EP0016732A1 - Process for producing photographic images, and suitable photographic material - Google Patents

Abstract

A process for producing photographic images, which is characterized in that (a) a photographic material is exposed imagewise, which at least during the silver halide development step in this order optionally a top layer (7), at least one silver halide emulsion layer (5), a layer containing a substantive azamethine compound (2) and a support (1) contains, optionally with one or more intermediate layers between each of these components, (b) treating the exposed photographic material with an aqueous processing bath to provide a solution or dispersion of a bleach developer compound in the silver halide emulsion layer (s) and thereby to develop latent silver image in the silver halide emulsion (s), and (c) at the positions without a latent image, the bleach developer compound runs in the opposite direction to the image from the silver halide emulsion layer (s) into which a substantive azamethine compound-containing layer diffuses in order to diffuse there d Bleach the compound to form a dye image.

Description

The present invention relates to novel silver halide photographic material and methods of processing the same to produce photographic images.

Since the invention of photography, silver halide salts have been used as a photosensitive agent and mostly developed silver has been used as an image. however, final dye images have replaced the silver image in color photography. In a large number of photographic materials, however, the final picture is still a silver picture, e.g. B. in X-ray materials microfilms and in films for the graphic arts industry as well as in normal highly sensitive black and white films. In recent times however the price of silver has risen so much that one has searched for ways in which silver halide can still be used as a light-sensitive agent, although a final dye image is formed in the photographic materials listed above. In this way, you can either almost completely recover the silver used or at least significantly reduce the amount of silver used.

In a color photography method, the photosensitive agent is a silver salt and a color developer is used which ent the silver halide wraps and at the same time releases a dye that diffuses from the light-sensitive layers into a receiving layer that can be peeled off from the light-sensitive layer. A final dye image is obtained while all the silver remains in the residual material and is therefore recoverable,

In published British patent application No. 2007378A, a photographic diffusion process is described which is not the diffusion of dyes but in which a final dye image is obtained.

• (a) ein photographisches Material bildweise belichtet, welches zumindest während der Silberhalogenidentwicklungsstufe in dieser Reihenfolge gegebenenfalls eine Deckschicht mindestens eine Silberhalogenidemulsionsschicht eine Schicht die einen ausbleichbaren Bildfarbstoff enthält und einen Phototräger enthält, wobei sich gegebenenfalls eine oder mehrere Zwischenschichten jeweils zwischen diesen Komponenten befinden,
• (b) das belichtete photographische Material mit einem wässrigen Verarbeitungsbad behandelt um eine Lösung einer Bleichentwicklerverbindung in der bzw, den Silberhalogenidemulsionsschicht(en) verfügbar zu machen und dadurch das latente Silberbild in der bzw den Silberhalogenidemulsion(en) zu entwickeln und
• (c) an den Stellen ohne latentes Bild die Bleichentwicklerverbindung gegenläufig zum Bild aus der bzw, den Silberhalogenidemulsionsschicht(en) in die den ausbleichbaren Bildfarbstoff enthaltende Schicht diffundieren lässt um dort den Bildfarbstoff unter Entstehung einer photographischen Abbildung zu bleichen,

British Patent Specification 2007378A describes a process for the production of a photographic image, in which stepwise:

• (a) image-wise exposing a photographic material which, at least during the silver halide development stage, in this order optionally a cover layer at least one silver halide emulsion layer, a layer which contains a bleachable image dye and contains a photo carrier, one or more intermediate layers optionally being located between these components,
• (b) treating the exposed photographic material with an aqueous processing bath to provide a solution of a bleach developer compound in the silver halide emulsion layer (s), thereby developing the latent silver image in the silver halide emulsion (s) and
• (c) at the locations without a latent image, the bleach developer compound diffuses in the opposite direction to the image from the silver halide emulsion layer (s) into the layer containing the bleachable image dye in order to bleach the image dye there with the formation of a photographic image,

British patent specification 2007378A defines bleach developer compounds as substances which are able to act both as a silver halide developer and as a bleaching agent for a bleachable dye

The preferred bleachable image dyes are specified in British patent specification 2007378A azo dyes of the type used in silver bleaching processes such as the well-known CIBACHROM process (registered trademark).

A further class of dyes has now been found which can be used as bleachable dyes in the process described in British patent specification 2007378A.

• (a) ein photographisches Material bildweise belichtet, welches zumindest während einer Silberhalogenidentwicklungsstufe in dieser Reihenfolge gegebenenfalls eine Deckschicht mindestens eine Silberhalogenidemulsionsschicht eine Schicht die eine mit der Schicht substantive Azamethinverbindung der allgemeinen Formel
  
  enthält, worin D die zur Ergänzung zu einem gegebenenfalls substituierten heterocyclischen oder aromatischen Ring erforderlichen Atome darstellt, und E einen gegebenenfalls substituierten heterocyclischen oder aromatischen Ring bedeutet, und einen Träger enthält, wobei sich gegebenenfalls eine oder mehrere Zwischenschichten jeweils zwischen diesen Komponenten befinden,
• (b) das belichtete photographische Material mit einem wässrigen Verarbeitungsbad behandelt um eine Lösung oder Dispersion einer Bleichentwicklerverbindung in der bzw. den Silberhalogenidemulsionsschicht(en) verfügbar zu machen und dadurch das latente Silberbild in der bzw den Silberhalogenidemulsion(en) zu entwickeln und
• (c) an den Stellen ohne latentes Bild die Bleichentwicklerverbindung gegenläufig zum Bild aus der bzw den Silberhalogenidemulsionsschicht(en) in die die Verbindung der Formel (1) enthaltende Schicht diffundieren lässt um dort die Verbindung zur Entstehung eines Farbstoffbilds zu bleichen,

The present invention accordingly relates to a process for producing a photographic image, which is characterized in that stepwise:

• (a) Imagewise exposing a photographic material which, at least during a silver halide development step in this order, optionally a cover layer, at least one silver halide emulsion layer, a layer containing an azamethine compound of the general formula which is substantive with the layer
  
  contains in which D represents the atoms required to supplement an optionally substituted heterocyclic or aromatic ring, and E represents an optionally substituted heterocyclic or aromatic ring, and contains a support, one or more intermediate layers optionally being located between these components,
• (b) the exposed photographic material with a treated aqueous processing bath in order to make a solution or dispersion of a bleach developer compound available in the silver halide emulsion layer (s) and thereby to develop the latent silver image in the silver halide emulsion (s) and
• (c) at the locations without a latent image, the bleach developer compound diffuses in the opposite direction to the image from the silver halide emulsion layer (s) into the layer containing the compound of the formula (1) in order to bleach the compound there to form a dye image,

D preferably represents the atoms required to complete a substituted heterocyclic ring

Among aromatic rings E, a phenylene ring substituted in the para position with an optionally substituted amino group and a phenylene ring substituted in the para position with a hydroxyl group are preferred. The phenylene ring can carry further substituents, e.g. B. each optionally substituted lower alkyl or alkoxy (C ₁ -C ₄ ), optionally substituted cycloalkyl halogen (chlorine bromine) or cyan.

Pyrazolones hydroxypyridone and alloxane are preferred as heterocyclic rings E.

