DE1921054C3 - Photographic fixer developer - Google Patents

Description

lent loss of density, gradation and more practical Sensitivity balanced, but beyond that compared to the conventional development with separate Fixage an increase in sensitivity and density performance can be achieved without it an increased application of halogen silver would be necessary. According to the invention, this object is achieved by a Fixing developer for the simultaneous development and fixing of photographic silver halide emulsions solved, which is characterized in that it has at least one developer-coupler compound as a developer substance contains the following general formula:

CH ₂ - NO

NH,

where R is H, alkyl, aralkyl. Is carboxymethyl, R. equals H. an alkyl radical with! up to 4 carbon atoms, Cl, Br or - COOH, Y 'is --Oil or - NH ₂ , with at least one of the positions 2 and 4 capable of coupling being unsubstituted.

Developer-coupler compounds corresponding to this formula and a process for their preparation are described in DT-OS 1 793 289.

The substances described are distinguished by the fact that, in addition to the silver image, they also have a build up a brown-black or blue-black dye image, a property that makes them particularly valuable for use in mono bathrooms. The density gain through the formation of this additional Dye image is far larger than that with optimal fix development in the absence of self-coupling Development compounds observed loss of density and speed, so that according to the present Process even light-sensitive materials with reduced halogen silver deposition very good sensitometric results can be prepared using the single bath method. The advantages this finding for the construction of halogen silver materials specially intended for single bath processing are obvious: the product costs can be reduced, the image performance can be improved by reducing the layer thickness, and the silver sludge deposition in the bathers is advantageously reduced by reducing the amount of dissolved silver salts.

That the compounds described use fixation development with such good results was surprising, because these connections, derived from p-aminophenol, have z. B. compared with hydroquinone only a small Development speed.

On the other hand, however, it is known that only developing substances that are characterized by rapid pumping and a high development speed can be used for the fixing process, because only if the development process begins at a point in time at which the exposed silver halide grains have not yet been significantly absorbed by the fixing agent present are dissolved, sufficient densities can be obtained. That such a rapid and excellent build-up of density would take place in the present case, despite the comparatively slow development rate, could not be expected without further ado.
The developer-coupler compounds can be used alone or in admixture with one another. The use of a mixture is always recommended if there are special requirements regarding the color of the finished picture

ίο be.

The compounds are expediently the one bath solution in the form of their salts in amounts of about 2 to 50 g / l, preferably 10 to 20 g / l processing solution added. Depending on the type of halogen silver emulsion used, e.g. B. depending on the halogen silver application and other factors, the desired effect can possibly even with smaller ones Quantities or, if necessary, larger quantities can be achieved without any impairment.

The monobath solutions according to the invention can, in addition to the essential components mentioned, namely at least one developer-coupler compound according to the invention, an alkali and a fixing agent, all additives common in developer chemistry, such as anti-oxidants, development accelerators, Contain stabilizers and the like.

In some cases it can be followed by a post-treatment with an alkaline solution to be carried out on the soaking process. the density of the generated image increases and the hue are favorably influenced.

Particularly advantageous results can be achieved with monobaths which the invention Compounds in combination with one of the known black and white developer substances superadditive effect or l-phenyl-3-pyrazolidone Contain N-methyl-p-aminophenol.

The processed with the monobaths according to the invention Photographic layers are characterized by sensitivity and density values that so largely to those who are preserved in the two-bath process with separate development and fixation are superior in that it is possible to use light-sensitive materials with reduced halogen silver coating can be processed with very good sensitometric results in the single bath method.

Furthermore, the image performance can be improved by reducing the layer thickness and the Separation of silver sludge in the baths is advantageous by reducing the amount of silver salts dissolved out be reduced.

The invention is illustrated by the following examples explained. The composition of the baths according to the invention is of course dependent on the respective to match the type of emulsion used, but this can easily be done in an optimal manner by any person skilled in the art can.

All examples have been used for simplicity the sensitivity given in relative values. d. that is, it becomes the multiple of sensitivity achieved compared to a comparison test. As a comparison experiment, the Processing with a conventional hydroquinone-1-phenyl-3-pyrazolidone developer with separate fixation (developer C, example 1) was selected and the sensitivity achieved in this way was set to 1.

