JPS5895342A - Processing method for photosensitive material - Google Patents

Abstract

PURPOSE:To maintain the performance of the 2nd processing machine constant in continuous processing of a photosensitive material by circulating the processing solns. of the 1st processing machine which processes film in large amts. and the 2nd processing machine which processes the films in small amts. forcibly between the 1st and the 2nd processing machines which differ considerably in processing amts. CONSTITUTION:If, for example, color developments of color negative films are extremely infrequent and processings of color paper are frequent, the color developing solns. and bleach-fix bath for negative films are fed forcibly to a color paper processing tank and the processing soln. from the color paper processing tank is circulated to a negative film processing tank, by which the amt. of the color developing solns. to be replenished is economized, the deterioration of the negative film processing solns. owing to stopping of processing is prevented, long-term continuous processing is made possible and the generation of precipitates, deterioration of pictures, etc. are obviated.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a continuous processing method for photographic light-sensitive materials, and more particularly to a method for processing photographic light-sensitive materials that improves the stability and utilization efficiency of processing solutions.

At color photo labs (hereinafter referred to as color labs), negative color films are developed to create negative images, and positive images based on the negative images are printed on color benches. The development process at our color lab plays an important role in maintaining the stability of photographic performance and providing products of excellent quality to our users. As a means of achieving this, when continuously processing photographic forest materials, it is necessary to renew the processing solution in order to compensate for the decrease in processing capacity depending on the usage status of the processing solution. A method is used in which a processing tank is replenished with a new processing solution in an amount proportional to the area of the photographic material being carried into the processing tank.

Further, even if the processing liquid does not process the photosensitive material, it deteriorates over time and the processing capacity decreases. This decrease in processing capacity tends to be greater as the processing liquid temperature increases. Further, the amount of the processing liquid evaporates over time. This evaporation loss tends to increase as the temperature of the processing liquid increases (VC/I). Under certain conditions, for example, in a roll color paper processing machine with a large throughput, it is possible to compensate for the decrease in processing liquid capacity over time by replenishing the processing liquid in an amount commensurate with the evaporation loss over time. Also, under certain conditions, for example, in a color negative processing machine with a small throughput, even if the amount of evaporation is small, the decrease in throughput over time may be greater. 2- It is necessary to perform forced replenishment with replenisher.

The above applies not only to development processing but also to fixing processing and other processing.

The basic process control of the development process in a color laboratory is as described in L. However, in general, the throughput of color negative film and color paper print in a color laboratory is extremely different. The reality is that processing tends to be intermittent due to the relationship between processing capabilities and film throughput, and in contrast to hVc, color paper processing requires negative processing and simultaneous printing or reprinting.
It is in operation all day long with orders such as. In addition, the consumption of processing liquid for color negatives continues to decrease due to the shift to smaller format color negative films.
Naturally, the amount of processing required for color paper is overwhelmingly larger than that for color negatives.

In this way, when it comes to processing color negatives, reducing the amount of processing solution consumed reduces running costs and is a positive direction for laboratory management. However, on the other hand, updating the processing solution for color negatives requires more days than processing solution for color paper. do. Therefore, concentration of the solution due to evaporation, especially during the processing of color negatives, and fatigue of the solution over time (for example, a decrease in the content of preservatives and herbal medicines due to air oxidation of the color developing solution, etc.)
(reduction in pH, reduction in content of other processing liquid components, pH fluctuation, etc.) reach a level that directly affects photographic performance. For this reason, in the case of color negatives, more complex evaporation correction and fatigue correction, ie forced correction, are required than in the case of processing liquids in which replenishment is necessary to maintain π photographic performance during continuous processing. However, although photographic performance should be maintained stably by replenishing the processing liquid originally required for image formation in the photosensitive material, a countermeasure is needed to correct the above-mentioned processing liquid fluctuations. Moreover, even though the amount of negative film to be processed is reduced, the cost benefit is small; rather, the amount of work required to maintain processing stability only increases.

As a way to improve this shortcoming,
For example, the first. The processing amount in the second photoprocessing machine is extremely different, and the rejected photoprocessing liquid from the first photoprocessing machine, which has a large processing amount, is stored in the -H replenisher tank, and the rejected photoprocessing liquid from the first photoprocessing machine flows in. The method of
No. 025 and No. 51-83528.

