JPS6375745A - Method for processing photographic sensitive material after bleaching silver and dye - Google Patents

Abstract

PURPOSE:To omit a rinsing step requiring a large amount of water, to shorten development processing steps, and yet to improve an image by processing a photosensitive material after undergoing a fixing step with aqueous solution containing a multivalent metal compound. CONSTITUTION:After imagewise exposure of the photosensitive material mentioned in the title, black-and-white developing, bleaching of a dye and silver and fixing, it is further processed with the aqueous solution containing the multivalent metal compound, such as MgSO4, and optionally, a pH buffer, an antimold, a hardener, a surfactant, and the like, by adding the replenishing solution of said aqueous solution in an amount of <=1l per 1m<2> of the photosensitive material, and then, it is dried, thus permitting the photosensitive material to be rapidly and economically processed, and an excellent image superior in storage stability to be obtained even by using a small amount of said aqueous solution.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for processing silver dye bleached photographic materials, and particularly to a processing method that can shorten the development process and obtain good images. It is related to.

[Conventional technology]

Conventionally, a washing process using a large amount of water has been provided at the end of the development process of a photosensitive material, and chemicals absorbed into the photosensitive material during the development process are removed by washing with water. Among these, stabilization treatment has been introduced to some of them in order to simplify the water washing treatment and speed up the treatment.

In addition, in recent years, the cost of supplying washing water for photographic processing has become high in urban areas, and discharging washing wastewater also costs a huge amount of money, so there is an increasing need to conserve water.Moreover, rising oil prices have made it necessary to heat washing water. However, there is also a problem that a large amount of expense is required, and therefore, it has been desired to simplify the water washing process. Therefore, for example, when processing black and white photographic paper, stabilization processing (Sta
Processing and regulations for stabilizing images without washing (T, H, James)
Theory of the Photography
Various patent applications have been filed since 1943 regarding this stabilization.For example, British Patent No. 589.560; US Patent No. 2.453.346; 453.347
No. 2.448.857, etc., and 19
Around 1965, a development process that did not require water washing (stabilization process for Fuji Quick photosensitive materials) was developed, in which a photosensitive material containing a built-in black and white developing agent was treated with a stabilizing solution containing Rodan's salt after alkali processing (stabilization process), which did not require water washing. ) was widely practiced.

Later, a patent (Western German Patent No. 1.772.945) was published that states that chromogenic color photosensitive materials can be stabilized only with a bleach-fix solution containing iron(III)-EDTA and ammonium thiosulfate after color development has stopped. However, the method disclosed in this patent not only resulted in coloring of the white background, but also resulted in poor color image stability, and photosensitive materials produced by this processing method were not widely available on the market.

On the other hand, the method using the above-mentioned stabilizing processing liquid for black-and-white light-sensitive materials specifically performs only image stabilization processing, and does not perform silver bleaching or fixing processing at all.

On the other hand, in order to improve the stability of color photographic images based on color development methods against light, heat and humidity, stabilization treatment using, for example, a formalin bath is used. This inactivates unreacted pyrazolone magenta coupler and has no effect on color images using silver dye bleaching photography, which operates on a different principle.

Silver dye bleaching photography is the bleaching of azo dyes, anthraquinone dyes, indigoids or other dyes to obtain color images in the presence of metallic silver or silver halide formed into images obtained after conventional black and white development. This is a color photographic method characterized by the ability to produce robust dye images, but further improvements are desired. In other words, in this method, the dye contained in the gelatin-silver halide emulsion is selectively bleached in proportion to the amount of silver produced by black-and-white development, and upon desilvering (silver bleaching and fixing), the original silver image is restored. In contrast, a color image that is inverted is obtained. That is, a positive color image can be obtained for the original (U.S. Pat. No. 1.517.049, U.S. Pat. No. 2.02).
No. 0.775, No. 2.184.022, No. 2, 2
No. 17.544, No. 2.255.463, No. 2.
No. 304.987, No. 2.311.015, No. 2
．． No. 322.084, No. 2, No. 341.034, Specification No. 2.699.394, etc.).

Therefore, in the development processing method for silver dye bleached photographic materials,
The azo dye contained in the photosensitive material is decomposed into 172 to 173 molecules during the dye bleaching process, and it is necessary to remove the large molecular weight decomposed products of the azo dye from the photosensitive material. requires large amounts of water, and the washing process was considered essential. For example, it is said that Yuzen dyeing, which is based on the same principle as the silver dye bleaching method, requires sufficient washing with water to bring out the vividness of the colors. Emphasis was placed on the washing process using water.

