JPH0789214B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention is a development processing method (hereinafter simply referred to as processing) for developing, bleaching and fixing an exposed silver halide color photographic light-sensitive material (hereinafter referred to as color light-sensitive material). In particular, the present invention relates to an improved development processing method capable of accelerating the bleaching action to shorten the processing time and perform sufficient bleaching to form a color photographic image with good image quality.

(Prior Art) Generally, the basic steps of processing a color light-sensitive material are a color development step and a desilvering step. That is, the exposed silver halide color photographic material is put into a color development step. Here, the silver halide is reduced by the color developing agent to produce silver, and the oxidized color developing agent reacts with the color developing agent to give a dye image. Then, the color photographic material is put into the desilvering process. Here, the silver produced in the previous step is oxidized by the action of an oxidizing agent (commonly called a bleaching agent), and then it is dissolved and removed by a complexing agent of silver ions, which is commonly called a fixing agent. Therefore, only a dye image is produced in the photographic material that has undergone these steps. In addition to the two basic steps of color development and desilvering described above, the actual development processing is an auxiliary step such as maintaining the photographic and physical quality of the image or improving the storability of the image. Is included. For example, a hardening bath for preventing excessive softening of the photosensitive layer during processing, a stopping bath for effectively stopping the development reaction, an image stabilizing bath for stabilizing an image, or a removing bath for removing the backing layer of the support. A membrane bath etc. are mentioned.

In the desilvering process described above, the bleaching bath and the fixing bath are separated from each other in two steps, and the bleaching bath and the fixing bath are allowed to coexist by simplifying the processing bath for the purpose of rapid processing and labor saving. It may be carried out in one step with a bleach-fix bath.

In recent years, in color photographic light-sensitive materials, from the viewpoint that rapid processing and prevention of environmental pollution have been demanded, ferric ion complex salts (for example, ferric ion complex salts of aminopolycarboxylic acid, such as ethylenediaminetetraacetate iron ( III)
A bleaching method mainly composed of complex salts is mainly used.

However, the ferric ion complex salt has a relatively small oxidizing power and an insufficient bleaching power. Therefore, a compound using this as a bleaching agent is a low-sensitivity silver halide color photographic light-sensitive material mainly composed of a silver chlorobromide emulsion. When the material is subjected to a bleaching treatment or a bleach-fixing treatment, the desired purpose can be achieved for a while, but the main component is a silver chlorobromoiodide or silver iodobromide emulsion, and a color-sensitized, highly sensitive halogenated When processing a silver color photographic light-sensitive material, especially a color reversal light-sensitive material for photography and a color negative light-sensitive material for photography using a high silver content emulsion, the bleaching action is insufficient and desilvering is unsuccessful, or it takes a long time to bleach. It has the drawback of being time consuming.

Further, in color light-sensitive materials, sensitizing dyes are generally used for the purpose of color sensitization. Especially when using tabular grains with high silver or high aspect ratio for the purpose of high sensitization, there is a problem that the sensitizing dye adsorbed on the surface of the silver halide inhibits bleaching of silver produced in the development of silver halide. Occurs.

Persulfate is known as a bleaching agent other than ferric ion complex salt, and it is usually used as a bleaching solution containing persulfate containing chloride. However, a drawback of the bleaching solution using persulfate is that it has a weaker bleaching power than the ferric ion complex salt and has a remarkably long time for bleaching.

Generally, bleaching agents that are not pollutant or corrosive to equipment have weak bleaching power, and therefore bleaching agents having weak bleaching power, especially bleaching solutions or bleach-fixing solutions using ferric ion complex salts or persulfates. There is a desire to increase the bleaching capacity of.

Conventionally, it has been proposed to add various bleaching accelerators to a processing bath as a means for enhancing the bleaching ability of a bleaching solution or a bleach-fixing solution containing a ferric ion complex salt such as ethylenediaminetetraacetic acid iron salt as a bleaching agent.

For example, U.S. Patent No. 3893858, British Patent No. 1138842.
Specification, various mercapto compounds as described in JP-A-53-141623, compounds having a disulfide bond as described in JP-A-53-95630, JP-B-53-9854 Thiazolidine derivatives as described in JP-A-53-94927, Isothiourea derivatives as described in JP-A-53-94927, JP-B-45-8506 and JP-B-49-26
Examples include thiourea derivatives as described in JP 586, thioamide compounds as described in JP-A-49-42349, and dithiocarbamate salts as described in JP-A-55-26506. To be

Some of these bleaching accelerators certainly have a bleaching promoting effect, but the effect is not always sufficient,
Further, particularly in a bleach-fixing solution, the stability is extremely poor and the effect is lost in a short time, so that it is not always suitable for practical use.

Further, as other bleaching accelerators, for example, US Pat.
There are onium compounds as described in US Pat. No. 748,136, phenylene-linked ammonium salts as described in JP-B-54-12056, amine compounds as described in US Pat. No. 4,552,834, and the like. Although these compounds are stable in a bleaching solution or a bleach-fixing solution, they have a weak bleaching promoting effect and are not necessarily suitable for practical use.

Further, the compounds described in JP-B-60-24936 have a bleaching promoting effect, but the processed photosensitive material causes stains.

(Problems to be Solved by the Invention) As described above, many of these bleaching accelerators do not always have a sufficiently satisfactory bleaching promoting effect, and even if the bleaching promoting effect is excellent, in the treatment liquid. Many of them have the drawback that they cannot withstand long-term storage due to the lack of stability of the treatment solution.

The compound described in JP-B-60-24936 has a bleach accelerating effect and can withstand long-term storage, but has a drawback that the processed light-sensitive material causes stains.

A first object of the present invention is to provide a color photographic processing method having low toxicity, meeting the requirement of pollution prevention, and excellent in bleaching speed.

A second object of the present invention is to provide a method capable of rapidly bleaching a processed color photographic light-sensitive material without causing any stain.

A third object of the present invention is to provide a method for enhancing the bleaching power without deteriorating other photographic characteristics in the bleaching process using a bleaching agent having a weak bleaching power, especially a ferric ion complex salt or a persulfate salt. That is.

A fourth object of the present invention is to provide a bleaching method using a processing solution which can increase the bleaching rate when the compound of the present invention is contained in a light-sensitive material or a bleaching solution and which has good stability. is there.

A fifth object of the present invention is to provide a method capable of rapidly bleaching a color photographic light-sensitive material having particularly high photographic sensitivity.

