DE2214381A1 - Coloured photographic images - by transferring colourless reagent from exposed silver halide emulsion to form image in register - Google Patents

Abstract

Coloured transfer images are produced by (a) imagewise exposing with electromagnetic radiation of a photographic material contg a silver halide emulsion layer which is sensitive or sensitised towards the electromagnetic radiation, and contains a developer which is diffusion resistant and is in a hydrophilic colloid medium, and contains, in active contact with the developer, at least one colourless reagent which is capable of (1) diffusing in an aqs. alkaline medium from this material to a receiving material, (2) forming a dye by oxidative, intermolecular or intramolecular coupling with another colourless reagent which can also diffuse in an aq. alkaline medium, and (3) forming with the oxidn pdt of the developer a cpd which is considerably more diffusion resistant than in the unreacted state, (b) contacting the exposed photographic material with an aq. alkaline activating liq in order to promote the reducing action of the developer, so that in the exposed parts a silver image and an oxidn pdt of the developer are formed this oxidn pdt coupling with the colourless reagent so as to form in the exposed parts of the emulsion layer one or more cpds which are more diffusion resistant than the unreacted reagent, and (c) transferring from the heated material an amt of reagent(s) which is capable of diffusion through an alkaline treatment liq to a registering material on which the transferred reagent is oxidatively coupled with an oxidant which is stronger than exposed silver halide, so that a coloured image is formed on the receiving material.

Description

Photographic processes for the production of color images.

The invention relates to photographic methods of manufacture of color images and on photographic materials for use in such processes.

There are different techniques for making both monochromatic ones as well as multicolored images through image-wise diffusion transfer of compounds has been proposed to be contained in one of the photographic processing fluids are soluble.

Among these methods is the one that is called upon to use Dye developer established is of practical importance.

In one such method, as disclosed, for example, in U.S. Patent 2,983 606, a silver halide photographic material is used containing a reagent which is a dye having a developing function and which, when oxidized, is a reaction product in a processing liquid of lower solubility than the unreacted reagent. By looking at This property of the dye developer supported, a F arb-Dif fusionsüb transfer process realized, which allows the production of positive, monochromatic or multicolored copies made possible, starting from a single-layer or Multilayer silver halide material, the appropriate dye developing agent contains.

A multilayer color photographic material suitable for use useful in this process has silver halide emulsion layers which for blue, green or

red light are spectrally sensitive and contains three alkali-permeable Colloid layers, each one of the emulsion layers being adjacent and one contains different dye-developing agent of a color that is complementary is to that for which the adjacent silver halide emulsion layer is spectral has been sensitized. One such multilayer color photographic material is not suitable for reflex exposure, as every dye developer layer is used as a an absorption layer for the reflected light acts, opposite the corresponding one Silver halide emulsion layer is sensitive.

According to the present invention, a photographic material contains that for use in a process for the preparation of dye images by image-wise diffusion transfer of compounds is suitable, which in an alkaline, are soluble in aqueous process fluids, photosensitive silver halide grains, dispersed in a hydrophilic colloid layer, and contains in or in water-permeable Relationship to such a layer at least one colorless reagent, which by an oxidative Coupling reaction to form a dye and in an aqueous, alkaline medium this material can diffuse to a receiver material. The photographic Material also contains a developing agent in effective contact with the silver halide grains, which is resistant to diffusion in a hydrophilic, colloidal medium, and that if it in the presence of an alkaline, aqueous liquid after the pictorial Exposure of the layer is activated, the exposed silver halide in the layer reduced and in the oxidized state with the colorless reagent couples to his Diffusion from the exposed parts of the photosensitive material into the receiver material to prevent.

The method of forming transfer color images according to the present invention Invention comprises the following steps (a) The imagewise exposure with electromagnetic Radiation, a photographic material containing a silver halide layer, those in effective contact with the silver halide grains that are sensitive or to which electromagnetic radiation has been sensitized, a developing agent possesses, which is resistant to diffusion in a hydrophilic, colloidal medium and which at least one colorless reagent in effective contact with the developing agent which is capable of (1) in an aqueous, alkaline medium from the material to one Diffuse receptor material, (2) by oxidative, intermolecular, or intramolecular Coupling, or by coupling with another colorless reagent, does the same is able to diffuse in an aqueous, alkaline medium to a dye and (3) a compound with the oxidation product of the developing agent to form, which has a much weaker diffusivity than in unreacted State, (b) the establishment of contact between the exposed photographic material and an aqueous alkaline activating liquid to perform the reduction activity of the developing agent so that it becomes visible in the exposed parts Form a silver image and an oxidation product of the developing agent, which is mixed with the colorless reagent (or the reagent) couples to the exposed parts of the Emulsion layer to form one or more compounds, which are a much weaker Diffusibility than the unreacted reagents have, (c) the transfer of a certain amount of the reagent molecules that remained diffusible from the so treated Material by means of the alkaline processing liquid to a receiver material, whereupon transferred, reagent molecules intermolecularly or intramolecularly oxidatively coupled or different reagent molecules oxidatively with help an oxidizing agent, said agent being a stronger oxidizing agent as exposed silver halide, resulting in the formation of a dye image results on the receiving material.

According to a first embodiment of the invention, the photosensitive Layer a pair of different, colorless reagents, or called A and B, for the formation of a dye by oxidative coupling and a developing agent, to develop this layer and to form an oxidation product, which is the diffusion prevented by at least one such reagent.

According to a second embodiment of the invention, the photosensitive Layer a colorless reagent for the formation of such a dye by oxidative, intermolecular or intramolecular coupling as well as a developing agent around them Layer to develop so that an oxidation product is formed, which is the diffusion this reagent prevented.

If a photosensitive layer is used, consider using it is suitable in accordance with the first embodiment, comprises the method of formation of a dye image by image-wise transfer of color-forming reagents the following steps (a) the imagewise exposure of a photographic material containing a silver halide emulsion layer which is in effective contact with the photosensitive silver halide grains has a developing agent which is contained in a hydrophilic colloidal medium which is resistant to diffusion and which is in effective contact with the developing agent contains a pair of colorless reagents that are present in this Medium by means of the aqueous alkaline liquid can diffuse and capable are to form a dye with one another by oxidative coupling, with at least one of these reagents is capable of reacting with the oxidation product of the developing agent a compound with much weaker diffusibility than in unreacted Condition to form (b) making contact between the exposed Absorption material and an aqueous, alkaline, activating liquid to to initiate the reduction activity of the developing agent, so that in the exposed parts a silver image and an oxidation product of the developing agent form, which couples with at least one of the colorless reagents to form in the emulsion layer to form a compound that has a much weaker diffusivity than the unreacted reagent has, (c) arrangement of the recording material thus treated in close relation to a receiving material so as to avoid the remaining, unaffected, transferring color-forming reagents by means of the processing liquid, and bringing about oxidative coupling of such reagents in or on it Receiving material by an oxidizing agent, which is stronger than that exposed Silver halide is what gives rise to the formation of a dye image in the receiving material (d) separating the photographic material from the receiving material.

By "effective contact" it is meant here that the substances that must cooperate in processing the exposed recording material, present in the recording material at the right time and in the right place must be in order to be able to effect the formation of the image in the desired manner.

If only one silver halide emulsion layer with the associated If developing agent and color-forming reagents are present, the process will result to form a monochromatic image. However, the photographic material can contain many photosensitive layers that are in different spectral domains are sensitive, and it may contain connected pairs of color domes, as above has been performed so that a multicolor image of a multicolor original on a Receiving material can be generated.

According to the first embodiment of the present invention, can a dye image of a single color on a receiving material by a photosensitive Recording material are formed, the a sheet-like support and a contains hydrophilic, colloidal silver halide emulsion layer, which in effective In contact with the silver halide, a p-phenylenediamine type non-diffusible developing agent and a mixture of a dye-forming compound A and a dye-forming compound Compound B contains both of which are able to escape from their hydrophilic colloid layer diffuse away by means of an alkaline, aqueous liquid.

Both compound A and compound B are in the same silver halide emulsion layer locked in; or either or both of them may be included in a colloid layer which is below the silver halide emulsion layer, so that the compound or the compounds that need to be immobilized by the oxidized Diffusion-resistant developing agents can be collected.

While in the production of the monochromatic images no measures must be taken to avoid unwanted coupling between separate, colorless, avoiding dye-forming reaction partners, this must be done in reproduction materials, by means of which multicolored images are to be produced is not the case. It is known to be able to produce an accurate multicolor print through a subtractive Multicolor reproduction system three dye images are formed in register which have the complementary colors yellow, purple or blue-green.

In a multicolor reproduction material used in the manufacture of Multi-color printing according to the present invention is suitable, the colorless, dye-forming reagents grouped into three pairs in which the reagents of each different pair on the receiver by oxidative coupling form a dye of a different complementary color, namely yellow, purple or blue-green.

In the practice of producing multicolor prints, the reactants must by each pair of partners who have not been visually immobilized Reaction with the developer oxidation product will be the same for each pair since otherwise the oxidative coupling between the visually transferred and the overall transferred Coupler, which occurs for all pairs according to the same reaction mechanism the receiving material would give wrong colors from oxidative coupling of a partner of a couple with a matchmaker of another couple.

However, it is in the case when both reactants during the Development have been immobilized, no matter what type of reagents is common to all couples.

The photographic material includes in or in any light-sensitive Layer a diffusion-resistant developing agent which under the conditions photographic processing-capable, preferably exposed silver halide to reduce to silver, i.e. an Iiatentbild in an exposed silver halide emulsion to develop.

If a photosensitive layer is used, that is for the use is suitable according to the second embodiment, the method comprises the formation of a dye image by image-wise transfer of color-forming reagent following steps (a) the imagewise exposure of a photographic material containing a silver halide emulsion layer which is in effective contact with the photosensitive silver halide grains has a developing agent contained in a hydrophilic colloidal medium which is resistant to diffusion and which is in effective contact with the developing agent contains a colorless reagent, which in this medium means the aqueous alkaline liquid can diffuse and is capable of oxidative intermolecular or intramolecular coupling to form a dye, and with the oxidation product of the developing agent a compound with much weaker diffusivity than it has in the unreacted state, to form, (b) the establishment of contact between the exposed recording material and an aqueous alkaline activating liquid to perform the reduction activity of the developing agent so that it becomes visible in the exposed parts Silver images are an oxidation product of the developing agent which forms with the colorless reagent couples to form a compound in the emulsion layer, which has a much weaker diffusivity than the unreacted reagent, (c) Arranging the recording material thus treated in close relation to one Incoming material, including the remaining, unaffected, color-forming reagents by means of the processing liquid, and bringing about a oxidative coupling of such reagents by an oxidizing agent, which is stronger than the exposed silver halide, resulting in the formation of a dye image in the Receiving material gives rise to (d) separation of the photographic material from the receiving material.

By "intermolecular, oxidative coupling, it is meant that two separate molecules of the colorless, dye-forming reagent oxidatively with each other couple to form a dye molecule.

By "intramolecular" oxidative coupling it is meant that two reactive parts of the same molecule of the colorless, dye-forming reagent oxidatively are coupled and form a dye molecule. Connections of one of these types of coupling are illustrated later by a specific example.

The colorless, color-forming reagents for intermolecular and intramolecular Coupling can be viewed as if it were made up of two chemically bound structural parts C1 and C2 exist, which form a compound which of the general formula 2 corresponds to C1 couples oxidatively with group C2 in the intermolecular reaction a second molecule C1-02; couples in the intramolecular reaction after a Rearrangement oxidatively with group C2 of the molecule to which C1 itself belongs.

Now that we have understood the principles of the invention and some preferred Embodiments and materials described and an introductory explanation Having given its applicability, we now provide details of preferred substances which are used in the present photographic process.

