JPH0746217B2 - Processing method of silver halide photographic light-sensitive material capable of obtaining a dye image with high maximum color density - Google Patents

Description

The present invention relates to a method for processing a silver halide color light-sensitive material, and more specifically, it uses a color developing solution which is excellent in pH stability over time and storage stability over time. Thus, the present invention relates to a method of processing a silver halide color light-sensitive material having a high maximum color density of the obtained dye image and low 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 light-sensitive materials, and particularly rapid processing is possible, and stable photographic characteristics with excellent aging stability of the color developer are obtained. Development processing of silver color photographic light-sensitive materials is desired.

That is, the silver halide color photographic light-sensitive material is run by an automatic developing device installed in a famous laboratory, but it is processed in the day when the development is accepted, and the photograph is already developed by the customer. 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.

The present inventors faced the following problems in the course of research in order to achieve rapid processing by raising the pH of the color developing solution.

That is, at high pH, the pH stability of the color developing solution was poor, the pH of the color developing solution decreased with time, and the maximum color density of the dye image decreased accordingly.

It is considered that this is because the stabilizing effect at high pH is not sufficient only with carbonates such as potassium carbonate and sodium carbonate which have been conventionally used as pH stabilizers.

Usually carbonate has a buffering property around pH 10, but it is higher
If the amount of carbonate is increased to provide buffering properties at pH,
There is a problem that precipitation of color developing agent and tar are promoted. To improve this, the pH that gives high pH stability
The use of stabilizing agents 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, even if dissolved, there is a problem that 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 contains sodium silicates, Research Disclosure (hereinafter simply referred to as RD) 16156, and in September 1977, aluminates and dibasic acids capable of forming complex salts with aluminium unions. Combined buffers, as well as borates, etc. 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 none of them could be put to practical use.

Attempts were also 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 (especially at low temperatures) and cloudiness of the developer.

The inventors of the present invention have made earnest studies to solve these problems and found the following.

Conventionally, in a color developing solution, a para-phenylenediamine aromatic primary amine type color developing agent is used as a color developing agent, and hydroxylamine and a preservative to prevent air oxidation of the color developing agent and the like. Contains sulfite. As a result of investigating the above-mentioned components, we found that hydroxylamine in the components markedly reduced the buffering property in a high pH range, especially 10.3 or higher, and further, at a high pH, silver development was carried out by hydroxylamine and the color development efficiency was widened. I found to lower.

Therefore, the present inventors have studied to remove or substantially reduce the hydroxylamine to zero, but when the hydroxylamine is removed, the retention of the color developing agent becomes insufficient and tar formation is promoted. Is the pH in the high pH range
However, it was still insufficient as a buffering capacity, but it was particularly insufficient when using an automatic processor having a large opening surface film, for example.

Therefore, the inventors of the present invention have obtained a silver halide color photographic light-sensitive material excellent in the maximum color density of a dye image obtained by using a color developing solution which is remarkably improved in pH stability over time and has excellent storage stability over time. As a result of examining the processing method of, by using a color developing solution in which a specific buffer agent and a specific preservative are used in combination, it is possible to achieve all of these problems that could not be achieved by the conventional method and could not be predicted. This is the one that completed the present invention.

Incidentally, a part of the general formula (I) used in the present invention is shown in Japanese Examined Patent Publication No.
No. 4036 and JP-A No. 59-180558 disclose that the compound is used in combination with hydroxylamine mainly for the purpose of preventing decomposition of a gradation adjusting agent or hydroxylamine by heavy metal ions. Further, in JP-B-51-21582, JP-B-45-22198 and JP-A-53-32035, an alkyl-substituted hydroxylamine represented by the general formula (II) is used as an auxiliary developing agent or stabilizing agent for a phenidone derivative. It is disclosed. However, these techniques disclose that the compounds represented by the general formulas (I) and (II) used in the present invention are used in combination to improve the stability with time at high pH and the stability of the color developing solution with time. However, the effect of preventing the decrease in the maximum color density over time was unpredictable from these techniques. Conventionally, for example, in JP-A-59-180558, a part of the compound represented by the general formula (I) is used in an amount of 0.10 to 10 g / l, whereas in the present invention, a large amount (in the case of 10 g / l or more is used, In particular, the effect is remarkable).

[Object of the Invention] Accordingly, an object of the present invention is to obtain a maximum color density of a dye image obtained by using a color developing solution which has a small pH decrease with time and does not generate tar, without silver development by a preservative. An object of the present invention is to provide a processing method of a silver halide color photographic light-sensitive material which is capable of excellent rapid processing.

[Constitution of the Invention] An object of the present invention is to provide a method of processing a silver halide photographic light-sensitive material after imagewise exposure with at least a color developing solution, wherein the color developing solution is represented by the following general formulas [I] and [II]. A compound of the general formula [I] R ₁ SO ₃ X (wherein R represents an alkyl group having 1 to 8 carbon atoms or a phenyl group, and R is an ethylenically unsaturated group, It may be a polymer having these repeating units, X is a hydrogen atom, a sodium atom, a potassium atom,
Represents a lithium atom or an ammonium group. ) General formula [II] (In the formula, R ₂ and R ₃ each represent an alkyl group or an alkoxy group having 1 to 3 carbon atoms. Further, R ₂ and R ₃ may combine to form a ring.) It was achieved when the pH of the liquid was above 10.0.

