JPH087423B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and more particularly to a processing method capable of remarkably preventing generation of magenta stain over time after processing. .

(Prior Art) In the processing method of a silver halide color photographic light-sensitive material, simplification, speeding up, stabilization, and reduction of pollution are important issues, and many studies have been made so far.

In particular, a method of reducing the replenishment amount of each treatment for the purpose of resource saving, low cost, and low pollution is highly practical and various developments have been made. However, reducing the amount of replenisher for each treatment liquid has caused many new problems. In particular, when the replenishment amount of the bleach-fixing solution is reduced, the ratio of the color developing solution, which is the pre-bath, is brought into the bleach-fixing bath increases, and as a result, there occurs a problem that the generation of magenta stain increases with time after the processing. It was

In particular, the above problem occurs even when a magenta coupler having high light fastness is used. For example, JP-A-59-162548 and JP-A-60-43.
No. 659, No. 59-171956, No. 60-172982, No. 60-33552
And the magenta couplers described in U.S. Pat. No. 3,061,432, Japanese Patent Publication No. 53-34044, Japanese Patent Laid-Open No. 55-62454, and No. 57.
Even when the couplers described in -35858 and the like are used, the problem that magenta stain is likely to occur occurs. Therefore, it can be considered to apply a conventional fading prevention technique or stain prevention technique to the processing of the above-mentioned photosensitive material. Specifically, U.S. Patent Nos. 2,360,290, 2,418,613, and 2,675,
No. 314, No. 2,701,197, British Patent No. 1,363,921, JP-A-5
Hydroquinone derivatives described in 8-24141, etc., U.S. Pat.Nos. 3,457,079, gallic acid derivatives described in 3,069,262, etc., U.S. Patent 2,735,765, p-alkoxyphenols described in JP-B-49-20977, US Patent 3,
432,300, 3,573,050, JP-A-52-35633, 52
-147434 and the like, p-oxyphenol derivatives, discoloration prevention techniques for bisphenols and the like described in U.S. Pat. No. 3,700,455, and JP-A-49-11330 and JP-A-50-57223,
It was not possible to obtain a sufficient effect even with the use of stain prevention techniques such as No. 56-85747 and Japanese Patent Publication No. 56-8346).

On the other hand, U.S. Pat. No. 3,615,508 and JP-A No. 50-140128 describe that the use of ammonium ion as a cation in a bleach-fixing solution improves desilvering performance. However, these patents make no mention of the use of bleach-fix solutions at low replenishment levels or of stains due to magenta couplers.

Further, the compound represented by the general formula (I), (II) or (III) is disclosed as a stain inhibitor in European Patent Application Publication No. EP 0,277,589. In the case of low replenishment processing such as bleach-fixing solution, washing, stabilizing solution, and / or rapid processing, the stain prevention effect may be insufficient, and further improvement has been desired.

(Problems to be Solved by the Invention) Therefore, the present invention is directed to the processing of a silver halide color photographic light-sensitive material which does not generate stains attributable to the magenta coupler after processing even if the replenishing amount of the bleach-fixing solution is reduced. The purpose is to provide a method.

(Means for Solving the Problems) In the present invention, a cation in the replenishing solution is a specific amount of ammonium ion as a technique for preventing particularly magenta stain attributable to a low replenishing rate of the bleach-fixing solution. This is based on the finding that the above problems can be effectively solved by using a replenisher.

That is, the following general formula (I), (II) or (III)
In a continuous processing method of a light-sensitive material, which contains at least one compound represented by the formula (1) and is subjected to image exposure on a silver halide color photographic light-sensitive material containing at least one kind of magenta coupler, and after color development processing, bleach-fixing processing is carried out. , Containing an aminopolycarboxylic acid iron ammonium salt as a bleaching agent, containing an ammonium thiosulfate salt as a fixing agent, and processing with a bleach-fixing solution containing an ammonium sulfite salt as a preservative, and with respect to a certain area of the photosensitive material to be processed, The bleach-fix replenisher was added in an amount of 0.5 to 15 times the amount of the color developing solution from the pre-bath brought in by the photosensitive material having a certain area, and the cation component Li ^{+ of the} salt contained in the bleach-fix replenisher was added. , Na ^+, halogen 94-100 mol% of the sum of K ⁺ and ammonium ions, characterized in that an ammonium ion Processing method of the silver color photographic light-sensitive material.

General formula (I) R ₁ A _n General formula (II) In the formula, R ₁ and R ₂ each represent an aliphatic group, an aromatic group, or a heterocyclic group. X represents a group which reacts with an aromatic amine developing agent and leaves, and A represents a group which reacts with an aromatic amine developing agent to form a chemical bond. n represents 1 or 0. B is a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group,
Represents an acyl group or a sulfonyl group, and Y represents a group which promotes addition of the aromatic amine developing agent to the compound of the general formula (II).

Here, R ₁ and X, Y and R ₂ or B may be bonded to each other to form a cyclic structure.

General formula (III) R-Z In the formula, R represents an aliphatic group, an aromatic group or a heterocyclic group. Z represents a nucleophilic group or a group that decomposes in the light-sensitive material to release a nucleophilic group.

The anti-staining compounds represented by the general formulas (I), (II) and (III) will be described in more detail.

The compounds represented by the general formulas (I) and (II) have a second-order reaction rate constant R ₂ (80 ° C.) with p-anisidine of 1.0 l / mol · sec measured by the method described in JP-A-63-158545. ~ 1 x 1
Compounds in the range of 0 ⁻⁵ l / mol · sec are preferred. on the other hand,
In the compound represented by the general formula (III), Z is Pearson's nucleophilic ⁿ CH ₃ I value (RG Pearlson, et al., J. Am. Chem. Soc., 90 , 31).
9 (1968)) is preferably a group derived from a nucleophilic functional group of 5 or more.

Among the compounds of the general formulas (I) to (III), it is preferable to use a compound of the formula (I) or (II) together with a compound of the formula (III).

Each group of the compounds represented by formulas (I), (II) and (III) will be described in more detail.

The aliphatic group represented by R ₁ , R ₂ , B and R represents a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group, which may be further substituted with a substituent. The aromatic group represented by R ₁ , R ₂ , B and R is either a carbocyclic aromatic group (eg phenyl, naphthyl) or a heterocyclic aromatic group (eg furyl, thienyl, pyrazolyl, pyridyl, indolyl). It may be a monocyclic or condensed ring system (for example, benzofuryl or phenanthridinyl). Furthermore, these aromatic rings may have a substituent.

The heterocyclic group represented by R ₁ , R ₂ , B and R is preferably a group having a 3-membered to 10-membered ring structure composed of carbon atom, oxygen atom, nitrogen atom, sulfur atom or hydrogen atom, and hetero. The ring itself may be a saturated ring or an unsaturated ring,
It may be further substituted with a substituent (for example, chromanyl,
Pyrrolidyl, pyrrolinyl, morpholinyl).

X in the general formula (I) represents a group which is released by reacting with an aromatic amine-based developer, represents an oxygen atom, a sulfur atom or a nitrogen atom, and binds to A via an oxygen atom, a sulfur atom or a nitrogen atom. Groups (for example, 2-pyridyloxy, 2-pyrimidyloxy, 4-pyrimidyloxy, 2- (1,2,3
-Triazine) oxy, 2-benzimidazolyl, 2-
Imidazolyl, 2-thiazolyl, 2-benzthiazolyl, 2-furyloxy, 2-thiophenenyloxy, 4-
Pyridyloxy, 3-isoxazolyloxy, 3-pyrazolidinyloxy, 3-oxo-2-pyrazolonyl,
2-oxo-1-pyridinyl, 4-oxo-1-pyridinyl, 1-benzimidazolyl, 3-pyrazolyloxy, 3H-1,2,4-oxadiazoline-5-oxy, aryloxy, alkoxy, alkylthio, arylthio, Substituted N-oxy) or halogen atoms are preferred.

A of the general formula (I) reacts with an aromatic amine type developing agent,
Represents a group forming a chemical bond, and a group containing an atom having a low electron density, for example, Contains. When X is a halogen atom, n represents 0. Here, L is a single bond, an alkylene group, -O-, -S
-, (For example, carbonyl group, sulfonyl group, sulfinyl group, oxycarbonyl group, phosphonyl group, thiocarbonyl group, aminocarbonyl group, silyloxy group, etc.). Y has the same meaning as Y in formula (II), and Y '
Represents the same meaning as Y.

R ′ and R ″, which may be the same or different, each represents —L—R _1. R represents a hydrogen atom, an aliphatic group (eg, methyl, isobutyl, t-butyl, vinyl, benzyl, octadecyl, cyclohexyl), It represents an aromatic group (eg phenyl, pyridylnaphthyl), a heterocyclic group (eg piperidinyl, pyranyl, furanyl, chromanyl), an acyl group (eg acetyl, benzoyl) and a sulfonyl group (eg methanesulfonyl, benzenesulfonyl).

