DD140176A5 - METHOD FOR PRODUCING PHOTOGRAPHIC PICTURES - Google Patents

Abstract

The invention relates to a novel process for the production of photographic images, which comprises (a) imagewise exposing a photographic material which, at least during the silver halide development step, in this order optionally a cover layer, at least one silver halide emulsion layer, a layer which is a modifiable Contains image substance, and contains a photocarrier, wherein optionally one or more intermediate layers in each case between these layers

Description

The present invention relates to novel methods of imagewise processing exposed silver halide photographic material to produce pbotographic images, as well as to novel photoswarfa hiddle material.

Characteristic of the known technical solutions

Since the invention of Photographic, silver halide salts have always been used as a photosensitive agent and mainly developed silver has been used as an image, whereby in color photography the color images have replaced the silver image. However, in a large number of photographic materials, the image is still a silver image, e.g. in X-ray materials, microfilms and in graphic arts films as well as in normal high speed black and white films. Recently, however, the price of silver has increased so much that it has sought new ways of producing images that still use silver halide as a photosensitive agent.

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also be formed in the above-mentioned photographic materials (e.g., X-ray materials). In this way one can either almost completely recover the silver used or at least substantially reduce the amount of silver consumed.

In a color photographic method, the photosensitive agent is a silver salt, and a color developer is used which develops the silver halide and at the same time releases a dye which diffuses from the photosensitive layers into a receiving layer which can be peeled off from the photosensitive layer. This gives a dye image, while the entire silver remains in the Hestmaterial and thus recoverable.

Aim of the invention

The aim of the invention is to provide an improved process for the preparation pbotographischer pictures using silver halide photographic material, which is very versatile, and provides very good images is considerably reduced in its application of the silver consumption _»r

Explanation of the essence of the invention

The invention has for its object to produce a novel photographic silver halide material, in the application of which the silver can either be completely recovered or the use of only a small amount of silver is necessary for the production of a good image.

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We have now found a novel photographic diffusion process which is not diffusion of dyes in the photographic material but which gives a color image.

The subject of the present invention is accordingly a process for the preparation of pbotographic images, which is characterized in that one steps in stages

a) imagewise exposing a photographic material containing, where appropriate, at least during the silver halide development step, an upper layer, at least one silver halide emulsion layer, a layer containing a modifiable image substance, and a support, optionally one or more there are several intermediate layers in each case between these layers,

b) treating the exposed photographic material with an aqueous processing bath to form in the silver halide emulsion layer (s) a solution or dispersion of a compound which modifies the image substance / silver halide and thereby form the latent silver image in the To develop silver halide emulsion (s), and

c) the compound which modifies the image substance / silver halide, diffused at the sites without latent image in opposite image from the or the silver halide emulsion layer (s) in the layer containing the modifiable image substance, to reductively there to the image substance modify.

Under "compound which modifies the image substance / silver halide" (hereinafter referred to as Dymodev®)

"7.3.1979 208 8 7 2 - 4 - UP GO3C / 2O8

bonding) is understood to mean a compound capable of developing a latent silver image and further to modify an image substance so as to obtain image differentiation in the image-forming layer corresponding to the undeveloped silver sites, thus obtaining a photographic image.

The choice of the Dymodev compound used in the method according to the invention depends on the image substance present in the image-substance layer. For example, if the image substance is a dye which is imagewise bleachable when present in a layer, then such Dymodev compound is capable of bleaching the image dye as the compound diffuses into the image substance layer. In other types of image-substance modification, it is a matter of either rendering a dye, which is originally substantive with the layer, either solvent-soluble or non-substantive with the layer so that it can be washed out of the layer in a further treatment step. Another type of image-substance modification is to alter the structure of the image dye to alter its spectral absorption. Suitable image dyes of this latter type are frequently complexes containing a metal of variable valency.

These Dymodev connections operate in such a way that the image substance remains at those locations of the image layer into which no Dymodev connection has diffused. In another method, however, the mode of action of the Dyraodev compound is, for example, an increase in the substantivity of the image substance. It is to the

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Sites to which the Dymodev junction has diffused, the image substance made noun for a special solvent. In the treatment with such a solvent, the image substance then remains in these places, while the image substance is removed in the other places by the solvent. Depending on the chosen combination of Dymodev compound and image substance, one can therefore obtain either a negative or a positive image.

It is understood that the term "image substance" also includes leuco dyes and other initially colorless substances that can be converted into visible images. For example, a leuco dye may be present in the image-forming layer, using such a Dymodev compound that, upon its diffusion into the image-subject layer, it may alter the leuco dye to produce a visible dye therefrom. MoO ~ is another example of an initially colorless substance that can be converted into a colored substance by the action of a Dymodev compound. When a reduced diazine (useful as a Dymodev compound hereinafter) acts on this substance, the initially colorless MoO is converted to a colored substance. On the other hand, a Dymodev compound can alter the leuco dye to inhibit its conversion into a visible dye. In this case, a further Beb-Andlungsstufe would be required to convert the leuco dye at the sites to which the Dymodev compound is not diffused into a visible 3ildfarbstoff.

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On the other hand, the preferred image-forming substances which can be used in the present invention are bleachable dyes, and the Dymodev compound is one which is capable of acting both as a silver halide developing agent and as an image-bleaching-compounding compound. Such compounds are referred to below as BI / developer compounds.

Accordingly, the subject of a preferred embodiment of the present invention is a process for the preparation of a photographic image which is characterized in that it is obtained in stages

(a) imagewise exposing a photographic material which, optionally at least during the silver halide development step, in that order contains a cover layer, at least one silver halide layer, a slide containing a substantively bleachable image dye, and a support, optionally one or more intermediate layers, respectively exist between these layers.

(b) treating the exposed photographic material with an aqueous processing bath to form a solution or dispersion of a bleach / developer compound in the silver halide emulsion composition (s) to thereby develop the latent silver image in the silver halide emulsion (s);

(c) diffusing the lead bb / developing agent at the non-latent image positions in the opposite direction from the silver halide emulsion layer (C)) into the image-dye-bleachable image-forming layer to form a photographic image by bleaching the image dye.

, , "3 .. 1979 2 08 8 72 - 7 - -J GO3C / 2O8

In either the method first described or the preferred method just described, the Dymodev compound or bleach / developer compound may be in the form of a preformed solution or dispersion applied to the exposed photographic material in step (b).

However, Dymodev compounds, and especially bleach / developer compounds, tend to be unstable, and other ways of treating the exposed photographic Scbicbt construction are therefore preferable to ensure that sufficient active Dymodev compound enters the silver halide emulsion layer (s), and in particular, sufficient Dymodev linkage diffused into the Bildsubstanzschicbt.

In such a method, therefore, the Dymodev (or Bich / Snwler) compound is in an inactive form, and a solution or dispersion of this compound is contacted with a substance, many of which activate the compound immediately before or during the dissolution or dispersion the exposed photographic layer structure is applied.

In another possible method, the photographic material contained in either the protective layer or under the overcoat layer but above the lowermost silver halide layer contains a layered compound capable of activating a solution or dispersion of inactive Dymodev compound. In this method, in step (b), a solution or dispersion of an inactive Dymodev compound (or bleach / developer compound)

¹⁷ -3.1979 2 08 8 72 - 8 - GO3C / 2O8

On the exposed photographic layer structure, the active compound is activated upon contacting with the activating compound and thus can develop the latent silver image.

In yet another possible method, the Dymode ™ compound (or bleach / developer compound) in a layer in the photographic material is initially in inactive form, and in step (b), a solvent for the compound is applied to the exposed photographic material. The solution of the inactive compound thus formed is treated in the material for conversion to the active form. The treatment of the Dymodev compound in the material may be effected by further providing in the material a layered substance which activates the inactive Dymodev compound. In another method, simultaneously or immediately after the solvent is applied in step (b), the photographic material is subjected to electrolysis. This converts the Dymodev connection in the material into the active form.

Also, electrolysis may be used to convert a solution or dispersion of the inactive Dymodev (or bleach / developer) compound to the active form, which electrolysis occurs just prior to or during the application of the solution or dispersion to the photographic material.

The term "phptographic material" of the kind specified (as used hereinafter) means a pbotographic material as in (a) of the two described above

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A method is defined, that is, a photographic material containing at least during the development of the silver halide emulsion, optionally a cover layer, at least one silver halide emulsion layer, a layer containing a modifiable image substance, and a support, optionally one or more intermediate layers between each of these layers available. As a modification, in this material, either in the overcoat or in another layer over the layer containing the modifiable image substance (optionally over the silver halide emulsion layer), there is a layer capable of activating the inactive Dymodev connection.

Therefore, when in the process of the invention, the exposed pbotographic material of the type defined above is coated with an aqueous processing bath to provide, in the silver halide emulsion layer (s), a solution or dispersion of the Dymodev compound at the latent image sites of the silver halide emulsion layers The Dymodev compound develops the latent silver image and is oxidized, rendering it inactive as both a silver halide developing agent and as a modifier for a modifiable image substance. At the sites of the silver halide emulsion layer (s) without a latent image, on the other hand, the Dymodev compound can diffuse through the silver halide emulsion in solution or dispersion with the silver halide without latent image having no influence on the compound. When the Dymodev compound reaches the modifiable substance layer, it modifies it, resulting in or forming a pbotographic image which is preferably co-effective with the one shown in FIG

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the silver halide layer (s)) is silver image. Thus, if the image formed in the silver halide emulsion layer (s) is a negative image, then a negative dye image is formed in the discardable dye slip. If the image formed in the silver halide emulsion layer (s) is a direct positive image, the dye image formed in the bleachable dye image is a direct positive image.

