JPH095962A - Color developer composition and processing method - Google Patents

Abstract

PURPOSE: To provide a color developer composition exhibiting high sensitivity and excellent color reproducibility even in rapid processing, by which stabilized photography is obtained even in continuous processing and with the color developing time shortened and to furnish a processing method using the composition. CONSTITUTION: This color developer contains a compd. shown by the general formula. In the formula, R1, R2, R3, R4 and R5 are independently hydrogen atom, aliphatic hydrocarbonic group, aryl, heterocyclic group, substituted or unsubstituted thioureido group, substituted or unsubstituted amino group, hydroxyl, alkoxyl, sulfonyl or acyl, where R1, R2, R3, R4 and R5 are not hydrogen atom, unsubstituted thioureido group, unsubstituted amino group or hydroxyl at the same time.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color developer composition for a silver halide color photographic light-sensitive material and a processing method using the same, and more particularly to a color developer containing a novel silver halide solvent. The present invention relates to a composition and a method for processing a silver halide color photographic light-sensitive material using the composition.

[0002]

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

In recent years, photo shops (called mini-labs) having small automatic processors installed in stores have become available in various places, and photo processing has become possible in the immediate vicinity of users, and the demand for rapid processing is ever increasing. . However, conventionally,
The speeding up of the processing was done in the desilvering process, and in the color developing process, C-41 introduced by Kodak Co. in 1972 was used.
Since the color development time was reduced to 3 minutes and 15 seconds by the processing, it was hardly shortened. Currently, the ratio of color development time to the total development processing time is about 40%,
For further speeding up, it is essential to develop a technique for significantly shortening the color development time.

For shortening the color development time, it is well known that the developing activity is increased by increasing the temperature of the developing solution, increasing the pH, and increasing the concentration of the color developing agent. However, in any of the methods, the speeding up is insufficient, the liquid is severely deteriorated, and the color reproducibility is deteriorated. On the other hand, there is a method of increasing the silver chloride content in order to accelerate the development rate of silver halide. As described above, exposed silver halide releases halogen ions when it is reduced by a color developing agent to produce silver, but the more easily the halogen ions are released (the higher the solubility of silver halide), the more developed The developing speed increases in the order of silver iodide, silver bromide, and silver chloride.
A method for increasing the silver chloride content and speeding it up is disclosed in JP-A-3-1495.
As disclosed in JP-A No. 46, there is a drawback that the sensitivity is lowered and the image quality such as graininess is also lowered when the content of silver chloride is increased, and it is particularly suitable for a color negative photosensitive material for photographing which requires high sensitivity and high image quality. Has not been applied yet.

JP-A-62-253161 discloses a method of increasing the solubility of silver halide and increasing the developing rate by using a color developing solution containing a silver halide solvent. The thiourea derivative represented by the general formula (I) described in the patent has high solubility in silver halide and is also used as a fixing agent. However, the stability of the thiourea derivative in a color developing solution is insufficient, and its solubility in silver halide containing silver iodide is also insufficient, so that a large increase in speed cannot be expected. Furthermore, it reacts with silver halide to produce silver sulfide, increasing the density of unexposed areas,
There was a problem that sensitivity was lowered.

[0006]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a color developer composition capable of shortening the color development time and a processing method using the same, and to provide a color developing solution with high sensitivity even with rapid processing. The object is to provide excellent photographic properties with excellent reproducibility and continuous processing.

[0007]

The above objects have been achieved by the following methods (a) and (b). That is, (a) a color developer composition containing at least one compound represented by formula (I). General formula (I)

[0008]

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R1, R2, R3, R4 and R5 are each independently a hydrogen atom, an aliphatic hydrocarbon group, an aryl group,
It represents a heterocyclic group, a substituted or unsubstituted thioureido group, a substituted or unsubstituted amino group, a hydroxy group, an alkoxy group, a sulfonyl group or an acyl group. However, R1,
R2, R3, R4 and R5 are not a hydrogen atom, an unsubstituted thioureido group, an unsubstituted amino group or a hydroxy group at the same time. Also, R1 and R3, R2 and R4,
R3 and R5, R4 and R5 may form a ring. However, R1, R2, R3, at least one of R4 and _{R5, -SO 3 M, -CO 2 Y} , amino group, at least one-substituted aliphatic hydrocarbon group for a hydroxy group, an aryl group, a heterocyclic It represents a ring group, a substituted thioureido group, a substituted amino group, an alkoxy group, a sulfonyl group or an acyl group. M and Y represent a hydrogen atom, ammonium, an alkali metal, or an alkaline earth metal. (B) A silver halide color characterized by color-developing an imagewise exposed silver halide color photographic light-sensitive material with a developer containing at least one compound represented by the general formula (I). Processing method of photographic light-sensitive material.

Next, the general formula (I) used in the present invention will be described in detail. In the general formula (I), the aliphatic hydrocarbon group represented by R1 to R5 is a linear, branched or cyclic alkyl group (for example, methyl, ethyl, isopropyl, n-propyl, t-butyl, n-octyl). , N-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, 2-sulfoethyl, sulfomethyl, 3-sulfopropyl, 2,3-disulfopropyl,
Carboxymethyl, 2-carboxyethyl, 1-carboxyethyl, 3-carboxypropyl, 1,2-dicarboxyethyl, 1,3-dicarboxypropyl, 2,3
-Dicarboxypropyl, 1-carboxy-2-methylpropyl, 1-carboxy-3-methylbutyl, hydroxymethyl, 2-hydroxyethyl, 1-hydroxyethyl, 1,2-dihydroxyethyl, 3-hydroxypropyl, 1,3 -Dihydroxypropyl, 2,3-dihydroxypropyl, aminomethyl, 2-aminoethyl,
1-aminoethyl, 1,2-diaminoethyl, 3-aminopropyl, 1,3-diaminopropyl, 2,3-diaminopropyl, 1-carboxy-2-hydroxyethyl, 1-carboxy-2-hydroxypropyl, 2 -Carboxy-2-hydroxyethyl, 1-carboxy-3
-Hydroxypropyl, 2-amino-1-carboxyethyl, 2-amino-1-carboxypropyl, 2-amino-2-carboxyethyl, 1-carboxy-2-methylthioethyl, 1-carboxy-2-methylthiopropyl, 1 -Carboxy-3-methylthiopropyl, 1-carboxy-2-ethylthioethyl, 1-carboxy-3
-Ethylthiopropyl, 2- (5-imidazolyl) -1
-Carboxyethyl, 1-carboxy-2-mercaptoethyl, 2-aminocarbonyl-1-carboxyethyl, 2-N, N-dimethylaminoethyl, 2-N, N-
Diethylaminoethyl, 2-N, N-dimethylaminopropyl etc.), alkenyl group (eg allyl, 2-butenyl, 3-pentenyl etc.), alkynyl group (eg piropagyl, 3-pentynyl etc.), aralkyl group (eg Benzyl, 4-sulfobenzyl, 4-carboxybenzyl, etc.) and the like.