L ', L "and L are -O-, -S- and Represents L further represents a single bond.

Above all, A The divalent group represented by is preferable.

Among the compounds represented by the general formula (I), more preferable compounds are those represented by the general formulas (Ia), (Ib) and (Ic)
Alternatively, it is represented by (Id) and has a second-order reaction rate constant k ₂ (80 ° C.) with p-anisidine of 1 × 10 ⁻¹ l / mol · sec to 1
It is a compound that reacts in the range of × 10 ^-5 l / mol · sec.

In the formula, R ₁ has the same meaning as R _{1 in} formula (I). Li
nk represents a single bond or -O-. Ar is R ₁ , R ₂ and B
Represents an aromatic group having the same meaning as defined above. However, what is released as a result of reacting with the aromatic amine-based developer is not a group useful as a photographic reducing agent such as a hydroquinone derivative or a catechol derivative. Ra, Rb and Rc
May be the same or different, and each represents a hydrogen atom,
An aliphatic group having the same meaning as defined for R ₁ , R ₂ and B,
Represents an aromatic group and a heterocyclic group. Ra, Rb and Rc are further an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, an amino group, an alkylamino group, an acyl group, an amide group, a sulfonamide group, a sulfonyl group, Alkoxycarbonyl group, sulfo group, carboxyl group, hydroxy group,
It represents an acyloxy group, a ureido group, a urethane group, a carbamoyl group, and a sulfamoyl group. Where Ra and Rb
Alternatively, Rb and Rc may combine with each other to form a 5- to 7-membered heterocyclic ring, and the heterocyclic ring may be further substituted with a substituent, form a spiro ring, a bicyclo ring, or the like, or form an aromatic ring. It may be condensed. Z ₁ and Z ₂ represent a non-metal atom group necessary for forming a 5- to 7-membered hetero ring, and this hetero ring is further substituted with a substituent, forms a spiro ring, a bicyclo ring or the like, or is an aromatic group. It may be condensed with a ring.

Among the general formulas (Ia) to (Id), particularly the general formula (Ia)
-A) second-order rate constant k ₂ with p-anisidine in a)
In order to adjust (80 ° C.) within the range of 1 × 10 ⁻¹ l / mol · sec to 1 × 10 ⁻⁵ l / mol · sec, when Ar is a carbocyclic aromatic group, it can be adjusted with a substituent. At this time, depending on the type of the R ₁ group, the sum of Hammett's σ values of each substituent is preferably 0.2 or more, and 0.
4 or more is more preferable, and 0.6 or more is further preferable.

When the compounds represented by the general formulas (Ia) to (Id) are added during the production of a photosensitive material, the total carbon number of the compound itself is preferably 13 or more. From the viewpoint of achieving the object of the present invention, it is not preferable that the compound of the present invention decomposes during development processing.

Y in the general formula (II) is an oxygen atom, a sulfur atom, ═N—R ₄ and Is preferred.

Here, R ₄ , R ₅ and R ₆ are hydrogen atoms, aliphatic groups (eg methyl, isopropyl, t-butyl, vinyl, benzyl, octadecyl, cyclohexyl), aromatic groups (eg phenyl, pyridyl, naphthyl), heterocycle Represents a group (eg piperidyl, pyranyl, furanyl, chromanyl), an acyl group (eg acetyl, benzoyl), a sulfonyl group (eg methanesulfonyl, benzenesulfonyl), and R ₅ and R ₆ may be bonded to each other to form a cyclic structure. Good.

Among the compounds represented by the general formulas (I) and (II), a particularly preferred compound is the general formula (I). Among them, the more preferable compound is a compound represented by the general formula (Ia) or the general formula (Ic), and particularly the general formula (I).
Compounds represented by -a) are preferred.

Z in the general formula (III) represents a nucleophilic group or a group which decomposes in a photosensitive material to release a nucleophilic group. For example, a nucleophilic group in which an atom chemically bonded directly to an oxidized product of an aromatic amine developer is an oxygen atom, a sulfur atom, or a nitrogen atom (for example, an amine compound, an azide compound, a hydrazine compound, a mercapto compound, a sulfide compound, Sulfinic acid compounds, cyano compounds, thiocyano compounds, thiosulfate compounds, seleno compounds, halide compounds, carboxy compounds, hydroxamic acid compounds, active methylene compounds,
Phenol compounds, nitrogen heterocyclic compounds, etc.) are known.

A more preferred compound among the compounds of the general formula (III) can be represented by the following general formula (III-a). General formula (IIIa) In the formula, M is an atom or atomic group forming an inorganic (eg, Li, Na, K, Ca, Mg, etc.) or organic (eg, triethylamine, methylamine, ammonia, etc.) salt, and Represents

Here, R ₁₅ and R ₁₆ may be the same or different and each represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. R ₁₅ and R ₁₆ may combine with each other to form a 5- to 7-membered ring. R ₁₇ , R ₁₈ , R ₂₀ and R ₂₁ may be the same or different and each represents a hydrogen atom, an aliphatic group, an aromatic group,
It represents a heterocyclic group, an acyl group, an alkoxycarbonyl group, a sulfonyl group, a ureido group and a urethane group. However, at least one of R ₁₇ and R ₁₈ , and R ₂₀ and R ₂₁
At least one of them is a hydrogen atom. R ₁₉ and R
₂₂ represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. R ₁₉ further represents an alkylamino group, an arylamino group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group. Here, at least two groups of R ₁₇ , R ₁₈ and R ₁₉ may be bonded to each other to form a 5- to 7-membered ring, and at least two groups of R ₂₀ , R ₂₁ and R ₂₂ May combine with each other to form a 5- to 7-membered ring. R ₂₃ represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group, and R ₂₄ represents a hydrogen atom, an aliphatic group, an aromatic group, a halogen atom, an acyloxy group or a sulfonyl group. R ₂₅
Represents a hydrogen atom or a hydrolyzable group.

R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ may be the same or different and each is a hydrogen atom, an aliphatic group (eg methyl, isopropyl, t-butyl, vinyl, benzyl, octadecyl, cyclohexyl), aromatic A group (eg phenyl,
Pyridyl, naphthyl), heterocyclic group (for example, piperidyl, pyranyl, furanyl, chromanyl), halogen atom (for example, chloro atom, bromine atom), -SR ₂₆ , -OR ₂₆ , Acyl group (eg, acetyl, benzoyl), alkoxycarbonyl group (eg, methoxycarbonyl, butoxycarbonyl, cyclohexylcarbonyl, octyloxycarbonyl), aryloxycarbonyl group (eg,
Phenyloxycarbonyl, naphthyloxycarbonyl), sulfonyl group (for example, methanesulfonyl, benzenesulfonyl), sulfonamide group (for example, methanesulfonamide, benzenesulfonamide), sulfamoyl group, ureido group, urethane group, carbamoyl group,
Sulfo group, carboxyl group, nitro group, cyano group, alcoxalyl group (eg, methoxallyl, isobutoxalyl, octyloxalyl, benzoyloxalyl), aryloxalyl group (eg, phenoxallyl, naphthoxalyl), sulfonyloxy group (eg, methanesulfonyloxy, benzene) Sulfonyloxy), And a formyl group. Here, R ₂₆ and R ₂₇ may be the same or different and each represent a hydrogen atom, an aliphatic group, an aromatic group, an acyl group, or a sulfonyl group. R ₂₈ and R ₂₉ may be the same or different and each is a hydrogen atom,
It represents an aliphatic group, an aromatic group, an alkoxy group and an aryloxy group.

Of these, for the -SO ₂ M group, Hammet of the benzene substituent
The sum of the σ values of t is preferably 0.5 or more in terms of the effect of the present invention.

Representative examples of these compounds are shown below, but the compounds used in the present invention are not limited thereby.

(I-7) ⁽ⁿ⁾ C ₁₈ H ₃₇ I (I-8) ⁽ⁿ⁾ C ₁₈ H ₃₇ Br _{(II-3) CH 2 =} CH-SO 2 -C 18 H 37 (n) (III-30) NaN ₃ These compounds are disclosed in JP-A-62-143048 and 63-115855.
No. 63-115866, No. 63-158545, European Patent No.
It can be synthesized by the method described in 255722 or a method analogous thereto.

The preferred compounds of the present invention are described in the above patents and
Compounds specifically exemplified in the specifications of 283338 and 62-229145 are also included.

Of the compounds represented by the general formulas (I), (II) and (III), those having a low molecular weight or those soluble in water may be added to the processing solution and incorporated into the photosensitive material in the development processing step. Good. A preferred method is to add it to the hydrophilic colloid layer in the photosensitive material at the stage of producing the photosensitive material.

In the latter method, usually, a high-boiling solvent (oil) having a boiling point of 170 ° C. or more at atmospheric pressure alone, a low-boiling solvent alone, or a mixed solvent of the oil and the low-boiling solvent is dissolved, and the solution is dissolved in gelatin or the like. It is prepared by emulsifying and dispersing in a hydrophilic colloid aqueous solution.