In a preferred embodiment of the present invention uses a silver halide developing agent derived from silver halide color photography is known and resistant to diffusion. It is able to work with a phenol type or reactive methylene group type Barb coupler. Such a developing agent is preferably an aromatic, primary amino developing agent, which in one hydrophilic, colloidal medium has been made substantially resistant to diffusion and which, in the oxidized state, forms a diffusion-resistant coupling product with a color-forming one Forms reagent which itself is not diffusion-resistant and one or more active ones Contains hydrogen atoms. Such a reagent forms upon diffusion into the receiver with its color-forming reaction partner a dye through oxidative coupling.

Preferably used developing compounds are of the p-phenylenediamine type and correspond to the following general formula 1.

in which R1 and R2 each represent an aliphatic group inclusive a substituted, aliphatic group, optionally any of these groups is substituted with a polar group such as an acid group such as a hydrophilic colloid like gelatin gives substantivity, and / or homogeneous distribution the compounds in a hydrophilic, colloidal medium facilitated. Preferred Groups are a sulfonic acid group, a carboxylic acid group or an alkylsulfonylamino group; or R1 represents the necessary methylene groups including substituted methylene groups represents a 5- or 6-membered, heterocyclic nucleus with the carbon atom to close in the 6-position of the benzene nucleus; or R2 provides the necessary Methylene groups including substituted methylene groups to form a 5- or 6-membered, heterocyclic nucleus with the carbon atom in the 2-position to close the benzene nucleus; or R1 and R2 together represent the necessary methylene groups including substituted methylene groups to a 5-membered, nitrogen-containing To close the core, R3 has the same or different substituents such as hydrogen, or substituents that have an influence on the properties, such as development capacity, Have binding force with the hydrophilic colloid or solubility in water, such as a or more alkyl groups z.I3. one or more methyl groups or an alkoxy group, like methoxy or xthoxy, with the condition that R3 in the cases where it is not Represents hydrogen, to the f- and / or 5-position, which are given above, is limited, and wherein the developing agent has one or more substituents Contains that in a hydrophilic colloidal medium for the desired diffusion resistance care for; e.g. at least one of the substituents contains more than four carbon atoms in a straight line #.

The free amino group in the above-mentioned p-phenylenediamine type compound may be with an alkyl group including a substituted alkyl group or an alkylene group which is ring-bonded in the specified 3-position is. The free amino group can be blocked in a reversible manner, e.g. by substitution with an alkyl group, which is further with an anionic group is substituted, e.g., a sulfonic acid group, a carboxylic acid group or a hypophosphorous acid group, such as in British Patents 691,815 and 783 887 and Belgian patents 535 687, 535 688 and 557 556 is.

Other reversibly blocked p-phenylenediamine-type developing agents, in which the free amino group reacts with an aldehyde to a Schiffsche Forming base are disclosed in US Pat. No. 2,507,114 and in French Patent 983 022 described. Other reversibly blocked p-phenylenediamine-type developing agents contain a phthalimide group as in U.S. Patents 2,911,410 and 2,930 693 is described.

Trialkyl-p-phenylenediamine and ikre are manufactured in the Belgian U.S. Patent 532,736.

The preparation of other p-phenylenediamine type developers according to the general Formula is known, for example, from British Patents 989,383 and 1,191,535. The introduction of a long, aliphatic chain (containing at least 4 carbon atoms in a straight line) can be carried out according to methods used in the manufacture used by non-diffusing color couplers.

The preparation of preferably used, non-diffusing p-phenylenedi amine-type development agents is described in German patent applications P 1931057.7 and P 2032711.1. Preferably used p-phenylenediamine non-diffusing developing agents are represented by the following general formula in which R1 denotes hydrogen, an alkyl group, preferably a C1-C5 alkyl group, e.g. methyl or methyl, or an alkoxy group, preferably an alkoxy group containing at most 3 carbon atoms, e.g. methoxy or ethoxy, R2 hydrogen or an alkyl group, preferably a C1 -C5-alkyl group, e.g. methyl or ethyl, R3 is a long-chain, aliphatic group, preferably a C8-C20-alkyl group, but mostly dodecyl, heptadecyl or octadecyl, X is hydrogen, a sulfonic acid group, a carboxylic acid group, a hydroxyl group or a sulfonamide group in which the amide group can be substituted with a short-chain alkyl, for example methyl or ethyl, n the numbers 1 to 4.

Particularly suitable, non-diffusing p-phenylenediamine-type developers are listed in Table 1 below The p-phenylenediamine type non-diffusing developing agents, which are also called primary developing agents herein, are preferably used in combination with another reducing agent (ie, an auxiliary developing agent) which increases the developing speed. In this regard, we refer to pyrazolin-3-one developing compounds which can be added to the photosensitive material and / or to the alkaline activating bath and which, for example, conform to the following general formula in which R1 is an aryl group including a substituted aryl group, for example phenyl, R2 is hydrogen or an acyl group such as acetyl, R3, R4, R5 and R6 (identical or different) are hydrogen, an alkyl group including a substituted alkyl group or an aryl group including a substituted aryl group.

Good results are obtained with the following auxiliary development compounds, those of the above formula III correspond to: 1-phenylpyrazolidin-3-one 1- (m-tolyl) -pyrazolidin-3-one 1-phenyl-2-acetyl-3-pyrazolidin-3-one, 1-phenyl-4-methyl-3-pyrazolidin-3-one, 1-phenyl-5-methyl-3-pyrazolidin-3-one 1-phenyl-4,4-dimethyl-3-pyrazolidin-3-one, 1-phenyl-5,5-dimethyl-5-pyrazolidin-3-one 1,5-diphenyl-3-pyrazolidin-3-one 1- (m-tolyl) -5-phenyl-3-pyrazolidin-3-one 1- (p-tolyl) -5-phenyl-3-pyrazolidin-3- on Pyrazolidin-3-one developing compounds can be prepared by the methods described in UK Patents 679,677, 679,678 and 703,669 and in U.S. Patent 2,772,282.

Other reducing agents which have the developing activity of the p-phenylenediamine type developing agent Enable are development compounds used in superadditive development as in British Patents 989,383, 1,191,535, 1,003,783 and 1 154 385 has been described.

Particularly good results are obtained with the following auxiliary development tools: When the auxiliary developing agents are used in the activating bath, they are preferably used in an amount of 50 mg to 2 g per liter.

In the first embodiment, a non-diffusing one is preferred p-phenylenediamine type developing agent used in combination with two reagents, capable of diffusing in an alkaline, hydrophilic, colloidal medium and in an alkaline medium by the action of a stronger oxidizing agent than exposed silver halide can couple oxidatively, so that a dye is formed which contains an azine group (= N-N =).

One of the reagents, which will later be called compound A, is capable of interacting with the non-diffusing oxidation product of the p-phenylenediamine type developing agent to couple so that the coupling product is prevented from turning into a receiving material to diffuse.

For example, compound A can be any compound that is suitable is to act in a dye-forming electrophilic substitution reaction; the diazo coupling is mentioned here as an example.

Compound A is preferably a compound of the type of one Quinone imine or azomethine dye with an oxidized N, N-dialkyl-p-phenylenediamine generated. Such compounds are well known to those skilled in the art and are used e.g. by Pierre Glafkides in Photographic Chemistry, Volume II- Fountain Press London (1960) on pages 596-604.

Suitable compounds A are e.g. «; Naphthol, phenol, reactive methylene type and reactive methyl couplings; i.e., diazo couplers such as those described in French patent specification 1 602 473 have been described. The compounds must have a chemical structure that allows them to use an alkaline, aqueous liquid diffuse in a hydrophilic colloidal medium such as gelatin.

To determine the rate of diffusion in an alkaline, hydrophilic, To improve colloidal medium, it is desirable that the coupling molecules a Contain carboxylic acid group or sulfonic acid group.

Useful couplers (for use as Compound A) are particularly the phenolic couplers which correspond to the following general formula in which R1 and R2 each represent a hydrogen atom, an alkyl group including a substituted alkyl group, an alkoxy group including a substituted alkoxy group or the group -NHR, in which R is a carboxylic acid acyl group or sulfonic acid acyl group including the groups in the substituted state, for example an aliphatic carboxylic acid aggro, a aromatic carboxylic acid acyl group, a heterocyclic carboxylic acid acyl group, for example a 2-furoyl group, or a 2-thienoyl group, an aliphatic sulphonic acid acyl group, an aromatic sulphonic acid acyl group, a sulphonylthienyl group, an aryloxy-substituted or phenyl-substituted carboxylic acid-substituted, aliphatic carboxylic acid-tolacyl-acyl group, a phenyl-substituted carboxylic acid-tolacylacyl group, a phenyl-substituted carboxylic acid acyl group, an aliphatic carboxylic acid group with the proviso that R1 and R2 do not represent hydrogen at the same time and the substituents are not of such a type that the diffusion of the phenolic compound in an alkaline, hydrophilic, ko illoidal medium is noticeably hindered. A polar substituent, such as a carboxylic acid or a sulfonic acid group, is preferably present as a substituent in order to improve the mobility of the phenolic couplers in the medium.

The manufacture of the color couplers within the above general formula is used, for example, in U.S. Patents 2,772,162 and 3,222 176 and in British Patent 975,773.

Examples of suitable phenol-type couplers are given in the following Table 2 listed.

Table 2 Usable couplers are also α-naphthol-type couplers, in particular α-naphthol-type couplers, which correspond to the following general formula: in which R represents an alkyl group including a substituted alkyl group, an aryl group including a substituted aryl group, preferably groups which are substituted by a carbonic acid or sulfonic acid group.

These ok-naphthol type couplers are produced, for example, by a condensation reaction made by the phenyl ester of 1-hydroxy-2-naphthoic acid and the associated Amine used.

Examples of useful ot-naphthol couplers are given in the following Table 3 listed.

Table 3 Suitable reactive methylene type couplers correspond to one of the following general formulas in which R1 and R2 (identical or different) each denote an alternative group including a substituted alkyl group, an aryl group including a substituted aryl group, an N-arylamino group including a substituted N-arylamino group or an Xether group including a substituted ether group, e.g. an alkoxy group, R ' an alkyl group including a substituted alkyl group or an aryl group including a substituted aryl group, R "an alkyl group including a substituted alkyl group, an aryl group including a substituted aryl group, carbethoxy, an alkoxy group, cyano, an N-arylamino group including a substituted N-arylamino group, an N -Acylamino group including a substituted N-acylamino group or an ureido group including a substituted ureido group.

Vericdren for making reactive methylene type couplers can e.g. can be found in the references provided by F.Glafkide's in his book "Photographic Chemistry ", Volume II (1960), pages 597-602, entitled" Yellow Couplers "and "Magenta Couplers" are given as well as in British Patents 934 017, -1 062 203, 1 039 965, 1 007 847, 1 066 334 and 1 069 533.

Preferred reactive methylene type couplers are shown in the table below 4 listed.

Table 4 To illustrate the preparation of the open chain ketomethylene type couplers, the preparation of Compounds 9, 10 and 11 of Table 4 is described.

Compound 9 A mixture of 31.4 g (0.15 mol) of dimethyl 5-aminoisophthalate and 31.7 g (0.165 mol) of ethyl benzoylacetate dissolved in 165 ml of p-xylene is 4 hours heated on the reflux condenser. The resulting ethanol (about 9 ml) is by application a fractionation column, which is provided with a dephlegmator, distilled. Then the reaction mixture is in a mixture of finely ground ice and Sodium chloride cooled.

The crude, reactive methylene coupler separates as an oily product which becomes crystalline upon stirring. The product is separated off by filtration, washed with cyclohexane and dried in a vacuum of 1 mm Hg at 50 ° C.