The term "layer noun" means that the azamethine dyes with the layer in which they are cast are substantive. As described below, the dyes are preferably in the form of solid dispersions, but they can also be present as oil dispersions or stained with a mordant or made substantive on the basis of their molecular size be,

worin R₁ gegebenenfalls substituiertes Amino oder Hydroxyl, R Substituentengruppen. die gleich oder verschieden sein können m 0 bis 3 und D₁ ein substituierter aromatischer Ring ist.A particularly preferred class of compounds of the formula (1) are those of the formula

wherein R _{1 is} optionally substituted amino or hydroxyl, R substituent groups. which may be the same or different, m is 0 to 3 and D _{1 is} a substituted aromatic ring.

Preferred compounds of the formula (2) which can be used in the process according to the invention are the hydroxypyridone dyes described in German Offenlegungsschrift No. 2808825,

ist, worin R₇ Wasserstoff oder gegebenenfalls substituiertes Alkyl, Aralkyl ,Cycloalkyl. Aryl oder ein heterocyclischer Rest oder gegebenenfalls substituiertes Amino Y Wasserstoff Hydroxyl Cyan -COOR¹ -CONR¹R², -COR¹.A preferred embodiment of the method according to the invention is therefore a method for producing a photographic image according to the method just described, the compound of the formula (1) being a hydroxypyridone compound of the general formula

is where R _{7 is} hydrogen or optionally substituted alkyl, aralkyl, cycloalkyl. Aryl or a heterocyclic radical or optionally substituted amino Y hydrogen hydroxyl cyano -COOR ¹ -CONR ¹ R ² , -COR ¹ .

optionally substituted alkyl. Aralkyl, cycloalkyl. Aryl or a heterocyclic radical and Z is _H , cyano, 3 -CONR ³ R ⁴ -SO ₃ H -SO ₃ ^⊖ or -COR ³ , where COOR ³ -CONR ³ R ⁴ -SO ₃ H, -SO ₃ ^⊖ or , wherein R ¹ R ^{2 '} , R ³ and R ⁴ are each independently hydrogen or optionally substituted alkyl aralkyl. Cycloalkyl aryl or a heterocyclic radical mean R ₂ . R ₃ and R ₄ are each independently hydrogen. Halogen optionally substituted alkyl, cycloalkyl or alkoxy and R ₅ and R ₆ each independently represent hydrogen or optionally substituted alkyl, aralkyl, cycloalkyl aryl or a heterocyclic radical, or R ₅ and R ₆ together with the nitrogen atom to which they are attached are a 5- or Form 6-membered nitrogen-containing heterocyclic ring or R ₃ and R ₅ and R ₅ and R ₆ each form two nitrogen-containing heterocyclic rings together with the nitrogen atom.

Compounds of the formula (3) which can be used in the process according to the invention are preferably 3 in which Z is cyan -COOR ³ , -CONR ³ R ⁴ or -COR ³ , and those with Z equal to cyan are particularly preferred.

Both Y and R ₇ are preferably optionally substituted alkyl, and particularly preferably alkyl with 1 to 4 carbon atoms. Another preferred class of compounds of the formula (3) which can be used in the process according to the invention are those in which R _{7 is} hydrogen and Y is alkyl with 1 to 4 Is carbon atoms. Such compounds can be in tautomeric form which can be formulated as

shows what the symbols have the meanings given above.

In the compounds of the formulas (3) and (4), R ² , R ₃ and R _{4 are} preferably each hydrogen. Y is preferably alkyl of 1 to 4 carbon atoms. R ₅ and R _{6 are} preferably both alkyl or alkoxy having 1 to 4 carbon atoms in the alkyl part.

Compounds of the formula

und

sind zur Verwendung beim erfindungsgemässen Verfahren besonders geeignet,

and

are particularly suitable for use in the method according to the invention,

Further suitable hydroxypyridone compounds are those of the general formula

wherein Z, Y R m and R have the meanings _{e-7 B} indicated.

An example of a compound of formula (7) is the compound of formula

worin R, R₁ und m die angegebenen Bedeutungen haben sowie T und R_S je für Wasserstoff oder ein Substituent sind, stellen eine weitere beim erfindungsgemässen Verfahren geeignete Klasse von Verbindungen der Formel (1) dar.Pyrazolone compounds of the general formula

wherein R, R ₁ and m have the meanings given and T and R _{S are} each hydrogen or a substituent, represent a further class of compounds of the formula (1) which is suitable in the process according to the invention.

In the pyrazolone compounds of the formula (9), m is preferably 0 and R _{1 is} dialkyl-substituted amino. Furthermore, R _{8 is} preferably aryl and particularly preferably substituted phenyl. Examples of such substituents include halogen, alkyl and alkoxy. T can be, for example, alkyl. Alkoxy, amino amido or aryl, all of which can optionally be further substituted or T can also be an acyl group, such as an ester or an acid group.

worin R R₁ und m die angegebenen Bedeutungen haben sowie R₉ und R₁₀ je Wasserstoff oder gegebenenfalls substituiertes Alkyl oder Aryl und Q Sauerstoff bzw. Schwefel ist.Further compounds of the formula (1) which can be used in the process according to the invention are barbituric acid or thiobarbituric acid derivatives of the general formula

wherein RR ₁ and m have the meanings given and R ₉ and R _{10 are} each hydrogen or optionally substituted alkyl or aryl and Q is oxygen or sulfur.

worin R, R₁ und m die angegebenen Bedeutungen habenThere are also ninhydrin derivatives of the general formula

wherein R, R ₁ and m have the meanings given

worin R, R₁ und m die angegebenen Bedeutungen haben und R₁₃ Wasserstoff, Alkyl oder Aryl ist und Derivate des Dimedons oder.der Meldrumschen Säure der allgemeinen Formel

worin R₁ R₁ und m die angegebenen Bedeutungen haben und X . -CH₂- oder -0- ist, in Betracht.and oxindole derivatives of the general formula

wherein R, R ₁ and m have the meanings given and R _{13 is} hydrogen, alkyl or aryl and derivatives of dimedone or Meldrum's acid of the general formula

wherein R ₁ R ₁ and m have the meanings given and X. -CH ₂ - or -0- is considered.

worin sowohl D₂ als auch E₁ die zur Ergänzung zu einem heterocyclischen Ring erforderlichen Atome darstellen wobei der Ring der Kupplungsteil eines gekuppelten Farbkupplers ist, D₂ und E₁ können gleich oder verschieden sein.Another suitable class of compounds of the formula (1) are those of the formula

wherein both D ₂ and E ₁ represent the atoms required to complete a heterocyclic ring, the ring being the coupling part of a coupled color coupler, D ₂ and E ₁ may be the same or different.

Particularly suitable as groups D ₂ and D ₃ are hydroxypyridone groups of the formula

worin T und R₈ die dafür im Zusammenhang mit Formelwherein YZ and R _{7 have} the meanings given in connection with formula (3) have pyrazolone groups of the formula

where T and R _{8 are} the same in connection with formula

worin R₉ und R₁₀ die dafür im Zusammenhang mit Formel(9) have the meanings given and barbituric acid groups of the formula

wherein R ₉ and R _{10 are} those in connection with formula

(10) have the meanings given,

A particularly suitable dye in this class is the murexide of the formula

Another suitable class of dyes of the formula (14) are the bis-hydroxypyridor dyes of the general formula

wherein R ₁₄ , R ₁₅ , R16 and R _{17 are} each selected from methyl or ethyl.

The hydroxypyridone compounds of the formula (3) can be prepared as described in German Offenlegungsschrift 2808825.

mit einer Nitrosoverbindung der allgemeinen Formel

wobei in den obigen beiden Formeln D und E die angegebenen Bedeutungen haben.The remaining compounds of formula (1) can be prepared by well-known literature methods, for example by condensation of the parent group of the formula

with a nitroso compound of the general formula

where in the above two formulas D and E have the meanings given.

