JPH07119980B2 - Color developing solution for silver halide color photographic light-sensitive material and method for processing silver halide color photographic light-sensitive material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a color developing solution for silver halide color photographic light-sensitive materials, and more specifically, it is a preservative that replaces hydroxylamine, which is harmful to humans and is a poisonous substance. And a color developing solution for a silver halide color photographic light-sensitive material.

BACKGROUND OF THE INVENTION In color development, exposed silver halide is reduced to silver and at the same time oxidized primary aromatic amine developing agent reacts with a coupler to form a dye. During this process, halogen ions generated by the reduction of silver halide are eluted and accumulated in the developer. Separately, components such as heavy metal ions contained in other processing solutions are also brought into and accumulated in the color developing solution by so-called back contamination.

A color developer used for such color development usually contains a sulfite or a water-soluble salt of sulfite and hydroxylamine as a preservative (antioxidant) in order to increase the preservability. Among them, like the former, when the sulfite is used alone, fogging occurs remarkably over time.Therefore, by using the sulfite and the water-soluble salt of hydroxylamine together, the stability of the developer is maintained. Is significantly increased, and the occurrence of fogging due to aged developer is reduced.

However, hydroxylamine has the following drawbacks and disadvantages.

First, it was reported that hydroxylamine is harmful to the human body [eg PGStecher, “The Merck
Index An Encyclopedia of Chemical and Drugs "8th.Ed. (195
3 years)].

Secondly, even in the Poisonous and Deleterious Substances Control Law, in order to handle and sell hydroxylamine salts, it is necessary to register a general sales agent for poisonous and deleterious substances and to set up a person in charge of handling, which is extremely inconvenient to handle. However, it is difficult for an amateur photographer to handle the image because it is dangerous when it is processed by himself.

Thirdly, hydroxylamine is a kind of black-and-white developing agent, and has a silver developing agent for silver halide. Therefore, the utilization efficiency of silver halide in the silver halide color photographic light-sensitive material is poor, and it is necessary to use more silver halide or coupler in the light-sensitive material in order to obtain a desired dye concentration, which is economical. Is extremely detrimental to.

Fourth, hydroxylamine decomposes when heavy metal ions (for example, iron ions or copper ions) are mixed in the color developing solution to produce ammonia, which causes fogging on the color light-sensitive material and also improves photographic performance. It has a drawback that it has a bad effect on From the viewpoint of economical efficiency and pollution, color developers tend to be low in replenishment in recent years, and the grade of raw materials such as potassium carbonate is being reduced for the purpose of cost reduction. The amount of the heavy metal ions accumulated in the developing solution is increasing more and more. Therefore, the occurrence of fogging, which is the fourth problem due to the decomposition of hydroxylamine, is becoming more severe.

Therefore, in the future, when conducting color photo processing in stores (so-called mini-labs) or color copying equipped with a color development system, further development of a preservative that replaces hydroxylamine is strongly desired due to pollution problems. .

As an alternative preservative to hydroxylamine, 2-anilinoethanol and dihydroxyalkene are disclosed in US Pat.
Proposed in 3,823,017 and 3,615,503 respectively. However, in both cases, the compound itself is unstable, and there is no preservative effect in the color developing solution.

On the other hand, in a developer (for black and white photography) containing hydroquinone or N-alkyl-p-aminophenol as a developing agent, sucrose (sucrose) is known as a preservative, but sucrose is an aromatic primary amine. A color developing solution containing as a developing agent has little effect as a preservative.

Further, ascorbic acid and its derivatives are known as preservatives for black-and-white photographic developing solutions and color developing solutions, but these are disadvantages that inhibit color development and cause a remarkable decrease in color density. Inferior to amines.

Further, α-hydroxy aromatic alcohols described in JP-A-52-7779, hydroxamic acid compounds described in JP-A-52-27638, α-aminocarbonyl compounds described in JP-A-52-143020 and JP-A-52-102727. , And the amino acid derivatives described in JP-A No. 52-140324 are disclosed.

However, when a large amount of monosaccharides and amino acid derivatives are used,
Although it shows a considerable degree of homeostasis at room temperature, it is easily decomposed by heat and has undesirable characteristics in terms of pollution.

And D-glucosamine hydrochloride is known as a typical compound of the α-aminocarbonyl compound, but this compound is inferior in preservability to hydroxylamine.

Further, the hydroxamic acid compound has the same level of preservative property as hydroxylamine, but has the disadvantage of high cost.

Therefore, the present inventor has investigated hydrazine, which is conventionally known as a photographic additive to be contained in a light-sensitive material, in order to solve the above-mentioned drawbacks and provide a preservative that substitutes for hydroxylamine. Compared with the above, the preservability was extremely insufficient, the solubility was poor, or even though the preservability was present, the silver developability was strong and the coloring efficiency was extremely low, so that it was not very practical.

Accordingly, the present inventor has conducted extensive research on such hydrazine derivatives, and has found that a certain specific hydrazine derivative exhibits considerably high preservative properties, and the decrease in color development efficiency is small.

However, further studies by the present inventors have revealed that the color developer containing this hydrazine derivative has a lower maximum dye concentration upon storage over time.

[Object of the invention] An object of the present invention, which solves the above-mentioned drawbacks, contains a preservative which is harmless to the human body and is easy to handle, and color development in which a decrease in the maximum dye concentration is suppressed even after long-term storage. The purpose is to provide a liquid.

[Means for Solving the Problems] The color developer for silver halide color photographic light-sensitive material of the present invention which achieves the above object comprises at least one compound represented by the general formula [A] and the general formula [B]. It is characterized by containing at least one kind of the compound shown and at least one kind of the hydroxylamine derivative shown by the general formula [C].

General formula [A] [In the formula, R ₁ represents a hydrogen atom, a carbamoyl group, an aryl group, an alkyl group, an acyl group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group or a heterocyclic group, and R ₂ represents a hydrogen atom, an alkyl group, an aryl group. , An alkoxy group, an aryloxy group, a hydroxy group, a heterocyclic group,
Represents an amino group or a hydrazino group, R ₃ represents a hydrogen atom, an alkyl group or an aryl group, l is 0 or 1, and when l is 0, Z is —CO—, -SO ₂ -, And when 1 is 1, Z is -CO-, -SO ₂ - represents a. R has the same meaning as R ₃ . ] General formula [B] [In the formula, R ₄ is a hydroxyalkyl group having 2 to 6 carbon atoms,
R ₅ and R ₆ are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms, a benzyl group or a formula In the above formula, n represents an integer of 1 to 6, X and Z each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 2 to 6 carbon atoms. ] General formula [C] [In the formula, R ₇ and R ₈ include a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and the alkyl group has a substituent. However, R ₇ and R ₈ are not hydrogen atoms at the same time. [Operation of the Invention] Although hydrazine is conventionally known as a photographic additive for a light-sensitive material, for example, some hydrazine derivatives are disclosed in US Pat.
3,227,552, JP-A-55-52020, 55-90940, 56-
No. 67843, No. 53-20921, No. 53-20932, No. 60-140340, mainly added to a light-sensitive material and used in a super-high contrast forming method of photoengraving, or for direct positive use. It was also used as a fogging agent.

Also, in U.S. Pat. No. 3,141,771, certain hydrazine derivatives were used as aldehyde scavengers in reversal treatment.

However, according to the research by the present inventor, it was found that a specific hydrazine derivative exhibits high preservative properties. However, it has been found that this hydrazine derivative causes a problem that the concentration of the color developer containing the hydrazine derivative decreases with time. This is probably because hydrazine and certain derivatives are decomposed during storage, and the decomposition products cause a decrease in concentration.

In order to solve such a problem, the present inventor has found that, when a specific hydrazine derivative and an alkanolamine derivative are used in combination, the problem of the concentration decrease, which is considered to be caused by the above decomposition product, can be solved. The alkanolamine derivative is described in, for example, U.S. Pat.No. 3,823,017 as being able to be used as an antioxidant of a color developing solution, but it was found that the effect of preventing the concentration decrease during storage with the use of a hydrazine derivative was observed. Was truly amazing.

Moreover, when a hydroxylamine derivative is used in combination with the present invention, a surprisingly advantageous effect is found, in which the preservative property is synergistically improved and the occurrence of stain, which is considered to be caused by so-called defective decolorization of the AI dye, is suppressed. I found out that

[Configuration of the Invention] The present invention will be described in detail below.

First, the general formula [A] will be described.

The carbamoyl group represented by R ₁ includes those substituted, and examples thereof include carbamoyl group, N, N-dimethylcarbamoyl group, N-methylcarbamoyl group and N, N-tetramethylenecarbamoyl group.

The aryl group represented by R ₁ includes substituted aryl groups such as phenyl group, p-methoxyphenyl group, p-
Aminophenyl group, p-hydrazinophenyl group, o-aminophenyl group, p-sulfophenyl group, 2,5-disulfophenyl group, p-tolyl group, p-sulfamoylphenyl group, p-carboxyphenyl group , P-guanidinophenyl group and the like.

