JPH07120003B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention is a development processing method (hereinafter simply referred to as processing) for developing, bleaching and fixing an exposed silver halide color photographic light-sensitive material (hereinafter referred to as color light-sensitive material). In particular, the present invention relates to an improved development processing method capable of accelerating the bleaching action to shorten the processing time and perform sufficient bleaching to form a color photographic image with good image quality.

(Prior Art) Generally, the basic steps of processing a color light-sensitive material are a color development step and a desilvering step. That is, the exposed silver halide color photographic material is put into a color development step. Here, the silver halide is reduced by the color developing agent to produce silver, and the oxidized color developing agent reacts with the color developing agent to give a dye image. Thereafter, the color photographic material is put into a desilvering process. Here, the silver generated in the previous step is oxidized by the action of an oxidizing agent (commonly referred to as a bleaching agent), and then it is dissolved and removed by a silver ionizing agent commonly known as a fixing agent. Therefore, only a dye image is formed on the photographic material that has undergone these steps. The actual development process is
In addition to the above two basic steps of color development and desilvering, auxiliary steps such as maintaining the photographic and physical quality of the image or improving the storability of the image are included. For example, a hardening bath for preventing excessive softening of the photosensitive layer during processing, a stopping bath for effectively stopping the development reaction, an image stabilizing bath for stabilizing an image, or a removal for removing the backing layer of the support. A membrane bath etc. are mentioned.

In the desilvering process described above, the bleaching bath and the fixing bath are separated from each other in two steps, and the bleaching bath and the fixing bath are allowed to coexist by simplifying the processing bath for the purpose of rapid processing and labor saving. It may be carried out in one step with a bleach-fix bath.

In recent years, in color photographic light-sensitive materials, ferric ion complex salts (for example, ferric ion complex of aminopolycarboxylic acid, etc., particularly ethylenediaminetetraacetate iron ( III) Complex salts) are mainly used for bleaching.

However, since the ferric ion complex salt has a relatively small oxidizing power and an insufficient bleaching power, the one using this as a bleaching agent is a low-sensitivity silver halide color photographic light-sensitive material mainly composed of a silver chlorobromide emulsion. When the material is subjected to a bleaching treatment or a bleach-fixing treatment, the desired purpose can be achieved for a while, but the main component is a silver chlorobromoiodide or silver iodobromide emulsion, and a color-sensitized, highly sensitive halogenated When processing a silver color photographic light-sensitive material, especially a color reversal light-sensitive material for photography and a color negative light-sensitive material for photography using a high silver content emulsion, the bleaching action is insufficient and desilvering is unsuccessful, or it takes a long time to bleach. It has the drawback of being time consuming.

Further, in color light-sensitive materials, sensitizing dyes are generally used for the purpose of color sensitization. Especially when tabular grains with high silver or high aspect ratio are used for the purpose of high sensitization, there is a problem that the sensitizing dye adsorbed on the surface of silver halide inhibits bleaching of silver produced by development of silver halide. Occurs.

Persulfate is known as a bleaching agent other than ferric ion complex salt, and it is usually used as a bleaching solution containing persulfate containing chloride. However, the disadvantage of the bleaching solution using persulfate is that it has a weaker bleaching power than the ferric ion complex salt and has a remarkably long time for bleaching.

Generally, bleaching agents which are not harmful to the environment or corrosive to equipment have a weak bleaching power, and therefore bleaching agents having weak bleaching power, especially bleaching solutions or bleach-fixing solutions using ferric ion complex salts or persulfates. There is a desire to increase the bleaching capacity of.

In contrast, Research Disclosure 24023 (198
(April 4, 2010), JP-A-60-230653 describes a treatment method in which two or more kinds of various ferric iron complex salts of aminopolycarboxylic acid are used in combination. These methods also show sufficient bleaching acceleration. It has not been effective yet.

(Problems to be Solved by the Invention) As the demand for high image quality of a light-sensitive material has increased in recent years, US Pat.
227,554, 3,701,783, 3,615,506, 3,617,2
The so-called DIR couplers described in No. 91 etc. are used and play a major role in improving the sharpness. A DIR having a timing group described in JP-A-54-145135, which is an improved version of these.
The use of a coupler gives higher sharpness, but it was not optimal because of problems such as stability of the compound.

Further, JP-A-56-114946, JP-A-58-98728, and JP-A-58-209.
Although the timing type DIR couplers described in Nos. 738, 58-209739 and 58-209740 have been improved in these drawbacks, the use of this DIR coupler slows down the desilvering process and further There was a problem that the cyan density of the density part was lowered specifically due to defective color restoration.

Therefore, a first object of the present invention is to provide a processing method for rapidly desilvering a color light-sensitive material.

A second object of the present invention is to provide a method for improving the decrease in cyan density due to color restoration failure.

(Means for Solving the Problem) As a result of intensive studies for solving the above-mentioned object, the present inventors have found that the object of the present invention can be effectively achieved by using the following means.

That is, in a method in which an imagewise exposed silver halide color photographic light-sensitive material is color-developed, then treated with a bleaching solution, and subsequently with a solution having a fixing ability, the silver halide color photographic light-sensitive material is treated with an aromatic group. The development of the silver halide by the electron transfer reaction via the ethylenic conjugated chain after the precursor of the compound that suppresses the development of silver halide is released by the coupling reaction with the oxidized product of the primary amine developer. Containing at least one development inhibitor-releasing coupler that releases a compound that suppresses the bleaching agent, and the bleaching solution comprises a ferric ethylenediaminetetraacetic acid complex salt as a bleaching agent and a ferric iron complex salt of 1,3-diaminopropanetetraacetic acid. Containing the latter in a molar ratio of 2 or less with respect to the latter, and having a pH of 2.0 to 5.0,
The object of the present invention has been achieved by a processing method of a silver halide color photographic light-sensitive material characterized in that the desilvering step takes 1 minute 30 seconds to 3 minutes.

Next, the precursor of the compound that suppresses the development of silver halide is released by the coupling reaction with the oxidized aromatic primary amine developing agent used in the present invention, and the precursor is mediated through the ethylenic conjugated chain. The development inhibitor-releasing coupler that releases a compound that suppresses the development of silver halide by the intramolecular electron transfer reaction will be described in detail.

The development inhibitor releasing coupler is represented by the following general formula [I].

General formula [I] In the formula, A ′ is a coupler residue which releases Q or less by a coupling reaction with an oxidized aromatic primary amine developing agent,
Is an oxygen atom, a sulfur atom or a substituted imino group, L is a vinylene group, l is an integer of 1 or 2, R ₁ and R ₂ are each independently a hydrogen atom, an alkyl group or an aryl group, W
Are components (compounds) that suppress development of silver halide. However, when 1 is 2, the vinylene groups may be the same or different. The vinylene group represented by L is preferably a constituent element of a benzene ring or a heterocycle.

Further, when Q represents a substituted imino group, the substitution is preferably bonded to L to form a nitrogen-containing ring having a 5- to 7-membered ring together with the nitrogen atom and L. Further, among the compounds represented by the general formula [I], the compounds represented by the following general formulas [II] to [V] are preferable.

General formula (II) General formula (III) General formula (IV) General formula [V] In the general formula [I] ~ [V], A ', R _1, R ₂ and W A in formula (I)' are respectively R _1, R ₂ and W synonymous, V ₁ and V ₂ Represents a non-metallic atomic group necessary for forming a 5- to 7-membered nitrogen-containing heterocyclic ring (which may have a substituent or may be a condensed ring) together with the atom group to be bonded, V ₃
Is a 5- to 7-membered heterocyclic ring (which may have a substituent or may be a condensed ring) or benzene ring (which may have a substituent or may be a condensed ring) together with the group of atoms to be bonded. ) Represents a group of non-metal atoms required to form), Z represents a substituted or unsubstituted methine group or a nitrogen atom, R ₃ represents a hydrogen atom or a monovalent group, and R ₁₁ and R ₁₂ are each independently Represents a monovalent group. However, R ₃ may combine with V ₂ to form a ring.

Next, in the general formulas [I] to [V], A ′, R ₁ , R ₂ , R ₃ ,
R ₁₁ , R ₁₂ , Z and W will be described in detail. Examples of the coupler residue represented by A'include a yellow color image-forming coupler, a magenta color image-forming coupler, a cyan color image-forming coupler and a so-called colorless coupler in which the coupling reaction product is substantially colorless. .

