JPS62242938A - Method for processing silver halide photographic sensitive material giving dye image with high maximum density of developed color - Google Patents

Abstract

PURPOSE:To inhibit the lowering of the pH of a liquid color developer with the lapse of time and to improve the shelf stability by adding a specified sulfonic acid deriv. and an alkyl substituted hydroxylamine to the developing soln. CONSTITUTION:A liquid color developer contg. a sulfonic acid deriv. represented by formula I, e.g., a compound represented by formula II and a hydroxylamine represented by formula III as a preservative, e.g., a compound represented by formula IV is used. In the formula I, R1 is 1-8C alkyl or phenyl and X is H, Na, K or the like. In the formula III, each of R2 and R3 is 1-3C alkyl or alkoxy. The pH of the developer is adjusted to >=10.0 with a carbonate. The preservative has superior stability, the pH of the developer is kept stable and tar is hardly produced, so the development of silver by the preservative is prevented and an image with high maximum density of developed color is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for processing silver halide color light-sensitive materials, and more specifically, the present invention relates to a method for processing silver halide color light-sensitive materials, and more specifically, the present invention relates to a method for processing silver halide color light-sensitive materials, using a color developing solution that has excellent pH stability over time and storage stability over time. The present invention relates to a method for processing a silver halide color light-sensitive material in which the obtained dye image has a high maximum color density and is low in pollution.

[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 materials, and in particular, halogenated materials that can be processed rapidly and provide stable photographic properties due to excellent stability over time of color developing solutions. Development processing of silver color photographic materials is desired.

In other words, silver halide color photographic light-sensitive materials are subjected to running processing in an automatic developing device installed in a famous laboratory, but the processing is done on the same day that the development is received and the customer is not informed of the finished product. It has become necessary to hand over photographic products, and in recent years, it has even been required to do so within a few hours of receiving the product, and there is an urgent need to develop technology that can process the process more quickly.

The present inventors encountered the following problems in the process of conducting research to achieve rapid processing by increasing the pH of the color developer.

That is, at high pH, the pH stability of the color developer is poor, and the I)H of the color developer decreases over time, resulting in a corresponding decrease in the maximum color density of the dye image.

This is thought to be due to the fact that 1) carbonates such as potassium carbonate and sodium carbonate, which have been conventionally used as H stabilizers, do not have sufficient stabilizing effects at high pH.

Normally, carbonate has a buffering property near DHIO, but if the molar content of carbonate is increased to provide M image quality at higher IIH, the problem is that the precipitation of color developing agent and tar are accelerated. There is a point. To improve this, it is possible to use a pH stabilizing agent that imparts high pH stability.

1) As a typical H stabilizer, phosphoric acid-based ItWj7I agent is mentioned, but phosphoric acid-based w'Wi
Its use is undesirable from a pollution standpoint, and
It is difficult to dissolve the amount required to obtain the effect as an H stabilizer, and furthermore, even if it is dissolved, it tends to form a precipitate together with additives such as color developing agents.

As other I)H stabilizers at high pH, for example, sodium silicates are disclosed in JP-A-55-25028;
(hereinafter simply referred to as RD) 16156.
In September 1977, a MWJ agent combining an aluminate, an aluminum ion, and a dibasic acid capable of forming a complex salt, as well as a borate, etc., were known.

However, even with these pH stabilizers at high pH, either the DH stabilizing effect was not sufficient or the generation of precipitation was unavoidable, and none of them could be put to practical use.

We also attempted to stabilize the pH by adding carbonate to the solution, but precipitates formed (especially at low temperatures) and the developer became cloudy, making it impossible to simply increase the amount of carbonate.

The inventor of the present invention has made the following findings as a result of intensive studies aimed at solving these problems.

Conventionally, in color developing solutions, aromatic primary amine color developing agents such as para-phenylenediamine are used as color developing agents, and hydroxylamine and preservatives are used as preservatives to prevent air oxidation of the color developing agents. Contains sulfites. As a result of examining the above components, we found that the hydroxylamine in the component significantly reduces the buffering property in the high pH region, especially at 10.3 or higher, and furthermore, at island pH, silver development by hydroxylamine occurs, greatly increasing the coloring efficiency. It was found that the width decreased significantly.

Therefore, the present inventors considered removing hydroxylamine or reducing it to substantially zero, but if hydroxylamine was removed, the preservation of the color developing agent would be insufficient and tar formation would be promoted. is p in the high pH region
Although the stability of H is improved, the buffering capacity is still insufficient, especially when an automatic processor with a large aperture membrane is used, for example.

Therefore, the present inventors used a color developing solution with significantly improved pH stability over time and excellent storage stability over time.
As a result of investigating a method for processing silver halide color photographic light-sensitive materials that has excellent maximum color density of dye images obtained, we found that by using a color developing solution containing a specific buffer agent and a specific preservative, The present invention has been completed by accomplishing all of these unachievable and unforeseen problems.

Note that a part of the general formula [I] used in the present invention is
No. 14036 and JP-A-59-180558 disclose that it is used in combination with hydroxylamine mainly for the purpose of preventing decomposition of hydroxylamine by heavy metal ions as a gradation adjusting agent. Also special public official number 51-21582
No. 45-22198 and JP-A-53-32035
In the No. 1, alkyl-substituted hydroxylamine represented by the general formula [I] is used as an auxiliary developer of phenito-1 conductor 1L.
)- or for stabilization.

However, these techniques can improve the stability over time at high pH and the stability over time of color developing solutions by using the compounds represented by the general formulas (I> and (II) used in the present invention in combination. This is not disclosed, and the effect of preventing the maximum color density from decreasing over time could not be predicted from these techniques.Furthermore, in the past, for example, in JP-A-59-180558, the general formula [ I]
While a part of the compound represented by is used at 0.10 to 10Q/It, in the present invention, a large amount (IOIJ/f
The effect is particularly significant when the value is greater than fi), thereby exhibiting the effect more efficiently.

[Object of the Invention] Therefore, the object of the present invention is to use a color developing solution that has a small pH decrease over time and does not generate tar, eliminates silver development using a preservative, and maintains the maximum color density of the resulting dye image. An object of the present invention is to provide a method for processing a silver halide color photographic material that enables excellent rapid processing.

[Structure of the Invention] An object of the present invention is to provide a method for processing a silver halide photographic light-sensitive material with at least a color developer after imagewise exposure, (i) the color developer is a compound represented by the following general formulas [II and III]; containing the general formula [II R15Oa X may be a polymer having a hydrogen atom, a sodium atom, a potassium atom,
Represents a lithium atom or an ammonium group. ) General formula [I[] R2-N-OH (wherein, R2 and R3 each represent an alkyl group or an alkoxy group having 1 to 3 carbon atoms.

Furthermore, R2 and R3 may be combined to form a ring. ) (2) This was achieved by setting the pH of the color developing solution to 10.0 or more.

[Specific Structure of the Invention] The color developing solution used in the processing method of the present invention has the general formula [
It contains the compound represented by II (hereinafter referred to as the sulfonic acid derivative of the present invention).

