EP0000511A1 - Photographic colour diffusion transfer process - Google Patents

Abstract

worin D einen heterocyclischen oder carbocyclischen Rest bedeutet und A' einen oxidierbaren Trägerrest. der an beliebiger Stelle an den Farbstoffrest angeknüpft wird und aus dem bei der Entwicklung entweder in oxidierter Form oder in nicht oxidierter Form mindestens ein Teil abgespalten wird unter Freisetzung des diffundierenden AzofarbstoffesNon-diffusing coloring compounds suitable for the photographic color diffusion transfer process, which release yellow AZO dyes substituted by a cyanoalkylamino group during development. These coloring compounds correspond to the formula

wherein D represents a heterocyclic or carbocyclic radical and A 'an oxidizable carrier radical. which is attached at any point to the dye residue and from which at least part is split off during development, either in oxidized form or in non-oxidized form, with the liberation of the diffusing azo dye

Description

The invention relates to a process for the production of color photographic images by the dye diffusion transfer process and to a photographic material suitable therefor which contains new diffusion-resistant, color-providing compounds which liberate yellow diffusing azo dyes having a cyanoalkylamino group.

Among the processes known to date for the production of colored photographic images by the color diffusion transfer process, those based on the use of diffusion-resistant embedded coloring compounds, from which diffusing dyes or dye precursor products are cleaved during development and transferred to an image-receiving layer, have recently become increasingly important become.

The color-providing compounds suitable for this purpose include, for example, the non-diffusing color couplers described in DT-PS 1 095 115, which develop during development as a result of a reaction with the oxidation product of a color consisting of a primary aromatic amine developer compound, free a pre-formed or diffused dye produced in the color coupling. The selection of the developer connection required is naturally limited to color developers.

Furthermore, reference is made to the non-diffusing coloring compounds described in DT-OS 1 930 215, which contain a pre-formed latent diffusible dye residue linked to a diffusion-proofing residue via a cleavable hydrazone group. These compounds are not to be referred to as color couplers, and it has also been found that the choice of developer compounds which are required to release the diffusing dye residue is in no way limited to the usual color developers, but also that black and white developers, for example Catechins are very useful.

DT-OS 1 772 929 also describes non-diffusing colored compounds with a special grouping which undergo an oxidative ring closure reaction during development and thereby release a pre-formed dye residue in a diffusing form. The connections presented there can be divided into two groups. For the development, the compounds of the one group require a customary color developer compound, with the oxidation product of which they couple and in a subsequent ring-salt reaction release the pre-formed dye residue in diffusing form. The compounds of the other group are themselves silver halide developing agents and can therefore, even in the absence of further developer compounds in the oxidized form, initiate the aforementioned ring closure reaction with the release of the diffusing dyes.

Finally, the non-diffusing coloring compounds of DT-OS 2 242 762 should also be mentioned at this point. These are sulfonamidophenols and sulfonamidoanilines which, after oxidation during development, under the influence of the developer alkali with the release of diffusing dyes with a free dye Sulfamoyl group are cleaved.

The coloring compounds mentioned above work without exception negative, i.e. the image-wise distribution of the released diffusing dye arises when standard (negative working) silver halide emulsions are used in accordance with the negative silver image produced during development. In order to generate positive dye images, it is therefore necessary to use direct-positive silver halide emulsions or else to use a suitable reversal process.

Non-diffusing coloring compounds are also known from DT-OSs 2 402 900 and 2 543 902, which in non-oxidized form are capable of a cleavage reaction under alkaline development conditions, a diffusing. the dye is released, and in which, on the other hand, the above-mentioned cleavage reaction is made difficult or prevented in oxidized form. Compounds of this type are suitable in combination with conventional negative emulsions for producing positive transfer color images.

It is difficult to select suitable ones from the hitherto known coloring compounds which are satisfactory in every respect, both on the one hand with regard to their sufficient reactivity and on the other hand with regard to their sufficient stability. They should not release the diffusing dyes already during the alkaline development, but rather only after imagewise oxidation by the imagewise developed silver halide has taken place. On the other hand, the diffusing dyes have to be released quickly enough either from the oxidized or from the non-oxidized form of the color-bound compounds and a rapid transfer of the diffusing dyes is also necessary. It is very important that the dyes can be adequately fixed in the image-receiving layer and that they also have excellent spectral properties and excellent stability against light and heat.

DT-OS 2 626 821 describes coloring compounds which provide yellow dyes for the color diffusion transfer process and which are to be distinguished by particularly advantageous absorption spectra and are said to have excellent color stability. However, it was found that the yellow dyes released from these color compounds left much to be desired in terms of their stability to light.

The invention is therefore based on the object of specifying new coloring compounds for the color diffusion transfer process, from which diffusing yellow dyes are set free during photographic processing, which have the desired spectral properties and good stain resistance, and which are furthermore distinguished by improved stability to light .

worin bedeuten:

• A¹ einen, einen diffusionsfestmachenden Rest enthaltenden oxidierbaren organischen Trägerrest, aus dem unter den Bedingungen der fotographischen Entwicklung entweder in oxidierter Form oder in nichtoxidierter Form durch Entwickleralkali mindestens ein Teil zusammen mit dem diffusionsfestmachenden Rest abgespalten wird unter gleichzeitiger bildmäîiger Freisetzung eines diffundierenden Azofarbstoffes;
• D einen heterocyclischen oder carbocyclischen aromatischen Rest, vorzugsweise eine Phenylgruppe,
• R Wasserstoff, Alkyl mit 1 bis 5 C-Atomen, Aralkyl oder Aryl,
• R und R³ (gleich oder verschieden), je einen der unter R¹ genannten Reste, Sulfo, -COOR⁴, Halogen, Trihalogenmethyl, Acylamino, _Acyloxy (wobei die genannten Acylreste sich ableiten von aliphatischen oder aromatischen Carbon-oder Sulfonsäuren, einschlieîlich aliphatischer und aromatischer Carbaminsäuren und Kohlensäuremonoester), ferner Carbamoyl, Sulfamoyl, -_OR⁴, -S_R ⁴, -SOR⁴, -SO₂-R⁴ (wobei R⁴ eine der für R angegebenen Bedeutungen hat), -NO₂ oder -CN
• 1, m und n jeweils O oder 1 mit der Maîgabe, daî 1 + m + n = 1
• r eine ganze Zahl von 1 bis 4, vorzugsweise 2 oder 3.

The present invention relates to a photographic color diffusion transfer process for the production of colored images, in which a photographic material with at least one photosensitive silver halide emulsion layer and an associated non-diffusing coloring compound is exposed imagewise and developed with a silver halide developing agent, whereby a diffusing dye from the developer alkali is not imagewise - The diffusing coloring compound is split off and transferred to an image receiving layer. The process is characterized in that a compound of the following formula I is used as the non-diffusing coloring compound:

in which mean:

• A ^{1 is} an oxidizable organic carrier residue containing a diffusion-proofing residue, from which, under the conditions of photographic development, either in oxidized form or in non-oxidized form, alkali is split off together with the diffusion-proofing residue by developer alkali, with simultaneous imagewise release of a diffusing azo dye;
• D is a heterocyclic or carbocyclic aromatic radical, preferably a phenyl group,
• R is hydrogen, alkyl having 1 to 5 carbon atoms, aralkyl or aryl,
• R and R ³ (same or different), each one of said radicals from R ^1, sulpho, -COOR ^4, halogen, trihalogenmethyl, acylamino, _A cyloxy (wherein the acyl radicals mentioned are derived from aliphatic or aromatic carboxylic or sulfonic acids, einschlieîlich aliphatic and aromatic carbamic acids and carbonic acid monoesters), also carbamoyl, sulfamoyl, - _O R ⁴ , -S _R ⁴ , -SOR ⁴ , -SO ₂ -R ⁴ (where R ^{4 has} one of the meanings given for R), -NO ₂ or -CN
• 1, m and n each O or 1 with the measure that 1 + m + n = 1
• r is an integer from 1 to 4, preferably 2 or 3.