Examples of the yellow image-forming coupler residue represented by A ′ include pivaloylacetanilide type, benzoylacetanilide type, malon diester type, malon diamide type, dibenzoyl methane type, benzothiazolyl acetamide type, malon ester monoamide type, benzo Thiazolyl acetate type, benzoxazolyl acetamide type, benzoxazolyl acetate type, malon diester type, benzimidazolyl acetamide type or benzimidazolyl acetate type coupler residue, U.S. Pat.
A coupler residue derived from a heterocyclic-substituted acetamide or a heterocyclic-substituted acetate contained in No. 0 or U.S. Patent 3,770,446, British Patent 1,459,171, West German Patent (OLS) 2,503,099, Japanese Published Patent 50-139,738 or Research. Examples thereof include a coupler residue derived from an acylacetamide described in Disclosure 15737 or a heterocyclic coupler residue described in US Pat. No. 4,046,574.

Examples of the magenta color image forming coupler residue represented by A ′ include a 5-oxo-2-pyrazoline nucleus and a pyrazolo [1,5
-A] A coupler residue having a benzimidazole nucleus, a pyrazoloimidazole nucleus, a pyrazolotriazole nucleus, a pyrazolotetrazole nucleus or a cyanoacetophenone type coupler residue is preferable.

As the cyan image forming coupler residue represented by A ′, a coupler residue having a phenol nucleus or an α-naphthol nucleus is preferable.

Furthermore, the effect as a DIR coupler is the same even when the coupler does not substantially form a dye after coupling with the oxidized product of the developing agent and releasing the development inhibitor. Examples of this type of coupler residue represented by A'include U.S. Pat. No. 4,052,21.
No. 3, No. 4,088,491, No. 3,632,345, No. 3,958,993 or No. 3,961,959, and the like.

Preferred examples of the coupler residue represented by A'are represented by the general formulas (C _p -1) to (C _p -9) described below.

R ₁ and R ₂ are each independently a hydrogen atom or a carbon atom number of 1 to 36.
Alkyl group (eg, methyl group, ethyl group, benzyl group, dodecyl group, cyclohexyl group) or aryl group having 6 to 36 carbon atoms (eg, phenyl group, 4-methoxyphenyl group, 4-chlorophenyl group, 4-nitro) Phenyl group, naphthyl group, etc.), but a hydrogen atom is most preferable.

R ₃ is a benzene ring or a 5- to 7-membered heterocycle (for example, pyrrole, pyrazole, 1,2,3-triazole, pyridine, pyridazine, pyrimidine) bonded to V ₂ in addition to the groups shown by R ₁ and R _2. , Thiophene, furan, etc.) can be formed.

R ₁₁ and R ₁₂ are each independently a hydrogen atom or a carbon atom number 1 to
30 aliphatic groups (eg methyl group, ethyl group, n-undecyl group, etc.), aromatic groups having 6 to 30 carbon atoms (eg phenyl group, p-tolyl group, 1-naphthyl group, p-nitrophenyl group) Etc.), halogen atom (eg fluorine atom, chlorine atom, bromine atom etc.), aliphatic oxy group having 1 to 30 carbon atoms (eg methoxy group, ethoxy group, benzyloxy group, dodecyloxy group etc.), carbon atom number 1 to 36 unsubstituted or substituted amino group (for example, amino group, dimethylamino group, pyrrolidino group, piperidino group, morpholino group, anilino group, n-dodecylamino group, octadecylmethylamino group, 2-chloro-5-tetradecanamide Phenylamino group, etc.), nitro group, cyano group, carboxy group, carbonamide group having 1 to 36 carbon atoms (for example, acetamide group, benzamide group, Tetradecane amide group, etc.) Sulfonamide group having 1 to 36 carbon atoms (for example, methyl sulfonamide group, n-hexadecisulfonamide group, p-tolyl sulfonamide group, etc.) or alkoxycarbonyl group having 2 to 36 carbon atoms ( For example, a methoxycarbonyl group,
Dodecyloxycarbonyl group). R ₁₁ and R ₁₂
Preferred as is a hydrogen atom or an aliphatic group.

Z represents a substituted or unsubstituted methine group or a nitrogen atom, and when Z represents a substituted methine group, R is a substituent.
_The substituents mentioned in ₁₁ and R ₁₂ can be mentioned as examples.

W is a triazolyl group, a tetrazolyl group, 1,3,4-
Oxadiazol-2-ylthio group, 1,3,4-thiadiazol-2-ylthio group, 1-indazolyl group, 1-benzimidazolyl group, 1-benzotriazolyl group, 2-
Benzotriazolyl group, 2-benzimidazolylthio group, 2-benzoxazolylthio group, 2-benzothiazolylthio group, 2-pyrimidylthio group, 2-pyridylthio group, 4-quinolylthio group, 1,3,5- Triazin-2-ylthio group, 2-imidazolylthio group, 1,2,4-triazol-5-ylthio group, 1,3,4-triazol-2-ylthio group, 1,2,3,4-tetrazole-5 Examples thereof include -ylthio group and the like, and these groups may have a substituent. Preferred groups for W are 1,2,3,4-tetrazol-5-ylthio group, 1,3,4-oxadiazole-2-
Ilthio group, 1,3,4-thiadiazol-2-ylthio group, 1-benzotriazolyl group, 2-benzothiazolylthio group, 2-benzoxazolylthio group, 1,3,4-triazole-2- It is an ylthio group or a 2-pyrimidylthio group, more preferably represented by the following general formulas [VI] to [XIII].

In the general formulas [VI] to [XIII], R ₄ has 1 to 16 carbon atoms.
Alkyl group (eg, methyl group, ethyl group, hexyl group, benzyl group, octyl group, etc.) or having 6 to 6 carbon atoms
24 aryl groups (eg phenyl group, 4-hydroxyphenyl group, 3-hydroxyphenyl group, 3-sulfamoylphenyl group, 3-succinimidophenyl group, 4-
A methylphenyl group, a 4-methoxyphenyl group, a 3-nitrophenyl group, a 3-acetamidophenyl group, a 3-methylsulfonamidophenyl group, a 4-methoxycarbonylphenyl group, etc., and R ₃ is a hydrogen atom, a halogen atom, Amino group, alkyl group having 1 to 16 carbon atoms (eg, methyl group, ethyl group, hydroxyethyl group, methoxyethyl group, butyl group, etc.), aryl group having 6 to 24 carbon atoms (eg, phenyl group, 4-methoxy group) Phenyl group, 4-chlorophenyl group, etc.), carbonamido group having 1 to 24 carbon atoms (eg, acetamide group, benzamide group, etc.), alkylthio group having 1 to 16 carbon atoms (eg, methylthio group, ethylthio group, benzylthio group, Octylthio group,
Methoxycarbonylmethylthio group, etc.), 6 to 6 carbon atoms
24 arylthio groups (for example, 4-acetamidophenylthio group, 4-methylsulfonamidophenylthio group, etc.), or sulfonamide groups having 1 to 24 carbon atoms (for example, methylsulfonamido group, tolylsulfonamido group, octylsulfonamido group) Group, etc., and R ₆ is a hydrogen atom, a halogen atom, a hydroxy group, or a carbon number of 1 to 16
An alkyl group (eg, methyl group, ethyl group, butyl group, etc.), an alkoxy group having 1 to 16 carbon atoms (eg, methoxy group, ethoxy group, butoxy group, methoxyethoxy group,
Benzyloxy group, etc.), nitro group, cyano group, amino group, carbonamide group having 1 to 24 carbon atoms (eg, acetamide group, benzamide group, etc.), sulfonamide group having 1 to 24 carbon atoms (eg, methylsulfonamide) Group, phenylsulfonamide group, etc.), alkoxycarbonyl group having 2 to 16 carbon atoms (eg, methoxycarbonyl group, ethoxycarbonyl group, etc.), aryloxycarbonyl group having 6 to 16 carbon atoms (eg, phenoxycarbonyl group,
4-methylphenoxycarbonyl group, etc.) or a sulfamoyl group having 0 to 16 carbon atoms (eg, sulfamoyl group, dimethylsulfamoyl group, butylsulfamoyl group, etc.), and R ₇ and R ₈ are hydrogen atoms or hydroxy groups. ,
It represents an amino group, an alkyl group having 1 to 8 carbon atoms (eg, methyl group, ethyl group, etc.) or an alkoxy group having 1 to 8 carbon atoms (eg, methoxy group, ethoxy group, methoxyethoxy group, etc.).

Among the compounds represented by the above general formulas [II] to [V], particularly preferred are the compounds represented by the general formula [IV], and more preferred among the compounds represented by the general formula [IV] are the following. It is represented by the general formula [XIV].

