula (1) can be used. In the fogging step, the reversal bath processing and the light fogging processing may be performed together. As described above, the method using the chemical fogging process rather than the light fogging process can maintain a stable fogging ability, can save the time and effort required for maintenance, and is concerned about running out of the light bulb in the case of the optical fogging method. It is advantageous in that there is no such thing. In a chemical fogging treatment, a borohydride compound (U.S. Pat. No. 2,984,567) and a heterocyclic amine borane compound (British Patent No. 1,011) are placed in an inversion bath.
(No. 1,000) can be added, but usually it is not necessary. The pH of the reversal bath (also referred to as a fogging bath) may range from an acidic side to an alkaline side, and may range from pH 2 to 12, preferably 2.5 to 2.5.
-10, particularly preferably 3-9.

The concentration of tin (II) ions in the reversal bath was 1 × 10 ^-3.
5 × 10 ⁻² mol / liter, preferably 2 × 10 ⁻³
1.5 × 10 ⁻² mol / l. The general formula (I
The concentration of the compound of the formula [I] to the general formula [VI] is 1 × 10 ⁻³ to 1
0 × 10 ⁻² mol / liter, preferably 2 × 10 ^{−3 to} 5 ×
It is 10 ^-2 mol / l, and the molar ratio thereof is 1 to 10 times, preferably 1.01 to 2 times, more preferably 1.1 to 1.2 times with respect to the tin (II) ion. In addition, the chelating agents of the general formulas (II) to (VI) may be used in combination, and in that case, each chelating agent may be reduced in weight as compared with the case of using alone, but the preferred range is the above range. .

The time of the reversal bath is from 10 seconds to 3 minutes, preferably from 20 seconds to 2 minutes, more preferably from 30 seconds to 90 seconds. The temperature of the reversal bath is preferably within the temperature range of the first development, followed by rinsing or rinsing and color development, or each bath, and is generally from 20 to 50 ° C, preferably from 33 to 45 ° C. The replenishing amount of the reversal bath is 10 to 2000 ml, preferably 20 to 2000 ml per m ² of the photosensitive material.
500 ml is appropriate.

The tin (II) chelate in the reversal bath is effective over a wide pH range, so that it is not necessary to add a pH buffer, but organic acids such as acetic acid, citric acid and malic acid, boric acid, Inorganic acids such as sulfuric acid and hydrochloric acid, alkali carbonate, caustic alkali, borax, potassium metaborate, etc.
It does not prevent the addition of acids, alkalis and salts for imparting H buffering properties. If necessary, a water softener such as aminopolycarboxylic acid or a swelling inhibitor such as sodium sulfate can be added. Although the hydroxylamine derivative of the general formula [I] is added to the reversal bath, an antioxidant such as p-aminophenol may be added.

After processing in the reversal bath, the process proceeds to 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-based color developing agent. As the color developing agent, a p-phenylenediamine compound is preferably used. p-
Representative examples of phenylenediamine-based compounds include 3-methyl-4-amino-N, N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, and 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, tetraphenylboron And p- (t-octyl) benzenesulfonate. If necessary, two or more of these developing agents may be used in combination. The preferable addition amount is 0.005 mol / l to 0.1 mol / l, preferably 0.01 mol / l.
It is about 0.05 mol / liter.

The pH of the color developer of the present invention is preferably in the range of 8 to 13, and most preferably 10.0 to 12.
5 Various buffers are used to maintain this pH. Examples of the buffering agent having a buffer region at pH 8.0 or more used in the present invention include carbonate, phosphate, borate, and the like.
5-sulfosalicylate, tetraborate, hydroxybenzoate, glycine, N, N dimethylglycine, leucine, norleucine, guanine, 3,4-dihydroxyphenylalanine, alanine, 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, carbonates, phosphates, 5-sulfosalicylates, tetraborates,
Hydroxybenzoate has the advantages of solubility, excellent buffering ability in the high pH range of pH 10.0 or higher, no adverse effects on photographic performance (stain, etc.) even when added to a color developer, and is inexpensive. It is particularly preferable to use these buffers.

Specific examples of these buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, and 5-sulfophosphate. Dipotassium salicylate, sodium borate, potassium borate,
Sodium tetraborate (borax), potassium tetraborate, o
-Sodium hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, 5-sulfo-
Examples thereof include sodium 2-hydroxybenzoate (sodium 5-sulfosalicylate) and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate). However, the invention is not limited to these compounds. These buffers may be added alone to the developer, or two or more of them may be added in combination.
Can be adjusted. The amount of the buffer added to the color developer was 0.1 mol / mol (when used in combination).
It is preferably at least liter, particularly preferably from 0.1 mol / l to 0.4 mol / l.