(Means for Solving the Problems) The above-mentioned various objects of the present invention are as follows in a color photographic processing method in which an exposed silver halide color photographic light-sensitive material is subjected to color development, and then bleaching and fixing. It was achieved by carrying out a bleaching treatment with a bleaching solution containing an aminopolycarboxylic acid ferric complex salt or a persulfate as a bleaching agent in the presence of a compound represented by the formula (I).

General formula (I) R ¹ and R ² each represent a hydrogen atom or an alkyl group. The alkyl group is unsubstituted and preferably has 1 to 10 carbon atoms, and a particularly preferred example is 1 to 5 carbon atoms. Also R ¹
And R ² may combine to form a heterocycle. Examples thereof include a piperidyl group, a pyrrolidinyl group, a morpholino group, an imidazolinyl group, a pyuzolinyl group and an indolinyl group.

A ¹ and A ² each represent an alkylene group having 2 to 4 carbon atoms which may have a substituent. Substituents are hydroxy, amino,
It is a carboxy group. Examples of A ¹ and A ² include ethylene, propylene, trimethylene, tetramethylene, 2-hydroxytrimethylene and aminotrimethylene. Preferably A ¹ and A ² are ethylene and trimethylene. n represents 2 or 3. Here, when n is 1 or less, it is not preferable in terms of bleaching promoting ability. Group (S-A ²⁾ Although it is repeating unit represented by A ² is in the same compound, or may be different from one be the same.

The compound of general formula (I) is preferably added to the bleaching solution (both may be replenishing solutions) or their pre-bath, but it is also possible to incorporate it in the light-sensitive material in advance and bring it into the bleaching solution. When added to the bleaching solution or their pre-bath, the addition amount is preferably 1 × 10 ⁻⁵ to 1 ×
10 ^-1 mol / l, more preferably 1 × 10 ^-3 to 2 × 10 ^-2 mol / l
l, most preferably 2 × 10 ⁻³ to 1 × 10 ⁻² mol / l.
In the case of incorporating a light-sensitive material, it is 1 × 10 ⁴ to 1 × 10 ⁻² mol / m ² , and more preferably 2 × 10 ⁻⁴ to 5 × 10 ⁻³ mol / m ² . The compounds of general formula (I) may be used alone or in combination of two or more as a bleaching accelerator.

Attempts have been made in the past to use thioether compounds such as the present invention as bleaching accelerators. For example, it is described in JP-B-60-24936. The compounds listed in this specification have a bleaching-accelerating effect, but the processed light-sensitive material causes stains.

Therefore, the inventors of the present invention conducted further research and found that
As compared with the compound examples described in JP-A-60-24936, they have found a compound which is more excellent in bleaching promoting effect and does not cause a stain on a light-sensitive material.

The compound of the present invention is characterized by containing 3 to 4 thioether bonds. The example of the compound described in JP-B-60-24936 contains two thioether bonds. Such a compound has a bleaching accelerating effect, but the processed photosensitive material causes stains. To do. It is surprising that the contamination of the processed light-sensitive material was remarkably improved by using 3 to 4 thioether bonds.

The compound of the present invention specifically has a large bleaching accelerating ability, is stable in a bleaching solution, and can be sufficiently used for long-term continuous processing using an automatic developing machine which is generally used at present. .

Next, specific compounds of the present invention will be described, but the present invention is not limited thereto.

(1) H ₂ NCH _{2 2} SCH _{2 2} SCH _{2 2} SCH _{2 2} NH ₂ (2) H ₂ NCH _{2 2} SCH _{2 2} SCH _{2 2} SCH _{2 2} SCH _{2 2} NH ₂ (3) H ₂ NCH _{2 3} SCH _{2 2} SCH _{2 2} SCH _{2 3} NH ₂ (4) H ₂ NCH _{2 3} SCH _{2 2} SCH _{2 2} SCH _{2 2} SCH _{2 3} NH ₂ (5) H ₂ NCH _{2 2} SCH _{2 2} SCH _{2 3} SCH _{2 2} SCH _{2 2} NH ₂ (6) H ₂ NCH _{2 3} SCH _{2 2} SCH _{2 3} SCH _{2 2} SCH _{2 3} NH ₂ The compound of the present invention can be easily synthesized by a well-known method, and a specific method will be described below.

Synthesis of Compound (1) Bismercaptoethyl sulfide 1 in 150 ml of ethanol
1.8 g and 2-chloroethylamine hydrochloride 17.8 g were added, and under a nitrogen atmosphere, sodium methoxide 28% methanol solution 5
9.2 g was added and the mixture was heated under reflux for 3 hours. After passing the inorganic salt,
25 ml of hydrogen chloride 25% ethanol solution was added to the liquid, and 200 ml of ethyl acetate was further added. The resulting crystals were collected and recrystallized from 300 ml of methanol and 200 ml of ethyl acetate to give compound (1)
Was obtained as the dihydrochloride. 17.5g (73%) Synthesis of compound (11) 1,4, synthesized by the method of J. Am. Chem. Soc., 91 4694 (1969)
A solution of 5 g of 8,11-tetrathiaundecane, 6.3 g of dimethylaminoethyl chloride hydrochloride and 150 ml of ethanol was added with 17 g of 28% methanol solution of sodium methoxide under a nitrogen atmosphere, and the mixture was heated under reflux for 3 hours. After passing the generated inorganic salt, 15 ml of hydrogen chloride 25% ethanol solution was added to the liquid, and further 200 ml of ethyl acetate was added. The resulting crystals were collected and recrystallized from 100 ml of ethanol and 250 ml of ethyl acetate to obtain the compound (11) as dihydrochloride. 5.5 (55%) Other compounds can be similarly synthesized.

The present invention is effective in any processing in which a bleaching bath, a fixing bath and the like are combined as a desilvering step. Examples of the desilvering process include, but are not limited to, the following.

No.1 Bleaching-fixing No.2 Bleaching-washing-fixing The desilvering step is usually carried out after the developing step, but a bath for washing, rinsing, bleaching acceleration or the like may be provided therebetween.

Further, each step is preferably a multi-stage treatment system of forward flow or counter flow. A two-stage or three-stage countercurrent system is particularly preferable.

In the present invention, an aminopolycarboxylic acid ferric iron complex salt as a bleaching agent used in a bleaching solution is a complex of a ferric ion and an aminopolycarboxylic acid or a salt thereof, and a typical example of the aminopolycarboxylic acid is It is as follows.