In the general formula [II, the number of carbon atoms represented by R+ is 1
The alkyl groups of ~8 may be linear or branched, and also include those having a substituent. Examples of substituents include halogen atoms (for example, chlorine atoms, Q atoms, etc.), aryl groups (for example, phenyl groups, etc.), hydroxyl groups, amine groups, nitro groups, carboxylic acid groups (including their salts), and sulfonic acid groups (including their salts). salt), etc. The number of carbon atoms represented by R1 is 1 to
8 alkylboxymethyl group, phenylmethyl group, ethyl group, hydroxyethyl group, sulfonylethyl group, propyl group, butyl group, heptyl group, octyl group, and the like.

The phenyl group represented by R1 includes those having a substituent, and examples of the substituent include a halogen atom (for example, a chlorine atom,
bromine atom, etc.), alkyl group (preferably 1 to 1 carbon atoms),
4 alkyl group, such as methyl group, ethyl group, propyl group, butyl group, etc.), hydroxyl group, amino group, nitro group, carboxylic acid group (including its salt), sulfonic acid group (including its salt), etc. The number of substituents on the phenyl group may be one or 2 to 5, and in the case of 2 to 5, the substituents may be the same or different.

Furthermore, R1 may be an ethylenically unsaturated group, and the polymer may have these repeating units.

R1 is preferably a phenyl group, preferably having a substituent, and the preferable substituent is one having a carbon atom number of 1
-4 alkyl groups, hydroxyl groups, carboxylic acid groups (including salts thereof), and sulfonic acid groups (including salts thereof).

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

Exemplary compound (1-1> (I-2) (I
-3) (1-4) (1-5
) (I-6-) (1-9)
(I-10) (I-15)
(1-16) (I-21)
(I-22) (I-23)
Cl-24>Cl-25)
(I-26) ((-27)
Cl-28) (I-35)
(1-36)H,C(SO,H)2
C, H,, SO*H (1-37)
(I-38)C,H,SO,H
C, H,, So, HC C, H, SO, HC, H, SO, H (I-41) (1-42)
C,H,,So,HHO,S-C,H,-So,H(I
-43) Cl-44) HO
-C2H, -8o, HHO2CCH, SO, H (I-4
5) (I-46) In the above exemplary compound, all of the X's in the sulfonic acid group and the carboxylic acid group are hydrogen atoms, but since it is used in a color developing solution which is an alkaline solution, the above example compound of the present invention Some of the sulfone M derivatives are disclosed in the above-mentioned British Patent Nos. 669.505 and 8.
37.491, JP-A-51-147322, JP-A No. 51
-80229, and is readily available to those skilled in the art.

The sulfonic acid derivatives of the present invention may be used alone or in combination of two or more.
．． Although it can be used in an amount of 0 to 200 g, 10 (1 to 150 g is particularly preferable) from the viewpoints of solubility, maximum color density, and effects of the present invention.

A compound represented by the general formula [I] is used as a preservative in the color developing solution used in the processing and method of the present invention.

Hereinafter, the compound represented by the general formula [I[] will be referred to as the preservative of the present invention.

In the general formula [I[], R2 and R3 are each
Represents an alkyl group or alkoxy group having 1 to 3 carbon atoms, and R2 and R3 have 1 to 3 carbon atoms.
The alkyl group includes those having a substituent, and examples of the substituent include a hydroxyl group, a halogen atom (eg, a chlorine atom, a fluorine atom, a bromine atom, etc.), and an alkenyl group (eg, an allyl group, etc.). R2 and R3
Specific examples of the alkyl group include methyl group, ethyl group, droxyethyl group, i-propyl group, n-propyl group, and the like. Examples of the alkoxy group represented by R2 and R3 include a methoxy group and an ethoxy group.

However, R2 and R3 may be combined to form a ring.

R2 and R3 preferably both have 1 to 3 carbon atoms
an alkyl group, more preferably R2 and R3
are both ethyl groups.

Specific examples of the compounds of the present invention used in the present invention are illustrated below, but the present invention is not limited thereto (1)
CH3 CH3-N-OH (2) CHa C2Hs -N-OH (3) C2H5 C2H3-N-OH (4) CH3 03Hz-N-OH (5) 02H5 C5H7-N-OH (6) 03H7 C3H7-N- OH (7) OCH3 CH3-N-OH (8) OCH3 C2H5-N-OH (9) C2H40H CH3-N-OH These preservatives of the present invention are usually salt m salt, 'fil'FI
It is used in the form of salts such as i salt, p-1-luenesulfonate, Shu M salt, phosphate, and acetate.

The concentration of the preservative of the present invention in the color developing solution is preferably the same as that of hydroxylamine commonly used as a preservative, for example 0.1 (ll#!~50a/ffi), and more preferably 0.5g/ffi~20tr
/l.

Among the compounds represented by the general formula [II] of the present invention, for example, N,N-diethylhydroxylamine can be used as a preservative for a black and white developing agent in a color developing solution containing a black and white developing agent. Are known.

Hydroquinone, hydroquinone monosulfonic acid, phenidone, para-aminophenol, etc., which are usually main agents for black and white phenomena, are relatively stable when used as black and white developing agents in a black and white developer, and sulfites are used as preservatives. However, when added to a color developing solution, a cross-oxidation reaction occurs with the color developing agent, and its storage stability is known to be extremely poor. To preserve the black and white developing agent added to these color developing solutions,
Hydroxylamine has little effect.

An example of using N,N-diethylhydroxylamine as a preservative for a black and white developing agent added to a color developing solution is to use a color developing solution containing a coupler to develop a color photographic light-sensitive material by an inversion method. It is known to be used together with phenidone in the so-called external color development method. The role of phenidone in this case is to increase the development rate of the external photosensitive material and increase the density of the dye image.

In a magenta color developing solution that does not contain phenidone, N,N-diethylhydroxylamine is
It is known that it actually has an adverse effect on the storage stability of external color developing solutions by destroying couplers (see Japanese Patent Publication No. 45-22198).

Another example of using a compound of the present invention, such as N,N-diethylhydroxylamine, as a preservative for a black and white developing agent added to a color developer is as follows: Techniques for preserving added phenidone derivatives (see JP-A-53-32035) and techniques for preserving phenidone derivatives together with hydroquinones (see JP-A-52-15343) can be mentioned. .

As mentioned above, the preservative of the present invention is conventionally known to be used as a preservative for black and white developing agents added to color developing solutions. It is not known as a preservative.

The above preservative of the present invention may be used in combination with other preservatives. Examples of preservatives that can be used in combination include sulfites such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, and aldehyde. Or the ketones heavy nitrogen 1iI! Examples of l'fII adducts include formaldehyde bisulfite adducts, glutaraldehyde bisulfite adducts, and the like.

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

A p-phenylenediamine compound having a water-soluble group is
Compared to 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 there is no contamination of the photosensitive material and it does not cause irritation to the skin, but in particular, in the present invention, by combining the compounds represented by the general formulas [I] and [I], the object of the present invention can be achieved. can be achieved efficiently.

Examples of the water-soluble group include those having at least one on the amino group or benzene nucleus of the p-phenylenediamine compound, and specific examples of the water-soluble group include -(CH2)n -CH20H1-(CH2)m - N
l-ISO2-(CH2)n-CH3,-(CH2)
,0-(CH2)n-CHa,-(CH2CH2
Preferred examples include nCiH2m++ (+a and n each represent an integer of 0 or more), -COOH group, -8O3HW, and the like.