The alkyl group represented by R ₁ includes linear, branched, and cyclic groups, and examples thereof include methyl group, ethyl group, isobutyl group, pentyl group, cyclopentyl group, cyclohexyl group, and the like. These alkyl groups are substituted. Including those having a group. The substituent also includes one having a substituent, and examples thereof include a halogen atom (eg, fluorine atom, chlorine atom, bromine atom), hydroxyl group, carboxyl group, alkoxycarbonyl group (eg, ethoxycarbonyl group), carbamoyl group (eg, carbamoyl group, N, N-dimethylcarbamoyl group), alkoxy group (for example, methoxy group, ethoxy group, butoxy group), sulfo group, alkylsulfonyl group (for example, methanesulfonyl group, ethanesulfonyl group),
Sulfamoyl group (eg, sulfamoyl group, N, N-dimethylsulfamoyl group, morpholinosulfonyl group),
Amino group (eg amino group, dimethylamino group), piperidino group, morpholino group, amide group (eg acetylamide group, benzoylamide group), vinyl group, aryl group (eg phenyl group, p-dimethylaminophenyl group, p- Examples thereof include a sulfophenyl group), an ammonium group (eg, metamethylammonium group, metaethylammonium group), a phosphonium group (eg, triphenylphosphonium group), and the like.

The acyl group represented by R ₁ includes aliphatic and aromatic groups, for example, acetyl group, propionyl group, benzoyl group, p-sulfobenzoyl group, p-N, N-dimethylaminobenzoyl group, p-carboxybenzoyl group. , M-hydroxybenzoyl group and the like.

The sulfamoyl group represented by R ₁ includes those having a substituent, and examples thereof include a sulfamoyl group, an N, N-dimethylsulfamoyl group, and a morpholinosulfonyl group.

Examples of the alkylsulfonyl group represented by R ₁ include respective groups such as methanesulfonyl group and benzylsulfonyl group, and examples of the arylsulfonyl group represented by R ₁ include benzenesulfonyl group, p-toluenesulfonyl group, p
Each group such as a carboxybenzenesulfonyl group may be mentioned.

The heterocyclic group represented by R ₁ includes saturated and unsaturated heterocyclic groups such as a furyl group, a thienyl group, a pyridyl group,
Examples thereof include sulfopyridyl group, pyrimidyl group, imidazolyl group, benzothiazolyl group and the like.

Next alkyl group represented by R _2, an aryl group and heterocyclic group, an alkyl group represented by R ₁ has the same meaning as the aryl group and a heterocyclic group, those having the same substituents as the substituent group at the R ₁ Including. The alkoxy group represented by R ₂ includes those having a substituent, for example, a methoxy group, an ethoxy group, 2-
Examples thereof include hydroxyethoxy group and 3-sulfopropoxy group.

The aryloxy group represented by R ₂ includes those having a substituent, and examples thereof include a phenoxy group.

The amino group represented by R ₂ includes those having a substituent, and examples thereof include an amino group, a methylamino group, an anilino group, and a p-aminocarbamidoanilino group.

Next alkyl and aryl groups represented by R ₃ has the same meaning as the alkyl group and aryl group represented by R _1, include those having the same substituents as the substituents having the R _1.

Specific compounds of the hydrazine derivative used in the present invention are shown below, but the present invention is not limited to these compounds.

[Exemplified compound] (9) HOCH ₂ CH ₂ -NHNH ₂ These compounds are usually used in the form of salts such as hydrochloride, sulfate, p-toluenesulfonate, oxalate, phosphate and acetate.

The above compounds may be added alone to the color developer, or 2
It is also possible to add a combination of two or more species.

The addition amount is preferably 0.1 g to 50 g, and more preferably 0.3 g to 30 g, per 1 color developing solution.

Next, the alkanolamine derivative represented by the above general formula [B] is used in combination with the hydrazine derivative represented by the above general formula [A] in the color developing solution of the present invention.

Among the compounds represented by the general formula [B], R ₄ is a hydroxyalkyl group having 2 to ₄ carbon atoms, and R ₅ and R ₆ are each an alkyl group having 1 to 4 carbon atoms or 2 to 4 carbon atoms.
Those having the hydroxyalkyl group of are preferred.

Preferred specific examples of the compound represented by the general formula [B] are as follows.

Ethanolamine, diethanolamine, triethanolamine, di-isopropanolamine, 2-methylaminoethanol, 2-ethylaminoethanol, 2-dimethylaminoethanol, 2-diethylaminoethanol, 1-diethylamino-2-propanol, 3-diethylamino-1 -Propanol, 3-dimethylamino-
1-propanol, isopropylaminoethanol, 3
-Amino-1-propanol, 2-amino-2-methyl-1,3-propanediol, ethylenediaminetetraisopropanol, benzylethanolamine, 2-amino-2- (hydroxymethyl) -1,3-propanediol.

Among these, ethanolamine and diethanolamine are preferable, and ethanolamine is most preferable.

The above compounds may be added alone to the color developer, or 2
It is also possible to add a combination of two or more species.

The addition amount is preferably 0.1 g to 50 g, and more preferably 0.3 g to 30 g, per 1 color developing solution.

A hydroxylamine derivative represented by the following general formula [C] is used in combination in the color developing solution of the present invention. By the combined use of the compound, the effect of synergistically improving the preservative property and suppressing the generation of stain, which is considered to be caused by so-called defective decolorization of the AI dye, can be obtained.

General formula [C] In the general formula [C], R ₇ and R ₈ are hydrogen atoms or have 1 to 1 carbon atoms.
The alkyl group of 5 includes those having a substituent. However, R ₇ and R ₈ are not hydrogen atoms at the same time.

Examples of the substituent include a sulfonic acid group, a hydroxy group, an alkoxy group (a methoxy group, an ethoxy group, a propyloxy group, etc.), a carboxy group, an amino group, and the like. For these, for example, U.S. Patents 3,287,125 and 3,293,034,
Examples thereof include hydroxylamines described in No. 3,287,124.

Among the compounds represented by the general formula [C], preferred are those in which one of R ₇ and R ₈ is a hydrogen atom and the other is a lower alkyl group.

Preferred specific exemplary compounds represented by the general formula [C] are shown below.

_{(1) CH 3 -NH-OH} (2) C 2 H 5 -NH-OH (3) iso-C 3 H 7 -NH-OH (4) C 3 H 7 -NH-OH (5) HO-CH _{2 -NH-OH (6) CH} 3 -O-C 2 H 4 -NH-OH (7) HO-C 2 H 4 -NH-OH (8) HOOC-C 2 H 4 -NH-OH (9) _{HO 3 S-C 2 H 4} -NH-OH (10) N 2 H-C 3 H 6 -NH-OH (11) C 2 H 5 -O-C 2 H 4 -NH-OH (12) HO- _{C 2 H 4 -O-C 2} H 4 -NH-OH These compounds are usually used in the form of salts such as hydrochloride, sulfate, p-toluenesulfonate, oxalate, phosphate and acetate.

The concentration of the compound represented by the above general formula [C] in the color developer is usually, for example, preferably 0.1 g / l to 50 g / l, more preferably 0.3 g / l to 30 g / l, particularly preferably Is 0.5g /
It is from 1 to 20 g / l.

Further, the above compounds may be used in combination of two or more kinds.

The mixing ratio of the compound represented by the general formula [A] and the compound represented by the general formula [B] is preferably 1: 100 to 50: 1, more preferably 1:50 to 25: 1.

Examples of the compound that can be used in the color developing solution of the present invention include sulfite and the like in addition to the compound represented by the general formula [A], [B] or [C]. Examples of the sulfite include sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, and the addition amount is 2 per 1 color developing solution.
^{X10 -4} mol or more, preferably 5 x 10 ^-4 mol or more, 2x
It is 10 ^-1 mol or less, preferably 1 × 10 ^-1 mol or less.

As the color developing agent used in the color developing solution of the present invention, a p-phenylenediamine compound having a water-soluble group is preferable from the viewpoint of obtaining the effect of the present invention.

The p-phenylenediamine compound having a water-soluble group is
Compared with p-phenylenediamine compounds that do not have a water-soluble group such as N, N-diethyl-p-phenylenediamine, not only has the advantage that the light-sensitive material is not contaminated, and that the skin is not easily fogged. Particularly in the present invention, the compound represented by the general formula [A] and the general formula [B]
The object of the present invention can be effectively achieved by combining with the compound represented by.

The water-soluble group are those having at least one is listed on the amino group or benzene nucleus of p- phenylenediamine compound, as a specific water-soluble _{group, - (CH 2) n -CH} 2 OH, - _{(CH 2) m -NHSO 2 -} (CH 2) n -CH 3, - (CH 2) m -O- (CH 2) n -CH 2, - (CH 2 CH 2 O) n C m H 2m + ₁ (m and n each represent an integer of 0 or more), —COOH group, —SO ₃ H group and the like are preferable.

Specific examples of the color developing agent preferably used in the invention are shown below.

[Exemplary color developing agent] The above color developing agents are usually used in the form of salts such as hydrochlorides, sulfates and p-toluenesulfonates, and are usually used in the range of 1 × 10 ⁻³ to 2 × 10 ⁻¹ mol per 1 color developing solution. However, from the viewpoint of rapid processing, color developer 1
The range of 1.5 × 10 ^{-3 to} 2 × 10 ^-1 mol is more preferable.

The color developer of the present invention may contain the following developer components in addition to the above components.

As the alkaline agent, for example, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, silicate, sodium metaborate, potassium metaborate, trisodium phosphate, tripotassium phosphate, borax, etc., alone or in combination. Can be used. Further, various salts such as disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium bicarbonate, potassium bicarbonate, borate are used for the necessity of preparation or for the purpose of increasing ionic strength. be able to.

Inorganic and organic antifoggants can be added as required.

