JPH06301176A - Color developer and processing method for silver halide color photosensitive material using the same - Google Patents

Abstract

PURPOSE:To maintain the preservation property of a color developer, prevent the deterioration in the photographic performance such as the reduction of a color density and the occurrence of photographic fog, reduce the odor, and contain no deleterious substance by containing a reaction product reacted with polyethyleneimine, formalin, and hydrogen peroxide. CONSTITUTION:A reaction product obtained without being separated when polyethyleneimine, formalin, and hydrogen peroxide are reacted is contained. The polyethyleneimine to be used is expressed by the formula, where (n) indicates an integer of 5-2,000. Any of the generally used aromatic first-grade amine color developing agent may be used as the color developing agent for a color developer. The color developer can contain normally used various constituents, e.g. an alkaline agent such as potassium hydroxide, sodium hydroxide, potassium carbonate, and sodium phosphate, an sulfite such as sodium sulfite and potassium sulfite, and a halide such as hydrogensulfite, and a development accelerator.

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 Color photographic light-sensitive materials are processed by exposing the light-sensitive material to image development, and then performing color development processing, silver bleaching processing, silver halide fixing processing, bleach-fixing processing in which bleaching processing and fixing processing are performed simultaneously, washing processing, and water washing. Rinsing treatment, stabilizing treatment, and drying treatment, which are alternatives to the treatment, are the basic treatments, and are added for use in the processing liquid, for increasing the physical strength of the processed light-sensitive material, and for increasing the stability. There is a processing step.

The processing of the silver halide color photographic light-sensitive material which is widely used at present is a method for obtaining a color print from a color negative film, and there is also a method for obtaining a positive color film and a print for directly obtaining a final image. The processing step 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.

Further, since the user of color printing desires to see the print as soon as possible, he / she wants to be able to print in a short time, and in order to cope with this, speeding up the processing is required.

In recent years, rapid processing of silver halide color photographic light-sensitive materials has become possible by improving light-sensitive materials. Further, in processing, a large amount of processing can be easily carried out by an automatic developing machine, and due to the development of the automatic developing machine, it becomes smaller and cheaper and many machines are used.

An aromatic primary amine type color developing agent such as para-phenylenediamine is used as a color developing solution used for processing a silver halide color photographic light-sensitive material. As a preservative for preventing air oxidation of the color developing agent, sulfite and hydroxylamine, as an alkali agent for keeping the color developer alkaline, alkali metal salts such as carbonic acid and phosphoric acid, and alkali hydroxide. , Inhibitors, water softeners, and other additives as needed.

[0007]

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

Therefore, when only sulfite, which is the same preservative, is used, the stability of the color developing solution can be maintained to some extent, but fog is generated in the color developing solution which has undergone processing and time has passed, Cannot be used.

Under these circumstances, the use of N, N-diethylhydroxylamine has become commonplace in place 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 general stores called a so-called minilab,
This odor is not preferable from the viewpoint of the environment or the processing work, and it is desirable to remove it.

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

On the other hand, in these photographic processings, an automatic developing machine is used in order to process a large amount of photographs quickly and easily, while replenishing a necessary processing solution as a replenisher while processing a photographic material. Processing is performed.

Since this replenisher is prepared in fixed amounts,
It takes a certain amount of time before it is used up, so the condition of the replenisher solution will differ from the beginning when a certain amount of time has passed, but when this happens, the quality of the processed photos will change. The stability of this replenisher should be kept good as it will occur.

The processing solution used in the automatic processor is
The amount corresponding to the constantly replenished amount is discharged,
During this time, there is a certain period of time, and stability within this period of time is also required.

A photograph processor requested by the photographer to meet the demand in a short period of time needs to perform the treatment promptly, and in particular, needs to accelerate the treating agent. For rapid color development, the color developer is a highly active processing solution. In such a case, the treatment liquid is severely deteriorated, and when it is used for a long period of time, the composition content is changed, the developing activity is lowered, the image quality is changed, and the entire paper is stained, which is not satisfactory.