Yield: 49 g or 90%.

Melting point: 15500.

Compound 10 A solution of 46.5 g (0.13 mol) of compound 9 from of Table 4 in a mixture of 465 ml of ethanol and 30 ml of 5N aqueous sodium hydroxide is heated for 5 hours on the reflux condenser with stirring. The precipitate formed, which is the product obtained by complete saponification sucked off and removed. A mixture of 500 ml of water and 50 ml of concentrated Hydrochloric acid is slowly added to the filtrate with stirring, whereupon the precipitate formed is separated off by filtration and dried.

The crude product is purified by crystallization with acetic acid and washed the crystals with chloroform. Purification is by recrystallization continued with n-butanol.

Yield: 35%.

Melting point: 214,000.

Compound 11 A solution of 46.5 g (0.13 mol) of compound 9 of the Table 4 in a mixture of 465 ml of ethanol and 120 ml of 5N aqueous sodium hydroxide is heated for 5 hours on the reflux condenser with stirring and then with concentrated Acidified hydrochloric acid. The precipitate formed is sucked off and washed with methanol. The crude product is boiled three times in fresh n-butanol and finally washed with chloroform.

Yield: 79%, melting point> 2600C.

Other suitable couplers are - N, N-dialkylanilines of the diffusing one type which has an acid substituent or as a further substituent of one of the alkyl groups contain a substituent containing an acid group.

The acid group can be present as a free acid or in salt form, for example a sulfonic acid substituent. The N dialkylanilines couple with an oxidized N, N-dialkyl-p-phenylenediamine-type developer and form a quino-diiminbetainypsaz according to the following reaction scheme in which M denotes hydrogen, a metallic cation or a cationic group, for example an -onium group, Y denotes a divalent organic group, for example an alkylene group, and R denotes an alkyl group.

The dialkylanilines can after the known alkylation reactions for anilines.

Useful N, N-dialkylanilines of the diffusing type are listed in Table 5 below Reagents, which are hereinafter referred to as compounds B and which by oxidative coupling with the above-described compounds A form a dye which contains an azine group (= NN =), are heterocyclic hydrazone compounds of the type which have diffusibility in an alkaline, hydrophilic, colloidal medium. Useful heterocyclic H-drazon compounds correspond to the following general formula in which denotes a -CONH2- or -SO2X group in which X is hydroxyl, an amino group including a substituted amino group, an alkyl group including a substituted alky group, an aryl group including a substituted aryl group, Z are the atoms necessary to form a 5- or To close a 6-membered, heterocyclic nucleus or a 5- or 6-membered, heterocyclic ring system, including such a nucleus or ring system in substituted form.

Preferred heterocyclic hydrazone compounds correspond to the following formula in which R1 as in formula X, R2 denotes a hydrogen atom, an aliphatic group including a substituted aliphatic group, e.g. an alkyl group including a substituted alkyl group, or an aromatic group including a substituted aromatic group, e.g. an aryl group including a substituted aryl group, L is a methine group or a nitrogen atom, N is the number 1 or 2, Z1 is the atoms necessary to form a 5- or 6-membered, heterocyclic, nitrogen-containing nucleus or a 5- or 6-membered, heterocyclic nitrogen-containing ring system, including one Nuclear or ring system in substituted form, for example a 2-benzothiazolylidene nucleus, a 2-indolinylidene nucleus or a 4-quinolinylidene nucleus.

With regard to an improved diffusivity in alkaline, These hydrazone compounds preferably contain hydrophilic, colloidal medium a carboxylic acid or sulfonic acid group.

Examples of useful hydrazone couplers are given in Table 6 The preparation of the ilydrazone compounds can be carried out by processes which are described, for example, in British patents 975,932, 990,628 and 1,068,595 and in US Pat. No. 3,293,032.

The synthesis of azine dyes by oxidative coupling is carried out by flünig described in the following publications, among others: Ang.Chem. 2 (1958), 215-222; Ann. 609: 143-160 (1957); Ann. 617, 203-210; Ann. 617: 216-220 (1958); Ann. 628, 69-75; Poor. 641: 104-112 (1961); Ann. Z, 77-82 (1961) and Ann. 651, 73-88 (1962).

The use of heterocyclic hydrazones in the formation of Dyes containing an azine group by oxidative coupling is e.g. S. Hünig in Angew. Chem. 2, 818-821 (1962) and Ann. 609: 160 (1957) Ann. 617, 181-202 (1958) Ann. 6-3: 191-203 (1959) Ann. 636: 21-51 (1960) Ann. 640, 98-110 (1961), Ann. 641: 94-103 (1961) Ann. fflg, 66-76 (1961), Ann. 651, 89-101 (1962) been.

Developing agents which, in an oxidized state, couple with the hydrazone compounds and can prevent these compounds from diffusing from a hydrophilic, colloidal layer to an input material, are aromatic 1,2-dihydroxy compounds which, when coupled with the hydrazone, form molecules of sufficient size, which in the hydrophilic colloid are immobile in which they are formed. Examples of such useful 1,2-dihydroxy compounds are shown in Table 7 below In order to produce a coupler molecule which has a sufficiently low diffusibility in a hydrophilic, colloidal medium, groups are introduced which improve the diffusion resistance. For this purpose organic groups are suitable which are photographically inert or at least do not give rise to fogging in a silver halide emulsion and which consist of or contain a straight or branched chain, aliphatic group of preferably at least 8 carbon atoms. Such groups can be attached to the compound that needs to be made diffusion-resistant, either directly through a carbon / carbon bond or through the intermediate groups, such as -CONH-, -S02NH-, SO-, -S02-, -O-, -S- or -NR-, where R is hydrogen or alkyl. However, the presence of a group which makes the developing agent molecule resistant to diffusion does not preclude the presence of one or more polar groups which improve the compatibility with the hydrophilic colloid and facilitate the homogeneous distribution of the developing agent in the hydrophilic colloid. Polar groups suitable for this purpose are, for example

Carboxyl groups and sulfonic acid groups in free acid or salt form.

In those cases where the molecule, which must be diffusion-resistant, is large enough (e.g. because there is more than one aromatic or heterocyclic nucleus and does not contain polar groups), is the introduction of long-chain, aliphatic Groups not necessary at all, or lower alkyl groups (C1-C4) are sufficient.

Apart from the hydrazones, which form azine dyes by oxidative coupling with, for example, a-naphthol, phenol or reactive methylene type couplers, other oxidative dye-forming compounds can be used, which are known, for example, from photographic, integral masking techniques, after which a dye image by oxidative coupling in a potassium cyanide (III) bleach bath. In the case of these colorless compounds, we refer, for example, to 4-aminopyrazolones, which correspond to the following general formula in which R1 and R3 each denote an alkyl group of at most 5 carbon atoms and an alkyl group of at most 5 carbon atoms, a phenyl group including a substituted phenyl group.

The preparation of 4-aminopyrazolones and their use in oxidative Coupling for mask use is disclosed in British Patents 880,862 and US Pat U.S. Patents 3,012,884 and 3,013,879.

Other suitable, oxidatively coupling, dye-forming compounds are p-phenylenediamines with sterically hindered amino groups and sterically hindered Phenols such as those described in British Patents 1,153,561 and 975,940, respectively became.

A multilayered photographic material suitable for use according to the first embodiment of the present invention for forming multicolor images by image-wise diffusion transfer of dye-forming reagents from one Photographic material useful in a receiving material includes: (1) one blue-sensitive silver halide emulsion layer which is a non-diffusing silver halide developing agent and a pair of colorless reagents in effective contact with the developing agent which are able to diffuse in the medium when mixed with an aqueous, alkaline liquid have been wetted and by oxidative coupling with each other to form a yellow dye. At least one of the reagents is capable of using the oxidation product of Developing agent connects to form, with a much weaker diffusivity than that Has reagent in an unreacted state, (2) a green-sensitive silver halide emulsion layer, which is a non-diffusing silver halide developing agent and is effective Contact with the developing agent contains a pair of colorless reagents that are capable are to diffuse in the medium when exposed to an aqueous, alkaline liquid have been wetted and are capable of forming a purple dye by oxidative coupling with each other to build. At least one of the reagents is capable of working with the oxidation product of the developing agent to form a compound with one essential weaker diffusivity than the reagent has in the unreacted state, (3) a red-sensitive silver halide emulsion layer which is a non-diffusing one Silver halide developing agent in effective contact with the developing agent contains a pair of colorless reagents capable of diffusing in the medium, if they have been wetted with an aqueous, alkaline liquid and are capable are to be formed by oxidative coupling with each other to form a blue-green dye. At least one of the reagents is capable of interacting with the oxidation product of the developing agent to form a compound, with a much weaker diffusivity when it has the reagent in an unreacted state; and any reagent, which none Forms connection with a much weaker diffusivity than such Unreacted reagent is a reagent common to all reagent pairs is common.

In making multicolor prints with such photographic Material must be one of the reaction partners of each partner pair common to all pairs be, and those partners who are not together, must-respond with one or more oxidation products of one or more developing agents immobile be made. The partner that is common to all couples can be hydrophilic Colloid layers should be present, which lie against the silver halide sulphon layers.

Each silver halide emulsion layer can be from a different silver halide emulsion layer be separated by a suitable spacer layer, e.g. a layer of Gelatin or polyvinyl alcohol. The spacer layer can be used as a kind of permeable A barrier layer that prevents the diffusion of the dye-forming compound (s) controlled, e.g. a layer of slowly permeable material such as a layer of cellulose acetate hydrogen phthalate, occasionally in combination with one more water-permeable spacer layer, e.g. a gelatin layer.

In the already mentioned second embodiment of the present invention for multicolor reproduction by subtractive color photography, with yellow, purple and blue-green dyes are generated ~ will be three different compounds C1 C2 is used in which a group C1 or C2 is the same in these three compounds Structure or is of the same chemical type, that is, they are of the same chemical Reaction mechanism preferably with substantially the same reaction rate (e.g. electrophilic or nucleophilic substitution) follows.

Useful assortments of color forming reagents C1-C, for tricolor Materials with real color reproduction possibilities in multicolor photography contain the same structural, color-forming part and can, for example through the following assortments of chemically bound, reactive molecular parts A, B, C, X, Y and Z are represented A-X A-X A-Y or B - X A-Z G-X The C1-C2 connections, which are suitable for intermolecular or intramolecular coupling preferably have an oil chemically structural part that is capable of a quinotlimin - or azomethine dye structure with an oxidized p-phenylenediamine type developing agent to form, and a C2 chemically structural part, which is a hydrazone group contains, which enables the G1-02 compound under oxidative conditions, a To form dye that contains an azine group (= N-N =).

In particularly suitable C1-02 compounds, part C1 is a group which contains the structure of an α-naphthol coupler and corresponds to the following formula: or is a group which has the structure of a reactive methylene type coupler and corresponds to one of the following general formulas: XIIJ. -HN-CO-CH-CO-R -HN-CO-CH2-CN in ellen Rn represents an alkyl group including a substituted alkyl group, an aryl group including a substituted aryl group, an alkoxy group or a substituted amino group, for example an alkyl or aryl-substituted amino group, and an alkyl group including a substituted alkyl group, including an aryl group a substituted aryl # frup ## P, a cyano group, an alkoxy group, a carbonylalkoxy group, an N-arylamino group including a substituted N-arylamino group, an N-acylamino group including a substituted N-acylamino group or a ureldo group including a substituted ureido group but with the proviso that the substituents in these compounds are not of the type which markedly impede the diffusibility of the color-forming compounds in an alkaline, hydrophilic, colloidal medium.

According to a preferred embodiment, the part C2 in these C1-c2 compounds corresponds to the following general formula: in which Z denotes the atoms necessary to close a 5- or 6-membered, heterocyclic nucleus or a 5- or 6-membered, heterocyclic ring system, including such a nucleus or ring system in substituted form.

