JPS63236037A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To reduce the change of processing performance of the titled material caused by less replenishing of a color developer by developing the titled material contg. at least one kind of a specified compd. and/or its alkali-unstable precursor with a color developer replenishing in an amount of <=9ml per 100cm<2> of the titled material. CONSTITUTION:The titled material contg. at least one kind of the compd. shown by formula I and/or its alkali-unstable precursor is developed with the color developer replenishing in the amount of 9ml per 100cm<2> of the titled material. In the formula, Ra and Rb are each hydrogen or halogen atom, etc., X is -CO- or -SO2- group, Rc is alkyl or aryl group, etc. Thus, the gradient difference and the stirring dependency of the titled material are reduced, thereby carrying out a stable processing of the titled material.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for processing silver halide color photographic light-sensitive materials, and in particular, it relates to a method for processing silver halide color photographic light-sensitive materials. This invention relates to an improved processing method that does not require

(Prior Art) In recent years, due to environmental protection issues and cost issues, research on reducing the amount of waste liquid in processing has been advanced, and practical use is being attempted in some processing steps. Particularly in the color development process, since the pollution load of waste liquid such as BOD and COD is extremely large, various low-pollution technologies have been proposed. For example, JP-A-54-37731, JP-A-54-37731, JP-A-54-37731;
-1048 No. 56 = 1'049 No. 56-27
No. 142, No. 56-33644, No. 56-14903
Regeneration method by electrodialysis described in No. 6 etc., Special Publication No. 55-1
571, the regeneration method using activated carbon described in JP-A-58-14831, the ion exchange membrane method described in JP-A-52-105820, and JP-A-53-132343 and JP-A-55.
Examples include regeneration methods using ion exchange resins as described in No. 144240, No. 57-146249, and US Pat. No. 4,348.475.

However, all of these methods require sophisticated management techniques such as analyzing the developer and controlling its composition, as well as expensive equipment, so they are only implemented in some large-scale photo labs. .

On the other hand, methods for reducing the amount of waste liquid by reducing the amount of replenishment of the color developing solution without relying on the above-mentioned regeneration have recently come into use.

This method is excellent in that it does not require expensive equipment and does not require compositional control by analysis.

However, in this method, the processing performance is affected by the oxidation of the preservative due to the increased residence time of the solution in the evaporation concentration processing tank due to the reduction in the amount of replenishment, and the deterioration of the developing agent caused by this. It has the major drawback of being highly variable.

The above-mentioned drawbacks are magnified as the degree of reduction in the amount of replenishment increases, and are particularly noticeable in small-scale photo labs with a small throughput.

Such fluctuations in processing performance are noticeable in changes in gradation and increase in staining of the color photosensitive material after processing.

Therefore, while this low replenishment processing method has the above-mentioned advantages, it also has the problem of processing performance fluctuation, and as a result, it is similar to the regeneration method in that it can only be applied to large-scale photo labs that carry out a large amount of processing. I had a problem.

Against this background, there has been a strong demand in the art for the development of a low replenishment processing method that has stable processing performance even when the processing amount is small.

On the other hand, it has been known that color contamination occurs in light-sensitive materials due to diffusion and movement of oxidized developing agent between different color-sensitive layers. As such a color stain preventive agent, for example, US Pat. No. 2,336,327, US Pat.
No. 18613, No. 2419613, No. 2732300
No., No. 3700453, No. 3960570, etc. describe alkyl and aryl hydroquinones, U.S. Pat. Hydroquinones substituted with groups are disclosed. Further, as some compounds included in the general formula (A), US Pat. No. 4,198,239 describes hydroquinones substituted with aliphatic acylamino groups, ureido groups, urethane groups, etc. .9ml20246
No. 5 proposes hydroquinones substituted with a sulfonamide group, and US Pat. No. 2,701,197 proposes hydroquinones having a sulfonic acid group and substituted with an acylamino group.

However, in low supplementation treatments these compounds
The effect on the performance of photosensitive materials after processing has not been known at all.

(Problems to be Solved by the Invention) Therefore, the first object of the present invention is to significantly improve the fluctuations in processing performance caused by low replenishment of color developer.

A second object of the present invention is to popularize low-pollution processing even to small-scale photo labs, and at the same time to reduce processing costs.

Furthermore, a third object is to provide a processing method capable of forming color images of excellent image quality.

(Means for Solving the Problem) The above object of the present invention is to provide a silver halide color photographic material containing at least one compound represented by the following general formula (A) and/or its alkali-labile precursor. The silver halide color photographic light-sensitive material is characterized in that it is processed with a color developing solution that is replenished in an amount of 9 ml or less per 1,004 ml of the silver halide color photographic light-sensitive material. This was achieved by a method for processing silver halide color photographic materials.

General formula (A) IJ lH In the formula, R,, R, is a hydrogen atom, a halogen atom, a sulfo group, a carboxyl group, an alkyl group, an acylamino group, an alkoxy group, an aryloxy group, an alkylthio group, or an alkylthio group.
ruthio group, sulfonyl group, acyl group, carbamoyl group,
It represents a sulfamoyl group, and R and R1 may jointly form a carbocyclic ring. X is -C〇- or -3o2-
represents. Rc is an alkyl group, an aryl group, a heterocyclic group,
Cycloalkyl group, alkoxy group, aryloxy group,
Represents an amino group. The total number of carbon atoms of R-, Rh, and RC is 10 or more. The compound of general formula (A) is substantially colorless and does not form a color image through a coupling reaction with a developing agent.

Next, the compound represented by general formula (A) will be explained in detail.

In the formula, R, Rb are hydrogen atoms, halogen atoms (e.g. chlorine, bromine, etc.), sulfo groups, carboxyl groups, alkyl groups (e.g. methyl, pentadecyl, t-hexyl, etc.), acylamino groups (e.g. acetylamino). group, benzoylamino group, etc.), alkoxy group (e.g., methoxy group,
butoxy group, etc.), aryloxy group (e.g., phenoxy group, etc.), alkylthio group (e.g., octylthio group, hexadecylthio group, etc.), arylthio group (e.g., phenylthio group, etc.), sulfonyl group (e.g., dodecanesulfonyl group, p-toluenesulfonyl group, etc.) ), an acyl group (e.g. acetyl group, benzoyl group, etc.), a carbamoyl group (e.g. N,N-dibutylcarbamoyl group, etc.), a sulfamoyl group (e.g. N,N-diethylfamoyl group, etc.), and R3 and R1 represent They may jointly form a carbocyclic ring. X represents -CO- or -8O□-. RC is an alkyl group (e.g. heptadecyl group, 1-hexylnonyl group, 1-(2!,4-di-t-amylphenoxy)propyl group, etc.), an aryl group (e.g. phenyl group, 3,5-
Bis(2-hexyldecanamido)phenyl L3.4-
bis(hexadecyloxycarbonyl)phenyl group, 2.
4-bis(tetradecyloxy)phenyl group, etc.), heterocyclic groups (e.g. 2゜6-dihexyloxypyridin-4-yl group, N-tetradecylpyrrolidin-2-yl group, N-octadecylpiperidin-3-yl group) yl group, etc.), cycloalkyl group (e.g. 3-decanamidocyclohexyl group, 3-
((2,4-di-t-amylphenoxy)butanamido)cyclohexyl group, etc.), alkoxy group (e.g. hexadecyloxy group, etc.), aryloxy group (e.g. 4-
t-octylphenoxy group, etc.), and an amino group (e.g., octadecylamino group, etc.). The total number of carbon atoms in R, , R, and Rc is 10 or more.