In the present invention, the general formulas (I), (II) and (III)
The compound represented by is preferably soluble in a high boiling point organic solvent. The particle size of the emulsified dispersion particles is not particularly limited, but is preferably 0.05 μ to 0.5 μ, and particularly preferably 0.1 μ to 0.3 μ. Particularly in view of the effects of the present invention, the general formulas (I) and (II)
The compounds represented by and (III) are preferably coemulsified with the coupler. In this case, the oil / coupler ratio is preferably 0.01 to 2.0 by weight.

In the present invention, the proportion of the compounds represented by the general formulas (I), (II) and (III) is 1 × 10 ⁻² to 10 mol, preferably 3 × 10 ⁻² , per mol of the coupler.
To 5 moles. If it is less than this range, the effect of the present invention tends to be difficult to obtain, and if it is too large, the color development reaction is hindered.

Further, the compounds represented by the general formulas (I), (II) and (III) may be contained in a layer containing no coupler (for example, an intermediate layer or an ultraviolet absorber-containing layer). When the molecular weight is small and it dissolves in the processing liquid, it may be introduced into the photosensitive material after being dissolved in the processing liquid.

The present invention employs a characteristic bleach-fixing step after color development of the silver halide color light-sensitive material, and the silver halide color light-sensitive material is processed, for example, by the following steps.

(I) Color development-bleach-fixing-washing-drying (ii) 〃-〃-stabilization-drying (iii) 〃-〃-washing-stabilization-drying In the above steps (i) to (iii), bleaching is performed. A fixing step can be provided after the fixing step, and a simple rinse step can be provided between color development and bleach-fixing.

 Next, each step will be described.

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

D-1 N, N'-diethyl-p-phenylenediamine D-2 2-amino-5-diethylaminotoluene D-3 2-amino-5- (N-ethyl-N-laurylamino) toluene D-4 4 -[N-Ethyl-N- (β-hydroxyethyl) amino] aniline D-5 2-methyl-4- [N-ethyl-N- [β-hydroxyethyl) amino] aniline D-6 4-amino-3 -Methyl-N-ethyl-N-
[Β- (methanesulfonamido) ethyl] -aniline D-7 N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide D-8 N, N-dimethyl-p-phenylenediamine D-94 -Amino-3-methyl-N-ethyl-N-methoxyethylaniline D-10 4-Amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline D-11 4-amino-3-methyl-N-ethyl-N-β
-Butoxyethylaniline Among the above p-phenylenediamine derivatives, 4-amino-3-methyl-N-ethyl-N- [β- is particularly preferable.
(Methanesulfonamido) ethyl] -aniline (Exemplary Compound D-6).

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 to be 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.

Further, as a compound which directly preserves the color developing agent, various hydroxylamines, hydroxamic acids described in Japanese Patent Application No. 61-186559, hydrazines described in 61-170756, and hydrazines, 61-188742. No. and No. 61-2032
No. 53 phenols, α-hydroxyketones and α-aminoketones described in 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.

As other preservatives, JP-A-57-44148 and 57-5
Various metals described in 3749, 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. Particularly preferred compounds include diethylhydroxylamine, N, N
And hydrazinodiacetic acid, triethanoheramine, catechol, trisulfonic acid and the like.

The color developer used in the present invention preferably has a pH of 9
-12, more preferably 9-11.0, and the color developing solution may contain other known developer component compounds.

In order to maintain the above pH, it is preferable to use various buffers. As the buffer, carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycyl salt,
N, N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3,4-dihydroxyphenylalanine salt, alanine butyrate, amino acid group, 2-amino-2-methyl-1,3-propanediol salt, Valine salt, proline salt, trishydroxyaminomethane salt, lysine salt and the like can be used. In particular, carbonates, phosphates, tetraborate and hydroxybenzoates are highly soluble and have a high pH of 9.0 or above.
It has excellent buffering ability in the H region, has no adverse effect on the photographic performance (fogging, etc.) even when added to a color developer, and has the advantage that it is inexpensive, and it is particularly preferable to use these buffering agents. preferable.

Specific examples of these buffers include sodium carbonate,
Potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borax), tetraborate Potassium acid, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, 5-
Sodium sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate)
And so on. However, the invention is not limited to these compounds.

The amount of the buffer added to the color developer 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 in the color developing solution as a precipitation preventing agent for calcium and magnesium, or for improving the stability of the color developing solution.

As the chelating agent, an organic acid compound is preferable, for example, aminopolycarboxylic acids described in JP-B-48-30496 and JP-B-44-30232, JP-A-56-97347, JP-B-56-39359 and West German Patent No. 2,227,639. Organic phosphonic acids described,
JP-A-52-102726, JP-A-53-42730, JP-A-54-121127
Nos. 55-126241 and 55-6559506, and phosphonocarboxylic acids described in JP-A-58-195845 and JP-A-58-195845.
Examples thereof include compounds described in 203440 and Japanese Patent Publication No. 53-40900. Specific examples are shown below, but the present invention is not limited thereto.

Hydroxyethyliminodiacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N-N ', N'-
Tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic 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 These chelating agents may be used in combination of two or more, if 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 Japanese Patent Publication No. 37-16088 and No. 3
7-5987, 38-7826, 44-12380, 45-9019
No. 3,813,247 and the like, thioether compounds, JP-A-52-49829 and JP-A-50-15554, p-phenylenediamine compounds, JP-A-50
-137726, JP-B-44-30074, JP-A-56-156826 and JP-A-52-43429, and the like, quaternary ammonium salts, U.S. Patents 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. 4,242,883 and U.S. Pat. No. 3,532,501, and others 1-phenyl-3-
Pyrazolidones, imidazoles, etc. can be added as necessary.

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, imidazole, hydroxyazaindolizine and adenine.

The color developer used in the present invention preferably contains a fluorescent whitening agent. As a fluorescent brightening agent, 4,4'-
Diamino-2,2'-disulfostilbene compounds are preferred. 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, aryl phosphonic acid, aliphatic carboxylic acid and aromatic carboxylic acid may be added.

The processing temperature of the color developer of the present invention is from 20 to 50 ° C, preferably from 30 to 40 ° C. Processing time is 20 seconds to 5 minutes, preferably 30
Seconds to 2 minutes. The replenishment amount is preferably smaller, but is preferably ^{20 to} 600 ml, and more preferably 50 to 300 ml, per m ^{2 of} the light-sensitive material. More preferably, it is 100 ml to 200 ml.

Bleach-fixing In the present invention, the effect of the present invention becomes more remarkable when the residence time of the light-sensitive material in the bleach-fixing step is shortened.
Therefore, it is desirable to set it to 2 minutes or less, more preferably 15 seconds to 60 seconds, whereby the processing time can be further shortened.

In the present invention, it is necessary to use a bleach-fix solution containing aminopolycarboxylic acid iron ammonium salt as a bleaching agent, ammonium thiosulfate salt as a fixing agent, and ammonium sulfite salt as a preservative. In the bleach-fixing solution, in the range that does not impair the object of the present invention,
Other known bleaching agents, fixing agents and preservatives other than the above may be contained.

Listed aminopolycarboxylic acid iron ammonium salt used in the present invention, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-diaminopropanetetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, Mention may be made of iron ammonium salts of aminopolycarboxylic acids such as iminodiacetic acid and glycol ether diamine tetraacetic acid.

The addition amount of aminopolycarboxylic acid iron ammonium salt is 0.
01 to 1.0 mol / l, preferably 0.05 to 0.50 mol / l. Various compounds can be used as a bleaching accelerator in the bleach-fixing solution. For example, U.S. Pat.No. 3,893,858, German Patent No. 1,290,812, JP-A-53-95630.
Publication, Research Disclosure No. 17129 (1978
July 1989), compounds having a mercapto group or a disulfide bond, JP-B-45-8506, and JP-A-52-20.
The thiourea compounds described in 832, 53-32735, U.S. Pat. No. 3,706,561 and the like, or halides such as iodine and bromine ions are preferable because of their excellent bleaching power.

In addition, the bleach-fixing solution used in the present invention includes bromide (eg, potassium bromide, sodium bromide, ammonium bromide) or chloride (eg, potassium chloride, sodium chloride, ammonium chloride) or iodide (eg,
A rehalogenating agent such as ammonium iodide) may be included. Boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, if necessary
One or more inorganic acids having a pH buffering ability such as phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, organic acids and alkali metal or ammonium salts thereof, or corrosion inhibitors such as ammonium nitrate and guanidine Etc. can be added.

The amount of the fixing agent per 1 is preferably 0.3 to 2 mol, more preferably 0.5 to 1.0 mol. The pH range of the bleach-fixing solution is preferably 3-10, and more preferably 5-9.

Further, the bleach-fixing solution may contain various other fluorescent whitening agents, defoaming agents or surfactants, polyvinylpyrrolidone, organic solvents such as methanol.

