JPH0746220B2 - Color developing solution and method for processing silver halide color photographic light-sensitive material using the color developing solution - Google Patents

Description

TECHNICAL FIELD The present invention relates to a color developing solution and a method for processing a silver halide color photographic light-sensitive material using the color developing solution, and in particular, precipitation may occur over time. Color developing solution suitable for rapid processing, which is stable and has a low pH drop and good developability, and a method for processing a silver halide color photographic light-sensitive material excellent in developability and maximum color density using the color developing solution. Regarding

BACKGROUND OF THE INVENTION In recent years, there has been an increasing demand in the industry for rapid processing technology for silver halide color photographic light-sensitive materials, particularly rapid processing is possible, and stable photographic characteristics with excellent temporal stability of the color developing solution are provided. It is desired to develop a silver halide color photographic light-sensitive material capable of obtaining

That is, the silver halide color photographic light-sensitive material is run by an automatic developing device installed in each laboratory. With the demand for handing over products, and nowadays even demanding hours from the reception desk, there is an urgent need to develop technologies that can be rapidly processed.

Generally, dye image formation in a silver halide color photographic light-sensitive material is performed by subjecting an exposed light-sensitive material to color development processing, bleaching processing, fixing processing (or one-bath bleach-fixing processing in which bleaching and fixing are performed in one bath), and then washing with water. However, in the rapid processing described above, shortening of the color development processing is technically the most important.

As a means of shortening the color development processing,
Increasing pH and increasing the concentration of color developing agent are considered effective.

The present inventors have used a commonly used color developer composition, that is,
It contains an aromatic primary amine color developing agent, contains a sulfite salt and a hydroxylamine salt as preservatives, and has a pH value of
Various problems in the course of research in order to achieve rapid development by increasing the pH in a color developer system containing 20 to 30 g / l of carbonate as a stabilizer and further containing various other additives. Faced the point.

That is, at high pH, the pH stability of the color developing solution was poor, the pH of the color developing solution decreased over time, and further precipitation was observed.

To improve this, impart pH stability at high pH
The use of a pH stabilizer is possible.

Typical examples of the pH stabilizer include phosphate buffers, but the use of phosphate buffers is not preferable from the viewpoint of pollution, and the effect as a pH stabilizer is also provided. Difficult to dissolve the amount needed to obtain,
Further, there is a problem that even if dissolved, a precipitate is easily formed together with an additive such as a color developing agent.

Other pH stabilizers at high pH include, for example, JP-A-55
-25028 is sodium silicate, Research Disclosure (hereinafter simply referred to as RD) 16156, and in September 1977, an aluminate and a dibasic acid capable of forming a complex salt with an aluminum ion are combined. Buffers, and borate salts are known.

However, even with these pH stabilizers at high pH, the pH stabilizing effect was not sufficient, or the occurrence of precipitation was unavoidable, and neither could be put to practical use.

In addition, an attempt was made to stabilize the pH by increasing the amount of carbonate, but it was not possible to simply increase the amount of carbonate due to precipitation of precipitates (especially at low temperature) and cloudiness of the developer.

The present inventors have the advantage that the technique of increasing the amount of the above-mentioned carbonate has a large effect on the pH stabilization of the color developing solution, and does not need to significantly change the conventional technique.
Further, as a result of continuing the study with this technique, it was found that the precipitation of the color developing solution with time can be suppressed by removing the salt of hydroxylamine used as one of the preservatives. This tendency became greater at higher pH.

However, the color developing solution from which the salt of hydroxylamine has been removed has a problem that the development activity is largely decreased over time and tar is likely to be generated, which cannot be put to practical use as it is. Further, in order to achieve the function as a preservative by increasing the amount of sulfite, it is known to those skilled in the art that sulfite ion causes a side reaction of the color developing agent to cause color inhibition, which is not practical and is not practical. .

As a result of further studies by the present inventors, by using a specific compound as a preservative in place of a salt of hydroxylamine, even when a specific amount or more of a carbonate is used, the color developing solution with time elapses. The present invention has been accomplished by finding that no precipitation occurs, the pH stabilizing effect is great, and the developability and the maximum color density are excellent.

[Object of the Invention] Therefore, a first object of the present invention is to provide a color developing solution suitable for rapid processing in which a decrease in pH over time is small and precipitation hardly occurs. A second object of the present invention is to provide a processing method of a silver halide color photographic light-sensitive material which is excellent in developability and maximum color density and enables rapid processing.

[Structure of the Invention] The first object of the present invention is to provide a color developing solution for processing a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer containing a dye-forming coupler, as a color developing agent. This is achieved by a color developing solution containing a p-phenylenediamine compound having a water-soluble group, containing 40 g or more of a carbonate per color developing solution, and further containing a compound represented by the following general formula [I].

The second object of the present invention is to carry out a treatment including at least a color developing step after imagewise exposure of a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer containing a dye-forming coupler. In the method for processing a silver halide color photographic light-sensitive material to be applied, the color developing solution used in the color developing step contains a p-phenylenediamine compound having a water-soluble group as a color developing agent, and carbon dioxide per 1 color developing solution. This can be achieved by a method of processing a silver halide color photographic light-sensitive material containing 40 g or more of a salt and further containing a compound represented by the following general formula [I].

General formula [I] [In the formula, R ₁ and R ₂ each represent a hydroxyl group, a nitro group or an alkyl group, and X ₁ and X ₂ represent —OM and —OR, respectively.
₃ or (M represents a hydrogen atom or an alkali metal atom, R ₃ represents an alkyl group, and R ₄ and R ₅ represent a hydrogen atom or an alkyl group, respectively). [Specific Structure of the Invention] In the color developer used in the present invention, the compound represented by the general formula [I] (hereinafter referred to as the compound of the present invention) is used as a preservative.

In the general formula [I], R ₁ and R ₂ are each a hydroxyl group,
It represents a nitro group or an alkyl group, and the alkyl group represented by R ₁ and R ₂ is preferably a lower alkyl group having 1 to 3 carbon atoms and includes those having a substituent. Examples of the substituent include a hydroxyl group and a carboxylic acid group.

Specific examples of the alkyl group represented by R ₁ and R ₂ include a methyl group, an ethyl group, a hydroxylmethyl group and a carboxymethyl group.

X ₁ and X ₂ are each -OM, -OR ₃ or Represents Here, M represents a hydrogen atom or an alkali metal atom, and examples of the alkali metal atom represented by M include a potassium atom and a sodium atom, and R ₃ represents an alkyl group but is represented by R _3. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms, and examples thereof include a methyl group, an ethyl group and a propyl group. R ₄ and R ₅ each represent a hydrogen atom or an alkyl group, and R ₄ and R _The alkyl group represented by ₅ is preferably an alkyl group having 1 to 3 carbon atoms, and examples thereof include a methyl group, an ethyl group and a propyl group.