General formula (XIV) In general formula [XIV], A ', R _1, R ₂ and W A in the formula (I)' are respectively R _1, R ₂ and W synonymous, R ₉ is -C 1-24 Alkyl group (eg, methyl group, benzyl group, dodecyl group, etc.) or having 6 to 6 carbon atoms
36 aryl groups (eg, phenyl group, 4-tetradecyloxyphenyl group, 4-methoxyphenyl group, 4-chlorophenyl group, 2,5-dichlorophenyl group, 4-methylphenyl group, 4-nitrophenyl group, etc.) , R ₁₀
Is a hydrogen atom, an alkyl group having 1 to 24 carbon atoms (eg, methyl group, ethyl group, undecyl group, etc.), an aryl group having 6 to 36 carbon atoms (eg, phenyl group, 4-methoxyphenyl group, etc.), 1 to 1 carbon atom 24 alkoxy groups (eg methoxy group, ethoxy group, dodecyloxy group etc.), cyano group, amino group having 0 to 36 carbon atoms (eg amino group, dimethylamino group, piperidino group, dihexylamino group, anilino group etc.), Carbonamide group having 1 to 24 carbon atoms (eg, acetamide group, benzamide group, tetradecane amide group, etc.), sulfonamide group having 1 to 24 carbon atoms (eg, methylsulfonamide group, phenylsulfonamide group, etc.), carboxy group, carbon Alkoxycarbonyl group having 2 to 24 carbon atoms (eg, methoxycarbonyl group, dodecyloxycarbonyl group, etc.) or C 1 to 24 carbon atoms It represents a luvamoyl group (for example, a carbamoyl group, a dimethylcarbamoyl group, a pyrrolidinecarbamoyl group, etc.).

A'in the general formula [XIV] is a cyan dye-forming coupler residue (for example, a phenolic cyan coupler residue,
α-naphthol type cyan coupler residue, etc. are preferable,
R ₁ and R ₂ are preferably hydrogen atoms, R ₉ is preferably an aryl group, R ₁₀ is preferably an alkyl group, and W is a compound represented by the general formulas [VI], [VII] and [VIII].
The group represented by is preferable.

In the following, a precursor of a compound that suppresses the development of silver halide is released by a coupling reaction with an oxidized product of an aromatic primary amine developing agent used in the present invention, and then the precursor is mediated by an ethylenic conjugated chain. Specific examples of the development inhibitor-releasing coupler that releases a compound that suppresses the development of silver halide by the intramolecular electron transfer reaction are shown below, but the invention is not limited thereto.

These development inhibitor releasing couplers are disclosed, for example, in U.S. Pat. No. 4,421,845, JP-A-57-188035, and JP-A-58-987.
No. 28, No. 58-209736, No. 58-209737, No. 58-209738
No. 58-209740 and the like.

The addition amount of the development inhibitor releasing coupler used in the present invention is 1 × 10 ^-5 mol to 1 × 10 ^-1 mol%, preferably 1 × 10 ^-4 mol to 1 × 10 ^-2 mol, based on the total coated silver amount. % Is preferred. The addition amount of these is determined by the coupling rate of the coupler, the release rate of the development inhibitor from the timing precursor, and the degree of inhibition of silver development of the released development inhibitor. If the rate is slow or the inhibition is weak, a large amount is added. It is necessary.

The coupler of the present invention may be added to any layer such as an emulsion layer and a non-sensitive intermediate protective layer. Further, two or more kinds may be used in combination, and there is no problem even if they are used by mixing with a coupler described below.

Hereinafter, the processing bath having the bleaching ability of the present invention will be described.

In the present invention, immediately after color development, processing is carried out in a processing bath having a bleaching ability.

The processing bath having a bleaching ability generally means a bleaching solution and a bleach-fixing solution, but in the present invention, it is a bleaching solution having an excellent bleaching power. Further, the desilvering process of the present invention includes, for example, the following processes.

Bleaching-fixing Bleaching-bleaching fixing Bleaching-washing-fixing The bleaching agent of the present invention comprises an ethylenediaminetetraacetic acid ferric iron complex salt and a 1,3-diaminopropanetetraacetic acid ferric iron complex salt in a molar ratio of 3 or more to the latter. Used together at a ratio of (including 0). The preferable molar ratio is 1.8 to 0.5. If the molar ratio exceeds 3, the bleaching power will decrease, resulting in poor desilvering.
Further, when the ratio of the ferric complex of 1,3-diaminopropanetetraacetic acid ferric salt becomes extremely high, slight bleaching fog may occur.

The addition amount of the bleaching agent of the present invention is 1 per bath having a bleaching ability.
The amount is 0.05 mol to 1 mol, preferably 0.1 mol to 0.5 mol.

In addition to the aminopolycarboxylic acid iron (III) complex described above, an aminocarboxylic acid salt can be added to the processing solution having bleaching ability of the present invention. Particularly, it is preferable to add the compound of the compound group (A).

Compound group (A) A-1 Ethylenediaminetetraacetic acid A-2 Diethylenetriaminepentaacetic acid A-3 Cyclohexanediaminetetraacetic acid A-4 1,2-Propylenediaminetetraacetic acid The preferred addition amount is 0.0001 mol to 0.1 mol / l, more preferably 0.003 mol. Mol to 0.05 mol / l.

The aminopolycarboxylic acid and its ferric iron complex salt are usually preferably used in the form of an alkali metal salt or an ammonium salt, and an ammonium salt is particularly preferable in view of its excellent solubility and bleaching power.

Further, the bleaching solution or the bleach-fixing solution containing the ferric ion complex may contain a metal ion complex salt other than iron, such as cobalt or copper.

Various bleaching accelerators can be added to the bath having the bleaching ability of the present invention.

Such bleaching accelerators are described, for example, in US Pat.
3,893,858 specification, German Patent 1,290,812 specification,
Compounds having a mercapto group or a disulfide group described in British Patent No. 1,138,842, JP-A No. 53-95630, and Research Disclosure No. 17129 (July 1978), JP-A No. 50-140129. Thiazolidine derivatives described in U.S. Pat. No. 3,706,561 thiourea derivatives, iodide described in JP-A-58-16235, polyethylene oxides described in German Patent 2,748,430, Japanese Patent Publication For example, the polyamine compound described in 45-8836 can be used. Particularly preferred are mercapto compounds as described in British Patent 1,138,842.

Particularly in the present invention, the following general formulas (IA) to (VIA)
The bleaching accelerator represented by the following can be preferably used because it has excellent bleaching ability and little bleaching fog.

In the general formula ^{(IA) R 1A -S-M} 1A formula, M ^1A represents a hydrogen atom, an alkali metal atom, an ammonium. R ^1A represents an alkyl group, an alkylene group, an aryl group or a heterocyclic residue. The alkyl group preferably has 1 to 5 carbon atoms, and most preferably 1 to 3 carbon atoms. The preferred carbon number of the alkylene group is 2 to 5. Examples of the aryl group include a phenyl group and a naphthyl group, and a phenyl group is particularly preferable. The heterocyclic residue is preferably a nitrogen-containing 6-membered ring such as pyridine or triazine, or a nitrogen-containing 5-membered ring such as azole, pyrazole, triazole or thiadiazole. Among them, at least two of the ring-forming atoms are nitrogen. Particularly preferred is an atom. R ^1A may be further substituted with a substituent. As the substituent, an alkyl group, an alkylene group, an alkoxy group, an aryl group, a carboxy group, a sulfo group, an amino group,
Examples thereof include an alkylamino group, a dialkylamino group, a hydroxy group, a carbamoyl group, a sulfamoyl group and a sulfonamide group.

Among the general formula (IA), preferred one is the general formula (IA-
It is represented by 1) to (IA-4).

General formula (IA-1) In the formula, R ^2A , R ^3A and R ^4A may be the same or different and each is a hydrogen atom or a substituted or unsubstituted lower alkyl group (preferably having a carbon number of 1 to 5, particularly preferably a methyl group, an ethyl group or a propyl group). ) Or an acyl group (preferably having 1 carbon atom)
To 3, such as an acetyl group and a propionyl group), and kA is an integer of 1 to 3. Z ^1A is an anion (chlorine ion, bromine ion, nitrate ion, sulfate ion, p-
Toluene sulfonate, oxalate, etc.).
kA represents 0 or 1, and iA represents 0 or 1.

