JPH1069045A - Continuous processing of photographic materials - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a simple, particularly low-cost and stable method for continuous processing of photographic materials. SOLUTION: The processing bath is constantly replenished according to the amount of the processed photographic material, and the chemical to be replenished is added to the processing bath in the form of at least two concentrated solutions. A method of continuously processing materials.

Description

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to the continuous processing of photographic material in at least one processing bath in which the processing bath is constantly replenished depending on the amount of photographic material processed.

Replenishing photographic processing baths perform a variety of functions: 1. Chemicals consumed by processing and chemicals lost by entrainment to the next bath or by overflow are always replaced in the bath. It must be replaced so that a certain state is maintained.

2. The loss of liquid must be balanced, for example, by introducing dry material into the bath and removing wet material.

[0004] Replenishment solutions, as well as related processing solutions,
Often contain many chemicals, all of which contribute to the success of the process. These chemicals, regardless of their concentration, are not stable in ordinary solutions for long periods of time.

[0005] Therefore, in practice, various chemical concentrates are supplied to the treatment bath or replenisher solution, and the user, ie, the operator of the process, generally adds them to the diluent (eg, water). Mix together and make up a treatment bath or make-up solution in this way, which is then consumed in the shortest possible time.

[0006] A significant amount of overflow may occur during processing (to remove harmful chemicals released by the material), either intentionally or unavoidably due to the use of relatively thin replenishment solutions, and this overflow may occur. Are expensive because they must be reprocessed or discarded.

[0007] Considerable efforts have been made to reduce the amount of overflow as much as possible in order to obtain simpler and cheaper treatments. For this reason, most recently, in order to maintain a constant concentration of chemicals and a constant fluid level in the treatment bath, supplementary chemicals are compressed into tablets and added to the treatment bath in this form together with a small amount of water (US 533).
4 492).

[0008] This approach is disadvantageous because the production of tablets incurs additional costs. Furthermore, tablets must on the one hand be dimensionally stable, on the other hand they must dissolve readily and quickly in water, only by using auxiliary chemicals which are themselves undesirable for the processing step. Generally achievable.

It is an object of the present invention to provide a replenishment method that is simple and particularly low in cost.

[0010] Surprisingly, this object is achieved in that the chemicals to be replenished to the treatment bath are added to the treatment bath in the form of at least two concentrated solutions.

The processing bath can be a color developing bath, a black and white developing bath, a bleach bath, a fixing bath, a bleach / fix bath or a stabilizing bath.
It is preferably a color developing bath, especially a color developing bath for color negative materials.

The color negative material can be a recording material (color negative film) or a printing material (color negative photographic paper or color display material).

The method according to the present invention can be used for both color negative film processing and color photographic paper processing,
Replenishment rates and concentrations are different.

In color photographic paper development, at least two concentrated solutions, each of which contains one to one color developing agent substance and an alkali or alkali donor, are from 1 to 1 in each case.
5 ml / m ² of color paper to be developed is preferably added to the developing bath in an amount of color paper to be developed, or a third solution is provided with an antioxidant in an amount of 1 to 15 ml / m ² of color paper to be developed Three concentrated solutions, as contained, are added.

Water may be added as needed, for example, if the total amount of concentrated solution added is not sufficient to compensate for liquid losses caused by entrainment and evaporation. This can easily be done with a level adjuster. In this case, there is no overflow from the developing agent.

If overflow is desired, for example to remove unwanted chemicals released from the material, the amount of water added may be increased accordingly.

In color film development, at least two concentrated solutions, each containing one or more of the solutions containing a color developing agent substance and an alkali or alkali donor, are prepared in three to three times.
The amount of the color film to be developed of 300 ml / m ² , more preferably 3 to 90 ml / m ² , is suitably added to the developing bath, or the third solution contains an antioxidant of 3 to 200 m / m ^2.
1 / m ² , more preferably from 3 to 90 ml / m ² , at least 3 such as contained in the amount of color paper to be developed.
A seed concentrated solution is added.

For color negative photographic paper, water may be added.

Color development is generally performed by bleaching, fixing and stabilizing, where bleaching and fixing may be combined in one step.

In another development, a replenishment of the bleach / fix bath is provided in the method according to the invention.

The direct addition of the concentrate in the process according to the invention avoids the production of a usual replenisher, where the concentrate is substantially more stable than the replenisher and less expensive than chemical tablets.

The direct addition of the concentrate is for minilab operation,
It is particularly suitable for decentralized photographic processors which are used only when necessary, such that the water coupling device and the spent chemical bath are not often reprocessed.