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

The compounds of the formula (1) and in particular the hydroxypyridone compounds of the formula (3) and pyrazolone compounds of the formula (9) are preferably present in the layer of the photographic material as a solid dispersion.

• Eine Aufschlämmung des Farbstoffs (5-20 g) in einem Alkylphenolalkoxylat (1,0 g 10%ige Lösung) und einem Alkylphenylpolyäthylenglykoläther (1,0 g 10%ige Lösung) in Wasser (78 g) wird in einer Kolloidmühle (z. B. einer mit 0,7 bis 1,0 mm grossen Mahlkörpern beschichteten Dyno Mill bei 3000 U.p.M.) auf eine Teilchengrössenverteilung von weniger als 1 µm Durchmesser (Mittelwert 0,4 bis 0,5 µm) vermahlen. Eine 0,15 % Netzmittel enthaltende 4%ige Gelatinelösung (von Kationen befreite Mischung, pH 6-7) wird allmählich unter Rühren zur Dispersion gegeben. Gewünschtenfalls kann man auf dieser Stufe einen Härter zusetzen. Die Konzentration der Dispersion wird so eingestellt, dass sich bei ymax eine Dichte von 3 (entsprechend Schichtgewichten von 20-30 mg/dm^-2 Gelatine und 8-10 mg/dm^-2 Farbstoff) ergibt.

A method of making a solid dispersion using gelatin as a binder is as follows:

• A slurry of the dye (5-20 g) in an alkylphenol alkoxylate (1.0 g 10% solution) and an alkylphenylpolyethylene glycol ether (1.0 g 10% solution) in water (78 g) is in a colloid mill (e.g. a Dyno Mill coated with 0.7 to 1.0 mm large grinding media at 3000 rpm) to a particle size distribution of less than 1 µm in diameter (mean 0.4 to 0.5 µm). A 4% gelatin solution containing 0.15% wetting agent (cation-free mixture, pH 6-7) is gradually added to the dispersion with stirring. If desired, a hardener can be added at this level. The concentration of the dispersion is adjusted so that a density of 3 (corresponding to layer weights of 20-30 mg / dm ^-2 gelatin and 8-10 mg / dm ^-2 dye) results at ymax.

Bleach developer compound is a compound. which is capable of developing a latent silver image and bleaching the compound of formula (1).

In the process just described, the bleach developer compound can be in the form of a preformed solution or dispersion which is applied to the exposed photographic material in step (b).

However, bleach developer compounds tend to be unstable and other ways of treating the exposed photographic material are therefore preferred to ensure that enough active bleach developer compound penetrates into the silver halide emulsion layer (s) and in particular that enough bleach developer compound diffuses into the layer containing the compound of formula (1)

In such a method, the bleach developer compound is thus in inactive form and a solution or dispersion of the compound is brought into contact with a substance which activates the compound immediately before or during the application of the solution or dispersion to the exposed photographic material

In an alternative method, the photographic material contains a compound in layer form either in the top layer or under the top layer but above the lowermost silver halide layer which can activate a solution or dispersion of an inactive bleach developer compound. In this method, a solution or dispersion of an inactive bleach developer compound is thus applied to the exposed photographic material in step (b) and the inactive compound is activated when it comes into contact with the activating compound and thus enables the latent silver image to develop.

Another alternative method is the Bleach developer compound first in inactive form in a layer of the photographic material, and in step (b) a solvent for the compound is applied to the exposed photographic material. and the solution of the inactive compound thus formed is treated in the material for converting the compound into the active form. The bleach developer compound can thereby be treated in the material. in that a substance in layer form is also provided which activates the inactive bleach developer compound. In another method, the photographic material is subjected to electrolysis simultaneously with or immediately after the application of the solvent in step (b). The bleach developer compound in the material is converted into the active form.

Electrolysis can also be used to convert a solution or dispersion of the inactive bleach developer compound into the active form, the electrolysis being carried out immediately before or during the application of the solution or dispersion to the photographic material.

The term photographic material of the type as defined below means a photographic material as described in (a), the two described above. The method defines d, h, a photographic material which, at least during the development of the silver halide emulsion, optionally a top layer, comprises at least one .silver halide emulsion layer, a layer which contains a compound of the formula (1) and a photocarrier, one or more intermediate layers optionally being between them Components.

If the exposed photographic material of the defined type is treated in the process according to the invention with an aqueous processing bath in order to have one in the silver halide emulsion layer (s) To make the solution or dispersion of the bleach developer compound available at the latent image points of the silver halide emulsion layer (s), the bleach developer compound thus develops the latent silver image and is thereby oxidized and therefore inactivated both as a silver halide developer and as a bleaching agent for the compound of the formula (1). At the locations of the silver halide emulsion layer (s) without a latent image, however, the bleach developer compound in solution or dispersion can diffuse through the silver halide emulsion, the compound being unaffected by the silver halide without a latent image. When the bleach developer compound reaches the layer containing the compound of formula (1), it bleaches it to form a photographic image which is in line with the silver image formed in the silver halide layer (s). Therefore, if the image formed in the silver halide emulsion layer (s) is a negative image, a negative dye image is formed in the bleachable dye layer. If the image formed in the silver halide emulsion layer (s) is a positive image, the dye image formed in the bleachable dye layer becomes a positive image.

It is understood that the image portion of the photographic material as just defined, that is, that portion of the material comprising both the layer containing the compound of formula (1) and the photocarrier, initially with the photosensitive portion of the material, that is, the silver halide emulsion layer (s) containing portion, or that the photosensitive portion of the material and its image portion can be present as separate components that are brought together during processing. The photographic material contains a separate one, initially not with the photosensitive one Share connected picture share 'so the two components can be separated after the picture is formed in the latter share. Sometimes, however, it is preferable to leave the two sheets connected after processing.

If the photographic material consists of two sections, the cover layer or any other layer is preferably formed such that it can serve as a support for the silver halide emulsion layer (s) and the remaining layers of this section of the material.

It goes without saying that the photographic material can contain a number of further layers apart from the top layer of the silver halide emulsion layer (s) of the image substance layer and the optional intermediate layer (s) between the image dye layer and the photocarrier and this is usually the case. For example, opaque layers of light-reflecting layers may have time control layers which release alkali or acid or other substances as required and / or pickling layers may be present. Examples of materials that can be used in the method according to the invention are shown in the following FIGS. 1 to 24. However, these are only typical representatives of a very large number of materials that can be used in the method of the present invention.

A bleach developer compound is a compound that is capable of both developing a latent silver halide image and bleaching a compound of formula (1). Various classes of bleach developer compounds are known. The reduced form of silver color bleaching catalysts is probably the best known of such classes. Silver color bleaching catalysts are used in the silver color bleaching process where they use the silver color bleaching process to bleach the Accelerate the dye very much in accordance with the silver spots. The silver color bleaching catalysts are used in an acidic solution. The most widely used color bleach catalysts are diazine compounds such as pyrazines, quinoxalines and phenazines.

Suitable diazines are, for example, pyrazine and its derivatives and quinoxaline compounds, in particular those which are substituted in the 2-, 3-, 5-, 6- and / or 7-position by methyl, methoxy or optionally acylated hydroxymethyl or amino.

The 1,4-diazine compounds are preferably used in the form of aqueous solutions. The solution can also contain a mixture of two or more diazines.