Possible causes for these are deterioration of the color developing agent and preservative used, a decrease in alkalinity, and accumulation of substances eluted from the processed light-sensitive material.

Further, when processing is carried out using an automatic processor, a waste liquid is generated corresponding to the processing amount of the light-sensitive material, but the amount of the waste liquid is reduced, that is, replenishment is considered in consideration of resource saving and environmental influence of waste. The amount will be reduced, but if the amount of replenishment is reduced, it will take time until the prepared replenisher is used, and the time of staying in the automatic developing machine will be longer, depending on the time. The deterioration of the processing liquid will proceed.

Therefore, the inventors of the present invention process the silver halide color photographic light-sensitive material, which is a non-deleterious substance with little odor, in which the color developing solution is kept stable, the color density is not lowered, and the fog is not generated. As a result of examining 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,
The present invention has been achieved.

Therefore, the object of the present invention is to maintain the stability of the color developing solution, to prevent the deterioration of photographic performance such as a decrease in color density and the occurrence of fog, and to produce a odorless and deleterious coloring. The present invention provides a developing solution and a method for processing a silver halide color photographic light-sensitive material using the same.

[0020]

According to the present invention, when a silver halide color photographic light-sensitive material is processed, the preservability of a color developer is maintained, the color density is lowered, and fog is generated. In a processing solution for a silver halide color photographic light-sensitive material using the same, a developing solution containing no deleterious substance, which does not deteriorate and has little odor,

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

(2) A silver halide color photographic light-sensitive material having any constitution and composition is imagewise exposed and then the color developing solution described in the above (1) is used in the color development processing. A method of processing a silver halide color photographic light-sensitive material.

(3) A silver halide color photographic light-sensitive material having any constitution and composition using the color developer shown in the above (1) using an automatic processor having any constitution and composition. Processing method. Was achieved by processing a silver halide color photographic light-sensitive material.

[0024]

EXAMPLES Regarding the reaction product of the present invention, generally, a compound newly obtained by the reaction of the compound is separated from the reaction system. Other compounds that are produced in the reaction system,
Compounds that have not been used in the reaction remain, and if they are contained, the target compound cannot exhibit its original properties, and the drawbacks of compounds other than the target compound will appear.

Also, from the viewpoint of storage stability, it is generally necessary to sufficiently raise the purity of the target compound, so that separation and purification are carried out, and many materials are required at this point as well. It is very inefficient.

However, the reaction product of the present invention is characterized by using the compound produced by the reaction and all the compounds in the reaction system and being stable without separation and purification, and is very efficient. It is characterized by obtaining a reaction product with good quality.

Many types of silver halide color photographic light-sensitive materials are commercially available today, and depending on the purpose, there are color negative films, color reversal films, and color print materials for negative positive and positive positive. Uses color negative film and negative positive print materials. There are many kinds of these silver halide color photographic light-sensitive materials, each of which has a different layer structure and has respective characteristics.

Further, the composition of the silver halide constituting this layer is also very ambiguous, and there are differences in the amounts of silver chloride, silver bromide and silver iodide used, differences in the composition ratio, and the grains of these silver halides. There are various characteristics such as size and particle size and shape.

Further, various different additives such as sensitizing dyes, stabilizers, sensitizers and inhibitors are used. The particle size is described on pages 277 to 278, etc. of "Basics of Photographic Industries-Silver Salt Photographs" (edited by The Photographic Society of Japan, Corona Publishing Co., Ltd.).

Further, although various couplers are used in the silver halide color photographic light-sensitive material, a great many substances are also used in this regard. The silver halide color photographic light-sensitive material having any constitution and composition used in the claims of the present invention means such a thing.

When processing a silver halide color photographic light-sensitive material, an automatic developing machine is generally used, and the automatic developing machine replenishes a type, a processing speed, a processing temperature, a processing step and a replenisher. There are various types of methods, handling of overflow liquid, etc., and each has its own characteristics. The automatic developing machine having any constitution used in the claims of the present invention means such a thing.