The compound of general formula (A) may form a bis-form, a tris-form, a polymer, or the like.

In general formula (A), preferable substituents for R-1Rh are a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, and an alkylthio group, and among these, a hydrogen atom, a halogen atom, and an alkyl group are more preferable.
Most preferably, it is a hydrogen atom.

As X in general formula (A), -co- is relatively preferable.

In general formula (A), preferred substituents as Rc are an alkyl group and an aryl group, and among these, an aryl group is most preferred.

In general formula (A), when Rc is an aryl group, there are no particular limitations on the substituents that are further substituted on the aryl group as long as they are generally known substituents on the aryl ring. The substituents listed in are relatively preferred. That is, halogen atoms, alkyl groups, amide groups, sulfonamide groups,
These are an alkoxy group, an alkoxycarbonyl group, and a carbamoyl group.

Furthermore, the substituent to be further substituted on the aryl group is preferably a group that does not contain a sulfo group, a carboxyl group, or the like. This is because the presence of these water-soluble groups may adversely affect the storage stability of the photosensitive material.

The purpose of the compound of general formula (A) is to prevent changes in gradation and increase in stain, which are problems when performing low replenishment processing of color developing solution. It is undesirable to form a color image during the development process.

Therefore, firstly, the compounds of the invention are substantially colorless.

Substantially colorless means 400nm to 70nm.
It means that it does not have absorption with a molar absorption coefficient of 5000 or more in the visible wavelength range down to 0 nm.

Secondly, the compound used in the present invention contains coupler residues (e.g., acylacetanilide residues, 5- It does not have pyrazolone residues, (1)-naphthol residues) and does not form a color image due to campling reaction during the development process.

The alkali-labile precursor of the compound represented by the general formula (A) of the present invention is a compound in which the hydroxyl group moieties at the 1st and 4th positions of the hydroquinone skeleton are protected and can be cleaved under alkaline conditions. Refers to a compound that has a group.

As a protecting group, an acyl group (for example, an acetyl group, a chloroacetyl group, a benzoyl group, an ethoxycarbonyl group,
etc.), β-leaving groups (eg, 2-cyanoethyl group, 2-methanesulfonylethyl group, 2-toluenesulfonylethyl group, etc.) are representative examples.

Specific examples of compounds included in the present invention will be summarized later in Table 7, but the present invention is not limited thereto.

These compounds represented by the general formula (A) of the present invention and their a! The Recali unstable precursor is US Patent No. 2,7
It can be easily synthesized according to the methods described in Japanese Patent Publication No. 01,197, Japanese Patent Publication No. 59ml37497, Japanese Patent Application Laid-open No. 59ml202465, and the like.

Specific examples of the compound represented by the general formula (A) and its alkali unstable precursor are listed below, but the present invention is not limited thereto.

Compound A (
-co CH2+-T-I In the present invention, the compound represented by general formula (A) can be added to any layer in the photosensitive material, but is preferably added to a non-photosensitive layer, and more preferably It is added to an intermediate layer of silver halide emulsion layers in which the non-photosensitive layers have different color sensitivities.

The compound represented by the general formula (A) of the present invention and/or its alkali-labile precursor can be added to the light-sensitive material by a method similar to the method for dispersing and adding couplers described below.

The total amount of these compounds added is 0.003 to 1.
2.0g/rrr, preferably 0.005 to 1.
0 g/♂, more preferably 0.02-0.3 g/
It is rrr.

The present invention will be explained in more detail below.

The present inventors found that when low replenishment was carried out to achieve low pollution and cost reduction, gradation changes and staining of color photographic light-sensitive materials increased, and in particular, when the color developing replenisher contained silver halide It has been found that this problem becomes more pronounced when the color photographic material is processed so that 9 ml or less is replenished per 100 C4 of color photographic material.

Generally, for color photographic materials containing silver iodide, such as color negative films, the amount of replenishment of color developer is 1
Approximately 12 - 001 cells were replenished, and no particularly large processing fluctuations were observed in such replenishment amounts. However, when the amount of replenishment is less than 9 ml, the gradation of the processed color photosensitive material tends to become darker and the staining also increases due to the concentration of the developer due to evaporation.

On the other hand, due to low replenishment, the residence time of the developer in the color developing tank increases, and as the amount of hydroxylamine and sulfite added as preservatives decreases, the contrast becomes more pronounced. As the oxidation of such preservatives progresses further,
The color developing agent is also oxidized and reduced, and as a result, the developing activity of the color developer decreases, and as a result, the above-mentioned gradation becomes softer.

It is possible to design the composition of the replenisher in consideration of such concentration and oxidation of the preservative when the amount of development processing is constant.

However, since the amount of processing in an actual photo lab varies widely during the first half of the week and between seasons, the problem cannot be solved only by considering the composition of the replenisher as described above.

Therefore, due to various factors such as fluctuations in processing amount, contact area between the developer and air in the color developing tank, and the length of operating time, the concentration of the solution and the oxidation state change, resulting in changes in the gradation of the color photosensitive material after processing. , the stain fluctuates widely, making it impossible to obtain a stable finish.

Conventionally, it has been impossible to achieve a sufficient reduction in replenishment because almost no solution has been found to the above-mentioned problem.

However, by incorporating the compound represented by the above-mentioned general formula (A) into the color light-sensitive material, the above problems are significantly improved, and it is surprising that stable processing performance can be obtained even when replenishing 9 ml or less per 1,004 ml. This has resulted in an effect.

In the present invention, the replenishment amount of color developer is 9 m per 100 d.
The effect is more obvious at 7-1 or less, and the effect is particularly noticeable at 5-1 or less.

Of course, in the present invention, there is a lower limit to the replenishment amount, and the replenishment amount is set at 1-9 ml or more, preferably 2-7 or less, and more preferably 2-5 or more.

In the present invention, the bromide concentration in the color developer replenisher is 4X
The bromide concentration is set at 10-" mol/p or less, but it is necessary to adjust the bromide concentration depending on the degree of low replenishment. Generally, as the replenishment amount decreases, the bromide concentration in the replenishment solution needs to be reduced. be.

At replenishment levels of 5 or less, at which the effects of the present invention are most apparent, the bromide concentration during color development is preferably substantially zero.

Preferred bromides include alkali metal salts such as potassium bromide and sodium bromide, and hydrobromic acid.

The aromatic primary amine color developing agents used in the color developer and color developer replenisher in the present invention include known ones that are widely used in various color photographic processes. These developers include aminophenol and p-phenylenediamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, since they are more stable than in the free state. In addition, these compounds are generally used in an amount of about 1 g to about 1 g per color developer 1β.
5g concentration, preferably about 3g for color developer 1β
Use at a concentration of ~Log.

Examples of aminophenol-based developers include O-aminophenol, p-aminophenol, and 5-amino-2-
Oxytoluene, 2-amino-3-oxytoluene, 2
-oxy-3-amino-1°4-dimethylbenzene and the like.

Particularly useful primary aromatic amino color developers are N, N'
-Dialkyl-p-phenylenediamine compound, and the alkyl group and phenyl group may be substituted with any substituent. Among them, the particularly useful compounds are 4
-(N-ethyl-N-dodecylamino)-2-methylaniline sulfate, 4-(N-ethyl-N-β-methanesulfonamidoethylamino)-2-methylaniline sulfate, 4-(N-ethyl -N-β-hydroxyethylamino)-2-methylaniline sulfate, 4-(N-ethyl-N
-β-methoxyethylamino)-2-methylaniline-p-toluenesulfonate, 4-(N,N-diethylamino)-2-methylaniline hydrochloride, N,N-diethyl-p-phenylenediamine hydrochloride, etc. be able to.

