DE2226770A1 - PRODUCTION AND REINFORCEMENT OF PHOTOGRAPHICAL IMAGES - Google Patents

Description

PATENT LAWYERS DR.-ING. WOLFF, H. BARTELS, DR. BRANDES, DR.-ING. HERO

Dipl.-Phys. Wolff

2C / 77

MONKS 22 Ti; i: -rXCHSTRASSE 8 TELEPHONE: (0811) 293297

May 29, 1972

Reg. No. 123

EASTMAN KODAK COMPANY, 343 State Street, Rochester, New York State, United States of America

Production and enhancement of photographic images

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The invention relates to a method of manufacture and reinforcement photographic images in which there is an oxidation-reduction between an oxidizing agent and a reducing agent for image intensification, and a working photographic solution and a photographic material to carry out the procedure.

It is well known to produce or enhance photographic images by processes involving redox reactions involved. For example, from Belgian patent specification 742 768 (cf. also DOS 1 813 920) Image intensification process known for which a redox reaction between a peroxy compound and a reducing agent, z. B. a photographic color developing agent, is characteristic. However, such redox systems are very unstable, d. H. the amplifier solutions used in the known methods decompose easily, so that they in particular cannot be used for long periods of time.

The United States patent specification 3,152,903 also gives a wide variety Redox systems have become known which are used to prevent undesired redox reactions from occurring physical barriers, e.g. B. a phase separation, operate. The oxidation properties proposed for these redox systems and reducing agents undergo a practically immediate redox reaction in the absence of a catalyst, if they are used in a solution using an inert solvent. There is nothing in the patent Indication of a stable redox system in the absence of a physical barrier.

From British patent specification 777 635 are further tographic bleaching baths have become known, which have an • Ittill) complex and optionally a reducing agent

contain. Is characteristic of photographic bleach baths

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furthermore a content of a silver halide solvent. In the presence of a silver halide solvent, the cobalt complex reacts directly with the silver and leaves consequently, no or practically no redox reaction occurs with the reducing agent which may be present.

It is also known to develop photographic images using so-called physical developer solutions. For example, it is from US Pat. No. 2,750,292 known by physically developing a photographic material having a metal image and a photographic one Color coupler with a solution containing a photographic color developing agent and a reducible metal salt, create a dye image simultaneously and "in situ" with the formation of a metal image. A major disadvantage the reason for using physical developers is that they are very unstable. One reason for this instability is that the reaction products of the redox reaction are catalysts for the course of further redox reactions, d. H. that the Reaction is autocatalytic. In addition, a system of this type is generally only used for the production of a single color Image is suitable because the same couplers and developers are used in each layer of one to carry out the process Diffuse recording material.

Finally, US Pat. No. 2,517,541 discloses photographic ones Silver halide emulsions have become known which are low Amounts, namely less than about 0.1% by weight of an alkali metal cobalt cyanide, based on the weight of the wet emulsion. Those using such emulsions produced and exposed photographic recording materials are developed in common photographic developer solutions. The low concentrations of cobalt cyanide are believed to be required to obfuscate the

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Avoid emulsion. Those used in the known method however, small amounts of potassium cobalt cyanide are unsuitable for imaging via a redox reaction not even if there is a redox reaction between the cobalt cyanide and the developer compound should expire in the districts where silver is being developed. However, it is unlikely that even very limited redox reactions take place, because potassium cobalt cyanide with typical Color developer compounds do not undergo redox reactions in the presence of pre-developed silver.

It is also known, see Rust "Fast Imaging Systems Using Photopolymers, Optical Spectra ", March / April 1968, lines 41-45, especially page 42, that the polymerization of photopolymers can be initiated by a radical, which is released by a light-catalyzed redox reaction can be set. Here too, however, there is no indication of the use of a stable combination of one Reducing agent and an oxidizing agent, which is suitable for carrying out redox reactions by means of a catalyst.

A method for producing photographic images is also known from British patent specification 1 194 581, using a photosensitive layer, injder When exposed to light, germs of a metal are generated that are more noble than silver, and the deposition of a non-noble metal catalyzed. In the known method, an image is thus de-energized

Deposition of a non-precious metal generated on the germs. Also in this patent there is no reference to a non-autocatalytic, stable redox system.

It is also known, e.g. B. from United States Patent 2 270 118, color photographic images on the way through a To produce dye bleaching process, for example by

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that colored layers with silver images' with an acidic solution which image-wise destroys the dye or dyes in the areas where silver is present. The destruction of the dyes can be accelerated by a wide variety of catalysts, for example phenazine will. The reactions taking place in such dye bleach systems are clearly more stoichiometric Base. For example, U.S. Patent 3,340,060, column 1, lines 18-21, states that four silver atoms are required for the destruction of an azo dye group.

British Patent No. 239,875 also discloses photographic ones Recording materials for carrying out the diazo process became known which a cobalt (III) metal complex and optionally contain silver halide. The diazo image generation process taking place when the known material is used however, it is based on a substitution reaction and not a redox reaction. Furthermore, the veils Cobalt (III) complex is the silver halide of the recording material.

It is also known that photographic images are of particular importance for the production of color photographic images Recording materials with photosensitive silver salts and color couplers, for example those color photographic Recording materials as found in the journal "American Scientists"; Volume 58, No. 6, November-December 1970, pages 648-660, and from Kirck-Othmer "Encyclopedia of Chemical Technology", Volume 5, 1964, pages 812-845. The density of the dyes or the amount of dye that can be generated using these recording materials, depends directly on the amount of oxidized color developing agent used in the development of the initially obtained

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latent images are formed with the oxidized color developing agent reacts with the color coupler (s) to produce one or more image dyes.

There has been no lack of attempts to improve the effectiveness of the known color photographic processes in particular by reducing the number of equivalents of oxidized color developing agent used to produce 1 mole of image dye is required. In particular, color couplers have been developed to produce 1 mol Image dye require only 2 equivalents of oxidized color developing agent and correspondingly 2 equivalents of silver and thus advantageously differ from the known 4-equivalent color couplers distinguish which four equivalents of oxidized color developing agent to produce 1 mole of image dye require.

In reducing the equivalency of the couplers, i. H. the amount of oxidized color developing agent required to form a Moles of image dye is required, however, the generation of oxidized developing agent remains directly on the crowd existing silver salt dependent.

Characteristic of the previously known photographic recording materials with colored image-producing layers are accordingly silver coatings of at least 100 mg silver / 0.0929 m 2 support area and in particular higher silver concentrations, for example of about 400 mg silver per 0.0929 m ^{2 support area} and above. The color couplers are added to the silver salt-containing layers, in particular silver halide emulsion layers, or layers adjacent thereto in approximately stoichiometric amounts, based on the silver, or occasionally also in a slight excess, based on the silver present. Furthermore, recording materials have also become known in which the

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or the color couplers in a larger excess, based on the existing silver, are available, obviously with the aim of achieving particularly balanced systems.

Color photographic systems have also become known, for example from U.S. Patents 2,614,808 and 2,173,739 in which Silver images are enhanced in the presence of a color coupler by using a color developer that a dye image is formed in addition to developing a silver image.

Finally, color photographic systems have also become known, for example from U.S. Patents 2,689,793, 2,742,832, 2,808,329 and 2,998,314, the so-called competing Use color couplers. In systems of this type, the general effectiveness of the silver-containing recording material is increased however, obviously diminished at the expense of an improvement in graininess, sharpness and contrast, this is because a larger amount of oxidized developer compound is generated than is actually used in the generation of the image dye (s).

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The object of the invention is to provide a compared to the usual known photographic development processes an improved method for making and enhancing photographic images To indicate pictures.

The invention is based on the surprising finding that cobalt (III) complexes are excellent oxidizing agents for carrying out oxidation-reduction reactions catalyzed by means of a catalyst between an oxidizing agent and a reducing agent and that the reaction products obtained in these oxidation-reduction reactions can be used in diverse and especially economical ways for the production of photographic images, if the oxidation-reduction reactions in the presence of a catalyst present in imagewise distribution, which consists of a different material from the reaction products obtained in the oxidation-reduction reactions, e.g. B. a silver picture, exists, expires.

The invention is therefore a process for the production and amplification of photographic images, in which a Oxidation-reduction reaction carried out between an oxidizing agent and a reducing agent for image enhancement, a photographic recording material made from a support and at least one layer which contains, in an imagewise distribution, a substance A which causes the oxidation-reduction reaction to take place able to catalyze, used and a reaction product obtained in the oxidation-reduction reaction with a reaction product that is reactive with the reaction product Compound B is reacted to form an image, which is characterized in that one is used as an oxidizing agent Cobalt (III) complex used.

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The cobalt (III) complexes used as oxidizing agents according to the invention can be used in a particularly advantageous manner in the form of photographic working solutions in which the complexes present as an active component. The cobalt (III) complexes however, they can also be used in the photographic recording materials used for carrying out the process of the invention are present.

The method of the invention can be used in a particularly advantageous manner thus carry out in such a way that you have a photographic recording material from a support and at least a layer applied thereon with a substance A present in imagewise distribution in the presence of a reducing agent treated with a photographic working or intensifying solution, the active component of which is a cobalt (111) complex contains.

The method of the invention thus enables images to be produced by:

1. on a catalytically active surface, i.e. the substance A present in imagewise distribution, one imagewise Oxidation-reduction reaction - hereinafter referred to as redox reaction for short - between one of a cobalt complex existing oxidizing agent and a reducing agent and that one

2. A picture is produced or enhanced by at least one of the reaction products of the redox reaction on chemical Ways with a reactive compound B with the reaction product.

The chemical reaction between the reaction product or products of the redox reaction with compound B takes place with a change in the so-called light value. Under a change

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the light value is meant, for example, that the reactive compound B by reaction with the reaction product the oxidation-reduction reaction undergoes a color change, d. H. that the reaction product has a different color value or hue than the reactive compound B, where an initially colorless reactive compound B can be converted into a colored compound or a colored reactive compound Compound B is converted into a colorless or practically colorless compound «On the other hand, the invention succeeds the formation of photographic images by using the ability of reactive compound B to change to bring about the light value, image-wise through implementation with inhibits a reaction product obtained during the redox reaction, the reaction products required for imagewise irradiation the redox reaction at the dome present in an image-wise distribution, catalytically active ?! Substance A can be generated. Finally, the change in light value can be achieved by changing the light value of either the oxidizing agent or the reducing agent step into action.

Those obtained in the redox reactions carried out according to the invention Reaction products do not have a catalyzing effect on the redox reaction.

The method of the invention can be particularly advantageous Manner in the context of color photographic processes for the production of colored images, in which, preferably primary aromatic amine color developing agents in the processing of exposed photographic images Silver halide emulsion layers are oxidized and the oxidized color developer compounds with color couplers under Generation of dyes are implemented. According to the invention will develop in the presence of a cobalt (III) complex carried out, the with the color developing agent in the presence of a substance A, z. B. metallic silver, a redox reaction comes in.

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According to the invention, for. B. a silver image initially generated in a photographic recording material as a catalyst the progress of a redox reaction between a primary aromatic amine color developing agent and catalyze a cobalt (III) complex, the color developing agent oxidized as a result of the redox reaction with a or more color couplers is reacted to form one or more dyes. The dyes produced can then can be transferred to an image receiving layer or complement or replace the silver image. To carry out the procedure can z. B. a photographic recording material of conventional structure lait at least one colloid or emulsion layer to be used with a silver image. The or, in the case of multicolor photographic recording materials, the color couplers can be contained in the layers having the silver image or in layers adjacent thereto. On the other hand, however, the color coupler (s) can also be introduced into the system in other ways, for example with the color developing agent and the cobalt (III) complex.

According to the invention, however, the redox reaction can also be used resulting reduced cobalt complex with a reactive compound B with the production of a colored reaction product implemented. This means that, for example, the catalyzed by a metallic silver image Redox reaction resulting cobalt complex can be reacted with a compound B which z. B. from the oxidized form of a Redox may consist of a component or a component that does not take part directly in the redox reaction.

The cobalt (III) complexes required for carrying out the process of the invention can, however, not only be in the form of photographic Working or intensifying solutions can be applied, but also in photographic materials. So suitable For example, for carrying out the method of the invention, recording materials are also advantageously used at least one direct-positive silver halide emulsion layer which contains a cobalt (III) complex. While the Incorporation of a cobalt (III) complex into customary external

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wrapable negative silver halide emulsions for desensitization of the emulsion, this problem of desensitization does not arise when they act as oxidizing agents Cobalt (III) complexes can be incorporated into direct-positive silver halide emulsions.

To carry out the method of the invention are thus suitable, for. B. common negative as well as direct positive photographic Recording materials.

Thus, for carrying out the method of the invention, for. B. negative photographic recording materials, consisting of a layer support and at least one, preferably at least two, color-forming units applied thereon each containing a photosensitive silver salt which is combined with an image dye-providing photographic color coupler is in contact.

However, further examples are particularly advantageous for carrying out the method of the invention also photographic film units consisting of:

a) a photosensitive recording material composed of a layer support and at least one applied to it light-sensitive silver halide emulsion layer, each of these silver halide emulsion layers not being diffusing color coupler that works with an oxidized developer compound to form a diffusing dye

capable of, containing or being in contact with a layer containing such a color coupler;

b) an image-receiving layer optionally arranged on a special layer support;

c) at least one container with an alkaline working fluid that can be split open by the action of pressure and

d) one consisting of a primary aromatic amine Color developing agent,

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which are characterized in that they have a cobalt (III) complex contain, which with the developing agent an imagewise redox reaction in the districts where metallic silver is developed, is able to enter.

When using such a film unit, after its exposure the development is initiated by splitting the container, producing at least one diffusing dye, which diffuses into the image receiving layer.

A photographic light-sensitive material usable for carrying out such a process can be, for example consist of a substrate on which are applied in the order given below: an image receiving layer, one for alkaline solutions permeable, practically opaque or non-transparent, light-reflecting layer and at least a photosensitive layer, the rupturable container being arranged to be exposed after exposure to the light-sensitive element can be placed between this and a practically opaque or non-transparent worksheet, which is placed over the outermost layer of the photosensitive element.

When pressure is exerted on the splittable container, the latter releases its contents, which are between the worksheet and the outermost layer of the photosensitive element is distributed.

The photosensitive part preferably consists of the photosensitive part Element consisting of a red-sensitive silver halide emulsion layer, which are in contact with a non-diffusing color coupler providing a cyan image dye which diffuses with an oxidized primary aromatic amine color developing agent capable of generating blue-green dye; a green-sensitive silver halide emulsion layer with a is in contact with purple-red image dye-producing, non-diffusing color coupler that reacts with oxidized,

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A primary aromatic amine color developing agent a diffusing magenta dye to it capable of producing, and a faiau-sensitive silver halide emulsion layer, which is in contact with a non-diffusing color coupler producing a yellow image dye, diffusing when reacting with an oxidized primary aromatic amine color developing agent capable of forming yellow dye.

The expression "is in contact" means that the color couplers in the silver halide emulsion layers themselves or in layers adjacent to this can be arranged. A color-forming unit can therefore consist of one layer or several Layers, e.g. B. two layers exist.

The cobalt (III) complex can be in the image receiving part or the image receiving sheet of such. Matarials to be included in the light-sensitive element, in the alkaline working fluid contained in the container which can be split open and / or in a Solution in a second splittable container when the pH of the alkaline working solution is so high that this will result the cobalt (III) complex used would be destroyed.

The method of the invention is thus of particular importance for the production of multicolor photographic images starting from photographic recording materials with several image-recording layers. The invention makes it possible thereby the production of color photographic images of excellent quality starting from recording materials with a comparatively low content of photosensitive silver salts, d. H. especially the achievement of high yields Image dyes based on comparatively small amounts of light-sensitive silver salts »Is of particular importance the invention for color photographic recording materials, especially two- and three-color recording materials, with those in every shift

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another image dye is generated and in which the image dyes have specific absorption characteristics.

According to the invention, the color-forming units of such photographic recording materials can particularly advantageously contain the color couplers in a stoichiometric excess, based on the effective silver present. "Effective silver" is to be understood as the developable silver present in the units, which after full exposure and about 1 minute of development in a silver halide developer, e.g. B. the color developer described in Example 10 below, leads at 38 ⁰ C to a given amount of metallic silver, which corresponds to the developable silver halide.

Multicolor photographic recording materials, consisting of a layer support and at least one, preferably at least two color-forming units applied thereto, each with a light-sensitive silver salt which is in contact with a color coupler providing an image dye, are thus particularly advantageously suitable for carrying out the process of the invention, wherein the color coupler is present in an equivalent excess of at least 40 % , preferably at least 70 4, above the amount required for a stoichiorometric reaction with the effective silver, ie the developable silver, in each layer. In a particularly advantageous manner, the color couplers that produce color images are present in each of the color-forming units in a weight concentration which is at least three times as great as the weight concentration of the silver. The light-sensitive silver salt, for example silver halide, is preferably present in the unit or units in an occupancy of up to 30 mg silver per 0.0929 m ^{2 of} support surface.

The weight concentration of the color couplers 3 to 20 times the concentration by weight of the silver.

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The invention thus also relates to a photographic one Recording material for carrying out the method according to the invention, consisting of a layer support and at least one, preferably at least two, separate color-forming units, each with a light-sensitive unit, applied to it Silver salt and a color coupler, which is characterized in that the color coupler or couplers in at least one 4Oligen stoichiometric excess, based on the developable Silver, is or are present.

Recording materials of this type have proven to be particularly advantageous which consist of a layer support as well as at least two color photographic units with photosensitive silver salts, in particular applied thereto Silver halide emulsion layers, which are used to record light in different regions of the spectrum are sensitized and wherein each of the silver salt layers is in contact with a photographic color coupler, which is able to provide an image dye and which in a stoichiometric excess at an equivalence ratio of at least 1.4: 1, preferably greater than 1.7: 1, based on the effective or developable silver in each of the color-forming Units are present, d. H. in a ratio of, for example, 2: 1, 3: 1 or the like.

Particularly advantageous recording materials for carrying out the method of the invention are furthermore those which consist of a layer support and blue-, green- and red-sensitive silver halide emulsion layers applied thereon, of which at least two have been applied to the layer support in such a way that on a support surface of 0.0929 m 1 to 25 mg of silver are omitted and which furthermore each contain at least one photographic color coupler which, when reacting with an oxidized color developing agent, is able to produce a dye whose light absorption is practically complementary to the sensitivity of the silver halide of the silver halide emulsion layer, wherein

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the color coupler is present in an at least 40% stoichiometric excess based on developable or effective silver present, and further preferably the concentration of the color coupler on a weight basis is 4 to 1 times the weight of the silver. Particularly advantageous results can be achieved if at least the green- and red-sensitive η layers each contain 1 to 25 mg silver per 0.0929 m ² carrier area and the color couplers in at least these layers are based in at least a 40% stoichiometric excess on the effective or developable silver present, in particular in an at least 70% stoichiorometric excess and / or if the color coupler concentration is 4 to 10 times the weight of the silver. An at least necessary stoichiometric coupling excess can be of particular advantage.

The photosensitive silver salt layers preferably have

2 a silver coverage of up to about 30 mg of silver per 0.0929 m of support area or up to 325 mg per m of support area, in particular from 1 to 30 mg per 0.0929 m or from 10 to 325 mg per m of support area, in particular of about 1 to 25 mg per 0.0929 m ² or 10 to 270 mg per m ^{2 of} support surface. Very particularly advantageous results are obtained with silver ^{coatings of 20 to 160 mg per m 2 of} support surface in the case of the green- and red-sensitive layers of customary multilayer color photographic films.

It can also be advantageous to use the silver halide in such concentrations that below a concentration lie, with which unwanted background images occur, thereby avoiding the need for bleaching or fixing. In these cases the silver halide becomes Advantageously used in concentrations that are less than the amount which, if the silver halide <$ röllig exposed and developed to a maximum silver density

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of less than 0.4, preferably less than 0.2, leads, e.g. B. by using silver halide with a silver coverage of less than about 20, preferably less than about 10 mg per 0.0929 m ^{2 support area} .

