JP2652499B2 - Color developing solution and processing method of silver halide color photographic light-sensitive material using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and more particularly to a method for processing a silver halide color photographic light-sensitive material which can be stably processed even during continuous color development. is there.

[0002]

2. Description of the Related Art A color photographic light-sensitive material is processed by exposing the light-sensitive material to an image and then performing color development, silver bleaching, silver halide fixing, bleach-fixing in which bleaching and fixing are performed simultaneously, washing, and washing. Rinsing, stabilizing, and drying instead of processing are the basic processing. In addition to these, for use in each processing solution, and to increase the physical strength of the photosensitive material after processing and to increase stability. There are additional processing steps.

[0003] Processing of silver halide color photographic light-sensitive materials, which is currently widely used, is a method of obtaining a color print from a color negative film, and there is also a method of obtaining a positive color film and a print for directly obtaining a final image. Is basically a processing method in which black-and-white development processing is added to the step of obtaining a color negative film or color print.

[0004] Furthermore, color print users desire to view prints as soon as possible, so that they can print in a short period of time, and in order to meet this demand, it is necessary to speed up processing.

In recent years, the processing of silver halide color photographic light-sensitive materials has become possible rapidly by improving the light-sensitive materials. Further, in processing, a large amount of processing can be easily performed by an automatic developing machine, and at the same time, with the development of the automatic developing machine, a small and inexpensive machine has been used and many machines have been used.

As a color developing solution used for processing a silver halide color photographic light-sensitive material, an aromatic primary amine color developing agent such as paraphenylenediamine is used. Sulfites and hydroxylamines as preservatives for preventing air oxidation of the color developing agent, and alkali metal salts such as carbonic acid and phosphoric acid and alkali hydroxides as alkaline agents for keeping the color developing solution alkaline. Inhibitors, water softeners, and other additives are used as needed.

[0007]

In the silver halide color photographic light-sensitive material for color paper, a silver chlorobromide emulsion having a high proportion of silver chloride is used in order to enable rapid processing. In the silver chlorobromide photographic material having a high silver chloride ratio, the color density is low with hydroxylamine which has been used so far.

For this reason, when only sulfite, which is the same preservative, is used, the stability of the color developer can be maintained to some extent. Can not be used.

[0009] Under such circumstances, N, N-diethylhydroxylamine is generally used instead of hydroxylamine. This N, N-diethylhydroxylamine has the same property of lowering the color density, though not as much as hydroxylamine.

To make matters worse, N, N-diethylhydroxylamine has a peculiar odor, and when it is processed at a part of a general store called a so-called minilab,
This odor is not unfavorable from an environmental point of view and also for the processing operation, and is a matter that is desirable to be eliminated.

On the other hand, as a preservative used in a color developing solution for a color negative film, hydroxylamine is generally used, but it is a compound which is not preferably used because this product is a deleterious substance.

On the other hand, in such photographic processing, an automatic processor is used to easily process a large number of photographs quickly, and in processing a photosensitive material, a necessary processing solution is replenished as a replenisher. Processing is performed.

Since this replenisher is prepared for each fixed amount,
Since a certain period of time elapses before the battery is used up, the state of the replenisher will be different between the beginning and the state after a certain period of time, but if this happens, the quality of the processed photograph will change Therefore, the stability of this replenisher must be good.

The processing solution used in the automatic processor is
The amount of replenishment that is constantly replenished is discharged,
During this time, a certain time elapses, and stability within this time elapse is also required.

A photographic processing company requested by a photographer to perform processing needs to perform the processing quickly in order to meet the request in a short time, and in particular, demands a faster processing agent. For rapid color development, the color developer becomes a highly active processing solution. In such a case, the processing liquid naturally deteriorates severely, and if used for a long period of time, the composition changes, the development activity decreases, the image quality changes, and the entire paper is stained, which is not satisfactory.

Possible causes are deterioration of the color developing agent and preservative used, a decrease in alkalinity, and accumulation of substances eluted from the photosensitive material to be processed.