A-1 ethylenediaminetetraacetic acid A-2 diethylenetriaminepentaacetic acid A-3 1,3-diaminopropanetetraacetic acid A-4 1,2-diaminopropanetetraacetic acid A-5 ethylenediamine-N- (β-oxyethyl)
-N, N ', N'-triacetic acid A-6 Nitrilotriacetic acid A-7 1,2-Cyclohexanediaminetetraacetic acid A-8 Iminodiacetic acid A-9 Dihydroxyethylglycine A-10 Ethyletherdiaminetetraacetic acid A-11 Glycol ether diamine tetraacetic acid A-12 ethylenediaminetetrapropionic acid and the like can be mentioned, but not limited to these exemplified compounds.

Among these compounds, especially A-1 to A-3, A-7,
A-8 and A-11 are preferred.

The ferric aminopolycarboxylic acid complex salt may be used in the form of a complex salt, or a ferric salt such as ferric sulfate or ferric chloride.
A ferric ion complex salt may be formed in a solution by using ferric nitrate, ferric ammonium sulfate, ferric phosphate and the like and an aminopolycarboxylic acid. When used in the form of complex salt,
One kind of complex salt may be used, or two or more kinds of complex salt may be used. On the other hand, when a complex salt is formed in a solution using a ferric salt and an aminopolycarboxylic acid, one or more ferric salts may be used. Furthermore, one or more aminopolycarboxylic acids may be used. Also,
In either case, it is preferable to use the aminopolycarboxylic acid in an excess amount over forming the ferric ion complex salt.

Aminopolycarboxylic acid and its ferric iron complex salt are usually preferably used in the form of an alkali metal salt or an ammonium salt, and an ammonium salt is particularly preferable in terms of solubility.

The bleaching solution containing the ferric ion complex may contain a metal ion complex salt of cobalt, copper or the like other than iron.

Examples of the persulfate include ammonium salt, potassium salt, sodium salt and the like.

In addition to the bleaching accelerator of the present invention, a compound conventionally known as a bleaching accelerator can be added to the bleaching solution or the prebath thereof. Examples of such a bleaching accelerator include, for example, U.S. Pat.No. 3,893,858, German Patent No. 1,290,812, British Patent No. 1,138,842, JP-A-53-95630, Research Disclosure No. 17129. (July 1978 issue), compounds having a mercapto group or a disulfide group, JP-A-50-14012.
Thiazolidine derivatives described in Japanese Patent Publication No. 3,70,70
Thiourea derivatives described in 6,561, JP-A-58-1623
5, iodide, polyethylene oxides described in German Patent 2,748,430, Japanese Examined Patent Publication No. 45-8836
It is possible to use the polyamine compounds described in the publication. Particularly preferred are mercapto compounds as described in British Patent 1,138,842.

These bleaching accelerators can also be used by adding them to the pre-bath of the processing solution having the bleaching ability of the present invention.

The bleaching solution constituting the present invention, in addition to the bleaching agent and the above compounds, bromide, such as potassium bromide, sodium bromide,
Rehalogenating agents such as ammonium bromide or chlorides such as potassium chloride, sodium chloride, ammonium chloride can be included. The concentration of rehalogenating agent is bleach 1
The amount is 0.1 to 5 mol, preferably 0.5 to 3 mol.
In addition, nitrates such as sodium nitrate and ammonium nitrate,
Boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc. One or more inorganic acids having pH buffering ability, organic Additives known to be used in ordinary bleaching solutions such as acids and salts thereof can be added.

In the present invention, the amount of the bleaching agent per bleaching solution is 0.05 mol to 1 mol, preferably 0.1 mol to 0.5 mol.

Further, the pH of the bleaching solution is preferably 4.0 to 8.0, particularly 5.0 to 6.5 when the bleaching agent is ferric aminopolycarboxylic acid salt, and is preferably 0.5 to 8.0, preferably 2.0 to 4.0 in the case of persulfate. . The bleaching solution can be processed at a temperature of 10 to 60 ° C, preferably 30 to 50 ° C, more preferably 35 to 45 ° C. The replenishing amount of the bleaching solution is preferably 50 to 2000 ml per 1 m ² of the light-sensitive material, more preferably 100 to 500 ml.

The pH of the fixing solution is 3.0 to 9.0, preferably 5.0 to 8.0, and the processing time is preferably 20 seconds to 10 minutes, more preferably 30 seconds to 4 minutes.
The amount of the fixing agent is 0.3 mol to 3 mol per 1 liter of the fixing solution,
It is preferably 0.5 mol to 2 mol. The preferred temperature range is the same as for the bleaching solution.

When the washing or stabilizing step follows immediately after the bleaching or fixing step, it is preferable to introduce a part or all of these overflow solutions into a processing solution for bleaching or fixing.

The color developing solution used in the present invention contains a known aromatic primary amine color developing agent. A preferred example is a p-phenylenediamine derivative, and representative examples thereof are shown below, but the invention is not limited thereto.

D-1 N, N-diethyl-p-phenylenediamine D-2 2-amino-5-diethylaminotoluene D-3 2-amino-5- (N-ethyl-N-laurylamino) toluene D-4 4- [ N-ethyl-N- (β-hydroxyethyl) amino] aniline D-5 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline D-6 4-amino-3-methyl -N-ethyl-N-
[Β- (Methanesulfonamido) ethyl] -aniline D-7 N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide D-8 N, N-dimethyl-p-phenylenediamine D-9 4-amino -3-Methyl-N-ethyl-N-methoxyethylaniline D-10 4-amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline D-11 4-amino-3-methyl-N-ethyl-N-β
-Butoxyethylaniline Of the above p-phenylenediamine derivatives, Exemplified Compound D-5 is particularly preferable.

Further, these p-phenylenediamine derivatives may be salts such as sulfates, hydrochlorides, sulfites and p-toluenesulfonates. The amount of the aromatic primary amine developing agent used is preferably about 0.1 g to about 20 g, more preferably about 0.5 g to about 10 g per developer.

Further, as a preservative, a sulfite salt such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, or a carbonyl sulfite adduct is added to the color developer as needed. be able to. However, in order to improve the color developability of the color developing solution, it is preferable that the sulfite ion is not substantially contained. The term "substantially free from" as used herein means that, per color developing solution, it is 0 in terms of sodium sulfite.
The content is 5 g / l or less, preferably 0.2 g / l or less, and more preferably none.

