DE1202638B - Photographic development process for producing color images by the color development process - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY GERMAN MTW ^ PATENT OFFICE

EDITORIAL

Int. α .:

Number:
File number:
Registration date:
Display day:

G03c

German class: 57 b -18/13

1202638
E23937IX a / 57b
November 30, 1962
October 7, 1965

The invention relates to a color developing method for color photographic material which Contains color coupler.

In the known, customary development process, the exposed, color coupler-containing photographic Multilayer materials are subjected to that made in a developer bath Color development treatments with a fixer, a bleach and again a fixer, whereby is washed in between. In the fixer, undeveloped silver halide should be extracted from the developed Emulsion layers are removed while the metallic silver is to be oxidized in the bleach bath, formed from the silver halide during development. The second fixer should contain the silver halide which was formed by the previous bleaching, so that the emulsion layers of residual silver and silver halide to be largely exempted. What remains is a colored picture of blue-green, purple-red and yellow-colored substances, during development by coupling the couplers embedded in the material with oxidation products of a primary aromatic, the color developer bath added developer compound are formed. Although this development process, in which the bleaching and the fixing are carried out in two separate sections, relative is time-consuming and complex, it has become established in practice.

The further known development methods using combined bleach-fix baths have namely the disadvantage that the bleach-fix baths are often not very durable and / or that the quality of the developed Image material leaves a lot to be desired.

Photographic development process for
Production of color images according to the
Color development process

Applicant:

Eastman Kodak Company, Rochester, N.Y.

(V. St. A.)

Representative:

Dr.-Ing. W. Wolff and H. Bartels, patent attorneys, Stuttgart N, Menzelstr. 40

Named as inventor:

Charleton Cordery Bard,

George Peter Varlan, Rochester, N.Y. (V. St. A.)

Claimed priority:
V. St. v. America December 5, 1961
(157096)

solved in that the so pretreated color photographic material then in a one metallic silver oxidizing compound containing bleach bath is treated.

According to the invention, an exposed photographic material is developed by that after the color development and after washing, one treatment combined with one Bleaching and fixing solution and then a treatment

In particular, it has been shown that this is followed by a separate bleaching solution. Between Shortened procedures the complete removal of the individual treatment baths is a washing

residual silver and silver halide from the exposed material is difficult, so that a material is obtained with a relatively strong base haze.

not mandatory. After the treatment in the bleach bath, the photographic material can be washed and then if necessary with a buffer

The invention was therefore based on the object of treating 40 baths of known composition, to create a color development process that is subject to the quality of the process of he

Finding images that can be produced results from the

Use of a bleach-fix bath containing a metallic silver oxidizing compound and a silver halide solvent results in color images of excellent quality, particularly with reduced ground fog. The process should also be particularly suitable for the development of photographic material with a high silver content, ie of about 2.1 g / m ² .

g producible
Drawing. It shows

F i g. 1 the color densities of an image produced by a known development process, F i g. Figure 2 shows the color densities of an image produced by the abbreviated method of the invention.

Such photographic materials can be processed according to the method of the invention, wellihi hhih

pp

The task at hand was developed in the context of a multi-layered photographic material development process, in which the color-developed rial with color material contained in the individual layers treated with a bleach-fix bath, couplers exist. Such photographic ma-

509 690/438

3 4

materials are, for example, in the USA. Patent funds include a variety of compounds, such as Writings 2 322 027, 2 407 210, 2 474 293, 2 640 776 e.g. carboxymethyl cellulose, ethyl cellulose, and 2,956,876. To the after gelatin, polyvinyl alcohol, collodion, polyvinyl driving photographic acetals, cellulose esters and the like that can be developed according to the invention.