The color developing solution of the present invention is an invention concerning the performance of the color developing solution itself, which is not affected by the above-mentioned various conditions.

The polyethyleneimine used in the present invention consists of repeating ethylene chain units linked to each other via nitrogen atoms. This is a well known and commercially available material.

As the color developing agent used in the color developing solution of the present invention, any of the commonly used aromatic primary amine type color developing agents can be used. Preferred color developing agents used in the present invention are, for example, Journal of American Chemical Society (J. Am. Chem.
Soc.,) 73 .3100 (1951 ) and Heist (Haist), modern photographic processing (Modern Photographic Processing) .1979.
John Wiley and S
ons). New York. Pp. 545 et seq.

Various components usually used in the color developer used in the present invention, for example, alkaline agents such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium phosphate, sodium phosphate, and sulfurous acid. Sodium, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metabisulfite, sulfites such as potassium metabisulfite, bisulfite, metabisulfite, potassium chloride, sodium chloride, potassium bromide, sodium bromide, A halogen compound such as potassium iodide or sodium iodide, a water softener such as aminopolycarboxylic acid, polystyrene sulfonic acid, or polyphosphonic acid, a thickening agent such as ethylene glycol, diethylene glycol, diethanolamine or triethanolamine, and a development accelerator are contained. Can That.

Further, as additives, nitrobenzimidazole, mercaptobenzimidazole, 5-methyl-
A compound of benzotriazole, 1-phenyl-5-mercaptotetrazole, an antistain agent, an antisludge agent, etc. are used.

The color developing solution of the present invention is preferably used at a pH of 9,5 or higher. Generally, by raising the pH to some extent, rapid processing is possible. It causes pollution.

In the color developing solution and the processing method of the present invention, the stability of the color developing solution over time is maintained, the color density is not lowered, and the fog is not generated. It can be treated with a non-native composition.

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

Specific examples of these 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, ethylenediaminetetrapropynoic acid, phenylenediaminetetraacetic acid, and the like Are alkali metal salts, ammonium salts, and water-soluble amine salts.

As the halogenating agent, hydrohalic acid and an alkali metal salt or ammonium salt of halogen are generally used. Specific examples thereof include hydrochloric acid, hydrobromic acid, sodium chloride and potassium chloride. , Ammonium chloride, sodium bromide, potassium bromide, ammonium bromide and the like.

As the buffer, an inorganic weak acid or organic acid and an alkaline agent are used in combination. The inorganic weak acids include carbonic acid, boric acid, phosphoric acid, and the organic acids include acetic acid, citric acid, succinic acid, and the like.
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, Examples thereof include ammonium citrate, sodium succinate, potassium succinate, ammonium succinate and the like.

In addition, additives for bleaching acceleration are used. Regarding these additives, JP-A-54-35727,
JP-A-55-25064, JP-A-60-12549, JP-A-60-76745
JP-A-60-95540, JP-A-60-125843, JP-A-60-
221754, JP60-230140, JP60-244950, JP61-50149, JP61-118752, JP62-80649
JP-A-62-89963, JP-A-62-131260, JP-A-62-
135835, JP 62-166344, JP 62-166345, JP 62-166346, JP 62-166347, JP 62-16634
No. 8, JP-A-62-168159, JP-A-63-8741, JP-A-63-
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-A1-170943
No. 1, JP-A 1-211757, JP-A 1-213650, JP-A 1-22
595, JP 1-245256, JP 2-44349, JP 2-
No. 93454, JP-A No. 2-103041, 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. Specific examples thereof include thiosulfate. Sodium, potassium thiosulfate, ammonium thiosulfate, sodium thiocyanate, potassium thiocyanate, ammonium thiocyanate, etc.
Compounds such as thiourea and thioether.

Examples of the preservative include sulfite, bisulfite, metabisulfite and the like, and specific examples thereof include sodium sulfite, potassium sulfite, ammonium sulfite, sodium bisulfite, potassium bisulfite, ammonium bisulfite and meta. Examples include sodium bisulfite and potassium metabisulfite.