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, various pyridinium compounds represented by U.S. Pat. No. 3,171,247 and other cationic compounds,
Cationic dyes such as phenosafranine, neutral salts such as thallium nitrate and potassium nitrate, JP-B-44-9304
No. 2,533,990, U.S. Pat.
Nos. 2,950,970 and 2,577,127, nonionic compounds such as polyethylene glycol and derivatives thereof, polythioethers, and the like, US Pat.
The thioether compound described in No. 42 may be used.
If necessary, benzyl alcohol and its solvent such as diethylene glycol, triethanolamine, diethanolamine and the like 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. Examples thereof include thiocyanate, 2-methylimidazole, and thioether compounds described in JP-A-57-63580.

In the color development step of the present invention, it is not necessary to prevent development fog. However, when running while replenishing the color film, various antifoggants are used for the purpose of maintaining the stability of the composition and performance of the liquid. You may make it contain.
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, 5-nitrobenzotriazole,
-Nitrogen-containing heterocyclic compounds such as -chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, hydroxyazaindolizine and 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole, 2-mercapto Mercapto-substituted heterocyclic compounds such as benzothiazole and further mercapto-substituted aromatic compounds such as thiosalicylic acid can be used. These antifoggants include those which elute from the color reversal photosensitive material during processing and accumulate in these developers.

Various preservatives can be used in the color developing solution according to the present invention. As typical preservatives, hydroxylamines and sulfites can be used.
These addition amounts are about 0 to 0.1 mol / liter. In some cases, it is more preferable that the color developer used in the invention contains an organic preservative in place of the hydroxylamine or the sulfite ion.

The term "organic preservative" as used herein means any organic compound which, when added to a processing solution for a color photographic light-sensitive material, reduces the deterioration rate of an aromatic primary amine color developing agent.
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-57-53.
749, JP-A-59-18058
No. 8, salicylic acids described in JP-A-63-239647.
JP-A-63-128340, JP-A-1-1869
Nos. 39 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. In particular, alkanolamines such as triethanolamine, N, N-diethylhydroxylamine, N, N
-A dialkylhydroxylamine such as di (sulfoethyl) hydroxylamine, a hydrazine derivative (excluding hydrazine) such as N, N-bis (carboxymethyl) hydrazine, or an aroma represented by catechol-3,5-disulfonic acid sodium The addition of an aromatic polyhydroxy compound 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 in combination.

Other color developing solutions according to the present invention include 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 20 g.
/ Liter, preferably about 0.1 g to 5 g / liter, and if necessary, two or more kinds may be used in combination.

Further, various surfactants such as alkyl sulfonic acid, aryl sulfonic acid, aliphatic carboxylic acid and aromatic carboxylic acid polyalkylenimine may be added as required. The processing temperature of the color developing solution applicable to the present invention is 20 to 50C, preferably 33 to 45C. The processing time is 20 seconds to 5 minutes, preferably 20 seconds to 4 minutes. The replenishing amount is preferably as small as possible so as to maintain the activity, but is suitably from 100 to 2000 ml, preferably from 200 to 1000 ml, per m ^{2 of} the light-sensitive material.

The color reversal photosensitive material after the color development is
Next, the silver is removed. 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

Among the above steps, 1, 3 are particularly preferable. 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. Also, in step 11,
A method may be employed in which an overflow of the bleaching solution is introduced into the bleach-fixing solution, an overflow of the fixing solution is introduced into the bleach-fixing solution in a countercurrent manner, and the two are allowed to overflow from the bleach-fixing bath.

As the bleaching agent for the bleaching bath or the bleach-fixing bath of the present invention, the aminopolycarboxylic acid iron (III) complex salt is most commonly used at present. Representative examples of these aminopolycarboxylic acids and salts thereof include: A-1 ethylenediaminetetraacetic acid A-2 ethylenediaminetetraacetic acid disodium salt A-3 ethylenediaminetetraacetic acid diammonium salt A-4 diethylenetriaminepentaacetic acid A-5 cyclohexanediamine Tetraacetic acid A-6 Disodium salt of cyclohexanediaminetetraacetic acid A-7 Iminodiacetic acid A-8 1,3-Diaminopropanetetraacetic acid A-9 Methyliminodiacetic acid A-10 Hydroxyethyliminodiacetic acid A-11 Glycol etherdiaminetetraacetic acid A -12 Ethylenediaminetetrapropionic acid A-13 N- (2-carboxyethyl) -iminodiacetic acid A-14 Ethylenediaminedipropionic acid A-15 β-alaninediacetic acid A-16 Ethylenediaminedimalonic acid A- 17 Ethylenediaminedisuccinic acid A-18 propylenediaminedisuccinic acid and the like.