However, as previously indicated, it is possible to produce an image representing an inversion of the developed silver image by using appropriate Dymodev / Image Substance combinations.

It will be understood that the image portion of the just-defined photographic material, that is, that portion of the material containing both the niodifiable image-containing layer and the support, initially contains the photosensitive portion of the material that bites the portion containing the silver halide emulsion layer (C) of the material, or the photosensitive portion of the material and its image portion may be present as separate components brought together during processing. If the photographic material contains a separate portion not initially associated with the photosensitive portion, the two components may be separated after the image has formed in the latter portion. Sometimes, however, it is preferable to keep the two sheets together after processing. ,

7.3.1979 08 8 72 ~ ¹¹ - - ^{? G0} 3 ° / ²⁰⁸

If the photographic material consists of two parts, then the protective layer or some other layer is preferably formed so that it can serve as a support for the silver balogen emulsion emulsions and the remaining slides of this section of the pusher structure.

It will be understood that the p-type material adjacent to the topsheet, the silver halide emulsion layer (s), slides the image substance, and optionally the intermediate slip (s) may contain a number of slips between the image dye layer and the support, and this is usually the case. In this case, for example impermeable layers, light-reflecting layers, time-controlled layers, the alkali or acid or other substances release as needed and / or Beizschiebten present. For example, the mordant layer (s) serve to pickle the liberated amines when bleachable azo dyes are used as the bleachable image dye.

In accordance with the invention, at least one opaque layer adjacent to a silver bilo-eride emulsion layer may be present in the pbotographic material. However, it may also be a Silberbalogenidemulsionssbbicht and on both sides of an opaque layer.

According to a further embodiment, in the pbotograpbischen material, a white reflecting layer, adjacent to the layer containing the modifiable image substance, on the side facing away from the wearer or between the second-mentioned licbtundurchlässigen sliding and

', ^ .3.1979 7 2 " ¹² " ^kP GO3C / 2O8 872

the layer containing the modifiable image substance is present.

In particular, the photographic material may consist, in order, of the following layers: a light-impermeable layer, a silver halide emulsion layer, an opaque layer, a layer containing a modifiable image substance, and a support. In this case, a separation point between the second-mentioned opaque layer and the layer containing the modifiable image substance can be present according to the invention.

Examples of materials which can be used according to the invention are shown in the following FIGS. 1 to 23. However, these materials are merely typical examples of their very large numbers that can be used in the process according to the invention.

The term "image substance" includes preformed image dyes of the type commonly used in photographic material, such as azo dyes, anthraquinone dyes and triphenylmethane dyes. It also includes colored compounds such as inorganic dyes, especially pigments that can form an image and can be modified. For example, it includes metal oxides such as manganese dioxide and molybdenum trioxide, which are imagewise modifiable.

It is understood that the term bleachable image dye applies to a uniform dye or a mixture of dyes of the same or different color.

72 " ¹³ ''' GO3C / 2O8 872

By bleachable image dye is meant a dye useful in a silver dye bleach process, for example, the well-known CIBACHR0M3 (Registered Trade Mark) silver dye bleach process.

Using the present invention, it is possible to produce either a negative dye image using a conventional silver halide emulsion or a direct positive dye image using a direct positive silver halide emulsion, preferably when it is surface-fogged. When using a conventional silver halide emulsion in the process of the present invention, the latent silver images after exposure will be at the locations of the silver halide emulsion which have been exposed. On the other hand, when using direct-positive silver bleach material in the process of the present invention, the latent silver images will be at the sites of the silver halide emulsion which have not been exposed.

In the conventional silver bleaching process, layer substantive dyes are reductively destroyed in the presence of pbotographically developed silver. These are usually azo dyes, and their destruction can be represented as follows:

EN = NR ¹ + 4H ⁺ . -M_ ^ BIiH ₂

For carrying out the process according to the invention it is possible to use the customary known azo dyes, for example those known from British Pat. Nos. 923,265, 999,996, 1,042,300 and 1,077,628 and U.S. Pat. No. 3,178,290,

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2 08 8 72 -

G03C / 208,872

3,178,291, 3,183,225 and 3,211,556 are known.

Suitable bleachable dyes are further described, for example, in the Coloor Index (Third Edition), edited by the Society of Dyers and Colourists, Land Humphrey, Bradford and London. In addition to azo dyes can be used to carry out the process according to the invention, for example, formazan, azoxy, xanthene, azine, Tripheny! Methane, anthraquinone, nitroso, indigo, nitro-substituted and phthalocyanine and other known dyes. Also, precursors thereof can be used with dyes such as hydrazo and diazonium compounds which yield azo dyes, and tetrazolium salts which produce formazan dyes. The ease with which the azo bonds can be broken reductively depends on the azo dyes on the nature of the substituents on the nitrogen atoms. The reduction may be a stoichiometric reaction in acidic solution with the photographic silver as the reducing agent. Usually this is done in the presence of a so-called color bleach catalyst, for example certain diazo compounds which form reversible redox systems. These compounds are reduced at the surface of the exposed silver and their reduction products diffuse to the dye and bleach it.

Suitable bleachable image dyes of the azo type are, for example:. ,

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? G03C / 208

Yellow:

SO ₃ H

N = N-

SO ₃ H purple:

SO ₃ H

SO ₃ H

OH

₌ N ~ ^ / X ^ -NHCO- (/% -NHCONH- ('% -CONH- (/% -N = JST-C

SO ^ H

SO ₃ H, N

SO ₃ H

CH ₀ CH,

-NHCO- // \\ -CONH-HO -

IH

SO ₃ H

CH SO ₃ H

NH

OH,

CH,

WS ₂ -N = N- I * VV-NH-CO-NH-

OH

HO ₃ S

SO ₃ H HO

HO ₃ S

SO ₃ H

208 8 72 - ¹⁶ -

07/03/1979

AP GO3C / 2O8 872

Blue green:

HO ₃ S

1/7

k-CO-NH OH

OCH,

-N = N-OCH,

By bleach / developer compound is meant a compound capable of both developing a latent silver halide image and bleaching a bleachable image dye. Various classes of bleach / developer compounds are known. The reduced form of silver dye bleach catalysts is arguably the best known such class. Silver stain catalysts are used in the silver bleaching process where they use the silver dye bleaching process to stain the dye

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Accelerate much according to the developed silver spots. With the Silberfarbbleicbkatalysatoren one works in acidic solution. The most widely used color bleach catalysts are diazo compounds, especially 1,4-diazines, for example, pyrazines, quinoxalines and phenazines in their reduced form.

Suitable are, for example diazines pyrazine and its derivatives and quinoxaline compounds, in particular those which in the 2-, 3-, 5- "6- and / or 7-position by Miederalkyl, hydroxyalkyl or alkoxy (C, -G _1), in particular methyl , Hydroxymethyl or methoxy and by acylated hydroxy methyl groups, (-CHP-SO ^ H), amino or acylated (acetylated) amino groups, carboxyl, sulfonic acid (SO-H), benzoyl, acetyl, phenyl, benzyl or pyridyl substituted.

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

The diazines may be present in the pbotographic material in suspension or as a solution in a high boiling solvent. In addition, one can incorporate the diazines in pbotographic material, in the photosensitive layer or one of these adjacent layer, in capsules that can break when pressure, temperature or pH change.

Useful Parbbleicbkatalysatoren are also described in DE-AS 2,010,707, 2,144,298 and 2,144,297, in the PE-PS 1,489,460 and in the US-PS 2,270,118.

From GB-PS 1 183 176 is known dali the reduced

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Form, such Diazoverbindungen can act as Silberbalogenidentwickler.

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

Metal ions capable of acting as latent silver image developers are well known (see, e.g., L. F. A. Mason, Photographic Processing Chemistry, 2nd Ed. 1975, Focal Press, pages 177-180). Such metal ions are the ions of metals of different valences in the lower valence state. In general, they are allowed to act at low pHs to keep them in their active lower valence state.

It has now been found that metal ions and complexes of metal ions with suitable ligands which are capable of acting as latent silver image developer in aqueous acidic solution in acidic solution are also capable of acting as bleaches for bleachable dyes. However, they are not silver dye bleach catalysts because they are oxidized to their higher valence state after flexure of the ausbleicbbaron dye and can not be reduced to their lower valence state by metallic silver, as is the case with silver dye bleach catalysts. "

Preferred metal ions for use as silver halide developers in the process of the invention are the chromium ion, ie Cr ⁺⁺ , the vanado ion, ie V ⁺⁺ , and the titanoion, ie

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Further, in the bleaching-developing solution containing such metal ions, a ligand, e.g. Aethylendiamintetraessigsäure be present, which influences the redox potential of the metal ions in an advantageous manner.

The preferred bleaching / developing compounds used in the present invention, i. the reduced dye bleach catalysts and the ions of metal salts or lower valence state complexes as defined above are both effective in aqueous acidic solution. However, the method of the invention is not limited to using Dymodev or bleach / developer compounds that are effective only as an aqueous acidic solution.

The photographic material of the type indicated can consist of two parts as described above, namely on the one hand the image portion and on the other hand the photosensitive portion. After exposure of the silver halide emulsion layer (s), processing liquid is introduced therebetween or poured onto one of the parts and the two parts are brought together in close contact.