In the case of the use of photographic recording materials of the types described with photosensitive silver salts It is essential that they contain at least so much photosensitive silver salt that they contain latent images, or at least photolytic silver can be obtained after imagewise exposure.

According to another particularly advantageous embodiment of the invention, the photographic materials of the invention consist of a substrate having at least two thereon a color forming units each having a Silberhalogenidemulsionsshicht, their image silver is developed in 30 $ of the time period in which at least 50 \, which is required to 95 \ develop developable silver of this layer, the layer further comprising at least one 401igen stöchioffistrischen upper excess, preferably an at least 70iigen stoichiometric excess of color coupler, based on existing effective developable h> SiJ ^ v _5, in contact stands. The expression "is in contact" means delc: \ "i ^ a ^ ^ i. ΆεΡ- the color coupler in the Silberhalo ^ enidemulsiösirsschiciii: se.: Tt or ie an adjacent layer eni-h & iteii leg . Recording materials of this type are ihsbe & ondem So "those with fine-grained silver halide amlsiogeu. ie emulsions" with silver halide grains of a medium size ". Kc" ri "size 6 of less than 0.8 microns. However, coarser-grained emulsions can also be used for the production of dormerial emulsions aterialien this beschriebeyiiJE Typr si.i? aen "I especially for the development" it from p-Fhe ^ yi.eriiiiiiminv-A existing F "i ' ⁵ > * ntwicklerverbin-

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The color couplers are also preferably used in such concentrations used that a density of at least 1.7, in particular at least 2.0, is achieved. The difference between D "" and D. should preferably be at least 0.6, especially

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which are at least 1.0. Each color-forming unit preferably contains at least 1 × 10 " ⁵ moles of color coupler / 0.0929 m ^{2 of} carrier area.

According to a further particularly advantageous embodiment of the invention, the recording materials consist of one Layer support and at least one silicon halide emulsion layer applied thereon, those based on a color coupler in an at least 40% stoichiometric excess on the silver, and at least one antifoggant is in contact. The antifoggant or agents are preferably located here in concentrations of 20 mg to 2 g per mole of silver.

The cobalt (III) complexes which can be used according to the invention represent so-called coordination complexes with a cobalt ion surrounded by a group of atoms, ions or other molecules which are generally referred to as so-called ligands. That puts cobalt ion at the center of these complexes a Lewis acid. The ligands are Lewis bases. Werner complexes are well known examples of such complexes.

Particularly suitable complexes for carrying out the process of the invention are those used by American chemists as so-called "inert" and by European chemists as

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so-called "robust" complexes are called.

The use of cobalt complexes which have ligands which, if a test sample of the complex in 0.1 molar concentration at 20 ^° C. in an inert solvent, for example water, already contains a 0.1 molar Concentration of a labeled uncoordinated ligand of the same type is present, is dissolved, lead to a negligible exchange of uncoordinated and coordinated ligands within a period of at least 1 minute, preferably from at least several hours to about 5 hours or more.

Such a test can advantageously be carried out under the pH conditions which are used in practice when carrying out the method of the invention. In the event of the use of photographic recording materials with silver halide layers, this means that at a pH from above about 8 is worked.

Many of the well-known cobalt (III) complexes that are used to carry out of the method of the invention can be used, show no or practical when performing the test described no exchange of uncoordinated and coordinated, within a period of several days. Ligands

The ones used to carry out the \ fa: driving of the invention Cobalt (III) complexes can have a wide variety of ligands. The ligands can be made from practically all Lewis bases exist, d. H. Substances with an electron pair that is not in common. Typical suitable ligands are thus for example Halide, e.g. B. chloride, bromide and fluoride, also nitrite, water and amine ligands, as well as such common ligands, as described on page 44 of the book by Basolo and Pearson, "Mechanism of Inorganic Reactions, A Study of Metal Complexes and Solutions", 2nd edition, 1967, published by John Wiley and Sons, Page 141.

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The lability of the ligands in the complex can be influenced by the nature of the ligands.

Cobalt (III) complexes that have proven to be particularly advantageous are those with a coordination number of 6. For carrying out the process of the invention, preference is given to using complexes with ligands which consist of ethylenediamine (s), diethylenetriamine (diene), triethylenetetramine (triene) , Amine (NH ₃ ), nitrate, nitrite, azide, chloride, thiocyanate, isothiocyanate, water, carbonate and ethylenediaminetetraacetic acid.

Cobalt (III) complexes which have proven to be particularly advantageous for carrying out the process of the invention are those which have (1) at least two ethylenediamine ligands or (2) at least five amine (NH ₃ ) ligands or (3) one triethylenetetramine ligand.

Cobalt hexamine salts have proven to be particularly advantageous, e.g. B. the chloride, bromide, sulfite, sulfate, perchlorate, nitrite and acetate salts.

Examples of further particularly advantageous cobalt (III) complexes for carrying out the method of the invention are:

^ Co (NH ₃ ) ₅ H ₂ O_7X; / ~ Co (NH ₃ ) ₅ CO

^ "Co (NH ₃ ) ₄ CO ₃ _7X; Z" Co (en ^ _7X; ^ ₂₃₂

trans - / "Co (en) ₂ C1 (NCS) _7X; trans- ^ ~ Co (en) ₂ (N ₃ ) ₂ "7X; cis - / "Co (en) ₂ (NH ₃ ) N ₃ _7X; cis - ^ 'Co (en) ₂ Cl ₂ _7X; trans ^ "Co (en) ₂ Cl ₂ _7X; Z'Co (en) ₂ (SCN) ₂ _7X and ^" Co (en) ₂ (NCS) ₂ X

where X stands for one or more anions, the number of which is replaced by the L * e "afs-" teutr * lisatioftfr * f ·! is determined .

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In the case of the complexes, the uncoordinated anions can exert an influence on the reducibility of the complexes. So did has shown, for example, that the anions listed in the following lead to an increase in the stability of cobalt (III) hexamine complexes in the order given: bromide, chloride, Nitrite, perchlorate, acetate, carbonate, sulfite and sulfate. As a result, the anions can be selected so that the ! »Complex to be used individually has the desired degree of reducibility. In addition to the specified anions, these can, for example, also consist of hydrochloride, nitrate, Thiocyanate, dithionate or hydroxide anions.

Neutral complexes are also suitable for carrying out the process of the invention, for example those of the formula: / "Co (diene) (SCN) ₂ OH_7. However, positively charged complexes have proven to be particularly advantageous.

A wide variety of reducing agents can also be used to carry out the process of the invention. Of particular importance are those reducing agents which are capable of reducing silver halide to metallic silver, for example those which are capable of developing imagewise exposed light-sensitive photographic silver halide. Thus, for performing the method of the invention & .In ^ pA example ktionsmittel such reducing compounds such as Ky -rochinone, catechols, aminophenols, 3-pyrazolidones, for example. B. l-phenyl-3-pyrazolidone, 1- »d- or iso & scorbic acid, reductones and phenylenediamines can be used.

In principle, any combination of cobalt (III) complex and reducing agent can be used in a catalytically active surface to carry out the method of the invention # 4ag # Sit. Preferably, you should

44 · <U «Μ»? 8 * # 11 «β £» takiUr Lö-

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Also suitable as reducing agents for carrying out the process of the invention are, for example, those dye developers such as those from the US patent 2,983,606 and which are advantageously used in combination with an auxiliary developing agent.

According to a particularly advantageous embodiment of the invention color developing agents composed of primary aromatic amines are used as reducing agents, for example p-phenylenediamines or ρ-aminophenols (which are particularly stable Redox combinations with cobalt (III) complexes are able to deliver, for example with / "Co (en), 7ci,).

The color developer compounds can consist of the customary known color developer compounds, for example from 3-acetamido-4-amino-N, N-diethylaniline, p-amino-N-ethyl-N- (ß-hydroxyethyl) aniline sulfate, p-aminoethyl-N-ß-hydroxyethylaniline, N, N-diethyl-p- phenylenediamine, 2-amino-5-diethylaminotoluene, N-ethyl-N- (£ -methanesulfonaraidoethyl) -3-methyl-4-aminoaniline, 4-amino-N-ethyl-3-methyl-N- (ß-sulfoethyl) aniline and 4-Amino-3-methyl- (N-ethyl-N-3-hydroxyethy | aniline.

For more details on how to perform the Developer compounds suitable for the method of the invention, reference is made to the journal J.A.C.S., Volume 73, (1951), pages 3100-3125, as well as the book by Mees and James "The Theory of the Photographic Process", 3rd edition, (1966), published by MacMillan Co., New York, pp. 278-311.

However, reducing agents which are not special silver halide developing compounds are also suitable for carrying out the process of the invention, for example Alkali metal borohydrides, aminoboranes, preferably trimethylamineborane, polyamineborane ·, phosphineboranes, arsineboranes, stilbene boranes and borazines, as for example in columns 3 and

->. 209881/0615

BAD OFUGtNAL

U.S. Patent 3,266,895.

Many of the reducing agents described here develop their greatest effectiveness at a high pH value, for example at a pH of around 8 to 13.

Substance A, which is present in an image-wise distribution and catalyzes the redox reaction, can not only consist of silver, but Rather, it can consist of a wide variety of substances that differ from the reaction products generated in the redox reaction differentiate between reducing agent and cobalt (III) complex. This means that the image-wise distribution Catalytically active substance A can consist of practically any catalytically active substance except silver, which one Initiates and promotes redox reaction between the cobalt complex and the reducing agent. The catalysts seem to be there cause electron transfer between the oxidizing agent and the reducing agent.

Substance A, which is present in an imagewise distribution, is preferably composed of a metal. This metal exists in particular of a metal from Groups IB and VIII of the Periodic Table of the Elements. Many of the to carry out the procedure of Catalysts which can be used in the invention therefore consist of zero-valent metals or of so-called metal nuclei. Special advantageous catalysts for carrying out the process of the invention thus consist of silver, for example from platinum, copper, gold, mercury, but also from substances such as coal, e.g. B. activated charcoal, and copper sulfide.

The amount of the reaction products obtained in the redox reaction is not limited to the amount of catalyst present.

BAO ORIGINAL

VW- ■ (K, 1 p

because the catalyzed redox reaction is not stoichiometric Base expires.

The image-wise distribution of the catalytically active substance A can be achieved in various ways, for example by:

1.) Photoreduction, e.g. B. by photoreduction of a silver salt, for example a silver halide to metallic silver * or by photoreduction of a palladium salt, z. B. Palladium oxalate to metallic palladium, or by photoreduction of a gold salt, e.g. B. a gold halide to metallic gold;

2.) Photooxidation, e.g. B. by photooxidation of metallic silver to Ag;

3.) photolytic formation of a suitable inhibitor, for example Phenylmercaptotetrazole, which can be released imagewise from compounds such as, for example in U.S. Patent 3,227,554;

4.) electrostatic precipitation of a catalyst on a latent image, e.g. B. charged carbon particles or Particles of a zero-valent metal;

5.) chemical precipitation of a catalyst on a latent image, for example precipitation of a zero-valent metal, for example silver or gold on exposed titanium dioxide or zinc oxide or

6.) mechanical precipitation of the catalyst.

For the production of catalysts or catalyst precursors can also take such measures, for example as described in the British patent

2 0 9 in i / 0 6 1 5 BAD ORIGINAL

font 1 194 581 and in the Belgian patent 750 182 are described in more detail.

Cobalt (III) complex and reducing agent are preferred selected such that if samples thereof are each in a 0.01 molar concentration in an inert solvent at 20 C, practically no redox reaction within of at least 15 minutes, preferably within several hours, in particular within 12 hours or several days or even months or even longer in the absence of the catalytically active substance A occurs.

However, combinations of cobalt complex and reducing agent can also be used to carry out the process of the invention which, in the absence of a catalyst, undergo a redox reaction within a shorter time than the specified time are included, especially in cases where the cobalt complex and reducing agent only last a short period of time be in reactive relationship with one another for a long time. Such a case exists, for example, when separate solutions of Cobalt complex and reducing agent on a recording material with a catalyst present in imagewise distribution be sprayed on or applied in any other way. In the presence of the catalyst present in an imagewise distribution the redox reaction can then take place, whereupon unreacted reducing agent and unreacted complex in different Ways can be removed, for example by means of an air stream of a liquid or a chemical neutralizing agent.

According to the invention it is also possible, for example, to bring a catalyst present in imagewise distribution together with an oxidizing agent (or reducing agent) present in non-imagewise distribution in contact with a reducing agent (or oxidizing agent) until a sufficient imagewise redox reaction has taken place.

209Bd i / 0615 BAD 0RK3INAL

The reducing agent (or oxidizing agent) can then be removed. In this embodiment of the method of the invention as well as other embodiments thus oxidizing and reducing agents are not particularly resistant to a redox reaction taking place in the absence of a catalyst to be stable.

As a rule, it has proven to be particularly advantageous to use a recording material with an image-wise distribution present catalyst with a combination of a cobalt complex and a reducing agent in contact. However, it is also possible to use a complex and catalyst that are not present in an imagewise distribution with an imagewise Distribution to bring the reducing agent present into contact. It is also possible to present them in an image-wise distribution Bring cobalt complex into contact with a combination of reducing agent and catalyst. Finally, in imagewise present catalyst with a not present in imagewise distribution cobalt complex with a Reducing agent are brought into contact or a catalyst present in an imagewise distribution with a not in imagewise distributed reducing agent is brought into contact with a cobalt complex.

A wide variety of measures can be taken to bring the cobalt complex, reducing agent and catalyst into contact with one another will. For example, a recording material with a catalyst which is present in an imagewise distribution can also be used a solution containing the cobalt complex and a reducing agent. This means that, for example a recording material having at least one hydrophilic Colloid layer applied to a layer support and contains the catalyst in an imagewise distribution, with an aqueous solution containing a cobalt (III) complex and a reducing agent contains, can be brought into contact. The con-

, π ι, 1 Π

concentration of reducing agent and oxidizing agent in such solutions can be very different. In individual cases optimal concentrations depend on such variables as contact time, the amount of catalyst present, and reactivity the cobalt complex used in the individual case and the selected cobalt complex-reducing agent combination away.

Concentrations of cobalt complex and reducing agent of about 0.1 to 50, in particular, each have proven to be particularly advantageous 1 to 15 g per liter of solution has been proven. The contact or dwell times can be up to 30 seconds, for example be about 2 hours or more.

The cobalt complex and / or the reducing agent can also optionally in photographic recording materials be housed in the form of splittable containers that are split open by the action of pressure and their Distribute content in photographic recording materials.

Another method to initiate the redox reaction exists therein, oxidizing agent and reducing agent in at least one layer, in particular a hydrophilic colloid layer To accommodate photographic recording material and then this with a plate with a metal catalyst relief image to bring in contact. The metallic relief image then initiates the redox reaction between the oxidizing agent and the Reducing agent in the layer or layers of the recording material. If necessary, parts of the Cobalt complex existing oxidizing agent or reducing agent in working or developing solutions for development of the photographic recording material and in one or more hydrophilic colloid layers of a recording material, the latter also being accommodated

2 0 9 8 8 1/0615

a catalyst supplier, e.g. photosensitive Silver halide.

Cobalt complexes and reducing agents suitable for carrying out the process of the invention generally have in water good solubility. Such compounds have proven to be particularly advantageous, of which at least 0.1, preferably at least 10 g are soluble in 1 liter of water. For the preparation of solutions of the cobalt complexes and / or reducing agents, i. also useful in preparing photographic working solutions suitable for practicing the method of the invention In addition to water, however, there are also other solvents, preferably polar organic solvents, such as, for example, methanol and ethanol. As a result, such reducing agents and cobalt complexes can also be used to carry out the process of the invention are used, which have only a very low solubility in water.

The method of the invention is eminently suitable for manufacture and amplification of weak and even invisible amounts of substance A, which is present in an image-wise distribution the process of the invention is excellent for the production and enhancement of photographic images of silver halide photographic light-sensitive materials, in which a latent silver image or a low density silver image to produce a visible one Image can be used. Furthermore, the method of the invention is advantageously suitable for supplementing a Image, e.g. B. a silver image or an image made of another zero-valent metal or one made of another catalyst, Oxidizing agents and / or reducing agents existing image. Finally, it is made possible by the method of the invention also to replace pre-formed images with other images.

BAD OFUGlNAL

2 0 9 8 ύ I / ü 6 1 5

As already stated, in the method of the invention at least a reaction product of the redox reaction taking place with a compound B which is reactive with the reaction product under a change in light value, d. H. to generate an image.

The embodiment of the method is of particular importance of the invention in which the reactant is oxidized to a compound which is compatible with the reactive compound B reacts with a photographic color coupler to form an image dye.

On the other hand, however, the reduced in the redox reaction can also be used Cobalt complex to a change in light value, d. H. for generation of an image, by reacting this cobalt reaction product with a reactive compound B. will.

The reactive compound can in this case, for example, from an 8-hydroxyquinoline, a formazan dye, a 2,4-diaminophenol, a ct-nitroso-3-naphthol or 1- (2 ', 4', 6'-trichlorophenyl) -3- / "3 ^M - (2" ^l, 4 ^MI -di-tert-amylphenoxyacetamido) benzamido_7-5-pyrazolone exist. In this embodiment of the process of the invention, it is also possible, for example, to use compounds such as 8-hydroxyquinoline, the coupling position of which is blocked. For example, e-Hydroxy-Sjy-dimethylquinoline can also be used as compound B, although both coupling positions of these compounds are blocked.

According to another embodiment of the method of the invention a reaction product resulting from the redox reaction is used to increase the reactivity of an image-generating Component or reactive compound B to reduce or to poison this compound.

BADORiGlNAL ₂₀ y ₈₀ j / Q615

According to a further embodiment of the method of the invention, photographic recording materials consisting of a layer support and at least one applied thereon layer of a crosslinkable colloid with dispersed therein Silver halide grains are used, in which case the colloid is imagewise in the areas where there is metallic Silver is developed, cross-linked, with no direct relationship to the amount of silver developed under reinforcement cross-linking or tanning. In this case, a photographic material having the combination of a cobalt complex and a reducing agent which undergo an imagewise redox reaction in the presence of metallic silver, brought into contact, the reduced form of the cobalt complex as a crosslinking agent for the crosslinking of the colloid is used. A customary photographic developer compound can be used as the reducing agent will. On the other hand, however, it is also possible that the oxidized form of the developer compound has the function of a cross-linking Connection takes over. That produced by the action of a photographic developer on the exposed silver halide metallic silver catalyzes the redox reaction.

Optionally, the photographic recording material can, after developing a silver image in a crosslinkable one Colloid layer with the combination of cobalt complex and reducing agent for the purpose of bringing about cross-linking in Be brought into contact. In practicing this latter embodiment of the invention, it is not necessary that the Reducing agent a selectively effective photographic silver halide developing agent is. Preferably, in this embodiment of the method of the invention, the ligands of the cobalt complex selected in such a way that ligands set free by the cobalt complex in the redox reaction

2 0 9 8;, l! / U 6 1 5

Do not disturb the networking process.

The method of the invention can be used in the context of the usual, photographic imaging processes employing tanning development can be employed in which suitable colloids, particularly gelatin, are crosslinked or hardened. Preferably, recording materials are included Silver halide emulsion layers used, which consist of unhardened or only partially hardened gelatin silver halide emulsions.

The invention also enables tanning or crosslinking with the aid of developer compounds, which were previously considered unsuitable for tanning development. On the other hand, the invention allows at Use of conventional tanning developer compounds to intensify the tanning process. As a result, a wide variety of known tanning developer compounds can be used in this embodiment of the method of the invention, for example pyrogallol and catechols, e.g. B. 4-phenyl catechol, and other photographic developing agents, which normally tan or crosslink colloids such as hydroquinones, pyrazolidones, e.g. B. 1-phenyl-3-pyrazolidone, p-phenylenediamines, ρ-aminophenols and the Diaminophenols. This embodiment of the method of the invention can thus be used, for example, in the context of dye absorption processes and colloid transfer processes as well as in the production of so-called photoresists, pianographic printing plates and lithographic printing plates are used.

