DE2238052A1 - PHOTOGRAPHIC IMAGE TRANSFER PROCESS AND PHOTOGRAPHIC FILM UNIT FOR CARRYING OUT THE PROCESS - Google Patents

Description

Photographic, image transfer and photographic Film unit for carrying out the process.

The invention relates to a photographic image transfer process, in which (A) a photographic recording material consisting of a support and at least one silver halide emulsion layer coated thereon, which have a contains immobile color coupler or is in contact with a layer containing an immobile color coupler, imagewise exposed, developed with a color developer compound and the diffusible which is obtained in image-wise distribution Dye is transferred to an image receiving layer or in which (B) a photographic recording material consisting of a layer support and at least one coated thereon Silver halide emulsion layer containing a mobile color coupler or with one containing a mobile color coupler Layer is in contact, imagewise exposed, with a color developing solution with imagewise immobilization of the color coupler and part of the mobile color coupler diffused into an image receiving layer and reacted with oxidized color developing agent.

It is known, for example, from U.S. Patents 3,227,552 and 2,559,643, Diffusion Transfer Photographic Images diffusible image dyes or diffusible, image dye-producing compounds in an image-receiving layer produce. These methods are becoming photographic recording materials with at least one silver halide emulsion layer and mobile or immobile color couplers used with p-phenylenediamines existing developer compounds will.

A disadvantage of the previously known color transfer processes of the types described is that the spectrophotometric characteristics of the dye images produced, the thermal and

3ü930 8/08 6 1

- 2 The light stability of the images generated is not yet fully satisfactory.

The object of the invention was therefore an improved photographic To indicate image transfer processes that produce images of improved heat and light stability as well as improved allows spectrophotometric characteristics and in which also the tendency of the developer compound used to Discoloration is decreased and emulsion desensitization is decreased is achieved by the color developing agent used, if this is done with the silver halide before the imagewise Exposure of the recording material is in contact.

The invention was based on the knowledge that the object set can be achieved by using the color developer compound alone or at least for the most part a p-aminophenol is used and if one also uses the development in the presence a positively charged onium compound, e.g. a quaternary Performs ammonium salt or, following the development, carries out a treatment with such an onium compound.

The invention thus relates to a photographic image transfer process, in which (A) a photographic recording material consisting of a support and at least one applied thereon a silver halide emulsion layer containing an immobile color coupler or with an immobile color coupler containing layer is in contact, imagewise exposed, developed with a color developing agent and the thereby diffusible dye occurring in imagewise distribution is transferred to an image-receiving layer or in which (B) a photographic recording material consisting of a support and at least one silver halide emulsion layer coated thereon containing or with a mobile color coupler a layer containing a mobile color coupler in contact

3 0 Π B ti 8 / ü 8 6 1

stands, exposed imagewise, with a color developer solution developed with imagewise immobilization of the color coupler and part of the mobile color coupler in an image receiving layer diffused and reacted with oxidized color developing agent, which is characterized in that one 1. as Color developing agent used alone or at least predominantly a p-aminophenol and that 2. the through Implementation of color couplers with p-aminophenol oxidation product The resulting indophenol dye is converted into an onium indophenol dye by reaction with an onium compound.

Under a p-aminophenol are here customary p-aminophenol developer compounds to be understood in the broadest sense.

The onium compounds are expediently used in concentrations which are sufficient to convert all indophenols into onium indophenoxides, for example in concentrations of 25 mg to 1000 mg per 0.09 to 29 m ^{2 of} carrier surface. '

The invention also relates to a photographic film unit for carrying out the method.

By the invention it is achieved that color images of improved heat and light stability as well as of improved spectrophotometric Characteristics of the image colorants can be obtained. The risk of discoloration by the developer compound is thereby reduced. It also causes emulsion desensitization reduced by the color developing agent used, if this is in contact with the silver halide prior to imagewise exposure.

- 3a -

a / 0 86 1

Finally, the onium indophenoxide dyes produced in the process of the invention avoid problems which were observed in the previously known processes in the image dyes generated in this way, in particular then, when the recording materials have been washed or left damp or wet for a long period of time. Will namely, polymeric onium compounds are used to carry out the method of the invention, they can be produced with them

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Onium indophenoxide does not wash out as easily as others in customarily produced dyes, for example indophenol dyes, which have been pickled with polyvinylpyridine. In addition, those incurred in the process of the invention tend to be Onium indophenoxide less like to wander or diffuse the dyes produced by the customary known processes, for example indophenols, which do not form onium indophenoxides implemented.

If an oxidized p-aminophenol is reacted with a color coupler, As is well known, this is how an indophenol is formed. The indophenols consist of the reaction products of oxidized ρ-aminophenols and color couplers, which can be represented by the following general formula:

CKUpP) = N-Ar-OH ■

where mean:.