When using a layered structure of this kind for carrying out the invention, the processing liquid may contain a preformed Dymodev compound or an inactive form thereof, which may act neither as a silver halide developing agent nor as a color bleaching agent. In the second layer, where the Dymodev compound is used as a bleach-developing agent, a metallic layer may be present in the photosensitive portion of the composition, preferably between the top layer and the silver bilide emulsion layer (s), as described below. Becomes

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the processing liquid is introduced between the image portion and the photosensitive portion, the bleach / developer compound diffuses into this metallic layer where it is reduced to its active state. Thereafter, it diffuses into the silver halide emulsion layer (s), and the latent image positions of the silver halide are developed there by the compound; on the other hand, at the sites without a latent image, the compound diffuses into the image portion and there bleaches the dye to form a dye image. Thereafter, the image portion containing the image dye may be subtracted from the photosensitive portion of the layer structure. When a preformed image / developing agent compound is used in a two-component composition, preferably, the upper layer contains the one component, and the photosensitive portion and the image portion are both cast on a photocarrier and contain the second component. Each exposure of the layer construction is introduced between the top layer and the emulsion layer containing the preformed bleach / developer processing liquid. The top 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 in context. "This avoids the formation of a photosensitive portion of the layer structure to be discarded.

The preparation of the photographic material in half is particularly useful when processing in the camera. In this case, the light

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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 can spread between the two held in close contact parts.

However, if the photographic material is initially integral, a release layer or release site may be present. This layer or site is between the silver halide emulsion layer (s) and the image dye layer. In the presence of such a release layer or separation point, in some cases, an additional process step in the process of the invention is required to effect the release effect to remove the portion of the photographic material containing the developed silver image from the portion containing the final dye image Pbototräger. separate.

If a separation layer is present, it can be dissolved in a final wash or last solution bath. As a release layer, for example, is a phthalated gelatin layer which is swellable in water. Usually, however, the separation effect occurs during processing because, 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 of such a kind that the adhesion between the two layers repealed

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can be. The abolition of adhesion can be caused for example by a pH or temperature change. The point of separation should be between the silver halide emulsion layer (s) and the image dye layer so that the final step in the process may be to initiate the release of the adhesion and thereby separate the photosensitive portion from the image portion. Usually, however, the release of the adhesion takes place towards the end of the processing, so that often no additional process step is required to start the separation process.

If the pbotographic material initially consists of two parts or there is either a release layer or a release site in the photographic material as defined above, all of the silver used as the photosensitive agent can be recovered since the silver-containing material fraction is separated from the final image can be.

However, one achieves a hereditary savings in silver, if the image part is not separated from the silver-containing part. In this case, the final image to be viewed is the dye image viewed through the transparent support, with a silver image also present in the photographic material, 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 necessary if the image to be viewed is formed in the silver halide emulsion layer (s)

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should.

The solution 'in the. Preferred biocide / developer compounds to be used in accordance with the present invention can be prepared in a very different manner and applied to the photographic layer structure.

For example, if the bleach / developer compound is a reduced diazine compound, then this compound can be applied as a preformed reduced compound to the photographic layer construction. The methods for forming a reduced derivative of a 1,4-diazine compound are described in GB-PS Ur. 1 I83 I76 described.

In another embodiment, which is preferred, the reduced diazine compound is formed during the processing step from a diazine compound or an N-oxide derived therefrom by the application of a layered reducing agent in an acidic medium, said reducing agent consisting of a metal that is in the electrochemical Tension row stands above the silver and covers the elements up to and including aluminum. This processing method is described in British Patent No. 1,333.

According to the invention, the reducing agents may be metals which are above the silver in the electrochemical series and comprise the elements up to and including lanthanum, preferably up to and including aluminum; such metals include copper, iron, lead, tin, nickel, cobalt, indium, gallium, cadmium, manganese, aluminum, lanthanum and the lanthanides. Furthermore, you can alloys

9 na 8 72 ⁷ · ³ · ¹⁹⁷⁹

/ Uöö / Ä -24- AP G03C / 208 872

which contain these metals or also use these metals in amalgamated form.

For example, one may use a vacuum evaporated metal strip, for example a tin or copper film carrier strip, and this or the exposed photographic material is coated with a solution or paste containing 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.

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

In another optional method, the reduced diazine compounds can be produced in the layer structure during the development stage by electrolysis «

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

For example, a ^) can be a preformed acidic solution

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use the metal ions, b ^) produce the acidic solution of the metal ions outside the photographic layer structure but the step in the processing sequence, or Cj) produce the acidic solution of the simple or complex reduced metal ions in place in the photographic material during the processing sequence.

In the above method a ^) can thus be the reduced metal ion by known methods, such as elektrolytiscbe reduction of a suitable oxidized form or formation of the required metal ion complex by admixture of suitable Aasgangsmaterialien in the required oxidation state.

Using method b 1), one uses a strip (foil) of a second metal or a strip coated with a fine colloidal dispersion of a second metal, the second metal having a sufficiently negative reduction potential to permit reduction of the oxidized ^ orm of the metal ion to achieve its reduced form. The metal strips are made of, for example, aluminum, iron, zinc or tin or indium or alloys containing such metals. When used in a fine colloidal dispersion, the metals used are, for example, zinc, tin, iron, nickel, aluminum or indium or, also gallium, lanthanum or alloys containing these metals.

This coated strip, which is then placed over the exposed photographic material, is coated with a solution or paste containing an oxidized form of the metal ion in acidic solution. The oxidized form of

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Metal ion is reduced by the second metal and diffuses into the photographic material where the reduced form of the metal ion in the presence of the acidic solution acts as a developer for the latent silver image. In Pail C / j), there may be a layer in the photographic layer structure which contains a fine or colloidal dispersion of a wide metal which can reduce oxidized forms of the metal ions to produce the active form of these ions. Such metals are aluminum, copper, zinc, tin, iron, nickel, gallium or indium as well as lanthanum or alloys including such metals. Further, 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 rapidly with the oxygen of the air and with water at room temperature *

If desired, it is also possible to use complexing agents for the metals during processing.

For example, the fluoride ion forms complexes with aluminum (III) ions, and the copper (I) ion is complexed, for example, by nitriles, olefins, chloride ions, bromide ions, and thioethers. A large number of ligands, as well as the stability constants of the complexes formed with different metal ions, are described in the book "Stability Constants of Metal-Ion Complexes", Special Publication no. 17, London: The Chemical Society, Burlington House, W.I., 1964. Bai's processing originates from that in the processing solution or in the material

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incorporated complexing agents (eg fluoride ions from NELP or CaP2 fü-cAl) and the metal, which is present in layer form in the photographic material or brought into contact with the pbotograpbischen material with the interposition of the processing bath during processing, a complex bound metal ion, thereby increasing the Reactivity of the metal is achieved.

The use of sparingly soluble compounds as suppliers of complexing agents such as CaPp ^a ^ - ^s Fluoridionenspender has the advantage that a sufficient amount of ligand for the complex formation is available, without at the same time vorbanden a currently undesirably high excess of ligand in the solution.

The metals may be distributed in the form of small particles in a silver salt-containing layer or in an optional adjoining auxiliary layer. Auxiliary layers may be inseparably or easily separably bonded to the silver salt emulsion layer. The particles may be dispersed directly in a layer colloid or additionally surrounded by a shell of a polymeric substance. Furthermore, the metal particles can be contained in capsules which can be aufbrecbbaren by pressure, temperature or pH change. Further, the metals may be used in the form of small metallic coated particles of a polymeric substance.

Execution; sbe is play

The invention will be explained in more detail below on some embodiments.

.7.3.1979 208 8 7 2 - 28 - AP GO3C / 2O8

Various embodiments of the photographic printing apparatuses which can be used according to the invention are described with reference to FIGS. 1 and 23

 In the attached drawing show:

FIGS. 1 to 13 materials containing either a separation point or a separation layer,

FIGS. 14 to 19 are materials which are coalescing; FIGS. 20 to 22 are materials containing a photosensitive portion and an image portion which are brought together only during processing, and FIGS

FIG. 23 shows a material made of two parts, which is suitable for processing in the camera.

For FIGS. 1 to 13, the term separation point has been used, although this may either be an interface between layers where the adhesion can be removed, or may indicate an actual release layer.

FIG. 1 shows a photographic material according to the invention which can be used as an X-ray film material.

As shown in Figure 1, the material consists of a transparent support 1 having a bleachable dye-in-gelatin layer 2 cast thereon. Above this there is the separation point 3. Above the separation point 3 is a soot layer 4 and above that a conventional silver bilide emulsion. thereafter a carbon black layer 6 and over this a capping layer 7. The silver halide emulsion film 5 is thus sandwiched between two carbon black layers 4 and 6 and the photographic material is allowed to settle

2 O 8 8 7 2 - 29 - AP GÖ30 / 208 872

therefore handle in daylight. The material can be exposed to X-rays and, after exposure to an aqueous acid solution of the bleach / developer compound as just described, processed to a negative silver image. The silver halide layer and the two layers of carbon black and the topcoat are then stripped from the dye layer to recover the silver. The negative dye image on the support can then be viewed in translucent light.

For the sake of simplicity, the term "X-rays" shall apply to all very short-wave, photographically useful radioactive rays emanating from an X-ray tube, radium or radioactive isotopes.

Figure 2 shows photographic material according to the invention which can be used as X-ray material for observation in reflected light. In this embodiment, in this order, a bleachable dye-in-gelatin layer 2, a white opaque layer 3 "a release point 4, a carbon black 5", a conventional silver halide emulsion layer 6, a carbon black layer and a cover layer 8 are cast on a transparent film support.

In this case, like the material of Figure 1, the photographic material is processed into a negative image. However, this material has a white opaque layer. This can consist for example of baryta or titanium oxide dispersed in gelatin. The white opaque layer acts as a reflection base for the negative dye image, which is reflected in

7.3.1979 2 08 8 72 - 30 - AP G03C / 208

light is viewed through the film support.