[Specific Structure of the Invention] The color developer used in the processing method of the present invention contains a compound represented by the general formula [I] (hereinafter referred to as a sulfonic acid derivative of the present invention).

In the general formula [I], the number of carbon atoms represented by R ₁ is 1
The alkyl groups of to 8 may be linear or branched and include those having a substituent. As the substituent, a halogen atom (eg, chlorine atom, bromine atom, etc.), an aryl group (eg, phenyl group, etc.), a hydroxyl group, an amino group, a nitro group, a carboxylic acid group (including a salt thereof), a sulfonic acid group (a salt thereof) (Including) and the like. ₁ to 1 carbon atoms represented by R ₁
Examples of the alkyl group of 8 include a methyl group, a carboxymethyl group, a phenylmethyl group, an ethyl group, a hydroxyethyl group, a sulfonylethyl group, a propyl group, a butyl group,
Examples thereof include a heptyl group and an octyl group.

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

Further, R ₁ may be a polymer having an ethylenically unsaturated group and these repeating units.

R ₁ is preferably a phenyl group and preferably has a substituent, and a preferable substituent has 1 carbon atom.
To alkyl groups, hydroxyl groups, carboxylic acid groups (including their salts), and sulfonic acid groups (including their salts).

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.

Exemplified compound In the above exemplified compounds, all of X of the sulfonic acid group and the carboxylic acid group are represented by hydrogen atoms, but since they are used in the color developing solution which is an alkaline solution, sodium salt, potassium salt, lithium Compounds of salts such as salts are naturally included.

Some of the sulfonic acid derivatives of the present invention, the British Patent No. 669,505, 837,491, JP-A-51-147322, 5
No. 1-80229, and can be easily obtained by those skilled in the art.

The sulfonic acid derivative of the present invention may be used alone or in combination of two or more kinds. The amount of the sulfonic acid derivative used is 2.0 per 1 color developer.
Although it can be used in an amount of up to 200 g, 10 g to 150 g is particularly preferable from the viewpoints of solubility, maximum color density and effects of the present invention.

In the color developer used in the processing method of the present invention, a compound represented by the general formula [II] or a preservative is used. Hereinafter, the compound represented by the general formula [II] is referred to as the preservative of the present invention.

In the general formula [II], R ₂ and R ₃ each represent an alkyl group or an alkoxy group having 1 to 3 carbon atoms, and as the alkyl group having 1 to 3 carbon atoms represented by R ₂ and R _3. Those having a substituent are also included, and examples of the substituent include a hydroxyl group, a halogen atom (eg, chlorine atom, fluorine atom, bromine atom, etc.), and an alkenyl group (eg, allyl group, etc.). Specific examples of the alkyl group of R ₂ and R ₃ include a methyl group, an ethyl group, a hydroxyethyl group, an i-propyl group, an n-propyl group and the like. Examples of the alkoxy group represented by R ₂ and R ₃ include a methoxy group and an ethoxy group.

However, R ₂ and R ₃ may combine to form a ring.

R ₂ and R ₃ are preferably both alkyl groups having 1 to 3 carbon atoms, and more preferably both R ₂ and R ₃ are ethyl groups.

Hereinafter, specific examples of the compound of the present invention used in the present invention will be exemplified, but the present invention is not limited thereto.

These preservatives of the present invention are usually used in the form of salts such as hydrochloride, sulfate, p-toluenesulfonate, oxalate, phosphate and acetate.

The concentration of the preservative of the present invention in the color developing solution is preferably the same level 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. It is from 1 to 20 g / 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 of a black and white developing agent in a color developing solution containing a black and white developing agent. Are known.

Usually, black and white developing agents such as hydroquinone, hydroquinone monosulfonic acid, phenidone and para-aminophenol are relatively stable when used as a black and white developing agent in a black and white developer, and phosphite is used as a preservative. However, it is known that its storage stability is extremely poor when it is added to the color developing solution, which causes a cross-oxidation reaction with the color developing agent. To maintain the black and white developing agent added to the color developer,
Hydroxylamine has little effect.

As a preservative for black and white developing agents added to color developers
As an example of using N, N-diethylhydroxylamine, it is known to use with phenidone in a so-called external color development method of developing a color photographic light-sensitive material by a reversal method using a color developer containing a coupler. ing. The role of phenidone in this case is to increase the development speed of the external photosensitive material having poor developability and to increase the density of the dye image.

In addition, for example, in a magenta color developing solution containing no phenidone, N, N-diethylhydroxylamine is known to have a bad influence on the storability of the external color developing solution, that is, destroying the coupler. Tokusho
45-22198).

As a preservative for black and white developing agents added to color developers
Other examples of using compounds of the present invention, such as N, N-diethylhydroxylamine, in internal color developers are:
A technique for preserving the phenidone derivative added to the color developing solution (see JP-A-53-32035), and a technique for preserving the phenidone derivative together with hydroquinones (JP-A-53-32035).
52-15343).

