EP0035235A2 - Process for the manufacture of photographic images; photographic material suitable to this process and photographic images obtained therewith - Google Patents

Abstract

Process for the production of photographic images by a) imagewise exposure of a photographic material which, during at least one silver halide development step, in this order from optionally a cover layer, at least one silver halide emulsion layer, a layer which contains a hydroxypyridonazamethine compound substantive therein of the general formula <IMAGE>, wherein R1 Hydrogen or optionally substituted alkyl, aralkyl, cycloalkyl, aryl or amino or an optionally substituted heterocyclic radical, Y is hydrogen, hydroxyl, -CN, -COOR¹, -CONR¹R² or -COR¹ or optionally substituted alkyl, aralkyl, cycloalkyl, aryl or an optionally heterocyclic Radical, Z is hydrogen, -CN, -COOR³, -CONR³R <4>, -SO3H, -SO3- or -COR³, where R¹, R², R³ and R <4> independently of one another are hydrogen or optionally substituted alkyl, aralkyl, cycloalkyl or aryl or an optionally heterocyclic radical, u nd E represents the atoms required to supplement an optionally substituted heterocyclic or aromatic ring, consists of intermediate layers optionally present between these layers and a support, one or more intermediate layers optionally being present between these layers, b) treatment of the exposed, photographic Material with an aqueous alkaline processing bath containing a silver halide developer, and c) imagewise diffusion of the silver halide developer from the unexposed image areas of the silver halide emulsion layer (s) into the layer containing the compound of formula (1) and bleaching of this compound by the silver halide developer to produce a photographic image. The developers used in this process show increased stability towards oxidizing agents.

Description

The present invention relates to new silver halide photographic materials, processes for processing these materials to produce photographic images, and images made with these materials.

Since the invention of photography, silver halide salts have been used as photosensitive compounds and mostly developed silver has been used as an image. However, in color photography, dye images have replaced the silver image. However, in a large number of photographic materials the final image obtained is still a silver image, e.g. in X-ray materials, microfilms and films for the graphics industry as well as in normal, highly sensitive black and white films. Recently, however, the price of silver has risen so much that attempts have been made to form color images even from the photographic materials mentioned above if silver halides are used as photosensitive compounds. In this way, the silver used can be almost completely recovered or at least the amount of silver consumed can be significantly reduced.

In a system in color photography, the photosensitive substance is generally a silver salt. A color developer is used to develop the silver halide and at the same time to release a dye that diffuses from the light-sensitive layers into a receiving layer. This can depend on the photosensitivity peeled layer. In the end, you get a color image, while all the silver remains in the residual material and can therefore be recovered.

British Patent 2,007,378 describes a novel photographic diffusion process in which no diffusion of dyes takes place, but a dye image is nevertheless obtained.

• a) bildweise Belichtung eines photographischen Materials, welches mindestens während der Silberhalogenidentwicklungsstufe in dieser Reihenfolge aus gegebenenfalls einer Deckschicht, mindestens einer Silberhalogenidemulsionsschicht, einer einen bleichbaren Farbstoff enthaltenden Schicht und einem Träger besteht, wobei gegebenenfalls zwischen diesen Schichten jeweils eine oder mehrere Zwischenschichten vorhanden sind,
• b) Behandlung des belichteten photographischen Materials mit einem wässrigen Verarbeitungsbad, um eine Lösung oder Dispersion eines Bleichentwicklers in die Silberhalogenidemulsionsschicht(en) einzubringen und um dadurch das latente Silberbild in der bzw. den Silberhalogenidemulsion(en) zu entwickeln, und
• c) bildweise Diffusion des Bleichentwicklers aus den unbelichteten Bildbereichen der Silberhalogenidemulsionsschicht(en) in die den bleichbaren Farbstoff enthaltende Schicht, und Bleichung des Bildfarbstoffs durch den Bleichentwickler unter Erzeugung eines photographischen Bildes.

British Patent 2 007 378 relates to a process for the production of photographic images by

• a) imagewise exposure of a photographic material which, at least during the silver halide development stage, consists in this order of optionally a top layer, at least one silver halide emulsion layer, a layer containing a bleachable dye and a support, one or more intermediate layers optionally being present between these layers,
• b) treating the exposed photographic material with an aqueous processing bath to introduce a solution or dispersion of a bleach developer into the silver halide emulsion layer (s) and thereby to develop the latent silver image in the silver halide emulsion (s), and
• c) imagewise diffusion of the bleach developer from the unexposed image areas of the silver halide emulsion layer (s) into the layer containing the bleachable dye, and bleaching of the image dye by the bleach developer to produce a photographic image.

In British Patent 2 007 378 bleach developers are known as Defines substances which can act both as a silver halide developer and as a bleaching agent for a bleachable dye.

From British Patent 2 007 378 it is known that azo dyes of the type used in the silver color bleaching process are preferred as bleachable image dyes.

Such azo dyes are bleached under acidic conditions. Therefore, the aqueous processing bath is acidic according to the examples given in British Patent 2,007,378. It is further stated there that reduced silver color bleaching catalysts of the diazine type and certain metal ions in their lower valence levels are preferred as bleach developers. These classes of compounds are capable of acting as silver halide developing agents under aqueous acidic conditions. However, both types of bleach developers are easily oxidized to their inactive forms. British Patent 2 007 378 describes various methods for ensuring the active form of the bleach developer in the aqueous processing solution.

It has now been found that certain dyes can be bleached imagewise under alkaline conditions by normal silver halide developers which are not as easily oxidizable as the bleach developers described in British Patent 2,007,378.

• a) bildweise Belichtung eines photographischen Materials, welches mindestens während einer Silberhalogenidentwicklungsstufe in dieser Reihenfolge aus gegebenenfalls einer Deckschicht, mindestens einer Silberhalogenidemulsionsschicht, einer Schicht, welche ein darin substantives Hydroxypyridonazamethin der allgemeinen Formel
  
  enthält, worin R Wasserstoff, gegebenenfalls substituiertes Alkyl, Aralkyl, Cycloalkyl, Aryl oder Amino oder ein gegebenenfalls substituierter heterocyclischer Rest, Y Wasserstoff, Hydroxyl, -CN, -COOR¹, -CONR¹R² oder -COR , gegebenenfalls substituiertes Alkyl, Aralkyl, Cycloalkyl oder Aryl oder ein gegebenenfalls substituierter heterocyclischer Rest, Z Wasserstoff, -CN, -COOR³, -CONR³R⁴, -S0₃H, -S0₃ oder -COR³ ist, wobei R¹, R², R³ und R⁴ unabhängig voneinander Wasserstoff, gegebenenfalls substituiertes Alkyl, Aralkyl, Cycloalkyl oder Aryl oder ein gegebenenfalls substituierter heterocyclischer Rest sind, und E die zur Ergänzung zu einem gegebenenfalls substituierten heterocyclischen oder aromatischen Ring erforderlichen Atome darstellt, aus gegebenenfalls zwischen diesen Schichten vorliegenden Zwischenschichten sowie aus einem Träger besteht, wobei gegebenenfalls zwischen diesen Schichten jeweils eine oder mehrere Zwischenschichten vorhanden sind,
• b) Behandlung des belichteten photographischen Materials mit einem wässrig-alkalischen Verarbeitungsbad, um eine Lösung oder Dispersion eines Silberhalogenidentwicklers in die Silberhalogenidemulsionsschicht(en) einzubringen, und um dadurch das latente Silberbild in der (den) Silberhalogenidemulsion(en) zu entwickeln und
• c) bildweise Diffusion des Silberhalogenidentwicklers aus den unbelichteten Bildbereichen der Silberhalogenidemulsionsschicht(en) in die die Verbindung der Formel (1) enthaltende Schicht, und Bleichung dieser Verbindung durch den Silberhalogenidentwickler unter Erzeugung eines photographischen Farbbilds.