The ferric aminopolycarboxylic acid complex salt may be used in the form of a complex salt, or a ferric ion complex salt may be formed in a solution using a ferric salt and an aminopolycarboxylic acid. Further, one or more aminopolycarboxylic acids may be used. In any case, the aminopolycarboxylic acid may be used in excess of forming a ferric ion complex salt. Further, the bleaching solution or the bleach-fixing solution containing the ferric ion complex may contain a metal ion complex salt such as cobalt and copper other than iron. These bleaching agents may be added in an amount of from 0.02 mol to 0.5 mol / l of a bath having a bleaching ability.
Mol, preferably 0.05 mol to 0.3 mol.

Various bleach-fixing accelerators can be added to the bleaching bath, the bleach-fixing bath, or the conditioning bath, which is a prebath thereof, of the present invention. Examples of such bleaching accelerators include, for example, U.S. Pat. No. 3,893,858,
British Patent No. 1,388,42, JP-A-53-1
No. 41623, various mercapto compounds, compounds having a disulfide bond as described in JP-A-53-95630, and JP-B-53-95630.
Thiazolidine derivatives as described in JP-A-9854, isothiourea derivatives as described in JP-A-53-94927, JP-B-45-8506 and JP-B-49-26586. Thiourea derivatives, thioamide compounds described in JP-A-49-42349, JP-A-55-26
No. 506, dithiocarbamate salts 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-
And mercaptobutyric acid. 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 added to the bleaching solution depends on the type of photographic material to be processed, the processing temperature, and the intended processing. Depending on the time, etc., 1 liter of processing solution
It is suitably from ^10-5 to ^10-1 mol, preferably 1 x 1
It is 0 ^{-4 to} 5 × 10 ^-2 mol.

In the bleaching solution used in the present invention, besides the bleaching agent and the above compounds, bromide such as potassium bromide, sodium bromide, ammonium bromide or chloride such as potassium chloride, sodium chloride, ammonium chloride, etc. May be included. In addition, nitrates such as sodium nitrate and ammonium nitrate, boric acid, borax,
PH of sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc.
Additives known for use in bleaching solutions, such as one or more inorganic acids, organic acids and salts thereof having a buffering capacity, can be added. The pH of the solution having the bleaching ability is preferably 4.0 to 8.0, and particularly preferably 5.0 to 7.0 when used.

In the bleach-fixing solution, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate, ammonium thiocyanate and potassium thiocyanate; ethylenebisthioglycolic 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.

When a fixing solution is used in the present invention, the fixing agent is also 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 dissolving agents such as thioureas. These may be used alone or in combination of two or more. Can be used. The concentration of the fixing agent is 0.1 mol to 3 mol, preferably 0.2 mol to 2 mol per liter of the fixing solution. In the solution having a fixing ability, in addition to the above-mentioned additives, sulfites (for example, sodium sulfite, potassium sulfite, ammonium sulfite), bisulfites, hydroxylamine, hydrazine, bisulfite adducts of aldehyde compounds (for example, 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, defoamers or surfactants, polyvinylpyrrolidone, antibacterial and antibacterial agents, and organic solvents such as methanol can be contained.

The replenishing amounts of the bleaching solution, fixing solution, bleach-fixing solution and the like in the present invention can be arbitrarily set as long as the functions of the respective processing baths are satisfied, but are preferably 30 ml to 2000 ml per 1 m ² of the photographic material. More preferably 50 ml or more
1000 ml. The processing temperature is preferably 20 ° C.
To 50 ° C, more preferably 33 ° C to 45 ° C. The processing time is 10 seconds to 10 minutes, preferably 20 seconds to 6 minutes.

After desilvering such as fixing or bleach-fixing, washing and / or stabilization are generally performed. 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 countercurrent method is described in Journal of the Society of Motion Picture and Television Engineers (Journal of the Society of Motion Picture).
and Television Engineers) Vol. 64, pp. 248-253 (1955
May issue). 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, and the generated suspended matter adheres to the photosensitive material. 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 which inactivate the remaining magenta coupler to prevent fading of the dye and generation of stain, methylol compounds described in US Pat. No. 4,786,583 and hexamethylenetetramine, 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 are added. Also, US4960687, U
As described in S4975356 and US5037725, it is also possible to add an image stabilizer or a precursor thereof to a prebath of a bleaching bath.

