DE2360326A1 - METHOD FOR PRODUCING PHOTOGRAPHIC IMAGES - Google Patents

Description

Process for making photographic images

The invention relates to a method for producing photographic ones Images, in which a photographic recording material consisting of a support and at least one then applied layer with a photosensitive. Metal salt The exposed material is exposed appropriately to the picture with an alkali Bringing working solution to produce a first metal image in contact, generating a second image and the metal image as well the photosensitive metal salt by means of a combination of 1.) a cobalt (III) complex and 2.) a solvent for the photosensitive Metal salt fades and fixes.

There are the most diverse photographic processes for the production

en

position of images known in the / a photographic this recording material consisting of a layer support and at least one layer with a photosensitive layer applied to it Salt exposed imagewise and brought into contact with an alkaline working solution to produce a first metal image in which a second image, e.g. a Dye image, and the metal image and the unused photosensitive metal salts are bleached and fixed. So includes, for example, the development process, the recording materials with exposed photographic silver halide emulsion layers are subjected to photographic complexes, typically a color development step and one of these Stage separate bleach-fix stage during dye development The color developing agent reduces exposed silver halide to metallic silver and the oxidized color developing agent reacts with the color coupler to produce a dye. In a separate process stage or in separate process stages the silver image and the unused silver halides are converted into soluble salts. These process steps are called bleaching and fixation stages have become known.

It would be advantageous if the image-forming steps, i.e. e.g. the color development and the bleaching and fixing stages, 'by means of a Working or procedural solution could be carried out.

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There are also, for example, US-PS 3,615,508 and GB-PS 777 635, bleach-fix solutions have become known which contain a cobalt (III) complex and a metal salt solvent. However, none of these patents suggests that described bleach-fixing solutions for the preparation of process solutions or for carrying out processes to be used with the Objective to achieve an image formation and a bleaching and fixing process by treatment with a procedural or working solution.

There are also, e.g. from the book "Monobath Manual" by Haist, publishing house The Fountain Press, London 1966, so-called single bath method and baths for the black and white photographic process known. The known single bath processes are known to be used in exposed photographic recording materials Generates silver images and fixes undeveloped silver halide in order to avoid further image recording by light. It has it has been shown that the single-bath processes have only a somewhat limited application in a certain respect, since the image silver remains in the image record developed in the monoad. The remaining silver interferes with the reproduction of color images and cannot be regained.

The object of the invention is to provide a method for producing photographic Specify images in which the image-forming process steps and the bleaching and fixing steps using a working .or Process solution can be carried out. In particular a so-called one-bath process should be created in which a metal image is created by reducing a light-sensitive metal salt generated and the metal image is enhanced by a second image and further the metal image and the unused photosensitive Metal salt can be bleached and fixed in a one-step process.

The invention is based on the knowledge that the task set is achieved by using the exposed material an alkaline working solution in the presence of a cobalt (III) compound

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plexes and a solvent for the photosensitive or ' brings photosensitive metal salt into contact.

The invention thus relates to a method for production photographic images using a photographic recording material of a layer support and at least one layer applied thereon, with a photosensitive metal salt exposes the exposed material with a alkaline working or process solution to produce a first metal image in contact * creates a second image and the metal image and the unused photosensitive metal salt by means of a combination of 1.) a cobalt (III) complex and 2.) bleaches a solvent for the photosensitive metal salt and fixed, which is characterized in that the alkaline working solution in the presence of the cobalt (I.I I) complex and the solvent for the photosensitive metal salt with the brings exposed recording material into contact.

According to the invention there is thus an imagewise exposed photographic material Recording material composed of a layer support and at least a layer coated thereon with a photographic metal salt in the presence of a reducing agent for the metal salt, a cobalt complex and a solvent for the metal salt developed. -

In the method of the invention, at least a substantial proportion is used of the developable metal salt is reduced to produce a first image: before the solvent and the cobalt complex Jas. Bleach the metal image and fix the metal salt. The second Image can be in different ways by the most diverse, at The reaction products resulting from the development process or by a blei chffektuiig are generated in the process described.

For example, if the reducing agent consists of a color developing agent, e.g. a silver halide developer compound consisting of a primary aromatic amine, the oxidizing

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BATH ORIGINAL

te developer compound with a color coupler to produce a Image dye react.

If, for example, the cobalt complex used contains amine ligands, the ammonia released can produce an image with a Substance react to form a dye, e.g. an azo dye, through an amine-induced reaction between a diazonium salt and a suitable color coupler. Is further For example, if the cobalt complex is a crosslinking agent in its reduced form, the reduced form of the cobalt complex can be used can be used for imagewise hardening of a binder consisting of a hydrophilic colloid. Finally can the reduced cobalt complex can be reacted, for example, with reactive compounds, for example with 8-hydroxyquinoline, or 2,4-diaminophenol to produce colored compounds.

The exact mechanism on which the method according to the invention is based is not yet clear in all details. However, it is believed that the following will run in the practice of the method of the invention Reactions from:

1.) (Cobalt) *** + reducing agent + exposed metal salt ^Metal > (cobalt) + oxidized reducing agent

2.) (Cobalt) + reducing agent + fixing agent + metal ⁰

(Cobalt) ** + reducing agent + (metal * fix ")

In the course of the first reaction, a reduced cobalt complex is formed and generates an oxidized reducing agent. At some point, possibly when a sufficient amount of fixative Reaching the reaction point, the potentials seem to be the To favor oxidation of the metal catalyst by the cobalt complex.

Thus, according to the method of the invention, there is a photographic one Recording material with a layer support and at least one

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Layer exposed imagewise with a photosensitive metal salt and then brought into contact with an alkaline process or working solution to produce a first metal image, it a second photographic image is created and it becomes that Metal image and the photosensitive metal salt using a combination of 1.) a cobalt (III) complex and 2.) one Solvent for the photosensitive and photosensitive metal salt bleached and fixed. According to the invention, the solvent for the photosensitive metal salt and the cobalt (III) · Complex for the purpose of bleaching and fixing * the metal image and the light-sensitive or photosensitive metal salt combined in the recording material, while the alkaline Working or process solution in contact with the recording material is located. According to the invention, the metal image is bleached and the metal salts are fixed by bringing them into contact of the photographic material with a single alkaline solution. The fading and fixing can be done after the second photographic image has been formed is. On the other hand, the second photographic image can also are generated later, e.g. as a function of the bleaching and fixing process, e.g. through.

1.) image-wise hardening of a hydrophilic colloid, e.g. gelatin, by the cobalt (II); which is made during the bleaching process the cobalt (III) is produced;

2.) Setting a ligand, for example an amine, free to produce colored compounds, for example an azo dye, or ^: ■■ .- ■.

3.) Implementation of the cobalt (II) with an active compound or active compounds producing colored compounds.

According to a particularly advantageous embodiment of the method of the invention, a photographic recording material is included at least one image dye-forming layer or unit (or layer structure) after image-wise exposure of the silver

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halide emulsion layer brought into contact with an alkaline process or working solution in the presence of the following components:

1.) a color developing agent, for example a group consisting of an aromatic primary amine developing agent;

2.) a photographic color coupler and

3.) a cobalt (III) complex which is able to bleach and fix metallic silver in the presence of a silver halide solvent.

Thereby :

a) a silver image is developed in the recording material;

b) the color developing agent oxidizes and in the areas of the silver image

c) generating the oxidized developing agent with the color coupler an image dye implemented.

According to the invention, a combined use of a silver halide solvent and a cobalt (III) complex takes place while the recording material is in contact with the alkaline working or process solution, with bleaching and fixing of the recording material after the image dye has been produced.