Specific examples of color developing agents are also shown. Examples of color developing agents [7] (8) C2H5
8/CH3H2 Among the color developing agents exemplified above, compounds shown in example No., (1), (3) and (4) are preferred for use in the present invention, and (1) is particularly preferred. .

The above-mentioned color developing agents are usually used in the form of salts such as basic acids, sulfates, p-toluenesulfonates, and the like.

The color developing agent having a water-soluble group that can be used in the present invention is usually 1 x 10-2 to 2X per liter of color developer.
It is preferable to use it in the range of 10-1 mol, but from the viewpoint of rapid processing, it is 1.5 x 10-2 per liter of color developer.
A range of ˜2×10” moles is more preferred.

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

Examples of alkaline agents include sodium hydroxide, potassium hydroxide, silicates, sodium carbonate, potassium carbonate,
Sodium metaborate, potassium metaborate, phosphoric acid 3
Potassium, tripotassium phosphate, borax, etc. can be used alone or in combination. Furthermore, various salts such as disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium bicarbonate, potassium bicarbonate, borates, etc. are used for purposes such as preparation needs or to increase ionic strength. be able to.

In the present invention, in order to more effectively achieve I)H stabilization of the color developer, it is preferable to use the above-mentioned carbonates, specifically potassium carbonate, sodium carbonate, etc. The amount is preferably 0.10 mol or more per liter.

In addition, inorganic and organic antifoggants can be added as necessary, and these antifoggants include:
For example, inorganic halide compounds such as sodium bromide, potassium bromide, sodium iodide, potassium iodide, etc.
6-nitrobenzimidazole as described in U.S. Pat. No. 2,496,940, 5-nitrobenzimidazole as described in U.S. Pat. No. 2,497,917 and U.S. Pat. Examples include mercaptobenzimidazole, mercaptobenzoxazole, thiouracil, 5-methylbenzotriazole, and the heterocyclic compounds described in Japanese Patent Publication No. 46-41675.

In addition to these various ingredients, there are also
Publications No. 45-6149, U.S. Patent No. 3,295,9
The development inhibitor compounds disclosed in No. 76 can be used.

Among the above antifoggants, bromide ions supplied from sodium bromide, potassium bromide, etc. are zero from the viewpoint of rapid processing.
．． It is preferably 3 to 3 g/2 or less. A development accelerator can also be used if necessary. As a development accelerator, U.S. Pat. No. 2,648,604 and U.S. Pat. No. 3,67
1,247 and Japanese Patent Publication No. 44-9503, other cationic compounds, cationic dyes such as phenosafranine, neutral salts such as thallium nitrate, and U.S. Patent No. 2. 533.990
No. 2,531.832, No. 2,950,97
No. 0, No. 2,577, No. 1l7, and Special Publication No. 1977-
Nonionic compounds such as polyethylene glycol and its derivatives and polythioethers described in Japanese Patent Publication No. 9504, organic solvents and organic amines described in Japanese Patent Publication No. 44-9509,
Includes ethanolamine, ethylenediamine, jetanolamine, triethanolamine, etc. In addition to benzyl alcohol and phenethyl alcohol described in US Pat. No. 2,304,925, acetylene glycol, methyl ethyl ketone, cyclohexanone, thioethers, pyridine, ammonia, hydrazine, and amines can also be mentioned.

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

[Formula] Water (10 (solvents with IP less than 0.4) other than water) ≦ 0.003 In the above, logp is the value determined from the partition coefficient P of n-octatool/water solvent, and P The value is obtained from the following formula.

The above values have been widely used as a measure of fat solubility; for example, in Chemical Review (chem
ical Review), Vol. 71, No. 6, 1971, pp. 555-613. moreover,
Although it can also be determined by the calculation method described in Ecochemistry Vol. 6, pages 3 to 11, it is preferable to use actually measured values, and in the present invention, the values are shown as values measured using n-ophthal.

In the present invention, solvents with a concentration of 10 (l P -0.4 or higher) which are not preferably added to the color developing solution in an amount exceeding the above range include aliphatic alcohols and aliphatic glycols having 5 to 20 carbon atoms. Ethers, cycloaliphatic alcohols and aromatic alcohols may be mentioned, specific examples being benzyl alcohol log p 1.100
-Hydroxynebenzyl alcohol log P 1.73 Cyclohexanol log P 1.232-
Benzitukijetanol IogP O, 41 Anisyl alcohol log p 0.7Q1-Pentanol log p O, 40 or more Phenylethyl alcohol log P 1.36p-Tolylcarbinol log p 1.36n-butano-) Lt log P O ,40 or more phenol logP O,40CLh
p-Hydroxybenzyl alcohol loo P O, 40 or more Benzylamine log p O, 40
Diethylene glycol monobutyl ether IQ (J P 0.41
etc.

Examples of solvents having a loa P of less than 0.4 include aliphatic alcohols having 0 to 4 carbon atoms, organic acids, and compounds having 5 or more carbon atoms and having highly polar functional groups. Specific examples include the following solvents.

Acetic acid, ethanol, ascent, propionic acid, propatool, ethylene glycol, diethylene glycol, triethylene glycol, triethanolamine, jetanolamine Among the above, t particularly represented by benzyl alcohol
For poorly soluble organic solvents with P of 0.4 or more, tar is likely to be generated due to long-term use of the color developing solution, especially during running processing in a low replenishment system. Adhesion to the paper photosensitive material may even lead to serious malfunctions that significantly impair 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 to prepare the color developing solution itself, but even with the use of such a stirring device, the dissolution rate is poor. Therefore, there is a limit to the development promotion effect.

Furthermore, poorly soluble organic solvents can reduce the biochemical oxygen demand fl
The pollution load value such as (BOD) is large, and it is impossible to dispose of it in sewers or rivers, etc., and treatment of the waste liquid requires a great deal of labor and cost. It is preferred to reduce or eliminate its use a. In the present invention, a system containing benzyl alcohol can also be used, but a system that does not contain benzyl alcohol is one of the preferred embodiments, especially in a system with a high pH, which is preferred from the viewpoint of rapid processing.

Furthermore, the color developing solution of the present invention contains various chelating agents as water softeners and heavy metal sequestering agents in addition to polyphosphoric acids or their salts such as sodium tetrapolyphosphate, tetranato pyrophosphate, and condensed phosphates. It can contain.

As the chelating agent preferably used in the present invention, RD
18837 and 18843.

Furthermore, the color developing solution of the present invention may contain ethylene glycol, methyl cellosolve, methanol, acetone, dimethylformamide, β-cyclodextrin, and others as required.
The compounds described in each publication can be used as organic solvents to increase the solubility of the developing agent.

Furthermore, auxiliary developers can also be used with the developing agents. These auxiliary developers include, for example, N-methyl-p-aminophenol hexulfate (methol).
, phenidone, N,N'-diethyl-p-aminophenol hydrochloride, N,N,N',N'-tetramethyl-p
-Phenylencinamine hydrochloride and the like are known, and its addition (2) is usually preferably 0.01 to 1.0 g/l. In addition, competitive couplers, fogging agents, colored couplers, and development inhibitor-releasing couplers (
It is also possible to add so-called DIR couplers) or development inhibitor releasing compounds.