Among them, 4-(N-ethyl-N-β-hydroxyethylamino)-2-methylaniline is preferred in the present invention.

The above compounds are usually used alone, but two or more types can be used in combination depending on the purpose. An example of a preferred combination is 4-(N-ethyl-N-β-hydroxyethylamino)-2-methylaniline and 4-(N-ethyl-N
-β-methanesulfonamidoethylamino)-2-methylaniline, or 4-(N-ethyl-N-β-hydroxyethylamino)-2-methylaniline and 4-(N-ethyl-N-β-methoxyethyl Mention may be made of the combination of amino)-2-methylaniline.

In addition, in the present invention, the following general formula (B) and/or (C
) It is desirable that the color developing solution contains at least one compound represented by the following.

In particular, it is preferable to contain both at least one compound represented by the following general formula (B) and at least one compound represented by the following general formula (C).

General formula (B) CHffiCOOM General formula (C) hO+P C-PO:+Mt H In the formula, n represents 1 or 2, R represents a lower alkyl group, and M may be the same or different (, hydrogen atom , represents an alkali metal atom or ammonium.

Note that R is particularly preferably a methyl group or an ethyl group, and M
is preferably a hydrogen atom or a sodium atom.

The compounds represented by the general formulas (B) and (C) are useful for preventing the deterioration of preservatives such as hydroxylamine under low replenishment processing conditions and for preventing the gradation of photosensitive materials from increasing in contrast after processing. It has excellent effects.

Specific examples of the compounds represented by general formulas (B) and/or (C) are shown below.

C■.

HzO3P-CPOJz Hz (hP CPOsHz u The compound of general formula (B) is 5X10- per color developer 1)
'~5X10-'' moles preferably lXl0-'~lXl
0-"mol added.

Further, the compound of general formula (C) is 1X per color developer 1)
l0-' to lXl0-' mole preferably 5 x 10-3 to
5×10-” moles are added.

When the compound of general formula (B) and the compound of general formula (B) are used together, the compound of general formula (C) is 2 to 20 times the molar ratio of the compound of general formula (B), preferably 3 to 15 times,
More preferably it is 3 to 10 times.

Among the above specific examples, B-1 and C-1 are particularly preferred.

In addition to the above-mentioned compounds, the color developing solution used in the present invention includes pH buffering agents such as alkali metal carbonates, borates, or phosphates; iodides, benzimidazoles,
Development inhibitors or antifoggants such as benzothiazoles or mercapto compounds; hydroxylamine,
diethylhydroxylamine, triethanolamine,
Patent application No. 61-265149 and West German patent application (OL
S) Compounds described in No. 2622950, preservatives such as sulfites or bisulfites; organic solvents such as diethylene glycol; benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, thiocyanates, 3. Development accelerators such as 6-thiaoctane-1,8-diol; dye-forming couplers; competitive couplers; nucleating agents such as sodium boron hydride; auxiliary developers such as 1-phenyl-3-pyrazolidone; viscosity-imparting agents. ; Ethylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, N-hydroxymethylethylenediaminetriacetic acid, organic phosphonic acid described in Research Disclosure 18170 (May 1979), aminotris (methylenephosphonic acid), ethylenediamine - Aminophosphonic acids such as N, N, N', N'-tetramethylenephosphonic acid, JP-A-52-102
No. 726, No. 53-42730, No. 54-121) 2
No. 7, No. 55-4024, No. 55-4025, No. 5
No. 5-126241, No. 55-65955, No. 55-
No. 65956 and Research Disclosure 1
8170 <May 1979) may contain a chelating agent such as a phosphonocarboxylic acid.

The pH value of the color developer used in the present invention is usually 8 or higher, most commonly about 9 to about 12, preferably 9.5.
~1).

The processing temperature of the color developer of the present invention is 20 to 50°C, preferably 30 to 45°C, particularly preferably 30 to 45°C.
The temperature is 5-42°C. The treatment time is 20 seconds to 10 minutes, more preferably 30 seconds to 5 minutes.

In the present invention, the light-sensitive material after color development is treated with a bleaching solution or a bleach-fixing solution.The bleaching agent used in these processes includes a ferric ion complex, an aminopolycarboxylic acid, an aminopolyphosphonate, and a ferric ion complex. It is a complex with a chelating agent such as an acid or a salt thereof. Aminopolycarboxylic acid salts or aminopolyphosphonic acid salts are salts of aminopolycarboxylic acids or aminopolyphosphonic acids with alkali metals, ammonium, or water-soluble amines.

Examples of alkali metals include sodium, potassium, and lithium, and examples of water-soluble amines include alkylamines such as methylamine, diethylamine, triethylamine, and butylamine, ring amines such as cyclohexylamine, arylamines such as aniline and m-toluidine,
and heterocyclic amines such as pyridine, morpholine, and piperidine.

Typical examples of chelating agents such as these aminopolycarboxylic acids and aminopolyphosphonic acids include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N-(β-oxyethyl)-N,N',
N”-)acetic acid, 1゜2-diaminopropanetetraacetic acid, 1,3-diaminopropanetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, dihydroxyethylglycine, ethyl ether diamine tetraacetic acid, glycol ether diamine tetraacetic acid Examples include acetic acid, ethylenediaminetetrapropionic acid, phenylenediaminetetraacetic acid, etc., but are not limited to these exemplified compounds.The ferric ion complex salt may be used in the form of a complex salt, or ferric salt, For example, ferric sulfate, ferric chloride, ferric sulfate, ferric ammonium sulfate, ferric phosphate, etc. and aminopolycarboxylic acid,
A ferric ion complex salt may be formed in a solution using a chelating agent such as aminopolyphosphonic acid or phosphonocarboxylic acid. When used in the form of a complex salt, one type of complex salt may be used. However, two or more types of complex salts may also be used.
On the other hand, when forming a complex salt in a solution using a ferric salt and a chelating agent, one or more types of ferric salts may be used. Furthermore, one type or two or more types of chelating agents may be used. In either case, the chelating agent is
It may be used in excess to form an iron ion complex salt. Among the iron complexes, aminopolycarboxylic acid iron complexes are preferred, and the amount added is 0.1 to 1 mol/E, preferably 0.2 to 0.4 in bleaching solutions for color photographic materials such as color negative films. mol/l, or in the bleach-fix solution from 0.05 to 0.5 mol/p, preferably from 0.1 to 0.3 mol/l. Further, in a bleaching solution or a bleach-fixing solution for color photographic light-sensitive materials for printing such as color paper, it is 0.03 to 0.3 mol/Il, preferably 0.05 to 0.2 mol/7! It is.

Further, a bleach accelerator may be used in the bleaching solution or bleach-fixing solution, if necessary. Specific examples of useful bleach accelerators include U.S. Pat. No. 3,893.858, West German Pat. No. 57831, same 3
7418, No. 53-65732, No. 53-72623
No. 53-95630, No. 53-95631, No. 53-104232, No. 53-124424, No. 5
Compounds having a mercapto group or disulfide group as described in No. 3-141623, No. 53-28426, Research Disclosure No. m17129 (July 1978), etc.; Thiazolidine derivatives as described in JP-A-50-140129. ; Japanese Patent Publication No. 45-8506, Japanese Patent Publication No. 52-20832, Japanese Patent Publication No. 53-32735,
Thiourea derivatives described in U.S. Patent No. 3,706,561; West German Patent No. 1,127,715, JP-A-58-1
Iodide described in No. 6235: West German Patent No. 966.410
Polyethylene oxides described in Japanese Patent Publication No. 2,748,430; Polyamine compounds described in Japanese Patent Publication No. 45-8836; Others 49ml No. 42434, Japanese Patent Publication No. 49m
No. 159644, No. 53-94927, No. 54-35
No. 727, No. 55=26506 and No. 5B-163
Examples thereof include the compound described in No. 940, iodine, bromine iodine, and the like. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and in particular, compounds described in U.S. Pat. Compounds are preferred.