Ammonium sulfite salt is converted to sulfite ion and is about 0.
It is preferably contained in an amount of 02 to 0.50 mol / l, and more preferably 0.04 to 0.40 mol / l.

Further, a buffering agent, a fluorescent whitening agent, a chelating agent, a defoaming agent, an antifungal agent and the like may be added as required.

In the present invention, in order to increase the amount of ammonium ion as a non-metal cation present in the bleach-fix bath,
Cations of salts that may be contained in the bleach-fix replenisher Li ⁺ , Na ⁺ ,
Among the total cation components of K ⁺ and ammonium ions, those having 94 to 100 mol% ammonium ions are used. 100 mol% means the above Li ⁺ , Na ⁺ and K
Means that no ⁺ is included. Therefore, in the bleach-fixing agent used in the present invention, aminopolycarboxylic acid iron ammonium salt is used as the bleaching agent, ammonium thiosulfate salt is used as the fixing agent, and ammonium sulfite salt is used as the preservative. , For example bleach accelerator,
It is preferable to use an ammonium salt as a rehalogenating agent, a pH buffering agent, etc., so that when these are dissolved in water, the ammonium ion in the bleach-fixing replenisher becomes 94 to 100 mol% of all the above cations. Need to be adjusted. As the bleach-fixing replenisher, even if the same concentration as the bleach-fixing solution in the above-mentioned bleach-fixing bath is used, 1.2 to
It may be 4.0 times more concentrated.

In the present invention, the bleach-fixing replenishment amount is, with respect to a certain area of the light-sensitive material to be processed, 0.5 to 1 of the amount of the color developing solution brought from the prebath by the light-sensitive material having the certain area.
It is characterized by being 5 times, preferably 1.0 to 14 times, more preferably 2 to 10 times, whereby resource saving, low cost and low pollution can be achieved. The replenishment amount is 1 m ²
It is preferably 20 to 200 ml. Here, the pre-bath is generally a color developing solution, and the carry-in amount differs depending on the model, the transport method, the strength of the squeegee, etc.
It is 10 ml to 150 ml, and most is about 20 to 100 ml per m ² .

In addition, the replenishment amount includes the amount of water and a preservative added to stabilize and dilute the liquid concentrated by evaporation during the treatment.

Rinsing / stabilization The amount of rinsing water in the rinsing process depends on the characteristics of the light-sensitive material (for example, depending on the materials used such as couplers) and uses, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment methods such as countercurrent and forward flow, and various other types. It can be set in a wide range depending on the conditions. Among these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is as follows: Journal of the Society of Motion Picture and Television Endonias (Journa
l of the Society of Motion Picture and Television
Engineers) Volume 64, p.248-253 (May 1955 issue). Usually, the number of stages in the multi-stage countercurrent system is preferably 2 to 6, and particularly preferably 2 to 4.

According to the multi-stage countercurrent method, the amount of washing water can be greatly reduced,
For example, 0.5 l to 1 or less per 1 m ^{2 of the} light-sensitive material is possible, and the effect of the present invention is remarkable. However, due to the increase in the residence time of water in the tank, bacteria propagate and the suspended matter produced becomes the light-sensitive material. Problems such as adhesion occur. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium and magnesium described in Japanese Patent Application No. 131632/1986 can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8542, chlorinated fungicides such as chlorinated sodium isocyanurate described in JP-A-61-120145, and JP-A-60-105487. Benzotriazole,
Copper Ion Others Described by Hiroshi Horiguchi in "Chemistry of Antibacterial and Antifungal Agents", "Sterilization, Sterilization and Antifungal Technology of Microorganisms" edited by Hygiene Technology Association, "Encyclopedia of Antibacterial and Antifungal Agents" edited by Japan Society of Antibacterial and Antifungal It is also possible to use the bactericide of.

Further, for washing water, a surfactant as a draining agent and a chelating agent typified by EDTA as a water softener can be used.

A compound having an image stabilizing function is added to the stabilizing solution, and examples thereof include an aldehyde compound typified by formalin, a buffering agent for adjusting a film pH suitable for stabilizing a dye, and an ammonium compound. Further, in order to prevent the growth of bacteria in the liquid and impart fungicidal properties to the processed photosensitive material, the above-mentioned various bactericides and fungicides can be used.

Further, a surfactant, a fluorescent whitening agent, and a hardener can be added. In the processing of the light-sensitive material of the present invention, when the stabilization is directly carried out without a water washing step, the method disclosed in JP-A-57-
Known methods described in Nos. 8543, 58-14834, 60-220345, etc. can all be used.

In addition, it is also a preferred embodiment to use a chelating agent such as 1-hydroxyethylidene-1,1-diphosphonic acid or ethylenediaminetetramethylenephosphonic acid, or a magnesium or bismuth compound.

In the present invention, a so-called rinse solution is also used as a washing solution or a stabilizing solution used after the desilvering process.

The pH of the washing step or stabilizing step of the present invention is 4-10, preferably 5-8. Temperature is the application of the photosensitive material
The temperature is generally 15 to 45 ° C., preferably 20 to 40 ° C., although it can be variously determined depending on the characteristics and the like. The time can be set arbitrarily, but the shorter the time, the more remarkable the effect of the present invention is, and preferably 30 seconds to 2 seconds.
Minutes, more preferably 15 seconds to 1 minute 30 seconds. The smaller the replenishing amount, the more preferable from the viewpoints of running cost, reduction of discharge amount, handleability, and the like, and the effect of the present invention is great.

A specific preferable amount of replenishment is 0.5 to 50 times, preferably 3 to 4 times the carry-in amount per unit area from the pre-bath.
It is 0 times. Alternatively, it is 1 or less, preferably 500 ml or less per 1 m ^{2 of the} light-sensitive material. Replenishment may be performed continuously or simply.

The liquid used in the washing and / or stabilizing step can be further used in the previous step. An example of this is to reduce the amount of waste liquid by replenishing the bleach-fixing bath with the overflow of the washing water reduced by the multi-stage countercurrent method into the bleach-fixing bath preceding the bath, and replenishing the bleach-fixing bath with a concentrated solution. Can be

The total process time of the bleach-fixing step, the washing step and the stabilizing step of the present invention is 4 minutes or less for magenta, more preferably 30 seconds to
3 minutes. The total time referred to here means the time from the contact of the silver halide color photographic light-sensitive material with the first bath of the bleach-fixing process to the exit from the last bath of the washing or stabilizing process. Airtime for is included.

Here, "the sum of the preferable processing times of the desilvering treatment, the washing treatment and the stabilizing treatment is 4 minutes or less" means that the treatments performed before the desilvering treatment and the drying step (more specifically, the washing treatment and / or the The sum of stabilization times is 4 minutes or less.

Processing Target The method of the present invention can be applied to any processing step as long as the processing uses a color developing solution. For example, it can be applied to the processing of color paper, color reversal paper, color direct positive photosensitive material, color positive film, color negative film, color reversal film, etc., but it is particularly preferably applied to color paper, color reversal paper and direct positive material. .

The silver halide emulsion of the light-sensitive material to be processed according to the present invention may have any halogen composition such as silver iodobromide, silver bromide, silver chlorobromide, and silver chloride. For example, when performing rapid processing or low replenishment processing of color paper or the like, a silver chlorobromide emulsion or a silver chloride emulsion containing 60 mol% or more of silver chloride is preferable, and the content of silver chloride is 90 to 100. The case of mol% is particularly preferable. When high sensitivity is required and fog during production, storage, and / or processing is required to be particularly low, a silver chlorobromide emulsion containing 50 mol% or more of silver bromide or an odor is used. A silver halide emulsion (which may contain silver iodide in an amount of 3 mol% or less) is preferable, and 70 mol% or more is more preferable. Silver iodobromide and silver chloroiodobromide are preferable for the color light-sensitive material for photographing, and the silver iodide content is 3 to.
15 mol% is preferred.

The coating amount of silver halide used in the present invention is preferably as small as possible, and more preferably at 0.8 g / m ² or less because the effect of the present invention is remarkable.

The silver halide grains used in the present invention may have different phases in the inside and surface layers, may have a multi-phase structure having a junction structure, or may have a uniform phase as a whole. Moreover, they may be mixed.

The average grain size distribution of the silver halide grains used in the present invention may be either narrow or wide. However, the value obtained by dividing the standard deviation value in the grain size distribution curve of the silver halide emulsion by the average grain size (fluctuation) Rate) within 20%, particularly preferably 15
It is preferred to use so-called monodisperse silver halide emulsions within the range of% in the present invention. Further, in order to satisfy the target gradation of the light-sensitive material, two or more kinds of monodisperse silver halide emulsions having different grain sizes in the emulsion layers having practically the same color sensitivity (the above-mentioned monodispersity is the same). It is preferable that those having a variation rate) be mixed in the same layer or multilayer-coated in different layers. Furthermore, two or more kinds of polydisperse silver halide emulsions or a combination of monodisperse emulsions and polydisperse emulsions can be mixed or laminated and used.