FIG. 3 shows another embodiment of the material of FIG. 2. In this figure, the layers have the same numbers as in FIG. 2, but the separation point is now offset between the lower soot layer 5 and the silver halide emulsion layer 6. After the silver halide emulsion layer is removed after processing The soot layer is then on the white opaque layer.

The main advantages of the photographic material of 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 thus can be handled in the unexposed state under normal daylight conditions.

However, the photographic material of the present invention can be used in a normal camera or processing camera by omitting the upper soot plate. Such material without any carbon black layer is shown in Figure 4, where in this order a bleachable dye-in-gelatin layer 2, a release point 3 "a silver halide emulsion layer 4, and a topcoat 5 are cast onto an opaque support 1. ***" Preferably, this material in layer Λ contains a direct positive emulsion and thus gives a direct positive dye image after processing, which is seen in reflected light. In this case, the material can not be chipped at any stage prior to stripping the silver halide be handled under daylight conditions.

'7.3.W9

.31. AP GO3C / 2O8 872

Yet another embodiment of the material according to the invention is shown in FIG.

In this material, a bleachable dye-in-gelatin layer 2, a release point 3, a carbon black slip 4, a silver halide emulsion layer 5, and a cover layer 6 are cast on a transparent support 1 in this order. The material provides a final dye image that can be viewed in translucent light. In the case of this material, the exposure must be done in a camera or other light-tight exposure chamber. However, if the material is processed by a method wherein an opaque activator metal foil in contact with the. Photographic material is placed on the top layer side, so the processing can be done under Tageslicbtbedingungen.

FIG. 6 shows a further embodiment of the invention, wherein in this sequence a bleachable dye-in-gelatin layer 2, a white opaque layer 3 "a soot layer 4, a separation point 5" a silver halide layer 6 and a cover layer 7 are cast onto a transparent carrier 1. The exposure must also be done here in a camera or a light-tight exposure chamber. The silver halide emulsion layer 6 may be a direct positive emulsion, and in this case, after the. Processing a direct positive image, which is viewed in reflected light. On the other hand, when a conventional silver halide emulsion is used, a negative image is formed, which is considered in reflected light, although, of course, in this case, one would rather use a material, many a direct-positive one

3/7/1979 2 08 8 72 - 32 - AP GO3C / 2O8

Image provides because one views the image in reflected light unless it is exposure to X-rays, usually viewing negative images.

The materials shown in Figures 1 to 6 can be processed by applying an acidic solution containing a leadbic / developing agent. This bleach / developer compound may be a preformed reduced azine, for example, the dihydro derivative of metbylacetylquinoxaline, which remains as an active compound for some time, especially when stored in a nitrogen atmosphere. Bleaching / developing compounds consisting of an aqueous acidic solution of metal ions in their lower valence state are particularly suitable, for example, with ethylenediaminetetraacetic acid- stabilized 1,1- dione ions Such solutions remain active for some time 5. mentions the inactive lead / developer solution together with an activator metal foil, eg aluminum or zinc foil, the metal reducing the inactive bleach / developer to active form upon contact with the photographic slide assembly.

Such processing methods are shown in Figs. 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 cast. A separation point 3 is located between layer 2 and layer 4, which is a black-opaque layer, and on layer 4, a silver halide layer 5 is cast on which a cast thin cover layer 6 is located.

7.3.1979 2 O 8 8 7 2 - 33 - AP G03C / 208

The inactive bleach / developer solution is applied to the topcoat 6 and the laminate is then contacted with a zinc paste layer 7 cast on a black-opaque paper backing 8.

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

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

FIG. 8 shows the material from FIG. 5 with an aluminum foil 7 above it. After exposure, the acidic inactive bleach / developer solution is applied to the topsheet 6 and the metal foil is compressed therewith.

Figures 9-13 show materials similar to those in Figures 1-6, each containing a release layer but, in the case of Materials 9-I3, each containing a metal-activating layer.

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

The layer structure of the material of Figure 10 is quite similar to that of Figure 4, except that on the metal layer 5, a further silver halide emulsion layer 6 and thereon a thin cover layer 7 is poured. The presence of the second silver halide emulsion layer serves to reinforce the dye image formed in layer 2.

7.3.1979 72 - 3A - - AP G03C / 208 8? 2

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

In the layer construction shown in Fig. 12, there is provided a translucent support 1 onto which a bleached dye-in-gelatin layer 2, a white reflective layer 3, a silver halide emulsion layer 5, a copper particle layer 6 and a silver halide emulsion layer 7 are cast An inactive bleach / developer solution is applied to the emulsion layer 7 and diffuses down into the metal layer 6 where it is activated The active bleach / developer compound de-excites the latent image in both silver halide emulsion layers and diffuses at the non-latent image locations the discolourable dye sheet 2 where it bleaches the dye to form a dye image, then the release layer A is activated and the dye image is visible through the support against the white reflective layer 3. The two silver halide emulsion coatings function by this in Layer 2 resulting dye image is enhanced.

The layer structure of the material shown in Figure I3 is similar to that shown in Figure 4, except that the cover layer 5 of Figure 4 contains a fine dispersion of Zinkinetallschuppen.

The materials shown in FIGS. 9-13 are processed by treating an acidic solution of an inactive bleach / degas.

7.3.1979 2 08872 - 35 - AP G03C / 208

Winder connection is applied to the top push. When the inactive bleach / developer compound reaches the metal layer, it becomes activated and can develop the latent silver image in the silver halide emulsion layer (s) and, upon diffusion into the bleachable dye layer, bleach the dye to form an image.

Integral pbotographic materials useful in the invention, i. those which remain integral after processing are shown in Figures 14-19.

In Fig. 14, in this order, a bleachable dye-in-gelatin slip 2, a white reflective layer 3, an opacifying carbon black 4, a silver halide emulsion layer 5, and a cover layer 6 are cast on a support 1. The exposure must be done in a camera or light-tight exposure chamber. The emulsion layer 5 may optionally produce a direct positive image or a negative image.

In Fig. 15, in this rubbing sequence, a bleachable dye-in-gelatin layer 2, a white reflective layer 3, an opacifying carbon black layer 4 *, a silver halide emulsion layer 5j, an opacifying carbon black layer 6, and a cap layer 7 are cast on a substrate 1. This material must be exposed to X-rays. The silver halide emulsion of this layer would normally be a conventional emulsion so as to give a negative image for reflection in reflected light, since X-ray films are usually processed into negative images.

-36- AP GO3C / 2O8

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

The material of Figure 17 is similar to that of Figure 16, except that the carbon black plus zinc layer is between the silver halide emulsion layer and the white reflective layer and has no upper carbon black layer.

The materials of Figs. 15 and 16 can be exposed only to X-rays, but are processable in daylight while the material of Fig. 17 is photosensitive and requires the usual precautions during exposure and also during processing, unless one during processing put a light-tight mask over the material.

In the material shown in FIG. 18, a bleachable dye layer 2, a white reflective layer 3, a silver halide emulsion layer 4, and a cap layer 5 containing fine zinc metal flakes are cast on a transparent substrate 1.

By applying the acid solution of an inactive 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

79 ⁷ · ³ · ¹⁹⁷⁹

/ £. - 37 - AP GO3O / 2O8

developed the latent silver image. In the places without a latent image, it diffuses into the bleachable dye film, where it bleaches the dye opposite the silver image to form a dye image.

The Scbicbtaufbau of Figure I9 is similar to that of Figure except that a further silver halide emulsion layer 6 is poured onto the layer 5. The second silver halide emulsion layer acts to enhance 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 initial silver present is still present in the final imagery. However, it is possible to apply a very low silver casting weight, which after exposure and processing of the material gives an image of very little blackening, which is too low to be useful as the final image. The final image in the materials of Figures 14-19, however, is a dye image of quite acceptable density for a final image. The amount of silver used may therefore be small, since the silver is used only as a radiation-sensitive agent and not as an image-providing substance; it is still present in the layer structure, but is invisible, since it lies on the side facing away from the dye image of the white reflective layer.

FIG. 20 shows a material which can be used according to the invention and which consists of two separate parts. The image component consists of a translucent support 1, on which a bleachable dye-in-gelatin layer 2 is cast.

7.3.1979 2 08 8 7 2 - 38 - AP GO3C / 2O8 872

The photosensitive component comprises a capping layer 6 which, while transparent, is sufficiently thick and rigid to act as a photocarrier. The layer 6 is coated with a metal powder (e.g., aluminum, zinc or copper) and a gelatin binder layer 5. On the layer, a high-sensitivity camera silver halide emulsion layer 4- is poured.

Between layer A and layer 2 is a sleeve 3, which is an acidic solution of a bleach / developer. Contains compound in its higher valence state, but which in its lower valence state is capable of serving both as a silver bilide developer and as a dye bleach.

The material of Figure 20 can be used in a self-processing camera of known type. In use, the material, preferably with the sleeve 3 already in the position between the two components of the material, exposed by the cover layer 6 imagewise. After exposure, the material is passed through a pair of driven rollers which break the sleeve 3 and allow the processing liquid contained therein to spread evenly between the two components and also "bring the two components together very closely Acid solution then diffuses into both components, but can neither develop the latent image in the silver halide nor bleach the dye until the compound has partially reached layer 5. There it is reduced to the active form, the reduced compound then diffuses through the material.

.. 07/03/1979 ..

- 39 - AP GO3C / 2O8

In layer 4, it develops the latent image sites and is deactivated. In the places without latent image, it diffuses further down through the thin solution layer between layers 4 and 2 and into layer 2 where it forms the bleach of the dye-bleachable dye to form a dye Color image causes.

Since a high speed camera emulsion is used in this case, the emulsion is preferably a negative emulsion. Thus, a negative dye image will arise.