Furthermore, if necessary, a development accelerator can also be used. U.S. Pat.No. 2,648,604 as a development accelerator,
No. 3,671,247, various pyridinium compounds represented by JP-B-44-9503 and other cationic compounds,
Cationic dyes such as phenosafranine, neutral salts such as thallium nitrate, US Pat. Nos. 2,533,990 and 2,531,832
No. 2, No. 2,950,970, No. 2,577,127 and Japanese Patent Publication No.
Polyethylene glycol and its derivatives, nonionic compounds such as polythioethers described in JP-B-44-950
Organic solvents, organic amines, ethanolamines, ethylenediamines, diethanolamines, triethanolamines, etc. described in JP-A-9 are included. Further, benzyl alcohol and phenethyl alcohol described in US Pat. No. 2,304,925 and acetylene glycol, methyl ethyl ketone, cyclohexanone, thioethers, pyridine, ammonia and the like can be mentioned.

Further, the color developing solution of the present invention, if necessary, ethylene glycol, methyl cellosolve, methanol, acetone, dimethylformamide, β-cyclodextrin, other JP-B-47-33378, 44-9509 described each publication An organic solvent for increasing the solubility of the developing agent can be used.

Further, an auxiliary developing agent can be used together with the developing agent. Examples of these auxiliary developers include N-methyl-p-aminophenol hexaulfate (methol), phenidone, N, N'-diethyl-P-aminophenol hydrochloride, N, N, N ', N'-tetrahydrochloride. Methyl-P-phenylenediamine hydrochloride and the like are known, and the addition amount thereof is usually preferably 0.01 g to 10 g / l. In addition to these, competing couplers, fogging agents, colored couplers, development inhibitor-releasing couplers (so-called DIR couplers), development inhibitor-releasing compounds and the like can be added as required.

Furthermore, other anti-stain agents, anti-sludge agents,
Various additives such as a multi-layer effect accelerator can be used.

A triazylstilbene-based optical brightening agent is preferably used in the color developing solution of the present invention, and as the triazylstilbene-based optical brightening agent, a compound represented by the following general formula [I] is preferably used.

General formula [I] In the formula, X ₁₁ , X ₁₂ , Y ₁₁ and Y ₁₂ are each a hydroxyl group, a halogen atom such as chlorine or bromine, a morpholino group, an alkoxy group (eg, methoxy, ethoxy, methoxyethoxy, etc.),
An aryloxy group (eg, phenoxy, p-sulfophenoxy, etc.), an alkyl group (eg, methyl, ethyl, etc.),
Aryl groups (eg phenyl, methoxyphenyl, etc.),
Amino group, alkylamino group (for example, methylamino, ethylamino, propylamino, dimethylamino, cyclohexylamino, β-hydroxyethylamino, di (β
-Hydroxyethyl) amino, β-sulfoethylamino, N- (β-sulfoethyl) -N′-methylamino,
N- (β-hydroxyethyl-N′-methylamino etc.), arylamino group (eg anilino, o-, m
-, P-sulfoanilino, o-, m-, p-chloroanilino, o-, m-, p-toluidino, o-, m-, p-
Carboxyanilino, o-, m-, p-hydroxyanilino, sulfonaphthylamino, o-, m-, p-aminoanilino, o-, m-, p-anidino and the like). M represents a hydrogen atom, sodium, potassium, ammonium or lithium.

Specifically, the following compounds can be mentioned, but not limited to these.

[Exemplified compound]

These triazyl stilbene-based brighteners can be synthesized, for example, by the usual method described on page 8 of “Fluorescent brightener” edited by Chemical Industry Association (published in August 1976).

These triazyl stilbene whitening agents are preferably used in the range of 0.2 to 20 g, and particularly preferably 0.4 to 10 g, per 1 color developing solution of the present invention.

The color developer used in the present invention has the following general formula [K-
I], [K-II] and [K-III] are preferably contained.

Formula [K-I] A-COOM Formula [K-II] B-PO ₃ M ₂ Formula [K-III] In the formula, A and B each represent a monovalent group or atom, and may be an inorganic substance or an organic substance. D represents an aromatic ring or a heterocycle which may have a substituent, and M represents a hydrogen atom or an alkali metal atom.

The chelating agent represented by the general formula [KI], [K-II] or [K-III] is represented by the following general formulas [K-IV] to [K-X].
V].

General formula [K-IV] Mm ₁ Pm ₁ O ₃ m ₁ General formula [K-V] Mn _{1 + 2} Pn ₁ O ₃ n _{1 + 1} General formula [K-VI] A ₁ -R ₁ -Z-R _2- COOH general formula [K-VII] Wherein, E is a substituted or unsubstituted alkylene group, a cycloalkylene group, a phenylene _{group, -R 7 OR 7 -, -} R 7 OR 7 OR 7
- or -R ₇ ZR ₇ - represents, Z is> N-R ₇ -A ₅ or> N
Represents -A _5, R ₁ ~R ₇ each represent a substituted or unsubstituted alkylene group, A ₁ to A ₅ are each a hydrogen atom, -OH, -CO
OM or —PO ₃ M ₂ , M represents a hydrogen atom or an alkali metal atom, m ₁ represents an integer of 3 to 6, and n ₁ represents an integer of 2 to 20.

In the general formula [K-VIII] _{R 8 N (CH 2 PO 3} M 2) 2 Formula, R ₈ is a lower alkyl group, an aryl group, an aralkyl group or a nitrogen-containing 6-membered Hajime Tamaki [-OH as a substituent, -OR Or-
COOM may be present], and M represents a hydrogen atom or an alkali metal atom.

General formula [K-IX] In the formula, R _{8 to} R ₁₁ are each a hydrogen atom, OH, a lower alkyl group (unsubstituted or as a substituent, —OH, —COOM or —PO ₃ M ₂
B _{1 to} B ₃ each represent a hydrogen atom, —OH, —COOM, —PO ₃ (M) ₂ or —N (J) ₂ , and J is a hydrogen atom or a lower group. alkyl group, C ₂ H ₄ OH or -PO
₃ represents M ₂ , M represents a hydrogen atom or an alkali metal, and n
₂ and m ₂ each represent 0 or 1.

General formula [K-X] In the formula, R ₁₂ and R ₁₃ each represent a hydrogen atom, an alkali metal atom, a C _{1 to} C ₁₂ alkyl group, a C _{1 to} C ₁₂ alkenyl group, or a cyclic alkyl group.

General formula [K-XI] In the formula, R ₁₄ is a C _{1 to} C ₁₂ alkyl group, a C _{1 to} C ₁₂ alkoxy group, a C _{1 to} C ₁₂ monoalkylamino group, and a C _{2 to} C
₁₂ dialkylamino groups, amino groups, C ₁ -C ₂₄ aryloxy groups, C ₅ -C ₂₄ arylamino groups and amyloxy groups, wherein Q ₁ -Q ₃ are -OH and C ₁ -C ₂₄ alkoxy, respectively. A group, -OM ₁ (M ₁ represents a cation), an amino group,
It represents a molporino group, a cyclic amino group, an alkylamino group, a dialkylamino group, an arylamino group or an alkyloxy group.

General formula [K-XII] General formula [K-XIII] In the formula, R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ are each a hydrogen atom, a halogen atom, a sulfonic acid group, a substituted or unsubstituted alkyl group having 1 to 7 carbon atoms, —OR ₁₉ , —COOR ₂₀ , Alternatively, it represents a substituted or unsubstituted phenyl group. R ₁₉ , R
₂₀ , R ₂₁ and R ₂₂ are each a hydrogen atom or a carbon atom of 1 to
Represents 18 alkyl groups. n represents an integer of 1 to 3. R ₁₅
May be the same or different. R ₁₅ is preferably a sulfonic acid group.

General formula [K-XIV] In the formula, R ₂₃ and R ₂₄ represent a hydrogen atom, a halogen atom or a sulfo group.

General formula [K-XV] In the formula, R ₂₉ and R ₃₀ each represent a hydrogen atom, a phosphoric acid group, a carboxylic acid group, —CH ₂ COOH, —CH ₂ PO ₃ H ₂ or a salt thereof, and X ₃ represents a hydroxyl group or a salt thereof, W ₁ , Z ₁ and Y ₁
Each represents a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a carboxylic acid group, a phosphoric acid group, a sulfonic acid group or salts thereof, an alkoxy group or an alkyl group. Also m
₃ is 0 or 1, n ₃ is an integer of 1 to 4, l ₁ is 1 or 2, p ₂
Is an integer of 0 to 3, and q ₁ is an integer of 0 to 2.

Specific examples of the chelating agent represented by the above general formulas [K-IV] to [K-XV] include the following.

[Exemplary chelating agent] (1) Na ₄ P ₄ O ₁₂ (2) Na ₃ P ₃ O ₉ (3) H ₄ P ₂ O ₇ (4) H ₅ P ₃ O ₁₀ (5) Na ₆ P ₄ O ₁₃ (15) (HOC ₂ H ₄ ) ₂ NCH ₂ COOH In the present invention, the general formulas [K-IV], [KV], [K
-VII], [K-VIII], [K-IX], [K-XII] or [K-XV] is more effective, and more preferably the general formula [K- VII], [K
-VIII] or [K-XV]. In the present invention, particularly preferred chelating agents (6), (7), (14), (19), (31) and (4
4), (81), (82), (90), (94) or (99) is used. These chelating agents can be used in combination of two or more kinds.

The above general formulas [KI] to [K-II] used in the present invention
The chelating agent represented by any one of [I] is the color developer 1
It is preferable to add it in the range of 1 × 10 ^-4 mol to 1 mol, more preferably 2 × 10 ^-4 to 1 × 10 ^-1 mol, and further preferably 5 × 10 ^{−. 4 to} 5 x 10
It can be added in the range of ^-2 mol.

Each component of the above color developing solution can be prepared by sequentially adding and stirring to constant water. In this case, a component having low solubility in water can be added by mixing with the above-mentioned organic solvent such as triethanolamine. More generally, a plurality of components, each of which can coexist stably, are prepared in a concentrated aqueous solution, or in a solid state in a small container prepared in advance by adding to water and stirring to prepare a color developing solution of the present invention. Obtainable.