In the general formula (I), the aryl group represented by R1 to R5 is a monocyclic or condensed ring aryl group, and is phenyl, 4-sulfophenyl, 4-carboxyphenyl, 2-carboxy-4-sulfo. Examples thereof include phenyl and naphthyl.

In the general formula (I), the heterocyclic group represented by R1 to R5 is a 3- to 10-membered saturated or unsaturated heterocyclic group containing at least one of nitrogen atom, oxygen atom and sulfur atom. It is a cyclic group. These may be monocyclic or may form a condensed ring with another aromatic. The heterocyclic group is preferably a 5- or 6-membered aromatic heterocyclic group, and examples thereof include a pyridyl group, a pyrazolyl group, an isoquinolinyl group, a thiazolyl group, a thienyl group, a furyl group and a benzothiazolyl group.

In the general formula (I), the thioureido groups represented by R1 to R5 include unsubstituted thioureido, N-methylthioureido, N-phenylthioureido, N-sulfoethylthioureido, N-carboxymethylthioureido, N-carboxyethyl thioureido etc. are mentioned.

In the general formula (I), the amino group represented by R1 to R5 is an unsubstituted amino group or an alkylamino group (eg, methylamino, ethylamino, isopropylamino, 2-hydroxyethylamino, 2). -Carboxyethylamino, carboxymethylamino, 2-sulfoethylamino, 2-aminoethylamino, 2-N, N-
Dimethylaminoethylamino, 2-N, N-diethylaminoethylamino, aminomethylamino, etc.), etc.,
An unsubstituted amino group, a 2-sulfoethylamino group, a carboxymethylamino group and a 2-carboxyethylamino group are preferable.

Examples of the alkoxy group represented by R1 to R5 in the general formula (I) include methoxy, ethoxy, isopropoxy, 2-hydroxyethoxy, 2-aminoethoxy, 2-carboxyethoxy and 2-sulfoethoxy. Etc., preferably methoxy, ethoxy, 2-sulfoethoxy, and 2-carboxyethoxy.

Examples of the sulfonyl group represented by R1 to R5 in the general formula (I) include methanesulfonyl group, ethanesulfonyl group, hydroxyethanesulfonyl group, paratoluenesulfonyl group, phenylsulfonyl group, methoxyethanesulfonyl group and An aminoethane sulfonyl group etc. are mentioned.

In the general formula (I), examples of the acyl group represented by R1 to R5 include acetyl, benzoyl, formyl and pivaloyl.

In the general formula (I), R1 and R3, R2 and R4
, R3 and R5, R4 and R5 may form a ring, for example, a pyrrolidine ring, an imidazolidine ring, a triazine ring,
And an oxazolidine ring.

The aliphatic hydrocarbon moieties, aryl moieties, heterocyclic moieties, thioureido moieties, amino moieties, alkoxy moieties, sulfonyl moieties, acyl moieties and R1 and R3 represented by R1 to R5 in the general formula (I). , R2 and R4,
The ring formed by R3 and R5, R4 and R5 may have a substituent, and examples of the substituent include a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.), an alkyl group (eg, methyl, Ethyl, isopropyl, n-propyl, t-butyl, n-octyl, cyclopentyl, cyclohexyl etc.), alkenyl group (eg allyl, 2-butenyl, 3-pentenyl etc.), alkynyl group (eg propargyl, 3-pentynyl etc.), Aralkyl groups (eg benzyl, phenethyl etc.), aryl groups (eg phenyl, naphthyl, 4-methylphenyl etc.), heterocyclic groups (eg pyridyl, furyl, imidazolyl, piperidyl, morpholyl etc.), alkoxy groups (eg methoxy,
Ethoxy, butoxy etc.), aryloxy group (eg phenoxy, 2-naphthyloxy etc.), sulfamoyl group (eg unsubstituted sulfamoyl group, N, N-dimethylsulfamoyl, N-phenylsulfamoyl etc.), carbamoyl group ( For example, unsubstituted carbamoyl, N, N-diethylcarbamoyl, N-phenylcarbamoyl and the like), thiocarbamoyl group (eg unsubstituted thiocarbamoyl,
N, N-diethylthiocarbamoyl, N-phenylthiocarbamoyl etc.), sulfonyl group (eg mesyl, tosyl etc.), sulfinyl group (eg methylsulfinyl,
Phenylsulfinyl etc.), alkyloxycarbonyl group (eg methoxycarbonyl, ethoxycarbonyl etc.), aryloxycarbonyl group (eg phenoxycarbonyl etc.), acyl group (eg acetyl, benzoyl, formyl, pivaloyl etc.), acyloxy group (eg acetoxy, Benzoyloxy etc.), phosphoric acid amide group (eg N, N-diethyl phosphoric acid amide etc.), alkylthio group (eg methylthio, ethylthio etc.), arylthio group (eg phenylthio etc.), cyano group, thiosulfonic acid group, sulfinic acid Group, a mercapto group, a phosphono group, a nitro group, a sulfino group, an ammonio group, (for example, trimethylammonio, etc.), a phosphonio group, a hydrazino group and the like. When there are two or more substituents, they may be the same or different.

In the general formula (I), R1, R2, R3 and R4
At least one of and _R5, -SO 3 _M, -C
O ₂ Y, an aliphatic hydrocarbon group substituted with at least one of an amino group (eg, unsubstituted amino, methylamino, dimethylamino, ethylamino, diethylamino, isopropylamino, acetamino, etc.) and a hydroxy group, aryl Group, heterocyclic group, substituted thioureido group,
It represents a substituted amino group, an alkoxy group, a sulfonyl group or an acyl group, preferably an -SO ₃ M, -CO ₂ Y, an aliphatic hydrocarbon group substituted with at least one of an unsubstituted amino group, and a substituted thioureido group. Represents a substituted amino group, and more preferably represents an aliphatic hydrocarbon group substituted with at least one of —SO ₃ M and —CO ₂ Y. In addition, M and Y represent a hydrogen atom, ammonium (eg, unsubstituted ammonium, triethylammonium, tetramethylammonium, etc.), alkali metal (eg, sodium, potassium, etc.) and alkaline earth metal (eg, calcium, magnesium, etc.), Preferred are hydrogen atom, ammonium and alkali metal, and more preferred are hydrogen atom and sodium. The most preferable M is sodium, and the most preferable Y is a hydrogen atom.