In addition, the bleaching solution or bleach-fixing solution of the present invention contains bromide (
For example, a rehalogenating agent of potassium bromide, sodium bromide, ammonium bromide) or chloride (eg potassium chloride, sodium chloride, ammonium chloride) or iodide (eg ammonium iodide) can be included. If necessary, one or more types having pH buffering ability such as boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium f4ate, citric acid, sodium citrate, tartaric acid, etc. Inorganic acids, organic acids, alkali metal or ammonium salts thereof, or corrosion inhibitors such as ammonium nitrate and guanidine can be added.

The above bleaching solution is usually used at a pH in the range of 4 to 7, preferably 4.5 to 6.5, particularly preferably 5 to 6.3.
It is. In addition, the pH of the bleach-fix solution is 4 to 9,
Preferably it is 5-8, particularly preferably 5.5-7.5. If the pH is higher than the above range, defective bleaching tends to occur, and if it is lower, defective color development of the cyan dye tends to occur.

The fixing agent used in the bleach-fixing solution of the present invention or the fixing solution used after processing with the bleaching solution is a known fixing agent, namely, a thiosulfate such as sodium thiosulfate or ammonium thiosulfate; sodium thiocyanate or ammonium thiocyanate. thiocyanates such as; Two or more types can be used in combination. Also, JP-A-51
A special bleach-fix solution made of a combination of a fixing agent described in Japanese Patent No. 155354 and a large amount of a halide such as potassium iodide can also be used. In the present invention, the use of thiosulfates, particularly ammonium thiosulfates, is preferred.

The amount of fixing agent per 1) is preferably 0.3 to 2 mol, particularly 0.8 to 2 mol in the processing of color photographic light-sensitive materials.
The amount is 1.5 mol, and in the processing of color photographic materials for printing, it is in the range of 0.5 to 1 mol.

The pHel range of the fixer in the present invention is preferably 4 to 9, particularly preferably 5 to 8. If the pH is lower than this, the deterioration of the liquid will be significant, and conversely, if the pH is higher than this, ammonia will volatilize from the ammonium salt it contains, and stain will easily occur! In order to adjust pl(), hydrochloric acid, sulfuric acid, nitric acid, acetic acid, bicarbonate, ammonia, caustic potash, caustic soda, sodium carbonate, potassium carbonate, etc. can be added as necessary.

The bleach-fix solution and fixer used in the present invention contain sulfites (e.g., sodium sulfite, potassium sulfite,
ammonium sulfite, etc.), bisulfites (e.g. ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.), metabisulfites (e.g. potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.), etc. Contains sulfite ion-releasing compounds.

These compounds are approximately 0.02 to 0.02 in terms of sulfite ion.
The content is preferably 0.50 mol/l, more preferably 0.04 to 0.40 mol/l.

Sulfites are commonly added as preservatives, but other preservatives include ascorbic acid, carbonyl bisulfite adducts,
Alternatively, a carbonyl compound or the like may be added.

Furthermore, buffering agents, optical brighteners, chelating agents, antifungal agents, etc. may be added as necessary.

After the fixing process or bleach-fixing process, processing processes such as water washing and stabilization are generally performed. Processing methods can also be used.

The water washing process removes processing liquid components that have adhered to or occluded in the color photosensitive material, or unnecessary components in the color photosensitive material, thereby improving image storage stability and film physical properties after processing. do.

On the other hand, the stabilization process is a process that improves the storage stability of images to a level that cannot be obtained by washing with water.

The washing process is sometimes carried out in one tank, but in many cases it is carried out in two tanks.
It is carried out using a multi-stage countercurrent water washing method with more than one tank.

The amount of water in the washing process can be set arbitrarily depending on the type and purpose of the color photosensitive material, but for example, as described in Journal of Motion Picture and Television Engineering, No. 64S, pp. 248-253 (May 1955).
“WaterFlow Rates in Immersion Winning the Motion Picture Film” (Month issue)
mmersion-Washing of Motion
nPicture Fi1m+ S, R, Goldw
It can also be calculated by the method described in J. Asser.

When reducing the amount of water used for washing, the growth of bacteria and mold becomes a problem.
It is preferable to use the washing water in which calcium and magnesium are reduced as described in the specification of No. 2. Also, fungicides and fungicides, such as those published in Journal of Antibacterial and Infectious Agents, An
tibacj.

Antifug, Agents) vol 1),
Compounds described in N1) 5, p. 207-223 (1983) and compounds described in "Chemistry of Antibacterial and Antifungal" by Hiroshi Horiguchi can be added. In addition, chelating agents such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid can also be added as water softeners.

When reducing the amount of water used for washing, the amount of water used is usually 100 to 2000 wN per rrl of color photosensitive material, but a range of 200 ml to 1000 wN is particularly preferable in terms of achieving both color image stability and water saving effect. used.

The pH in the water washing step is usually in the range of 5 to 9. Other various compounds are added to the stabilizing bath for the purpose of stabilizing the image. For example, various buffers (e.g. borate, metaborate, borax,
phosphates, carbonates, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acids, dicarboxylic acids, polycarboxylic acids, etc.), chelating agents, disinfectants, etc. that can be added to washing water, In addition, a fluorescent whitening agent can be added depending on the purpose, and various ammonium salts such as ammonium chloride, ammonium sulfite, ammonium sulfate, ammonium thiosulfate, etc. can be added.

p) of the stabilizing bath is usually 3 to 8, but depending on the type of sensitive material and the purpose of use, a low pH range of 3 to 5 is sometimes preferably used.

The present invention can be applied to various color photosensitive materials. Typical examples include color negative films for general use or movies, and color reversal films for slides or televisions.

The silver halide emulsion used in the present invention is described in Research Disclosure, vol. 176, Item+
17643. It can be prepared using the method described in section (1).

In the silver halide color photographic light-sensitive material used in the present invention, any silver halide including silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride may be used. In the case of high-sensitivity photosensitive materials, silver iodobromide (3 to 20 mol % silver iodide) is preferred.

The silver halide grains in the photographic emulsion may be so-called regular grains having regular crystal bodies such as cubes, octahedrons, dodecahedrons, and rhombidodecahedrons, or may have regular crystals such as spherical shapes. It may be shaped, have crystal defects such as twin planes, or a combination thereof.

The grain size of silver halide may be fine grains of 0.1 micron or less or large grains with a projected area diameter of up to 10 microns, and may be a monodisperse emulsion with a narrow distribution or a monodisperse emulsion with a wide distribution. .

A typical monodisperse emulsion is an emulsion in which silver halide grains have an average grain diameter of greater than about 0.1 micron, and at least about 95% by weight of the silver halide grains are within ±40% of the average grain diameter. At least about 95% by weight or at least about 95% by number of silver halide grains having an average grain diameter of about 0.25 to 2 mm are included in an average grain diameter of ±20 mm.
% can be used in the present invention.

The crystal structure may be uniform, the inside and outside may have different halogen compositions, or it may have a layered structure. These emulsion grains are described in British Patent No. 1,027,1
No. 46, U.S. Patent No. 3,505.068, U.S. Patent No. 4,44
No. 4,877 and Japanese Unexamined Patent Publication No. 1-143331.