[Problem that the invention seeks to solve]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a method for processing a silver dye-bleached photographic material, which can omit the large amount of water washing step performed at the end of the processing step and shorten the development step. A further object of the present invention is to provide a processing method in which excellent images can be obtained even if the large amount of water washing step is omitted, and the storage stability of the photosensitive material is also good.

[Means for solving problems]

The present invention shows that, contrary to conventional knowledge, processing with an aqueous solution containing a polyvalent metal compound can produce better images than washing with a large amount of water, and also has good storage stability. This was done based on knowledge.

That is, the present invention uses an aqueous solution containing a polyvalent metal compound in the final stage after the imagewise exposed silver dye-bleached photographic light-sensitive material has been substantially subjected to black-and-white development, dye bleaching, silver bleaching, and fixing steps. The replenishment amount of the aqueous solution is
Provided is a method for processing a silver dye bleached photographic light-sensitive material, characterized in that the light-sensitive material is processed under conditions of 12 or less per n'' and then dried.

In the processing method of the present invention, the image-exposed silver dye bleached photographic material is developed in the following steps (1)→(x).

(i) Black and white development (ii) Washing with water (iii) Dye bleaching (iv) Washing with water (v) Silver bleaching (vi) Washing with water (vii) Establishment (vii) Washing with water (ix) Stabilization (x) Drying Next, each process will be explained.

(i) Black and white development process Developed in black and white to create a reduced silver image.

Conventionally known black and white development formulas, such as 072 and D76
A prescription based on (Kodak prescription name) is used.

(ii> Dye bleaching treatment step The dye is bleached according to the amount of silver in the reduced silver image by treatment with a dye bleaching bath consisting of a mineral acid or organic acid, a compound that forms a silver complex or a silver salt.

In addition to the following bleaching agents and silver salts or compounds that form silver complexes, this dye bleaching bath contains the following bleaching agents, which bleach dyes efficiently in a short time and evenly bleach various dyes in multilayer photosensitive materials. For this reason, dye bleaching accelerating catalysts are usually added as well.

Examples of these compounds are specifically listed below.

(1) Bleaching agents: Mineral acids such as hydrochloric acid, sulfuric acid, and nitric acid, or organic acids such as sulfamic acid, succinic acid, and acetic acid. (2) Compounds that form silver salts or silver complexes: potassium bromide,
Potassium iodide, potassium cyanide, urea, thiourea,
Semicarbazide, thiosemicarbazide (3) Dye bleach accelerating catalyst: A compound mainly having a two-electron oxidation-reductant, and the following compounds are conventionally known.

Pyrazine, naphthazine, quinoline, U.S. Patent No. 2, 27
0.118 (e.g., quinoxalines, phenazines, anthraquinones, naphthoquinones), 2,3-substituted quinoxaline compounds described in U.S. Pat. No. 3,656,953, U.S. Pat. 2.4
10.025, diphenyl or triphenylmethane derivatives, U.S. Pat. No. 2.541
．． N-substituted isoalloxazines as described in U.S. Pat. No. 884, indofenadines as described in U.S. Pat.
floquinoxalines and chetzkipurines as described in British Patent No. 17; simazines and alloxazines as described in British Patent No. 657.374; and the orthophenylenediamine derivatives described in Japanese Patent Publication No. 45-22195.

Both (v) silver bleaching and (vii) fixing can be carried out using bleaching solutions and fixing solutions known from chromogenic color photography.

Water washing steps (ii), (iv), (vi) and (v)
F71) is carried out to wash away the processing liquid adhering to the photosensitive material from the prebath, and usually uses 2 to 20 times the amount of water brought in from the prebath. however,
In the present invention, the water washing steps (ii), (iv),
(vi) and (vm) are optional and can be omitted.