Further, in the washing water, a surfactant as a draining agent and a chelating agent represented by EDTA as a hardening agent can be used. Continue with the above washing process or
Alternatively, it can be processed directly with an image stabilizer without going through a washing step. The image stabilizing solution contains a compound having an image stabilizing function. Examples thereof include an aldehyde compound represented by formalin, and a film pH suitable for stabilizing a dye.
And ammonium compounds for preparing the above. Further, in order to prevent the growth of bacteria in the liquid and impart fungicidal properties to the processed photosensitive material, the above-mentioned various bactericides and fungicides can be used. Further, a surfactant, a fluorescent whitening agent and a hardening agent may be added.

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.

A so-called rinsing liquid is also used as a washing liquid or a stabilizing liquid used after the desilvering treatment. The preferred pH of the washing step or the stabilizing step is 4 to 10, and more preferably 5 to 8. The temperature can be set variously depending on the use and characteristics of the photosensitive material, but is generally 20 ° C to 50 ° C, preferably 25 ° C to 45 ° C. Drying is performed following the washing and / or stabilizing step. 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, drying can be accelerated by adjusting the blowing angle of the drying air to the photosensitive material and removing the exhaust air.

Further, in order to prevent various molds and bacteria which propagate in the hydrophilic colloid layer and degrade the image, the light-sensitive material according to the present invention is protected by the method described in JP-A-63-271247. It is preferred to add a fungicide.

Next, the color reversal film according to the present invention will be described. In this film, photosensitive units are arranged in the order of red-sensitive unit, green-sensitive unit, and blue-sensitive unit in order from the one near the support, and between the red-sensitive unit and the green-sensitive unit, or between the green-sensitive unit and the blue-sensitive unit. A silver halide color photographic material having two or more non-color-forming layers on at least one of the units.

A photosensitive material having a three-layered photosensitive unit is as follows:
It is preferable to coat the low-speed emulsion layer, the medium-speed emulsion layer, and the high-speed emulsion layer in this order from the side close to the support, and a non-color-forming intermediate layer or halogen is interposed between these light-sensitive emulsion layers. A layer containing a silver halide emulsion may be applied. The photosensitive unit preferably has a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer, all of which 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. Other combinations of couplers may be mixed for the purpose of adjusting color reproducibility.

Among the units having the three-layer structure, the coating amount of the silver halide emulsion is 10% to 60% for the high-sensitivity layer and 1% for the intermediate layer, based on the total weight of the silver halide emulsion coated on the unit.
Preferably, 0% to 50% and 30% to 70% are distributed to the low-sensitivity layer, and the silver / coupler ratio in each photosensitive layer is set so that the low-sensitivity layer is maximized. Preferably, there is.

It is preferable to have a non-color-forming intermediate layer between units having different color sensitivity. The non-color-forming intermediate layer may contain a light-sensitive, non-light-sensitive or pre-fogged silver halide emulsion. In particular, it is preferable that the intermediate layer has a structure of two or more layers and five or less layers. In this case, the layer located farther from the support is provided with a colloidal silver grain or a silver halide emulsion whose surface or inside is previously fogged. Is preferably contained. When a silver halide emulsion is contained in the intermediate layer, a color mixture inhibitor is preferably added 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 consist of three light-sensitive emulsion layers, which are close to the support. To low, medium, and high sensitivity. The silver / coupler ratio in each of these light-sensitive layers is the largest in the low-speed layer, and the silver / coupler ratio in the green-sensitive emulsion layer having the highest visual sensitivity of a color image is 2 in particular.
5-150 is preferred. In this case, the silver / coupler ratio of the intermediate layer is 5 to 30, and the silver / coupler ratio of the high sensitivity layer is 2 to 30.
20 is preferred.

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 contains colloidal silver grains or a previously fogged silver halide emulsion. The thickness of the intermediate layer is 0.5 to 5 μm in total for the two layers.
m, and more preferably 1.0 to 3.0 μm.
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 antihalation layer is provided on the side closer to the support than the red-sensitive unit, and the intermediate layer is provided with at least one protective layer on the side farther from the support than the blue-sensitive unit. Preferably contains a silver halide emulsion.