The method of the invention also enables improvement photographis rather processes in which a metal image (e.g. a silver image) in a photographic recording material is replaced by a dye image and in which the recording material is treated with an alkaline working or process solution to create the metal image with a combination of a Color developing agent such as a primary aromatic amine color developing agent and a cobalt (IH) complex to bring into contact, to produce an oxidized color developing agent and in which the oxidized coloring utv / ickl; . -

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compound with a photographic color coupler to produce a dye is reacted, the cobalt (III) complex is selected to undergo redox reaction with the color developing agent is subject to practically only in the presence of the metal image. According to the invention, the method is thereby amends that a silver halide solvent and the cobalt (III) complex combined can be applied while the recording material is treated with the alkaline process or working solution, the silver halide solvent and the cobalt (III) complex bleach the recording material and fix after the metal image has been enhanced by the dye. The metal image can be in the most varied of suitable Ways can be generated, e.g. photolytically, or by chemical or physical evolution. Before performing the invention Process, the photosensitive salts, e.g. the photosensitive silver salts, optionally from the Recording material are fixed and washed out.

The invention also relates to modified photographic process or working solutions with a color developer compound, e.g., a primary aromatic amine color developing agent which contains silver and dye images in an imagewise exposed photographic material having at least one silver halide emulsion layer and a photographic color coupler in contact therewith able to develop. The working or according to the invention Process solutions are characterized in that they additionally a bleach-fix combination, made from a silver halide solvent and a cobalt (III) complex.

As the "solvent for photosensitive or light-sensitive metal salts" and "silver halide" are those compounds and such concentrations thereof to be understood that when used in aqueous solution at 60 ⁰ C 10 times the amount by weight of the metal salt (silver chloride in the case vonSilberhalogenidlösungsmitteln) to can dissolve as water of 6O ⁰ C. "

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The concentration of a solvent, ^ that is required to fix a silver halide, thereby, the Koenzen - concentration of the solvent 'in a liquid bath is what pi * au ak "table AND ALL silver £ a photOHgraphischeii to $ calibration voltage material with a single SiIberbromid -gelatin ■ emulsion layer with 30 mg of silver per 0,0929 m ² substrate surface in 1 1/2 minutes at 4O ⁰ C at a pH value of 4.0 to ₁ O 1I removed

The concentration of Silberhalogenidlösungsmittei which requires lent is to fix a Silberhalogeiiidschicht in the individual case, it depends on a number of variables, including 1) the Piclke and the nature or composition of a Oberzügssehieht _t 2st) the concentration of the silver halide, 3 .) the type of silver halide used, 4.) the activity of the developer compound and whether all or part of the developer compound is accommodated in the photographic recording material, 5.) the pH of the working or process solution, (U) the Temperature of the process and 7.) whether there is movement or not when the development process is carried out.

Finally, it is the reactivity of the supercapacity solvents different »The cheapest or optimal in the individual case Concentration can be determined for each silver halide solvent in the method to be carried out by means of a test.

Advantageously, for example, alkaline working or process solutions can be used which contain 0.5 to 250 g of silver halide solvents, e.g. sodium thiosulphate, per liter of more alkaline Solution included. It has proven to be particularly advantageous when using most developer compounds and recording materials a concentration of silver halide solvent, e.g. sodium thiosulphate, from 2 to 50 g per liter of alkaline solution.

However, the method of the invention is not limited to the use of silver halide solvents in the working or process solution limited. Rather, it is also possible to use silver halide solvents in photographic recording materials

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accommodate yourself. Typical such silver halide solvents are for example isothiuronium and thiurpnium compounds - fertilize, * also bis-isothiuronium compounds and, 3-S-thiuronium salts. Solvents of this type are exemplified in U.S. Patents 3,506,444, 3,669,670 and 3,330.1,678 are known.

Recording materials containing such silver halide solvents can be developed according to the invention without the additional use of silver halide solvents is required in the alkaline working or process solution.

In general, to carry out the method of In the present invention, the various conventional known silver halide solvents use which in combination with the used Cobalt complex silver fade and faded silver and To fix silver halide.

Typical suitable solvents for carrying out the process of the invention are, for example, the water-soluble thiosulfates, for example sodium thiosulfate, potassium thiosulfate and ammonium thiosulfate, thiourea, ethylene thiourea , water-soluble thiocyanates, for example sodium thiocyanate, potassium thiocyanate and ammonium thiocyanate and water-soluble, sulfur-containing acids. Further suitable solvents are, for example, water-soluble diols, for example those of the following formula:

HO (CH ₂ CH ₂ ?) CH ₂ CH ₂ OH *
where mean:.

ρ is a number from 2 to 13 and

Z is an oxygen or sulfur atom - * with the proviso that at least 1/3 of the atoms represented by Z are sulfur atoms and furthermore at least two consecutive Z atoms Are sulfur atoms.

Further typical suitable diols are those of the following

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Formula:

CH ₂ CH ₂ OH,

where mean:

X and X are oxygen or sulfur atoms such that when X is an oxygen atom, X ^{1 is} a sulfur atom and, when X is a sulfur atom, X is an oxygen atom ^

c, d, e, f and g are integers from 1 to 15, such that the sum

of c + d + e + f + g represents an integer from * 6 to 19,

where it holds that at least 1/3 of all represented by X and X ^ Atoms are sulfur and furthermore there are at least two consecutive ones represented by X and / or X. Atoms are sulfur atoms.

Typical diols suitable for carrying out the process of the invention are, for example:

1.) S.o-Dithia-i.e-octanediol

HIGH ₂ CH ₂ SCH ₂ Ch ₂ SCH ₂ CH ₂ OH

2.) 3,6,9-trithia-1,11-undecanediol

HIGH ₂ CH ₂ SCH ₂ CH ₂ SCH ₂ CH ₂ SCH ₂ CH ₂ Oh

3.) 3,6,9,12-tetrathia-1,14-tetradecanediol HO (Ch ₂ CH ₂ S) ₄ CH ₂ CH ₂ OH

4.) 9-0x0-3,6,9,12,15-tetrathia-1,17-heptadecanediol

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5.) 9,12-DiOXa-SiOjIS, 18 ^ tetrathia-1 _f 20-eiQOSändioi

6 \) 3,6-Dioxa-9,12-dithia-1,4-tetradecanediol HO (CH ₂ CH ₂ O) ₂ (CH ₂ CH ₂ S) ₂ CH ₂ Ch ₂ OH

7.) SJ ^ -Dioxa-eg-dithia-ijUrtetradecandiöl 'H0CH>, CH _o 0 (CH-CH.S) -CHoGH-OCH-CH-OH

β «) SjlS-Dioxa-o ^ iiZ.lS-tetrathia ^ i ^ Oi HOCH ₂ CH ₂ O (CH ₂ CH ₂ S) ₄ Ch ₂ CH ₂ OCH ₂ CH ₂ OH

9.) ΐ'2, Τ8-Ρίόχα-3; ϊ6, ΐί «Ί5,2ΐ, 24; Ζ7-Η ^

HO (CH ₂ CH ₂ S) 3CH ₂ Oh ₂ OCH ₂ CH ₂ SCH ₂ CH ₂ O (CH ₂ GH ₂ S) ₃ CH ₂ CH ₂ OH

10.) 6,9,15 * 18-Tetrathia-3,12,21-trioxa-i, 23-tricpsandiol

Dibasic acids which are suitable as solvents and contain water-soluble sulfur are those of the following formula:

HOOCCH ^ (SC «^ CH ₂ ) _q SCH ₂ CO0H · ν r. -. ,

where q is an integer from d to 3 inclusive and the acids can also be present in the form of their alkali metal salts and ammonium salts. Typical examples of such solvents are:. . . , .., - ..; ■,. .

1.) Ethylene-bis-thioglycolic acid,. '. ,

HOOCCH ₂ SCH ₂ CH ₂ SCH ₂ COOh
2.) 3,6,9-trithiahendecanedioic acid ^% I ^ lv: -.i HOOCCH ₂ (SCh ₂ CH ₂ ) ₂ sch ₂ cooh. - ,,

3.) 3,6,9,12-tetrathiatetradecanedioic acid ...