However, in method L, the overflow liquid from the first processing machine, which has a large processing volume, flows into the second processing machine, which has a small processing volume, so that the processing liquid performance in the processing machines, which have different effects such as evaporation and oxidation, is kept the same. It is difficult to say that this is a satisfactory method.

Therefore, it is an object of the present invention to provide a method for diagonally processing photographic materials that improves the efficiency of using processing liquid. An object of the present invention is to provide a method for processing photographic materials in which the stability of a processing solution is improved.

As a result of various studies regarding the problem mentioned above, the present inventors have found that in a continuous processing method for photographic light-sensitive materials: It has been found that the above object can be achieved by a method for processing photographic light-sensitive materials in which different types of light-sensitive materials are continuously processed without circulating the processing liquid between a first processing machine with a large amount and a second processing machine with a small processing amount. .

The method of the present invention will be explained in more detail below.

The continuous processing machine for photographic light-sensitive materials according to the present invention generally processes silver halide color photographic light-sensitive materials of a negative-positive system, such as color negative film for photography and color paper for printing to obtain a positive image from a negative film. . This continuous processing machine is an electrical machine that performs continuous processing by arbitrarily combining processing tanks such as a color developer tank, a bleach-fix tank (or a bleach tank and a fixer tank), and a washing water bath as needed. Depending on the method of conveying the material, processing machines with names such as a cine-type automatic processor (hereinafter referred to as a cine processor) or a hanger-type automatic processor (hereinafter referred to as a hanger processor) are applied.

In the present invention, the processing machine that processes a large amount of color photosensitive materials, typified by color paper, is referred to as Processing Machine I, and the processing machine that processes a small amount of color photosensitive materials, typified by color negative film, is referred to as Processing Machine 2. It is called a processing machine. The first processing machine and the second processing machine according to the present invention are mainly used for developing processing, but may also be used for processing such as bleaching and fixing as described above, if necessary.

The present invention is characterized in that different types of color photosensitive materials are continuously processed in state B in which the processing liquids of the first processing machine and the second processing machine are mutually circulated. As a method, for example, a hollow pipe for circulation may be connected between both processing machines and the processing liquid may be circulated by a circulation pump, and chips from the color paper support and dust from the negative film may be mutually removed. It may be configured such that the processing liquid is circulated by stirring or the like using the same processing tank partitioned by filter plates so as not to cause any adverse effects.

Furthermore, the different types of color photosensitive materials referred to in the present invention are:
It refers to color photosensitive materials that have different photographic performance, such as sensitivity and gradation. Specifically, color negative films with high sensitivity and low gamma are compared to color negative films with relatively low sensitivity and low gamma. High gamma color paper for printing can be mentioned.

In the present invention, the processing liquids used in the first processing machine and the second processing machine have the same composition as illustrated in the examples below. It is also possible to use processing liquids with slightly different pH, halogen composition, temperature, etc. in each processing machine. Such a relationship also applies to replenishers.

The photographic processing method of the present invention is not particularly limited and can be applied to any processing method. For example, a typical example is
A method of performing color development followed by bleach-fixing treatment as described in U.S. Pat. No. 3,582,322, followed by washing and stabilizing treatment if necessary; color development as described in U.S. Pat. No. 910,002. After that, bleaching and fixing are carried out separately, followed by further washing with water and stabilizing treatment if necessary; or prehardening, neutralization, color development, and stopping as described in U.S. Pat. No. 3,582,347. A method of fixing, washing with water, bleaching, fixing, washing with water, post-hardening, and washing with water in this order;
A method of performing color development, washing with water, supplementary color development, stopping, bleaching, fixing, washing with water, and stabilization in this order as described in JP-A No. 50-54330; as described in U.S. Pat. No. 3,607,263. A method in which pre-hardening, neutralization, washing with water, first development, stopping, washing with water, color development, stopping, washing with water, bleaching, fixing, and washing with water are carried out in this order; as described in JP-A-50-36126. A method of hardening, neutralization, first development, stopping, washing with water, color development, stopping, bleaching, organic acid bath, fixing, and washing with water; first development as described in JP-A-50-81538. , non-fixing silver dye bleach, water washing, color development, acid rinsing, water washing, bleaching, water washing, fixing, water washing, stabilization, water washing; US Patent No. 2,623,8
No. 22, No. 2,814,565, the developed silver produced by color development is subjected to halogenation bleaching, and then color development is performed again to increase the amount of dye produced; or the development method described in U.S. Pat. No. 674,990, No. 3,761,265, West German patent (OLS) 2
, No. 056,360, JP-A-47-6638, JP-A-47-47
-10538, West German Patent (OLS) 2,226,
No. 7709-, JP-A No. 48-9728, JP-A No. 48-9729, etc., in which a low-silver content photosensitive material is processed using an amplifier agent such as a peroxide or a cobalt complex salt, etc. The method may be used for processing. In addition, these treatments cannot be carried out quickly and are sometimes carried out at high temperatures of 30°C or higher;
It may be done below. Generally, it is advantageous to carry out the reaction at a temperature in the range of 70°C to 70°C. Note that the set temperature for each step in the series of processing may be the same or different.