The photographic composition of the diazines can be in suspension or as a solution in a high-boiling solvent. In addition, the diazines can be incorporated in the photographic material, in the light-sensitive layer or an adjacent layer, in capsules, which can break when the pressure, temperature or pH changes.

Color bleach catalysts that can be used are also described in German Patents 2-010 707, 2 144 298 and 2 144 297, in French Patent 1,489,460 and in U.S. Patent 2,270,118.

From British Patent 1,183,176 it is known that the reduced form of such diazine compounds can act as a silver halide developer.

Salts of metal ions and complexes of metal ions with suitable ligands capable of acting as silver halide developers are another particularly useful class of bleach developer compounds.

Metal ions capable of acting as developers for latent silver images are well known (see, for example, BLFA Mason "Photographic Processing Chemistry", Focal Press, 2nd edition 1975, pages 177-180). Such metal ions are the ions of metals of variable valence in the low valence state. Generally these are allowed to act at low pH to keep them in their active lower valence state.

In British Patent 2 007 378A it has been shown that metal ions and complexes of metal ions with suitable ligands, which are capable of acting as developers for latent silver images in aqueous acidic solution, are also capable in acidic solution as bleaching agents for compounds of the formula (1) act. However, they are not silver color bleaching catalysts since after the bleachable dye has been bleached they are oxidized to their higher valence state and cannot be reduced to their lower valence state by metallic silver, as is the case with silver color bleaching catalysts.

Metal ions preferred for use as silver halide developers in the process according to the invention are the chromium ion, ie Cr ⁺⁺ , the vanadoion, ie V ⁺⁺ , and the titanoion, ie Ti ⁺⁺⁺ .

Furthermore, in the bleach developer solution containing such metal ions, a ligand e.g. B. ethylenediaminetetraacetic acid is present, which modifies the redox potential of the metal ions in an advantageous manner.

As described above, the photographic material of the type specified can consist of two components, namely the image portion on the one hand and the light-sensitive portion on the other. After exposure of the silver halide emulsion layer (s), processing liquid is introduced therebetween or poured onto one of the portions and the two portions are brought into close contact.

When using a material of this type to practice the invention, the processing liquid can be a bleach developer compound or an inactive form of which cannot act as a silver halide developer or a color bleach. in the second case, a metallic layer as described above can be present in the light-sensitive portion of the material, preferably between the cover layer and the silver halide emulsion layer (s). If the processing liquid is introduced between the image portion and the light-sensitive portion, the bleach developer compound diffuses into this metallic layer and is reduced there to its active state. Then it diffuses into the silver halide emulsion layer (s) and the latent image areas of the silver halide are developed there by the compound; on the other hand, at the points without a latent image, the compound diffuses into the image portion and there bleaches the dye to form a dye image. Then the image portion containing the image dye can be subtracted from the light-sensitive portion of the material. If a pre-formed bleach developer compound is used in a two-component structure, the cover layer preferably contains one component, and the light-sensitive component and the image component are both cast onto the photo carrier and contain the second component. After exposure of the material, the processing liquid containing the pre-formed bleach developer is introduced between the top layer and the emulsion layer. The cover layer can be separated from the second component after processing.

Sometimes, however, it is preferable not to separate the two parts of the material after processing, but to keep them related. This avoids the occurrence of a light sensitive to be rejected. share of the material.

Forming the photographic material in half is particularly useful when processing is to be done in the camera. In this case, the light-sensitive portion and the image portion in the photographic material can be in mutual contact, but not connected. After exposure of the silver halide emulsion layer (s), the processing liquid can be introduced between the two parts, possibly by means of a sleeve between the two parts, the sleeve breaking and the liquid being able to spread between the two parts held in close contact.

However, if the photographic material is initially in one piece, a separation layer or separation point may be present. This layer or position lies between the silver halide emulsion layer (s) and the image dye layer. In the presence of such a separation layer or separation point, a final stage in the process according to the invention is required in some cases in order to bring about the separation effect and to separate the proportion of the photographic material which contains the developed silver image from the proportion which contains the final dye image on the photocarrier .

If there is a separating layer, this can be dissolved in a last wash or a last solution bath. For example, a phthalated gelatin layer that is swellable in water is suitable as the separation layer. However, the separation effect usually occurs during processing, since, for example, phthalated gelatin is swellable in acidic processing solution.

On the other hand, a separation point can be provided, that is, an interface between two layers in such a way that the adhesion between the two layers can be removed. Liability can be removed, 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, so that the last stage of the process can be to initiate the removal of the adhesion and thus to separate the light-sensitive portion from the image portion Liability towards the end of processing, so that often no actual step of starting the separation is required.

If the photographic material initially consists of two parts or if there is either a separation layer or a separation point in the photographic material as defined above, then all of the silver used as the light-sensitive agent can be recovered, since the material part containing the silver is separated from the finished image part can.

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

The solution of the bleach developer compound to be used in the preferred process according to the invention can be prepared in very different ways and applied to the photographic material.

For example, if the bleach developer compound is a reduced diazine compound, this compound can be applied to the photographic material as a preformed reduced compound. The methods for forming a reduced derivative of a 1,4-diazine compound are described in British Patent No. 1183176.

In another embodiment, which is preferred, the reduced diazine compound is produced during use from a diazine compound or an N-oxide derived therefrom by application a reducing agent in layer form in an acidic medium, said reducing agent consisting of a metal which is in the electrochemical series above the silver and comprises the elements up to and including aluminum. This processing method is described in British Patent No. 1330755.

For example, a vacuum-coated metal strip can be used, for example a tin or copper film carrier strip, and this or the exposed photographic material is coated with a solution or paste which contains a 1,4-diazine compound in acidic solution. The diazine compound is reduced by the metal and diffuses into the photographic material, where the reduced diazine compound acts as a developer for the exposed silver halide in the presence of the acidic solution.

A layer can also be present in the photographic material which contains a fine or colloidal dispersion of a metal which is above the silver in the electrochemical series and comprises the elements up to and including aluminum. A colloidal aluminum dispersion is particularly useful.

In a further optional method, the reduced diazine compounds can be generated during the development stage by electrolysis.

If the same developer compound contains simple or complex metal ions in the reduced state, these ions can be produced in a similar manner and applied to the photographic material in very different ways.

For example, (a) a preformed acidic solution of the metal ions used, (b), the acidic solution of the metal ions outside of the photographic _M aterialsjedoch as a step in the processing sequence, generate, or (c), the acidic solution of simple or complex reduced metal ions in situ Position in Make photographic material during the processing sequence.

In the above method (a), the reduced metal ion can thus be pre-formed according to known methods, such as electrolytic reduction of a suitable oxidized form or formation of the required metal ion complex by admixing suitable starting materials in the required oxidation state.

When using method (b), a strip of a second metal or a strip coated with a fine colloidal dispersion of a second metal is used, the second metal having a sufficiently negative reduction potential to reduce the oxidized form of the metal ion to it to achieve reduced form; come z. B. zinc, tin, iron, gallium or indium or alloys containing such metals.

This coated strip, which is then placed on the exposed photographic material, is coated with a solution or paste which contains an oxidized form of the metal ion in acid solution. The oxidized form of the metal ion is reduced by the second metal and diffuses into the photographic material, where the reduced form of the metal ion acts as a developer for the latent silver image in the presence of the acidic solution. In case (c) there may be a layer in the photographic material that contains a fine or colloidal dispersion of a second metal that can reduce oxidized forms of the metal ions to produce the active form of the ions. Such metals are aluminum, zinc, tin, gallium or indium. Furthermore, in method (c), the reduced metal ions can be electrolytically formed in the material during the silver halide development step.