In the treatment method of the present invention, substantially the above step (i)
, (iii), (v), and (vj), a specific aqueous solution is used for treatment. Therefore, the process (iji
) and (v) can also be carried out in the same bath, and step (v)
) and (vi), or steps (iii), (V), (v
i) may be carried out in the same bath. Furthermore, if an oxidizing agent is added to the dye bleaching solution, silver bleaching can be performed at the same time as dye bleaching (JP-A-51-66828, JP-A-54-2352).
No. 9), silver bleaching and fixing can be performed simultaneously by using a mixture of a bleaching solution and a fixing solution (Special Publication No. 54-35
No. 930, No. 54-35931). Furthermore, by adding a silver halide bath agent and an oxidizing agent to the dye bleaching solution, dye bleaching, silver bleaching, and fixing can be carried out in a bath. In short, it is sufficient that black and white development, dye bleaching, silver bleaching, and fixing are performed before the above-mentioned processing.

In the present invention, after the fixing process is performed by the above-mentioned processing operations, the photosensitive material is treated with an aqueous solution containing a polyvalent metal compound to stabilize it.

As the polyvalent metal compound used in the present invention,
Examples include compounds of metals of Groups 1, 2, 3, and 3. Among these, metals of group 1 include magnesium, calcium, zinc, cadmium, strontium, barium, etc., and metals of group 2 include aluminum, gallium, scandium, indium, thallium, etc.

In addition, examples of metals in group 1 include chromium, molybdenum, and tungsten, and metals in group 2 include manganese.

Compounds containing these metals include inorganic acid salts such as hydroxides, sulfates, carbonates, nitrates, hydrochlorides, and phosphates, acetates, oxalates, citrates, and lactates of these metals. Examples include one or a mixture of two or more of organic acid salts.

These polyvalent metal compounds are preferably water-soluble, and divalent to tetravalent, particularly divalent or trivalent metal compounds are preferred. In the present invention, an aqueous solution containing any of these compounds can be used, but the polyvalent metal ion is 0.002 to 1 mol per 11, preferably 0.01 mol.
It is preferable to use it at a concentration of ~0.4 mol.

In other words, if polyvalent metal ions are present in the final processing bath used at such a concentration, the azo dye in gelatin and the polyvalent metal ions will form a salt, which will prevent the hue shift of the processed photosensitive material. It can be done.

A pH-reducing El agent is further added to the aqueous solution used in the present invention to adjust the pH of the aqueous solution to 2 to 5, preferably 2 to 4.
．． It is preferable to keep it at 5. Furthermore, the aqueous solution contains
Various compounds may be added. For example, antibiotics (chloramphenicol;
Kanamycin; erythromycin; leucomycin; tetracycline, etc.) or food additives (sodium benzoate; thiapentasol; salicylic acid; diphenyl; potassium sorbate; dehydroacetic acid; propionic acid; hydroxybenzoic acid, etc.) may be added. Furthermore, if necessary, a hardening agent (such as formalin), a fluorescent whitening agent, a surfactant, etc. may be added.

Further, after the treatment with the aqueous solution, washing with water, such as rinsing, spray washing, etc., may be performed as necessary.

The above treatment in the present invention is usually carried out at a temperature in the range of 10 to 60°C for 30 seconds to 2 minutes.

In the above-mentioned processing of the present invention, it is important to use the above-mentioned aqueous solution and to carry out the processing under conditions where the amount of replenishment of the aqueous solution is 11 or less, preferably 50 to 500 ml per 1 m'' of the light-sensitive material. The bath may have a one-stage or multiple-throttle configuration, but it is preferable to use a 3- to 4-stage countercurrent water washing system.Also, from the viewpoint of rapid processing, the treatment is carried out in 10 to 12 stages.
It is desirable to carry out the reaction for 0 seconds, preferably for 20 to 60 seconds.

In the present invention, following the above treatment, the photosensitive material is dried. The drying is preferably carried out at a temperature of 30°C or higher, preferably 50 to 100°C.

〔Effect of the invention〕

According to the present invention, excellent images can be obtained even when processed using a small amount of aqueous solution, the storage stability of the photosensitive material is also good, and a rapid and economical processing method is provided.

Further, according to the present invention, the hue of the photosensitive material, particularly red color, may be affected by a pH drop due to components from a pre-bath such as a fixing bath being brought into the bath used in the process with the aqueous solution used in the present invention, or by mixed components. Fewer processing methods are provided.

Next, the present invention will be explained with reference to examples.

