JPH10333303A - Color developer for silver halide color photographic sensitive material and treatment using that - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a color developer liquid which maintains preservability and does not cause deterioration in photographic performances such as decrease in the color developing density and production of fog, and which hardly produces odor or does not contain acutely toxic substances by incorporating N,N-bis(3- alkoxy-2-hydroxypropyl)hydroxylamine into a color developer liquid. SOLUTION: In the treatment of a silver halide color photographic sensitive material, N,N-bis(3-alkoxy-2-hydroxypropyl)hydroxylamine is incorporated into a color developer liquid. The color developer liquid may contain an alkali agent such as potassium hydroxide, sodium hydroxide, potassium carbonate and sodium phosphate, sulfites such as sodium sulfite and sodium metabisulfite, bisulfites, metabisulfites, halogen compd. such as potassium chloride, water softening agent such as aminopolycarboxylic acid and polyphosphonic acid, thickening agent such as diethyleneglycol, diethanolamine and triethanolamine, and development accelerating agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color developing solution for a silver halide color photographic light-sensitive material and a processing method using the same. In particular, the present invention relates to a color developing solution which can be stably processed even during continuous color developing. And a method for processing a silver halide color photographic light-sensitive material using the same.

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

In recent years, processing of silver halide color photographic light-sensitive materials has been made possible by rapid improvement of 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-based 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.

[0005]

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. Therefore, when only the same preservative, sulfite, is used, the stability of the color developing solution can be maintained to some extent, but the color developing solution, which has been processed for a long time, may cause fogging and must be used. Can not.

[0006] Under these circumstances, the use of N, N-diethylhydroxylamine instead of hydroxylamine has become common. 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 the treatment is performed in a part of a general store called a so-called mini lab, the odor is reduced from the environmental point of view and the treatment. It is not desirable for work, but it is desirable to be removed. 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 developing machine is used to easily process a large number of photographs quickly and easily. 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, a certain period of time elapses until it is completely used, so the state of the replenisher differs from the initial period and the state after a certain period of time. When things happen,
The stability of this replenisher must be good as the quality of the processed pictures changes. In addition, the processing solution used in the automatic processor is discharged in an amount corresponding to the amount of replenisher that is constantly replenished, but during this time there is still a certain period of time, and stability within this period is also required. It is.

[0008] A photographic processing company requested by a photographer to perform processing needs to perform the processing promptly in order to meet the request in a short time, and in particular, it is required to speed up the process of the 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 of these 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.

To solve these problems, Japanese Patent Application Laid-Open No.
No. 52, JP-A-3-63646, U.S. Pat. No. 5,508,155, International Patent Application WO 96 /
No. 28761 proposes various hydroxylamine derivatives. However, these compounds have been improved in terms of odor and treatment liquid stability, but are not sufficiently satisfactory.

Therefore, the inventors of the present invention process a silver halide color photographic light-sensitive material which maintains the preservation of the color developing solution, does not lower the color density, and has no fouling and a low odor. 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,
The object of the present invention is to maintain the preservation of the color developing solution, to prevent deterioration in photographic performance such as reduction in color density and generation of fog, and to have a low odor, And a method for processing a silver halide color photographic light-sensitive material using the same.

[0012]

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. (1) N, N-bis (3-alkoxy-2-) A color developing solution comprising (hydroxypropyl) hydroxylamine. (2) In the processing of color development after image exposure of the silver halide color photographic light-sensitive material, it is achieved by processing the silver halide color photographic light-sensitive material, wherein the color developing solution according to claim 1 is used. Was.

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The embodiments of the present invention will be described below in detail. As the color developing agent used in the color developing solution of the present invention, any of commonly used aromatic primary amine 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. Further, 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. In general, raising the pH to a certain extent enables rapid processing, but deteriorates with time to cause fog and contamination of the base. Cause.

In the color developing solution and the 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, generates no fog, and has little odor. It can be treated with a liquid that is not a substance. 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 of these include ethylenediaminetetraacetic acid, 1,3-propylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N-
(Β-oxyethyl) -N, N ′, N′-triacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, iminodiacetic acid, cyclohexanediaminetetraacetic acid, dihydroxyethylglycine citric acid, ethyletherdiaminetetraacetic acid, ethylenediaminetetrapropionic acid,
Phenylenediaminetetraacetic acid and the like, and alkali metal salts, ammonium salts and water-soluble amine salts of these acids.

As the halogenating agent, hydrohalic acids and alkali metal salts and ammonium salts of halogens are generally used, and specific examples thereof include sodium chloride and potassium chloride such as hydrochloric acid and hydrobromic acid. , Ammonium chloride, sodium bromide, potassium bromide, ammonium bromide and the like. As the buffer, a combination of an inorganic weak acid or an organic acid and an alkali agent is used. As inorganic weak acids, carbonic acid, boric acid, phosphoric acid, and as organic acids, acetic acid,
Citric acid, maleic acid, succinic acid and the like, and 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, ammonium maleate and the like.