Further, when processing is performed using an automatic developing machine, a waste liquid corresponding to the processing amount of the photosensitive material is generated, but the amount of the waste liquid is reduced in consideration of resource saving and environmental effects due to waste.
That is, the replenishment amount is reduced, but if the replenishment amount is reduced, it takes time until the prepared replenisher is used, and the time that the replenisher stays in the automatic developing machine becomes longer. Accordingly, the deterioration of the processing liquid proceeds.

Accordingly, the present inventors process a silver halide color photographic light-sensitive material which is not deleterious and has a low odor and a low odor without the reduction in color density, maintaining the preservation of the color developing solution. As a result of studying a color developing solution and a processing method using the same, it was found that these problems can be solved by processing with a color developing solution containing a specific composition,
This has led to the present invention.

Accordingly, it is an object of the present invention to provide a color developer which maintains the preservation of the color developer, does not deteriorate the photographic performance such as a decrease in the color density and the occurrence of fog, has a low odor, and does not contain a deleterious substance. An object of the present invention is to provide a developer and a method for processing a silver halide color photographic material using the same.

[0020]

According to the present invention, in processing a silver halide color photographic light-sensitive material, the preservation of the color developing solution is maintained, and the photographic performance such as a decrease in color density and generation of fog is maintained. In a color developing solution which does not deteriorate and has little odor, does not contain deleterious substances, and a method for processing a silver halide color photographic light-sensitive material using the same,

(1) A color developing solution containing a reaction product obtained by reacting polyethyleneimine with hydrogen peroxide (hydrogen peroxide solution) without separating the reaction product.

(2) A silver halide color photographic light-sensitive material, which may have any composition and composition, is characterized in that after the image exposure, the color developing solution shown in the above (1) is used in the color developing process. For processing silver halide color photographic light-sensitive materials.

(3) A silver halide color photographic light-sensitive material having any structure and composition, using an automatic developing machine having any structure and composition, and using the color developing solution shown in (1) above. This was achieved by processing a silver halide color photographic light-sensitive material characterized by a processing method.

[0024]

DETAILED DESCRIPTION OF THE INVENTION With respect to the reaction products of the present invention, compounds newly obtained by reaction of compounds are generally separated from the reaction system. It is the other compound that is formed in the reaction system,
Compounds not used in the reaction remain, and if they are contained, the target compound cannot exhibit its original properties, and disadvantages of compounds other than the target compound appear.

In addition, from the viewpoint of storage stability, separation and purification are generally performed because it is necessary to sufficiently raise the purity of the target compound. At this point, many materials are required, and The efficiency becomes very poor.

However, the reaction product of the present invention is characterized by the use of the compound produced by the reaction and all the compounds in the reaction system and the fact that they are stable without separation and purification, and are very efficient. It is characterized by obtaining a reaction product with good performance.

At present, many types of silver halide color photographic light-sensitive materials are commercially available. Depending on the purpose, there are color negative films, color reversal films, and color print materials for negative positive and positive positive. Uses a color negative film and a negative positive print material. These silver halide color photographic light-sensitive materials are of a very large number of types, each having a different layer structure, and has its own characteristics.

Furthermore, the composition of the silver halide constituting this layer is also very polymorphic, the difference in the amount of silver chloride, silver bromide and silver iodide used, the difference in the composition ratio, and the grain size of these silver halides. Each has characteristics such as the size of particles and the difference in particle size and shape.

Further, various different additives such as sensitizing dyes, stabilizers, sensitizers, and inhibitors are used. The particle size is described in, for example, pages 277 to 278 of "Basics of the Photographic Industry-Photograph of Silver Halide Photography" (edited by The Photographic Society of Japan, Corona).

Further, various couplers are used in the silver halide color photographic light-sensitive material, and a great many substances are also used for these. The silver halide color photographic light-sensitive material of any constitution and composition used in the claims of the present invention refers to such a matter.