Example 1 An undercoat layer was provided on polyethylene-coated paper, and a red-sensitized silver bromide emulsion containing the following cyan dye (C-1) was coated thereon (dry film thickness of approximately 3.5 μm). , an intermediate layer of gelatin (approximately 1.5 μm in buffy coat) is provided on top of the gelatin layer.
On top of this, a green-sensitized silver bromide emulsion containing the following magenta dye (M-1) is coated (approximately 3 μm in soft film), and then yellow fine particles of reduced silver are further dispersed on top of this. A gelatin intermediate layer (approximately 3 μm in soft film) was provided, and a blue-sensitized silver chlorobromide (silver bromide 75 mol %) emulsion containing the following yellow dye (Y-13) was coated on this layer ( Approximately 2 in pia mater
．． 5μ) and a protective layer of gelatin (approximately 1μ for buffy coat).
A photosensitive material for silver dye bleaching photography was prepared using

The coated silver amount of the photosensitive material thus produced was 0.8 g/m' in terms of silver nitrate.

This photosensitive material was used as Fujichrome Professional 120.
(Daylight type) transparencies were enlarged 5 times and printed using an enlarger set up (10 second exposure under a tungsten lamp at 2854°) and processed using the following procedure.

Black and white developer formulation Anhydrous sodium sulfite 60g Hydroquinone 6g Phenidone
0.3g Nabok x (NaBO2-
4LO) 30 g Borax (N12B4Of
f ・10H20) 9 g boric acid (H,
80,) 2 g potassium bromide
1g benzotriazole
Add 0.1 g water
11 Using the above formulation, treatment was performed at 38° C. for 1 minute and 30 seconds.

Next, dye bleaching and silver bleaching were performed in one bath at 38° C. for 1 minute.

Dye bleaching - silver source white liquor formulation 96% sulfuric acid 20rd/14-mercaptobutyric acid 1ml/'1 potassium iodide 10g/12m-sodium nitrobenzenesulfonate 7g/j! 2,3.6-trimethylquinoxaline 2 g/1 Next, using the following formulation, fixing treatment was performed at 38° C. for 1 minute.

Fixer formulation Ammonium thiosulfate 220g/j' Sodium pyrosulfite LOg/l Sodium sulfite 40g/β As the next step, treated with a pooled water wash and a pool water wash containing the polyvalent metal ion of the present invention as shown below. I did it. In addition, both processes are 38
℃, 1 minute.

Retained water washing treatment liquid containing polyvalent metal ions Potassium light bread 10g/β magnesium sulfate 1g/lg water Citric acid
2.6gL (1 nonionic surfactant
0.05 g/ll (pH 2,7; polyvalent metal ion molar concentration: 0.08%/L,/p) In the above process, the amount of fixing bath components (Fix) carried into the washing bath (washing treatment bath) was The maximum red color density (DIL) of the light-sensitive material was measured when the light-sensitive material was changed.

The results are shown in Figure 1, and when the washing treatment liquid of the present invention was used (indicated by △-△), compared to the case of the stored water type washing using simple tap water (indicated by ○-○). , it can be seen that even if the proportion of components carried over from the pre-bath increases, the D+tL value decreases little. That is, according to the present invention, the fixer (Fi
When the amount of x) mixed in is up to 10%, DIL hardly changes.

In the above processing, F1 x 8% corresponds to the replenishment amount of the aqueous solution of the present invention of 1β per 1 m' of photosensitive material.

Example 2 The photosensitive material of Example 1 was treated with the following two types of stabilizing processing solutions instead of the stabilizing solution of Example 1.

First stabilizing solution> Add 20 g of citric acid/βNaOH to pH 2.0; 2.5; 3.0; 3.5; 4
．． 0; 4.5; 5. Processing is performed by changing the temperature to 0; 5.5;

<Second stabilizing liquid> Potassium light bread 30g/β citric acid
Add 2.6 g/l NaOH to pH 2,o; 2.5; 3.0; 3.5; 4
．． The treatment was performed by changing the values as follows: 0; 4.5; 5.0;

FIG. 2 shows the RLa degree of the black part immediately after processing and drying.

As can be seen from FIG. 2, when the stabilization treatment is performed, the color immediately after treatment and drying may take on a reddish tinge depending on the pH of the stabilization solution (the first stabilization solution does not contain polyvalent metal ions), but the present invention Stabilizing liquid containing potash light bread (second stabilizing liquid)
It can be seen that when treated with , the pH range where reddishness occurs is narrowed and a good black part is easily obtained.