As described above, the preservative of the present invention is conventionally known to be used as a preservative for a black and white developing agent added to a color developing solution, but the preservative for the color developing agent in an ordinary color developing solution is known. Not known as a preservative.

The preservative of the present invention may be used in combination with other preservatives, examples of preservatives that can be used in combination include, for example, sodium sulfite, potassium sulfite, sodium bisulfite, sulfite salts such as potassium bisulfite, and further aldehydes. Alternatively, bisulfite adducts of ketones such as formaldehyde bisulfite adduct, glutaraldehyde bisulfite adduct and the like can be mentioned.

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

The p-phenylenediamine compound having a water-soluble group is
Compared with para-phenylenediamine compounds that do not have a water-soluble group such as N, N-diethyl-p-phenylenediamine, not only does it have the advantage of not contaminating the light-sensitive material and being less prone to skin rash, The object of the present invention can be efficiently achieved by combining the compounds represented by the general formulas [I] and [II] in the invention.

The water-soluble group are those having at least one is listed on the amino group or benzene nucleus of p- phenylenediamine compound, as a specific water-soluble group _{- (CH 2) n-CH} 2 OH, - ( CH ₂ ) m-NHSO _2- (CH ₂ ) n
_{-CH 3, - (CH 2)} mO- (CH 2) n-CH 3, - (CH 2 CH 2 O)
Preferred examples include nCmH ₂ m + 1 (m and n each represent an integer of 0 or more), —COOH group, —SO ₃ H group and the like.

Specific examples of the water-soluble group-containing color developing agent that can be used in the invention are shown below.

Illustrative color developing agent Among 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 a salt such as hydrochloric acid chloride, sulfuric acid salt, and p-toluenesulfonic acid salt.

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

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

Examples of the alkaline agent include sodium hydroxide, potassium hydroxide, silicate, sodium carbonate, potassium carbonate,
Sodium metaborate, potassium metaborate, phosphoric acid 3
Sodium, tripotassium phosphate, borax and the like can be used alone or in combination. Further, for the purpose of preparation, or for the purpose of increasing ionic strength, disodium hydrogen phosphate, dipotassium hydrogen phosphate,
Various salts such as sodium bicarbonate, potassium bicarbonate and borate can be used.

In the present invention, in order to more effectively achieve pH stabilization of the color developing solution, the carbonate, specifically potassium carbonate,
It is preferable to use sodium carbonate and the like, and the addition amount thereof is preferably 0.10 mol or more per 1 color developer.

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 Patent Publication No. 46-19039 and 45-614
The development inhibitor compounds disclosed in each of No. 9 and US Pat. No. 3,295,976 can be used.

Among the above antifoggants, bromide ion supplied from sodium bromide, potassium bromide, etc. is 0.
It is preferably 3 to 3 g / l or less. If necessary, a development accelerator can also be used. As the development accelerator, U.S. Pat.Nos. 2,648,604, 3,671,247 and JP-B-44-9
Various pyridinium compounds represented by Japanese Patent No. 503,
Other cationic compounds, cationic dyes such as phenosafranine, neutral salts such as thallium nitrate, U.S. Patent Nos. 2,533,990, 2,531,832, and 2,950,970,
No. 2,577,127, and polyethylene glycol and its derivatives described in JP-B-44-9504, nonionic compounds such as polythioethers, organic solvents and organic amines described in JP-B-44-9509, ethanolamine, ethylenediamine, Diethanolamine, triethanolamine and the like are included. Further, benzyl alcohol, phenethyl alcohol described in U.S. Pat. No. 2,304,925, and acetylene glycol, methyl ethyl ketone, cyclohexanone, thioethers, pyridine, ammonia, hydrazine, amines and the like can be mentioned.

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. For example, chemical review (chemical R
eview), 1971, No. 6, pp. 555 to 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-octal.

In the present invention, as the solvent having a logP of 0.4 or more, which is not preferably added to the color developer in the above range, as the solvent having 5 to 20 carbon atoms, each aliphatic alcohol, aliphatic glycol ether, alicyclic group Examples thereof include alcohols and aromatic alcohols, and specific examples thereof include benzyl alcohol logP1.10 o-hydroxyne benzyl alcohol logP1.73 cyclohexanol logP1.23 2-benzinoxyethanol logp0.41 anisyl alcohol logP0.70 1- Bentanol logP 0.40 or higher Phenylethyl alcohol logP1.36 p-Tolylcarbinol logP1.36 n-Butanol logP0.40 or higher Phenol logP0.40 or higher p-Hydroxybenzyl alcohol logP0.40 or higher Benzylamine logP0.40 or higher Diethylene glycol monobutyl ether logP0 .41, etc.

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, ascent, bropionic acid, brovanol, ethylene glycol, diethylene glycol, triethylene glycol, triethanolamine, diethanolamine In the above, lo is 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 to use a stirring device to adjust 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 we have problem stores that require labor and costs,
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 a system containing no benzyl alcohol is one of the preferred embodiments in a system having a high pH which is preferable from the viewpoint of rapid treatment.

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.