In processing a silver halide color photographic light-sensitive material, an automatic processor is generally used. The automatic processor replenishes a type, a processing speed, a processing temperature, a processing step, and a replenisher. There are various types such as a method and a method of handling an overflow liquid, and each has its own characteristics. The automatic developing machine of any configuration used in the claims of the present invention refers to such a thing.

The color developing solution of the present invention is an invention relating to the performance of the color developing solution itself, which is not affected by the above conditions.

The polyethyleneimine used in the present invention consists of repeating ethylene chain units linked to one another via a nitrogen atom. This is a well-known commercial material.

As the color developing agent used in the color developing solution of the present invention, any of commonly used aromatic primary amine-based color developing agents can be used. Preferred color developing agents used in the present invention include, for example, Journal of American Chemical Society (J. Am. Chem. So
c.,) 73 .3100 (1951 ) and Heist (Haist), processing of Contemporary Photography (Modern Photographic Processing) .1979. John Wiley & Sons (John Wiley and Son
s). New York. On page 545 et seq.

In the color developer used in the present invention, various components usually used, for example, alkali agents such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium phosphate and sodium phosphate, sulfurous acid Sodium, potassium sulfite, sodium bisulfite, potassium bisulfite, sulfites such as sodium metabisulfite, potassium metabisulfite, bisulfite, metabisulfite, potassium chloride, sodium chloride, potassium bromide, sodium bromide, It contains halogen compounds such as potassium iodide and sodium iodide, water softeners such as aminopolycarboxylic acid, polystyrenesulfonic acid and polyphosphonic acid, thickeners such as ethylene glycol, diethylene glycol, diethanolamine and triethanolamine and development accelerators. With That.

Furthermore, as additives, nitrobenzimidazole, mercaptobenzimidazole, 5-methyl-
Benzotriazole, 1-phenyl-5-mercaptotetrazole compounds, stain inhibitors, sludge inhibitors and the like are used.

The color developing solution of the present invention is preferably used at pH 9.5 or higher. Generally, raising the pH to some extent enables rapid processing. May cause contamination.

In the color developing solution and processing method of the present invention, the color developing solution maintains the preservation of the color developing solution over time, does not lower the color density, does not generate fog, and has a low odor. It can be treated with a non-product composition.

The bleaching agent used in the bleaching solution used in the present invention is a metal complex salt of an organic acid. Examples of the complex salt include an organic acid such as aminopolycarboxylic acid and citric acid and a metal such as iron, cobalt and copper. . The most preferred organic acids used to form such metal complexes of organic acids are polycarboxylic acids, and these polycarboxylic acids or aminopolycarboxylic acids are alkali metal salts, ammonium salts, water-soluble amine salts. There may be.

Specific examples thereof include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N- (β-oxyethyl) -N, N ′,
N'-triacetic acid, propynediaminetetraacetic acid, nitrilotriacetic acid, iminodiacetic acid, cyclohexanediaminetetraacetic acid, dihydroxyethylglycine citric acid, ethyletherdiaminetetraacetic acid, ethylenediaminetetrabropinic acid, phenylenediaminetetraacetic acid and the like and these acids Are alkali metal salts, ammonium salts, and water-soluble amine salts.

As the halogenating agent, hydrohalic acids and alkali metal salts and ammonium salts of halogens are generally used. Specific examples thereof include hydrochloric acid, hydrobromic acid, etc., sodium chloride, potassium chloride and the like. , Ammonium chloride, sodium bromide, potassium bromide, ammonium bromide and the like.

As the buffering agent, an inorganic weak acid and an organic acid are used in combination with an alkali agent. Examples of the inorganic weak acid include carbonic acid, boric acid, phosphoric acid, and the organic acid include acetic acid, citric acid, and succinic acid. Specific examples thereof include:
Sodium carbonate, potassium carbonate, ammonium carbonate, sodium borate, potassium borate, ammonium borate, sodium phosphate, potassium phosphate, ammonium phosphate, sodium acetate, potassium acetate, ammonium acetate, sodium citrate, potassium citrate, Ammonium citrate, sodium succinate, potassium succinate, ammonium succinate and the like.