R1, R2 and R3 in the general formula (I) are described below.
, Preferred combinations of R4 and R5 are described.

In the general formula (I), R1, R2, R3 and R4
And each as the R5 independently represent a hydrogen atom, an aliphatic hydrocarbon group, or a substituted thioureido group and a substituted amino group, R1, R2, R3, R4 and at least one -SO ₃ M among R5, -CO ₂ Y And an aliphatic hydrocarbon group substituted with at least one of an unsubstituted amino group, a substituted thioureido group and a substituted amino group.
Further, in the general formula (I), R1, R2, R3, R4 and R5 are each a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and at least one of R1, R2 and R5 is-
1 to 10 carbon atoms substituted with SO ₃ M and —CO ₂ Y
Is preferably an alkyl group. The most preferred combination of R1, R2, R3, R4 and R5 is that R1 and R2 are hydrogen atoms or have 1 to 5 carbon atoms.
Is an alkyl group (eg methyl, ethyl, etc.) of R3
And R4 is a hydrogen atom, R5 is at least one -SO ₃ M, -CO ₂ Y-substituted alkyl group having 1 to 5 carbon atoms (e.g., 2-sulfoethyl, carboxymethyl, 2-carboxyethyl, etc.) Is.

Specific examples of the compound represented by formula (I) are shown below, but the invention is not limited thereto.

[0024]

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[0025]

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[0026]

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[0027]

[Chemical 6]

[0028]

[Chemical 7]

[0029]

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[0030]

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[0031]

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These compounds are disclosed, for example, in JP-A 64-35.
Method described in Japanese Patent No. 550, Synthesis, 24
3-292 (1973), Journal of the American Chemical Society (J. Am. Chem. So
c.), Vol. 69, 2136 (1967), etc. for easy synthesis.

The amount of the compound of the present invention to be added depends on the color developer 1
The amount is preferably 0.1 mmol or more and 50 mmol or less, more preferably 0.3 mmol or more and 10 mmol or less, and most preferably 0.5 mmol or more and 5.0 mmol or less.
It is below millimolar.

If the addition amount is less than 0.1 mmol, the effect of the present invention is small, and if the addition amount is more than 50 mmol, the silver development in the unexposed area is increased. Further, the compound of the present invention
Two or more kinds may be used in combination depending on the purpose.

The color developer composition of the present invention will be described below. The color developer composition of the present invention basically comprises an alkaline aqueous solution containing at least one compound of the present invention and at least one color developing agent.

In the present invention, the color developing agent is preferably a p-phenylenediamine derivative, of which representative examples are shown below. (D-1) 2-methyl-4- [N-ethyl-N- (β
-Hydroxyethyl) amino] aniline (D-2) 2-methyl-4- [N-ethyl-N- (3
-Hydroxypropyl) amino] aniline (D-3) 2-methyl-4- [N-ethyl-N- (4
-Hydroxybutyl) amino] aniline (D-4) 2-methyl-N, N-diethyl-p-phenylenediamine (D-5) 2-methyl-4- [N-ethyl-N- (β
-Methanesulfonamidoethyl) amino] aniline (D-6) 2-methoxy-4- [N-ethyl-N-
(Β-Hydroxyethyl) amino] aniline (D-7) 4-amino-3-methoxy-N, N-bis (3-hydroxypropyl) aniline (D-8) 4-amino-3-isopropoxy-N,
N-bis (β-hydroxyethyl) aniline (D-9) 1- (β-hydroxyethyl) -5-amino-6-methyl-indoline (D-10) 1,2,3,4-tetrahydro-1-
(3,4-dihydroxybutyl) -2,2,4,7-tetramethyl-6-amino-quinoline (D-11) 1,2,3,4-tetrahydro-1- (β
-Hydroxyethyl) -4-hydroxymethyl-6-amino-7-methyl-quinoline

In the present invention, D-1, D-2, D-
3, D-6, D-7, D-8, D-10, and D-11 are particularly preferred, and D-1, D-2, and D-3 are more preferred.
D-1 is most preferred.

The concentration of the color developing agent is preferably 15 mmol or more and 80 mmol or less, more preferably 20 mmol or more and 60 mmol or less, and particularly preferably 25 mmol or more and 50 mmol or less, per liter of the developing solution. Within the concentration range of the developing agent, the amount of the developing agent is 2
It is also possible to use a combination of two or more species.

The color developing solution of the present invention is not limited to hydroxylamine, diethylhydroxylamine, and JP-A-3-144.
Hydroxylamines represented by the general formula (I) of No. 446, sulfites, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, various preservatives such as catecholsulfonic acid, Organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, 1-phenyl-3
-Auxiliary developing agents such as pyrazolidone, viscosity imparting agents, various chelating agents represented by aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid , Diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid,
1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo
-N, N, N-trimethylenephosphonic acid, ethylenediamine-
Representative examples are N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof.

Of the above, substituted hydroxylamine is most preferable as the preservative, and among them, diethylhydroxylamine, monomethylhydroxylamine or an alkyl group substituted with a water-soluble group such as a sulfo group, a carboxy group or a hydroxyl group is used as a substituent. Those having are preferred. The most preferable examples include N, N-bis (sulfonate ethyl) hydroxylamine, monosulfonate ethylhydroxylamine, diethylhydroxylamine and the like.

Any antifoggant can be added to the color developer used in the present invention, if necessary. As the antifoggant, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide and organic antifoggants can be used. Examples of the organic antifoggants include benzotriazole, 6-nitrobenzimidazole,
5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-
Representative examples thereof include nitrogen-containing heterocyclic compounds such as benzotriazole, 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine.