der entweder über die Gruppe D oder den Rest R oder über den dargestellen Benzolring mit einem diffusionsfestmachenden oxidierbaren organischen Trägerrest verbunden ist. Dieser Trägerrest ist dabei von solcher _Art, daî er entweder in oxidierter Form oder in nichtoxidierter Form unter den Bedingungen der fotografischen Entwicklung durch Entwickleralkali aus den farbgebenden Verbindungen abgespalten wird, so daî diffundierende Azofarbstoffe in Freiheit gesetzt werden. Trägerreste A¹ mit derartigen Funktionen sind bekannt. Hier sei beispielsweise auf die in der eingangs erwähnten DT-OS 2 242 762 beschriebenen Sulfonamidophenole und Sulfonamidoaniline hingewiesen, die nach der bei der Entwicklung erfolgten Oxidation unter Einfluî des Entwickleralkalis unter Freisetzung diffundierender Farbstoffe mit einer freien Sulfonamidgruppe gespalten werden. Weiterhin sei beispielsweise verwiesen auf die in DT-OS 2 505 248 und in der deutschen Patentanmeldung P 2 645 656.4 beschriebenen Verbindungen, z.B. die 3-Sulfonamidoindolverbindungen, die in ähnlicher Weise, wenn sie oxidiert sind, einer Spaltung durch das Entwickleralkali unterliegen und hierbei diffundierende Farbstoffe in Freiheit setzen. Auch diese Verbindungen ermöglichen somit einen Farbübertrag an Stellen, in denen eine Entwicklung stattfindet. Weiterhin müssen an dieser Stelle die DT-OSen 2 402 900 und 2-543 902 erwähnt werden. In diesen beiden Offenlegungsschriften sind farbgebende Verbindungen beschrieben, die in einer Spaltungsreaktion unter alkalischen Entwicklungsbedingungen aus der nicht oxidierten Form diffundierende Farbstoffe in Freiheit setzen und bei denen andererseits in oxidierter Form die obenerwähnte Spaltungsreaktion erschwert oder verhindert.wird. Derartige Verbindungen ermöglichen somit.einen Farbübertrag nur an solchen Stellen, in denen nicht eine durch die Entwicklung bedingte Oxidation.stattgefunden hat. Sie sind somit zur Herstellung positiver _bertragsbilder geeignet.The coloring compounds according to the invention thus contain. an azo dye residue of the formula

which is connected to a diffusion-proofing oxidizable organic carrier residue either via group D or the radical R or via the benzene ring shown. This carrier residue is of such _{a type} that it is split off from the coloring compounds either in oxidized form or in nonoxidized form under the conditions of photographic development by developer alkali, so that diffusing azo dyes are released. Carrier remnants A ¹ with such functions are known. Attention is drawn here, for example, to the sulfonamidophenols and sulfonamidoanilines described in the above-mentioned DT-OS 2 242 762, which are cleaved with a free sulfonamide group after the oxidation which has occurred during development under the influence of the developer alkali with the release of diffusing dyes. Furthermore, reference is made, for example, to the compounds described in DT-OS 2 505 248 and in German patent application P 2 645 656.4, for example the 3-sulfonamidoindole compounds, which, when oxidized, undergo cleavage by the developer alkali and thereby release diffusing dyes. These connections therefore also enable color transfer at locations where development takes place. DT-OSen 2 402 900 and 2-543 902 must also be mentioned here. These two published documents describe coloring compounds which, in a cleavage reaction under alkaline development conditions, liberate diffusing dyes from the non-oxidized form and, on the other hand, in oxidized form the above-mentioned cleavage reaction is made more difficult or prevented. Such compounds thus enable a color transfer only in those places in which no development-related oxidation has taken place. They are therefore suitable for producing positive transfer patterns.

worin bedeuten

• _A ² einen gegebenenfalls über ein Bindeglied X angeknüpften einen diffusionsfestmachenden Rest enthaltenden oxidierbaren organischen Trägerrest in o-, m- oder p-Stellung zur Azogruppe, aus dem unter den Bedingungen der fotografischen Entwicklung entweder in oxidierter Form oder in nicht oxidierter Form durch Entwickleralkali mindestens ein Teil zusammen mit dem diffusionsfestmachenden Rest abgespalten wird unter gleichzeitiger bildmäîiger Freistellung eines diffundierenden Azofarbstoffes;
• A³ einen gegebenenfalls über ein Bindegleid X angeknüpften einen diffusionsfestmachenden Rest enthaltenden oxidierbaren organischen Trägerrest, der entweder direkt oder über einen der Substituenten R² und R³ in o- oder m-Stellung an den die Cyanalkylaminogruppe tragenden Phenylring angeknüpft ist und aus dem unter den Bedingungen der foto- . grafischen Entwicklung entweder in oxidierter Form oder nicht oxidierter Form durch Entwickleralkali mindestens ein Teil zusammen mit dem diffusionsfest machenden Rest abgespalten wird unter gleichzeitiger bildmäîiger Freisetzung eines diffundierenden Azofarbstoffes,
• A⁴ einen gegebenenfalls über ein Bindeglied X angeknüpften, einen diffusionsfestmachenden Rest enthaltenden oxidierbaren organischen Trägerrest, der mit dem Substituenten R¹ verknüpft ist und aus dem unter den Bedingungen der fotografischen Entwicklung entweder in oxidierter Form oder in nicht oxidierter Form durch Entwickleralkali mindestens ein Teil zusammen mit dem diffusionsfestmachenden Rest abgespalten wird, unter gleichzeitiger bildmäîiger Freisetzung eines diffundierenden Azofarbstoffs;
• R⁵ und R (gleich oder verschieden) je einen Substituenten der bei der Erläuterung der Formel I für _R ² und R angegebenen Art, vorzugsweise Wasserstoff, Halogen wie Chlor, Alkyl wie Methyl, Alkoxy wie Methoxy, Acylamino wie Acetamino oder Nitro,
• X ein bivalentens Bindeglied der Formel
  
  worin R einen Alkylenrest mit 1 bis 6 C-Atomen
  
  einen gegebenenfalls substituierten
  
  deutet und wobei die beiden Reste R gleiche oder verschiedene Bedeutungen haben können;
• L -O-, -CO-, -CONR⁷ , -SO₂NR⁷ , -O-CO-NR⁷ , -S-, -SO₂-, -SO- bedeutet (R7 = Wasserstoff oder Alkyl)
• p = 0 oder 1
• q = 0 oder 1 , wobei q = 1, falls p = 1
• s = 0 oder 1

und worin R¹, R², R³, 1, m, n und r die bereits angegebene Bedeutung haben.Compounds preferably used according to the invention correspond to the following formula II:

in what mean

• _A ² an oxidizable organic carrier residue, optionally linked via a link X and containing a diffusion-proofing residue, in the o-, m- or p-position to the azo group, from which, under the conditions of photographic development, either in oxidized form or in non-oxidized form by developer alkali part is split off together with the diffusion-proofing residue with simultaneous visual release of a diffusing azo dye;
• A ^{3 is} an oxidizable organic carrier residue which is optionally attached via a bond X and contains a diffusion-fixing residue, which is attached either directly or via one of the substituents R ² and R ³ in the o- or m-position to the phenyl ring bearing the cyanoalkylamino group and from which under the Conditions of the photo. graphic development either in oxidized form or non-oxidized form by means of developer alkali, at least part of it is split off together with the rest which makes it resistant to diffusion, with simultaneous imagewise release of a diffusing azo dye,
• A ^{4 is} an oxidizable organic carrier residue which is optionally linked via a link X and contains a diffusion-proofing residue and which is linked to the substituent R ¹ and of which at least part together under the conditions of photographic development either in oxidized form or in non-oxidized form by developer alkali is split off with the diffusion-proofing residue, with simultaneous imagewise release of a diffusing azo dye;
• R ⁵ and R (identical or different) each have a substituent of the type given for the explanation of the formula I for _R ² and R, preferably hydrogen, halogen such as chlorine, alkyl such as methyl, alkoxy such as methoxy, acylamino such as acetamino or nitro,
• X is a bivalent link in the formula
  
  wherein R is an alkylene radical having 1 to 6 carbon atoms
  
  an optionally substituted one
  
  indicates and where the two radicals R may have the same or different meanings;
• L denotes -O-, -CO-, -CONR ⁷ , -SO ₂ NR ⁷ , -O-CO-NR ⁷ , -S-, -SO ₂ -, -SO- (R7 = hydrogen or alkyl)
• p = 0 or 1
• q = 0 or 1, where q = 1 if p = 1
• s = 0 or 1

and wherein R ¹ , R ² , R ³ , 1, m, n and r have the meaning already given.