As the color developing agent, p-phenyldiamine type is representative, and the following are preferred examples.

4-Amino-N, N-diethylaniline, 3-methyl-
4-amino-N, N-diethylaniline, 4-amino-
N-ethyl-N-β-hydroxyethylaniline, 3-
Methyl-4-amino N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulponamidoethylaniline, 3-
Methyl-410- -amino-N-ethyl-N-β-methoxyethylaniline, 3-β-methanesulfonomidoethyl 4-amino-
N,N-diethylaniline, 3-methoxyethylamino-N-ethyl-N-β-hydroxyethylaniline, 3
-methoxy-4-amino-N-ethyl-N-β-methoxyethylaniline, 3-acetamido-4-amino-N
, N-diethylaniline, 4-amino-N, N-dimethylaniline, N-ethyl-N-β-[β-(β-methoxyethoxy)ethoxy]ethyl-3-methyl-4-aminophosphoniline, N-ethyl -N-β(β-methoxyethoxy)ethyl-3-methyl-4-methylaminoaniline and salts thereof, such as sulfur WI salt, hydrochloride, sulfite, and p-toluenesulfonate. Furthermore, JP-A-48-6493
No. 2, No. 50-131526, Patent Application 1982-1724
No. 6 and Hent et al., Journal of the American Chemical Society, Vol. 73, pp. 3100-3125 (
1951) Research Disclosure (Reaoa)
rch Disclosure) 1617643.
Compounds described in 1978 (Reference-1) and the like can also be used.

Moreover, various additives can be added to the color developer 1# solution as needed. The main examples are alkaline agents (
For example, alkali metal and ammonium hydroxides, carbonates, and phosphorus! 1! (salts), l) H-adjusting or buffering agents (e.g. weak acids and bases such as acetic acid and boric acid and their salts);
Development accelerators (e.g. U.S. Pat. No. 2,648,604;
Various pyridinium compounds and cationic compounds, potassium nitrate and nitric acid described in U.S. Patent No. 3,671,247, etc.)
No. 2,577, L27, No. 2,950,97
Polyethylene glycol condensates and their derivatives as described in No. 0 etc., British Patent No. 1,020,032
Nonionic compounds such as polythioethers, such as those described in U.S. Pat. pyridine, ethanolamines, organic amines, benzyl alcohol, hydrazines, etc.), anti-capri agents (e.g. alkali bromide, alkali iodide and U.S. Pat. No. 2,496)
, 940 and 2,656,271, mercaptobenzimidazole, 5-methylbenzotriazole, 1-phenyl-5-mercaptotetrazole, U.S. Patent No. 3,11
No. 3,864, No. 3,342,596, No. 3,2
No. 95,976, No. 3,615,522, No. 3,
597,199, etc., nitrobenbrozoic acid described in JP-A-49-106832, benzothiazolium derivatives as described in JP-A-50-137136, or JP-A-1983-1986. - Phenazine N oxide as described in No. 41675, antifoggants as described in Sonoike 1 Scientific Photography Handbook - Volume 2, pages 29-47), and other U.S. Patent No. 3,161,513 issue,
3.161,514, British Patent No. 1,030,4
No. 42, No. 1,144,481, No. 1,251,
No. 558, stain or sludge inhibitors, as well as interlayer effect promoters and preservatives (e.g. sulfites, acid sulfites, hydroxylamine hydrochloride, form sulfides, alkanolamine sulfide adducts, etc.).