The present invention accordingly relates to a method for producing photographic images by

• a) imagewise exposure of a photographic material, which at least during a silver halide development step in this order from optionally a cover layer, at least one Silver halide emulsion layer, a layer which has a hydroxypyridonazamethine of the general formula therein
  
  contains, wherein R contains hydrogen, optionally substituted alkyl, aralkyl, cycloalkyl, aryl or amino or an optionally substituted heterocyclic radical, Y hydrogen, hydroxyl, -CN, -COOR ¹ , -CONR ¹ R ² or -COR, optionally substituted alkyl, aralkyl , Cycloalkyl or aryl or an optionally substituted heterocyclic radical, Z is hydrogen, -CN, -COOR ³ , -CONR ³ R ⁴ , -S0 ₃ H, -S0 ₃ or -COR ³ , where R ¹ , R ² , R ³ and R ^{4 are} independently hydrogen, optionally substituted alkyl, aralkyl, cycloalkyl or aryl or an optionally substituted heterocyclic radical, and E represents the atoms required to supplement an optionally substituted heterocyclic or aromatic ring, from intermediate layers optionally present between these layers and from there is a carrier, one or more intermediate layers being optionally present between these layers,
• b) treating the exposed photographic material with an aqueous alkaline processing bath to introduce a solution or dispersion of a silver halide developer into the silver halide emulsion layer (s), and thereby to develop the latent silver image in the silver halide emulsion (s) and
• c) imagewise diffusion of the silver halide developer from the unexposed image areas of the silver halide emulsion layer (s) into the layer containing the compound of formula (1), and bleaching of this compound by the silver halide developer to produce of a photographic color image.

Another object of the invention relates to the photographic material suitable for the method according to the invention.

The invention further relates to the photographic images produced with the photographic material.

As aromatic rings which are completed by E, preference is given to phenylene rings which are substituted in the para position by an optionally substituted amino group or by a hydroxyl group. There may also be other substituents on the phenylene ring.

Particularly preferred heterocyclic rings completed by E are pyrazolone or hydroxypyridone rings.

The term "substantive" means that the azamethine dyes are embedded diffusion-resistant in the layer in which they are cast. As described further below, the dyes are preferably in the form of solid dispersions, but they can be present as oil dispersions or also pickled with a mordant. They can also be substantive for reasons of molecular size.

worin R₁ Wasserstoff, gegebenenfalls substituiertes Alkyl, Aralkyl, Cycloalkyl, Aryl oder Amino oder ein gegebenenfalls substituierter heterocyclischer Rest, Y Wasserstoff, Hydroxyl, -CN, -COOR¹, -CONR¹R² oder -COR¹ oder gegebenenfalls substituiertes Alkyl, Aralkyl, Cycloalkyl oder Aryl oder ein gegebenenfalls substituierter heterocycli- scher Rest ist, Z Wasserstoff, -CN, -COOR³, -CONR³R⁴, -SO₃H, -SO₃ oder -_CO_R ³ ist, wobei _R ¹, R², R³ und R⁴ unabhängig voneinander Wasserstoff, gegebenenfalls substituiertes Alkyl, Aralkyl, Cycloalkyl oder Aryl oder einen unsubstituierten heterocyclischen Rest darstellen, R₂, R₃ und R₄ unabhängig voneinander Wasserstoff, Halogen, gegebenenfalls substituiertes Alkyl, Cycloalkyl oder Alkoxy und R₅ und R₆ unabhängig voneinander Wasserstoff oder gegebenenfalls substituiertes Alkyl, Aralkyl, Cycloalkyl oder Aryl oder ein gegebenenfalls substituierter heterocyclischer Rest sind, oder zusammen mit dem Stickstoffatom, an das sie gebunden sind, einen 5- oder 6-gliedrigen Ring bilden, oder R₃ und R₅ sowie R₅ und R₆ jeweils zusammen mit dem Stickstoffatom zwei kondensierte Ringe bilden.A particularly preferred class of compounds of the formula (1) are those of the formula

wherein R _{1 is} hydrogen, optionally substituted alkyl, aralkyl, cycloalkyl, aryl or amino or an optionally substituted heterocyclic radical, Y is hydrogen, hydroxyl, -CN, -COOR ¹ , -CONR ¹ R ² or -COR ¹ or optionally substituted alkyl, aralkyl , Cycloalkyl or aryl or an optionally substituted heterocyclic radical, Z is hydrogen, -CN, -COOR ³ , -CONR ³ R ⁴ , -SO ₃ H, -SO ₃ or - _C O _R ³ , where _R ¹ , R ² , R ³ and R ^{4 are} independently hydrogen, optionally substituted alkyl, aralkyl, cycloalkyl or aryl or an unsubstituted heterocyclic radical, R ₂ , R ₃ and R _{4 are} independently hydrogen, halogen, optionally substituted alkyl, cycloalkyl or alkoxy and R ₅ and R _{6 are} independently hydrogen or optionally substituted alkyl, aralkyl, cycloalkyl or aryl or an optionally substituted heterocyclic radical, or together with the nitrogen atom to which they g are bonded, form a 5- or 6-membered ring, or R ₃ and R ₅ and R ₅ and R ₆ each form two condensed rings together with the nitrogen atom.

The optionally substituted alkyl radicals represented by Y, R ₁ , R, R, R and R are preferably lower alkyl groups or substituted lower alkyl radicals, with methyl, ethyl, n-propyl, n-butyl, hydroxy-lower alkyl such as β-hydroxymethyl, lower alkoxyalkyl as special examples 1 to 6 carbon atoms in the alkoxy and alkyl radicals, such as β- (methoxy or ethoxy) ethyl and y-methoxypropyl, cyano-lower alkyl such as cyanomethyl, carbamoylmethyl, carbäthoxymethyl and acetylmethyl may be mentioned. Furthermore, n-octyl, n-decyl and n-dodecyl can also be used.

Examples of Y, R and R ¹ , R ² , R ³ and R ⁴ in the meaning of aralkyl are benzyl and β-phenylethyl.