In a preferred embodiment, the individual concentrates contain the following characteristic chemicals in the following concentrations:

1) Color negative photographic paper developing agent Concentrate A: 15-160 g / l diethylhydroxylamine Concentrate B: 30-605 g / l 4- (N-ethyl-N-2-methylsulfonylaminoethyl)- 2-methyl--p- phenylenediamine sesquisulfate monohydrate (CD-3) concentrate C: 40400 g / l of K ₂ CO _{3 2)} color negative photographic paper developing agent concentrate a: the 15~400g / l Hydroxylamine concentrate B: 45-200 g / l 4- (N-ethyl-N-2-hydroxyethyl) -2-methyl-p-phenylenediamine (CD-4) concentrate C: 150-600 g / l K ₂ CO _{3 3)} bleach / fixing bath concentrate for color photographic paper a: 350~700g / l of ammonium thiosulphate concentrate B: 300~610g / l of iron / Ann Um ethylenediaminetetraacetic acid complex salt concentrated solution C: 100~640g / l of CH ₃ COO
H.

If the bleaching / fixing properties of the material to be processed allow, the concentrate C can be omitted.

The concentration of the concentrated liquids A to C is 1 to 20 ml / m
²

"Characteristic chemical" means that the compound should actually be present only at the concentrations indicated, but is not present in the other two concentrates, ie Otherwise it means their stability will be compromised.

[0028]

EXAMPLE 1 Blue-sensitive silver halide emulsion layer coated on both sides with polyethylene and containing (starting from the support) a yellow coupler containing a yellow coupler, an intermediate layer, a magenta coupler Layer, an intermediate layer, a red-sensitive silver halide emulsion layer containing a cyan coupler, a colloid layer containing an ultraviolet absorber and a protective layer,
Layer thickness of 9 μm dry thickness, 90 mol% of silver halide
The above consisted of AgCl and was calculated as AgNO ₃ 1.1.
A color negative photographic paper having a silver halide application rate of g / m ² and gelatin as binder in all layers is imagewise exposed and processed continuously using the following method: a) Color developing agent -45 seconds -35 ± 1 ° C. caprolactam 12 g N, N-diethylhydroxylamine 4.0 g CD-3 5.0 g of potassium carbonate 30.0g anhydrous maleate 2.5g hydroxyethane diphosphate (HEDP) 0.2 g optical bright coloring agent (4,4'-diaminostilbene-sulphonic acid derivative) 2.0 g and 1000ml potassium bromide 0.02g water, KOH or H ₂ SO ₄ to pH values
Adjust to pH 10.2 with.

B) Bleaching / fixing bath—45 seconds at −35 ° C. 75.0 g of ammonium thiosulfate 18 g of sodium thiosulfate 45.0 g of ethylenediaminetetraacetic acid (EDTA) (iron / ammonium salt) The solution was adjusted to 1000 ml with water, and the pH was adjusted to ammonia (25%). %) Or acetic acid to pH 6.0.

C) Rinse-90 seconds at −33 ° C. d) Dry rinse may be replaced by a stabilizing bath: c) Stabilized—90 seconds at −33 ° C. Sodium benzoate 1 g Sodium sulfite 2 g Sodium hexametaphosphate 2 g HEDP 3 Make up to 1000 ml with 0.5 g water and adjust the pH to 5.5 with acetic acid or ammonia.

The bath is replenished in the following manner: 1. Color developing agent 300 g caprolactam / l 60 g N, N-diethylhydroxylamine / l 40 g optical brightener / l 50 mg tetraethyl perfluorooctanesulfonate 2.8 ml concentrate A / m ² containing ammonium salt / l, 120 g CD-3 / l 5 g Na ₂ SO ₃ / l 5.25 ml concentrate B containing 2.5 g HEDP / l / M ² , 3 ml of concentrate C containing 300 g of K ₂ CO ₃ / l 82 g of KOH / l 45 g of polymaleic anhydride / l 0.25 g of KBr / l

About 24 ml of water.

There is no overflow. Loading ratio is 30 ~
40 ml / m ² .

2. Bleaching / fixing bath 523 g ammonium thiosulfate / l 3.6 g NH ₃ / l 98 g Na ₂ S ₂ O ₅ / l 17.5 ml concentrate containing 59 g NH ₄ HSO ₃ / l A / m ² 14 ml concentrate B / m ² containing 504 g EDTA iron / ammonium salt / l 12 g acetic acid / l.

14 ml of water.

3. Stabilizing bath 40 g of sodium benzoate / l 80 g of Na ₂ SO ₃ / l 5.1 g of acetic acid / l 6 ml of concentrate A / m ² 140 g of HEDP / l 80 g of hexametaphosphoric acid 6 ml of concentrate B / m ² prepared from 30 g of NaOH / l of sodium / l.