Preferred among these metals are those which do not react quickly with atmospheric oxygen and water at room temperature.

If desired, complexing agents can also be used for the metals during processing.

For example, the fluoride ion forms complexes with aluminum (III) ions, and the copper (I) ion is complexly bound, for example, by nitriles, olefins, chloride ions, bromide ions and thioethers. A large number of ligands and the stability constants of the complexes they form with various metal ions are described in the book "Stability Constants of Metal-Ion Complexes", Special Publication No. 17) London: The Chemical Society, Burlington House, W. 1., 1964. During processing, the complexing agent (e.g. fluoride ions from NH ₄ F or CaF ₂ for Al) built into the processing solution or in the material and the metal which is present in the form of a layer in the photographic material or during processing with the photographic material with interposition is formed the processing bath, a complex medallion. thereby increasing the reactivity of the metal.

The use of poorly soluble compounds as suppliers of complexing agents such. B. CaF ₂ as a fluoride ion donor has the advantage that a sufficient amount of ligand is available for complex formation, without at the same time a currently undesirably high excess of ligand is present in the solution.

The metals can be distributed in the form of small particles in a layer containing silver salt or, if appropriate, in an adjacent auxiliary layer. Auxiliary layers can be inseparable or easily separable from the silver salt emulsion layer. The particles can be dispersed directly in a layered colloid or additionally surrounded by a shell made of a polymeric substance. Furthermore, the metal particles can be broken up by pressure, temperature or pH changes Karseln be included Furthermore, the metals can be used in the form of small, provided with a metallic coating particles of a polymeric substance.

Various embodiments of the photographic materials which can be used according to the invention will now be described with reference to the attached FIGS. 1 to 24.

• Figuren 1 bis 13 Materialien, die entweder eine Trennstelle oder eine Trennschicht enthalten,
• Figuren 14 bis 19 einstückige Materialien,
• Figuren 20 bis 22.Materialien, welche einen lichtempfindlichen Anteil und einen Bildanteil enthalten, die erst während der Verarbeitung zusammengebracht werden, und
• Figuren 23 und 24 ein Material in zwei Abschnitten, das sich zur Verarbeitung in der Kamera eignet.

Show it:

• FIGS. 1 to 13 materials which contain either a separation point or a separation layer,
• FIGS. 14 to 19 one-piece materials,
• Figures 20 to 22.Materials which contain a light-sensitive portion and an image portion, which are brought together only during processing, and
• Figures 23 and 24 a material in two sections, which is suitable for processing in the camera.

The term separation point was used for FIGS. 1 to 13, although this can either be an interface between layers where the adhesion can be removed or can indicate an actual separation layer.

1 shows an inventive photographic material which is useful as Rönt enfilmmaterial ^g.

As shown in FIG. 1, the material consists of a transparent support with a bleachable dye-in-gelatin layer 2 cast thereon. Above the separation point 3 is a soot layer 4 and above that a conventional silver halide emulsion layer 5, which lies between two soot layers 4 and 6 are included, and the photographic material can therefore be handled in daylight. The material can be exposed to X-rays and after exposure to an aqueous acidic solution of the bleach developer compound can be processed into a negative silver image as just described. The silver halide layer and the two soot layers as well as the The top layer is then peeled off the dye layer to recover the silver. The negative dye image on the support can then be viewed in transparency.

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

FIG. 2 shows photographic material according to the invention, which can be used as X-ray material for observation in supervision. In this embodiment, a bleachable dye-in-gelatin layer 2, a white-opaque layer 3, a separation point 4, a soot layer 5, a conventional silver halide emulsion layer 6, a soot layer 7 and a cover layer 8 are cast on 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.

FIG. 3 shows a further embodiment of the material according to FIG. 2. In this figure the layers have the same numbers as in FIG. 2, but the separation point is now offset and lies between the lower soot layer 5 and the silver halide emulsion layer 6. After the silver halide emulsion layer has been stripped off after processing the soot layer is then on the white-opaque layer.

The main advantages of the photographic Materials as described with reference to Figures 1 to 3 are that all of the silver in the silver halide emulsion layer is recoverable and the film material is insensitive to daylight and can thus 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 bleachable dye-in-gelatin layer 2, a separation point 3, a silver halide emulsion layer 4 and a cover layer 5 are cast onto an opaque carrier 1. This material preferably contains a direct-positive emulsion in layer 4 and thus results in a directly-positive dye image after 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, a bleachable dye-in-gelatin layer 2, a separation point 3, a carbon black layer 4, a silver halide emulsion layer 5 and a cover layer 6 are cast on a transparent substrate 1 in this order. The material provides a final dye image that can be viewed transparently. In the case of this material, the exposure must take place in a camera or another light-tight exposure chamber. However, if the material is processed by a method in which an opaque activator metal foil is brought into contact with the photographic material on the outer layer side, the processing can take place under daylight conditions.

Figure 6 shows a further embodiment of the Invention, wöber in this order a bleachable dye-in-gelatin layer 2, a white-opaque layer 3, a carbon black layer 4, a separation point 5, a silver halide layer 6 and a cover layer 7 are cast on a transparent substrate 1. The exposure must also take place here in a camera or a light-tight exposure chamber. The silver halide emulsion layer 6 can be a direct positive emulsion, and in this case a direct positive image is formed after processing, which is viewed under supervision. If, on the other hand, a conventional silver halide emulsion is used, a negative image is formed, which is viewed under supervision, although in this case, of course, one would rather use a material which provides a direct positive image, since one looks at the image under supervision, if it is is not exposure to X-rays, usually looking at negative images.

The materials shown in Figures 1 to 6 can be processed by applying an acidic solution containing a bleach developer compound. This bleach developer compound can be a preformed reduced azine. Bleach developer compounds, which consist of an aqueous acidic solution of metal ions in their lower valence state, are particularly suitable, e.g. B. stabilized with ethylenediaminetetraacetic acid. Such solutions remain active for some time. On the other hand, as mentioned with reference to Figure 5, the inactive bleach developer solution together with an activator metal foil, e.g. As aluminum or zinc foil, use, the metal reduces the inactive bleach developer to the active form in contact with the photographic structure.

Such processing methods are shown in Figures 7 and 8. In FIG. 7, the photographic material consists of a white-reflective support 1, onto which a bleachable dye-in-gelatin layer 2 is poured is. A separation point 3 is located between layer 2 and layer 4, which is a black opaque layer, and a layer of silver halide 5 is cast on layer 4, on which there is a cast thin cover layer 6.

The inactive bleach developer solution is applied to the cover layer 6 and the material is then brought together with a zinc paste layer 7 which is cast onto a black-opaque paper carrier 8.

The material according to FIG. 7 can be processed in the light after being brought together with the black paper.

A dye image is obtained in the image layer 2 and layers 4-8 are removed.

FIG. 8 shows the material from FIG. 5 with an aluminum foil 7 above it. After exposure, the acidic inactive bleach developer solution is added to the cover layer 6 and the metal foil is pressed together.

FIGS. 9-13 show materials which are similar to those in FIGS. 1-6 in that they each contain a separating layer, but in the case of materials 9-12 each further contain a metal-activating layer.

The material from FIG. 9 is similar to that from FIG. 4, but here there is a dispersion of powdered zinc in the top layer 5.

The material from FIG. 10 is quite similar to that from FIG. 4, except that a further silver halide emulsion layer 6 and a thin cover layer 7 are cast onto the metal layer 5. The presence of the second silver halide emulsion layer serves to enhance the dye image formed in layer 2.