Cyclohexyl may be mentioned as an example of a cycloalkyl radical for _Y and R ¹ , R ¹ , R2, _R ³ and _R ⁴ . The represented by Y, R ₁ , R ¹ , R ² , R ³ and R ⁴ The optionally substituted aryl radicals are phenyl or optionally substituted phenyl, such as phenyl, tolyl, chlorophenyl, methoxyphenyl and ethoxyphenyl. Are Y, R ¹ , R, R, R and R optionally substituted heterocyclic radicals, where are 5- or 6-membered heterocyclic rings, such as 2-pyridyl, 2-thiazolyl, 1-piperidinyl and 1-morpholinyl, which are each substituted can be preferred.

Piperidine, morpholine, piperazine and pyrrolidine may be mentioned as examples of 5- and 6-membered heterocyclic rings formed by linking R ₅ and R ₆ with the nitrogen atom or R ₃ and R ₅ or R ₄ and R ₆ with the nitrogen atom.

Z is preferably -CN, -COR ³ , -COOR ³ or -CONR ³ R ⁴ , with -CN being particularly suitable. R ³ and R ⁴ are independently hydrogen or alkyl having 1 to 3 carbon atoms.

R ₁ is preferably alkyl with 1 to 4 carbon atoms such as methyl, ethyl, propyl or butyl or hydrogen, the latter meaning being particularly preferred.

Also of interest is the process for the preparation of dyes of the formula (1), in which R _{1 is} hydrogen, alkyl having 1 to 6 carbon atoms, hydroxyalkyl having 1 to 6 carbon atoms, alkoxyalkyl each having 1 to 6 carbon atoms in the alkyl and alkoxy radical, phenyl, Benzyl, β-phenylethyl or cyclohexyl, R _{2 is} hydrogen, chloroalkyl, hydroxyalkyl or alkoxy each having 1 to 6 carbon atoms, R _{3 is} hydrogen, alkyl or alkoxy having 1 to 6 carbon atoms, R _{4 is} hydrogen or alkyl having 1 to 6 carbon atoms, R ₅ and R ₆ independently of one another are hydrogen, alkyl or hydroxyalkyl each having 1 to 6 carbon atoms, alkoxyalkyl each having 1 to 6 carbon atoms in the alkyl and alkoxy radical, carboxyalkyl having 1 to 3 Koh lenstoffatomen in the alkyl radical, β-methylsulfonamidoethyl or sulfo-n-butyl, Y is hydrogen, cyano, carbomethoxy, carbäthoxy, carbamoyl or alkyl having 1 to 6 carbon atoms and Z -CN, carbomethoxy, carbäthoxy or carbamoyl.

worin R₁ Wasserstoff, Alkyl mit 1 bis 6 Kohlenstoffatomen oder Hydroxyalkyl mit 2 bis 4 Kohlenstoffatomen ist, R₅ und R₆ Alkyl mit 1 bis 4 Kohlenstoffatomen, Hydroxyalkyl mit 2 bis 4 Kohlenstoffatomen oder Sulfo-n-butyl sind oder R₅ und R₆ zusammen mit dem Stickstoffatom, an das sie gebunden sind, einen Piperidin-, Morpholin-, Piperazin- oder Pyrrolidinring darstellen. In ganz besonders bevorzugten Farbstoffen der Formel (2a) sind R Alkyl mit 1 bis 6 Kohlenstoffatomen und R₅ und R₆ Aethyl oder Hydroxyalkyl mit 2 bis 4 Kohlenstoffatomen.Preferred dyes are those of the formula

wherein R _{1 is} hydrogen, alkyl with 1 to 6 carbon atoms or hydroxyalkyl with 2 to 4 carbon atoms, R ₅ and R _{6 are} alkyl with 1 to 4 carbon atoms, hydroxyalkyl with 2 to 4 carbon atoms or sulfo-n-butyl or R ₅ and R ₆ together with the nitrogen atom to which they are attached represent a piperidine, morpholine, piperazine or pyrrolidine ring. In very particularly preferred dyes of the formula (2a), R is alkyl with 1 to 6 carbon atoms and R ₅ and R _{6 are} ethyl or hydroxyalkyl with 2 to 4 carbon atoms.

Further compounds of the formula (2) which are suitable for use in the process according to the invention are those in which Z is -CN, -COOR ³ , -CONR ³ R ⁴ or -COR ³ , where R ³ and R ^{4 have} the meanings given above; those in which Z is -CN are particularly preferred.

Both Y and R are preferably alkyl or substituted alkyl. Y and R ₁ are particularly preferred as alkyl having 1 to 4 carbon atoms. Examples of this are described above.

beschrieben werden, worin die Symbole die oben angegebenen Bedeutungen haben.Another preferred class of compounds of the formula (1) for use in the process according to the invention are those in which R ₁ Is hydrogen. Such compounds can be used as tautomers of the formula

are described, in which the symbols have the meanings given above.

R ₂ , R ₃ and R ₄ in the compounds of the formulas (2) and R ₂ and R ₃ in formula (3) are preferably hydrogen atoms. Y is preferably alkyl of 1 to 4 carbon atoms. R ₅ and R ₆ are preferably alkyl or alkoxy, in which the alkyl part contains 1 to 4 carbon atoms each.

und

Eine weitere geeignete Klasse von Hydroxypyridonverbindungen sind solche der allgemeinen Formel

worin Z, Y und R₁ bis R₄ die oben angegebenen Bedeutungen haben.Compounds which are particularly suitable for use in the process according to the invention are the compounds of the formulas

and

Another suitable class of hydroxypyridone compounds are those of the general formula

wherein Z, Y and R ₁ to R _{4 have} the meanings given above.

An example of a compound of formula (6) is the compound of formula

worin ^R ₁₄, ^R _15' ^R ₁₆ und R₁₇ je Alkyl mit 1 bis 4 Kohlenstoffatomen, wie Methyl, Aethyl, Propyl, i-Propyl, Butyl oder t-Butyl, sind. Diese Reste können durch Halogen, wie Chlor oder Brom, Hydroxyl, Cyan oder Alkoxy mit 1 bis 4 Kohlenstoffatomen weiter substituiert sein.Another suitable class of dyes of the formula (1) are bishydroxypyridone dyes of the general formula

wherein ^R ₁₄ , ^R _{15 '} ^R ₁₆ and R _{17 are} each alkyl having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, i-propyl, butyl or t-butyl. These radicals can be further substituted by halogen, such as chlorine or bromine, hydroxyl, cyano or alkoxy having 1 to 4 carbon atoms.

worin R₁₄ und R₁₅ die oben angegebenen Bedeutungen haben.Another suitable class of dyes of the formula (1) are dyes of the formula

wherein R ₁₄ and R _{15 have} the meanings given above.