Specific examples of the tartaric acid derivative of the present invention represented by the general formula [I] are shown below, but the present invention is not limited thereto.

Exemplified compound The concentration of the compound of the present invention in the color developing solution is preferably the same as that of hydroxylamine usually used as a preservative, for example, 0.1 g / l to 50 g / l is preferably used, and more preferably 0.5 g / l to It is 20 g / l.

It is known that some of the compounds of the present invention described above are added to US Pat. No. 2,384,663 as an antioxidant, a so-called preservative, for black and white developers and color developers.

However, there are various other compounds known as antioxidants, such as ascorbic acid, U.S. Pat.
2-anilinoethanol described in US Pat. No. 823,017, polyethyleneimine described in US Pat. No. 4,252,892, and JP-A-52-
Α-phenethyl alcohol described in 7729, JP-A-52-1
Amino acid compounds and the like described in 40324 are known,
Even if these are used in place of the salt of hydroxylamine, which is one of the conventional preservatives, the effect of preventing precipitation of the color developer over time, which is the effect of the present invention, and the pH stabilizing effect cannot be obtained. However, the present invention cannot be easily achieved, and in particular, an unexpected effect is obtained in combination with a carbonate described in detail below.

In the present invention, the compound of the present invention not only acts effectively as a preservative of the color developing agent, but also the carbonate described below in a system of 40 g / l or more, without causing precipitation, pH We have found that the stability of is greatly improved.

The compound of the present invention may be used in combination with other preservatives, and examples of the preservatives that can be used in combination include sodium sulfite, potassium sulfite, sodium bisulfite, sulfite salts such as potassium bisulfite, and further aldehydes or ketones. Bisulfite adducts such as formaldehyde bisulfite adduct and glutaraldehyde bisulfite adduct.

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

The p-phenylenediamine compound having a water-soluble group is
Compared with para-phenylenediamine-based compounds that do not have water-soluble groups such as N, N-diethyl-p-phenylenediamine, not only does it have the advantage that the light-sensitive material is not contaminated and that the skin is less likely to gobble, In the invention, the object of the present invention can be efficiently achieved by combining with the compound represented by the general formula [I].

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-C
_{H 2 OH, - (CH 2} ) m-NHSO 2 - (CH 2) n-CH 3 -, - (CH 2) mO- (CH 2) n-CH 3, - (CH 2 CH 2 O) nCmH 2m ₊₁ (m and n each represent O or an integer, respectively.), -COOH group, and as -SO ₃ H group and the like.

Specific examples of the water-soluble group-containing color developing agent used in the present invention are shown below, but the present invention is not limited thereto.

Specific examples of the water-soluble group-containing color developing agent used in the present invention are shown below, but the present invention is not limited thereto.

Illustrative color developing agent Of the above-illustrated color developing agents, the compounds shown in Exemplified Nos. (1), (3) and (4) are preferable for use in the present invention, and (1) is particularly preferable.

The color developing agent is usually used in the form of salt such as hydrochloride, sulfate, p-toluenesulfonate.

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

Further, the color developing solution of the present invention contains a carbonate as a pH stabilizer in an amount of 40 g or more, preferably 50 g or more, per 1 color developing solution.

Examples of the carbonate used in the present invention include potassium carbonate and sodium carbonate, with potassium carbonate being preferred.

By using the carbonate in combination with the compound of the present invention represented by the general formula [I], a color developing solution having a large pH stabilizing effect without the occurrence of precipitation can be provided.

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

As the alkaline agent other than the carbonate, for example, sodium hydroxide, potassium hydroxide, silicate, sodium metaborate, potassium metaborate, trisodium phosphate, tripotassium phosphate, borax, etc., alone or in combination, The effect of the present invention, that is, the precipitation is not generated, and it can be used in combination within a range of maintaining the pH stabilizing effect. Further, various salts such as disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium bicarbonate, potassium bicarbonate and borate are used for the necessity of preparation or for the purpose of increasing ionic strength. be able to.

If necessary, inorganic and organic antifoggants can be added, and as these antifoggants,
For example, inorganic halide compounds such as sodium bromide, potassium bromide, sodium iodide and potassium iodide, 6-nitrobenzimidazoles described in US Pat. No. 2,496,940, and 5 described in US Pat. Nos. 2,497,917 and 2,656,271. -Nitrobenzimidazole, o-phenylenediamine, mercaptobenzimidazole, mercaptobenzoxazole, thiouracil, 5-methylbenzotriazole, or JP-B-46-4
The heterocyclic compounds described in 1675 can be used.

In addition to these various components, Japanese Examined Patent Publication Nos. 46-19039 and 45-614
The development inhibitor compounds disclosed in Japanese Patent No. 9 and US Pat. No. 3,295,976 can be used.

Among the above antifoggants, the bromide ion supplied from sodium bromide, potassium bromide or the like is preferably 0.3 to 3 g / l or less from the viewpoint of rapid treatment.

Further, a development accelerator can be used if necessary.
US Pat. Nos. 2,648,604 and 3,67 as development accelerators.
1,247, 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.No. 2,533,990, No. 2,531,832,
No. 2,950,970, No. 2,577,127, and Japanese Patent Publication No. 44-9
Polyethylene glycol and its derivatives, nonionic compounds such as polythioethers described in JP-A-504,
The organic solvent described in 44-9509, organic amine, ethanolamine, ethylenediamine, diethanolamine, triethanolamine and the like are included. Also U.S. Pat.
Examples thereof include benzyl alcohol, phenethyl alcohol described in No. 4,925, and acetylene glycol, methyl ethyl ketone, cyclohexanone, thioethers, pyridine, ammonia, hydrazine, amines and the like.

However, in the color developing solution of the present invention, it is preferable that the organic solvent contains a solvent in the range of the volume ratio defined below.

In the above, logP is a value obtained from the partition coefficient P of n-octanol / water solvent, and the P value is obtained from the following formula.

The above values are values that have been widely used as a measure of lipophilicity, and can be found, for example, in Chemical Review (Chemical Review).
eview), 1971 Vol. 71, No. 6, 555-613. Further, although it can be determined by the calculation method described in Ecochemistry Vol. 6, pp. 3 to 11, it is preferable to use the actual measured value, and in the present invention, it is shown by the value measured using n-octanol.

Solvents having a log P of 0.4 or more, which are not preferably added to the color developer in the present invention in the above range or more, include aliphatic alcohols having 5 to 20 carbon atoms, aliphatic glycol ethers and alicyclic alcohols, respectively. And aromatic alcohols, and specific examples include benzyl alcohol logP 1.10 o-hydroxybenzyl alcohol logP 0.73 cyclohexanol logP 1.23 2-benzyloxyethanol logP 0.41 anisyl alcohol logP 0.70 1-pentanol logP 0.4 or more phenylethyl alcohol logP 1.36 p-tolylcarpinol logP 1.36 n-butanol logP 0.4 or more phenol logP 0.4 or more p-hydroxybenzyl alcohol logP 0.4 or more benzylamine logP 0.4 or more diethylene glycol monobutyl ether logP 0.41 and the like.