Furthermore, silver halides having different compositions may be joined by epitaxial joining.

By using tabular grains in the silver halide photographic emulsion used in the present invention, it is possible to improve sensitivity including improvement in color sensitization efficiency by sensitizing dyes, improve the relationship between sensitivity and graininess, improve sharpness, and improve development progress. Improvements in performance, covering power, crossover, etc. can be achieved. Here, tabular silver halide grains are grains with a diameter/thickness ratio of 5 or more, such as grains exceeding 8 or 5 or more and 8 or more.
There are the following:

The tabular grains may have a uniform halogen composition or may consist of two or more phases having different halogen compositions. For example, when silver iodobromide is used, the silver iodobromide tabular grains may have a layered structure consisting of a plurality of phases each having a different iodide content. JP-A-58-1) 3928 or JP-A-59
Preferred examples of the halogen composition of tabular silver halide grains and the intragrain distribution of halogen are described in No. ml99433 and the like.

A preferred method of using the tabular silver halide grains in the present invention is as follows: Research Disclosure 1) h2
2534 (January 1983), same floor 25330 (1'
May 1985), which discloses a method of use based on the relationship between the thickness and optical properties of tabular grains, for example.

The silver halide photographic emulsion that can be used in the present invention can be produced by a known method, for example, as described in Research Disclosure (
RD), 17643 (December 1978), 22
~page 23, “■, Emulsion pre
18716 (January 1979), p. 64B.

Various photographic additives that can be used in the present invention include, for example, the aforementioned Research Disclosure No. 17643, 23-
28 and pages 648-651 of issue 18716. The types of these additives and their detailed description are shown below: Additive type RD17643
RD18716 ■ Chemical sensitizers Page 23 Page 648 Right column 2 Sensitivity enhancers Same as above 4 Brightening agents Page 24 8 Dye image stabilizers Page 25 9 Hardeners Page 26 Page 651 Left column 10
Binder, page 26 Same as above 1) Plasticizer, lubricant, page 27, page 650, right column Various color couplers can be used in the photosensitive material that can be used in the processing of the present invention.

The term "color coupler" as used herein refers to a compound capable of producing a dye through a coupling reaction with an oxidized product of an aromatic primary amine developer. Typical examples of useful color couplers are naphthol or phenolic compounds, pyrazolone or pyrazoloazole compounds, and open chain or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers that can be used in the present invention are given in Research Disclosure (RD) 17643 (1).
18717 (December 1978)
It is described in the patent cited in January 1999).

The color coupler incorporated in the light-sensitive material is preferably diffusion-resistant by having a parasitic group or being polymerized. A two-equivalent coupler substituted with a coupling-off group is preferable to a four-equivalent coupler in which the coupling active position is a hydrogen atom, since the amount of coated silver can be reduced. Further, a coupler in which the coloring dye has appropriate diffusivity, a colorless coupler, a DIR coupler that releases a development inhibitor or a coupler that releases a development accelerator upon coupling reaction can also be used.

A representative example of the yellow coupler that can be used in the present invention is an oil-protected acylacetamide coupler. A specific example is U.S. Patent No. 2,40
7.210, 2.875.057 and 3
．． No. 265,506, etc. The use of two-equivalent yellow couplers is preferred for the present invention; U.S. Pat.
No. 3.933,501 and No. 4.022゜62
The oxygen atom separation type yellow coupler described in No. 0, Japanese Patent Publication No. 58-10739, and U.S. Patent No. 4.
No. 401,752, No. 4,326.024, RD1
8053 (April 1979), British Patent No. 1,425
．． 020, West German Application No. 2,219,917, West German Application No. 2.261,361, West German Application No. 2.329,587 and West German Application No. 2.433.812, etc. Yellow coupler is a typical example. α-pivaloylacetanilide couplers have excellent color fastness, especially light fastness, while α-benzoylacetanilide couplers provide high color density.

Magenta couplers that can be used in the present invention include oil-protected indacylon or cyanoacetyl couplers, preferably pyrazoloazole couplers such as 5-pyrazolone and pyrazolotriazoles. The 5-pyrazolone coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group from the viewpoint of the hue and color density of the coloring dye, and representative examples thereof include those described in U.S. Pat. No. 2, 31). No. 082, same No. 2゜3
No. 43.703, No. 2.600,788, No. 2,
No. 908.573, same No. 3. 062. No. 653, No. 3,152,896 and No. 3936.015
It is written in the number etc. As a leaving group for a two-equivalent 5-pyrazolone coupler, U.S. Patent No. 4,310,619
or U.S. Pat. No. 4,3
Particularly preferred are the arylthio groups described in No. 51,897.

Further, the 5-pyrazolone coupler having a ballast group described in European Patent No. 73,636 provides high color density.

As a pyrazoloazole coupler, U.S. Patent No. 3,
Pyrazolobenzimidazoles as described in US Pat. (1
Examples include pyrazolotetrazoles described in Research Disclosure 24230 (June 1984) and JP-A-60-33552, and pyrazolopyrazoles described in Research Disclosure 24230 (June 1984) and JP-A-60-43659. Imidazo(1,2-b)pyrazoles described in U.S. Pat. No. 4,500.630 are preferred from the viewpoint of low yellow side absorption and light fastness of color-forming dyes; Pyrazolo (1,5-
b) (1,2°4) Triazoles are particularly preferred.

Preferably, the magenta coupler is a pyrazole-eliminating 2-equivalent magenta coupler described in U.S. Pat. No. 4,367.282 and the like, and U.S. Pat.
．． A 2-equivalent magenta coupler with arylthio elimination described in No. 23.7 and No. 4,522゜915 is also used.

Cyan couplers include oil-protected naphthol couplers and phenol couplers, and naphthol couplers described in U.S. Pat. No. 2,474,293, preferably U.S. Pat.
Typical examples include two-equivalent naphthol couplers of the oxygen atom dissociative type described in No. 146,396, No. 4,228.233, and No. 4,296.200.

Further, specific examples of phenolic couplers are shown in U.S. Pat.
No. 369,929, same No. 2. 801. No. 171, No. 2,772,162, No. 2,895.826, etc. Cyan couplers that are stable against humidity and temperature are preferably used in the present invention, and a typical example thereof is as described in U.S. Pat. Phenolic cyan coupler with U.S. Patent No. 2
No. 772.162, No. 3.758,308, No. 4,126,396, No. 4,334,01), No. 4.327,173, West German Patent Publication No. 3,329 ，
729 and European Patent No. 121.365, and U.S. Pat. Nos. 3,446,622 and 4.3.
Phenolic couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position, etc., described in No. 33.999, No. 4.451,559, and No. 4427.767, etc. It is. Special request Showa 59ml9
3605, 59ml264277 and 59ml2
The cyan coupler described in No. 68135, in which the 5-position of naphthol is substituted with a sulfonamide group, an amide group, etc., also has excellent fastness of a colored image and can be preferably used in the present invention.

In order to correct unnecessary absorption in the short wavelength range of dyes generated from magenta and cyan couplers, it is preferable to use colored couplers in combination with color negative light-sensitive materials for photography. Yellow colored magenta couplers described in U.S. Pat. No. 4,163.670 and Japanese Patent Publication No. 57-39413, etc. or U.S. Pat. No. 4,004,929, No. 4,138.258 and British Patent No. 1,146 ．．
Typical examples include the magenta-colored cyan coupler described in No. 368.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Examples of such blur couplers include magenta couplers in U.S. Pat. No. 4,366,237 and British Patent No. 2,125,570.
Also, European Patent No. 96゜570 and West German Application No. 3
．． No. 234,533 describes specific examples of yellow, magenta or cyan couplers.