R ₁₈ , R ₁₉ and R ₂₀ are each hydrogen or alkyl. These alkyl groups can have 1 to 6 carbon atoms, for example methyl, ethyl, propyl, butyl, pentyl or hexyl or their isomers. They are optionally substituted by halogen such as chlorine or bromine, hydroxyl, alkoxy with 1 to 4 carbon atoms, such as methoxy, ethoxy or butoxy, or a carboxylic acid group. The alkyl groups are preferably unsubstituted. Preferred alkyl radicals have 1 to 4 carbon atoms. Methyl is particularly preferred. R ₁₈ , R ₁₉ and R ₂₀ furthermore each represent aryl, for example phenyl or naphthyl, optionally substituted by halogen, such as chlorine or bromine, hydroxyl, cyano, nitro or a carboxylic acid group. R ₁₈ , R ₁₉ and ^R ₂₀ are preferably phenyl optionally substituted by chlorine, hydroxyl or cyano. Phenyl is the most suitable residue for R ₁₈ , R ₁₉ and R ₂₀ . The ^importance of ^B e R _18, R ₁₉ and R ₂₀ may be the same or different.

Die Hydroxypridone der Formel (2) werden gemäss DE-OS 2 808 825 hergestellt.An example of a dye of the formula (9) is the dye of the formula

The hydroxypridones of the formula (2) are prepared in accordance with DE-OS 2 808 825.

mit einer Nitrosoverbindung der allgemeinen Formel

wobei R₁, Y, Z und E die oben angegebenen Bedeutungen haben.The other compounds of the formula (1) can be prepared by methods well known from the literature, for example by condensation of the starting group of the formula

with a nitroso compound of the general formula

where R ₁ , Y, Z and E have the meanings given above.

The reaction is expediently carried out in a solvent, preferably acetone, ethanol or acetic acid, if appropriate with heating.

The compounds of formula (1) are preferably present in the layer of the photographic material as a solid dispersion.

• Eine Aufschlämmung von 5 bis 20 g des Farbstoffs mit 1 g 10%iger Lösung des Addukts von 1 Mol Octylphenol und 10 Mol Aethylenoxyd und 1 g 10%ige Lösung des Natriumsalzes des sulfonierten Addukts aus 1 Mol Octylphenol und 8 Mol Aethylenoxyd in 78 g Wasser wird in einer Kolloidmühle (z.B. einer mit 0..7 bis 1.0 mm grossen Mahlkörpern beschickten Dyno-Mill bei 3 000 U/min.) auf eine Teilchengrössenverteilung von weniger als 1 um Durchmesser (Durchschnitt 0,4 bis 0,5 pm) vermahlen.

Solid dispersions using gelatin as a binder can be prepared as follows:

• A slurry of 5 to 20 g of the dye with 1 g of a 10% solution of the adduct of 1 mol of octylphenol and 10 mol of ethylene oxide and 1 g of a 10% solution of the sodium salt of the sulfonated adduct from 1 mol of octylphenol and 8 mol of ethylene oxide in 78 g of water is cut to a particle size in a colloid mill (for example a Dyno-Mill loaded with 0..7 to 1.0 mm large grinding media at 3,000 rpm) distribution of less than 1 µm in diameter (average 0.4 to 0.5 pm).

A 4% gelatin solution (decationed grade, pH 6-7) containing 0.15% wetting agent is gradually added to the dispersion with stirring. At this stage you can add a hardener. The concentration of the dispersion is adjusted so that it is at λ max. a density of 3 results (corresponding to casting weights of 20-30 mg / dm ² gelatin and 8-10 mg / dm ² dye).

Silver halide developer is a compound that is capable of developing a latent silver image under alkaline conditions.

All of the silver halide developers known from black and white photography can be used in the process according to the invention. These include polyhydroxyphenols, for example hydroquinone, bromohydroquinone, chlorohydroquinone and pyrogallol, aminophenols, for example p-aminophenol and p-methylaminophenol (metol) and glycine, and 1-phenyl-3-pyrazolidinone and ascorbic acid.

Mixtures of these developers can be used which contain two or more different compounds. A mixture of hydroquinone and 1-phenyl-3-pyrazolidine is preferably used.

Furthermore, some rather unusual silver halide developers can be used in the process according to the invention.

worin R₂₅ Wasserstoff, Alkyl oder Aryl und Y -0- oder -NH- ist.These include compounds of the formula

wherein R _{25 is} hydrogen, alkyl or aryl and Y is -0- or -NH-.

bevorzugt, worin R₂₁ bis R₂₄ je Wasserstoff, Methyl oder Aethyl sind. Vorzugsweise sind R₂₁, R_22' R₂₃ und R₂₄ Methyl. Diese Verbindung ist als Tetramethylreduktinsäure bekannt.Preferred alkyl groups have 1 to 4 carbon atoms, for example methyl, ethyl and butyl. Phenyl is suitable as the aryl group (compounds of this class are closely related to ascorbic acid). Furthermore, compounds of the formula

preferred, wherein R ₂₁ to R _{24 are} each hydrogen, methyl or ethyl. R ₂₁ , R _{22 ',} R ₂₃ and R ₂₄ are preferably methyl. This compound is known as tetramethyl reductic acid.

The method according to the invention can be used to form a color image in a layer removed from the silver halide emulsion layer or to form a color image which enhances the silver image; in the latter case the bleachable dye layer lies in the material next to the silver halide emulsion layer.

If the process according to the invention is used to produce a color image in a layer removed from the silver halide emulsion layer, the photographic material of the type defined above can consist of two components, on the one hand the image part and on the other hand the light-sensitive part, preferably with a separating layer or location between the ( silver halide emulsion layer (s) and the image dye layer.

However, the method according to the invention can be used for processing the camera, the processing liquid preferably being introduced from a sleeve between two layers of the photographic material and bringing the two parts of the material into intimate contact.

It is necessary that the silver halide developer is not in the processing solution, as this would bleach the bleachable dye instantaneously, but that the developer is placed in the photographic material on the side of the silver halide emulsion layer facing away from the bleachable dye layer. The developer is preferably in the form of a solid dispersion. Hydroquinone or a hydroquinone derivative such as e.g. Bromohydroquinone, chlorohydroquinone or pyrogallol.

If a separation layer or separation point is present, a final stage in the process according to the invention is sometimes required in order to bring about the separation effect and to separate the part of the photographic material containing the developed silver image from the part having the finished color image on the support.

If there is a separation layer, it can be dissolved in a final wash or in a solution bath. A water-swellable phthalated gelatin layer, for example, is suitable as the separating layer. Usually, however, the separation effect takes place during the processing ng t _u, as for example, phthalated gelatin is swellable in an alkaline processing solution.

Otherwise, a separation point can be provided. The interface between two layers is then such that the adhesion between the two layers can be removed. This removal of liability can be brought about, for example, by changing the pH or temperature. The separation point should be between the silver halide emulsion layer (s) and the image dye layer. The last stage of the process is then to remove the liability in order to separate the light-sensitive part from the image part. Usually, however, liability is lifted towards the end of processing, so that no actual separation step is often required.

If either a separation layer or a separation point is present in the photographic material, all of the silver used as a light-sensitive agent can be recovered, since the part of the material containing the silver can be separated from the finished image part.