The developing agent, bleach / fix bath and stabilizing bath concentrate have a minimum shelf life of 6 months at 20 ° C. when opened and 1 year or more at 20 ° C. when not opened. Photometer results are typical.

Example 2 Example 1 is repeated, but the individual baths are replenished as follows: 1. Color developing agent 70 ml / m ² caprolactam 30 g / l N, N-diethylhydroxylamine 6 g / l CD-3 12 g / l potassium carbonate 30 g / l polymaleic anhydride 4.5 g / l optical brightener 3.8 g / l KBr 0.03 g / l HEDP 0.25 g / l 2. bleach / fix bath 110 ml / m ² thio Ammonium sulfate 84 g / l Na ₂ S ₂ O ₅ 15.7 g / l NH ₄ HSO ₃ 9.3 g / l NH ₄ FeEDTA 63 g / l acetic acid 11.1 g / l 3. Stabilization bath 250 ml / m ² sodium benzoate 1 g / l sodium sulfite 2 g / l sodium hexametaphosphate 2 g / l HEDP 3.5 g / l acetic acid 0.15 g / l The results of the sensitometer are typical. The freshly prepared replenishment solution has the following maximum shelf life for typical results:

Color developing agent: 6 weeks Bleaching / fixing bath: 6 weeks Stabilizing bath: 8 weeks Example 3 A color negative film having a silver halide application rate of about 3 g Ag / m ² is imagewise exposed and Process continuously using the method.

A) Color developing agent 185-200 seconds / 38 ° C. 2.6 g of diethylenetriaminepentaacetic acid (DTPA) 2.6 g of hydroxylammonium sulfate 2.2 g of CD-4 4.5 g of sodium sulfite 4 g of potassium carbonate 35 g of potassium bromide 1.5 g with water Make up to 1000 ml and adjust the pH to pH 10.1 with KOH or H ₂ SO ₄ .

B) Bleaching / fixing bath 1, 260 sec, 35-41 ° C. Ammonium / iron EDTA salt 120 g Ammonium bromide 140 g Nitric acid 10 g Acetic acid 30 g Make up to 1 l with water, pH value to 6 with ammonia (25%) or acetic acid Adjust.

Bleaching / fixing bath 2, 200 seconds, 35-41 ° C. Propylenediaminetetraacetic acid (PDTA) 60 g Ammonium / iron salt Ammonium bromide 35 g Ammonium nitrate 40 g Ammonium acetate 45 g Acetic acid 90 g Water is adjusted to 1 liter with water and the pH is adjusted to ammonia or acetic acid. Adjust to pH 4.8 with.

Bleaching / fixing bath 3, 200 seconds, 35-41 ° C. Iron β-alanine diacetate 45 g Ammonium bromide 60 g Nitric acid 45 g Adjust to pH 1 with water and adjust pH to 4.4 with ammonia or nitric acid.

C) Rinsing optionally, for 60 seconds d) Fixing bath 1, 240 seconds, 35-41 ° C. 120 g / l ammonium thiosulphate 20 g / l sodium sulphite Make up to 1 l with water and adjust the pH to pH 7 with ammonia.

Fixing bath 2, 60 seconds, 35-41 ° C. Ammonium thiosulfate 115 g / l Sodium sulfite 20 g / l Ammonium thiocyanate 130 g / l The pH value is adjusted to pH 7 with ammonia.

E) Rinsing optionally, 24 sec at 41-41 ° C. f) Stabilizing bath, 0.5 g of formalin , 24 sec at 41-41 ° C. 0.5 ml of 0.5% by weight solution 0.5 ml of water to 1 l. .

G) Replenish the drying bath in the following manner: 1) 280 g of color developing agent hydroxylammonium sulfate or (11)
4.7 g of concentrate A / m ² containing 3 g) of hydroxylamine, 131 g of CD-4 112 g of Na ₂ SO ₃ / l (or 85 g of Na ₂ S ₂ O)
19.2 ml of concentrate B / m ² containing ₅ and 21.5 g of KOH), 31.8 ml of 290 g of K ₂ CO ₃ / l 55.2 g of DTPA sodium salt / l 39 g of KOH / l Concentrate C / m ² 284 ml / m ² water 2) Bleach bath 1 240 g / l ammonium / iron EDTA salt 355 g ammonium bromide 47 ml concentrate A / m ² containing 23 g / l nitric acid

6 ml of concentrate B / m ² containing 640 g / l acetic acid.

Bleaching bath 2 135 g ammonium / iron EDTA salt 80 g ammonium bromide 100 g / l ammonium nitrate 100 g / l ammonium acetate 245 g concentrate A / m ² containing 219 g / l acetic acid, 640 g / l 5 ml of concentrate B / m ² containing 1 acetic acid.