The silver halide grains used in the present invention have a regular shape such as a cube, an octahedron, a rhodohedron and a tetradecahedron.
It may be a compound having different crystal forms or a coexistent form thereof, may have an irregular crystal form such as a sphere, or may have a composite form of these crystal forms. Further, tabular grains may be used, and particularly, an emulsion in which tabular grains having a length / thickness ratio value of 5 to 8 or 8 or more account for 50% or more of the total projected area of grains may be used. It may be an emulsion composed of a mixture of these various crystal forms.

These various emulsions may be either a surface latent image type which forms a latent image mainly on the surface or an internal latent image type which forms a latent image inside the grains.

The photographic emulsion used in the present invention is described in Research Disclosure Vol. 170 Item No. 17643 (I, II, III) (197).
It can be prepared using the method described in 8.12).

The emulsion used in the present invention is usually one that has been physically ripened, chemically ripened and spectrally sensitized. Additives used in such processes are described in Research Disclosure, Vol. 176, No. 17643 (1978.112) and Vol.
No. 18716 (November, 1979), the relevant places are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above-mentioned two Research Disclosures, and the locations described in the table below are shown.

The light-sensitive material to be processed in the present invention contains at least one type of magenta coupler, and can also contain various color couplers. Here, the color coupler means a compound capable of forming a dye by a coupling reaction with an oxidation product of an aromatic primary amine developing agent. Typical examples of useful color couplers are naphthol or phenol compounds, pyrazolone or pyrazoloazole compounds and open chain or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers which can be used in the present invention are Research Disclosure (RD) 17643 (December 1978), Section VII-D and the same.
18717 (November 1979).

The color coupler incorporated in the light-sensitive material preferably has a ballast group or is polymerized to be diffusion resistant. The amount of donated silver can be reduced in the case of a two-equivalent color coupler in which a coupling active position is substituted with a leaving group, rather than a four-equivalent color coupler in which a hydrogen atom is present. It is also possible to use a coupler in which the color-forming dye has an appropriate diffusibility, a non-coloring coupler, or a DIR coupler which releases a development inhibitor with a coupling reaction or a coupler which releases a development accelerator.

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.

As the yellow coupler, for example, U.S. Pat.
No. 501, No. 4,022,620, No. 4,326,024, No. 4,40
1,752, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,020
No. 1,476,760 and the like are preferred.

Examples of the magenta coupler which can be used in the present invention include oil-protection type indazolone type or cyanoacetyl type, preferably 5-pyrazolone type and pyrazoloazole type couplers such as pyrazolotriazoles. The 5-pyrazolone-based coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group, from the viewpoint of the hue and color density of the color forming dye, and typical examples thereof are U.S. Pat.Nos. 2,311,082 and 2,343,703. ,
No. 2,600,788, No. 2,908,573, No. 3,062,653
No. 3,152,896 and No. 3,936,015. As a leaving group of a 2-equivalent 5-pyrazolone-based coupler, a nitrogen atom leaving group described in US Pat. No. 4,310,619 or US Pat. No. 4,351,897 and international patent application W
The arylthio groups described in O88 / 04795 are preferred.
Further, it has a ballast group described in European Patent No. 73,636. 5
-High color density can be obtained with pyrazolone couplers.

As the pyrazoloazole-based coupler, US Pat.
369,879 pyrazolobenzimidazoles, preferably pyrazolo [5,1] described in U.S. Pat.
-C] [1,2,4] triazoles, pyrazolotetrazoles described in Research Disclosure 24220 (June 1984) and Research Disclosure 24230.
(June 1984), and pyrazolopyrazoles.

When the magenta coupler in the light-sensitive material to be processed according to the present invention is represented by the following general formula (IV) or (V), the anti-staining effect is further improved.

(In the formula (IV), R ₁ represents a hydrogen atom or a substituent, and X 1
Represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidized product of an aromatic primary amine developing agent. Za, Zb
And Zc represent methine, substituted methine, = N- or -NH-, and one of the Za-Zb bond and the Zb-Zc bond is a double bond and the other is a single bond. When Zb-Zc is a carbon-carbon double bond, it includes the case where it is part of an aromatic ring. Furthermore, the case where R ₁ or X forms a dimer or higher multimer is also included. When Za, Zb or Zc is a substituted methine, the case where the substituted methine forms a dimer or more multimer is also included.

In the formula (V), Ar is a phenyl group or a phenyl group having a substituent, and Y is a group which is released when a dye is formed by coupling with an oxidation product of an aromatic primary amine color developing agent. Represent. V is a halogen atom, an alkoxy group,
An alkyl group, an amino group, R is a group capable of substituting on a benzene ring, and n is 1 or 2. When n is 2, R may be the same or different. The magenta coupler represented by the general formula (IV) is disclosed in
No. 62-30250, and those disclosed herein can be used.

In the formula (IV), the term “multimer” means one having two or more groups represented by the general formula (IV) in one molecule, and a bis form and a polymer coupler are also included therein.
Here, the polymer coupler may be a homopolymer consisting only of a monomer having a portion represented by the general formula (IV) (preferably having a vinyl group, hereinafter referred to as vinyl monomer), or an aromatic primary amine developing agent. Copolymers may be made with non-chromogenic, ethylene-like monomers that do not couple with the oxidation products of.

The compound represented by the general formula (IV) is a 5-membered-5-membered fused nitrogen heterocyclic coupler, and its coloring mother nucleus shows isoelectronic aromaticity with naphthalene, and is generally called azapentalene. It has a structure. Among the couplers represented by formula (IV), preferred compounds are 1H-imidazo [1,2-b] pyrazoles and 1H-pyrazolo [1,5-b].
Pyrazoles, 1H-pyrazolo [1,5-c] [1,2,4] triazoles, 1H-pyrazolo [1,5-b] [1,2,4] triazoles, 1H-pyrazolo [1,5 -D] tetrazole and 1H-pyrazolo [1,5-a] benzimidazole, which are represented by the general formulas (IVa) (INb) (IVc) (IVd) (IV
e) and (IVf). Of these, particularly preferred compounds are (IVa), (IVc) and (IVd). A more preferred compound is (Id).

The substituents R ₂ , R ₃ and R ₄ in the general formulas (IVa) to (IVf) are each independently a hydrogen atom, a halogen atom, an alkyl group,
Aryl group, heterocyclic group, cyano group, alkoxy group, aryloxy group, heterocyclic oxy group, acyloxy group,
Carbamoyloxy group, silyloxy group, sulfonyloxy group, acylamino group, anilino group, ureido group, imide group, sulfamoylamino group, carbamoylamino group, alkylthio group, arylthio group, heterocyclic thio group, alkoxycarbonylamino group, aryl An oxycarbonylamino group, a sulfonamide group, a carbamoyl group, an acyl group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, X is a hydrogen atom, a halogen atom,
A carboxy group or a group which couples with a carbon at a coupling position via an oxygen atom, a nitrogen atom or a sulfur atom to cause coupling off.

The case where R ₂ , R ₃ , R ₄ or X becomes a divalent group to form a bis form is also included. Further, when the moiety represented by the general formulas (IVa) to (IVf) is present in the vinyl monomer, R ₂ , R ₃ or R ₄ represents a mere bond or a linking group, through which the general formula The vinyl groups are bonded to the moieties represented by (IVa) to (IVf). Further details of R ₂ , R ₃ and R ₄ are disclosed in JP-A-62-30.
No. 250 is disclosed.

X is a hydrogen atom, a halogen atom, a carboxyl group,
Alternatively, a group linked by an oxygen atom (eg, acetoxy group), a group linked by a nitrogen atom (eg, benzenesulfonamide group, N-ethyltoluenesulfonamide group, etc.), a group linked by a sulfur atom (eg, phenylthio group) , 2-carboxyphenylthio group, 2-butoxy-5
-T-octylphenylthio group).

When R ₂ , R ₃ , R ₄ or X is a divalent group to form a bis derivative, the divalent group may be described in more detail. A substituted or unsubstituted alkylene group (eg, methylene group, ethylene group, 1,10-decylene _{group, -CH 2 CH 2 -O-CH} 2 CH
_2- , etc.), a substituted or unsubstituted phenylene group (for example, a 1,4-phenylene group, a 1,3-phenylene group, -NHCO-R ₅ -CONH- group (R ₅ is. A substituted or unsubstituted alkylene or phenylene group), and the like.

When the one represented by the general formulas (IVa) to (IVf) is present in the vinyl monomer, the linking group represented by R ₂ , R ₃ or R ₄ is an alkylene group (a substituted or unsubstituted alkylene group , For example, methylene group, ethylene group, 1,10-decylene group, —CH ₂ CH ₂ OCH ₂ CH ₂ —, etc., phenylene group (substituted or unsubstituted phenylene group, for example, 1,4-phenylene group) , 1,3-phenylene group, -NHCO-, -CONH-, -O-, -OCO-, and nalalkylene groups (e.g., Etc.) and groups that are established by combining those selected from the above.