Regarding various techniques and inorganic and organic materials which can be used for the silver halide photographic emulsion according to the present invention and the color reversal film using the same, Research Disclosure No. 308119 is generally used.
(1989), and in addition to that, 37038 (1995), EP 436,938.
A2 is described in the following places and in the patents cited below.

Item The relevant point 1) Layer structure Page 146, line 34 to page 147, line 25 2) Can be used in combination Page 147, line 26 to page 148, line 12 Silver halide emulsion 3) Page 137, line 35 to page 146, line 33; 14th yellow coupler, page 9, lines 21 to 23 4) Page 149, line 24 to line 28, which can be used in combination; European Patent No. 42 Magenta coupler 1, 453 A1, page 3, line 5 to page 25, line 55 5) Cyanide that can be used in combination page 149, lines 29 to 33; EP 432 Coupler, page 3 of 804A2 Line 28 to page 40, line 2 6) Polymer coupler, page 149, lines 34 to 38; EP 435, 334A2, page 113, line 39 to page 123, line 37 7) Colored coupler Page 53, line 42 to 13 Page 34, line 149, page 39, line 45 to line 8 8) Can be used together Page 7, line 1 to page 53, line 41, page 149, 46 Functional coupler line to page 150, line 3 From EP 435,334A2, page 3, line 1 to page 29, line 50 9) Antiseptic and antifungal agents, page 150, lines 25 to 28 10) Formalin, page 149, line 15 to 17th line Scavenger 11) Others that can be used in combination page 153, lines 38 to 47; Additives of EP 421, 453A1, page 75, line 21 to page 84, line 56, page 27, 40 Lines to page 37, line 40 12) Dispersion method Page 150, lines 4 to 24 13) Supports page 150, lines 32 to 34 14) Film thickness / film properties Page 150, line 35 To 49th line 15) Color development step, page 150, line 50 to page 151, line 47 16) Desilvering step, 15th Page 48 line, second 152 page 53 line 17) automatic developing machine # 152, page 54 line-page 153, line 2 18) washing and stabilizing steps page 153, line 3 to 37 row

[0104]

【Example】

(Embodiment 1) Hereinafter, the present invention will be described in detail with reference to embodiments, but is not limited thereto. 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. Number indicates the addition amount per 1 m ^2. The effect of the added compound is not limited to the use described.

First layer: antihalation layer Black colloidal silver 0.15 g Gelatin 2.00 g UV absorber U-1 0.10 g UV absorber U-3 0.040 g UV absorber U-4 0.10 g High boiling organic solvent Oil-1 0.10 g Microcrystalline solid dispersion of dye E-1 0.10 g

Second layer: Intermediate layer Gelatin 0.30 g Compound Cpd-C 5.0 mg Compound Cpd-J 5.0 mg Compound Cpd-K 5.0 mg High boiling organic solvent Oil-3 0.10 g Dye D-4 0.80 mg

Third layer: Intermediate layer A fine-grain silver iodobromide emulsion whose surface and inside are fogged (average particle size: 0.06 μm, variation coefficient: 18%, AgI content: 1 mol%) Silver amount 0.030 g Yellow colloidal silver Silver amount 0.050 g gelatin 0.30g

Fourth layer: low-sensitivity red-sensitive emulsion layer Emulsion A silver amount 0.40 g Emulsion B silver amount 0.35 g gelatin 0.80 g coupler C-11 0.10 g coupler C-1 0.05 g coupler C-9 0.010 g compound Cpd-C 5.0mg Compound Cpd-J 5.0mg High boiling organic solvent Oil-2 0.10g High boiling organic solvent Oil-4 0.05g Additive P-1 0.10g

Fifth layer: Medium-speed red-sensitive emulsion layer Emulsion B Silver content 0.25 g Emulsion C Silver content 0.25 g Gelatin 0.80 g Coupler C-11 0.05 g Coupler C-1 0.10 g Coupler C-2 0.05 g High boiling organic solvent Oil-2 0.10 g High boiling organic solvent Oil-1 0.10 g Additive P-1 0.10 g

Sixth layer: High-sensitivity red-sensitive emulsion layer Emulsion D Silver amount 0.80 g Gelatin 1.10 g Coupler C-11 0.20 g Coupler C-2 0.10 g Coupler C-3 0.60 g Additive P-1 0.10 g

