JP2794034B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

Description: 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 method for improving the white background and enhancing the image storability of a dye image after processing. The present invention relates to a method for processing a silver halide color photographic light-sensitive material having a silver halide emulsion layer containing silver halide grains comprising 90 mol% or more of silver chloride.

BACKGROUND OF THE INVENTION Generally, in a method of forming a dye image by processing a silver halide color photographic light-sensitive material, an imagewise exposure is applied, and then an oxidized p-phenylenediamine-based color developing agent and a dye image forming coupler are used. To form a dye image. In this method, a color reproduction method based on an ordinary color reduction method is applied, and cyan, magenta and yellow dye images corresponding to red, green and blue are formed on respective photosensitive layers. In recent years, in forming such a dye image, in order to shorten the development processing time, high-temperature development processing and omission of processing steps are generally performed. In particular, in order to shorten the development time, it is extremely important to increase the development speed in color development. The development speed in color development is affected in two directions. One is a silver halide color photographic light-sensitive material, and the other is a color developing solution. In the former case, in particular, the composition of the silver halide emulsion grains used greatly affects the development speed, and in the latter case, the conditions and composition of the color developing solution greatly affect the development speed.

In view of the prior art, for example, the rapid processing technology has a specific structure as described in JP-A-56-64339, for example, as described in JP-A-51-77223. A technique of adding 1-aryl-3-pyrazolidone to a silver halide color photographic light-sensitive material, further described in JP-A-57-144457, JP-A-58-50534, JP-A-58-50535,
A technique of adding a 1-arylpyrazolidone as described in JP-A-58-50536 to a silver halide color photographic light-sensitive material is known, and an exposed silver halide color photographic light-sensitive material is converted to an aromatic silver photographic light-sensitive material. A technique of using a color development accelerator when developing using a primary amine color developing agent is also known. For example, as such a color development accelerator, U.S. Pat. Nos. 2,950,970, 2,515,147,
496,903, 4,038,075, 4,119,462, UK patent
Nos. 1,430,998, 1,455,413, JP-A-53-15831, and 5
5-62450, 55-62451, 55-62452, 55-62
No. 453, No. 51-12422, No. 55-62453, Special Publication No. 51-124
22 and 55-49728.

However, these conventional techniques have problems in that rapid processing is insufficient, and there are problems in the storability of photosensitive materials and processing solutions.

However, Japanese Patent Application Laid-Open Nos. 62-246051, 62-249148 and
No. 62-246055 discloses a technique capable of rapid processing by converting silver halide to high silver chloride. However, as the color development processing time is reduced, the white background, which is thought to be related to the dyeing property of the fluorescent whitening agent, greatly fluctuates, particularly when benzyl alcohol is present. It has been found.

Also, it was thought that the storage stability of the dye image was reduced by rapid processing, but surprisingly, the dark fading property of the dye image,
In particular, it has been found that the effect is great for the dark fading property of cyan.

[Object of the Invention] An object of the present invention is to provide a method for processing a silver halide color photographic light-sensitive material, which has improved photographic characteristics, especially white background, and excellent storage stability of a dye image obtained by processing. It is.

[Constitution of the Invention] The processing method of the present invention that achieves the above object is to provide a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer containing at least 90 mol% of silver chloride on a support. In the step of performing color development, bleach-fixing and washing with water, the color developer for color development contains a hydroxylamine derivative represented by the following general formula [I] and a sulfite of 4 × 10 ^−. Contains not more than ³ mol / 1, contains substantially no benzyl alcohol, has a color development processing time of 3 seconds to 20 seconds, a bleach-fix processing time of 5 to 30 seconds, and a water-washing processing time of 5 to 30 seconds. 50 seconds, and all the processing steps of the color development processing time, the bleach-fixing processing time, and the washing processing time are 13 seconds or more and 1 minute and 35 seconds or less.

In the formula, R ₁ and R ₂ each represent an alkyl group or a hydrogen atom. However, both R ₁ and R ₂ are not hydrogen atoms at the same time. R ₁ and R ₂ may form a ring.

In a preferred embodiment of the present invention, the amount of washing water in the washing process is 0.
1 to 50 times.

[Effect of the Invention] A silver halide color photographic light-sensitive material (hereinafter sometimes referred to as a silver chloride light-sensitive material) in which a photosensitive silver halide emulsion contains 90 mol% or more of silver chloride is a conventional silver chlorobromide, chloroiodide or silver chloroiodide. Compared to a color photographic light-sensitive material composed of a silver halide emulsion containing silver bromide or silver iodide, such as silver bromide or silver iodobromide emulsion, bromide ion or iodide is developed more rapidly and suppresses the development reaction. Since ions are not accumulated in the color developing solution, it is extremely useful for rapid processing. And silver halide
In the case of an emulsion containing 90 mol% or more of silver chloride, even if a color developing solution containing no benzyl alcohol is used, a dye image which is not inferior to the case where benzyl alcohol is added can be obtained in a short time, In addition, it was found that the whiteness was also improved.

As a result of further study by the present inventors, the silver halide emulsion had a silver chloride content of 90 mol% or more, the color development processing was 3 seconds or more and 20 seconds or less, and the entire processing up to the water washing processing was carried out. The effect of the present invention is remarkably enhanced when the process is performed for a total of 13 seconds or more and 1 minute and 35 seconds or less, and the surprising fact that extremely high rapid processing property and stability of white background and dye preservation are obtained can be obtained. Reached.

Furthermore, the present inventors can achieve a high degree of optimization of the coupling rate and the silver halide development rate when the color developer contains hydroxylamine derivatives substantially without hydroxylamine. Further, the present inventors have found that the bleach-fixing processing time and the rinsing processing time in addition to the color development processing time are specified, and that the dye preservability can be improved by shortening the processing time of all these processing steps. Has succeeded in achieving the above objectives.

The present invention relates to a photosensitive material containing a specific amount of silver chloride, in which a color developing solution contains a specific hydroxylamine derivative and 4 × 10
^-3 mol / l or less with a sulfite, containing substantially no benzyl alcohol, and furthermore, each time of color development, bleach-fix and washing, and the total processing time of all the processing steps of the present invention. It must be within the regulations, and any of the requirements will not achieve the purpose of the present invention.

[Specific Structure of the Invention] The color developing solution used in the present invention includes a compound represented by the general formula [I] (hereinafter referred to as a preservative of the present invention) instead of hydroxylamine conventionally used as a preservative. May be used for speed.

(In the formula [I], R ₁ and R ₂ each represent an alkyl group or a hydrogen atom, provided that R ₁ and R ₂ are not both hydrogen atoms at the same time, and R ₁ and R ₂ form a ring. May be.

Therefore, in the present invention, it is also important not to contain hydroxylamine sulfate.

In the general formula [I], represents R ₁ and R ₂ are each an alkyl group or a hydrogen atom are not hydrogen atoms at the same time, R ₁
And the alkyl groups represented by R ₂ may be the same or different, and are each preferably an alkyl group having 1 to 3 carbon atoms. R ₁
And the alkyl group of R ₂ includes those having a substituent, and R ₁ and R ₂ may combine to form a ring, for example, to form a heterocyclic ring such as piperidine or morpholine.

Specific examples of the hydroxylamine compound represented by the general formula [I] are described in U.S. Pat. Nos. 3,287,125 and 3,293,034.
No. 3,287,124, etc., and particularly preferred specific exemplary compounds are shown below.

These compounds of the present invention usually contain free amine, hydrochloride, sulfate, p-toluenesulfonate, oxalate,
It is used in the form of phosphate, acetate and the like.

The concentration of the compound represented by the general formula [I] of the present invention in the color developing solution is usually 0.2 g / to 50 g /, preferably 0.5 g /
3030 g /, more preferably 1 g / 〜15 g /.

The compound represented by the general formula [I] of the present invention is used in a conventional color developing solution for a silver halide color photographic light-sensitive material in place of hydroxylamine sulfate which has been widely used as a preservative. However, among the compounds of the present invention, for example, N, N-diethylhydroxylamine is known to be used as a preservative for a black-and-white developing agent in a color developing solution to which a black-and-white developing agent is added. In the so-called external color developing method in which a color photographic light-sensitive material is developed by a reversal method using a contained color developing solution, there is a technique used together with phenidone (Japanese Patent Publication No.
22198).

The color developing solution used in the present invention has a sulfite concentration of 4 × 10 ⁻³ mol or less, more preferably 0 to 2 × 10 ⁻⁴ mol per color developing solution 11. When the concentration of sulfurous acid in the color developing solution is high, it is much more susceptible to the effect than a conventionally used silver bromide-containing emulsion, and causes a significant decrease in the concentration.

Examples of the sulfite used in the present invention include sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, and the like.

The color developer used in the present invention contains at least one compound selected from a compound represented by the general formula [II] and a compound represented by the general formula [III] (hereinafter, referred to as a chelating agent of the present invention). Is preferred.