R ^2A and R ^3A may combine to form a ring. R ^2A , R ^3A , R
^4A is preferably a hydrogen atom or a substituted or unsubstituted lower alkyl group.

Here, the substituent that R ^2A , R ^3A and R ^4A have is preferably a hydroxy group, a carboxy group, a sulfo group, an amino group or the like.

General formula (IA-2) General formula (IA-3) General formula (IA-4) In the formula, R ^5A is a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, etc.), an amino group, a substituted or unsubstituted lower alkyl group (preferably having a carbon number of 1 to 5, particularly a methyl group, an ethyl group, a propyl group). Is preferred), an amino group having an alkyl group (methylamino group, ethylamino group,
(Dimethylamino group, diethylamino group, etc.) represents a substituted or unsubstituted alkylthio group.

Examples of the substituent of R ^5A include a hydroxy group, a carboxy group, a sulfo group, an amino group, and an amino group having an alkyl group.

In the general formula ^{(IIA) R 1A -S-S} -R 6A formula, R ^1A is the same as R ^1A of the general formula (IA), R ^6A is R ^1A
Is synonymous with. R ^1A and R ^6A may be the same or different.

Among the general formula (IIA), the preferable one is the general formula (IIA-
It is represented by 1).

General formula (IIA-1) In the formula, R ^7A , R ^8A and R ^9A have the same ^meanings as R ^2A , R ^3A and R ^4A . hA
, HA and kA the general formula (IA-1) kA and Z ^1A is to be the same as Z ^1A. iB represents 0, 1 or 2.

General formula (IIIA) In the formula, R ^10A and R ^11A may be the same or different and each is a hydrogen atom, an alkyl group which may have a substituent (preferably a lower alkyl group such as a methyl group, an ethyl group or a propyl group), A phenyl group which may have a substituent, or a heterocyclic residue which may have a substituent (more specifically, at least one hetero atom such as a nitrogen atom, an oxygen atom or a sulfur atom is contained. Heterocyclic groups such as pyridine ring, thiophene ring, thiazolidine ring, benzoxazole ring, benzotriazole ring, thiazole ring, imidazole ring). R ^12A is a hydrogen atom or a lower alkyl group which may have a substituent (eg, a methyl group, an ethyl group, etc.).
It preferably has 1 to 3 carbon atoms).

Here, the substituent that R ^10A to R ^12A has includes a hydroxy group, a carboxy group, a sulfo group, an amino group, a lower alkyl group and the like.

R ^13A represents a hydrogen atom, an alkyl group, or a carboxy group.

General formula (IVA) In the formula, R ^14A , R ^15A and R ^{16A, which} may be the same or different, each represents a hydrogen atom or a lower alkyl group (eg, methyl group, ethyl group, etc., preferably having 1 to 3 carbon atoms). kB represents an integer of 1 to 5.

X ^1A represents an amino group which may have a substituent, a sulfo group, a hydroxy group, a carboxy group or a hydrogen atom. The substituent represents a substituted or unsubstituted alkyl group (eg, methyl group, ethyl group, hydroxyalkyl group, alkoxyalkyl group, carboxyalkyl group, etc.), and the two alkyl groups may form a ring.

R ^14A , R ^15A and R ^16A may ^combine with each other to form a ring. R ^{14A to} R ^16A are particularly preferably a hydrogen atom, a methyl group or an ethyl group, and X ^1A is preferably an amino group or a dialkylamino group.

General formula (VA) Here, A ^1A is an n-valent aliphatic linking group, an aromatic linking group, or a heterocyclic linking group (when n = 1, A ^1A represents a simple aliphatic group, aromatic group, or heterocyclic group) The aliphatic connector group represented by A ^{1A has 3} to ¹ carbon atoms.
There may be mentioned 2 alkylene groups (eg trimethylene, hexamethylene, cyclohexylene, etc.).

Examples of the aromatic linking group include an arylene group having 6 to 18 carbon atoms (eg, phenylene, naphthylene, etc.).

Examples of the heterocyclic linking group include a heterocyclic group (for example, thiophene, furantriazine, pyridine, etc.) containing one or more heteroatoms (for example, oxygen atom, sulfur atom, nitrogen atom).
Piperidine).

Here, the aliphatic linking group, the aromatic linking group, and the heterocyclic linking group are usually one, but two or more may be linked, and the linking form may be direct or a divalent linking group (for example,- O-,
-S-, It may be —SO ₂ —, —CO— or a linking group that can be formed from these linking groups, and R ^20A represents a lower alkyl group. ).

Further, the aliphatic linking group, aromatic linking group and heterocyclic linking group may have a substituent.

Examples of the substituent include an alkoxy group, a halogen atom, an alkyl group, a hydroxy group, a carboxy group, a sulfo group, a sulfonamide group, and a sulfamoyl group.

X ^2A is -O-, -S-, (R ^21A represents a lower alkyl group (eg, methyl group, ethyl group, etc.)), R ^17A and R ^18A represent a substituted or unsubstituted lower alkyl group (eg, methyl group, ethyl group,
Propyl group, isopyropyl group, pentyl group, etc., and the substituents include hydroxy group, lower alkoxy group (eg, methoxy group, methoxyethoxy group, hydroxyethoxy group, etc.), amino group (eg, unsubstituted amino group, Dimethylamino group, N-hydroxyethyl-N-methylamino group and the like) are preferable. Here, when there are two or more substituents, they may be the same or different.

R ^19A represents a lower alkylene group having 1 to 5 carbon atoms (methylene, ethylene, trimethylene, methylmethylene, etc.), and Z ^2A is an anion (halide ion (chlorine ion, bromine ion, etc.), nitrate ion, sulfate ion, p- Toluene sulfonate, oxalate, etc.).

R ^17A and R ^18A are linked via a carbon atom or a hetero atom (eg, oxygen atom, nitrogen atom, sulfur atom), and are a 5- or 6-membered hetero ring (eg, pyrrolidine ring, piperidine ring, morpholine ring, triazine). Ring, imidazolidine ring, etc.) may be formed.

R ^17A (or R ^18A ) and A are linked via a carbon atom or a hetero atom (eg, oxygen atom, nitrogen atom, sulfur atom), and are a 5-membered or 6-membered hetero ring (eg, hydroxyquinoline ring, hydroxyindole ring). , Isoindoline ring, etc.) may be formed.

Further, R ^17A (or R ^18A ) and R ^19A are linked via a carbon atom or a hetero atom (for example, an oxygen atom, a nitrogen atom, a sulfur atom), and a 5- or 6-membered hetero ring (for example, a piperidine ring, Pyrrolidine ring, morpholine ring, etc.) may be formed.

1A represents 0 or 1, mA represents 0 or 1, nA represents 1, 2 or 3, pA represents 0 or 1, and qA represents 0, 2 or 3.

General formula (VIA) Wherein, X ^1A, kB is X ^1A of the general formula (IVA), the same as kB.

M ^2A is a hydrogen atom, an alkali metal atom, ammonium, or Represents R ^22A represents a hydrogen atom or a lower alkyl group (having 1 to 5 carbon atoms and optionally having a substituent).

Specific examples of the compounds represented by formulas (IA) to (VIA) are shown below.

Among the above bleaching accelerators, particularly preferred compounds are IA-2, IA-5,
IA-13, IA-14, IA-15, IA-16, IA-19, IIA-1, IIA-11,
VA-1, VIA-1, and VIA-2. The amount of the bleaching accelerator added is 0.01 g to 20 g, preferably 0.1 g per 1 solution having bleaching ability.
~ 10g.

The bleaching solution constituting the present invention, in addition to the bleaching agent and the above compounds, bromide, such as potassium bromide, sodium bromide,
Rehalogenating agents such as ammonium bromide or chlorides such as potassium chloride, sodium chloride, ammonium chloride can be included. The concentration of rehalogenating agent is bleach 1
The amount is 0.1 to 5 mol, preferably 0.5 to 3 mol. In addition, sodium nitrate, ammonium nitrate and other nitrates, boric acid, borax, 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 to be usually used in a bleaching solution such as one or more kinds of inorganic acids, organic acids and salts thereof having ability can be added.

The pH of the bleaching bath of the present invention is 5.8 to 1.5, most preferably 5.3 to 2. In the preferred pH range, there is little bleaching fog and the desilvering performance is excellent.

The replenishing amount of the bleaching bath of the present invention is 5 per 1 m ² of the light-sensitive material.
It is 0 ml to 2000 ml, preferably 100 ml to 1000 ml.

In the present invention, after the treatment with a bath having a bleaching ability, the treatment is generally performed with a bath having a fixing ability.