worin die Symbole R¹, _R ², _R ³, _R ⁵, _R ⁶, X, _r und _s die
bereits angegebene Bedeutung haben und A⁵ den mit mindestens einem diffusionsfestmachendem Rest substituierten Rest einer der folgenden Formeln bedeutet

worin

• sierten gegebenenfalls substituierten carbocyclischen oder heterocyclischen Ringes steht, und
• R⁸ Wasserstoff, Alkyl, _Alkoxy, Aryl, eine heterocyclische Gruppe Carboxyl, Carbamoyl oder Alkoxycarbonyl bedeutet.

Particularly preferred compounds of the present invention correspond to the following formula III

wherein the symbols R ¹ , _R ² , _R ³ , _R ⁵ , _R ⁶ , X, _r and _s the
have already given meaning and A ^{5 means} the radical of one of the following formulas which is substituted by at least one diffusion-proofing radical

wherein

• based optionally substituted carbocyclic or heterocyclic ring, and
• R ⁸ represents hydrogen, alkyl, _A lkoxy, aryl, a heterocyclic group carboxyl, carbamoyl or alkoxycarbonyl.

A ⁵ thus represents in the preferred embodiment of the present invention together with the linking. -NH-SO ₂ grouping a non-diffusible oxidizable organic carrier residue, namely a carrier residue which is only subjected to cleavage by the developer alkali in the oxidized form. Dye diffusion therefore only takes place at those points in the photographic material where silver halide development takes place. Color-imparting compounds with carrier residues of the type represented by A ⁵ are described in DT-OS 2 242 762, in DT-OS 2 5o5 248 and the German patent application P 2 645 656.4.

und

The bivalent link X shown in general formulas II to III can be, for example, a radical of one of the following formulas:

and

It should be pointed out that the coloring compounds according to the invention should not diffuse as intact molecules in the layers of the photographic material. For this purpose they contain a diffusion-proofing residue e.g. the rest Z.

Adequate diffusion resistance of the coloring compounds can already be provided even if the coloring compounds. Compounds do not contain any longer alkyl residues, because then the molecule can have a sufficient size, depending on the dye residue. Otherwise it is possible to make the coloring compounds sufficiently diffusion-resistant by selecting residues of a suitable size.

Residues which allow the compounds according to the invention to be stored diffusion-resistant in the hydrophilic colloids which are customarily used in photographic materials are to be regarded as residues which prevent diffusion. Organic radicals are preferably suitable for this purpose, the generally straight-chain or branched aliphatic groups and optionally also isocyclic or heterocyclic or aromatic groups with generally 8-20 C atoms. contain. These radicals are either directly or indirectly connected to the rest of the molecule, for example via one of the following groups: -NHCO-, -NHSO ₂ -, -NR-, where R is hydrogen or alkyl, -O- or -S-. In addition, the diffusion-proofing radical can also contain water-solubilizing groups, such as sulfo groups or carboxyl groups. groups, which may also be in anionic form. Since the diffusion properties depend on the molecular size of the total compound used, it is sufficient in certain cases, for example if the "total molecule used is large enough, to use shorter-chain residues as" diffusion-resistant residues ".

During development, at least part of the carrier residue is split off from the non-diffusing coloring compounds according to the invention together with the diffusion-proofing residue, with the liberation of a diffusing azo dye. At the same time, chemical conversion can take place in the split off carrier residue, e.g. an intramolecular rearrangement in the form of a ring closure reaction.

wobei R¹, R², R³, R⁵, R⁶, r und die bereits angegebene Bedeutung haben.The released diffusing azo dyes, for example in the case of the non-diffusing coloring compounds of the formula III, have a free sulfamoyl group and correspond to the following formula IV

where R ¹ , R ² , R ³ , R ⁵ , R ⁶ , r and have the meaning already given.

Verbindung Nr. 10

R max: 420 nmExamples of suitable coloring compounds according to the present invention are the following:

Compound No. 10

R max: 420 nm

Preparation of Compound No. 2 a) 3- (4-N-Methyl-N-cyanoethyl-aminobenzene-azole-4-chlorobenzenesulfonic acid

To a suspension of 69.2 g of 3-amino-4-chlorobenzenesulfonic acid (90%) in 500 ml of H ₂ 0 and 90 ml of concentrated hydrochloric acid was a solution of 20.7 g of sodium nitrite in 60 ml of H ₂ 0 at 0-5ÝC dripped. The suspension was stirred for 30 minutes. Excess nitrite was destroyed with amidosulfonic acid. The suspension was introduced at 5-10ÝC in a solution of 48 g of 3- (N-methyl-anilino) propiononitrile in 240 ml of acetone. The pH was then adjusted to 3.5 with 20% sodium acetate solution. The mixture was stirred at 5-10 ° C. for 3 hours and then overnight without cooling. The dye was filtered off, washed with 10% saline and dried. Yield 93 g; Mp .:> 225Ý (Z).

b) 3- (4-N-methyl-N-cyanoethyl-aminobenzene-azo) -4-chlorobenzenesulfonic acid chloride

22.8 ml of POCl ₃ were introduced into an initial charge of 140 ml of dimethylformamide. The solution was cooled to 25 ° C. and 19 g of 3- (4-N-methyl-N-cyanoethyl-aminobenzene-azo) -4-chlorobenzenesulfonic acid were introduced at 25 ° C. The mixture was stirred at 25 ° C for 1 hour. The mixture was then discharged onto ice and the precipitate which formed was filtered off with suction, washed with water and dried. Yield 18 g; Fp.:>155Ý(z).

c) Compound No. 2.

die durch Umsetzung von 2-(2,4-Ditert.-pentylphenoxybutyl- amino-carbonyl)-3-amino-5-methoxy-indol (dessen Darstellung nach einer in der deutschen Patentanmeldung.P 2 645 656.4 beschriebenen Methode erfolgt) mit 3-Nitrobenzolsulfonsäurechlorid und anschlieîend katalytischer Hydrierung hergestellt wurde, wurde mit 100 ml Chloroform und 3,2 ml Pyridin angeschlämmt und mit 4,4 g 3-(N-Methyl-N-cyan- äthyl-aminobenzol-azo)-4-chlorbenzolsulfonsäurechlorid versetzt. Der Ansatz wurde 10 Stunden bei 40ÝC gerührt. Anschlieîend wurde der Ansatz gekühlt und unter Zugabe von 350 ml Methanol 30 Minuten gerührt. Der ausfallende Niederschlag wurde abgesaugt; mit Methanol gewaschen und getrocknet.6.48 g of the compound of the following formula

by the reaction of 2- (2,4-ditert.-pentylphenoxybutylamino-carbonyl) -3-amino-5-methoxy-indole (which is prepared by a method described in German patent application P 2 645 656.4) with 3 -Nitrobenzenesulfonyl chloride and then catalytic hydrogenation was prepared, was suspended with 100 ml of chloroform and 3.2 ml of pyridine and mixed with 4.4 g of 3- (N-methyl-N-cyano-ethyl-aminobenzene-azo) -4-chlorobenzenesulfonic acid chloride. The mixture was stirred at 40ÝC for 10 hours. The mixture was then cooled and stirred for 30 minutes with the addition of 350 ml of methanol. The precipitate was filtered off; washed with methanol and dried.