Ar is an arylene radical with preferably 6 to 20 carbon atoms, which can optionally be substituted and the further optionally fused-on ring systems may have and preferably of a phenylene radical consists, which in a particularly advantageous manner by one or more halogen atoms or radicals with halogen atoms substituted in the ortho or meta position of the ring can be and

Kupp is a color-forming coupler radical linked by a carbon atom is bonded to the nitrogen atom, for example a phenolic coupler radical, a pyrazolone coupler radical or a coupler remainder with an open active

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Methylene group and the like, preferably a soluble one Coupler radical that makes the coupler a diffusing one Matchmaker makes. When treated with a positively charged onium compound, the indophenols are converted into onium indophenoxides, which can be represented by the following structural formula:

(Kupp) -N-Ar-O ⁹ M ^§

wherein Kupp and Ar have the meaning already given and M is an onium compound, preferably one represents quaternary ammonium compound. Compounds of this type are referred to herein as onium indophenoxides.

The attached drawing serves to explain the invention in more detail. In the drawing there are absorption curves from three to dyes produced according to the method of the invention are compared to three dyes produced according to the prior art. The curves are so-called normalized curves, i.e. curves recorded using spectrophotometric data, namely not at the maximum density of the image dyes but rather at a density of 1.00.

According to one embodiment of the method of the invention, the or the onium indophenoxide dyes are generated in the recording material used to carry out the process of the invention. To carry out the method of the invention can use photographic image transfer processes spectrally sensitized emulsion layers of the type known from U.S. Patent 2,661,293 used in each of the spectrally sensitized emulsion layers containing a mobile color coupler can be used. Such recording materials

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are developed after the image-appropriate exposure by using an alkaline / IftKM £ O £ Ä £ MpXMMt silver halide developer, which consists at least predominantly of a p-aminophenol. In the areas in which the silver halide emulsion layer or layers were exposed imagewise, the p-aminophenol reduces the silver halide to silver and is itself oxidized, whereupon the oxidized p-aminophenol reacts with the color coupler or the color couplers to form a relatively immobile reaction product. The one or more unreacted color coupler as well as non-oxidized p-aminophenol of the non-exposed areas migrate contrast, brought about by atmospheric oxygen in an image-receiving layer in which a reaction with a OxidaSionsmittel or oxidation is _s, followed by a coupling reaction between oxidized developer and color coupler connects . The coupling reaction can be carried out in the presence of an onium compound, for example a quaternary mordant. The onium compound can be present, for example, in the image receiving layer or in a layer in contact therewith, or it can be added by subsequent treatment.

The usual known ones, for example, can be used as mobile color couplers Pyrazolone type color couplers, phenolic color couplers and open chain ones Ketomethylene color couplers can be used. The alkali-soluble and diffusible ones are typical of such color couplers Color coupler of the US patents 2 407 210, 2 298 443, 2 875 057, 3 265 506, 3 408 194, 3 447 928, 2 396 489, 2 600 788, 2 908 573, 3 062 253, 3 419 391, 3 519 429, 3 152 896, 2 423 730, 2,474,293, 3,476,563, 2,772,162 and 3,002,836 of the known type.

According to XO ^- second, particularly advantageous embodiment of the invention, immobile color couplers are used in photographic image transfer materials. Typically, image transmission elements of the type disclosed in U.S. Patents 3,227

/ Solution or liquid in the presence of a

309808/0861,

and 3,227,552 and that of Belgian patents 959 and 757 960

known type can be used.

Typical non-diffusing color couplers for this embodiment of the method of the invention advantageously have the following structure:

Ballast group link (coupler residue-solubilizing residue) where mean:

1) the connecting link is a connecting link,

for example an azo, mercury, oxy, alkylidene, thio, Dithio, azoxy or aminoalkyl radical, e.g. that from the USA patent 3,419,390, a sulfonyloxy radical such as that known from U.S. Patent 3,415,652 Type, an acyloxy group, e.g. of the type known from U.S. Patent 3,311,476, or an imido group, e.g. U.S. Patent 3,458,315 of the known type;

2) the coupler radical is a 5-pyrazolone or a pyrazolotriazole coupler radical, a phenolic coupler radical or an open-chain ketomethylene coupler radical, the coupler radical in its coupling position is substituted by the link;

3) the ballast group is a photographically inert organic ballast group such a molecular size and configuration that the color coupler during development in an alkaline Developing liquid remains non-diffusing;

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4) the solubilizing radical is a hydrogen atom or a acidic solubilizing group when the color developing agent has an acidic solubilizing group or an acidic solubilizing residue if the color developing agent is used is free from an acidic solubilizing residue and -

5} η = 1 or 2, provided that the link is an alkylidene radical , and = 1, provided that the link consists of an azo, mercury, Oxy, thio, dithio or azoxy radical, or one of the usual, under 1) specified residues. · ,. The acidic solubilizing radicals by which / diffusing dye-forming couplers may be substituted,

which can consist of solubilizing residues, / if they are attached to the Coupler residues or detachment residues of the dyes are bound, make the dyes diffusible in alkaline developing media. As a result, the radicals xats can, for example, from Carboxylic acid, sulfonic acid »ionizable sulfonamide and hydroxy-substituted radicals exist, which are the dyes give negative charges.