Materials include photographic materials 5 More stable combined bleaching and fixing solutions of the so-called negative-positive type as well as the reverse type, for example, can be prepared. The according to the method of the invention using a ferric chloride solution, which workable color photographic multilayer, a complexing agent, such as the tetramaterials consist for example of a material, sodium salt of ethylenediaminetetraacetic acid and which three selectively sensitized emulsion layers i ° fixing compound, such as sodium one side of a photographic thiosulfate. Other stable combined Lö-carrier are applied. The sensitized or solutions can, for example, starting from a sensitive layer of the material of the invention, sulfur-containing dibasic acid, such as ethylene containing color-forming couplers to form the complement bis-thioglycolic acid, as the stabilizing silver tarry dye, against a layer of halide solvent . Solutions is sensitized in each case. In the case of the latter type sensitized in this way, for example, the top layer is normally described in U.S. Pat. No. 2,748,000.
blue-sensitized and normally contains a. Of course, other complexing yellow dye-forming couplers can also be used. The constituent compounds in the combined solutions next layer normally consists of a ° of the invention to be used. For example, the ge filter layer, which is yellow in color and blue, is 1,3-diamino-2-propanol-tetraacetic acid. is absorbent and is located under the top layer. Further suitable complexing agents are exemplified in order to absorb the majority of the blue light, as described in "Organic Sequestering Agents", which creates an undesirable blue exposure is avoided under the filter layer. 25 John A. Wiley and Sons publisher.
The next layer is generally green-sensitive. The separate bleaching solution made in accordance with the invention

and usually contains a coupler, which can be prepared by forming a magenta dye. The emulsion layer adjacent to the support dissolving a suitable amount of a silver bleaching agent is normally red-agent of the type described above in water, sensitized and usually contains a dye coupler which forms a cyan dye. In ge are normally sufficiently soluble in water, so the multi-layered photographic materials know that the required concentration of the bleaching agent graphic materials can be achieved according to the invention in an aqueous bath. Such work can be carried out, in addition to silver halide solutions, other constituents can also hold emulsion layers or other intermediate layers, such as borax, sodium bromide, for special purposes. In photographic copier chloride and the like suitable work-up materials, the yellow filter layer which can be used in the present invention is often left away and the arrangement of the silver halide layers are described, for example, in the U.S. patent emulsion layers may be different to one writing 2 748 000, 2 113 329 and 2 252 718.
The photographic silver halide emulsions enable particularly accurate reproduction of the color negative. of the material that can be reprocessed according to the invention

The bleach-fix baths can be prepared according to known methods starting from. Various silver bleaching compounds and methods include, for example, that of silver halide fixing compounds prepared in U.S. Patent 2,618,556. Suitable bleaching agents can, for example, with the same advantage, emulsions can also consist of an alkali metal dichromate, e.g. B. processed that were made by other methods of sodium dichromate or potassium dichromate, one. These emulsions can be sensiti-alkali metal ferricyanide, e.g. B. potassium ferricyanide or be siert, z. With chemical sensitizers such as sodium ferricyanide, ferricyanide bromide, permanganate, they are described in U.S. Patents 2,540,085, 2,597,856 e.g. B. potassium permanganate, quinone and the like. Such 5 ° and 2,597,915 have been described, or with azaine compounds, freshly prepared fixative compounds such as those in the USA patent can be added to solutions. Suitable fixing agents 2,716,062 are described, with condensation consisting, for example, of alkali metal thiocyanates, products of alkylene oxides, as they are in the USA.-z. B. sodium thiocyanate and potassium thiocyanate, Am- Patent 2,400,532, or with monium thiocyanate, alkali metal thiosulfates, z. B. Na- 55 the additives mentioned in US Pat. No. 2,937,089 trium thiosulfate or potassium thiosulfate, ammonium. In short, the photographic cyanates which can be worked up according to the verthiosulfate, thioureas and alkali metal selenium of the invention, e.g. B. Sodium selenocyanate and potassium emulsions contain additives or not,
selenocyanate). Such combined baths are, however, the work-up according to the method of the invention

only stable for a very short time, which is why optimal 60 bar photographic materials can under Results achieved only when using fresh solutions using all emulsions described can be. Some improvement may be made. The emulsions of the type described The stability of such baths can be achieved as separate layers on suitable supports if thickeners are added to the baths, be applied, which are very general for production which lead to the formation of a viscous solution. Such photographic elements are of the type used viscous solutions can be used as a surface layer. For example, they can consist of cellulose the photographic material to be processed, loose acetate films, plastic films, paper, etc. are suitably applied will. Among the suitable thickening photographic materials, the various

Have layers and are therefore referred to as multilayer or multilayer material are for example described in U.S. Patents 1 055 155, 2 304 940 and 2 322 027.