The material from FIG. 11 is similar to that shown in FIG. 1, except that there is a fine dispersion of aluminum metal particles in the soot layer 6 from FIG. 11.

In the material shown in FIG. 12 there is a translucent carrier 1 on which a bleachable one Dye-in-gelatin layer 2, a white reflecting layer 3, a silver halide emulsion layer 5, a copper particle layer 6 and a silver halide emulsion layer 7 are cast. After exposure, an inactive bleach developer solution is applied to the emulsion layer 7, and this diffuses down into the metal layer 6, where it is activated. The active bleach developer compound develops the latent image in both silver halide emulsion layers and diffuses at the locations without a latent image to the bleachable dye layer 2, where it bleaches the dye to form a dye image. Then the separating layer 4 is activated and the dye image is visible through the support against the white reflecting layer 3. The two silver halide emulsion layers act in such a way that the dye image formed in layer 2 is enhanced.

The material shown in FIG. 13 is similar to that shown in FIG. 4, except that the cover layer 5 from FIG. 13 contains a fine dispersion of zinc metal flakes.

The materials shown in Figures 9-13 are processed by applying an acidic solution of an inactive bleach developer compound to the top layer. When the inactive bleach developer compound reaches the metal layer, it is activated and can develop the latent silver image in the silver halide emulsion layer (s) and after diffusion into the bleachable dye layer there bleach the dye to form an image.

Integral photographic materials useful in the present invention, i.e. those that remain integral after processing are shown in Figures 14-19.

In this order, FIG. 14 shows a bleachable dye-in-gelatin layer 2, a white reflective layer 3, an opaque soot layer 4, a silver halide emulsion layer 5 and a cover layer 6 are cast onto a carrier 1. The exposure must take place in a camera or light-tight exposure chamber. The emulsion layer 5 can optionally generate a direct positive image or a negative image.

In FIG. 15, a bleachable dye-in-gelatin layer 2, a white-reflecting layer 3, an opaque soot layer 4, a silver halide emulsion layer 5, an opaque soot layer 6 and a cover layer 7 are cast onto a carrier 1 in this order. This material must be exposed to X-rays. The silver halide emulsion provides a negative image for observation when viewed from above, since X-ray films are usually processed into negative images.

In a further embodiment shown in FIG. 16, the layer 6 consists of an opacifying zinc powder + carbon black layer instead of an opaque carbon black layer. After exposure, such material can be processed into a dye image by applying the acidic solution of an unreduced bleach developer compound such that the reduced form acts as a silver halide developer.

The material from FIG. 17 is similar to that from FIG. 16, except that the soot + zinc layer lies between the silver halide emulsion layer and the white-reflecting layer and there is no upper soot layer.

The materials from FIGS. 15 and 16 can only be exposed to X-rays, but they can be processed in daylight, while the material from FIG. 17 is sensitive to light and requires the usual precautions during exposure and also during processing, unless one is used during processing puts a light-tight mask over the structure.

In the material shown in Figure 18 is a bleachable dye layer 2, a white reflective Layer 3, a silver halide emulsion layer 4 and a cover layer 5, which contains fine zinc metal flakes, are cast onto a transparent support 1.

By applying the acidic solution of an i-active bleach developer, it is allowed to diffuse into the metal layer where it is activated and then into the silver halide emulsion layer where the bleach developer compound develops the latent silver image. At the spots without a latent image, it diffuses into the bleachable dye layer, where it bleaches the dye in the opposite direction to the silver image to form a dye image.

The material from FIG. 19 is similar to that from FIG. 18, except that a further silver halide emulsion layer 6 is poured onto the layer 5. The second silver halide emulsion layer has the effect of enhancing the final dye image in layer 2.

None of the materials shown in Figures 14-19 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 apply a very low Silbergiessgewicht what a picture of very low density results after exposure and processing of the material _`which is far too low to be useful as a final image. The final image in the materials of Figures 14-19, however, is a dye 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 radiation-sensitive agent and not also as an image-providing substance; it is still present in the material, but it is invisible because it lies on the side of the white reflective layer facing away from the dye image.

FIG. 20 shows a material which can be used according to the invention and which consists of two separate components. The image component consists of a translucent carrier 1, on which a bleachable dye-in-gelatin layer 2 is poured. The light-sensitive component contains a cover layer 6, which is transparent but sufficiently thick and rigid to be used as a foundation for the photo. Layer 6 is coated with a metal powder (e.g. aluminum, zinc or copper) and a gelatin binder layer 5. A highly sensitive camera silver halide emulsion layer 4 is cast on the layer 5.

Between layer 4 and layer 2 there is a sleeve 3 which contains an acidic solution of a bleach developer compound in its higher valence state, but which in its lower valence state is capable of serving both as a silver halide developer and as a dye bleach.

The structure from FIG. 20 can be used in a self-processing camera of a type known per se. In use, the structure, preferably with the sleeve 3 already in its position between the two components of the material, is exposed imagewise through the cover layer 6. After the exposure, the material is passed through a pair of driven rollers, which break the sleeve 3 and the processing liquid contained therein can be spread evenly between the two components and also bring the two components into very close contact. The unreduced bleach developer compound in the acidic solution then diffuses into both components, but cannot develop the latent image in the silver halide or bleach the dye until the compound has partially reached layer 5. There it is reduced to the active form. The reduced connection then diffuses through the material.

In layer 4, it develops the latent image areas and is deactivated. At the locations without a latent image, it diffuses further down through the thin solution layer between layers 4 and 2 and into layer 2, where it bleaches the dye which can be bleached imagewise to form a dye image causes.

In this case, since a highly sensitive camera emulsion is used, the emulsion is preferably a negative emulsion. This will result in a negative dye image.

The material from FIG. 21 is similar to that from FIG. 20, except that fine zinc dust particles are also present in the silver halide emulsion layer 4 and the metal layer 5 is missing.

FIG. 22 shows a further photographic material which can be used according to the invention and which contains two separate components. The lower component consists of a translucent carrier, a neutralizing layer 2 and a layer 3 with one or more bleachable dyes + gelatin. The upper component consists of a layer 5 cast on a paper support 4 with zinc powder + binder, a silver halide emulsion layer 6 and a cover layer 7. The lower component can be part of a long material web.

In use, the upper component is placed after the imagewise exposure in a camera through the cover layer 7 next to the lower component, layer 7 and layer 3 facing each other. Then an inactive form of bleach developer compound is spread over either layer 7 or layer 3, either as a dispersion or as a solution, and the two components are held together in close contact.

The inactive bleach developer compound then diffuses into layer 5 where it is converted to the active form. Then it diffuses into the layer 6, where it develops the latent silver image at the latent image points, while at the positions without a latent image it diffuses in opposite image through the protective layer 7 into the dye layer 3, where it bleaches the dye, so that a Farbstoffbild.ent stands. Then you can remove the top component and recover the silver from it. The image can be viewed through the translucent support. In practice, if the bottom component is part of a web, a series of dye images along the length of the web will result if the procedure is repeated using a series of exposed top components.

FIG. 23 shows a photographic material which can be used according to the invention and which contains two separate components. The first component consists only of a cover layer 5. The other component contains a translucent carrier 1, on which a bleachable image dye layer 2, a white-reflecting layer 3 and a silver halide layer 4 are cast in this order. Between the cover layer 5 and the silver halide layer 4, a sleeve 6 can be seen, which contains a pre-formed bleach developer compound.