The dye-forming couplers and the special couplers described above may form dimers or more polymers. A typical example of a polymerized dye-forming coupler is U.S. Pat. No. 3,451,82.
No. 0 and No. 4,080°21). Specific examples of polymerized magenta couplers include British Patent No. 2.102,173 and U.S. Patent No. 4,367.282.
No. 60-75041 and No. 60-1) 35
96.

Two or more types of couplers can be used in combination in the same photosensitive layer, or the same compound can be introduced into two or more different layers in order to satisfy the characteristics required for the photosensitive material. .

Typical amounts used for color couplers range from o,oot to 1 mole per mole of photosensitive silver halide, preferably from 0.01 to 0.00 mole for yellow couplers.
5 mole, 0.003 to 0.3 for magenta coupler
moles, and for cyan couplers 0.002 to 0.3
It is a mole.

The present invention may also include a coupler that releases a development inhibitor upon development, a so-called DIR coupler.

As a DIR coupler, for example, U.S. Pat. No. 3.227
．． Those that release heterocyclic mercapto-based development inhibitors as described in Japanese Patent Publication No. 58-9942, etc.; those that release benzotriazole derivatives as development inhibitors described in Japanese Patent Publication No. 58-9942, etc.; Japanese Patent Publication No. 51-16141, etc. A so-called colorless DIR coupler described in JP-A No. 52-90932 which releases a nitrogen-containing heterocyclic development inhibitor with decomposition of methylol after separation; US Pat. No. 4,248.96
2 and JP-A-57-56837, which release a development inhibitor with an intramolecular nucleophilic reaction after separation; JP-A-56-1) 4946, JP-A-57-154234;
No. 57-188035, No. 58-98728, No. 5
No. 8-209736, No. 58-209737, No. 58
-209738, 58-209739 and 5
B-209740, etc., which releases a development inhibitor by electron transfer via a conjugated system after separation; JP-A-57
-151944 and 58-217932, etc., which release a diffusible development inhibitor whose development suppressing ability is deactivated in the developer; Japanese Patent Application No. 59 ml 38263, 5!1
Examples include those which release a reactive compound described in No. 39653, and generate a development inhibitor or deactivate the development inhibitor by reaction in the film during development. Among the above-mentioned DIR couplers, those that are more preferable in combination with the present invention are the developer-deactivated type represented by JP-A-57-151944; U.S. Pat. No. 4,248.9.
62 and JP-A-57-154234; a reaction-type as typified by Japanese Patent Application No. 59-151944 and JP-A-58-217932. Developer deactivated type D described in No. 60-218644, No. 60-225156, and No. 60-233650, etc.
These are IR couplers and reactive DIR couplers described in Japanese Patent Application No. 59ml39653.

In the photosensitive material that can be used in the present invention, compounds that release a nucleating agent, a development accelerator, or a precursor thereof (hereinafter referred to as "development accelerator, etc.") in an image form during development can be used. .

Typical examples of such compounds are described in British Patent No. 2. 097
．． No. 140 and No. 2,131,188, and is a coupler that releases a development inhibitor etc. by a coupling reaction with an oxidized product of an aromatic primary amine developer, that is, a DAR coupler.

It is preferable that the development accelerator released from the DAR coupler has an adsorption group for silver halide.
No. 7638 and No. 59ml 170840. Particularly preferred are DAR couplers that produce N-acyl-substituted hydrazines having monocyclic or fused heterocycles as adsorption groups, which are separated from the camping active site of photographic couplers with sulfur or nitrogen atoms. A specific example of the coupler is JP-A-60-128446.
listed in the number.

Compounds described in JP-A-60-37556 which have a development accelerator moiety in the coupler residue, or JP-A-60-107029 which releases a development accelerator etc. through an oxidation-reduction reaction with a developing agent. The compounds described in can also be used in the photosensitive material of the present invention.

The DAR coupler is preferably introduced into the light-sensitive silver halide emulsion layer of the light-sensitive material, and is
As described in No. 72640 or JP-A-60-128429, it is preferable to use substantially non-photosensitive silver halide grains in at least one of the photographic constituent layers.

The photosensitive material used in the present invention contains hydroquinone derivatives, aminophenol derivatives, amines, gallic acid derivatives, catechol derivatives, ascorbic acid derivatives, colorless couplers, sulfonamidophenol derivatives, etc. as color fogging inhibitors or color mixing inhibitors. may be contained, or a known anti-fading agent may be used. Known anti-fading agents include hydroquinones, 6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-
Alkoxyphenols, hindered phenols mainly including bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl group of each of these compounds. is cited as a representative example. Also, (bissalicylaldoximide) nickel complex and (bis-N, N
-Dialkyldithiocarpamato) metal complexes represented by nickel complexes can also be used.

In the photosensitive material used in the present invention, an ultraviolet absorber can be added to the hydrophilic colloid layer.

For example, U.S. Pat. No. 3,553,794, U.S. Pat.
6.013, Japanese Patent Publication No. 51-6540, and European Patent No. 57,160, benzotriazoles substituted with aryl groups, U.S. Patent No. 4,450.2
29 and 4,195.999, cinnamate esters described in U.S. Pat. No. 3,705,805 and 3,707.375, U.S. Pat. No. 215,530 and British Patent No. 1
．． 321,355, U.S. Pat. No. 3,761,272 and U.S. Pat. No. 4,431,
A polymer compound having an ultraviolet absorbing residue such as that described in No. 726 can be used. U.S. Patent No. 3.499
, 762 and 3,700.455 may be used. A typical example of ultraviolet absorber is RD24239 (June 1984)
etc. are listed.

Other coating aids, antistatic, improved slipperiness, emulsification and dispersion,
One or more surfactants may be included for various purposes such as preventing adhesion and improving photographic properties (for example, accelerating development, increasing contrast, and sensitizing).

Furthermore, a water-soluble dye may be contained in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation or halation. As such dyes, oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, anthraquinone dyes, and azo dyes are preferably used, and in addition, cyanine dyes, azomethine dyes, triarylmethane dyes, and phthalocyanine dyes are also useful. . An oil-soluble dye can be emulsified by an oil-in-ice dispersion method and added to the hydrophilic colloid layer.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of high boiling point solvents used in the oil-in-ice dispersion method are described in US Pat. No. 2,322,027 and the like.

The steps, effects, and specific examples of latex for impregnation of latex dispersion methods are described in U.S. Pat. etc. are listed.

(Examples) The present invention will be explained below using Examples, but the present invention is not limited thereto.

Example 1 On a subbed cellulose triacetate film support,
Sample 101, which is a multilayer color light-sensitive material, was prepared by coating layers having the compositions shown below.

(Photosensitive layer composition) The numbers corresponding to each component indicate the coating amount expressed in g/rd units, and for silver halide, the coating amount is expressed in terms of silver. However, for sensitizing dyes, the coating amount is expressed in moles per mole of silver halide in the same layer.