Particularly suitable C1-C2 compounds contain a group C2 which corresponds to the following general formula: in which denotes a hydrogen atom, an aliphatic group including a substituted, aliphatic group or an aromatic group including a substituted, aromatic group, L is methine or nitrogen, n is the number 1 or 2, Z1 is the atoms necessary to form a 5- or 6- to close a membered, heterocyclic nucleus or a 5- or 6-membered, heterocyclic ring system; the core or the ring system are either in substituted form or not.

Compounds which create a dye through oxidative, intramolecular coupling (with the exception of compound 18 which couples intermolecularly) and which contain a common naphthol-methylene coupler part C1 and a hydrazone part C2 are illustrated by the following examples in Table 8 below Compound melting point (° C) These compounds can be prepared by methods well known to those skilled in the art. The steps of preparation of Compounds 6, 14, 15, 16 and 17 are listed below for illustrative purposes. Preparation of Compound 6 Reaction Scheme The intermediate compound (III) (melting point 210 ° C.) has been prepared by a known process for the preparation of α-hydroxy-naphthoic acid anilene, starting from p-fluorosulfonyl aniline and the phenyl ester of α-hydroxy-β-naphthoic acid.

The intermediate compound (III) was left with hydrazine hydrate, which in Dioxane was dissolved, reacting to form a sulfonylhydrazine (IV) (melting point 245 ° C).

This sulfonylhydrazine (IV) was used in the preparation of the compounds 1 to 6 and 8 to 13 are used.

In particular, in the preparation of compound 6, the sulfonylhydrazine (IV) in a condensation reaction with 1-methyl-2-phenyl-6-fluorosulfonyl-4-chloro-quinoli.iuninethylsulfate applied, its flerstetlung in the Belgian patent 745 438 described is.

Compound 1 is converted from compound 6 by saponification of the fluorosulfonyl group made with sodium hydroxide.

Preparation of Compound 14 Reaction Scheme A 30.4 g of sulfonyl hydrazide (II) are dissolved in 300 ml of a mixture of chloroform and dry ethanol (volume fraction 1: 1).

The solution is left with 59 g of the quinolium compound (I) with stirring and reflux for 2 hours.

The solvents are then distilled; to become a residue Add 300 ml of a hydrochloric acid solution (10) in ethanol. The heating the reflux condenser is then continued for 4 hours. After cooling, the obtained The hydrochloride is separated off and washed with acetone. The hydrochloride is in a dissolved minimal amount of pyridine and poured into ten times the amount of water.

The product (III) obtained is first thoroughly washed with water and then washed with methanol.

Yield: 52.6 g.

Felting point: about 2400C.

Reaction scheme B 24.3 g (0.05 mol) of the amine (III) and 120 ml (0.7 mol) of the ester (IV) are heated on an oil bath at 1000.degree.

The reaction mixture is poured into 600 ml of p-xylene with stirring, the precipitate sucked off and thoroughly washed one after the other with p-xylene, light gasoline, Washed methanol and acetone and dried. The product (V) decomposes between 180-1850C.

Yield: 20.5 g.

Reaction scheme C Compound 14 20 g of the sulfofluoride (V), 33 ml sodium hydroxide (30% by weight in water) and 200 ml acetone are refluxed for 30 minutes while stirring.

The reaction mixture is cooled and the acetone from the separated, decanted oily product, which is washed twice with acetone, which in turn removed by decantation.

The oily product is dissolved in 40 ml of water. When adding 2N hydrochloric acid precipitates out a solid product which is separated off by suction filtration and washed with water until the acid is completely removed. After a Thorough washing with acetonitrile causes compound 14 to melt with decomposition 260 ° C.

Yield: 18 g.

Preparation of compound 16 Reaction scheme A solution of 4.9 g (0.03 mol) of the pyrazole compound (II) in 48.5 ml of acetic acid is added to a solution of 9.7 g (0.02 mol) of the amino compound (1) in 48.5 ml of acetic acid given. The reaction mixture is stirred for 5 hours at 200 ° C., after which it is poured into 1 liter of water, salted out and stirred for 30 minutes. The hydrochloride (III) obtained is separated off by suction filtration, washed with methanol and dried.

Melting point: 2100C (decomposition).

Yield: 12 g.

Establishing connection 17 11 g (0.0227 mol) of amino compound (I) are dissolved in a mixture of 70 ml of dimethylformamide and 5.5 ml of triisopropanolamine. 7.35 g of the pyrazole compound (II) dissolved in 40 ml of dimethylformamide are added to the resulting solution.

The mixture is stirred for 4 hours at room temperature and then an additional 3.67 g amount of the pyrazole compound was added. Roof will stirring continued for a further 2 hours.

The reaction mixture is then acidified with 2N hydrochloric acid and poured into 500 ml of water. The precipitation is sucked off and washed with water until neutral. Another thorough wipe with acetonitrile and methanol gives 7 g of the compound (III).

Melting point:> 260 ° C.

A particular advantage of the intramolecularly reactive compounds C1-C2 relies on the fact that the reactive parts C1 and C2 are the received material Reach in perfect stoichiometric amounts, so that practically no undesirable Color haze is generated in the diffusion transfer image and one is very clear Weiss receives.

Since two oxidatively color-forming parts are combined in one molecule, only one molecule of the oxidized developing agent is needed to produce the combined To immobilize parts. However, if these these parts separate connections represent, each of them must be at the expense of two molecules of the oxidized Developing agent and a correspondingly larger amount of silver halide immobile be made.

Because in this second embodiment only three color-forming reagents need to be transferred by diffusion, it is much easier to change the composition in a color equilibrium than in a process in which at least four Reagents can be used as in the first embodiment for multicolor reproduction the case is.

According to the second embodiment of the present invention for the formation of a dye image of an individual color on a receiver uses a photosensitive recording material which has a film seam contains a carrier and a hydrophilic, colloidal silver halide emulsion layer, which is in effective contact with the silver halide, a non-diffusing p-phenylenediamine type developing agent and the compound C1-C2 contains which of the hydrophilic ones is capable of Colloid layer by means of a hydrophilic colloid layer of an alkaline, liquid liquid igness tu diffuse.

Compound C1-C2 becomes in the same silver halide emulsion layer or in a colloid layer below the silver halide emulsion layer so that the connection that needs to be immobilized is replaced by the oxidized, non-diffusing developing agents can be blocked.

The silver halide of the photosensitive layer (s) can be any Be the type known in silver halide photography. For the production of a positive dye image on the image-receiving material becomes a silver halide emulsion of the negative type used. Silver halide emulsions are preferably used, wherein gelatin is the carrier for the silver halide. However, the invention can can be carried out with any other hydrophilic colloidal carrier suitable for the purpose known in silver halide emulsion preparation.

The silver halide emulsion layer composition can be spectral contain sensitizing agents.

Useful spectral sensitizing agents can be found in the Class of methine dyes, e.g. the cyanine dyes, hemicyanine, merocyanine, Oxonol, hemi-oxonol and styryl dyes and polynuclear methine dyes such as rhodacuanine dyes and neocyanine dyes. Such sensitizing agents are described by F.M. Hamer in his book "The Cyanine Dyes and Related Compounds", 1964.

Preferably used cyanine dyes have a betaine-like structure, which means they are not present on the nitrogen atom of at least one of the heterocyclic nuclei of an alkyl group Group in which R1 and R2 each represent a hydrogen atom or a carbon atom group; at least one of them is hydrogen.

Suitable spectral sensitizing dyes of this type are used e.g. in the German patent application P 2 117 054.7 and in the published, Dutch patent application 7004174.

Preferably used merocyanine dyes are the so-called Zeromethine and dimethine merocyanine dyes that have a barbituric or thiobarbituric acid nucleus such as in U.S. Patent 2,170,807 and U.S. Patent the DDR 12 477 is described.

The silver halide emulsion layer (s) may further include the usual ones Contain additives, such as anti-fogging agents, chemical, sensitizing Agents, stabilizers, development accelerators, plasticizers, hardeners and Wetting agents.

The photosensitive material can contain any type of support which is known for silver halide photographic materials, but preferably contains a flexible carrier, e.g. a paper or plastic film base in foil, fabric ' or band shape. A photographic material is used for reflex exposure purposes a transparent or semi-transparent (at least 50 ° / 0Li light transmission) Carrier used.

According to a preferred embodiment, the image-receiving material is a flexible plastic film or a paper sheet covered with a hydrophilic colloid layer is coated, which contains an oxidizing agent that is capable of oxidative To effect coupling of the couplers (as defined above) and has a structure which makes it difficult or impossible to diffuse the hydrophilic colloid layer to leave in an aqueous, alkaline liquid.

Examples of suitable oxidizing compounds are non-diffusing, organic peroxides, long-chain, (C8-C20) -aliphatic, -onium salts of peracids and compounds which easily split off halogen in an aqueous medium, such as halogen amides and imides; Examples thereof are bromosuccinimide and non-diffusing chloramine-T and dichloramine-T compounds. Examples of such compounds are listed in Table 9 Usable receiver materials contain in a hydrophilic colloid layer, for example enclosed in gelatin, an amount of 0.01-0.0.5 moles of dibenzoyl peroxide per m 2.

The image-receiving material may contain agents that serve as mordants can be used or otherwise fix the dyes, e.g. azine dyes by oxidative coupling. The image receiving material contains, for example, a polymer, preferably a cationic polymer used as a mordant for anionic dyes acts as described, for example, in British patent specification 1,221,195. That The caustic agent can be mixed with the oxidizing agent or in a layer which is adjacent to the layer with the oxidizing agent.

The aqueous, alkaline, activating liquid preferably has a pH value between 8 and -13 and contains e.g. from 10 to 50 g sodium carbonate per liter. It can accelerate development Contain compounds, viscosity controlling agents, e.g. hydroxyethyl cellulose, wetting agent1 and with Water-miscible, organic liquids to improve density of the dye image on the receptor material.

The activating liquid can be applied to the photosensitive material after its exposure by any known technique of application of liquids can be applied to film materials, e.g. by spreading, soaking, liquid Coating or spraying, and similarly applied to the image receiving material are before the latter and the photosensitive material in superimposed Relationship or contact is brought to the diffusion transfer of the oxidative performing coupling connections from the undeveloped parts.

The alkaline agent can also be in sachets or in pressure-breaking Microcontainers are added, e.g. in microcapsules, which on contact with the recipient material to be emptied.

When producing a multicolor image according to the first embodiment of the present invention by selective, image-wise, modulated diffusion transfer the appropriate pair of oxidatively coloring compounds A and B. preferably multi-layer photosensitive materials are used, as described in shown in the accompanying figures 1 and 2.

A multi-layered, photosensitive material as shown in the illustration 1 contains a blue-sensitive silver halide emulsion layer 1 with a niclit-diffusing one Silver halide thickener, its oxidation products in an alkaline medium couple with an alkali-soluble coupler A1, which in turn in the presence of a stronger oxidizing agent (than exposed silver halide is) oxidatively couples with an alkali-soluble reagent B and after diffusion into a stronger one Receptor containing oxidizing agent which forms a yellow dye.

The material 2 is a hydrophilic colloidal spacer layer, e.g. a gelatin layer.

Material 3 is a green-sensitive silver halide emulsion layer, which is essentially insensitive to blue and red light and is non-diffusing Contains silver halide developing agent, its oxidation products in alkaline Coupling the medium with an alkali-soluble copper A2, which in turn, if present a stronger oxidizing agent (than exposed silver halide is) Couples oxidatively with an alkali-soluble reagent B and after diffusion into a the stronger oxidizing agent-containing receptor material is a purple dye forms.