The material of Fig. 21 is similar to that of Fig. 20, except that in the silver halide emulsion layer 4, fine zinc dust particles are further present and the metal layer 5 is absent.

Figure 22 shows another photographic material usable in the invention containing two separate parts. The lower part consists of a translucent support, a Neutralisierscbicbt 2 and a layer 3 with one or more bleachable dyes plus gelatin. The upper part consists of a layer 5 ^m 2 of zinc powder plus binder cast on a paper support 4, a silver halide emulsion layer 6 and a cover layer 7. The lower part can form part of a long material web.

In use, after imagewise exposure in a camera, the upper part is laid through the cover layer 7 adjacent to the lower component, with the layer and layer 3 facing each other. Then, an inactive form of bleach / developer compound is used as either

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Dispersion or as a solution either over layer 7 or layer 3, and the two components are kept close together.

The inactive biocide / 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 areas, while diffusing in the opposite direction at the non-latent image areas through the layer 7 in the dye layer 3, where it bleaches the dye, so that a dye image is formed. Then you can remove the upper component and recover the silver from it. The image is to be viewed through the translucent support. In practice, if the lower component is part of a web, a series of dye images will result along the length of the web, repeating the procedure using a series of exposed upper components.

Figure 23 shows a photographic material useful in the invention containing two separate parts. The first part consists of only one cover layer 5. The other part contains a translucent support 1 on which a bleachable image dye layer 2, a white reflective layer 3 and a silver halide layer 4 are cast in this order. Between the cover layer 5 and. the silver bleach layer 6 is attached a sleeve 6 containing a preformed bleach / developer compound.

The material of FIG. 23 is in a self-processing

7.3.1979 -, O / L - 41 - AP G03C / 208 872

In use, the material is exposed imagewise in a camera with the cover layer 5 in close contact with the silver halide emulsion layer 4. Preferably, the sleeve 6 is layered with its exit between two edges of the top layer and the silver halide bonders; However, it is in such a position that it does not interfere with 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 uniformly between the cover layers 5 and 5. let the silver halide phosphor 4 spread. The preformed bleach / developer compound then diffuses into the silver halide layer and develops therein the latent image at the latent image locations. In the places without a latent image, it diffuses in an opposite way through the white reflective slide 3 and into the layer 2 of dye (s) plus gelatin, where it bleaches the bleachable layer to form a dye image. -The image can then be viewed in reflected light through the carrier 1.

As the white reflecting film for use in the material of Figs. 2, 3, 6, 8, 12, 14-19, and 23, for example, the following is suitable:

Titanium dioxide (average particle size 1.5 / i) 15 S Gelatine (4% aqueous solution) 50 ml Fatriumdodecylsulfat (28% aqueous solution) 0.3 ml

208

7.3.1979 -.42 - AP G03C / 208,872

Arylälkyl-polyäthylenoxyd-

condensation product 3.0 ml

(6% solution in 50/50 ethanol esters),

those using a homogenizer or

-? Ultrasonic mixer dispersed and su shed a 27 g m TiOp-containing layer.

As the carbon black layer for use in the material of Figs. 1-3, 5-8, 11 and 14-17, for example, the following is suitable: gelatin: 3g

Water 40 ml

Carbon black dispersion 5 ml

Wetting agent. 2.5 ml

(5% aqueous solution),

-2 mixed gently for two minutes and poured into a layer containing 2.7 g of mC.

Further layers may be present in the photographic material of the present invention, for example, a plasticizer layer, a time control layer, a mordanting layer which may be used to scavenge amines released as the image dye during bleaching, or a gelatin swelling control layer. The optional above layers are preferably between the topsheet and the silver halide emulsion layer or between the dye layer and the support so as not to prolong or interfere with the diffusion path of the leadb developing agent to the dye-bleachable dye layer.

As a binder for all layers, gelatine is preferred.

7.3.W9 -43- AP GO3C / 2O8

Trains t. However, so-called gelatin extenders may be present, for example, those derived from synthetic colloid latexes, especially acrylic latexes. Other natural or synthetic binders may be used either alone or in admixture with gelatin, for example albumin, casein, polyvinyl alcohol and polyvinylpyrrolidone.

The halide content and the halide ratio of silver halide present in the silver halide emulsion layer depend on how the material is to be used, but all common pure bromide, chloride bromide, iodobromide and chloride bromide iodide silver halides are suitable for the photographic material used in the process of the present invention. Furthermore, all conventional additives present in silver halide emulsion slices may also be present therein, such as sulfur and gold sensitizers, emulsion stabilizers, wetting agents and antifoggants.

The carrier used may consist of any of the supports commonly used for photographic materials; in the case of a transparent support, this may for example consist of cellulose triacetate, cellulose acetate butyrate, oriented and subbed polystyrene, polycarbonate or polyesters such as polyethylene terephthalate. If the support is opaque, it may be any of the above film support materials pigmented with, for example, barium sulfate or titanium dioxide to reflect its pebbled surface, or a paper support having a barite coating thereon or a polycarbonate support may also be used.

07/03/1979

_ΔΡ G03C / 208

Ääthylenkaschierter paper carrier be. This may also be a porous polyester carrier.

As stated above, the processing is preferably carried out in an aqueous medium, and this is preferably acidified to a pH between 0 and 4 with a suitable acid or buffer mixture. The processing and development rates as well as the gradation can be varied within wide limits, depending on the pH. Suitable acids are preferably: aliphatic, aromatic or heterocyclic mono-, di- and tricarboxylic acids, which may also contain substituents such as chlorine, bromine and iodine atoms or hydroxyl, nitro, Aaino- or Äcylaminogruppen, as well as aliphatic or aromatic sulfonic acids or phosphoric acid and mineral acids such as HP, HCl, HBr, HClO ₄ , HITO-, H ₂ SO ₄ , H ₃ PO ₄ and H ₂ CO ₃ ; furthermore HSO ₃ ⁰ , SO ₂ and suifamic acid. Suitable buffers are: Al (H ₂ O) ₆ I ₁ HBP ₄ , Na ₃ S ₂ O ₇ or

Preferably, an antifoggant is present in the aqueous acidic processing medium, for example iodide or bromide ions or i-pbenyl-5-flierkaptotetrazole.

The following examples also serve to illustrate the invention.

EXAMPLE 1 . -. '

Photographic material as shown in FIG. 4 is produced by sequentially applying the following layers to a 0.1 mm white pigmented cellulose trisimide.

3/7/1979 2 08 8 7 2 - * 5 - AP GO3C / 2O8

Acetate carrier pours.

1. Sine gelatin layer containing 0.2 g of the dye

-2 in 4.0 g of gelatin.

2. A phthalic anhydride modified gelatin

existing release layer with a gelatin order weight

"2

from 1.0gi.

3. A photosensitive silver halide / gelatin emulsion layer containing 1.2 grams of silver in the form of silver chlorobromide (70 mole percent AgCl and 30 mole percent AgBr).

4. Sine 1.0 g of gelatin-containing topcoat.

After a gray wedge exposure, the material is processed in the dark by bringing the emulsion side together with an aluminized carrier on which is applied a processing composition of the formula: pyrazine 0.2 g

Sulfuric acid (5n) 8.0 ml

Calcium fluoride 0.1 g

Hydroxyethyl cellulose 1.0 g

(Natrosolt Type 250 HH) water to "100 ml

After five minutes remove the aluminized carrier. During this time, the processing solution has the

07/03/1979

9 U S 8 7 O " ⁴⁶ " ^{Αρ G} ° 3 ^C / ²⁰⁸

Phthalic anhydride modified gelatin layer is softened, and on stripping the aluminized support, the silver bleach layer and the topcoat are removed therewith, leaving a blue-green image of the existing wedge on the support. This illustration has a color image that is sufficiently dark as a finished image.

EXAMPLE 2

The material shown in FIG. 15 is produced by successively applying the following layers to a 0.1 mm thick, uncolored transparent cellulose triacetate support:

1. A gelatin layer containing the same dye as used in Example 1.

2. A white reflective layer.

3. A black-opaque layer.

4. An emulsion layer as used in Example 1.

5. Zinc powder with a black opaque soot layer.

-2

6. An upper layer containing 1.0 g of gelatin.

After exposure to X-rays behind a lead wedge, the material is processed by immersion in a solution of the following composition:

2-Acetyl-3-methylquinoxaline 0.3 g

Sulfuric acid 5n 8.0 ml

1-phenyl-5-mercaptotetrazole 0.1 g

Water to 100 ml

After three minutes, a negative blue-green image of the wedge is obtained, which can be viewed through the support.

7.3.1979. 208872 - 4-7 - AP G03C / 208

The zinc powder / opacifying layer used in this example is prepared as follows:

A dispersion of zinc powder in gelatin is prepared according to the following formula:

4% gelatin solution 100 ml

Hatriumalkylnaphthalenesulfonate. 1 ml (10% aqueous solution).

Zinc powder 10 g

20 ml of the above dispersion are added to the carbon black dispersion as described above.

EXAMPLE 3

Photographic material as shown in FIG. 4 is prepared by sequentially applying the layers 1-4 described in Example 1 to a 0.1 mm thick white pigmented cellulose triacetate support.

After exposure behind a gray wedge, the material is processed in the dark by immersion in a processing solution of the following formula for 1 minute:

Chromium-III-cbloride 50 g

Concentrated HCl 100 ml

Water to 1 liter

The active metal ion (cbromo-II-ion) is generated by shaking this solution with 100 g of amalgamated zinc.