In the general formulas [II] and [III], R ₁ , R ₂ , R ₃ and R ₄ are each a hydrogen atom, a halogen atom, a sulfonic acid group, an alkyl group having 1 to 7 carbon atoms, —OR ₅ , —COOR ₆ , Or, it represents a phenyl group. n ₁ represents an integer of 0 to 3. R ₅ , R ₆ , R ₇ and R ₈ each represent a hydrogen atom or a carbon atom
To 8 alkyl groups. However when R ₂ represents -OH or a hydrogen atom, R ₁ represents a halogen atom, a sulfonic acid group, an alkyl group having 1 to 7 carbon atoms, -OR _5, -COOR _6, Or, it represents a phenyl group.

Examples of the alkyl group represented by R ₁ , R ₂ , R ₃ and R ₄ include a methyl group, an ethyl group, an isopropyl group, an n-propyl group, a t-butyl group, an n-butyl group, a hydroxymethyl group, Examples thereof include a hydroxyethyl group, a methylcarboxylic acid group and a benzyl group. The alkyl group represented by R ₅ , R ₆ , R ₇ and R ₈ has the same meaning as described above, and further includes an octyl group.

Examples of the phenyl group represented by R ₁ , R ₂ , R ₃ and R ₄ include a phenyl group, a 2-hydroxyphenyl group and a 4-aminophenyl group.

Representative specific examples of the chelating agent of the present invention are shown below, but are not limited thereto.

(II-1) 4-isopropyl-1,2-dihydroxybenzene (II-2) 1,2-dihydroxybenzene-3,5-disulfonic acid (II-3) 1,2,3-trihydroxybenzene-5- Carboxylic acid (II-4) 1,2,3-trihydroxybenzene-5-carboxymethyl ester (II-5) 1,2,3-trihydroxybenzene-5-carboxy-n-butyl ester (II-6) 5-t-butyl-1,2,3-trihydroxybenzene (II-7) 1,2-dihydroxybenzene-3,5,6-trisulfonic acid (II-8) 1,2-dihydroxybenzene-3, 4,5-trisulfonic acid (III-1) 2,3-dihydroxynaphthalene-6-sulfonic acid (III-2) 2,3,8-trihydroxynaphthalene-6-sulfonic acid (III-3) 2,3 -Dihydroxynaphthalene-6-carboxylic acid (III-4) 2,3-dihydroxy-8-isoprop Pill - naphthalene (III-5) 2,3- dihydroxy-8-chloro - in-6-sulfonic acid above compounds, particularly preferred compounds used in the present invention include 1,2-dihydroxybenzene-3,5
Examples thereof include disulfonic acid, which can be used as an alkali metal salt such as a sodium salt and a potassium salt.

In the present invention, the chelating agent of the present invention is a developer 1
It can be used in the range of 5 mg to 20 g per day, and preferably 10 mg to 10 g, more preferably 20 mg to 3 g, to obtain good results.

The chelating agent of the present invention may be used alone or in combination of two or more. Furthermore, aminopolyphosphonic acids such as aminotri (methylenesulfonic acid) or ethylenediaminetetraphosphoric acid, oxycarboxylic acids such as citric acid or gluconic acid, phosphonocarboxylic acids such as 2-phosphonobutane-1,2,4-tricarboxylic acid, Other chelating agents such as polyphosphoric acid such as tripolyphosphoric acid or hexametaphosphoric acid may be used in combination.

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

The p-phenylenediamine-based compound having a water-soluble group has less contamination of the photosensitive material than the p-phenylenediamine-based compound having no water-soluble group, such as N, N-diethyl-p-phenylenediamine, and has an effect on skin. Not only has the advantage that the skin is less susceptible to irritation, and in particular, the object of the present invention can be effectively achieved by combining it with the compound represented by the general formula [I] in the present invention.

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

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

[Exemplary color developing agent] Among the color developing agents exemplified above, those preferably used in the present invention are exemplified by Nos. (A-1), (A-2), and (A-
3), (A-4), (A-6), (A-7) and (A-
15), particularly preferably No. (A-
1).

The above color developing agents are usually used in the form of salts such as hydrochloride, sulfate, p-toluenesulfonate and the like.

The color developing agent having a water-soluble group used in the present invention is usually preferably used in the range of 1 × 10 ^-2 to 2 × 10 ^-1 mol per color developing solution, but from the viewpoint of rapid processing, the color developing agent is preferably used. The range is more preferably from 1.5 × 10 ^-2 to 2 × 10 ^-1 mol per liquid.

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

As the alkaline agent, for example, sodium hydroxide, potassium hydroxide, silicate, sodium metaborate, potassium metaborate, trisodium phosphate, potassium triphosphate,
Borax and the like can be used alone or in combination in such a range that the above-mentioned effect, that is, no precipitation occurs, and the pH stabilizing effect is maintained. Furthermore, various salts such as disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium bicarbonate, potassium bicarbonate, and borate are used for the purpose of preparation or for the purpose of increasing ionic strength. can do.

If necessary, inorganic and organic antifoggants can be added.

Furthermore, if necessary, a development accelerator can be used. U.S. Patent 2,648,604 as a development accelerator
No. 3,671,247, various pyridinium compounds represented by JP-B-44-9503, other cationic compounds, cationic dyes such as phenosafranine, neutral salts such as thallium nitrate, U.S. Pat. , 2,53
No. 1,832, No. 2,950,970, No. 2,577,127 and Japanese Patent Publication No. 44
Nonionic compounds such as polyethylene glycol and derivatives thereof and polythioethers described in
Organic solvents, organic amines, ethanolamine, ethylenediamine, diethanolamine, triethanolamine and the like described in JP-A-44-9509 are included. Also U.S. Patent 2,304,
Examples include phenethyl alcohol described in No. 925 and acetylene glycol, methyl ethyl ketone, cyclohexanone, thioethers, pyridine, ammonia, hydrazine, amines and the like.

Benzyl alcohol is not used in the present invention, and it is preferable to eliminate the use of poorly soluble organic solvents represented by the above-mentioned phenethyl alcohol in order to efficiently achieve the object of the present invention. The use of the color developing solution for a long period of time, particularly in the running process in a low replenishment system, tends to generate tar, and the generation of such tar significantly impairs the commercial value due to adhesion to the processed paper photosensitive material. Even a serious failure.

In addition, poorly soluble organic solvents have poor solubility in water, so that not only is it necessary to use a stirrer to adjust the color developing solution itself, but also the use of such a stirrer causes a poor dissolution rate. Therefore, the effect of accelerating the development is limited.

Furthermore, poorly soluble organic solvents have large pollution load values such as biochemical oxygen demand (BOD) and cannot be disposed of in sewers or rivers. Since it has problems such as requiring labor and cost, it is preferable to reduce or eliminate not only benzyl alcohol but also other poorly soluble organic solvents as much as possible.

Further, the color developing solution of the present invention may contain, as necessary, ethylene glycol, methyl cellosolve, methanol, acetone, dimethylformamide, β-cyclodextrin, and other JP-B-47-33378, JP-B-44-9509. Can be used as an organic solvent for increasing the solubility of the developing agent.

Further, an auxiliary developer can be used together with the developing agent. These auxiliary developers include, for example, N-methyl-p-aminophenol hexalfate (methol), phenidone, N, N'-diethyl-p-aminophenol hydrochloride, N, N, N ', N'-tetra Methyl-p-phenylenediamine hydrochloride and the like are known, and the addition amount thereof is usually preferably 0.01 g to 1.0 g /. In addition, if necessary, a competitive coupler, a fogging agent, a colored coupler, a development inhibitor releasing type coupler (a so-called DIR coupler), a development inhibitor releasing compound and the like can be added.

Furthermore, various additives such as a stain inhibitor, an anti-sludge agent, and a layering effect promoter can be used.

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

In the present invention, the above-mentioned color developing solution can be used in an arbitrary pH range, but is preferably from pH 9.5 to 13.0, more preferably from pH 9.8 to 12.0, from the viewpoint of rapid processing.

The processing temperature of color development using the color developing solution of the present invention,
30 ° C. or higher and 50 ° C. or lower, and the higher the temperature, the faster the processing can be performed in a shorter time, which is preferable.However, it is preferable that the stability is not so high from the viewpoint of the stability of the processing solution. .

Conventionally, the color development time is generally about 3 minutes and 30 seconds, but in the present invention, it is preferable to perform the color development in the range of 20 seconds to 3 seconds in order to achieve the effects of the present invention.

In the present invention, a color developer containing the compound represented by the general formula [I], and at least one compound selected from the compound represented by the general formula [II] and the compound represented by the general formula [III] It is preferable to use, as a specific example of application, including a single bath treatment, other various methods, for example, a spray method of spraying a treatment liquid, or a wet method by contact with a carrier impregnated with the treatment liquid Alternatively, various processing methods such as a developing method using a viscous processing solution can be used, but the processing steps are substantially color development, bleach-fixing, and washing with water (including stabilizing treatment instead of washing).
And the like.