Seventh layer: Intermediate layer A silver iodobromide emulsion whose surface and inside are fogged (average particle size: 0.06 μm, variation coefficient: 16%, AgI content: 0.3 mol%) Silver content 0.020 g Yellow colloidal silver Silver content 0.010 g Gelatin 1.70 g Additive M-1 0.10 g Compound Cpd-I 4.0 mg Dye D-5 0.020 g Dye D-6 0.010 g Compound Cpd-J 5.0 mg Additive P-1 0.05 g High boiling organic solvent Oil-3 0.20 g

Eighth layer: low-sensitivity green-sensitive emulsion layer Silver / coupler ratio 26.3 Emulsion E silver amount 0.25 g Emulsion F silver amount 0.30 g Emulsion G silver amount 0.30 g gelatin 0.70 g Coupler C-4 0.08 g Coupler C-7 0.08 g Coupler C-8 0.04 g Compound Cpd-B 0.030 g Compound Cpd-D 0.020 g Compound Cpd-E 0.020 g Compound Cpd-F 0.040 g Compound Cpd-J 10 mg High boiling organic solvent Oil-1 0.02 g High boiling organic solvent Oil -2 0.15g

Ninth layer: Medium-sensitive green-sensitive emulsion layer Emulsion G Silver content 0.25 g Emulsion H Silver content 0.10 g Gelatin 0.50 g Coupler C-4 0.08 g Coupler C-7 0.08 g Coupler C-8 0.04 g Compound Cpd-B 0.030 g Compound Cpd-D 0.020 g Compound Cpd-E 0.020 g Compound Cpd-F 0.050 g High boiling organic solvent Oil-2 0.050 g

Tenth layer: High-sensitivity green-sensitive emulsion layer Emulsion I Silver amount 0.45 g Gelatin 1.20 g Coupler C-4 0.25 g Coupler C-7 0.25 g Coupler C-8 0.20 g Compound Cpd-B 0.080 g Compound Cpd-E 0.020 g Compound Cpd-F 0.040 g Compound Cpd-K 5.0 mg High boiling organic solvent Oil-1 0.020 g High boiling organic solvent Oil-2 0.100 g

Eleventh layer: Yellow filter layer Yellow colloidal silver Silver content 0.010 g Gelatin 1.70 g High boiling organic solvent Oil-3 0.10 g Dye E-2 microcrystalline solid dispersion 0.030 g Dye E-3 microcrystalline solid dispersion Thing 0.020g

12th layer: low-sensitivity blue-sensitive emulsion layer Emulsion J silver amount 0.30 g emulsion K silver amount 0.30 g gelatin 0.80 g coupler C-5 0.20 g coupler C-6 0.05 g coupler C-10 0.30 g compound Cpd-I 0.02g

13th layer: Medium-sensitivity blue-sensitive emulsion layer Emulsion L Silver content 0.25 g Emulsion M Silver content 0.25 g Gelatin 0.90 g Coupler C-5 0.20 g Coupler C-6 0.05 g Coupler C-10 0.60 g

Fourteenth layer: Highly sensitive blue-sensitive emulsion layer Emulsion N silver amount 0.20 g Emulsion O silver amount 0.15 g gelatin 1.20 g Coupler C-5 0.20 g Coupler C-6 0.10 g Coupler C-10 0.60 g High boiling organic solvent Oil-2 0.15g

Fifteenth layer: First protective layer Gelatin 0.70 g UV absorber U-1 0.20 g UV absorber U-2 0.050 g UV absorber U-5 0.30 g Color mixing inhibitor Cpd-A 0.10 g Formalin scavenger Cpd- H 0.40 g Dye D-1 0.15 g Dye D-2 0.050 g Dye D-3 0.10 g High boiling organic solvent Oil-3 0.10 g

Sixteenth layer: Second protective layer Colloidal silver Silver content 0.10 mg Fine grain silver iodobromide emulsion (average particle size 0.06 μm, AgI content 1 mol%) Silver content 0.10 g Gelatin 0.40 g

Seventeenth layer: Third protective layer Gelatin 0.40 g Polymethyl methacrylate (average particle size 1.5 μ) 0.10 g Copolymer of methyl methacrylate and acrylic acid 4: 6 (Average particle size 1.5 μ) 0.10 g Silicone oil SO-1 0.030g Surfactant W-1 3.0mg Surfactant W-2 0.030g

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.

[0123]

[Table 1]

[0124]

[Table 2]

[0125]

[Table 3]

[0126]

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[0127]

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[0128]

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[0129]

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[0130]

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[0131]

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[0132]

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[0133]

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[0134]

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[0135]

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[0136]

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[0137]

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[0138]

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[0139]

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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.
The slurry was pulverized for 8 hours at a peripheral speed of about 10 m / sec and a discharge rate of 0.5 L / min. The beads were removed by filtration and diluted with water to a dye concentration of 3%.
Heat at 0 ° 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 (particle size standard deviation × 100 / average particle size) was 18%.