The reason for this is unknown, but due to the inclusion of polyvalent metal salts,
Even with insufficient water washing, the image immediately after processing and drying (mainly a cyan image) is stabilized.

Example 3 Using the same treatment solution as in Example 1, simple washing with tap water or treatment with the aqueous solution of the present invention was performed. However, simple water washing is performed by washing with hot water at 38°C for 2 minutes with 41/split water, and in processing using the aqueous solution of the present invention, the amount of replenishment is 360 mJ per ml of photosensitive material at 38°C for 1 minute! I did it.

Two types of samples obtained in this way were subjected to xenon light (80,000 lux) fading tests (2 weeks, 3 weeks, 4 weeks), heat fading tests (100°C, 8 days, 12 days, 1
6 days and 20 days later) and compared the two. the result,
Compared to the water-washed sample, the sample stabilized by the method of the present invention showed significantly lower cyan photobleaching.

(The photobleaching of RL after 4 weeks with xenon was 3.
9%; 86% with stabilization treatment) In addition, the RLO thermal fading of the stabilized product was good even in thermal fading at 100°C (81% with water washing treatment; 96% with stabilization treatment). Example 4 The exposed photosensitive material of Example 1 was processed in the following procedure, and the sample stabilized in the same manner as in Example 1 had better light fastness than the water-washed sample.

For example, R after 3 weeks of fading under xenon light (150,000 lux)
Photobleaching of L was 49% when washed with water; 68% when stabilized.
%Met.

Next, processing conditions are shown.

(1) Black-and-white development Development was carried out at 24° C. for 2 minutes using a black-and-white developer having the following formulation, followed by washing with water for 2 minutes.

Black and white development formula EDTA-2Na 1g Sodium sulfite 60g Hydroquinone
10g potassium hydroxide (48% aqueous solution)
5 cc diethylene glycol 2.
0 cc Dimedone 0.7g Sodium carbonate 20g Potassium bromide 9g Thiadiazole
Add 0.05 g water
11 (EDTΔ=ethylenediaminetetraacetic acid) (
2) Dye bleaching Treat with a dye bleaching solution of the following recipe at 24°C for 2 minutes, and wash with water for 1 minute.
I did it for a minute.

Dye bleaching solution formulation Sulfamic acid 60g Tetracyanoethylene 12mg Potassium iodide
Add 25g water
II! (3) Desilvering Treated with Brix solution with the following formulation at 24°C for 2.5 minutes,
A sample was washed with water for 3 minutes, and a sample was stabilized for 1 minute at 24° C. with a stabilization treatment solution instead of washing with water.

Brix liquid prescription ammonia water (28%) 3 ccED
TA-FeINH4150gEDTA・2
N84 20g potassium iodide
Add 300g water
1β stabilization treatment solution formulation sulfuric acid band (27W%”) 40m1/1 (A
j22 (S mouth,),) Citric acid/anhydride 2.6 g/(1
Surfactant 0.15 g/β(p
H2,10: polyvalent metal ion concentration 0.03 mol/A) Example 5 The same results as in Example 3 were obtained even when the following formulation was used instead of the stabilization treatment formulation in Example 10.

Stabilization treatment liquid formulation Magnesium sulfate 7 g/I! Sulfuric acid was added to adjust the pH to 4.0.

(Mg ion concentration 0.06moji!/f)

[Brief explanation of the drawing]

Figure 1 shows the mixing rate of the pre-bath component (FiX) and the maximum red density of the processed photosensitive material when the washing process in Example 1 of the present invention and the pooled water washing process using tap water were performed in a comparative example. (Dit), and FIG. 2 shows the relationship between pH and DIL of each stabilizer when the second stabilizer of Example 2 of the present invention and the first stabilizer for comparison are used. shows. Fix contamination rate

Claims (1)

[Claims] In the final step after the imagewise exposed silver dye-bleached photographic light-sensitive material has undergone substantially black-and-white development, dye bleaching, silver bleaching and fixing steps, an aqueous solution containing a polyvalent metal compound is used,
A method for processing a silver dye bleached photographic light-sensitive material, characterized in that the light-sensitive material is processed under conditions where the amount of replenishment of the aqueous solution is 1 liter or less per 1 m^2 of the light-sensitive material, and then dried.