In the present invention, it is preferable to provide a bleach-fixing step immediately after the color development processing step from the viewpoint of quickness and the effects of the present invention.

The bleaching agent that can be used in the bleach-fixing solution used in the present invention is not limited, but is preferably a metal complex salt of an organic acid. The complex salt is obtained by coordinating metal ions such as iron, cobalt and copper with an organic acid such as polycarboxylic acid, 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.

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

[1] Ethylenediaminetetraacetic acid [2] Diethylenetriaminepentaacetic acid [3] Ethylenediamine-N- (β-oxyethyl)
-N, N ', N'-triacetic acid [4] propylenediaminetetraacetic acid [5] nitrilotriacetic acid [6] cyclohexanediaminetetraacetic acid [7] iminodiacetic acid [8] dihydroxyethylglycine citric acid (or tartaric acid) [9] Ethyl ether diamine tetra acetic acid [10] Glycol ether amine tetra acetic acid [11] Ethylene diamine tetrapropionic acid [12] Phenylenediamine tetra acetic acid [13] Ethylene diamine tetra acetic acid disodium salt [14] Ethylene diamine tetra acetic acid tetra (trimethyl ammonium) salt [15] ] Ethylenediaminetetraacetic acid tetrasodium salt [16] Diethylenetriaminepentaacetic acid pentasodium salt [17] Ethylenediamine-N- (β-oxyethyl)
-N, N ', N'-triacetate sodium salt [18] Propylenediaminetetraacetate sodium salt [19] Nitriloacetate sodium salt [20] Cyclohexanediaminetetraacetate sodium salt These bleaching agents are 5-450 g /, more preferably. Is 20-2
Use at 50g /. To the bleach-fixing solution, a solution having a composition containing a silver halide fixing agent in addition to the bleaching agent as described above and, if necessary, a sulfite as a preservative is applied. Also, a bleach-fixing solution having a composition in which a large amount of a halide such as ammonium bromide is added to the above-mentioned silver halide fixing agent and a bleaching agent of ethylenediaminetetraacetate (III) acetic acid, A special bleach-fixing solution having a composition comprising a combination of a bleaching agent and a large amount of a halide such as ammonium bromide can be used. As the halide, besides ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide,
Ammonium iodide and the like can also be used.

As the silver halide fixing agent contained in the bleach-fix solution, a compound capable of forming a water-soluble complex salt by reacting with silver halide as used in ordinary fixing processing, such as potassium thiosulfate, sodium thiosulfate, and ammonium thiosulfate And thiocyanates such as potassium thiocyanate, sodium thiocyanate and ammonium thiocyanate, thiourea, thioether and the like. These fixing agents are used in an amount of at least 5 g / dissolveable range, but generally used in an amount of 70 g to 250 g /.

In addition, boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate,
Various pH buffers such as sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide can be used alone or in combination of two or more. Furthermore, various fluorescent whitening agents, antifoaming agents or surfactants can be added. Preservatives such as hydroxylamine, hydrazine and bisulfite adducts of aldehyde compounds; organic chelating agents such as aminopolycarboxylic acids; and stabilizers such as nitro alcohols and nitrates; organic compounds such as methanol, dimethylsulfamide and dimethylsulfoxide. A solvent or the like can be appropriately contained.

The bleach-fix solution used in the present invention includes JP-A-46-280,
JP-B-45-8506 and JP-B-46-556, Belgian patent 770,910
No., JP-B-45-8636, JP-B-53-9854, and JP-A-54-7163.
Various bleaching accelerators described in JP-A Nos. 4 and 49-42349 can be added.

The pH of the bleach-fix solution is used at 4.0 or higher.
H 4.0 or more, used at pH 9.5 or less, desirably used at pH 4.5 or more, pH 8.5 or less, and furthermore, the most preferred p
H is processed at 5.0 or more and 8.5 or less. Processing temperature is 80 ℃
Hereinafter, it is desirably used at 55 ° C. or lower while suppressing evaporation and the like.
The processing time for bleach-fixing is from 5 seconds to 30 seconds.

In the present invention, a water washing process is performed following the color development and bleach-fixing steps, and the water washing process is performed with a replenishment amount of 0.1 to 50 times the carry-in amount of the prebath per unit area of the photosensitive material. It is sometimes preferable for the effect of the present invention, particularly for stabilizing a dye image.

Hereinafter, a preferred embodiment of the water washing process will be described.

Compounds preferably used in the washing solution include chelating agents having a chelate stability constant for iron ions of 8 or more, and these are preferably used to achieve the object of the present invention.

Here, the chelate stability constant is LGSillen ・ AEMa
rtell, “Stability Constants of Metalion Complex
es ", The Chemical Society, London (1964). S. Chabere
k ・ AEMartell, “Organic Sequestering Agents”, W
It means a constant generally known by iley (1959) and the like.

Examples of the chelating agent having a chelating stability constant for iron ions of 8 or more, which are preferably used in the washing liquid, include an organic carboxylic acid chelating agent, an organic phosphoric acid chelating agent, an inorganic phosphoric acid chelating agent, and a polyhydroxy compound. Note that the iron ion means ferric ion (Fe ³⁺ ).

Specific examples of the chelating agent having a chelate stability constant with ferric ion of 8 or more 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, among which 1-hydroxyethylidene-1,1
Diphosphonic acid is most preferably used.

The amount of the above chelating agent is 0.01-50g per washing liquid
And more preferably in the range of 0.05 to 20 g.

Further, as a compound to be added to the washing liquid, an ammonium compound is mentioned as a particularly preferred 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, fluoride Ammonium, ammonium acid fluoride, ammonium fluoroborate, ammonium arsenate, ammonium bicarbonate, ammonium bifluoride,
Ammonium hydrogen sulfate, 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, ammonium ethylenediaminetetraacetate, ethylenediaminetetraacetic acid second Ammonium iron, ammonium lactate, ammonium malate, 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, etc. . Among these ammonium compounds, ammonium thiosulfate is particularly preferred for achieving the effects of the present invention.

The amount of the ammonium compound to be added is preferably 1.0 × 10 ⁻⁵ or more, more preferably in the range of 0.001 to 5.0 mol, and more preferably in the range of 0.002 to 1.0 mol per washing solution.

Further, it is desirable that the washing liquid contains a sulfite within a range in which bacteria are not generated.

The sulfite to be contained in the washing liquid may be any substance such as an organic substance and an inorganic substance as long as it releases sulfite ions, but is preferably an inorganic salt, and preferred specific compounds include sodium sulfite, potassium sulfite, and ammonium sulfite. , Ammonium bisulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite and hydrosulfite, cartalaldehyde bis sodium bisulfite, succinate aldehyde bis sodium bisulfite and the like. Can be

The above sulfite is preferably added in an amount of at least 1.0 × 10 ⁻⁵ mol /, more preferably 5 × 10 ⁻⁵ mol / to 1.0 × 10 ⁻¹ mol / in the washing solution. A large amount is added. The addition method may be directly to the washing solution, but it is preferably added to the washing replenisher.

The water washing solution used in the present invention desirably contains an anti-biological agent, whereby the prevention of sulfidation and the image storability can be further improved.

Preferred antibacterial agents added to the washing liquid of the present invention are sorbic acid, benzoic acid compounds, phenol compounds, thiazole compounds, pyridine compounds, guanidine compounds, carbamate compounds, triazole compounds, morpholine compounds, They are quaternary phosphonium compounds, ammonium compounds, urea compounds, isoxazole compounds, propanolamine compounds, sulfamide compounds, pyronone compounds and amino compounds.

The benzoic acid-based compound includes salicylic acid, hydroxybenzoic acid and an ester compound of hydroxybenzoic acid, such as methyl ester, ethyl ester, and propyl ester.
There are butyl ester and the like, preferably n-butyl ester, isobutyl ester, propyl ester and salicylic acid of hydroxybenzoic acid, and more preferably a mixture of the three hydroxybenzoic acid esters.

The phenolic compound is a compound which may have a halogen atom, a nitro group, a hydroxyl group, a carboxylic acid group, an amino group, an alkyl group (particularly, an alkyl group having 1 to 6 alkyl groups) or a phenyl group as a substituent. Preferred are orthophenylphenol and orthocyclohexylphenol, nitrophenol, chlorophenol, cresol, guaiacol, aminophenol, phenol and the like.

The thiazole compound is a compound having a nitrogen atom and a sulfur atom in a five-membered ring, preferably 1,2-benzisothiazolin-3-one, 2-methyl-4-isothiazoline-3-one, 2-octyl-4-isothiazoline. 3-one, 5-chloro-2-methyl-4-isothiazoli-3-none, 2- (4-thiazolyl) benzimidazole.