The vinyl group in the vinyl monomer has the general formula (IV
It also includes the case where it has a substituent other than those represented by a) to (IVf). Preferred substituents are a hydrogen atom, a chlorine atom, or a lower alkyl group having 1 to 4 carbon atoms.

Acrylic acid is a non-color-forming ethylene-like monomer that does not couple with the oxidation product of an aromatic primary amine developer.
α-chloroacrylic acid, α-alkacrylic acid (for example,
Methacrylic acid, etc.) and esters or amides derived from these acrylic acids (eg, acrylamide, diacetone acrylamide, methacrylamide, methyl acrylate, t-butyl acrylate, lauryl acrylate, ethyl methacrylate, n-butyl methacrylate and β-hydroxy). Methacrylate), methylenedibisacrylamide, vinyl esters (eg vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylonitrile, aromatic vinyl compounds (eg styrene and its derivatives, vinyltoluene, divinylbenzene). ,
Vinyl acetophenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ether (eg vinyl ethyl ether), maleic acid, maleic anhydride, maleic acid ester, N-vinyl-2-pyrrolidone , N-vinyl pyridine, and 2- and 4-vinyl pyridine.
It also includes the case where two or more non-color-forming ethylenically unsaturated monomers used here are used together.

Examples of compounds of the couplers represented by the general formulas (IVa) to (IVf), synthetic methods, and the like are described in the following documents.

The compound of the general formula (IVa) is described in JP-A-59-162548,
The compound of the general formula (IVb) is described in JP-A-60-43659, the compound of the general formula (IVc) is described in JP-B-47-27411, and the compound of the general formula (IVd) is described in JP-A-59-171956. And 60-172
982 and the like, compounds of the general formula (IVe) are disclosed in JP-A-60-33552.
Etc. and compounds of general formula (IVf) are described in US Pat.
It is listed in 1,432 mag.

Also, JP-A-58-42045, JP-A-59-214854, JP-A-59-17755
3, 59-177544 and 59-177557, the highly chromogenic ballast group is represented by the above general formula (IVa) ~ (IVf)
Applies to any of the compounds

Specific examples of the compound represented by the above general formula (IV) used in the present invention include one or a mixture of two or more of M-1 to M-67 in JP-A-62-30250. And those described in the examples are particularly preferred.

As the magenta coupler represented by the general formula (V), those disclosed in JP-A-60-262161 and JP-A-60-238832 and International Patent WO88 / 04795 can be used.

In the formula, Ar is a phenyl group, especially a substituted phenyl group. As a substituent, a halogen atom, an alkyl group (preferably C ₁ to ₅ ), an alkoxy group (preferably C ₁ to ₅ )
₁ to ₅ ), an aryloxy group, an alkoxycarbonyl group,
Cyano group, carbamoyl group, sulfamoyl group, sulfonyl group, sulfonamide group, acylamino group, Ar
The phenyl group represented by may have two or more substituents. Particularly preferred is halogen, and more preferred is chlorine.

Y represents a group that is released when a dye is formed by coupling with an oxidation product of an aromatic primary amine color developing agent.

Specifically, for example, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, an arylthio group, an alkylthio group, (Z represents an atomic group necessary for forming a 5- or 6-membered ring with an atom selected from a carbon atom, an oxygen atom, a nitrogen atom, and a sulfur atom together with a nitrogen atom).

V represents a halogen atom, an alkoxy group, an alkyl group or an amino group. Here, the alkoxy group and the alkyl group preferably have 1 to 5 carbon atoms. Also, an alkoxy group,
The alkyl group and amino group may have various substituents. Particularly, a halogen atom is preferable.

R represents a group capable of substituting on the benzene ring, and n represents an integer of 1 or 2. When n is 2, R may be the same or different.

Examples of the group capable of substituting the benzene ring represented by R include a halogen atom, R'-, R'O-, R ′, R ″ and R may be the same or different,
It represents a hydrogen atom or an alkyl group, an alkenyl group or an aryl group, each of which may have a substituent. Of these, R′CONH−, R′SO ₂ NH−, Is.

Specific examples of the magenta coupler represented by the above formula (V) include M-1 disclosed in JP-A-60-262161.
To M37 and M-1 disclosed in JP-A-60-238832
To M-34, or a mixture of two or more thereof. Of these, the following and those used in the examples are preferable.

The amount of the coupler added is preferably 1 m ² of the light-sensitive material.
It is about 0.01 to 20 mM, more preferably about 0.1 to 5 mM.

If necessary, a 5-pyrazolone magenta coupler or a polymer coupler may be used in combination.

Cyan couplers that can be used in the present invention include oil-protective naphthol-based and phenol-based couplers, naphthol-based couplers described in U.S. Pat.No. 2,474,293, preferably U.S. Pat.Nos. 4,052,212, 4,146,396, No. 4,228,233 and No. 4,296,200
As a representative example, the oxygen atom-releasing two-equivalent naphthol-based couplers described in JP-A No. 1994-242242 can be mentioned. Further, specific examples of the phenol-based coupler are described in U.S. Patent Nos. 2,369,929 and 2,80.
1,171, 2,772,162, 2,895,826 and the like. Cyan couplers which are fast against humidity and temperature are preferably used in the present invention, and typical examples thereof include a phenol having an alkyl group of ethyl group or higher at the meta-position of the phenol nucleus described in U.S. Pat. No. 3,772,002. Cyan couplers, U.S. Pat.Nos. 2,772,162, 3,785,308, 4,126,396, 4,334,011,
No. 4,327,173, West German Patent Publication No. 3,329,729 and Japanese Patent Application No. 58-42671, and 2,5-diacylamino-substituted phenol couplers and U.S. Pat.No. 3,446,622.
No. 4,433,999, No. 4,451,559 and No. 4,427,
Nos. 767 and the like include phenol couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position.

The graininess can be improved by using a coupler in which the color forming dye has an appropriate diffusibility. Such dye-diffusing couplers are described in U.S. Patent No. 4,366,237 and British Patent No.
Specific examples of magenta couplers are described in 2,125,570, and specific examples of yellow, magenta or cyan couplers are described in EP 96,570 and German Offenlegungsschrift 3,234,533.

Dye-forming couplers and the above-mentioned special couplers may form polymers of dimers or more. Typical examples of polymerized dye forming couplers are described in US Pat. Nos. 3,451,820 and 4,080,211. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102,173 and U.S. Patent No. 4,367,282.

The various couplers used in the present invention can be used in combination of two or more kinds in the same layer of the light-sensitive layer in order to satisfy the properties required for the light-sensitive material, and the same compound can be used in two or more different layers. Can also be introduced.

The standard amount of the color coupler used is in the range of 0.001 to 1 mol per mol of the photosensitive silver halide,
Preferably 0.01 to 0.5 moles for yellow couplers,
It is 0.003 to 0.3 mol for the magenta coupler and 0.002 to 0.3 mol for the cyan coupler.

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 organic solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. Further, the process of the latex dispersion method, the effect, specific examples of the latex for impregnation, U.S. Pat. No. 4,199,
363, West German Patent Application (OLS) Nos. 2,541,274 and
No. 2,541,230.

The photographic light-sensitive material used in the present invention is coated on a rigid support such as a commonly used plastic film, cellulose nitrate, cellulose acetate, polyethylene terephthalate, paper or other flexible support or glass. . For details on the support and coating method, see RESE
ARCH DISGLOSURE Volume 176, Item 17643 Item XV (P.27) Item XVII (P28) (December 1978 issue).

In the present invention, a reflective support is preferably used.

The "reflective support" is one which enhances the reflectivity and makes the dye image formed on the silver halide emulsion layer clear, and such a reflective support includes titanium oxide, zinc oxide, Examples include those coated with a hydrophobic resin containing a light reflecting substance such as calcium carbonate and calcium sulfate dispersed therein, and those using a hydrophobic resin containing a light reflecting substance dispersed therein as a support.

(Example) Hereinafter, the present invention will be described in detail based on examples.

Example 1 On a paper support laminated on both sides with polyethylene,
A multilayer photographic paper having the following layer configuration was produced. The coating liquid was prepared as follows.

(Preparation of coating liquid for first layer) Yellow couplers (ExY-1) and (ExY-2) respectively
Ethyl acetate 27.2cc and high boiling point solvent (Solv-1) 7.7cc (8.0g) in 10.2g, 9.1g and 4.4g of color image stabilizer (Cpd-1)
g) was added and dissolved, and this solution was added with 185 cc of 10% gelatin aqueous solution containing 10 cc of sodium dodecylbenzenesulfonate 8 cc.
Emulsified and dispersed. This emulsified dispersion and emulsion EM1 and EM2
And were mixed and dissolved, and the gelatin concentration was adjusted so that the following composition was obtained to prepare a coating solution for the first layer. The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. The gelatin hardener for each layer is 1-oxy-3,5-dichloro-
The s-triazine sodium salt was used.