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

Each component of the above color developing solution can be adjusted by sequentially adding and stirring to a certain amount of water. In this case, the component with low solubility in water can be added by mixing with the above-mentioned organic solvent such as triethanolamine. More generally, a plurality of components, each of which can stably coexist, is prepared in advance in a small container as a raw aqueous solution or in a solid state, which is added and stirred into water, and the color development time of the present invention is adjusted. You can get things.

In the present invention, the above-mentioned color developing solution can be used in any pH range, but from the viewpoint of rapid processing, the pH is between 10.3 and 13.
0, more preferably pi-1l0
, 7-1l. Used in 5. In the present invention, even at a high pH of pl-1l0.3 or higher, which is particularly suitable for rapid processing,
Sulfone M of the present invention [By using the conductor and the preservative of the present invention in combination, the pH of the color developer decreases little over time, and the color developer has excellent stability without generating tar. , it is possible to provide a method for processing a silver halide color photographic light-sensitive material which is excellent in maximum color density by processing the silver halide color photographic light-sensitive material using the color developing solution.

In the present invention, as a processing method for color development, 30
C. or more and 50.degree. C. or less, the higher the temperature, the faster the processing is possible, which is preferable. However, from the viewpoint of image storage stability, it is better not to be too high, and it is preferable to process at a temperature of 33.degree. C. to 45.degree. C. or lower.

Conventionally, the processing time is generally about 3 minutes and 30 seconds for color development, 1 minute and 30 seconds for bleach fixing, and 3 minutes for washing alternative stabilization treatment, but in the present invention, the color development time can be within 2 minutes. Furthermore, it is also possible to carry out the test within a range of 30 seconds to 1 minute and 30 seconds.

Further, the total amount of the above processing can be completed within 6 minutes.

The present invention can be applied to any system that uses a color developing solution containing the preservative of the present invention and the sulfone N derivative of the present invention, such as bath treatment and various other methods. Various processing methods can be used, such as a spray set in which the processing liquid is atomized, a web method using contact with a carrier impregnated with the processing liquid, or a developing method using a viscous processing liquid. It consists of steps such as color development, bleach-fixing, washing with water, or alternative stabilization treatment.

The bleach-fixing step may be a bleaching step and a fixing step provided separately, or may be a bleach-fixing bath that processes bleaching and fixing in one bath.

The bleaching agent that can be used in the bleach-fix solution used in the present invention is a metal complex salt of a linebetsu acid. The complex salt contains aminopolycarboxylic acid, oxalic acid, citric acid, etc. 1! It is made by coordinating metal ions such as iron, cobalt, and copper with acid. The most preferred organic acids used to form such metal complex salts of organic acids include polycarboxylic acids. 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 Koshiethylenetriaminepentaacetic acid [3] Ethylenediamine-N-(β-oxyethyl)-N, N', N
' - Triacetic acid [4] Propylenediaminetetraacetic acid [5 Conitrilotriacetic acid [6] Cyclohexanediaminetetraacetic acid [7] Iminodiacetic acid [8] Dihydroxyethylglycincitric acid (or tartaric acid) - [9] Ethyl etherdiamine tetraacetic acid [ 10] Greenyl ether diamine tetraacetic acid [1l] Ethylenediaminetetrabrobionic acid [1l]
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] Propylene diamine tetraacetic acid sodium salt [19] Nitriloacetic acid sodium salt [20] cyclohexanediamine tetraacetic acid sodium salt These bleaches are It is used at 45 h/l, more preferably from 20 to 250 Q/i. The bleach-fixing solution contains a silver halide fixing agent in addition to the above bleaching agent, and if necessary, a sulfite salt as a preservative. Also, iron(III) ethylenediaminetetraacetate
A bleach-fixing solution consisting of a complex salt bleach and a small amount of a halide such as ammonium bromide other than the silver halide fixing agent mentioned above, or conversely, a bleaching solution consisting of a composition containing a large amount of a halide such as ammonium bromide. A fixing solution, and even a special bleach-fixing solution having a composition consisting of a combination of an ethylenediaminetetraacetic acid iron (I[) complex salt bleaching agent and a large amount of a halide such as ammonium bromide, etc., can also be used. As the halides, in addition to ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. can also be used. can.

The silver halide fixing agents contained in the bleach-fixing solution include compounds that react with silver halide to form water-soluble complex salts, such as potassium thiosulfate, sodium thiosulfate, and thiosulfate, which are used in ordinary fixing processes. Typical examples include thiosulfate M salts such as ammonium sulfate, thiocyanine 1m such as potassium thiocyanate, sodium thiocyanate, and ammonium thiocyanate, thiourea, and thioether. These fixing agents are used in an amount of 59/2 or more, within the range that can be dissolved, but generally 70o~250g/2
Use with.

The bleach-fix solution contains boric acid, borax, sodium hydroxide,
Various pH 1L 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.

Furthermore, various optical brighteners, antifoaming agents, or surfactants can be contained. In addition, preservatives such as hydroxylamine, hydrazine, bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids, stabilizers such as nitroalcohols and nitrates, and organic A solvent or the like may be appropriately contained.

The bleach-fix solution used in the present invention includes JP-A-46-280, JP-B No. 45-8506, JP-B No. 46-556, Belgian Patent No. 770.910, JP-B No. 45-8836,
Various bleach accelerators described in JP-A-53-9854, JP-A-54-71634 and JP-A-49-42349 can be added.

The pH of the bleach-fix solution is used at 4.0 or higher, but generally it is used at 1) H5.0 or higher and pH 9.5 or lower, preferably p) (H5.0 or higher and pH 8.5 or lower, and further described. The most preferable pH is 6.5 or more and 8.5 or less.The processing temperature is 80°C or less, which is 3°C or more, preferably 5°C or more lower than the temperature of the processing solution in the color developing tank. However, it is preferably used at a temperature of 55° C. or lower to prevent evaporation.

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

The water washing substitute stabilizing liquid applicable to the present invention will be explained below.

The above-mentioned treatment with a stabilizing liquid refers to a stabilizing treatment that is performed immediately after a treatment that has fixing ability, and does not substantially involve washing with water. It is called a water washing alternative stabilizing solution, and the treatment tank is called a stabilizing bath or stabilizing tank.

The water washing substitute stabilizing solution applicable to the present invention can contain various additives such as an alkaline agent as a pH11 agent, an acid agent, a fungicide, a chelating agent, and a sulfite.

The pH of the water washing alternative stabilizing solution applicable to the present invention is preferably in the range of 5.5 to 10.0, more preferably p)
-16.3 to 9.5, particularly preferably pH
It ranges from 7.o to 9.0.

The treatment temperature for the stabilization treatment is preferably in the range of 15°C to 60°C, preferably 20°C to 45°C. In addition, from the viewpoint of rapid processing, it is preferable that the processing time be as short as possible, but it is usually 20 seconds or more.
The treatment time is 10 minutes, most preferably 1 to 3 minutes, and in the case of multiple tank stabilization treatment, it is preferable that the first stage tank be treated for a short time and the second stage tank be treated for a long time. Especially 20% of the anterior tank
It is preferable to process sequentially with a 50% increase in processing time. After the stabilization treatment applicable to the present invention, no water washing treatment is required at all, but rinsing with a small amount of water within an extremely short period of time, surface cleaning, etc. can be optionally performed as necessary.