HOOCCH ₂ (SCH ₂ CH ₂ ) jSCH ^ COpH

4.) Ethylene-bis-thioglycolic acid, disodium salt 5.) Ethylene-bis-thioglycolic acid, dikaelium salt 6.) Ethylene-bis-thioglycoic acid, Dianunon rum salt 7.) 3,6,9-Trithiahendecanedioesäure, disodium salt ί 8.) 3,6,9,12-Tetrathiätetradecandioesäure, Disatriumsa ^ z.

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According to the invention, the recording materials are thus through a combined use of a cobalt complex and a solvent such as a silver halide solvent is bleached. In those cases where it is advantageous or desirable to produce metal images, or in those cases where pre-formed metal images are enhanced with or by a dye image, the bleach-fix reaction for a certain Period of time can be delayed until a sufficient Metal or dye image has been created '. The desired delay in the bleach-fix reaction can be done in several ways can be achieved, for example, by using solvents such as silver halide solvents which are comparatively Diffuse slowly through hydrophilic colloid layers by incorporating developer compound into the recording material, by incorporating the cobalt complex into the recording material, by using comparatively thick coatings or top layers of hydrophilic colloids, by incorporating silver halide solvent in the recording material, taking action can be taken to release the silver halide to retard and using silver halide layers, e.g., Lippmann emulsion layers, over the layers to be bleached and are to be fixed.

All cobalt (III) complexes which form silver images in the presence of a silver halide solvent Sj are suitable for carrying out the process of the invention e.g. sodium or potassium thiosulphate, able to bleach. Such cobalt (III) complexes are preferred used, which with a primary aromatic amine color developing agent in a redox reaction Able to enter the presence of metallic silver. Such complexes consist of a molecule with a cobalt atom or ion. The cobalt atom, or cobalt ion, is from a group of atoms Surrounding ions or molecules, which are generally referred to as ligands. The cobalt atom or cobalt ion at the center of this. A Lewis acid represents complexes. In contrast, the ligands are Lewis bases. Werner complexes are well known examples

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for such complexes. The cobalt complexes typically exist in at least two different valence states. The use of cobalt complexes which American chemists refer to as inert complexes and European chemists to robust complexes has proven to be particularly advantageous. Particularly suitable are complexes of a cobalt ion with a ligand which, if a test sample of the same in Ο, Ί molar concentration at 2O ⁰ C in an inert solvent solution, which also has a 0.1 molar concentration of a labeled ligand of the same type, the is uncoordinated, contains, show practically no exchange of uncoordinated and coordinated ligands at least within one minute, preferably within several hours, for example up to 5 hours or more. This test can advantageously be carried out under the pH conditions which are used when the method of the invention is used. In the case of silver halide photography, these are generally a pH above about 8. Many cobalt complexes which are suitable for performing the method of the invention _s show virtually no exchange of ünkoordinierten and coordinated ligands within several days. The term “inert” in connection with the cobalt complexes and the method of determining a ligand exchange using radioactive isotopes for labeling ligands is known, for example from the article by Taube, published in the journal Chem.Rev. ₉ Volume 50, page 69 (1972) and the book by Basolo and Pearson, "Mechanisms of Inorganic Reactions, a Study of Metal Complexes and Solutions", 2nd Edition, 1967, published by John Wiley and Sons, page 141.

For further details regarding the measurement of a ligand exchange see the article by Adamson and co-workers, published in J. Am. Chem. Soc., Volume 73, (1951), Page 4789. ·

The inert cobalt complexes are SO-called unstable complexes versus which, when tested in the manner described, have a response half-life of generally below one

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Minute. Cobalt chelates are special cobalt complexes where the same ligand or molecule is bound to the central cobalt ion at two or more different points is. The cobalt chelates are generally somewhat slower Ligand exchange as non-chelated complexes. Unstable types of chelates can have a half-life of several seconds or possibly have a little longer.

As particularly advantageous cobalt complexes for carrying out the Methods of the invention have those with coordination numbers out of 6 proven to be known as so-called octahedral complexes are.

Cobalt coaplexes can be used to carry out the process of the invention can be used with a wide variety of ligands. So are suitable practically all Lewis bases, i.e. compounds, for the preparation of the complexes with an unshared pair of electrons. Typical suitable ligands are, for example the halides, e.g. chloride, bromide, fluoride, also the nitrate rest, Water and amines, as well as such customary ligands, as they are, for example, on page 44 of the cited book by Basolo and Pearson are described.

The lability of a complex depends on the nature of the ligands of the complex affected.

Particularly advantageous cobalt complexes have a coordinate number of 6 and further at least one ligand, which consists of:

Ethylenediamine (s); Diethylenetriamine (diene); Triethylenetetrasmin (triene); Ammine (NH ₃ ); Nitrate; Nitrite; Azide; Chloride; Thiocyanate; Isothiocyanate; Water; Carbonate and propylenediamine (tn).

Particularly advantageous complexes are those with amniotic ligands, e.g. cobalt hexamine salts. Advantageous cobalt complexes are both

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for example those of the following formulas:

[Co CNH ₃ ) ₅ H ₂ O] X; (to '(NHj) ₅ CO ₃ JX; [bo (NH ₃ ) ₅ Cl] X and [Co (NH ^ ₄ CO ₃ ] X,

where X represents one or more anions, according to the charge neutralization rule and xiobei X preferably represents one or more organic anions made up of several atoms, ie so-called polyatomic organic anions _t .

In the case of many complexes, for example in the case of cobalt hexammine complexes, the anions can significantly influence the reducibility of the complex. The ion shown below are listed in the ReÜenfolge in which they increase the stability of Cobalthexaaminkomplexes: bromide, chloride ₀ nitrite, perchlorate, acetate, carbonate, sulfate, and sulfate.

Accordingly, the ions are expediently selected such that Complexes of the desired degree of reducibility are obtained, the. In addition to the anions mentioned, for example, nitrate, Thiocyanate, dithionate and hydroxide anions are suitable anions.

In addition, neutral complexes can also be used to carry out the process of the invention, for example those of the following formula:

[Co (diene) (SCN) ₂ OHl

however, positively charged complexes have proven to be particularly advantageous proven. =

Particularly advantageous has proven esj, for performing the method of the invention, cobalt (111) to use ion complexes which either have at least three ammine (NH ₃₎ ligands and / ODET a positive charge, which is preferably. 3 A cobalt (III) ion with six (NH ₃ ) ligands has a charge of +3. A cobalt (III) ion with five (KH ₃ ) ligands and one chlorine ligand has a charge of +2. A cobalt (III) ion with two ethylenediamine (en) Li

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ligands and 2 (NH ^ -Azidliganden has a charge of +1. Quite common all the best results are obtained when cobalt (III) complexes with a charge of +3 and / or when cobalt (III) -Koraplexe with at least 3 and preferably at least 5 amine ligands can be used.

The cobalt (III) complexes can be used in the photographic recording materials be incorporated in the form of ion pairs which are insoluble in water. The use of ion pairs that are insoluble in water of cobalt (III) ion complexes is described in more detail in the German patent application P 23 57 589.5. These ion pairs advantageously consist of a cobalt (III) ion complex and an anionic organic acid having an equivalent weight of at least 70 based on acid groups. The acid groups preferably consist of sulfonic acid groups.

The most favorable concentration of cobalt complex in the procedural or working solution depends on several variables, i.e. the optimum concentration in each individual case must be for each Recording material and each solution can be determined. In general However, it has been shown that advantageous results are obtained when the complex, for example cobalt hexammine chloride, is present in a concentration of about 0.2 to 20, in particular in a concentration of 0.4 to 1.0 g / l process or working solution.

To carry out the process of the invention, a wide variety of customary known, from primary aromatic Color developing agents existing in amines can be used, e.g., p-aminophenols and p-phenylenediamines. Typical dye developer compounds, which are advantageously suitable for carrying out the method of the invention are:

3-acetamido-4-amino-N, N-diethylaniline; 4-amino-N-ethyl-N-ß-hydroxyethylaniline sulfate; Ν, Ν-diethyl-p-phenylenediamine; 2-amino-5-diethylaminotoluene; N-ethyl-N-ß-methanesulfonamidoethyl-S-methyl ^ -aminoaniline and 4-amino-N-ethyl-3-methyl-N - ^ - sulfoethyl) aniline.