However, considerable silver savings are achieved if the image part is not separated from the part containing the silver. In this case, the finished image to be viewed is the color image which can be seen through the transparent support, a silver image also being present in the photographic material, which is usually separated from the color image by a white-opaque layer. In such material, the amount of silver halide present in the silver halide emulsion layer (s) may be less than would be required if the image to be viewed were formed in the silver halide emulsion layer (s).

If the method according to the invention is used in a method for producing a dye image which enhances the silver image, it is usually necessary to provide a silver halide fixing step in which unexposed silver halide is removed from the photographic material.

Various embodiments of photographic materials which can be used in the method according to the invention will now be described with reference to the attached FIGS. 1 to 11.

It should be noted that both negative silver halide emulsions and positive emulsions can be used.

Under intermediate layers are e.g. To understand separation layers, gelatin layers, white reflective or white opaque layers as well as soot layers.

• Figuren 1 bis 6 Materialien, die entweder eine Trennstelle oder eine Trennschicht enthalten,
• Figuren 7 und 8, Materialien ohne Trennschicht oder -stelle,
• Figur 9 ein Material, das sich zur Verstärkung eines Silberbilds durch ein Farbbild eignet, und
• Figuren 10 und 11 zur Verarbeitung der Kamera geeignete Materialien, die aus zwei Teilen bestehen.

Show it:

• FIGS. 1 to 6 materials which contain either a separation point or a separation layer,
• FIGS. 7 and 8, materials without a separating layer or site,
• FIG. 9 shows a material which is suitable for enhancing a silver image by means of a color image, and
• Figures 10 and 11 materials suitable for processing the camera, which consist of two parts.

The term separation point is used in FIGS. 1 to 6. This can either be an interface between layers, between which the adhesion can be removed, or an actual separation layer.

FIG. 1 shows a photographic material according to the invention which is suitable for use as X-ray film material.

As shown in FIG. 1, the material consists of a transparent support 1 with a layer 2 of gelatin cast thereon with fine bleachable dye. Above the separation point 3 there is a soot layer 4 and above it a conventional silver halide emulsion layer 5, then a soot layer 6 and above it a top view 7. The silver halide emulsion layer 5 is thus enclosed between two soot layers 4 and 6 and the photographic material is left therefore handle in daylight. The material can be exposed to X-rays and, after exposure, processed into a negative silver image using an aqueous, alkaline solution of the bleach developer as just described. The silver halide layer and the two soot layers and the top view are then used for the recovery of the Silver stripped from the dye layer. The negative color image on the support can then be viewed in transparency.

For the sake of simplicity, the term “X-rays”, as used in this patent specification, is intended to apply to all very short-wave, photographically usable actinic rays, such as those emanating from an X-ray tube, radium or radioactive isotopes and nuclear radiation including β-particles.

FIG. 2 shows photographic material according to the invention which can be used as an X-ray monitoring material. In this embodiment, a layer 2 of gelatin with bleachable dye, a white-opaque layer 3, separation point 4, a carbon black layer 5, a conventional silver halide emulsion layer 6, a carbon black layer 7 and a cover layer 8 are cast onto a transparent film carrier 1 in this order.

In this case, as with the material of Figure 1, the photographic material is processed into a negative image. However, there is an additional white-opaque layer in this material. This can consist, for example, of barite or titanium oxide dispersed in gelatin. The white-opaque layer acts as a reflection base for the negative color image, which is viewed from above through the film carrier.

Figure 3 shows an alternative to the material of Figure 2 embodiment. The layers here are as in figure. 2 numbered, but the separation point is now relocated, and it is located between the lower soot layer 5 and the silver halide emulsion layer 6. When the silver halide emulsion layer is removed after processing, the soot layer adheres to the white-opaque layer.

The main advantages of the photographic material according to FIGS. 1 to 3 are that all the silver in the silver halide emulsion layer can be recovered and the film material is insensitive to daylight and can therefore be handled in the unexposed state under normal daylight conditions. However, the photographic material according to the invention can also be used in a normal camera or processing camera if the upper soot layer is omitted. Such material without any soot layer is shown in the attached FIG. 4, where in this order a layer 2 of gelatin with bleachable dye, a silver halide emulsion layer and a cover layer 5 are cast on an opaque carrier 1. This material preferably contains a direct positive emulsion in layer 4 and thus provides a direct positive color image during processing, which is viewed from above. In this case, the material cannot be handled at any stage prior to stripping the silver halide layer under daylight conditions.

Yet another embodiment of the material according to the invention is shown in the attached FIG. 5. With this material there is a layer in this row. 2 cast from gelatin with bleachable dye, a separation point 3, carbon black layer 4, silver halide emulsion layer 5 and top layer 6 on a transparent support 1. The material provides a final color image that can be viewed in transparency. In the case of this material, the exposure must take place in a camera or in another light-tight exposure camera.

FIG. 6 shows a further embodiment of the invention, in which a layer 2 of gelatin with bleachable dye, white-opaque layer 3, carbon black layer 4, separation point 5, silver halide layer 6 and cover layer 7 are cast onto a transparent support 1. The exposure must also take place here in a camera or a light-tight exposure chamber. The silver halide Emulsion layer 6 preferably contains a direct positive emulsion, a direct positive image viewed in supervision being formed after processing. If, on the other hand, a conventional silver halide emulsion is used, a negative image viewed from above is produced, although in this case, of course, one would rather use a material that provides a direct positive image, since the image is viewed from above, unless it is exposure deals with X-rays, usually looking at negative images.

The materials shown in Figures 1 to 6 can be processed by applying an aqueous alkaline solution containing a silver halide developer.

Integral photographic materials useful in the present invention, i.e. those that are not separated after processing are shown in FIGS. 7 to 9.

In FIG. 7, a layer 2 of gelatin with a bleachable dye of the formula (1), a white-reflecting layer 3, an opaque carbon black layer 4, a silver halide emulsion layer 5 and a cover layer 6 are cast onto a carrier 1 in this order. The exposure must take place in a camera or light-tight exposure chamber. The emulsion layer 5 can optionally generate a positive or negative image.

In this order, FIG. 8 shows a layer 2 of gelatin with bleachable dye of the formula (1), a white-reflecting layer 3, an opaque soot layer 4, a silver halide emulsion layer 5, an opaque soot layer 6 and a top layer 7 poured a carrier 1. This material has to be exposed with X-rays. The silver halide emulsion of this layer would normally be a conventional emulsion, which therefore gives a negative image to be viewed from above, since X-ray films usually processed into negative images.

None of the materials shown in Figures 7 or 8 contain a separation site or layer. This means that all of the silver initially present is still present in the final artwork. However, it is possible to get by with a very low silver casting weight, but this results in an image of very little blackening after exposure and processing of the material, which is too low to be usable as the final image. The final image in the materials of Figures 7 and 8, however, is a color image with an acceptable density for a final image. The amount of silver used can therefore be small, since the silver is only used as a photosensitive and not also as an image-providing substance, although it is still present in the material but is invisible, since it is on the side of the white-reflecting layer facing away from the color image .