The color developer of the present invention can be used in any pH range, but from the viewpoint of rapid processing, it is preferably pH 9.5 to 12.0, more preferably pH 9.8 to 12.0, and particularly preferably 10.0 to 11.5.
Used in.

The processing temperature for color development using the color developing solution of the present invention is 30
C. or higher and 50.degree. C. or lower are preferable, and the higher the temperature, the quicker the treatment can be performed, which is preferable. However, on the contrary, there is also a problem that the preservability is easily deteriorated.

After color development processing using the color developing solution of the present invention, processing is performed with a processing solution having fixing ability. When the processing solution having fixing ability is a fixing solution, bleaching processing is performed before that. As the bleaching agent used in the bleaching solution or the bleach-fixing solution used in the bleaching step, a metal complex salt of an organic acid is preferably used, and the metal complex salt oxidizes the metal silver produced by development and converts it into silver halide. At the same time, it has a function of coloring the uncolored portion of the color-developing agent, and its structure is such that an organic acid such as aminopolycarboxylic acid or oxalic acid or citric acid is coordinated with a metal ion such as iron, cobalt or copper. The most preferable organic acid used for forming such a metal complex salt of an organic acid includes a polycarboxylic acid or an aminopolycarboxylic acid. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

The following can be mentioned as specific representative examples of these.

[1] Ethylenediaminetetraacetic acid [2] Diethylenetriaminepentaacetic acid [3] Ethylenediamine-N- (β-oxyethyl)
-N, N, ', N'-triacetic acid [4] Propylenediaminetetraacetic acid [5] Nitrilotriacetic acid [6] Cyclohexanediaminetetraacetic acid [7] Iminodiacetic acid [8] Dihydroxyethylglycine citric acid (or tartaric acid) [9 ] Ethyletherdiaminetetraacetic acid [10] Glycoletheraminetetraacetic acid [11] Ethylenediaminetetrapropionic acid [12] Phenylenediaminetetraacetic acid [13] Ethylenediaminetetraacetic acid disodium salt [14] Ethylenediaminetetraacetic acid tetra (trimethylammonium) salt [ 15] Ethylenediaminetetraacetic acid tetrasodium salt [16] Diethylenetriaminepentaacetic acid pentasodium salt [17] Ethylenediamine-N- (β-oxyethyl)
-N, N ', N'-triacetic acid sodium salt [18] Propylenediaminetetraacetic acid sodium salt [19] Nitrilotriacetic acid sodium salt [20] Cyclohexanediaminetetraacetic acid sodium salt The bleaching solution used is an organic acid as described above. In addition to containing the metal complex salt of 1) as a bleaching agent, various additives can be included. As the additive, it is particularly preferable to contain an alkali halide or an ammonium halide, for example, a rehalogenating agent such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide, a metal salt or a chelating agent. In addition, borate, oxalate, carbonate, phosphate and other pH buffers, alkylamines, polyethylene oxides and the like, which are known to be added to ordinary bleaching solutions, can be appropriately added.

Further, the fixer and the bleach-fixer are ammonium sulfite,
Sulfites such as potassium sulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, boric acid, borax, sodium hydroxide,
A pH buffering agent composed of various salts such as potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide can be used alone or in combination of two or more kinds.

When processing is performed while replenishing the bleach-fixing solution (bath) with a bleach-fixing replenisher, the bleach-fixing solution (bath) may contain thiosulfate, thiocyanate, sulfite or the like. The replenisher may contain these salts and may be replenished to the treatment bath.

In order to increase the activity of the bleaching solution and the bleach-fixing solution, air may be blown thereinto or oxygen may be blown in the bleaching-fixing bath and the storage tank of the bleach-fixing replenisher, or a suitable oxidizing agent such as, for example, Hydrogen peroxide, bromate, persulfate and the like may be added appropriately.

The pH of the bleach-fixing solution preferably used in the present invention is 3.0 to 9.0.
Is preferable, and more preferably in the range of 4.0 to 8.0.

Incidentally, in the treatment with a washing solution or a substitute solution for washing with water after the bleach-fixing treatment, of course, silver may be recovered by a known method from a processing solution containing a soluble silver complex salt such as a fixing solution and a bleach-fixing solution. For example, electrolysis method (French patent 2,299,667), precipitation method (JP-A-52-73037, German patent 2,331,220), ion exchange method (JP-A 51-17114, German patent 2,548,237).
No.) and metal substitution method (UK Patent No. 1,353,805) can be effectively used.

After bleaching and fixing (or bleach-fixing) after the color development processing using the color developing solution of the present invention, it is possible to carry out stable processing without washing with water, or to carry out stabilizing processing after washing with water. , In addition to the above steps, hardening, neutralization, black and white development,
Known auxiliary steps such as inversion and a small amount of water washing step may be added as necessary. Representative examples of preferred treatment methods include the following steps.

(1) Color development → bleach-fixing → water washing (2) Color development → bleach-fixing → small amount water washing → water washing (3) Color development → bleach-fixing → water washing → stable (4) Color development → bleach-fixing → stable (5) Color development → bleach-fixing → 1st stability → 2nd stability (6) Color development → water washing (or stable) → bleach-fixing → water washing (or stable) (7) color development → stop → bleach-fixing → water washing (or stable) (8) Color development → Bleaching → Washing → Fixing → Washing → Stable (9) Color developing → Bleaching → Fixing → Washing → Stable (10) Color developing → Bleaching → Washing with a small amount of water → Fixing → 1st stability →
Second stability (11) Color development → bleaching → washing with a small amount of water → fixing → washing with a small amount of water →
Washing → Stable (12) Color development → Bleaching → Fixing → Stable (13) Color development → Stop → Bleaching → Washing with a small amount of water → Fixing → Rinsing with a small amount of water → Washing → Stable The color developing solution of the present invention is a color paper, a color film or a color positive. Film, color positive paper, color reversal film for slides, color reversal film for movies,
It can be applied to color photographic light-sensitive materials such as color reversal film for TV and reversal color paper.

There is no particular limitation on the light-sensitive material processed by the color developing solution of the present invention. For example, the crystals of silver halide grains may be normal crystals, twin crystals, or others, and have [1.0.0] planes and [1.
1.1] Any aspect ratio can be used. Further, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may be a layered or phase structure (core shell type) having different inside and outside. . Further, these silver halides may be of a type that forms a latent image mainly on the surface or may be of a type that is formed inside the grain. Further, tabular silver halide grains (JP-A-58-1)
13934 and Japanese Patent Application No. 59-170070).

The silver halide grains are preferably substantially monodisperse grains, which may be obtained by any preparation method such as an acidic method, a neutral method or an ammonia method.

Since the particle size distribution of the monodisperse emulsion is almost normal, the standard deviation can be easily obtained. The relational expression If the breadth of distribution (%) is defined by
Those having a monodispersity of 20% or less are preferable, and more preferably 10% or less. In the case of spherical silver halide grains, the grain size is the diameter thereof, and in the case of other than spheres, the grain size is calculated as spheres having the same area.

The above silver halide may be one in which seed grains are formed by an acidic method and further grown by an ammonia method having a high growth rate to grow to a predetermined size. When growing silver halide grains, the pH, pAg, etc. in the reaction vessel are controlled, and an amount of silver ions corresponding to the growth rate of silver halide grains as described in JP-A-54-48521, for example. It is preferable to sequentially and simultaneously inject and mix halide ions with halide ions.

These silver halide emulsions include active gelatin; sulfur sensitizers such as allylthiocarbamide, thiourea, and cystine; sulfur sensitizers; selenium sensitizers; reduction sensitizers such as stannous salt and thiourea dioxide. Noble metal sensitizers such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, and 2-aurothio-3-.
Sensitizers of methylbenzothiazolium chloride and the like or water-soluble salts such as ruthenium, palladium, platinum, rhodium and iridium, specifically ammonium chloroparadate, potassium chloroplatinate and sodium chloroparadate (these or Some of them act as sensitizers or antifoggants depending on the amount.) Etc. alone or in combination as appropriate (eg combination of gold sensitizer and sulfur sensitizer, gold sensitizer and selenium sensitizer). It may be chemically sensitized by the combined use with a sensitizer).

The silver halide emulsion is chemically ripened by adding a sulfur-containing compound, and before, during, or after the chemical ripening, at least one hydroxytetrazaindene and at least one nitrogen-containing heterocyclic compound having a mercapto group are contained. You may make it contain 1 type.

The silver halide contains a sensitizing dye in an amount of 5 to 1 mol of silver halide in order to impart photosensitivity to a desired photosensitive wavelength range.
Optical sensitization may be carried out by adding × 10 ^{-8 to} 3 × 10 ^-3 mol.
Various kinds of sensitizing dyes can be used, and one kind or a combination of two or more kinds of sensitizing dyes can be used.

The light-sensitive material to which the present invention can be applied includes a red-sensitive silver halide emulsion layer, a blue-sensitive silver halide emulsion layer and a green-sensitive silver halide emulsion layer, each of which is a coupler, that is, a dye which reacts with an oxidant of a color developing agent. Those containing a compound capable of forming are preferred.