After color development processing, the color photosensitive material used in the present invention is
Bleaching is carried out using conventional methods. This process may be performed simultaneously with fixing or separately. This processing solution can also be used as a bleach-fixing bath by adding a fixing agent if necessary.

Various compounds are used as bleaching agents, and they can be applied to various dye image forming methods.

Further, the color photographic light-sensitive material used in the present invention is more effective when it is a color light-sensitive material containing a small amount of silver halide as described in West German Patent (OLS) No. 2,357,964 isobaric.

The color light-sensitive material has a concentration of about 65 to 3 per unit, for example, a fraction of that of a normal color light-sensitive material.
75 w/m silver halide.

Color photographic materials with reduced silver halide i are disclosed, for example, in U.S. Pat. Nos. 2,623,822 and 2.814.
, U.S. Pat. No. 3,674,490, U.S. Patent No. 3, U.S. Pat. , No. 671,265 West German Patent No. (OLS) No. 2,056,360, Japanese Patent Application Publication No. 4
No. 7-6338, No. 47-10538, etc., or using the peroxide described in West German Patent No. 47-10538, etc.
S) 2.226,770, JP-A No. 48-9728, etc., it is possible to obtain good results by applying the development processing method using color intensification using cobalt complex salts.

Among them, Akama salt, dichromate, iron (III) aminopolycarboxylic acid, aliphatic polycarboxylic acid metal salt, persulfate, British Patent No. 774,194, same m 1,032,
No. 024, No. 949,440, Belgian Patent No. 71
Copper complex salts as described in No. 7,139, Cobalt complex salts as described in West German Patent No. 934.512, British Patent No. 777.635, Japanese Patent Publication No. 110-1988
Iodine as described in No. 68, Special Publication No. 41-11
Salad flour and sulfamic acid as described in U.S. Pat. No. 2,507,183, U.S. Pat.
9,981, U.S. Pat. No. 2,748,000; p as described in U.S. Pat.
-Sulfophenylquinones, nitrone compounds, etc. alone or in appropriate combinations can be mentioned as general examples.

Additionally, bleach or bleach-fix solutions are described in U.S. Patent No. 3.042.
, No. 520, No. 3,241,966, Special Publication No. 1973-
Various additives can also be added, including the bleaching accelerators described in Japanese Patent No. 8056, No. 45-8836, and the like.

However, the processing method of the present invention can be applied to various dye image forming methods.

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 [Processing System 1] A commercially available 110 size color negative film was photographed to prepare a sample for processing with a color negative processor. In addition, a sample was prepared from a standard developed color negative film using a commercially available color printing paper (89 mm width) for KM printing and then processing with a color paper processor. Cine type color film processor (Noritz Koki QSF-
6OL-2) and a roll paper processor (QRP-2300 manufactured by Noritsu Koki) were modified so that they could be processed by the following processing steps, and the samples were continuously processed (referred to as running processing).

[Processing process]

(Color negative processing) (L) Color development 38℃ 3 minutes 15 seconds (2)
Bleach fixing 33℃ 6 minutes 30 seconds (3) Water
Washing 30℃ 4 minutes 44 seconds (4) Drying
43-52℃ 1 minute 42 seconds (color paper processing) (1) Color development 38℃ 3 minutes 30 seconds (2) Bleach fixing 33℃ 1 minute 45 seconds (3) Washing with water
30℃ 3 minutes 30 seconds (4) Drying 60-80'C1
Minutes 48 seconds The following treatment liquid composition was used in the above treatment step.

(Color developer) Magnesium chloride 0.3g 1-hydroxyethylidene 1.1-diphosphonic acid (60% aqueous solution) 0.8m
l! Hydroxylamine sulfate 3.0.9 Potassium sulfite (50% aqueous solution) 4.0
me4-Amino-N-(β-methoxyethyl)-N-ethyl-3-methylaniline-C-P-toluenesulfonate (Kodak CD-6) 6.09 Potassium carbonate
26, l; 1 potassium bromide
1.3y of water and KOH
The pH was adjusted to 10.0 VC.