In addition, additives are used for the action of accelerating bleaching. 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, etc.
Specific examples thereof include sodium sulfite, potassium sulfite, ammonium sulfite, sodium bisulfite, potassium bisulfite, ammonium bisulfite, sodium metabisulfite, potassium metabisulfite, and the like.

As the buffer, an inorganic weak acid or an organic acid is 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.

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. In addition, additives are used to promote bleach-fixing. Regarding these additives, Japanese Patent Publication No. 45-8506, Japanese Patent Publication No. 45-8836,
-280, JP-B-46-556, JP-A-49-42349, JP-B-53
No. -9854, JP-A-54-71634 and Belgian Patent No. 770910.

The washing treatment in the present invention is performed by washing with water 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, the N, N-bis (3-
Examples of specific compounds of (alkoxy-2-hydroxypropyl) hydroxylamine will be given. However, the present invention is not limited to these compounds. [1]

Embedded image [2]

Embedded image [3]

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[9]

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The N, N-bis (3-alkoxy-2-hydroxypropyl) hydroxylamine used in the present invention can be easily synthesized by a known method. A typical example is “Journal of Chemical Society (J. Chem. Soc.,), 75 , 1009 (1899), J. Chem.
c., oxidation reaction of secondary amine using aqueous hydrogen peroxide described in 1963 , 3144 and the like. Journal of Chemical Society (J. Chem. Soc.,), 79 , 964 (1957), J. Chem. Soc., 195
5, 769, etc. Cope elimination reaction of the amine oxides described, also typical substitution reaction to a halogenated alkyl hydroxylamine, the addition amount reactions to olefins hydroxylamine, the ring-opening reaction of the hydroxylamine and the oxirane compound No.

[0024]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited by these examples. Example 1 A color developing solution (A) having the following composition was prepared,
It was left open in a 1 l beaker at room temperature. Four weeks later, the evaporated water was supplemented, and the amount of the remaining color developing agent was measured by high performance liquid chromatography. The results are as shown in Table 1. Color developing solution (A) Diethylenetriaminepentaacetic acid 2.0 g Sodium chloride 5.0 g Potassium carbonate (anhydrous) 25.0 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate Salt (color developing agent) 5.0 g Triethanolamine 15.0 g Optical brightener (4,4'-diaminostilbene) 2.0 g Compound described in Table 1 0.022 mol Water was added to 1.0 l pH ( Using potassium hydroxide or sulfuric acid) 10.05

[Table 1] Compound A Diethylhydroxylamine Compound B

Embedded image (Compound described in JP-A-3-259145) Compound C

Embedded image (Compound described in JP-A-2-191950) Compound D

Embedded image (Compound described in JP-A-1-298352) From the results in Table 1, the N, N-bis (3-alkoxy-2-hydroxypropyl) hydroxylamine of the present invention is
It can be seen that the compound has an excellent residual effect not found in a hydroxylamine derivative simply substituted with a hydroxyl group or an alkoxyl group.

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

[Table 2] The replenishment amount is represented by the amount per 1 m ² of the light-sensitive material. The stabilization process was a four-tank countercurrent system.

Color developing solution Tank solution Replenisher Water 800 ml 800 ml Diethylenetriaminepentaacetic acid 2.0 g 2.0 g Sodium chloride 5.0 g カ リ ウ ム Potassium carbonate (anhydrous) 25.0 g 25.0 g Triethanolamine 12.0 g 12.0 g Fluorescent brightener (4 4'-diaminostilbene) 2.5 g 4.0 g Compounds described in Table 3 0.022 mol 0.055 mol sodium sulfite 0.1 g 0.2 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline Sulfate 5.5g 11.0g Add water 1.0l 1.0l pH (using potassium hydroxide or sulfuric acid) 10.05 11.00

Bleach-fixing solution Tank solution Replenisher Water 600 ml 600 ml Ammonium thiosulfate (75%) 93 ml 155 ml Ammonium sulfite monohydrate 27.0 g 45.1 g Ammonium iron (III) ethylenediaminetetraacetate 55.0 g 91.2 g Ethylenediaminetetraacetic acid 4.5 g 7.5 g Add water 1.0l 1.0l pH (using acetic acid) 6.00 5.50

Stabilizing solution (common to tank solution and replenishing solution) Water 900 ml 2-Aminobenzothiazole 0.1 g 1-Hydroxyalkylidene-1,1-diphosphonic acid 4.0 g Add water 1.0 l

The processing amount of the photosensitive material was such that 8 m ² of color paper was processed per day, and the processing was carried out until the amount of the color developing solution tank was replenished. 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 (ΔDmin), change in sensitivity point (ΔLD), and change in contrast (ΔHD-LD) are observed. Was. A reflection densitometer (X-RITE310) was used for the measurement, and the results are as shown in Tables 3 and 4.