The material from FIG. 23 can be used in a self-processing camera of a type 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. The sleeve 6 preferably lies in the construction with its exit between two edges of the cover and silver halide layers, but is in such a position that it does not impair the close optical contact between these two layers.

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 cover layer 5 and the silver halide layer 4. The pre-formed bleach developer compound then diffuses into the silver halide layer and develops the latent image therein at the latent image locations. In the places without latent The image diffuses in opposite directions through the white reflective layer 3 and into the layer 2 of dye (s) + gelatin, where it bleaches the bleachable layer to form a dye image. The image can then be viewed through the carrier 1 under supervision.

FIG. 24 shows a photographic material which can be used according to the invention and which likewise contains two separate components. The first component consists of a cover layer 8 with a layer 7 cast thereon, which consists of powdered zinc in a gelatin binder. The other component comprises a translucent carrier 1, on which a bleachable image dye layer 2, a white-reflecting layer 3, a silver halide layer 4 and a cover layer 5 are cast in this order. Between the cover layer 5 and the zinc layer 7, a sleeve 6 can be seen, which contains an unreduced bleach developer compound.

The material from FIG. 24 can also be used in a self-processing camera of a type known per se. In use, the structure with the zinc layer 7 is exposed image-wise in a camera in close contact with the cover layer 5. The sleeve 6 preferably lies in the construction with its exit between two edges of the cover and zinc layers, but is in such a position that it does not impair the close optical contact between these two layers.

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 zinc layer 7. The unreduced bleach developer compound is reduced by the zinc layer, then diffuses into the silver halide layer and develops the latent image in the latent image areas. It diffuses in places without a latent image image in the opposite manner by the white-reflec- _re nde layer 3 and into the layer 2 of dye (s) + gelatin where it bleaches the bleachable layer under formation of a dye image. The image can then be viewed through the carrier 1 under supervision.

die unter Verwendung eines Homogenisierapparats oder Ultraschallmischers dispergiert und zu einer 27 g.m^-2 TI0₂ enthaltenden Schicht vergossen wird.The following is suitable, for example, as a white reflecting layer for use in the material from FIGS. 2, 3, 6, 8, 12, 14-19, 23 and ₂ 4:

which is dispersed using a homogenizer or ultrasonic mixer and poured into a layer containing 27 gm ^-2 TI0 ₂ .

die zwei Minuten gelinde vermischt und zu einer 2.7 g.m^-2C enthaltenden Schicht vergossen wird.For example, the following is suitable as a soot layer for use in the material according to FIGS. 1-3, 5-8, 11 and 14-17:

the two minutes are mixed gently and poured into a layer containing 2.7 gm ^-2 C.

* From the company Chemische Werke Brockhues A.G. Niederwellent / Rheingau available.

Further layers may be present in the photographic material according to the invention, for example a neutralizing layer, a time control layer, a Pickling layer which can serve to trap amines released during the bleaching process, if any, as a dye used as image dyes, or also a layer to control the swelling of the gelatin layers. The above layers, if any, are preferably located between the top layer and the silver halide emulsion layer or between the dye layer and the support in order not to extend or interfere with the diffusion path of the bleach developer compound 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 gelatin, for example albumin, casein, polyvinyl alcohol and polyvinyl pyrrolidone.

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, but all the usual pure bromide, chloride bromide, iodide bromide and chloride bromide iodide silver halides 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, such as sulfur and gold sensitizers, emulsion stabilizers, wetting agents and antifoggants, can also be present.

The support used can be any of the supports commonly 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 wearer is opaque, he can consist of any of the film carrier materials listed above, which has been pigmented with barium sulfate or titanium dioxide, for example, in order to make its cast surface reflective, or it can also be a paper carrier with a barite coating thereon or a polyethylene-coated paper carrier. A porous polyester support can also be used.

As indicated above, the processing is preferably carried out in an aqueous medium, and this is preferably acidified to a pH between 0 and 4, preferably with a suitable acid or buffer mixture. The processing and Entwicklungsgeschwin- _d accuracy, and the gradation can be a function of the pH value may vary within wide limits. Suitable acids are preferably: aliphatic, aromatic or heterocyclic mono-, di- and tricarboxylic acids, which can also contain substituents such as chlorine, bromine and iodine atoms or hydroxyl, nitro, amino or acylamino groups, and also aliphatic or aromatic sulfonic acids or phosphoric acid and mineral acids such as HF, HC1, HBr, HClO ₄ , HNO ₃ , H ₂ SO ₄ , H ₃ PO ₄ and H ₂ CO ₃ ; further HSO ₃ ^e , S0 ₂ and sulfamic acid. The following are suitable as buffers: [Al (H ₂ O) ₆ ] 3 ^⊕ and HBF ₄ .

An antifoggant is preferably present in the aqueous acidic processing medium, for example iodide or bromide ions or l-phenyl-5-mercaptotetrazole.

The following examples serve to explain the invention.

EXAMPLE 1

• Teil 1
• ₁. Eine Gelatineschicht, die 0,9 g/m^-2 des Farbstoffs der Formel (5) in 5 g/m^-2 Gelatine enthält.
• 2. Eine weiss-reflektierende Schicht.
• 3. Eine lichtempfindliche Silberhalogenidgelatineemulsionsschicht, die 5,1 g/m^-2 Silber in Form von Silberbromidjodin (98.5 Mol-% AgBr und 1,5 Mol-% AgJ) enthält.
• 4. Eine Deckschicht, die 1,0 g/m^-2 Gelatine enthält.

A material as shown in FIG. 24 is produced by successively pouring the following layers onto a 0.1 mm thick, translucent cellulose triacetate support:

• part 1
• _1st A gelatin layer containing 0.9 g / m ^{-2 of} the dye of formula (5) in 5 g / m ^-2 gelatin.
• 2. A white reflective layer.
• 3. A photosensitive silver halide gelatin emulsion layer containing 5.1 g / m ^-2 silver in the form of silver bromide iodine (98.5 mol% AgBr and 1.5 mol% AgJ).
• 4. A top layer containing 1.0 g / m ^-2 gelatin.

Part 2

1. A zinc powder layer containing 1.6 g / m ^-2 zinc dust in 3.2 g / m ^-2 gelatin.

• Nach Belichtung des lichtempfindlichen Teils des Aufbaus hinter einem Grauteil verarbeitet man das Material im Dunkeln, indem man die Emulsionsseite mit der Zinkpulverschicht des Teils 2 zusammenbringt, auf dem eine Verarbeitungszusammensetzung der folgenden Formel aufgebracht ist:
  

This. Material is not tested in a camera but under darkroom conditions using the following test method:

• After exposing the photosensitive part of the structure behind a gray part, the material is processed in the dark by bringing the emulsion side together with the zinc powder layer of part 2, on which a processing composition of the following formula is applied:
  

After 40 seconds the two material parts are separated. A blue image part is obtained in layer 1, the density of which is sufficiently dark for a finished image.

EXAMPLE 2

The dye of formula (6) is cast and tested as described above. The material parts are separated after 80 seconds. You get a blue part of the picture. This image has a sufficiently dark density as a finished image.

EXAMPLE 3

The dye of formula (18) (murexide) is cast and tested as described above. The material parts are separated after 60 seconds. You get a purple one Illustration whose density is sufficient for a finished picture. . is dark.