The chelating agent preferably used in the present invention is RD18
Examples include those described in 837 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 described each publication The compound can be used as an organic solvent for increasing 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 amine hydrochloride and the like are known,
The amount added is usually preferably 0.01 to 1.0 g / l. In addition to these, competitive couplers, fogging agents, colored couplers, development inhibitor releasing type couplers (so-called
DIR couplers), or development inhibitor releasing compounds can also 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 adjusted by sequentially adding and stirring to a certain amount of 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. More generally, a plurality of components, each of which can coexist stably, are prepared in a concentrated aqueous solution or in a solid state in a small container, which is prepared in advance by adding and stirring in water to obtain a color developing solution of the present invention. be able to.

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.
Even at pH, by using the sulfonic acid derivative of the present invention in combination with the preservative of the present invention, a decrease in pH of the color developing solution over time is small, and a color developing solution excellent in stability without tar generation. It is possible to provide a method for processing a silver halide color photographic light-sensitive material excellent in maximum color density by processing a silver halide color photographic light-sensitive material using the color developing solution.

In the present invention, the processing method for color development is 30 ° C.
As described above, the higher the temperature is 50 ° C. or lower, the quicker the processing can be performed in a shorter time, which is preferable. However, it is preferable that the temperature is not so high from the viewpoint of image storage stability.

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 completed within 6 minutes.

In the present invention, any system can be applied as long as it is a system using the color developing solution containing the preservative of the present invention and the sulfonic acid derivative of the present invention. For example, one bath treatment and other various methods can be applied. It is also possible to use various processing methods such as, for example, a spray method in which the processing solution is atomized, a web method by contact with a carrier impregnated with the processing solution, or a developing method with a viscous processing solution, but the processing step is substantially performed. The process typically includes color development, bleach-fixing, washing with water, or a stabilizing treatment as an alternative thereto.

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 Etherdiaminetetraacetic acid [10] Glucolic etherdiaminetetraacetic 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 a halogenide such as ammonium bromide other than the above-mentioned silver halide fixing agent and an ethylenediaminetetraacetic acid iron (III) complex bleaching agent is added, or conversely, a halide such as ammonium bromide. Use a bleach-fixing solution with a composition containing a large amount of added, and a special bleach-fixing solution with a composition comprising a combination of an ethylenediaminetetraacetic acid iron (III) complex salt bleaching agent and a large amount of a halide such as ammonium bromide. You can 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, JP-B-46-556, and Verigi Patent 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.

The water-washing alternative stabilizing solution applicable to the present invention will be described below.

The treatment with the stabilizing solution refers to a treatment for stabilizing treatment in which the stabilizing treatment is carried out immediately after the treatment having fixing ability and substantially no washing treatment is performed, and the treating liquid used for the stabilizing treatment is It is called a stabilizing solution as a substitute for washing with water, and the treatment tank is called a stabilizing bath or stabilizing tank.

The water-washing alternative stabilizing solution applicable to the present invention may contain various additives such as an alkaline agent, an acid agent, an antifungal agent, a chelating agent and a sulfite as a pH adjusting agent.

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.

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 preferable to sequentially perform the treatment with the treatment time increased by 20% to 50% in 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 short 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.

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 processing method of the silver halide color photographic light-sensitive material of the present invention is a color development processing of the silver halide color photographic light-sensitive material using the color developing solution containing the preservative of the present invention and the sulfonic acid derivative of the present invention. Is to be performed.

The silver halide emulsion which can be used in the silver halide color light-sensitive material used in the processing method of the present invention includes silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide and silver iodobromide. Any silver halide such as silver chloroiodobromide may be used.

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 emulsion on the flat plate is reported by Cugnac.Chateau and Duffin's "Photographic Emulsion Chemistry" (Fo
Published by cal Prss. New York 1966) Pages 66-72 and APO
Trivelli, WF Smith, photo.joural 80 (1940) 285
As described on the page, JP-A Nos. 58-113927 and 58-1139.
It can be easily adjusted by referring to the methods described in No. 28 and No. 58-127921.

The 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.

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 the silver halide grains are grown, the pH, pAg, etc. in the reaction vessel are controlled, and an amount of silver corresponding to the growth rate of silver halide grains as described in JP-A-54-48521 is used. Ions and halide ions are preferably sequentially and simultaneously injected and mixed.

Known silver halide solvents can be used. Examples of silver halide solvents that are often used include ammonia, thioethers, thioureas, thiocyanate salts and thiazoline thiones. Regarding thioethers, U.S. Pat.
Reference can be made to 3,574,628 and 3,790,387. Regarding thioureas, JP-A-53-82408,
55-77737, U.S. Pat.No. 2, regarding thiocyanate salts.
Regarding 222,264, 2,448,534, 3,320,069 and thiazoline thiones, JP-A-53-144319 can be referred to.