Examples of yellow couplers that can be used include closed ketomethylene compounds, active-point-o-aryl-substituted couplers, active-point-o-acyl-substituted couplers, active-point hydantoin compound-substituted couplers, and active-point urazole compound-substituted so-called 2-equivalent type couplers. Couplers and active-point succinimide compound-substituted couplers, active-point fluorine-substituted couplers, active-point chlorine or bromine-substituted couplers, active-point-o-sulfonyl-substituted couplers and the like can be used as effective yellow couplers. Specific examples of yellow couplers that can be used include U.S. Patents 2,875,057 and 3,2.
65,506, 3,408,194, 3,551,155, 3,582,32
No. 2, No. 3,725,072, No. 3,891,445, West German Patent 1,547,8
68, West German Application Publication No. 2,219,917, No. 2,261,361, No. 2,
414,006, British Patent 1,425,020, Japanese Patent Publication No. 51-10783,
JP-A-47-26133, 48-73147, 51-102636, 5
0-6341, 50-123342, 50-130442, 51-21827
No. 50, No. 50-87650, No. 52-82424, No. 52-115219, No. 5
Examples thereof include those described in 8-95346.

As magenta couplers that can be used, pyrazolone type,
Examples thereof include pyrazolotriazole compounds, pyrazolinobenzimidazole compounds, and indazolone compounds.
These magenta couplers are the same as the yellow couplers 4
Not only the equivalent type coupler but also a two equivalent type coupler may be used. Specific examples of magenta couplers that can be used include U.S. Patents 2,600,788, 2,983,608 and 3,062,653.
Issue 3,127,269, 3,311,476, 3,419,391,
3,519,429, 3,558,319, 3,582,322, 3,6
15,506, 3,834,908, 3,891,445, West German patent 1,
810,464, West German patent application (OLS) 2,408,665, 2,41
7,945, 2,418,959, 2,424,467, Japanese Patent Sho 40-60
31, JP-A-51-20826, JP-A-52-58922, JP-A-49-129538
No. 49, No. 74027, No. 50-159336, No. 52-42121, No. 4
9-74028, 50-60233, 51-26541, 53-55122
And Japanese Patent Application No. 55-110943.

Examples of cyan couplers that can be used include phenol-based and naphthol-based couplers. And these cyan couplers may be not only 4-equivalent type couplers but also 2-equivalent type couplers like the yellow couplers. Specific examples of cyan couplers that can be used include U.S. Patents 2,369,929, 2,434,272, and 2,474,293.
Issue, Issue 2,521,908, Issue 2,895,826, Issue 3,034,892,
3,311,476, 3,458,315, 3,476,563, 3,5
83,971, 3,591,383, 3,767,411, 3,772,00
No. 2, No. 3,933,494, No. 4,004,929, West German patent application (O
LS) 2,414,830, 2,454,329, JP-A-48-59838,
51-26034, 48-5055, 51-146827, 52-696
No. 24, No. 52-90932, No. 58-95346, and Japanese Patent Publication No. 49-11572.

Couplers such as colored magenta or colored cyan couplers and polymer couplers may be used in combination in the silver halide emulsion layer and other photographic constituent layers. For the colored magenta or colored cyan coupler, reference can be made to the description in Japanese Patent Application No. 59-193611 by the present applicant, and for the polymer coupler, reference can be made to the description in Japanese Patent Application No. 59-172151 by the present applicant.

The amount of the above coupler added is not limited, but is preferably 1 × 10 ^{−3 to} 5 mol, and more preferably 1 × 10 ³ per mol of silver.
^{It is −2 to} 5 × 10 ⁻¹ mol.

The silver halide color photographic light-sensitive material to which the present invention can be applied may contain various photographic additives in addition thereto. For example, antifoggant, stabilizer, ultraviolet absorber, described in Research Disclosure Magazine 17643,
A color stain preventing agent, a fluorescent whitening agent, a color image fading preventing agent, an antistatic agent, a hardening agent, a surfactant, a plasticizer, a wetting agent and the like can be used.

In the silver halide color photographic light-sensitive material, the hydrophilic colloid used for preparing the emulsion is gelatin,
Derivative gelatin, graft polymer of gelatin and other polymers, albumin, protein such as casein, hydroxyethyl cellulose derivative, cellulose derivative such as carboxymethyl cellulose, starch derivative, polyvinyl alcohol, polyvinyl imidazole, polyacrylamide, etc. Any compound such as a combined synthetic hydrophilic polymer is included.

Examples of the support of the silver halide color photographic light-sensitive material include a reflective support such as baryta paper and polyethylene-coated paper and a transparent support, and these supports are appropriately selected according to the intended use of the light-sensitive material.

In the light-sensitive material to which the present invention can be applied, it is optional to provide an intermediate layer having an appropriate thickness according to the purpose, and further various layers such as a filter layer, an anti-curl layer, a protective layer and an antihalation layer are constituent layers. Can be used in appropriate combination. A hydrophilic colloid which can be used in the emulsion layer as described above can be similarly used as a binder in these constituent layers, and various hydrophilic colloids can be contained in the emulsion layer as described above. The above photographic additives can be incorporated.

An AI dye can be used in a light-sensitive material for so-called sharpness improvement and sensitivity adjustment. However, when an AI dye is used, stain is likely to occur, and in particular, the following general formulas [AI], [AI-I
I], [AI-III] or [AI-IV] tends to occur when the AI dye is contained. Therefore, the present invention has an effect that stain is less likely to occur even when the above dye is used.

General formula [AI-I] In the formula, Rf, Rf ₁ , Rf ₂ , Rf ₃ , Rf ₄ and Rf ₅ are hydrogen atoms; halogen atoms (eg chlorine atom, bromine atom, fluorine atom); hydroxy group; alkyl group, preferably having 1 carbon atom.
~ 4 alkyl groups (methyl group, ethyl group, propyl group); alkoxy groups (eg, methoxy group, ethoxy group,
Propoxy); -; represents a or -NHCH ₂ SO ₃ M group SO ₃ M.
M is a cation and represents an alkali metal (for example, sodium atom, potassium atom); ammonium, an organic ammonium salt (for example, pyridium, piperidinium, triethylammonium, triethanolamine) and the like.

Typical specific examples of the compound represented by the above general formula [AI-I] are shown below, but the present invention is not limited thereto.

[Exemplified compound] General formula [AI-II] In the formula, Rf ₆ and Rf ₆ ′ each represent a hydrogen atom, or an alkyl group, an aryl group or a heterocyclic group, respectively, and the aryl group may be a 4-sulfophenyl group, a 4- (δ-sulfobutyl) phenyl group, a 3 -Sulfophenyl group, 2,5
-Disulfophenyl group, 3,5-disulfophenyl group, 6,8
-Disulfo-2-naphthyl group, 4,8-disulfo-2-naphthyl group, 3,5-dicarboxyphenyl group, 4-dicarboxyphenyl group, etc., and this aryl group is a sulfo group, a sulfoalkyl group, a carboxy group , An alkyl group having 1 to 5 carbon atoms (eg, methyl group, ethyl group, etc.), a halogen atom (eg, chlorine atom, bromine atom, etc.), an alkoxy group having 1 to 4 carbon atoms (eg, methoxy group, ethoxy group, etc.), or phenoxy It also includes those having a substituent such as a group.

The sulfo group may be bonded to the aryl group via a divalent organic group, and for example, a 4- (4-sulfophenoxy) phenyl group, a 4- (2-sulfoethyl) phenyl group, a 3-
Examples thereof include (sulfomethylamino) phenyl group and 4- (2-sulfoethoxy) phenyl group.

The alkyl group represented by Rf ₆ and Rf ₆ ′ may be linear, branched or cyclic and preferably has 1 to 4 carbon atoms, and examples thereof include an ethyl group and a β-sulfoethyl group.

Examples of the heterocyclic group include a 2- (6-sulfo) benzthiazolyl group and a 2- (6-sulfo) benzoxazolyl group, and a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom). In addition, those having a substituent such as an alkyl group (eg, methyl group, ethyl group, etc.), an aryl group (eg, phenyl group, etc.), a carboxyl group, a sulfo group, a hydroxy group, an alkoxy group (eg, phenoxy group, etc.) are also included.

Rf ₇ and Rf ₇ ′ are each a hydroxy group; an alkoxy group having 1 to 4 carbon atoms (eg, a methoxy group, an ethoxy group, an isopropoxy group, an n-butoxy group); a substituted alkoxy group, such as a halogen atom or up to 2 carbon atoms. Alkoxy group having 1 to 4 carbon atoms substituted with an alkoxy group (for example, β-chloroethoxy group, β-methoxyethoxy group); cyano group; trifluoromethyl group; -COORf ₈ ; -CONHRf ₈ ; -NHCORf
₈ (Rf ₈ is a hydrogen atom; an alkyl group, preferably 1 to 1 carbon atoms
Or an aryl group such as a phenyl group or a naphthyl group, wherein the alkyl group and the aryl group include those having a sulfo group or a carboxy group as a substituent. ); Amino group; Substituted amino group substituted with an alkyl group having 1 to 4 carbon atoms (for example, ethylamino group, dimethylamino group, diethylamino group, di-n-butylamino group); or (Where p and q are 1 to represent the integer 2, X is an oxygen atom, a sulfur atom, -CH ₂ -. Represents a group) cyclic amino group represented by (e.g. a morpholino group, piperidino group, piperazino group) Represents

The methine group represented by L is substituted with an alkyl group having 1 to 4 carbon atoms (eg, methyl group, ethyl group, isopropyl group, tert-butyl group, etc.) or aryl group (eg, phenyl group, tolyl group, etc.) Including those that exist.

Further, at least one of the sulfo group, sulfoalkyl group and carboxy group of the compound is an alkali metal (eg sodium, potassium), an alkaline earth metal (eg calcium, magnesium), ammonium or an organic base (eg a diethylamine group, a triethylamine group, A morpholino group, a pyridine group, a piperidino group, etc.). n represents 0, 1 or 2. m represents 0 or 1.