Specific examples of the pyridine-based compound include 2,6-dimethylpyridine, 2,4,6-trimethylpyridine, sodium-2-pyridinethiol-1-oxide and the like, and preferably sodium-2-pyridinethiol-1. -An oxide.

Specific examples of the guanidine-based compound include cyclohexidine, polyhexamethylenebiguanidine hydrochloride, dodecylguanidine hydrochloride and the like, and preferably dodecylguanidine and its salts.

The carbamate compound is specifically methyl-1-
(Butylcarbamoyl) -2-benzimidazole carbamate, methylimidazole carbamate and the like.

Specific examples of the morpholine-based compound include 4- (3-nitrobutyl) morpholine and 4- (3-nitropropyl) morpholine.

The quaternary phosphonium-based compound includes a tetraalkylphosphonium salt and a tetraalkoxyphosphonium salt, and is preferably a tetraalkylphosphonium salt. More specifically, preferred compounds are tri-n-butyl-tetradecylphosphonium chloride and tri-tributylphosphonium chloride. Phenyl nitrophenyl phosphonium chloride.

Specific examples of the quaternary ammonium compounds include benzalkonium salts, benzethonium salts, tetraalkylammonium salts, and alkylpyridium salts.More specifically, dodecyldimethylbenzylammonium chloride,
Dodecyl dimethyl ammonium chloride, lauryl pyridinium chloride and the like.

The urea-based compound is specifically N- (3,4-dichlorophenyl) -N '-(4-chlorophenyl) urea, N-
(3-trifluoromethyl) -N '-(4-chlorophenyl) urea and the like.

Specific examples of the isoxazole-based compound include 3-hydroxy-5-methyl-isoxazole.

The propanol amino compounds include n-propanols and isopropanols. Specifically, DL-2-benzylamino-1-propanol and 3-diethylamino-
1-propanol, 2-dimethylamino-2-methyl-
1-propanol, 3-amino-1-propanol, idpropanolamine, diisopropanolamine, N,
N-dimethyl-isopropanolamine and the like.

Specific examples of the sulfamide compound include o-nitrobenzenesulfamide, p-aminobenzenesulfamide,
Fluorinated sulfamide, 4-chloro-3,5-dinitrobenzenesulfamide, α-amino-p-toluenesulfamide, sulfanilamide, acetosulfaguanidine, sulfathiazole, sulfadiazine, sulfamerazine, sulfamethazine, sulfaiso Oxazole, homosulfamine, sulfamidine, sulfaguanidine, sulfamethizole, sulfapyrazine, phthalisosulfathiazole, succinylsulfathiazole and the like.

Specific examples of the pyronone-based compound include dehydroacetic acid.

The amino acid compound is specifically N-lauryl-β-
There is alanine.

Specific examples of the triazole-based compound include 2-aminotriazole, benzotriazole, and 5-methyl-benzotriazole.

Compounds preferably used in the present invention among the above anti-binders are thiazole compounds, sulfamide compounds and pyronone compounds.

The amount of the anti-bubble agent added to the washing solution is 0.00
It is preferably used in the range of 1 to 30 g, more preferably in the range of 0.003 to 5 g.

The water washing solution in the present invention preferably contains a metal salt in combination with a chelating agent.

Such metal salts include Ba, Ca, Ce, Co, In, La, Mn, Ni, B
i, Pb, Sn, Zn, Ti, Zr, Mg, Al or Sr metal salts, inorganic salts such as halides, hydroxides, sulfates, carbonates, phosphates, acetates or water-soluble chelates Can be supplied as an agent. The amount used is in the range of 1 × 10 ^-4 to 1 × 10 ^-1 mol, preferably 4 × 10 ^-4 to 2 × 10 ^-2 mol, per washing liquid.

The aldehydes other than those described above are included in the washing solution of the present invention. Here, the aldehyde means a compound having an aldehyde group.

 As specific compounds, 1 formaldehyde 2 acetaldehyde 3 propionaldehyde 4 isobutyraldehyde 5 n-butyraldehyde 6 n-valeraldehyde 7 isovaleraldehyde 8 methylethylacetaldehyde 9 trimethylacetaldehyde 10 n-hexaaldehyde 11 methyl-n-propylacetaldehyde 12 Isohexaldehyde 13 Glyoxal 14 Malonaldehyde 15 Succinaldehyde 16 Glutaraldehyde 17 Adipaldehyde 18 Methylglyoxal 19 Acetoacetaldehyde 20 Glycolaldehyde 21 Ethoxyacetaldehyde 22 Aminoacetaldehyde 23 Betainealdehyde 24 Chloral 25 Chloracetaldehyde 26 Dichloroacetaldehyde 27 Bromalaldehyde 28 Dibromoacetaldehyde 29 Y It can be exemplified de acetaldehyde 30 alpha-chloro propionic acetaldehyde 31 alpha-bromo propionic acetaldehyde 32 furfural.

The aldehydes are preferably contained in the range of 0.1 to 50 g, particularly preferably in the range of 0.5 to 10 g, per washing liquid.

Further, in the present invention, a water washing solution treated with an ion exchange resin may be used.

The pH of the washing solution applicable to the present invention is in the range of 5.5 to 10.0. As the pH adjuster that can be contained in the washing liquid applicable to the present invention, any of generally known alkali agents and acid agents can be used.

The treatment temperature of the water washing treatment is preferably from 15C to 60C, and more preferably from 20C to 45C. The shorter the processing time, the more preferable from the viewpoint of effectively achieving the object of the present invention. The water washing treatment time of the present invention is 5 seconds to 50 seconds,
In the case of a multiple-tank washing treatment, it is preferable that the treatment be performed in a shorter time as in the front tank and the treatment time be longer in the rear tank. Especially 20% of the front tank
It is desirable to process sequentially with a processing time of 50% increase.

In the case of a multi-tank countercurrent method, it is preferable to supply a washing liquid in a washing treatment step applicable to the present invention to a post-bath so as to overflow to a preceding bath.
Of course, it can also be processed in a single tank. As a method for adding the above compound, various methods such as adding the compound and other additives to the washing liquid to be supplied to the washing tank, or adding the compound and other additives to the washing liquid to be supplied to the washing tank, and using this as a supply liquid to the washing replenisher can be used. However, any of these addition methods may be used.

The amount of washing water in the washing step of the present invention is the amount of the carry-in of the pre-bath (usually bleach-fixing solution or fixing solution) per unit area of the photosensitive material.
It is preferably 0.1 to 50 times, particularly preferably 0.5 to 30 times.

The washing tank in the washing treatment applicable to the present invention is 1 to 5
It is preferably a tank, particularly preferably 1 to 3 tanks, and preferably at most 9 tanks or less.

The silver halide grains used in the silver halide color photographic light-sensitive material applied to the present invention contain silver chloride of at least 90.
The silver halide grains contain at least 95 mol%, more preferably at least 95 mol%, and even more preferably at least 97 mol%.

The silver halide emulsion containing the silver halide grains of the present invention can contain silver bromide and / or silver iodide as a silver halide composition in addition to silver chloride.
It is at most 5 mol%, preferably at most 5 mol%, more preferably at most 3 mol%, and when silver iodide is present, at most 1 mol%, preferably at most 0.5 mol%. Such silver halide grains consisting essentially of silver chloride comprise at least one silver halide grain.
It may be applied to all silver halide emulsion layers, but preferably applied to all silver halide emulsion layers.

The crystal of the silver halide grains used in the present invention may be a normal crystal, a twin crystal or other crystal, and may have [1.0.0] plane and [1.1.
1] Any ratio of planes can be used. Further, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may be a layered structure (core-shell type) in which the inside and the outside are different. These silver halides may be of a type in which a latent image is mainly formed on the surface or of a type in which a latent image is formed inside a grain. Further, tabular silver halide grains (see JP-A-58-113934 and JP-A-59-170070) can also be used.

The silver halide grains used in the present invention may be those obtained by any preparation method such as an acid method, a neutral method or an ammonia method.

Further, for example, a method may be used in which seed particles are formed by an acidic method and further grown by an ammonia method having a high growth rate to grow to a predetermined size. When growing silver halide grains, controlling the pH, pAg, etc. in the reaction vessel, for example, an amount of silver ion corresponding to the growth rate of the silver halide grains as described in JP-A-54-48521. And halide ions are preferably sequentially and simultaneously injected and mixed.

The preparation of the silver halide grains according to the present invention is preferably carried out as described above. The composition containing the silver halide grains is referred to herein as a silver halide emulsion.