As the buffer agent, a weak inorganic or organic acid and an alkaline agent are used in combination. The inorganic weak acids include carbonic acid, boric acid, phosphoric acid, and the organic acids include acetic acid, citric acid, succinic acid, and the like.
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, Examples thereof include 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 the bleaching agent used in the bleaching solution, the fixing agent is the fixing agent used in the fixing solution, and the buffering agent is the bleaching solution and the fixing agent. It is a buffer used in liquid.

In addition, additives are used to accelerate bleach-fixing. For these additives, see Japanese Patent Publication No.
No. 4, JP-B-45-8836, JP-A-46-280, JP-B-46-556
JP-A-49-42349, JP-B-53-9854, JP-A-54-71
No. 634, Belgian Patent No. 770910, etc.

The washing treatment in the present invention is carried out by washing treatment or a stabilizing treatment in place of it. 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 buffering agent that can be contained in the stabilizing solution is any of commonly 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) Polyethyleneimine (average molecular weight 10,000)
400 ml of water was added to 100 g, and formalin 20 was added with stirring.
g and stirred at 50 ° C. for 5 minutes, then 40 g of 35% hydrogen peroxide solution was added, and the mixture was heated with stirring at 60 ° C. for 1 hour.
Bring to room temperature and make up to 1 liter with water.

(2) 400 ml of water was added to 100 g of polyethyleneimine (average molecular weight 1,800), 10 g of formalin was added with stirring and the mixture was stirred at 50 ° C. for 5 minutes, and then 40 g of 35% hydrogen peroxide solution was added to 50 ° C. After heating and stirring for 1 hour, the temperature is returned to room temperature and the total amount is made up to 1 liter with water.

(3) Polyethyleneimine (average molecular weight 6
000) 400 g of water was added to 100 g of the mixture, 30 g of formalin was added to the mixture with stirring, and the mixture was stirred at 50 ° C. for 5 minutes, then 50 g of 35% hydrogen peroxide solution was added, and the mixture was heated with stirring at 70 ° C. for 2 hours and then returned to room temperature. To make 1 liter with water.

(4) Polyethyleneimine (average molecular weight 6
00) 400 g of water was added to 100 g of the mixture, 30 g of formalin was added thereto with stirring, and the mixture was stirred at 50 ° C. for 5 minutes, and then 35%.
After adding 10 g of hydrogen peroxide water and heating and stirring at 60 ° C. for 1 hour, the temperature is returned to room temperature and the total amount is made up to 1 liter with water.

(5) Polyethyleneimine (average molecular weight 1
20,000) 400 g of water was added to 100 g of the solution with stirring, 10 g of formalin was added, and the mixture was stirred at 50 ° C. for 5 minutes, and then 10 g of 35% hydrogen peroxide solution was added, and the mixture was heated with stirring at 70 ° C. for 1.5 hours and then at room temperature. And make up to 1 liter with water.

(6) Polyethyleneimine (average molecular weight 1
20,000) 100 g, and 400 ml of water added to the mixture under stirring for 3
40 g of 5% hydrogen peroxide solution was added, and the mixture was heated with stirring at 60 ° C. for 1 hour, then 10 g of formalin was added and further heated at 50 ° C. for 1 hour.
After stirring for 0 minutes, the temperature is returned to room temperature and the total amount is made up to 1 liter with water.

The reaction product thus prepared can be used as it is as a composition of a color developing agent,
This is an unprecedented breakthrough.

As described above, according to the present invention, the color developing solution obtained by using the reaction product of polyethyleneimine, formalin and hydrogen peroxide solution as it is as a composition of the color developing agent maintains the preserving property and develops the color. It was possible to provide a method of processing a silver halide color photographic light-sensitive material using a color developing solution that does not deteriorate the photographic performance such as a decrease in density and fog, and does not contain a deleterious substance having a small odor.