In addition, additives for bleach accelerating action are used. Regarding these additives, JP-A-54-35727,
JP-A-55-25064, JP-A-60-12549, JP-A-60-76745
No., JP-A-60-95540, JP-A-60-125843, JP-A-60-95540
221754, JP-A-60-230140, JP-A-60-244950, JP-A-61-50149, JP-A-61-118752, JP-A-62-80649
No., JP-A-62-89963, JP-A-62-131260, JP-A-62-89963
135835, JP-A-62-166344, JP-A-62-166345, JP-A-62-166346, JP-A-62-166347, JP-A-62-16634
8, JP-A-62-168159, JP-A-63-8741, JP-A-63-168159
No. 73247, JP 63-163853, JP 63-256953, JP 63-261362, JP 1-2048, JP 1-13550,
JP-A-1-15739, JP-A-1-102559, JP-A-1-70943
No., JP-A 1-211757, JP-A 1-213650, JP 1-22
No. 595, JP-A-1-245256, JP-A-2-44349, JP-A-2-
No. 93454, JP-A-2-03041 and the like.

The fixing agent used in the fixing solution used in the present invention is a compound which reacts with silver halide to form a water-soluble complex salt, such as thiosulfate and thiocyanate. Sodium, potassium thiosulfate, ammonium thiosulfate, sodium thiocyanate, potassium thiocyanate, ammonium thiocyanate, etc.,
Compounds such as thiourea and thioether.

Preservatives include sulfites, bisulfites, metabisulfites, and the like. Specific examples thereof include sodium sulfite, potassium sulfite, ammonium sulfite, sodium bisulfite, potassium bisulfite, ammonium bisulfite, and metabisulfite. Sodium bisulfite, potassium metabisulfite and the like.

As the buffer, a combination of an inorganic weak acid or an organic acid and an alkali agent is used. Examples of the inorganic weak acid include carbonic acid, boric acid, phosphoric acid, and the organic acid include acetic acid, citric acid, and succinic acid. Specific examples thereof include:
Sodium carbonate, potassium carbonate, ammonium carbonate, sodium borate, potassium borate, ammonium borate, sodium phosphate, potassium phosphate, ammonium phosphate, sodium acetate, potassium acetate, ammonium acetate, sodium citrate, potassium citrate, Ammonium citrate, sodium succinate, potassium succinate, ammonium succinate and the like.

The bleaching agent used in the bleach-fixing solution used in the present invention is a bleaching agent used in the bleaching solution, the fixing solution is a fixing agent used in the fixing solution, and the buffering agent is the bleaching solution and the fixing agent. Buffer used in liquid.

Further, additives for promoting bleach-fixing are used. Regarding these additives, see JP-B-45-8506.
No., JP-B-45-8836, JP-A-46-280, JP-B-46-556
No., JP-A-49-42349, JP-B-53-9854, JP-A-54-71
No. 634, Belgian Patent No. 770910 and the like.

The water washing treatment in the present invention is carried out by water washing or a stabilizing treatment instead. In the case of stabilizing treatment instead of washing with water, the pH of the stabilizing solution to be used is 5 to 8, and the buffer which can be contained in the stabilizing solution is any one of generally known alkali agents or acid agents. Can also be used.

Next, specific reaction examples of the composition of the present invention will be described. (1) 219 g of polyethylene imine (molecular weight: about 800)
200 ml of water was added to the mixture, and under stirring, 48% aqueous 35% hydrogen peroxide was added.
Add 5 g, keep at 60 ° C. or lower, return to room temperature, and make up to 1 liter with water.

(2) Polyethyleneimine (molecular weight of about 15
00) 200 g of water was added to 217 g, and 485 g of 35% hydrogen peroxide solution was added with stirring, the temperature was kept at 60 ° C. or lower, the temperature was returned to room temperature, and the whole amount was made up to 1 l with water.