However, the method of the present invention is also applicable to the processing of color photographic Materials in which the emulsions are mixed and not separate layers form. In addition, the materials processed according to the invention can have special emulsions, which have color formers for the production of partially colored images. The processable emulsions can furthermore, as already stated, in addition to the color formers (couplers) sensitizing Dyes and the usual additives that are normally added to emulsions, contain.

The photographic materials that can be processed according to the invention normally contain sensitizing agents Dyes that sensitize the emulsions to parts of the spectrum. Such a one Sensitization is usually referred to as optical sensitization. She is for example described in U.S. Patent 2,640,776.

The method of the invention is particularly advantageous applicable if the emulsions are a dispersant for the color formers in addition to the color formers contain. This dispersant can for example consist of the water-insoluble, however, the water permeable materials described in U.S. Patents 2,304,940 and 2,322,027 are made of water-insoluble, but water-permeable cellulose esters, e.g. B. water-insoluble, but water-permeable cellulose acetate, cellulose acetate phthalate, cellulose nitrate, etc., from water-insoluble, but water-permeable cellulose ethers, water-insoluble, but water-permeable natural ones and synthetic resins, high-boiling, essentially water-insoluble crystalloidal materials, such as N-n-amylphthalimide, tetrahydrofurfuryl benzoate, Triphenyl phosphate, n-butyl phthalate, and the like (see also U.S. Pat 2 801 717).

The process of the invention is particularly advantageously applicable to emulsions in which the color former is dispersed in one or more of the above-mentioned substantially water-insoluble, high-boiling crystalloidal materials. These crystalloidal materials are of an organic nature and have boiling points above about 175 ^° C. These crystalloidal materials have a high dissolving activity for the color formers and for the dyes which are formed from the color formers, and are permeable to photographic processing solutions. These crystalloidal materials have also been referred to as "oil formers" because they have the property of forming an oily or liquid solution when mixed with the couplers, even if the coupler is a solid. The crystalloidal materials are generally liquid or low-melting solid substances at normal temperatures (below 100 ^° C.). Particularly useful compounds of this type contain one or more polar groups, such as e.g. B. halogen, hydroxyl, carboxylic acid, amide, ketone groups, etc.

The following compilation lists color couplers which are used in the inventive workable photographic materials may be present. It goes without saying that the following is List not exhaustive. Only a few particularly typical couplers are listed.

Cyan image forming coupler 5- (Amylphenoxybenzenesulfonamino) -l-naphthol, 5- (N-Benzyl-N-naphthalenesulfonamino) -1-naphthol,

5- (n-Benzyl-N-n-valerylamino) -l-naphthol, 5-caproylamino-l-naphthol, 2-chloro-5- (N-n-valeryl-N-p-isopropylbenzyl-

amino) -l-naphthol,
2,4-dichloro-5- (p-nitrobenzoyl- _/ So-hydroxy-

ethylamino) -l-naphthol, 2,4-dichloro-5-palmithylamino-l-naphthol, 2,2'-dihydroxy-5,5'-dibromostilbene, 5-diphenylethersulfonamido-l-naphthol, l-hydroxy-2- ( N-isoamyl-N-phenyl) -naphthamide, 1-hydroxy-2- (Np-sec.amylphenyl) -naphthamide, 8-hydroxy-1 - «- naphthoyl-12,3,4-tetrahydroinoline. 2-lauryl-4-chlorophenol,
1-naphthol-2-carboxylic acid-a-naphthalide, 1-naphthol-S-sulfocyclohexylamide, 5-phenoxyacetamino-1-naphthol, 5 - ^ - phenylpropionylamino-1-naphthol, monochloro-5- (N-7-phenylpropyl-Np -sec.-amyl-

benzoylamino) -! - naphthol, 2-acetylamino-5-methylphenol, 2-benzoylamino-3,5-dimethylphenol, 2- - (p-tert-amylphenoxy) -n-butyrylamino-5-methylphenol.