During the processing time, the phthalic anhydride modified gelatin layer is softened, and on stripping, the silver halide layer is removed,

3/7/1979 2 08 8 7 2 " ⁴⁸ " ^{AP G} ° 3 ^C / ²⁰⁸

a blue-green image of the wedge appears on the support. This figure has a finished image as sufficiently dark color density ·

In a modification of the processing solution used, this 0.05 g of i-pbenyl-5-nierkaptotetrazole is added to obtain a substantial improvement in the ratio of the maximum to the minimum color density.

EXAMPLE 4

The material shown in FIG. 15 is produced by successively applying the following layers to a 0.1 mm thick, uncolored transparent gellulosetriacetate support.

1. A gelatin layer containing the same dye as in Example 3.

2. A white reflective layer.

3. A black-opaque layer.

4. An emulsion layer as for Example 3 (conventional silver halide).

5. Zinc powder with a black topping coat.

* -2

6. An upper layer containing 1.0 g of gelatin.

After exposure to X-rays behind a lead wedge, the material is processed by immersion in a solution of the following composition:

Chromium-III-chloride 50 g

Concentrated hydrochloric acid 100 ml

Water on. 1 liter

After 3 minutes, a negative blue-green image of the wedge is obtained, which is passed through the support.

^: \ 7.3.1979

208 8 7 2 - 49 - AP G03C / 208 872

can strive.

The zinc / opacifying layer used in this example is prepared as follows:

A dispersion of zinc powder in gelatin is prepared according to the following formula:

("") 4% gelatin solution, 100 ml

^ Sodium alkylnaphthalenesulfonate 1 ml

(10% aqueous solution)

Zinc powder 10 g

20 ml of the above dispersion are added to the carbon black dispersion as described above.

The zinc pulser present in the photographic material in this example reduces the chromium (III) chloride to chromium (II) chloride.

EXAMPLE 5

A material as shown in Figure 14, it is characterized ^v "are prepared by reacting sequentially applying the following layers on a 0.1 mm-thick, unstained transparent cellulose triacetate

 "1. Sine gelatin layer containing 0.2 g of magenta dye

^ "" V - N = N - Λ - ΝΗ - CO - NH - </ Λ - N = N -

- OH HO.S SO ₃ H HO

- 50 - AP G03C / 208 8? 2

_2

in 4.0 g of gelatin.

2. A white reflective slide.

3. Bine black opaque layer.

4. A sirber halide emulsion preparation as for Example 4

(Conventional silver halide emulsion).

-2

5 * a 1.0 g gelatin-containing topcoat.

After exposure behind a gray wedge, the material is processed in the dark by soaking it for one minute with a solution of the following composition:

Vanadyl sulfate 10 g

Water to 1 liter

pH 0.7

and then mix the emulsion side of the material with a piece of tin foil for 2 minutes. After removal of the film, a purple image of the wedge is obtained, which can be viewed through the support.

In this example, the tin foil reduces the vanadyl sulfate to vanadosulfate.

EXAMPLE 6

A material as depicted in Pigur 14 is prepared by sequentially applying the following layers to a 0.1 mm thick, uncolored transparent cellulose triacetate support:

1. A gelatin layer containing 0.2 gm of the magenta dye of Example 5 in 4.0 g of gelatin.

2. A white reflective layer.

3. A black-opaque layer.

4. A direct positive silver halide emulsion containing 1.2 g

3/7/1979 208872 -51 - AP GO3C / 2O8 872

m "" ² Silver in the form of silver chloride bromide (70 mol% AgCl

and 30 mol% AgBr). "

-2

5. Sine 1, OgDi gelatin-containing topcoat.

After exposure behind a gray wedge, the material is processed in the dark by adding it for one minute

Solution of the following composition soaks:

Vanadyl sulfate 10 g ·

Water to 1 liter

pH 1.2

and then mix the emulsion side of the material with a piece of bare iron foil for 2 minutes. After removal of the film, a positive purple image of the wedge is obtained, which can be viewed through the support.

In this example, the iron foil reduces the vanadyl sulfate to vanadosulfate.

EXAMPLE 7

The material as shown in FIG. 23 is produced by successively coating the following layers on a 0.1 mm thick, undyed, transparent cellulose tris

acetate carrier applies:

-2

1. A gelatin layer containing 0.2 g of purple

p

Azo dye from Example 5 in 4-, O g m contains gelatin.

2. Sine white reflective layer.

3. A highly sensitive, direct-positive camera silver

-2

halide emulsion containing 1.2 grams of silver in the form of silver iodobromide (98 mole percent bromide, 2 mole percent iodide).

3/7/1979 2 - 52 - AP G03G / 208

125 ml 8th S 10 G 1 liter

The cover layer is a thin (0.1 mm) cellulose triacetate film.

The fragile sleeve contains a processing solution of the following formula:

Titanium trichloride (15% solution) 100 ml of diethylenetetramine pentaacetic acid

(DTPA) (as a 25% solution) potassium bromide hydrostathylcellulose water

pH. 0.75

After exposure behind a gray wedge, the material is processed by passing the assembly (in the dark) through a pair of rollers to break the sleeve and distribute the processing solution. Upon examination of the setup after 90 seconds, a direct positive dye image is visible through the support.

An aqueous solution of titanium ions in the trivalent state as Diäthylentetraminpentaessigsäurekomplex is stable in the absence of oxygen. Trivalent titanium ions are capable of acting as a bleach-developer compound in aqueous acidic solution.

EXAMPLE 8

To produce the pbotographic material shown in FIG. 20, the following layers are applied in liquid form to a transparent polyester support and then dried.

208872

07/03/1979.

AP G030 / 208 872

1. A dispersion of an aluminum powder of the middle

Particle size 5 p & in gelatin with an order of

ρ 300 mg Al / m; the dry chip thickness is 2.5 / im.

2. A gelatin solution for forming a Gelatinezwischenscbicht of 3 P- ^m thickness. , , - ·

3. A photosensitive gelatin-containing silver halide emulsion having 30 mole% AgBr and 70 mole% AgCl with a

p application weight of 1.2 g Ag / m; the layer thickness is

2.5 / im.

The receiving material consists of a gelatin layer also cast on a transparent polyester carrier

2 of 2 pm thickness, the 3OO mg / m of the cyan dye of

formula. - "

OCH

-Cl

SO ₃ KH ₃ CO KO ₃ S

contains.

After image-wise exposure of the recording material, this and an equal-sized piece of the receiving material are treated for 10 seconds at AO ⁰ C in the following leadb developing solution:

^H 2 ^S0 4 ethylene glycol monoethyl ether 2-methyl-3-acetylquinoxaline NH ₄ F water

20 g (0.2 mol) of 3OO ml

2.5 S (0.01 mol) 0.35 g (0.01 mol) 1,000 ml

Mar. 7, 1979 208872 -54- AP G03C / 208

The recording and receiving materials are then squeezed together with a pair of rollers, with the "wetted sides facing each other." The two materials are separated after 60 seconds at 30 ^° C. The receiver shows a negative dye image for exposure it then watered for a minute.

EXAMPLE 9 .

The material system described in Example 8 is processed after exposure in the same manner with the bleach / developer solutions 1 to 16 of Table 1, with similar results as in Example 8 being obtained. The bleach / developer solutions are each made up to 1 liter with water.

TABLE 1

07/03/1979

AP GO3O / 2O8 872

Bleach / developer acid solvent diazine fluoride number 1 H ₃ SO ₄ 0.2 m Ethylene glycol mono- ethyl ether 3OO ml ^ S * ^ CH ₃ NH ₄ F 0.01 m CVJ H ₂ SO ₄ 0.2 m Ethylene glycol mono- ethyl ether 3OO ml O NH ₄ F 0.01 m 3 H ₂ SO ₄ 0.2 m Aetbylene glycol monoethyl ether 3OO ml HOOC - ^ ⁵ ^^ OH ^ NH ₄ F 0.01 m

TABLE 1 (continued)

07/03/1979

AP GO3C / 2O8 872

Bleach / developer acid Solvent. diazine fluoride Mr. H- H ₂ SO ₄ 0.2 m Aetbylene glycol monocatyl ether 3OO ml for ^N r ^C00H - ^^ w ^ CH ₂ O ₆ H ₅ KH ₄ F 0.01 m 5. H ₂ SO ₄ 0.2 m Aetbylene glycol monoethyl ether 3,000 ml 0 Ii ^ AAO ₆ H ₅ M ₄ F 0.01 m 6 H ₂ SO ₄ 0.2 m Ethylene glycol monoethyl ether 300 ml ff γ ^ C-C ₄ -Hf- Ii ο ρ 0 UH ₄ F 0.01 m

- 57 - TABLE 1 (Porting)

07/03/1979

AP GO3C / 2O8 872

Bleach / developer acid !solvent diazine Pluorid No. 7 H ₂ SO ₄ 0.2 m - MH ₄ P 0.01 m 8th H ₂ SO ₄ 0.2 m - Mi ₄ P 0.01 m 9 H ₂ SO ₄ 0.2 m Ethylene glycol monoethyl ether 3OO ml ril ^ f 3 mO-SGE ^ S ^^ OH ₃ NH ₄ P 0.01 m 10 H ₂ SO ₄ 0.2 m Ethylene glycol mono- ethyl ether 3OO ml NaOoS '^^^ lr ^ COCH ₃ EH ₄ P 0.01 m

TABEIIiE 1 (continued)

7.3.1979 -

AP GO3C / 2O8 872

Pale/

developer

acid

solvent

diazine

fluoride

No. 11

Sulfamic acid 0.5 Vi

Aethylenglykolmono ethyl ether 3OO ml

IiH ₄ F 0.01 m

12

0.5 m

Aetbylene glycol monoethyl ether 3OO ml

GH

EH ₄ F 0.01 m

13

1m

Aethylenglykolmono ethyl ether 3OO ml

COOH

M ₄ F 0.01 m

14

HOLO ₄ 0.2 m

Aethylenglykolmono ethyl ether 3OO ml

NH ₄ F 0.01 m

- 59 TABLE 1 (continued)

7.3.1979 '-ΔΡ GO3G / 208

Bleaching / rolling acid solvent diazine fluoride No. 15 H ₃ SO ₄ 0.2 m Aetbylene glycol monoethyl ether 3OO ml ^ ^ W ^ COCH ₃ CaF ₂ 0.5 g / l dispersed 16 H ₂ SO ₄ 0.2 m N-methylpyrrolidone 300 πα ΛΠ f ^ f ^^ f 3 ^ iT ^ COCHo WH ₄ F 0.01 m

3/7/1979 2 O 8 8 7 2 - 60 -. AP G03C / 208

EXAMPLE 10

The photosensitive member of the photographic material shown in Fig. 20 is prepared by applying the following layers:

1. A dispersion of a copper powder of average particle size 15 microns in gelatin with a job

of 2 g Cu / m; the dry film thickness is 3 μτ &.