These silver halide emulsions include active gelatin; sulfur sensitizers such as allylthiocarbamide, thiourea, and cystine; sulfur sensitizers; selenium sensitizers; reduction sensitizers such as stannous salt and thiourea dioxide. Noble metal sensitizers such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, and 2-aurothio-3-.
Sensitizers of methylbenzothiazolium chloride and the like or water-soluble salts such as ruthenium, palladium, platinum, rhodium and iridium, specifically ammonium chloroparadate, potassium chloroplatinate and sodium chloroparadate (these or Some of them act as sensitizers or antifoggants depending on the amount.) Etc. alone or in combination (for example, gold sensitizer and sulfur sensitizer, gold sensitizer and selenium sensitizer). It may be scientifically sensitized by combining with a sensitizer).

These examples are described in US Pat.
574,944, 2,278,947, 2,410,689, and
No. 2,728,947, No. 3,656,955, etc., for reduction sensitization method, U.S. Patent Nos. 2,419,974, 2,983,609, 4,05
No. 4,458, US Patent No. 2,399,0 for the noble metal sensitizer method
No. 83, No. 2,448,060, US Pat. No. 618,061 and the like.

A 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 hydroxytetrazaindene and a mercapto group-containing nitrogen-containing hetero emulsion. You may include 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 No. 929,080, U.S. Pat.
No. 58, No. 2,493,748, No. 2,503,776, No. 2,519,001
No., No. 2,912,329, No. 3,656,959, No. 3,672,897,
Examples thereof include those described in 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. 52-24844 and the like. Examples of sensitizing dyes used in green-sensitive silver halide emulsions include, for example, U.S. Patents 1,939,201, 2,072,908 and 2,739,149.
Nos. 2,945,763 and British Patent No. 505,979, cyanine dyes, merocyanine dyes or complex cyanine dyes can be mentioned as typical ones. Further, sensitizing dyes used in red-sensitive silver halide emulsions include, for example, U.S. Patents 2,269,234 and 2,270,378.
No. 2,442,710, No. 2,454,629, No. 2,776,280, and the like, cyanine dyes, merocyanine dyes, or complex cyanine dyes can be mentioned as typical ones. Furthermore, U.S. Patents 2,213,995 and 2,4
93,748, 2,519,001, West German Patent 929,080, and the like, an asinine dye, a merocyanine dye, or a complex cyanine dye 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 tourism material of the present invention may be optionally optically sensitized to a desired wavelength range by a spectral sensitization method using a cyanine or merocyanine dye alone or in combination.

A particularly preferable example of the spectral sensitization method is, for example, Japanese Patent Publication No. 43-4936, which relates to a combination of benzimidazolocarbocyanine and benzoxazolocarbocyanine.
No. 43, No. 42884, No. 45-18433, No. 47-37443, No. 48
-28293, 49-6209, 53-12375, JP-A-52-23
No. 931, No. 52-51932, No. 54-80118, No. 58-153926,
Examples thereof include the methods described in Nos. 59-116646 and 59-116647.

Further, examples of the combination of carbocyanine having a benzimidazole nucleus with other cyanine or mesocyanin include, for example, Japanese Examined Patent Publication Nos. 45-25831, 47-11114, and 47-253.
No. 79, No. 48-38406, No. 48-38407, No. 54-34535, No.
55-1569, JP-A-50-33220, 50-38526, 51-10
No. 7127, No. 51-115820, No. 51-135528, No. 52-104916
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,
Japanese Patent Application Laid-Open No. 57-1483 and merocyanine include, for example, Japanese Patent Publication Nos. 48-384018, 48-41204 and 50-40662.
No. 56-25728, No. 58-10753, No. 58-91445,
No. 59-116645, No. 50-33828 and the like.

Further, examples of combinations of thiacarbocyanine with other carbocyanines include, for example, Japanese Patent Publication Nos. 43-4932 and 43-49.
No. 33, No. 45-26470, No. 46-18107, No. 47-8741, JP-A No. 59-114533, and the like, further using zero methine or dimethine merocyanine, monomethine or trimethine cyanine and styryl dyes. The method described in JP-A-49-6207 can be advantageously used.

In order to add these sensitizing dyes to the silver halide emulsion according to the present invention, a dye solution may be prepared in advance as a dye solution such as methyl alcohol, ethyl alcohol, acetone, dimethylformamide, or a fluorinated alcohol described in JP-B-50-40659. It is used by dissolving it in the 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 layer of the silver halide photographic light-sensitive material used in the present invention contains a dye (AI, which is decolorized by a water-soluble or color developing solution).
Dyes) can be added, and the AI dyes include oxonol dyes, hemioxonol dyes, merocyanine dyes and azo dyes. Of these, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful. Examples of AI dyes that can be used include British Patent 58-4.
609, 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 ^{−4 to} 5 × 10 ⁻² mol, and more preferably 1 × 10 ⁻³ to 1 × 10 ⁻² mol.

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

As the coupler usable in the present invention, various yellow couplers, magenta couplers and cyan couplers can be used without particular limitation. These couplers may be so-called 2-equivalent type or 4-equivalent type couplers, and it is also possible to use diffusible dye releasing type couplers in combination with these couplers.