Further, as a compound for directly preserving the color developing agent, various hydroxylamines, hydroxamic acids described in Japanese Patent Application No. 61-186559, hydrazines described in 61-170756, and hydrazides, 61-188742. No. and No. 61-203253
No. 61-188741, α-hydroxyketones and α-aminoketones, and / or the same.
It is preferable to add various sugars described in No. 61-180616.
Further, in combination with the above compound, Japanese Patent Application Nos. 61-147823 and 61-
166674, 61-165621, 61-164515, 61-17078
No. 9, and monoamines described in No. 61-168159, etc., No. 61
-173595, 61-164515, 61-186560 and the like diamines, 61-165621, and 61-169789 polyamines described, 61-188619 polyamines described, 6
Nitroxy radicals described in 1-197760, 61-186561
, And alcohols described in 61-197419, 61-198987
It is preferable to use oximes described in No. 61-265149 and tertiary amines described in No. 61-265149.

As other preservatives, JP-A-57-44148 and 57-53749
Various metals described in JP-A-59-180588, alkanolamines described in JP-A-54-3532, polyethyleneimines described in JP-A-56-94349, and U.S. Pat. If desired, the aromatic polyhydroxy compound described in JP-A No. 1994-001 may be contained. It is particularly preferable to add an aromatic polyhydroxy compound.

The color developer used in the present invention preferably has a pH of 9 to 1.
2, more preferably from 9 to 11.0, and the color developing solution may contain other known developing solution component compounds.

In order to maintain the above pH, it is preferable to use various buffers.

Specific examples of the buffer include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, Sodium tetraborate (borax), potassium tetraborate, o-
Sodium hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, 5-sulfo-
Examples thereof include sodium 2-hydroxybenzoate (sodium 5-sulfosalicylate) and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate). However, the present invention is not limited to these compounds.

The amount of the buffer added to the color developing solution is preferably 0.1 mol / l or more, and particularly preferably 0.1 mol / l to 0.4 mol / l.

In addition, various chelating agents can be used in the color developing solution as a precipitation preventing agent for calcium and magnesium, or for improving the stability of the color developing solution.

The chelating agent is preferably an organic acid compound, and examples thereof include aminopolycarboxylic acid salts, organic phosphonic acids, and phosphonocarboxylic acids. Specific examples are shown below, but the present invention is not limited thereto.

Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid,
Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid, 1,2
-Diaminopropane tetraacetic acid, hydroxyethyliminodiacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N , N'-Bis (2-hydroxybenzyl) ethylenediamine-N, N'-diacetic acid These chelating agents may be used in combination of two or more, if necessary.

The amount of these chelating agents added may be an amount sufficient to block the metal ions in the color developing solution. Eg 1
It is about 0.1g to 10g.

If necessary, any development accelerator can be added to the color developing solution. However, it is preferable that the color developing solution of the present invention does not substantially contain benzyl alcohol from the viewpoints of pollution, solution preparation and color contamination prevention. Here, "substantially" means that the amount of the developer is not more than 2 ml, preferably not contained at all.

Other development accelerators include JP-B-37-16088 and 37-5
No. 987, No. 38-8726, No. 44-12380, No. 45-9019, and thioether compounds represented in U.S. Pat.No. 3,813,247, etc., represented by JP-A Nos. 52-49829 and 50-15554. p-Phenylenediamine compound, JP-A-50-137726
JP-B-44-30074, JP-A-56-156826 and 52-43
429, etc., quaternary ammonium salts, US Pat. Nos. 2,494,903, 3,128,182, 4,230,796, and
3,253,919, Japanese Patent Publication No. 41-11431, U.S. Pat.No. 2,482,546
Nos. 2,596,926 and 3,582,346, etc., amine compounds, JP-B-37-16088, JP-B-42-25201, U.S. Pat.No. 3,128,183, JP-B-41-11431, 42-23883 and US If necessary, polyalkylene oxide represented by Japanese Patent No. 3,532,501 and the like, 1-phenyl-3-pyrazolidones, imidazoles and the like can be added.

In the present invention, any antifoggant can be added if necessary. As the antifoggant, an alkali metal halide such as sodium chloride, potassium bromide or potassium iodide, and an organic antifoggant can be used. Examples of the organic antifoggant include benzotriazole and 6-
Nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-
Representative examples thereof include nitrogen-containing heterocyclic compounds such as thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine.

The color developer used in the present invention may contain a fluorescent whitening agent. As the fluorescent whitening agent, 4,4'-diamino-2,2'-disulfostilbene compound is preferable. The addition amount is 0 to 5 g / l, preferably 0.1 g to 4 g / l.

If necessary, various surfactants such as alkyl sulfonic acid, aryl phosphonic acid, aliphatic carboxylic acid and aromatic carboxylic acid may be added.

The processing temperature of the color developer of the present invention is preferably 20 to 50 ° C.
30 to 45 ° C. The processing time is 20 seconds to 5 minutes, preferably 30 seconds to 3 minutes. The replenishment amount is preferably small, but it is 100 to 1500 ml, preferably 100 to 800 ml, per 1 m ^{2 of} the light-sensitive material.
More preferably, it is 100 ml to 400 ml.

If necessary, the color developing bath may be divided into two or more baths, and the color developing replenisher may be replenished from the frontmost bath or the last bath to shorten the developing time or the replenishing amount.

The processing method of the present invention can also be used for color reversal processing. In the present invention, as the black and white developing solution used at this time, what is commonly known as a black and white first developing solution used for reversal processing of a color photographic light-sensitive material or one used for processing a black-and-white light-sensitive material can be used. Further, various well-known additives which are generally added to the black and white developer can be contained.

Typical additives include a developing agent such as 1-phenyl-3-pyrazolidone, metol and hydroquinone, a preservative such as sulfite, and an accelerator composed of an alkali such as sodium hydroxide, sodium carbonate or potassium carbonate. , Potassium bromide, 2-methylbenzimidazole,
Inorganic or organic inhibitors such as methylbenzthiazole, water softeners such as polyphosphates, trace amounts of iodides, and development inhibitors composed of mercapto compounds can be mentioned.

The washing water used in the washing step may contain known additives, if necessary. For example, water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, bactericides and antifungal agents that prevent the growth of various bacteria and algae (eg, isothiazolone, organochlorine bactericides, benzotriazole, etc.) , A drying load, and a surfactant for preventing unevenness can be used. Or LE
West, “Water Quality Criteria”, Phot.Sci.and Eng., V
The compounds described in ol. 9, No. 6, pages 344 to 359 (1965) and the like can also be used.