2. A photosensitive gelatin-containing silver halide emulsion having 30 mole% AgBr and 70 mole% AgGl at a coating weight of 1.2 g Ag / m; the layer thickness is 2.5 pm.

As a receiving material, the material is used as described in Example 8.

After image-wise exposure of the photosensitive member of the assembly, it is treated for 10 seconds at 40 ^° C. in the following activator solution, as well as an equally sized piece of the receiving material:

70% HClO ₄ 36 ml

2-methyl-3-acetylchinosalin 3 g

Ethylene glycol monoethyl ether «, 40 ml

Allyl alcohol 150 ml

Polyethylene glycol (MW 4,000) 30 g

Water to 1 000 ml.

Subsequently, receiving and receiving material are squeezed zusanmenge with a pair of rollers, wherein the potted sides are facing each other. After 60 seconds at 3 ° C., the two materials are separated. "The receiver has a negative dye image for presentation. To the picture

, 3/7/1979 2 08 8 7 2 - 61 - AF G03C / 208

It is then watered for another minute.

EXAMPLE 11 .

An example 10 similar photographic material is prepared, but instead of copper contains a brass powder of average particle size 10 pm and the following elemental composition: copper 85%, zinc 14%, and aluminum 1%. Exposure and processing are similar to Example 10, as is the resulting dye negative.

EXAMPLE 12

A photographic material as shown in Figure 18 is prepared by applying the following layers to a transparent polyester support. 1. A gelatin layer containing 3OO mg / m of the magenta dye of the formula

203872

 07/03/1979

AP.GO30 / 208 872

3/7/1979 2 08 8 72 - 63 - AP GO3C / 2O8

contains. The layer thickness is 3 / im.

2. A gelatin layer containing 10 mg / m TiO ₂ in finely dispersed form. The gelatin application is 3.5 g / m ² .

3. A photosensitive silver bleach emulsion has the composition and thickness given in Example 8.

4. Sine gelatin layer with aluminum powder of the same composition as in Example 8.

The emulsion layer (4) is imagewise exposed through the layer containing the aluminum powder and then swollen for 10 seconds in the bleaching / developing solution according to Example 8 at AO ⁰ C, then stripped and left the rest for ¹ minute at ¹ ^ O ⁰ G. After this time, the negative dye image is developed and visible through the transparent support on the white background of the titanium dioxide-containing layer. By watering for one minute, the image is preserved.

B EXAMPLE 13

Photographic material according to FIG. 4 is produced by applying the following layers to a 0.1 mm thick, white-pigmented cellulose triacetate support. '

1. A gelatin layer containing 200 mg / m of Example 1

used cyan dye in 4 g per m gelatin

contains.

2. As a release layer 3, a layer of phthalic anhydride modified gelatin is used. The order is

1 g / m ² .

7.3.1979 08872-64- \ AP GO3C / 2O8 872

3. A photosensitive silver halide emulsion layer,

ρ containing 1.2 g of silver per m in the form of silver chloride / bromide (70 mole percent silver chloride and 30 mole percent silver bromide).

4 ·. A 1 g gelatin per m containing topcoat.

After exposure to light under a gray scale, the photographic material on the emulsion side is brought into contact with an aluminum support on which is applied a bleaching / developing solution containing the following components: pyrazine

Sulfuric acid (5-normal) ammonium fluoride '. Hydroxyätbylcellulose (thickener) water

The contact with the aluminum carrier takes place in the dark and lasts 5 minutes. During this time, the bleach / developer solution swelled the release layer (3). Thereafter, the silver halide emulsion and the overcoat are separated together with the aluminum support. On the cellulose triacetate support, a cyan negative image of the gray wedge having a sufficient color density is obtained.

Bg lSPiaL 14-

0.2 S 8.0 ml 0.1 S 1.0 S 100 ml

i as shown in Fig. 16, photographic material is prepared as follows:

A 0.1 ton strong transparent cellulose acetate support

-65- AP G03C / 208 8? 2

is watered as follows:

1. Gelatibe dye layer as in Example I3.

2. A white reflective layer.

3. A black-opaque layer. '

4. A photosensitive silver halide emulsion layer as in Example 6. /

5. A black opaque layer, the finely divided zinc ''

contains powder.

6. Place a cover containing 1 g of gelatin per m.

After imagewise exposure of this material to X-rays behind a lead step wedge, the material is developed in a solution containing the following components:

2-Acetyl-3-methylquinoxaline 0.3 g

Sulfuric acid (5 normal) 8.0 ml

1-phenyl-3-mercaptotetrazole 0.1 g

Water to ". 100 ml j

After 3 minutes, a blue-green negative |

visible in the step wedge; the image can be viewed through the I transparent support.

The layer (5) is obtained from the following dispersions:.

a) 4% aqueous gelatin solution 100 ml 10% aqueous sodium alkyl

- naphthalenesulfonate solution 1 ml

Zinc powder 10 g

b) Gelatin 3g water, 40 % of final dispersion, ml of polyglycidyl condensation product

(5%, aqueous) "2.5

07/03/1979

2 O 8 8 7 2 ~ ⁶⁶ ~, AP G03C / 208

The composition (b) is mixed for 2 minutes, stirred with 20 ml of the composition (a) and then cast as a layer.

Instead of the specified developer solution can also

use the following solution:

Chromium chloride (CrOl--). 50 g

Hydrochloric acid (37%) 100 ml

Water to 1 liter

The zinc powder in layer (6) reduces the chromium (III) chloride to the chromium (II) chloride.

EXAMPLE 15 .., .. '

As shown in Example I3 photographic material (according to Figure 4) is imagewise exposed behind a gray wedge and then treated for 1 minute in the dark with the following solution, which was previously shaken with 100 g of zinc amalgam:

Chromium chloride (CrClO, 50 g

Hydrochloric acid (37%) 100 ml

Water to 1 liter

During this treatment time, the separating layer is swollen. After separation of the silver halide emulsion layer from the dye layer, a blue-green negative image of the gray wedge is obtained with a sufficient color density,

If one adds to the treatment solution still 0.05 S 1-phenyl-5-mercaptotetrazole, so you can achieve a significant improvement in the ratio of the maximum to the minimum color density.

07/03/1979

8 7 2 " ⁶⁷ - ^Ap

EXAMPLE 16

As shown in Figure 14, the pbotographic material is prepared by placing the following layers on a 0.1 mm thick transparent cellulose triacetate.

carrier.

1. A gelatin coated containing 200 mg / m of Example 5

contains purple colorants in 4 g gelatin per m.

2. A white reflective layer (as in Example 10).

3. A black opaque layer (as in Example 14).

4. A photosensitive silver halide emulsion layer

(as in Example 13).

5. A 1 g gelatin per m containing layer.

After imagewise exposure behind a gray wedge, the photographic material is treated in the dark for 1 minute with the following solution:

Vanadyl sulfate 10 g

Water to 1 liter

(pH of the solution 0.7)

The material is then brought into contact with a tin foil on the emulsion side for 2 minutes. The tin foil reduces the vanadyl IV sulfate to vanadium II sulfate. After removal of the tin foil, a negative purple image of the step wedge is obtained, which can be viewed through the transparent support.