In FIG. 9, a layer 2 of gelatin with a bleachable dye of the formula (1), a silver halide emulsion layer 3 and a cover layer 4 are cast onto a carrier 1 in this order. This material must be exposed in a light-tight exposure chamber such as a camera or an X-ray film cassette. The exposed film must also be processed in the dark room. During processing, i.e. When an alkaline processing bath is applied to the top view, a silver image reinforced by a dye image is obtained, since the silver halide developer diffuses through the layer of gelatin and dye at the locations without a latent image and there the dye bleaches imagewise, leaving behind a dye image that develops Silver picture corresponds. This dye image enhances the silver image and enables the silver casting weight to be reduced without any reduction in the density of the final image.

The emulsion layer 3 can optionally provide either a negative or a positive image.

FIG. 10 shows a photographic material which can be used according to the invention and which comprises two components. The first component consists only of a cover layer 5. The other component comprises a transparent support 1, on which a bleachable image dye layer is placed in this order. 2, a white reflecting layer 3 and a silver halide layer 4 are cast. Between the cover layer 5 and the silver halide layer 4, a sleeve 6 can be seen which contains an aqueous alkaline silver halide developer solution.

The material according to FIG. 10 can be used in a self-processing camera known per se. In use, the material with the cover layer 5 is exposed in a camera in close contact with the silver halide emulsion layer 4. Preferably, the sleeve 6 lies in the material with its exit between two edges of the cover layer and silver halide layers, but is in such a position that the close optical contact between these two layers is not impaired.

After exposure, the material is passed through a pair of driven rollers which break the sleeve 6 and the processing liquid contained therein can be spread uniformly between the top layer 5 and the silver halide layer 4. The silver halide developer then diffuses into the silver halide layer and develops the silver image there at the latent image points. At the locations without a latent image, it diffuses through the white reflective layer 3 and into the gelatin layer 2 containing dye (s), where it bleaches the bleachable dye to form a color image. The image can then be viewed through the carrier 1 under supervision.

FIG. 11 shows a further photographic material which can be used according to the invention and which contains two separate components. The first component consists of a carrier 1 and a bleachable dye of the formula (1) in a gelatin layer 2, and the second component comprises a cover layer 4, a silver halide layer 5, a gelatin layer 6 with a developer, e.g. Hydroquinone, and a carrier 7. Between the bleachable dye layer 2 and the cover layer 4, a sleeve 3 can be seen, which contains an aqueous alkaline solution.

The material according to FIG. 11 can be used in a self-processing camera known per se.

In use, the silver halide layer of the second component is exposed through the carrier 7 in a camera. The sleeve 3 lies in the material with its exit between the edges of the cover layer 4 and the bleachable dye layer 2. After exposure, the structure is guided by a pair of driven rollers which break the sleeve 3 and the processing liquid contained therein is uniform between the cover view 4 and let layer 2 spread out. The alkaline processing liquid diffuses into the layer containing the embedded developer, where it releases and dissolves the developer, and this then diffuses into the exposed silver halide layer. The developer develops the exposed silver halide at the latent image areas and is consumed; however, at the locations without a latent image, the developer diffuses into layer 2 containing the bleachable dye, where it bleaches the bleachable dye to form a color image. The contact between the first component and the second component can then be removed and the color image can be seen directly or through the support base.

For example, the is suitable as a white reflecting layer for use in the materials according to FIGS. 2, 3, 6, 7, 8 and 10 the following:

These components are dispersed using a homogenizer or ultrasonic mixer and cast into a layer containing 27 g / m ^{2 of} TiO ₂ . For example, the following is suitable as a soot layer for use in the materials according to FIGS. 1 to 3 and 5 to 8:

These components are mixed gently for two minutes and poured into a layer containing 2.7 g / m ² .

Further layers may also be present in the photographic material according to the invention, for example a neutralizing layer, a time control layer or a layer for regulating the swelling of the gelatin layers. The above-mentioned layers are optionally preferably located between the top view and the silver halide emulsion layer or between the dye layer and the support, in order not to extend or disturb the diffusion path of the developer to the bleachable dye layer.

Gelatin is preferred as the binder for all layers. So-called gelatin extenders can, however, be present, for example those which are derived from synthetic colloidal latices, in particular acrylic latexes. Other natural or synthetic binders can be used either alone or in a mixture with the gelatin, for example albumin, casein, polyvinyl alcohol and polyvinyl pyrrolidine.

The halide content and the halide ratio of the silver halide present in the silver halide emulsion layer depend on how the material is to be used. All conventional silver halides such as pure bromide, chlorobromide, iodobromide and chlorobromojodid are suitable for the photographic material used in the process according to the invention. Furthermore, all the usual additives present in silver halide emulsion layers can also be present, such as sulfur or gold sensitizers, emulsion stabilizers, wetting agents and antifoggants.

The support used can be any of the usual supports used for photographic materials; In the case of a transparent support, this can consist, for example, of cellulose triacetate, cellulose acetate butyrate, oriented and subbed polystyrene, polycarbonate or polyester, such as polyethylene terephthalate. If the support is opaque, it can consist of any of the film support materials listed above, which has been pigmented with barium sulfate or titanium dioxide, for example, in order to make its cast surface reflective. It can also be a paper carrier with a barite coating or a polyethylene-coated paper carrier. Furthermore, this can be a polyester carrier interspersed with cavities.

As indicated above, the processing is preferably carried out in an aqueous medium, which is preferably made alkaline with a suitable alkali or buffer mixture, expediently to a pH between 9 and 11. The processing and development speed and gradation can be varied within wide limits depending on the pH value.

The aqueous alkaline processing medium preferably contains an antifoggant, for example iodide or bromide ions or 1-phenyl-5-mercaptotetrazole.

The following examples serve to explain the invention.

• 1. eine Gelatineschicht, die. 2,0 g/m² des Azamethinfarbstoffs der Formel
  
  in Gelatine mit einem Giessgewicht von 4 g/m² enthält,
• 2. eine lichtempfindliche Silberhalogenidgelatineemulsionsschicht, die 1,6 g/m² Silber in Form von Silberbromid in 2,0 g/m² Gelatine enthält und
• 3. eine 1,0 g/m² Gelatine enthaltende Deckschicht.

Example 1: Three samples of a photographic material according to FIG. 9 are produced by successively pouring the following layers onto a 0.1 mm thick colorless transparent cellulose triacetate support:

• 1. a layer of gelatin that. 2.0 g / m ^{2 of} the azamethine dye of the formula
  
  contains in gelatin with a casting weight of 4 g / m ² ,
• 2. a photosensitive silver halide gelatin emulsion layer containing 1.6 g / m ^{2 of} silver in the form of silver bromide in 2.0 g / m ^{2 of} gelatin and
• 3. a top layer containing 1.0 g / m ^{2 of} gelatin.