The invention also allows the addition to be made more substantial Amounts of sulfite, for example sodium sulfite, developer solutions to be tanned without the tanning effect of these developer solutions being lost. The usual known tanning The amount of sulfite that can be added to developers is known to be limited,

20988 1/0615

because the sulfite has an inhibiting effect on the tanning development. The invention thus enables the manufacture of more stable ones tanning developer solutions due to a higher tolerance limit for sulfite stabilizers.

If necessary, it can be advantageous to take precautions: that .one of the reaction products that arise in the redox reaction / reacts with the reactive compound B. this can be easily achieved by using a so-called blocking agent, which reacts with the compound B. avoids. The use of a blocking agent can be advantageous, for example, when as a redox combination a cobalt (III) complex as an oxidizing agent, one of a primary aromatic amine as a reducing agent, metallic silver as a catalyst and a photographic color coupler can be used as the reactive compound B. In the presence of the silver catalyst the trivalent cobalt is reduced to divalent cobalt while the developing agent is oxidized. Both the cobalt (II) as well as the oxidized developing agent, work with many photographic color couplers to produce a change in the light value to react. When the only desired change in light value is caused by the reaction product of oxidized developing agent and color coupler is to be caused, the blocking agent is used to cause a reaction between the reduced oxidizing agent (in this case Co) and the photographic color coupler. As a blocking agent A wide variety of compounds can be used, for example so-called chelating agents, e.g. B. Ethylenediaminetetraacetic acid, sodium hexametaphosphate, sodium tetraphosphate as well as 2-hydroxypropylenediaminetetraacetic acid, if the reactivity of the cobalt is inhibited shall be.

209881 / 061S

Although in the case of the use of multicolor photographic recording materials with color-forming units of the type described, at least two of the color-forming units preferably have a silver salt in a concentration of up to 30 mg silver per 0.0929 m ^{2 support area} and the developable silver halide preferably in a concentration, based on silver of less than 30 mg / 0.0929 m is present, however, it is also possible to use emulsion mixtures to produce the silver halide emulsion layers and to apply these in higher concentrations as long as no more than 30 mg of silver develops per 0.0929 m of support area will. For example, emulsions can be used to produce the silver halide emulsion layers which contain silver halide grains which are relatively insensitive to light or which contain so-called development retarders or substances which suppress development, for example color couplers which release development inhibitors.

It may be desirable to include emulsions with relatively light-insensitive grains or development inhibitors for example to obtain a uniform coating using a less accurate feeder to reach.

By besoiiueivÄ. Ve ??, sv £: 'ί: the implementation of the method of the invention can be those photographic recording materials with at least black color-forming units, each of which contains a silver layer which, with regard to its effective coverage and developability, can be defined as one which, if, after complete exposure and 1 minute! close development in eiiiem color developer in the later folgmid ^ n example 10 composition of 38 ⁰ C indicated

2 0 9 8 b / 0615

less than 30 mg metallic silver per 0.0929 m ² carrier area

before, preferably less than 15 mg of silver per 0.0929 m of support area. The term "effective silver" refers to refer to the silver cone, which occurs when the described experiment is developed. In addition, the stated ratios of coupler to silver relate to "effective silver" which is generated in the type of development described. In most cases the amount is on effective »silver as silver halide in the undeveloped, unexposed photographic recording material practically equal to the amount of total silver present as silver halide.

A completely exposed or exposed silver halide emulsion layer is understood to be one which is shown in known to be exposed in the usual manner until D is reached has been, for example by exposure to a 500 watt, 3000 ° K lamp with an exposure time of about 10 seconds and

a total exposure in the film plane of 11.3 × 10 ergs / cm

Preferably for the production of the recording materials fine-grain emulsions used, d. H. those with an average silver halide grain size of less than 0.8 microns, which deliver a high concentration of effective silver in a short period of time. The use of such fine-grain emulsions is particularly advantageous because this enables rapid development processes to be carried out, particularly when using color developing agents such as, for example, ρ-phenylenediamines. In addition, high development speeds enable the rapid development of exposed areas without building up a background veil. In addition, at high development speeds, silver halide emulsions can be used which have one have experienced higher levels of chemical sensitization without

20 98 81/06 1 p

that a significant D. -Building in development

mm

he follows.

The mean grain size of the emulsions can be determined according to the usual known methods, as for example in Chapter 2 of the book by Mees and James "The Theory of the Photographic Process "3rd Edition, 1966, MacMillan Co., USA.

The term color coupler used here stands for all the compounds with the oxidation products of primary aromatic amines present color developing agents in photographic processing to form an image dye able to react and in hydrophilic colloidal Binders, e.g. B. gelatin, do not diffuse, as well as for those color couplers which are used to build up color photographic images suitable image dyes provide when combined with an oxidized primary aromatic amine color developing agent be implemented with the involvement of couplers in freedom-setting mechanisms. The color couplers can generate diffusing or non-diffusing dyes.

- 36 -

209881/0615

Typical ones used in the manufacture of a photographic recording material Color couplers suitable according to the invention are so-called phenolic or naphtholic color couplers and also color couplers based on 5-pyrazolones and from open-chain ketomethylene compounds existing color couplers. Suitable for producing cyan, magenta and yellow dye images Color couplers, which are present in the cyan, magenta and yellow dye-forming color-forming units of the color photographic Materials according to the invention may be present, for example, those disclosed in the United States patent 3,046,129, column 15, line 45 to column 18, line 51 are known.

The color couplers can be dispersed in the emulsion layers by customary known methods, for example using solvents and methods known from U.S. Patents 2,322,027 and 2,801,171. Suitable color couplers include, for example, those of the so-called Fischer type, such as those from U.S. Patent 1,055,155 are known, and in particular non-diffusing Fischer-type couplers having a branched carbon chain such as those shown in FIG U.S. Patent 2,376,679, column 2, lines 50-60. Recording materials with such color couplers can be used, for example, according to the foreign US patent specification 3,046,129, columns 23 and 24, known methods Use of a cobalt (III) complex reducing agent combination develop according to the invention.

Recording materials with color couplers can advantageously be used to carry out the method of the invention which are insoluble in water and with the aid of a coupler solvent, which preferably consists of a moderate polar solvent in which emulsion layers have been incorporated. Typical solvents suitable for this purpose

2 0 9 8 B 1/0 6 1 5

3 *

are for example tri-o-cresyl phosphate, di-n-butyl phthalate, Diethyl lauramide, 2,4-diarylphenol and liquid dye stabilizers, as for example in the article "Improved Photographic Dye Image Stabilizer-Solvent" published in of the journal "Product Licensing Index", Volume 83, March 1971, pages 26-29.

Coupler solvent recording materials also appear to soak up color developing agents to support such processes in which the recording material is transferred from a developer bath to an intensifier bath will.

The term "non-diffusing" is used in its usual sense; H. are under non-diffusing color couplers to understand such color couplers which in the cases occurring in practice are not affected by photographic hydrophilic colloid layers, from gelatin, for example, migrate, in particular not during the development process in aqueous alkaline solutions. The term "non-diffusing" is thus synonymous with the expression "immobile". The opposite meaning is the expression "diffusing" or "mobile".

In the case of the multicolor photographic recording materials according to the invention having at least two color-forming units each with a photosensitive silver salt which is generally spectrally sensitized to a region of the light spectrum the color-forming units can optionally be separated from one another by simple separating layers or separating layers with scavenging compounds for oxidized color developing agents and the like to prevent individual color-forming units from being separated. The effective isolation of the color-forming units from one another is known and therefore does not require any further explanation here.

20983 1/0615

The color couplers are preferably selected in such a way that they give a good neutral image. The cyan dye to be produced preferably has its main absorption at about 600 to 680 n $, the magenta dye to be produced has its main absorption between about 500 and 580 nm and the yellow dye to be produced has its main absorption at about 400 to 480 nm.

The one intended for carrying out the method of the invention Customary known additives can be incorporated into photographic recording materials, with which the development characteristics and image properties can be influenced. In those cases in which developed silver is used as a catalyst, it is desirable to only add such additives use which are not or at least not strongly absorbed by the silver surface in order to avoid that the surface available as a catalyst is reduced. So it has generally proven desirable, for example, to use larger amounts of iodide salts and organic compounds with free mercapto groups which have a provide a high degree of heat of adsorption, for example the use of larger amounts of phenyl mercaptotetrazole, alkali metal iodide salts and the like. Which provide silver salts are more insoluble in water than silver bromide, to be avoided *

Advantageously, silver halide antifoggants can be added to the light-sensitive layers of a photographic recording material according to the invention, it being particularly advantageous to use only those antifoggants which are derived from silver after its development cannot be firmly adsorbed. Such silver halide antifoggants are known and consist of, for example heterocyclic organic compounds such as tetrazoles, azaindenes, triazoles and the like.

209881/06 16

Her

Typical silver halide antifoggants useful in making the recording materials of the invention let use are, for example, methylbenzotriazole, benzotriazole, S-methyl-l.S-benzothiazolium bromide, 5-nitrobenzimidazole, Decamethylene bis (benzothiazolium bromide) and the like. as Antifoggants are also suitable compounds such as nitrone, also nitroindazoles and those antifoggants, for example, in French patents 2,084,802 and 2,091,544 and the USA patents 2,131,038, 2,694,716, 2,886,437, 2,444,605 and 3,287,135 and British Patent 623,448. In Advantageously, such antifoggants can be added to the silver halide emulsions in concentrations of about 20 mg up to about 2g per mole of Ag can be added.

For the production of the photographic recording materials according to the invention, the customary known colloidal Binders can be used alone or in combination with one another, namely naturally occurring binders, for example Proteins, e.g. B. gelatin and gelatin derivatives, also cellulose derivatives and polysaccharides, such as dextran, Gum arabic and the like, as well as synthetic polymers existing substances, e.g. B. water-soluble polyvinyl compounds, such as B. poly (N-vinyl pyrrolidone) and acrylamide polymers. Typical binders are e.g. In U.S. Patent 3,039,873, column 13. The photographic emulsion layers and other layers of a photographic recording material according to the invention * Furthermore, they can be used as binders alone or in combination with hydrophilic, water-permeable colloidal ones Binders contain other synthetic polymeric compounds, e.g. B. dispersed polyvinyl compounds, ζ. B. in latex form, especially those that lead to an increase contribute to the dimensional stability of the photographic material.

20988 1/061 p

In the production of the recording materials, the hydrophilic colloids can be used in conventionally known concentrations. Layer thicknesses corresponding to at least 100 mg, for example 100 to 400 mg, of colloidal binder per 0.0929 m ^{2 of} carrier surface have proven to be particularly advantageous.

To produce the recording materials according to the invention, unwashed or for the purpose of removal can also be used soluble salts washed silver halide emulsions can be used. In the latter case, the soluble salts can be prepared, for example, by quenching the emulsion and leaching it be removed or by a so-called coagulation wash, as it is, for example, from the USA patents 2,618,556, 2,614,928, 2,565,418, 3,241,969, and 2,489,341 are known.

For the chemical sensitization of the silver salts of the photographic Recording materials according to the invention can use the conventionally known chemical sensitizers are, for example reducing sensitizers, as well as sulfur, selenium or tellurium compounds, furthermore Gold, platinum and palladium compounds or combinations thereof. Usual known sensitization methods can be used such as those known from U.S. Patents 1,623,499, 2,399,083, 3,297,447 and 3,297,446, for example are.

The supports of the photographic materials according to the invention can consist of the usual known supports, z. B. from films made of cellulose nitrate, cellulose esters, polyvinyl acetals, polystyrene, polyesters, e.g. polyethylene terephthalate, Polycarbonates and other resinous substances, but also z. B. made of glass, paper, metal and the like. If appropriate, the layer supports can be subjected to a corona discharge in order to improve the adhesion of the emulsion layers to be applied be subjected.

20988 I / 061 5

■ fa,

The layer support typically consists of a photographic one Recording material according to the invention from a flexible layer support, in particular from a paper layer support, which may be partially acetylated or have a barite layer and / or a layer of an α-olefin polymer can, in particular a layer of a polymer of an α-olefin having 2 to 10 carbon atoms, for example a layer of polyethylene, polypropylene or a copolymer of ethylene and butene.

The individual color-forming units can be on the same Be arranged side of the support or on both sides of the support, for. B. when a more transparent Film base is used.

For additional sensitization of the light-sensitive silver salts Conventional spectral sensitizing dyes can be used. For example, an additional spectral sensitization obtained by treating the emulsions with a solution of one or more sensitizing dyes treated in an organic solvent. On the other hand, the dyes can also be in the form, for example incorporate a dispersion into the emulsions, e.g. B. by methods such as those from British patent specification 1,154,781 are known. To achieve optimal results, the dyes can be added to the emulsions at the end of the emulsion preparation or added at an earlier point in time.

To sensitize the recording materials according to the invention suitable sensitizing dyes are, for example, from US Patents 2,526,632, 2,503,776, 2,493,748 and 3,384,486 known.

The sensitizing dyes suitable for spectral sensitization can, for example, complex from cyanines, merocyanines, complex tri- or tetranuclear merocyanines

20988 1/0615

tri- or tetranuclear cyanines, holopolar cyanines, Styryl dyes, hemicyanines, ζ. B. enamine hemicyanines, Oxonols and hemioxonols exist.

Dyes of the cyanine classes can contain the usual basic nuclei, e.g. B. thiazoline, oxazoline, pyrroline, Pyridine, oxazole, thiazole, selenazole and imidazole nuclei. The nuclei can be substituted in the customary known manner, for example by alkyl, alkylene, hydroxyalkyl, sulfoalkyl, carboxyalkyl, aminoalkyl and / or enamine groups. Furthermore, the cores to carbocyclic or be fused on heterocyclic ring systems, which in turn can optionally be substituted, for example by Halogen atoms, aryl radicals, e.g. B. phenyl radicals, and / or alkyl, haloalkyl, cyano or alkoxy radicals. The dyes can be symmetrical or asymmetrical in nature, the Methine group or polymethine chain of the dyes can also be substituted, for example by alkyl, aryl, ζ. B. phenyl, enamine and / or heterocyclic substituents.

The merocyanine dyes can also be those listed contain basic nuclei as well as acidic nuclei, e.g. B. thiohydantoin, rhodanine, oxazolidendione, thiazolidinedione, Barbituric acid, thiazolinone and malonitrile cores. The acidic nuclei can also be substituted, for example by Alkyl, alkylene, aryl, e.g. B. phenyl, carboxyalkyl, sulfoalkyl, hydroxyalkyl, alkoxyalkyl or alkylamino radicals or heterocyclic nuclei.

Optionally, for the spectral sensitization of the photographic recording materials according to the invention combinations of different sensitizing dyes can also be used. Finally, supersensitizing additives can also be added which are not themselves visible Absorb light, for example ascorbic acid derivatives, azaindenes and / or cadmium salts.

2098 8 1/0615

The various layers of a photographic material according to the invention, including photographic ones Layer, can also optionally contain light-absorbing substances and filter dyes, for example those as known from U.S. Patents 3,253,921, 2,274,782, 2,527,583, and 2,956,879. If necessary, the Dyes are pickled, for example by methods such as are known from US Pat. No. 3,282,699.

The sensitizing dyes and other additives that may be used can be prepared from aqueous solutions or solutions prepared using organic solvents * Methods such as those from the USA patents can be used 2 912 343, 3 342 605, 2 996 287 and 3 425 835 are known.

The individual layers of the photographic recording materials according to the invention can furthermore contain conventionally known hardeners, plasticizers, lubricants, surface-active compounds, optical brighteners and the like.

The individual layers of the photographic recording materials according to the invention can be prepared according to conventionally known methods Methods are applied to the substrate, including among other things by an extrusion coating under Use of coating devices such as are known, for example, from US Pat. No. 2,681,294. Optionally, two or more layers can be used at the same time be applied, e.g. By methods such as those disclosed in U.S. Patents 2,761,791 and 3,508,947 and British Patent 837 095 are known.

The photographic materials of the invention are used for carrying out color image transfer processes are used, methods can be used here, such as

209881/0615

HS

they from U.S. Patents 3,087,817, 3,185,567,

2 983 6Q6, 3 253 915, 3 227 550, 3 227 551, 3 227 552,

3,415,644, 3,415,645, and 3,415,646 are known. In case of Methods such as those disclosed in U.S. Patent 2,882,156 can be used to perform wicking transfer processes.

Are so-called cleavable color couplers of the so-called preformed dye type used or so-called redox couplers referred to in American as "redox release couplers" - at least two of the color-forming units have one at least 40ligen stoichiometric excess on the couplers, based on the silver in the color-forming units.

The method of the invention can also be used in an advantageous manner within the framework of the known subtractive multicolor processes perform in which color couplers or color formers are introduced into the silver halide emulsion layers during the development process. Processes of this type are known, for example, from US Pat. No. 2,252,718. To the Suitable color couplers exist to carry out this process for example from pyrazolones soluble in aqueous alkali and phenolic and open-chain ketomethylene color couplers, which react with the reaction products of common color developing agents, for example ρ-phenylenediamines, to form purple, blue-green and yellow dyes. To the Color couplers suitable for carrying out this process are, for example, from US Pat. No. 3,165,407, in particular column 2, lines 20 to column 3, line 47, and also from US Pat U.S. Patent 2,801,171 and U.S. Patent 2,875,057.

In the case of color systems of the type described, subtractive dye images can be produced by what is known as a color negative process, as is described, for example, in the magazine "Journal of the Society of Motion Picture and Television

20980 1/0615

Engineers ", Volume 61 (1953), pages 667-701, or by color reversal processes in which silver reversal images generated, for example by using direct positive emulsions or using negative emulsions, which are initially exposed imagewise, developed in a black-and-white developer to produce a negative silver image and thereafter experienced at least one additional exposure or subjected to a fogging treatment, whereupon by additional development the desired subtractively colored dye images can be generated.

As a color developer connection for carrying out these processes the usual known color developing agents can be used, especially phenylenediamines and substituted ones Derivatives thereof, as described, for example, in U.S. Patents 2,548,574, 2,552,240-2 and 2,566,271 are known.

The process of the invention can also be used in other photographic processes for the production of multicolor Use images, for example in the context of color diffusion transfer processes, as described, for example, in US 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 and US patent application 169,667 are known.

The process of the invention can also be used in color photographic processes to produce diffusing ones Perform image dyes, as described in more detail, for example, in US patent application 176,751. So can for example a cobalt (III) complex, e.g. B. a cobalt (III) hexamine chloride complex, used in the last-described process to enhance the generation of the image dyes

20980 1/06 15

will. The developer compound, consisting of a black and white developer compound or a color developing agent, the redox reaction occurs with the cobalt complex subjected, the resulting oxidized form of the reducing agent being a non-diffusing compound, e.g. B. a p-sulfonamidoaniline or a p-sulfonamidophenol, which after oxidation forms a diffusing color-forming residue in Freedom sets.

The method of the invention is used in the context of color diffusion transfer processes applied, they may consist of, for example, those in which the image receiving sheet is separated from the photosensitive recording material after development, for example such as those from the U.S. Patent 3,362,819 or those employing photographic film units in which the photosensitive part and the image-receiving layer form an integral unit, as they are, for example, in the USA patent applications 115 459 and 115 552 are described in more detail.

Since the invention includes the use of photographic recording materials With thinner layers, therefore, smaller amounts of developing materials are used to develop them are required can include considerable cost of developing materials can also be saved. So lets go to development such recording materials e.g. B. working solutions with smaller amounts of solvent can also be used, thereby reducing the problems associated with evaporation of solvents after processing of photographic materials are connected. If the recording materials used to carry out the process contain opacifiers or so-called opacifying compounds, these compounds are selected so that they are not catalysts represent for the redox reaction.

20988 1/0615

The customary known silver halides can be used to produce the photosensitive silver salt layers. d. H. Silver bromide, silver iodide, silver chloride, or mixed Silver halides, e.g. B. silver chloride bromide, silver chloride bromide iodide, Silver chloride iodide, silver bromide iodide.