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With regard to other color developer compounds, for example referenced the work of Bent et al., published in the journal JACS, Volume 73 (1951), pages 3100 to 3125 and the book by Mees and James "The Theory of the Photographic Process", 3rd Edition, 1966, published by MacMillan ■ * & Co., New York, pages 278-311.

Color developing agents consisting of primary aromatic amines which give particularly good results are, for example, the following: · .- "■" ·

4-amino-N, N-diethylaniline hydrochloride; 4-amino-3-methyl-N, N-diethylaniline hydrochloride; 4-Amino-3-methyl-N-ethyl-N-ß- (methanesulfonamido) ethylaniline sulfate hydrate; ^ - Amino-S-methyl-N-ethyl-N-ß-hydroxyethylaniline sulfate; 4-amino-3-dimethylamino-N, N-diethylaniline sulfate hydrate; 4-amino-3-methoxy-N-ethyl-N-ß-hydroxyethylaniline hydrochloride; 4-Amino-3-ß-Cmethanesulfonamido) ethyl-N, N-diethylaniline dihydrochloride and 4-amino-N-ethyl-N- (2-methoxyethyl) -m-toluidine-di-p-toluenesulfonate.

In combination with the color developing agent, black and white developing agents can optionally be used. These can be applied in the working or procedural solution, be, or in the photographic recording material itself, as it is, for example, in German patent application P 23 57 694.5 is described in more detail. During the development of the silver halide, the oxidized black and white developing agent may die Color developing agents oxidize to produce oxidized color developing agents which then react with color couplers to produce dyes. If necessary, the color developing agent can be incorporated in the recording material itself will. -

In the procedural or working solution, the concentration of Color developing agent can be very different. It has proven advantageous to use the color developer compound in the process

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rens or working solution in concentrations of about 1 to 20, in particular, in concentrations of about 2 to 10 g / l of solution although greater or lesser concentrations can be used.

Those used to carry out the method of the invention Recording materials can have the usual known layer supports, e.g. those made of films made of cellulose nitrate, Cellulose esters, polyvinyl acetals, polystyrene, polyethylene terephthalate, polycarbonates and the like. The support can however, for example, also made of glass, paper or metal. Typically, the recording materials have a flexible substrate, in particular a paper substrate, which can be partially acetylated or can have a barite layer and / or a layer made of an α-olefin polymer, in particular a layer made of a polymer of an α-olefin with 2 to 10 carbon atoms, e.g. a layer of polyethylene, polypropylene or an ethylene-butene copolymer.

In the case of color photographic recording materials with at least one color-producing layer or at least one Color-producing layer assemblies, these layers or assemblies can be arranged on the same side of the layer carrier or on different sides of the layer carrier, e.g. when using a transparent film layer carrier.

For carrying out the method of the invention, color photographic recording materials are particularly suitable Layer support and at least one dye applied thereon generating layer structure. Of particular importance are multicolored photographic recording materials with at least two such dye-producing layer assemblies, each of these associations primarily records light from a different region of the light spectrum. The layered ligaments or Layer units each contain a light-sensitive silver salt, which is generally in relation to a specific area

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of the light spectrum is spectrally sensitized and that with einöm photographic color coupler is in contact. This means that the color coupler can be contained in the silver salt layer itself can or in a layer adjacent to it. The dye-producing layer assemblies are advantageously made from continuous layers Layers built up which are effective by others. Layer assemblies isolated by separating layers or spacer layers are or by layers which contain scavenging compounds for scavenging oxidized developer compounds to avoid color contamination or staining between the individual layers or to avoid layered associations.

To carry out the method of the invention, however, can also Recording materials are used, their layer units or layer structures built up from discontinuous layers which contain so-called mixed packages, which are more effective Are isolated from each other, for example from the U.S. Patent 2,698,794 is known. The effective isolation of each Layer associations or layer units are otherwise known ' and is used in many commercial color photographic recording materials applied. . ".", ..-. .

Advantageously, in the working or process solutions or so-called single baths according to the invention, recording materials can be developed which consist of a film carrier and at least one dye-generating agent applied thereto Layer or a layer association with a light-sensitive. Silver salt, preferably silver halide, with which a color coupler in one: at least 40 leagues and preferably at least 70 leagues stoichiometric excess is in contact. - ■ - '

lis is known that in color couplers between so-called 4-; equivalent color couplers and so-called 2-equivalent color couplers differs. 4-equivalent color couplers are those that have 4 moles oxidized color developing agent, which in turn requires the To develop 4 moles of silver require one mole of dye is produced. Accordingly, corresponds to a stoichiometric

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Reaction with silver halide gives an equivalent weight of the 4-equivalent coupler 0.25 moles.

Recording materials are advantageously used according to the invention used with color-producing layers or color-producing layer associations that contain at least a 40ligen excess of the Have the equivalent weight of the color image-forming color coupler in excess of the amount necessary to react on a stoichiametric basis with the developable silver is necessary. The color couplers are preferably used in a stoichiometric excess used. According to a particularly advantageous embodiment of a recording material, the color coupler is used in one at least 10% stoichiometric excess, based on silver, used.

It is also preferred to use recording materials in which the ratio of coupler to silver is effective Silver is related. The ratio can further be defined as an equivalent excess in a coupler: silver ratio of at least 1.4: 1, preferably of at least 1.7: 1 (i.e. * 2: 1 represents an excess of IQOs).

Advantageously, the photographic color couplers can also be used in the layer assemblies or layer units producing image dyes in concentrations which are at least three times, preferably 3 to 20 times, as great as the weight of the silver of the corresponding silver halide emulsion layer, the silver in the emulsion layer being more advantageous Way in concentrations of up to 30 mg, for example in concentrations of 1 to 30 mg / O, 0929 m ^{2 of} layer support surface, is present.

Advantageously, coupler: silver ratios of 4 to 15 parts by weight of coupler per 1 part by weight of silver are used. The couplers are advantageously present in an amount which sufficient to achieve a density of at least 1.7 - preferably min-

409824/1016

- 21 - 236032a

at least 2.0.

Preferably, the difference between the maximum density should be and the minimum density (which may comprise unbleached silver) are at least 0.6, preferably at least 1.0.

The photosensitive silver salt layers of the recording materials developed according to the method of the invention particularly advantageously have silver coatings of up to about 30 mg silver / 0.0929 m ² support surface (325 mg / m ² ), preferably from 1 to 30 mg / 0.0929 m 2 ² support area (10 to 325 mg / m ² ) and in particular from 1 to 25 mg silver / 0.0929 m ² support area, ie 10 to 270 mg per m ² support area. Particularly advantageous results are obtained when the green- and red-sensitive layers of conventional multilayer color photography rather recording materials have about 2 to 15 mg silver / 0.0929 m ² support area, ie 20 to 160 mg silver / m ² support area. -

It is known that the density of the dye images depends may depend on the developer connection used and the color coupler used. As a result, the amount of color coupler can be adjusted in each individual case so that the desired density is achieved. Each layer or each layer structure preferably contains per 0, Mole color coupler.

dressing at least 1 χ 10 ~ ⁵ per 0.0929 m ^{2 of substrate surface}

The color couplers are advantageously selected in such a way that that good neutral dye images are obtained. Preferably should ■ the cyan dye produced will have its main light absorption at about 600 to 700 nm, the magenta dye its main absorption at around 500 to 600 nm and the yellow one The main absorption of the dye is around 400 to 500 nm.

For carrying out the method of the invention, recording materials composed of and on a layer support are particularly suitable

409824/1016

applied red-, green- and blue-sensitive silver halide emulsion layers or layer assemblies with such emulsions layers, the layers or layer assemblies containing blue-green, magenta and yellow color couplers producing dyes.