All acylaminophenol couplers can also be used to generate blue-green images U.S. Patent 2,423,730 can be used.

Magenta Image Forming Couplers

l-p-sec.amylphenyl-S-n-amyl-S-pyrazolone, 2-cyanoacetyl-5- (p-sec.amylbenzoylamino) -

coumaron,
2-cyanoacetylcoumaron-5- (Nn-amyl-p-tert.amylsulfanilide),

2-cyanoacetylcoumarone-5-sulfone-N-n-butylanilide, 2-cyanoacetyl-5-benzoylaminocoumarone, 2-cyanoacetylcoumarone-5-sulfonedimethylamide, 2-cyanoacetylcoumarone-5-sulfone-N-methylanilide, 2-cyanoacetylcoumaron-5- (N-y-phenylpropyl) -

p-tert-amylsulfonanilide, l-p-Laurylphenyl-S-methyl-S-pyrazolone, l-ß-naphthyl-S-amyl-S-pyrazolone, l-p-nitrophenyl-S-n-amyl-S-pyrazolone, l-p-phenoxyphenyl-S-n-amyl-S-pyrazolone, l-PhenyW-n-amyl-S-pyrazolone, 1,4-phenylene-bis-3- (l-phenyl-5-pyrazolone), l-phenyl-S-acetylamino-S-pyrazolone.

Yellow image forming couplers

N-amyl-p-benzoylacetaminobenzenesulfonate, N- (4-anisoylacetaminobenzenesulfonyl) -

N-benzyl-m-toluidine,
N- (4-Benzoylacetaminobenzenesulfonyl) -

N-benzyl-m-toluidine,
N- (4-Benzoylacetaminobenzenesulfonyl) -

Nn-amyl-p-toluidine,
N- (4-Benzoylacetaminobenzenesulfonyl) -N-benzylaniline,

co- (p-Benzoylbenzoyl) -acetanilide, oj-Benzoylacet-2,5-dichloroanilide,

7 8

ω-benzoyl-p-sec.amylacetanilide, material used. Individual sections of the material

N, N'-di- (w-benzoylacetyl) -p-phenylenediamine, were exposed to a colored picture and

N, N'-di- (acetoacetamino) -diphenyl, worked up according to the following information, with a

4,4'-Di (acetoacetamino) -3,3'-dimethyldiphenyl, section after the previously known conventional

p, p'-di- (acetoacetamino) -diphenylmethane, 5 method (method A) was worked up and the

Ethyl p-benzoylacetaminobenzenesulfonate, second stage after the process of the invention

Nonyl p-benzoylacetaminobenzenesulfonate (Method B). N-phenyl-N'-ip-acetoacetaminophenyty urea.

To the development of the exposed photographic ίο time

Silver halide emulsion layers showing coupler color development 7 minutes 30 seconds

of the invention, each color-forming wash can take 15 seconds

Developer to be used, the one primary fusing 4 minutes

Contains amino group. These developers include washing for 4 minutes

also those containing two primary amino groups. 15 bleaching 8 minutes

hold, as well as those where one of the amino washes is 4 minutes

groups is substituted or the substituents in the fixation 4 minutes

Ring sit, such as the alkylphenylene wash for 7 minutes

diamine. These connections are usually buffered for 1 minute

used in the form of their salts, such as as 20 washing 2 seconds

Hydrochlorides or as sulfates, which are more stable than total time 39 minutes 47 seconds

the amines themselves. Particularly suitable compounds

are for example diethyl-p-phenylenediamine hydro- method B (21 ⁰ C)

chloride, monomethyl-p-phenylenediamine hydrochloride,.