The yellow coupler includes an open-chain ketomethylene compound and an active site called a so-called 2-equivalent type coupler.
o-aryl substituted coupler, active point-o-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, active point -o
-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. Patents 2,875,057 and 3,265,506.
No. 3,408,194, 3,551,155, 3,582,322,
3,725,072, 3,891,445, West German patent 1,547,868
No. 2, West German Application Publication No. 2,219,917, No. 2,261,361, No. 2,41
4,006, British Patent 1,425,020, Japanese Patent Publication No. 51-10783, JP-A-47-26133, 48-73147, 51-102636, 50-
6341, 50-123342, 50-130442, 51-21827
No. 50, No. 50-87650, No. 52-82424, No. 52-115219, No. 5
Examples thereof include those described in 8-95346.

Examples of the magenta coupler used in the present invention include pyrazolone-based, pyrazolotriazole-based, pyrazolinobenzimidazole-based and indazolone-based 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. Patents 2,600,788, 2,983,608 and 3,06.
2,653, 3,127,269, 3,369,897, 3,311,476
Issue 3,419,391, Issue 3,519,429, Issue 3,558,319,
Same 3,582,322, same 3,615,506, same 3,834,908, same 3,8
91,445, West German patent 1,810,464, West German patent application (OLS)
2,408,665, 2,417,945, 2,418,959, 2,42
4,467, Japanese Patent Publication No. 40-6031, JP-A Nos. 51-20826, 52-5
8922, 49-129538, 49-74027, 50-159336
No. 52, No. 42-1211, No. 49-74028, No. 50-60233, No. 51
-26541, No. 53-55122, Japanese Patent Application No. 55-110943 and the like can be mentioned.

Further, useful cyan couplers used in the present invention include, for example, phenol type and naphthol type couplers. And 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. Patents 2,369,929 and 2,434,272.
No., No. 2,474,293, No. 2,521,908, No. 2,772,162,
2,805,826, 3,034,892, 3,311,476, 3,4
58,315, 3,476,563, 3,583,971, 3,591,38
No. 3, No. 3,758,308, No. 3,767,411, No. 3,772,002,
3,933,494, 4,004,929, 4,126,396, 4,3
34,011, 4,327,173, West German patent application (OLS) 2,414,
No. 830, No. 2,454,329, No. 3,329,729, JP-A-48-5983
No. 8, No. 51-26034, No. 48-5055, No. 51-146827, No. 5
2-69624, 52-90932, 58-95346, Japanese Patent Sho 49-11
Examples thereof include those described in No. 572.

Further, in the present invention, Japanese Patent Application No. 59-172151
The polymer couplers described in No. 1 are also preferably used.

The couplers used in the present invention can be used in combination of two or more kinds in the same layer in order to satisfy the characteristics required for a light-sensitive material, and it is of course possible to add the same compound to two or more different layers. Absent.

In order to correct unnecessary absorption in the short wavelength region which the coloring dyes of magenta and cyan couplers have, it is preferable to use a colored coupler in combination with the color photographic material for photographing. Yellow colored magenta couplers described in U.S. Pat.No. 4,163,670 and Japanese Patent Publication No. 57-39413 or U.S. Pat.
4,929, 4,138,258 and British Patent 1,146,368
Examples include magenta colored cyan couplers described in No.

Further, as a color forming dye diffusion type coupler, U.S. Pat.
Examples of magenta couplers are given in 237 and British Patent 2,125,570, and examples of yellow, magenta and cyan are given in EP 96,873 and West German Patent Publication (OLS) 3,324,533.

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

As the DIR coupler, for example, those releasing a heterocyclic mercapto type development inhibitor described in U.S. Pat.No. 3,227,554: those releasing a benzotriazole derivative described in JP-B-58-9902 as a development inhibitor: Japanese Patent Publication No. 51-1
So-called colorless DIR couplers described in 6141: JP-A-SHO-5
Release of nitrogen-containing heterocyclic development inhibitor with decomposition of methylol after separation described in 2-90932: US Patent No.
4,248,962 and JP-A-57-56837, which release a development inhibitor with an intramolecular nucleophilic reaction after the separation: JP-A-56-114946, 57-154234 and 57-188033. issue,
58-98723, 58-209736, 58-209737, 58-2
09738, 58-209739, 58-209740, etc., which release a development inhibitor by electron transfer through a conjugated system after separation: JP-A-57-151944, 58-217932, etc. Those releasing a diffusible development inhibitor whose development inhibiting ability is deactivated in the developing solution described: Releasing the reactive compound described in Japanese Patent Application Nos. 59-38263 and 59-39653, Those which generate a development inhibitor or deactivate the development inhibitor by the reaction in the film: and the like.

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

Specific examples include compounds described in JP-A-57-150845.

The color silver halide 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 brightening agent, a color image fading preventing agent, an antistatic agent, a hardener, a surfactant, a plasticizer, a wetting agent, a development aid and the like can be used.

In the silver halide color photographic light-sensitive material used in the present invention, hydrophilic colloids used for preparing an emulsion include gelatin, derivative gelatin, a graft polymer of gelatin and other polymers, proteins 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 halogenated color silver 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 taping 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. Pat.No. 2,761,79
A simultaneous coating method of two or more layers by the method described in No. 1 and No. 2,941,898 can also be used.

In the light-sensitive material used in the present invention, it is optional to provide an intermediate layer having an appropriate thickness according to the purpose, and further various layers such as a filter layer, an anti-curl layer, a protective layer and an antihalation layer are constituent layers. Can be used in appropriate combination. 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.