The color developing solution used in the present invention preferably has a pH range of about 9.5 to 10.5. If the developing activity can be maintained, it is preferable that the pH of the developing tank liquid is low also in the sense of preventing the generation of ammonia gas from the waste liquid. The most preferable pH of the tank liquid is 9.9 to 1
It is about 0.4. In order to maintain the above pH, it is preferable to use various buffers. As the buffer, carbonate,
Phosphate, borate, tetraborate, hydroxybenzoate, glycyl salt, N, N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3,4-dihydroxyphenylalanine salt, alanine salt, amino Butyrate,
2-amino-2-methyl-1,3-propanediol salt, valine salt, proline salt, trishydroxyaminomethane salt, lysine salt and the like can be used. Particularly, use of a carbonate is preferred. The amount of the buffer added to the developer is
It is preferably 0.1 mol / liter or more, and particularly
It is particularly preferably from 0.1 mol / liter to 0.4 mol / liter. Further, a compound having biodegradability is preferable as the chelating agent. An example of this is Japanese Patent Laid-Open No. 63-
146998, JP-A-63-199295, JP-A-63-267750, JP-A-63-267751,
JP-A-2-229146, JP-A-3-186841
Examples thereof include chelating agents described in German Patent No. 3739610, European Patent No. 468325, and the like. It is preferable that the processing solution in the color developing solution replenishing tank or the processing tank is shielded with a liquid agent such as a high-boiling point organic solvent to reduce the contact area with air. Liquid paraffin is most preferred as the liquid shielding agent. It is particularly preferable to use it as a replenisher. The processing temperature of the color developer in the present invention is 3
The temperature is 0 to 55 ° C, preferably 35 to 55 ° C. The processing time is 20 seconds to 5 minutes, preferably 30 for the photographic light-sensitive material.
Second to 3 minutes and 20 seconds, 30 seconds to 9 from the viewpoint of rapid processing
0 second is more preferable, and 45 seconds to 75 seconds is the most preferable.
In addition, the replenishment amount is 30 to 800 per square meter of sensitive material.
ml, preferably about 50 to 500 ml.

When the reversal process is carried out, black and white development is usually carried out before color development. In this black-and-white developer, known black-and-white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol are used alone. Alternatively, they can be used in combination. Any development accelerator can be added to the developer used in the present invention, if necessary. As development accelerators, JP-B-37-16088, JP-B-37-5987, JP-B-38-7826
Nos. 44-12380, 45-9919 and U.S. Pat.
Thioether compounds represented by JP-A No. 247, etc.
-49829 and 50-15554, p-phenylenediamine compounds, JP-A-50-137726, JP-B-44-300
74, quaternary ammonium salts represented by JP-A-56-156826 and JP-A-52-43429, U.S. Pat. No. 2,494,903,
No. 3,128,182, No. 4,230,796, No. 3,253,919, Japanese Patent Publication No. 41-11431, U.S. Patent No. 2,482,546, No. 2,596,92
6 and 3,582,346, etc., amine compounds, JP-B-37-16088, JP-B-42-25201, U.S. Pat.
No. 4, Japanese Patent Publication Nos. 41-11431 and 42-23883, and U.S. Pat.
Polyalkylene oxides represented by 532,501 and the like,
In addition, 1-phenyl-3-pyrazolidones, imidazoles, and the like can be added as needed.

In the present invention, after color development processing, desilvering processing is carried out in the desilvering step. The details of the desilvering process will be described below. The desilvering process generally has a bleaching process, a bleach-fixing process, and a fixing process, and there are various processes. Specific steps are shown below, but are not limited thereto.

(Step 1) Bleach-fixing (step 2) Bleach-bleach-fixing (step 3) Bleach-bleach-fixing-fixing (step 4) Fixing-bleach-fixing (step 5) Bleach-fixing

As the bleaching agent used in the processing solution having bleaching ability, aminopolycarboxylic acid iron (III) complex, persulfate, bromate, hydrogen peroxide, red blood salt and the like can be used. The polycarboxylic acid (III) complex can be most preferably used. The ferric iron complex salt used in the present invention may be added and dissolved as a complexed iron complex salt in advance, and the complex forming compound and the ferric iron salt (for example, ferric sulfate, ferric chloride) may be added. Iron, ferric bromide, iron (III) nitrate, iron (III) ammonium sulfate, etc.) may coexist to form a complex salt in a liquid having a bleaching ability. The complex-forming compound may be slightly in excess of the amount required for complex formation with ferric ion, and when it is added in an excess amount, it is usually 0.01 to 1
It is preferable to make it excessive in the range of 0%.

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

The concentration of the ferric complex salt in the treatment solution having a bleaching ability of the present invention is appropriately in the range of 0.005 to 1.0 mol / liter, and 0.01 to 0.50 mol / liter.
It is preferably in the range of liter, more preferably 0.02.
０．３0.30 mol / liter. The concentration of the ferric complex salt in the replenisher for the processing solution having bleaching ability is
The amount is preferably 0.005 to 2 mol / liter, more preferably 0.01 to 1.0 mol / liter.

Various compounds can be used as a bleaching accelerator in a bath having a bleaching ability or a prebath thereof. For example, compounds having a mercapto group or a disulfide bond described in U.S. Pat. No. 3,893,858, German Patent 1,290,812, JP-A-53-95630 and Research Disclosure No. 17129 (July 1978). And Japanese Patent Publication No. 45-8506, Japanese Patent Laid-Open Nos. 52-20832, 53-3
2735, U.S. Pat. No. 3,706,561 and the like, and thiourea compounds or halides such as iodine and bromine ions are preferable because of their excellent bleaching power.

Other bleaching baths applicable to the present invention include bromide (eg potassium bromide, sodium bromide, ammonium bromide) or chloride (eg potassium chloride, sodium chloride, ammonium chloride). Alternatively, a rehalogenating agent such as iodide (eg, ammonium iodide) can be included. PH of borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, malonic acid, succinic acid, glutaric acid, etc. It is possible to add one or more kinds of inorganic acids and organic acids having a buffering capacity and their alkali metal or ammonium salts, or corrosion inhibitors such as ammonium nitrate and guanidine. Further, the bath having a bleaching ability may contain various other fluorescent whitening agents, antifoaming agents or surfactants, polyvinylpyrrolidone, organic solvents such as methanol.