The material 4 is a hydrophilic colloidal spacer layer, e.g. a gelatin layer.

Material 5 is a red sensitive silver halide emulsion layer, which is essentially insensitive to blue and green light and is non-diffusing Contains silver halide developing agent, its oxidation products in alkaline Coupling the medium with an alkali-soluble coupler A3, which for its part in presence a stronger oxidizing agent (than exposed silver halide is) Couples oxidatively with an alkali-soluble reagent B and after diffusion into a the receptor material containing the stronger oxidizing agent is a cyan dye forms.

The material 6 is an adhesive layer for a gelatin silver halide colloid layer and a support 7 which is, for example, a film support or a semi-transparent paper base is.

A multi-layered, photosensitive material as shown in the illustration 2 contains a blue-sensitive silver halide emulsion layer 1 with a non-diffusing one Silver halide developing agent and an alkali-soluble coupler B, »which in alkaline Medium using a stronger oxidizing agent (than exposed silver halide represents) couples to a yellow Forming dye Zll with one alkali-soluble coupler A1, which is contained in a hydrophilic, water-permeable colloid layer 2 is present.

The coupler A1, which diffuses from the colloid layer 2 and into the exposed emulsion layer 1 penetrates, reacts therein with the non-diffusing Developer oxidation products and is thereby prevented from further migration.

The material 3 is a hydrophilic, colloidal spacer layer, e.g. a gelatin layer.

Material 4 is a green-sensitive silver halide emulsion layer, which is essentially insensitive to blue and red light and is non-diffusing Silver halide developing agent and an alkali-soluble coupler B containing in an alkaline medium by means of a stronger oxidizing agent (than exposed Represents silver halide) couples to form a purple dye with a alkali-soluble coupler A2, which is in the hydrophilic, water-permeable colloid layer 5 is present.

The material 6 is a hydrophilic colloidal spacer layer, e.g. a gelatin layer.

Material 7 is a red sensitive silver halide emulsion layer, which is essentially insensitive to blue and green light and is non-diffusing Silver halide developing agent and an alkali-soluble coupler B containing in an alkaline medium by means of a stronger oxidizing agent (than exposed Represents silver halide) couples to form a cyan dye with a alkali-soluble coupler A3, which is in the hydrophilic, water-permeable colloid layer 8 is present.

The material 9 is an adhesive layer such as a gelatin layer and Material 10 is a carrier such as a paper carrier.

In the composition of the photographic recording materials, As illustrated in Figures 1 and 2, the following reactants become A and B that are capable of being in an alkaline medium through a hydrophilic, colloidal Diffuse mass, mentioned as examples.

As the usual mobile reactant B, a hydrazone compound having the following structural formula can be used The following reactive, alkali-soluble methylene compounds (A'1) and (all) can be used as the mobile reactants A1 which are able to form a yellow azine dye with the usual partner B The yellow azine dye formed from compound (A'1) and hydrazone B has the following structure As the mobile reactants A2 capable of forming a purple azine dye with the ordinary partner B, the following reactive alkali-soluble aromatic hydroxy couplers (A'2) and (A "2) can be used The purple azine dye formed with compound (A'2) and hydrazone B has the following structure The following reactive, alkali-soluble, sulfo-substituted N, N-dialkylanilines (A'3) and (A ?? 3) can be used as mobile reactants A3, which are able to form a blue-green azine dye with the usual partner B The blue-green azine dye formed with the connection (h'3) and the hydrazone B has the following structure In order to improve the coupling ability with the oxidation products of a non-diffusing p-phenylenediamine type developing agent, a reactive -CH2- group can be introduced into one of the alkyl groups, as explained, for example, in the following N, N-dialkylaniline coupler The reactive methylene group introduced does not affect the absorption of the azine dye formed last in the visible spectrum, since the chromophoric system that is formed with the help of this methylene group only causes absorption in the invisible, short-wave W range.

A p-phenylenediamine type developing agent which is resistant to diffusion in an alkaline hydrophilic colloidal medium and which is particularly useful for use in the present invention has the following formula A multilayered photographic material which is suitable for use according to the second embodiment of the present invention for the formation of multicolor images by image-wise diffusion transfer of intramolecular or intermolecular dye-forming reagents from a photographic material into a receiving material contains (1) a blue-sensitive silver halide emulsion layer which is a non-diffusing Silver halide developing agent and in effective contact with the developing agent contains a colorless reagent AX capable of diffusing with the aid of an alkaline aqueous liquid in the medium, forming a yellow dye by intramolecular or intermolecular coupling, and a compound with the oxidizing product of the developing agent with a much weaker diffusivity than the reagent has in the unreacted state, (2) a green-sensitive silver halide emulsion layer which has a ni diffusing silver halide developing agent and in effective contact with the developing agent contains a colorless reagent AY or BX, which is capable of diffusing with the aid of an alkaline aqueous liquid in the medium to form a purple dye by intramolecular or intermolecular coupling, and with the oxidation product of the developing agent one To form compound, with a much weaker diffusibility than it has the reagent in the unreacted state, (3) a red-sensitive silver halide emulsion layer containing a non-diffusing silver halide developing ink and in effective contact with the developing agent a colorless reagent AZ or CX capable of is to diffuse in the medium with the aid of an alkaline aqueous liquid, to form a cyan dye by intramolecular or intermolecular coupling, and to form a compound with the oxidation product of the developing agent with a much weaker diffusivity than the reagent has in the unreacted state.

Each silver halide emulsion layer can be from a different silver halide emulsion layer be separated by a suitable spacer layer, for example a layer of Gelatin or polyvinyl alcohol. The spacer layer can act as a kind of permeability controlling Acting barrier layer and consists of a layer of slowly penetrating Material such as a layer of cellulose acetate hydrogen phthalate on occasion in combination with a more water-permeable spacer layer, e.g. a gelatin layer.

The principles as mentioned before and in two embodiments are not only used in combination with different spectrally sensitive, superimposed silver halide emulsion layers applicable, which on a Ordinary supports are layered, but can also be used in conjunction with photographic Materials used are the so-called? Package emulsions? contain, in which a single continuous, hydrophilic, colloidal carrier layer separate, tiny, contains differently spectrally sensitized silver halide emulsion portions, encased in resin shells (or plastic shells) that form microcapsules that are used for an aqueous, permeable to alkaline liquids. Each silver halide emulsion part contains the non-diffusing developing agent and also at least the reagent that must react with an oxidation product of the developing agent. When the first Embodiment is applied, the reagent that does not interact with the oxidation product of the developing agent reacts into the continuous, hydrophilic, colloidal phase which contains the microcapsules.

The methods of making "packet emulsions" are those of skill in the art well known; we refer, for example, to British patent specification 947 168.

In the production of a multicolor image by image-wise diffusion transfer of oxidative dye-forming compounds C1-C2 are preferably multilayered, photosensitive material is used, the layer arrangement is such that L ~ t ' as illustrated in the accompanying Figures 1 and 2 will.

In this case, the multilayered photosensitive material contains according to Figure 1, a blue-sensitive silver halide emulsion layer 1 with a non-diffusing silver halide developing agent, its oxidation products couple in an alkaline medium with an alkali-soluble coupler A-X, which in turn in the presence of a stronger oxidizing agent (than exposed silver halide represents) oxidatively couples intramolecularly or intermolecularly and after diffusion forms a yellow dye in a receiver material, the receiver material which contains stronger oxidizing agent.

The material 2 is a hydrophilic, colloidal spacer layer e.g. a gelatin layer.

Material 3 is a green-sensitive silver halide emulsion layer, which is essentially insensitive to blue and red light and is non-diffusing Contains silver.halogenide developing agent, the oxidation products of which are in alkaline Coupling the medium with an alkali-soluble reagent A = Y or B-X, which in turn contributes to Presence of a stronger oxidizing agent (than exposed silver halide represents) oxidatively couples intramolecularly or intermolecularly and after diffusion forms a purple dye in a receiver material, the receiver material which contains stronger oxidizing agent.

The material 4 is a hydrophilic colloidal spacer layer, e.g.

a gelatin layer.

Material 5 is a red sensitive silver halide emulsion layer, tiie is essentially insensitive to blue and green light and e.in nichLdiffiiii <Iierendes syllable phalogenL '<1 -developer, whose Oxidation products in an alkaline medium with an alkali-soluble reagent A-Z or C-X coupled read in turn in the presence of a stronger one Oxidizing agent (as it represents exposed silver halide) oxidatively intramolecularly or intermolecularly couples and, after diffusion into a receiver material, a blue-green dye forms, with the receiver material containing the stronger oxidizing agent.

The material 6 is an adhesive layer for a gelatin silver halide colloid layer, and the support 7 is, for example, a film support or a semitransparent paper support.

For use in the second embodiment of the invention, a multilayer, photosensitive material according to Figure 2 a blue-sensitive Silver halide emulsion layer 1 containing a non-diffusing silver halide developing agent contain. The reagent A-X, which in alkaline medium by a stronger, oxidizing Medium (as it represents exposed silver halide) intramolecular or intermolecular couples to form a yellow dye is in the hydrophilic, water-permeable Colloid layer 2 present.

The reagent A-X, which diffuses from the colloid layer 2 and into the exposed emulsion layer ~ 1 penetrates, reacts therein with the non-diffusing Developer oxidation products and is thereby prevented from further migration.

The material 3 is a hydrophilic, colloidal spacer layer e.g. a gelatin layer.

Material 4 is a green-sensitive silver halide emulsion layer, which is essentially insensitive to blue and red light and is non-diffusing Contains silver halide developing agent. The reagent A-Y or B-X made with the help of a stronger oxidizing agent (than exposed silver halide is) in alkaline medium couples intramolecularly or intermolecularly to form a purple dye to form is contained in a hyArophilic, water-negligible colloid layer 5.

The material 6 is a hydrophilic, colloidal spacer layer e.g. a gelatin layer.

Material 7 is a red sensitive silver halide emulsion layer, which is essentially insensitive to blue and green light and is non-diffusing Contains silver halide developing agent. The reagent A-Z or C-X made with the help a stronger oxidizing agent (than exposed silver halide is) in alkaline medium couples intramolecularly or intermolecularly to form a cyan dye is contained in a hydrophilic, water-permeable colloid layer 8.

The material 9 is an adhesive layer such as a gelatin layer and Material 10 is a carrier such as a paper carrier.

In the composition of the photographic recording materials, as illustrated in Figure 1 and also in Figure 2, the the following reactants preferred to the second embodiment.

As the common part A in the general formula of the color-forming reagents AX, AY and AZ, a monovalent group is used which is derived from a heterocyclic hydrazone compound belonging to the quinolin-4-one compound class, with one group being particularly preferred, the following structural formula Has Part X in the reagent ~ is able to form a yellow azine dye by intramolecularly oxidative coupling with part A and is preferably a bezoylacetic anilide group; however, a group shown in the square brackets of the following formula is more preferable The yellow azine dye formed with such a compound has the following structural formula Part Y in the second reagent is capable of oxidative, intramolecular coupling with part A to form a purple azine dye and is preferably a pyrazolin-5-one group; however, a group shown in the square brackets of the following formula is more preferable The purple azine dye formed with such a compound has the following structural formula Part Z in the third reagent is able to form a blue-green dye by oxidative, intramolecular coupling with part A and is preferably an <i-hydroxynaphthoic acid aniline group; more preferable, however, is a group represented in the square clans of the following formula The blue-green azine dye formed with this compound has the following structural formula: p-phenylenediamine type developing agent which does not diffuse in an alkaline hydrophilic colloidal medium and which is particularly useful for use in the present invention has the following formula It is clear that in order to bring the final, positive, multicolor image produced on the receiver material into the correct color balance, the reaction speed and diffusivity of the compounds that actively participate in the recording and dye formation, through their chemical structure and through their chemical and physical properties and dimensions such as thickness and permeability of the separate colloid layers forming part of the multilayer recording material can be appropriately adjusted or controlled.