Hereinafter, the present invention will be described in detail 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 steps and treatment solutions shown in Table 1 were used.

[Table 1]

Color developer (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 Optical brightener (4,4'-diaminostilbene type) 2.0 g Diethylhydroxylamine 2.7 g Water was added to 1.0 l pH (potassium hydroxide Use) 10.05

Color developing replenisher (A) Diethylenetriaminepentaacetic acid 2.0 g Potassium carbonate (anhydrous) 25.0 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 7 0.0 g sodium sulfite 0.7 g optical brightener (4,4′-diaminostilbene type) 2.3 g diethylhydroxylamine 4.0 g water added 1.0 l pH (using potassium hydroxide) 10.45

Color development 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 Optical brightener (4,4'-diaminostilbene type) 2.5g Diethylhydroxylamine 5.4g Water was added to 1.0l pH (using potassium hydroxide) 10.65

Color developer (C) Reaction product of the present invention: See Tables 2 and 3 below for usage amount Diethylenetriaminepentaacetic acid 2.0 g Sodium chloride 1.4 g Potassium carbonate (anhydrous) 25.0 g Sodium sulfite (anhydrous) 0 0.5 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0 g Optical brightener (4,4′-diaminostilbene type) 2.0 g Water was added. 1.0 l pH (using potassium hydroxide) 10.05

Color development replenisher (C) Reaction product of the present invention For the amount used, see Tables 2 and 3 below. Ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 9.0 g Optical brightener (4,4′-diaminostilbene type) 2.5 g Water was added to 1.0 l pH (using potassium hydroxide) 10.65

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

Color developer (C), color developer replenisher (C)
The amounts of the reaction products of the present invention used in Table 2 are shown in Tables 2 and 3.

[Table 2]

[Table 3]

[0066] 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 Replenish 80 ml of color developing replenisher (B),
To replenish the bleach-fixing solution, use the bleach-fixing solution (A) for the photosensitive material 1 m ²
Replenish 220 ml each. The color developing solution (C) of the present invention is supplemented with 80 ml of the color developing replenishing solution (C) per 1 m ² of the light-sensitive material, and the bleach-fixing solution is the same as above.

Color paper 15m ² processing per day, 1
150 m ² was processed in 0 days. At this time, the state at the start and end of the treatment is measured by a commercially available control strip, and the change in the minimum density (ΔDmin), the change in the sensitivity point (ΔLD), and the change in the contrast (ΔHD-LD) are measured. saw. For the measurement, a reflection type densitometer (X-RITE310)
Was used and the results are shown in Tables 4 and 5.

[Table 4]

[Table 5] In the table, the upper row shows blue light density, the middle row shows green light density, and the lower row shows red light density.

As can be seen from the above results, no problems occur when color paper is continuously processed while a large amount of color developing replenisher is replenished. (Experiment No. 1) However, when the replenishing 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 occur. (Experiment No. 2)

However, in the processing method using the color developing solution of the present invention, it can be seen that during continuous processing, stable processing can be performed without any problem even if the replenishing amount of the color developing replenishing solution is small. (Experiment No. 8 to No. 12)

On the other hand, Japanese Patent Publication No. Sho 63-18733 describes that poly (alkyleneimine) is effective as an antioxidant for a color developing solution.
It was found that the effect of preventing the oxidation of the color developing solution and suppressing the fluctuation of the characteristics during continuous processing is not recognized when the above is added to the color developing solution as it is. (Experiment No. 3 to No.
4)

It was also found that the reaction product of polyethyleneimine and aqueous hydrogen peroxide causes a minimum increase in concentration during continuous treatment, although no fluctuations in sensitivity and contrast are observed. (Experiment No. 5 to No. 7)

That is, when the processing is carried out using the color developing composition of the present invention, the preserving property of the color developing solution is maintained, the color density is not lowered and the fog is not generated. A silver color photographic light-sensitive material can be processed, and since this color developing composition has very little odor, it can be used in a favorable environment.

