JP2990311B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and more particularly, to a silver halide color photographic material in which scum does not occur in a color developing solution and magenta dye generation failure is improved. The present invention relates to a method for processing a photosensitive material.

[0002]

2. Description of the Related Art Usually, a method of forming a dye image by processing a silver halide color photographic light-sensitive material is performed after imagewise exposure is performed, color development is performed with a color developing solution, and then unnecessary. After the desilvering step of removing the silver image, the film is treated by a washing step and a stabilizing step for stabilizing the dye. Desilvering is a bleaching process that oxidizes developed silver to form silver ions such as silver halide, and a fixation that changes silver ions into a water-soluble form such as silver thiosulfate to remove silver from the film. Although they are divided into steps, a bleach-fixing process in which these steps are performed simultaneously is also generally performed.

After the fixing process, washing is usually performed to remove unnecessary components in the light-sensitive material. Recently, however, a mini-lab installed in a store or a stabilizing solution instead of washing is used instead of washing for the purpose of saving water. The number of systems for performing so-called anhydrous washing processing has been increasing. In the case of photosensitive materials for photographing such as color negative films and color reversal films, so-called stabilization processing for stabilizing dyes is performed as a final processing step after washing with water or the above-mentioned stabilization processing instead of washing, and minilabs In the treatment, a one-component stabilizer in which this stabilization treatment is performed simultaneously with the washing stabilization alternative treatment is also known.

[0004] On the other hand, recently, in order to reduce the cost of the processing agent or reduce the amount of waste liquid to reduce pollution, low replenishment processing for reducing the replenishment amount of the processing liquid has been actively performed. When such a low replenishment process is performed, when continuous processing is performed by an automatic developing machine, the pre-bath component adheres to a photosensitive material, a transport belt, a leader, a short reader, and the like, and the ratio of being brought in increases.

In particular, when a stabilization treatment is performed as a final processing step, a belt, a short leader, a leader, etc., to which a stabilizing solution component has adhered, are dried by a dryer and are not washed, and are placed at the top of the next photosensitive material. When mounted and reused, the stable liquid component is brought into the color developing solution. For this reason, when the color developing solution is subjected to a low replenishment process, this effect becomes remarkable, and scum is generated in the color developing solution particularly in a short leader type automatic developing machine,
Moreover, it was found that the color development of the magenta dye was suppressed.

[0006]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to prevent the occurrence of scum in a color developing solution even when a low replenishment process of the color developing solution is performed, and to form a magenta dye. An object of the present invention is to provide a method for processing a silver halide color photographic light-sensitive material in which defects are improved.

[0007]

The method for processing a silver halide color photographic light-sensitive material of the present invention to achieve the above object, according to an aspect of the silver halide color photographic material to color development processing, the processing solution having fixing ability (although The processing solution having the fixing ability
White fixer, 1 × 10 ^{-3 to} 2.0 mol per liter
(Excluding the case of containing a bromide ion) , and then processing with a stabilizing solution, wherein the replenishment amount of the color developing solution is per 1 m ^{2 of the} silver halide color photographic material. 10-900ml,
The stabilizer is characterized in that it contains at least one compound selected from the compounds represented by the following general formula [I].

The general formula [I]

[0009]

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[Wherein, Z represents a group of atoms necessary for forming a substituted or unsubstituted carbon ring or a substituted or unsubstituted heterocyclic ring, X represents an aldehyde group,

[0011]

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(R ₁ and R ₂ each represent a lower alkyl group), and n represents an integer of 1-4. Further, as a preferred embodiment of the present invention, in the above-mentioned stabilizing solution and processing method for a silver halide color photographic light-sensitive material, Z in the general formula (I) represents an aromatic carbon ring having a substituent or a substituent. The stabilizer has substantially no formaldehyde, the stabilizer has a water-soluble surfactant, and the stabilizer has a fungicide.

[0013] In another preferred embodiment of the present invention,
The substituent of Z is an aldehyde group, a hydroxyl group, an alkyl group,
Aralkyl groups, alkoxy groups, halogen atoms, nitro groups, sulfo groups, carboxy groups, amino groups, hydroxyalkyl groups, aryl groups, cyano groups, aryloxy groups,
Acyloxy group, acylamino group, sulfonamide group,
A sulfamoyl group, a carbamoyl group or a sulfonyl group.

[0014]

The present inventor believes that the above-mentioned problem is caused by formalin which has been conventionally used in the stabilizing solution. When the compound of the present invention was used in place of formalin in the stabilizing solution, the color developing process was a low replenishment process. However, the inventors have found that all of the above-mentioned problems can be solved, and have reached the present invention.

[0015]

Next, the compound represented by formula (I) used in the present invention will be described. In the general formula (I), Z represents a group of atoms necessary for forming a substituted or unsubstituted carbocyclic or heterocyclic ring, and the carbocyclic or heterocyclic ring may be a single ring or a condensed ring; Preferably Z is
It is an aromatic carbocyclic or heterocyclic ring having a substituent. When the substituent of Z is an aldehyde group, a hydroxyl group, an alkyl group (eg, methyl, ethyl, methoxyethyl, benzyl, carboxymethyl, sulfopropyl, etc.), an aralkyl group, an alkoxy group (eg, methoxy, ethoxy, methoxyethoxy, etc.) , A halogen atom, a nitro group, a sulfo group, a carboxy group, an amino group (eg, N, N-dimethylamino, N-ethylamino, N-phenylamino, etc.), a hydroxyalkyl group, an aryl group (eg, phenyl, p- Methoxyphenyl, etc.), cyano group, aryloxy group (eg, phenoxy, p-carboxyphenyl, etc.), acyloxy group, acylamino group, sulfonamide group, sulfamoyl group (eg, N-ethylsulfamoyl, N, N-dimethyl) A carbamoyl group (eg, sulfamoyl)
It is preferably a carbamoyl, N-methylcarbamoyl, N, N-tetramethylenecarbamoyl or the like or a sulfonyl group (for example, methanesulfonyl, ethanesulfonyl, benzenesulfonyl, p-toluenesulfonyl, etc.).

The carbon ring represented by Z is preferably a benzene ring, and the heterocyclic ring represented by Z is preferably 5
Or a 6-membered heterocyclic group. For example, as a 5-membered ring, thiophene, pyrrole, furan, thiazole, imidazole, pyrazole, succinimide, triazole,
And a six-membered ring includes pyridine, pyrimidine, triazine, thiadiazine and the like. Examples of the condensed ring include naphthalene, benzofuran, indole, thionaphthalene, benzimidazole, benzotriazole, quinoline and the like.

Preferred examples of the compound represented by the formula [I] are shown below.

[0018]

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Illustrative compounds (1) to (48) can be obtained by inserting various substituents into 1 to 6 in the above formula as shown in the following table.

[0020]

[Table 1]

[0021]

[Table 2]

[0022]

[Table 3]

[0023]

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[0024]

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[0025]

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Among the specific examples of the compound represented by the general formula [I], more preferable compounds are (2), (3),
(4), (6), (23), (24), (57), and (59),
Most preferably, (3) is mentioned.

The compound represented by the general formula [I] can be easily obtained as a commercial product.

The compound represented by the formula [I] is contained in a stabilizer for a silver halide color photographic light-sensitive material. Note that, within a range that does not impair the effects of the present invention, a processing solution used in a pre-bath of a processing bath having bleaching ability together with a stabilizing solution,
It can be contained in a processing solution having a bleaching ability, a processing solution having a fixing ability, and the like.