In those used to carry out the method of the invention As already stated, the color couplers can be present in the same layers as the light-sensitive silver salts for recording materials. However, they can also be sent to the Silver salt layers adjoining layers can be accommodated as long as only the coupler is in effective contact with the corresponding Silver halide emulsion layers stand so that the dye-forming reactions can take place before significant ones Amounts of color developer oxidation reaction products are able to diffuse into adjacent color-forming layers or layer units.

By "photographic color couplers" and "color couplers producing image dyes" are to be understood here as compounds which to react with the oxidation products of developer compounds consisting of primary aromatic amines in the photographic development process to produce an image dye (or to be able to couple).

The photographic color couplers can be used in the alkaline Working or process solution are brought to use or in the photographic recording material itself, as it is for example in the journal "Product Licensing Index", Volume 92, from December 1971 on page 110 under Section XXII will.

If the color couplers are accommodated in the recording material, so For this purpose, such color couplers are preferably used which are contained in a hydrophilic colloidal binder, e.g. gelatin, such as for the production of photographic silver halide emulsions

409824/1016

turns; not diffuse. Furthermore you can use for the production color photographic recording materials, for example those color couplers are used which dye images by reaction with oxidized color developers of the primary type. aromatic amines are reacted, e.g. according to the usual known Matchmaker-Liberating Mechanisms. The Color Coupler Jcö ^ en ^ daljeiiydiffusing or generate non-diffusing dyes. Typical advantageous color couplers for manufacture of the recording materials are the well-known phe.nolischen , Color couplers, color couplers based on 5-pyrazolones and diefSpgfinannt ^ jL ^ open chain ketomethylene color coupler. Typical cyan, magenta and yellow dye image-forming color couplers, which can be used in the process of the invention are, for example, in US Pat. No. 3,046,129, column 15, Line 45 to column 18, line 51. The color couplers can be dispersed in the usual known manner, e.g. at Use of Solvents and Procedures, see US Pat 2,322,027 and 2,801,171 are known.

When using coupler solvents, it has proven to be particularly advantageous if weight ratios of color coupler to coupler solvent of about 1: 3 to 1: 0.1 are used. Suitable color couplers include so-called Fischer-type color couplers, such as are known, for example, from US Pat. No. 1,055,155, in particular non-diffusing Fischer-type color couplers which have branched carbon chains, for example those described in the references which is referred to in US Pat. No. 2,376,679 at column 2, lines 50 to 60 , - '■■ · -

Non-diffusing ones have proven to be particularly advantageous color couplers Color couplers have been shown to produce non-diffusing dyes.

In an advantageous manner, according to a particularly advantageous ^first

4038 2 4/1018

- 24 - 2360320

Embodiment of the invention for carrying out the method of Invention recording materials with layers or layer assemblies are used which contain water-insoluble color couplers containing which using a coupler solvent. were incorporated into the layers, which are preferably made of a moderately polar solvent. Typical such Examples of solvents are tri-o-cresyl phosphate; Di-n-butyl phthalate; Diethyl lauramide; 2,4-Diarylphenol and liquid dye stabilizers, as described, for example, in an article under under the heading "Improved Photographic Dye Image Stabilizer-Solvent" published in the journal "Product Licensing Index, Volume 83, pages 26-29, March 1971.

In a particularly advantageous manner, the couplers may be in the photographic recording materials characterized incorporated that they are in a water-miscible low-boiling solvent having a boiling point of less than 175 ° C, preferably less than 125 ⁰ C, for example in an ester of an aliphatic alcohol and acetic acid or propionic acid such as ethyl acetate are dispersed. Typical known processes for incorporating color couplers into photographic recording materials by this process and suitable solvents for carrying out the process are known, for example, from US Pat. No. 2,949,360, column 2, 2,801,170 and 2,801,171.

The term "non-diffusing" is used herein in the art to understand the usual sense of color photography and denotes connections which for all practical purposes are not in or through photographic hydrophilic colloid layers, e.g., gelatin layers, migrate, especially not during development of the Recording materials with aqueous alkaline solutions. the The term "immobile" has the same meaning, while the Expressions "diffusing" and "mobile" have the opposite meaning to have.

409824/1016

- 25 - 5360328

The invention is also of great importance to others photographic processes for the production of multicolored images, e.g. for dye diffusion transfer processes such as those disclosed in U.S. Patents 2,983,606, 3,146,102, 3,087,817, 3,227,551, 3,227,554, 3,243,294, 2,337,550, 2,756 142-, 3,227,552, 3,443,940, 3 443 943, 3 415 644, 3 415 645 and 3 415 646 as well as the German Patent application DT-OS 2 238 052 are known. "-";

The method of the invention is also more suitable Way for creating diffusing dye images according to procedures such as those for example.! in DT-OS 2 260 and in U.S. Patent Application Serial Mumber 351,673 in more detail to be discribed.

The method of the invention is also suitable for dye diffusion transfer systems, _such as those in which the dye receiving material or the picture sheet are used. positive recording material is separated after the development process has been carried out, as is known, for example, from Auster US Pat. No. 3,362,819, and. für'FarbaiffüsioHiÜbaTtffsgissigssysteEiSp for those recording units. used willow _a --bei cte.raea the image receiving layer an integral part ά®τ Aufzeichnungsein- 'is integrated. Such Aufzeichnuftgseiaheit & sä-§ lad. for example from BE-PS 757 959 and 757

The method of the invention enables dye transfer processes of the type described in an advantageous manner to be modified using an inventively-compatible bleach-fix bath, the desired solid images being retained in the layers of the recording material which have been exposed imagewise werdea _s uad wherein unwanted dyes complexed silver salts, and the like on a special sheet or a special layer diffuse that 1.) skierungsschicht the image layers by an appropriate M of the one or more image layers can be stripped or 2 ') of the or

4098 24/101

- 26 - 2360328 ■

can be separated. So it has been found to be particularly beneficial proven when the image to be produced remains in the layers that have been exposed so that problems of known processes can be avoided »which consisted in being fuzzy Images are obtained when image dyes pass through hydrophilic colloid layers diffuse onto an image-receiving material or into an image-receiving layer when, for example, transparencies are produced should be.

To carry out the method of the invention, recording material! s which have been prepared using various types of emulsions can be used. The other, the emulsions used to prepare the Aufzeichnungsmäterialien example, development modifier _s antifoggants, stabilizers, developing agents, hardeners and spectrally sensitizing compounds _s included such as those described in the journal "Product Licensing Index", Volume 92, December 1971, publication 9232, page A 10? to 110, are described in more detail. Furthermore, for the production of the photographic recording materials which can be used for carrying out the process of the invention, the more usual: known binders _p layer supports, plasticizers _s plasticizers, coating auxiliaries, matting agents ₉ brighteners, absorbing dyes and filter dyes and antistatic layers, as described in of the cited journal can be used.

The following examples are intended to illustrate the invention in more detail

Example 1 illustrates the comparatively poor results, which are obtained when an ordinary photograph is ehe f. Recording material is developed with a color developer solution of the prior art and if the material is then only washed and dried.

409824/1016

Example 1 (comparative example)

1360326

A) First, a photographic recording material was produced in that the following layers were applied to a layer support made of cellulose acetate (the concentration data given below each relate to a layer support area of 0.0929 m ² ):

1.) A gelatine silver bromide iodide emulsion layer _9, the silver halide of which consisted of about 6 mol of iodide, with 35 mg of silver, 100 mg of gelatine and 61 mg of the color coupler 2- [α- (2,4-di- tert-amylphenoxy) butyramido3-4, o-dichloro-S-methylphenol, dispersed in tricresyl phosphate;

2.) A gelatin layer with 400 mg gelatin and 4-hydroxymethyl-4 = methyl-1-phenyl-3-pyrazolidone as a black and white developer compound.

Sections of the recording material (recording material 1-A) were then exposed through a test object with graduated density levels and then developed as follows;

Color development 5 min.