Further, examples of the solvent having a logP of less than 0.4 include aliphatic alcohols having 0 to 4 carbon atoms, organic acids and the like, or compounds having 5 or more carbon atoms having a functional group having high polarity. Specific examples include the following solvents.

Acetic acid, ethanol, acetone, propionic acid, propanol, ethylene glycol, diethylene glycol, triethylene glycol, triethanolamine, diethanolamine.

In the above, especially lo represented by benzyl alcohol
For a poorly soluble organic solvent having a gP of 0.4 or more, tar is likely to be generated particularly in a running process in a low replenishment system by using a color developing solution for a long period of time. Adhesion to the product may even cause a serious failure that significantly impairs its commercial value.

In addition, since poorly soluble organic solvents have poor solubility in water, not only is it troublesome that a stirring device is required for the preparation of the color developing solution itself, but also the use of such a stirring device results in poor solubility. Therefore, there is a limit to the effect of promoting development.

Furthermore, poorly soluble organic solvents have a large pollution load value such as biochemical oxygen demand (BOD) and cannot be disposed of in sewers or rivers. Since it has problems such as labor and cost,
It is preferable to reduce or eliminate the amount used. In the present invention, it can be used in a system containing benzyl alcohol, but it is preferable from the viewpoint of rapid processing, and particularly in a system having a high pH, a system containing no benzyl alcohol is one of the preferable embodiments.

Furthermore, the color developer of the present invention contains sodium tetrapolyphosphate, tetrasodium pyrophosphate, polyphosphoric acid such as condensed phosphate or a salt thereof, and various chelating agents as a water softener or a heavy metal sequestering agent. be able to.

Examples of the chelating agent preferably used in the present invention include RD 1
Examples include those described in 8837 and 18843.

Further, the color developing solution of the present invention, if necessary, ethylene glycol, methyl cellosolve, methanol, acetone, dimethylformamide, β-cyclodextrin, other JP-B-47-33378, 44-9509 JP The compound can be used as an organic solvent to increase the solubility of the developing agent.

Further, an auxiliary developing agent can be used together with the developing agent. Examples of these auxiliary developers include N-methyl-p-aminophenol hexalphate (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 / l. Besides this,
If necessary, a competitive coupler, a fogging agent, a colored coupler, a development inhibitor releasing type coupler (so-called DIR coupler), a development inhibitor releasing compound or the like can be added.

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

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

In the present invention, the color developing solution can be used in any pH range, but from the viewpoint of rapid processing, it is preferably pH 10.3 to 13.0, more preferably pH 10.7 to 12.5. In the present invention, a pH of 10.3 or higher, which is particularly suitable for rapid processing, is used.
Also in terms of pH, by containing the compound of the present invention and the carbonate at a concentration of 40 g / l or more, a stable color developing solution with a small pH decrease over time of the color developing solution and no precipitation of a precipitate is provided. In addition, the obtained dye image is stable without changing the developability, and has excellent characteristics such that the maximum color density does not decrease.

In the present invention, as the processing temperature of color development is 30 ° C. or higher, the higher the temperature is 50 ° C. or less, the faster the rapid processing becomes possible, which is preferable, but it is better not so high from the viewpoint of image storage stability. It is preferable to perform the treatment at a temperature of not lower than 45 ° C.

Conventionally, the processing time is generally 3 minutes and 30 seconds for color development, 1 minute and 30 seconds for bleach-fixing, and 3 minutes for stabilizing stabilization by washing with water. However, in the present invention, the color development time is 2 minutes or less. It is also possible to perform the operation within the range of 30 seconds to 1 minute and 30 seconds. In addition, the total of the above processing can be set within 6 minutes.

In the present invention, the compound and carbonate of the present invention are
It can be applied to any system as long as it is a system using a color developing solution containing a color developing agent having a water-soluble group of 40 g / l or more, and various other methods such as one-bath processing, for example, a processing solution can be used. Various processing methods such as a spray method for atomizing, or a web method by contact with a carrier impregnated with a processing solution, or a developing method with a viscous processing solution can be used, but the processing step is substantially color development, It consists of steps such as bleach-fixing, washing with water, or an alternative stabilizing treatment.

In the bleach-fixing step, the bleaching step and the fixing step may be separately provided, or a bleach-fixing bath in which bleaching and fixing are processed in one bath may be used.

The bleaching agent that can be used in the bleach-fixing solution used in the present invention is a metal complex salt of an organic acid. The complex salt is obtained by coordinating a metal ion such as iron, cobalt or copper with an aminopolycarboxylic acid or an organic acid such as oxalic acid or citric acid. The most preferable organic acid used for forming such a metal complex salt of an organic acid includes a polycarboxylic acid.
These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. Specific examples of these include the following.

[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 Etherdiamine toteracetic acid [10] Glycol ether diantetraacetic acid [11] Ethylenediaminetetrapropionic acid [12] Phenylenediaminetetraacetic acid [13] Ethylenediaminetetraacetic acid disodium salt [14] Ethylenediaminetetraacetic acid tetra (trimethylammonium) salt [15] Ethylenediaminetetraacetic acid tetrasodium salt [16] Diethylenetriaminepentaacetic acid pentasodium salt [17] Ethylenediamine-N- (β-oxyethyl)-
N, N ', N'-triacetic acid sodium salt [18] Propylenediaminetetraacetic acid sodium salt [19] Nitriloacetic acid sodium salt [20] Cyclohexanediaminetetraacetic acid sodium salt These bleaching agents are preferably 5-450 g / l. 20-250g
Use with / l. As the bleach-fixing solution, a solution having a composition containing a silver halide fixing agent in addition to the above-mentioned bleaching agent and, if necessary, a sulfite as a preservative is applied. Further, a bleach-fixing solution having a composition in which a small amount of an ethylenediaminetetraacetic acid iron (III) complex bleaching agent and a halide such as ammonium bromide other than the above silver halide fixing agent are added in a small amount, or conversely, a halogenating agent such as ammonium bromide is used. A bleach-fixing solution having a composition containing a large amount of a halide, and a special bleach-fixing solution having a composition comprising a combination of an ethylenediaminetetraacetic acid iron (III) complex bleach and a large amount of a halide such as ammonium bromide are used. be able to. As the halide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. may be used in addition to ammonium bromide. it can.

The silver halide fixing agent contained in the bleach-fixing solution is a compound which forms a water-soluble complex salt by reacting with silver halide as used in ordinary fixing processing, for example, potassium thiosulfate, sodium thiosulfate, thiol. Typical examples thereof include thiosulfates such as ammonium sulfate, potassium thiocyanate, sodium thiocyanate, thiocyanates such as ammonium thiocyanate, thiourea and thioether. These fixing agents are used in an amount in the range of 5 g / l or more so that they can be dissolved, but generally 70 g to 250 g / l are used.