The amount of the compound represented by the general formula [I] is preferably 0.05 to 20 g, more preferably 0.1 to 15 g, and particularly preferably 0.5 to 10 g per liter of the stabilizing solution.

The compound represented by the general formula [I] is characterized in that it has better image storability even under low humidity conditions as compared with known formaldehyde substitute compounds.

In the present invention, the stabilizer preferably contains a chelating agent having a chelate stability constant for iron ions of 8 or more. Here, the chelate stability constant is
"Stability Constants" by LGSillen and AEMartell
of Metal-ion Complexes ”, The Chemical Sociery, Lo
ndon (1964), by S. Chaberek AE Martell, "OrganicSe
questering Agents ", Willey (1959) and the like. The chelating agent having a chelate stability constant for iron ions of 8 or more includes organic carboxylic acid chelating agents, organic phosphoric acid chelating agents, and inorganic phosphorus. Examples include an acid chelating agent, a polyhydroxy compound, etc. The above-mentioned ion means ferric ion (Fe ³⁺ ).

The chelate stability constant with ferric ion is 8
Specific examples of the chelating agent described above include the following compounds, but are not limited thereto. That is, ethylenediamine diorthohydroxyphenylacetic acid, diaminopropanetetraacetic acid, nitrilotriacetic acid, hydroxyethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, Diaminopropanoltetraacetic acid, transcyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, ethylenediaminetetrakismethylenephosphonic acid, nitrilotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 1,1-diphosphonoethane-2-carboxylic acid , 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxy-1-phosphonopropane-1,2,3-tricarboxylic acid, catechol-3,
5-diphosphonic acid, sodium pyrophosphate, sodium tetrapolyphosphate, sodium hexametaphosphate, and particularly preferably diethylenetriaminepentaacetic acid, nitrilotriacetic acid, nitrilotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid and the like. Yes, especially 1
-Hydroxyethylidene-1,1-diphosphonic acid is most preferably used.

The above chelating agent is used in an amount of 1 liter of the stabilizing solution.
Good results are obtained in the range of preferably 0.01 to 50 g, more preferably 0.05 to 20 g.

A preferable compound to be added to the stabilizer is an ammonium compound. These are supplied by ammonium salts of various inorganic compounds,
Specifically, ammonium hydroxide, ammonium bromide, ammonium carbonate, ammonium chloride, ammonium hypophosphite, ammonium phosphate, ammonium phosphite,
Ammonium fluoride, ammonium acid fluoride, ammonium fluoroborate, ammonium arsenate, ammonium bicarbonate, ammonium bifluoride, ammonium bisulfate, ammonium sulfate, ammonium iodide, ammonium nitrate, ammonium pentaborate, ammonium acetate, ammonium adipate, Ammonium laurate tricarboxylate, ammonium benzoate, ammonium carbamate, ammonium citrate, ammonium diethyldithiocarbamate, ammonium formate, ammonium hydrogen malate, ammonium hydrogen oxalate, ammonium phthalate, ammonium hydrogen tartrate, ammonium thiosulfate, ammonium sulfite, ethylenediamine Ammonium tetraacetate, ferric ammonium ethylenediaminetetraacetate, Moniumu, ammonium malic acid,
Ammonium maleate, ammonium oxalate, ammonium phthalate, ammonium picrate, ammonium pyrrolidine dithiocarbamate, ammonium salicylate, ammonium succinate, ammonium sulfanilate, ammonium tartrate, ammonium thioglycolate, 2,4,6-trinitrophenol ammonium And so on. These may be used alone or in combination of two or more. 0.001 to 1.0 per liter of the stabilizing solution in the range of the amount of the ammonium compound added.
It is preferably in the range of mol, more preferably in the range of 0.002 to 2.0 mol.

Further, it is preferable that the stabilizing solution contains a sulfite. The sulfite may be any organic or inorganic substance as long as it releases sulfite ions.
Preferred are inorganic salts. Preferred specific compounds include sodium sulfite, potassium sulfite, ammonium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite and hydrosulfite.

The above sulfite is contained in the stabilizing solution at least 1 ×.
It is preferable to add an amount so as to be 10 ⁻³ mol / l, more preferably an amount such that it becomes 5 × 10 ⁻³ to 10 ⁻¹ mol / l. It has a preventive effect. As an addition method, it may be directly added to the stabilizing solution, but is preferably added to the stable replenishing solution.

The stabilizer preferably contains a metal salt in combination with the chelating agent. Such metal salts include B
a, Ca, Ce, Co, In, La, Mn, Ni, Bi, Pb, Sn, Zn, T
There are metal salts of i, Zr, Mg, Al or Sr, which can be supplied as inorganic salts such as halides, hydroxides, sulfates, carbonates, phosphates, acetates or water-soluble chelating agents. The amount used is preferably in the range of 1 × 10 ^-4 to 1 × 10 ^-1 mol, more preferably in the range of 4 × 10 ^-4 to 2 × 10 ^-2 mol per liter of the stabilizing solution.

[0038] Stabilizing solutions include organic acid salts (citric acid, acetic acid,
Succinic acid, oxalic acid, benzoic acid, etc.), pH adjusters (phosphate, borate, hydrochloric acid, sulfate, etc.) can be added. These compounds may be used in any combination in amounts that are necessary to maintain the pH of the stabilizing solution and that do not adversely affect the stability during storage of color photographic images and the occurrence of precipitation. I can't tell.

In the present invention, known fungicides can be used alone or in combination as long as the effects of the present invention are not impaired.

The stabilizer can contain a surfactant. Examples of the surfactant include compounds represented by formulas [I] to [II] and water-soluble organic siloxane compounds described in JP-A-62-250449.

In the treatment of the present invention, silver may be recovered from the stabilizing solution. In addition, the stable solution is subjected to ion exchange treatment, electrodialysis treatment (see Japanese Patent Application No. 59-96352) and reverse osmosis treatment (Japanese Patent Application No. 59-96352).
-96532). It is also preferable to use water which has been previously deionized from water used for the stabilizing solution. That is, the antifungal property of the stabilizer, the stability of the stabilizer, and the image storability are improved. As a means of the deionization treatment, any method may be used as long as the Ca and Mg ions of the washing water after the treatment are reduced to 5 ppm or less. For example, a treatment with an ion exchange resin or a reverse osmosis membrane may be used alone or in combination. Is preferred. Ion exchange resins and reverse osmosis membranes are described in detail in Published Technical Report No. 87-1984.

The salt concentration in the stabilizer is preferably 1000 ppm or less, more preferably 800 ppm or less.

The presence of a soluble iron salt in the stabilizing solution is preferred for achieving the effects of the present invention. The soluble iron salt is preferably used in the stabilizer at a concentration of at least 5 × 10 ⁻³ mol / l, more preferably in the range of 8 × 10 ^{−3 to} 150 × 10 ⁻³ / l mol / l, More preferably, 12 × 10 ^{-3 to} 100 ×
It is in the range of 10 ^-3 mol / l.

In the present invention, the pH of the stabilizer is 5.5 to 10.0.
Is preferable. The pH adjusting agent that can be contained in the stabilizing solution may be any of commonly known alkali agents and acid agents.

The processing temperature for the stabilization processing is 15 to 70 ° C.
And more preferably in the range of 20 to 55 ° C. The processing time is preferably 120 seconds or less, more preferably 3 to 90 seconds, and most preferably 6 to 50 seconds.

The replenishing amount of the stabilizing solution is 900 per m ² of the light-sensitive material.
ml or less, more preferably 500 ml or less.

The stabilization tank is preferably composed of a plurality of tanks, preferably two or more tanks and six tanks or less, particularly preferably two to three tanks, more preferably two tanks, and a counter current system ( It is preferable to supply to the post-bath and overflow from the pre-bath).