Rinse with acidic rinsing solution for 1 min.

Bleach 5-min.

Wash 2 min.

Fix 5 min.

Wash 5 min. Dry

The color developer bath used had the following composition:

Sodium polyphosphate 2g

Na ₂ SO ₃ 4g

4-Amino-3-methyl-N, N ^ diethy! Aniline 3g. :

Na ₂ CO ₃ H ₂ O 20 g

409 8 2A / 1016

KBr. 2g "

Made up with water to 1 liter pH = 10.65

B) A section of the photographic recording material exposed in the manner described (recording material 1-B) was developed, washed and dried in a color developer ^{at a temperature of 35 ° C., the following times being used:}

Treatment in color developer 10 min.

Wash S min.

dry

The color developer used this time had the following composition:

Na ₂ SO ₃ 2.0 g

4-Amino-N-ethyl-N- (2-methoxyethyl) -mtoluidine-di-p-toluenesulfonic acid 5.0 g

Na ₂ CO ₃ 20.0 g

KBr. 1.0 g

o-mercaptobenzoic acid 0.2 g

Chlorohydroquinone 0.007 g

Na ₂ S ₂ O ₃ 4.0 g

Made up with water to 1 liter pH = 10.0

Two identical strips were then produced from the developed section, whereupon one strip (recording material 1-B) was bleached, fixed, washed and dried, whereas the other strip was not treated any further.

The following sensitometric results were obtained with respect to of the recorded red images in the case of recording materials 1-A and 1-B are obtained:

409-824 / 1016

D.

Max

D,
ι min 1 , 0 O , 08

Recording material 1-A 3.2

Recording material 1-B 1.12

The silver density was determined from the strip that was not treated further measured. It was 0.32 for D _ and 0.03 for D.

° max mm

From the results of Example 1 it can be seen that when treated of the recording material with the color developer solution and washing and drying only a color image of low maximum density and that further undeveloped silver is undesirable Way is withheld. From the following section C the advantages of using a bath and a method according to the invention.

C) Another section of the recording material produced was developed in a single bath according to the following process:

Development in a single bath 10 min.

Wash 5 min.

dry

The single bath this time contained a cobalt complex and had the following Composition:

Na ₂ SO ₃ 2, Qg

4-Amino-N-ethyl-N- (2-methoxyeth) rl) -m-toluidinedi-p-toluenesulfonic acid 5.0 g

Na ₂ CO ₃ '20.0 g

KBr ~ ■■.: ■ ,. 1.0 g

o-mercaptobenzoic acid 0.2 g

Chlorohydroquinone 0.007 g

Na ₂ S ₂ O ₃ "4.0 g

CCo (NH ₃ ) _{6 lci 3} 1.6 g Made up to the liter _{with H 2 O}
pH = 10.0

-4.0 9 82 4 / TOT 6

Two identical strips were made from the developed section, whereupon one strip (recording material 1-C) was bleached, fixed and washed, while the other strip (Recording material 1-D) was not treated any further.

The following table shows the sensitometric densities of the red recordings of the recording materials 1-C and 1-A listed.

D D-

max min

Recording material 1-C -2.3 0.3 Recording material. 1-A 3.2 1.0

The silver content was determined in recording material 1-D. The following values were obtained: D _max * 0.08 and D. = 0.04.

From the results obtained, it can be seen that when using a one-step bath according to the invention, a dye image is produced which is practically the same as the dye image after a conventional color development process as described in Example 1-A for the recording material 1-A and further, that the developed silver is effectively removed by the monobath without the need for additional bleaching and fixing treatment.

Corresponding results, as described under B), were then obtained when the cobalt complex has been incorporated into the photographic recording material, for example by the method described in more detail in German patent application P 23 57 589.5 is described. Furthermore, the same results were obtained when other cobalt complexes and / or other silver halide solvents were used.

Furthermore, particularly good results are obtained when instead of the recording material used in Example 1

409824/1016

Is used recording material · containing a red-sensitive emulsion layer containing a cyan dye-forming color coupler, further comprising a green-sensitive emulsion layer containing a magenta dye-forming coupler, and finally a blue-sensitive emulsion layer containing a yellow dye-forming color coupler; "

Such recording materials can in particular under Ver. Using comparatively low silver concentrations, they can also contain black-and-white developer compounds and a cobalt complex that forms an ion pair. _: *. "

Example 2 ■

First, a color photographic recording material was produced by applying the following layers to a cellulose acetate support in the following order (the concentrations given below relate * again to a support area of 0.0929 m ² ):

1.) A blue-sensitive gelatin silver bromide iodide emulsion i their Silver halide about 6.-MoL - V consisted of iodide, with 16 mg of silver, 120 mg gelatin, 16 mg ^ -hydroxymethyl ^ -methyl-i-phenyl-3-pyrazolidone and 60 mg α- £ 4- (4-Benzyloxyphenylsulfonyl) phenoxyJ-a-pivalyl-2-chloro-5- £ γ- (2,4-di-tert-amylphenoxy) butyrami-, dojacetanilid, dispersed in tricresyl phosphate;

2.) an intermediate layer of 100 τη ^ gelatin and 5 mg of dioctylhydroquinone;

3.) a green-sensitive gelatin-silver bromide jqdidemulsion with • 6 MoI-I iodide, from 10 mg silver, 130 mg gelatine and 25 mg 1- (2,4,6-Trichloropheny1) -3- [2-chloro-5- (α- {4-hydroxy-3-tert-butylphenoxy} tetradecanamido) anilinoJ-5-pyrazolone, dispersed in dibutyl phthalate;

24/1016

4.) an intermediate layer of 160 mg gelatin and 5 mg dioctylhydroquinone;

5.) a red-sensitive gelatin silver bromide iodide emulsion with 6 mol-I iodide, with 6 mg silver, 90 mg gelatin and 35 mg 2- (a-diamylphenoxy-n-butyrylamino) -4,6-dichloro-S-methylphenol, dispersed in dibutyl phthalate;

6.) a top layer of 100 mg gelatin.

The recording material was exposed imagewise and for 4 minutes long in a single bath of the composition given below developed:

KOH
Na ₂ SO ₃ 4-Amino-N-ethyl-N- (2-methoxyethyl) -into luidine-di-p-toluenesulfonic acid

Na ₂ CO ₃ Diaminopropanol tetraacetic acid (complexing agent) [Co (NH ₃ ] NaS ₂ O ₃ Made up with water to 1 liter pH = 10.5

The recording material was then washed for 5 minutes. Excellent color images and the recording material were obtained was sufficiently bleached and set.

Another section of the recording material was used for comparison purposes developed with a single bath solution that is not a silver halide solvent contained. In this case the developed material contained visible amounts of unbleached silver.

10 ml 2 G 5 G 40 G 10 G 2 G 10 G

4098 24/10

. Example 3 Recording material 3-A

Another multilayer, multicolor photographic recording material was produced by applying the following layers to a layer support in the order given below (the concentration data given below again relate to a layer support area of 0.0929 m ² ):

1.) A blue-sensitive gelatin-silver halide emulsion with 16 mg silver, 122 mg gelatin and 60 mg of the color coupler α-pivalyl-4- (4-benzyloxyphenylsulfonyl) phenpxy-2-chloro-5-fY- (2,4-di-tert-amylphenoxy) butyramido] acetanilide, dispersed in 15 mg of di-n-butyl phthalate;

2.) a gelatin layer with 100 mg gelatin;

3.) a green-sensitive gelatin-silver halide emulsion layer with 10 mg silver, 132 mg gelatine and 25 mg of the color coupler 1- (2,4,6-Trichlorophenyl) -3- {5-J] a- (3-tert-butyl-4-hydroxyphenoxy) tetradecanamidoj-2-chloroanilino} -5-pyrazolone, dispersed in 12.5 mg tricresyl phosphate;

4.) a gelatin layer with 160 mg gelatin;

5.) a red-sensitive gelatin-silver halide emulsion layer with 6 mg silver, 90 mg gelatin and 35 mg of the coloring coupler 2-jja- (2,4-di-tert-amylphenoxy) butyramidoJ-4,6-dichloro-5-methylphenol, dispersed in 17.5 mg of di-n-butyl phthalate;

6.) a gelatin layer with 100 mg gelatin.