The different silver halide emulsion layers need not be the same Developing agents included, so that when appropriate substituents are introduced in the developing molecule the coupling rate is controlled and the appropriate one Level can be adjusted for each silver halide emulsion layer.

In a multilayered silver halide recording material that is suitable for reflective exposure of the type illustrated by Figures 1 and 2 is, no yellow filter layer is used, so that the blue sensitivity of the Silver halide emulsion layers which are appropriately desensitized to green and red, respectively are as low as m (ig must be kept. To this end It is preferable to use silver chloride grains that are only for ultraviolet and Extreme violet are sensitive by taking away from the exposure light every extreme Excludes violet, which is irrelevant for color rendering, can be found in the final multicolored picture obtained very pure colors in a multi-layered one Silver halide recording material based on the present invention works and that is intended for direct exposure, a yellow filter layer can can be used as a selective blue-absorbing layer, which is characterized by the usual, multilayered silver halide materials of multicolor reproduction is known.

When producing a recording material according to the present invention Invention, dye-forming ingredients are preferably used which have a have high diffusivity in the alkaline medium and in the hydrophilic, colloidal one Medium are included in a finely divided, dispersed state. The colloidal Medium is preferably slightly acidic and thereby preserves the alkali-soluble ingredients before migration into an underlying, previously applied colloid layer.

Mixing devices can be used for a suitable dispersion of the ingredients such as a colloid mill, an ultrasonic wave generator and a Sand mill.

The coating of the colloid layers can be done according to any technique, which is known to every person skilled in the art of silver halide layers.

For suitable coating techniques we refer e.g.

to "Photographic Emulsion Chemistry" by G.F. Duffin - The Focal Press, London (1966), pp. 153-156.

The present link is illustrated by the following examples Unless otherwise indicated, the percentages are in% by weight example 1 recording material for the production of monochromatic (purple) color images.

A dispersion A is prepared by in a sand mill 5 g of p-phenylenediamine type developing agent No. 1 in Table 1 and 1.1 g of des Phenol type coupler No. 1 of Table 2 and 1.6 g of hydrazone type compound No. 1 of Table 6 in 50 ml of a 2% strength aqueous solution of a naphthalene sulfonate condensate intimately mixes as a dispersant, which is available under the name LOMAR D from Nopco Chemical Company, Newark, N.J. USA is traded.

An equal volume of a 10% strength, given aqueous gdatin solution containing 2% heptadecylbenzimidazole disodium sulfonate contains as a wetting agent.

The pH is adjusted to 5 by adding 2 ml of 1N aqueous acetic acid admits.

20 g of the dispersion obtained are mixed with 20 g of an aqueous gelatin silver chloride emulsion mixed containing an amount of green sensitized silver chloride that is 62.5 g Silver nitrate is equivalent per kg; the weight ratio of silver to gelatin is 1.45. 8 ml of water and 0.5 g of chrome alum are added to the mixture obtained admitted.

The mixture is on a semi-transparent, polyethylene-coated Paper base with a weight of 90 g per m2 applied so that you have an emulsion layer with an amount of silver halide that corresponds to 3 g of silver nitrate per m2.

Receiver material The receiver material is produced by 25 g of dibenzoyl peroxide, dissolved in 75 ml of diethyl carbonate at 60 ° C., in a composition dispersed, the 25 ml of a mixture of dibutyl phthalate / tricresyl phosphate (volume ratio 3: 8) unct 250 g of a 10%, aqueous gelatin solution, the 12.5 ml of a 20%, aqueous solution of n-Dodecylphenylt1L-Fonsäurenatriumsalz as a wetting agent contains. After (lift Dispersion treated in a high speed mixer the dispersion is made at 6000 with water up to an amount of 500 g diluted. The particle size of the dispersed phase is less than 0.5 microns.

The dispersion is made on an opaque paper base of 90 g per m2 using a top layer of 8 g dibenzoyl peroxide per m2 applied.

Image-wise exposure and treatment The recording material is Reflectographically exposed with an opaque original, the purple line parts contains. The development and image transfer is done in an ordinary diffusion transfer developing machine, by first treating the exposed material with an aqueous, alkaline activator liquid moistened the 50 g sodium carbonate and 500 mg 1-phenyl-pyrazolidin-3-one per liter contains. The material is pressed against the above-mentioned receiver material while it is still wet and thus kept in contact for 30 seconds and finally pulled off. On the receiving Material contains a crimson image, which corresponds to the crimson image parts of the original is equivalent to.

In the preparation of the purple color image, the developing agent described above can advantageously be replaced by developing agents 2 to 4 of Table 1 or by an aromatic 1,2-dihydroxy developing agent which couples with the hydrazone in an oxidized form and has one of the following structural formulas The hydrazone type coupler may be replaced with the hydrazone type coupler No. 2 or No. 5 of Table 6.

The # Phene tPhenol type coupler can be identified by the K ## pp t ('fl, 2 to -11 the table e pse L z 1; who # I # ~ n.

Example 2 Recording material for the production of monochromatic (yellow) images.

A dispersion B is prepared by in a sand mill 5 g of the developing agent No. 1 of Table 1, 1.6 g of the reactive methylene type coupler No. 1 of Table 4 and 1.6 g of the hydrazone type compound No. 1 of Table 6 in 50 ml of water and 5.1 ml of LOMAR D (trade name) mix intimately.

An equal volume of a 10% strength, given aqueous gelatin solution containing 2% heptadecylbenzimidazoid sodium sulfonate contains as a wetting agent.

The pH is adjusted to 4.65 by adding 2 ml of 1N aqueous Add acetic acid.

20 g of the dispersion obtained are mixed with 20 g of a blue-sensitive, aqueous gelatin silver chloride emulsion of the type as described in Example 1 is described.

The photosensitive dispersion obtained is made in the same manner applied as in Example 1, but now on an opaque paper base.

The imagewise exposure is a direct exposure in an optical enlarger, in which a multi-colored line slide with yellow Image sharing is used. The development and image transfer are analogous the example 1.

A yellow image is obtained on the receiving material.

When producing a yellow dye image, the above-described, reactive methylene type couplers advantageously by means of couplers 2 to 7 of the table 4 to be replaced.

Example 3 Recording material for the production of monochromatic (blue green) color 1-dem.

A dispersion C is prepared by in a sand mill 5 g of developing agent No. 1 of Table 1, 1.5 g of the N, N-alkylsulfoalkylaniline compound No. 2 of Table 5 and 1.6 g of the hydrazone type compound No. 1 of Table 6 in 50 ml of water and 5 ml of LOMAR D (trade name) mix intimately.

An equal volume of a 10 igen, given aqueous gelatin solution containing 2% heptad (benzimidazole disodium sulfonate contains as a wetting agent. The pH is adjusted to 5 by adding 2 ml of 1N aqueous Add acetic acid.

20 g of the dispersion obtained are mixed with 20 g of a red-sensitive, aqueous gelatin silver chloride emulsion of the type as described in Example 1 will.

The photosensitive dispersion obtained is made in the same manner applied to a semi-transparent paper base as described in Example 1.

The "pictorial exposure and processing" are as in example 1, but using an original that contains blue-green parts of the image.

When producing the blue-green dye image, the above-described reactive aniline-type couplers advantageously by couplers 1, 3, 4 or 5 of the Table 5 and Coupler 10 of Table 2 can be replaced.

The hydrazone couplers listed in Table 6 under numbers 4, 9 and 11 can be used in the same way for the production of blue-green Use dye images when they are in Kombinati OIJ with hydroxynaphthoic acid amides and phenolic couplers can be used.

To realize a multicolored photographic material that contains a multitude of superimposed silver halide emulsion layers, it is advantageous to have emulsion layers containing the separate, color-forming reagents A and B of the first embodiment, with emulsion layers to combine the color-forming reagents C1-C2 of the second embodiment of the present invention.

In the top emulsion layer and optionally in the one below (i.e. in the second) color-forming reagents C1-C2 are preferably used. These reagents only require a relatively small amount of silver halide and Developing agent. The separate, color-forming reaction partners A and B become preferably used in the third silver halide emulsion layer, and optionally in the second emulsion layer. These reactants have a relatively low Molecular weight and consequently a higher diffusion rate, which for the long way they have to travel to the receiving material means corresponding compensation.

A photographic material composed in this way offers a fast and well-balanced E # diffusion transfer of the various oxidative color-forming reagents.

Example 4 below illustrates one such material and its Editing.

Example 4 Preparation of the Green-Sensitive Silver Halide Emulsion (Dispersion A) The following ingredients are dispersed in a sand mill in such a way that solid particles with an average size of −1 P are obtained. Developer compound 1 of label 1 40 g 40% aqueous solution of LOMAR D (trade name) as a dispersant 43 ml water 960 ml The resulting mixture is added to ciem the same volume of 10% aqueous gelatin solution containing chrome alum as hardening agent, and is diluted with L # 0 ml des Wetting agent ULTRAVON W (disodium salt of heptadecylbenzimidazole disulfonic acid from Ciba AG, Switzerland) mixed.

480 g of this dispersion is mixed with 325 g of a green-sensitized Mixed silver chloride emulsion containing an amount of silver chloride per kg, so that, 62.5 grams of silver nitrate is equivalent.

The pH of the mixture is adjusted to 5 3.

Preparation of the blue-sensitive silver halogen emulsion (dispersion B) The following ingredients are dispersed in a sand mill so that solid particles with an average size of 1 are obtained. Developer compound 1 in Table 1 12.5 g 40% aqueous solution of LOMAR D (trade name) as dispersing agent water 240 ml The resulting mixture is added to the same volume of 10% aqueous gelatin solution containing chrome alum as hardening agent and is mixed with 5 ml of the wetting agent ULTRAVON W ( Disodium salt of heptadecylbenzimidazole disulfonic acid from Ciba AG, Switzerland).

480 g of this dispersion are mixed with 400 g of a blue-sensitive silver chloride emulsion mixed, which contains an amount of silver chloride per kg that is equivalent to 62.5 g of silver nitrate is.

The pH of the mixture is adjusted to 5.3.

Preparation of the red-sensitive silver halide emulsion (dispersion ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ C) The following ingredients are in a sand mill dispersed so that solid particles with an average size of 1 µ are obtained Developer compound 1 of Table 1 24 g of compound 1 of Table 8 24 g 110 ° term, aqueous solution of LOMAR D (trade name) D dispersant 32 ml water 800 ml The mixture obtained becomes 800 ml of a 10 0% strength aqueous gelatin solution given, the chrome alum entiii'lt as hardening agent, and is with 1t- ml of the wetting agent ULTBAVOH W (disodium salt of hept ad ecylbeiizim dazoldisulfonic acid from Ciba AG., Switzerland) mixed.

320 g of this dispersion are mixed with 160 g of a red-sensitive silver chloride emulsion mixed, which contains an amount of silver chloride per kg, the 62.5 g of silver nitrate equivalent i.st.

An additional 1C0 ml of a r L.% aqueous solution is then added Gelatin solution added.

The pH of the mixture is adjusted to 5.3.

Production of the multi-colored, photographic material The dispersions A, B and C are made on a semi-transparent, polyethylene-coated paper base applied, which has a weight of 90 g per m2.

Dispersion A is applied at 180 g per m2 and dried.

A 2% aqueous gelatin solution with 200 g per m2 is then applied Weight and on this gelatin intermediate layer the dispersion B in a ratio of 100 g per m2 applied.