After the stabilization treatment, no water washing treatment is required, but rinsing by small amount of water washing and surface washing in a very short time can be arbitrarily performed as necessary.

The color developing agents used in the color developing step of the present invention include aminophenol compounds and p-
There are phenylenediamine compounds, but in the present invention, p-phenylenediamine compounds having a water-soluble group are preferred.

The water-soluble group has at least one on the amino group of the p-phenylenediamine compound or on the benzene nucleus. Specific examples of the water-soluble group include-(CH ₂ ) n-
_{CH 2 OH, - (CH 2} ) m-NHSO 2 - (CH 2) n-CH 3, - (CH 2) m-O-
_{(CH 2) n-CH 3} , - (CH 2 CH 2 O) nCmH 2 m +1 (m and n represent an integer of 0 or more, respectively.), - COOH group, those -SO ₃ H group and the like It is listed as. Specific examples of the color developing agent preferably used in the present invention include those described in Japanese Patent Application No.
Nos. 1,324,507, 2,234,776 and the like.

The amount of the color developing agent added was 1 liter of the color developing solution.
It is preferably at least 0.5 × 10 ^-2 mol per mol, more preferably in the range of 1.0 × 10 ^{-2 to} 1.0 × 10 ^-1 mol, most preferably 1.5 × 10 ^{-2 to} 7.0 × 10 ^-2 mol. It is a range.

The color developing solution used in the color developing step can contain a compound usually used in a developing solution.

[0053] The replenishment rate of the color developing solution in the present invention is 10~900ml / m ² from the viewpoint of the desired effect of the present invention, preferably 20~500ml / m ^2, more preferably 30~350ml / m ² is there.
The color development processing time in the present invention is preferably within 150 seconds, but in order to better achieve the effects of the present invention, more preferably 10 to 120 seconds, more preferably 20 to 100 seconds, and most preferably 30 to 70 seconds. Range.

When the color developing solution contains a compound represented by the following general formula [A] or [B], the effects of the present invention are more favorably exhibited and the generation of tar is also improved. There is also.

General formula [A]

[0056]

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In the general formula [A], R ₁ and R ₂ are simultaneously an alkyl group which may have a substituent which is not a hydrogen atom;
An optionally substituted aryl group, represents an R'-CO- or a hydrogen atom, an alkyl group represented by R ₁ and R ₂ may be the same or different, 1 to 3 carbon atoms, respectively Alkyl groups are preferred.

R 'represents an alkoxy group, an alkyl group or an aryl group. The alkyl group and aryl group of R _1, R ₂ and R ′ include those having a substituent, and R ₁ and R ₂ may combine to form a ring, for example, piperidine, pyridine, triazine and morpholine. And a heterocyclic ring such as

A specific example of the hydroxylamine compound represented by the general formula [A] is described in US Pat. No. 3,287,125.
And 3,293,034 and 3,287,124, etc., and particularly preferred specific exemplary compounds are shown below.

[0060]

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[0061]

[Table 4]

[0062]

[Table 5]

[0063]

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[0064]

[Table 6]

[0065]

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Next, the compound represented by the formula [B] will be described.

[0067]

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In the above general formula [B], R ₁₁ , R ₁₂ and R ₁₃
Is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and particularly preferably, R ₁₁ and R ₁₂ are each a hydrogen atom.

In the general formula [B], R ₁₄ is preferably an alkyl group, an aryl group, a carbamoyl group or an amino group, particularly preferably an alkyl group and a substituted alkyl group. Here, preferred substituents of the alkyl group include a carboxyl group,
Sulfo group, nitro group, amino group, phosphono group and the like.

Hereinafter, specific examples of the compound represented by the formula [B] will be shown.

[0071]

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[0072]

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[0073]

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Illustrative Compounds B-26 to B-33 on page 69 of Japanese Patent Application No. 2-239283 These compounds represented by the general formula [A] or [B] are usually free amines, hydrochlorides, sulfates, It is used in the form of salts, p-toluenesulfonate, oxalate, phosphate, acetate and the like.

The concentration of the compound represented by formula (A) or (B) in the color developing solution is usually 0.4 to 100 g / l,
Preferably it is 1.0 to 60 g / l, more preferably 2 to 30 g / l. Among the specific examples of the compound represented by the general formula [A] or [B], those particularly preferably used in the present invention include A-1, A-2, A-10, A-13 and A-16. ,
A-17, A-20, A-35, A-38, B-5, B-19, B
−20.

The compound represented by the general formula [A] or [B] can be used in combination with a conventionally used hydroxylamine and various organic preservatives, but preferably no hydroxylamine is used. It is more preferable from the viewpoint of developability. The compounds represented by the general formula [A] or the general formula [B] may be used alone or in combination of two or more.

Usually, a sulfite can be used as a preservative in the color developing solution, but the sulfur dioxide concentration in the color developing solution is 5 × 10 ⁻³ mol / l or more, preferably 1 × 10 ⁻² mol. / l or more, particularly preferably 2 × 10 ^-2 mol / l or more. As the sulfite, sodium sulfite, potassium sulfite,
Examples thereof include sodium bisulfite and potassium bisulfite.

The color developing solution may contain a certain concentration or less of chloride. Here, the chloride may be any compound that releases chloride ions in the color developing solution, and specific compounds include potassium chloride, sodium chloride, lithium chloride, and magnesium chloride. The chloride is preferably contained in an amount of at least 3 × 10 ^-2 mol per liter of the color developing solution, particularly 3.5 × 10 ² mol / l of the color developing solution.
^{-2 to} 20 × 10 ^-2 mol, especially 1 liter of color developing solution
Good results can be obtained with 4.0 × 10 ^{-2 to} 12 × 10 ^-2 moles per mole.

When the color developer contains a compound represented by the following general formula [D], not only can the effects of the present invention be exhibited more favorably, but also the oxidation of the color developer with air can be prevented. Are more preferably used because they show an improvement effect.

Formula [D]

[0081]

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In the general formula [D], R ₂₁ has 2 to 2 carbon atoms.
6 hydroxyalkyl group, R ₂₂ and R ₂₃ are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, acetic acid group, 2 carbon atoms
A hydroxyalkyl group, a benzyl group or a compound of the formula

[0083]

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Wherein n _{1 in} the above formula is 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. Preferred specific examples of the compound represented by the general formula [D] are as follows.

(D-1) ethanolamine, (D-2) jetanolamine, (D-3) triethanolamine, (D-4) di-isopropanolamine, (D-5) 2-methylaminoethanol, (D-6) 2-ethylaminoethanol, (D-7) 2-dimethylaminoethanol, (D-8) 2-diethylaminoethanol, (D-9) 1-diethylamino-2-propanol, (D-10) 3-Dethylamino-1-propanol, (D-11) 3-dimethylamino-1-propanol, (D-12) isopropylaminoethanol, (D-13) 3-amino-1-propanol, (D-14) 2 -Amino-2-methyl-1,3-propanediol, (D-15) ethylenediaminetetraisopropanol, (D-16) benzyldiethanolamine, (D-17) 2-amino-2- (hydroxymethyl) -1,3 - Lopandiol (D-18) dihydroxyethylglycine (D-19) hydroxyethyliminodiacetic acid From the viewpoint of the effects of the present invention, these compounds represented by the general formula [D] are used in an amount of 1 to 100 per liter of the color developing solution. And more preferably in the range of 3 to 50 g.