The fixing agent component in the bleach-fixing solution or the fixing solution is
Known fixing agents, ie, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; sodium thiocyanate,
Thiocyanates such as ammonium thiocyanate; ethylenebisthioglycolic acid, 3,6-dithia-1,8-
It is a water-soluble silver halide dissolving agent such as a thioether compound such as octanediol, a mesoionic compound and thioureas, and these can be used alone or as a mixture of two or more. Further, a special bleach-fixing solution containing a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can be used. In the present invention, the use of thiosulfates, particularly ammonium thiosulfate and sodium thiosulfate, is preferred. The amount of fixer per liter is 0.3
Is preferably 2 to 2 mol, more preferably 0.5 to 1.0 mol. The bleach-fixing solution or fixing solution of the present invention preferably contains a sulfite (or bisulfite or metabisulfite) as a preservative, but is preferably 0.08-
0.4 mol / liter, more preferably 0.1 to 0.3
It is preferable that the content is mol / liter. By using this concentration range and further using the final bath of the present invention, not only the magnetic recording performance was remarkably improved, but also desirable results were shown in terms of image storability. The bleach-fixing solution or fixing solution of the present invention is a sulfite (for example, sodium sulfite, potassium sulfite, ammonium sulfite) or bisulfite (for example, ammonium bisulfite, sodium bisulfite, potassium bisulfite) described above as a preservative. In addition to containing sulfite ion-releasing compounds such as metabisulfite (eg, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite), aldehydes (benzaldexide, acetaldehyde, etc.), ketones (acetone, etc.) , Ascorbic acid, hydroxylamines and the like can be added as necessary.

Further, a bleaching solution, a bleach-fixing solution and a fixing solution may be added with a buffering agent, a fluorescent whitening agent, a chelating agent, a defoaming agent, an antifungal agent and the like, if necessary. In the bleaching solution and the bleach-fixing solution used in the present invention, the preferred pH range is 4.5.
It is -6.2 and more preferably 5-6. Magnetic recording performance may not be sufficiently exhibited at a pH higher or lower than the main pH. In the case of a fixer, the pH is 5-8.
A degree is desirable.

Bleaching solution, bleach-fixing solution used in the present invention,
The replenishing amount of the fixing solution is 50 to 200 per 1 m ² of the light-sensitive material.
0 ml. Particularly preferably 100 to 100
It is 0 ml. Further, washing water as a post-bath or overflow solution of a stabilizing bath may be replenished as necessary.
The processing temperature of the bleaching solution, the bleach-fixing solution and the fixing solution is 20 to 50 ° C.
And preferably 30 to 45 ° C. Processing time is 1
It is 0 second to 3 minutes, preferably 20 seconds to 2 minutes.

The processing liquid having a bleaching ability of the present invention is particularly preferably subjected to aeration during processing because the photographic performance can be kept extremely stable. Any means known in the art can be used for aeration, and air can be blown into a processing solution having bleaching ability, or air can be absorbed using an ejector. When blowing air, it is preferable to release air into the liquid through a diffuser having fine pores. Such an air diffuser is widely used as an aeration tank in activated sludge treatment. Regarding aeration, Eastman Kodak's Z-121, Using Process C-41 No. 3
The matters described in the edition (1982), pages BL-1 to BL-2 can be used. In the processing using the processing solution having the bleaching ability of the present invention, it is preferable that the stirring is strengthened.
Page, upper right column, line 6-lower left column, line 2
Can be used as is.

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

The automatic processor used in the light-sensitive material of the present invention is disclosed in JP-A-60-191257, JP-A-60-191258 and JP-A-60-1912.
It is preferable to have a photosensitive material conveying means described in No. 59. As described in the above-mentioned JP-A-60-191257, such a conveying means can remarkably reduce the carry-in of the treatment liquid from the front bath to the rear bath, and is highly effective in preventing the performance deterioration of the treatment liquid. Such an effect is particularly effective for reducing the processing time in each step and reducing the replenishing amount of the processing solution.

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

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

The stabilizing solution used in the stabilizing step is a processing solution for stabilizing the dye image, such as an organic acid or a pH of 3 to 10.
6, a solution containing an aldehyde (for example, formalin or glutaraldehyde), or the like. The stabilizing solution may contain all compounds that can be added to the washing water, and in addition, if necessary, ammonium compounds such as ammonium chloride and ammonium sulfite, metal compounds such as Bi and Al, optical brighteners and hardeners. Agents such as alkanolamines described in US Pat. No. 4,786,583 can be used.

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

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

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

The N-methylol compound is preferably an N-methylol compound of pyrazole or its derivative, an N-methylol compound of triazole or its derivative, or an N-methylol compound of urazole or its derivative. Specific examples of these N-methylol compounds include 1-hydroxymethylpyrazole, 1-hydroxymethyl-2-methylpyrazole, 1-hydroxymethyl-2,4-dimethylpyrazole, 1-hydroxymethyl-1,2,4. -Triazole, 1-hydroxymethylurazole and the like can be mentioned. Of these, particularly preferred are 1-hydroxymethylpyrazole and 1-hydroxymethyl-1,2,4-triazole. N above
The methylol compound can be easily synthesized by reacting an amine compound having no methylol group with formaldehyde or paraformaldehyde. When the above N-methylol compound is used, it is preferable that an amine compound having no methylol group is allowed to coexist in the treatment liquid, and it is preferable that the N-methylol compound is present at a molar concentration of 0.2 to 10 times.

As the azolylmethylamine compound,
1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine and 1,4-bis (pyrazol-1-ylmethyl) piperazine may be mentioned, which may be combined with an azole such as 1,2,4-triazole or pyrazole. Combined use (Japanese Patent Laid-Open No.
No. 359249), the image stability is high and the formaldehyde vapor pressure is small, and thus it is particularly preferable. The addition amount of the formaldehyde substitute compound is 0.003 to 0.2 mol, preferably 0.005 to 0.05 mol, per liter of the treatment liquid. Two or more of these formaldehyde substitute compounds may be used in combination in the bath.