(3) Polyethyleneimine (molecular weight of about 15
000) 215 g, water 200 ml and 35%
485 g of aqueous hydrogen peroxide is added, the temperature is kept at 60 ° C. or lower, the temperature is returned to room temperature, and the total volume is adjusted to 1 l with water.

The reaction product thus produced can be used as it is as a composition for a color developer.
This is an exciting breakthrough.

As described above, according to the present invention, the color developer obtained by using the reaction product of polyethyleneimine and aqueous hydrogen peroxide as it is as a composition of a color developer maintains preservation and maintains the color density. No deterioration in photographic performance such as generation of fog and less odor, no harmful substances,
A method for processing a silver halide color photographic material using this color developing solution could be provided.

Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto. [Example 1] Using a commercially available color paper, after image exposure,
The treatment was performed using the treatment steps and treatment liquids shown in Table 1.

[Table 1]

Color developing solution (A) Diethylenetriaminepentaacetic acid 2.0 g Sodium chloride 1.4 g Potassium carbonate (anhydrous) 25.0 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-amino Aniline sulfate 5.0 g Sodium sulfite (anhydrous) 0.5 g Fluorescent brightener (4,4'-diaminostilbene) 2.0 g Diethylhydroxylamine 2.7 g Water was added to 1.0 l pH (potassium hydroxide Use) 10.05

Color development replenisher (A) Diethylenetriaminepentaacetic acid 2.0 g Potassium carbonate (anhydrous) 25.0 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 7 1.0 g Sodium sulfite 0.7 g Optical brightener (4,4'-diaminostilbene type) 2.3 g Diethylhydroxylamine 4.0 g Water was added 1.0 l pH (using potassium hydroxide) 10.45

Color developing replenisher (B) Diethylenetriaminepentaacetic acid 2.0 g Potassium carbonate (anhydrous) 25.0 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 9 0.0g Sodium sulfite (anhydrous) 0.7g Fluorescent whitening agent (4,4'-diaminostilbene) 2.5g Diethylhydroxylamine 5.4g Water was added 1.0l pH (using potassium hydroxide) 10.65

Color developing solution (C) See Table 2 below for the amount of the reaction product used in the present invention. Diethylenetriaminepentaacetic acid 2.0 g Sodium chloride 1.4 g Potassium carbonate (anhydrous) 25.0 g Sodium sulfite (anhydrous) 0.5 g N -Ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0 g Fluorescent brightener (4,4′-diaminostilbene) 2.0 g 0 l pH (using potassium hydroxide) 10.05

Color developing replenisher (C) See Table 2 below for the amount of the reaction product of the present invention. Diethylenetriaminepentaacetic acid 2.0 g Potassium carbonate (anhydrous) 25.0 g Sodium sulfite (anhydrous) 0.7 g N-ethyl-N -(Β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 9.0 g Fluorescent whitening agent (4,4′-diaminostilbene) 2.5 g Water was added to 1.0 l pH (water 10.65 (using potassium oxide)

Bleaching / fixing solution (A) Ammonium thiosulfate 70.0 g Sodium sulfite (anhydrous) 17.0 g Iron (III) ammonium ethylenediaminetetraacetate 55.0 g Disodium ethylenediaminetetraacetate 5.0 g Water was added to 1.0 l pH ( Using acetic acid) 6.0

Color developing solution (C), color developing replenisher (C)
Table 2 shows the amounts of the reaction products of the present invention used in the above.

[Table 2] The values in parentheses in the table indicate the amounts used in the color developing replenisher.

[0063] hit the handle, the color developer in an automatic developing machine (A) and bleach-fixing solution using (A), supplemented color developer replenisher of the photosensitive material 1 m ² per 160ml of (A), also the photosensitive material 1 m ² 80 ml of color developing replenisher (B) per replenisher,
The replenishment of the bleach-fixing solution is performed by adding the bleach-fixing solution (A) to 1 m ² of the photosensitive material.
Refill 220 ml per serving. The color developing solution (C) of the present invention is replenished with 80 ml of the color developing replenisher (C) per m ² of the light-sensitive material, and the bleach-fixing solution is the same as described above.