Since negative as well as direct-positive recording materials can be used to carry out the method of the invention, A wide variety of silver halide emulsions can also be used to prepare the same. So can to manufacture the recording materials negative emulsions as well as z. B. such emulsions are used, their silver shark ogenide grains are characterized by a high internal sensitivity. Furthermore are suitable for the production of Recording materials e.g. B. veiled direct-positive emulsions of the US Patents 2,497,875, 2,563,785, 3 501 305, 3 501 306 and 3 501 307 and the Belgian patents 770 222, 770 223 and 770 292 and 770 293 Type.

It can prove to be advantageous for the production of the recording materials To use silver halide emulsions whose silver halide grains are less than 6 mol-I, in particular less than 3 mol% or even less than 0.25 mol% consist of iodide in order to avoid an accumulation of iodide ions in the amplifier and / or developer solutions used.

Advantageously, for the production of the recording materials silver halide emulsions are also used, the silver halide grains of which consist of a core and a shell, wherein the core can have a high silver iodide content. Such silver halide emulsions are, for example known from U.S. Patent 3,505,068. Silver halide emulsions this type can be found in particular in the frame

81/0615

Use such methods with advantage where an accumulation of iodide ions is undesirable, which is when using the described Silver halide emulsions is achieved in that the core shell contains at most a low concentration of iodide.

The ones used to make the recording materials Silver halide emulsions can be coarse-grained or fine-grained emulsions produced by conventionally known methods and the usual known chemical sensitizers, optical sensitizers, stabilizers, compounds that increase sensitivity, plasticizers, Hardening agents and coating auxiliaries may contain, such as those from the US patent 3,039,873, columns 9-12.

The emulsion layers can be used to increase the exposure latitude have different sensitivities.

Another particularly advantageous class of photosensitive, Catalyst-generating substances consists, for example, of silver and spectral sensitizing dyes Complexes, e.g. Of the type known from U.S. Patents 3,446,619 and 3,206,309. As particularly advantageous Photosensitive substances of this type have the reaction products of silver ions with cyanine, merocyanine, Oxonol, hemioxonol, hemicyanine, styryl or benzylidene dyes proven.

2098 «1/0615

SV

The drawings serve to explain the invention in more detail. In Figures 1-6, sensitometric curves are more photographic
Recording materials shown, their production
and development will be further described in the following examples.

20988 1/0615

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

From Examples 1 to 4 it can be seen that a photographic Ways generated silver image is able to catalyze a redox reaction within the meaning of the invention. In this redox reaction exists the reducing agent from a photographic color developing agent, imagewise represented by the oxidizing agent used cobalt complex is oxidized, whereupon the oxidized color developing agent with a color coupler to produce an image dye couples. The dye image produced thereby intensifies or intensifies the silver image or replaces it the silver image, if this is subsequently removed by bleaching.

Examples 1 to 4 also show that a large number of color developing agents are used as reducing agents can be used and that cobalt complexes can also be used with a wide variety of ligands, in particular with amine, ethylenediamine (en), diethylenetriamine (diene), triethy-1entetramine (triene), Azido, chloro, thiocyanato and isothiocyanato ligands and anions such as nitrate, chloride, bromide, perchlorate, thiocyanate and dithionate anions.

It can be seen from Examples 5 and 6 that a latent image composed of silver spots or silver particles is a. Redox reaction after able to catalyze the invention. In the case of the example, the image is produced by the reaction of an oxidized color developing agent generated with a dye-forming coupler. In contrast, the image of Example 6 is produced by the reaction of the reduced oxidizing agent (cobalt (II) ions) with a reactive Compound, namely 8-hydroxyquinoline, is generated.

209881/0615

It can be seen from Examples 7 and 8 that the process of the invention is particularly advantageous for direct development of color photographic recording materials composed of color negative films. By the method of the invention become higher dye densities with a lower fog than in the previously known and customary processes generated.

Example 9 shows the implementation of an image transfer process in which the reduced form of the oxidizing agent, i.e. the reduced form of the cobalt complex, imagewise a color coupling prevents.

Example 10 illustrates the application of the method of FIG Invention as part of the development of a color reversal film.

Examples 11 and 13 show that a wide variety of catalytically active agents can be used to carry out the process of the invention Substances such as carbon and gold are suitable, and the most diverse methods are also used for this purpose can to obtain the catalyst in an imagewise distribution.

Example 14 describes the application of the method of the invention to the development of a pre-developed silver image producing a color image whose density is higher than the density of the originally present silver image.

Example 15 shows that a cobalt complex of the type described increases the tanning power of known common tanning developer compounds, such as pyrogallol and pyrocatechol, and as from conventional photographic developer compounds, such as p-phenylenediamines, aminophenols and Diaminophenols, which by themselves exhibit little or no tanning activity when used alone, are effective tanning developers can be obtained.

2 0 9 F.!; Ί / 0 6 1 5

Examples 17 and 18 illustrate the advantages of higher maximum image densities and greater relative sensitivity, which are achieved in carrying out the process of the invention in comparison to known conventional processes.

Finally, Example 19 shows the formation of a dye image by coupling a diaminophenol-silver halide developer. ler connection with cobalt (II) ions, which arise when carrying out a redox reaction according to the invention. The dye image intensifies or strengthens the silver image or replaces the silver image if the silver image is bleached.

- 53 -

■ II- ! / '"■■ :; 1 ¹ J

example 1

(A) A gelatin silver bromide iodide emulsion prepared as described in "The Photographic Journal", Volume LXXIX, 1939, pages 330 to 338, in which the halide of the silver halide grains consisted of about 2 mol-I of iodide, was applied to a conventional cellulose acetate film support such that a support area of 0.0929 m 100 mg silver and 300 mg gelatin as well as 150 mg of the blue-green dye-forming color coupler 5- ^ ~ <x- (2,4-di-tert-amylphenoxy) hexanamido_7-2-heptafluorobutyramido- phenol, dissolved in 75% dibutyl phthalate as a coupler solvent, was omitted.

The recording material obtained was cut into twelve strips, which were exposed in the same way through a step wedge with density levels of 0.3 in an intensity scale sxtometer. Subsequently, negative silver images were developed in the strips by developing for 2 minutes at 24 ^° C. in a developer solution A of the composition given below, diluted with water in a ratio of 1: 1.

Water, about 50 ^° C. 500 ml of p-methylaminophenol sulfate 3 g

Sodium sulfite, dehydrated 45.0 g

Hydroquinone 12.0 g

Sodium carbonate, monohydrate 80.0 g, potassium bromide 2.0 g

Made up to 1 liter with water

The specimens were then fixed for 5 minutes, washed for 5 minutes and then dried.

• i.l »r; -Mj β

ff * '

The sensitometric curves of the specimens were filtered through a red filter read, which consisted of a narrow bandwidth optical filter, namely a Wratten No. 29 filter, the laminated to a 2 mm thick plate of Corning No. 9780 glass had been. The red filter transmitted light with a wavelength between 600 and 700 nm, with a peak transmission at 630 nm.

The silver image of each of the twelve test specimens corresponds to curve A in FIG. 1.

The amounts of silver in levels 2 and 9 of the sensitometric curve of a of the developed test specimens were determined analytically. The amounts of silver were 60 and 35 mg per 0.0929 m Support surface.

(B) Four of the twelve test specimens were then ^{treated at a temperature of 24 0} C with the color developer solution I of the composition given below for 2, 4, 8 or 16 minutes, whereupon the test specimens were washed for 2 minutes, fixed for 5 minutes, Washed and dried for 5 minutes.

Color developing solution I

4-amino-N-ethyl-N-ß-hydroxyethyl

aniline sulfate 20.0 g

1-phenyl-3-pyrazolidone 0.1 g

Na ₂ SO ₃ 40.0 g

KBr 0.5 g

Ethylenediamine acetic acid 8.0 g made up to 1 liter with water
pH adjusted to 11.0 with NaOH

• 2098 Ii Ϊ / 0 6 1 5

The sensitometer curves of the images of these four test items (read through the red filter described) are also represented by curve A of FIG. This curve is thus a direct duplicate of the sensitometer curve that is generated by the black-and-white development described was obtained, from which it can be seen that by treating the initially formed silver images with the color developer solution I no dye is generated will.

The amounts of silver in levels 2 and 9 of the sensitometer curve were again determined. It turned out that there was no change in the amount of silver was done. All four curves obtained had the same shape.

(C) Another set of four of the twelve test specimens was developed in the same way as described under (B), with the exception, however, that this time a color developer solution I of the specified composition was used, which additionally contained 2.5 g of the cobalt complex / " Co (NH ₃ ), -7C1, In this case the color developing solution thus contained a reducing agent, ie the color developing agent, and an oxidizing agent, ie the cobalt hexamine complex.

The amount of silver of grades 2 and 9 of each of the four test specimens was again determined. It was found that the amount of silver remained unchanged.

In the case of these four samples, no characteristic curves of the silver and dye images were recorded. However, a visual inspection of the test specimens revealed an increased density with an increased development time.

(D) The remaining four specimens of the twelve strips were developed according to the method described under (C). This time however, the silver was bleached and then removed from the

20988 1/0615

5+

Test specimens removed by fixing and washing them. Specifically, the test pieces were made after treatment with the color developing solution I further treated as follows:

Bleach 5 min.

Wash 2 min.

Fix 5 min.

Wash 5 min.
dry

The developed test specimens only had the dye images, which were indicated by the sensitometer curves B, C, D and E in Fig. being represented.

In the case of this example, the pre-formed silver image is catalyzed an oxidation-reduction reaction between the oxidizing agent, d. H. the cobalt (III) hexamine complex, and the reducing agent, d. H. the color developing agent.

Similar results were obtained when the used Color developing agent; d. H. 4-amino-N-ethyl-N-ß-hydroxyethylaniline sulfate has been replaced by one of the following color developing agents:

4-amino-3,5-dimethoxy-N, N-diethylaniline; 4-amino-3-methyl- (N-ethyl-N-β-methanesulfonamidoethyl) aniline; 4-amino-3-methyl- (N-ethyl-N-ß-methoxyethyl) anilinedibenzenesulfonate; 4-amino-N-ethyl-N-3-hydroxyethylaniline sulfate; 4-amino-3-methyl-N, N-diethylaniline; 4-amino-2,6-dibromophenol; 4-amino-3-methyl-N-ethyl-N-B- (methanesulfonamidoethyl) aniline; 4-amino-3-methyl- (N-ethyl-N-β-methoxyethyl) aniline-1,5-naphthalene disulfonate; 2,4-diaminophenol and 4-amino-3-methyl- (N-ethyl-N-ß-hydroxyethyl) aniline p-toluenesulfonate.

2098 81/0615

- Vh-

The described color developer solution I with the reducing agent, d. H. the color developing agent, and the oxidizing agent, d. H. the cobalt complex, could be stored at room temperature for several hours and even longer without any noticeable changes will. In contrast to this, developer solutions of the type known from Belgian patent 743 768 decompose Type with a peroxy compound and a color developing agent composed of an aromatic arain in a very short time, therefore, such developer solutions must be prepared shortly before they are used.

Example 2

Additional new strips of photographic material of the type described in Example 1 were prepared. The strips were exposed as described in Example 1, whereupon negative silver images were produced in them. The test specimens were then washed, fixed and dried in the manner described. Sections of the test specimens were then treated for 16 minutes at a temperature of 24 ^° C. in the color developer solution I of Example 1, which in each case additionally contained 2.5 g of one of the cobalt complexes specified below as an oxidizing agent:

(1) cis- / ~ Co (en) ₂ (N ₃ ) ₂ _7N0 ₃

(2) trans - / "Co (en) ₂ C1 (NCS) _7nCS

(3) trans - ^ "Co (en) ₂ (N ₃ ) ₂ _7ci0 ₄

(4) cis- ^ Co (en) ₂ (NH ₃ ) (N ₃ ) _7S ₂ O ₆

(5) cis- / ~ Co (en) ₂ Cl ₂ -7ci

(6) trans- / ~ Co (en) ₂ Cl ₂ -7Cl

(7) / ~ Co (en) ₂ (SCN) ₂ _7Cl

(8) / "Co (en) ₂ (NCS) ₂ _7sCN

(9) ^ "Co (NH ₃ ) ₆ .7Br ₃

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S3

The specimens were then subjected to the following usual color development steps at 24 ° C subject to:

bleaching 5 min. To wash 2 min. Fix 5 min. To wash 5 min. dry

Each of the samples had essentially the same blue-green dye image on. Furthermore, the test specimens all had a sensitometer curve corresponding to curve E in FIG. 1.

Example 3

The procedure described in Example 1 was repeated with the exception, however, that the complex / "Co (NH ₃ ), 7Cl _{3 was} replaced by an equivalent amount of one of the cobalt complexes given below:

/ "Co (en) 2 (dien) _7C1 ₂ · HCl, /" Co (NH ₃ ) ₅ (H ₂ O) J (ClO ₄ ) 3, / "Co (NO ₂ ) 3 (NH ₃ ) 3_7, / "Co (NH ₃ ) ₄ (CO ₃ ) _7nO ₃ , trans - /" Co (en) ₂ (Cl) ₂ _7ci »HCl, trans - /" Co (en) ₂ (N ₃ ) (NO ₂ ) .7 ^ O ₆ , / "Co (trien) (NO ₂ ) ₂ _7n0 ₃ · H ₂ O, cis /" Co (trien) (Cl) ₂ _7ci, / "Co (en) 2 (NO ₂ ) 2_7 (ClO ₄ ) ₃ , / "Co (triene) (N ₃ ) ₂ _7nO ₂ or /" Co (en) ₂ (NH ₃ ) ₂ _7ci ₃ .

With each of the oxidizing agent complexes, blue-green dye images of excellent density were obtained.

209881/061 p

Example 4

There were eight further strips of the recording material described in Example 1 in that described in Example 1 Way exposed, whereupon negative silver images were produced in the manner described in Example 1 in them. Afterward the specimens were fixed, washed and dried. The sensitometric curves (read through a red filter, as in Example 1) of the silver images of the test specimens are shown by curve 1 in FIG.

(A) Four of the samples were then developed in color developing solutions II, III, IV and V, respectively, for 16 minutes at 24 ° C, whereupon the specimens were washed for 2 minutes, fixed for 5 minutes, washed again for 5 minutes and then dried. The concentrations given in the following table relate to g / l. The pH of the solutions was 11.0.

Composition of the color developer solutions

Solution _M "^ _n XnTc ⁺ n _n ^ _av color developer compound N " * 2 * Ο ₅ ADTE Borax ^ Ty- T ^

No. "* 2 * Ο ₅ ADTE borax

II 10.0 8.0 10.0 4.0

III 10.0 8.0 10.0 --- 8.2

IV 10.0 8.0 10.0 - --- 5.2

V 10.0 8.0 10.0-9.3

ADTE * ethylenediaminetetraacetic acid II. 4-Amino-3-methyl-N-N-diethylaniline

III. 4-Amino-3-methyl-N-ethyl-N-ß- (methanesulfonaraido) -ethylaniline

IV. 4-Amino-N-ethyl-N-ß-hydroxyethylaniline

V. 4-Amino-3methyl- (N-ethyl-N-β-methoxyethyl) aniline, 1,5-naphthalene disulfonate

2098U1 / 0615

The images generated in the four test objects are represented by the sensitometer curve 1 of FIG. In all cases the curves were congruent and also congruent with the curve obtained by black-and-white development Test specimen. No increase in density was found.

(B) The four test specimens still present were treated as described under (A), with the exception, however, that the color developer _{solutions II, III, IV and V each had 2.5 g / "Co (NH 3} ) ₆ - 7ci ₃ per liter of solution The images obtained when these color developing solutions were used are represented by curves 2, 3, 4 and 5 in FIG.

This example shows that a wide variety of color developing agents can be used as reducing agents.

Results

Equally favorable XMXXMKKM was obtained when the reducing agent used was the color developer compound 4-amine-p-2 ₄ 6-dibromophenol. Correspondingly favorable / were obtained when the cobalt (III) hexamine chloride was replaced by another complex with a complex cation of the following structural formulas:

/ "Co (en) ₂ (N ₃ ) ₂ _7 ⁺¹ , / 'Co (en) ₂ C1 (NCS) _7 ⁺¹ , /" Co (en) ₂ (NH ₃ ) ₂ N ₃ .7 ⁺² , / "Co (en) -Cl ₂ J * ^X , /" Co (en) ₇ (SCN) -7 ⁺¹ , Z "Co (en) ₂ (NCS) ₂ - 7 ⁺¹ .

Finally , correspondingly favorable results were also obtained when the process described in Example 3 was repeated using recording materials in which the color coupler in the silver halide emulsion layer was replaced by another color coupler , for example 150 mg of a magenta dye-forming dye.

209881/061 5

IsZ

coupler, e.g., by Color Coupler II of U.S. Patent 2,908,573, i.e. H. 1- (2,4,6-trichlorophenyl) -3- ^ ~ 3- {a- (3-pentadecylphenoxy) -butyraraido} -benzamido_7-5-pyrazolone, or by a yellow dye-forming agent Color couplers, e.g. B. Color Coupler III of U.S. Patent 3,408,194; d. H. by α-pivalyl-ot- (4-carboxyphenoxy) -2-chloro-5- / ~ Y- (2,4-di-tert-amylphenoxy) -butyramido_7acetanilide.

Corresponding results with somewhat lower dye densities were obtained when recording materials of the type described were used in which the silver halide emulsion layer was applied in such a way that not 100 mg of silver but only 10 mg of silver were present ^{on a support area of 0.0929 m 2.}

Example 5

(A) Four strips of a recording material of the structure described in Example 1 were exposed in an intensity scale sensitometer through a step wedge with density levels of 0.3, whereupon the test specimens were placed in a conventional fixing bath with ammonium thiosulphate at 24 ^° C. for 45 seconds. The test specimens were then washed for 30 seconds. The specimens now contained invisible latent silver spots in relation to the intensity of the exposure, but no developable silver halide.

(B) Two of the test items, hereinafter referred to as A and B, were then treated for 2 or 4 hours with a developer solution of the following composition:

209881/06 1 p

4-amino-N-ethyl-N-ß-hydroxy-

ethylaniline 20.0g

Piperidinohexose reductone 1.0 g

Na ₂ SO ₃ 40.0g

KBr _ 2.0 g

Ethylenediaminetetraacetic acid 0.5 g Made up to 1 liter with water pH - 11.0

The two specimens were then washed for 5 minutes and then dried.

(C) The other two test specimens, hereinafter referred to as C and D, were treated as described under (B), with the exception, however, that this time a developer solution of the specified composition was used which additionally contained 10.0 g of des per liter of solution As an oxidizing agent serving complex ^ "Co (NH-) ₆ _7ci ₃ contained. The developer solution used in this case thus contained a combination of an oxidizing agent and a reducing agent characterizing the process of the invention.

Sensitometric curves were recorded on the specimens using a red filter of the type described in Example 1.

The sensitometric curves obtained on the basis of the specimens subjected to method (B) are shown in Fig. 3 represented by curves A and B. The sensitometric curves obtained on the basis of the specimens, the developed by the method (C) are shown by curves C and D in FIG. It can be seen from the curves that only a fog density was generated in the case of samples A and B, i.e. H. only a haze density then became obtained when the specimens in a developer solution without

209881/0615

Cobalt complex oxidizers were treated. The strips made with a developer solution with a combination of oxidizing agents and reducing agents, on the other hand, produced normal curves (see curves C and D of FIG. 3).

This example shows that even very small amounts of catalyst consisting of a latent silver image forming Silver particles are sufficient to produce images of excellent intensity.

Example 6

Two samples A and B of a photographic film with a fine-grained gelatin silver bromide iodide emulsion layer, the silver halide grains of which consisted of 94 mol of bromide and 6 mol of iodide, were for 5 seconds through a step wedge with a neutral density of 0.3 exposed. The test specimens were then placed in a dilute sodium thiosulfate fixing bath at 24 ^° C. for 30 seconds and then washed for 1 minute. The specimens now contained only invisible latent image silver spots, but no developable silver halide.