As for the method of supplying the water-washing substitute stabilizing solution in the stabilization treatment step that can be applied to the present invention, when a multi-tank countercurrent system is used, it is preferable to supply it to the after bath and overflow from the front bath. Of course, it can also be treated in a fish tank. The above compounds can be added as a concentrated solution to the stabilization tank, or the above compounds and other additives may be added to the washing alternative stabilizing solution supplied to the stabilizing tank, and then added to the washing alternative stabilizing replenishment solution. Although there are various methods such as using it as a supply liquid, it may be added by any method.

The number of stabilization tanks in the stabilization treatment that can be applied to the present invention is 1 to 5.
The number of tanks is preferably 1 to 3, particularly preferably 1 to 3, and preferably 9 or less at most.

The method for processing a silver halide color photographic light-sensitive material of the present invention includes color development processing of a silver halide color photographic light-sensitive material using a color developing solution containing the preservative of the present invention and the sulfonic acid derivative of the present invention. This process includes:

Silver halide emulsions that can be used in the silver halide color light-sensitive material used in the processing method of the present invention include silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, and silver iodobromide. Any silver halide such as silver chloroiodobromide may be used.

The crystals of the silver halide grains may be normal crystals, twin crystals, or other crystals, and any ratio of [100] planes to [1l1] planes can be used. Furthermore, even though the crystal structure of these silver halide grains is uniform from the inside to the outside,
It may have a layered structure (core-shell type) in which the inside and outside are different. Further, these silver halides may be of a type that forms a latent image mainly on the surface or of a type that forms a latent image inside the grain. Further, silver halide grains on a flat plate (JP-A-58-113934, Japanese Patent Application No. 59-17)
0070) can also be used.

The silver halide emulsion on the plate was Cugnac.

Chateau's report and [Luffin's "P.
photographicE mulsion Chem
istry”< Published by Focal pr rss.

New York (1966), pp. 66-72, and A.

P, ○, Trivelli, W, F, Sm1
th edition, Photo.

Journal Asia (1940), page 285, but JP-A No. 58-113927, No. 58-113
It can be easily adjusted by referring to the methods described in No. 928 and No. 58-117921.

Silver halide grains particularly preferably used in the present invention are:
It is substantially monodisperse, and may be obtained by any preparation method such as an acidic method, a neutral method, or an ammonia method.

Alternatively, for example, the seed grains may be grown by an acidic method (furthermore, by an ammonia method which has a faster growth rate) to grow to a predetermined size. When growing silver halide grains, the pH in the reaction vessel may be It is preferable to simultaneously implant and mix m silver ions and halide ions in proportion to the growth rate of silver halide grains, for example, as described in JP-A No. 54-48521.

Known silver halide solvents can be used. Examples of frequently used silver halide solvents include ammonia, thioethers, thioureas, thiocyanate salts, thiazolinthiones, and the like. Regarding thioethers, see U.S. Pat. No. 3,271.157, U.S. Pat.
You can refer to the number etc. Regarding thioureas, JP-A No. 53-82408 and JP-A No. 55-77737, and regarding thiocyanate salts, US Pat.
No. 264, No. 2,448,534, No. 3.320
．． No. 069, regarding thiazolinthions, JP-A No. 5
No. 3-144319 can be referred to.

These silver halide emulsions contain activated gelatin; sulfur sensitizers such as allylthiocarbamide, thiourea, cystine; selenium sensitizers; reduction sensitizers such as stannous salts, thiourea dioxide, Polyamines, etc.: Member metal sensitizers, such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-o-0-thio-3-
Sensitizers such as methylbenzothiazolium chloride or water-soluble salts such as ruthenium, palladium, platinum, rhodium, iridium, etc., specifically ammonium chlorovaladate, potassium chloroaurate and sodium chloroparadate (these These substances act as sensitizers or fog suppressants depending on the amount. It may also be scientifically sensitized by using a sensitizing agent (eg, in combination with a sensitizer).

Specific examples of these include U.S. Patent No. 1 for sulfur sensitization.
, No. 574,944, No. 2,278,947, No. 2,410,689, No. 2,728,947, No. 3,656,955, etc., regarding the reduction sensitization method in the United States. Patent No. 2,419,974, Patent No. 2,983,609
No. 4.054.458, and U.S. Pat.
, 060 and British Patent No. 618.061.

The silver halide emulsion according to the present invention is chemically ripened by adding a sulfur-containing compound, and before, during, or after this chemical ripening, a nitrogen-containing emulsion having at least one hydroxytetrazaindene and mercapto group is produced. It may contain at least one type of telocyclic compound.

The silver halide used in the present invention is mixed with an appropriate sensitizing dye in an amount of 5 x 10-8 to 3
Optical sensitization may be achieved by adding 3 moles. Various sensitizing dyes can be used, and each sensitizing dye can be used alone or in combination of two or more. Examples of sensitizing dyes that can be advantageously used in the present invention include the following.

That is, examples of sensitizing dyes used in blue-sensitive silver halide emulsions include West German Patent No. 929.080, US Pat. No. 2,231,658, US Pat.
, No. 503.776, No. 2,519,001, No. 503.776, No. 2,519,001, No.
2,91l, No. 329, 3, 656.959, same.
No. 3,672,897, No. 3,694,217, No. 4.025.349, No. 4,046,572, British Patent No. 1,242.588, Japanese Patent Publication No. 44-14030, No. 52- Examples include those described in No. 24844 and the like. Further, as a sensitizing dye used in a green-sensitive silver halide emulsion, for example, U.S. Patent No. 1.939.201
No. 2.072.908, No. 2.739.149, No. 2.945.763, British Patent No. 505.979, etc. This can be cited as a representative example. Further, as sensitizing dyes used in red-sensitive silver halide emulsions, for example, US Pat.
No. 9,234, No. 2,270.378, No. 2,44
No. 2,710, No. 2,454,629, No. 2, 7
Cyanine dyes such as those described in 76, 280@ etc.
Typical examples include merocyanine dyes and complex cyanine dyes. Furthermore, US Patent 2
, No. 213,995, No. 2.493.748, No. 2.
Cyanine dyes, merocyanine dyes or composite cyanine dyes such as those described in German Patent No. 519,001 and German Patent No. 929.080 can be advantageously used in green-sensitive silver halide emulsions or red-sensitive silver halide emulsions.

These sensitizing dyes may be used alone or in combination.

The photographic tourism material of the present invention may be optically sensitized in a desired wavelength range by a spectral sensitization method using cyanine or merocyanine dyes alone or in combination, if necessary.

A typical particularly preferred spectral sensitization method is, for example, Japanese Patent Publication No. 43-493 concerning the combination of benzimidazolocarbocyanine and benzoxazolocarbocyanine.
No. 6, No. 43-22884, No. 45-18433, No. 47-37443, No. 48-28293, No. 4
No. 9-6209, No. 53-1l375, JP-A-Shotsutsu 52
-23931, 52-51932, 54-80
No. 1l8, No. 58-153926, No. 59-1l66
46, No. 59-116647, and the like.