Yield 6.1 g; Fp .: 244-246Ý (Z).

The other coloring compounds of the present invention can also be prepared in an analogous manner.

For the absorption measurement and light-fastness test (see example 2), the diffusing dyes split off from the coloring compounds according to the invention are used. The preparation of the dye released from compound 2 is described here as an example.

Dye from compound 2:

1.73 g of 3-aminobenzenesulfonamide were suspended in 40 ml of chloroform and 3.2 ml of pyridine and mixed with 4.4 g of 3- (4-N-methyl-N-cyanoethyl-aminobenzene-azo) -4-chlorobenzenesulfonic acid chloride (90 %) offset. The mixture was stirred at 40ÝC for 4 h. A further 0.4 g of sulfochloride were added and the mixture was stirred again at 40 ° C. for 3 hours. The precipitate was filtered off and washed with chloroform and dried. The filter cake was stirred with 2N hydrochloric acid, suction filtered, washed with 2N hydrochloric acid and H ₂ 0. The substance was then purified by extracting several times with ethyl acetate and concentrating the mother liquor. Yield 3.5; Mp .: 120-122Ý (Z).

The compounds according to the invention are colored yellow. They are incorporated in casting solutions for the layers of photographic material using one of the usual methods. The amount of coloring compound used per liter of casting solution varies within relatively wide limits, the most favorable concentration being determined on the basis of simple experiments. For example, 5 to 80 g, preferably 20 to 40 g, of coloring compound are used per liter of pouring solution.

und 1 099 414 bis 1 099 417 beschrieben.

möglich, wäîrige Dispersionen der farbgebenden Verbindungen herzustellen und den jeweiligen Gieîlösungen zuzusetzen. Hierzu werden wäîrige Aufschlämmungen der farbgebenden Verbindung beispielsweise durch intensives Rühren unter Zusatz von scharfkantigem Sand oder durch Anwendung von Ultraschall fein vermahlen. In einer weiteren Ausführungsform kann es beispielsweise erwünscht sein, die farbgebenden Verbindungen gemeinsam mit Silberhalogenid und gegebenenfalls Entwicklersubstanzen in Form sogenannter Mikrokapseln in die Schicht einzulagern, wobei auch zwei oder mehr verschieden sensibilisierte lichtempfindliche Silberhalogenid-Emulsionen und die entsprechenden diffusionsfesten Verbindungen in einer einzigen Schicht nach der Art der sogenannten Mischkorn-Emulsionen vereinigt werden, wie dies beispielsweise in der amerikanischen Patentschrift 2 698 794 beschrieben ist. Die nicht diffundierenden farbgebenden Verbindungen können in einer lichtempfindlichen Schicht selbst oder in einer Nachbarschicht untergebracht sein. Beispielsweise ist der rotempfindlichen Schicht eine einen blaugrünen Farbstoff abspaltende Verbindung, der grünempfindlichen Schicht eine einen purpurnen Farbstoff abspaltende Verbindung, und der blauempfindlichen Schicht eine der erfindungsgemäîen einen gelben Farbstoff abspaltende farbgebende Verbindung zugeordnet.The association between diffusion-resistant coloring compound and silver halide required to achieve the desired effect can be established, for example, by introducing the diffusion-resistant compounds into the casting solutions using aqueous-solubilizing groups from aqueous alkaline solutions. The non-diffusing coloring compounds can also be in the layers according to one of the known Emulsification processes are incorporated. Such procedures are, for example, in the English

and 1,099,414 to 1,099,417.

possible to prepare aqueous dispersions of the coloring compounds and add them to the respective casting solutions. For this purpose, aqueous slurries of the coloring compound are finely ground, for example by intensive stirring with the addition of sharp-edged sand or by using ultrasound. In a further embodiment, it may be desirable, for example, to store the coloring compounds together with silver halide and, if appropriate, developer substances in the form of so-called microcapsules, two or more differently sensitized light-sensitive silver halide emulsions and the corresponding diffusion-resistant compounds in a single layer after the Type of the so-called mixed grain emulsions can be combined, as is described, for example, in US Pat. No. 2,698,794. The non-diffusing coloring compounds can be accommodated in a light-sensitive layer itself or in a neighboring layer. For example, the red-sensitive layer is assigned a compound that cleaves a blue-green dye, the green-sensitive layer is assigned a compound that cleaves a purple dye, and the blue-sensitive layer is assigned a coloring compound that cleaves a yellow dye according to the invention.

• N-Methylaminophenol
• 1-Fhenyl-3-pyrazolidon
• 1-Phenyl-4,4-dimethyl-3-pyrazolidon
• 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidon
• Aminophenole
• N,N-Diäthyl-p-phenylendiamin
• N--thyl-N-hydroxyäthyl-p-phenylendiamin
• N--thyl-N-ω-sulfobutyl-p-phenylendiamin
• 3-Methyl-N,N-diäthyl-p-phenylendiamin
• N,N,N',N'-Tetraalkyl-p-phenylendiamine wie Tetramethyl-p-phenylendiamin, 1,4-Bis-pyrrolidinobenzol, Reduktone.

“Assignment” and “assigned” mean that the mutual arrangement of silver halide emulsion and coloring. A connection of this kind is that an interaction between them is possible, which is a pictorial correspondence between the silver image formed (in the case of negative working coloring compounds) or undeveloped silver halide (for positive working coloring compounds) on the one hand and pictorial distribution of the releasing, diffusing dye on the other hand. The assigned coloring compound is expediently incorporated into the silver halide emulsion itself or into a layer adjacent to the silver halide emulsion layer, this adjacent layer preferably being located behind the silver halide emulsion layer (viewed in the direction of the light incident during exposure). The color-imparting compounds according to the invention are oxidized image-wise during the development of the silver image of developer oxidation products and are then subjected to a cleavage reaction under the influence of the developer or activator alkali, in which the dye residues are generally released in the form of dye sulfonamides in diffusing form. The usual photographic developer compounds are suitable for development, and they are capable of oxidizing the color-imparting compounds according to the invention in oxidized form. Examples of suitable developers are as follows: hydroquinone

• N-methylaminophenol
• 1-fhenyl-3-pyrazolidone
• 1-phenyl-4,4-dimethyl-3-pyrazolidone
• 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone
• Aminophenols
• N, N-diethyl-p-phenylenediamine
• N - ethyl-N-hydroxyethyl-p-phenylenediamine
• N - thyl-N-ω-sulfobutyl-p-phenylenediamine
• 3-methyl-N, N-diethyl-p-phenylenediamine
• N, N, N ', N'-tetraalkyl-p-phenylenediamines such as tetramethyl-p-phenylenediamine, 1,4-bis-pyrrolidinobenzene, reductones.

It should be pointed out in particular that the selection of developer substances in the process according to the invention is not limited to color developers, but that conventional black and white developers can also be used, which is to be regarded as an advantage because of the lower tendency to discolouration of the latter. The developers can already be contained in the layers of the color photographic material, where they are activated by the alkaline activator liquid, or in the alkaline processing liquid or paste. Since the coloring compounds according to the invention themselves have developer properties, the use of auxiliary developer compounds can be dispensed with in individual cases. In this case, the coloring compound is immediately oxidized by developable silver halide.

If the pictorial distribution of the diffusing dye released during development matches the developed silver image, as is the case with the coloring compounds of the type as described in DT-OSen 2 242 762, 2 505 248 and also DT-OS 1 772 929, the use of direct-positive silver halide emulsions or, if conventional negative emulsions are used, the use of a suitable reversal process is required to generate positive colored transfer images. In the case of the coloring compounds of the last-mentioned DT-OS, the diffusing dyes are not released as a result of an alkali cleavage, but rather as a result of an intramolecular displacement reaction with a ring closure. Also, the dyes released do not have a free sulfamoyl group like the dyes split off from the coloring compounds preferably used according to the invention, but a sulfinic acid group. However, the invention is in no way limited to those coloring compounds in which the cleavage is carried out by alkali.