The bath having fixing ability of the present invention means a bleach-fixing bath or a fixing bath.

Examples of the fixing agent for the bath having these fixing ability include thiosulfates such as sodium thiosulfate, ammonium thiosulfate, sodium ammonium thiosulfate and potassium thiosulfate, thiocyanates such as sodium thiocyanate, ammonium thiocyanate and potassium thiocyanate, and thiosulfates. urea,
Thioether or the like can be used. The amount of these fixing agents is 0.3 mol to 3 mol, preferably 0.5 mol to 2 mol, per treatment liquid.

The bath having fixing ability contains sulfite as a preservative, for example, sodium sulfite, potassium sulfite, ammonium sulfite, and bisulfite adduct of hydroxylamine, hydrazine, and aldehyde compound, such as acetaldehyde sodium bisulfite. be able to. Further, various fluorescent whitening agents, antifoaming agents or surfactants, polyvinylpyrrolidone, organic solvents such as methanol can be contained, and especially as a preservative, Japanese Patent Application No. 60-28
It is preferable to use the sulfinic acid compound described in 3831.

The replenishing amount of the bath having fixing ability is 300 per 1 m ² of light-sensitive material.
ml to 3000 ml is preferred, more preferably 300 ml to 1
It is 000 ml.

Furthermore, it is preferable to add various aminopolycarboxylic acids and organic phosphonic acids to the bath having fixing ability of the present invention for the purpose of stabilizing the liquid.

The shorter the total time of the desilvering process of the present invention, the more remarkable the effect of the present invention can be obtained, but in the present invention, it is 1 minute 30 seconds to 3 seconds.
Minutes. The processing temperature is 25 to 50 ° C, preferably 35 ° C to
45 ° C. In the preferable temperature range, the desilvering rate is improved, and the stain generation after the processing is effectively prevented.

In the desilvering process of the present invention, it is preferable that stirring is strengthened as much as possible in order to more effectively exhibit the effects of the present invention.

As a concrete method for strengthening stirring, JP-A-62-183460,
No. 62-183461, a method of impinging a jet of a processing solution on the emulsion surface of the light-sensitive material, a method of increasing the stirring effect by using the rotating means of JP-A No. 62-183461, and a wiper provided in the solution. Examples include a method of moving the light-sensitive material while bringing the bleed and the emulsion surface into contact with each other to make the emulsion surface turbulent, thereby improving the stirring effect, and a method of increasing the circulation flow rate of the entire processing solution. Such stirring improving means is effective in 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, as a result, increases the desilvering rate.

Further, the agitation improving means is more effective when a bleaching accelerator is used, and it is possible to remarkably increase the accelerating effect and eliminate the fixing inhibiting effect of the bleaching accelerator.

The automatic processor used in the present invention is disclosed in JP-A-60-191257.
No. 191258, No. 191259, it is preferable to have the photosensitive material conveying means. As described in 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 has a high effect of preventing the performance price of the treatment liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The color developing solution used in the present invention contains a known aromatic primary amine color developing agent. A preferred example is a p-phenylenediamine derivative, and representative examples thereof are shown below, but the invention is not limited thereto.

De-1 N, N-diethyl-p-phenylenediamine De-2 2-amino-5-diethylaminotoluene De-3 2-amino-5- (N-ethyl-N-laurylamino) toluene De-4 4- [ N-Ethyl-N- (β-hydroxyethyl) amino] aniline De-5 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline De-6 4-amino-3-methyl -N-ethyl-N-
[Β- (Methanesulfonamide) ethyl] -aniline De-7 N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide De-8 N, N-dimethyl-p-phenylenediamine De-9 4-amino -3-Methyl-N-ethyl-N-methoxyethylaniline De-10 4-amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline De-11 4-amino-3-methyl-N-ethyl-N-β
-Butoxyethylaniline Among the above p-phenylenediamine derivatives, Exemplified Compound De-5 is particularly preferable.

Further, these p-phenylenediamine derivatives may be salts such as sulfates, hydrochlorides, sulfites and p-toluenesulfonates. The amount of the aromatic primary amine developing agent used is preferably about 0.1 g to about 20 g, more preferably about 0.5 g to about 10 g per developer.

Further, as a preservative, a sulfite salt such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, or a carbonyl sulfite adduct is added to the color developer as needed. be able to.

The preferable addition amount is 0.5 g to 10 g, and more preferably 1 g to 5 g, per color developing solution.

Further, as a compound for directly preserving the color developing agent, various hydroxylamines, hydroxamic acids described in Japanese Patent Application No. 61-186559, hydrazines described in 61-170756, and hydrazides, 61-188742. No. and No. 61-2032
Phenols described in No. 53, α-hydroxyketones and α-aminoketones described in No. 61-188741, and / or
It is preferable to add various sugars described in JP-A No. 61-180616. Further, in combination with the above compound, Japanese Patent Application No. 61-147823,
61-166674, 61-165621, 61-164515,
61-170789, and 61-168159 and the like monoamines, 61-173595, 61-164515, 61-186560.
Diamines described in No. 61-165621, and No. 61-165621
Polyamines described in No. 169789, polyamines described in No. 61-1888619, nitroxy radicals described in No. 61-197760, No. 61-186561, and alcohols described in No. 61-197419, No. 61-198987. The described oximes, and 61-26
It is preferable to use the tertiary amines described in 5149.

Other preservatives are disclosed in JP-A-57-44148 and 57-537.
Various metals described in JP-A-49-58, salicylic acids described in JP-A-59-180588, alkanolamines described in JP-A-54-3532, polyethyleneimines described in JP-A-56-94349, U.S. Pat. The aromatic polyhydroxy compound described in 3,746,544 may be contained as necessary. It is particularly preferable to add an aromatic polyhydroxy compound.

The color developer used in the present invention preferably has a pH of 9 to 1.
2, more preferably from 9 to 11.0, and the color developing solution may contain other known developing solution component compounds.

In order to maintain the above pH, it is preferable to use various buffers.

Specific examples of the buffer include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, 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 present invention is not limited to these compounds.

The amount of the buffer added to the color developing solution is preferably 0.1 mol / l or more, and particularly preferably 0.1 mol / l to 0.4 mol / l.

In addition, various chelating agents can be used as a precipitation inhibitor of calcium or magnesium in the color developing solution or for improving the stability of the color developing solution.

The chelating agent is preferably an organic acid compound, and examples thereof include aminopolycarboxylic acids, organic phosphonic acids, and phosphonocarboxylic acids. Specific examples are shown below, but the present invention is not limited thereto.

Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid,
Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid, 1,2
-Diaminopropane tetraacetic acid, hydroxyethyliminodiacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N , N'-bis (2-hydroxybenzyl) ethylenediamine-N, N'-diacetic acid, and these chelating agents may be used in combination of two or more kinds as necessary.

The amount of these chelating agents added may be an amount sufficient to block the metal ions in the color developing solution. Eg 1
It is about 0.1g to 10g.

If necessary, any development accelerator can be added to the color developing solution. However, it is preferable that the color developing solution of the present invention does not substantially contain benzyl alcohol from the viewpoints of pollution, solution preparation and color contamination prevention. Here, "substantially" means that the amount of the developer is not more than 2 ml, preferably not contained at all.

Other development accelerators include JP-B-37-16088 and 37
-5987, 38-7826, 44-12380, 45-9019
And the thioether compounds represented by U.S. Pat. No. 3,813,247, p-phenylenediamine compounds represented by JP-A-52-49829 and JP-A-50-15554, and JP-A-50
-137726, Japanese Patent Publication No. 44-30074, Japanese Unexamined Patent Publication Nos. 56-156826 and 52-43429, and the like, quaternary ammonium salts, U.S. Patent Nos. 2,494,903, 3,128,182, and 4,23.
0,796, 3,253,919, Japanese Patent Publication No. 41-11431, U.S. Patent Nos. 2,482,546, 2,596,926 and 3,582,346, etc., amine compounds described in Japanese Patent Publication Nos. 37-16088, 42-2.
5201, U.S. Pat.No. 3,128,183, Japanese Patent Publication No. 41-11431,
Polyalkylene oxides represented by U.S. Pat. No. 42-23883 and U.S. Pat. No. 3,532,501, and others 1-phenyl-3
-Pyrazolidones, imidazoles, etc. can be added as required.

In the present invention, any antifoggant can be added 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 antifoggant include benzotriazole and 6-
Nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-
Representative examples thereof include nitrogen-containing heterocyclic compounds such as thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine.