Similarly, solid dispersions of dyes E-2 and E-3 were obtained. Average particle size 0.54μm and 0.56μ
m.

Exposure The sample 101 obtained as described above was set to a width of 35 (135
The resultant was exposed to light of CIE illuminant D65 through a wedge for sensitometry at an exposure amount of 10 CMS.

Development The exposed sample was subjected to the following color reversal treatment. In this example, the following development processing was performed. Processing time Time 1st development 6 minutes 38 ° C First rinse 2 minutes 38 ° C Inversion 2 minutes 38 ° C Color development 6 minutes 38 ° C Pre-bleaching 2 minutes 38 ° C Bleaching 6 minutes 38 ° C Settling 4 minutes 38 ° C Second water rinse 4 minutes 38 ° C Final rinse 1 minute 25 ° C Dry 6 minutes 60 ° C

The composition of each processing solution was as follows. [First developer solution] [Tank solution] Nitrilo-N, N, N-trimethylenephosphonic acid · pentasodium salt 1.5 g Diethylenetriaminepentaacetic acid · pentasodium salt 2.0 g Sodium sulfite 30 g Hydroquinone potassium monosulfonate 20 g Carbonic acid Potassium 15 g Potassium bicarbonate 12 g 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 1.5 g Potassium bromide 2.5 g Potassium thiocyanate 1.2 g Potassium iodide 2.0 mg Diethylene glycol 13 g Add water to 1000 ml pH 9.60 pH was adjusted with sulfuric acid or potassium hydroxide.

[Inverting solution] [Tank solution] Chelating agent (described in Table 4) 0.02 mol Stannous chloride dihydrate 1.0 g p-aminophenol 0.1 g Sodium hydroxide 8 g Glacial acetic acid 15 ml Additive (Table Described in 4) 1000 ml of 0.02 mol water was added. PH 6.00 The pH was adjusted with acetic acid or sodium hydroxide.

[Color developing solution] [Tank solution] Nitrilo-N, N, N-trimethylenephosphonic acid · pentasodium salt 2.0 g Sodium sulfite 7.0 g Trisodium phosphate · 12 hydrate 36 g Potassium bromide 1.0 g Iodine Potassium iodide 90 mg Sodium hydroxide 3.0 g Citrazinic acid 1.5 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline / 3/2 sulfuric acid monohydrate 11 g 3,6 -Dithiaoctane-1,8-diol 1.0 g 1000 ml by adding water pH 11.80 The pH was adjusted with sulfuric acid or potassium hydroxide.

[Pre-bleaching] [Tank solution] Ethylenediaminetetraacetic acid disodium salt dihydrate 8.0 g Sodium sulfite 6.0 g 1-thioglycerol 0.4 g Formaldehyde sodium bisulfite adduct 30 g Add water to 1000 ml pH 6.30 pH was adjusted with acetic acid or sodium hydroxide.

[Bleaching solution] [Tank solution] Ethylenediaminetetraacetic acid disodium salt dihydrate 2.0 g Ethylenediaminetetraacetic acid Fe (III) ammonium ammonium dihydrate 120 g Potassium bromide 100 g Ammonium nitrate 10 g Water In addition, 1000 ml pH 5.70 pH was adjusted with nitric acid or sodium hydroxide.

[Fixing Solution] [Tank Solution] Ammonium thiosulfate 80 g Sodium sulfite 5.0 g Sodium bisulfite 5.0 g Water was added to adjust the pH to 1000 ml. The pH was adjusted with acetic acid or aqueous ammonia.

[Stabilizing solution] [Tank solution] 1,2-benzoisothiazolin-3-one 0.02 g Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.3 g Polymaleic acid (average molecular weight: 2,000) 0.1 g The 1000 ml pH 7.0 reversal bath with water was adjusted by changing the chelating agent and additives, and each was treated. In order to examine the stability over time of the reversal bath, each reversal bath was put in a polyethylene bottle and sealed, aged at 40 ° C. for 4 weeks, and then developed again using the bath.