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J. W L ^ Λ.

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example 1

3 strips of a panchromatically sensitized document film with a gelatin-silver halide emulsion of 70 molar percent AgCl and 30 mol percent AgBr, a gelatin-silver nitrate weight ratio of 0.6 and a casting amount corresponding to 47 mg AgNO ₃ per square decimetre were 0.02 seconds on a DJN device (Osram tungsten lamp Wi 40/1, 2600 ^D K) exposed with a wedge (wedge constant 0.25 / cm, illuminance at the wedge 125 lux) and processed according to A, B and C.

A 15 g sulfate of N- (2'-hydroxy-5'-aminobenzyl) -

3-hydroxyaniline,
0.3 g of l-phenyl-3-pyrazolidone,
15OgNaBO ₂ -4H ₂ O,
50 g Na ₂ SO ₃ anhyd.,
5 g KOH,

40g Na ₂ S ₂ O ₃ -5 H, O,
3 g KBr,

1 g ethylenediaminetetraacetic acid dinalrium

salt,

8 ml ethylene glycol,
on 11 water pH = 11.4.

In this solution, strip 1 was developed in a ^{fixative manner at 20 °} C. for 3 minutes. This was followed by watering for 3 minutes, aftertreatment for 3 minutes in a final bath of 0.15 g of ascorbic acid, 0.4 g of NaOH and 5 g of Na ₂ CO per liter of water and drying.

B Strip 2 was processed in a fixing developer analogous to A with 15 g of hydroquinone instead of N- (2'-hydroxy-5'-aminobenzyl) -3-hydroxy-aniline for 3 minutes at 20 ^° C., rinsed for 3 minutes and dried.

C Strip 3 became the following under the same conditions in a conventional developer Composition developed, fixed and dried after soaking: 40 -

15 g hydroquinone,
0.3g l-phenyl-3-pyrazolidone,

50 g Na ₂ CO ₃ , anhyd.,

60 g Na ₂ SO ₃ , anhyd., 0.3 g K ₂ S ₂ O ₅ ,

2 g disodium hexametaphosphate,

1.1 g ethylenediaminetetraacetic acid disodium

salt,
0.2 g KNO ₃ ,

3 g KBr,

0.1 g benzotriazole,
on 1 l of water pH = 11.0.

_v per square meter were 2 seconds on an exposure device (2 Osram lamps Wi 9, 2600 ^J K, two blue Jena filter types BG 3 (1.9 mm) and BG 38 (1.5 mm), illuminance on the gray gradient wedge 20 lux (wedge constant 0.15 / cm) exposed and processed according to A, B and D.

A 20 g sulfate of N- (2'-hydroxy-5'-aminobenzyl> -

3-hydroxyaniline,
150 g NaBO ₂ -4H ₂ O,
50 g Na ₂ SO ₃ , anhyd.,
14g KOH,

40 g Na ₂ S ₂ O ₃ -5H ₂ O,
1 g ethylenediaminetetraacetic acid disodium salt,
3 g KBr,

0.3 g thiosalicylic acid,
on 1 water pH = 12.3.

Strip 1 was developed in a fixative manner for 3 minutes at 20 ^° C. in the developer described under A and watered, aftertreated and dried according to the information in Example 1.

B Strip 2 was in the developer described under A, which also contained 0.5 g of 1-phenyl-3-pyrazolidone contained, developed fixation for 3 minutes at 20'C and according to the information from Example 1 watered, treated and dried.

C strip 3 was developed in a fixative manner analogously to Example 2 B for 3 minutes at 20 ^° C. with 20 g of hydroquinone instead of N - (2 '- hydroxy - 5' - aminobenzyl) - 3 - hydroxyaniline, washed and dried.

D strip4 was at 20 "C for 3 minutes in the Processed developer described under Example 1 C with subsequent fixation.