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

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

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

Photosensitive materials applicable to the processing of the present invention include color negative films and color reversal films (internal type,
External type), color papers, color reversal papers, color negative films for movies, color positive films for movies, color negative slides, color reversal films for televisions, direct positive color papers, and the like. For example, JP-A-3-33847, No. 3-293662, No. 4-13
No. 0432 and the like. Further, the type of silver halide used in the support of the light-sensitive material of the present invention; coating method; silver halide emulsion layer, surface protective layer (eg, silver iodobromide, silver iodochlorobromide, silver bromide). , Silver chlorobromide, silver chloride), its particle shape (eg, cubic, tabular, spherical), its particle size, its variability, its crystal structure (eg, core / shell structure, multiphase structure, homogeneous phase structure). , Its manufacturing method (eg, single jet method, double jet method),
Binders (eg gelatin), hardeners, antifoggants, metal doping agents, silver halide solvents, thickeners, emulsion precipitants, size stabilizers, adhesion inhibitors, stabilizers, color mixing inhibitors, dye images Stabilizers, anti-staining agents, chemical sensitizers, spectral sensitizers, sensitivity enhancers, supersensitizers, nucleating agents, couplers (for example, pivaloyl acetanilide type or benzoyl acetanilide type yellow couplers, 5- Pyrazolone type or pyrazoloazole type magenta coupler, phenol type or naphthol type cyan coupler, DIR coupler,
Bleach accelerator-releasing coupler, competitive coupler, colored coupler), coupler dispersion method (for example, oil-in-water dispersion method using a high boiling point solvent), plasticizer, antistatic agent, lubricant,
Coating aid, surface active agent, whitening agent, formalin scavenger, light scattering agent, matting agent, light absorbing agent, ultraviolet absorbing agent,
Filter dye, irradiation dye, development improver,
There are no particular restrictions on matting agents, preservatives (for example, 2-phenoxyethanol), antifungal agents, and the like. For example, Product Licensing 92
Volume 107-110 (December 1971) and Research Disclosure (hereinafter referred to as RD) No. 17643 (December 1978), R
D magazine No. 18716 (November 1979), RD magazine No.
It is also possible to refer to the description of 307105 (November 1989) and the like.

In the processing method of the present invention, any color light-sensitive material can be used, but in using the present invention, preferable dry film thickness, swelling ratio and swelling rate of all the constituent layers of the color light-sensitive material are as follows. JP-A-5-66527, paragraphs "0099" to "0100", and the silver halide contained in the photographic emulsion layer of the color light-sensitive material may have any silver halide composition. For example, silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver iodochloride or silver iodochlorobromide. In the case of color photographic materials for photography and color reversal photographic materials (for example, color negative film, reversal film, color reversal paper),
Silver iodobromide, silver iodochloride, or silver iodochlorobromide containing 0.1 to 30 mol% of silver iodide is preferable. Particularly, silver iodobromide containing 1 to 25 mol% of silver iodide is preferable. In the case of a direct positive color light-sensitive material using an internal latent image type emulsion which has not been previously covered, silver bromide or silver chlorobromide is preferred, and silver chloride is also preferred for rapid processing. In the case of a light-sensitive material for paper, silver chloride or silver chlorobromide is preferable, particularly silver chloride is 80 mol% or more, and more preferably 95.
A silver chlorobromide content of not less than mol% and most preferably not less than 98 mol% is preferred.

Various color couplers can be used in the color light-sensitive material applied to the processing of the present invention. Specific examples thereof are RD No. 17643, VII-C to G, and the same No.
307105, VII-C to G and the patents disclosed in JP-A-62-21
5272, JP-A-3-33847, 2-33144, European Patent Publication Nos. 447969A and 482552A. Yellow couplers include, for example, U.S. Pat.
No. 4,022,620, 4,326,024, 4,40
1,752, 4,248,961, Japanese Patent Publication 58-10739, British Patent 1,425,020, 1,476,760, U.S. Patent
3,973,968, 4,314,023, 4,511,649,
No. 5,118,599, European Patent No. 249,473A, No. 0,44
7,969, JP 63-23145, JP 63-123047, JP
Those described in 1-250944, 1-213648 and the like can be used in combination unless the effects of the present invention are impaired. Particularly preferred yellow couplers are yellow couplers represented by the general formula (Y) described in JP-A-2-139544, page 18, upper left column to page 22, lower left column, JP-A-5-2248, EP-A-0447.
Examples thereof include an acylacetamide yellow coupler characterized by an acyl group described in 969, and a yellow coupler represented by the general formula (Cp-2) described in JP-A-5-27389 and EP-A-0446863A2.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferred, and US Pat. Nos. 4,310,619, 4,351,897 and European Patent 73,6 are preferred.
36, U.S. Pat. Nos. 3,061,432 and 3,725,067, Research Disclosure No. 24220 (6 June 1984)
Mon.), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, 61
-72238, 60-35730, 55-118034, 60-18595
Those described in US Pat. No. 4,500,630, US Pat. No. 4,540,654, US Pat. No. 4,556,630, and WO88 / 04795 are more preferable. Particularly preferred magenta couplers are the pyrazoloazole-based magenta couplers of the general formula (I) on page 3, lower right column to page 10, lower right column of JP-A-2-139544 and JP-A-2-139544. Examples include 5-pyrazolone magenta couplers represented by the general formula (M-1) from page 17, lower left column to page 21, upper left column. Most preferable are the above-mentioned pyrazoloazole-based magenta couplers. Examples of cyan couplers include phenol-based and naphthol-based couplers, and are described in U.S. Patent Nos. 4,052,212, 4,146,396, and
No. 4,228,233, No. 4,296,200, No. 2,369,929,
No. 2,801,171, No. 2,772,162, No. 2,895,826
No. 3,772,002, No. 3,758,308, No. 4,33
No. 4,011, No. 4,327,173, West German Patent Publication No. 3,329,729
No. 4,121,365A, No. 0,249,453A, U.S. Pat.Nos. 3,446,622, 4,333,999, 4,771
No. 5,616, No. 4,451,559, No. 4,427,767, No.
No. 4,690,889, No. 4,254, 212, No. 4,296,199,
Those described in JP-A-61-42658 are preferred. Furthermore, JP-A Nos. 64-553, 64-554, 64-555, 64-5
Pyrazoloazole couplers described in 56, EP 0,488,248, pyrrolotriazole couplers described in EP 0,491,197, pyrroloimidazole couplers described in EP 0,456,226A, Described pyrazolopyrimidine-based coupler, U.S. Pat.
No. 672, imidazole couplers described in JP-A-2-33144, cyclic active methylene-type cyan couplers described in JP-A-64-32260, JP-A-1-183658, JP-A-2-226655, JP-A-2-32.
Couplers described in 85851 and 3-48243 can also be used.

Typical examples of polymerized dye-forming couplers are shown in US Pat. Nos. 3,451,820, 4,080,211, 4,367,282, 4,409,320 and 4,576,910.
, British Patent 2,102,137, European Patent 341,188A and the like. U.S. Pat.No. 4,366,237 and British Patent No.
Preferred are those described in 2,125,570, European Patent No. 96,570, and West German Patent (Published) No. 3,234,533. Couplers that release a photographically useful residue upon coupling can also be used in the present invention. DIR releasing development inhibitor
The couplers are described in the aforementioned RD Magazine No. 17643, Patents described in VII to F, JP-A-57-151944, JP-A-57-154234, and JP-A-57-154234.
Nos. 60-184248, 63-37346, U.S. Pat.No. 4,248,962,
Those described in JP-A-4,782,012 are preferable. Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent Nos. 2,097,140 and 2,131,188.
Preferred are those described in JP-A Nos. 59-157638 and 59-170840.