Further, regarding the combination of carbocyanine having a benzimidazole nucleus with other cyanine or medianine, for example, Japanese Patent Publication Nos. 45-25831 and 47-111
No. 14, No. 47-25379, No. 48-38406, No. 48-38407, No. 54-3453.5, No. 55-1569, JP-A-50-33220, No. 50
-38526, 51-1071l7, 51-
1l5820, 51-135528, 52
-104916, No. 52-104917, and the like.

Further, regarding combinations of benzoxazolocarbocyanine (Ogisa carbocyanine) and other carbocyanines, for example, Japanese Patent Publication No. 44-32753, No. 46
-1l627, JP-A No. 57-1483, and regarding merocyanine, for example, JP-B No. 48-38401.
No. 8, No. 48-41l04, No. 50-40662,
JP 56-25728, JP 58-10753, JP 58-91445, JP 59-1l6645, JP 5
No. 0-33828 and the like.

Regarding combinations of deacarbocyanine and other carbocyanines, for example, Japanese Patent Publication No. 43-4932,
No. 43-4933, No. 45-26470, No. 46
-18107, No. 47-8741, JP-A-59-1
No. 14533, etc., and the method described in Japanese Patent Publication No. 49-6207, which uses zeromethine or dimethine merocyanine, monomethine or trimethine cyanine, and 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 fluorinated alcohol described in Japanese Patent Publication No. 40659/1984 is used in advance. It is used by dissolving it in a hydrophilic organic solvent.

The addition may be made at any time such as at the start of chemical ripening of the silver halide emulsion, during ripening, or at the end of ripening, and in some cases, it may be added in the step before emulsion coating M.

The photographic constituent layers of the silver halide photographic light-sensitive material used in the present invention contain dyes (A
The AI dyes include oxonol dyes, hemioxonol dyes, merocyanine dyes, and azo dyes. Among them, oxonol dyes, hemioxonol dyes, merocyanine dyes, etc. Examples of AIl dyes that can be used include:
British Patent No. 58-4609, British Patent No. 1.277, 429,
JP 48-85130, JP 49-99620, JP 49-1l4420, JP 49-1l9537,
US Patent No. 52-1081l5, US Patent No. 59-25845, US Patent No. 59-1l1640, US Patent No. 59-1l1641, US Patent No. 2,274,782, US Pat. 3,1l5,448
No. 3,148,187, No. 3,177.073
No. 3.247.1l7, No. 3.260.601
No. 3.540.887, No. 3,575,704, No. 3.653.905, No. 3,718,472,
Examples include those described in 4.071.31l and 4,070,352.

These l dyes are generally present in an amount of 2 per mole of silver in the emulsion layer.
It is preferable to use X 10-'' to 5X10-2 moles, more preferably lX10-3 to 1×10=2 moles.

Each of the silver halide emulsion layers used in the present invention can contain a coupler, that is, a compound capable of reacting with an oxidized product of a color developing agent to form a dye.

Various yellow couplers, magenta couplers and cyan couplers can be used as the mixer mentioned above that can be used in the present invention without any particular limitations. These couplers may be so-called 2-equivalent type couplers or 4-equivalent type couplers, and in combination with these couplers, it is also possible to use diffusible dye-releasing type couplers.

The above-mentioned YeO-coupler includes an open-chain ketomethylene compound and an active point-
〇-aryl substituted coupler, active point -〇-acyl substituted coupler, active point hydantoin compound substituted coupler, active point urazole compound substituted coupler and active point succinimide compound substituted coupler, active point fluorine substituted coupler, active point chlorine or bromine substituted coupler Coupler, active point -〇-
Sulfonyl-substituted couplers and the like can be used as effective yellow couplers. Specific examples of yellow couplers that can be used include U.S. Pat.
No. 3,265,506, No. 3.408.194, No. 3.551.155, No. 3.582.322,
No. 3,725,072, No. 3.891,445,
West German Patent No. 1.547.868, West German Application Publication No. 2,21
No. 9,917, No. 2,261,361, No. 2,414
, No. 006, British Patent No. 1,425,020, Special Publication No. 5
1-'10783, JP-A-47-26133, JP-A No. 4
No. 8-73147, No. 51-102636, No. 50-
No. 6341, No. 50-1l3342, No. 50-130
No. 442, No. 51-21827, No. 5G-87650
No. 52-82424, No. 52-1l5219,
Examples include those described in No. 58-95346.

Examples of magenta couplers used in the present invention include pyrazolone, pyrazolotriazole, pyrazolinobenzimidazole, and indacylon compounds. These magenta couplers may be not only 4-equivalent type couplers but also 2-equivalent type couplers like the yellow couplers. Specific examples of magenta couplers include U.S. Pat. Nos. 2,600,788 and 2,983.
, No. 608, No. 3.062,653, No. 3,1l7
, No. 269, No. 3,369,897, No. 3,31l
, No. 476, No. 3,419,391, No. 3,519,
No. 429, No. 3.558.319, No. 3.582.3
No. 22, No. 3,615.506, No. 3.834.90
No. 8, No. 3,891,445, West German Patent No. 1,810,
464M, West German patent ratio 1ff (OLS) 2.408
, No. 665, No. 2,417,945, No. 2,418
, No. 959, No. 2, No. 424.467, Special Publication No. 1977-6
No. 031, JP-A No. 51-20826, JP-A No. 52-589
No. 22, No. 49-1l9538, No. 49-74027
No. 50-159336, No. 52-421l1,
No. 49-74028, No. 50-60233, No. 51
-26541, 53-551l2, patent application 1982-
Examples include those described in No. 110943 and the like.

Further, useful cyan couplers used in the present invention include, for example, phenol couplers, naphthol couplers, and the like. These cyan couplers may be not only 4-equivalent type couplers but also 2-equivalent type couplers like the yellow couplers. Specific examples of cyan couplers include U.S. Pat. Nos. 2,369,929 and 2.
, No. 434,272, No. 2.474,293, No. 2
, No. 521,908, No. 2.772.162, No. 2
, No. 805,826, No. 3,034,892, No. 3,
31l, No. 476, No. 3,458,315, No. 3.4
76,563, 3,583.971, 3,59
No. 1,383, No. 3.758.308, No. 3.767
．． No. 41l, No. 3,772,002, No. 3,93
No. 3,494, No. 4,004,929, No. 4,1l6
, No. 396, No. 4,334,01l, No. 4,327,
No. 173, West German Patent Application (OLS) 2.414.830
No. 2,454,329, No. 3.329.72
No. 9, JP-A-48-59838, JP-A No. 51-26034
No. 48-5055, No. 51-146827,
No. 52-69624, No. 52-90932, No. 58
Examples thereof include those described in Japanese Patent Publication No. 49-11572 and Japanese Patent Publication No. 49-11572.

In addition, in the present invention, the patent application filed in 1988-17 by the applicant
Polymer couplers described in No. 2151 are also preferably used.

Two or more types of couplers used in the present invention can be used together in the same layer in order to satisfy the characteristics required of a photosensitive material, and the same compound can of course be added to two or more different layers. do not have.