In the color developer, a chelating agent which is usually used is added. When a chelating agent represented by the following general formula [E] is used, the preservability is further improved.
Further, since it also has a development accelerating effect, it is particularly preferably used in combination with the present invention. General formula [E]

[0087]

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In the general formula [E], A ₁ to A ₅ may be the same or different and represent —COOM ₁ or —PO ₃ M ₂ M ₃ . M ₁ , M ₂ and M ₃ may be the same or different and represent a hydrogen atom, an alkali metal atom or an ammonium ion, and n represents 1 or 2. Specific compounds represented by the general formula [E] are known as diethylenetriaminepentaacetic acid and triethylenetetraminehexaacetic acid, diethylenetriaminepentamethylenephosphonic acid and triethylenetetraminehexamethylenephosphonic acid, and salts thereof (potassium, potassium,
Alkali metal salts such as sodium and lithium, and ammonium salts) are also known and can be obtained as commercial products.

The compound represented by the general formula [E] is
It is preferably in the range of 0.1 to 20 g, particularly preferably in the range of 0.5 to 10 g, particularly preferably 1 to 10 g per liter of the color developing solution.
A range of ５5 g is used.

Among the compounds represented by the general formula [E], diethylenetriaminepentaacetic acid and salts thereof are particularly preferably used from the viewpoint of the effects of the present invention.

The pH of the color developing solution is usually used in the range of 9.0 to 12.0, preferably in the range of 10.0 to 11.0.

The processing steps in the processing method of the present invention include the following steps, but are not limited thereto.

(1) Color development → bleach-fix → washing → stable (2) Color developing → bleach → fixing → washing → stable (3) Color developing → bleach → bleach-fix → washing → stable (4) Color developing → bleach-fix → Fixing → Washing → Stable (5) Color development → Bleaching / fixing → Bleaching → Washing → Stable (6) Color development → Fixing → Bleaching / fixing → Washing → Stable (7) Color development → Bleaching → Bleaching → Fixing → Washing → Stable (8) Black-and-white development → washing → reversal → color development → washing → adjustment →
Bleaching → fixing → washing → stable (9) Black and white development → washing → inversion → color development → washing → adjustment →
(10) Color development → bleaching → fixing → stable (12) Color developing → bleaching → bleach-fixing → stable (13) Color developing → bleach-fixing → fixing → Stable (14) Color development → Bleaching and fixing → Bleaching and fixing → Stable (15) Color developing → Fixing → Bleaching and fixing → Stable (16) Color developing → Bleaching → Bleaching and fixing → Fixing → Stable (17) Black and white development → Washing → Reversing → Color development → washing → adjustment →
Bleaching → Fixing → Stable (18) Black and white development → Washing → Inversion → Color development → Washing → Adjustment →
Bleaching-fixing → stable In the present invention, preferred processing steps are (1), (2),
(8), (10), (11), (17) step, more preferably
In the steps (2), (8), (11), and (17), (1)
This is step 1).

That is, in the most preferred embodiment of the processing method of the present invention, the stabilizing solution immediately after the processing with the processing solution having the bleaching ability and / or the processing solution having the fixing ability, preferably after the processing with the processing solution having the fixing ability, Is performed. In the present invention, a processing solution having bleaching ability refers to, for example, a bleaching solution or bleach-fix in the above-mentioned processing step, and a processing solution having fixing ability refers to, for example, a fixing solution or a bleach-fixing solution. .

As a bleaching agent used in the bleaching solution or the bleach-fixing solution, a metal complex salt of an organic acid is used. The metal complex salt has an action of oxidizing a metal salt formed by development to convert it to silver halide. The composition is such that it is complexed with a metal ion such as iron, cobalt or copper with an organic acid such as aminopolycarboxylic acid or oxalic acid or citric acid. Most preferred organic acids used to form such metal complexes of organic acids include polycarboxylic acids or aminopolycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

Specific representative examples of these organic acids include:
The following can be mentioned.

[1] Ethylenediaminetetraacetic acid [2] Diethylenetriaminepentaacetic acid [3] Ethylenediamine-N- (β-oxyethyl) -N,
N ', N'-triacetic acid [4] 1,3-propylenediaminetetraacetic acid [5] nitrilotriacetic acid [6] cyclohexanediaminetetraacetic acid [7] iminodiacetic acid [8] dihydroxyethylglycine citric acid

[9] Ethyl ether diamine tetraacetic acid [10] Glycol ether diamine tetraacetic acid [11] Ethylene diamine tetrapropionic acid [12] Phenylenediamine tetraacetic acid The bleaching solution used contains a metal complex salt of an organic acid as described above as a bleaching agent. In addition, various additives can be included. As the additives, in particular, alkali halides or ammonium halides, for example, potassium bromide, sodium bromide, sodium chloride, rehalogenating agents such as ammonium bromide, metal salts, chelating agents, acetates and commonly known bleaching accelerators. Desirably, it is contained. Further, pH buffers such as borates, oxalates, acetates, carbonates, and phosphates, and alkylamines, polyethylene oxides, and the like which are known to be added to normal bleaching solutions can be appropriately added. .

Further, the fixing solution and the bleach-fixing solution include sulfites such as ammonium sulfite, potassium sulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, boric acid, borax, sodium hydroxide, and the like. A single or two or more pH buffers comprising various salts such as potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide can be contained.

In the present invention, in order to increase the activity of the bleaching solution or the bleach-fixing solution, air may be blown in the bleaching bath or the bleach-fixing bath and in the storage tank of the bleaching replenisher or the bleach-fixing replenisher, or oxygen may be added. You may blow in,
Alternatively, a suitable oxidizing agent such as hydrogen peroxide, bromate,
Persulfate and the like may be appropriately added.

The pH of the bleaching solution used in the present invention is usually 2.
5 to 6.5, preferably 3.0 to 5.0.

The pH of the fixing solution used in the present invention is usually 5.
It is 0-8.0, preferably 5.5-7.5. The pH of the bleach-fix solution is preferably used in the range of 4.5 to 6.8.

Another preferred embodiment of the processing method of the present invention is a method in which part or all of the overflow solution of the color developing solution of the present invention flows into a bleaching solution or a bleach-fixing solution in the subsequent step. Can be This is because when a certain amount of the color developing solution flows into the bleaching solution or bleach-fixing solution, the generation of sludge in the bleaching solution or bleach-fixing solution is suppressed, and more surprisingly, the effect of recovering silver from the bleach-fixing solution is improved. Is also improved.

In addition to the above-mentioned method, when the part or all of the overflow of the stabilizing solution in the subsequent step is poured into the bleach-fixing solution or the fixing solution, the above-mentioned effect is particularly excellent. The silver halide used in the silver halide emulsion layer of the light-sensitive material used in the processing method of the present invention is not particularly limited. For example, silver chlorobromide, silver iodobromide, silver chloride and silver chloroiodobromide are used. Can be The total coating amount of silver in the light-sensitive material is preferably 2 g / m ² or more, more preferably in the range of 3 to 10 g / m ^2.

When the silver halide emulsion is made of a solid solution crystal such as silver chlorobromide or silver chloroiodobromide, silver bromide or silver iodide is localized at a specific portion of the silver halide grain crystal. preferable. When the silver halide grains are silver chlorobromide, the silver bromide is preferably at or near the term point of the silver halide crystal. Such a silver halide emulsion is prepared by adsorbing a sensitizing dye or an inhibitor onto silver chloride or silver chlorobromide crystal grains and then ripening by adding silver bromide fine particles, or adding a water-soluble bromide solution. It can be obtained by addition and halogen substitution.