Other couplers usable in the color photographic element of the present invention include competitive couplers described in US Pat. No. 4,130,427 and US Pat. Nos. 4,283,472 and 4,33.
No. 8,393, multi-equivalent coupler described in 4,310,618, etc.
DIR described in JP-A-60-185950 and JP-A-62-24252
Redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound or DIR redox releasing redox compound, EP 17
No. 3,449, No. 11449, No. 24241, RD Magazine, No. 24241, JP-A-61-2
01247 and the like, bleach accelerator releasing couplers described in U.S. Pat.No. 4,553,477 and the like, couplers releasing leuco dyes described in JP-A-63-75747,
Couplers which emit a fluorescent dye described in U.S. Pat. No. 4,774,181 are exemplified. Suitable supports that can be used in the present invention include, for example, the aforementioned Research Disclosure (RD) No. 17643, page 28, and No. 1871.
6, page 647, right column to page 648, left column.

Particularly when a color negative film is used, the support has a layer having a conductive layer and a transparent magnetic layer on one side, as described in JP-A-4-62543, and International Publication WO 90/04205. No., FIG. 1A
Having a magnetic recording layer described in
It is also preferable to have a stripe magnetic recording layer described in No. 24628 and a transparent magnetic recording layer adjacent to the stripe magnetic recording layer. On top of these magnetic recording layers,
It is preferable to provide a protective layer described in JP-A-4-73737.

The thickness of the support is preferably 70 μm to 120 μm, and the material for the support is described in JP-A-4-12463.
No. 6, page 5, upper right column, line 1 to page 6, upper right column, line 5 can be used, and preferred are cellulose derivatives (eg, diacetyl-, triacetyl-, propionyl-, butanoyl-). Acetylpropionyl-acetate) and JP-B-48-40414.
(E.g., polyethylene terephthalate, poly-1,4-cyclohexane dimethylene terephthalate, polyethylene naphthalate). It is preferable to use polyester for the support of the film used in the present invention since a higher draining effect can be obtained.

The package (patrone) for accommodating the color negative film of the present invention may be any currently used or publicly known one, but especially US Pat. No. 4,834,30.
No. 6, FIG. 1 to FIG. 3 or
U.S. Pat. No. 4,846,418, FIG. 1-FI
G. Those described in No. 3 are preferred. In addition, a color negative film used in the present invention is disclosed in JP-A-4-125558.
No. 1, page 14, upper left column, line 1 to page 18, lower left column, line 11 are preferable.

[0077]

EXAMPLES The present invention will be described in more detail with reference to specific examples, but the present invention is not limited to the examples unless it exceeds the gist of the present invention. Example 1 1) Support The support used in this example was prepared by the following method. Polyethylene-2,6-naphthalate polymer 100
After drying 2 parts by weight of Tinuvin P.326 (manufactured by Ciba-Geigy) as an ultraviolet absorber, 300 ° C.
After being melted at, it was extruded from a T-die, stretched 3.3 times at 140 ° C, then stretched 3.3 times at 130 ° C, and heat-fixed at 250 ° C for 6 seconds to form a 90 μm thick PEN.
I got a film. The PEN film has a blue dye, a magenta dye, and a yellow dye (public technical report: I-1, I-4, I-6, I-24, I-26, I-26 described in the official gazette number 94-6023). 27, II-5)
Was added in an appropriate amount. Further, the support was wound around a stainless steel core having a diameter of 20 cm to give a heat history of 110 ° C. and 48 hours, thereby providing a support that was not easily curled.

2) Coating of undercoat layer The above-mentioned support was subjected to corona discharge treatment, UV discharge treatment, and glow discharge treatment on both surfaces thereof, and then gelatin 0.1 g / m ² and sodium α-sulfodione were formed on each surface. -2-ethylhexyl succinate 0.01 g / m ² , salicylic acid 0.04 g / m ² , p
-Chlorophenol 0.2 g / m ² , (CH ₂ = CHSO ₂ CH ₂ CH ₂ NHCO) ₂
CH ^₂ 0.012g / m _2, polyamide - epichlorohydrin polycondensate was coated an undercoat solution ^{0.02g / m 2 (10cc / m} 2, a bar coater used), provided with a subbing layer hotter side at the time of stretching. Dry 1
The test was carried out at 15 ° C for 6 minutes (all rollers and transport devices in the drying zone were at 115 ° C). 3) Coating of Back Layer An antistatic layer, a magnetic recording layer and a sliding layer having the following composition were coated as a back layer on one surface of the support after the undercoat.

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

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

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

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

First Layer (Antihalation Layer) Black Colloidal Silver Silver 0.09 Gelatin 1.60 ExM-1 0.12 ExF-1 2.0 × 10 ^-3 Solid Disperse Dye ExF-2 0.030 Solid Disperse Dye ExF-3 0.040 HBS-1 0.15 HBS- 2 0.02

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

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

Fourth Layer (Medium-Sensitivity Red-Sensitive Emulsion Layer) Silver Iodobromide Emulsion C Silver 0.70 ExS-1 3.5 × 10 ^-4 ExS-2 1.6 × 10 ^-5 ExS-3 5.1 × 10 ^-4 ExC-1 0.13 ExC-2 0.060 ExC-3 0.0070 ExC-4 0.090 ExC-5 0.015 ExC-6 0.0075 Cpd-2 0.023 HBS-1 0.10 Gelatin 0.78

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

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

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

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

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

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

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

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

13th layer (first protective layer) UV-1 0.19 UV-2 0.075 UV-3 0.065 HBS-1 5.0 × 10 ^-2 HBS-4 5.0 × 10 ^-2 gelatin 1.8

14th layer (second protective layer) Silver iodobromide emulsion M Silver 0.10 H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.15 B-3 0.05 S-1 0.20 Gelatin 0.70

Further, in order to improve storage stability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property, W-1 to W-3, B-4 to B- are appropriately added to each layer. 6, F
-1 to F-17, and iron salts, lead salts, gold salts, platinum salts,
It contains a palladium salt, an iridium salt, and a rhodium salt.