As the stabilizing solution used in the stabilizing step, a processing solution that stabilizes the dye image is used. For example, a liquid having a buffering capacity of pH 3 to 6, a liquid containing an aldehyde (for example, formalin), and the like can be used. In the stabilizing solution, if necessary, an ammonium compound, Bi, a metal compound such as Al,
A fluorescent whitening agent, a chelating agent (for example, 1-hydroxyethylidene-1,1-diphosphonic acid), a bactericidal agent, an antifungal agent, a hardener, a surfactant and the like can be used.

The washing step and the stabilizing step are preferably a multi-stage countercurrent system, and the number of stages is preferably 2 to 4. The amount of replenishment is 1 to 50 times, preferably 2 to 30 times, more preferably 2 to 15 times, the amount carried in from the previous bath per unit area.

As the water used in these washing step or stabilizing step, in addition to tap water, Ca such as ion exchange resin,
Water, halogen, deionized to a Mg concentration of 5 mg / l or less,
It is preferable to use water sterilized by an ultraviolet sterilization lamp or the like.

In the above processing steps of the photosensitive material, when the continuous processing by the automatic developing machine is performed, the processing solution may be concentrated by evaporation, which is remarkable especially when the processing amount is small or the processing solution has a large opening area. Becomes In order to correct such concentration of the treatment liquid, it is preferable to replenish an appropriate amount of water or the correction liquid.

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

The silver halide emulsion used in the present invention can be prepared by the method described in Research Disclosure, vol. 176, Item No. 17643, item [I].

Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used in the silver halide color photographic light-sensitive material used in the present invention.

The silver halide grains in the photographic emulsion may be so-called regular grains having regular crystals such as cubes, octahedra and tetradecahedrons, and grains having an irregular crystal form such as spheres, dihedral grains. It may have a crystal defect such as a crystal plane or a composite form thereof.

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

Monodisperse emulsions are silver halide grains having an average grain diameter of greater than about 0.1 micron, at least about 95
Emulsions are typically such that the weight percentage is within ± 40% of the average grain diameter. Have an average particle diameter of about 0.25 to 2 microns and at least about 95% by weight or at least about 95% in trace amounts
An emulsion in which the above silver halide grains are within the range of average grain diameter ± 20% can be used in the present invention.

The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. These emulsion grains are described in British Patent No. 1,027,146,
U.S. Pat.Nos. 3,505,068, 4,444,877 and JP-A-60
-143331 etc. Further, 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, the sensitivity including the improvement of the color sensitizing efficiency by the sensitizing dye, the improvement of the relationship of the graininess of the sensitivity, the improvement of the sharpness, and the development progress It is possible to improve the sex, the covering power, and the crossover. Here, the tabular silver halide grains have a diameter / thickness ratio of 5 or more, for example, more than 8, or 5 or more and 8 or more.
There are the following:

Silver iodobromide is particularly preferred for use in high-sensitivity light-sensitive materials. In the case of silver iodobromide, the silver iodide content is usually 40 mol% or less, preferably 20 mol% or less, more preferably 15 mol% or less.
It is not more than mol%. Further, silver chloride and silver chlorobromide are particularly preferable for the light-sensitive material for printing.

The tabular grains may have a uniform halogen composition or may have two or more phases having different halogen compositions. For example, when silver iodobromide is used, the tabular silver iodobromide grains having a layered structure composed of a plurality of phases each having a different iodide content can be used. JP-A-58-113928 and JP-A-59-99433 disclose preferable examples of the halogen composition of tabular silver halide grains and the distribution of halogen within the grains.

The preferred use of tabular silver halide grains in the present invention is Research Disclosure No. 22534.
(January 1983) and No. 25330 (May 1985), for example, a use method based on the relationship between tabular grain thickness and optical properties is disclosed.

Next, a silver halide solvent is useful for promoting the ripening of silver halide grain formation. For example, it is known to have excess halogen ions present in the reactor to accelerate aging. As ripening agents other than halogen ions, ammonia or amine compounds, thiocyanate salts such as alkali metal thiocyanate salts, especially sodium and potassium thiocyanate salts, and ammonium thiocyanate salts can be used. The use of thiocyanate ripening agents is described in US Pat. No. 2,222,264.
No. 2,448,534 and 3,320,069 teach. It is also possible to use a commonly used thioether ripening agent as described in U.S. Pat. Nos. 3,271,157, 3,574,628 and 3,737,313. Alternatively, JP-A-53-8
It is also possible to use thione compounds as disclosed in 2408 and 53-144319.

Silver halide emulsions are usually chemically sensitized. The chemical sensitization is most preferably performed in the presence of a gold compound and a thiocyanate compound, or a sulfur-containing compound or hypo described in U.S. Pat. And the like in the presence of a sulfur-containing compound such as.

The silver halide photographic emulsion used in the present invention may be spectrally sensitized with methine dyes and the like. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes.

These sensitizing dyes may be used alone or in combination thereof, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization. Along with the sensitizing dye, a dye that does not itself have a photosensitizing action or a substance that does not substantially absorb visible light and exhibits supersensitization may be included in the emulsion.

As these dyes and the like, those described in Research Disclosure, vol.176, Item No.17643, IV (December 1978) can be used.

The spectral sensitization of the silver halide emulsion used in the present invention can be carried out at any stage of emulsion preparation. In U.S. Pat.Nos. 4,183,756 and 4,225,666, a spectral sensitizing dye is added by adding a spectral sensitizing dye to an emulsion after the formation of a stable silver halide grain, thereby increasing the photographic sensitivity and the spectral sensitizing dye by silver halide grains. It is disclosed that there are advantages such as enhanced adsorption of

In the photographic emulsion layer of the photographic light-sensitive material of the present invention, for the purpose of increasing sensitivity, increasing contrast, or promoting development, for example, polyalkylene oxide or its derivative such as ether, ester, amine, thioether compound, thiomorpholines, quaternary ammonium. It may contain a salt compound, a urethane derivative, a urea derivative, an imidazole derivative, 3-pyrazolidones and the like.

In the silver halide photographic emulsion used in the present invention, for the purpose of preventing fog during the manufacturing process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance,
Various compounds can be included. That is, azoles such as benzothiazolium, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazole. , Benzotriazoles,
Nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole)
Etc .; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a,
7) Tetraazaindenes), pentaazaindenes and the like; many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide and the like can be added.