All three samples are imagewise exposed under a negative and then processed for 45 seconds at 40 ° C in a silver halide developer solution of the following composition:

Sample 1 This sample is fixed for 40 seconds in ammonium thiosulfate solution and watered, but not further processed. In sample 1, a positive silver image reinforced by a positive color image remains in the material after processing.

Sample 2 After the above processing in a silver halide developer solution to positive silver and color images, this sample is fixed for 40 seconds in a fixing bath based on ammonium thiosulfate, soaked for 5 minutes and then for 4 minutes at pH 10 with a 0.2% solution of 1-phenyl- Treated 3-pyrazolidinone. The 1-phenyl-3-pyrazolidinone bleaches all remaining dye, so that only a positive silver image results. The sample is finally fixed again in ammonium thiosulfate solution.

Sample 3 After the above processing in a silver halide developing solution to the positive silver and dye images, this sample is processed for 5 minutes in a bath containing 5% copper-II-bromide to bleach the developed silver image. The sample is then treated in an ammonium thiosulfate fixing bath for 4 minutes. The result is only a positive color image.

Beispiel 2: Drei weitere Proben werden wie in Beispiel 1 hergestellt und nach bildweiser Belichtung unter einem Negativ 45 Sekunden bei 40°C. in einer Silberhalogenidentwicklerlösung folgender Zusammensetzung verarbeitet:

Then you compare the densities of the final images in the three samples:

Example 2: Three further samples are produced as in Example 1 and after imagewise exposure under a negative for 45 seconds at 40 ° C. processed in a silver halide developer solution of the following composition:

Sample 1 is left as in Example 1 to provide a positive silver and color image

Sample 2 is further treated as in Example 1 in order to only provide a positive silver image,

Sample 3 is further treated as in Example 1 in order to provide only a positive color image.

Then you compare the densities of the final images in the three samples:

• 1. eine Gelatineschicht, die 2,0 g/m² des Azamethinfarbstoffs der Formel (4) in Gelatine mit einem Giessgewicht von 4,0 g/m² enthält,
• 2. eine lichtempfindliche Silberhalogenidgelatineemulsionsschicht, die Silberjodobromid (Br ⊖ 98,4% und J ^⊖ 1,6%) enthält (Silbergiessgewicht 4,5 g/m² und Gelatinegiessgewicht 5,0 g/m²), und
• 3. eine 1,0 g/m² Gelatine enthaltende Deckschicht.

Example 3: Three samples of photographic material according to FIG. 9 are produced by successively pouring the following layers onto a 0.1 mm thick, colorless, transparent cellulose triacetate support:

• 1. a gelatin layer containing 2.0 g / m ^{2 of} the azamethine dye of the formula (4) in gelatin with a casting weight of 4.0 g / m ² ,
• 2. a photosensitive silver halide gelatin emulsion layer containing silver iodobromide (Br ⊖ 98.4% and J ^⊖ 1.6%) (silver ^{casting weight} 4.5 g / m ² and gelatin ^{casting weight} 5.0 g / m ² ), and
• 3. a top layer containing 1.0 g / m ^{2 of} gelatin.

All three samples are exposed imagewise under a step wedge and then processed for 20 seconds at 40 ° C in a silver halide developer solution of the following composition:

Sample 1 is left as in Example 1 to provide a silver and color image.

Sample 2 is further treated as in Example 1 in order to provide only a silver image.

Sample 3 is further treated as in Example 1 in order to provide only a color image.

Then you compare the densities of the final images in the three samples.

in Gelatine mit einem Giessgewicht von 4 g/m2 enthält, und einem 0,1 mm dicken farblosen transparenten Celluloseträger 7.Example 4: A sample of photographic material according to FIG. 11 is produced. The first component comprises a 0.1 mm thick, colorless, transparent cellulose triacetate carrier 1, onto which a gelatin layer 2 is poured. Contains 2.0 g / m ^{2 of} the azamethine dye used in Example 1. The second component consists of a gelatin top layer 4 containing 0.1 g / m ^{2 of} gelatin, a light-sensitive silver halide emulsion layer 5 as used in Example 1, a gelatin layer 6 which contains 2.0 g / m ^{2 of} developer of the formula

in gelatin with a casting weight of 4 g / m2 and a 0.1 mm thick colorless transparent cellulose carrier 7.

The silver halide emulsion layer in the second component is exposed through the cover layer 4 under a step wedge.

1-M sodium hydroxide solution is poured onto the top layer 4 at room temperature and the dye layer 2 is pressed against the top layer for 1 minute, the processing solution being enclosed in between. After 1 minute, the first component, i.e. the dye layer 2 on the carrier 1, separated from the top layer and washed. In the image layer 2, a clear dark blue image with respect to the step wedge is obtained.

• 1. eine Gelatineschicht, die. 2,0 g/m² des Azamethinfarbstoffs der Formel
  
  in Gelatine mit einem Giessgewicht von 4 g/m² enthält,
• 2. eine Titandioxydschicht,
• 3. eine lichtempfindliche Silberhalogenidgelatineemulsionsschicht, die Silberjodidbromid (Br ^⊖ 98,4% und J ^⊖ 1.6%) enthält (Silbergiessgewicht 4,5 g/m² und Gelatinegiessgewicht 10 g/m²), und
• 4. eine 1,0 g/m² Gelatine enthaltende Deckschicht.

Example 5: A sample of photographic material according to FIG. 7, but with the opaque layer 4 omitted, is produced by successively coating the following layers to a thickness of 0.1 mm

• 1. a layer of gelatin that. 2.0 g / m ^{2 of} the azamethine dye of the formula
  
  contains in gelatin with a casting weight of 4 g / m ² ,
• 2. a titanium dioxide layer,
• 3. a photosensitive silver halide ^{gelatin emulsion layer} containing silver iodide ^bromide (Br ^⊖ 98.4% and J ^⊖ 1.6%) (silver ^{casting weight} 4.5 g / m ² and gelatin ^{casting weight} 10 g / m ² ), and
• 4. a top layer containing 1.0 g / m ^{2 of} gelatin.

Man erhält ein klares, dunkelblaues Bild mit D max 1,30 und D min 0,44, welches man durch den transparenten Träger hindurch gegen die opake Titandioxydschicht als Hintergrund betrachten kann.The sample is imagewise exposed under a step wedge and then processed for 40 seconds at 40 ° C in a silver halide developer solution of the following composition:

A clear, dark blue image with D max 1.30 and D min 0.44 is obtained, which can be seen as a background through the transparent support against the opaque titanium dioxide layer.

Example 6: A sample of photographic material according to FIG. 10, but with an integral cover layer instead of the cover layer, is produced by using a gelatin layer containing 2.0 g / m ^{2 of} the azamethine dye of the formula (103). 2 poured onto a 0.1 mm thick colorless transparent cellulose triacetate support. A titanium dioxide layer 3 produced as described above is poured over this layer. A light-sensitive silver halide ^{emulsion layer} 4 containing silver ^iodobromide (Br ⊖ 98.4% and J ^⊖ 1.6%) is ^{poured over it} . The silver ^{casting weight} is 5.0 g / m ² and the gelatin ^{casting weight} is 10 g / m ^2. m ² top layer containing gelatin poured.