When the silver halide grains are silver chloroiodobromide, the silver iodide is preferably localized inside the silver iodide grains. A silver halide emulsion in which silver iodide is localized inside the grains can be obtained by depositing silver chloride or silver chlorobromide on a core containing silver iodide. For the deposition of silver chloride or silver chlorobromide, a known silver halide crystal growth method such as a double jet method or Ostwald ripening method can be used.

The core preferably has a silver iodide content of 10 mol% or more, more preferably 15 to 40 mol%.
The core is preferably silver iodobromide.

The above silver halide emulsion is described in JP-A-64-694.
No. 1, 64-26839 and JP-A-1-121848, 1-138550
The method can be made by the method described in Japanese Patent Publication No.

When the silver halide grains according to the present invention contain silver iodide, the content relative to the whole grains is preferably 20 mol% or less, more preferably 12 mol% or less, and particularly preferably 0 to 5 mol%.

The silver halide grains according to the present invention may be normal crystals such as cubic, tetradecahedral or octahedral, or twins such as tabular. The shape of the crystal can be controlled by appropriately selecting pAg, pH and the like during mixing. or,
Octahedral and tabular grains are described, for example, in JP-A-58-11935 and
-11936, 58-11937, 58-108528, 62-163046
As described in JP-A Nos. 63-41845 and 63-212932, the silver halide grains can be obtained by growing crystals in the presence of an adsorbing sensitizing dye or a control agent.

The silver halide grains according to the present invention preferably have an average grain size of 0.05 to 10 μm, more preferably
It is 0.1-5 μm, particularly preferably 0.2-3 μm.

The silver halide grains according to the present invention can be used in combination with other silver halide grains as long as the effects of the present invention are not impaired. At this time, the weight of the silver halide grains according to the invention is preferably at least 30%, more preferably at least 50%, particularly preferably at least 80%.

The localization of halogen in a silver halide grain is represented by X
It can be confirmed by examining sections of silver halide grains dispersed in a resin by a X-ray microanalysis method or a line diffraction method.

The silver halide emulsion according to the present invention is preferably monodisperse.

In the present invention, the monodispersity means an average particle diameter d.
Means that the weight of silver halide contained within a grain size range of ± 20% is 70% or more of the total weight of silver halide,
It is preferably at least 80%, more preferably at least 90%.

Here, the average particle diameter d is defined as the particle diameter di when the product ni × di ³ of the frequency ni and di ³ of the particles having the particle diameter di becomes maximum (three significant digits, the minimum digit). The number is 4
Round off 5). Here, the particle diameter is a diameter when a projected image of the particle is converted into a circular image having the same area.

The particle size can be measured, for example, by dispersing the particles on a flat sample table so as not to overlap, taking an image at a magnification of 10,000 to 50,000 times with an electron microscope, and measuring the particle diameter on the print or the diameter at the time of projection. The highly preferred monodisperse emulsion of the present invention can be obtained by actually measuring the area (the number of measured particles is indiscriminately 1000 or more). ) X 100 = width of distribution
The distribution defined by (%) is less than or equal to 20%,
It is more preferably at most 15%.

Here, the method for measuring the particle size is in accordance with the above-mentioned measuring method, and the arithmetic mean of the average particle size is used.

Average grain size = (Σdini) / Σni In the silver halide color photographic light-sensitive material of the present invention, a silver halide emulsion other than the silver halide emulsion of the present invention is Research Disclosure 308119 (hereinafter abbreviated as RD308119).
Can be used. The following table shows the locations. [Item] [Page of RD308119] Iodine composition 993 IA Item Production method 993 IA and 994 E Crystal habit Normal crystal 993 IA item Twin 〃 Epitaxial 〃 Halogen composition Uniform 993 IB Item 1 Unsatisfactory 〃 Halogen conversion 994 IC section 置換 Substitution 〃 Metal-containing 994 ID section Monodisperse section 995 IF Section Solvent addition 潜 Latent image formation position Surface 995 Ig section Inside 〃 Applicable photosensitive material negative 995 IH Item Positive (including internal fog grains) 用 い る Use of a mixture of emulsions Item 995 IJ Item Desalting Item 995 II-A In the present invention, the silver halide emulsion is prepared by physical ripening, chemical ripening and spectral sensitization. Use Additives used in such processes are
No.17643, No.18716 and No.308119 (hereinafter referred to as RD1
7643, RD18716 and RD308119).

The following table shows the locations described.

[Item] [Page of RD308119] [RD17643] [RD18716] Chemical sensitizer 996 Section III-A 23 648 Spectral sensitizer 996 IV-AA, B, C, D, E, H, I, J Item 23-24 648-9 Supersensitizer 996 IV-AE, J Item 23-24
648-9 Antifoggants 998 VI 24-25 649 Stabilizers 998 VI 24-25 649 Known photographic additives which can be used in the present invention are also described in the above-mentioned Research Disclosure. The following table shows relevant descriptions.

[Item] [RD308119 page] [RD17643] [RD18716] Anti-turbidity agent 1002 VII-I 25 650 Dye image stabilizer 1001 VII-J 25 Brightener 998 V 24 UV absorber 1003 VIII C , XIII C 25-26 Light absorber 1003 VIII 25-26 Light scattering agent 1003 VIII Filter dye 1003 VIII 25-26 Binder 1003 IX 26 651 Static inhibitor 1006 XIII 27 650 Hardener 1004 X 26 651 Plasticizer 1006 XII 27 650 Lubricant 1006 XII 27 650 Activator / Coating aid 1005 XI 26-27 650 Matting agent 1007 XVI Developer (contained in photosensitive material) Section 1011 XX-B Various photosensitive materials used in the present invention Couplers can be used, examples of which are described in Research Disclosure, supra. The following table shows relevant descriptions.

[Item] [Page of RD308119] [RD17643] [RD18716] Yellow coupler 1001 VII-D VIIC-G Magenta coupler 1001 VII-D VII C-G cyan coupler 1001 VII-D VIIC ~ G DIR coupler 1001 VII-F VIIF BAR coupler 1002 VII-F Other useful residue releasing coupler 1001 VII-F Alkali-soluble coupler 1001 VII-E The additive used in the present invention is: It can be added by the dispersion method described in RD308119 XIV or the like.

In the present invention, the aforementioned RD17643, page 28, RD
The supports described in pages 18716 647-8 and RD308119 XIX can be used.

The light-sensitive material of the present invention includes the aforementioned RD308119 VII
An auxiliary layer such as a filter layer or an intermediate layer described in the section -K can be provided.

The light-sensitive material of the present invention is the same as that of the aforementioned RD308119 VII-K
Various layer configurations such as a normal layer, a reverse layer, and a unit configuration described in the section can be adopted.

In the present invention, when the magenta coupler represented by the following general formula [MI] is used, the intended effects of the present invention are exhibited more favorably.

[0127]

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In the general formula [MI], Z represents a group of nonmetal atoms necessary to form a nitrogen-containing heterocyclic ring, and the ring formed by Z may have a substituent. X represents a hydrogen atom or a group capable of leaving by reaction with an oxidized form of a color developing agent, and R represents a hydrogen atom or a substituent.

The substituent represented by R is not particularly limited, but typically includes groups such as alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, and cycloalkyl. Other halogen atoms and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano,
Alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclicthio Each group, a spiro compound residue, a bridged hydrocarbon compound residue and the like are also included.

