JP2000162750A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent deterioration of preservable property and color developing density and occurrence of fog even in the case of reducing a replenishing amount to a developing solution for the silver halide color photographic sensitive material. SOLUTION: This silver halide color photographic sensitive material containing a silver halide emulsion high in silver chloride content is developed with the color developing solution containing a compound represented by formula I and replenished with a replenishing solution containing a sulfite concentration of <=5×10-3 mol in a replenishing amount of <80 ml/m2. In formula I, R1 is an alkylene or alkan-tri-yl group optionally substituted by a 2-8C alkyl group and in the case of the alkylene group, l is 0, and in the case of the alkan- tri-yl group, l is 1, and when l is 1, A is a polymer represented by formula; and formula I becomes a 3-dimensional structure; (m) is an integer of 0-30; and (n) is an integer of 10-10,000.

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 color developing solution which can be stably processed even during continuous color development processing, and a silver halide color photographic material using the same. More particularly, the present invention relates to a method for processing a silver halide color photographic light-sensitive material which continuously forms a stable color photographic image which is hardly influenced by the processing amount of the light-sensitive material even when the replenishment amount is reduced. 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. 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. Also, increasing the amount of addition increases the stability,
As in the case of hydroxyamine, the color density is low.

[0006] Under these circumstances, it has become common to use N, N-diethylhydroxylamine or a combination of N, N-diethylhydroxylamine and sulfite instead of hydroxylamine. This N, N-diethylhydroxylamine is not as good as hydroxylamine,
Similarly, it has the property of lowering the color density. 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, 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. In particular, this problem is serious for a photographic processor having a small throughput. The addition of sulfite is effective when the processing amount is small, but conversely, when the processing amount is large, the coloring density is lowered.

For example, Japanese Patent No. 2,620,581 proposes various hydroxyamine derivatives. Among these compounds, some compounds do not contain an odor in terms of odor.However, when the replenishment amount is reduced, the compound is sufficiently satisfactory in that the oxidation of the color developing solution is effectively prevented. Not something you can do. Further, Japanese Patent Application No. 2652503 proposes a polymerized hydroxyamine derivative. Although these compounds are satisfactory in terms of odor, they are not satisfactory in terms of effectively preventing oxidation of the color developing solution when the replenishment amount is reduced, and furthermore, these compounds are used. Color developing solutions have the disadvantage of generating undesirable insolubles when taken out to the subsequent desilvering step, bleach-fix. U.S. Pat. No. 5,466,565 discloses a polymerized hydroxylamine derivative having an ether bond. Among these compounds, a color developing solution using the same is described. It has the drawback of generating undesirable insoluble substances when taken out to the bleach-fixing step of desilvering.

Therefore, the present inventors have found that even if the replenishment amount of the color developing solution is reduced, the preservation of the color developing solution is maintained, the color density is not reduced, and no fog is generated.
As a result of examining the processing method of silver halide color photographic light-sensitive material which has little odor and the color density is not affected by the amount of processing and does not generate insoluble substances in the subsequent bleach-fix solution, The inventors have found that these problems can be solved by processing, and have arrived at the present invention. The purpose of the present invention is to eliminate these problems and to maintain a stable photographic performance even when the replenishment amount is reduced. An object of the present invention is to provide a method for processing the obtained silver halide color photographic light-sensitive material.

[0012]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for developing an exposed silver halide color photographic material using a color developing solution containing a P-phenylenediamine-based color developing agent. In a method for processing a silver halide color photographic light-sensitive material, wherein the silver halide color photographic light-sensitive material is continuously processed while replenishing a replenishing solution,
The color developer contains a high silver chloride emulsion comprising 90% mol or more of silver chloride, and the color developer has the following general formula [I]
The replenisher of the color developer contains a compound represented by the following formula (2), the sulfur dioxide concentration of the replenisher is 5 × 10 ⁻³ mol or less, and the replenishment amount is less than 80 ml / m ^2. This has been achieved by a processing method for silver halide color photographic light-sensitive materials. General formula [I]

Embedded image In the formula, R ₁ represents an alkylene group or an alkanetriyl group which may be substituted by an alkyl group having 2 to 8 carbon atoms. In the case of an alkylene group, 1 is 0, and in the case of an alkanetriyl group, 1 is. When 1 is 1, A represents a polymer represented by the general formula [I], and the general formula [I] has a three-dimensional structure. m shows the integer of 0-30. n is 10 to 10000
Indicates an integer.