After imagewise exposure of the material under a step wedge, a processing solution of the following composition is then applied to the cover layer and left in contact with it for 40 seconds:

A clear, bluish image with D min 0.44 and D max 1.30 is obtained in layer 2.

• 1. eine Gelatineschicht, die 5 mg/dm² feste Dispersion des Farbstoffs der Formel
  
  in Gelatine bei einem Giessgewicht von 30 mg/dm² enthält,
• 2. 10 mg/dm² photographischer Silberhalogenidemulsion in 37 mg/dm² Gelatine und
• 3. eine Deckschicht mit mg/dm² Gelatine.

Example 7: A sample of photographic material according to FIG. 9 is produced by successively placing the following layers on a 0.1 mm thick colorless transparent cellulose triacetate carrier casts:

• 1. a gelatin layer, the 5 mg / dm ² solid dispersion of the dye of the formula
  
  contains in gelatin at a casting weight of 30 mg / dm ² ,
• 2. 10 mg / dm ² photographic silver halide emulsion in 37 mg / dm ² gelatin and
• 3. a top layer with mg / dm ² gelatin.

This material is exposed through a gray wedge for 30 seconds and then processed in a developer solution of the following composition for 1 minute:

A combined silver and color image of the wedge is obtained with a silver density of 2 and a dye density of 0.7.

Claims (21)

1. Process for producing photographic images by (a) imagewise exposure of a photographic material which, during at least one silver halide development step, in this order from optionally a cover layer, at least one silver halide emulsion layer, a layer which contains a hydroxypyridonazamethine compound of the formula therein

contains, wherein R _{l is} hydrogen, optionally substituted alkyl, aralkyl, cycloalkyl, aryl, amino or an optionally substituted heterocyclic radical, Y is hydrogen, hydroxyl, -CN, -COOR ¹ , CONR ¹ R ² or - _C OR ¹ , optionally substituted alkyl , Aralkyl, cycloalkyl, aryl or an optionally substituted heterocyclic radical, Z is hydrogen, -CN, -COOR ³ , -CONR ³ R ⁴ , -S0 ₃ H, -SO ₃ ^- or -COR ³ , where R ¹ , R ² , R ³ and R ^{4 are,} independently of one another, hydrogen, optionally substituted alkyl, aralkyl, cycloalkyl or aryl or an optionally substituted heterocyclic radical, and E represents the atoms required to supplement an optionally substituted heterocyclic or aromatic ring, optionally from those present between these layers Intermediate layers and consists of a carrier, one or more intermediate layers being optionally present between these components, (b) Treating the exposed photographic material with an aqueous alkaline processing bath to make a solution or dispersion of a silver halide developer in the silver halide emulsion layer (s) and thereby to develop the latent silver image in the silver halide emulsion (s), and (c) imagewise diffusion of the silver halide developer from the unexposed image areas of the silver halide emulsion layer (s) into the layer containing the compound of formula (1), and bleaching of this compound by the silver halide developer to produce a color photographic image. 2. The method according to claim 1, characterized in that the compound of the formula

where R ₂ , R ₃ and R _{4 are} independently hydrogen, halogen, optionally substituted alkyl, cycloalkyl or alkoxy and R _S and R _{6 are} independently hydrogen, optionally substituted alkyl, aralkyl, cycloalkyl or aryl or an optionally substituted heterocyclic radical or together with the nitrogen atom to which they are attached form a 5- or 6-membered ring, or R ₃ and R or R ₄ and R ₆ each form two fused rings together with the nitrogen atom, and R ₁ , Y and Z have the meanings given in claim 1. 3. The method according to claim 2, characterized in that the compound of the formula

corresponds in which R ₁ , R ₂ , R ₃ and R ₄ , Y and Z have the meanings given in Claim 2. 4. The method according to claim 1, characterized in that the compound of formula

corresponds in which R14, R _{15 '} R ₁₆ and R _{17 are} methyl or ethyl. 5. The method according to claim 1, characterized in that the compound of the formula

in which ^R _{18 '} ^R ₁₉ and ^R _{20 are} independently hydrogen, alkyl having 1 to 6 carbon atoms or optionally substituted aryl and R ₁₄ and R _{15 have} the meanings given in claim 4. 6. The method according to claim 1, characterized in that the dye is present as a solid dispersion in a layer of the photographic material. 7. The method according to claim 1, characterized in that the silver halide developer is hydroquinone or a hydroquinone derivative. 8. The method according to claim 1, characterized in that the silver halide developer is present in the photographic material from the beginning before its exposure and processing, the silver halide developer being on the side of the silver halide emulsion layer which is remote from the layer containing the dye of the formula (1). 9. The method according to claim 1, characterized in that the photographic material is produced as a one-piece material which contains the top layer, the silver halide emulsion layer and the layer containing a compound of formula (1) on a support. 10. The method according to claim 9, characterized in that in the photographic material used between the silver halide emulsion layer and the layer containing a compound of formula (1) either a separation layer or a separation point is present. 11. The method according to claim 1, characterized in that there is at least one light-opaque layer in the photographic material in addition to a silver halide emulsion layer. 12. The method according to any one of claims 1 and 26. characterized in that in the photographic material there is a white reflective layer next to the layer containing a compound of formula (1) on the side facing away from the support. 13. The method according to claim 1, characterized in that the photographic material in this order a cover layer, a light-opaque layer, a silver halide emulsion layer, a light-opaque layer, a layer containing a compound of formula (1), and one Carrier comprises, the material optionally containing a separation point or separation layer or a white reflective layer. 14. The method according to claim 1, characterized in that the photographic material is produced in two sections, one section comprising the top layer and the silver halide emulsion layer (s) and the other section comprising the layer containing a compound of formula (1). 15. Photographic material, characterized in that it optionally comprises in this order a cover layer, at least one silver halide emulsion layer, a layer containing a bleachable dye according to claim 1, a support and, if appropriate, one or more intermediate layers between each of these layers. 16. Photographic material according to claim 15, characterized in that the photographic material is produced as a one-piece material. 17. Photographic material according to claim 16, characterized in that the photographic material in this order a cover layer, a light-opaque layer, a silver halide emulsion layer, a light-opaque layer, a layer that a compound of formula (1), and comprises a carrier. 18. Photographic material according to claim 15, characterized in that the photographic material is produced in two sections, one section comprising the top layer and the silver halide emulsion layer (s) and the other section comprising the layer containing a compound of formula (1). 19. Photographic material according to claim 18, characterized in that between the silver halide layer and an intermediate layer there is a sleeve which contains an aqueous silver halide developer solution. 20. Photographic material according to claim 18, characterized in that between the layer containing the bleachable dye and an intermediate layer containing a developer there is a sleeve which contains an aqueous alkaline solution. 21. The photographic images produced with the photographic material according to claim 15.

Images