(Sample 101) 1st layer; antihalation layer black colloidal silver silver 0.18 gelatin
0.40 second layer; middle layer 2.5-di-t-pentadecylhydroquinone 0.18EX-10,
07 EX-30,02 EX-160,004 U-10,08 U-20,08 HBS-10,10 HBS-20,02 Gelatin 1.04 3rd layer (1st
Red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0.6μ) ' Silver 0.55 Sensitizing dye 1
6.9X 10-5 Sensitizing Dye II
1.8X10-5 sensitizing dye III
3. IX, 10-' sensitizing dye IV
4. OX 10-5EX-20,3
50 HBS-10,00S EX-100,020 Gelatin 1.20 4th layer (2nd
Red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 8 mol%, average grain size 0.8 μ) Silver 1.0 sensitizing dye I
5. IX 10-' Sensitizing dye II
1.4X 10-' Sensitizing Dye II [2
, 3X 10-' Sensitizing dye IV 3. OX 10-5
EX-20,300 EX-30,050 EX-100,015 HBS-20,050 Gelatin 1.30 5th layer (3rd
Red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 16 mol%, average grain size 1.1
μ) Silver 1.60 sensitizing dye IX
5.4X 10-' sensitizing dye n
1.4X10-5 sensitizing dye III
2.4X 10-' Sensitizing Dye IV
3. IX 10-5EX-50,150 EX-30,oss EX-40,060 HBS-10,32 Gelatin 1.63 6th layer (middle layer) Gelatin 1.06 7th layer (1st layer)
Green-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0.6μ) Silver 0.40 sensitizing dye V
3. OX 10-5 sensitizing dye Vl
1.0X10-'sensitizing dye■
3.8
Green-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 9 mol%, average grain size 0.7μ) Silver 0.80 sensitizing dye V
2. IX 10-5 sensitizing dye Vl
7. OX 10-'sensitizing dye■
2.6X 10-'EX-130,01
8 EX-80,010 EX-10,008 EX-70,012 HBS-10,60 HBS-40,06 Gelatin 0.10 9th layer (3rd
Green-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 12 mol%, average grain size 1.0
μ) Silver 1.2 sensitizing dye V
3.5X 10-5 sensitizing dye Vl
s, ox i o-5 sensitizing dye■
3. OX 10-'EX-60,065 EX-130,030 EX-10,025 HBS-20,55 HBS-40,06 Gelatin 1.74 10th layer (yellow filter single layer) Yellow colloidal silver Silver 0.05A-50 ,0
8 HBS-10,03 Gelatin 0.95 1st) layer (1st blue-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0.6μ) Silver 0.24 sensitizing dye■
3.5X10-'EX-90,85 EX-80,12 HBS-10,28 Gelatin 1.28 12th layer (second blue-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 10 mol%, average grain Diameter 0.8
μ) Silver 0.45 sensitizing dye■
2. IXl 0-'EX-1) 0,20 EX-100,015 HBS-10,03 Gelatin 0.46 13th layer (third blue-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 1 mol%, average Particle size 1.3μ) Silver 0.77 mulch dye■
2.2X 1'O-'EX-1)0
,20 HBS-10,07 Gelatin 0.69 14th layer (first protective layer) Silver iodobromide emulsion (silver iodide 1 mol%, average grain size 0.07μ) Silver 0.5U-10,1
) U-20,17 HBS-10,90 Gelatin 1.00 15th layer (second protective layer) Polymethyl acrylate particles (diameter approximately 1.5 μm) 0.543-1
0.053-2
0.20 gelatin
0.72 In addition to the above components, gelatin hardening agent H-1 and a surfactant were added to each layer.

(Sample 102.103) A- of the 10th layer (yellow filter single layer) of sample 101
1 was replaced with compound (6) of the present invention, 0.15g
/ m, and sample 102.1
It was set as 03.

(Sample 104.105.106) Comparative compound A-
1. Compound (6) of the present invention, Q31 each at 0.15
g/rrr coating amount, and then add HB S
-1,0,05g/n (sample 104.105
．． It was set to 106.

Samples 101 to 106 prepared as described above were cut into 351-width pieces, subjected to wedge exposure at 4800°K and 20 CMS, and processed in an automatic processor using the steps listed in Table 1.

The treated sample obtained here was designated as S. S. is obtained when the treatment solution is fresh.

Next, after subjecting the sample 101 to photography, 35 m
The cumulative amount of color developer replenishment for processing a width of 20 m is 201
It was carried out until

Table-1 Processing Method Step Processing Time Processing Temperature Replenishment Amount Tank Capacity Color Development 3 minutes 15 seconds 37.8℃ Listed in Table-2 107!
Bleach 6 minutes 30 seconds 37.8℃ 3d
20jl! Fixation 3 minutes 15 seconds 37.8℃
8mR101) Water wash n+ 1 *oo seconds 35
．． 0℃ From (2) to (1) 47! Countercurrent piping system % formula % *Replenishment amount is per 100 samples Table 2 Processing details Next, the composition of the processing liquid is described.

(Color developer) Mother solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 5.0 6.0 Sodium sulfite 4.0 4.4 Potassium carbonate
30.0 37.0 Potassium bromide
1.3 Potassium iodide listed in Table-2
1.2■ -Hydroxylamine sulfate 2.6 2.84-(N-
Ethyl-N-β-hydroxyethylamino)-2= methylaniline sulfate 4.7 Listed in Table-2 Add water 1.0β 1.0βp H10
, 0010:05 (Bleach solution) Mother liquor (g) Replenishment solution axis) Ethyleneditriaminetetranoic acid ferric ammonium dihydrate 100.0 120.0 Ethylenediaminetetraacetic acid disodium dihydrate 10.0 12.
0 Ammonium bromide 160.0 180.0 Ammonium nitrate 30.0 50.0 Ammonia water (27%> 7.0ml! 5.0m
Add ff1 water 1.0J 1.0
j'p H6,05,7 (Fixer) Mother liquor (g) Replenisher (g) Ethylenediaminetetranoic acid disodium salt 0.5, 0.7 Sodium sulfite 7.0 B, 0 Sodium bisulfite 5.0 5 .5 ammonium thiosulfate aqueous solution (70%>170.(ld 200
．． Add 0mf water 1. On! 1
．． ipH'6.7 6.6 (Water solution) Common to mother liquor and replenisher 5-chloro-2-methyl-4 monoisothiazolin-3-one
6.0 ■ 2-Methyl-4-isothiazolin 3-one 3.0 ■ Ethylene glycol 1.5 Add water
1.01p H5,0-7,0 (Stable solution) Mother liquor, replenisher common formalin (37%) 3.0ynl
Ethylene glycol 2. Add Og surfactant 0.4g water
1.01pH5.0-8.0 At the end of the processing of 1 to 1) kL4, samples 101 to 106 were again subjected to the same wedge exposure and processed, and this was designated as sample S2. S2 is a sample when the processing liquid is in a steady running state.

For each sample thus obtained, S.

The difference in gradation and minimum density (SZ-S) between and 82 was calculated and listed in Table 3 as representative values of performance fluctuations between the new solution and the running state.

Here, the gradation refers to the average gradation from +0.2 to +1.5 of the lowest density. Also, the difference in minimum density indicates a change in stain.

As shown in Table 3, according to the present invention, even if the replenishment amount is reduced, both the gradation difference and the minimum density difference are extremely small, and stable processing can be performed.

Example-2 Example-1 was carried out in the same manner as Example-1 except that the treatment steps and treatment liquid composition were changed as follows.

The results are the same as in Example 1, and according to the present invention, the gradation difference and minimum density difference (difference in stain) between the start and end of running were extremely small compared to the comparative example, and stable performance was obtained.

Table 4 Treatment method steps Treatment time Treatment temperature Replenishment amount 1 Tasik capacity bleaching 1 minute 00 seconds 38℃ 5-4
1 Bleach fixing 3 minutes 15 seconds 38℃ 8-81
Water washing (2) 1 minute 00 seconds 35℃ 8 boats 4i
Stability 40 seconds 38℃ 5 td
, 41 Drying 1 minute 15 seconds 55°C *Replenishment amount per 35 m width and 1 m length Next, write down the composition of the processing solution.