Such a reversal process is available in the silver salt diffusion process. The photographic reversal by means of the silver salt diffusion process for the production of positive color images by using conventional color couplers is for example in the _US - _PS described 2,763,800. By exchanging the color couplers for the coloring compounds mentioned, a light-sensitive element is obtained which is suitable for the dye diffusion transfer process. Such a light-sensitive element has, for example, at least one combination of a light-sensitive silver halide emulsion layer and a binder layer associated therewith, which contains development nuclei for physical development and a coloring compound.

During the development, the exposed portion of the silver halide is chemically developed in the light-sensitive silver halide emulsion layer; the unexposed portion is transferred by means of a silver halide solvent into the binder layer containing the associated development nuclei and is physically developed there. If a developer is used for the physical development, which is able to release a diffusing dye in oxidized form as a result of a reaction with the coloring compound present in this layer, then an image-wise distribution of diffusing dyes results, which is applied to an image receiving layer can be transferred and form a positive colored image there.

When reversed using compounds which release imagewise development inhibitors, the photosensitive element consists of at least one layer combination of a photosensitive silver halide emulsion layer and a second, unexposed, developable emulsion layer containing the coloring compound. The light-sensitive silver halide emulsion layer is developed, for example, with color developers in the presence of certain compounds which release development-inhibiting substances on reaction with oxidized color developers. The development-inhibiting substances released in the photosensitive layer diffuse into the neighboring, unexposed, developable emulsion layer and inhibit development there. The uninhibited (positive) portions of the unexposed developable emulsion layer are developed by the remaining developer, whose oxidation products then react with the non-diffusing coloring compounds according to the invention with the release of diffusing dyes, which are transferred imagewise to the image receiving element. Suitable compounds which split off development-inhibiting substances on reaction with color developer oxidation products are, for example, the known DIR couplers (DIR m development inhibitor releasing), which are color couplers which contain a detachable inhibitor residue in the coupling point. Such DIR couplers are described, for example, in US Pat. No. 3,227,554.

Another group of compounds which release development-inhibiting substances upon reaction with color developer oxidation products is described in US Pat. No. 3,632,345. These are not color couplers. Accordingly, no dyes are formed when the development-inhibiting substances are released. According to DT-PS 1 229 389, suitable substituted, non-diffusing hydroquinone compounds can also be used in such a process, which are oxidized to the corresponding quinones in the reaction with developer oxidation products and thereby release development-inhibiting mercaptans.

kommen beispielsweise solche Silberhalogenidemulsionen, in deren durch Belichten oder durch chemische Behandlung ein entwickelbarer Schleier erzeugt worden ist, der unter Einhaltung bestimmter Bedingungen bei
der bildmäîigen Pelichtung bildmäîig zerstört wird. An den wbelichteten Stellen bleibt der Schleien erhalten, so daî

Entwicklung ein direkt positives Silberid erralten find, und in _bereinstimmung damit

maîige vertailung an diffundi dem Farbstoff,

der direkt positiven Silberhalogenidemulsion eine erfindungsgemäîe farb- gebende Varbindang zugeordnet ist.In principle, all directly positive silver halide emulsions are suitable as direct positive silver halide emulsions which, with simple development, produce a positive silver image and a corresponding image-like distribution of developer oxidation products.

come, for example, those silver halide emulsions in which a veil that can be developed by exposure to light or by chemical treatment has been created, which adheres to certain conditions
the pictorial direction is visually destroyed. The tench remains in the exposed areas, so daî

Development will get a directly positive silveride, and in accordance with it

moderate entanglement with diffundi the dye,

the directly positive silver halide emulsion is assigned a color-imparting varnish dye according to the invention.

ein Silberbild mit ausreichender Dichte entsteht. '

a silver image with sufficient density is created. '

The selective veiling of the imagewise exposed, unveiled direct positive emulsions can be done before or. during development by treatment with a ver _. lubricants are made. Suitable fogging agents are reducing agents such as hydrazine or substituted hydrazines. Reference is made, for example, to US Pat. No. 3,227,552, the obscurant also being able to be embedded in a diffusion-resistant manner.

Unveiled direct positive emulsions are, for example, those that are inside the silver halide grains; Have defects (US 2,592,250) or silver halide emulsions with layered grain structure (DT-OS 2,308,239).

If coloring compounds according to the invention are used with a non-diffusing oxidizable carrier residue of the type described in DT-OSs 2'402 900 and 2 543 902 is described, ie a carrier residue which is only split off by alkali in the non-oxidized form, while in the oxidized form the splitting is difficult or prevented, e: a is of course required to produce positive transfer. pictures no direct positive emulsions and no reverse processes, but usual negative emulsions are sufficient.

The emulsions can also be chemically sensitized, e.g. by adding sulfur-containing compounds during chemical ripening, for example allyl isothiocyanate, allyl thiourea, sodium thiosulfate and the like. As chemical pensitizers such reducing agents such. B. the tin compounds described in Belgian patents 493 464 and 568 687, also polyamines such as diethylenetriamine, or aminomethanesulfinic acid derivatives, e.g. B. Geräî the Belgian patent 547 323 can be used.

Precious metals or noble metal compounds such as gold, platinum, palladium, iridium, ruthenium or rhodium are also suitable as chemical sensitizers. This method of chemical sensitization is described in the article by R. Koslowsky, Z. Wiss. Phot. 46, 65-72 (1951).

It is also possible to sensitize the emulsions with polyalkylene oxide derivatives, e.g. with polyethylene oxide of a molecular weight, between 1000 and 20,000, also with condensation products of alkylene oxides and aliphatic alcohols, glycols, .cyclic dehydration products of hexitols, with alkly-substituted phenols, aliphatic carboxylic acids, aliphatic amines, aliphatic diamines and amides. The condensation products have a molecular weight of at least 700, preferably more than 1000. To achieve special effects, these sensitizers can of course be used in combination, as described in Belgian patent 537 278 and British patent 727 982.

The emulsions can also be spectrally sensitized, e.g. through the usual mono- or polymethine dyes, such as acidic or basic cyanines, hemicyanines, streptocyanines, merocyanines, oxonols, hemioxonols, styryl dyes or other, also trinuclear or polynuclear methine dyes, for example rhodacyanines or neocyanines. Such sensitizers are described, for example, in F.M. Hamer's work "The Cyanine Dyes and Related Compounds" (1964) Interscience Publishers John Wiley and Sons.

The emulsions can contain the usual stabilizers, e.g. homeopolar or salt-like compounds of mercury with aromatic or heterocyclic rings; such as mercaptotriazoles, simple mercury salts, sulfonium mercury double salts and other mercury compounds. Also suitable as stabilizers are azaindenes, preferably tetra- or penta-azaindenes, in particular those which are substituted by hydroxyl or amino groups. Such connections are in the Birr article. Z. Wiss. Phot. 47, 2-27 (1952). Other suitable stabilizers include heterocyclic mercapto compounds, e.g. Phenyl mercaptotetrazole, quaternary benzothiazole derivatives, benzotriazole and the like.

kann in der üblichen Weise erfolgen, beispielsweise mit Formaldehyd oder halogensubstituierten Aldehyden, die- eine Carboxylgruppe enthalten, wie Mucobromsäure, Diketonen, Methansulfonsäureester, Dialdehyden.Gelatin is preferably used as the binder for the photographic layers. However, this can be replaced in whole or in part by other natural or synthetic binders. Examples of suitable natural binders are alginic acid and its derivatives such as salts, esters or amides, cellulose derivatives such as carboxymethyl cellulose, alkyl cellulose such as hydroxyethyl cellulose, starch or their derivatives such as ether or esters or caragenates. Synthetic binders include polyvinyl alcohol, partially saponified polyvinyl acetate, polyvinyl pyrrolidone and the like

can be carried out in the usual manner, for example with formaldehyde or halogen-substituted aldehydes which contain a carboxyl group, such as mucobromic acid, diketones, methanesulfonic acid esters, dialdehydes.