The alkyl group represented by R preferably has 1 to 32 carbon atoms, and may be linear or branched. As the aryl group represented by R, a phenyl group is preferable.
Examples of the acylamino group represented by R include an alkylcarbonylamino group and an arylcarbonylamino group. Examples of the sulfonamide group represented by R include an alkylsulfonylamino group and an arylsulfonylamino group. The alkyl component and the aryl component in the alkylthio group and the arylthio group represented by R include the alkyl group and the aryl group represented by R. The alkenyl group represented by R is preferably a group having 2 to 32 carbon atoms, and the cycloalkyl group is preferably a group having 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms. The alkenyl group may be linear or branched.
The cycloalkenyl group represented by R has 3 to 3 carbon atoms.
12, especially 5-7 are preferred. Examples of the sulfonyl group represented by R include an alkylsulfonyl group and an arylsulfonyl group; examples of the sulfinyl group include an alkylsulfinyl group and an arylsulfinyl group; An acylcarbonyl group such as an alkylcarbonyl group or an arylcarbonyl group; a carbamoyl group such as an alkylcarbamoyl group or an arylcarbamoyl group; a sulfamoyl group such as an alkylsulfamoyl group or an arylsulfamoyl group; As an acyloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group, etc .; as a carbamoyloxy group, an alkylcarbamoyloxy group, an arylcarbamoyloxy group, etc .; A killureido group, an arylureido group or the like; a sulfamoylamino group such as an alkylsulfamoylamino group or an arylsulfamoylamino group; or a 5- to 7-membered heterocyclic group is preferable. A furyl group, a 2-thienyl group, a 2-pyrimidinyl group, a 2-benzothiazolyl group or the like; the heterocyclic oxy group preferably has a 5- to 7-membered heterocyclic ring, for example, 3,4,5,6-tetrahydropyranyl -2-oxy group, 1
-Phenyltetrazole-5-oxy group and the like; As the heterocyclic thio group, a 5- to 7-membered heterocyclic thio group is preferable.
Pyridylthio group, 2-benzothiazolylthio group, 2,4-diphenoxy-1,3,5-triazole-6-thio group and the like; siloxy groups such as trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group and the like; imide As a succinimide group, 3-heptadecylsuccinimide group, phthalimide group, glutarimide group, etc .; as a spiro compound residue, spiro [3.3] heptane-1-yl etc .; as a bridged hydrocarbon compound residue bicyclo [2.2.1] heptane-1-yl, tricyclo [3.3.1.1 ^{3 7]} decan-1-yl, 7,7-dimethyl - bicyclo [2.2.1] heptane-1-yl, and the like.

Examples of the group capable of leaving by reaction with the oxidized form of the color developing agent represented by X include, for example, a halogen atom (a chlorine atom, a bromine atom, a fluorine atom, etc.), alkoxy, aryloxy, heterocyclic oxy, acyloxy, sulfonyl Oxy, alkoxycarbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocyclic ring bonded with an N atom,
Alkyloxycarbonylamino, aryloxycarbonylamino, carboxyl,

[0132]

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(R ₁ ′ has the same meaning as R, Z ′ has the same meaning as Z, and R ₂ ′ and R ₃ ′ represent a hydrogen atom, an aryl group, an alkyl group or a heterocyclic group.) And preferably a halogen atom, particularly a chlorine atom.

Examples of the nitrogen-containing heterocyclic ring formed by Z or Z 'include a pyrazole ring, an imidazole ring, a triazole ring, and a tetrazole ring. Those mentioned are mentioned.

The compound represented by the general formula [MI] is more specifically represented by the following general formulas [M-II] to [M-VII].

[0136]

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In the general formulas [M-II] to [M-VII], R _{1 to} R ₈ and X have the same meanings as R and X.

Among the general formulas [MI], preferred are those represented by the following general formula [M-VIII].

[0139]

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In the general formula [M-VII], R, X and Z ₁ have the same meanings as R, X and Z in the general formula [MI].

Among the magenta couplers represented by the general formulas [M-II] to [M-VII], particularly preferred are magenta couplers represented by the general formula [M-II].

A substituent which the ring formed by Z in the general formula [MI] and the ring formed by Z ₁ in the general formula [M-VIII] may have;
As R _{2 to} R ₈ in -II] to [M-VI], those represented by the following general formula [M-IX] are preferable.

In the formula [M-IX] -R ¹ -SO ₂ -R ² , R ¹ represents an alkylene group, and R ² represents an alkyl group, a cycloalkyl group or an aryl group.

The alkylene group represented by R ¹ preferably has 2 or more carbon atoms in the straight-chain portion, more preferably 3 to 6 carbon atoms.
And may be linear or branched.

The cycloalkyl group represented by R ² is preferably a 5- or 6-membered cycloalkyl group.

When used for positive image formation, the most preferable substituents R and R ₁ on the heterocyclic ring are those represented by the following general formula [MX].

[0147]

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In the formula, R ₉ , R ₁₀ and R ₁₁ have the same meanings as R described above.

Two of R ₉ , R ₁₀ and R ₁₁ , for example, R ₉ and R ₁₀ are bonded to form a saturated or unsaturated ring (for example, cycloalkane, cycloalkene, heterocycle). R ₁₁ may be bonded to the ring to form a bridged hydrocarbon compound residue.

Among the general formulas [M-X], preferred are:
(i) when at least two of R _{9 to} R ₁₁ are an alkyl group, (ii) one of R _{9 to} R ₁₁ , for example, R ₁₁ is a hydrogen atom, and the other two R ₉ and R 11 _{When 10} are combined to form a cycloalkyl with the root carbon atom.

[0151] Even more preferred among the (i) is, R ₉ ~
Two of R ₁₁ are alkyl groups and the other one is a hydrogen atom or an alkyl group.

[0152] Further, when used in negative image formation, the most preferred as substituents R and R ₁ on the heterocyclic is represented by the following general formula [M-XI]. General formula [M-XI] R ₁₂ -CH ₂ -In general formula [M-XI], R ₁₂ has the same meaning as R described above. Preferred as R ₁₂ is a hydrogen atom or an alkyl group.

The following are typical specific examples of the compound represented by the formula [MI].

[0154]

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[0155]

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Exemplified compounds 11 to 19 described in Japanese Patent Application No. 2-239283, pp. 103-104.

[0157]

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Illustrative compounds 25 to 28 described on page 106 of Japanese Patent Application No. 2-239283.

[0159]

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Illustrative compounds 34 to 38 described on page 108 of Japanese Patent Application No. 2-239283.

[0161]

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Illustrative compounds 44 to 56 described on pages 110 to 112 of Japanese Patent Application No. 2-239283.

[0163]

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[0164]

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Illustrative compounds 66 to 73 described on pages 115 to 116 of Japanese Patent Application No. 2-239283.

[0166]

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[0167]

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Illustrative Compounds 84 to 90 described in Japanese Patent Application No. 2-239283, pp. 119 to 120 In addition to the typical specific examples of the compounds represented by the general formula [MI], Specific examples of the compound represented by the formula [MI] include compounds Nos. 1 to 4 and 6 among compounds described on pages (18) to (32) of JP-A-62-166339. , 8-1
7,19-24,26-43,45-59,61-104,106-121,123-
162, 164 to 223.

The coupler represented by the general formula [MI] is available from Journal of the Chemical Society (Journal).
of the Chemical Society), Perkin I (197
7), 2047-2052, U.S. Pat.No. 3,725,067, JP-A-59-994
No. 37, No. 58-42045, No. 59-162548, No. 59-171956
No. 60-33552, No. 60-43659, No. 60-172982,
The compounds can be synthesized with reference to JP-A-60-190779, JP-A-62-209457 and JP-A-63-307453.

