DE2102713A1 - Hardening bleach-fix baths - Google Patents

Description

AGFA-GEVAERTAG

PATENT DEPARTMENT

hs-mka Leverkusen

20 JAN.

Hardening bleach-fix baths

The invention relates to a color photographic processing method using a hardness bleach-fixer.
The processing methods for silver halide color photographic materials are known to include the steps
imagewise exposure, color development, bleaching (ie oxidation of the silver image resulting from color development) and
Fixing (ie complexing dissolving of the unused silver halide and the silver salts formed during bleaching). Occasionally, treatment with a gelatin hardener is also interposed. The latter is becoming more and more important, as it is with the modern rapid processing methods
higher demands are placed on the materials to be processed with respect to their hardening, either because of the higher processing temperatures used, or because of
the used aggressive baths, for example strong
can be acidic or highly alkaline.

^A " ^{a 766} 209813/0376

At the same time, however, one also strives to reduce the number of processing to keep the required bathrooms as small as possible. It has therefore There has been no lack of attempts to combine two or more different necessary processing steps in a single treatment bath. As a result of these efforts, for example Mentioned: hardening developer baths, fixer developer baths, hardness fixer baths, bleach-fixer baths or shading Developer baths.

Of course, only such punctures can be used in a bathroom are combined with each other that do not cancel each other out. For example, it is inconceivable that development and Bleaching of a silver image can be carried out at the same time.

It has now been found that in the processing of color photographic Silver halide materials hardening, bleaching and fixation can be combined in a single bath.

The present application therefore relates to a method for producing colored images using a color photographic material with at least one silver halide emulsion layer, preferably with at least 3 differently sensitized, optionally containing color couplers Silver halide emulsion layers comprising the process steps of image-wise exposure, color development, hardening and bleaching and fixing, characterized in that the process steps of hardening, bleaching and fixing are carried out simultaneously in a hardness bleach-fixing bath which contains a gelatin hardener, a bleaching oxidizer and sodium thio sulfate.

Baths that simultaneously have both a silver picture in one operation to bleach as well as to dissolve any residual halogen silver and also to harden the photographic emulsion layers, are unknown until now. The following properties are required of such a bath:

AG 766 -Z-

209833/0876

It must contain a bleaching oxidizing agent that is capable of oxidizing finely divided silver on the one hand, and the on the other hand Fixing agent and hardening agent does not attack. The hardening agent, in turn, must not use either the oxidizing agent or a For the bleach fixation indispensable additive, e.g. a complexing agent, react. Finally, the fixative must be included be compatible with the bleaching and hardening agents. Such a hardness bleach-fixer is also required to be unfolds its functions in a pH range that the individual components of the photographic material, e.g. dyes or color couplers, tolerated without disadvantage.

In the case of gelatin hardeners used in photographic practice, in particular those that are used in an aqueous treatment bath are usually involved formaldehyde or other water-soluble aldehydes, preferably aliphatic dialdehydes. The mentioned connections are known to be easily oxidizable substances. It must therefore be regarded as extremely surprising that the gelatin hardeners in the hardness bleach-fix baths of the present invention can be combined with the corresponding oxidizing bleaching agents without any adverse effect. It is on At this point it is expressly pointed out that the baths according to the invention are extremely stable, that is to say maintain their activity even if stored for a longer period of time.

Suitable gelatin hardeners for the hardness bleach-fix baths according to the invention are therefore preferably formaldehyde or aliphatic dialdehydes with 4-5 carbon atoms, the carbon chain of which can also be interrupted by an oxygen, sulfur or nitrogen atom. Examples are: formaldehyde, succinaldehyde, glutaraldehyde, bis (formylmethyl) ether, bis-teormyL-methyl ^ Lg ₁₁ If id. or bis- {formy line thy I } -amine, the latter optionally further substituted on the nitrogen, for example by methyl, hydroxyethyl or formylmethyl.

A-G 766 - 3 -

209833/0876

The gelatin hardening agents mentioned are in the present invention Hardness bleach-fixing baths in quantities of 3-2Og per liter, preferably from 5 to 15 g per liter. These aldehydes cure best in the weakly alkaline range; one preferred therefore a pH range of 7-9, especially between 8 and 8.5.