The color developer used in the present invention may contain a fluorescent whitening agent. As the fluorescent whitening agent, 4,4'-diamino-2,2'-disulfostilbene compound is preferable. The addition amount is 0 to 5 g / l, preferably 0.1 g to 4 g / l.

If necessary, various surfactants such as alkyl sulfonic acid, arylphosphonic acid, aliphatic carboxylic acid, aromatic carboxylic acid may be added.

The processing temperature of the color developer of the present invention is preferably 20 to 50 ° C.
30 to 45 ° C. The processing time is 20 seconds to 5 minutes, preferably 30 seconds to 3 minutes. The replenishment amount is preferably small, but it is 100 to 1500 ml, preferably 100 to 800 ml, per 1 m ^{2 of} the light-sensitive material. More preferably, it is 100 ml to 400 ml.

If necessary, the color developing bath may be divided into two or more baths, and the color developing replenisher may be replenished from the frontmost bath or the last bath to shorten the developing time or the replenishing amount.

The processing method of the present invention can also be used for color reversal processing. In the present invention, as the black and white developing solution used at this time, what is commonly known as a black and white first developing solution used for reversal processing of a color photographic light-sensitive material or one used for processing a black-and-white light-sensitive material can be used. Further, various well-known additives which are generally added to the black and white developer can be contained.

Typical additives include a developing agent such as 1-phenyl-3-pyrazolidone, metol and hydroquinone, a preservative such as sulfite, and an accelerator composed of an alkali such as sodium hydroxide, sodium carbonate or potassium carbonate. , Potassium bromide, 2-methylbenzimidazole,
Examples thereof include inorganic or organic inhibitors such as methylbenzthiazole, water softeners such as polyphosphates, trace amounts of iodides, and development inhibitors composed of mercapto compounds.

The processing method of the present invention comprises the above-mentioned processing steps such as color development, bleaching, bleach-fixing and fixing. Here, after the bleach-fixing or fixing step, treatment steps such as washing and stabilizing are generally carried out, but after the bath having fixing ability, the stabilizing treatment is carried out without substantially washing with water. A simple treatment method to be carried out can also be used.

The washing water used in the washing step may contain known additives, if necessary. For example, hard water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, bactericides and antifungal agents that prevent the growth of various bacteria and algae (eg, isothiazolone, organochlorine bactericides, benzotriazole, etc.) , A drying load, and a surfactant for preventing unevenness can be used. Or LE
West, “Water Quality Criteria”, Phot.Sci.and Eng., V
The compounds described in ol. 9, No. 6, pages 344 to 359 (1965) and the like can also be used.

As the stabilizing solution used in the stabilizing step, a processing solution that stabilizes the dye image is used. For example, a liquid having a buffering capacity of pH 3 to 6, a liquid containing an aldehyde (for example, formalin), and the like can be used. The stabilizer contains ammonium compounds, metal compounds such as Bi and Al, if necessary,
A fluorescent brightening agent, a chelating agent (for example, 1-hydroxyethylidene-1,1-diphosphonic acid), a bactericidal agent, an antifungal agent, a hardener, a surfactant and the like can be used.

The washing step and the stabilizing step are preferably a multi-stage countercurrent system, and the number of stages is preferably 2 to 4. The amount of replenishment is 1 to 50 times, preferably 2 to 30 times, more preferably 2 to 15 times, the amount carried in from the previous bath per unit area.

Water used in these washing or stabilization processes includes tap water and Ca, M
It is preferable to use water deionized to a g concentration of 5 mg / l or less, water sterilized with halogen, an ultraviolet sterilizing lamp or the like.

In each of the above processing steps of the photosensitive material, when the continuous processing by the automatic developing machine is performed, the processing solution may be concentrated by evaporation, which is remarkable especially when the processing amount is small or the opening area of the processing solution is large. Becomes In order to correct such concentration of the treatment liquid, it is preferable to replenish an appropriate amount of water or the correction liquid.

Further, the amount of waste liquid can be reduced by using a method in which the overflow liquid of the washing process or the stabilizing process is caused to flow into a bath having a fixing ability as a pre-bath.

The silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver chloride, silver bromide, silver chlorobromide, silver iodochloride, silver chloroiodobromide or silver iodobromide.

Silver halide grains in photographic emulsions have regular crystals such as cubes, octahedra and tetradecahedrons, grains having irregular crystal forms such as spheres and plates, twin planes, etc. It may have a crystal defect of, or a composite form thereof.

The grain size of silver halide may be fine grains of about 0.2 μm or less, or large grains having a projected area diameter of up to about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion.

The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD), No. 17643 (1978.
December), pp. 22-23, "I. Emulsion preparati
on and types) ”, and No. 18716 (November 1979),
648, Graphide, "Physics and Chemistry of Photography", published by Paul Montel (P.Glafkides, Chemic et Phisique Photogr
aphique Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GFDuffin, Photographi
c Emulsion Chemistry (Focal Press, 1966)), "Production and coating of photographic emulsions" by Zelikmann et al., published by Focal Press (VLZelikman et al, Making and Coating Phogra
Phic Emulsion, Focal Press, 1964) and the like.

Monodisperse emulsions described in US Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferable.

Further, tabular grains having an aspect ratio of about 5 or more can be used in the present invention. Tabular grains are described in Gutoff, Photographic Science and Engineerin.
g), Vol. 14, pp. 248-257 (1970); U.S. Pat. No. 4,43.
4,226, 4,414,310, 4,433,048, 4,439,520
It can be easily prepared by the method described in Japanese Patent No. 2,112,157 and the like.

The crystal structure may be uniform, may have different halogen compositions inside and outside, may have a layered structure, and may have a different composition by epitaxial bonding. Alternatively, it may be bonded to a compound other than silver halide such as silver rhodanide and lead oxide.

Also, a mixture of particles having various crystal forms may be used.

As the silver halide emulsion, those which are physically ripened, chemically ripened and spectrally sensitized are usually used. Additives used in such processes are Research Disclosure No.176.
43 and No. 18716, and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant portions are shown in the following table.

Various color couplers can be used in the present invention, specific examples of which are described in the patents described in Research Disclosure (RD) No. 17643, VII-CG.

Yellow couplers include, for example, U.S. Pat.
No. 1, No. 4,022,620, No. 4,326,024, No. 4,401,7
Those described in No. 52, Japanese Patent Publication No. 58-10739, British Patent Nos. 1,425,020, 1,476,760 and the like are preferable.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. No. 4,310,61
No. 9, No. 4,351,897, European Patent No. 73,636, U.S. Patent No. 3,061,432, No. 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-33552.
Issue, Research Disclosure No. 24230 (June 1984
JP-A-60-43659, U.S. Pat. Nos. 4,500,630 and 4,540,654 are particularly preferable.

Examples of cyan couplers include phenol-type and naphthol-type couplers, and U.S. Pat.
4,146,396, 4,228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162,
No. 2,895,826, No. 3,772,002, No. 3,758,308
No. 4,334,011, No. 4,327,173, West German Patent Publication No. 3,329,729, European Patent 121,365A, U.S. Patent No. 3,4.
46,622, 4,333,999, 4,451,559, 4,
Those described in 427,767, EP 161,626A and the like are preferable.

Colored couplers to correct unwanted absorption of colored dyes are Research Disclosure No. 17643 VII-
Section G, U.S. Patent No. 4,163,670, Japanese Patent Publication No. 57-39413, U.S. Patent Nos. 4,004,929, 4,138,258, British Patent No. 1,
Those described in No. 146,368 are preferable.

As the coupler in which the color forming dye has an appropriate diffusibility, those described in U.S. Pat. No. 4,366,237, British Patent 2,125,570, European Patent 96,570 and West German Patent (Publication) 3,234,533 are preferable.

Typical examples of polymerized dye-forming couplers are U.S. Pat.Nos. 3,451,820, 4,080,211 and 4,367,282.
No. 2,102,173 and the like.

Couplers that release a photographically useful residue upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors are disclosed in the above-mentioned RD17643, VII to F patents, JP-A-57-151944 and JP-A-57-154234.
Nos. 60-184248 and U.S. Pat. No. 4,248,962 are preferred.

Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent Nos. 2,097,140 and 2,13.
Those described in 1,188 and JP-A-59-157638, 59-170840 are preferable.