The bleach-fix solution contains boric acid, borax, sodium hydroxide,
Various pH buffering agents such as potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide can be contained alone or in combination of two or more kinds. Furthermore, various fluorescent whitening agents, antifoaming agents or surfactants may be contained. In addition, preservatives such as bisulfite adducts of hydroxylamine, hydrazine, and aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids, stabilizers such as nitroalcohol and nitrates, organic agents such as methanol, dimethylsulfamide, dimethylsulfoxide, etc. A solvent and the like can be contained as appropriate.

The bleach-fixing solution used in the present invention includes JP-A-46-280, JP-B-45-8506, Copper-46-556, Belgian Patent No. 770,910,
Various bleaching accelerators described in JP-B-45-8836, JP-B-53-9854, JP-A-54-71634 and JP-A-49-42349 can be added.

The bleach-fix solution is used at a pH of 4.0 or higher, but it is generally
Used at pH 5.0 to pH 9.5, preferably pH 6.0 to pH
Used below 8.5, further stated the most preferred pH is 6.5
Processed above 8.5. The processing temperature is 80 ° C. or lower and 3 ° C. or higher, preferably 5 ° C. higher than the processing solution temperature in the color developing tank.
Although it is used at a lower temperature, it is preferably used at 55 ° C or lower while suppressing evaporation and the like.

In the present invention, subsequent to the color development and bleach-fixing steps, washing with water or an alternative stabilizing treatment with washing with water is performed.

Hereinafter, the stabilizing solution for washing substitute which can be applied to the present invention will be described.

The pH of the water substitute alternative stabilizing solution applicable to the present invention is preferably
It is in the range of 5.5 to 10.0, more preferably in the range of pH 6.3 to 9.5, and particularly preferably in the range of pH 7.0 to 9.0.
As the pH adjusting agent that can be contained in the water-washing substitute stabilizing solution applicable to the present invention, any of generally known alkali agents or acid agents can be used.

The treatment temperature for stabilizing treatment is 15 ° C to 60 ° C, preferably 20 ° C.
The range of ~ 45 ℃ is good. The treatment time is also preferably shorter from the viewpoint of rapid treatment, but is usually 20 seconds to 10 minutes, most preferably 1 minute to 3 minutes. However, it is preferable that the treatment time is longer in the latter-stage tank. In particular, it is desirable to perform the treatment sequentially with a treatment time that is 20% to 50% longer than that of the previous tank. After the stabilization treatment applicable to the present invention, washing treatment is not required at all, but rinsing by a small amount of washing in a very short time, surface washing, etc. can be optionally performed.

When the multi-tank counter current method is used as the method for supplying the stabilizing solution for washing with water in the stabilization treatment step applicable to the present invention, it is preferable to supply the stabilizing solution to the post-bath and cause the overflow from the pre-bath. Of course, it can also be processed in a single tank. As a method of adding the above compound, the compound and other additives are added to the stabilizing tank as a concentrated solution, or the above washing alternative stabilizing solution supplied to the stabilizing tank is added to the washing alternative stabilizing replenisher. There are various methods such as whether to use the supply liquid, but any addition method may be used.

As described above, in the present invention, the treatment with the stabilizing solution refers to the treatment for stabilizing treatment in which the stabilizing treatment is carried out immediately after the treatment with the treating solution having a bleach-fixing ability and the washing treatment is not substantially carried out. The treatment liquid used for the chemical treatment is called a water washing substitute stabilizer, and the treatment tank is called a stabilizing bath or a stabilizing tank.

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

The method for processing a silver halide color photographic light-sensitive material of the present invention comprises the color developer of the present invention, that is, a p-phenylenediamine compound having a water-soluble group as a color developing agent and a compound of the present invention as a preservative. Further, using a color developing solution containing 40 g / l or more of carbonate, color development processing is performed on a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer containing an imagewise exposed dye-forming coupler. Is to be performed.

In the method of processing a silver halide color photographic light-sensitive material of the present invention, a color paper is a silver halide color photographic light-sensitive material as long as it is a light-sensitive material processed by a so-called internal development method containing a coupler in the light-sensitive material. , A color negative film, a color positive film, a slide color reversal film, a movie color reversal film, a TV color reversal film, a reversal color paper, and the like, which can be applied to any silver halide color photographic light-sensitive material.

The photographic coupler used in the present invention is preferably a phenol-based compound or a naphthol-based compound as a cyan coupler, for example, U.S. Patents 2,369,929 and 2,434,2.
72, 2,474,293, 2,895,826, 3,253,924
Issue 3,034,892, Issue 3,311,476, Issue 3,386,301,
3,419,390, 3,458,315, 3,476,563, 3,5
No. 91,383, etc., and methods for synthesizing these compounds are also described in the publication.

Examples of magenta couplers for photography include pyrazolone-based, pyrazolotriazole-based, pyrazolinobenzimidazole-based, and indazolone-based compounds. As a pyrazolone-based magenta coupler, US Pat.
No. 3, No. 3,062,653, No. 3,127,269, No. 3,311,476,
3,419,391, 3,519,429, 3,558,318, 3,6
84,514, 3,888,680, JP-A-49-29639, 49-11
No. 1631, No. 49-129538, No. 50-13041, Japanese Patent Publication No. 53-4716
Nos. 7, 54-10491 and 55-30615; pyrazolotriazole-based magenta couplers include couplers described in US Pat. No. 1,247,493 and Belgium Patent 792,525, and have diffusion resistance As the colored magenta coupler of, a compound in which an arylazo substitution is generally used at the coupling position of a colorless magenta coupler is used, for example, U.S. Pat.Nos. 2,801,171 and 2,983,608,
3,005,712, 3,684,514, British Patent 937,621,
Examples thereof include compounds described in JP-A-49-123625 and JP-A-49-31448.

Further, a colored magenta coupler of the type described in U.S. Pat. No. 3,419,391, in which a dye flows out into a processing solution upon reaction with an oxidized product of a developing agent, can also be used.

As the photographic yellow coupler, an open-chain ketomethylene compound has been conventionally used, and a benzoylacetanilide type yellow coupler and a pivaloylacetanilide type yellow coupler which are generally widely used can be used. Further, a 2-equivalent type 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. Examples of these are U.S. Patents 2,875,057 and 3,265,506.
No., No. 3,664,841, No. 3,408,194, No. 3,227,155,
3,447,928, 3,415,652, Japanese Patent Publication No. 49-13576, JP-A-48-29432, 48-68834, 49-10736, 48-1.
22335, 50-28834, 50-132926 and the like, together with the synthetic method.

The amount of the above diffusion-resistant coupler used in the present invention is generally from 0.05 to 1 mol per mol of silver in the photosensitive silver halide emulsion layer.
2.0 mol.