Bleaching bath 3 148 g / l β-alanine diacetate iron salt 208 g ammonium bromide 73 g / l nitric acid 30 ml concentrate A / m ² containing 35 g / l acetic acid, 218 g / l nitric acid 12 ml of concentrate B / m ² containing.

3) Fixing bath 1 A constant electrolysis reduces the silver content below 2 g / l.

25 ml / m ² containing 600 g of ammonium thiosulfate and 170 g of sodium sulfite.

Fixing bath 2 Ammonium thiosulfate 240 g Ammonium thiocyanate 270 g 300 ml / m ² containing 50 g of sodium sulfite.

+300 ml / m ² water or stabilizing bath overflow 4) Stabilizing bath 8 ml / m ² formalin 50 g / l wetting agent, containing 50 ml / l 0.5% by weight solution together with 800 ml / m ² water I do.

Each of the bleaching baths 1 to 3 and each of the fixing baths 1 and 2 should be considered as a two or three alternative.

Example 4 Example 3 is repeated, but replenishing the individual baths as follows: 1) Color developing agent: 1180 ml / m ² KBr 0.5 g / l DTPA 2.6 g / l K ₂ CO ₃ 35 g / l hydroxylammonium sulfate 3.1 g / l (or hydroxylamine 1.3 g / l) sodium sulfite 4.8 g / l CD-4 6 g / l 2) bleach bath 1 825 ml / m ² ammonium bromide 165 g / l ammonium / Iron EDTA salt 120 g / l acetic acid 8.5 g / l HNO ₃ 15 g / l bleach bath 2 825 ml / m ² ammonium / iron EDTA salt 50 g / l ammonium bromide 30 g / l ammonium nitrate 30 g / l ammonium acetate 50 g / l acetic acid 60 g / l bleach baths 3 550ml / m ² β- alanine diacetic acid iron salt 55 g / l ammonium bromide 70g l nitrate 40 g / l 3) fixing bath 1 825 ml / m ² Ammonium thiosulfate 140 g / l sodium sulphite 15 g / l fixing bath 2 825 ml / m ² Ammonium thiosulfate 120 g / l of ammonium thiocyanate 130 g / l sodium sulphite 50 g / l 4) stable Bath formalin 0.5 g / l Intrasol 0.5 g / l fungicide The results of the sensitometer are typical. The freshly prepared replenishment solution has the following maximum shelf life for typical results:

Color developing agent: 4 weeks Bleaching bath: 3 months Fixing bath: 8 weeks Stabilizing bath: 8 weeks The main features and aspects of the present invention are as follows.

1. A process for continuously processing photographic material in at least one processing bath in which the processing bath is constantly replenished in accordance with the amount of processed photographic material, wherein the replenishing chemical is at least two concentrated solutions. A method characterized in that it is added to the treatment bath in form.

2. The photographic material is (1) color development, (2)
A color photographic silver halide material processed using the steps of bleaching / fixing and (3) rinsing or stabilizing, wherein the color developer bath is replenished with at least three concentrated solutions. Method according to 1.

3. The photographic material is color negative photographic paper, the color developing agent contains the following characteristic chemicals at the indicated concentrations in three concentrates: Concentrate A: 15-160 g / l diethylhydroxylamine Concentrate B : 30 to 605 g / l of 4- (N-ethyl-)
N-2- methylsulfonyl-aminoethyl) -2-methyl -p- phenylenediamine sesquisulfate monohydrate (CD-3) concentrate C: 40400 g / supplemented by that as well as supplemented with of K ₂ CO ₃ l Is carried out using 1 to 15 ml of each concentrate per 1 m ² of color negative photographic paper.

4. The photographic material is color negative photographic paper, the bleach / fix bath contains two or three concentrates containing the following characteristic chemicals at the indicated concentrations: Concentrate A: 350-700 g / l ammonium thiosulphate concentrate B: 300~610g / l of iron / ammonium ethylenediaminetetraacetic acid complex salt concentrated solution C: 100~640g / l of CH ₃ being supplemented with COOH, replenishment of 1~20ml per color negative photographic paper 1 m ² A process according to claim 1, characterized in that it is carried out with each concentrate and in the case of only two concentrates the concentrate C can be omitted.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Herbert Mitstwinger Germany 51789 Lindler Romersberger Bake 3

Claims (1)

[Claims] 1. A method of continuously processing photographic material in at least one processing bath in which the processing bath is constantly replenished depending on the amount of photographic material processed, wherein the replenishing chemical is at least two chemicals. A method characterized in that it is added to the treatment bath in the form of a concentrated solution of the seed.