Claims (50)

   . '; 7.3.1979 _. 2 03 8 72 - 68 - AP G03C / 208 872 Erfindungsansprueh 1. A process for the preparation of photographic images, characterized in that one stepwise (a) imagewise exposing a pbotographic material which, optionally at least during the silver halide development step, contains in this order an overcoat, at least one silver halide emulsion layer, a layer containing a modifiable image substance and a support, optionally one or more intermediate layers between each Layers are present (b) treating the exposed photographic material with an aqueous processing bath to form in the silver halide emulsion layer (s) a solution or dispersion of a compound which modifies the image substance / silver halide and thereby form the latent silver image in the silver halide emulsion ( to develop and (c) diffusing the compound which modifies the image substance / developing silver halide at the sites without latent image in counter-image form from the silver halide emulsion layer (s) into the layer containing the modifiable image substance to reductively modify the image substance therein , 2. Method according to item 1, wherein the modifiable image substance is a bleachable image dye and the compound which modifies the image substance / silver halide is a bleach / developer compound, 7.3.1979 2 08 8 7 2 - 69 - AP GQ3C / 208 8? 2 characterized by comprising the stepwise exposure (a) of a photographic material containing, optionally at least during the silver halide development step, in this order an overcoat, at least one silver halide emulsion layer, a layer containing a substantive image dye, and a support, optionally one or more intermediate layers are present between each of these components, (b) treating the exposed photographic material with an aqueous processing bath to obtain in the bzvi. forming the silver halide emulsion layer (s) a solution or dispersion of a bleach / developer compound to thereby develop the latent silver image in the silver halide emulsion (s); (c) diffusing the bleach / developer compound at the non-latent image positions in reverse image form from the silver halide emulsion layer (s) into the image-imageable dye-bleachable layer to form a photographic image by bleaching the image dye , 3. The method according to item 1 or 2, characterized in that the compound which modifies the image substance / silver halide develops, as a preformed solution or dispersion, which is applied in step b) on the exposed photographic material. 4. Method according to item 1 or 2, characterized by - 7.3.1979 208 8 72 -70- AP G03C / 208 872 in that the compound which modifies the image precipitate / develops silver halide is in an inactive form and a solution or dispersion of this compound is brought together with a substance which activates the compound immediately before or while the solution or dispersion in step b) is exposed to the light photographic material is applied. 5. A process according to item 1 or 2, characterized in that a solution or dispersion of an inactive substance of the compound which modifies the image substance / silver halide is applied in stage b) to the photographic material which is either in the topcoat or below the overcoat and over the lowermost silver halide emulsion layer contains a compound in layer form which activates the inactive compound which modifies the image substance / silver halide. 6. Method according to item 1 or 2, characterized in that the compound which modifies the image substance / silver halide is present in a layer of the photographic material initially in inactive form and in step b) a solvent for the compound on the exposed photographic Material is applied so that the thus formed solution of the inactive compound in the material is converted into the active Eorm. 7. Method according to item 6, characterized in that the solution of the inactive form of the compound which modifies the image substance / silver halide is developed, 7.3.1979 2 08 8 7 2 - 71 - AP.G03C / 208 activated by bringing them together with a substance which activates them and is also present in layer form in the photographic material. 8. The method according to item 1 or 2, characterized in that the compound which modifies the image substance / silver halide develops, is present in an inactive form and a solution or dispersion of this compound is subjected to an electrolysis to convert the inactive compound in the active form immediately before or while the solution or dispersion is being applied to the photographic material. 9. The method according to item 8, characterized in that subjecting the photographic layer structure simultaneously with or immediately after the application of the solvent to the material of the electrolysis, thereby converting the inactive form of the compound into the active form in the material. 10. The method according to item 1 or 2, characterized in that one prepares the photographic material in two parts, wherein a part of the cover layer and the Sirberbalogenideniulsionsschicht (s) and.the other part comprises the layer containing the modifiable image substance or the bleachable image dye and the carrier. A method according to item 1 or 2, characterized in that the photographic material is prepared in a part containing the overcoat layer, the silver halide emulsion layer (s) and the slide containing the 7.3.1979 2 03 8 7 2 - 72 - AP G03C / 208 contains modifiable image stamping or the bleachable image dye, all of which are cast on the support. , 12. The method according to item 11, characterized in that in the photographic material used, either a release layer or a separation site between the silver halide emulsion layer (s) and the slide containing the modifiable image substance is disposed. 13. The method according to item 12, characterized in that the separating layer contains phthalated gelatin. 14 ·. A method according to any one of items 1 to I3, characterized in that the silver halide emulsion is a negative-working silver halide emulsion. 15. The method according to any one of items 1 to I3, characterized in that the silver halide emulsion is a direct-positive silver halide emulsion. 16. A method according to any one of items 2 to 7, characterized in that the bleachable image dye is an azo dye. 17. A process according to any one of items 2 to 16, characterized in that the bleach / developer compound is an azine compound in its reduced form and the aqueous processing bath is an aqueous acid bath. 18. The method according to item 17, characterized in that the azine is pyrazine. i. UOO / L _ 73 _ P GO3C / 2O8 872 19. The method according to item 17 »characterized in that the azine is an optionally in the 2-, 3-, 5-» 6- and / or 7-position by alkyl, hydroxyalkyl or alkoxy each having Tbis 4- carbon atoms, acylated hydroxymethyl, Amino or acylated amino, carboxyl, sulfonic acid, benzoyl, acetyl, phenyl, benzyl or pyridyl substituted quinoxaline compound. Process according to any one of items 2 to 18, characterized in that the leadbic / developing agent is a metal ion which is capable of acting in acidic solution as a silver halide developing agent. 21. The method according to item 20, characterized in that the metal ion is a chromo, vanado- or Titanoion. 22. The method according to any one of items 17 and 20, characterized in that one brings together a non-reduced azine or a metal ion in a higher valence state than the active form in acidic solution or dispersion with a reducing agent, immediately before or while it is applied to the photographic material. 23. A method according to item 22, characterized in that the reducing agent is a metal which is above the silver in the electrochemical series and comprises the elements up to and including lanthanum. 24. The method according to item 22, characterized in that the reducing agent is a metal which is above the silver in the electrochemical series and comprises the elements up to and including aluminum. 07/03/1979 2 08 8 72 - 74 -; - δρ go3c / 2os 25. The method according to item 23, characterized in that the metal is in the form of a metal strip. 26. The method according to item 25, characterized in that the metal strip consists of aluminum, iron, zinc, tin or indium or alloys containing such metals. 27. Method according to item 23, characterized in that the metal is present in the form of a paste with which a carrier is coated. 28. The method according to item 27, characterized in that the paste contains aluminum, iron, nickel, zinc, tin or indium or alloys containing such metals. 29. The method according to any one of items 17 to 21, characterized in that applying an unreduced azine or a metal ion in a higher valence state than the active form as an acidic solution or dispersion on the photographic material, which in one of its layers a dispersion of a metal which is above the silver in the electrochemical stress and comprises the elements up to and including lanthanum, preferably up to and including aluminum. 30. The method according to item 29, characterized in that one uses as metal aluminum, copper, iron, ITiekel, zinc, tin, indium, gallium, lanthanum or alloys containing such metals. 7.-3.1979 2 0 8 8 72 - 75 - AP G03C / 208 31. The method according to any one of items 1 to 30, characterized in that in the photographic material at least one opaque layer is adjacent to a silver halide emulsion layer. 32. The method according to item 3I, characterized in that a Silberbalogenidemulsionsschicht and on both sides thereof is an opaque layer. 33. The method according to any one of items 1 to 32, characterized in that in the photographic material, a white reflective layer adjacent to the layer containing the modifiable image substance is present on the side facing away from the wearer. 34. The method according to any one of items 1 to 3I »characterized in that the photographic material in this order contains a cover layer, an opaque layer, a silver bleach emulsion layer, an opaque layer, a layer containing a modifiable image substance, and a support. 35. The method according to item 34- », characterized in that a separation point or separation layer between the second mentioned lichtundurcblüten layer and the layer containing the modifiable image substance is present. 36. The method according to item 34, characterized in that a white-reflecting layer is present between the second-mentioned opaque layer and the layer containing the modifiable image substance. 79, 7.3.1979 I £. - 76 - .._ AP G03C / 208 872 37 «Method according to item 36», characterized in that there is a separation point between the second-mentioned opaque layer and the white-reflecting layer. 38. The method according to item 1, characterized in that the modifiable image substance is a metal oxide. 39. The method according to item 38, characterized in that the metal oxide is manganese dioxide or molybdenum trioxide. 4-0. A photographic material comprising, in that order, a topcoat, optionally at least one intermediate layer, at least one silver halide emulsion layer, at least one intermediate layer, a layer containing a modifiable image-forming substance, and a support, characterized in that either in the topcoat or in another layer over the layer containing the modifiable image substance, there is a layer containing a substance capable of activating a non-active compound (Dymodev) which modifies the image dye / silver halide. 4-1. Photographic material according to item 4-0, characterized in that an opaque layer and / or a white reflecting layer is present between the silver halide emulsion layer and the layer containing a modifiable image substance. 42. Pbotographical material according to item A-O, marked 7.3.1979 2 03 8 72 - 77 - AP G ° 3C / 208 872 in that there is an opaque layer between the cover layer and the silver halide emulsion layer. · 4-3 »Photographic material according to item 40, characterized in that the activator substance is a metal which is above the silver in the electrochemical series and comprises the elements' up to and including lanthanum, preferably up to and including aluminum. 44. Photographic material according to any one of items 40 to 42, characterized in that there is a separation or separation layer between the silver halide emulsion layer and the layer containing the modifiable image substance. A pbotographic material according to item 40, characterized in that it comprises a cover layer, a silver halide emulsion layer, a layer containing a substance capable of activating a non-active Dymodev compound, a silver halide emulsion layer, optionally at least one intermediate layer, a layer containing a modifiable image substance and a support. 46. Photographic material according to item 45, characterized in that a white-reflecting layer between the second-mentioned silver halide emulsion layer and the pbototic carrier. 7.3.1979 2 08872 -78- AP G03G / 208 872 4-7. A photographic material according to item 46, characterized in that there is a separation or separation layer between the second-mentioned silver halide emulsion layer and the white-reflecting layer. Photographic material according to one of the items 4-0 to 4-7, characterized in that it contains, either in the top layer or in an intermediate layer over the topmost silver halide emulsion layer, a layer containing, in inactive form, a compound which modifies the image substance. Developed silver halide. 4-9. A photographic material according to any one of items 40 to 48, characterized in that the modifiable image substance is an azo dye suitable for use in the silver-bar method. 50. Photographic material according to item 49 »characterized in that it contains a mordanting layer which is capable of pickling amine compounds liberated in the course of the photographic process. 51. Photographic material according to any of items 40 to 50, characterized in that it contains a neutralization layer. Dazu_jL.Seiten drawings