In the present invention, a DIR compound is preferably used in addition to the above diffusion resistant coupler.

Further, in addition to the DIR compound, a compound that releases a development inhibitor upon development is also included in the present invention.
297,445, 3,379,529, West German patent application (OLS) 2,41
7,914, JP-A Nos. 52-15271, 53-9116, and 59-12383.
No. 8, No. 59-127038, etc. are mentioned.

The DIR compound used in the present invention is a compound capable of reacting with an oxidized product of a color developing agent to release a development inhibitor.

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

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

Furthermore, JP-A Nos. 54-145135, 56-114946 and
When reacted with an oxidant of a color developing agent as described in 57-154234, the mother nucleus forms a dye or a colorless compound, while the released timing group undergoes an intramolecular nucleophilic substitution reaction or an elimination reaction. The so-called timing DIR compounds, which are compounds that release development inhibitors by, are also included in the present invention.

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

The amount of the DIR compound contained in the light-sensitive material is preferably in the range of 1 × 10 ^-4 mol to 10 × 10 ^-1 mol per mol of silver.

The silver halide in the silver halide emulsion layer of the silver halide color photographic light-sensitive material used in the present invention includes silver chloride,
Any of silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, silver chloroiodobromide, and mixtures thereof can be used, but the effect of the present invention is more preferable. Substantially silver chlorobromide is preferable as it is efficiently achieved.

The term "substantially silver chlorobromide" as used herein means that a small amount of silver iodide may be contained in addition to silver chlorobromide, for example, 0.3 mol% or less, and more preferably 0.1 mol% or less of silver iodide. Means silver chlorobromide. However, silver chlorobromide containing no silver iodide is most preferred in the present invention.

The crystal of the silver halide grain may be normal crystal, twin crystal or other crystal, and any ratio of [100] plane to [111] plane can be used. Further, the crystal structure of these silver halide grains may be uniform from the inside to the outside or may have a layered structure (core / shell type) in which the inside and the outside are different. Further, these silver halides may be of a type that forms a latent image mainly on the surface or may be of a type that is formed inside the grain. Further, tabular silver halide grains (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 of the acid method, the neutral method and the 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, the pH, pAg, etc. in the reaction vessel are controlled, and an amount of silver ions corresponding to the growth rate of silver halide grains as described in JP-A-54-48521, for example. It is preferable to sequentially and simultaneously inject and mix halide ions with halide ions.

The silver halide grains according to the present invention are preferably prepared as described above. The composition containing the silver halide grains is referred to herein as a silver halide emulsion.

These silver halide emulsions include activated gelatin; sulfur sensitizers such as allylthiocarbamide, thiourea and cystine sulfur sensitizers; selenium sensitizers; reduction sensitizers such as stannous salt and thiodioxide. Urea, polyamine and the like; noble metal sensitizers such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-aurothio-3-methylbenzothicazolium chloride and the like or ruthenium, palladium, platinum, etc. Sensitizers for water-soluble salts such as rhodium and iridium, specifically ammonium chloroparadate, potassium chloroplatinate and sodium chloroparadate (some of these are sensitizers or antifoggants depending on the amount) Acting as an agent, etc.) or in combination as appropriate (eg, gold sensitizer and sulfur sensitizer). Combination of agents, together like a gold sensitizer and a selenium sensitizer) may be chemically sensitized with.

The silver halide emulsion according to the present invention is chemically ripened by adding a sulfur-containing compound, and before, during, or after the chemical ripening, at least one kind of nitrogen-containing heteroaryl having a hydroxytetrazaindene and a mercapto group. You may make it contain at least 1 sort (s) of a ring compound.

The silver halide used in the present invention contains a suitable sensitizing dye in an amount of 5 × 10 ^{−8 to} 3 × 10 ^{−3 with} respect to 1 mol of silver halide in order to impart photosensitivity to a desired wavelength region. It may be optically sensitized by adding a mole. Various kinds of sensitizing dyes can be used, and one kind or a combination of two or more kinds of sensitizing dyes can be used. Examples of the sensitizing dye that can be advantageously used in the present invention include the following.

That is, as a sensitizing dye used in a blue-sensitive silver halide emulsion, for example, West German Patent 929,080 and U.S. Pat.
No. 2,493,748, 2,503,776, 2,519,001,
2,912,329, 3,656,959, 3,672,897, 3,6
94,217, 4,025,349, 4,046,572, British patent 1,
242,588, Japanese Patent Publication Nos. 44-14030, 52-24844 and the like can be mentioned. Examples of sensitizing dyes used in green-sensitive silver halide emulsions include, for example, U.S. Patents 1,939,201, 2,072,908, 2,739,149 and 2,9.
Representative examples thereof include cyanine dyes, merocyanine dyes, and complex cyanine dyes such as those described in 45,763 and British Patent 505,979. Further, sensitizing dyes used in red-sensitive silver halide emulsions include, for example, U.S. Patents 2,269,234, 2,270,378 and
Representative examples thereof include cyanine dyes, merocyanine dyes, or complex cyanine dyes as described in 2,442,710, 2,454,629, 2,776,280 and the like. Furthermore, U.S. Patents 2,213,995 and 2,493,748
Cyanine dyes, merocyanine dyes or complex cyanine dyes such as those described in U.S. Pat. No. 2,519,001 and West German Patent 929,080 can be advantageously used in a green-sensitive silver halide emulsion or a red-sensitive silver halide emulsion.

These sensitizing dyes may be used alone or in combination.

The photographic light-sensitive material of the present invention may be optically sensitized to a desired wavelength region by a spectral sensitization method using a cyanine or merocyanine dye alone or in combination, if necessary.

Representative examples of particularly preferable spectral sensitization methods are, for example,
Japanese Examined Patent Publication Nos. 43-4936 and 4 on the combination of benzimidazolocarbocyanine and benzoxazolocarbocyanine
No. 3-22884, No. 45-18433, No. 47-37443, No. 48-28293
No. 49-6209, No. 53-12375, JP-A-52-23931,
52-51932, 54-80118, 58-153926, 59-11
6646, 59-116647, etc. are mentioned.

Further, as a combination of carbocyanine having a benzimidazole nucleus and other cyanine or merocyanine, for example, Japanese Patent Publication Nos. 45-25831, 47-11114 and 47
-25379, 48-38406, 48-38407, 54-34535
No. 55-1569, JP-A No. 50-33220, No. 50-38526,
51-107127, 51-115820, 51-135528, 52-
No. 104916, No. 52-104917 and the like.

Further, as a combination of benzoxazolocarbocyanine (oxacarbocyanine) with other carbocyanine, for example, Japanese Patent Publication Nos. 44-32753 and 46-11627,
JP-A-57-1483 and merocyanine include, for example, JP-B-48-38408, JP-A-48-41204, and JP-A-50-40662.
No. 56-25728, No. 58-10753, No. 58-91445,
No. 59-116645, No. 50-33828 and the like.