The light-sensitive material applicable to the present invention may be any of color reversal film for slide, color reversal film for movie, color reversal film for TV, color reversal photographic paper for printing, color reversal photographic paper for photographing and the like.

[Specific effects of the invention] As described above, in the present invention, a color developing solution having excellent liquid properties of the color developing solution, that is, preservability, pH stability, and prevention of tar generation is used. A method for processing a silver halide color photographic light-sensitive material excellent in maximum color density of a dye image obtained without silver development with a preservative can be provided.

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) Potassium bromide 1.0g Potassium sulfite (50% solution) 6.0ml Preservative (shown in Table 1) 3.0g Sodium tetrapolyphosphate 2.0g Color developing agent (sulfate of Exemplified Compound (1)) 6.0g Potassium carbonate 30 g Sulfonic acid derivative of the present invention (Exemplary compound (I-9)) Table (1) Amount described in Table 1 Water is added to adjust to pH 12.0 with potassium hydroxide and sulfuric acid.

The above color developing solution was allowed to stand at room temperature (about 25 ° C.) for 8 days, and the pH value and liquid appearance at that time were evaluated.

The appearance of the solution was determined by evaluating the degree of coloring of the color developing solution, and was used as a representative property of the stability of the color developing agent.

The liquid appearance was divided into the following four stages.

++ Generation of a large amount of tar ++ Blackening ＋ Browning − Almost no discoloration As is clear from the results in Table (1), hydroxylamine, which has been used as a preservative from the past, has a large pH drop, and when hydroxylamine is not added, the buffer property improves but the liquid appearance becomes black, It is considered that the color-developing agent (1) is oxidized and tar formation starts to occur.

When the preservative of the present invention is used and the sulfonic acid derivative of the present invention is not used, the pH stability is clearly improved as compared with hydroxylamine, but the buffering property is considerably insufficient, and the sulfonic acid derivative of the present invention is It is clear from the present example that the combined use of and surprisingly markedly improves the buffering property and also has good preservability.

Example (2) A photosensitive material sample was prepared by sequentially coating the following layers from the support side on a polyethylene-supported paper support.

Layer 1 ... 1.0 × 10 ⁻³ mol g dissolved in 1.2 g / m ² gelatin, 0.40 g / m ² (silver equivalent, the same applies below) blue-sensitive silver chlorobromide emulsion and 0.50 g / m ² dioctyl phthalate A layer containing / m ² of the following yellow coupler (Y-1).

Layer 2 ... Intermediate layer consisting of 0.7 g / m ² of gelatin.

Layer 3 dissolved in 1.25 g / m ² gelatin, 0.25 g / m ² green sensitive silver chlorobromide emulsion and 0.30 g / m ² dioctyl phthalate 1.
A layer containing 0 × 10 ⁻³ mol g / m ² of the following magenta coupler (M-1).

Layer 4 ... An intermediate layer consisting of 1.2 g / m ² of gelatin.

Layer 5 ... 1.5 g dissolved in 1.4 g / m ² gelatin, 0.25 g / m ² red-sensitive silver chlorobromide emulsion and 0.20 g / m ² dibutyl phthalate.
A layer containing x10 ^-3 mol g / m ² of the following comparative cyan coupler (C-1) and the coupler of the present invention shown in Table 2.

Layer 6 A layer containing 0.30 g / m ² of Tinuvin 328 (UV absorber manufactured by Ciba Geigy) dissolved in 1.0 g / m ² of gelatin and 0.20 g / m ² of dioctyl phthalate.

Layer 7 ... A layer containing 0.5 g / m ² of gelatin.

As a hardening agent, 2,4-dichloro-6-hydroxy-s-triazine sodium was added in layers 2, 4 and 7,
Each of them was added in an amount of 0.017 g per 1 g of gelatin.

Next, these samples were subjected to wedge exposure by a conventional method, and then subjected to the following developing treatment in order to check silver developability.

Standard processing steps (processing temperature and processing time) [1] Development 35 ° C 45 seconds [2] Fixing 35 ° C 1 minute [3] Washing treatment 25-30 ° C 1 minute 30 seconds [4] Drying 75-80 ° C About 1 minute 30 seconds However, the development was performed using the color developer No. 2 used in Example (1),
Using only the color developing agent from 4. and 6,
The fixer used had the following composition.

(Fixer) Ammonium thiosulfate (70% solution) 150 ml Ammonium sulfite (40% solution) 20 ml Water was added to bring the total amount to 1, and the pH was adjusted to 7.00 with ammonium hydroxide or acetic acid.

Samples after development processing are PDA-65 (Konishi Roku Photo Industry Co., Ltd.)
The spectral reflection density of Dmax of the sample was measured by using orange light, and the difference between the spectral reflection density of Dmax and the spectral reflection density of Dmin was used as the representative characteristic of silver concentration.

The results are shown in Table (2).

As is clear from the results of Table (2), sample Nos. 8 and 11 using hydroxylamine as a preservative undergo remarkable silver development, but sample Nos. 9 and 12 using the preservative of the present invention. Has no silver development regardless of the amount of KBr.