Typical specific examples of the compound represented by the above general formula [AI-II] are shown below, but the present invention is not limited thereto.

[Exemplified compound] General formula [AI-III] In the formula, r represents an integer of 1 to 3, W represents an oxygen atom and a sulfur atom, L represents a methine group, and Rf _{31 to} Rf ₃₄ represent a hydrogen atom, an alkyl group, an aryl group, an aralkyl group,
Alternatively, it represents a heterocyclic group, and at least one or more is a substituent other than a hydrogen atom. The methine group represented by L has the general formula [AI
-II].

The alkyl group represented by Rf _{31 to} Rf ₃₄ has the general formula [AI
-II], the same as the alkyl groups of Rf ₆ and Rf ₆ ′ mentioned in the section [II], and the alkyl group includes those having a substituent, and examples of the substituent include, for example, those of the general formula [AI-II]. In terms of Rf ₆
And various examples of the substituent introduced into the group of Rf ₆ ′ are mentioned, preferably each group of a sulfo group, a carboxy group, a hydroxy group, an alkoxy group, an alkoxycarbonyl group, a cyano group and a sulfonyl group. Is.

The aryl group represented by Rf _{31 to} Rf ₃₄ is preferably a phenyl group, and the substituent introduced into this phenyl group is introduced into the groups Rf ₆ and Rf ₆ ′ in the general formula [AI-II]. Examples of the substituent include various substituents, but it is desirable to have at least one group selected from a sulfo group, a carboxy group and a sulfamoyl group on the aromatic ring.

The aralkyl group represented by Rf _{31 to} Rf ₃₄ is preferably a benzyl group or a phenethyl group, and these include those having a substituent, and the substituent is the same as the substituent of the aryl group of Rf ₃₁ to Rf ₃₄ described above. I can list things.

The heterocyclic group represented by Rf ₃₁ ~Rf _34, such as a pyridyl group, and a pyrimidyl group, the heterocyclic group includes those having a substituent, examples of the substituent, Rf ₃₁ described above The same substituents as the aryl group of Rf ₃₄ can be mentioned.

As the group represented by Rf _{31 to} Rf ₃₄ , an alkyl group and an aryl group are preferable, and further, a carboxy group, a sulfo group, and a sulfo group in the molecule of barbituric acid and thiobarbituric acid represented by the general formula [AI-III]. It is desirable to have at least one group of each group of sulfamoyl groups, and the symmetrical type is preferable.

Typical specific examples of the compound represented by the above general formula [AI-III] are shown below, but the present invention is not limited thereto.

[Exemplified compound] General formula [AI-IV] In the formula, l represents an integer of 1 or 2, L represents a methine group, Rf ₄₁ has the same meaning as Rf ₆ and Rf ₆ ′ in the general formula [AI-II], and preferably alkyl. Group and aryl group, and the aryl group preferably has at least one sulfo group.

Rf ₄₂ also includes those having a substituent represented by Rf ₇ and Rf ₇ ′ of the general formula [AI-II], and preferably an alkyl group, a carboxy group, an alkoxycarbonyl group, a carbamoyl group, a ureido group, an acylamino group, an imide. And a cyano group.

Rf ₄₃ is --OZ ₁ group or Where Z ₁ , Z ₂ and Z ₃ are each a hydrogen atom,
It represents an alkyl group, Z ₂ and Z ₃ may be the same or different, and may be bonded to each other to form a ring.

Examples of the alkyl group represented by Z ₁ , Z ₂ and Z ₃ include a methyl group, an ethyl group, a butyl group, a hydroxyalkyl group (such as a hydroxyethyl group), an alkoxyalkyl group (such as a β-ethoxyethyl group) and carboxy. Alkyl group (such as β-carboxyethyl group), alkoxycarbonylalkyl group (such as β-ethoxycarbonylethyl group), cyanoalkyl group (such as β-diaminoethyl group), sulfoalkyl group (such as β-sulfoethyl group, (γ-sulfopropyl group, etc.) and the like, and the alkyl group includes those having a substituent.

Z ₂ and Z ₃ may combine with each other to form a 5- or 6-membered ring, and specific examples thereof include a morpholino group, a piperidino group, a pyrrolidino group and the like.

Rf ₄₄ represents a hydrogen atom, an alkyl group, a chlorine atom, or an alkoxy group. Examples of the alkoxy group include a methoxy group,
Examples thereof include an ethoxy group.

Typical specific examples of the general formula [AI-IV] are shown below, but the present invention is not limited thereto.

[Exemplified compound] The above general formula [AI-I], [AI-II], [AI-III] or [A
I-IV] is represented by US Pat. Nos. 3,575,704 and 3,2.
No. 47,127, No. 3,540,887, No. 3,653,905 specifications,
JP-A-48-85130, 49-99620, 59-111640, 5
It can be synthesized by the synthesis method described in each publication of 9-111641-59-170838. When it is contained in the light-sensitive material, it is preferably contained in the non-photosensitive hydrophilic colloid layer, and the organic / inorganic alkali salt of the AI dye compound is dissolved in water to obtain a dye having an appropriate concentration, which is added to the coating solution. Then, coating may be performed by a known method.

The content of these AI dye compounds is the area of the photosensitive material.
Preferably it is applied so as to 1 m ² per 1～800Mg, more preferably set to be in the 2 to 200 mg / m ^2.

The above general formula [AI-I], [AI-II], [AI-III] or [A
Two or more compounds represented by [I-IV] may be used in combination.

The light-sensitive material may contain a DIR compound.
In addition to the compound, it is also possible to include a compound that releases a development inhibitor upon development, for example, U.S. Pat.
No. 445, No. 3,379,529, West German patent application (OLS) 2,417,914
No. 52-15271, No. 53-9116, No. 59-123838,
Examples thereof include those described in No. 59-127038.

The DIR compound is a compound capable of reacting with an oxidized product of a color developing agent to release a development inhibitor or a development inhibitor precursor, and may be a non-diffusible DIR compound or a diffusible DIR compound. .

A typical example of such a DIR compound is a DIR coupler in which a group capable of forming a compound having a development inhibitory action when released from the active site is introduced into the active site of the coupler, for example, British Patent 935,454. , U.S. Patent 3,227,5
54, 4,095,984, 4,149,886, etc.

The above-mentioned DIR coupler has a property that, when it undergoes a coupling reaction with an oxidized product of a color developing agent, the coupler nucleus forms a dye, while releasing a development inhibitor. Further, in the present invention, U.S. Patent Nos. 3,652,345, 3,928,041, and 3,958,993.
No. 3,961,959, No. 4,052,213, JP-A-53-110529
No. 54-13333, No. 55-161237 and the like, when a coupling reaction with an oxidant of a color developing agent, a development inhibitor is released, but a compound which does not form a dye is also included. .

Furthermore, JP-A Nos. 54-145135, 56-114946 and
When reacted with an oxidant of a color developing agent as described in 57-154234, the mother nucleus forms a dye or a colorless compound, while the released timing group undergoes an intramolecular nucleophilic substitution reaction or an elimination reaction. A so-called timing DIR compound that is a compound that releases a development inhibitor by

Further, when reacting with an oxidized product of a color developing agent described in JP-A-58-160954 and JP-A-58-162949, a timing group as described above is present in the coupler mother nucleus which forms a completely diffusible dye. It may be a timing DIR compound attached.

EFFECTS OF THE INVENTION According to the present invention, it is possible to provide a color developing solution containing a preservative (an antioxidant of a developing agent), which is harmless to the human body and is easy to handle, in place of hydroxyamine which is a poisonous substance. It is possible to prevent a decrease in density when the solution is stored for a long period of time, that is, a decrease in the maximum density (Dmax) in the dye concentration of the processed photographic material, and stable photographic characteristics during long-term processing. Can be given.

Further, by using at least one kind of the hydroxylamine derivative represented by the general formula [C] together, the preservative property is synergistically improved, and the generation of stain, which is considered to be caused by the so-called defective decolorization of AI dye, is suppressed. The effect is obtained.

Specific Examples of the Invention Hereinafter, the present invention will be specifically described with reference to Examples, but the embodiments of the present invention are not limited to these.

Reference Example 1 A color developer having the following composition was prepared.

(Color developer) Benzyl alcohol 15 ml Ethylene glycol 10 ml Potassium sulfite 2.0 × 10 ^-2 mol Potassium bromide 1.0 g Sodium chloride 0.3 g Potassium carbonate 25.0 g Preservative (listed in Table 1) 5.0 g Polyphosphoric acid (TPPS) 2.0 g Color development Developing agent [Exemplified compound 1)] 5.0 g Fluorescent brightening agent [Exemplified compound (4)] 2.0 g Potassium hydroxide and water were added to make it 1. The pH is 10.2
It was set to 0.

Ferric ion 4ppm each color developer, copper ions 2ppm and calcium ions 100 ppm (each by dissolving _{FeCl 3, CuSO 4 · 6H 2} O and CaCl ₂ added) was added, the opening ratio 30c at 50 ° C.
It was stored in a glass container of m ² / l (30 cm ^{2 of} air contact area for 1 developer).

The appearance (coloring degree) of the color developing solution after 10 days was observed.

However, the appearance of the liquid was divided into the following 5 stages.

As is clear from Table 1, it is clear that the combination of the compounds of the present invention can be a sufficient alternative to hydroxylamine sulfate for the storage stability of liquids. Rather, the homeostasis is slightly better than that of hydroxylamine. Developer
The preservatives (1) of No. 15 to 17 are respectively (6), (8) or (1
N is also applicable to the color developing solution that is changed only by changing to 1).
Results similar to those of o.15 to 17 were obtained.