Dimethyl-p-phenylenediamine hydrochloride and 2-amino-25 ^e "

S-diethylaminotoluene hydrochloride. The p-amino color development 7 minutes 30 seconds

Phenols and their substitution products can also ^{express ".ashen ······..,. 15}

used where the amino group is unsubstituted acidic interruption .. 2 minutes

is. All of these developers have an unsubstituted bleach-fix for 4 minutes

Amino group, the ^grooves, the oxidation of the decision-30 "f ^lc T ⁿ I Mi

Rollers capable of washing / minutes with the color-forming compounds

to couple to form a color image. flf ^{1 e} ™ ^{L Mmute}

The color formers (couplers) can be washed in the emul for 2 seconds

ions are introduced in any suitable manner, total time 25 minutes 47 seconds z. B. by adding a dispersion of the coupler in 35

a water-insoluble but water-permeable The processing solutions had the following Material for the emulsion, as already stated, compositions: or by adding a dispersion of the alkali metal color developer of the coupler in water. The couplers can also be added to the emulsion in crystalloidal materials. Water 950.0 ml

be set, such as in oil-boiling benzyl alcohol 3.8 ml

organic crystalloidal materials to make a sodium sulfite 2.1 g

to form an oily mixture, which is then dissolved in water, sodium hydroxide 0.45 g

can be dispersed or by means of a binding 4-amino-N-ethyl-N - (/ 3-methanesulfon-

by means of a known type of colloidal 45 amidoethyl) -meta-toluidinsesqui-

(Reference is made, for example, to the USA patent sulfate monohydrate 5.0 g

2 640 776). Dispersions of a coupler in sodium bromide 0.86 g

a binder can be added by means of a homogenizing sodium carbonate (anhydrous) 42.7 g

Device, a colloid mill or the like. Made up to 1.01 with water

will. The dispersions can continue through 50 pH 10.75 at 21 ° C

The addition of known emulsifying compounds fixer can be stabilized.

The sensitizing dyes are the emul water 600.0 ml

sion normally before adding the coupler or sodium thiosulfate 240.0 g

added to the coupler dispersion. (Reference is made to 15.0 g for sodium sulfite

for example, U.S. Patents 2,640,776 glacial acetic acid 13.4 g

and 2,407,210.) Particularly suitable sensitizing boric acid 7.5 g

Dyes that reproduce the aluminum potassium sulfate according to the process of the invention

Workable emulsions can be added, (Alk (SO ₄ ) ₂ · 12 H ₂ O) 15.0 g

are described, for example, in U.S. Patent 60 Made up to 1.01 with water

Writings 2,478,366.2 213,238.2 231,658 and 2,515,913. PH 4.2 at 21 ° C

The following examples are intended to illustrate the process of

Illustrate the invention in more detail. Bleach bath

_R. . , Water 800.0 ml

^{example x} 65 potassium ferricyanide 50.0g

A multilayer photographic material, potassium bromide 20.0 g

as described in U.S. Patent 2,322,027 Made up to 1.01 with water

is, was used as a multilayer sensitized test pH 6.5 at 21 ° C

Buffer bath

Water 800.0 ml

Disodium hydrogen phosphate 8.2 g

Glacial acetic acid 4.5 ml

Made up to 1.01 with water

pH 5.0 at 21 ^° C

Acid interruption bath

Water 600.0 ml

Sodium sulfite 15.0 g

Glacial acetic acid 15.0 ml

Made up to 1.01 with water

Acetic acid or sodium hydroxide were used to adjust the final pH to 4.2.

Bleach-fix bath

Ferric chloride (6H ₂ O) 24.0 g _ao

Tetrasodium salt of ethylenediamine

tetraacetic acid 40.0 g

Sodium thiosulfate (5H ₂ O) 150.0 g

Sodium sulfite 15.0 g

pH 7.0 at 21 ^° C

In both methods of the example, the color development caused silver, cyan, magenta and Yellow dye densities in the sensitive or sensitized layers of the sections and after development the emulsion layers became free of silver and silver halides in each process, whereby the corresponding color densities remained in situ.