(Color developer) Mother liquid axis) Replenisher axis) Diethylenetriaminepentaacetic acid 1.0 1.1)-Hydroxyethyrythene-1,1-diphosphonic acid 3.0 3.2 Sodium sulfite 4.0 4.4 Potassium carbonate
30.0 37.0 Potassium iodide
1.5■ -Hydroxylamine sulfate 2.4 2.84-(N-
Add ethyl-N-β-hydroxyethylamino)-2-methylaniline sulfuric acid water 1. (H! 1.0j2
pH 10,0510,10 (Bleach solution) Common to mother liquor and replenisher (unit: g) Ethyleneditriaminetetraacetic acid ferric ammonium dihydrate 120.0 Ethylenediaminetetraacetic acid disodium salt 10.0 Ammonium bromide ioo.

Ammonium nitrate 10.0 Bleach accelerator 0.005M Ammonia water (27%)■s, omp Add water 1.0βp H6
, 3 (Bleach-fix solution) Common to mother liquor and replenisher (unit: g) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 50.0 Ethylenediaminetetraacetic acid dibasic sodium salt 5.0 Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution (70% ) 240.0mj
! Ammonia water (27%'I 6.0
Add ml water to 1.0'!
pH 7,2 (Washing solution) Mother liquor and replenisher Common tap water was mixed with an H-type strongly acidic cation exchange resin (Amberlite IR'-120B manufactured by Rohm and Haas) and an OH-type anion exchange resin (Amberlite IR-400 manufactured by Rohm and Haas). ) was passed through a mixed bed column packed with calcium and magnesium ions to bring the concentration of calcium and magnesium ions to 3■/I! The following treatment was followed by the addition of 20 g/l of sodium isocyanurate dichloride and 1.5 g/l of sodium sulfate.

The pH of this solution was in the range of 6.5-7.5.

(Stabilizing solution) Common to mother solution and replenisher solution (Unit: g) Formalin (3
7%) 2.0yd polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 Ethylenediaminetetraacetic acid disodium salt 0.05 Add water 1.07! pH5,0-
8,0 Example-3 The same procedure as in Example-1 was carried out, except that the treatment in Example-1 was changed as follows, and the amount of sample 101 to be processed was changed to 10 m of 35-salt cloth per day. .

Table-5 Processing method steps Processing time Processing temperature Replenishment amount "'l Sink amount" Color development 2 minutes 15 seconds 40℃ Listed in Table-6 8
1 Bleach fixing 3 minutes 00 seconds 40℃ 20mR81
2Washing (2) 20 seconds 35℃ 10-2β
Constant 20 seconds 35℃ lQ*l
21 Drying 50 seconds 65° C. *The replenishment amount was 35 wm per 1 m length. In the color development tank, the circulation flow rate of the liquid during processing was 51)/win.

Table 6 Processing details *As shown in the processing solution composition below, color developer A consists of diethylenetriaminepentaacetic acid and 1-hydroxyethylidene-1,1
-diphosphonic acid, whereas color developer B contains only diethylenetriaminepentaacetic acid.

(Color developer A) Mother solution (g) Replenisher (g) Diethylenetriamine pentacholic acid 2.0 2.21-Hydroxyethyrythene-1,1-diphosphonic acid 3.0 3.2 Sodium sulfite 4.0 5.5 potassium carbonate
30.0 37.0 Potassium Bromide 1
．． 4 Potassium iodide listed in Table-6 1.
5■ -Hydroxylamine sulfate 2.4 3.04-(N-ethyl-N-β-hydroxyethylamino)-2-methylaniline sulfate 5.0 Add water as shown in Table 6 1. Oj! 1. ONp H1
0,1010,20 (Color developer B) Mother solution (g) Replenisher (g) Diethylenetriaminepentachoic acid 1.0 1.1 Sodium sulfite 4.0 5.5 Potassium carbonate
30.0 37.0 Potassium Bromide 1.
4 Potassium iodide listed in Table-6 1.5
■ -Hydroxylamine sulfate 2.4 3.04-[N-ethyl-N-(β-hydroxyethyl)amino]-2-methylaniline sulfate 5.0 Add water as shown in Table 6 1. O# 1.01p H10,
1010,20 (Bleach-fix solution) Common to mother liquor and replenisher (unit: g) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 50.0 Ethylenediaminetetraacetic acid disodium salt 5.0 Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution (70% ) 260. (ld
Acetic acid (98%') 5.0m
l Bleach accelerator 0.01 mol Add water to 1.01 pH H6,
0 (Water wash solution) Mother solution and replenisher Common tap water was filled with H-type strongly acidic cation exchange resin (Amberlite IR-120B, manufactured by Rohm and Haas) and OH-type anion exchange resin (Amberlite IR-400, manufactured by Rohm and Haas). Water is passed through the mixed bed column to reduce the concentration of calcium and magnesium ions to 3■/7! The following treatment was followed by sodium dichloride isocyanurate 20/I and sodium sulfate 130/I! was added.

1)H of this liquid is in the range of 6.5-7.5.

(Stabilizing solution) Common to mother solution and replenisher solution (Unit: g) Formalin (3
7%) 2. (ld Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 Ethylenediaminetetraacetic acid disodium salt 0.05 Add water 1.07! pH 5,0-8
, 0 The gradation difference and stirring dependence of each sample at the start (new solution) and end of running were investigated and the results are listed in Table 7.

However, the stirring dependence was shown by the change in yellow gradation of each sample when the circulation rate of the color developing solution in the tank was increased from 51)/min to 81/min at the end of the running.

As shown in Table 7, it is clear that according to the present invention, gradation differences and stirring dependence are reduced, and stable processing can be performed.

Also, color developer A using diethylenetriaminepentaacetic acid and 1-hydroxyethylidene-1,1-diphosphonic acid is better than color developer B using diethylenetriaminepentaacetic acid alone.
It is also clear that the effect is even more excellent.

Claims (4)

[Claims] (1) A silver halide color photographic material containing at least one compound represented by the following general formula (A) and/or its alkali-labile precursor is added per 100 cm^2 of the silver halide color photographic material. 1. A method for processing a silver halide color photographic light-sensitive material, comprising processing with a color developing solution that is replenished in an amount of 9 ml or less. General formula (A) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_a and R_b are hydrogen atoms, halogen atoms, sulfo groups, carboxyl groups, alkyl groups, acylamino groups,
It represents an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a sulfonyl group, an acyl group, a carbamoyl group, or a sulfamoyl group, and R_a and R_b may jointly form a carbon ring. X is -CO- or -
Represents SO_2-. R_c represents an alkyl group, an aryl group, a heterocyclic group, a cycloalkyl group, an alkoxy group, an aryloxy group, or an amino group. R_a, R_b, R_
The total number of carbon atoms in c is 10 or more. The compound of general formula (A) is substantially colorless and does not form a color image through a coupling reaction with a developing agent. (2) The color developer has the following general formula (B) and/or (C)
A method for processing a silver halide color photographic light-sensitive material according to claim 1, which contains at least one compound represented by the following. General formula (B) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula (C) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ In the formula, n represents 1 or 2, R represents a lower alkyl group, M may be the same or different and represent a hydrogen atom, an alkali metal atom or ammonium. (3) The color developer replenisher does not substantially contain bromide, and the silver halide color photographic light-sensitive material 100c
2. The method for processing a silver halide color photographic material according to claim 1, wherein 5 ml or less of the color developer replenisher is replenished per m^2. (4) The method according to any one of claims 1, 2, and 3, characterized in that the color developing solution is immediately followed by processing with a bleach-fixing solution without passing through any other solution. A method for processing silver halide color photographic materials.