[0170] The couplers represented by formula (M-I) usually 1 mol of silver halide per 1 × 10 ^{- 3} mol to 1 mol, preferably 1 × 10 ^-2 mol to 8 × 10 ^-1 mol range Can be used.

The above couplers can be used in combination with other types of magenta couplers. The present invention can be applied to color photographic light-sensitive materials such as color negative films for general use or movies, and color reversal films for slides or televisions.

[0172]

EXAMPLES Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited to these examples.

Example 1 On a triacetylcellulose film support, each layer having the following composition was formed sequentially from the support side to prepare a multilayer color photographic material sample.

The amount of addition in the silver halide photographic light-sensitive material indicates the number of grams per 1 m ² unless otherwise specified. Silver halide and colloidal silver are shown in terms of silver. However, the sensitizing dye is represented by the number of moles per mole of silver halide in the same layer.

(Photosensitive Material Sample) First Layer; Anti-halation Layer Black Colloidal Silver 0.2 UV Absorber (UV # 1) 0.23 High Boiling Solvent (Oil # 1) 0.18 Gelatin 1.4 Second Layer; First Intermediate Layer Gelatin 1.3 3 layers; low-sensitivity red-sensitive emulsion layer Silver iodobromide emulsion (average particle size 0.4 μm, AgI 2.0 mol%) 1.0 sensitizing dye (SD─1) 1.8 × 10 ^-5 (mol / silver 1 mol) sensitizing dye (SD─2) 2.8 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (SD─3) 3.0 × 10 ^-4 (mol / silver 1 mol) Cyan coupler (C (1) 0.70 Colored cyan coupler (CC ─1) 0.066 DIR compound (D─1) 0.03 DIR compound (D-3) 0.01 High boiling solvent (Oil ─1) 0.64 Gelatin 1.2 Fourth layer; middle-sensitivity red-sensitive emulsion layer Silver iodobromide emulsion (average grain size) 0.7 μm, AgI 8.0 mol%) 0.8 Sensitizing dye (SD─1) 2.1 × 10 ^-5 (mol / silver 1 mol) Sensitizing dye (SD─2) 1.9 × 10 ^-4 (mol / silver 1 mol) Impression Element (SD─3) 1.9 × 10 ^-4 (mol / silver 1 mol) Cyan coupler (C─2) 0.28 Colored cyan coupler (CC─1) 0.027 DIR compound (D─1) 0.01 High boiling solvent (Oil─1) 0.26 gelatin 0.6 5th layer; high-sensitivity red-sensitive emulsion layer Silver iodobromide emulsion (average particle size 0.8 μm, AgI 8.0 mol%) 1.70 sensitizing dye (SD─1) 1.9 × 10 ^-5 (mol / silver 1) (Mol) Sensitizing dye (SD # 2) 1.7 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (SD # 3) 1.7 × 10 ^-4 (mol / silver 1 mol) Cyan coupler (C # 1) 0.05 Cyan coupler (C # 2) 0.10 Colored cyan coupler (CC # 1) 0.02 DIR compound (D # 1) 0.025 High boiling point solvent (Oil # 1) 0.17 Gelatin 1.2 6th layer; Second intermediate layer Gelatin 0.8 7th layer; Low-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion (average particle size 0.4 μm, AgI 2.0 mol%) 1.1 Sensitizing dye (SD (4) 6.8 × 10 ^-5 (mol / silver 1 mol) Sensitizing dye (SD─ 5) 6.2 × 10 ^-4 ( Mol / silver 1 mol) Magenta coupler (M─1) 0.54 Magenta coupler (M─2) 0.19 Colored magenta coupler (CM─1) 0.06 DIR compound (D─2) 0.017 DIR compound (D─3) 0.01 High boiling solvent (Oil # 1) 0.81 seratin 1.8 eighth layer; middle-sensitivity green-sensitive emulsion layer silver iodobromide emulsion (average particle size 0.7 .mu.m, AgI 8.0 mol%) 0.7 sensitizing dye (SD @ 6) 1.9.times.10.sup.- ⁴ ( Mol / silver 1 mol) Sensitizing dye (SD─7) 1.2 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (SD─8) 1.5 × 10 ^-5 (mol / silver 1 mol) Magenta coupler (M # 1) 0.07 Magenta coupler (M # 2) 0.03 Colored magenta coupler (CM # 1) 0.04 DIR compound (D # 2) 0.018 High boiling solvent (Oil # 2) 0.30 Gelatin 0.8 Ninth layer; High sensitivity green-sensitive emulsion layer silver iodobromide emulsion (average particle size 1.0 .mu.m, AgI 8.0 mol%) 1.7 sensitizing dye (SD─6) 1.2 × 10 ^-4 (mol / mole of silver) sensitizing dye (SD─7 1.0 × 10 ^-4 (mol / mole of silver) Sensitizing dye (SD─8) 3.4 × 10 ^-6 (mol / mole of silver) Magenta Coupler (M─1) 0.09 Magenta Coupler (M─3) 0.04 Colored magenta Coupler (CM # 1) 0.04 High boiling point solvent (Oil # 2) 0.31 Gelatin 1.2 10th layer; Yellow filter layer Yellow colloidal silver 0.05 Color stain inhibitor (SC-1) 0.1 High boiling point solvent (Oil-2) 0.13 Gelatin 0.7 Formalin Scavenger (HS-1) 0.09 Formalin Scavenger (HS-2) 0.07 11th layer; low-sensitivity blue-sensitive emulsion layer Silver iodobromide emulsion (average grain size: 0.4 μm, AgI: 2.0 mol%) 0.5 Silver iodobromide Emulsion (average particle size 0.7 μm, AgI 8.0 mol%) 0.5 sensitizing dye (SD─9) 5.2 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (SD─10) 1.9 × 10 ^-5 (mol / (1 mol of silver) Yellow coupler (Y # 1) 0.65 Yellow coupler (Y # 2) 0.24 DIR compound (D # 1) 0.03 High Boiling point solvent (Oil # 2) 0.18 Gelatin 1.3 Formalin scavenger (HS-1) 0.08 12th layer; high-sensitivity blue-sensitive emulsion layer Silver iodobromide emulsion (average particle size 1.0 μm, AgI 8.0 mol%) 1.0 Sensitizing dye ( SD─9) 1.8 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (SD─10) 7.9 × 10 ^-5 (mol / silver 1 mol) Yellow coupler (Y (1) 0.15 Yellow coupler (Y─2 ) 0.05 High boiling solvent (Oil # 2) 0.074 Gelatin 1.30 Formalin scavenger (HS-1) 0.05 Formalin scavenger (HS-2) 0.12 13th layer; 1st protective layer Fine grain silver iodobromide emulsion (average particle size 0.08 μm, AgI 1.0 mol%) 0.4 Ultraviolet absorber (UV─1) 0.07 Ultraviolet absorber (UV─2) 0.10 High boiling solvent (Oil─1) 0.07 High boiling solvent (Oil─3) 0.07 Formalin scavenger (HS-1) 0.13 Formalin Scavenger (HS-2) 0.37 Seuratin 1.3 Layer 14; 2 Protective layer Alkali-soluble matting agent (average particle size 2 μm) 0.13 Polymethyl methacrylate (average particle size 3 μm) 0.02 Slip agent (WAX-1) 0.04 Gelatin 0.6 In addition to the above composition, coating aids Su-1, Dispersing aid Su-2, viscosity modifier, hardener H-1, H-2, stabilizer ST-1, antifoggant AF-1, Mw: 100000 and M
w: 1.100000 two kinds of AF-2 were added.