• 2) eine Bildempfangsschicht
• 3) eine lichtundurchlässigeSchicht
• 4) ein lichtempfindlichen Element mit aindostens
  
  
  und mindestens einer dieser zugaordneten nichtdiffundierenden, farbgebenden verbindung
• 5) eine Verzögerungsschicht
• 6) eine saure Polymerschicht
• 7) einen
  
  Schichtträger

To carry out the dye diffusion transfer process according to the present invention, a light-sensitive element is used which contains one or more silver halide emulsion layers and the associated non-diffusing, coloring compounds, and an image-receiving element in which the diffusing dyes transferred by the image transfer the desired Color image is generated. For this purpose, it is necessary that there is firm contact between the photosensitive element and the image-receiving element for at least a finite period within the development period, so that the image-wise distribution of diffusing dyes in the photosensitive element as a result of the development occurs on the image. . pfangselement can be transferred. The contact can be made after development has started or it can have been made before development begins. The latter is the case, for example, if a material is used to carry out the dye diffusion transfer process in which the light-sensitive element and the image-receiving element form an integral unit, also referred to below as mono-sheet material, which continues to exist even after the development process has ended; that is, a separation of the photosensitive element from the image receiving element is not provided even after the color transfer. Such an embodiment is described, for example, in DT-OS 2 019 430

• 2) an image receiving layer
• 3) an opaque layer
• 4) a photosensitive element with aindostens
  
  
  and at least one of these associated non-diffusing, coloring compound
• 5) a retardation layer
• 6) an acidic polymer layer
• 7) one
  
  Layer support

The mono-sheet material can be composed in such a way that two different parts are produced separately from one another, namely the light-sensitive part (layer elements 1-4) and the cover sheet (layer elements 5-7), which are then placed on one another on the layer side and connected to one another, if appropriate using spacer strips so that a space is formed between the two parts for receiving a precisely measured amount of a working fluid. The layer elements 5 and 6, which together form the neutralization system, can also be arranged, albeit in the opposite order, between the layer support and the image-receiving layer of the light-sensitive part.

Means may be provided to introduce a working fluid between the photosensitive member and the cover sheet, e.g. in the form of a laterally arranged, splitable container which, when subjected to mechanical forces, pours its contents between two adjacent layers of the mono-sheet material.

An essential part of the photographic material according to the present invention is the photosensitive element _; which, in the case of a single-dye transfer process, contains a photosensitive silver halide emulsion layer and associated with it, a non-diffusing coloring compound. The non-diffusing compound can be in a layer adjacent to the silver halide emulsion layer, or in the silver halide emulsion layer itself, in the latter case the color of the image dye is preferably selected so that the predominant absorption range of the color-imparting compound does not match the predominant sensitivity range of the silver halide emulsion layer. To produce multicolored transfer images in true-to-life colors, however, the photosensitive element contains three such assignments of coloring compound and photosensitive silver halide emulsion layer _; sorpticnsbereich the coloring compound with the range of spectral sensitivity of the associated silver halide emulsion layer will substantially match. The prerequisite for the highest possible sensitivity, however, is that the color-providing combination is arranged in a separate binder layer (seen in the direction of the light incident during the exposure) behind the silver halide emulsion layer.

• Blauempfindliche Silberhalogenidemulsionsschicht
• Schicht mit nichtdiffundierender, einen diffundierenden Gelbfarbstoff freisetzender Verbindung.
• Trennschicht,
• Crürisensibilisierte Silberhalogenidemulsionsschicht,
• Schicht mit nichtdiffundierender, einen diffundierenden Purpurfarbstoff freisetzender Verbindung
• .Trennschicht
• Rotsensibilisierte Silberhalogenidemulsionsachicht,
• Schicht mit nichtdiffundierender, einen diffundierenden BlaugrUnfarbstoff freisetzender Verbindung.

The developer oxidation products resulting from the development of a silver halide emulsion may of course only have an effect on the assigned coloring compound. Separating layers are therefore generally present in the photosensitive element, which effectively prevent the diffusion of the developer oxidation products into other unassigned layers. These separating layers can contain, for example, suitable substances which react with the developer oxidation products, for example non-diffuse dating hydroquinone derivatives, or if the developer is a color developer substance, non-diffusing color couplers. In a preferred embodiment, the photosensitive element therefore has the following structure (from top to bottom):

• Blue sensitive silver halide emulsion layer
• Layer with non-diffusing compound which releases a diffusing yellow dye.
• Interface,
• Crisis-sensitized silver halide emulsion layer,
• Layer with non-diffusing compound which releases a diffusing purple dye
• Separating layer
• Red-sensitized silver halide emulsion layer,
• Layer with a non-diffusing compound that releases a diffusing cyan dye.

Of course, the silver halide emulsion layers can also be arranged in a different order, but the assigned layers must also be interchanged with the coloring systems, so that the assignment is retained.

The opaque layer located under the photosensitive element is permeable to aqueous alkaline treatment solutions and thus to the diffusing dyes. It has two main functions. First, it serves to cover the image silver remaining in the original photosensitive element after development, as well as the coloring compounds remaining as color negatives, so that when viewed through the transparent layer support of the photosensitive part, only the positive color transfer image is visible. Second, it closes the light-sensitive element in a light-tight manner on the side of the image-receiving layer (downward). The latter is particularly important if, after exposure, the mono-sheet material is still brought into contact with the alkaline processing compound in the camera, then is to be pulled out of the camera and developed outside the camera.

Layers with sufficient opacity, but sufficient permeability for diffusing dyes can, for example, with suspensions of inorganic or organic darker; preferably black pigments, e.g. with suspensions of Ruî in suitable binders e.g. be made in gelatin solutions. In general, 0.5 to 2 / u thick layers containing 10 to 90% by weight (based on the total dry weight) of ruin in gelatin are sufficient in order to ensure sufficient exclusion of the light during development. The particle size of the pigments used is relatively uncritical as long as it does not significantly exceed 0.5 u.

In addition to the black pigment layer, the opaque layer preferably also comprises a white pigment layer arranged underneath. This has the task of covering the black layer and creating a white background for the picture. All white pigments are suitable for this, provided that their opacity is sufficiently high for layers that are not too large. Examples include barium sulfate, oxides of zinc, titanium, silicon, and aluminum minium and zircon, also barium stearate or kaolin. Titanium dioxide is preferred as the white pigment. The same information applies to the binder, the concentration and the particle size as for the black pigments. The thickness of the white pigment layer can be varied depending on the desired white background. Thicknesses between 5-20 / u are preferably used.

Instead of the opaque layer, means for producing such an opaque layer may also be arranged in the monosheet material according to the present invention between the photosensitive element and the image-receiving layer, e.g. in the form of a laterally arranged container with a working fluid containing an opacifying agent (pigment) which, when subjected to mechanical forces, pours its contents between the layers mentioned, so that such a pigment layer forms there.

The image-receiving layer essentially consists of a binder which contains dye mordants for fixing the diffusing dyes.

Long-chain quaternary ammonium or phosphonium compounds or ternary sulfonium compounds, for example those as described in US Pat. Nos. 3,271,147 and 3,271,148, are preferably used as mordants for acidic dyes. Certain metal salts and their hydroxides, which are sparingly soluble with the acidic dyes, may also be used Form connections, be used. The dye mordants are dispersed in the receiving layer in one of the usual hydrophilic binders, for example in gelatin, polyvinylpyrrolidone, completely or partially hydrolyzed cellulose residues and the like. Of course, some binders can also act as pickling agents, for example

Copolymers or polymer mixtures of vinyl alcohol and N-vinylpyrrolidone as described for example in DT-AS 1 130 284, furthermore those which are polymers of nitrogen-containing quaternary bases, for. B. Polymers of N-methyl-2-vinylpyridine, as described, for example, in US Pat. No. 2,484,430. Further usable binding agents are, for example, guanylhydrazone derivatives of acylstyrene polymers, as described, for example, in DT-OS 2,009,498 however, the last-mentioned pickling binders other binders, for example Add gelatin.