Strip 1
Strip 2
Strip 3

Relative
sensitivity Maximum
density 1.6
0.5
1.0 over 4.5
3.8
over 4.5

Example 2

4 strips of an X-ray film coated on both sides with a gelatin silver halide emulsion of 98.3 mol percent AgBr and 1.7 mol percent AgI, a Gclatinc silver nitrate weight ratio of 1.0 and a coating corresponding to 60 mg AgNO, strip 1
Strip 2
Strip 3
Strip 4

Relative Maximum sensitivity density 1.2 1.8 1.3 2.4 0.4 0.9 1.0 1.3

gradation

1.4
1.4
0.8
1.4

Example 3

Two exposed X-ray film strips were processed in the following fixing developer for 3 minutes at 20 ^° C.:

20 g sulfate of N- (2'-hydroxy-5'-aminobenzyl) -

3-aminoaniline,
1 g of N-methyl-p-aminophenol,
150 g NaBO ₂ -4H ₂ O,
50 g Na ₂ S ₂ O ₃ -5H ₂ O,
14g KOH,
5 g KBr,
on 11 water pH = 12.5.

Then strip 1 was watered, aftertreated and dried as in Example 1A.

Strip 2 was not treated afterwards, only watered and dried.

In addition, a strip (strip 3) was fixicrentwickelt without N-mcthyl-p-aminophenol 3 minutes at 20 ⁰ C and then processed without aftertreatment.

Strip 1
Strip 2
Strip 3

Relative sensitivity, related on strip 4. Example 2

1.6
1.5

1.2

Maximum density

2.7 2.5 1.9

gradation

2.6 2.5 2.0 strips 1
Strip 2

Relative sensitivity, related on strip 4, Example 2

1.7
1.6

gradation

2.1 2.0

Example 4

Two exposed X-ray film strips were processed in the following fixing developer for 3 minutes at 20 ^° C.:

20g sulfate of N-methyl-N- (2'-hydroxy-

5'-aminobenzyl) -3-aminoaniline, 0.5 g of 1-phenyl-3-pyrazolidone. 150 g NaBO ₂ -4H ₂ O,
40g. Na ₂ S ₂ O ₃ -5H, O.
14g KOH,
1 g ethylenediaminetetraacetic acid disodium

salt,

3 g KBr,

0.1 g thiosalicylic acid,
on 11 water pH = 12.9.

Then strip 1 was made as in Example 1A watered, treated and dried.

Strip 2 was not treated afterwards, only watered and dried.

Example 6

An exposed X-ray film strip was in a fix developer of the following composition for 3 minutes processed at 20 ° C:

10g N- (2'-Hydroxy-5'-aminobenzyl) sulfate

3-hydroxyaniline,
10g N- (2'-Hydroxy-5'-aminobenzyl) sulfate

3-aminoaniline,
14 g KOH,

150 g NaBO ₂ -4H ₂ O,
50 g Na ₂ SO ₃ , anhyd.,
40 g Na ₂ S ₂ O ₃ -5H ₁ O,

SgKBr,

0.5g l-phenyl-3-pyrazolidone, 1 g ethylenediaminetetraacetic acid disodium

salt.
on 1 l of water pH = 12.5.

It was then watered as in Example 1A and dried.

Strip 1
Strip 2

Relative sensitivity, related on strip 4, Example 2

1.7
1.5

Maximum density

2.8

Cj radation

2.6

2.3

Relative sensitive wedge, based on Strip 4, example 2

1.3

Maximum density

2.7

gradation

2, f)

Example 5

Two exposed X-ray film strips were processed in the following monobath 3 minutes at 2O ⁰ C:

20 g sulfate of N- <2'-hydroxy-5'-aminobenzyl) -

3-amino-6-carboxy-aniline, 0.5 e l-phenyl-3-pyrazolidone, 150 g NaBO ₂ · 4Η, Ο,
60 g Na ₂ S ₂ O ₃ -5H ₂ O,
14g KOH,
1 g ethylenediaminetetraacetic acid disodium

salt,
5 g KBr,
on 1 l of water pH = 12A

Strip 1 was then watered, aftertreated and dried as in Example IA.

Strip 2 was not treated afterwards, only watered and dried.