Reference Example 2 The following layers were sequentially coated on a polyethylene-laminated paper support from the support side to prepare an internal latent image type photosensitive material sample.

First layer: cyan-forming red-sensitive silver halide emulsion layer Cyan coupler, 2,4-dichloro-3-methyl-6-
[Α- (2,4-di-tert-amylphenoxy) butylamide] phenol 90 g, 2,5-di-tert-octylhydroquinone 2 g, tricresyl phosphate 50 g, paraffin 200 g and ethyl acetate 50 g are mixed and dissolved to give dodecyl. A gelatin solution containing sodium benzenesulfonate was added and dispersed so that the average particle size was 0.6 μm (US Pat.
Internal latent image type silver halide emulsion (prepared by the conversion method according to Reference Example 1 described in No. 2,250) (AgBr: A).
(gCl = 70: 30) was added, and the amount of silver was 400 mg / m ² , the example of AI dye (II-10) was 20 mg / m ² , and the amount of coupler was 360 mg / m ² .

Second layer: intermediate layer containing 5 g of gray colloidal silver and 10 g of 2,5-di-tert-octylhydroquinone dispersed in dibutyl phthalate 2.
100 ml of 5% gelatin solution was applied so that the amount of colloidal silver was 400 mg / m ² .

Third layer: magenta-forming green-sensitive silver halide emulsion layer Magenta coupler, 1- (2,4,6-trichlorophenyl) -3- (2-chloro-5-octadecylsuccinimidoanilino) -5-pyrazolone 100 g, 2 , 5-di-tert
-Octylhydroquinone 5 g, Sumilizer MDP (Sumitomo Chemical Co., Ltd.) 50 g, paraffin 200 g, dibutyl phthalate 100 g and ethyl acetate 50 g are mixed and dissolved, and a gelatin solution containing sodium dodecylbenzenesulfonate is added,
An internal latent image type silver halide emulsion (AgBr: A) prepared in the same manner as the first layer, dispersed so that the average grain size is 0.6 μm.
gCl = 60: 40) was added, and coating was carried out so that the amount of silver was 400 mg / m ² , the example of AI dye (II-8) was 20 mg / m ² , and the amount of coupler was 400 mg / m ² .

Fourth layer: yellow filter layer A 2.5% gelatin solution containing 5 g of yellow colloidal silver and 5 g of 2,5-di-tert-octylhydroquinone dispersed in dibutyl phthalate was applied so that the colloidal silver was 200 mg / m ² . .

Fifth layer: yellow-forming blue-sensitive silver halide emulsion layer Yellow coupler, α- “4- (1-benzyl-2-phenyl-3,5-dioxo-1,2,4-triazolidinyl)]
-Α Bivalyl-2-chloro-5- [γ- (2,4-di-ter
t-amylphenoxy) butyramide] acetanilide 1
20 g, 2,5-di-tert-octylhydroquinone 3.5 g, paraffin 200 g, Tinuvin (manufactured by Ciba Geigy) 100 g, dibutyl phthalate 100 g and ethyl acetate 70 ml were mixed and dissolved, and a gelatin solution containing sodium dodecylbenzenesulfonate was added, An internal latent image type silver halide emulsion (AgBr: AgCl = 80: 20) prepared in the same way as the first layer, dispersed so that the average grain size is 0.9 μm, was added, and the silver amount was 400 mg / m ^2. ,
The amount of coupler was 400 mg / m ² .

Sixth layer: protective layer It was coated so that the amount of gelatin was 200 mg / m ² .

It should be noted that all of the above layers contained saponin as a coating aid. As a hardener, 2,4-dichloro-6-hydroxy-S-triazine sodium was added to layers 2, 4 and 6 so that the amount was 0.02 g per 1 g of gelatin.

The internal latent image type photosensitive material sample was exposed through an optical wedge and then processed in the next step.

Treatment process (38 ℃) Immersion (color developer) 8 seconds Color development 120 seconds (first 10 seconds, uniform exposure of the entire surface with 1 lux light) Bleach fixing 60 seconds Water washing 60 seconds Drying 60-80 ℃ 120 seconds each The composition of the treatment liquid is as follows.

[Color Developer] The color developers Nos. 1, 2, 10, 11, 15 to 20 used in Example 1, which were sealed at 50 ° C. for 5 days, were used.

[Bleach-fixing solution] Pure water 550 ml Ethylenediaminetetraacetic acid iron (III) ammonium salt 65 g Ammonium thiosulfate (70% aqueous solution) 85 g Sodium hydrogen sulfite 10 g Sodium metabisulfite 2 g Ethylenediaminetetraacetic acid-2 sodium salt 20 g Pure water was added to 1 and PH with aqueous ammonia or diluted sulfuric acid
Adjust to 7.0.

The light-sensitive material was subjected to stepwise exposure by a conventional method and processed by the method described above, and the fluctuation value of the maximum reflection density (blue density) was measured. However, the fluctuation value of the maximum reflection density (blue density) is a value obtained by subtracting the maximum reflection density (blue density) before storage from the maximum reflection density (blue density) after storage.

The results are shown in Table 2.

As is clear from Table 2, according to the reference example of the present invention, it is possible to suppress the concentration decrease with time.

Reference Example 3 Instead of the exemplified compound 1) of the color developing agent used in Reference Example 1, 3) and also exemplified compounds 4), 11) and 12) were examined, but the same results as in Tables 1 and 2 were obtained. I was able to get However, potassium sulfite was changed to 1.5 × 10 ^-2 mol, sodium iodide was added at 2.0 mg / l, benzyl alcohol, ethylene glycol and optical brightener were not added, and pH was adjusted to 10.03.

Reference Example 4 The following layers were sequentially coated on a polyethylene-coated paper support from the side of the support to prepare a light-sensitive material.

The polyethylene coated paper has an average molecular weight of 100,
000, density 0.95 polyethylene 200 parts by weight and average molecular weight 20
A mixture of 20 parts by weight of polyethylene with a density of 00 and a density of 0.80 was added with 6.8% by weight of anatase-type titanium oxide, and a coating layer with a thickness of 0.035 mm was formed on the surface of a fine paper with a weight of 170 g / m ² by the extrusion coating method. The thing which provided the coating layer of thickness 0.040 mm only with polyethylene was used for this. After pretreatment by corona discharge on the polyethylene-coated surface of this support, the following layers were sequentially applied.

First layer: a blue-sensitive silver halide emulsion layer comprising a silver chlorobromide emulsion containing 4 mol% of silver bromide, said emulsion containing 350 g of gelatin per mol of silver halide and having the following structure per mol of silver halide. Sensitizing dye (I) 2,5-di-t-butylhydroquinone 200 mg / m ² sensitized with 2.5 × 10 ⁻⁴ mol (using isopropyl alcohol as a solvent) and dissolved and dispersed in dibutyl phthalate Further, as a yellow coupler, [Y-1] having the following structure is contained in an amount of 2.0 × 10 ^-1 mol per mol of silver halide, and the amount of silver is 300 mg / m ² .

Second layer: di-t-octylhydroquinone 300 mg / m ² dissolved and dispersed in dibutyl phthalate, 2-
(2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-
5'-t-butylphenyl) benzotriazole, 2-
(2'-Hydroxy-3'-t-butyl-5'-methylphenyl) -5-chloro-benzotriazole, 2-
Mixture of (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chloro-benzotriazole (1: 1:
1: 1) gelatin layer containing 200 mg / m ² gelatin 1900 mg /
It is applied so that it will be m ² .

Third layer: a green-sensitive silver halide emulsion layer comprising a silver chlorobromide emulsion containing 2 mol% of silver bromide, said emulsion containing 450 g of gelatin per mol of silver halide and having the following structure per mol of silver halide. Sensitizing dye (II) 2,5-di-t-butylhydroquinone and magenta coupler sensitized with 2.5 × 10 ^-4 mol and dissolved and dispersed in a solvent consisting of dibutyl phthalate and tricresyl phosphate 2: 1. Of the following structure as [M-1]
Containing 1.5 × 10 ^-1 mol per mol of silver halide,
30 mg / m ² and AI dye [II-8] are coated at 50 mg / m ² . In addition, 0.30 mol of 2,2,4-trimethyl-6-lauryloxy-7-t-octylchroman was added as an antioxidant per mol of the coupler.

Fourth layer: di-t-octylhydroquinone 30 mg / m ² dissolved and dispersed in dioctyl phthalate and 2 as an ultraviolet absorber
-(2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-
5'-t-butylphenyl) benzotriazole, 2-
(2'-Hydroxy-3'-t-butyl-5'-methylphenyl) -5-chloro-benzotriazole, 2-
Mixture of (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chloro-benzotriazole (2: 1.
5: 1.5: 2) a gelatin layer containing 50 mg / m ^2, is coated so as to gelatin 1900 mg / m ^2.

Fifth layer: a red-sensitive silver halide emulsion layer consisting of a silver chlorobromide emulsion containing 3 mol% of silver bromide, said emulsion containing 500 g of gelatin per mol of silver halide and having the following structure per mol of silver halide: Sensitizing dye (III) was sensitized with 2.5 × 10 ⁻⁵ mol of 2,5-di-t-butylhydroquinone 150 mg / m ² dissolved and dispersed in dibutyl phthalate and a cyan coupler of the following structure [C -1] is 3.5 × 10 ^-1 per mol of silver halide
Molar content, silver amount 280 mg / m ² , AI dye exemplified compound [II-
9] to 40 mg / m ² .

Sixth layer: It is a gelatin layer and is coated with gelatin at 900 mg / m ² .