One day, 15 m ² of color paper is treated and
150 m ² was treated in 0 days. At this time, the state at the start and end of the processing is measured using a commercially available control strip, and the minimum density change (ΔDmin), sensitivity point change (ΔLD), and contrast change (ΔHD-LD) are determined. saw. The measurement was performed using a reflection densitometer (X-RITE310).
And the results are as shown in Tables 3 and 4.

[Table 3]

[Table 4] In the table, the upper row shows the blue light density, the middle row shows the green light density, and the lower row shows the red light density.

As can be seen from the above results, no problem occurs when the color paper is continuously processed while replenishing the color developing replenisher in a large amount. (Experiment No. 1) However, when the replenishment amount of the color developing replenisher is small, various problems such as an increase in minimum density, a decrease in sensitivity, and a decrease in contrast have occurred. (Experiment No. 2)

However, in the processing method using the color developing solution of the present invention, it can be seen that stable processing can be performed without any problem even if the replenishing amount of the color developing replenisher is small during continuous processing. (Experiments No. 3 to No. 6)

On the other hand, JP-B-63-18733 describes that poly (alkyleneimine) is effective as an antioxidant in a color developing solution.
Was added to the color developing solution as it was, and it was found that the effect of the color developing solution as an antioxidant was not recognized. (Experiment Nos. 7 to 9)

That is, when processing is carried out using the color developing composition of the present invention, the preservation of the color developing solution is maintained, the color developing density is not reduced, and the halogenation is carried out without fogging. The silver color photographic light-sensitive material can be processed, and since the color developing composition has very little odor, it can be used in a good use environment.

Example 2 Using a commercially available color paper, after image exposure, processing was performed using the processing steps and processing solutions shown in Table 5.

[Table 5]

Color developer (D) See Tables 6 and 7 below for the amount of the reaction product used in the present invention. Diethylenetriaminepentaacetic acid 2.0 g Sodium chloride 1.4 g Potassium carbonate (anhydrous) 25.0 g Sodium sulfite (anhydrous) 5 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0 g Optical brightener (4,4′-diaminostilbene) 2.0 g Water is added. 1.0 l pH (using potassium hydroxide) 10.05

Color developing replenisher (D) See Tables 6 and 7 for the amount of the reaction product of the present invention. Diethylenetriaminepentaacetic acid 2.0 g Potassium carbonate (anhydrous) 25.0 g Sodium sulfite (anhydrous) 0.7 g N-ethyl -N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 7.0 g Fluorescent brightener (4,4′-diaminostilbene) 2.5 g Add water 1.0 l pH (Using potassium hydroxide) 10.45

Stabilizer (A) 2-Aminobenzothiazole 0.1 g 1-Hydroxyalkylidene-1,1-diphosphonic acid 4.0 g Water was added to 1.0 L pH (using sodium hydroxide) 7.0

Color developing solution (D), color developing replenisher (D)
Table 6 and 7 show the amounts of the reaction products of the present invention used in the above.

[Table 6]

[Table 7] The values in parentheses in the table indicate the amounts used in the color developing replenisher.

In processing, the color developing solution (A), the bleach-fixing solution (A) and the stabilizing solution (A) of Example 1 were used in an automatic developing machine, and 160 ml of the color developing solution (A) per m ^{2 of} the light-sensitive material was used. The replenishment of the bleach-fix solution is carried out by replenishing 220 ml of the bleach-fix solution (A) per 1 m ² of the light-sensitive material. For replenishment of the stabilizer, the stabilizer (A) was used at a rate of 250 m / m ²
Replenish. The color developing solution (D) of the present invention is replenished with 160 ml of a color developing replenisher (D) per 1 m ² of the light-sensitive material.

A day, 5 m ² of color paper is treated and 30
150 m ² was processed per day. (Processing amount II) (Example 1)
The processing of the color developing solution (A) is referred to as (processing I). At this time, the state at the start and end of the treatment was measured using a commercially available control strip, and the change in minimum density (△ Dmi
n), a change in sensitivity point (ΔLD) and a change in contrast (ΔHD-LD) were observed. Note that a reflection densitometer (X-RITE310) was used for the measurement, and the results are as shown in Table 8.