Example 7

An exposed X-ray film strip was processed for 3 minutes at 20 C in a fix developer with the following composition:

20 g hydrochloride of 4-amino-2- (m-hydroxybenzylamino) phenol (according to GB-PS 900155),

0.5g l-phenyl-3-pyrazolidone, 150 g NaBO, 5H ^ O,
50 ε Na ₂ SO ₃ . anhyd.,
40g Na ₂ S ₂ O ₃ -5H, O.
14 g KOH,

I g ethylenediaminetetraacetic acid disodium salt,

3 g KBr,
on 11 water pH = 11.6.

This was followed by watering for 3 minutes and drying.

Relative sensitivity, based on Strip 4, example 2

0.5

Maximum density

1.0

gradation

1.0

509632/27;

Claims (4)

Patent claims: 1. Photographic paper · Fixing developer for simultaneous Developing and fixing photographs of halogenated silver emulsions containing a Alkali, an alkali or alkaline earth thiosulfate as a fixing agent and a developing substance thereby characterized as being a developing agent at least one developer-coupler compound contains the following general formula: OH NH, where R is H, alkyl, aralkyl, carboxymethyl, R ₁ is H, an alkyl radical with 1 to 4 carbon atoms, Cl, Br or - COOH, Y 'is - OH or - NH ₂ , with at least one of the for coupling qualified positions 2 and 4 is unsubstituted. 2. Photographic fixing developer according to claim 1, characterized in that it has a Contains developer-coupler compound of the following formula: OH CH ₁ -NH 30th 35 OH 3. A photographic fixing developer according to claim 1. characterized by being a developer-coupler compound of the following Formula contains: OH 45 f. -CH, -NH NH ₂ 4. Photographic fixing developer according to one of the preceding claims, characterized in that that he is in addition to at least one developer-coupler compound as a developer substance nor 1-phenyl-3-pyrazolidone or N-methyl-p-aminophynol contains. 60 The present invention is a photographic fixing developer for simultaneous Developing and fixing of halogen silver emulsions. Development and fixation of pholographic halo-silver emulsions are generally carried out in separate baths in practice. It exists however, it is also possible to combine the two processing steps in one bath, the so-called monobath, to unite. Such monobaths make it possible to simplify the overall processing process and make it essential to be shortened, so that they are of increased importance, especially in recent times, when one strives for ever shorter processing times. The main reason is that monobaths have not found their way into practice to a greater extent the fact that when using the monobaths compared to the conventional two-bath processing usually has to accept a loss of density and sensitivity. During the fusing development, the development and fusing process run side by side at the same time, that is, as the development begins, the fixing process also begins. Part of the exposed halogen silver the layer is therefore already dissolved before the chemical development could take place. By In a physical development process, part of the dissolved halogen silver is reduced again and attached to the image silver. However, due to its shape, this silver is very weak Opacity, which inevitably leads to the fact that the sensitivity utilization in almost all cases of the is inferior to conventional two-bath processing. Fixing developers are also known from the literature which, compared to two-bath processing, have should work with little or no loss of sensitivity. All of these baths are in common that they are l-phenyl-3-pyrazolidone or Aminonyrazolines in a superadditive mixture with a conventional developer substance, usually hydroquinone, contain. Such fixing developers are e.g. B. described in the French patent 1 204 273: the German patent specification 1 024 798; the German Auslegeschrift 1 149 247 and German Patent 1 151 175. Due to the simultaneous process of development and fixation and the incomplete process associated with it Utilization of the halogen silver will however in all cases also be the maximum developable density the gradation can be lower than with conventional two-bath processing. To compensate for this disadvantage, It is common in practice to use light-sensitive materials intended for fixation development are to be provided with an increased amount of halogen silver. In GB-PS 900155 there are 2,4-diaminophenol compounds as a developer ^ described, which is particularly suitable for the fixation development of diffusion transfer materials. From p. 2. Lines 60 to 64 of the above The patent states that these compounds do not form colored oxidation products, i. do not deposit any dye image. So it is not possible with these connections either. To produce pictures, which, in addition to the silver image, also contain a dye image and are therefore characterized by an increased density distinguish. The invention is based on the object of providing a photographic fixing developer for halogen silver emulsion layers to create that in its performance in terms of sensitive wedge utilization. contrast and maximum density is significantly superior to the previously known single-bath systems. It should not only the otherwise unavoidable