 Moreover, (Cpd-2) was used as a thickener.

(Layer constitution) The composition of each layer is shown below. Numbers represent coating weight (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver.

Support Polyethylene laminated paper [The first layer of polyethylene contains white pigment (Tio2) and bluish paint. ] 1st layer (blue-sensitive layer) Monodisperse spectrally sensitized with sensitizing dye (ExS-1) Silver chlorobromide emulsion (EM1) 0.13 Monodisperse spectrally sensitized with sensitizing dye (ExS-1) Silver chlorobromide emulsion (EM2) 0.13 Gelatin 1.86 Yellow coupler (ExY-1) 0.44 Yellow coupler (ExY-2) 0.39 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-1) 0.35 Second layer (prevention of color mixture) Layer) Gelatin 0.99 Color mixing inhibitor (Cpd-3) 0.08 Third layer (green sensitive layer) Monodisperse silver chlorobromide emulsion (EM3) 0.05 sensitized by spectral sensitization with sensitizing dye (ExS-2,3) Monodisperse silver bromide emulsion (EM4) 0.11 gelatin 1.80 Magenta coupler 5.5 × 10 ^-4 mol Color image stabilizer (Cpd-4) 0.20 Anti-staining agent Table 2 Spectral sensitized with dye (ExS-2,3) Reference solvent (Solv-2) 0.12 Solvent (Solv-3) 0.25 Fourth layer (UV absorbing layer) Gelatin 1.60 UV absorber (Cpd-7 / Cpd-8 / Cpd-9 = 3/2/6: weight ratio) 0.70 color mixture Stopper (Cpd-10) 0.05 Solvent (Solv-4) 0.27 Fifth layer (red sensitive layer) Monodisperse silver chlorobromide emulsion (EM5) 0.07 spectrally sensitized with sensitizing dye (ExS-4,5) Monodispersed silver chlorobromide emulsion (EM6) 0.16 gelatin 0.92 Cyan coupler (ExC-1) 0.32 spectrally sensitized with sensitizing dyes (ExS-4,5) Cd-8 / Cpd-9 / (Cpd-12 = 3/4/2: weight ratio)
0.17 Dispersing polymer (Cpd-11) 0.28 Solvent (Solv-2) 0.20 Sixth layer (UV absorbing layer) Gelatin 0.54 UV absorber (Cpd-7 / Cpd-9 / Cpd-12 = 1/5/3: weight Ratio) 0.21 Solvent (Solv-2) 0.08 Seventh layer (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (Degree of modification
(17%) 0.17 Fluid paraffin 0.03 At this time, (Cpd-13, Cpd-14) was used as the dye for preventing irradiation.

Further, for each layer, alkanol XC (Dupont), sodium alkylbenzene sulfonate, succinate and Megafac F-120 (manufactured by Dainippon Ink and Chemicals) were used as an emulsifying dispersant and a coating aid. (Cpd-15, 16) was used as a stabilizer for silver halide.

 Details of the emulsion used are as follows.

Emulsion name Particle size (μ) Br content (mol%) Coefficient of variation EM1 1.0 80 0.08 EM2 0.75 80 0.07 EM3 0.5 83 0.09 EM4 0.4 83 0.10 EM5 0.5 73 0.09 EM6 0.4 73 0.10 The structural formula of the compound used is as follows. is there.

Solv-1 dibutyl phthalate Solv-2 tricresyl phosphate Solv-3 trioctyl phosphate Solv-4 trinonyl phosphate The color photographic paper obtained as described above was exposed to 250 CMS, and then the composition of the bleach-fix solution was changed, and the color photographic paper was processed in the following processing steps. Processing process Temperature Time Color development 38 ℃ 3 minutes 30 seconds Bleach fixing 30-34 ℃ 1 minute 30 seconds Rinse 30-34 ℃ 20 seconds Rinse 30-34 ℃ 20 seconds Rinse 30-34 ℃ 20 seconds Dry 70-80 ℃ 50 Second (Rinse → 3 tank countercurrent system) The composition of each processing solution is as follows.

Color developer Water 800 ml Triethanolamine 10 g 1-Hydroxyethylidene-1,1-diphosphonic acid (60
%) 2.0 g Benzyl alcohol 15 ml Lithium chloride 1.5 g Hydroxylamine / sulfate 3.0 g Potassium bromide 1.2 g Potassium carbonate 30 g N-ethyl-N- (β-methanesulfonamidoethyl)
-3-Methyl-4- aminoaniline sulphate 5.5g Sodium sulphite 1.8g Fluorescent brightener (UVITEX-CK Ciba-Geigy) 1.5g Add water 1000ml pH (25 ℃) 10.25 Bleach-fixing solution Color development in the pre-bath The running equilibrium liquid into which the liquid was brought was estimated and the treatment liquids (a) to (h) shown in Table 1 were prepared.

Rinse liquid Ion-exchanged water (both calcium and magnesium ions 3 ppm or less) was used.

Next, as described above, samples A, B, C, D, E, F, G, H, I, and J in which the magenta coupler and the anti-staining agent were changed were prepared, and treated with treatment liquids (a) to (h). Processed and processed photosensitive material
Table 2 shows the results of measuring the increase in magenta density (magenta stain) in the unexposed area with a Macbeth densitometer after one month at 80 ° C.

Based on Table 2, magenta stains were prevented in the treatments (f) and (g) of the present invention, and magenta stains were also prevented in F, G, H, I and J using the stain inhibitor of the present invention. To be done. However, samples F, G,
By carrying out the treatment of the present invention on H, I and J, the generation of stain is remarkably prevented, and the effect is remarkable in the samples G, H, I and J using the particularly preferable magenta coupler.

Example 2 The same treatment as in Example 1 was carried out except that the bleaching agents (f) and (to) in Example 1 ethylenediaminetetraacetic acid iron (III) ammonium were changed to diethylenetriaminepentaacetic acid iron (III) ammonium in an equimolar amount. An excellent anti-stain effect was obtained.

Example 3 The same treatment as in Example 1 was carried out except that the bleaching agents (f) and (to) in Example 1 were changed to equimolar amounts of iron (III) ammonium diaminediaminetetraacetate in cyclohexanediaminetetraacetate. However, the same excellent stain prevention effect as in Example 1 was obtained.

Example 4 Photosensitive materials A to E shown in Table 3 were prepared by changing the amount of silver coated on each layer of color photographic paper to the sample H of Example 1 as shown in the table below.

The photographic printing papers A to E were processed in the same manner as in Example 1 and the stain after the processing was examined. However, the bleach-fixing solutions used were (a), (f), and (g). The results are shown in Table 4.

According to the present invention, the anti-staining agents represented by the general formulas (I), (II) and (III) of the present invention are treated with the treating liquid of the present invention to prevent the treatment liquid from magenta stain. Is remarkable.

Example 5 Samples K, L, M, N, O, similar to Sample F of Example 1, but with the magenta coupler modified as follows:
P, Q, R and S were created.

Sample N PM-3 〃 O PM-4 〃 P PM-8 〃 Q PM-16 〃 R m-2 〃 S m-5 Next, the above-mentioned materials are imagewise exposed, and a tank of bleach-fixer in the following processing steps. A running test was performed until the volume was replenished to twice the capacity. However, as the composition of the bleach-fixing solution, as shown in Table 5, a running test was carried out for each solution in which the ratio of ammonium ions was changed.

Treatment process temperature Time Replenishment amount Tank capacity Color development 38 ℃ 1 minute 40 seconds 290ml 17l Bleach fixing 33 ℃ 30 seconds 120ml 9l Rinse 30-34 ℃ 20 seconds 4l Rinse 30-34 ℃ 20 seconds 4l Rinse 30-34 ℃ 20 seconds 364ml 4l Dry 70 to 80 ° C 50 seconds Per 1 m ^{2 of} light-sensitive material (Rinse → 3 tank countercurrent method) The amount brought in from the previous bath was 4 ml / m ² .

 The composition of each processing solution is as follows.

Bleach-fixing solution As shown in Table 5, two kinds of formulations were used.

 The tank solution was used by diluting the replenisher solution to 2/3.

The replenishing amount of the bleach-fixing solution is 120 ml, which is three times the amount brought in from the previous bath.

Rinse liquid (tank liquid and replenisher are the same) Ion-exchanged water (calcium and magnesium are each 3ppm or less) Water was added to each to make 100 ml, and the pH was adjusted to 6.0 with acetic acid.

Samples K, L, M, and
N, O, P, Q, R and S were wedge-shaped exposed and then processed. After the treatment, the magenta density of the white background portion (Dmin) was measured, and the magenta density was measured again after 1 month elapsed at 60 ° C./60% RH. The amount of residual silver in the maximum density part (Dmax) was measured by fluorescent X-ray. The results are shown in Table 6.