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The embodiments of the present invention will be described below in detail. Examples of specific compounds of the general formula [I] used in the present invention will be given. However, the present invention is not limited to these compounds. [I-1]

Embedded image [I-2]

Embedded image [I-3]

Embedded image [I-4]

Embedded image [I-5]

Embedded image [I-6]

Embedded image [I-7]

Embedded image [I-8]

Embedded image

The alkylene group which may be substituted with an alkyl group in the compound represented by the general formula [I] refers to one hydrogen atom from the carbon atoms at both chain ends of a linear saturated hydrocarbon which may be substituted with an alkyl group. Represents a divalent group derived from each other, specifically,

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image And the like. The alkanetriyl group refers to a trivalent group having three or more carbon atoms having a free valence at both ends and an intermediate carbon atom of the chain, and specifically,

Embedded image

Embedded image

Embedded image And the like. The compound represented by the general formula [I] is
Copolymers containing two or more of these groups may be used.

The description of these groups is described in Basics of Organic Chemistry, Separate Volume Nomenclature of Organic Compounds, p. 15 (1994), published by Baifukan Co., Ltd. The compound represented by the general formula [I] 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. Soc., 1963, 3144, etc., oxidation reaction of secondary amine using hydrogen peroxide solution. Journal of Chemical Society (J. Chem. Soc.,), 79,964 (19
57), J. Chem. Soc., 1955, 769, etc., a cope elimination reaction of amine oxide, a general substitution reaction of hydroxylamine with alkyl halide, an addition reaction of hydroxylamine to olefin, hydroxyl A ring opening reaction between an amine and an oxirane compound is exemplified.

The following is an example of a method for synthesizing the compound of the formula [I]. Synthesis of Compound (I-2) 174 g of diethylene glycol diglycidyl ether
(1.0 mol), 50% aqueous hydroxylamine solution 6
6 g (1.0 mol) is mixed with 450 ml of water,
For 2 hours. When the concentration of the hydroxylamino group in the obtained aqueous solution was determined using Fehling's solution, it was confirmed that 0.109 mol / 100 g of the hydroxylamino group was contained. Further, when unreacted hydroxylamine was measured by liquid chromatography, it was confirmed that no unreacted hydroxylamine remained. The resulting aqueous solution has almost no odor. Examples of the P-phenylenediamine-based color developing agent used in the color developing solution of the present invention include, for example, Journal of American Chemical Society (J. Am. Chem. Soc.,) 73.3100 (1951) and Haist. Modern Photographic Processing
Processing). 1979. John Wileyand Sons. New York. On page 545 et seq.

Preferred examples of the compound used in the present invention are shown below. (A-1) 4-Amino-3-methyl-N-diethylaniline hydrochloride (A-2) 4-Amino-N-ethyl-N- (β-hydroxyethyl) aniline sulfate (A-3) 4- Amino-3-methyl-N-ethyl-N-
(Β-methylsulfonamidoethyl) aniline 3/2
Sulfate monohydrate (A-4) 4-amino-3-methyl-N-ethyl-N-
(Β-hydroxyethyl) aniline sulfate monohydrate (A-5) 4-amino-3- (β-methylsulfonamidoethyl) -N-diethylaniline hydrochloride (A-6) 4-amino-N- Ethyl-N- (β-methoxyethyl) aniline / 2-paratoluenesulfonate (A-7) 4-amino-N-butyl-N- (β-butylsulfonate) aniline sulfate

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.

Also, a fluorescent whitening agent for improving a white background, various surfactants for improving the solubility of a poorly soluble substance such as a color developing agent, and nitrobenzimidazole and mercaptobenzimidazole as additives. , 5-methyl-benzotriazole, 1-phenyl-5-mercaptotetrazole, and the like, a stain inhibitor, a sludge inhibitor, and the like. Further, the color developing solution of the present invention,
It is preferable to use at a pH of 9.5 or more. Generally, by raising the pH to some extent, rapid processing becomes possible, but it is deteriorated with time and causes fog and contamination of the base.

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 alkalis of these acids 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 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 for bleach accelerating action can be used. Regarding these additives, see JP-A-54-35.
727, JP-A-60-12549, JP-A-60-7
No. 6745, JP-A-60-95540, JP-A-2-1
No. 03041 describes a usage example.

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 accelerating bleach-fixing can be used. 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 carried out 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 may be any known alkali agent or acid agent. Can also be used.

[0026]

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 and 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 (polymer compound has hydroxylamino group) 1.0 l pH (using potassium hydroxide or sulfuric acid) 10.05

[Table 1] Compound A Diethylhydroxylamine Compound B

Embedded image (Compound described in Japanese Patent No. 2620581) Compound C

Embedded image (Compound described in Japanese Patent No. 2652503) From the results shown in Table 1, the polymer type hydroxylamine compound of the present invention having an ether bond in the polymer main chain and further substituting the polymer main chain with hydroxy is N, N -It has an excellent residual effect not found in dialkylhydroxylamine or mere polymer type hydroxylamine compounds.