These silver halide emulsions include active gelatin; sulfur sensitizers such as allyl thiocarbamide, thiourea, and cystine; selenium sensitizers; reduction sensitizers such as primary sensitizers
Tin salts, thiourea dioxide, polyamines and the like; noble metal sensitizers such as gold sensitizers, specifically, potassium aurithiocyanate, potassium chloroaurate, 2-aurothio-3
Sensitizers of methylbenzothiazolium chloride and the like or water-soluble salts such as ruthenium, palladium, platinum, rhodium and iridium, specifically ammonium chloroparadate, potassium chloroplatinate and sodium chloroparadate (of these Certain compounds act as sensitizers or fogging inhibitors depending on the size of the compounds, etc.) alone or in combination (for example, a combination of a gold sensitizer and a sulfur sensitizer, a combination of a gold sensitizer and selenium). Chemical sensitization in combination with a sensitizer).

The silver halide emulsion according to the present invention is subjected to chemical ripening by adding a sulfur-containing compound, and before, during or after the chemical ripening, a nitrogen-containing heteroatom having at least one hydroxytetrazaindene and a mercapto group. At least one kind of a ring compound may be contained.

The silver halide used in the present invention may contain a sensitizing dye in an amount of, for example, 5 × 10 ^{−8 to} 3 × 10 ⁻³ mol per mol of silver halide in order to impart photosensitivity to a desired photosensitive wavelength range. It may be added for optical sensitization. Various sensitizing dyes may be used, and one or two sensitizing dyes may be used.
It can be used in combination of more than one species.

To the photographic constituent layers of the silver halide color photographic light-sensitive material of the present invention, a dye (AI dye) which is decolorizable with a water-soluble or color developing solution can be added. Examples of the AI dye include an oxanol dye and a hemioxanol. The dye, merocyanine dye and azo dye are allowed to break. Among them, oxanol dyes,
Hemioxanol dyes and merocyanine dyes are useful.

The photographic coupler used in the present invention is not limited, and may be a 2-equivalent type or a 4-equivalent type. As the cyan coupler, phenolic and naphthol compounds are preferable.For example, U.S. Pat.Nos. 2,369,929, 2,434,272, and
2,474,293, 2,895,826, 3,253,924, 3,03
4,892, 3,311,476, 3,386,301, 3,419,390
No. 3,458,315, 3,476,563, 3,531,383, etc., and methods for synthesizing those compounds are also described in the publication.

Examples of the magenta coupler for photography include pyrazolone-based, pyrazolotriazole-based, pyrazolinobenzimidazole-based and indazolone-based compounds. Pyrazolone-based magenta couplers include U.S. Pat.
Nos. 3,062,653, 3,127,269, 3,311,476,
3,419,391, 3,519,429, 3,558,318, 3,6
Nos. 84,514 and 3,888,680, JP-A-49-29639 and 49-296
No. 111631, No. 49-129538, No. 50-13041, Tokiko Sho 53
-47167, 54-10491 and 55-30615; pyrazolotriazole-based magenta couplers include U.S. Pat. No. 1,247,493 and Belgian Patent 792,5
Coupler described in No. 25, as a non-diffusible colored magenta coupler is generally used an arylazo substituted compound at the coupling position of a colorless magenta coupler, for example, U.S. Pat.Nos. 2,801,171 and 2,983,6
08, 3,005,712, 3,684,514, UK Patent 937,62
1, compounds described in JP-A-49-123625 and JP-A-49-31448.

Further, a colored magenta coupler of a type in which a dye hardly flows into a processing solution due to a reaction of an oxidized form of a developing agent as described in US Pat. No. 3,419,391 can also be used.

As a photographic yellow coupler, an open-chain ketomethylene compound has been conventionally used, and a benzoylacetanilide-type yellow coupler generally used widely,
Bivaloylacetanilide type yellow couplers can be used. Further, a 2-equivalent yellow coupler in which the carbon atom at the coupling position is substituted with a substituent capable of leaving during the coupling reaction is also advantageously used. These examples are described in U.S. Pat.Nos. 2,875,057, 3,265,506, 3,663.
4,841, 3,408,194, 3,277,155, 3,447,928
No. 3,415,652, JP-B-48-29432, JP-B-48-68834
Nos. 49-10736, 49-122335, 50-28834,
No. 50-132926 and the like, together with the synthesis method.

However, particularly useful cyan couplers include cyan couplers represented by the following general formulas [C-1] to [C-3] in which the effects of the present invention are more favorably exhibited.

In the formula [C-1], one of R and R ₁ is a hydrogen atom,
The other is at least linear or branched alkyl group having 2 to 12 carbon atoms, X represents a group capable of splitting off upon coupling reaction with an oxidation product of a hydrogen atom or an aromatic primary amino color developing agent, R ₂ Represents a ballast group.

In the formula [C-3], Y represents —COR ₄ , -CONHCOR ₄ or -CONHSO ₂ R ₄ (where R ₄ is an alkyl group,
Alkenyl group, a cycloalkyl group, an aryl group or a heterocyclic group, R ₅ is a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or a heterocyclic group, bond and R ₄ and R ₅ together To form a 5- or 6-membered heterocycle. R ₃ represents a ballast group; Z represents a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidized form of an aromatic primary amino color developing agent.

The cyan coupler according to the present invention has the general formula [C-
1] to [C-3], and represented by the general formula [C
-1] will be further described.

In the present invention, the linear or branched alkyl group having 2 to 12 carbon atoms represented by R ₁ and R in the general formula [C-1] is, for example, an ethyl group, a propyl group, or a butyl group.

In the general formula [C-1], the ballast group represented by R ₂ gives the coupler sufficient bulk to prevent the coupler from being substantially dispersed from the layer to which the coupler is applied to another layer. An organic group having a size and shape. Representative ballast groups include alkyl or aryl groups having a total of 8 to 32 carbon atoms, but preferably have a total of 13 to 28 carbon atoms. The alkyl group and the aryl group may have a substituent, and examples of the substituent of the aryl group include an alkyl group, an aryl group, an alkoxy group,
Allyloxy group, carboxy group, acyl group, ester group, hydroxy group, cyano group, nitro group, carbamoyl group, carboxamide group, alkylthio group, arylthio group, sulfonyl group, sulfonamide group, sulfamoyl group, halogen, and the like. Examples of the substituent of the alkyl group include the substituents of the aryl group except for the alkyl group.

Preferred as the ballast group are those represented by the following general formula.

R ₃₃ represents an alkyl group having 1 to 12 carbon atoms, Ar represents an annealing group such as a phenyl group, and the aryl group may have a substituent. Examples of the substituent include an alkyl group, a hydroxy group, a halogen atom, and an alkylsulfonamide group, and the most preferable one is a branched alkyl group such as a t-butyl group.

The group capable of leaving by coupling with the oxidized form of the color developing agent defined by X in the general formula [C-1] determines the number of equivalents of the coupler, as well known to those skilled in the art, It affects the reactivity of the coupling. Representative examples include chlorine, fluorine represented by halogen, aryloxy groups, substituted or unsubstituted alkoxy groups, acyloxy groups, sulfonamide groups, arylthio groups, heteroylthio groups, heteroyloxy groups, sulfonyloxy groups, carbamoyloxy groups And the like. More specific examples include JP-A-50-10135, JP-A-50-120334, and JP-A-50-1
No. 30414, No. 54-48237, No. 51-146828, No. 54-1473
No. 6, No. 47-37425, No. 50-123341, No. 58-95345
No., JP-B-48-36894, U.S. Pat.Nos. 3,476,563 and 3,73
Groups described in 7,316, 3,227,551 and the like.

Next, the general formula [C-2] or [C-
3] will be described. In the general formulas [C-2] and [C-3], Y is -CO
R ₄ , It is a group represented by -CONHCOR ₄ or -CONHSO ₂ R ₄ . Here, R ₄ is an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms (eg, each group of methyl, ethyl, t-butyl, dodecyl, etc.), an alkenyl group, preferably an alkenyl group having 2 to 20 carbon atoms (eg, Allyl group, heptadecenyl group, etc.),
A cycloalkyl group, preferably a 5- to 7-membered ring (eg, cyclohexyl), an aryl group (eg, phenyl, tolyl, naphthyl, etc.), a heterocyclic group, preferably a nitrogen atom, an oxygen atom or a sulfur atom; Represents a 5- to 6-membered heterocyclic group containing up to 4 (for example, a furyl group, a thienyl group, a benzothiazolyl group, etc.). R ₅ represents a hydrogen atom or a group represented by R ₄ . R ₄ and R ₅ may combine with each other to form a 5- to 6-membered heterocycle. Note that R ₂ and
Any substituent can be introduced into R ₃ , for example, an alkyl group having 1 to 10 carbon atoms (eg, methyl, i-propyl,
i-butyl, t-butyl, t-octyl, etc.), an aryl group (eg, phenyl, naphthyl, etc.), a halogen atom (fluorine, chlorine, bromine, etc.), a cyano, nitro, sulfonamide group (eg, methanesulfonamide, butanesulfone) Amide, p-toluenesulfonamide, etc.), sulfamoyl group (eg, methylsulfamoyl, phenylsulfamoyl, etc.), sulfonyl group (eg, methanesulfonyl,
p-toluenesulfonyl), a fluorosulfonyl group,
Carbamoyl group (eg, dimethylcarbamoyl, phenylcarbamoyl, etc.), oxycarbonyl group (eg, ethoxycarbonyl, phenoxycarbonyl, etc.), acyl group (eg, acetyl, benzoyl, etc.), heterocyclic group (eg, pyridyl group, pyrazolyl group, etc.), alkoxy group , An aryloxy group, an acyloxy group and the like.