When the bleach-fixing solution of the present invention is used and the magenta coupler represented by the general formula (IV) is used (N, O, P,
It can be seen that magenta stains in Q, R, and S) are remarkably reduced over time, especially after treatment. Further, the amount of residual silver is reduced and the desilvering property is excellent.

Example 6 A multilayer color photographic paper having the following layer constitution was prepared on a paper support laminated on both sides with polyethylene. The coating liquid was prepared as follows.

Preparation of 1st layer coating solution Yellow coupler (ExY) 19.1g and color image stabilizer (Cp
d-1) 4.4 g and color image stabilizer (Cpd-7) 0.7 g were dissolved by adding ethyl acetate 27.2 cc and solvent (Solv-3) 8.2 g.
Add this solution to 10% sodium dodecylbenzene sulfonate.
It was emulsified and dispersed in 18.5 cc of 10% gelatin aqueous solution containing 8 cc. On the other hand, silver chlorobromide emulsion (cubic average grain size 0.88
μ, the coefficient of variation of the grain size distribution is 0.08, and 0.2 mol% of silver bromide is contained on the grain surface as a proportion of the whole grain), and the following blue-sensitive sensitizing dyes were added at 2.0 × 10 ⁻⁴ mol per mol of silver. What was later subjected to sulfur sensitization was prepared. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a coating liquid for the first layer having the composition shown below. The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer.
As the gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used.

 The following were used as the spectral sensitizing dye in each layer.

Blue-sensitive emulsion layer (2.0 × 10 ^-4 moles per mole of silver halide) Green-sensitive emulsion layer (4.0 × 10 ⁻⁴ mol per mol of silver halide) and (7.0 × 10 ^-5 mol per mol of silver halide) Red-sensitive emulsion layer (0.9 × 10 ⁻⁴ mol per mol of silver halide) The following compounds were added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ⁻³ mol per mol of silver halide.

Further, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to each of the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer per mol of silver halide.
8.5 × 10 ^-5 mol, 7.7 × 10 ^-4 mol and 2.5 × 10 ^-4 mol were added.

The following paints were added to the emulsion layer to prevent irradiation.

(Layer constitution) The composition of each layer is shown below. Numbers represent coating weight (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver.

Support Polyethylene laminated paper [Polyethylene on the first layer side contains white pigment (TiO ₂ ) and bluish dye (ultra-blue)] First layer (blue sensitive layer) Silver chlorobromide emulsion 30.0 Gelatin 1.86 Yellow coupler (ExY) 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-3) 0.35 Color image stabilizer (Cpd-7) 0.06 Second layer (color mixing prevention layer) Gelatin 0.99 Color mixing inhibitor (Cpd-5) 0.08 Solvent (Solv -1) 0.16 solvent (Solv-4) 0.08 third layer (green-sensitive layer) silver chlorobromide emulsion (having a cubic average grain size of 0.55 µ,
0.39μ of 1: 3 mixture (Ag mol) ratio), variation coefficient of particle size distribution 0.10, 0.08, and AgBr 0.8 mol% were locally contained on the particle surface.

0.12 Gelatin 1.24 Magenta coupler (ExM) 0.27 Color image stabilizer (Cpd-3) 0.15 Color image stabilizer (anti-staining agent) See Table 7 Solvent-2 0.54 Fourth layer (UV absorbing layer) Gelatin 1.58 UV absorber (UV-1) 0.47 Color mixing inhibitor (Cpd-5) 0.05 Solvent (Solv-5) 0.24 Fifth layer (red sensitive layer) Silver chlorobromide emulsion (with cubic average grain size 0.58μ,
A 0.45μ mixture of 1: 4 (Ag mole ratio), a variation coefficient of the particle size distribution of 0.0.9, 0.11 and AgBr of 0.6 mole% were locally contained in a part of the particle surface.

0.23 Gelatin 1.34 Cyan coupler (ExC) 0.32 Color image stabilizer (Cpd-6) 0.17 Color image stabilizer (Cpd-10) 0.04 Color image stabilizer (Cpd-7) 0.40 Solvent (Solv-6) 0.15 Sixth layer ( UV absorbing layer) Gelatin 0.53 UV absorbing agent (UV-1) 0.16 Color mixing inhibitor (Cpd-5) 0.02 Solvent (Solv-5) 0.08 Seventh layer (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (modified) Every time
17%) 0.17 Liquid paraffin 0.03 As shown in Table 7, Samples 6-A, B, C, D, E, and F were prepared by changing the color image stabilizer of the third layer, and after the imagewise exposure, each of them was subjected to the following processing steps. Continuous processing was carried out until the tank was replenished with twice the capacity of the color developing solution.

The processing solutions used are as follows.

Bleach-fixing solution (same as tank solution and replenisher) The following two types were used.

The replenishing amount of the bleach-fixing solution is 4 times the carrying amount of the color developing solution per unit area of these samples (photosensitive materials).
It was twice.

Washing solution Ion-exchanged water (calcium and magnesium ions, 3ppm or less for each) The magenta concentration of the white background (Dmin) after the treatment was measured, and the magenta concentration after 1 month at 60 ° C / 70% RH was measured again. The results are shown in Table 7.

As is clear from the results shown in Table 7, the samples (6-B to F) containing the magenta stain inhibitor of the present invention were treated with the bleach-fixing solution () of the present invention to obtain a magenta stain after the treatment. It can be seen that the occurrence of is significantly prevented.

Example 7 Photosensitive materials G-1 to 20 were prepared in the same manner as the photosensitive material G of Example 1 except that the stain inhibitor was as described in Table 8. About these photosensitive materials G-1 to G-20, the processing liquids (b), (f) and (g) of Example 1 were used to prepare Example 1
The same process was carried out. The results are shown in Table 8.

(Effect of the invention) According to the present invention, by reducing the replenishing amount of the bleach-fixing solution, resource saving, low cost and low pollution can be achieved, and further, the occurrence of stain due to the coupler after processing can be suppressed. It is possible to provide a color photograph with excellent image quality even after long-term storage.

Claims (2)

[Claims] 1. The following general formula (I), (II) or (III)
In a continuous processing method of a light-sensitive material, which contains at least one compound represented by the formula (1) and is subjected to image exposure on a silver halide color photographic light-sensitive material containing at least one kind of magenta coupler, and after color development processing, bleach-fixing processing is carried out. , Containing an aminopolycarboxylic acid iron ammonium salt as a bleaching agent, containing an ammonium thiosulfate salt as a fixing agent, and processing with a bleach-fixing solution containing an ammonium sulfite salt as a preservative, and with respect to a certain area of the photosensitive material to be processed, The bleach-fixing replenisher is added to the bleach-fixing replenisher in an amount of 0.5 to 15 times the amount of the color developing solution brought in by the light-sensitive material having a certain area, and the cation components Li ⁺ and Na ^{+ of the} salt contained in the bleach-fixing replenisher. the silver halide color, characterized in that 94 to 100 mole percent of the sum of K ⁺ and ammonium ions is an ammonium ion Processing method of the photographic light-sensitive material. General formula (I) R ₁ A _n X General formula (II) In the formula, R ₁ and R ₂ each represent an aliphatic group, an aromatic group, or a heterocyclic group. X represents a group which reacts with an aromatic amine developing agent and leaves, and A represents a group which reacts with an aromatic amine developing agent to form a chemical bond. n represents 1 or 0.
B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group or a sulfonyl group, and Y represents a group which promotes addition of the aromatic amine developing agent to the compound of the general formula (II). Represents Here, R ₁ and X, Y and R ₂ or B may be bonded to each other to form a cyclic structure. General formula (III) R-Z In the formula, R represents an aliphatic group, an aromatic group or a heterocyclic group. Z represents a nucleophilic group or a group that decomposes in the light-sensitive material to release a nucleophilic group. 2. The silver halide color photographic light-sensitive material comprises:
The processing method according to claim 1, which contains at least one magenta coupler represented by the following general formula (IV) or (V). (In the formula (IV), R ₁ represents a hydrogen atom or a substituent, and X represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidized product of an aromatic primary amine developer. Za, Zb and Zc represents methine, substituted methine, = N- or -NH-, one of a Za-Zb bond and a Zb-Zc bond is a double bond, and the other is a single bond. In the case of a carbon double bond, it includes a case where it is a part of an aromatic ring, and further includes a case where R ₁ or X forms a dimer or higher multimer, and a substitution of Za, Zb or Zc. In the case of methine, this includes the case where the substituted methine forms a dimer or higher polymer.In the formula (V), Ar is a phenyl group or a phenyl group having a substituent, and Y is an aromatic group. Represents a group that leaves when a dye is formed by coupling with an oxidized product of a primary amine color developing agent. V is a halogen atom, an alkoxy group, an alkyl group, an amino group, R is a group capable of substituting on a benzene ring,
n represents 1 or 2. When n is 2, R may be the same or different. )