As the transparent layer support for the monosheet material according to the invention, the usual transparent support materials used in photographic practice, e.g. Films made of cellulose esters, polyethylene terephthalate, polycarbonate or other film-forming polymers can be used.

The alkaline processing composition sets a relatively high pH in the light-sensitive material (about 1 _' 1 to 14), which triggers the development and the imagewise dye diffusion. It has been shown that the dyes and thus the images obtained are not particularly stable at this high pH. It is therefore necessary that the material is made almost neutral or weakly acidic after development is complete. This can be achieved in a known manner in that the material additionally contains an acidic polymer layer, which is only gradually accessible to the alkaline processing composition in the course of development. An acidic polymer layer is understood to mean a binder layer which contains polymeric compounds with acid groups, preferably sulfo or carboxyl groups. These acidic groups react with the cations of the processing mass to form salt and lower the pH of the mass. Of course, the polymeric compounds and thus the acidic groups embedded in the above-mentioned layer in a diffusion-resistant manner. In many cases, the acidic polymers are derivatives of cellulose or derivatives of polyvinyl compounds, but other polymeric compounds can also be used. Examples of useful acidic polymers which may be mentioned are: cellulose derivatives with a free carboxyl group, for example celulose dicarboxylic acid semiesters with a free carboxyl group, such as cellulose acetate hydrogen phthalate, cellulose acetate hydrogen glutarate, ethyl cellulose acetate hydrate succinate, cellulose acetate with hydrogen dehydrogenated sulfide, sulfate dehydrogenated sulfonate, sulfonic acid, are modified, for example, with o-sulfobenzoic anhydride, carboxymethyl cellulose, also polystyrene sulfonic acid, polyvinyl hydrogen phthalate, polyvinyl acetate hydrogen phthalate, polyacrylic acid, acetals of polyvinyl alcohol with aldehydes which are substituted by carboxy or sulfo groups, such as o-, m- or p-benzaldehyde acid, partial acid or partial ester carboxylic acid Ethylene-maleic anhydride copolymers, partially esterified methyl vinyl ether-maleic anhydride copolymers and the like.

The acidic polymer layer must contain enough acid groups to lower the pH of the processing mass from the beginning 11 to 14 to such an extent that the material is finally almost neutral or slightly acidic (pH 5 to 8).

The time delay of the lowering of the pH value is achieved in a known manner in that the acidic polymer layer is coated with a so-called delay layer. This delay layer represents an alkali-permeable layer, which preferably consists of a counter Alkali-inert polymers, for example polyvinyl alcohol or a partially acetalized polyvinyl alcohol. By a suitable choice of the thickness and the composition of this delay layer, the time delay of the lowering of the pH value can be adjusted in the desired manner. A _B remsschicht with polymers of a novel permeability behavior is, for example, in DT-OS 2455762 described.

Neutralization systems, which are understood to mean a combination of an acidic polymer layer and a retardation layer, are described, for example, in DT-PS 1 285 310. Such layer combinations can be present in the material according to the invention, for example in the light-sensitive part between the transparent layer support and the image-receiving layer. Another possibility is to arrange the neutralization system from the acidic polymer layer and a retardation layer on the cover sheet. Of course, these two layers must be arranged in such an order that the alkali of the processing composition is the delay layer. must penetrate to get into the acidic polymer layer.

ausgezogen wird, wobei die seitlich angeordneten

aufgespalten werden und ihren Inhalt zwischen

des Monoblattmaterials entlassen.The dye diffusion transfer method according to the invention can advantageously be carried out in or by means of a suitable self-developing camera. This can be provided, for example, with devices which, after the light-sensitive element has been exposed, allow a working solution to be distributed between it and the cover sheet and to cover the light-sensitive material in an opaque manner. Such a camera is preferably with two crimped against each other rollers provided between which the mono-sheet material

is pulled out, the laterally arranged

be split and their content between

of the mono-sheet material released.

Since the light-sensitive element is protected from unwanted exposure by opaque layers on both sides after passing through the nip rollers, the exposed material can be pulled out of the camera immediately after development has started.

To process the imagewise exposed mono-sheet material, the light-sensitive element is brought into contact with the aqueous alkaline working solution. In this case, the imagewise exposed silver halide emulsion layers are developed in the presence of the developer compound, an imagewise distribution of oxidation products of the developer compound being produced in accordance with the positive silver image thus formed, which oxidizes the assigned coloring compound, whereupon these react the diffusing dye with the alkali of the activator splits off. The aqueous alkaline working solution can contain viscosity-increasing additives, e.g. Hydroxyethyl cellulose. Development accelerators, stabilizers, silver salt solvents, foggants, antioxidants and other additives can also be contained in the working solution in a known manner.

example 1

• 1) Eine Beizschicht aus 6 g eines Polyurethans aus 4,4-Diphenylmethandiisocyanat, N--thyldiäthamlamin und Epichlorhydrin und 6,0g Gelatine.
• 2) Eine Reflektionsschicht aus 24 g Ti0₂ und 2,4 g Gelatine..
• 3) Eine Ruîschicht aus 1,9 g Ruî und 2 g Gelatine.
• 4) Eine Farbstoffschicht aus 0,5 g der Verbindung I (blaugrün) und 0,9 g Gelatine.
• 5) Eine rot sensibilisierte Emulsionsschicht mit einer unverschleierten direkt-positiv arbeitenden Silberohloridbromidemulsion, Silberauftrag 2,6 g,Gelatine 1,3 g und 0,04 g N-[α -(2,4-ditert.-amylphenoxy)-acetyl]-N'-phenyl-hydrazin als Schleiermittel
• 6) Eine Sperrschicht aus 0,5 g Octadecylhydrochinonsultosäure und 1,3 g Gelatine.
• 7) Eine Farbstoffschicht aus 0,5 g der Verbindung II (purpur) und 0,9 g Gelatine.
• 8) Eine grün sensibilisierte Emulsionssachicht mit einer unverschleierten direkt positiv arbeitenden Silberchloridbromidemulsion, Silberauftrag 2,5 g, Gelatine 1,28 g und ₀,₀4 g N-[α -(2,4-ditert.-amylphenoxy)-acetyl]-N'-phenyl-hydrazin als Schleiermittel.
• 9) Eine Sperrschicht identisch mit Schicht 6).
• 10) Eine Farbstoffschicht aus 0,65 g der Verbindung III (gelb) und 1,0 g Gelatine.
• 11) Eine blau sensibilisierte Emulsionsschicht mit einer unverschleierten direkt-positiv arbeitenden Silbwrchloridbromidemulsion, Silberauftrag 2,7 g, Gelatine 1,4 g und 0,04g N-[α-(2,4-ditert.-amylphenoxy)-acetyl]-N'-phenyl-hydrazin als Schleiermittel.
• 12) Eine Schutzschicht aus 0,8 g Gelatine und 0,8 g einer Verbindung der folgenden Formel (Härtungsmittel):
  
• 13) Ein -transparentes Deckblatt aus Polyäthylenterephthalat mit einer Neutralisationsschicht und einer Verzögerungsschicht.

A photosensitive element of a photographic material according to the invention was produced by successively applying the following layers on a transparent support made of polyester film. The quantities given relate in each case to 1 m ² .