Procedure A, the conventional procedure, took 39 minutes and 47 seconds. It required 10 work-up steps including development, whereas the work-up according to the process of the invention (Method B) required 25 minutes and 47 seconds and included 8 work steps. The method of the invention reverses the normal process in effect by adding a bleach bath subsequently to the fixing bath is used to make the photographic material of silver and silver halides to free in the emulsion layers.

The sensitometric results of this example are shown in the drawing. Here shows F i g. 1 the sensitometric curves obtained, starting from the material prepared according to method A. was obtained. F i g. 2 shows the sensitometric curves obtained with a comparable Material worked up by method B was obtained.

In Fig. 1, the sensitometric curve 10 shows the total cyan dye density of the processed Section, as shown in a known manner by means of an Eastman Electronic Densitometer Using a tungsten light source and using a red light transmitting filter was determined. The sensitometric curves 11 and 12 show the total magenta and yellow dye densities, the same way using a green light transmitting filter for the Determination of the magenta dye density and a blue light permeable filter for the determination the yellow dye density.

In Fig. 2 show the sensitiometric curves 13, 14, and 15 show the total cyan, magenta, and yellow dye densities similarly through Examination of a section were determined, which was processed according to method B. the Density measurements were carried out in the same way as in the determination of the in FIG. 1 reproduced Results using red light, green light, and blue light transmitting sources.

The silver remaining in the processed sections was in each case about 10.6 mg / m ² or less, ie for the sections processed according to method A and according to method B. The determination takes place in a known manner, for. B. by X-ray fluorescence analysis. The photographic material processed in this example had a silver content of more than about 2.15 g silver / m ² prior to processing.

Example II

Separate multilayer photographic materials of the type described in Example I were made exposed to a multicolored image in a known manner, whereupon a strip of the exposed Material according to a conventional method (Method C) and another strip after the process of the invention (process D) have been worked up.

Procedure C

Color development 12 minutes

Interrupt bath 2 minutes

First fixation 2 minutes

Wash 2 minutes

Bleach 4 minutes

Wash 2 minutes

Hardening-fixing 2 minutes

Wash 8 minutes

Formalin hardener 3 minutes

Wash 3 minutes

Buffer 3 minutes

Total time 43 minutes

Method D

Color development 12 minutes

Acid hardener bath 2 minutes

Bleach-fix 2 minutes

Bleach 4 minutes

To wash ,. 8 minutes

Buffer 3 minutes

Total time 29 minutes

The new machining solutions had the following compositions:

Color developer

Benzyl alcohol 12.6 ml

Sodium hexametaphosphate 2.0 g

Sodium sulfite 2.1 g

Sodium carbonate 26.8 g

Potassium bromide 0.48 g

Sodium chloride 0.70 g

Hydroxylamine sulfate 2.1 g

4-Amino-N-ethyl-N- (j8-methanesulfonamidoethyl) -meta-toluidine-sesqui-

sulfate monohydrate 4.2 g

Made up to 1.01 with water

pH 9.96 at 24 ° C

509 690/438

Interrupt bath

Glacial acetic acid 17.0 ml

Sodium sulfite 20.0 g

Made up to 1.01 with water

pH 4.64 at 24 ° C

First fixer

Boric acid 5.0 g

Aluminum potassium sulfate 24.0 g

Sodium thiosulfate 223.0 g

Sodium bisulfite 12.0 g

Sodium acetate (anhydrous) 14.0 g

Sodium citrate (anhydrous) 1.7 g

Made up to 1.01 with water

pH 4.40 at 24 ° C

Bleach bath

Sodium nitrate 45.0 g

Potassium ferricyanide 22.5 g

Potassium bromide 8.2 g

Boric acid 7.5 g

Borax 0.97 g

Made up to 1.01 with water

pH 7.30 at 24 ° C

Hardening fixer

Glacial acetic acid 15.0 g

Zinc sulfate ... 7.5 g

Sodium citrate 2.5 g

Zirconium sulfate 0.46 g

Sodium bisulfite 17.9 g

Boric acid 7.2 g

Aluminum potassium sulfate 35.5 g

Sodium thiosulfate 167.7 g

Made up to 1.01 with water

pH 4.40 at 24 ° C

Formalin hardening bath

Calgon (sodium hexametaphosphate) .. 0.75 g

Sodium carbonate 8.8 g

Formaldehyde (37% solution) 25.5 ml

Made up to 1.01 with water

pH 10.90 at 24 ° C

Buffer bath

Citric acid 30.0 g

Borax 20.4 g

Formalin (37 ⁰ "solution /) 17.0 ml

Zinc sulfate 10.0 g

Water, 1.01

pH 3.5 at 24 ^° C

Acid hardening bath

Water 600.0 ml

Sodium sulphate 15.0 g

Glacial acetic acid 13.4 g

Boric acid 7.5 g

Aluminum potassium sulfate 15.0 g

Made up to 1.0 1 with water

Bleach-fix bath

Ferric chloride (6H ₂ O) 24.0 g

Ethylenediaminetetraacetic acid 40.0 g

Sodium thiosulfate (5H ₂ O) 150.0 g

Thiourea 5.0 g

Sodium sulfite 15.0 g

Made up to 1.01 with water

pH 7.0 at 21 ⁰ C 12

The processing time of the standard process (method C) of the example was 43 minutes compared to 29 minutes for method D. In both cases essentially the same sensitometric results were obtained. Also, the same amount of remaining silver was found in both cases. Each element had a silver content of more than 2.15 g / m ² prior to processing.

Example III

Strips of photographic material as described in U.S. Patent 2,322,027; layered on a paper support, were in a known manner versus a transparent multicolored Positively exposed and then processed separately according to the following procedures, by which the method E from a conventional inverse method and Method F consisted of an inverse method in accordance with the present invention.

Method E

Pre-soak

Let it expire

First development ... First interruption.

To wash

Reverse exposure

Color development

Second interruption

To wash

bleaching

To wash

Hardening-fixing

To wash

Stabilize

Total
Processing time

2 minutes

2 minutes

6 minutes

3 minutes

7 minutes, 15 seconds

7 minutes, 15 seconds 3 minutes

7 minutes, 15 seconds 7 minutes, 15 seconds 7 minutes, 15 seconds 7 minutes, 15 seconds 14 minutes, 30 seconds 1 minute

75 minutes

Method F

Pre-soak

Let it expire

First development

First interruption

To wash

Reverse exposure

Color development

Second interruption

Bleach-fix

bleaching

To wash

Stabilize

Total
Processing time

2 minutes

2 minutes

6 minutes

3 minutes

7 minutes, 15 seconds

7 minutes, 15 seconds

3 minutes

4 minutes 4 minutes

14 minutes, 30 seconds 1 minute

54 minutes

The work-up solutions that were used in this example and have not yet been described possessed the following compositions:

First developer

N-methyl-p-aminophenol sulfate 0.9 g

Sodium sulfite 8.0 g

Hydroquinone 2.35 g

Potassium bromide 0.55 g

Sodium metaborate (8H ₈ O) 25.5 g

6-nitroberizimidazole nitrate

(0.5% solution) 12.0 ml

Made up to 1.01 with water

pH 10.03 at 24 ° C

1

First break bath

Sodium acetate 3.0 g

Glacial acetic acid 19.0 g

Made up to 1.01 with water

(A pH of 3.7 was set at 24 ° C with sodium hydroxide.)