Suitable oxidizing bleaches for the invention Hardness bleach-fix baths are, for example, complex compounds of metals, which are in a higher valence level of several possible, with certain complex-forming aminoacetic acid derivatives, E.g. the complexes of trivalent iron (compare German patent specification 866 605) and trivalent iron Cobalt (compare German patent specification 954 475) with nitrilotriacetic acid, Ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid and the same. The iron (III) complex of ethylenediaminetetraacetic acid is preferably used. the The solubility of this iron complex in solutions containing sodium ions is limited. Quantities between 20 and 40 g are preferred used per liter. To avoid dark, dull-red haze, add one to the bleach-fix baths Complexing agents, usually the complexing agent, the iron (III) or cobalt (III) complexes of which are used.

The hardening "bleach-fix" baths according to the invention contain as a fixing agent which reacts neither with the hardening agent nor with the bleaching agent Sodium thiosulphate in an amount between 50 and 300 g per liter, preferably between 100 and 200 g per liter.

About the durability of the hardness bleach-fix baths according to the invention To increase it further, either sodium sulfite or an organic sulfinic acid is added to the bath, optionally in the form

A-G 766. - 4 -

209833/0876

their alkali or alkaline earth salts, both have proven themselves aliphatic and aromatic sulfinic acids. Preferred benzenesulfinic acid is used in the form of its sodium salt in quantities of 5-10 g per liter.

The activity of such a bath in terms of bleaching and / or fixation can furthermore be achieved by adding further substances increase. Possible additives are, for example: water-soluble iodides (see German patent specification 1 127 715), organic compounds with thioketo groups (see Swiss Patent 336 257), polyethylene oxides (see German patent specification 966 410) and polythioether (see German patent specification 1,146,363).

The hardness bleach-fix baths according to the invention are suitable for processing color photographic materials based on silver halide, preferably for those materials in which the colored images are produced by chromogenic development. Not only color photographic negative materials are processed with the help of the hardness bleach-fix baths according to the invention, but also positive materials, for example those in which the process step of color development is preceded by black and white development and uniform fogging by exposure or by a chemical treatment bath. The bleach-fixer baths according to the invention are of course also suitable for processing color photographic materials in which the colored image is not produced by a chromogenic process, but by image-wise degradation of dyes, for example in the silver dye bleaching process. The Sirberfarbbleichbäder generally contain 10 to 15 $> concentrated sulfuric acid and access consequently not completely hardened gelatin layers sharply. For this reason, a hardening bath is normally included in the processing stage, usually before the silver color bleaching, and occasionally afterwards. It has now been shown that this hardening treatment can also be carried out with the aid of the hardness bleach-fixing bath according to the invention,

A-G 766 - 5 -

209833/0876

that in place of the usual bleach-fix bath in normal Silver dye bleaching process occurs. The combination of hardening and bleaching fixation thus saves a bath and thus to a simplification of the whole process. This is not only true, as described in Example 5, for positive positive working, but also for negative-positive working silver dye bleach materials, such as those in Examples 7 and 8 of DOS 1,814,834 are described.

example 1

2 liters of a hardness bleach-fix bath of the following composition are added composition to:

Tetrasodium salt of ethylenediaminetetraacetic acid (technical product with 30 % more active

Ethylenediaminetetraacetic acid) mercaptotriazole

Sodium thiosulphate, anhydrous Sodium sulfite, anhydrous

Sodium salt of the iron (III) complex of

Make up ethylenediaminetetraacetic acid with water

50 ml of 30% formalin are added to one liter of this solution (aqueous formaldehyde solution), divides the solutions again into each two parts and adjusts them to the following pH values:

10, o G 1, o G 100, ο G 12.6 G 30, o G 1000 ml

No. 1 without Formalin PH 7.0 No. 2 without Formalin pH 8.5 No. 3 with Formalin pH 7.0 No. 4th with Formalin PH 8.5

With the formalin-containing baths you can do the usual color photographic commercial chromogenic materials after prior color development at room temperature within Bleach, fix and harden perfectly for 5-10 minutes.

A-G 766 - 6 -

209833/0876

To demonstrate the excellent hardening effect of the formalinhalti baths, non-hardened gelatin layers are subjected to the following treatments and finally the melting point is determined. For this purpose, half of the gelatine layers are immersed in cold water, the temperature of which is continuously increased by 5 ^° C. per minute. The temperature at which the layer runs off the base with streaking is known as the melting point. If the melting point is "100 ^° C.", the tables also indicate after how many minutes at this temperature the layer runs off the substrate.