Example 2 Commercially available color paper was used, and after imagewise exposure, the treatment steps shown in Table 6 and the treatment solutions were used.

[Table 6]

Color developer (D) Reaction product of the present invention For the usage amount, see Tables 7 and 8 below: 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 type) 2.0 g Water was added. 1.0 l pH (using potassium hydroxide) 10.05

Color development replenisher (D) Reaction product of the present invention For the amount used, see Tables 7 and 8 below 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 Optical brightener (4,4'-diaminostilbene type) 2.5 g Water was added to 1.0 l pH 10.45 (using potassium hydroxide)

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 developer (D), color developer replenisher (D)
The amounts of the reaction products of the present invention used in Table 1 are shown in Tables 7 and 8.

[Table 7]

[Table 8]

Upon 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 1 m ^{2 of} the light-sensitive material was used. ), And the bleach-fixing solution is replenished with 220 ml of the bleach-fixing solution (A) per 1 m ² of the light-sensitive material. Stabilizer (A) is added 250m per 1m ² of photosensitive material.
l Replenish. The color developer (D) of the present invention is supplemented with 160 ml of the color developer replenisher (D) per 1 m ² of the light-sensitive material.

Color paper is treated with 5 m ² per day for 30
150 m ² was processed per day. (Processing amount II) (Example 1)
The processing of the color developer (A) is referred to as (Processing I). ) At this time, the state at the start and end of the treatment was measured with a commercially available control strip, and the change in the minimum concentration (ΔDmi
n), change in sensitivity point (ΔLD), and change in contrast (ΔHD-LD) were observed. A reflection type densitometer (X-RITE310) was used for the measurement, and the results are shown in Table 9.

[Table 9] In the table, the upper row shows blue light density, the middle row shows green light density, and the lower row shows red light density.

As can be seen from the above results, when the color paper is processed continuously, no problem occurs when the amount of processing per day is large (Experiment No.
1) When the amount of treatment is small, various problems such as an increase in minimum density, a decrease in sensitivity, and a decrease in contrast occur. (Experiment N
o. 13)

However, in the method of using the color developing solution of the present invention, it can be seen that during continuous processing, stable processing can be carried out without causing any problems even if the processing amount per day is small. (Experiment No. 14-17)

That is, when the processing is carried out using the color developing composition of the present invention, the preservability of the color developing solution is maintained, the color density is not lowered, and the fog is not generated. A color photographic light-sensitive material can be processed, and since this color developing composition has very little odor, it can be used in a favorable environment.

Example 3 A commercially available color negative film was used, and after imagewise exposure, the treatment steps and treatment solutions shown in Table 10 were applied.

[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 was added to 1.0 l pH (using potassium hydroxide) 10.00

Color development 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- [beta] -hydroxyethyl) aminoaniline sulfate 5.0 g Water was added to 1.0 l pH (using potassium hydroxide) 10.00

Color developer (F) Reaction product of the present invention For the usage amount, see Table 11 below. Potassium carbonate (anhydrous) 35.0 g Sodium sulfite (anhydrous) 4.0 g Potassium iodide 0.002 g Sodium bromide 1.3 g Diethylenetriaminepentaacetic acid 2.0 g 2-Methyl-4- (N-ethyl-N-β-hydroxyethyl) aminoaniline sulfate 4.5 g Water was added to 1.0 l pH (using potassium hydroxide) 10. 00

Color development replenisher (F) Reaction product of the present invention Refer to the following Table 11 for usage amount Potassium carbonate (anhydrous) 35.0 g Sodium sulfite (anhydrous) 4.5 g Sodium bromide 0.9 g Diethylenetriaminepentaacetic acid 2. 0 g 2-Methyl-4- (N-ethyl-N-β-hydroxyethyl) aminoaniline sulphate 5.0 g Water added 1.0 l pH (using potassium hydroxide) 10.00

Bleach (A) Ethylenediaminetetraacetic acid iron (III) ammonium 100.0 g Ammonium bromide 150.0 g Glacial acetic acid 13.0 g Water was added to 1.0 l pH (using ammonia water) 6.00