Further, as a combination of thiacarbocyanine with other carbocyanine, for example, Japanese Patent Publication Nos. 43-4932 and 43-4932
No. 4933, No. 45-26470, No. 46-18107, No. 47-8741,
JP-A-59-114533 and the like, and the method described in JP-B-49-6207 using zeromethine or dimethine merocyanine, monomethine or trimethine cyanine and a styryl dye can be advantageously used.

In order to add these sensitizing dyes to the silver halide emulsion according to the present invention, a dye solution such as methyl alcohol, ethyl alcohol, acetone, dimethylformamide, or a fluorinated alcohol described in JP-B-50-40659 can be prepared in advance. It is used by dissolving it in a hydrophilic organic solvent.

The silver halide emulsion may be added at any time from the start of chemical ripening, during ripening, and at the end of ripening, and in some cases, it may be added immediately before the emulsion coating.

The photographic constituent layers of the silver halide color photographic light-sensitive material of the present invention may contain a dye (AI dye) which is water-soluble or decolorizes with a color developing solution. Examples of the AI dye include oxonol dyes and hemioxonol dyes. Dyes, merocyanine dyes and azo dyes are included. Oxonol dye,
Hemioxonol dyes and merocyanine dyes are useful. Examples of AI dyes that can be used are British Patent 584,609.
No. 1,277,429, JP-A-48-85130, 49-99620
No. 49, No. 114420, No. 49-129537, No. 52-108115,
59-25845, 59-111640, 59-111641, US Patents 2,274,782, 2,533,472, 2,956,879, 3,1
25,448, 3,148,187, 3,177,078, 3,247,12
No. 7, No. 3,260,601, No. 3,540,887, No. 3,575,704,
3,653,905, 3,718,472, 4,071,312, 4,0
The thing described in 70,352 can be mentioned.

These AI dyes are generally 2x per mole of silver in the emulsion layer.
It is preferable to use 10 ^{−3 to} 5 × 10 ⁻¹ mol, and more preferably 1 × 10 ⁻² to 1 × 10 ⁻¹ mol.

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

In the silver halide color photographic light-sensitive material used in the present invention, the hydrophilic colloid used for preparing the emulsion includes gelatin, derivative gelatin, a graft polymer of gelatin and another polymer, a protein such as albumin and casein. , Hydroxyethyl cellulose derivatives, cellulose derivatives such as carboxymethyl cellulose, starch derivatives, polyvinyl alcohol, polyvinyl imidazole,
Any one such as a single or copolymer synthetic hydrophilic polymer such as polyacrylamide is included.

As the support of the silver halide color photographic light-sensitive material used in the present invention, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, a transparent support provided with a reflective layer, or in combination with a reflector, such as a glass plate, Examples thereof include polyester films such as cellulose acetate, cellulose nitrate or polyethylene terephthalate, polyamide films, polycarbonate films, polystyrene films and the like, and other usual 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. U.S. Patent 2,761,791
No. 2,941,898, the method of simultaneous coating 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 light-sensitive material for photographic paper, it is preferable to sequentially arrange a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer from the support side. . Each of these light sensitive silver halide emulsion layers may consist 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 depending on the purpose, and further, a filter layer,
Various layers such as an anti-curl layer, a protective layer and an antihalation layer can be appropriately combined and used as constituent layers.
A hydrophilic colloid which can be used in the emulsion layer as described above can be similarly used as a binder in these constituent layers, and various hydrophilic colloids can be contained in the emulsion layer as described above. The above photographic additives can be incorporated.

[Specific effects of the invention] As described above, in the present invention, a color developing solution suitable for rapid processing in which a decrease in pH of the color developing solution with time is small even at a high pH and precipitation is hardly generated. It was also possible to provide a processing method in which a silver halide color photographic light-sensitive material was processed to enable rapid processing excellent in developability and maximum color density.

EXAMPLES Specific Examples of the Invention Hereinafter, the present invention will be described in more detail with reference to Examples, but the embodiments of the present invention are not limited thereto.

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

[Color developer A] Ethylene glycol 10.0 g Nitrilotrimethylene phosphinic acid 2.0 g Potassium sulfite 5.0 g Color developing agent (sulfate of Exemplified Compound No. (1)) 2 × 10
^-2 mol Potassium bromide 1.0 g Sodium chloride 2.0 g pH stabilizer (listed in Table-1) 60 g Preservative (listed in Table-1) 3.0 g Water to 1 and potassium hydroxide and sulfuric acid to pH 11.0 Adjust to.

The color developer A was left standing at room temperature for 12 days under an open condition, and the pH value after standing and the state of precipitation were visually determined. Further, the concentration of the color-developing agent remaining in the color-developing solution was analyzed by high performance liquid chromatography of the color-developing solution and determined as a residual ratio (%) with respect to the amount added immediately after preparation. In addition,
At this time, those having a precipitate were determined for those not containing the precipitate and those obtained by re-dissolving the precipitate.

In addition, the occurrence status of precipitation was evaluated by the following four-stage evaluation.

 -No precipitation occurs.

 + A slight amount of precipitate is observed.

 ++ Precipitation is observed.

++ Significant amount of precipitate is observed.

The above results are summarized in Table-1.

As is clear from Table 1, in color developing solutions in which the types of pH stabilizers and the types of preservatives were changed, in the experiments Nos. 1 to 7 in which comparative pH stabilizers were used, A large amount of precipitates were generated in all cases where conventional hydroxylamine was used as an agent, and precipitation was also generated in cases where the compound of the present invention was used as a preservative. Further, even if carbonate is used as a pH stabilizer, Experiment No. 9 using conventional hydroxylamine as a preservative, Experiment Nos. 10 to 1 using a comparative compound
In the case of 6, precipitation occurred and pH stabilization was insufficient. Further, in Experiment No. 8 in which hydroxylamine was not used, precipitation also occurred, but it can be seen that the concentration of the main drug is low and decomposition is progressing even in the case of re-dissolving the precipitate as the residual ratio of the main drug.

On the other hand, in Experiment Nos. 17 to 22 of the constitution of the present invention, there was no precipitation even if the kind of the preservative was changed, the pH decrease was small, the main ingredient residual rate was high, and the stability over time was excellent. You can see that

Furthermore, in the above Experiment No. 17, instead of the exemplified compound (1) as a preservative, each of the exemplified compounds (7) to (1)
Similar results were obtained using 6), confirming the effect of the present invention.

Example-2 The following color developer B was prepared.

[Color developer B] Immediately after preparation of the above color developer B, it is left at room temperature for 12 days,
The pH value and the occurrence of precipitation on the same day, 4th day, 8th day and 12th day were determined in the same manner as in Example-1. The results are also shown in Table-2.