Various color couplers can be used in the present invention, specific examples of which are described in the patents described in Research Disclosure (RD) No. 17643, VII-CG. As the dye-forming coupler, a coupler that gives the three primary colors of the subtractive method (that is, yellow, magenta and cyan) by color development is important, and the
Specific examples of the equivalent or 2-equivalent coupler are RD17643, VII described above.
-In addition to the couplers described in the patents of C and D,
The following can be preferably used in the present invention.

A typical example of the yellow coupler that can be used in the present invention is an oil protect type acylacetamide coupler. A specific example is U.S. Pat. No. 2,407,21.
No. 0, No. 2,875,057 and No. 3,265,506. In the present invention, it is preferable to use a 2-equivalent yellow coupler, and U.S. Pat.Nos. 3,408,194 and 3,447,9.
No. 28, No. 3,933,501 and No. 4,022,620 oxygen atom desorption type yellow couplers described in JP-B-55-10739, U.S. Pat.No. 4,401,752, No. 4,326,0
No. 24, RD18053 (April 1979), British Patent No. 1,425,020
Representative examples thereof include nitrogen atom-releasing yellow couplers described in West German Application Publication Nos. 2,219,917, 2,261,361, 2,329,587, and 2,433,812. The α-pivaloyl acetanilide type coupler is excellent in the fastness, especially the light fastness, of the color forming dye, while the α-benzoyl acetanilide type coupler can obtain a high coloring density.

Examples of the magenta coupler that can be used in the present invention include oil-protection type indazolone type or cyanoacetyl type, preferably 5-pyrazolone type and pyrazoloazole type couplers such as pyrazolotriazoles. The 5-pyrazolone-based 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 color forming dye, and typical examples thereof are U.S. Pat.Nos. 2,311,082 and 2,343,703. ,
No. 2,600,788, No. 2,908,573, No. 3,062,653
No. 3,152,896 and No. 3,936,015. As the leaving group of the 2-equivalent 5-pyrazolone-based coupler, the nitrogen atom leaving group described in US Pat. No. 4,310,619 or the arylthio group described in US Pat. No. 4,351,897 is preferable. Further, the 5-pyrazolone-based coupler having a ballast group described in EP 73,636 provides a high color density.

As a pyrazoloazole-based coupler, US Pat.
Pyrazolobenzimidazoles described in 9,879, preferably pyrazolo [5,1] described in U.S. Patent No. 3,725,067.
-C] [1,2,4] triazoles, pyrazolotetrazoles described in Research Disclosure 24220 (June 1984) and Research Disclosure 24230
(June 1984), and pyrazolopyrazoles. The imidazo compound described in European Patent 119,741 [1,2-
b] Pyrazoles are preferred, and the pyrazolo [1,5-b] [1,2,4] triazoles described in EP 119,860 are particularly preferred.

Cyan couplers that can be used in the present invention include oil-protected naphthol-based and phenol-based couplers, and naphthol-based couplers described in U.S. Pat.No. 2,474,293, preferably U.S. Pat.
Representative examples are the oxygen atom-elimination type two-equivalent naphthol couplers described in 4,146,396, 4,228,233 and 4,296,200. Further, specific examples of the phenol-based coupler are described in U.S. Patent Nos. 2,369,929 and 2,801,1.
No. 71, No. 2,772,162, No. 2,895,826 and the like. Cyan couplers that are fast against humidity and temperature are preferably used in the present invention, and typical examples thereof include a phenol having an alkyl group of ethyl group or higher at the meta-position of the phenol nucleus described in U.S. Pat.No. 3,772,002. Cyan couplers, U.S. Pat.Nos. 2,772,162 and 1
3,758,308, 4,126,396, 4,334,011, 4,327,173, West German Patent Publication No. 3,329,729 and 2,5-diacylamino-substituted phenol couplers and U.S. Pat. Third 3,446,622
Nos. 4,333,999, 4,451,559 and 4,42
Nos. 7,767 and the like include phenolic couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position.

The graininess can be improved by using a coupler in which the color forming dye has an appropriate diffusibility. Such couplers are
Specific examples of magenta couplers are described in US Pat. No. 4,366,237, and specific examples of yellow, magenta or cyan couplers are described in European Patent No. 96,570.

The dye-forming coupler and the above-mentioned special coupler may form a dimer or higher polymer. Typical examples of polymerized dye forming couplers are described in US Pat. No. 3,451,820. Specific examples of the polymerized magenta coupler are described in US Pat. No. 4,367,282 and the like.

Couplers that release a photographically useful residue upon coupling are also preferably used in the present invention. As the DIR coupler releasing the development inhibitor, the couplers of the patents described in the above-mentioned RD17643, VII to F are useful.

In the light-sensitive material of the present invention, a coupler capable of releasing a nucleating agent or a development accelerator or a precursor thereof imagewise during development can be used. Specific examples of such compounds are described in British Patent Nos. 2,097,140 and 2,131,188. In addition, DIR described in JP-A-60-185950
Redox compound-releasing couplers, couplers which release dyes that recolor after separation described in EP 173,302A, and the like can be used.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of the high boiling point organic solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. Further, the steps of the latex dispersion method, effects, specific examples of latex for impregnation, U.S. Pat.
363, West German Patent Application (OLS) Nos. 2,541,274 and
It is described in No. 2,541,230.

The light-sensitive material used in the present invention is, as a color antifoggant or a color mixture inhibitor, a hydroquinone derivative, an aminophenol derivative, an amine, a gallic acid derivative, a catechol derivative, an ascorbic acid derivative, a colorless coupler, a sulfonamidephenol derivative, etc. May be included.

A known anti-fading agent can be used in the light-sensitive material used in the present invention. Known anti-fading agents include hydroquinones, 6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols, hindered phenols centering on bisphenols, gallic acid derivatives, methylenedioxy. Representative examples include benzenes, aminophenols, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl groups of these compounds.

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

Typical examples of the ultraviolet absorber are described in RD24239 (June 1984) and the like.

The light-sensitive material used in the present invention comprises one or more surfactants for various purposes such as coating aid, antistatic property, sliding property improvement, emulsion dispersion, adhesion prevention and photographic property improvement (for example, development acceleration, contrast enhancement, sensitization). May be included.

The light-sensitive material used in the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as prevention of irradiation or halation. As such dyes, oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, anthraquinone dyes, and azo dyes are preferably used. In addition to these, cyanine dyes, azomethine dyes, triazolemethane dyes, and phthalocyanine dyes are also useful. The oil-soluble dye can be emulsified by the oil-in-water dispersion method and added to the hydrophilic colloid layer.