Other couplers that can be used in the light-sensitive material of the present invention include competitive couplers described in U.S. Pat.No. 4,130,427, multi-equivalent couplers described in U.S. Pat.Nos. 4,283,472, 4,338,393, and 4,310,618. , JP 60-1
DIR redox compound releasing coupler described in 85950,
Examples thereof include couplers that release a dye that restores color after separation described in EP 173,302A.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027.

There is also a method of using a polymer as a coupler dispersion medium, and various disclosures are made in JP-B-48-30494, US Pat. No. 3,619,195, West German Patent 1,957,467, and JP-B-51-39835.

The steps of the latex dispersion method, effects, and specific examples of latex for impregnation are described in US Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

Suitable supports that can be used in the present invention include, for example, the aforementioned R
Page 28 of D.No.17643 and page 647 of the same No.18716 From right column 6
See page 48, left column.

(Examples) Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.

Example 1 On a subbed cellulose triacetate film support,
Sample 101 was prepared by applying multiple layers having the compositions shown below in multiple layers.

(Photosensitive Layer Composition) The numbers corresponding to the respective components indicate the coating amount expressed in g / m ² unit, and for silver halide, the coating amount in terms of silver. However, for sensitizing dyes, silver halide 1 in the same layer
The coating amount per mol is shown in mol.

(Sample B) First layer: antihalation layer Black colloidal silver 0.18 gelatin 0.40 Second layer: intermediate layer 2,5-di-t-pentadecylhydroquinone 0.18 EX-1 0.07 EX-3 0.02 EX-12 0.002 U- 1 0.06 U-2 0.08 U-3 0.10 HBS-1 0.10 HBS-2 0.02 Gelatin 1.04 Third layer (first red-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (6 mol% silver iodide, average grain size 0) .
6μ, coefficient of variation for particle size 0.15) Silver 0.55 Sensitizing dye I 6.9 × 10 ^-5 Sensitizing dye II 1.8 × 10 ^-5 Sensitizing dye III 3.1 × 10 ^-4 Sensitizing dye IV 4.0 × 10 ^-5 EX-2 0.350 HBS-1 0.005 EX-10 0.020 Gelatin 1.20 4th layer (2nd red-sensitive emulsion layer) Tabular silver iodobromide emulsion (10 mol% silver iodide, average grain size 0.7)
μ, average aspect ratio 5.5, average thickness 0.2 μ) Silver 1.0 Sensitizing dye I 5.1 × 10 ⁻⁵ Sensitizing dye II 1.4 × 10 ⁻⁵ Sensitizing dye III 2.3 × 10 ⁻⁴ Sensitizing dye IV 3.0 × 10 ⁻⁵ EX-2 0.400 EX-3 0.050 EX-10 0.015 Gelatin 1.30 Fifth layer (third red emulsion layer) Silver iodobromide emulsion (16 mol% silver iodide, average grain size 1.1μ)
Silver 1.60 Sensitizing dye IX 5.4 × 10 ^-5 Sensitizing dye II 1.4 × 10 ^-5 Sensitizing dye III 2.4 × 10 ^-4 Sensitizing dye IV 3.1 × 10 ^-5 EX-3 0.240 EX-4 0.120 HBS-1 0.22 HBS-2 0.10 Gelatin 1.63 6th layer (intermediate layer) EX-5 0.040 HBS-1 0.020 EX-12 0.004 Gelatin 0.80 7th layer (1st edge emulsion layer) Tabular silver iodobromide emulsion (silver iodide 6 Mol%, average particle size 0.
6μ, average aspect ratio 6.0, average thickness 0.15) Silver 0.40 Sensitizing dye V 3.0 × 10 ^-5 Sensitizing dye VI 1.0 × 10 ^-4 Sensitizing dye VII 3.8 × 10 ^-4 EX-6 0.260 EX-1 0.021 EX- 7 0.030 EX-8 0.025 HBS-1 0.100 HBS-4 0.010 Gelatin 0.75 Eighth layer (second edge emulsion layer) Monodisperse silver iodobromide emulsion (9 mol% silver iodide, average grain size of 0.
7μ, coefficient of variation for particle size 0.18) Silver 0.80 Sensitizing dye V 2.1 × 10 ^-5 Sensitizing dye VI 7.0 × 10 ^-5 Sensitizing dye VII 2.6 × 10 ^-4 EX-6 0.180 EX-8 0.010 EX-1 0.008 EX-7 0.012 HBS-1 0.160 HBS-4 0.008 Gelatin 1.10 Ninth layer (third edge emulsion layer) Silver iodobromide agent (silver iodide 12 mol%, average diameter 1.0 μ) Silver 1.2
Sensitizing dye V 3.5 × 10 ^-5 Sensitizing dye VI 8.0 × 10 ^-5 Sensitizing dye VII 3.0 × 10 ^-4 EX-6 0.065 EX-11 0.030 EX-1 0.025 HBS-1 0.25 HBS-2 0.10 Gelatin 1.74 10 layers (yellow filter layer) Yellow colloidal silver 0.05 EX-5 0.08 HBS-3 0.03 Gelatin 0.95 11th layer (1st blue sensitive emulsion layer) Tabular silver iodobromide emulsion (6 mol% silver iodide, average grain) Diameter 0.
6μ, average aspect ratio 5.7, average thickness 0.15) Silver 0.24 Sensitizing dye VIII 3.5 × 10 ^-5 EX-9 0.85 EX-8 0.12 HBS-1 0.28 Gelatin 1.28 12th layer (2nd blue-sensitive emulsion layer) Monodisperse iodine Silver bromide emulsion (silver iodide 10 mol%, average grain size 0.
8μ, variation coefficient for grain size 0.16) Silver 0.45 Sensitizing dye VIII 2.1 × 10 ^-4 EX-9 0.20 EX-10 0.015 HBS-1 0.03 Gelatin 0.46 13th layer (3rd blue emulsion layer) Silver iodobromide emulsion (Silver iodide 14 mol%, average particle size 1.3μ)
Silver 0.77 Sensitizing dye VIII 2.2 × 10 ^-4 EX-9 0.20 HBS-1 0.07 Gelatin 0.69 14th layer (1st protective layer) Silver iodobromide emulsion (1 mol% silver iodide, average particle size 0.07μ)
Silver 0.5 U-4 0.11 U-5 0.17 HBS-1 0.90 Gelatin 1.00 Fifteenth layer (second protective layer) Polymethyl acrylate particles (diameter about 1.5 μm) 0.54 S-1 0.15 S-2 0.05 Gelatin 0.72 Above for each layer In addition to the above ingredients, a gelatin hardening agent H-1 and a surfactant were added.

EX-11; same as EX-1, but R = H HBS-1; tricresyl phosphate HBS-2; diptyl phthalate HBS-3; bis (2-ethylexyl) phthalate Sensitizing dye Next, in Sample 101, Comparative DIR Coupler A (EX-10) was changed to the following DIR Coupler in equimolar amounts to Samples 102, 103, 1
04

Sample 102 (D-13) Sample 103 (D-14) Sample 104 (D-22) Samples 101 to 104 produced as described above were subjected to wedge exposure of 10 cMS with a light source having a color temperature of 4800 ° K, and shown below. The treatment was performed in the treatment process and the treatment liquid. The following composition of Engineering enough processing time temperature color developing 3 min 15 sec 38 ° C. Bleaching 1 minute 38 ° C. Fixing 1 min 15 sec 38 ° C. Stabilizing 1 min 38 ° C. Drying 1 min 60 ° C. were then used treatment liquid Shown in.

(Color developer) Diethylenetriaminepentaacetic acid 5.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.3 Potassium iodide 1.2 mg Hydroxyamine sulfate 2.0 4- [N-ethyl-N-β-hydroxyethylamino]
-2-Methylaniline sulfate water was added to 1.0l pH 10.00 (bleaching solution) Bleach accelerator ^* 1,3-diaminopropanetetraacetic acid 4.0g Ammonium bromide 100.0g Ammonium nitrate 30.0g Add water 1.0l pH See Table 1 The pH was adjusted with ammonium water and acetic acid.

(Fixer) 1-Hydroxyethylidene-1,1-diphosphonic acid 5.0 g Sodium sulfite 7.0 g Sodium bisulfite 5.0 g Ammonium thiosulfate aqueous solution (70%) 170.0 ml Water is added 1.0 l pH 6.7 (Stabilizer) Formalin (37 %) 1.2 ml 5-chloro-2-methyl-4-isothiazolin-3-one 6.0 mg 2-methyl-4-isothiazolin-3-one 3.0 mg Surfactant 0.4 [C ₁₀ H ₂₁ -OCH ₂ CH ₂ O ₁₀ H] Ethylene glycol 1.0 Water was added to 1.0 l pH 5.0-7.0 The bleaching solution was treated by adding the first bleaching agent and the second bleaching agent as shown in Table 1. With respect to the processed sample, the amount of residual silver at the point where the yellow density became 1.5 was examined by fluorescent X-ray. The sample containing the image with the same density was treated with the bleaching solution below for 10 minutes to recolor the cyan image, washed with water, and dried again, and the density of the cyan image was measured again. The decrease in the concentration due to the defect was examined. The obtained results are shown in Table 1.