• 1) A pickling layer of 6 g of a polyurethane made of 4,4-diphenylmethane diisocyanate, N-thyldiethamlamine and epichlorohydrin and 6.0 g of gelatin.
• 2) A reflective layer made of 24 g Ti0 ₂ and 2.4 g gelatin ..
• 3) A layer of soot consisting of 1.9 g of soot and 2 g of gelatin
• 4) A dye layer consisting of 0.5 g of compound I (blue-green) and 0.9 g of gelatin.
• 5) A red-sensitized emulsion layer with an unveiled direct-positive working silver chloride bromide emulsion, silver application 2.6 g, gelatin 1.3 g and 0.04 g N- [α - (2,4-ditert.-amylphenoxy) -acetyl] - N'-phenyl-hydrazine as a fogging agent
• 6) A barrier layer consisting of 0.5 g octadecyl hydroquinone sulto acid and 1.3 g gelatin.
• 7) A dye layer of 0.5 g of compound II (purple) and 0.9 g of gelatin.
• 8 g) A green-sensitized emulsion layer having a property unfogged direct-positive working silver chlorobromide, silver applied 2.5, gelatin 1.28 g and _{0, 0} 4 g of N- [α - (2,4-di-tert-amylphenoxy) acetyl] - N'-phenyl-hydrazine as a fogging agent.
• 9) A barrier layer identical to layer 6).
• 10) A dye layer of 0.65 g of compound III (yellow) and 1.0 g of gelatin.
• 11) A blue-sensitized emulsion layer with an unveiled direct-positive working silver chloride bromide emulsion, silver application 2.7 g, gelatin 1.4 g and 0.04 g N- [α- (2,4-ditert.-amylphenoxy) -acetyl] -N '-phenyl-hydrazine as an haze.
• 12) A protective layer of 0.8 g of gelatin and 0.8 g of a compound of the following formula (hardening agent):
  
• 13) A transparent cover sheet made of polyethylene terephthalate with a neutralization layer and a delay layer.

After exposure through a step wedge, the light-sensitive element was covered with the transparent cover sheet on the layer side. A splitable container with an alkaline working fluid of the following composition was used to develop the imagewise exposed photosensitive element:

made up to 1000 ml of water.

The image set was passed through a pair of squeeze rollers, the developer paste being distributed between the photosensitive element and the cover sheet. The paste strength was 110 / u. To adjust this, spacer strips of appropriate thickness were attached laterally along the edge of the image between the photosensitive element and the cover sheet.

Further photosensitive elements were produced in the same way with the only exception that the dye III of the layer by one of the inventive Compounds No. 3 to No. 7 has been replaced. After the same processing, direct-positive multicolored images of the original (film sets BF) also resulted.

After a development time of 1 hour, the Dmax and Dmin values of the image-receiving layers listed in the following table were determined using a reflection densitometer using a blue filter.

It can be seen from the results obtained that higher transfer color densities can be achieved with the coloring compounds of the present invention.

Formula appendix to example 1

The lightfastness test and the absorption measurement were carried out on the transfer dyes themselves, which are released from the coloring compounds in diffusing form.

The dye to be investigated was pickled by continuously immersing a transparent layer support with a pickling layer which corresponds to layer 1 from Example 1 in an aqueous dye solution. It was then watered and dried for 2 minutes.

The absorption measurement was carried out with a spectrophotometer.

To test the light-fastness, a strip of the materials obtained was fastened with the dyes to be compared on a TiO ₂ base and one for 24 hours in a Xenotest device from Hanau Exposure to 1.10 ⁵ lx exposed (approx. 20ÝC; approx. 60% relative humidity). The residual density remaining after the irradiation was calculated according to the following equation.

The measurement was carried out in the density range (before exposure) from 1.0 to 1.5.

The residual densities obtained are shown in the following table.

Claims (3)

1. Photographic color diffusion transfer process for the production of colored images, in which a photographic material with at least one light-sensitive silver halide emulsion layer and an associated non-cliffing coloring compound is exposed imagewise and developed with a silver halide developing agent, whereby a diffusing dye from the non-diffusing and coloring compound is released by the developer alkali is transferred to an image-receiving layer, characterized in that a compound of the following formula I is used as the non-diffusing coloring compound:

in which mean: A ^{1 is} an oxidizable organic carrier residue containing a diffusion-proofing residue, from which, under the conditions of photographic development, either in oxidized form or in non-oxidized form, alkali is split off together with the diffusion-proofing residue by developer alkali, with simultaneous imagewise release of a diffusing azo dye; D is a heterocyclic or carbocyclic aromatic radical. R is hydrogen, alkyl having 1 to 5 carbon atoms, aralkyl or aryl, R ² and R ³ (identical or different), each one of the radicals mentioned under R ¹ , sulfo, -COOR ⁴ , halogen, trihalomethyl, acylamino, acyloxy, carbamoyl, sulfamoyl, -OR ⁴ - -SR ⁴ , -SOR ⁴ , -S0 ₂ -R ⁴ (where R ^{4 is} one of those specified for R ¹ Has meaning), -N0 ₂ or -CN 1, n and n each 0 or 1 with the measure that 1 + m + n 1 r is an integer from 1 to 4. 2. The method according to claim 1, characterized in that a compound of the following formula II is used as the non-diffusing coloring compound:

in what mean _A ² an oxidizable organic carrier residue, optionally linked via a link X and containing a diffusion-proofing residue, in the o-, m- or p-position to the azo group, from which, under the conditions of photographic development, either in oxidized form or in non-oxidized form by developer alkali Part 'is split off together with the diffusion-proofing rest with simultaneous visual release of a diffusing azo dye; _A ^{3 is} an oxidizable organic carrier residue which may be attached via a bond X and contains a diffusion-fixing residue, which is attached either directly or via one of the substituents R and R in the o- or m-position to the phenyl ring bearing the cyanoalkylamino group and from which under the conditions of photographic development either in oxidized form or non-oxidized form by means of developer alkali, at least part of it is split off together with the rest that makes it resistant to diffusion, with simultaneous imagewise release of a

the azo dye, A ⁴ one if necessary

linked an oxidizable organic carrier residue containing a diffusion-proofing residue, which is linked to the substituent R ¹ and from which, under the conditions of photographic development, either in oxidized form or in non-oxidized form, is split off by developer alkali together with the diffusion-proofing residue simultaneous release of a diffusing azo dye ;. R ^{1 is} hydrogen, alkyl having 1 to 5 carbon atoms, aralkyl or aryl R ² , R ³ , R ⁵ and R ⁶ (identical or different), each one of the radicals mentioned under R, sulfo, -COOR, halogen, trihalomethyl, acylamino, acyloxy, carbamoyl, sulfamoyl, -OR ⁴ , -SR ⁴ , -SOR ⁴ , -S0 ₂ -R ⁴ (where R ^{4 has} one of the meanings given for R ¹ ), -N0 ₂ or -CN X is a bivalent link of the formula -R- (L) _p - (R) _q -,
in which R is an alkylene radical having 1 to 6 carbon atoms or an optionally substituted phenylene radical and where the two radicals R can have the same or different meanings; L -O-, -CO-, -CONR ⁷ , -S0 ₂ NR ⁷ , -O-CO-NR ⁷ , -S-, -S0 ₂ -, -SO means (R ⁷ = hydrogen or alkyl p - 0 or 1 q = 0 or 1, where q = 1 if p = 1 1, m and n each 0 or 1 with the measure that

· Process according to claim 1, characterized in that a compound of the following formula III is used as the non-diffusing coloring compound:

in what mean R ^{1 is} hydrogen or alkyl having 1 to 5 carbon atoms R ² , R ³ , R ⁵ and R ⁶ (identical or different) are hydrogen, chlorine, methyl, methoxy, acylamino, nitro A ⁵ denotes the radical of one of the following formulas substituted with at least one diffusion-proofing radical

wherein Z stands for a diffusion-proofing residue Y 'represents a residue required to complete a benzene or naphthalene ring Y "stands for the completion of a fused-on optionally substituted carboxyclic or heterocyclic ring, and R is hydrogen, alkyl, _A lkoxy, aryl, a heterocyclic group, a carboxyl, carbamoyl or alkoxycarbonyl, X is a bivalent link of the formula -R- (L) _p - (R) _q -,
wherein R represents an alkylene radical having 1 to 6 carbon atoms or an optionally substituted phenylene radical and the two radicals R can have the same or different meanings; L denotes -O-, -CO-, -CONR ⁷ , -S0 ₂ NR ⁷ , -O-CO-NR ⁷ -S-, -S0 ₂ -, -SO- (R ⁷ = hydrogen or alkyl) p = 0 or 1 q = 0 or 1, where q = 1 if p = 1 r = 2 or 3 s = 0 or 1.