(Color development replenisher) Magnesium chloride 0.6g 1-Hydroxyethylidene 1.1 diphosphonic acid (60% aqueous solution) x, 2g Hydroxylamine sulfate 4.5g Potassium sulfite 01 aqueous solution) 5.7d4-
Amino-N-(βmethoxyethyl)-N-x”7-
/L, -3methylanilyy-c-p-toluenesulfonate 9.8. ! i! potassium carbonate
28 f/le and L K with water
OH Te pH 10,791c Adjustment 11 Lt:.

I j1. White (bleach-fix solution) Ethylene diamine ferric acetate (m) ammonium salt
68.9 Ethylenediaminetetraacetic acid diammonium salt 5g Ammonium sulfite (40% aqueous solution) 42 Ammonium cothiosulfate (70% aqueous solution) 22o1nl Bisthiourea
The amount was made up to 1 g with 0.5.9 water, and the pH was adjusted to 6.9K with aqueous ammonia (28% aqueous solution).

(Bleach-fixing replenisher) (AJ solution Potassium carbonate 20 fl Ethylenediaminetetraacetic acid iron (m) ammonium salt 200 g Finished with water. The pH was adjusted to 7.6 with potassium carbonate.

(B) Liquid ammonium sulfite 200 ml Ammonium thiosulfate (70% aqueous solution) 445 ml Ethylenediaminetetraacetic acid 15 pL-Ascorbic acid 0.1. The mixture was brought to tg with @water and the pH was adjusted to 5.2KN using glacial acetic acid.

Replenishment of color developer replenisher during running processing is 4.45 m per color negative film (110 size Sae photo shoot)
J, Color paper (89 width) 14.5ml per In
The bleach-fixing replenisher should be added at 2 rnl each of the above ((transfer) solution and (B) solution per color negative film, and (A) solution and (B) solution per color paper In).
1 solution was replenished 3 and 2 times, respectively. The running process continued during the closing period while processing 4,100 pieces of photographed color negative film and 500 m of printed color paper per day. The tank liquid renewal coefficient for color development and bleach-fixing processing tank liquid for 60 days is 1.07. The bleach-fixer was 0.83, the color developer was 5.37 and the bleach-fixer was 9.6 in the color paper processor.

As a result of the processing, the color negative film began to develop fog and a decrease in color density during the running process, and after 40 days of the running process, the photographic performance had deteriorated to the point that normal prints could no longer be obtained. It happened. The color paper process maintained running start photographic performance constant during closing.

In addition to the photographic performance, a large amount of pale yellow precipitate was generated in the bleach-fix processing tank of the color negative processor during the 46 days of running processing, causing problems such as adhesion to the film and making normal processing difficult.

[Processing system-2] The color development processing tank of the color negative processor used in processing system-1, the color development processing tank of the color paper processor, and the bleach-fixing processing tank of each processor are connected through a hard PVC hollow space and circulated in the middle. A pump was installed to forcibly circulate the liquid between the treatment tanks, and continuous treatment was carried out for 60 days under the same conditions as treatment system-1.

The total tank solution renewal coefficient was 4.43 for the color developer and 5.06 for the bleach-fixer. As a result of the processing, the photographic performance at the start was maintained at a constant V throughout (a) days divided by running processing for both color negative film and color paper processing, and no malfunctions such as precipitation were observed.

As is clear from the comparison of Processing System-1 and Processing System-2, it is necessary to process color film and color paper, which have different processing areas, by using the method of the present invention by using first and second processing machines with different throughputs. It is understood that by forcibly circulating a processing solution of the same composition as used in processing, the photographic performance obtained by a processing machine with a small throughput can be maintained at a constant level at normal pressure.

The effects particularly obtained by the method of the present invention described above are exhibited in a low replenishment system where the replenishment of replenisher is less, and is particularly advantageous in a low replenishment system that requires less replenishment of replenisher.
It is highly effective when processing disc films such as those shown in K.

In addition to the above examples, the entire amount of overflow liquid generated by replenishment from the color paper processor during running processing in the processing system was flowed into the color negative processor and processed in the same manner for ω days, but the performance of the color negative film was maintained constant. I couldn't let it happen.

Agent Yoshimi Kuwahara −ru− 273-

Claims (1)

[Claims] In a continuous processing method for photographic light-sensitive materials, tRI, which has extremely different throughput, circulates the processing liquid between the first processor, which has a higher throughput, and the second processor, which has a lower throughput, between the second processor. 1. A method for processing photographic light-sensitive materials, which comprises sequentially processing different light-sensitive materials.