Test item A (comparison test item) was then immersed in a solution consisting of:

Developer solution A (according to Example 1) 4 ml of water 16 ml

Stige aqueous solution of

8-hydroxyquinoline 5 ml

brought to a temperature of 24 ° C. The specimen B was treated with an appropriate solution containing in addition 0.15 g ^ "Co (NH _{3) 6} _7ci. ₃

2 0 9 8 8 1/0615

CA '

In the case of Sample A, no visible image was obtained. In the case of sample B, a red image was obtained, the density of which was proportional to the light exposure of the sample.

Example 7

First, a photographic material was prepared by a gelatin-silver halide emulsion was coated in such a Celluloseacetatfilmschichtträger that on a support surface of 0,0929 ^z m accounted for 300 mg of gelatin, 100 mg of silver as silver bromoiodide, and 150 mg of color coupler 5 / ~ a- (2,4-Di-tert-amylphenoxy) hexamido_7-2-heptafluorobutyramidophenol, dissolved in 75 mg of dibutyl phthalate.

Strips of the recording material were then exposed in an intensity scale sensitometer with a step wedge with neutral density levels of 0.3.

(A) Four specimens were developed in the following manner at 24 ⁰ C:

development

(Color developer solution I from Example 1) 1, 2, 4 or 8 min.

Wash 2 min. Bleach 5 min. Wash 2 min. Fix 5 min.

To wash . 5 min. Drying

(B) a further four samples were developed as described under A, "it the Ausnmhme, however, that this time, a developing solution was used, the additional grams per liter of solution contained 2.5 of the complex /" Co (NH _{3) 6} _7ci. ₃

209881/061 p

The obtained sensitometric curves of the blue-green dye images of the eight developed samples are shown in FIG Curves A-I, A-2, A-4, A-8, B-I, B-2, B-4 and B-8 are shown.

The curves show the higher maximum image dye densities and the improved image-fog ratios, which are achieved when the test pieces are developed in a color developing solution according to the invention.

Example 8

The procedure described in Example 6 was repeated with a development temperature of 32 ° C. The sensitometric curves obtained are shown in FIG. Similar results were obtained when the procedure described in Example 6 was repeated at a temperature of 43 ⁰ C.

Example 9

First of all, a photographic master was produced by placing a photographic recording material with a fine-grain negative gelatin-silver bromide iodide emulsion layer, the silver halide of which consisted of 94 mol-1 of broaid and 6 mol-1 of iodide, in a sensitoneter through a step wedge with neutral density levels of 0, 3 exposed, 2 minutes at 24 ⁰ C in a developer solution A (Example 1), which had been diluted i * ratio 1: 1 with water, developed, washed for 2 minutes, fixed for 5 minutes, washed again for 5 minutes and was dried. The die had a negative silver image on to a ^D _max ^value ~ v ° ⁿ ° ^'6 * ^and * ^"D _a i _n" ^{value of} 0.09.

At the same time, a photographic image-receiving material was prepared by placing a mordant layer on a support

20988 1/0615

from a mixture of 60 parts by weight of methyl tri-n-dodecylammonium p-toluenesulfonate and 30 parts by weight of N-n-hexadecyl-N-morpho1inium ethosulfate was applied, after which the image receiving material for one minute in a 0.5 wt .-% aqueous Solution of 8-hydroxyquinoline adjusted to pH 11 was immersed and washed for 30 seconds.

The subsequent development took place at 24 ⁰ C in the following way:

Step 1. The template and image receiving material were placed in an aqueous solution of 500 ml of the described black-and-white developer solution A and 500 ml of a false solution of 1'Co (JHE ^) ^ Jjci ^ .

Step 2. The stencil and image receiving material were pressed together and left in contact for 5 minutes. Included a redox reaction took place between the developer and the cobalt complex in the areas in which the developer and cobalt complex came into contact with the silver image catalyst. One migrated reduced form of the oxidizing agent with cobalt (II) ions thereby in image-wise distribution in the image receiving material. After 5 minutes, the template and image receiving material became separated from each other. The template was washed for 5 minutes and then dried. The D "" values and D values of the silver

° max mm

image in the die remained unchanged. The image receiving material was washed for 1 minute and then immersed for 30 seconds in an aqueous solution containing 20.0 g of the color developer 4-amino-N-ethyl-N-β-hydroxyethylaniline sulfate and 40.0 g of sodium sulfite and a pH of 11 . The color developer was prepared by immersing the image-receiving material in a Hige aqueous solution of potassium persulfate (^ S _{2 Og)}} having a pH value of 11 ^ 30 seconds oxidized. This was followed by washing for 5 minutes. The oxidized color developing agent coupled with the 8-hydroxyquinoline except in the districts in which

, 2 0 9 8 8 1/0615

coupling was inhibited by migrated cobalt (II) ions. In this way, a positive cyan dye image with a ^D _max ^{value of} O »51 and a D. -Value of 0.34 obtained.

This example illustrates the picture-wise poisoning of the color coupler by a reaction product produced in the reaction between an oxidizing agent consisting of a cobalt complex and a reducing agent is produced in the presence of a catalyst according to the invention.

Example 10

First, a multicolor photographic material of the reverse type was produced by applying the battles given in the following order to a paper support pigmented with titanium dioxide and having a polyethylene layer (all weights refer to mg per 0.0929 m ^{2 support area} ):

Layer 1: a silver halide emulsion layer of 200 mg gelatin, 40 mg blue sensitized silver in the form of Silver chlorobromide and a solution of 120 mg of the yellow dye-forming coupler dispersed therein a- / ~ 4- (4-Benzyloxyphenyl sulfonyl) -phenoxy-7-ot-pivalyl-2-chloro-5 - / "y- (2,4-di-tert-amylphenoxy) -butyramido 7-acetanilide dissolved in 30 mg of di-n-butyl phthalate;

Layer 2: a gelatin layer with 100 mg gelatin;

Layer 3: a silver halide emulsion layer containing 200 mg of gelatin; 8 mg silver in the form of green-sensitized silver chloride bromide and a solution of 30 mg of the magenta dye forming coupler dispersed in the layer

20988 1/0615

1- (2,4,6-Trichlorophenyl) -3- {5- / ~ ct- (3-tert-butyl-4-hydroxyphenoxy) -tetradecanamido_7-2-chloroanilino} -5-pyrazolone, dissolved in 15 mg tricresyl phosphate;

Layer 4: a filter layer with 241 mg gelatin and a solution of 65 mg of the filter dye dispersed therein 2- (2'-Hydroxy-3 ', 5'-di-tert-amylphenyl) -benzotriazole, dissolved in 32.5 mg of 2- (2-butoxyethoxy) ethyl acetate;

Layer 5: a silver halide emulsion layer containing 150 mg of gelatin; 5.25 mg of silver in the form of red-sensitized silver chloride bromide and a solution of 23.4 mg of the blue-green dye-forming coupler 2- ^ ~ a- (2,4-di-tert-amylphenoxy) -butyramido_7-4,6-dichloro-5-methylphenol, dissolved in 11.7 mg of di-n butyl phthalate;

Layer 6: a gelatin layer with 100 mg gelatin.

A control strip (1) of the described multicolor recording material was exposed in an intensity sensitometer through a step wedge with 0.3 neutral density levels and then developed at 30 ^° C. in the manner described:

Development with black and white developer solution + 1.5 min.

acidic interrupter bath 1 min.

Wash 1 min. Re-exposure to white light, Color development ⁺⁺ 10 min. Bleach-fix 1.5 min. Wash 1 min. Stabilize 1 min. Black and white developer solution:

209801/0615

N-methyl-p-aminophenol sulfate Sodium sulfite, anhydrous Hydroquinone Sodium carbonate, monohydrate Potassium bromide Topped up with water

2 g g 8 g

52.5 g 5.0 g 1.0 liter

Color developing solution:

Benzyl alcohol Sodium sulfite, anhydrous hydroxylamine sulfate Sodium bromide Sodium chloride

4-Amino-N-ethyl-N- (2-methoxyethyl) -m-toluidine-di-p-toluene sulfonate

Sodium carbonate, anhydrous Filled up with water to pH »10.75 at 24 ^° C

10.0 ml 2.0 G 2.0 G 0.5 G 0.5 G 5.0 G 30.0 G 1 liter

Another strip (2) of the described multicolor recording material was exposed and developed in the same way, with the exception, however, that a color developer solution was used which additionally contained 1.6 g of the complex ^ "Co (NH ₃ ^ Cl ₃ contained.

Another strip (3) of the multicolor recording material described was exposed in the same manner as that Strips (L) and (2) but developed at 30 ° C in the following way:

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Development with black and white developer solution acidic bath wash

bleaching

".... ++++
Clear up

To wash

Reexponierung with white light, color development with the specified color developer containing per liter of solution 1.6 g ^ -CO (NH _{3) 6} _7 bleach-fixing

To wash

Stabilize

1.5 min.

1 Min. 1 Min. 1 Min. 1 Min. 1 Min. 10 Min. 1, S min. 2 Min. 1 Min.

Bleach-fix bath: Kali ^ umdichromdiumsulfat
Sodium bisulfate
Topped up with water

Clarifier:
Sodium sulfite (anhydrous) Make up with water

10 S. 50 G 50 G 1 liter 101 , 07 g 1 liter

The ^D _max " ^{values and D} min ^{values of the} dye images obtained are compiled in the following table:

Stripes (1) Max Stripes (2) D.
Max Stripes (3) Max ^D «in 0.72 D.
mm 1.6 min 1.6 Red 0.15 1.03 1.6 2.4 0.19 2.4 green 0.17 1.27 2.4 1.8 0.18 1.8 blue 0.18 1.8 0.20

209881/0615

2726770

From the results shown in the table, it is found that a reversal type photographic material (Strip 3) processed by the process of the invention to dye images of low D. Values and

higher D values can be developed than a corresponding max

Recording material (strip 1) which has been developed in the usual known manner. In the case of strip (2) with D

min values corresponding to D values, it can be seen that after the black-and-white development and before the color development, the inclusion of a bleaching stage is necessary if according to the invention a color developer is present because the silver developed during the black-and-white development undergoes the oxidation-reduction reaction between the cobalt complex and the primary amine color developer.

The following example illustrates the enhancement of a faint carbon image with a dye image.

Example 11

On a paper pigmented with a customary white pigment - in the present case, paper pigmented with titanium dioxide applied a layer of uncured gelatin. The material was then put into a commercially available xerographic Copying device exposed through a master copy consisting of a line image and using a toner very finely ground activated carbon particles and heating the tinted gelatin surface to a temperature just above its softening point using an infrared lamp and cooling the surface and removing untrapped carbon particles developed by means of a high-speed air stream. In this way a faint charcoal image was obtained.

2 0 9 8 d i / 0615

13th

The paper showing the weak charcoal image was then treated for 20 minutes with a solution of the following composition:

4-amino-N-ethyl-N- (2-methoxy-

ethyl) -m-toluidine 5 g

/ "Co (NH ₃ ) ^ Cl ₃ 1.6 g

1-phenyl-3-methyl-S-pyrazolone 4 g

Sodium sulfite, anhydrous 5 g Potassium carbonate 60 g Potassium bromide 2 g Made up to 1 liter with water

The paper was then washed and dried for 2 minutes. In this way the faint charcoal image was replaced by a dense one purple dye image intensified.

Example 12

A photographic recording material was produced by applying an emulsion layer to a paper support pigmented with titanium dioxide with a polyethylene layer in such a way that a layer support

2
area of 0.0929 m the following components were omitted:

/ ~ Co (en) ₂ (N ₃ ) ₂ _7ci0 ₄ 50 mg

p-phenylenediamine 13 mg

1-naphthol 16 mg

Gelatin 150 mg

A freshly prepared suspension was then applied to the surface of the recording material by means of a rubber stamp colloidal gold, made by mixing 1 g of auric chloride, 1 g of stannous chloride and 1 liter of water. In this way, the image-wise distribution

20983 1/0615

. Λ

generated from metallic gold existing nuclei or cores as a catalyst for a redox reaction according to the invention. The recording material was then left in an atmosphere for 3 hours brought a 100th relative humidity, with a blue-green dye image, corresponding to the gold nuclei present in an imagewise distribution, was obtained.

Example 13

280 g of particulate titanium dioxide were added with stirring to 269 ml of water and 11 ml of 10% ethylenediaminetetraacetic acid (Designation Unitane-0520, manufacturer American Cyanamid Company, USA) given. A first solution of 320 ml of a 7.5% polyvinyl alcohol solution was then added to the mixture obtained and 11 ml of a 101% aqueous solution of a condensed Sodium sulfonic acid salt (Tamol N, manufacturer Röhm and Haas Company, USA) and a second solution of 2 ml of a 7.5 tigen Saponin solution and 10 ml of a 0.1% aqueous tannic acid solution were added. After the tannic acid had been added, the solution took off a deep yellow color. In this way, a coating composition was obtained in which the tannic acid was present as a complex ligand with ortho-hydroxyl substituents as chelate-forming groups. The coating solution was then in a Layer thickness of 0.010 cm, measured wet, applied to a layer of paper coated with a polyethylene layer and dried to give a photographic material.

Part of the recording material obtained was exposed for 15 seconds through a step wedge and then immersed in a lying aqueous silver nitrate solution for 5 seconds, whereby silver nuclei were obtained in an imagewise distribution. The recording material was then immersed in a for 30 minutes Immersed solution of the following composition:

209881/0615

(NCS) -7SCN 50g

4-Amino-N _f N-diethylaniline 15 g

1-naphthol 16 g of water 1 liter

The material was then washed and dried. on thus a cyan dye image excellent in density was obtained.

Example 14

Six test pieces of a recording material with a fine-grained Negative type gelatin silver bromide iodide emulsion layer, 94 mol% of their silver halide consists of bromide and 6 mol% comprised of iodide were examined in an intensity scale sensitometer exposed through a step wedge with 0.3 neutral density steps and then developed at 24 ° C in the following way:

Develop (developer solution A

from Example 1) (diluted with

Water in a ratio of 1: 1) 2 min.

Wash 1/2 min.

Fix 5 min.

Wash 5 min. Dry

The test specimens each contained a pre-developed silver image, which consisted of a negative reproduction of the step wedge. One of the specimens (1) was used for comparison purposes. A pre-developed test specimen (2) was treated for 8 minutes at 24 ⁰ C with a solution which contains per liter 2.5 g of the formazan dye o- {2- ^ ~ TDC (2-hydroxy-5-sulphophenylazo) -benzyliden_7-hydrazinobenzoic , Sodium salt contained in 1 liter of water and the pH of which had been adjusted to 9.8 with NaOH. Of the

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The test specimen was then immersed in a 0.5% strength by weight NaOH solution for 2 minutes dipped, washed with water for 2 minutes, fixed for 5 minutes, washed again for 5 minutes and dried.

Another pre-developed test specimen (3) was treated for 8 minutes at 24 ° C. in a solution of 10 g of cobalt (III) hexara chloride treated in one liter of water (pH adjusted to 9.8 with NaOH), then for 2 minutes in a 0.5% strength by weight NaOH solution washed, then washed with water for 2 minutes, fixed for 5 minutes, washed again for 5 minutes and dried.

The pre-developed three remaining specimens (4, 5 and 6) were 2, 4 and 8 minutes at 24 ⁰ C in a solution containing 2.5 g of the formazan dye o- {2- / ~ a- (2-hydroxy-5- sulfophenylazo) benzyliden_7-hydrazino} -beazoic acid, sodium salt and 10 g of cobalt (III) hexamine chloride in one liter of water while adjusting the pH to 9.8 with NaOH, immersed for 2 minutes with 0.5% by weight NaOH Solution and then washed with water for 2 minutes, fixed for 5 minutes, washed again for 5 minutes and dried.

The developed images were sensitometric using a red filter as described in Example 1 in all cases recorded. The sensitometric curves obtained are shown in FIG. Curves 2 and 3 of test items 2 and 3, the only with a formazan dye solution or a Cobalt (IE) hexamine chloride solution a slight decrease in density compared to the reference sample (curve 1). Curves 4, 5 and 6 of the test items 4, 5 and 6, which are treated for different lengths of time in a solution with both a formazan dye and the cobalt complex show a remarkable increase in densities as a function of the duration of treatment.

203881/0615

Example 15

First, three photographic recording materials A, B and C were prepared by applying gelatin silver bromide iodide emulsions to transparent substrates. A support area of 0.0929 m ² each accounted for 1222 mg of a gelatin mixture of unhardened gelatin, 30% by weight of bone gelatin and 70% by weight of skin gelatin. The individual silver halide emulsion layers

of the three recording materials contained 475, 158 and 47.5 mg of silver bromide iodide per 0.0929 m of support surface.

Test strips of the recording materials produced were exposed through the substrate, namely through a template, which consisted of a test sheet with graduated density levels.

The exposed specimens were then placed at 21 ° C in one of the following Developer solutions developed:

Developer solution I

4-phenyl catechol 4.0 g

Sodium carbonate 108.0 g

Made up with water to 1 liter pH = 11.0

Developer solution I_I

Ascorbic acid 1.0 g

Pyrogallol 3.0 g

ρ-methylaminophenol sulfate 3.0 g

5-methylbenzotriazole 0.05 g

Sodium bromide 2.15 g

Sodium carbonate 105.0 g

Made up with water to 1 liter pH 11.0

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- vr-

Developer solution III

4-Amino-N-ethyl-N- (2-methoxyethyl) -m-tolu-idin-di-p-toluenesulfonic acid

Sodium sulfite sodium Potassium bromide Topped up with water

pH »10.5

G

2> 0 g 25.0 g 2.0 g 1 liter

Developer solution IV

2,4-diaminophenol

Sodium sulfite sodium Potassium bromide Topped up with water

pH - 10.0

7.3 g 5.0 g 20.0 g 0.3 g 1 liter

Developer solution V

2,4-diaminophenol

Sodium sulfite Potassium bromide Topped up with water

pH - 6.4, adjusted with NaOH 3.65 g 1.0 g 0.5 g 1 liter

The test strips were then each at 21 ° C. for 1 minute placed in an interrupter bath of the following composition

Boric acid

Sodium sulfite Topped up with water

35.0 g 35.0 g 1 liter

The test strips were then fixed at 21 ° C. for 2 minutes. The test strips were then ^{washed for 3 minutes at 49 °} C. to remove untanned parts of the emulsion. The Stripes were then immersed in a 1 by weight aqueous solution for 3 minutes.

2 0 B88 1/06 1

buffered solution of the cyan dye-4,8-Diaminoanthrarufin-2,6-disulfonic acid of 21 ⁰ C submerged. The dye was absorbed imagewise in proportion to the tanning of the remaining gelatin portions of the emulsion layer. The test strips were then placed in an aqueous acetic acid solution for 1 minute and then dried.

Further test strips of the recording materials described were treated in the same way, with the exception, however, that this time a developer solution was used which contained / "Co (NH ₃ ) ₆ _7C1_.

The dye densities produced by the test strips were read through a red filter of the type described in Example 1 and recorded. The results compiled in the following table were obtained:

Film test strips

Ag / 0.0929 2

Development

Added wick

Development amount of

ler- / Co (NH ₃ ) ₆ _7C1- permanent solution ₄ »u .. in min.

Dye density

D. D mm max

A A A A B B C C C C A A

475

475

475

475

158

158 47.5 47.5 47.5 47.5

475

475

475

475

III

III

II

II

IV

IV

0 5 0 5 0 5 0 5 0 5 0 5 0 5

4 4 7 7 4 4 4 4 3 3 1 1 3 3

0.06 0.06

0.06 0.04 0.04 0.03 0.03 0.04 0.04

1.72 1.98

3.08 1.96 2.16 0.77 1.48 0.58 0.76

0.08 73.2 0.06 73.2

no tanning, all gelatin was washed with hot water removed.