A) Soak in the hardness bleach-fix bath for 5 minutes and then do the washing up;

B) Soak in the hard bleach-fix bath for 5 minutes, then 5 minutes water and then dry for 10 minutes at 35 ° C;

ö) bathe in the bleach-fix bath for 5 minutes, then soak for 5 minutes, then dry for 10 minutes at 35 ° C and then store for 36 hours at 57 ° C and 34% relative humidity.

Table 1 shows the results of such an experiment: Table 1

A. (7 Melting point B. ( ^{( 3} C) C. (10 Min.) Bleach-fix bath 37 ° (9 37 ° 39 ° (10 Min.) number 1 37 ° 37 ° 39 ° No. 2 100 ° 100 ° 100 ° No. 3 100 ° Min.) 100 ° (5 Min.) 100 ° No. 4 Min.) (7 Min.) Example 2

A larger amount of a hardness bleach-fix base solution is used the following composition:

A-G 766 - 7 -

209833/0876

Tetrasodium salt of ethylenediaminetetraacetic acid (technical product with 30 % active ethylenediaminetetraacetic acid) 10 g / l

Sodium salt of the iron (III) complex of ethylenediaminetetraacetic acid 30 g / l

Sodium benzenesulfinate 10 g / l

Sodium thiosulphate, anhydrous 100 g / l

Formalin 30 % 45 ml / l

You subdivide this basic solution and add to it

No. 5: Potassium iodide 1 g / l

No. 6: thiourea 5 g / l

No. 7: Reaction product of ammonia with

20-30 mol of ethylene oxide 5 ml / l

No. 8: Reaction product of 0.54 mol of thiodiglycol and 1 mol of octaethylene glycol with the molecular weight 740 and 3.7% sulfur 1 g / l

All baths are then adjusted to pH 8.5 with trisodium phosphate.

These baths can be used to produce commercially available chromogenic color material Bleach, fix and cure perfectly within 5 "to 10 minutes.

The hardening test was carried out as described above with the following results:

Table 2

Test results with freshly made baths:

Hardness bleach-fixer melting point ( ⁰ C)

AWAY

No. 5
No. 6
No. 7
No. 8

A-G 766

100 ° (10 Min.) 100 ° (10 Min.) 100 ° (10 Min.) 100 ° (10 Min.) 100 ° (10 Min.) 100 ° (10 'Min.) 100 ° (10 Min.) 100 ° (10 Min.) - 8th - 209833 / 087 6th

The same results were obtained when the above-mentioned hardness bleach-fix baths previously stored in closed bottles at room temperature for 5 months.

Example 3

According to the basic recipe of Example 2, a bleach-fix bath is prepared, but instead of formalin, 60 ml of one per liter 25% glutaraldehyde solution and its pH value with Trisodium phosphate is adjusted to 8.5. A perfectly bleaching and hardening fixer is obtained. Its hardening power is sufficient to harden a non-hardened gelatin layer within 5 minutes so that it is over Can be kept in boiling water for 10 minutes before it begins to melt.

Instead of glutaraldehyde, dialdehydes can be used with the same success, the carbon chain of which is interrupted by an oxygen, sulfur, selenium or nitrogen atom, e.g. bis (formylmethyl) ether (diglycolaldehyde OHC-CH ₂ -O- CH ₂ -CHO), bis (formylmethyl) sulfide, bis (formylmethyl) selenide or bis (formylmethyl) amine.

Example 4

With stirring, 0.5 g of sodium p-toluenesulfinate and 5.4 ml of concentrated sulfuric acid are successively dissolved in 800 ml of water on. 4.0 ml of 2,5-dimethoxytetrahydrofuran are then left pour in and stir for 15 minutes. It is then neutralized with concentrated sodium hydroxide solution. By adding

10 g ethylenediaminetetraacetic acid as tetrasodium salt (technical product with approx. 30 % active ethylenediaminetetraacetic acid)

10 g of sodium benzenesulfinate

30 g of the sodium salt of the iron (III) complex of ethylenediaminetetraacetic acid and
100 g sodium thiosulphate, anhydrous

A-G 766 - 9 -

209833/0876

and by making up to 1000 ml with water you get a very active hardening and bleaching fixer. Unhardened gelatin layers can harden within 5 minutes.