Further, in order to examine the influence on the photographic properties due to the fact that the solution of the reversal bath is carried along with the film into the color developing tank in the next step, the solution of each reversal bath was added to the color developing solution for 10 minutes.
%, And the mixture is allowed to stand for one day. After that, development processing is performed using the liquid, the maximum color density portion of the blue light-sensitive layer is measured, and the decrease in density value ( _{ΔD Bmax} ) due to the mixing of the reversal bath is determined. Was.

Measurement The developed sample was measured according to the measurement conditions of international standards (ISO 5-2 and ISO 5-4), and its characteristic curve was determined. As the evaluation scale, the yellow density (blue filter light density) of the maximum density (Dmax) part of the characteristic curve and the color balance (Db-Dg and Dr-
Dg) was measured. Effect of contamination of the color developer of the reversal bath was evaluated by the difference between D _B max obtained by developing solution developed with D _B max obtained by inverting bath 10% added after aging in fresh solution (Table 4
Roh △ D _B max column). Further, the stability over time of the reversal bath was evaluated by a change in color balance between development with the new solution and development with the solution over time (Db-Dg and Dr-Dg obtained with the new solution in the column of color balance in Table 4). The difference between Db-Dg and Dr-Dg obtained with the aged solution was subtracted from the difference in the color balance change value. Note that Dr, Dg and Db
Are the red, green, and blue filter light densities of status A, respectively. , D _B max is the blue filters light concentration of maximum density (Dmax) unit, also, Fresh Table 4 is the mean of the new liquid

Results The results are shown in Table 4.

[0154]

[Table 4]

In Table 4, the reversal bath of the present invention containing the hydroxylamine derivative was added to the color developing solution of the next step, and the change in photographic properties (D _B max) was reduced even when the color developing solution was aged. That is, it is shown that the adverse effect of mixing the reversal bath is small. In particular, when mixed into color developer is a reversal bath of Comparative Example with the addition of hydroxylamine or diethylhydroxylamine, although D _B max is significant decrease but the hydroxylamine derivatives of the present invention effectively D _B max It is also shown that a decrease in the temperature is prevented. In addition, the reversal bath of the present invention showed little change in color balance between each reversal bath new solution and the aged solution obtained by aged at 40 ° C., showing little change. On the other hand, as for the aged solution, the solution to which the hydroxylamine derivative of the present invention was added did not cause precipitation, but the comparative sample became turbid. In particular, when the tin (II) chelate is a reversal bath using tin (II) ions and the general formula [II] or [III], △ D _B max (a change value of the light density of the blue filter) is more effectively suppressed. Is also shown.

[0156]

In the reversal color treatment, the reversal bath containing the stannous chelate and the hydroxylamine derivative represented by the general formula [I] has high stability against air oxidation and prevents deterioration of the liquid over time. Especially tin (II) chelate is tin (II)
In the case of comprising the ion and the chelating agent represented by the general formula [II] or [III], the photographic properties can be further improved and the water quality of phosphorus can be controlled. In addition, the chelating agents represented by the general formulas [II] and [III] also have the advantage of higher biodegradability than conventionally known chelating agents. By using the above compound, even if the processing solution is brought into the color developing tank together with the photosensitive material, the influence on the developing characteristics can be suppressed.

Claims (3)

[Claims] 1. A reversal bath composition for color reversal, comprising at least a tin (II) chelate and a hydroxylamine derivative represented by the following general formula [I]. General formula [I] (In the formula [I], L represents an alkylene group which may be substituted, and A represents a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid residue, a hydroxyl group, an amino group which may be alkyl-substituted, or an alkyl-substituted group. An optionally substituted ammonio group, an optionally substituted carbamoyl group, an optionally substituted alkyl sulfonyl group or an optionally substituted alkylsulfonyl group, and R represents a hydrogen atom or an optionally substituted alkyl group. Further, L and R may be linked to form a ring.) 2. The reversal bath according to claim 1, wherein the tin (II) chelate is a chelate comprising tin (II) ions and a chelating agent represented by the following general formula [II] or [III]. Composition. General formula [II] (Wherein, M ₁ , M ₂ and M ₃ represent a hydrogen atom, an alkali metal atom or an ammonium atom group. M and n represent 1
Or X represents an integer, and X represents a hydrogen atom or a substituent. ) General formula [III] (Wherein, M ⁴ , M ⁵ , M ⁶ and M ⁷ represent a hydrogen atom, an alkali metal atom or an ammonium atom group.
And Y and Z each represent a hydrogen atom or a substituent. ) 3. The photographed color photographic light-sensitive material according to claim 1.
Or a color reversal treatment method, wherein the treatment is performed using the reversal bath composition according to 2.