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

Fixer (A) Ammonium thiosulfate 120.0 g Disodium ethylenediaminetetraacetate 1.0 g Sodium bisulfite 12.0 g Sodium hydroxide 2.5 g Water was added to 1.0 l pH (using acetic acid) 6. Fifty

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

Stabilizer (B) Wetitol (product of Chugai Photo Chemicals Co., Ltd.) 15.0 ml Formalin (37%) 7.0 ml Water was added to 1.0 l

Color developing solution (F), color developing replenishing solution (F)
Table 11 shows the amount of the reaction product used for.

[Table 11]

Upon processing, a color developing solution (E), a bleaching solution (A), a fixing solution (A) and a stabilizing solution (A) were applied to an automatic processor.
50 ml of color development replenisher (E) is replenished for each of the 35 light-sensitive materials and 135 films taken. For replenishment of the bleaching solution, the bleaching replenisher (A) is replenished with 30 ml per one light-sensitive material, For replenishment, the fixing replenisher (A) is replenished by 50 ml per the same light-sensitive material, and the stabilizing solution is replenished by 50 ml per the light-sensitive material. The color developing solution (F) of the present invention is replenished with 50 ml of the color developing replenishing solution (F) per the same light-sensitive material, and other processing solutions are the same as above.

Processing 10 color negative films a day,
300 lines were processed in 30 days. At this time, the state at the start and end of the treatment was measured with a commercially available control strip, and the change in the minimum density (ΔDmin), the change in the sensitivity point (ΔLD), and the change in the contrast (ΔHD-LD) saw. A transmission densitometer (X-RITE310) is used for the measurement.
Was used and the results are shown in Table 12.

[Table 12] In the table, the upper row shows blue light density, the middle row shows green light density, and the lower row shows 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 problems even when the color negative film is continuously processed. It turns out that (Experiment N
o. 19-21)

That is, when the processing is carried out using the color developing composition of the present invention, the preservability of the color developing solution is maintained, the color density is not lowered, and the fog is not generated. The silver color photographic light-sensitive material can be processed, and further, this coloring composition does not use deleterious substances and can be used in a favorable environment.

[0098]

As described above, according to the present invention, in the color development processing, polyethyleneimine is reacted with forimarin and hydrogen peroxide (hydrogen peroxide solution) to obtain a reaction product without separation. When a silver halide color photographic light-sensitive material is continuously processed using a color developer containing all reaction products, stable processing can be performed,
It is possible to process a silver halide color photographic light-sensitive material in a state in which the color developing solution is maintained stable, the color density is not reduced, and fog is not generated, and the color developing composition has less odor. Since it does not use deleterious substances, it can be used in a good environment, so the reaction product does not need to be separated and purified, and can be used as it is, and it is safe and has great advantages in use. .

Claims (7)

[Claims] 1. A color developing solution containing a reaction product obtained by reacting polyethyleneimine with formalin and hydrogen peroxide (hydrogen peroxide solution). 2. The color developer according to claim 1, wherein the polyethyleneimine has the following formula (Formula 1). [Chemical 1] In the formula, n represents an integer of 5 to 2000. 3. The color developer according to claim 1, wherein the polyethyleneimine has a hydroxyl group at the terminal. 4. The color developer according to claim 1, wherein 20 to 800 g of polyethyleneimine is reacted with 1 mol of hydrogen peroxide. 5. 40 to 40 per mol of formaldehyde
The color developer according to claim 1, wherein 100 g of polyethyleneimine is reacted. 6. The color developing solution according to claim 1, 2, 3, 4 or 5 is used in the process of color development after image exposure of a silver halide color photographic light-sensitive material having any constitution and composition. A method of processing a silver halide color photographic light-sensitive material, comprising: 7. A silver halide color photographic light-sensitive material having any constitution and composition using the color developing solution according to claim 1, 2, 3, 4, or 5 using an automatic processor having any constitution. Processing method.