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 rate is expressed in an amount per photosensitive material 1 m ^2. The stabilization process was a four-tank countercurrent system.

Color developing solution 160 ml / m² 60-80ml / m²  Replenisher for tank liquid Replenisher for water 800ml 800ml 800ml Diethylenetriaminepentaacetic acid 2.0g 2.0g 2.0g Sodium chloride 5.0g 1.5g 0.5g Potassium carbonate (anhydrous) 25.0g 25.0g 25.0g Triethanolamine 12.0g 12.0g 12.0g Fluorescence Brightener (4,4'-diamino stilbene) 2.5 g 4.0 g 4.0 g Compound described in Table 2 0.022 mol 0.055 mol 0.066 mol Sodium sulfite 0.2 g Described in Table 3 Described in Table 3 N-ethyl-N- ( β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.5 g 8.0 g 11.0 g Add water 1.0 l 1.0 l 1.0 l pH (using potassium hydroxide or sulfuric acid) 10.05 10.40 11.00

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

Stabilizing solution (the tank solution and the replenisher are common) Water 900 ml 2-Aminobenzothiazole 0.1 g 1-hydroxyalkylidene-1,1-diphosphonic acid 4.0 g Add water 1.0 l

The throughput of the photosensitive material, and a minor amount processing for processing a color paper 5 m ² per day, were performed each 20 days and a large amount processing of 30 m ² process. At the end, a commercially available control strip is processed and the sample is taken with a reflection densitometer (X
-RITE), the minimum density of the magenta dye in the unexposed area where fogging is likely to be a problem and the maximum density of the yellow density at which the developing speed is slow and the color density is difficult to appear are measured. or,
The occurrence of insoluble substances in the bleach-fix solution was visually checked. Table 3 shows the results.

[Table 3] Compound D

Embedded image (Described in US Pat. No. 5,466,565)

As is clear from Table 3, when the replenishment amount is large, the treatment can be carried out without any problem using conventional hydroxylamines regardless of the amount of treatment (Experiment 8). However, when the replenishment amount is reduced and conventional hydroxylamines are used, when the processing amount is small, the magenta density in the unexposed portion increases. Further, when an attempt is made to increase the sulfite concentration in order to suppress the increase in the magenta concentration, the yellow concentration is reduced when the processing amount is large.
Compound C compound D is a high molecular weight hydroxylamine.
Such compounds generate insoluble substances in the bleach-fix solution (Experiments 9, 10, 11, 12).

However, the high molecular weight hydroxylamine represented by the general formula [I] of the present invention is 80 ml / m ²
It can be seen that even with a low replenishment of less than 2, no addition of sulfite is required, and no matter what amount of processing is performed, stable processing is possible without generating insoluble substances in the bleach-fix solution (Experiment 13-16).

[0034]

As described above, according to the present invention, in color development, a high-molecular-weight human droxylamine represented by the general formula [I] is used, and a silver halide color photographic light-sensitive material is processed in a small amount. Regardless, low replenishment processing can be performed stably, the preservation of the color developing solution is maintained, there is no decrease in color density, and there is no generation of fog and generation of insoluble substances in the desilvering process. Silver halide color photographic light-sensitive material can be processed in the absence of the color developing solution.
Since there is no odor, it can be seen that it can be used in a good use environment.

Claims (1)

[Claims] 1. When an exposed silver halide color photographic material is developed with a color developer containing a P-phenylenediamine-based color developing agent, the color developer is continuously added while replenishing the replenisher. In the method for processing a silver halide color photographic light-sensitive material to be processed, the silver halide color photographic light-sensitive material contains a high silver chloride emulsion containing 90% or more mol of silver chloride, and the color developer contains When the replenisher of the color developer contains a compound represented by the following general formula [I] (Chemical Formula 1), the sulfur dioxide concentration of the replenisher is 5 × 10 ⁻³ mol or less, and the replenishment amount is less than 80 ml / m ² . A method for processing a silver halide color photographic light-sensitive material. General formula [I] In the formula, R ₁ represents an alkylene group or an alkanetriyl group which may be substituted by an alkyl group having 2 to 8 carbon atoms. In the case of an alkylene group, 1 is 0, and in the case of an alkanetriyl group, 1 is. When 1 is 1, A represents a polymer represented by the general formula [I], and the general formula [I] has a three-dimensional structure. m shows the integer of 0-30. n is 10 to 10000
Indicates an integer.