[Table 3]

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

As is evident from the results in Tables 3 and 4, even under the processing conditions in which the replenishment of the processing liquid is long in the tank with a low replenishment,
It can be seen that when the color developing solution containing N, N-bis (3-alkoxy-2-hydroxypropyl) hydroxylamine of the present invention is used, stable processing can be performed without increasing the minimum density and decreasing the sensitivity. (Experiment No. 4 ~
6). On the other hand, when the color developing solutions of the comparative experiments (Experiment Nos. 1 to 3) were used, the minimum density increased and the sensitivity decreased,
It was difficult to maintain stable processing.

Example 3 Using a commercially available color negative film, after image exposure, processing was performed using the processing steps and processing solutions shown in Table 5.

[Table 5] The replenishment amount is 35 mm of photosensitive material and 1.1 m width (24 Ex.
1 equivalent). The fixing process was a two-tank countercurrent system. The washing process was performed in a three-tank countercurrent system.

Color developer tank solution replenisher water 800 ml 800 ml diethylenetriaminepentaacetic acid 2.0 g 2.0 g sodium sulfite 4.0 g 4.5 g potassium carbonate 35.0 g 35.0 g potassium iodide 0.002 g ナ ト リ ウ ム sodium bromide 1.3 g 0.9 g Compound described 0.024mol 0.036mol 2-Methyl-4- (N-ethyl-N-β-hydroxyethyl) aminoaniline sulfate 4.5g 5.0g Water was added to 1.0l 1.0l pH (use potassium hydroxide or sulfuric acid) And) 10.00 10.15

Bleaching solution Tank solution Replenisher Water 600 ml 600 ml 1,3-diaminopropanetetraacetic acid iron (III) ammonium 130.0 g 195.0 g ammonium bromide 70.0 g 105.0 g ammonium nitrate 14.0 g 21.0 g acetic acid 40.0 g 60.0 g 1.0l 1.0l pH (using ammonia water or sulfuric acid) 5.3 3.5

Fixing solution Tank solution Replenisher Water 600 ml 600 ml Ammonium sulfite 45.0 g 45.0 g Ammonium thiosulfate (75%) 260 ml 260 ml Ethylenediaminetetraacetic acid 10.0 g 10.0 g Add water 1.0 l 1.0 l pH (add ammonia water or acetic acid ) 6.85 6.75

Washing water (tank liquid and replenisher are common) Water 900ml 900ml Wettor (Chugai Photo Chemical Co., Ltd.) 15ml 15ml Formalin (37%) 7ml 7ml Add water 1.0l 1.0l

The processing amount of the light-sensitive material was such that 50 color negative films (24EX) were processed a day and replenished by the amount corresponding to the color developing tank capacity. 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 (△ Dmin) and the change in sensitivity point (△
LD) and change in contrast (ΔHD-LD).
A transmission densitometer (X-RITE310) was used for the measurement, and the results are as shown in Table 6.

[Table 6] The upper row in the table shows the blue light density, the middle row shows the green light density, and the lower row shows the red density.

As can be seen from the above results, the processing method using the color developing solution of the present invention is capable of performing stable processing without any problem even when processing color negative films continuously. (Experiment N
o. 2, 3).

[0038]

As described above, according to the present invention, in color development, a color developing solution containing N, N-bis (3-alkoxy-2-hydroxypropyl) hydroxylamine is used to prepare a silver halide color photograph. When the photosensitive material is processed continuously, it can be processed stably, the preservation of the color developing solution is maintained, the color density is not reduced, and the silver halide color photograph is free from fogging. It can be understood that the photosensitive material can be processed, and furthermore, this color developing solution can be used in a good use environment because it has little odor and does not use a deleterious substance.

Claims (3)

[Claims] 1. A color developing solution for a silver halide color photographic light-sensitive material, comprising N, N-bis (3-alkoxy-2-hydroxypropyl) hydroxylamine. 2. The color developing solution according to claim 1, wherein the N, N-bis (3-alkoxy-2-hydroxypropyl) hydroxylamine has the following formula (Formula 1). Embedded image In the formula, R ₁ and R ₂ represent an alkyl group having 1 to 5 carbon atoms. 3. A method for processing a silver halide color photographic light-sensitive material, wherein the color developing solution according to claim 1 is used in the color development after the image exposure of the silver halide color photographic light-sensitive material. .