[0098]

[Table 1]

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

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

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

[0102]

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[0103]

[Chemical 12]

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[0109]

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[0112]

[Chemical 21]

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[0114]

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[0115]

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[0116]

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[0117]

[Chemical formula 26]

The light-sensitive material prepared as described above is used in a 24 mm width,
Cut to 160 cm, and then apply a 2 mm square perforation 0.7 mm from the width of one side of the length of the photosensitive material
Two are provided at 5.8 mm intervals. These two sets were prepared at intervals of 32 mm, and were described in FIGS. 1 to 7 of US Pat. No. 5,296,887.
In a plastic film cartridge described in (1). An FM signal was recorded on this sample at a feed rate of 1,000 / s during the above-mentioned perforation of the light-sensitive material by using a head gap having a head gap of 5 μm and a turn count of 2,000 from the coated side of the magnetic recording layer.

After recording the FM signal, the following development treatment was carried out in exactly the same manner except that the photosensitive layer side was exposed according to the following evaluation, and the silver halide solvent in the color developing solution was changed as shown in Table 2. did. Each developing process was run by a cine-type automatic developing machine (until the cumulative replenishment amount of the color developing solution became three times the tank capacity).

(Processing process) Processing process Temperature Time Replenishment amount * Color development 45 ° C 50 sec 10 ml Bleach fixing 45 ° C 65 sec 10 ml Stable (1) 45 ° C 13 sec --Stable (2) 45 ° C 13 sec- Stable (3) 45 ℃ 13 seconds 10 ml Dry 75 ℃ 30 seconds-(Stable was the 3 tank counter-current method from (3) to (1).) * 24mm × 160cm per bottle

The composition of each processing liquid is as follows. (Color developer) (Unit: g) Tank solution Replenisher Diethylenetriaminepentaacetic acid 4.0 4.0 4,5-Dihydroxybenzene-1,3-disulfonic acid disodium salt 0.5 0.5 Sodium sulfite 4.0 8.0 Potassium carbonate 38.0 38.0 Potassium bromide 2.0- Potassium iodide 1.3 mg-Silver halide solvent 0.8 mmol 1.0 mmol Disodium N, N- (disulphonate ethyl) hydroxylamine 15.0 20.0 2-Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] Aniline sulfate 11.0 (0.038M) 14.5 Add water 1.0 liter 1.0 liter pH (adjust with potassium hydroxide and sulfuric acid) 10.05 10.40

(Bleach-fixing solution) (Unit: g) Tank solution Replenishing solution 2-{[1- (carboxyethyl) -carboxymethylamino] ethyl} -carboxymethylaminoaminoiron (III) benzoate ammonium monohydrate 0.08 mol 0.10 mol Ethylenediaminetetraacetic acid iron (III) ammonium dihydrate 0.10 mol 0.12 mol Ammonium thiosulfate aqueous solution (700 g / l) 300 ml 350 ml Ammonium iodide 1.0 --Ammonium sulfite 20.0 50.0 Ammonium methanethiosulfinate 5.0 7.0 Succinic acid 12.0 12.0 1.0 liter by adding water 1.0 liter pH (adjusted with nitric acid and ammonia water) 6.0 5.5

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

After each development process, the sensitivity, color reproducibility, sensitivity variation rate, and magnetic information read error rate were determined as follows. (Sensitivity) Wedge exposure is performed with white light having a color temperature of 4800K, and after each development process, the absorption density of cyan is measured to obtain a characteristic curve, and exposure that gives a cyan density of +0.3 of the cyan density of the unexposed area The logarithm of the reciprocal of the quantity was obtained. When no silver halide solvent is added to the color developer (Experiment 0
This value of 1) is set to 100, and the relative value is shown in Table 2 as sensitivity. The larger the sensitivity value, the higher the sensitivity of the image obtained, and the higher the speed. (Color reproducibility) After uniform exposure of 0.2 cms with green light, wedge exposure with blue light, and after each development process, magenta at an exposure amount giving a yellow density of minimum density +1.6. The color reproducibility was evaluated by obtaining a value obtained by subtracting the magenta density at the exposure amount that gives the minimum density of yellow from the density. The smaller this value is, the less the color turbidity is, and the larger the value is, the more vivid the color looks, and the excellent the color reproducibility is. (Sensitivity fluctuation rate) Sensitivity value (S) immediately before the end of the running process and sensitivity value (S ₀ ) immediately after the start of the running process
Was determined as described above, and the sensitivity variation rate for each development process was determined as follows. The smaller this value is, the smaller the fluctuation in photographic property during continuous processing is, which means that stable photographic property can be obtained. Sensitivity fluctuation rate (%) = {(S−S ₀ ) ÷ S ₀ } × 100 (error rate) The signal is read at the same speed as when the signal was recorded by the head before processing, and an error was detected with respect to the number of input bits. The ratio of the number of generated bits (error rate) was calculated. The smaller the error rate, the better. Table 2 summarizes the obtained results.

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[Table 2]

[0126]

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From these results, it can be seen that by processing with the color developing solution containing the silver halide solvent of the present invention, a color image having high sensitivity and excellent color reproducibility can be stably obtained rapidly. I understand. Further, in recent years, recording of magnetic information on a light-sensitive material has come to be performed. It is also understood that the error rate of reading magnetic information after processing is remarkably reduced by using the color developing solution of the present invention.

Claims (2)

[Claims] 1. A color developer composition comprising at least one compound represented by formula (I). General formula (I) R1, R2, R3, R4 and R5 are each independently a hydrogen atom, an aliphatic hydrocarbon group, an aryl group, a heterocyclic group, a substituted or unsubstituted thioureido group, a substituted or unsubstituted amino group, a hydroxy group or an alkoxy group. Represents a sulfonyl group or an acyl group. However, R1, R2, R3,
R4 and R5 are not a hydrogen atom, an unsubstituted thioureido group, an unsubstituted amino group or a hydroxy group at the same time. R1 and R3, R2 and R4, R3 and R5,
R4 and R5 may form a ring. However, R1 and R2
At least one of R3, R3, R4 and R5 is -SO
₃ M, —CO ₂ Y, an amino group, an aliphatic hydrocarbon group substituted with at least one of a hydroxy group, an aryl group, a heterocyclic group, a substituted thioureido group, a substituted amino group, an alkoxy group, a sulfonyl group or an acyl group. Represents M and Y
Represents a hydrogen atom, ammonium, an alkali metal or an alkaline earth metal. 2. A halogenated product characterized by color-developing an imagewise exposed silver halide color photographic light-sensitive material with a developer containing at least one compound represented by the general formula (I). Processing method of silver color photographic light-sensitive material.