20988 1/06 15

In a further series of tests, 5 to 10 g of ethylenediaminetetraacetic acid per liter were added to the _{developer solutions containing the cobalt complex ^ "Co (NH_) 6} _7ci _3. When using these solutions, no improvements in terms of tanning were achieved compared to those developer solutions which did not contain ^ Co (NH ₃ ) , 7ci .. Since ethylenediaminetetraacetic acid is an extremely effective complexing agent for cobalt (II) ions, it follows that the cobalt (II) ions (reduced oxidizing agent according to the invention) play an essential role in the tanning mechanism.

Example 16

First, a photosensitive silver dye emulsion was prepared according to the method known from US Pat. No. 3,446,619, which was applied to a gray substrate with a density, determined using a red filter, of 0.30. The emulsion layer contained on a support area of 0.0929 m ² 5.6 mg AgNO ₃ , 400 mg gelatin, 130 mg of the coupler 5 - ^ "a- (2,4-di-tert-amylphenoxy) - which forms a blue-green dye. hexamido_7-2-heptafluorobutyramidophenol, dissolved in 65 mg of the coupler solvent dibutyl phthalate, and 0.066 mg of the sensitizing dye l-carboxymethyl-5- ^ ~ 3-ethyl-2-benzoxazolinylidene) -äthyliden_7-3-phenyl-2-thiohydantoin.

A test strip 1 of the recording material produced was exposed through a test sheet with graduated density levels and then developed for 15 minutes in a developer solution I of the composition given below at 30 ^° C., washed, fixed, washed and dried.

209881/0615

Bk

Developer solution I

4-amino-N-ethyl-N-3-hydroxy-
ethyl aniline sulfate 10.0 g Sodium sulfite 10.0 g Sodium bromide 1.0 g Sodium carbonate (anhydrous) 30.0 g Tetrasodium salt of ethylenediamine
tetraacetic acid 1.0 g Benzyl alcohol 5.0 ml Topped up with water 1 liter pH - 10.8

The procedure described was repeated with further test strips 2-9, with the exception, however, that this time 1.6 g per 1 / ~ Co (NH ₃ ) .7Cl were added to the developer solution I and that the pH of the developer solution I was increased 9.3; 9.5; 10.0; 10.2; 10.4 or 10.8 was set.

These test strips were then developed for 15 minutes, with the exception of the case where a pH of 10.8 was applied in which case strips were developed for 5, 10 and 15 minutes, respectively.

The process was finally repeated with another test strip 10, but this time for 15 minutes a developer solution I with a pH of 10 at 38 ° C was developed.

In further experiments, test strips 11 and 12 were developed for 15 minutes at 30 ^° C. in a developer solution II or in a developer solution II of the composition given below, to which an additional 1.6 g per liter of Co (NH ₃ ) _{6 was added} became.

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Developer solution II

4-Amino-3-methyl- (N-ethyl-N-2-methoxyethyl) anilinedibenzenesulfonate Sodium sulfite Sodium bromide Sodium carbonate (anhydrous)

Tetrasodium salt of ethylenediaminetetraacetic acid

Benzyl alcohol Topped up with water

pH - 10.8

5.0 G 10.0 G 1.0 G 30.0 G 1.0 G 5.0 G 1 liter

The developed dye densities were determined from the developed test strips using a red filter. They are compiled in the following table:

10 Development / Co (NH ₃ ) ₆ .7ci ₃ pH Development Temp. min Max 11 wick-
learning g / liter 10.8 wick- ⁰ C 0.30 0.50 test
streak 12th solution 0 9.3 lung
duration 30th 0.34 0.78 fen example I. 1.6 9.5 in min. 30th 0.38 1.14 1 I. 1.6 10.0 15th 30th 0.40 1.35 2 I. 1.6 10.2 15th 30th 0.44 1.50 3 I. 1.6 10.4 15th 30th 0.48 1.70 4th I. 1.6 10.8 IS 30th 0.45 1.08 5 I. 1.6 10.8 15th 30th 0.60 1.60 6th I. 1.6 10.8 15th 30th 0.77 2.18 7th I. 1.6 10.8 5 30th 0.62 2.60 8th I. 1.6 10.8 10 38 0.28 0.32 9 I. 0 10.8 15th 30th 0.69 1.72 II 1.6 15th 30th II 15th 17th 15th

First, a photographic recording material was prepared by applying a gelatin-silver chloride brojeid internal grain emulsion to a cellulose acetate film support

2 0 9 8 8 1/0615

which was prepared by the method described in US Pat. No. 2,497,875, column 2, line 21 to column 3, line 2, this emulsion being applied to the substrate in such a way that a substrate area of 0.0929 m ² 100 mg of silver and 100 mg of the color coupler 5- / ~ a- (2,4-di-tert-amylphenoxy) -hexamido_7-2-heptafluorobutyramidophenol, which produces a blue-green dye, were omitted.

Four samples of photographic material were exposed through a wedge with density 0.3 neutral density step, after which test strips of the recording material 1 minute were developed at 24 ⁰ C in developer solutions A, B, C and D long. These developer solutions had the following. constricting SPECIFIED-ene composition, plus 0, 0.25, 0.50 and 1.0 g / "Co (NH _{3) 6} _7C1 ₃ per liter of solution.

Formyl-4-methylphenylhydrazine 0.1 g

Sodium carbonate (anhydrous) 40.0 g

Piperidinohexose reductone 0.2 g

5-methylbenzimidazole 0.05 g

4-amino-N-ethyl-N-S-hydroxy-

ethyl aniline sulfate 20.0 g

Made up to 1 liter with water

pH - 12.0

The specimens were then placed in a break bath, fixed, bleached, fixed, washed and dried. The image densities obtained were determined by a red filter of the type described in Example 1. The following table shows the relative sensitivities and D _ax ^{values obtained} .

20 98 8.1 / 06 1 5

- WF D.
Max 2226770 Developer- '·
solution g / liter 0.2
1.7
2.8
2.7 Relative
sensitivity A.
B.
C.
D. O
0.25
0.50
1.00 1.6
1.9
1.9
2.0 Example 18

After the imagewise exposure, a test strip of a recording material of the type described in Example 17 was developed for 1 minute at 24 ^° C. in a developer solution of the composition given below. Further test strips of the same construction were developed in a developer solution of the specified composition, but which was previously 0; 0.1; 0.25; 0.5; 1.0; 2.5 and 5 g per liter of the complex / "Co (NH ₃ ), 7ci, respectively, were added.

The basic developer solution had the following composition:

Formyl-4-methylphenylhydrazone
Sodium carbonate (anhydrous)
Sodium sulfite
5-methylbenzimidazole

4-amino-N-ethyl-N-ß-hydroxyethylaniline sulfate

Topped up with water
pH = 12.0

0.1 g 40.0 g 2.0 g 0.05 g

20.0 g 1 liter

The specimens were placed in a break bath, fixed, bleached, fixed, washed and dried. The received Image densities were determined by a red filter. In the following table are the relative sensitivities obtained and the D values recorded.

Iu 3-Jv

209881/0615

iff

developer
solution / "Co (NH _{3) 6} _7C1 ₃
g / liter Max Relative
sensitivity E. O 0.70 1.65 F. 0.1 1.05 1.90 G 0.25 1.05 2.00 H 0.50 1.30 2.00 I. 1.0 1.80 2.10 J 2.5 2.60 2.10 K 5.0 2.65 1.95 Example 19

First, a recording material was prepared by using a negative type fine grain gelatin-silver bromide iodide emulsion with 94 mol-I bromide and 6 mol-I iodide on a layer support was applied.

A test strip A of the material (comparison material) was used then exposed through a step wedge with 0.3 neutral density levels and for 5 minutes at 24 ° C in a developer in the following composition developed:

2,4-diaminophenol 7.3 g

Sodium sulfite 23.0 g ^v

Potassium bromide 0.3 g

Made up with water to 1 liter pH * 6.90 without additive

The test strip was then washed, fixed, washed and dried.

Another test strip B of the same recording material was developed in the same manner as the test strip A, with the exception, however, that the developer solution this time in addition per liter of solution 5.0 of the cobalt complex / Co (NH ₃₎ g containing ₆ _7ci. ₃

209881/0615

-μ-

222677Q

Another test strip C of the same recording material was developed as test strip A, with the exception that this time a developer solution was used which additionally contained 10.0 g per liter of solution ethylenediaminetetraacetic acid. (Ethylenediaminetetraacetic acid is a chelating agent that forms a complex with cobalt (II) ions.)

Finally, another test strip D of the same recording material was developed as test strip A, with the exception, however, that this time an Esit developer solution of the specified composition was used, which per liter additionally contains 5.0 g ^ "Co (NH ₃ ) ₆ _7ci, and 10 , 0 g ethylenediaminetetraacetic acid contained.

The image densities produced by the test strips were determined using a blue filter. These are compiled in the following table.

Test strips A and B were then placed in a silver bleach bath for 5 minutes, washed, fixed, washed and dried. The image densities of these test strips were again determined using a blue filter. The received The results are compiled in the following table.

test developer
solution
/ Co (NH ₃ ) ₆ .7C1 ₃
(g / liter) Athylendi
amintetra
acetic acid
(g / liter) Dye-
and silver Dye image Max streak
fen 0 0 ^D min ^max min 0.32 A. 5.0 0 0.30 2.74 0.08 2.58 B. 0 10.0 0.40> 3.8O 0.14 C. 5.0 10.0 0.30 2.70 D. 0.50 3.08

209801/0615

- ΧΓ-

Test strip B developed by the method of the invention had a silver image and a dye image generated by the reaction of cobalt (II) ions with the diaminophenol developer.

The following Examples 20, 21, 22, 24 and 25 show that oxidizing agent-reducing agent combinations according to the invention can be advantageously used in photographic film units and processes in which development of exposed silver halide with an oxidized color developing agent leads directly or indirectly to a release of image dyes, which in a stained Ability to diffuse image receiving layer.

Example 20

First, a photographic light-sensitive material was made produced in that on a cellulose triacetate support the layers specified in the following order have been applied. The specified Concentrations refer to mg per 0.0929 m of support surface.

Layer 1

(a) Palladium seeds: 0.5 mg

(b) 90 mg of the colorless image transfer coupler

OH

NHCOCHO

Vo 988 1/0615

dissolved in 90 mg of dibutyl phthalate (c) gelatin: 300 mg

Layer 2

(a) 50 mg of the ballasted, oxidized color developing agent scavenging coupler:

NHCO

NHCOCHO

dissolved in 50 mg of a coupler solvent, e.g. Bt Dibutyl phthalate (b) gelatin: 200 mg

Layer 3

(a) Gelatin: 300 mg

(b) silver bromide iodide with an iodide content of 6 mol-I, applied corresponding to a silver coverage of 100 mg

(c) 100 mg of the coupler releasing a development inhibitor:

CONH (CH ₂ )

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dissolved in about 100 mg of coupler solvent (e.g., dibutyl phthalate).

The recording material described was sensitometric exposed through an original with graduated density levels, then in a developer solution of the composition given below immersed and then brought into contact with an image receiving layer.

The developer solution used contained an oxidizing agent-reducing agent combination according to the invention. The immersion time was 10 seconds. An image receiving element was used as the image receiving material, consisting of a paper backing with a gelatin layer with cetyltrimethylammonium bromide as a pickling agent, used, which had been immersed in the following developer solution for 1 minute. The contact time of recording material and the image receiving layer was 2 minutes. After the image-receiving layer was separated, it remained behind a positive dye image with a maximum density of 0.90 of the test article.

Developer solution

Na ₂ SO ₃ 50 g *

NaOH 5 g

1-phenol-3-pyrazolidone 0.1 g

4-Amino-N-ethyl-N - $ - hydroxyethylaniline sulfate (color developer compound) 10.0 g

/ "Co (NH ₃ ) ₆ _7C1 ₃ (oxidizing agent) 2.5 g Make up to 1 liter with water

Example 21

The procedure described in Example 20 was repeated except that this time a recording material was used was that in the layer 1 0.5 mg silver nuclei instead

209881/0615

Contained from Palladio unique germs. Furthermore, the exposed Recording material brought into contact with the developer solution for 30 seconds. After separating the image receiving element of the recording material, a positive dye image with a maximum density of 0.81 became in the image-receiving layer visible.

Example 22

A further photosensitive recording material of the type described in Example 20 was first prepared, which differed from the recording material described in Example 20 in that layer 1 contained 10 mg of silver nuclei per 0.0929 m ^{2 of} substrate area and that the colorless image transfer coupler was 90 mg of the colored image transmission coupler of the following structural formula:

0 - </ ^ V-N = N

209881/0615

After a contact time of 5 minutes with the photosensitive element, a positive remained in the image-receiving layer Dye image with a maximum density of 0.66.

The following Example 23 shows that only reduced density images are obtained when during development and processing of the recording materials in the dye transfer process l an oxidizing agent consisting of a cobalt complex, is present.

Example 23

The procedure described in Example 22 was repeated except that this time a developing solution was used which did not contain a cobalt (III) hexamine chloride complex. Furthermore, a developer solution containing 25 g per liter of NaOH and 1.5 g per liter of the silver solvent bis (methylsulfonyl) methane. The maximum density of the transferred dye image was only 0.50.

Example 24

Another photosensitive recording material became available of the type described in Example 20, with the exception, however, that in layer 1 50 mg of cobalt (III) hexamine chloride were incorporated per 0.0929 m of support surface.

The material was developed using a solution of the composition given in Example 20, but which did not contain a cobalt complex contained.

A positive dye transfer image with a obtained maximum density of 1.08.

209881/0615

Example 25

The procedure described in Example 20 was repeated except that this time a developing solution was used containing a silver halide solvent such as bis (methylsulfonyl) methane at a concentration of 0.15 g contained per liter. The maximum density of the positive transfer image was 1.10.

The procedure was repeated, but this time using a developer solution which did not contain a cobalt complex was used. This time the maximum density of the positive dye transfer image was only 0.48.

Corresponding results were obtained when using other cobalt (III) complexes instead of cobalt (III) hexamine chloride was worked, for example with the following, as oxidizing agent effective complexes:

Z "Co (en) ₂ dien_7ci ₂ -HCl; /" Co (NH _{3 4} J (H ₃ O) ₂ _7 (C1O _3);.. / "Co (NH) H ₉ O 7 (ClO) ,; trans -NH. / "Co (NH.,) ₉ (NO ₉ ). 7; /" Co (NO ₂ ) ₃ (NH ₃ ) ₃ - 7; / "Co (NH ₃ ) ₄ CO ₃ - 7nO ₃ ; /" Co (NH ₃ ) 5CO _3- trans- / ~ Co (en) ₉ Cl _o /Cl.HCl; trans- / ~ Co (en) ₉ (N _) (NO ₉ ) ~ / l Z "Co (en) ₂ ( N0 ₃ ) ₂ _7N0 ₃ ; / "Co (diene) (SCN) ₂ (OH) J; /" Co (triene) (NO ₉ ) .7NO ... H ₇ O; cis - / "Co (triene) Cl ₉ _7ci; / "Co (en) ₂ (NO ₂ ) ₂ _7 (ClO ₄ ) ₃ ; / 'Co (trien) (N ₃ ) ₂ .7n0 ₃ ; or

The above examples show that the process of the invention is excellent for producing colored and multicolored positive dye transfer images. The cobalt complexes can generally be added to the developer solution.

209881/0615

are set or in the light-sensitive recording material are accommodated, preferably in the layer or layers of the photosensitive recording material, the one Includes image transfer coupler. Multicolored light-sensitive ones are particularly suitable for carrying out the method Elements of that described in U.S. Patent 3,227,551 or British Patent 904,364, page 19, lines 1-40 Construction. Particularly advantageous results can also be obtained when the cobalt complex is a working or developer solution is added, as used in the process known from US Pat. No. 3,227,550, or when the cobalt complex is incorporated into a multicolor light-sensitive material of the US patent 3,227,550 of the known type is incorporated, preferably in a veiled direct-positive emulsion layer of such Materials.

The following examples serve in particular for further explanation photographic recording materials containing silver halide for carrying out the method of the invention.

Example 26

First, a photographic recording material of the structure described below was produced by applying the layers indicated in the following order to a layer support: (The concentrations given below again relate to mg per 0.0929 m ^{2 of} layer support area.)

Layer 1

A blue sensitive silver chlorobromide emulsion layer with 200 mg gelatin and 40 mg silver in the form of blue-sensitive silver chloride bromide grains, 150 mg of the 2-equivalent

209881/0615

Color coupler α- / ~ 4- (4 ~ BenzyloxypheRylsulfonyl) phenoxy_7-apivalyl-2-chloro-5 - / "Y- (2,4-di-partially amylphenoxy) butyramido_7-acetanilides, dissolved in dibutyl phthalate as a coupler solvent, with a weight ratio of coupler to coupler solvent of 1: 1/4, with a stoichiometric ratio of silver to color coupler of 1: 0.9;

Layer 2

an intermediate gelatin layer containing 100 mg gelatin;

Layer 3

a green-sensitive silver chlorobromide emulsion layer with 200 mg gelatin and 10 mg silver in the form of green-sensitive Silver chlorobromide grains and 45 mg of the 4-equivalent color coupler 1- (2,4,6-Trichlorophenyl) -3 - ^ "2-chloro-5- (a- (4-hydroxy-3-tert-butylphenoxy) tetradecanoamido) anilino_7-5-pyrazolons, dissolved in tricresyl phosphate as a coupler solvent, at a weight ratio of coupler to coupler solvent 1: 1/2 with a stoichiometric silver to coupler ratio of 1: 2.5;

Layer 4

an intermediate gelatin layer containing 240 mg of gelatin;

Layer 5

a red-sensitive silver chlorobromide emulsion layer with 150 mg gelatin and about 5 mg silver in the form of red-sensitive Silver chlorobromide grains and 35 mg of the 2-equivalent color coupler 2- / ~ a- (2,4-di-tert-diamylphenoxy) -n-butyrylamino_7-4,6-dichloro-5-methylphenol, dissolved in dibutyl phthalate as a coupler solvent, at a weight ratio of coupler to coupler solvent of 1: 1/2 and a stoichiometric ratio of silver to coupler of 1: 3.1;

Layer 6

a gelatin layer with 100 mg gelatin,

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The support used consisted of a paper support with a titanium dioxide-containing one applied thereon Polyethylene layer.

The recording material written on was exposed to a colored object so that a neutral one by reversal development An image generated by a cyan dye, a magenta dye and a yellow dye could be obtained Dye,

The exposed recording material was developed as follows:

First it was made in a commercially available black and white developer the composition given below 1.5 minutes long black and white developed at 30 ° C:

Water, about 5O ⁰ C 500 ml p-methylaminophenol sulfate 2.0 g

Sodium sulfite (anhydrous) 90.0 g, hydroquinone 8.0 g

Sodium carbonate, monohydrate 52.5 g, potassium bromide 5.0 g

Made up to 1 liter with cold water.

The material was then placed in a break bath, then in a dichromate bleach bath and finally In a clarifying bath for 1 minute, consisting of an aqueous solution with about 100 g per liter of sodium sulfite. It was then the material uniformly reexposed to light and then for 10 minutes at 24 ° C in a color developer B of the im following specified composition color developed:

209881/0615

G 222 B 7 7 0 G per liter G 10 ml G 2.0 G 2.0 G 0.5 G 0.5 5.0 30.0 1.6

Benzyl alcohol

Na ₂ SO ₃

Hydroxylamine sulfate

^ Amino-S-methyl-N-ethyl-N-

ß-methoxyethylaniline-di-p-

toluenesulfonate

Ne ₂ ^CO 3 (anhydrous)

/ "Co (NH _{3) 6} _7C1 ₃

pH «10.75 at 24 ^° C

The film recording material was then bleached, fixed and dried in the usual manner. The minimum and maximum densities for red (cyan dye) were 0.19 and 1.6, respectively; for green (purple dye) at 0.18 and 2.4, respectively, and for blue (yellow dye) at 0.20 and 1.8, respectively.

Corresponding results were obtained when other non-halogenating bleach baths were used after the black-and-white development were used, for example bleach baths based on ferric nitrate, cobaltihexamine nitrate, quinone and sulfuric acid.