In the light-sensitive material used in the present invention, as a method for introducing a lipophilic compound such as a photographic coupler into the hydrophilic organic colloid layer, various methods such as oil-in-water dispersibility, latex dispersion method, solid dispersion method and alkali dispersion method can be used. A method can be used, and a preferable method can be appropriately selected depending on the chemical structure and physicochemical properties of the compound to be introduced.

(Examples) Examples of the present invention will be shown below, but the present invention is not limited thereto. The compounds of the present invention in the examples are represented by the numbers of the specific examples in the text.

The structures of comparative compounds used in the examples are as follows.

Bleach accelerator (B) H ₂ NCH _{2 2} SCH _{2 2} SCH _{2 2} NH ₂ (same as above) (C) HOCH _{2 2} SCH _{2 2} SCH _{2 2} OH (same as above) Example 1 On a subbed cellulose triacetate film support,
A multi-layer color light-sensitive material A having the following composition was prepared.

(Composition of photosensitive layer) The coating amount of silver halide and colloidal silver is silver.
The amount represented in units of g / m ^2, also couplers, moles per 1 mol of silver halide in the same layer for the amount for the additives and gelatin represented in units of g / m ^2, also the sensitizing dye Indicated by.

First layer (antihalation layer) Black colloidal silver 0.2 Gelatin 1.3 ExM-9 0.06 UV-1 0.03 UV-2 0.06 UV-3 0.06 Solv-1 0.15 Solv-2 0.15 Solv-3 0.05 Second layer (intermediate layer) Gelatin 1.0 UV-1 0.03 ExC-4 0.02 ExF-1 0.004 Solv-1 0.1 Solv-2 0.1 Third layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, uniform AgI type, equivalent spherical diameter 0.5)
μ, coefficient of variation of equivalent spherical diameter 20%, plate-like particles, diameter / thickness ratio
3.0) Coating silver amount 1.2 Silver iodobromide emulsion (AgI 3 mol%, uniform AgI type, spherical equivalent diameter 0.3
μ, coefficient of variation of equivalent spherical diameter 15%, spherical particles, diameter / thickness ratio
1.0) Silver coating amount 0.6 Gelatin 1.0 ExS-1 4 × 10 ^-4 ExS-2 4 × 10 ^-5 ExC-1 0.05 ExC-2 0.50 ExC-3 0.03 ExC-4 0.12 ExC-5 0.01 4th layer (high sensitivity) Red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 6 mol%, core-shell ratio 1: 1 internal high A)
gI type, equivalent sphere diameter 0.7μ, variation coefficient of equivalent sphere diameter 15%, plate-shaped particles, diameter / thickness ratio 5.0) Coating silver amount 0.7 Gelatin 1.0 ExS-1 3 × 10 ^-4 ExS-2 2.3 × 10 ^-5 ExC-6 0.11 ExC-7 0.05 ExC-4 0.05 Solv-1 0.05 Solv-3 0.05 Fifth layer (intermediate layer) Gelatin 0.5 Cpd-1 0.1 Solv-1 0.05 Sixth layer (low-sensitivity green-sensitive emulsion layer) Odor Silver halide emulsion (AgI 4 mol%, core-shell ratio 1: 1 surface height A
gI type, equivalent sphere diameter 0.5μ, coefficient of variation of equivalent sphere diameter 15%, plate-like grain, diameter / thickness ratio 4.0) Coating silver amount 0.35 Silver iodobromide emulsion (AgI 3 mol%, uniform AgI type, equivalent sphere diameter 0.3)
μ, coefficient of variation of equivalent spherical diameter 25%, spherical particles, diameter / thickness ratio
1.0) Coating amount 0.20 Gelatin 1.0 ExS-3 5 × 10 ^-4 ExS-4 3 × 10 ^-4 ExS-5 1 × 10 ^-4 ExM-8 0.4 ExM-9 0.07 ExM-10 0.02 ExY-11 0.03 Solv- 1 0.3 Solv-4 0.05 7th layer (high sensitivity green emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, core shell ratio 1: 3, internal high A)
gI type, equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter 20%, plate-like grain, diameter / thickness ratio 5.0) Coating silver amount 0.8 Silver iodobromide emulsion (AgI 3 mol%, uniform AgI type, equivalent sphere diameter 0.3)
μ, coefficient of variation of equivalent spherical diameter 25%, spherical particles, diameter / thickness ratio
1.0) Silver coating amount 0.8 Gelatin 0.5 ExS-3 5 × 10 ^-4 ExS-4 3 × 10 ^-4 ExS-5 1 × 10 ^-4 ExM-8 0.1 ExM-9 0.02 ExY-11 0.03 ExC-2 0.03 ExM- 14 0.01 Solv-1 0.2 Solv-4 0.01 Eighth layer (intermediate layer) Gelatin 0.5 Cpd-1 0.05 Solv-1 0.02 Ninth layer (donor layer having multi-layer effect on red-sensitive layer) Silver iodobromide emulsion (AgI2 mol%) , Core shell ratio 2: 1 internal high A
gI type, equivalent sphere diameter 1.0μ, variation coefficient of equivalent sphere diameter 15%, plate-like grain, diameter / thickness ratio 6.0) Silver coating amount 0.35 Silver iodobromide emulsion (AgI 2 mol%, core shell ratio 1: 1) A
gI type, equivalent sphere diameter 0.4μ, coefficient of variation of equivalent sphere diameter 20%, plate-like particles, diameter / thickness ratio 6.0) Coating silver amount 0.20 Gelatin 0.5 ExS-3 8 × 10 ^-4 ExY-13 0.11 ExM-12 0.03 ExM-14 0.10 Solv-1 0.20 10th layer (yellow filter layer) Yellow colloidal silver 0.05 Gelatin 0.5 Cpd-2 0.13 Solv-1 0.13 Cpd-1 0.10 11th layer (low sensitivity blue emulsion layer) Silver iodobromide emulsion (AgI 4.5 mol%, uniform AgI type, sphere equivalent diameter 0.7
μ, coefficient of variation of spherical equivalent diameter 15%, plate-like particles, diameter / thickness ratio
7.0) Coating silver amount 0.3 Silver iodobromide emulsion (AgI 3 mol%, uniform AgI type, spherical equivalent diameter 0.3
μ, coefficient of variation of equivalent spherical diameter 25%, plate-shaped particles, diameter / thickness ratio
7.0) Coating silver amount 0.15 Gelatin 0.5 ExS-6 2 × 10 ^-4 ExC-16 0.05 ExC-2 0.10 ExC-3 0.02 ExY-13 0.07 ExY-15 1.0 Solv-1 0.20 12th layer (high-sensitivity blue-sensitive emulsion layer) ) Silver iodobromide emulsion (AgI 10 mol%, internal high AgI type, spherical equivalent diameter 1.
0μ, coefficient of variation of equivalent sphere diameter 25%, multiple twin plate particles, diameter / thickness ratio 2.0) Coating silver amount 0.5 Gelatin 0.5 ExS-6 1 × 10 ^-4 ExY-15 0.20 ExY-13 0.01 Solv-1 0.10 13th layer (1st protective layer) Gelatin 0.8 UV-4 0.1 UV-5 0.15 Solv-1 0.01 Solv-2 0.01 14th layer (2nd protective layer) Fine grain silver bromide emulsion (AgI 2 mol%, uniform AgI type, Equivalent diameter
0.07μ) 0.5 Gelatin 0.45 Polymethylmethacrylate particles Diameter 1.5μ 0.2 H-1 0.4 Cpd-5 0.5 Cpd-6 0.5 In addition to the above components in each layer, emulsion stabilizer Cpd-3 (0.0
4 g / m ² ) Surfactant Cpd-4 (0.02 g / m ² ) was added as a coating aid.