In order to correct unnecessary absorption in the short wavelength range of the magenta and cyan coupler coloring dyes, it is preferable to use a colored coupler in combination with the color photosensitive material for photographing. U.S. Patent No. 4.163.670 and Japanese Patent Publication No. 57-39
Yellow-colored magenta couplers described in US Pat. No. 4,004,929, No. 4,138, etc.
Examples include magenta-colored cyan couplers such as those described in US Pat. No. 258 and British Patent No. 1,146,368.

In addition, as coloring dye diffusive couplers, U.S. Patent Nos. 4 and 3
Specific examples of magenta couplers are found in No. 66.237 and British Patent No. 2,1l5,570, and in European Patent No. 96°, 873j3 c) 5 J: 'CF West German Patent Publication (
OLS) No. 3.324.533 describes examples of yellow, magenta and cyan.

DIR couplers that can be used in the present invention will be described below.

DIR couplers include, for example, U.S. Pat. No. 3,227
．． Those that release hete-a-ring mercapto-based development inhibitors described in Japanese Patent Publication No. 554, etc.: Those that release benzotriazole derivatives as development inhibitors described in Japanese Patent Publication No. 58-9902, etc.: Japanese Patent Publication No. 51-16141. The so-called colorless DIR coupler described in JP-A No. 52-90932 releases a nitrogen-containing heterocyclic development inhibitor with decomposition of methyl 0-ol after separation as described in U.S. Pat. 248,9
62 and JP-A-57-56837, which release the development inhibitor with an intramolecular nucleophilic reaction after separation:
Japanese Patent Publication No. 56-1l4946, 57-154234
No. 57-188033, No. 58-98723, No. 58-209736, No. 58-209737
No. 58-209738 and No. 58-2097
39, 58-209740, etc., which release a development inhibitor by electron transfer through a conjugated system after separation: JP-A-57-151944, JP-A-58-217932
Those that release a diffusible development inhibitor whose development inhibitory ability is deactivated in the developer described in @ etc.: Japanese Patent Application No. 59-38263,
Examples include those described in No. 59-39653, etc., which release a reactive compound and generate a development inhibitor or deactivate the development inhibitor through a reaction in the film during development.

In the present invention, a compound capable of forming a development accelerator or a fogging agent during silver development can be used.

Specifically, compounds described in JP-A-57-150845 and the like can be mentioned.

The halogenated color silver photographic material used in the present invention may contain various other photographic additives. For example, antifoggants, stabilizers, ultraviolet absorbers, color stain inhibitors, fluorescent whitening agents, color image fading inhibitors, antistatic agents, hardeners, and surfactants described in Research Disclosure No. 17643. Agents, plasticizers, wetting agents, development aids, etc. can be used.

In the halogenated color silver photographic material used in the present invention, hydrophilic colloids used to prepare the emulsion include gelatin, derivative gelatin, graft polymers of gelatin and other polymers, and proteins such as albumin and casein. , cellulose derivatives such as hydroxyethyl cellulose derivatives and carboxymethyl cellulose, starch derivatives, single or copolymer synthetic hydrophilic polymers such as polyvinyl alcohol, polyvinylimidazole, and polyacrylamide.

Supports for the halogenated color silver photographic light-sensitive material used in the present invention include, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, transparent supports provided with a reflective layer or combined with a reflector, such as glass roots, Examples include polyester films such as cellulose acetate, cellulose nitrate, and polyethylene terephthalate, polyamide films, polycarbonate films, and polystyrene films, and other usual transparent supports may be used. These supports are appropriately selected depending on the intended use of the photosensitive material.

For coating the silver halide emulsion layer and other photographic constituent layers used in the present invention, various coating methods can be used, including tipping coating, air doctor coating, curtain coating, and hopper coating. Also, U.S. Patent No. 2,76
1,791 and 2,941,898 can also be used to simultaneously coat two or more layers.

In the photosensitive material used in the present invention, it is optional to provide an intermediate layer of an appropriate thickness depending on the purpose, and in addition, a filter layer, an anti-curl layer, a protective layer, and a protective film. Various layers such as an I layer and an antihalation layer can be used in appropriate combinations as constituent layers. Hydrophilic colloids that can be used in the emulsion layers as described above can be used as binders in these constituent layers, and various types of colloids that can be contained in the emulsion layers as described above can be used in these layers. Photographic additives may be included.

The photosensitive material applicable to the present invention may be any of color reversal film for slides, color reversal film for movies, color reversal film for TV, color reversal photographic paper for printing, color reversal photographic paper for photography, etc. .

[Specific Effects of the Invention] As explained above, in the present invention, a color developing solution is used which is excellent in the liquid properties of the color developing solution, that is, the stability, the stability of I)H, and the prevention of tar generation. Thus, it has been possible to provide a method for processing silver halide color photographic materials that does not require silver development using a preservative and has excellent maximum color density of the obtained dye image.

[Specific Example 1 of the Invention] Hereinafter, the present invention will be explained in more detail with reference to Examples, but the embodiments of the present invention are not limited to these.

Example (1) A color developing solution having the following composition was prepared.

(Color developer) Potassium bromide 1. OQ potassium sulfite (50% solution) 6.0tj2 preservative (listed in Table 1) 3. OQ Sodium Tetrapolyphosphate 2.09 Color developing agent (
6.0Q Potassium Carbonate 300 Sulfone m derivative of the present invention (Exemplary Compound (I-9)') Table (1) Amount listed in Table (1) Add water to make 1 liter, potassium hydroxide and am pH 1l, 0
Adjust to.

The above color developing solution was left at air temperature (approximately 25° C.) for 8 days, and the pH value and appearance of the solution at that time were evaluated.

The appearance of the liquid was determined as a representative characteristic of the stability, particularly the stability of the color developing agent, by evaluating the degree of coloration of the color developer.

The liquid appearance was divided into the following four levels.

++ 10 Generating a large amount of tar + 10 Blackening + Browning As is clear from the results in Table (1), hydroxylamine, which has traditionally been used as a preservative, has a significant DH reduction, and hydroxylamine is not added. In this case, although the buffer properties are improved, the appearance of the liquid becomes black, and it is thought that a considerable amount of the color developing agent is oxidized and tar formation begins to occur.

When using the preservative of the present invention without using the sulfone R derivative of the present invention, the DH stability is clearly improved compared to hydroxylamine, but the buffering property is extremely insufficient.
It is clear from this example that the combined use of the sulfonic acid derivative of the present invention surprisingly improves the buffer properties significantly and also provides good storage stability.

Example (2) On a paper support laminated with polyethylene, the following layers were sequentially coated from the support side to prepare a photosensitive material sample.

Layer 1: 1.2 g/f gelatin, 0.40 CI/m
' Blue-sensitive silver chlorobromide emulsion and 0
, 50! A layer containing 1, OX 1Q-3 mol 9/f of yellow coupler (Y-1) dissolved in It/f dioctyl phthalate.

Layer 2: Intermediate layer consisting of gelatin of 0.7 (1/f).

1! J3...1.25 (1/l' gelatin, 0.2
A layer containing 9/f of the following magenta coupler (M-1>) dissolved in a 51 J/l' green-sensitive silver chlorobromide emulsion and 0.30 Mf of dioctyl phthalate.

Layer 4: Intermediate layer consisting of gelatin of 1.2 [J/f.