Example 27

The procedure described in Example 26 was repeated, except that ₆ _7ci ₃ equivalent amounts indicated in the following cobalt complexes were used in place of the cobalt complex / "Co (NH_):

/ "Co (en) 2 (diene) _7C1 ₂ · HCl, /" Co (NH ₃ ) ₅ (H ₂ O_7 (ClO ₄ ) ₃ , / "Co (NO ₂ ) ₃ (NH ₃ ) ₃ _7, /" Co (NH ₃ ) ₄ (CO ₃ ) .7NO ₃ , trans - / "Co (en) ₂ (Cl) ₂ _7ci · HCl, trans - /" Co (en) ₂ (N ₃ ) (NO ₂ ) Js ₂ O ^,

209881/0615

^ "Co (trien) (NO ₂ ) ₂ _7νΟ ₃ · Η ₂ Ο, cis /" Co (trien) (C1) ₂ _7C1, / "Co (en) ₂ (N ₃ ) ₂ _7N0 _3f / 'Co (en ) ₂ (NO ₂ ) ₂ - 7 (ClO ₄ ) 3, / "Co (triene) (N ₃ ) ₂ - 7N0 ₂ , /" Co (en) ₂ (NH ₃ ) ₂ .7Cl ₃ , / "" Co (Tn ) ₃ / "Co (tn) ₂ (en) _7ci ₃ or / * Co (tn) (en) ₂ _7ci _r

In all cases, favorable results have been obtained, with the dye densities achieved were at most slightly lower.

Example 28

Three photographic recording materials A, B and C were prepared by applying gelatin silver bromide iodide emulsions, the silver halide grains of which consisted of 0.77 mol of iodide, at a silver concentration of 10 mg and a gelatin concentration of 300 mg per 0, on cellulose acetate film supports. 0929 in ² layer support surface.

The emulsion layer of the recording material A additionally contained 150 mg of the 4-equivalent coupler 5 - ^ "ot- (2,4-di-tert-amylphenoxy) hexamido_7-2-heptafluorobutyramidophenol, dissolved in dibutyl phthalate, which forms a blue-green dye Coupler solvent in a weight ratio of coupler to coupler solvent of 1: 1/2 at a stoichiometric one Ratio of silver to coupler of 1:10.

The recording material B contained a corresponding amount of the yellow dye-forming material in the emulsion layer Coupler α- (4-carbocarboxyphenoxy) -a-pivalyl-2-chloro-S - ^ "Y- (2,4-di-t.-araylphenloxy) butyramido_7acetanilide, dissolved in the same coupler solvent as described had been.

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The recording material C corresponded to the recording material A except that the coupler used is the magenta dye-forming coupler 1- (2,4,6-trichlorophenyl) -3- {3- / ~ ct- (3-pentadecylphenoxy) butyramido_7benzamido} -5-pyrazolone contained.

The recording materials A, B and C were sensitometrically exposed to white light and developed for 32 minutes at 24 ⁰ C in a developer of the composition indicated below:

4-Amino-N-ethyl-N-8-hydroxyethyl aniline sulfate

1-phenyl-3-pyrazolidone Na ₂ SO ₃

Ethylenediaminetetraacetic acid, tetrasodium salt

20.0 G 0.1 G 40.0 G 0.5 G 8.0 G 2.5 G 10.0 G 1 liter

borax

Topped up with water

pH - 11.0

After the recording materials had been developed, they were washed in water for 10 minutes. The recording materials were not bleached or fixed.

The minimum and maximum densities of the blue-green, yellow, and purple dye images of recording materials A, B and C were 0.6 and 2.6; 0.2 and 0.8 or 0.2 and 1.1.

A comparison of these recording materials with comparison materials which were produced and developed in a corresponding manner, but after the development in the usual manner bleached and fixed shows that the

209881/0615

The silver images remaining in the processing materials do not contribute to the generation of a measurable density in the dye images.

The total density of the silver images in the unbleached recording materials was below 0.4.

Excellent multicolor images were made without bleaching or fixing obtained when the described photosensitive layers of the recording materials A, B and C on the usual Layer support is applied and the silver halide grains of the layers are sensitized to red, blue and green light where the green-sensitive layer is preferably between the red- and blue-sensitive layer on the support was applied.

Example 29

A reversed type multicolor photographic material was prepared by clicking on one containing titanium dioxide pigmented and coated with a polyethylene layer paper support applied the following layers were, all of the weight amounts given below refer to a support area of 0.0929 m:

Layer 1

a blue-sensitive silver chloride bromide emulsion layer with 200 mg gelatin, 40 mg blue-sensitive silver chloride bromide and a solution of 120 mg of the coupler a- / ~ 4- (4-benzyloxyphenylsulfonyl) phenoxy J -a-pivalyl- dispersed in the emulsion layer 2-chloro-S- l ~ y- (2,4-di-tert-amylphenoxy) butyramido_7acetanilide, dissolved in 30 mg of di-n-butyl phthalate;

Layer 2

a gelatin layer with 100 mg gelatin;

209881/0615

Layer 3

a green-sensitive silver chlorobromide emulsion layer with 200 mg gelatin and 800 mg green-sensitized silver chlorobromide and a solution of 30 mg of the purple-red dye-forming color coupler 1- (2,4,6-trichlorophenyl) -3 { 5- / ~ a- (3-tert-butyl-4-hydroxyphenoxy) -tetradecanamido_7-2-chloroanilino} -5-pyrazolone, dissolved in 15 mg tricresyl phosphate;

Layer 4

a gelatin layer with 241 mg of gelatin, and dispersed therein a solution of 65 mg of the filter dye 2- (2-hydroxy-3 ^{f 1,} 5'-di-tert-amylphenyl) benzotriazole, dissolved in 32.5 mg of 2- (2- Butoxyethoxy) ethyl acetate;

Layer 5

a red-sensitive silver chlorobromide emulsion layer with 150 mg gelatin and 5.25 mg silver in the form of red-sensitized Silver chlorobromide with a solution of 23.4 mg of the cyan dye-forming dye dispersed in the layer Color coupler 2- / ~ a- (2,4-di-tert-amylphenoxy) butyramido_7-4,6-dichloro-5-methylphenol, dissolved in 11.7 mg of di-n-butyl phthalate;

Layer 6

a gelatin layer with 100 mg gelatin.

For comparison purposes, a strip (1) of the recording material produced was exposed after exposure through a step wedge with neutral density steps in an intensity sensitometer and then developed at 30 ^° C. as follows:

209881/0615

40ή

Develop in black and white developer. Treat with an acidic break bath To wash

Re-exposure to white light, color development ⁺⁺

Bleach-fix

To wash

Stabilize

Minutes 1.5 1
1

10
1.5 1
1

Black and white developer:

N-methyl-p-aminophenol sodium sulfite, anhydrous Hydroquinone

Sodium carbonate, monohydrate potassium bromide

Made up to 2 g g with water

8 g 52.5 g

5 g

1 liter

Color developer:
Benzyl alcohol
Sodium sulphite, anhydrous Hydro xy 1 amine sulphate sodium bromide
Sodium chloride

4-Amino-N-ethyl-N- (2-methoxyethyl) - m-toluidine-di-p-toluenesulfonate sodium carbonate, anhydrous Made up with water to pH - 10.75 at 24 ° C

10 m] L. G 2.0 G 2.0 G 0.5 G 0.5 G 5.0 G 30.0 1 liter

Another strip (2) of the described multicolor recording material was exposed and developed in the same way, with the exception, however, that a color developer was used for developing the material, which additionally contained 1.6 g per liter of the complex ^ "Co (NH ₃ ) ₆ _7C1 contained _3.

209881/0615

Wed

A further strip (3) of the multi-color recording material described as the exposed strip (1) and (2), subsequently developed, but at 3O ⁰ C in the following order:

Time in minutes Develop in black and white developer

as with strips (1) 1.5

Treatment with an acidic interrupter bath 1

Washing 1

Bleach ⁺⁺⁺ 1

Clarify ** " ¹ " * 1

Washing 1

Re-exposure with white light, Color developing with color developer like

for strips (1) +1.6 g / l

/ "C (NH) ₆ 7ci ₃ 10

Bleach-fix 1.5

Washing 2

Stabilize 1

Bleach bath:

Potassium dichromate Sodium sulfate Sodium bisulfate Topped up with water

Killrbad:

Sodium sulfite (anhydrous) Topped up with water The determined D. - ^{and D.} -Values of in the case of the stripes

max mn

(1), (2) and (3) obtained strips are summarized in the following table:

10 G 50 G 50 ISO 1 liter 101 , 07 g 1 liter

209881/0615

Stripes min D. (D Stripes ^D , (2) Stripes (3) D. .15
.17 O
1 Max ^D min 1
2 Max D. D.
in the max Red
green O
O , 72
, 03 1,
2, , 6
, 4 0.19 1.6
0.18 2.4 , 6
, 4

blue 0.18 1.27 1.8 1.8 0.20 1.8

From the results obtained, it was found that a photographic Reverse-type multicolor recording material (strip 3) according to the method of the invention yields color images with lesser ones D. Values and higher D values than before (Streimin max

fen 1) can be developed.

In the case of the strip (2), the ^D _m 4 _n ^values & ^{en D} _max values, from which it follows that a bleaching stage must be switched on after the black-and-white development and before the color development if a color developer is used after the Invention is used because the developed silver of the black and white development stage catalyzes the oxidation-reduction reaction between the cobalt (III) hexamine chloride and the primary aromatic amine color developer.

Example 30

First, a multi-layer color photographic material was used produced in that the specified in the following order on a paper support Layers were applied. The concentration data given below relate to mg per 0.0929 m Support surface.

The following were applied to the paper backing:

209881/0615

1. A blue-sensitive silver halide emulsion layer containing 50 mg of silver, 200 mg of gelatin and 120 mg of the one yellow dye supplying 2-equivalent coupler of layer 1 of Example 29, dissolved in 30 mg of di-n-butyl phthalate;

2. an intermediate layer of 100 mg gelatin;

3. a green-sensitive silver halide emulsion layer containing 54 mg of silver, 222 mg of gelatin and 55 mg of the one purple 4-equivalent dye-providing coupler of layer 3 of Example 29 dissolved in 27.5 mg of tricresyl phosphate;

4. an intermediate layer of 231 mg gelatin;

5. a red-sensitive silver halide emulsion layer containing 35 mg of silver, 159 mg of gelatin and 35 mg of the one blue-green Dye-providing 2-equivalent coupler of layer 5 of Example 29, dissolved in 17.5 mg of di-n-butyl phthalate;

6. a top layer of 100 mg gelatin.

A second recording material - hereinafter referred to as material B - was produced like the described material A, with the exception, however, that the silver concentration in the Layer 1 was reduced to 10 mg, in layer to 10.8 mg and in layer 5 to 7.0 mg.

Development:

(A) A strip of recording material A was exposed to a multicolored test object with graduated density levels in a sensitometer and then developed at 27 ^° C. in the following manner:

209881/061 5

Color developing 3.5 min. Bleach-fix 1.5 min. Wash 2 min.

Stabilize for 1 min. Drying

The bleach-fix bath described in Example and the stabilizer bath described in Example 29 were used for bleach-fixing and stabilization. The color developer used had the following composition:

water

Potassium sulfite (anhydrous) Hydroxylamine sulfate Potassium bromide

4-Amino-N-ethyl-N- (2-ethoxyethyl) -m-toluidine-di-p-toluenesulfonic acid

Potassium carbonate (anhydrous) Made up with water pH - 10.8

In the following table the D. Values, D values and

mm max

γ values of the yellow, magenta and cyan dye images produced in layers 1, 3 and 5 are compiled.

300 ml 5 G 3 G 1 G 10 G 50 G 1 liter

D. D. Max Y mm 2.02 2.1 yellow 0.12 2.26 2.4 purple 0.14 2.20 2.3 blue green 0.11

The results obtained show that, when the color photographic recording material is developed in the customary known manner, a good reproduction of the photographed test object is obtained.

209881/0615

(B) The development process described under (A) was carried out with a test strip of the recording material B with low Silver content repeated. This gave yellow, magenta and cyan dye images, the very low maximum

Densities (D _me ^) and a low contrast (γ), max

(C) In another attempt, the procedure was repeated

repeated with a test strip of material B, however this time the development time increased from 3 1/2 to 7 minutes became. In this case too, only images with very low maximum densities and low contrast were obtained, such as results from the data compiled in the following table:

yellow

purple blue green

(D) In a further experiment was developed a stripe of recording material B for 7 minutes in the manner described, but using this time a color developing solution of the composition indicated was used which additionally 1.6 g / "Co (NH _{3) 6} _7C1 ₃ and 1 g of ethylenediaminetetraacetic acid, tetrasodium salt were added In this case, the sensitometrically determined values compiled in the following table were obtained, which largely correspond to the values obtained when using recording material A, ie the silver-rich material.

min D. Max 0 γ 0.14 1 , 16 1 , 7 0.14 1 , 54 1 , 5 0.12 1 , 76 , 6

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-yd -

min Max 1 γ 0.11 1.52 ⁺ 2 , 3 ⁺ 0.12 2.24 2 , 4 0.12 2.24 ,8th

purple

blue green

The comparatively low D and γ values of the yellow color

UtO-X

the fabric image can be easily

En shear recording materials, the / ¹ silver content in the blue-sensitive silver halide emulsion layer (layer 1) is increased to concentrations of up to about 30 mg silver per 0.0929 m ² .

The data obtained clearly show that the recording materials according to the invention have a low silver content and a high ratio of color coupler to silver to color photographic images develop excellent properties permit.

Example 31

The recording materials described in Example 30 were exposed to a multicolored test object with graduated density levels and then developed at 27 ^° C. in the manner indicated in Example 30, with the exception, however, that this time a color developer solution was used which contained 10 g / l 4- Amino-3-methyl-N, N-diethylaniline, hydrochloride instead of the specified color developer compound. Similar results as described in Example 30 were obtained. ^

Example 32

Another color photographic recording material was produced by placing it on a cellulose acetate support the layers indicated in the following order were applied, the concentration data in each case being based on

2 09881/0615

λη

mg per 0.0929 m ² substrate area:

1) a blue-sensitive silver bromide iodide emulsion layer in which the halide content of the silver halide grains consisted of 1.14 % iodide, in a concentration of 61 mg Ag (grain size 1.0 micron) and also 132 mg of the coupler α-pivalyl which provides a yellow dye -ot- (4-carboxyphenoxy) 2-chloro-5- ^ γ- (2,4-di-tert-amylphenoxy) -butyramido_7acetanilide, dissolved in tricresyl phosphate in a ratio of 1: 1, and 253 mg gelatin;

2) a gelatin layer containing 43 mg of gelatin;

3) a red-sensitive silver chlorobromide emulsion layer with a ratio of chloride to bromide of 80:20 and a grain size of 0.25 microns with a silver content of 10 mg and 79 mg of the coupler 2-l'a- (2, 4-di-tert-amylphenoxy) butyramido_7-4,6-dichloro-5-methylphenol, dissolved in di-n-butyl phthalate in a ratio of coupler to solvent of 1: 3, and 207 mg of gelatin;

4) a gelatin layer containing 43 mg of gelatin;

5) a green-sensitive silver chlorobromide emulsion layer with a silver chloride to silver bromide ratio of 80:20 and a grain size of 0.25 microns with a silver coating of 20 mg and 139 mg of the one purple-red Dye-supplying color coupler l- (2,4-dimethyl-6-chlorophenyl) -3- / ~ a- (3-n-pentadecylphenoxy) butyramido_7-5-pyrazolone, dissolved in di-n-butyl phthalate in a ratio of 1: 1;

6) a gelatin layer containing 68 mg of gelatin.

209881/0615

Test strips of the recording material were exposed in a sensitometer and then developed, fixed, washed, bleached, washed, fixed and stabilized in a dichromate bleach bath for ^{8 minutes at 24 ° C. in the developers A and B indicated below.}

Developer A had the following composition:

g / liter

Ethylenediaminetetraacetic acid,
Tetrasodium salt 4

K ₂ CO ₃ 40

KBr 2

K ₂ SO ₃ 4

4-Amino-3-methyl-N, N-diethylanilino hydrochloride 3.0

Made up to 1 liter with water

pH »10.65 at 24 ^° C

The developer B corresponded to the composition of the developer A, except that it additionally g per liter of the complex contained 1.6 / "Co (NH _{3) 6} _7ci. ₃

The densities of the dye images obtained using the developers are shown in the following table compiled:

Developer A min
ι I ■ ■ I I) Max Developer B Max 4th , 6 D. ,1 3 ,1 D.
min above 4th .6 0 ,1 1 , 6 0.1 above 4th ,8th 0 , i 1 , 2 0.1 above 0 0.1

blue green

purple

From the results obtained, it can be seen that photographic Recording materials according to the invention with a comparatively greatly reduced silver content are outstanding

209881/0615

excellent for producing colored recording materials with cyan, yellow and magenta dye images high density values in the D -districts.

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Claims (1)