Dispersion C with 80 g per m2 weight is used as a fourth layer applied. The multi-layered composition comes with a top layer one 2% by weight, aqueous gelatin solution with 100g per m2 of weight.

Manufacture of the receiver material On a paper basis, with a thin polyethylene terephthalate film is laminated to the paper on the To make the receiving side impermeable to water, a layer that is a polyionic Contains polymer as a mordant for the oxidatively formed dyes, with 100 g per m2 weight of the following composition applied 10 ° zSige, aqueous gelatin solution 600 g water 492 ml DOW ECR 34 (a copolymer based on vinylbenzyltrimethylammonium chloride and styrene from DOW Chemical Company, Midland, Mich. USA) 102 g chrome alum hardener 0.1 g A second layer is applied to the first layer, the oxidizing Agents for the oxidative coupling of the transferred color-forming agent or agents contains and which is based on the following composition m-methyldibenzoyl peroxide, Dissolved in diethyl carbonate at 600C 75 ml mixture of dibutyl phthalate / Tri cre syl phosphate (Volume ratio 3: 8) 25 ml 10% aqueous gelatin solution, the 12.5 ml 20 4 / o aqueous solution of n-dodecylphenylsulfonic acid sodium salt contains 250 -g After dispersing in a high-speed mixer, the dispersion becomes diluted with water at 6000, so that an amount of 500 g is obtained.

The particle size of the dispersed phase is less than 0.3 microns.

The hiding power of this dispersion on the etching layer is 100 g per m2.

Image-wise exposure and processing The photosensitive material is exposed to white light through a multi-colored halftone slide and developed for 20 seconds at 2000 using a solution containing the following ingredients contains sodium carbonate 50 g potassium hydroxide 10 g 1-phenylpyrazolidill-3-one 0.1 g Water 1 liter The so treated, photosensitive material is then between a pair of rubber rollers with the exposed side in contact with the receiving material is located. After two minutes of contact, they will separated.

A positive multicolor image is obtained on the receiving material of the original.

Example 5 This example illustrates the use of a color forming Compound that couples oxidatively intermolecularly.

A dispersion is made by mixing in a sand mill, which contains the following ingredients color-forming compound 18 of Table 8 1.1 g of developer compound 1 from Table 1 1.2 g of 40% aqueous solution from LOMAR D (trade name) as a dispersant 2 ml 10% aqueous gelatin solution 40 ml of water LCO ml of 24 g of this dispersion become 36 g of a blue-sensitive one Given silver chloride emulsion containing an amount of silver chloride per kg 62.5 grams of silver nitrate is equivalent.

The dispersion is on a baryta-coated paper carrier in a Coverage of 100 g per m2 applied. Pictorial exposure and processing are analogous to those of Example 1. One receives a on the receiving material yellow, positive image of an original that contains yellow image features.

Claims (37)