In the general formulas [C-2] and [C-3], R ₃
Represents a ballast group necessary for imparting diffusion resistance to the cyan coupler represented by the general formulas [C-2] and [C-3] and a cyan dye formed from the cyan coupler. It is preferably an alkyl group having 4 to 30 carbon atoms, an aryl group or a heterocyclic group. For example, a linear or branched alkyl group (for example, t-butyl, n-octyl, t-octyl, n-dodecyl, etc.), an alkenyl group, a cycloalkyl group, a 5- or 6-membered heterocyclic group and the like can be mentioned.

In the general formulas [C-2] and [C-3], Z
Represents a hydrogen atom or a group capable of leaving during a coupling reaction with an oxidized product of a color developing agent. For example, a halogen atom (eg, chlorine, bromine, fluorine, etc.), a substituted or unsubstituted alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, a sulfonyloxy group, an alkylthio group, an arylthio group, a heterocyclic group Examples thereof include thio groups and sulfonamide groups.More specific examples include U.S. Pat.No. 3,741,563, JP-A-47-37425, JP-B-48-36894, JP-A-50-10135, and 50-117422. issue,
No. 50-130441, No. 51-108841, No. 50-120343, No.
No. 52-18315, No. 53-105226, No. 54-14736, No. 54-
48237, 55-32071, 55-65957, 56-1938
No. 56-12643, No. 56-27147, No. 59-146050,
Nos. 59-166696, 60-24547, 60-35731, 60
-37557 and the like.

In the present invention, the following general formulas [C-4] and [C-
The cyan coupler represented by [5] or [C-6] is more preferable from the viewpoint of achieving the object of the present invention.

In the general formula [C-4], R ₃₄ is a substituted or unsubstituted aryl group (particularly preferably a phenyl group). When the aryl group has a substituent, the substituent includes -SO ₂ R
_37, a halogen atom (fluorine, bromine, chlorine, etc.), - CF _{3,
-NO 2, -CN, -COR 37,} -COOR 37, -SO 2 OR 37, And at least one substituent selected from the group consisting of:

Here, R ₃₇ is an alkyl group, preferably having 1 to 20 carbon atoms.
Alkyl groups such as methyl, ethyl, tert-butyl,
Dodecyl groups, etc.), alkenyl groups, preferably alkenyl groups having 2 to 20 carbon atoms (such as allyl group and heptadecenyl group), cycloalkyl groups, preferably 5- to 7-membered ring groups (such as cyclohexyl), aryl groups ( For example, a phenyl group, a tolyl group, a naphthyl group, etc.), and R ₃₈ is a hydrogen atom or a group represented by R ₃₇ .

In a preferred compound of the cyan coupler of the present invention represented by the general formula [C-4], R ₃₇ is a substituted or unsubstituted phenyl group, and as a substituent on the phenyl group, cyano, nitro, or —SO ₂ R ₃₉ (R ₃₉ is an alkyl group), a halogen atom, and trifluoromethyl.

In the general formulas [C-5] and [C-6], R ₃₅ and R ₃₆
Is an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms (e.g., each group of methyl, ethyl, tert-butyl, dodecyl, etc.), an alkenyl group, preferably an alkenyl group having 2 to 20 carbon atoms (an allyl group, an oleyl group) ), A cycloalkyl group, preferably a 5- to 7-membered ring group (eg, cyclohexyl), an aryl group (eg, phenyl group, tolyl group, naphthyl group, etc.), a heterocyclic group (eg, nitrogen atom, oxygen atom,
Alternatively, a 5- to 6-membered heterocyclic ring containing 1 to 4 sulfur atoms is preferable, and examples thereof include a furyl group, a thienyl group, and a benzothiazolyl group. ).

R ₃₇ , R ₃₈ and the general formulas [C-5] and [C-6]
Any substituent can be further introduced into R ₃₅ and R ₃₆ , and specifically, it can be introduced into R ₄ or R ₅ in general formulas [C-2] and [C-3]. Is a substituent such as As the substituent, a halogen atom (such as a chlorine atom or a fluorine atom) is particularly preferable.

In the general formulas [C-4], [C-5] and [C-6], Z and R ₃ have the same meanings as in the general formulas [C-2] and [C-3], respectively. A preferred example of the ballast group represented by R ₃ is a group represented by the following general formula [C-7].

In the formula, J represents an oxygen atom, a sulfur atom or a sulfonyl group, K represents an integer of 0 to 4, 1 represents 0 or 1, and K represents
Is two or more, two or more R ₄₁ may be the same or different. R ₄₀ represents a substituted alkylene group such as a straight-chain or branched, and aryl groups having 1 to 20 carbon atoms, R ₄₁ represents a monovalent group, preferably a hydrogen atom, a halogen atom (for example, chromium, bromine), An alkyl group, preferably a linear or branched alkyl group having 1 to 20 carbon atoms (for example, methyl, t-butyl, t-pentyl, t-octyl, dodecyl, pentadecyl, benzyl, phenethyl, etc.),
Aryl group (for example, phenyl group), heterocyclic group (preferably nitrogen-containing heterocyclic group) alkoxy group, preferably linear or branched alkoxy group having 1 to 20 carbon atoms (for example, methoxy, ethoxy, t-butyloxy, octyl) Oxy, decyloxy, dodecyloxy, etc.), aryloxy group (eg, phenoxy group), hydroxy group, acyloxy group, preferably alkylcarbonyloxy group, arylcarbonyloxy group (eg, acetooxy group, benzoyloxy group), carboxy, Alkyloxycarbonyl group, preferably a linear or branched alkylcarbonyl group having 1 to 20 carbon atoms, preferably a phenoxycarbonyl group, an alkylthio group, preferably an acyl group having 1 to 20 carbon atoms, preferably having 1 to 20 carbon atoms. Linear or branched alkylcarbonyl group, acyl group Amino group, preferably 1 to carbon atoms
20 linear or branched alkyl carbamide groups, benzene carbamide groups, sulfonamide groups, preferably linear or branched alkyl sulphonamide groups or benzene sulphonamide groups having 1 to 20 carbon atoms, carbamoyl groups, preferably carbon atoms A linear or branched alkylaminocarbonyl group or phenylaminocarbonyl group having 1 to 20 carbon atoms, a sulfamoyl group, preferably a linear or branched alkylaminosulfonyl group or phenylaminosulfonyl group having 1 to 20 carbon atoms.

A method for synthesizing the cyan couplers represented by the general formulas [C-1] to [C-3] and specific exemplary compounds are described in
No. 61-92655, pages 76 to 124,
Cyan coupler (CC-) shown on pages 81 to 85 of the same specification.
Specific examples thereof include cyan couplers (C-1) to (C-100) shown in 1) to (CC-28) and pages 98 to 123.

In order to efficiently achieve the object of the present invention, it is particularly preferable to use a cyan coupler represented by the following general formula [MI].

In the 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. 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. Atom 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, heterocyclic thio groups And spiro compound residues, bridged hydrocarbon compound residues, and the like.

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 has 2 to 32 carbon atoms, and the cycloalkyl group has 3 to 12 carbon atoms, particularly 5 carbon atoms.
To 7 are preferable, and the alkenyl group may be linear or branched.

The cycloalkenyl group represented by R has 3 carbon atoms.
~ 12, especially 5-7 are preferred.

As the sulfonyl group represented by R, an alkylsulfonyl group, an arylsulfonyl group, or the like; As the sulfinyl group, an alkylsulfinyl group, an arylsulfinyl group, or the like; As the phosphonyl group, an alkylphosphonyl group, an alkoxyphosphonyl group, an aryloxyphosphonyl group An acyl 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 alkylcarbamoyl group, an arylcarbamoyloxy group, etc .; As a ureido group An alkylureido group, an arylureido group or the like; a sulfamoylamino group such as an alkylsulfamoylamino group or an arylsulfamoylamino group; a heterocyclic group preferably having 5 to 7 members; -A furyl group, a 2-thienyl group, a 2-pyrimidinyl group, a 2-benzothiazolyl group or the like; As the heterocyclic oxy group, those having a 5- to 7-membered heterocyclic ring are preferable. And the like. As the heterocyclic thio group, a 5- to 7-membered heterocyclic thio group is preferable, for example, a 2-pyridylthio group, a 2-benzothiazolylthio group. , 2,4-diphenoxy-1,3,5-triazole-6-thio group and the like; Siloxy groups include trimethylsiloxy, triethylsiloxy, and dimethylbutylsiloxy groups. Group or the like; succinimide group as imide group, 3-heptadecyl succinic acid imide group, a phthalimide group, a glutarimide group and the like; spiro [3.3] As a spiro compound residue heptane -
1-yl and the like; bicyclo [2.2.1] as a bridged hydrocarbon compound residue
Heptan-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 an oxidized form of the color developing agent represented by X include a halogen atom (a chlorine atom, a bromine atom, a fluorine atom, etc.), alkoxy, aryloxy,
Heterocyclic oxy, acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyl,
Alkyl oxalyloxy, aroxy oxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxycarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocycle linked by an N atom, alkyloxycarbonylthiamino, aryloxycarbonylamino,
Carboxyl, (R ₁ ′ has the same meaning as R, Z ′ has the same meaning as Z, and R ₂ ′ and R ₃ ′ each 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. Examples of the substituent that the ring may have include those described above for R. Is mentioned.