As is clear from Table-2, in the experiments in which the pH value during preparation was variously changed, in Experiments 23 to 30 using hydroxylamine, which is a conventional preservative, in particular, it was observed that the pH was all over the range up to 12.5. Precipitation has occurred in the area, and the rate of pH decrease is large. At pH 13.0, no precipitation occurs, but the pH drops significantly over time. On the other hand, in the constitution of the present invention, no precipitation is observed at any pH, and it can be seen that the stability of pH with time is also excellent.

Example-3 The following color developer C was prepared.

[Color developer C] The pH value and the state of occurrence of precipitation of the above color developing solution C were determined in the same manner as in Example-1. The results are shown in Table-3.

As is clear from Table 3, in experiments in which the kind and amount of carbonate were changed, in any of Experiments No. 39 to 46 using hydroxylamine, which is a conventional preservative, the occurrence of precipitation was observed. . On the other hand, in the constitution of the present invention, the occurrence of precipitation is basically suppressed as compared with the comparative experiment, and the pH decrease with time is small. Further, focusing on the type of carbonate, it was found that potassium carbonate is preferable to sodium carbonate even if the amount of addition is large, since precipitation is less likely to occur, and if the amount of addition of carbonate is too large, precipitation occurs.

Example-4 In the color developer C of Example-3, the amount of potassium carbonate as a carbonate and the preservative are shown in Tables 4-1 and 4- below.
The same color developing solutions D-1 and -2 were prepared as shown in Table 2, except that the initial pH value was set to 11.00 in Table 4-1 and the initial pH value was set to 10.30 in Table 4-2. . For each of them, the pH value and the state of occurrence of precipitation were determined in the same manner as in Example-1. The results are shown in Table 4-1 and Table 4-2, respectively.

Further, the following color papers were prepared, and after stepwise exposure, the color developing solutions D-1 and D-2 were stored for 12 days, respectively, and developed under the following developing conditions. An optical densitometer (PDA-6
5, the maximum density of yellow was measured with blue light from Konishi Roku Photo Industry Co., Ltd.). Further, the color tone of the black portion of the white exposed portion was visually evaluated according to the following three-stage evaluation.

 ◯: The black part looks completely black.

 X: The black part looks a little blue, and is a level of a little problem.

XX: The black portion looks blue, which is not practical.

The above results are also combined in Table 4-1 and Table 4-2, respectively.
Shown in.

[Color Paper] The following layers were sequentially coated on a polyethylene-coated paper support from the support side to prepare a light-sensitive material.

The polyethylene coated paper has an average molecular weight of 100,
000, density 0.95 polyethylene 200 parts by weight and average molecular weight 2,
000, 6.8 wt% of anatase type titanium oxide was added to a mixture of 20 parts by weight of polyethylene having a density of 0.80, and a coating layer having a thickness of 0.035 mm was formed on the surface of the fine paper having a weight of 170 g / m ² by the extrusion coating method, The back side was provided with a coating layer of 0.040 mm thickness made of polyethylene only. After pretreatment by corona discharge on the polyethylene-coated surface of this support, each layer was sequentially coated.

First layer: a blue-sensitive silver halide emulsion layer comprising a silver chlorobromide emulsion containing 60 mol% of silver bromide, said emulsion containing 350 g of gelatin per mol of silver halide and having the following structure per mol of silver halide: Sensitizing dye Sensitized with 2.5 × 10 ^-3 mol (using isopropyl alcohol as solvent), dissolved in dibutyl phthalate and dispersed in 2,5-di-t-butyl hadroquinone 200 mg / m
² and α- [4- (1-benzyl-2-phenyl-3,5-dioxo-1,2,4-triazolydyl)] α-bivalyl-2-chloro-5- [γ- (2, Four
- di -t- amylphenoxy) butylamide] acetanilide per mol of silver halide per 2 × 10 ^- includes moles,
It is coated so that the amount of silver is 330 mg / m ² .

Second layer: di-t-octylhydroquinone 300 mg / m ² dissolved and dispersed in dibutyl phthalate, and as a UV absorber 2-
(2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-
5'-t-butylphenyl) benzotriazole, 2-
(2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole and 2-
200 mg / (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chloro-benzotriazole mixture
The gelatin layer containing m ² was coated so that the amount of gelatin would be 2000 mg / m ² .

Third layer: a green-sensitive silver halide emulsion layer comprising a silver chlorobromide emulsion containing 60 mol% of silver bromide, the emulsion containing 450 g of gelatin per mol of silver halide and having the following structure per mol of silver halide. Sensitizing dye Sensitized with 2.5 × 10 ^-3 mol, 2,5-di-t-butylhydroquinone 150 mg dissolved and dispersed in a 2: 1 mixed solvent of dibutyl phthalate and tricresyl phosphate
/ m ² and 1- (2,4,6-trichlorophenyl) -3- (2-chloro-5-octadecenylsuccinimidoanilino) -5-pyrazolone as a magenta coupler at 1.5 per mol of silver halide. × 10 ^-1 mol content, silver amount 300 mg / m ²
Is applied so that As an antioxidant
0.3 mol of 2,2,4-trimethyl-6-lauryloxy-7-t-octylchroman was contained per mol of the coupler.

Fourth layer: Di-t-octylhydroquinone 30 mg / m ² dissolved and decomposed in dioctyl phthalate and 2 as an ultraviolet absorber
-(2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-
5'-t-butylphenyl) benzotriazole, 2-
(2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole and 2-
(2'-hydroxy-3 ', 5'-t-butylphenyl)
A mixture of -5-chloro-benzotriazole (2: 1.5: 1.
5: 2) in a gelatin layer containing 500 mg / m ^{2 and the} amount of gelatin is 200
It is coated so that it will be 0 mg / m ² .

Fifth layer: a red-sensitive silver halide emulsion layer comprising a silver chlorobromide emulsion containing 60 mol% of silver bromide, the emulsion containing 500 g of gelatin per mol of silver halide and having the following structure per mol of silver halide: Sensitizing dye 2,5-di-t-butylhydroquinone 150 mg / m ² sensitized with 2.5 × 10 ^-3 mol and dissolved in dibutyl phthalate and dispersed as a cyan coupler 2,4-dichloro-3-methyl- 6- [γ- (2,4-Diamylphenoxy) butyramide] phenol was contained in an amount of 3.5 × 10 ^-1 mol per mol of silver halide, and the coating amount was 300 mg / m ² .

Sixth layer: The gelatin layer is coated so that the amount of gelatin is 10,000 mg / m ² .

The silver halide emulsion used for each light-sensitive emulsion layer (first, third, fifth layer) was prepared by the method described in JP-B-46-7772, and sodium thiosulfate pentahydrate was used for each. Chemically sensitized, 4-hydroxy-6-methyl-1, as a stabilizer,
It contained 3,3a, 7-tetrazaindene, bis (vinylsulfonylmethyl) ether as a hardener and saponin as a coating aid.