<Bleaching solution used for color restoration> (Unit: g) Ethylenediaminetetraacetic acid sodium ferric trihydrate 100.0
Ethylenediaminetetraacetic acid disodium salt 10.0 Ammonium bromide 140.0 Ammonium nitrate 30.0 Ammonia water (27%) 6.5ml Add water 1.0l pH 6.0 As is clear from Tables 1-1 to 1-3, favorable results were obtained by the processing method of the present invention with both the amount of residual silver and the color restoration failure. The ratio of the first bleach to the second bleach is 2.
Particularly preferable results are obtained when it is 0 or less, and the pH of the bleaching solution is
Even better results were obtained especially at 5.0-2.0.

However, when the molar ratio of the bleaching agent is 0.1 or less, although desilvering and color restoration are good, another problem of bleaching fog occurs, so it is more preferable that the molar ratio is not 0.1 or less.

Example 2 A multilayer color light-sensitive material 201 was prepared by applying multiple layers of the following composition on a cellulose triacetate film support which had been undercoated.

(Photosensitive Layer Composition) The numbers corresponding to the respective components indicate the coating amount in g / m ² unit, and for silver halide, the coating amount in terms of silver.
However, regarding the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer.

1st layer (antihalation layer) Black colloidal silver 0.2 Gelatin 1.0 UV absorber UV-1 0.05 Same UV-2 0.1 Same UV-3 0.1 Dispersion oil OIL-1 0.02 Second layer (intermediate layer) Fine silver bromide (average) Grain size 0.07μ) 0.15 Gelatin 1.0 Third layer (first red-sensitive emulsion layer) Monodispersed emulsion (silver iodide 6 mol%, average grain size 0.4 μm variation coefficient 15%) 1.42 Gelatin 0.9 Sensitizing dye A 2.0 × 10 ^-4 sensitizing dye B 1.0 x 10 ^-4 sensitizing dye C 0.3 x 10 ^-4 Cp-b 0.35 Cp-c 0.052 Cp-d 0.047 Di-1 0.023 Di-2 0.035 HBS-1 0.10 HBS-2 0.10 4th Layer (intermediate layer) Gelatin 0.8 Cp-b 0.10 HBS-1 0.05 Fifth layer (second red emulsion layer) Monodisperse emulsion (silver iodide 6 mol%, average grain size 0.5 μm, coefficient of variation 15%) 1.38 Gelatin 1.0 Sensitizing dye A 1.5 × 10 ^-4 Sensitizing dye B 2.0 × 10 ^-4 Sensitizing dye C 0.5 × 10 ^-4 Cp-b 0.150 Cp-d 0.027 Di-1 0.005 Di-2 0.010 HBS-1 0.050 HBS- 2 0.060 6th layer (3rd layer Emulsion-sensitive layer) Monodisperse emulsion (7 mol% silver iodide, average grain size 1.1 μm, coefficient of variation 16%) 2.08 Gelatin 1.5 Cp-a 0.060 Cp-c 0.024 Cp-d 0.038 Di-1 0.006 HBS-1 0.12 Seven layers (intermediate layer) Gelatin 1.0 Cpd-A 0.05 HBS-2 0.05 Eight layer (first edge sensitive layer) Monodisperse silver iodobromide emulsion (3 mol% silver iodide, average grain size 0.4 μm)
m, coefficient of variation 19%) 0.64 Monodisperse silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0.7μ
m, coefficient of variation 18%) 1.12 Gelatin 1.0 Sensitizing dye D 1 × 10 ^-4 Sensitizing dye E 4 × 10 ^-4 Sensitizing dye F 1 × 10 ^-4 Cp-h 0.20 Cp-f 0.61 Cp-g 0.084 Cp -K 0.35 Cp-l 0.036 Di-3 0.041 Di-4 0.018 HBS-1 0.25 HBS-2 0.45 9th layer (second edge sensitive emulsion layer) Monodisperse silver iodobromide emulsion (7 mol% silver iodide, average) Particle size 1.0μ
m, coefficient of variation 18%) 2.07 Gelatin 1.5 Sensitizing dye D 1.5 × 10 ^-4 Sensitizing dye E 2.3 × 10 ^-4 Sensitizing dye F 1.5 × 10 ^-4 Cp-f 0.007 Cp-h 0.012 Cp-g 0.009 HBS -0.088 10th layer (intermediate layer) Yellow colloidal silver 0.06 Gelatin 1.2 Cpd-A 0.3 HBS-1 0.3 11th layer (first blue-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide 6 mol%, Average particle size 0.4μ
m, coefficient of variation 20%) 0.31 monodisperse silver iodobromide emulsion (silver iodide 5 mol%, average grain size 0.9μ
m, coefficient of variation 17%) 0.38 Gelatin 2.0 Sensitizing dye G 1 × 10 ^-4 Sensitizing dye H 1 × 10 ^-4 Cp-i 0.63 Cp-j 0.57 Di-1 0.020 Di-4 0.015 HBS-1 0.05 12th Layer (second blue-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide 8 mol%, average grain size 1.3 μm)
m, coefficient of variation 18%) 0.77 Gelatin 0.5 Sensitizing dye G 5 × 10 ^-5 Sensitizing dye H 5 × 10 ^-5 Cp-i 0.10 Cp-j 0.10 Di-4 0.005 HBS-2 0.10 13th layer (intermediate layer) ) Gelatin 0.5 Cp-m 0.1 UV-1 0.1 UV-2 0.1 UV-3 0.1 HBS-1 0.05 HBS-2 0.05 14th layer (protective layer) Monodisperse silver iodobromide emulsion (4 mol% silver iodide, average) Particle size 0.05
μ, coefficient of variation 10%) 0.1 Gelatin 1.5 Polymethylmethacrylate particles (average 1.5 μ) 0.1 S-1 0.2 S-2 0.2 Other surfactants K-1 and gelatin hardener H-1 were added.

Next, samples 202 and 203 were obtained by changing the DIR coupler Di-1 of sample 201 to the following DIR coupler.

Sample 202 (D-13) Sample 203 (D-14) After imagewise exposure to the sample prepared as described above, continuous processing (running test until the tank capacity of the color developing solution was replenished in the following processing step) ) Was done. For the processed sample, the residual silver amount and the color restoration defect were examined in the same manner as in Example 1. The results are shown in Table 2.

The automatic developing machine used was a belt-conveying system described in JP-A-60-191257, and each processing bath was a jet-stirring system described in JP-A-62-183460.

The processing steps are shown below.

The composition of each treatment liquid used is shown below.

(Stabilizer) Mother liquor and replenisher common Formalin (37%) 1.2 ml 5-chloro-2-methyl-4-isothiazolin-3-one 6.0 mg 2-methyl-4-isothiazolin-3-one 3.0 mg Surfactant 0.4 [ C ₁₀ H ₂₁ -OCH ₂ CH ₂ O ₁₀ H] Ethylene glycol 1.0 Add water 1.0 l pH 5.0-7.0 As described above, in the processing using the samples 202 and 203 of the present invention, desilvering color recovery is good.

Claims (1)

[Claims] 1. A method of subjecting an imagewise exposed silver halide color photographic light-sensitive material to color development, followed by processing with a bleaching solution and subsequently with a solution having a fixing ability. A precursor of a compound that suppresses the development of silver halide is released by a coupling reaction with an oxidation product of an aromatic primary amine developer, and then the precursor is subjected to an electron transfer reaction through an ethylenically conjugated chain to produce a silver halide. Containing at least one development inhibitor-releasing coupler that releases a compound that suppresses development, and the bleaching solution contains a ferric ethylenediaminetetraacetic acid complex salt as a bleaching agent and 1,3-diaminopropanetetraacetic acid ferric acid. A halogenated compound containing a complex salt in a molar ratio of the former to the latter of 2 or less, a pH of 2.0 to 5.0, and a desilvering step time of 1 minute 30 seconds to 3 minutes. Silver Color photographic light-sensitive material processing method.