[Table 8] In the table, the upper row shows the blue light density, the middle row shows the green light density, and the lower row shows the red light density.

As can be seen from the above results, it can be said that no problem occurs when the color paper is continuously processed and the amount of processing per day is large.
1) When the processing amount is small, various problems such as an increase in minimum density, a decrease in sensitivity, and a decrease in concrust have occurred. (Experiment N
o. 10)

However, in the method using the color developing solution of the present invention, it can be seen that stable processing can be performed without any problem even if the processing amount per day is small during continuous processing. (Experiment Nos. 11 to 14)

That is, when processing is carried out using the color developing composition of the present invention, the preservation of the color developing solution is maintained, the color density is not reduced, and the silver halide is not fogged. The color photographic light-sensitive material can be processed, and furthermore, since the color developing composition has very little odor, it can be used in a good use environment.

Example 3 Using a commercially available color negative film, after image exposure, processing was performed using the processing steps and processing solutions shown in Tables 9 and 10.

[Table 9]

[Table 10]

Color developer (E) Potassium carbonate (anhydrous) 35.0 g Sodium sulfite (anhydrous) 4.0 g Potassium iodide 0.002 g Sodium bromide 1.3 g Hydroxylamine sulfate 2.0 g Diethylenetriaminepentaacetic acid 2.0 g 2-Methyl-4- (N-ethyl-N-β-hydroxyethyl) aminoaniline sulfate 4.5 g Water 1.0 L pH (using potassium hydroxide) 10.00

Color developing replenisher (E) Potassium carbonate (anhydrous) 35.0 g Sodium sulfite (anhydrous) 4.5 g Sodium bromide 0.9 g Hydroxylamine sulfate 3.0 g Diethylenetriaminepentaacetic acid 2.0 g 2-methyl-4 -(N-ethyl-N-β-hydroxyethyl) aminoaniline sulfate 5.0 g Water was added to 1.0 l pH (using potassium hydroxide) 10.00

Color developing solution (F) See Table 11 below for the amount of the reaction product used in the present invention. Potassium carbonate (anhydrous) 35.0 g Sodium sulfite (anhydrous) 4.0 g Potassium iodide 0.002 g Sodium bromide 1.3 g 9. diethylenetriaminepentaacetic acid 2.0 g 2-methyl-4- (N-ethyl-N-β-hydroxyethyl) aminoaniline sulfate 4.5 g Water is added to 1.0 l pH (using potassium hydroxide) 00

Color Developing Replenisher (F) The reaction product of the present invention is shown in Table 11 below. Potassium carbonate (anhydrous) 35.0 g Sodium sulfite (anhydrous) 4.5 g Sodium bromide 0.9 g Diethylenetriaminepentaacetic acid 0 g 2-methyl-4- (N-ethyl-N-β-hydroxyethyl) aminoaniline sulfate 5.0 g Add water 1.0 l pH (using potassium hydroxide) 10.00

Bleaching solution (A) Ammonium iron (III) ethylenediaminetetraacetate 100.0 g Ammonium bromide 150.0 g Glacial acetic acid 13.0 g Water was added to 1.0 l pH (using aqueous ammonia) 6.00

Bleaching replenisher (A) Ammonium iron (III) ethylenediaminetetraacetate 120.0 g Ammonium bromide 170.0 g Glacial acetic acid 15.0 g Water was added to 1.0 l pH (using aqueous ammonia) 5.70

Fixer (A) Ammonium thiosulfate 120.0 g Disodium ethylenediaminetetraacetate 1.0 g Sodium bisulfite 12.0 g Sodium hydroxide 2.5 g Add water 1.0 L pH (using acetic acid) 50

Fixing replenisher (A) Ammonium thiosulfate 140.0 g Disodium ethylenediaminetetraacetate 1.5 g Sodium bisulfite 15.0 g Sodium hydroxide 3.0 g Water was added to 1.0 l pH (using acetic acid) 6 .50

Stabilizing solution (B) Wettor (product of Chugai Photochemical Co., Ltd.) 15.0 ml Formalin (37%) 7.0 ml Add water to 1.0 l

Color developer (F), color developer replenisher (F)
Table 11 shows the amounts of the reaction products used for the reaction.