Recording material 3-B

This recording material became the same as Recording material 3-A produced with the exception, however, that the silver concentration in layer 5, i.e. the red-sensitive layer, is 24 mg was increased.

409 824/1016

10.0 ml G G 2.0 G 10.0 G. 20.0 G 10.0 G 11.25 2.0

Portions of the recording materials, a multi-colored test object were exposed graduated density, behandlet 4 minutes a single bath of the composition shown below at 35 ⁰ C, washed and dried.

A bath

Benzyl alcohol Na ₂ SO ₃

4-Amino-3-methyl-N-ethyl-N-ß-t-methanesulfonamido) ethylaniline sulfate hydrate

Na ₂ CO ₃

Diaminopropanol tetraacetic acid Na ₂ S ₂ O ₃ · 5 H ₂ O [Co (NH ₃ ) ₆ ] ci ₃ Made up with H ₂ O to 1 liter pH = 12.5

The D values of the H and D curves were as follows: Max

Recording material 3-A Recording material 3-B

From the results obtained, it is found that an increased concentration of silver halide in the outermost emulsion layer in relation to the amount of silver halide in the other two emulsion layers, obviously the rate of diffusion of the silver halide solvent from the process or working solution: in delays the photographic material and leads to a considerable improvement in image reproduction.

Example 4

This example illustrates another improvement that can be made can be achieved if the amount of hydrophilic colloid, e.g. gelatin, in the top protective cover layer of the photograph!

Red green blue 0.15 0.28 1.12 0.75 1.44 1.58

409824/1016

Max Red green blue 0.75 1.44 1.58 2.03 1.82 1.90

see recording material is increased.

Another photographic recording material (recording material 4-A) was produced in exactly the same way as recording material 3-B, with the exception, however, that layer 6 contained 400 mg of gelatin per 0.0929 m ^{2 of} substrate area. The recording material was then developed as described in Example 3, whereupon the results obtained were compared with those of Example 3-B. The data obtained are summarized in the following table. ,.

Recording material 3-B
Recording material 4-A

A comparison of the H and D curves shows the further improvement the image reproduction that is achievable when the amount of hydrophilic Colloid in the top layer is increased.

The improvement is obviously due to the push back the rate of diffusion of the silver halide solvent from the »process solution into the recording material through the Gelatin »i-, ^.:> ν-ϊέ, '

Example 5 -. - _;; . .-... '■', -. ..;

This example illustrates a further improvement which can be achieved by the additional arrangement of an auxiliary black-and-white developer compound in the blue-sensitive layer, ie the yellow color image-forming silver halide emulsion layer of a multicolor photographic material. This improvement is quite obviously the result of 1.) one ^: acceleration of the silver halide development rate and ^Λ 2.) the cross-wise oxidation between oxidized black-and-white developing agent and color developing agent. ^ ^:

40 9 8 24/10 16

A photographic material (recording material 5-A) exactly like recording material 4-A produced with with the exception, however, that layer 1 (the blue-sensitive SiI overhalide emulsion layer) this time 10 mg of 4-hydroxymethyl-4-methyl-i-phenyl-3-pyrazolidone contained per 0.0929 m ^ substrate area. The recording material 5-A was exposed and as in Example 3, developed. The data obtained were compared with those of the recording material 4-A. They are in compiled in the following table.

Recording material 4-A Recording material 5-A

Red
I7Ü3

2.14

Max

green
2.50

blue TT9Ü

2.52

Example 6 ■

This example shows the ability of a bath according to the invention, To produce high density dye images while effectively removing developed image silver. The example illustrates the course of the dye-generating reaction; and the course of the subsequent bleach-fix reaction.

A section (section 1) of the recording material described in Example 5 was exposed and treated for 4 minutes in a monobath of the composition given in Example 3 with the exception that the bath contained no [Co (NHj) ₆ ICl ₃ . The recording material was then washed and dried as described in Example 3.

Another section (section 2) of the recording material 5-A was exposed and treated for 4 minutes in a single bath of the composition given in Example 3, which contained 2 g of [Co (NHj) ₆ ] Cl ₃ per liter of solution. The recording material was then washed and dried as indicated in Example 3.

40982 47 10-1 6

The densities of the dye images produced and those in the layers remaining silver densities were as follows:

Dye density

Silver density

1 Red green blue Test item 2 1.65 2.05 2.2 "" Test item 2.14 2.38 ; 2.5

Red
Ü76 "2

0.02

Green Ü778

0.02

Blue 0.04

The dye density was determined after the recording materials had been subjected to the action of a bleach-fix bath of the following composition:

Bleach-fix bath

Diaminopropanol tetraacetic acid acetic acid.

(NHJ ₇ S ₀ O, 5 H ₇ O (in the form of an oOUgen solution ^{3 L.}

Na ₂ SO ₃ ■

3.0 G 20.0 ml 150.0 ml 15.0 G 3.0 G

(NE ₃ ) ₆ ] Cl ₃
Made up with water to 1 liter pH = 4.5.

The recording material 5-A was, as described in Example 3, developed and compared with recording material 3-A, which is described in accordance with that described in German patent application P 22 26 771 Process would be developed using the color development process consisted of a one minute color development, one 1 1/2 minutes permanent fortification, a one minute bleach-fix bath, washing and drying.

It was found that the recording material in the invention Single bath, had practically the same maximum density and sensitivity as the recording material, according to that described in German patent application P 22 26 771 Procedure was developed.

40 9 8 24/1 0 ^ l 6

Example 7

This example shows that a positive picture drawing in a exposed photographic recording material can be prepared using an immersion bath according to the invention.

First, a photographic recording material (recording material 7-A) was produced in that a gelatin-silver halide emulsion layer was applied to a layer support in such a way that the following amounts to a support area of 0.0929 m ² : 100 mg silver, 200 mg gelatin, 10 mg-4-hydroxymethyl-4-methyl-1-phenyl-3-pytazolidone and 60 mg of the compound I given below, dissolved in 90 mg of 1 ^ -cyclohexanediol-di - ^ - ethylhexoate).

Compound I had the following structure: OH

CONH (CH ₂ ) ₄ O-T

OCOOC ₂ H ₅

The recording material 7-A became a test object with graduated Density steps exposed and then for 30 seconds in a single bath of the composition given below at room temperature treated:

Ethanol ami n
fco (NH ₃ ) JCl ₃
Na ₂ S ₂ O ₃

Diaminopropanol tetraacetic acid Made up to 1 liter with water, adjusted to 13.0 with NaOH

50 ml

1 g

75 g 10 g

409824/1016

The recording material was then treated for 1 minute in a dye stabilizer solution of the following composition:

Ethanolamine, 25 ml

Made up to 1 liter with water

The recording material was then left for 3 minutes; washed and dried.

It became a positive magenta dye image of the photographed Test object received.

Thus, it follows that a dye image can be obtained by separating or setting a diffusing one in freedom Dye in relation to development, with the remaining immobile dye remaining in the form of the recorded image. Silver and silver halide are thereby absorbed by the bath removed. ,

Example 8

This example shows that starting from photographic recording materials, developed in a single bath according to the invention improved image properties can be obtained when the color coupler in a carrier using a so-called nonsolvent technique is dispersed.

Two cyan dye image forming coupler dispersed ions made as follows:

20.0 g of the coupler 2- (a- • diamylphenoxy-n-butyrylamino) -4,6-dichloro-5-methylphenol (see US Pat. No. 2,801,171) were added at 50 ^° C. in 60 g Dissolved ethyl acetate.