Patent claims 1. A method for producing color transfer images, thereby characterized in that it contains the following steps (a) the imagewise exposure with electromagnetic radiation of a photographic material having a silver halide layer contains that are in effective contact with the silver halide grains that are delicate or have been sensitized to electromagnetic radiation, a developing agent possesses, which is resistant to diffusion in a hydrophilic, colloidal medium and which at least one colorless reagent in effective contact with the developing agent which is capable of (1) in an aqueous, alkaline medium from the material to one Diffuse receptor material, (2) by oxidative, intermolecular, or intramolecular Coupling, or by coupling with another colorless reagent, does the same is able to diffuse in an aqueous, alkaline medium to form a dye, and (5) to form a compound with the oxidation product of the developing agent, which has a significantly weaker diffusivity than in the unreacted state, (b) the establishment of contact between the exposed photographic material and -An aqueous, alkaline, activating liquid to reduce the activity of the developing agent so that it becomes visible in the exposed parts Form a silver image and an oxidation product of the developing agent, which is mixed with the colorless reagent (or the reagent) couples to the exposed parts of the Emulsion layer to form one or more compounds, which are a much weaker Diffusibility than the unreacted reagents have, (c) the transfer of a certain amount of the reagent molecules that remained diffusible from the so treated Material by means of the alkaline processing liquid to a Receiver material, upon which reagent molecules transferred intermolecularly or intramolecularly oxidatively coupled or different reagent molecules oxidatively using a Oxidizing agent are coupled, said agent being a stronger oxidizing agent is as exposed silver halide, from which the formation of a color image results on the receiving material. 2. The method according to claim 1, characterized in that the silver halide emulsion layer contains a non-diffusing silver halide developing agent, its oxidation product capable of producing a reaction product with a phenol type or reactive methylene type coupler to build 3. The method according to claim 1 or 2, characterized in that the Contacting the exposed photographic material with an alkaline aqueous solution Liquid in the presence of a primary developing agent that is resistant to diffusion is, and an auxiliary development agent happens. 4. The method according to any one of claims 1 to 3, characterized in that that a hydrophilic colloid layer of the photographic material appears to be colorless Reagent contains a compound capable of intermolecular or intramolecular to be coupled oxidatively, the compound corresponding to the following general formula C1 - C2 in which C1 means a chemical structural part that is capable of producing a quinone imine or azomethine dye structure with an oxidized p-phenylenediamine type developing agent and C2 is a chemical structural part that is chemically bonded to part r and contains a hydrazone group which enables the compound to undergo oxidative Conditions to form a dye which contains an azine group (= N-N =). 5. The method according to each of the preceding claims, characterized characterized in that the: receiving material in a water-permeable (1-permeable, image-receiving Layer as an oxidizing agent, - ('1 contains at least one compound of the group, which is a non-diffusing, organic peroxide, a long-chain, aliphatic -Oniua salt contains a peracid and a compound that works in aqueous medium Splits off halogen. 6. The method according to claim 5, characterized in that the receiving material as a mordant for the dye (or dyes) formed thereon, a polymer with cationic groups. 7. The method according to any one of the preceding claims, characterized in that that the alkaline, aqueous processing liquid as an alkaline substance at least contains a compound of the group, the alkali metal carbonates, alkali metal hydroxides and contains aliphatic amines. 8. Process for the formation of multicolor images by image transfer of color-forming reagents from a photographic material which three superimposed Contains silver halide emulsion layers that represent blue, green and red light, respectively are sensitive,> the method comprising the following steps (a) exposure of a photographic material according to a multicolored light pattern which contains (1) A blue-sensitive silver halide emulsion layer which is a non-diffusing one Silver halide developing agent and in effective contact with the developing agent contains a pair of colorless reagents capable of diffusing in the medium, when they have been wetted with an aqueous, alkaline liquid and through oxidative coupling together to form a yellow dye, at least one of the reagents is capable of reacting with the oxidation product of the developing agent one To form a connection, with a much weaker one Diffusibility than it has the reagent in the unreacted state, (2) a green sensitive A silver halide emulsion layer which is a non-diffusing silver halide developing agent and a pair of colorless reagents in effective contact with the developing agent which are able to diffuse in the medium when mixed with an aqueous, alkaline liquid have been wetted and by oxidative coupling with each other to form a purple dye, at least one of the reagents being capable of to form a compound with the oxidation product of the developing agent, and although with a much weaker diffusivity than the L'eagens in unreacted state, (3) a red-sensitive silver halide emulsion layer, which is a non-diffusing silver halide developing agent and is effective Contact with the developing agent contains a pair of colorless reagents that are capable are to diffuse in the medium when exposed to an aqueous, alkaline liquid have been wetted and a cyan dye by oxidative coupling with each other to form, at least one of the reagents being capable of interacting with the oxidation product of the developing agent to form a compound with one essential diffuse ability weaker than that of the reagent in the reacted state; and any reagent that does not contain a compound with a significantly weaker diffusivity biL.let, as such a reagent in an unreacted state, is a reagent that is common to all Reagent pairs are common, (b) touching the exposed photographic material with an aqueous, alkaline processing liquid, the reduction activity of the developing agent (or several developing agents) triggers and thereby in agreement with the latent silver image portions of each silver halide emulsion layer a visible silver image and a developer oxidation product that forms in its Silver halide emulsion layer containing at least one of the colorless reagents of the Couples a pair of reagents which correspond to the respective silver halide emulsion layer, to form compounds that are relevant to the unreacted reagent (s) have a significantly reduced diffusivity, (c) transfer from treated Material from residual, unaffected, color-forming reagents by means of the alkaline processing liquid into a receiver material in which the dye-forming Reagents of each pair are coupled together oxidatively by means of an oxidizing agent that is stronger than exposed silver halide, with the generation results in a positive, four-color image in the receiver material. 9. Process for the formation of multicolor images by image transfer of color-forming reagents C1-C2 according to claim 4 from a photographic Material containing three superimposed silver halide emulsion layers; which are sensitive to blue, green or red light, the procedure being as follows Steps include (a) exposing a photographic material after a multicolored one Light pattern which contains (1) a blue-sensitive silver halide emulsion layer, which is a non-diffusing silver halide stripping agent and is effective Contact with the developing agent contains a colorless reagent C1-C2 that is capable is to diffuse in the medium with an aqueous, alkaline liquid through oxidative intramolecular or intermolecular coupling to a yellow dye form, and with the oxidation product of the developing agent a compound with a much weaker diffusivity than in the unreacted state form, (2) a green-sensitive silver halide emulsion layer, which is a non-diffusing silver halide elimination agent and is effective Contact with the developing agent contains a colorless reagent C1-C2 that is capable is to diffuse through in the medium with an aqueous alkaline liquid oxidative intramolecular or intermolecular coupling to a purple dye form, and with the oxidation product of the developing agent a compound with a much weaker diffusivity than in the unreacted state (3) a red-sensitive silver halide emulsion layer which is a non-diffusing Silver halide developing agent and in effective contact with the developing agent contains a colorless reagent C1-C2 which is capable of reacting in the medium with an aqueous, diffuse alkaline liquid, through oxidative intramolecular or intermolecular Coupling to form a cyan dye, and with the oxidation product of the developing agent a compound with a much weaker diffusivity than in unreacted State, (b) contacting the exposed photographic material with an aqueous, alkaline processing liquid that does the reduction activity of the developing agent (or several developing agents) triggers and thereby in Correspondence with the latent silver image parts of each silver halide emulsion layer a visible silver image and a developer oxidation product that forms in its Coupling silver halide emulsion layer with the colorless dye-forming reagent, corresponding to the relevant silver halide emulsion layer to form a compound to form, which in terms of the unreacted reagent significantly decreased a Has diffusivity, (c) transfer from the treated material from the various remaining, unaffected, colorless, dye-forming reagents by means of the alkaline processing liquid into a receiver material in which the various dye-forming reagents intramolecularly or intermolecular be coupled oxidatively by means of an oxidizing agent that is stronger than exposed Silver halide is capable of producing a positive, multicolored image results in the receiving material. 10. Photographic material used for the production of dye images is suitable by image-wise diffusion transfer of compounds that are in a are soluble in aqueous, alkaline processing fluids, characterized in that that this material contains a) photosensitive silver halide grains, which in a hydrophilic colloid layer are dispersed, b) in such a layer or in water-permeable relation to such a layer at least one colorless one Reagent capable of forming a dye through an oxidative coupling reaction to form and in an aqueous, alkaline medium from this material in a Diffuse receiver material, and c) in effective contact with the silver halide grains Developing agent which is diffusion-resistant in a hydrophilic, colloidal medium is and what if it is in the presence of an aqueous, alkaline liquid is activated, after the imagewise exposure of the layer, the exposed silver halide reduced in the layer and coupled with the colorless reagent in the oxidized state, around its diffusion from the exposed parts of the photosensitive material in to prevent the receiving material. 11. Photographic material according to claim 10, characterized in that that the non-diffusing silver halide developing agent is a compound contains, the oxidation product of which with a «-naphthol-, phenol-, reactive methylene type coupling or an N, N-dialkylaniline type coupler, a diffusion-inhibited reaction product forms. 12. Photographic material according to claim 11, characterized in that that the developing agent is an aromatic primary amino developing agent. 13. Photographic material according to claim 12, characterized in that a developing agent is present which corresponds to the following general formula in which R1 and R2 each represent an aliphatic group including a substituted aliphatic group, or R1 represents the necessary methylene groups including substituted methylene groups to form a 5- or 6-membered, heterocyclic nucleus with the carbon atom in the 6-position of the benzene nucleus conclude; or R2 represents the necessary methylene groups including substituted methylene groups in order to close a 5- or 6-membered, heterocyclic nucleus with the carbon atom in the 2-position of the benzene nucleus; or R1 and R2 together represent the necessary methylene groups, including substituted methylene groups, in order to close a 5-membered, nitrogen-containing nucleus, and the same or different substituents such as, for example Hydrogen, an alkyl group and an alkoxy group, provided that that R3 is in the 3- and / or 5-position in the cases where it is not hydrogen, given above, and wherein the developing agent is or contains several substituents that are common in a hydrophilic colloidal medium for the ensure the desired diffusion resistance. 14. Photographic material according to claim 10, characterized in that that as a reagent capable of binding with the developer oxidation product to form with a much weaker diffusion rate than they do in unreacted State has a phenol, # -naphthol, a reactive methylene type or an N, N-dialkylaniline type coupler is present. 15. Photographic material according to claim 14, characterized in that a phenol is present which corresponds to the following general formula: in which R1 and R2 each denote a hydrogen atom, an alkyl group including a substituted alkyl group, an alkoxy group including a substituted alkoxy group or the group -NHR in which R is a carboxylic acid acyl group or sulfonic acid acyl group including the groups in the substituted state, provided that that R1 and R2 do not represent hydrogen at the same time and the substituents are not of such a type that the diffusion of the phenolic compound in an alkaline, hydrophilic, colloidal medium is markedly hindered. 16. Photographic material according to claim 14, characterized in that a 4-naphthol is present which corresponds to the following general formula in which R represents an alkyl group including a substituted alkyl group or an aryl group including a substituted aryl group. 17. Photographic material according to claim 14, characterized in that the reagent corresponds to one of the following general formulas: PI -CO-CH2-CO-R2 R1 -CO-CH2-CN in which R1 denotes an alkyl group including a substituted alkyl group, an aryl group including a substituted aryl group, an N-arylamino group including a substituted N-arylamino group or an ether group including a substituted ether group, R2 an alkyl group including a substituted alkyl group or an aryl group including a substituted aryl group , R 'an alkyl group including a substituted alkyl group or an aryl group including a substituted aryl group, R "an alkyl group including a substituted alkyl group, an aryl group including a substituted aryl group, an N-arylamino group including a substituted N-arylamino group, an N-acylamino group including one substituted N-acylamino group or a ureido group including a substituted ureido group, but on condition that the substituents in the compounds are not of a type which markedly hinders the diffusibility of the reactive methylene compounds in an alkaline, hydrophilic, colloidal medium. 18. Photographic material according to claim 14, characterized in that the N, N-dialkylaniline is a compound which corresponds to the general formula: in which M denotes hydrogen, a metal cation or a cationic group, Y denotes a divalent organic group and R denotes an alkyl group. 19. Photographic material according to claim 10, characterized in that one of the reagents is a heterocyclic hydrazone compound which corresponds to the following general formula: in which R1 denotes a -CONH2- or -SO2X-G 'group, in which X represents hydroxyl, an amino group including a substituted amino group, an alkyl group including a substituted alkyl group, an aryl group including a substituted aryl group, and Z the necessary Atc-me to close a 5- or 6-membered, heterocyclic nucleus or a 5- or 6-membered, heterocyclic ring system, including such a nucleus or ring system in substituted form. 20. Photographic material according to claim 19, characterized in that that the material is an aromatic 1,2-dihydroxy compound as a developing agent contains. 21. Photographic material according to claims 10 to 20, thereby characterized in that the silver halide emulsion is applied to a flexible support which is optionally provided with a subbing layer for the silver halide emulsion layer is provided. -22. Photographic material according to claim 21, characterized in that <##, that the carrier is a paper or plastic film backing that is suitable Reflex exposure% lzl cisen. 23. Photographic material according to claim 10, characterized in that Let it be used in the formation of multicolor image elelids by imagewise Diffusion transfer of dye-forming reagents from a photographic material is suitable as a receiving material, the 'containing photographic material (1) A blue-sensitive silver halide emulsion layer which is a non-diffusing one Silver halide developing agent and in effective contact with the developing agent contains a pair of colorless reagents capable of diffusing in the medium, when they have been wetted with an aqueous, alkaline liquid and through oxidative coupling together to form a yellow dye, at least one of the reagents is capable of reacting with the oxidation product of the developing agent to form a compound with a much weaker diffusivity, when it has the reagent in the unreacted state, (2) a green-sensitive silver halide emulsion layer, This is a non-diffusing silver halide developing agent and is effective Contact with the developing agent contains a pair of colorless reagents that are capable are to diffuse in the medium when exposed to an aqueous, alkaline liquid been wetted sintl and by oxidative coupling with each other a purple dye to form, at least one of the reagents being capable of interacting with the oxidation product of the developing agent a compound with a much weaker diffusibility to form when it has the reagent in the unreacted state, (3) a red-sensitive A silver halide emulsion layer which is a non-diffusing silver halide developing agent and in effective contact with the developing agent, a pair of colorless reagents which are able to diffuse in the medium when mixed with an aqueous, alkaline liquid has been wetted are and by oxidative Coupling together to form a cyan dye, at least one of the Reagent is able to combine with the oxidation product of the developing agent with a much weaker diffusivity than the reagent has in an unreacted state; and any reagent that is not associated with a significantly weaken diffusivity forms, as such in unreacted reagent State is a reagent that is common to all reagent pairs. 24. Photographic material according to claim 10, characterized in that that the color-forming reagent capable of interacting with the oxidation product of the developing agent to form a compound with a much lower diffusion rate, than it has in the unreacted state, the following general formula corresponds to C1 - C2 in which C1 means a chemical structural part that is capable of imin- or Azomethine dye structure with an oxidized p-phenylenediamine type developing agent and C2 is a chemical structural part that is chemically bonded to part C1 and contains a hydrazone group that forms the compound under oxidative conditions capable of forming a (! n dye which contains an A1ine group (= N-N =). 25. Photographic material according to claim 24, characterized in that part C1 is a group which contains the structure of a "-naphtholkup" and corresponds to the following formula 26. Photographic material according to claim 24, characterized in that part C1 is a group which contains the structure of a reactive methylene-type coupler and corresponds to one of the following general formulas -HN-CO-CH2-CO-R2 -HN-CO-CH2 -CN in which R2 denotes an alkyl group including a substituted alkyl group, an aryl group including a substituted aryl group, an alkoxy group or an alkyl- or aryl-substituted amino group, and R "denotes an alkyl group including a substituted alkyl group, an aryl group including a substituted aryl group, cyano, an alkoxy group, a carbonylalkoxy group, an N-arylamino group including a substituted N-arylamino group, an N-acylamino group including a substituted N-acylamino group or a ureido group including a substituted ureido group, but with the proviso that the substituents in the compounds are not of a type that diffusivities noticeably prevents the @dye-forming compounds in an alkaline, hydrophilic, colloidal medium. 27. Photographic material according to claim 24, characterized in that a hydrophilic colloid layer of the hotographic material contains a colorless compound of structure C1- (J, in which part C2 contains a heterocyclic hydrazone group which corresponds to fo Fender, general formula: in which Z represents the atoms necessary to close a 5- or 6-membered, heterocyclic nucleus or such a ring system, including such a nucleus or ring system either in substituted form or not. 28. Photographic material according to claim 27, characterized in that the group corresponds to the following general formula in which, R2 denotes hydrogen, an aliphatic group including a substituted, aliphatic group or an aromatic group including a substituted, aromatic group, L methine or nitrogen, n the numbers 1 or 2, Z1 the necessary atoms to make a 5- or 6 -membered, heterocyclic nucleus or such a ring system, including such a nucleus or ring system in substituted form or not. 29. Photographic material according to claim 28, characterized in that that the material is an aromatic 1,2-dihydroxy compound as a developing agent contains. 30. Photographic material according to claim 24, characterized in that that the silver halide emulsion is applied to a flexible support which optionally provided with a subbing layer for the silver halide emulsion layer is. 31. Photographic material according to claim 30, characterized in that that the support is a paper or plastic film support capable of reflex exposure to allow. 32. Photographic material according to claim 24, characterized in that that it is for use in forming multicolored images by imagewise Diffusion transfer of dye-forming reagents from a photographic material as a receiver material, the photographic material containing (1) A blue-sensitive silver halide emulsion layer which is a non-diffusing one Silver halide developing agent and in effective contact with the developing agent contains a colorless reagent C1-C2 which is capable of reacting in the medium with an aqueous, diffuse alkaline liquid, through oxidative intramolecular or intermolecular Coupling to form a yellow dye, and with the oxidation product of the developing agent a compound with a much weaker diffusivity than in unreacted Condition to bit # {en, (2) a green sensitive silver halide emulsion layer, which is a non-diffusing silver halide developer and is effective Contact with the developing agent contains a colorless reagent CH2C1-C2 that is capable is to diffuse in the medium with an aqueous, alkaline liquid through oxidative intramolecular or intermolecular coupling to a purple dye form, and with the oxidation product of the developing agent a compound with one much weaker: diffusivity than in the unreacted state bil (ln, (3) a red-sensitive silver halide layer, a non-diffusing one Silver halide developing agent and in effective contact with the developing agent contains a colorless reagent C1-C2, ctas capable t, in the medium with an aqueous, ' diffuse alkaline liquid, by intramolecular or oxidative intermolecular coupling hasten blue-green dye to form, and with the oxidation product of the developing agent a compound with an essential Weaker on diffusivity than to wild in an unreacted state. 33. Photographic material according to claim 10, characterized in that it that it is for use in forming multicolored images by imagewise Diffusion transfer of dye forming reagents from a photographic Material suitable for a receiving material, the photographic material a surface layer, one or two silver halide emulsion layers, like that is described in claim 32, while the other silver halide emulsion layer (s) is (are) composed according to claim 23. 34. Receiving material to be used in accordance with the Procedure each of claims 1 to 9 is suitable, characterized in that the receiving layer consists of a hydrophilic colloid layer which is a non-diffusing oxidizing agent which is stronger than exposed silver halide. 35. Receiver material according to claim 34, characterized in that that the material contains a mordant for the dye (or dyes), which is (are) formed in the material. 36. Receiver material according to claim 35, characterized in that that # the mordant is a polymer that contains cationic groups. 37. Chemical compound, characterized in that it corresponds to the following general formula: in which Z denotes the atoms necessary to close a 5- or 6-membered, heterocyclic nucleus or a 5- or 6-membered, heterocyclic ring system, including such a nucleus or ring system in substituted form, and Y denotes the group or a group which has the structure of a reactive methylene type coupler and corresponds to one of the following formulas -HN-C0-CH2-CO-R2 -HN-C0-CH2-CN in which R2 denotes an alkyl group including a substituted alkyl group, an aryl group including a substituted aryl group, an alkoxy group or a substituted amino group, for example an alkyl- or aryl-substituted amino group, and R "denotes an alkyl group including a substituted alkyl group, an aryl group including a substituted aryl group, cyano , an alkoxy group, a carbonylalkoxy group, an N-arylamino group including a substituted N-arylamino group, an N-acylamino group including a substituted N-acylamino group, or a ureido group including a substituted ureido group.