[Table 11] The values in parentheses in the table indicate the amounts used in the color developing replenisher.

In processing, a color developing solution (E), a bleaching solution (A), a fixing solution (A), and a stabilizing solution (B) are supplied to an automatic processor.
Replenishing 50 ml of color developing replenisher (E) per 36 sheets of 135 film, replenishing bleaching solution, replenishing 30 ml of bleach replenisher (A) per photosensitive material, replenishing fixing solution For replenishment, 50 ml of the fixing replenisher (A) is replenished per photosensitive material, and for replenishment of the stabilizer, 50 ml of the stabilizer (A) is replenished per photosensitive material. The color developing solution (F) of the present invention is replenished with 50 ml of the color developing replenisher (F) per photosensitive material, and the other processing solutions are the same as described above.

Processing 10 color negative films a day
300 were processed in 30 days. At this time, the state at the start and end of processing is measured using a commercially available control strip, and the change in minimum density, (△ Dmin), change in sensitivity point (△ LD), and change in contrast (△ HD-LD) are measured. saw. The measurement was performed using a transmission densitometer (X-RITE310).
And the results are shown in Tables 12 and 13.

[Table 12]

[Table 13] In the table, the upper row shows the blue light density, the middle row shows the green light density, and the lower row shows the red light density.

As can be seen from the above results, the processing method using the color developing solution of the present invention enables stable processing without any problem even when processing color negative films continuously. It turns out that it is. (Experiment N
o. 17-20)

That is, when processing is carried out using the color developing composition of the present invention, the preservation of the color developing solution is maintained, the color developing density is not reduced, and the halogenation is carried out without fogging. The silver color photographic light-sensitive material can be processed, and furthermore, this coloring composition does not use a deleterious substance and can be used in a good use environment.

[0094]

As described above, according to the present invention, in a color development process, polyethyleneimine is reacted with hydrogen peroxide (hydrogen peroxide solution) without separating reaction products.
When a color developing solution containing all of the obtained reaction products is used to continuously process a silver halide color photographic light-sensitive material, the processing can be performed stably and the preservation of the color developing solution can be achieved. Is maintained, the color density is not reduced, and the silver halide color photographic light-sensitive material can be processed in a state where no fogging occurs. Further, since the color developing composition has a low odor and does not use harmful substances, In addition to being able to be used in a good use environment, the reaction product does not require separation and purification, and can be used as it is and is safe, so that efficient materials can be used.

Further, the present invention can be widely applied to various couplers used in silver halide color photographic light-sensitive materials, and can also be applied to various automatic developing machines.

Claims (6)

(57) [Claims] 1. A color developing solution comprising a reaction product obtained by reacting polyethyleneimine with hydrogen peroxide (hydrogen peroxide solution). 2. The color developing solution according to claim 1, wherein the polyethyleneimine has the following formula (Formula 1). Embedded image In the formula, n represents an integer of 5 to 2000. 3. The color developing solution according to claim 1, wherein the polyethyleneimine has a hydroxyl group at a terminal. 4. The color developer according to claim 1, wherein 40 to 800 g of polyethyleneimine is reacted per mole of hydrogen peroxide. 5. Use of the color developing solution according to claim 1, 2, 3 or 4 in a color development process after image exposure of a silver halide color photographic light-sensitive material having any constitution and composition. Characteristic processing method of silver halide color photographic light-sensitive material. 6. Processing of a silver halide color photographic light-sensitive material having any structure and composition using the color developing solution according to claim 1, 2, 3, or 4 using an automatic developing machine having any structure. Method.