Second break bath

Potassium iodide 0.2 g

Sodium bisulfite 15.0 g

Glacial acetic acid 20.0ml

Potassium aluminum sulfate 30.0 g

(A pH of 3.0 was adjusted with sodium hydroxide or sulfuric acid.) I _S

Bleach bath

Sodium nitrate 30.0 g

Potassium ferricyanide 30.0 g

Potassium bromide 15.0 g

Borax 1.0 g

Boric acid 15.0 g

Made up to 1.01 with water

pH 6.7 at 24 ° C

Hardening-fixing bath ^a5

Boric acid 50.0 g

Sodium thiosulfate 225.0 g

Sodium bisulfite 10.0 g

Sodium acetate 15.0 g

Potassium aluminum sulfate 20.0 g

Sodium citrate 2.0 g

Made up to 1.01 with water

pH 4.6 at 24 ° C

stabilization

Formalin (37% solution) 10.0 ml

Made up to 1.01 with water

The work-up time was reduced from 75 minutes to minutes. The basic veil was thereby significantly reduced, as can be seen from the following results:

45

638

Basic veil Red green blue Method E 22nd
18th
4th 22nd
17th
5 26th
18th
9 Method F Change of reason
veil

The basic fog values were determined in a known manner by reflection density measurement, with the integral color densities in blue-green, purple-red and yellow using red, green and blue translucent filters were determined.

According to the method of the invention, a reduction in the base fog is thus achieved and, in addition, very good color densities are obtained. The achievement of very good color densities is certainly based on the fact that any leuco dyes that may still be present in the final bleaching bath are oxidized, as a result of which a full color intensity is obtained. The process of the invention can process photographic materials containing from about 2.15 to about 6.45 g silver / m ² with optimum photographic results.

Claims (7)

Patent claims: 1. A photographic development process for the production of color images from color photographic material containing color couplers in a silver halide emulsion layer, in particular with a high silver content, about 2.1 g / m ² , the exposed color photographic material after color development by treatment with an aqueous solution a) a metallic silver oxidizing compound and b) a silver halide solvent, is fixed and bleached, characterized in that the so pretreated color photographic Material is then treated in a bleaching bath containing a metallic silver oxidizing compound. 2. The method of claim 1, wherein the exposed silver halide emulsion layer with a An aqueous silver halide developing solution containing one consisting of a primary amine Developer, developed and the development is interrupted with an acidic interrupter, followed by treatment with an aqueous solution containing the material a) a metallic silver oxidizing compound and b) a silver halide solvent, is fixed and bleached, characterized in that the emulsion layer pretreated in this way is subsequently treated in an aqueous solution containing metallic silver oxidizing compound and then washed. 3. The method of claim 1, wherein the exposed silver halide emulsion layer after Reverse process developed with an aqueous solution containing a black-and-white developer, the development with an acidic interrupt bath stopped and the emulsion layer with Water, followed by a reverse exposure and then a development with an aqueous silver halide developing solution containing one of a primary Amine existing developer, continued a development interruption with an aqueous, acidic Solution carried out and then a treatment with an aqueous solution containing a) a metallic silver oxidizing compound and b) a silver halide solvent is carried out, characterized in that the emulsion layer pretreated in this way is then carried out treated with an aqueous solution containing a metallic silver oxidizing compound and then washed. 4. A photographic development process according to claims 1 to 3, characterized in that a photographic material is treated which contains about 2.15 to about 6.45 g of silver per 1 m ² . 5. A photographic development process according to any one of claims 1 to 3, characterized in draws that the aqueous, a metallic silver oxidizing compound and a silver halide solvent containing a complexing agent is added. 6. A photographic development process according to claim 5, characterized in that the Complexing agent consists of ethylenediaminetetraacetic acid. 7. Photographic development process according to one of Claims 1 to 6, characterized in that that the color photographic material after color development with an aqueous Solution containing ferric chloride, ethylenediaminetetraacetic acid, sodium thiosulfate and sodium sulfite and then in a bleaching bath containing ferricyanide bromide as a silver oxidizing agent, is treated. Considered publications: German Patent No. 866 605; German patent application A 19285 IVa 57b (published August 25, 1955); German Auslegeschriften P14322 IVa 57 b (published on August 30, 1956); P14326 IVa 57b (published 10/11/1956); Patent No. 23,348 of the Office for Invention and Patents in the Soviet Zone of Occupation Germany. 1 sheet of drawings 509 690/438 9.65 ® Bundesdruckelei Berlin