[Processing process] <Bleaching and fixing tank liquid> As is clear from the results in Tables 4-1 and 4-2, pH
In both the 11.00 system and the pH 10.30 system, those using hydroxylamine, which is a conventional preservative, both cause precipitation over time when 20 to 60 g of carbonate is added, resulting in a significant decrease in pH. . On the other hand, it can be seen that any of those using the preservative of the present invention is a color developing solution in which no precipitation occurs, a decrease in pH is small, and stability with time is excellent. Further, in the result of processing a silver halide color photographic light-sensitive material using this color developing solution, the difference in maximum density is markedly shown. Further, in particular, the color tone of the black portion is bluish except for the constitution of the present invention, which is a problem, whereas in the present invention, there is no problem, the developability and the maximum color density are excellent, and rapid processing is possible. You can see that it was done.

Example-5 A color developing solution E was prepared in the same manner as in the color developing solution C of Example-3 except that the amount of the carbonate was 60 g and the color developing agent and the preservative were as shown in Table 4. It was determined in the same manner as in Example 1, which shows the pH value and the occurrence of precipitation over time. The results are shown in Table-5.

Further, after the color paper sample prepared in Example-4 was subjected to stepwise exposure and the above-mentioned color developer E was stored for 12 days, the same procedure as in Example-4 was carried out except that the development time was 60 seconds. It was developed. The maximum yellow density of the obtained color paper sample was measured in the same manner, and the results are shown in Table-5.

As is clear from Table 5, in the system in which the type and the concentration of the color developing agent are variously changed, the toner of the present invention is compared with Comparative experiments 75 to 90 using the conventional preservative hydroxylamine. In Experiments 91 to 106 using the preservative, the pH stabilizing effect over time was large and the occurrence of precipitation was suppressed. However, in Experiments 91 to 94 in which a color developing agent other than the present invention having no water-soluble group was used, there were drawbacks in that precipitation occurred and the maximum yellow density was insufficient. On the other hand, the experiment 95-
In the case of 106, the pH stabilizing effect was large, almost no precipitation occurred, and the maximum yellow density was also satisfactory.

Example-6 In the color developer C of Example-3, the amount of the carbonate was 60 g, and the preservatives were as shown in Table-6 (hydroxylamine sulfate (3 g / l), 3 g of the exemplified compound (1)). / l,
Color developers E and F in the same manner except that the three types (10 g / l) were used.
And G were prepared.

Further, in the color paper sample prepared in Example-4, the color paper samples having the silver halide compositions of the silver halide compositions of the first, third and fifth layers as shown in -6 were subjected to the stepwise exposure and then the above color development. Preparation of Solution Using the color developing solution stored on the same day and stored for 10 days, development processing was carried out in the same manner as in Example-4. However, the development temperature was 35 ° C. and the development time was 50 seconds.
The maximum yellow density of the obtained color paper sample was measured in the same manner as in Example-4, and from the maximum yellow density obtained from the color developing solution on the same day as the developer preparation and after storage for 10 days, the yellow dye density was calculated by the following formula. The rate of decrease was calculated.

The results are also shown in Table-6.

As is apparent from Table-6, in any of the silver halide compositions used in the silver halide color photographic light-sensitive material, the compound of the present invention was used in comparison with the system using hydroxylamine which is a conventional preservative. It can be seen that the one used as a preservative has a low reduction rate of the yellow dye concentration, that is, the maximum color density does not decrease even with the use of a color developing solution over time, and is an excellent processing method. Further, in more detail, as compared with a silver halide color photographic light-sensitive material containing silver iodide or 100 mol% silver bromide, a silver halide color photographic light-sensitive material containing silver chlorobromide was used in the present invention. It can be seen that the degree of improvement in the density reduction rate when processed with the color developing solution is large and is preferable.

Front Page Continuation (72) Inventor Masao Ishikawa 1 Sakura Town, Hino City, Tokyo, Konishi Roku Photo Industry Co., Ltd. (72) Inventor Yoko Matsushima 1 Sakura Town, Hino City, Tokyo Roku Konishi Photo Industry Co., Ltd. (56 ) Reference JP-A-55-25028 (JP, A) Research Disclosure e16156

Claims (10)

[Claims] 1. A color developing solution for processing a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer containing a dye-forming coupler, and a p-phenylenediamine system having a water-soluble group as a color developing agent. A color developing solution containing a compound, containing 40 g or more of a carbonate per color developing solution, and further containing a compound represented by the following general formula [I]. General formula [I] [In the formula, R ₁ and R ₂ each represent a hydroxyl group, a nitro group or an alkyl group, and X ₁ and X ₂ represent —OM and —OR, respectively.
₃ or (M represents a hydrogen atom or an alkali metal atom, R ₃ represents an alkyl group, and R ₄ and R ₅ represent a hydrogen atom or an alkyl group, respectively). ] 2. The color developing solution according to claim 1, wherein the pH of the color developing solution is 10.3 or higher. 3. The color developing solution according to claim 1 or 2, wherein the carbonate is potassium carbonate. 4. A color developing solution containing 50 g or more of the carbonate in an amount of at least 50 g.
The color developer according to item (2) or (3). 5. A p-phenylenediamine compound having a water-soluble group is contained in an amount of 1.5 × 10 ⁻² mol or more per 1 color developing solution.
The color developing solution according to item (2), (3) or (4). 6. A silver halide color photographic light-sensitive material which is subjected to a process including at least a color developing step after imagewise exposure of a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer containing a dye-forming coupler. In the material processing method, the color developing solution used in the color developing step contains a p-phenylenediamine compound having a water-soluble group as a color developing agent, and contains 40 g or more of carbonate per 1 color developing solution, A processing method of a silver halide color photographic light-sensitive material, which further comprises a compound represented by the following general formula [I]. General formula [I] [In the formula, R ₁ and R ₂ each represent a hydroxyl group, a nitro group or an alkyl group, and X ₁ and X ₂ represent —OM and —OR, respectively.
₃ or (M represents a hydrogen atom or an alkali metal atom, R ₃ represents an alkyl group, and R ₄ and R ₅ represent a hydrogen atom or an alkyl group, respectively). ] 7. The method for processing a silver halide color photographic light-sensitive material according to claim 6, wherein the pH of the color developing solution is 10.3 or more. 8. The method of processing a silver halide color photographic light-sensitive material according to claim 6 or 7, wherein the carbonate is potassium carbonate. 9. The method according to claim 6, wherein the carbonate contains 50 g or more per color developing solution.
Item 7. The method for processing a silver halide color photographic light-sensitive material according to Item (7) or (8). 10. The p-phenylenediamine compound having a water-soluble group is contained in an amount of 1.5 × 10 ⁻² mol or more per 1 color developer.
Item 7. The method for processing a silver halide color photographic light-sensitive material according to Item (7), Item (8) or Item (9).