15...1.4! It /f gelatin, 0.25!
II/f red-sensitive silver chlorobromide emulsion and 0.20Q/f
1.5X 10-3 dissolved in dibutyl phthalate of
A layer containing the following comparative cyan coupler (C-1) in molar g/f and the couplers of the invention described in Table-2.

1l6 ・1.0 (1/f gelatin and 0.20 CI
0,30(
A layer containing 1/f Tinuvin 328 (ultraviolet absorber manufactured by Ciba Geigy).

Layer 7...0.5! II/f gelatin-containing layer.

In addition, as a hardening agent, 2.4-dichloro-6-hydroxy-6-triazine sodium was added in layers 2.4 and 7.
Each was added in an amount of 0.017 (l C-) per 1 g of gelatin.

These samples were exposed to light using a conventional method using a wedge, and then subjected to the following development process to examine silver developability.

Semi-processing process (ll!X temperature and processing time)] Development
35°C 45 seconds] Fixing 35°C 1 minute] Washing process 25-30°C 1 minute 30 seconds] Drying
The temperature was 75-80°C for about 1 minute and 30 seconds, and the development was carried out using the color development method 2.4. used in Example (1). and 6 except that only the color developing agent was removed, and the fixing solution had the following composition.

(Fixer) Ammonium thiosulfate (70% solution) 150% ammonium sulfite (40% solution) 20% Water was added to make a volume of 1 liter, and the solution was adjusted to 7.00 with ammonium hydroxide or acetic acid.

The spectral reflection density of Dn+ax of the sample was measured with orange light using PDA-65 (manufactured by Konishiroku Photo Industry Co., Ltd.) after the development process, and the spectral reflection density of Dmax and [) m
The difference from the spectral reflection density of in was taken as the representative characteristic of silver concentration.

The results are shown in Table (2).

Table 2 As is clear from the results in Table (2), the sample Nα8.1l using hydroxylamine as a preservative was developed with silver significantly, but the sample Nα9.1l using the preservative of the present invention had a K
No silver development was carried out at all, regardless of the bad nature of Br.

Example (3) The photosensitive material used in Example (2) was subjected to wedge exposure in the same manner as in Example (2), and then processed according to the following processing steps and processing solution. However, the color developer is Example (1)
Nα2.4 and 6 used in 1) were changed to H11,5 and used.

Processing process (processing temperature and processing time) [1] Color development 35°C 45 seconds [2]
Bleaching constant @ 35℃ 1 minute [3] Washing treatment 25-30℃ 1 minute 30 seconds [4] Drying
75-80°C 1 minute 30 seconds [Bleach-fixing tank liquid] Ethylenediaminetetraacetic acid ferric ammonium dihydrate 609 Ethylenediaminetetraacetic acid Iff 39 Ammonium thiovN acid (70% solution) +oo1. (A'afa7
',t''c Ni (40% solution) 27.5d water was added to bring the total volume to 1 liter, and the pH was adjusted to 7.10 with ammonium hydroxide or glacial acetic acid.

The maximum reflection density of each of blue, green, and red was measured using PDA-65 (manufactured by Konishiroku Photo Industry Co., Ltd.) for the developed sample. The results are shown in Table 3.

Table 3 As is clear from Table 3, sample Nu14 processed with a color developer using hydroxylamine has a lower co-concentration of blue, green, and red compared to sample Nα13 processed with a color developer that does not use hydroxylamine. You can see that it is happening. In contrast, sample No. 1 treated with the color developer of the present invention
It can be seen that Sample No. 5 obtained the same excellent maximum color density as sample Nα13 containing no preservative at all.

Example (4) A color developing solution having the following composition was prepared.

(Color developer) Potassium bromide 1.0g Potassium sulfite (50% solution) 6. O,g preservative (
(listed in Table 4) 3. og sodium tetrapolyphosphate 2. Og color developing agent (sulfate salt in illustrative order (1)) 6.0Ω sulfonic acid derivative or 2
C03 (described in Table (4)) Feng Shui described in Table (4) was added to make 1 liter, and adjusted to 1) HIZ with potassium hydroxide and sulfuric acid.

The above color developing solution was left in room m (approximately 25° C.), and the pH value was measured. The results are shown in Table 4.

As is clear from Table 4, when hydroxylamine is used as a preservative, the decrease in f)H over time is so large that even if the buffer agent is CO2 or a sulfonic acid derivative, it cannot be put to practical use. Similarly, when 2 COa is combined with the preservative of the present invention, the decrease in I)H is too large (
Moreover, when 110 g of 2 COa was added, precipitation of the color developing agent was observed.

When a preservative was not added and in combination with the sulfonic acid derivative of the present invention, pH fluctuations were quite small, but taring started on the 6th day and completely tarred on the 13th day. Also, in the present invention, sulfonic acid derivatives are 59/
In the case of 2, the I)H fluctuation is large, and it can be seen that it is preferable to use a sulfonic acid derivative having a value of IOg/ffi or more for stabilizing the pH.

From the above, it is clear from Table 4 that only the combination of the preservative of the present invention and the sulfonic acid derivative can maintain the preservability of pH stabilization and prevention of tar formation.

The same results as above were also obtained using Exemplified Compound (1) as the preservative and Exemplified Compounds (I-15) and (I-25) as the sulfone M derivatives.

Example (5) Using the color developing solution used in Example (4), the pH value was set as shown in Table (5), and the pH was measured after being left at room temperature (approximately 25° C.) for 6 days.

The results are shown in Table 5.

As is clear from Table 5, in p)-19,8, sulfonic acid derivatives or 2CO3 as preservatives and buffer agents were used.
1) In areas where the pH is higher than Hlo, 3 or more, especially 10,3, the preservative of the present invention is more effective than hydroxylamine, and the sulfonic acid derivative of the present invention is more favorable than K2CO2. l) The decrease in H is reduced, and by using the preservative of the present invention and the sulfonic acid derivative in combination, the stability of pH is greatly improved as in Example (4).

Claims (5)

[Claims] (1) A method in which a silver halide photographic light-sensitive material is treated with at least a main color developing solution after imagewise exposure, wherein [1] the color developing solution contains compounds represented by the following general formulas [I] and [II]. It has the general formula [I] R_1SO_3X (wherein R represents an alkyl group having 1 to 8 carbon atoms or a phenyl group, and R is an ethylenically unsaturated group and a polymer having these repeating units) (X represents a hydrogen atom, sodium atom, potassium atom, lithium atom, or ammonium group.) General formula [II] ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_2 and R_3 are each a carbon atom Number 1~
3 represents an alkyl group or an alkoxy group. Further, R_2 and R_3 may be combined to form a ring. )
[2] A method for processing a silver halide color photographic material, characterized in that the color developer has a pH of 10.0 or more. (2) The color developer contains at least 10.0 g of at least one compound represented by the general formula [I] per 1 liter of the color developer. A method for processing silver halide color photographic materials. (3) The color developer has a pH of 10.3 or more.
) A method for processing a silver halide color photographic light-sensitive material. (4) The color developer contains at least one carbonate at 0.10 mol or more per liter of the color developer. The method for processing a silver halide color photographic material according to item (3). (5) The silver halide color photograph according to claim 1, 2, or 4, wherein the color developer has a pH of 10.5 or more. How to process photosensitive materials.