Another solution was prepared by adding 20.0 g of des same coupler in 60 g of ethyl acetate ^ and 10.0 g of di-n-butylphtha- ■ lat were resolved.

40982A / 10 1 6

The coupler solutions were then stirred at 50 ° C, respectively to 208 ml portions of an aqueous solution of 0.8 g tri-isopropylnaphthalenesulfonic acid, Sodium salt (Alkanol XC) was added. The resulting mixtures were then passed through a colloid mill 5 times given. The ethyl acetate was then extracted from the solutions, in each case by bubbling nitrogen gas through them for two hours through the dispersions.

The table below shows the solvent ratios of the coupler dispersions prepared after drying or washing stated for the purpose of removing the ethyl acetate:

Dispersion ratio of coupler protective colloid No. to solvent

1 1: 0 without

2 1: 1/2 gelatin

The coupler dispersions described were then mixed with silver chlorobromide emulsions (with 20 mol / l bromide), whereupon the emulsions obtained were applied to cellulose acetate film substrates in such a way that 3.75 mg of Ag, 8.4 mg of the coupler and 31.5 mg of gelatin ^{per dm 2 of substrate area} accounted for.

Sections of the recording materials obtained were then exposed to a 3000 ° K light source for a fifth of a second. The recording materials were then developed for 4 minutes in a single bath of the composition shown below at 35 ⁰ C. The development took place with constant movement of the bath by means of an N ₂ stream. After development, the materials were washed and dried for 5 minutes.

The single bath had the following composition:

Benzyl alcohol 10.0 ml

Sodium sulfite 2.0 g

4/1016

4-Amino-3-methyl-N-ethyl-N-ß- (methanesulfonamido) -ethylaniline 10.0 g

Sodium carbonate 20.0 g

Diaminopropanol tetraacetic acid 10.0 g

Sodium thiosulfate 5.0 g

Cobalt hexanone trichloride 2.0 g

Make up to 1 liter with distilled water
pH = 12.5.

The following results were obtained:

Coupler ratio of coupler DD
dispersion ^: to solvent - ^ L

2 1: 1/2 1.84 0.08

1 . 1: 0 2.38 0.14

The results obtained show that when using of recording materials, in their production the color coupler was only dispersed with a low-boiling solvent, better cyan densities can be achieved than when using of recording materials with color couplers made using ' a high-boiling coupler solvent into the recording material were incorporated.

409824/1016

Claims (20)

Patent claims · ■ * 1. Process for the production of photographic images, in which one a photographic recording material consisting of a layer support and at least one layer applied thereon exposed with a photosensitive metal salt, the exposed material with an alkaline working solution with production brings a first metal image into contact, generates a second image and the metal image and the unused photosensitive Metal salt by means of a combination of 1.) a cobalt (III) complex and 2.) a solvent for the photosensitive Metal salt bleaches out and fixes, characterized in that the alkaline working solution is in the presence of the cobalt (III) complex and bringing the solvent for the photosensitive metal salt into contact with the exposed recording material. 2. The method according to claim 1, wherein a photographic recording material, consisting of a support and at least one silver halide emulsion layer applied thereon exposed material with an alkaline working solution to produce a first silver image in Brings contact, generated a second photographic image and the silver image and the unconsumed photosensitive silver halide with a combination of 1.) a cobalt (III) complex and 2.) a solvent for the silver halide bleaches and fixed, characterized in that the alkaline working solution in Presence of the cobalt (III) complex and the solvent for the Silver halide in contact with the exposed recording material brings. 3. Process according to Claims 1 and 2, characterized in that one the solvent for the photosensitive metal salt in the alkaline Working solution and the cobalt (III) complex in the alkaline Working solution or accommodated in the photographic recording material. "409824 / 1.016 4. The method according to claims 2 and 3, wherein a photographic A recording material having at least one image dye-forming, color coupler-containing silver halide emulsion layer or at least one image dye forming visual band with a silver halide emulsion layer and a color coupler in contact with it exposed, in the silver halide emulsion sends: by means of a alkaline working solution develops a silver image and by reacting the color coupler with oxidized, · from a primary aromatic Amine existing color developing agent is an image dye generated, characterized in that the alkaline working solution used to develop the recording material in the presence of the cobalt (ITI) complex and the solvent for the silver halide in contact with the exposed recording material. 5. The method according to claim 4, characterized in that the Farberit developer compound and the 'cobalt (IH) complex in which recording material are included. . 6. The method according to claim 4, characterized in that the solvent for the silver halide in the alkaline working solution is included. 7. Process according to Claims 4 to 6, characterized in that one a recording material for producing multicolor photographic images used, one sensitive to red, one sensitive to green and one sensitive to blue Silver halide emulsion layer and one cyan, one magenta, and one yellow image dye generating color coupler contains. · 8 '.. Process according to Claims 4 to 7, characterized in that a recording material for producing multicolor photographic images used the at least two image dye forming silver halide emulsion layers or silver halide emulsion layers has containing layer assemblies with color couplers, in which the color couplers in a stoichiometric amount of at least 40 '409824 / 101B ■ metric excess, based on effective silver are. 9. The method according to claim 8, characterized in that a recording material is used, the silver halide emulsion layers of which contain 1 to 30 mg of Ag ^{per 0.0929 m 2 of substrate area.} 10. The method according to claim 9, characterized in that one is a Recording material used in which the color couplers are contained in a concentration which is 3 to 20 times the amount by weight of the available silver. 11. The method according to claims 1 to.5, characterized in that one a cobalt (III) complex with a coordination number of 6 and a positive charge of 3 is used. 12. The method according to claim 11, characterized in that as Cobalt (III) complex cobalt hexammine chloride is used. 13. The method according to claims 2 to 6, characterized in that one as a silver halide solvent, sodium or potassium thiosulfate used. 14. The method according to claims 1 to 13, characterized in that a photographic recording material is used which - For the purpose of suppressing the diffusion of the solvent for the photosensitive metal salt into the recording material and to ensure sufficient silver development and dye formation - a hydrophilic colloid layer of sufficient thickness having. 15. The method according to claim 7, characterized in that one Recording material is used, which consists of a layer substrate on which are applied in the following order: 409824/1016 a) a blue-sensitive gelatin-silver halide emulsion layer, the color couplers which produce a yellow image dye is in contact; b) a green-sensitive gelatin-silver halide emulsion ^{layer which contains less than 15 mg of effective silver per 0.0929 m 2 of} substrate area and which is in contact with a color coupler producing a magenta image dye, which is in at least a 40% stoichiometric excess, based on effective silver , is present, and c) a red-sensitive gelatin-silver halide ^ which is less than 15 mg effective per 0.0929 m of substrate area Contains silver and those with a cyan image dye generating color coupler is in contact., which is in at least one 40 $ stoichiometric excess, based on effective silver, is present. 16 .. Process according to claims 2 to 15, characterized in that one uses a photographic recording unit comprising: a) a light-sensitive recording part made from a layer support and at least? a light-sensitive layer applied to it Silver halide emulsion layer, with the proviso that each A silver halide emulsion layer containing an image dye the generating substance is in contact, b) a splittable container with an alkaline working solution, and if necessary c) a B, ildejnpf fear part or an image receiving layer, characterized in that the recording unit is a cobalt ' (III) complex and a silver halide solvent. 17. The method according to claim 16, characterized in that one Recording unit used in the photosensitive recording part as an image dye-forming substance at least one Contains color coupler. 40982471016 18. The method according to claims 4 to 17, characterized in that _y. a recording material is used having at least one layer containing a color coupler into which the color coupler has been incorporated without the use of a high-boiling coupler solvent. 19. Alkaline photographic working solution for color photographic development Recording materials with a color developing agent consisting of a primary aromatic amine, characterized in that it is a bleach-fix combination of a silver halide solvent and a cobalt (III) complex contains .. 20. Alkaline photographic working solution according to claim 19, characterized characterized in that it contains a water-soluble thiosulfate and cobalt hexammine chloride as a bleach-fix combination. 4098 2 4/1016