PATENT CLAIMS 1. Process for making and amplifying photographic images Images in which an oxidation-reduction reaction occurs between an oxidizing agent and a reducing agent for image intensification carried out a photographic recording material of a layer support and at least one layer which contains a substance A in an imagewise distribution, the Able to catalyze the course of the oxidation-reduction reaction, used and one in the oxidation-reduction reaction Resulting reaction product with a compound B which is reactive with the reaction product to produce a Image is implemented, characterized in that a cobalt (III) complex is used as the oxidizing agent. 2. The method according to claim 1, characterized in that the substance A present in imagewise distribution is made of a metal consists. 3. The method according to claim 2, characterized in that the Substance A present in an image-wise distribution consists of silver. 4. The method according to claim 1, characterized in that the cobalt (III) complex consists of a coordination complex of the Cobalt in which the cobalt has the coordination number 6, consists. 5. Process according to Claims 1 and 4, characterized in that a cobalt (III) complex is used, the ligands of which from NH_-, ethylenediamine, diethylenetriamine, triethylenetetramine, Nitrate, nitrite, azide, chloride, thiocyanate, isothio 209881/0615 Cyanate, water and / or carbonate ligands exist, with applies that the complex 1.) at least five NIL ligands, 2.) at least two ethylenediamine ligarids or 3.) at least contains a triethylenetetramine ligand. 6. Process according to Claims 1, 4 and 5, characterized in that a cobalt (III) complex of the following structural formula is used used: Z "Co (en) ₂ (N ₃ ) ₂ _ / X; / ~ Co (en) ₂ Cl (NCS) _7x; / "Co (en) ₂ (NH ₃ ) IN ₃ _ / X; / ~ Co (en) ₇ Cl? X; / "Co (en) ₂ (SCN) ₂ _ / X; / "Co (en) _n (KCS) ₉ ? X; or /" Co (NH ₃ ) ₆ _7X in which X stands for at least one chloride, bromide, nitrite, Nitrate, perchlorate, acetate, carbonate, sulfite, sulfate, hydrochloride, thiocyanate, isothiocyanate or hydroxide anion and en stands for an ethylenediamine ligand. 7. The method according to claim 6, characterized in that there is used as cobalt (III) complex cobalt hexamine chloride. 8. The method according to claim 1, characterized in that a silver halide reducing agent is used as the reducing agent used. 9. The method according to claims 1 and 8, characterized in that that a photographic developing agent is used as the reducing agent. BATHROOM 0RK31NAL 209881/0615 10. The method according to claim 9, characterized in that a color developer compound is used as the reducing agent. 11. The method according to claim 10, characterized in that a color developer compound is used as the reducing agent, which consists of a primary aromatic amine. 12. The method according to claim 1, characterized in that the resulting in the oxidation-reduction reaction reduced oxidizing agent with a compound B which reacts chemically with the reduced oxidizing agent Generating a reaction product converts whose hue or light value from that of the compound B is different. 13. The method according to claim 12, characterized in that as compound B: an 8-hydroxyquinoline,
a formazan dye,
a 2,4-diaminophenol,
an α-nitroso-3-naphthol or
a color coupler used. 14. The method according to claim 13, characterized in that the photographic color coupler is a 5-pyrazolone color coupler used. 15. Process according to Claims 7 and 13, characterized in that the cobalt (III) complex is cobalt hexamine chloride and used as compound B 8-hydroxyquinoline. 16. The method according to claims 1, 10 and 12, characterized in that a color developer compound is used as the reducing agent and a color coupler is used as compound B. 209881/0615 BAD ORlOlNAL 17. The method according to claim 14, characterized in that the 5-pyrazolone color coupler 1- (2 ·, 4 ', o'-trichlorophenyl) -3- / 3 "- (2'", 4 " ^t -di-tert. -amylphenoxyacetamido) benzamido_7-5-pyrazolone is used. 18. The method according to claim 1, characterized in that the resulting in the oxidation-reduction reaction, from the reduced form of the oxidizing agent existing reaction product used by reaction with a reactive compound B whose ability to change to bring about the hue or light value, to inhibit imagewise. 19. The method according to claim 1, characterized in that one of a photographic recording material with at least an exposed light-sensitive silver halide emulsion layer with a developed silver image (substance A) goes out. 20. The method according to claims 1 to 18, characterized in that one (1) of a recording material with at least an imagewise exposed photographic silver halide emulsion layer with a developed silver image (substance A) (2) the developed silver halide emulsion layer with a hydroquinone, a methyl-p-aminophenol developing agent and containing a cobalt (III) complex Solution treated, (3) the treated material with an image-receiving sheet, consisting of a substrate and one of an image-receiving layer formed by a hydrophilic colloid and 8-hydroxyquinoline, and (4) the image-receiving sheet brought into contact with a solution of oxidized color developing agent to form a dye image. 21. The method according to claim 20, characterized in that one of a recording material with a veiled direct-positive silver halide emulsion layer goes out. 209881/0615 22. The method of claim 1, wherein a metallic silver image of a photographic recording material is reinforced or replaced by a dye image, characterized in that that you 1.) the silver image (substance A) with a combination of a primary aromatic amine existing color developing agent and a cobalt (III) complex and 2.) the oxidized color developing agent to form a dye image with a color coupler (Compound B) brings into contact. 23. The method according to claim 22, characterized in that the metallic silver image is removed after the dye production . 24. The method of claims 1, 10, 13, 22 µm. ¹ 23, characterized in that one starts from an exposed multilayer photographic recording material with red-, green- and blue-sensitive silver halide emulsion layers with silver images (substance A) developed in the layers and color couplers (compound B) producing blue-green, magenta and yellow image dyes, the latter are present in the emulsion layers or in layers adjacent thereto. 25. The method according to claim 24, characterized in that one of an exposed multilayer recording material goes out, its red, green and blue sensitive layers or adjacent layers of phenolic or naphtholis color couplers, 5-pyrazolone color couplers or open-chain ones Contain ketomethylene color couplers, the diffusing or non-diffusing blue-green, purple or yellow dyes form. 26. The method according to claims 1 and 13 to 25, characterized in that that the oxidation-reduction reaction in the presence of a reaction between reduced cobalt (III) · complex and color coupler preventing chelating agent through- 209881/0615 BATH OFUGINAL 27. The method according to claim 26, characterized in that there is used as the chelating agent ethylenediaminetetraacetic acid. 28. The method according to claims 24 to 2 7, characterized in that one of recording materials with veiled direct-positive silver halide emulsion layers goes out. 29. The method according to claims 22 to 28, characterized in that the photographic recording material exposed in an imagewise manner developed in an aqueous developer solution containing per liter of solution: about 10 g of 4-amino-3-methyl- (I-ethyl-N-ß- methoxy-ethyl) anilinedibenzenesulfonate; about 2 g of cobalt (III) hexamine chloride and about 1 g of ethylenediaminetetraacetic acid. 30. The method according to claim 1, characterized in that one of a photographic recording material consisting of a layer support and at least one applied gelatin layer with silver bromide iodide grains and 5 ~ l ~ δ- (2,4-di-tert-amylphenoxy) -hexanamido_7 -2-heptafluorobutyramidophenol as a color coupler dissolved in dibutyl phthalate, goes out with a developed silver image (substance A) and that the developed material is bathed in an aqueous solution which contains per liter of solution: about 20 g of 4-amino-N-ethyl-N- ß-hydroxyäthylanilinsulfonat as color developer compound, about 3 g of cobalt (III) hexamine chloride and about 8 g of ethylenediaminetetraacetic acid. 31. The method according to claim 1, characterized in that one starts from a photographic recording material, whose substance A, which is present in image-wise distribution, consists of metallic silver, which is produced by image-wise reduction BATHROOM 0RK3INAL 209881/0615 an imagewise exposed photosensitive layer containing the reaction product of a silver ion and a photographic spectral sensitizing dye. 32. The method according to claim 31, characterized in that one starts from a recording material, which in image-wise Distribution of the present substance A consists of metallic silver, which by imagewise reduction of the reaction product from a silver salt, in particular silver nitrate, and a merocyanine dye. 33. The method according to claims 1 to 9, characterized in that a photographic recording material with at least a silver halide emulsion layer, the silver halide grains thereof s ϊ-ικί dispersed in a crosslinkable colloidal binder after an image-appropriate exposure and developing a metallic silver image with a combination of a photographic developer compound and a cobalt (III) complex - with imagewise reduction of the cobalt (III) complex in the presence of the metallic silver image - developed and the reduced cobalt (III) complex as a crosslinking agent for crosslinking of the colloidal binder is used. 34. The method according to claim 33, characterized in that one a recording material having at least one silver halide emulsion layer used, their crosslinkable colloidal binder in whole or at least partially unhardened gelatin. 35. Process according to Claims 33 and 34, characterized in that the photographic developer compound is a hardening one or tanning developer compound used. BAD OFUGINAL 209881/0615 36. The method according to claim 35, characterized in that there is used as a hardening or tanning developer compound 4-phenylpyrocatechol is used. 37. Process according to Claims 33 to 36, characterized in that the cobalt (III) complex is cobalt (III) hexamine chloride used. 38. The method according to claims 1 to 37, characterized in that the cobalt (111) complex in the form of a solution to the allows photographic recording material to act. 39. Process according to Claims 1 to 9, characterized in that a photographic recording material is used with at least one direct-positive silver halide emulsion layer with a developed silver image and that the cobalt (III) complex is contained in the emulsion layer. 40. The method according to claim 39, characterized in that one of a primary aromatic is used as the reducing agent Amine existing color developing agent is used. 41. Process according to Claims 39 and 40, characterized in that a photographic recording material is used with at least one fogged direct-positive silver halide emulsion layer, containing a photographic color coupler runs out. 42. Process according to Claims 1 to 12 and 24 to 28, in which a photosensitive material is used for producing color photographic transfer images by the diffusion transfer process Photographic recording material, consisting of a layer support and at least one light-sensitive Silver halide emulsion layer containing a non-diffusing color coupler that is oxidized with an 209881/0615 bad orksinal Developer compound capable of forming a diffusing dye, contains or with such a color coupler containing layer is in contact, 1.) exposed imagewise, 2.) the exposed material with an alkaline developer solution with a primary aromatic amine color developing agent to develop the exposed silver halide emulsion layer or layers developed with a silver halide developing agent and 3.) at least a portion of the imagewise exposure of the silver halide emulsion layers in each diffusing image dyes produced by the layers diffuse into an image receiving layer, characterized in that that one carries out the development in the presence of a cobalt (III) complex, which in the areas of development metallic silver enters into an imagewise redox reaction with the developer compound. 43. The method according to claim 42, characterized in that a photographic recording material is used which consists of: a layer support and at least one red-sensitive, one green-sensitive and one blue-sensitive Silver halide emulsion layer, each one upon reaction with oxidized color developing agent a diffusing cyan dye, a diffusing magenta dye, and a diffusing yellow dye, respectively Contain dye-producing, non-diffusing color couplers or with corresponding color couplers Layers are in contact. 44. The method according to claims 42 and 43, in which a recording material is used as characterized in claim 42 with (a) an image receiving layer arranged on a support and (b) at least one splittable container with a working liquid causing the development of the exposed recording material BAD ORKSINAL 2 09881/0615 KX (C. forms a film unit, characterized in that one uses a film unit which 1.) one of a primary aromatic amine existing color developing agent and 2.) contains a cobalt (III) complex, with the proviso that the Cobalt (111) complex in the one composed of support and image receiving layer formed image receiving element, the photosensitive recording material and / or a splittable Containers can be included. 45. Photographic working solution for performing the method according to claims 1 to 44, containing a combination the end: 1. an oxidizing agent consisting of a cobalt (I II) complex and 2. at least one reducing agent, the cobalt (111) complex able to reduce only in the presence of a catalytically active compound. 46. Photographic working solution according to claim 45, characterized in that it is a compound as a reducing agent which is able to reduce silver halide to metallic silver. " 47. Photographic working solution according to claims 45 and 46, characterized in that it is a cobalt (III) complex with the coordination number 6 and XIu-, ethylenediamine, Diethylenetriamine, triethylenetetramine, nitrate, nitrite, Azide, chloride, thiocyanate, isothiocyanate, water and / or carbonate ligands, it being understood that the complex 1.) at least 5 NlU ligands, 2.) at least two ethylcinediamine ligands or 3.) contains at least one Triäthylentet raminliganden. 48. Photographic working solution according to claim 47, characterized in that that it is a complex as a cobalt (I I I) complex contains one of the following formulas: 209881/0615 _{BAD 0RK} > _{| NAL} 4l4 / "Co (en) ₂ (N ₅ ) ₂ _? Χ;
/ ~ Co (en) ₂ C1 (NCS) _7Χ;
/ "Co (en) ₂ (NH ₃ ) N ₃ JX ;
/ "Co (On) ₂ Cl ₂ -7X;
/ "Co (en) ₂ (SCN) ₂ _? X;
/ "Co (en) - (NCS) ₉ ? X or
/ "Co (NII _{3) 6} _7X in which: en is an ethylenediamine ligand and X is at least a chloride, bromide, nitrite, nitrate, perchlorate, acetate, carbonate, sulfite, sulfate, hydrochloride, thiocyanate, Isothiocyanate or hydroxide anion. 49. Photographic working solution according to claims 45 to 48, thereby characterized in that it contains a cobalt (III) hexamine salt as the cobalt (III) complex. 50. Photographic working solution according to claims 45 to 49, thereby characterized in that it uses a primary aromatic amine color developing agent as the reducing agent contains. 51. Photographic working solution according to claims 45 to 50, characterized in that it additionally contains a chelating agent for binding the reduced cobalt (III) complex contains. 52. Photographic working solution according to claims 45 to 51, characterized in that it consists of an aqueous solution consists of 0.1 to 50 g of a cobalt (III) complex and at least one reducing agent per liter of solution contains. BATHROOM 0RK3INAL 209881/0615 53. Photographic working solution according to claims 45 to 52, characterized in that it consists of an aqueous solution consists, which as a reduction part.) one of a priwären aromatic amine existing color developer compound and 2.) a from a hydroquinone, pyrocatechol, aminophenol, 3-pyrazol.idone, 1-, d- or isoascorbic acid or a reducing agent consisting of a silver halide reducing agent contains. 54. Photographic working solution according to claims 45 to 53, characterized in that it additionally contains a sulfite and Contains potassium bromide in concentrations customary for photographic working solutions. 55. Photographic working solution according to claims 45 to 54, characterized in that it consists of an aqueous solution which contains approximately: per liter of solution: 20 g of 4-amino-N-ethyl-N-3-hydroxyethylaniline sulfate as a color developing agent; 0.1 g of 1-phenyl-3-pyrazolidone;
40 grams of sodium sulfite;
0.5 g of potassium bromide; 2.5 g of a cobalt (III) complex and 8 g of ethylenediaminetetraacetic acid and their pH is adjusted to about 11 with sodium hydroxide. 56. Photographic working solution according to claims 45 to 49, characterized in that it additionally has at least one Contains photographic color couplers soluble in an aqueous alkaline solution. BAD ORfGINAL 209881/0615 57. Photographic working solution according to claims 45 to 49, characterized in that it is a reducing agent contains hardening or tanning developer compound. 53. The photographic working solution of claim 57, characterized in characterized in that they use 4-phenylcatechol as the developer compound contains. 59. Photographic working solution according to claims 57 and 58, characterized in that it contains sulfite ions to improve the stability to oxidation by light. 60. Photographic working solution according to claims 45 to 59, characterized in that it is a cobalt (III) complex Contains cobalt (IH) hexamine chloride. 61. Photographic recording material for carrying out the process according to claims 1 to 44, consisting of a layer support and at least two separate, color-forming units applied to it, each with a light-sensitive silver salt and a color coupler, characterized in that the color coupler is at least 40 % - igen stoichiometric excess, based on the developable silver, is present. 62. Photographic recording material according to claim 61, characterized in that each of the color-forming units contains the silver salt in a concentration of up to 30 mg Ag per 0.0929 m ² support surface. 63. Photographic recording material according to claims 61 and 62, characterized in that one of the color-forming units is a green-sensitive silver halide emulsion layer BAD OFUGiNAL 209881/0615 and a magenta dye forming dome One and another color-forming layer includes a red sensitive silver halide emulsion layer and one blue having green dye-forming color couplers. 64. Photographer's record keeping according to claims 61 to 63, characterized in that daiJ. the silver halide eye sion layers of the color-forming units the silver halide in a concentration corresponding to 1 to 30 mg Ag contained per 0.0929 m of support area and that the color couplers are each present in a concentration that is 3 to 20 times the weight of silver. 65. A photographic recording material according to claims 63-64, dadurclijgekennzeichnet that each of the color-forming units having a Silberhalogenidemulsionsscliicht in which after complete Kxponierun "· and 1 minute of development in a developer of 33 ° C (100 ⁰ F) of the composition specified in the following : Benzyl alcohol 10 ml K ₂ SO ₃ 2 κ KBr 0.4 g Hydroxylamine sulfate 2 g 4-amino-N-ethyl-N- (2-methoxy- ethyl) -m-toluidinedi-p-toluenesulfaonate 5 g K ₂ CO ₃ 30 g Ethylenediaminetetraacetic acid,
Tetrasodium salt 5 g made up to 1.0 liter with water pH = 10.1 less than 30 mg of metallic silver per 0.0929 m of support surface to be developed. BAD ORK3INAL 2 0 9 8 8 1/0615 66. Photographic recording material according to claims 61 to 65, there, characterized by the fact that there are color-forming units with Silberhnlogenidemulsiousschichten has opposite are sensitive to blue, green or red light, and that at least two of the color-forming line units are image dyes generating color couplers in a, based on the syllable of the lines, at least 40 "stoichiometric Contain excess. 67. Photographic recording material according to claims 61 to 66, characterized in that the color couplers in at least two of the color-forming units are based on one on the silver of the units, at least 70 "jigen stoichiometric Surplus are included. 68. A photographic recording material according to claims 61 to 67, characterized in that the color coupler of farhbi 1.! Forming Linheiten are selected such that they provide image dyes with Lichtabsorptionscbarakteristika that Λοη primary effective light sensitivities of the Silberhfilogenide of the units are substantially complementary. 60. Photographic recording material according to claims 61 to 68, characterized in that each of the color-forming units has a silver halide emulsion layer which develops at least 50 % of its image silver in 30 % of the time required to add 95 % of the developable silver to the layer to develop. 70. Photographic recording material according to claims 61 to 69, characterized in that each of the color-forming units has a silver halide emulsion layer, the silver halide grains of which have an average grain diameter of less than 0.8 microns. BAD ORK31NAL 20 9 881/0615 AU, 71. Photographic recording material according to claims 61 to 70, characterized in that there is at least one Contains antifoggants. "':. ,'! ο to * rapl. is - ', it Auf'zeichi.ungsina t.-ri al n.icii claims oil his 71, daduiv.i - \ ι ·' Ί ennze icuiiet that joi. it- -tr colors i] ucnuη LinheLten a '■ il'? ιϊ; έ, 1 u ^ cmj i Jer.-uls ionssc.ucl.ti: .with such a Silbeiiu: lo <: eiu ι. .U 1 eating ^ u Γι / t: i .s 1, da f. ' After exposure and from I 1 it .irK-Li.ct 'i developed a n.ixir.al overdensity of less than Ο, ί, preferably less than 0.2, and that the color couplers are present in a concentration that is necessary for the generation of a r'urbsto f fuirlite of iuinUest ens 1,7, preferably ι: i iid at least 2, u, awsi eic! it. '■ "i. Rhotographis /'ches' vufzeic.inun ^ sr.alerif.l ni.u: ii Aiisprüchet. M to 72, best ^ eii! One of a. Schient carrier.; Iit jiierauf uueretnander au ft, et ru _; ; onon bl;: u-, r, π "'η- unJ ι vi einpi i nul i cliei: Silberlia lo ^ eii iiiei..il s iohi'.scli ic! ten, e.ie a ^ oibc-i., eii.cn purj't: rroten bzv ;. a blue; · green Vc rl .s te f. "forming Γ <.: γο-isippJer contain ■, u thus j ekenuze i ciino t, uaiJ r.iinuestei.s two of the Silberhaloyeni demulsionssch i hurried nacii completely lieltchtunp and development results in an iniixiiiuile direction of less than 0.4, preferably less than 0.2, and that the color couplers in each of these layers are present in a concentration which is necessary for the production of a color density of at least 1.7, preferably at least 2 , 0, is sufficient. - !. Photographic recording material according to claims Eq to 73, consisting of a substrate on which the are plotted in the following order: a color-forming line (u) with a blue-sensitive one Silver halide emulsion class and one yellow dye-providing color coupler; BATHROOM 0RK3INAL 209881/0615 Ml cine color-forming unit (b) with a green-sensitive one Silver halide emulsion layer and a magenta dye 1 icferuden color coupler; a color-forming unit (c) with a red-sensitive one Silver halide emulsion layer with a one blue-green dye-providing color couplers, characterized in that 1.) at least the color couplers of the color-forming units (b) and (c) are present in these units in an at least 40 ~ i, stoichiometric excess, based on the developable silver, and that 2.) the concentration of the developable silver halide is at least in the silver halide emulsion layers of the color-forming units (b) and (c) up to 30, preferably less than 15 mg per 0.0929 m ^{2 support} area. 75. Photographic recording material according to claims 61 to 74, characterized in that the silver halide of the silver halide emulsion layers is less than 3 mol% consists of iodide. 76. Photographic recording material according to claims 61 to 75, characterized in that each of the color-forming units has a non-diffusing, optionally in a common solvent for the solution or dispersion of color couplers dissolved or dispersed · color coupler contains. 77. Photographic recording material according to claim 76, characterized in that the color couplers are dissolved or dissolved in dibutyl phthalate or tricresyl phosphate as the coupler solvent. present dispersed. ' ^: BAD' ORIGINAL 20 9 8 8.1 / 0615 78. Photographic recording material according to claims 61 to 77, characterized in that at least one of the color-forming units, preferably all of the color-forming units Units containing a silver halide antifoggant capable of forming a silver salt which is present in Water is more soluble than silver bromide. 79. Photographic recording material according to claims 71 and 78, characterized in that at least one of the color-forming units is an antifoggant based on azole · or Contains azide base. 80. Photographic recording material according to claims 71, 78 and 79, characterized in that it contains a tetrazole, triazole or azaindene as antifoggant. 81. Photographic recording material according to claims 71 and 78 to 80, characterized in that it is the antifoggant in a concentration of 20 mg to 2 g per Contains moles of silver. 82. Photographic recording material according to claims 61 to 81, characterized in that the silver halide emulsion layers of the color-forming units consist of direct-positive silver halide emulsion layers. 83. Photographic recording material according to claims 61 to 81, characterized in that the silver halide emulsion layers of the color-forming units consist of those of the negative type. 84. Photographic recording material according to claims 61 to 84, characterized in that the color-forming units contain color couplers which react with the Oxidation products of color developing agents produce non-diffusing image dyes. BAD ORKaINAL 20988 1/0615 Blank page