Solv-1 Tricresyl Phosphate Solv-2 Dibutyl Phthalate The sample prepared as described above was used with a light source with a color temperature of 4800 ° K for 10
The substrate was exposed to CMS and treated with the treatment steps and treatment solutions shown below. The bleaching solution used was one to which each accelerator shown in Table 1 was added and one to which nothing was added.

Processing process Processing time Temperature Color development 2 minutes 30 seconds 40 ° C Bleaching 1 minute 30 seconds 40 ° C Settling 2 minutes 30 seconds 40 ° C Washing 1 minute 30 seconds 40 ° C Stability 30 seconds 40 ° C Drying 1 minute 60 C <Color developer> Diethylenetriamine pentaacetic acid 1.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 g Sodium sulfite 4.0 g Potassium carbonate 30.0 g Potassium bromide 1.4 g Potassium iodide 1.3 mg Hydroxyamine sulfate 2.4 g 4- ( N-Ethyl-N-β-hydroxyethylamino) -2-methylaniline sulfate 5.0 g Water was added to 1 pH 10.20 <bleaching solution> Ethylenediaminetetraacetic acid ferric ammonium dihydrate 12
0 g Ethylenediaminetetraacetic acid disodium salt 10.0 g Ammonia water 7.0 ml Ammonium nitrate 10.0 g Ammonium bromide 100.0 g Bleaching accelerator (Table 1) Add water 1 pH 6.0 << Fixer >> Ethylenediaminetetraacetic acid disodium salt 2.0 g Sodium sulfite 4.0 g Ammonium thiosulfate aqueous solution (70% w / v) 175.0 ml Sodium bisulfite 4.6 g Add water 1.0 l pH 6.6 << Stabilizer >> Formalin (37% w / v) 2.0 ml Polyoxyethylene-p-monononylphenyl Ether (average degree of polymerization: 10) 0.3 g Water was added, 1.0 l In addition, the compounds shown in Table 1 were added to the bleaching solution, and the bleaching accelerating ability of each was compared by the value of the residual silver amount. The amount of residual silver was determined by fluorescent X-ray analysis.

Furthermore, the stain of the processed light-sensitive material was evaluated by visual observation.

The results are shown in Table-1.

As can be seen from Table-1, when the compound of the present invention is used as a bleaching accelerator, rapid desilvering processing becomes possible.

Example-2 When the same test was performed except that the bleaching solution of Example-1 was changed to the following formulation, the same result was obtained.

<Bleach> 1,3-Diaminopropanetetraacetic acid ferric ammonium salt 3
0 g Ethylenediaminetetraacetic acid ferric ammonium dihydrate 90
g Ethylenediaminetetraacetic acid disodium salt 10.0 g Ammonia water (27%) 7.0 ml Ammonium nitrate 10.0 g Ammonium bromide 100.0 g Bleach accelerating agent (each compound in Table 1 and no additive) Water added 1 pH 5.5 Example-3 A light-sensitive material C was prepared in the same manner as in Example 7 of Japanese Patent Application No. 62-143467 (Japanese Patent Application Laid-Open No. 63-306448), exposed in the same manner as in Example 7, and developed by the following processing. The desilvering acceleration properties were compared.

Treatment process time Temperature 1st development 6 minutes 38 ° C 1st water wash 45 seconds 〃 Reversal 45 seconds 〃 Color development 6 minutes 〃 Bleach acceleration 45 seconds 〃 Bleach 1 minute 〃 Second water wash 45 seconds 〃 Fixed 3 minutes 〃 Third Washing 2 minutes 〃 Stabilization 1 minute 〃 Drying 2 minutes 50 ℃ 《First developer》 《First washing solution》 《Reversal solution》 《Color development》 《Fixer》 《Stabilizer》 Above, Japanese Patent Application No. 62- No. 143467 (Japanese Patent Laid-Open No. 63-306448), the same as in Example 7, the “second washing solution” and the “third washing solution” is disclosed in Japanese Patent Application No. 62-143467.
No. 2 (Japanese Patent Laid-Open No. 63-306448) << Second washing liquid >>
Same as <Bleaching accelerator> Ethylenediaminetetraacetic acid disodium salt 3.0g Bleach accelerator (each compound shown in Table 5) Water was added 1.0l pH 4.5 << Bleaching solution >> Potassium persulfate 33g Sodium chloride 18g Monosodium phosphate 7.0g Phosphoric acid (85%) 14.7g Water was added and 1.0l pH result is shown in Table-5.

As can be seen from Table-5, the compound of the present invention showed a large bleaching promoting ability even in the treatment with the persulfuric acid bleaching solution.

Claims (1)

[Claims] 1. An image-exposed silver halide color photographic light-sensitive material is prepared by using a ferric aminopolycarboxylic acid complex salt or persulfate as a bleaching agent in the presence of a compound represented by the following general formula (I). A method of processing a silver halide color photographic light-sensitive material, which comprises bleaching with a bleaching solution. General formula (I) (In the formula, R ¹ and R ² each represent a hydrogen atom or an alkyl group, and A ¹ and A ² each have 2 to 4 carbon atoms which may have a substituent.
Represents an alkylene group, and n represents 2 or 3. )