EXAMPLE 4

entspricht, wird wie oben angegeben vergossen und geprüft.Die Materialteile werden nach 100 Sekunden getrennt. Man erhält eine braune Abbildung, die für ein fertiges Bild ausreichend dunkel ist.A pyrazolone dye of the formula (9) which is of the formula:

is cast and checked as indicated above, the material parts are separated after 100 seconds. A brown image is obtained which is sufficiently dark for a finished picture.

Claims (28)

1. A process for producing photographic images, characterized in that one after the other: (a) Imagewise exposing a photographic material which, at least during a silver halide development step, in this order optionally a top layer, at least one silver halide emulsion layer, a layer containing an azamethine compound of the general formula which is substantive with the layer

contains in which D represents the atoms required to supplement an optionally substituted heterocyclic or aromatic ring and E represents an optionally substituted heterocyclic or aromatic ring, and contains a carrier, one or more intermediate layers optionally being located between these components, (b) treating the exposed photographic material with an aqueous processing bath to provide a solution or dispersion of a bleach developer compound in the silver halide emulsion layer (s), thereby developing the latent silver image in the silver halide emulsion (s), and (c) at the locations without the latent image bleaching developing agent to the image of the silver halide emulsion (s) in which can diffuse (1) layer containing the compound of formula opposite to where the _'compound under formation of a dye image to bleach. 2. The method according to claim 1, characterized. that the azamethine compound of the general formula

in which R _{1 is} optionally substituted amino or hydroxyl and R substituent groups, which may be the same or different, and m 0 to 3 and D _{1 are} the atoms required to supplement a substituted aromatic ring. 3. The method according to claim 2, characterized in that the azamethine compound is a hydroxypyridone compound of the general formula

is in which R _{7 is} hydrogen or optionally substituted alkyl. Aralkyl, cycloalkyl, aryl or a heterocyclic radical, or _c yclischer optionally substituted amino, Y is hydrogen. Hydroxyl, cyan, -COOR ¹ , -CONR ¹ R ² , -COR ¹ , optionally substituted alkyl, aralkyl, cycloalkyl, aryl or a heterocyclic radical and ZH cyan, -COOR ³ , -CONR ³ R ^4. -SO ₃ H, -SO ₃ ^- or-COR ³ , where R ¹ , R ² , R ³ and R are each independently water Substance or optionally substituted alkyl, aralkyl, cycloalkyl, aryl or a heterocyclic radical, R ₂ , R ₃ and R ₄ independently of one another per hydrogen halogen optionally substituted alkyl, cycloalkyl or alkoxy and R ₅ and R ₆ independently of one another are each hydrogen or optionally substituted alkyl Aralkyl, cycloalkyl, aryl or a heterocyclic radical or R ₅ and R ₆ together with the nitrogen atom to which they are attached form a 5- or 6-membered nitrogen-containing heterocyclic ring or R ₃ and R ₅ and R ₅ and R ₆ each form two nitrogen-containing heterocyclic rings together with the nitrogen atom. 4. The method according to any one of claims 1 to 3, characterized in that the azamethine compound is present in the layer of the photographic composition as a solid dispersion. 5. The method according to any one of claims 1 to 4, characterized in that the bleach developer compound is in the form of a preformed solution or dispersion. which is applied to the exposed phctographic material in step (b). 6. The method according to any one of claims 1 to 4, characterized in that the bleach developer compound is in inactive form and its solution or dispersion is brought into contact with a substance which immediately before or during the application of the solution or dispersion to the exposed photographic material in Stage (b) activated the connection. 7. The method according to any one of claims 1 to 4, characterized. that in step (b) a solution or dispersion of an inactive form of the bleach developer compound is applied to the photographic material. this either in the top layer or under the Cover layer and above the lowermost silver halide emulsion layer contains a compound activating the inactive bleach developer compound in layer form. 8. The method according to any one of claims 1 to 4, characterized in that the bleach developer compound is initially inactive in a layer of the photographic material and in step (b) a solvent for the compound is applied to the exposed photographic material and the solution of the inactive compound thus formed is treated in the material for converting the compound into the active form. 9. The method according to any one of claims 1 to 4, characterized in that the photographic material construction is produced in two sections, one section of the cover layer and the silver halide emulsion layer (s) and the other section the layer which connects the fermel ( 1) contains, and includes the carrier. 10. The method according to any one of claims 1 to 4, characterized in that the photographic material construction is produced as a one-piece construction, the top layer, the silver halide emulsion layer (s) and the layer containing the compound of the fermel (1), comprises, all of which are cast onto the carrier. 11. The method according to claim IC, characterized in that in the photographic material used either a separating layer or a separating point is arranged between the silver halide emulsion layer (s) and the layer containing the compound of formula (1). 12. The method according to any one of claims 1 to 11, characterized in that the silver halide emulsion is a negative-working silver halide emulsion. 13. The method according to any one of claims 1 to 11, characterized in that the silver halide emulsion is a direct-positive silver halide emulsion. 14. The method according to any one of claims 1 to 13, characterized in that an azine compound is present in its reduced form as the bleach developer compound. ₁₅ , Method according to one of claims 1 to 13, characterized in that the bleach developer compound is a metal ion which can act as a silver halide developer in acidic solution, 16. The method according to any one of claims 1 to 15 da-16. Method according to one of claims 1 to 15 characterized. that at least one light-opaque layer is present in the photographic material in addition to a silver halide emulsion layer 17. The method according to any one of claims 1 to 16, characterized in that in the phctographic material a white reflective layer is arranged next to the layer containing a compound of formula (1) on the side facing away from the support. 18. The method according to any one of claims 1 to 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 contains a layer containing the compound of formula (1) and a carrier. 19. Photographic material, characterized in that it comprises in this order a top layer, optionally at least one intermediate layer, a silver halide emulsion layer, at least one intermediate layer, a layer containing a compound of formula (1), and a support, either in the A cover layer or in another layer above the layer containing the compound of the formula (1) is arranged a layer which contains a substance which can activate an inactive bleach developer compound. 20. Fhctogrephisches material according to claim 19, characterized in that a light-opaque layer is arranged between the silver halide emulsion layer and the layer containing the compound of formula (1). 21. Photographic material according to claim 19, characterized in that a white reflective layer is arranged between the silver halide emulsion layer and the layer containing a compound of formula (1). 22. Photographic material according to one of claims 20 and 21, characterized in that a light-opaque layer is arranged between the cover layer and the silver halide emulsion layer. ₂₃ . Photographic material according to one of Claims 19 to 22, characterized in that a separation point or separation layer is arranged therein between the silver halide emulsion layer and the layer containing a compound of the formula (1). _24th Phctographic material. characterized. that there is a top layer. a silver halide emulsion layer, a layer containing a substance. which can activate an inactive lead developer compound, a silver halide emulsion layer, optionally at least one intermediate layer, a layer which contains a compound of the formula (1) as a substance, and a carrier. _25th Photographic material according to claim 24, characterized. that a white reflecting layer is arranged between the second-mentioned silver halide emulsion layer and the carrier. ₂₆ . Photographic material according to claim 25, characterized in that between the second-mentioned silver halide emulsion layer and the white reflec tating layer a separation point or layer is arranged. _27th Photographic material according to one of Claims 19 to 26, characterized in that it has a layer either in the top layer or in an intermediate layer over the uppermost silver halide emulsion layer which contains a bleach developer in inactive form. ₂ 8. Photographic material according to one of claims ₁₉ to _27, characterized in that the photographic material further contains a pickling layer which can pickle released amine compounds during processing of the photographic material. 29. Photographic material according to one of claims 19 to 28, characterized. that it also contains a neutralizing layer.

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