Instead of ethylenediaminetetraacetic acid, other complexing agents can be used based on aminoacetic acid, e.g. other aliphatic or cycloaliphatic 1,2- or 1,3-diamino-tri- or -tetraacetic acids, like 2-0xypropane-1,3-diamine tetraacetic acid, Diethylenetriaminepentaacetic acid, oxyethylethylenediamine triacetic acid and 1,2-cyclohexanediaminetetraacetic acid.

Instead of the iron (III) complex of ethylenediaminetetraacetic acid can also the iron (III) - and the cobalt (III) complexes of the other complexing agents mentioned are used.

Example 5

A photosensitive photographic material for the silver dye bleaching process, essentially consisting of a red-sensitive gelatin silver bromide emulsion layer on a base, containing a blue-green azo dye, a green-sensitive silver bromide gelatin emulsion layer, which contains a purple azo dye, a yellow filter layer and a blue-sensitive layer on top A silver bromide gelatin emulsion layer containing a yellow azo dye is exposed behind a colored original and processed as follows:

1. Develop for 5 minutes in a bath of the following composition:

1g Methylaminophenol sulfate - 10 - 3 g Hydroquinone 13 g Sodium sulfite anhydrous 26 g Sodium carbonate anhydrous 1 g Sodium bromide A-G 766

209833/0876

fill up with water to 1000 ml

2. Soaking for 5 minutes

3. Silver dye bleaching for 10 minutes at 30 ° in a silver dye bleach bath the following composition:

100g concentrated sulfuric acid

5g Na H ₂ PO ₂ . H ₂ O 10g potassium iodide
O, O75g t, 5-diazanaplitalin

Water to 1000 ml

4. Soaking 10 minutes

5. Hardness bleach fixation for 15 minutes at room temperature in a hardness bleach fixer bath of the following composition:

Tetrasodium salt of ethylenediaminetetraacetic acid (technical product with approx. 30 I » active ethylenediaminetetraacetic acid 10 g / l sodium salt of the iron (III) complex of ethylenediaminetetraacetic acid 30 g / l benzenesulfine acidic sodium 10 g / l sodium thiosulfate anhydrous 100 g / l 2- , 3,4-trias5Ol 5 g / l

Formalin $ 30> ig 45 g / l

6. Soaking 10 minutes

A perfectly bleached, fixed and hardened positive color image of the original is obtained, which protects against mechanical damage is insensitive and shows no tendency to stick.

A-G 766 - 11 -

209833/0876

Claims (6)

Claims 1. Method of making colored images using of a color photographic material having at least one silver halide emulsion layer, comprising the process steps imagewise exposure, color development, hardening, bleaching and fixing, characterized in that, that the process steps of hardening, bleaching and fixing are carried out simultaneously in a hardness bleach-fixing bath containing a gelatin hardening agent, an oxidizing agent and sodium thiosulfate. 2. The method according to claim 1, characterized by the use of a hardness bleaching fixer, the aliphatic mono- or dialdehydes as hardeners, iron (III) or cobalt (III) complexes of complex-forming aminoacetic acid derivatives contains as a bleach and sodium thiosulfate as a fixative. 3. The method according to claim 2, characterized by the use of a hardness bleach-fixing bath containing formaldehyde or an aliphatic dialdehyde as the hardening agent with 4 or 5 carbon atoms, the carbon chain of which is interrupted by an oxygen, sulfur or nitrogen atom can be contains. 4. The method according to claim 2, characterized by the use of a hardness bleaching fixer as a bleaching agent an iron (III) or cobalt (III) complex of nitrilotriacetic acid or of aliphatic or cycloaliphatic 1,2- or 1,3-diamino-tri- or -tetraacetic acids. A-G 766 - 12 - 209833/0876 5. The method according to claim 4, characterized by the use of a hardness bleaching fixer as a bleaching agent the iron (III) complex of ethylenediaminetetraacetic acid contains. 6. hardness bleach-fixing bath for carrying out the method according to claim 1, characterized by the content of a gelatin hardener, a bleach and sodium thiosulfate. 7 · Hardness bleach-fix bath according to claim 6, characterized by the content of formaldehyde or an aliphatic dialdehyde with 4 or 5 carbon atoms, its carbon chain can be interrupted by an oxygen, sulfur or nitrogen atom, as a hardening agent and on the iron (III) complex of ethylenediaminetetraacetic acid as a bleaching agent. A-G 766 -13- 209893/0876