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

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

Preferred among the general formula [MI] are those represented by the following general formula [M-VIII].

In the formula [M-VIII], R ₁ , X and Z ₁ represent the general formula [MI]
Has the same meanings as R, X and Z.

Among the magenta couplers represented by the general formulas [M-II] to [M-VII], a magenta coupler represented by the general formula [M-II] is particularly preferable.

Formula [M-I] is formed by Z in the ring and the formula [M-VIII] may be possessed by the ring formed by Z ₁ in the substituent, and the general formula [M-II] ~ formula As R _{2 to} R _{8 in} [M-VI], those represented by the general formula [M-IX] are preferable.

In the general formula ^{[M-IX] -R 1 -SO} 2 -R 2 Formula [M-IX], R ¹ is an alkylene group, 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 straight-chain carbon atoms, more preferably 3 to 6 carbon atoms, and may be straight-chain or branched.

The alkyl group represented by R ² preferably have 5-6 membered.

When used for positive image formation, the substituents R and R ₁ on the heterocyclic ring are most preferably represented by the following general formula [M-
X].

In the formula [MX], R ₉ , R _10, and R ₁₁ have the same meanings as R described above.

Further, two of R ₉ , R ₁₀ and R ₁₁ , for example, R ₉ and R ₁₀ are bonded to each other to form a saturated or unsaturated ring (for example, cycloalkane,
Cycloalkene, heterocyclic ring) may be formed, it may constitute the bridged hydrocarbon compound residue bound R ₁₁ further ring.

Preferred specific examples of the cyan coupler include compounds 1 to 77 described on pages 15 to 31 of Japanese Patent Application No. 62-220060.

In addition to the typical specific examples of the compound according to the present invention, specific examples of the compound according to the present invention include compounds described on pages 66 to 122 of Japanese Patent Application No. 61-9791. Among them, No. 1-4, 6, 8, 17, 17, 19-24, 26-43, 45-59, 61-104, 1
Compounds represented by 06 to 121,123 to 162,164 to 223 can be exemplified.

In addition, the coupler is used in the Journal of the Chemical Societe
y), Perkin I (1977), 2047-2052, U.S. Pat. No. 3,725,067, JP-A-59-99437, and JP-A-58-42045.
Nos. 59-162548, 59-171956, 60-33552
No. 60-43659, No. 60-177292 and No. 60-190779.

In the present invention, the amount of the above-mentioned diffusion-resistant coupler to be used is generally from 0.05 to 2.0 per mol of silver in the photosensitive silver halide emulsion layer.
0 mole.

In the present invention, in addition to the above-described diffusion-resistant coupler, various DIRs
Compounds and the like are preferably used.

The silver halide color photographic light-sensitive material used in the present invention may further contain various photographic additives. For example, antifoggants, stabilizers, ultraviolet absorbers described in Research Disclosure Magazine No. 17643,
Color stain inhibitors, fluorescent brighteners, color image fading inhibitors, antistatic agents, hardeners, surfactants, plasticizers, wetting agents and the like can be used.

In the silver halide color photographic light-sensitive material used in the present invention, the hydrophilic colloid used for preparing the emulsion is preferably gelatin. In addition, derivative gelatin, a graft polymer of gelatin and another polymer, albumin , A protein such as casein, a hydroxyethylcellulose derivative, a cellulose derivative such as carboxymethylcellulose, a starch derivative, a single or copolymer synthetic hydrophilic polymer such as polyvinyl alcohol, polyvinylimidazole, and polyacrylamide. You.

Examples of the support of the silver halide color photographic light-sensitive material used in the present invention include baryta paper and polyethylene-coated paper,
Polypropylene synthetic paper, transparent support combined with reflective layer,
Examples thereof include a glass plate, a polyester film such as cellulose acetate, cellulose nitrate or polyethylene terephthalate, a polyamide film, a polycarbonate film, a polystyrene film, and the like, and other ordinary transparent supports may be used. These supports are appropriately selected according to the purpose of use of the light-sensitive material.

Various coating methods such as dipping coating, air doctor coating, curtain coating, and hopper coating can be used for coating the silver halide emulsion layer and other photographic constituent layers used in the present invention. Also U.S. Pat.
No. 791, No. 2, 941, 898, a simultaneous coating method of two or more layers can also be used.

In the present invention, the coating position of each emulsion layer can be arbitrarily determined. For example, in the case of a full-color photographic paper light-sensitive material, it is preferable to form an array of a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer sequentially from the support. . Each of these light-sensitive silver halide emulsion layers may be composed of two or more layers.

In the light-sensitive material of the present invention, it is optional to provide an intermediate layer having an appropriate thickness according to the purpose. Further, various layers such as a filter layer, an anti-curl layer, a protective layer, and an antihalation layer may be appropriately used as constituent layers. It can be used in combination. In these constituent layers, a hydrophilic colloid which can be used in the above-mentioned emulsion layer can be similarly used as a binder, and various layers which can be contained in the above-mentioned emulsion layer can be contained in the layer. Photographic additives.

In the method for processing a silver halide color photographic light-sensitive material of the present invention,
If the photosensitive material is processed by a so-called internal development method containing a coupler in the photosensitive material, color paper, color film, color positive film, color reversal film for slide, color reversal film for movie, color reversal film for TV, It can be applied to any silver halide color photographic light-sensitive material such as reversal color paper.

[Effects of the Invention] According to the present invention, there is provided a processing method for a silver halide color photographic light-sensitive material which is excellent in whiteness of a color paper obtained by processing and excellent in storage stability of a dye image obtained. Can be.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but embodiments of the present invention are not limited thereto.

Example 1 The following layers were sequentially coated on a polyethylene-coated paper support from the support side to prepare a photosensitive material.

The average molecular weight of polyethylene coated paper is 10
200 parts by weight of polyethylene with a density of 0,000 and a density of 0.95 and an average molecular weight
A mixture of 2,000 and 20 parts by weight of polyethylene having a density of 0.80 was added with 6.8% by weight of anatase-type titanium oxide, and a coating layer having a thickness of 0.035 mm was formed on the surface of high-quality paper having a weight of 170 g / m ² by an extrusion coating method. The one provided with a coating layer having a thickness of 0.040 mm using only polyethylene was used. After pretreatment by corona discharge was performed on the polyethylene-coated surface of the support, the following layers were sequentially applied.

First layer: A blue-sensitive silver halide emulsion layer comprising a silver chlorobromide emulsion containing 1.0 mol% of silver bromide, wherein the emulsion contains 350 g of gelatin per mol of silver halide and has the following structure per mol of silver halide. 2,5-di-t-butylhydroquinone 200 mg / m ² sensitized with 2.5 × 10 ^-4 mol of sensitizing dye [I] (using isopropyl alcohol as a solvent), and dissolved and dispersed in dibutyl phthalate. And [Y-1] having the following structure as a yellow coupler in an amount of 2.0 × 10 ⁻¹ per mol of silver halide.
It is coated so as to have a silver content of 300 mg / m ² , including moles.

Second layer: 300 mg / m ^{2 of} di-t-octylhydroquinone dissolved and dispersed in dibutyl phthalate, ^{2 as} an ultraviolet absorber
-(2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-
5'-t-butylphenyl) benzotriazole, 2-
(2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chloro-benzotriazole and 2-
Mixture of (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chloro-benzotriazole (1: 1:
1: 1) Gelatin gelatin layer containing 200mg / m ² 1900mg /
is applied so that the m ^2.

Third layer: A green-sensitive silver halide emulsion layer comprising a silver chlorobromide emulsion containing 1 mol% of silver bromide, wherein the emulsion contains 450 g of gelatin per mol of silver halide and has the following structure per mol of silver halide. 2,5-Di-t-butylhydroquinone and magenta coupler sensitized using 2.5 × 10 ^-4 mol of sensitizing dye [II] and dissolved in a solvent consisting of dibutyl phthalate and tricresyl phosphate 2: 1 [M-1] having a structure of 1.5 × 10 ⁻¹ mol per mol of silver halide and silver amount of 230 mg
/ m ² , AI dye is applied to be 50 mg / m ² . As an antioxidant, 0.30 mol of 2,2,4-trimethyl-6-lauryloxy-7-t-octylchroman was added per 1 mol of the coupler.