The emulsion used in the above sample was a monodisperse surface-low silver iodide-containing emulsion, which was optimally subjected to gold / sulfur sensitization according to a conventional method. Incidentally, the average particle size is shown by a particle size converted into a cube.

[0177]

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[0178]

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[0179]

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[0180]

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[0181]

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[0182]

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[0183]

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[0184]

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After exposing the color negative film produced by the above method, the film was processed by a short reader type automatic developing machine using the following processing steps and processing solutions.

The short reader was used repeatedly without washing.

Processing Step Processing Time Processing Temperature Complementary Amount Color Development 3 min 15 sec 38 ° C Described in Table 1 Bleaching 30 sec 38 ° C 155 ml Fixing 60 sec 38 ° C 500 ml Stabilizing 20 sec 38 ° C 775 ml Drying 60 sec 40 to 70 ° C. - (. replenishing amount is a value per photosensitive material 1 m ²⁾ * stable Kaso is a method in 3 tank countercurrent.

[Color developing tank solution] diethylenetriaminepentaacetic acid 1.0 g potassium sulfite 3.6 g potassium carbonate 30.0 g sodium bromide 1.2 g potassium iodide 1.8 mg hydroxylamine sulfate 2.5 g 4-amino-3-methyl-N-ethyl-N -(β-Hydroxyethyl) aniline sulfate 4.2g Add water to make up to 1L, and adjust to pH 1 with sulfuric acid or KOH solution.
Adjust to 0.01.

[Color developing replenisher] diethylenetriaminepentaacetic acid 1.0 g potassium sulfite 4.6 g potassium carbonate 3.0 g hydroxylamine sulfate 3.2 g 4-amino-3-methyl-N-ethyl-N- (β-hydroxylethyl) aniline sulfate 5.6g Add water to make up to 1L, and add sulfuric acid or KOH solution to pH1.
Adjust to 0.01.

The composition of the bleaching solution used is as follows.

Ferric ammonium 1,3-propylenediaminetetraacetate 100.0 g 1,3-propylenediaminetetraacetic acid 5.0 g Ammonium bromide 120.0 g Glacial acetic acid 50.0 ml Water was added to make 1 liter, and ammonia water or glacial acetic acid was used. PH was adjusted to 3.50.

The composition of the bleaching replenisher used was as follows.

1.3- Ferric ammonium ferric propylenediaminetetraacetate 130.0 g Disodium ethylenediaminetetraacetate 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 70.0 ml Water was added to 1 liter, and the pH was adjusted to 4.40 with aqueous ammonia or glacial acetic acid. adjust.

The compositions of the fixing tank liquid and the fixing replenisher used are as follows.

Ammonium thiosulfate 150.0 g Ammonium thiocyanate 170.0 g Anhydrous sodium bisulfite 12.0 g Sodium metabisulfite 2.5 g Disodium ethylenediaminetetraacetate 0.5 g Water was added to make 1 liter, and p was adjusted with acetic acid and aqueous ammonia.
Adjust to H7.0.

The compositions of the stabilizing tank liquid and the stabilizing replenisher used are as follows.

Compounds described in Table 1 5-Chloro-2-methyl-4-isothiazolin-3-one 0.05 g Emulgen 810 1.0 ml Polyvinylpyrrolidone K-17 (manufactured by BASF) 0.05 g Water was added to make 1 l, and ammonia water and PH at 50% sulfuric acid
Adjusted to 7.0.

As shown in Tables 7 and 8 below, continuous processing was carried out by changing the replenishing amount of the color developing solution and the additives in the stabilizing solution. The continuous processing was performed continuously such that the total amount of the replenisher for color development replenished was 5 times the capacity of the color development tank.

The state of occurrence of scum in the color developing tank was observed, and evaluations were made of no occurrence, slight occurrence, and occurrence. Those marked with two marks represent an intermediate rating.
(The same applies to the following examples.) When the green transmission density of the highest density portion of the processed film sample is measured after the running test is completed, and a formaldehyde-added stabilizing solution (formaldehyde 37% solution 1.2 ml / l) is used. The deviation from the reference density with respect to the density at the start of the continuous processing is shown in%.

Further, the processed film sample was stored at 60 ° C. and 60% for 10 days, and the difference in green density around density 1.0 before and after storage was determined.

The above results are summarized in Tables 7 and 8.

[0202]

[Table 7]

[0203]

[Table 8]

As shown in Tables 7 and 8 above, when the compound of the present invention was added to the stabilizing solution, even after storage of the photographic material under high temperature and high humidity, there was no decrease in green density near 1.0, and the photographic material was continuous. In the processing, even if the stabilizing solution is brought into the color developing solution by the short reader, the scum which is generated when the stabilizing solution containing formaldehyde is used is not generated.

Further, when a stabilizing solution containing formaldehyde is used, the concentration of green is remarkably reduced as the replenishing rate is reduced. However, when the stabilizing solution containing the compound of the present invention is used, continuous processing is performed. In the range of the replenishing amount according to the present invention, especially when the replenishing amount is 30 to 300 ml per 1 m ^{2, the} effect of preventing a decrease in green density is large.

Example 2 The same experiment as in Example 1 was carried out except that the total amount of silver halide applied to the light-sensitive material used in Example 1 was changed as shown in Table 9. However, Exemplified Compound A is contained in the color developer.
-1 was added in place of hydroxylamine sulfate. Table 9 shows the results.

[0207]

[Table 9]

As shown in Table 9, the use of the stabilizer to which the compound of the present invention was added, as compared with the case where the stabilizer to which formaldehyde was added was used, the occurrence of scum was also reduced.
Also, it can be seen that the effect of reducing the density of the green is large particularly when a photosensitive material having a coated silver amount of 2.0 g or more per m ² of the photosensitive material is processed.

Example 3 The magenta coupler (M-2) in the color negative film sample prepared in Example 1 was replaced with a magenta coupler represented by the above general formula [M-1], specifically, exemplified magenta couplers 1 and 2. , 4,10,20,21,31,40,60,63,64,74,
The same experiment as in Example 1 was carried out, except for changing to 76 and 81, respectively.

As a result, the green density was further reduced by 10%.
~ 20% improvement. The scum was also slightly improved overall.

[0211]

According to the present invention, by adding the compound of the present invention to a stabilizing solution, it is possible to prevent the occurrence of scum in the color developing solution even when the color developing solution is replenished at a low level, and to provide a magenta dye. Is improved.

Continuation of front page (58) Field surveyed (Int.Cl. ⁶ , DB name) G03C 11/00 501

Claims (2)

(57) [Claims] 1. A silver halide color photographic light-sensitive material was color developing processing having fixing ability liquid (however, the constant-Chakuno
The processing solution has a bleach-fixing solution, and is 1 × 1 per liter.
0 ^-3 except when containing 2.0 moles of bromide ions
Was treated with Ku), then the method for processing a silver halide color photographic material to be processed with a stabilizing solution, the replenishment rate of the color developer is a silver halide color photographic light-sensitive material 1 m ² per 10～900Ml,且前Symbol The stabilizer is represented by the following general formula [I]
A method for processing a silver halide color photographic light-sensitive material, characterized by containing at least one compound selected from the compounds represented by the following formula: General formula [I] [In the formula, Z represents a group of atoms necessary to form a substituted or unsubstituted carbon ring or a substituted or unsubstituted heterocyclic ring,
X is an aldehyde group, (R ₁ and R ₂ each represent a lower alkyl group.)
n represents an integer of 1 to 4. ] 2. The silver halide color photographic light-sensitive material according to claim 1, wherein Z in the general formula [I] is a substituted aromatic carbon ring or a substituted heterocyclic ring. Processing method.