The silver halide emulsion used for each photosensitive emulsion layer (first, third and fifth layers) was prepared by the method described in JP-B-46-7772, and sodium thiosulfate pentahydrate was used for each. Chemically sensitized, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (2.5 g per mol of silver halide) as a stabilizer, and bis (vinylsulfonylmethyl) ether ( 10 mg per 1 g of gelatin) and saponin as a coating aid.

After the color paper prepared by the above method was exposed, continuous processing was performed using the following processing steps and processing solutions.

Processing process (1) Color development 35 ° C 45 seconds (2) Bleach fixing 35 ° C 45 seconds (3) Washing alternative stabilization treatment 30 ° C 90 seconds (4) Dry 60 ° C to 80 ° C 1 minute 30 seconds Treatment liquid composition [coloring Development tank liquid] Potassium chloride 2.0g Potassium sulfite 6.5 × 10 ^-3 mol Color developing agent 1) 5.0g Preservative (listed in Table 3) 5.0g Triethanolamine 10.0g Potassium carbonate 30.0g Ethylenediaminetetraacetic acid sodium salt 2.0g Fluorescence Whitening agent (4) 2.0g Add water to make 1 and adjust pH to 1 with potassium hydroxide and 20% sulfuric acid.
Set to 0.15.

[Color development replenisher] Potassium chloride 2.5g Potassium sulfite (50% solution) 7.0 × 10 ^-3 mol Color developing agent 1) 8.0g Preservative (see Table 3) 7.0g Triethanolamine 10.0g Potassium carbonate 30.0g Ethylenediamine Sodium tetraacetate 2.0g Add water to make 1 and adjust pH to 1 with potassium hydroxide and 20% sulfuric acid.
Set to 0.40.

[Bleaching fixing tank liquid] Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60.0g Ethylenediaminetetraacetic acid 3.0g Ammonium thiosulfate (70% solution) 100.0ml Ammonium sulfite (40% solution) 27.5ml Ammonia water or glacial acetic acid pH5.50 And add water to bring the total to 1.

[Bleach-fixing replenisher] ethylenediaminetetraacetic acid ferric ammonium dihydrate 70.0g ammonium thiosulfate (70% solution) 120.0ml ammonium sulfite (40% solution) 35.0ml ethylenediaminetetraacetic acid 3.0g Add water to bring the total volume to 1 .

The pH of this solution is adjusted to 5.4 with glacial acetic acid or aqueous ammonia.

[Stabilizing tank replacement solution and replenisher] Orthophenylphenol 0.2g 1-Hydroxyethylidene-1,1-diphosphonic acid (60% aqueous solution) 2.0g Ammonia water 3.0g Water to 1 and pH 7.8 with ammonia water and sulfuric acid And

An automatic developing machine is filled with the above-mentioned color developing tank solution, bleach-fixing tank solution and stabilizing tank solution, and while processing the color paper sample, the above-mentioned color developing replenishing solution, bleach-fixing replenishing solution and stable replenishing solution are provided every 3 minutes. A running test was performed while replenishing the solution through a metering pump. The replenishment amount is ² m2 for each color developing tank per 1 m ² of color paper.
As a replenishing amount to the bleach-fixing tank, a replenishing amount of 220 ml was added to the bleach-fixing tank.

The stabilization processing bath of the automatic processor is a stabilizing bath that is the first to third baths in the direction of the flow of the photosensitive material, and the replenishment is performed from the final bath, and the overflow liquid from the final bath is transferred to the preceding bath. A multi-tank countercurrent system was adopted in which the overflow liquid was made to flow, and this overflow liquid was made to flow again to the tank at the preceding stage.

The color paper was subjected to running treatment until the total replenishment amount of the color developing solution became three times the capacity of the color developing tank, and then the stepwise exposed paper sample was passed through and stored by the method of Reference Example 1 (however, the opening ratio The number of days until tar generation and the maximum reflection density (blue density) according to Reference Example 2 were stored in a glass container of 15 cm ² / l for 7 days.
The variation value of was measured.

The results are shown in Table 3.

As is clear from Table 3, when a part of the preservatives of the present invention was used in combination, tar generation was slow and the concentration decreased with time, which was also a good result.

Example 1 In each of Sample Nos. 35 to 39, the exemplified compounds (1), (2), (3), (11), (13), (17), of the general formula [C],
The same experiment as in Reference Example 4 was carried out in the same manner except that each of (19), (20) and (24) was added in an amount of 5 g / l, and the number of days until the occurrence of tar was extended by about 1 week each. Furthermore, regarding stains that are considered to be due to defective decolorization of AI dye 54
When the spectral absorptions at 0 nm and 640 nm were measured, the spectral absorption was 1/3 or less, respectively, as compared with the sample before addition of the exemplary compound of the general formula [C].

Front Page Continuation (72) Inventor Masahiko Ima No. 1 Sakuramachi, Hino City, Tokyo, Konishi Roku Photo Industry Co., Ltd. (72) Inventor Yoko Matsushima, No. 1, Sakuramachi, Tokyo Hino City, Konishi Roku Photo Industry Co., Ltd. (56 ) References JP-A-63-146042 (JP, A) JP-A-63-146043 (JP, A)

Claims (3)

[Claims] 1. At least one compound represented by the general formula [A] and at least one compound represented by the general formula [B].
And a hydroxylamine derivative represented by the general formula [C], and a color developing solution for a silver halide color photographic light-sensitive material. General formula [A] [In the formula, R ₁ represents a hydrogen atom, a carbamoyl group, an aryl group, an alkyl group, an acyl group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group or a heterocyclic group, and R ₂ represents a hydrogen atom, an alkyl group, an aryl group. , An alkoxy group, an aryloxy group, a hydroxy group, a heterocyclic group,
Represents an amino group or a hydrazino group, R ₃ represents a hydrogen atom, an alkyl group or an aryl group, l is 0 or 1, and when l is 0, Z is , And when 1 is 1, Z is -CO-, Represents R has the same meaning as R ₃ . ] General formula [B] [In the formula, R ₄ is a hydroxyalkyl group having 2 to 6 carbon atoms,
R ₅ and R ₆ are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms, a benzyl group or a formula In the above formula, n represents an integer of 1 to 6, X and Z each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 2 to 6 carbon atoms. ] General formula [C] [In the formula, R ₇ and R ₈ include a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and the alkyl group has a substituent. However, R ₇ and R ₈ are not hydrogen atoms at the same time. ] 2. An exposed silver halide color photographic light-sensitive material comprising at least one compound represented by the following general formula [A] and at least one compound represented by the following general formula [B] and a general formula [A]. C] A method of processing a silver halide color photographic light-sensitive material, which comprises processing with a color developer containing at least one hydroxylamine derivative represented by the formula C]. General formula [A] [In the formula, R ₁ represents a hydrogen atom, a carbamoyl group, an aryl group, an alkyl group, an acyl group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group or a heterocyclic group, and R ₂ represents a hydrogen atom, an alkyl group, an aryl group. , An alkoxy group, an aryloxy group, a hydroxy group, a heterocyclic group,
Represents an amino group or a hydrazino group, R ₃ represents a hydrogen atom, an alkyl group or an aryl group, l is 0 or 1, and when l is 0, Z is , And when 1 is 1, Z is -CO-, Represents R has the same meaning as R ₃ . ] General formula [B] [In the formula, R ₄ is a hydroxyalkyl group having 2 to 6 carbon atoms,
R ₅ and R ₆ are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms, a benzyl group or a formula In the above formula, n represents an integer of 1 to 6, X and Z each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 2 to 6 carbon atoms. ] General formula [C] [In the formula, R ₇ and R ₈ include a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and the alkyl group has a substituent. However, R ₇ and R ₈ are not hydrogen atoms at the same time. ] 3. A silver halide color photographic light-sensitive material having the following general formula [AI-I], [AI-II], [AI-II] or [AI-I].
A processing method for a silver halide color photographic light-sensitive material according to claim 2, characterized in that it contains an AI dye shown in V]. General formula [AI-I] [In the formula, Rf, Rf ₁ , Rf ₂ , Rf ₃ , Rf ₄ and Rf ₅ are hydrogen atoms,
A halogen atom, a hydroxy group, an alkyl group, an alkoxy group, -SO ₃ M or -NHCH ₂ SO ₃ M (where, M is an alkali metal atom, ammonium or organic ammonium salt) represents a. ] General formula [AI-II] [In the formula, Rf ₆ and Rf ₆ ′ are a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, Rf ₇ and Rf ₇ ′ are a hydroxy group, an alkoxy group, a cyano group, a trifluoromethyl group, an amino group, and a carbon number. A substituted amino group substituted with an alkyl group of 1 to 4 or L is a methine group, X is an oxygen atom, a sulfur atom, or -CH
_2- , m is 0 or 1, n is 0, 1 or 2, p and q are 1
Or represents 2. ] General formula [AI-III] [Wherein, W is an oxygen atom or a sulfur atom, L is a methine group, Rf
₃₁ , Rf ₃₂ , Rf ₃₃ or Rf ₃₄ is a hydrogen atom, an alkyl group,
An aryl group, an aralkyl group or a heterocyclic group, and r represents an integer of 1 to 3. ] General formula [AI-IV] [In the formula, Rf ₄₁ is the same as Rf ₆ , Rf ₄₂ is the same as Rf _7, and Rf ₄₃ is −
OZ ₁ or Rf ₄₄ represents a hydrogen atom, an alkyl group, a chlorine atom or an alkoxy group, Z ₁ , Z ₂ and Z ₃ represent a hydrogen atom, an alkyl group, L represents a methine group, and 1 represents 1 or 2. ]