Fourth layer: 30 mg / m ^{2 of} di-t-octylhydroquinone dissolved and dispersed in dioctyl phthalate and 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole as an ultraviolet absorber , 2- (2'-hydroxy-5'-t-butylphenyl) benzotriazole, 2
-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5'-chloro-benzotriazole and 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) 5-chloro - mixture of benzotriazole (2: 1.5: 1.5: 2) a gelatin layer containing 500 mg / m ^2, is coated so as to gelatin 1900 mg / m ^2.

Fifth layer: A red-sensitive silver halide emulsion layer comprising a silver chlorobromide emulsion containing 1.0 mol% of silver bromide, which emulsion contains 500 g of gelatin per mol of silver halide and has the following structure per mol of silver halide. Sensitized with 2.5 × 10 ^-5 mol of sensitizing dye [III],
2,5-di-t- dissolved and dispersed in dibutyl phthalate
Butyl hydroquinone 150 mg / m ² and [C-1] having the following structure as a cyan coupler were added in an amount of 3.5 per mole of silver halide.
× 10 ^-1 mol, silver amount 280 mg / m ² , AI dye 40 mg / m ² .

Sixth layer: This is a gelatin layer, which is coated with gelatin at a concentration of 900 mg / m ² .

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

After exposing the color paper produced by the above method, the treatment was performed using the following treatment steps and treatment liquid.

[Color developing tank solution A] Benzyl alcohol 5 g Ethylene glycol 10 g Exemplary compound [II-7] 0.3 g Potassium bromide 0.01 g Potassium chloride 2.3 g Potassium sulfite (50% solution) 0.5 ml Color developing agent (3-methyl-4-) Amino-N-ethyl-N- (β-methanesulfonamidoethyl) -aniline sulfate 5.0 g Diethylhydroxylamine (85%) 5.0 g Triethanolamine 10.0 g Potassium carbonate 30 g Ethylenediaminetetraacetic acid sodium salt 2.0 g Fluorescent brightener (Nichiba PK-Conc) 2.0g Add water to finish to 1 and add potassium hydroxide or sulfuric acid
The pH was adjusted to 10.15.

[Color developing replenisher A] Benzyl alcohol 7 g Ethylene glycol 10 g Potassium bromide 0.15 g Potassium chloride 3.0 g Potassium sulfite (50% solution) 1.5 mL Color developing agent (3-methyl-4-amino-N-ethyl-N- ( β-methanesulfonamidoethyl) -aniline sulfate 8.0 g diethylhydroxylamine (85%) 7.0 g triethanolamine 10.0 g potassium carbonate 30 g ethylenediaminetetraacetate sodium salt 2.0 g fluorescent whitening agent (PK-Conc, manufactured by Nichiba) 2.5g Add water to make 1 and add potassium hydroxide or sulfuric acid
The pH was adjusted to 10.40.

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

[Bleaching and fixing replenisher] Ferric ammonium ammonium diamine diamine 70.0 g Ethylene diamine tetraacetic acid 3.0 g Ammonium thiosulfate (70% solution) 120.0 ml Ammonium sulfite (40% solution) 35 ml Adjusted to pH 5.40 with aqueous ammonia or glacial acetic acid Adjust the total amount to 1
And

[Washing tank liquid and replenisher] Orthophenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazoline-3-
On 0.02 g 2-methyl-4-isothiazolin-3-one 0.02 g ethylene glycol 1.0 g 2-octyl-4-isothiazolin-3-one 0.01 g 1-hydroxyethylidene-1,1-diphosphonic acid (60
% Aqueous solution) 3.0 g BiCl ₃ (45% aqueous _{solution) 0.65g MgSO 4 · 7H 2 O} 0.2g PVP ( polyvinylpyrrolidone) 1.0 g of aqueous ammonia (25% aqueous ammonium hydroxide) 2.5 g nitrilotriacetic acid, trisodium salt 1.5g Water To 1 and to pH 7.0 with aqueous ammonia and sulfuric acid.

In the running process, the above-described color developing tank solution A, the color developing solution B obtained by removing benzyl alcohol from the color developing tank solution A, the bleach-fixing tank solution and the washing tank solution were filled in the automatic developing machine, and the color paper sample was processed. The replenishing solution for color development, the replenishing solution for bleaching and the replenishing solution for washing were replenished through a metering pump at intervals of 3 minutes.

The amount of replenishment to the color developing tank is 1m of color paper
² per 180 ml, was supplemented 1 m ² per blix replenisher as volume 220ml to bleaching tank, a 1 m ² per washing replenisher as replenisher amount to the washing tank and 250ml refill.

The rinsing bath of the automatic developing machine is a rinsing tank which becomes the first tank and the second tank in the direction of the flow of the photosensitive material. The replenishment is performed from the last tank, and the overflow solution from the last tank flows into the preceding tank. A two-tank countercurrent system was used.

The processing time of color development was adjusted by a speed controller.

When the amount of the color developing replenisher replenished in the color developing tank becomes three times the capacity of the color developing tank, the wedge-exposed check sample is passed through the check sample, and the blue color is measured with a PDA-65 (manufactured by Konica Corporation) densitometer. Was measured for the lowest reflection density. Further, a relative value was determined when the maximum density (reflection density) of Blue when the color developing solution B was processed at 35 ° C. for 45 seconds was 100, and is shown in Table 1.

According to Table 1, when the sample containing 90 mol% or more of silver chloride was examined for the minimum and maximum concentration (Dmax) of Blue with and without benzyl alcohol, rapidity (relative value of Dmax) was obtained almost independently of benzyl alcohol. However, when viewed at the lowest density of Blue, the fluctuation range and the absolute value with respect to the change in the color development time are high, but when benzyl alcohol is not contained, the change range and the absolute value are low, especially 20%. Below seconds, a remarkable effect is seen.

Example 2 The treated samples Nos. 1 to 6 used in Example 1 were treated at 60 ° C.
After storage at 75% (relative humidity) for 3 weeks, fading of the cyan dye image was observed. The fading rate (%) was determined from the density of the cyan dye image before and after storage.

 Table 2 shows the results.

As is clear from Table 2, the shorter the color development processing time, the better the cyan discoloration.

Example 3 The magenta coupler used in Example 1 was prepared using the following M-2 to
M-11 or cyan coupler
61-192655, C-1, C-3, C-19, C-30, C-5 in the exemplified compounds shown on pages 76 to 124.
The same evaluation as in Example 2 was performed except that CC-2 or CC-8 was used instead of 8, C-76 or the exemplified compounds shown on pages 81 to 85 of the same specification.

As a result, the magenta fading was improved by about 30%, and the cyan fading was improved by 55%.

Example 4 Using the color developer B of Example 1, the color development processing time was reduced.
The same evaluation as in Example 2 was performed except that the bleach-fixing time and the washing time were set as shown in Table 3 for 20 seconds.

 Table 4 shows the results of the fading rate (%) of the cyan dye image.

As is clear from Table 4, the shorter the total processing time, the lower the fading rate of the cyan dye image.

Reference Example 1 A silver halide emulsion in a silver halide color photographic light-sensitive material was subjected to the same processing (color development processing time of 20 seconds) as in Example 1 as shown in Table 5, and the same as in Example 1 at 35 ° C. for 45 seconds. The relative value when the maximum density of Blue after color development processing was set to 100 was determined.

 Table 5 shows the results.

As is clear from Table 5, it is understood that the silver chloride content must be at least 90 mol% or more in order to obtain a sufficient dye concentration for practical use.

Example 5 Instead of the diethylhydroxylamine used in Example 1,
Although the exemplified A-2, A-3, A-18, A-21 and A-22 were used, almost the same effects could be obtained.

A-18 and A-21 had better developing characteristics than diethylhydroxylamine.

Claims (1)

(57) [Claims] (1) at least 90 mol% of silver chloride on a support
In the step of subjecting a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer containing the above to color development, bleach-fixing and washing with water, the color developer for color development is represented by the following general formula [ I], containing 4 × 10 ⁻³ mol / 1 or less of sulfite, containing substantially no benzyl alcohol, and having a color development processing time of 3 seconds or more and 20 seconds or less. The bleach-fix processing time is 5 to 30 seconds, the rinsing processing time is 5 to 50 seconds, and the total processing steps of the color development processing time, the bleach-fix processing time and the rinsing processing time are 13 in total.
A processing method for a silver halide color photographic light-sensitive material, wherein the processing time is from 1 second to 1 minute 35 seconds. In the formula, R ₁ and R ₂ each represent an alkyl group or a hydrogen atom. However, both R ₁ and R ₂ are not hydrogen atoms at the same time. R ₁ and R ₂ may form a ring.