Example (3) The light-sensitive 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 solutions. However, the color developing solution was used in Example (1).
Nos. 2, 4 and 6 used in 1. were adjusted to pH 11.5 and used.

Processing process (processing temperature and processing time) [1] Color development 35 ° C 45 seconds [2] Bleach fixing 35 ° C 1 minute [3] Washing treatment 25-30 ° C 1 minute 30 seconds [4] Drying 75-80 ° C 1 minute 30 seconds [Bleaching / fixing tank liquid] Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100ml Ammonium sulfite (40% solution) 27.5ml Add water to make the total amount 1 and add water. The pH was adjusted to 7.10 with ammonium oxide or glacial acetic acid.

Samples after development processing are PDA-65 (Konishi Roku Photo Industry Co., Ltd.)
Manufactured), and the maximum reflection densities of blue, green, and red were measured. The results are shown in Table 3.

As is clear from Table 3, sample No. 14 processed with the color developing solution using hydroxylamine has lower blue, green and red co-concentrations than sample No. 13 processed with the color developing solution not using hydroxylamine. You can see that it has become. On the other hand, Sample N treated with the color developing solution of the present invention
It can be seen that o.15 has the same maximum color density as Sample No. 13 containing no preservative.

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

(Color developer) Potassium bromide 1.0g Potassium sulfite (50% solution) 6.0ml Preservative (see Table 4) 3.0g Sodium tetrapolyphosphate 2.0g Color developing agent (sulfate of Ex. No. (1)) 6.0 g Sulfonic acid derivative or K ₂ CO ₃ (described in Table (4)) The amount described in Table (4) was added to 1 and adjusted to pH 12 with potassium hydroxide and sulfuric acid.

The above color developing solution was left at room temperature (about 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, even if K ₂ CO ₃ or a sulfonic acid derivative is used as the buffering agent, the pH drops significantly over time and is not practically usable. Similarly, when the preservative of the present invention and K ₂ CO ₃ are combined, the pH drop is large and K ₂ CO ₃ 120g
Upon addition, precipitation of the color developing agent was observed.

In the case where the preservative was not added, when the combination with the sulfonic acid derivative of the present invention was used, the fluctuation of pH was considerably small, but the tarring started from 6 days after the lapse of time and was completely tarted at 13 days. Further, in the present invention, when the sulfonic acid derivative is 5 g / l, the pH fluctuation is large, and it is preferable to use 10 g / l or more of the sulfonic acid derivative 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 maintains the preservative properties of stabilizing pH and preventing tarring.

Also, the same results as above were obtained by using the exemplified compounds (1) and (6) as the preservatives and the exemplified compounds (I-15) and (I-25) as the sulfonic acid derivative.

Example (5) Using the color developer used in Example (4), the pH values shown in Table (5) were set, and the mixture was allowed to stand at room temperature (about 25 ° C.) for 6 days to reach pH.
Was measured.

The results are shown in Table 5.

As is clear from Table 5, at pH 9.8, almost the same tendency is exhibited regardless of the sulfonic acid derivative or K ₂ CO ₃ used as a preservative or buffer, but at a pH higher than 10.3, especially higher than 10.3. Is less than the hydroxylamine preservative of the present invention and K ₂ CO ₃ of the sulfonic acid derivative of the present invention has a smaller decrease in pH. By using the preservative of the present invention and the sulfonic acid derivative in combination, Similar to (4), pH stability is greatly improved.

 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Masayuki Kurematsu No. 1 Sakuramachi, Hino-shi, Tokyo Photo of Konishi Roku Photo Industry Co., Ltd. Within

Claims (5)

[Claims] 1. A method of treating a silver halide photographic light-sensitive material with at least a color-developing main solution after imagewise exposure, wherein the color-developing solution contains compounds represented by the following general formulas [I] and [II]. Of the general formula [I] R ₁ SO ₃ X (wherein R represents an alkyl group having 1 to 8 carbon atoms or a phenyl group, and R is an ethylenically unsaturated group having repeating units thereof). It may be a polymer. X represents a hydrogen atom, a sodium atom, a potassium atom, a lithium atom or an ammonium group.) General formula [II] (In the formula, R ₂ and R ₃ each represent an alkyl group or an alkoxy group having 1 to 3 carbon atoms. Further, R ₂ and R ₃ may combine to form a ring.) A method of processing a silver halide color photographic light-sensitive material, which has a pH of 10.0 or higher. 2. The color developing solution contains at least one compound represented by the general formula [I].
The method for processing a silver halide color photographic light-sensitive material according to claim (1), characterized in that the content is 10.0 g or more. 3. The method for processing a silver halide color photographic light-sensitive material according to claim 1 or 2, wherein the color developing solution has a pH of 10.3 or higher. 4. The color developing solution according to claim 1, wherein at least one kind of carbonate is contained in an amount of 0.10 mol or more per color developing solution. A method for processing a silver halide color photographic light-sensitive material according to the item (3). 5. The silver halide color photograph according to claim 1, wherein the color developing solution has a pH of 10.5 or higher. Method of processing photosensitive material.