The nature of the ballast groups of diffusible dyes generating coupler is not critical as long as it is only the Making the coupler non-diffusible »Typical ballast groups consist of long-chain alkyl radicals that directly or indirectly bound to the coupler molecules, also from aromatic residues of the benzene and naphthalene series, which can be bound directly to coupler molecules or indirectly through splittable bonds or through a removable or non-removable, but on the other hand non-functional He bond, depending on the nature of the coupler used. In general, such ballast groups have at least eight carbon atoms on.

3 09 8Q8 / 0 8S 1

V-

The coupling position of such color couplers is known * See above couple, for example, the known 5-pyrazolone couplers on Carbon atom in the 4-position, the phenolic couplers, including the known «-naphthols on the carbon atom in the 4-position and the open-chain ketoraethylene couplers on the carbon atom of the methylene radical of a coupler unit of the formula given below

O O

Il Il

-C-CH ₂ -C-

where the "+" denotes the clutch position. Suitable pyrazolotriazole couplers and their coupling positions are described, for example, in U.S. Patent 3,061,432 and Belgian 724,427.

The terms "immobile" and "non-diffusing" used here are used in the usual sense in the field of color photography, i.e. they identify compounds that are used in a for for practical purposes does not migrate sufficiently through organic colloid layers, e.g. gelatin layers or diffuse.

In contrast, the terms "mobile" and "diffusing" indicate formed from the non-diffusing or immobile color couplers Dyes which have the property of effectively passing through colloidal layers of photographic light-sensitive materials

of being able to wander, namely in the presence / non-diffusing Substances from which they are formed.

When implementing color couplers of the general structure: ballast group-connecting link- (coupler residue-solubilizing ReSt) _n

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with oxidized color developing agents, splits the link from, namely 'to produce a diffusing dye from the oxidation product of the color developing agent and the coupling part of the color coupler, whereupon the dye produced able to diffuse imagewise into the image receiving layer.

The diffusibility of the dyes is based on their presence at least one acidic solubilizing residue, which can be in a non-coupling position of the coupler part of the color coupler or on the color developer connection. The part of the coupler which has a load group remains immobile. In the case of using color couplers of this type the hue of the diffusing dyes is determined by the hue of the onium indophenoxide used in the development process is generated according to the invention.

The production of diffusing indophenols or onium indophenoxides is a function of the reduction of developable SiI overhalide images, wherein direct development or reverse development of the silver halide emulsion layers with a p-aminophenol developing agent can be done.

Are recording materials for carrying out the method of the invention with one or more direct positive silver halide emulsion layers used, for example, layers consisting of internal image emulsions or internal grain emulsions or solarizing If emulsions are generated which can be developed in non-exposed areas, positive images can be found in the Image receiving layers or, in the case of the use of photographic transfer units, obtained in the image receiving parts. In the embodiment of the method of the invention using direct positive silver halide emulsions, they cannot diffusing color coupler advantageously in

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housed the silver halide emulsion layer or layers themselves will. After exposure of the photographic material, such as an image transfer unit or film unit, the material is developed with an alkaline developing solution, which penetrates the various layers of the material or the unit and the development of the exposed photosensitive Silver halide emulsion layer or silver halide emulsion layers initiates. The p-aminophenol color developing agent, which can be present in the unit, for example when using a transmission unit, is developed in the process each of the silver halide emulsion layers in the unexposed areas (since the silver halide emulsion layers are direct-positive silver halide emulsion layers), the developing agent being oxidized imagewise, accordingly the unexposed areas of the direct-positive silver halide emulsion layers. The oxidized developer compound then reacts with the non-diffusing color coupler (s) in the silver halide emulsion layer or layers with the formation of indophenols in an imagewise distribution as a function of the imagewise distribution Exposure of the silver halide emulsion layer or layers. At least part of the in Image-wise distribution generated diffusing indophenols then diffuses into the image-receiving layer in which the indophenols come into contact with an onium compound to form one or more onium indophenoxide dyes.

In an advantageous manner, recording materials or photographic materials are used for carrying out the process of the invention Image transfer units are used which contain a pH-reducing layer. After bringing the alkaline developing liquid with the recording material or the image transfer unit thus reduces the pH-reducing layer - if one is present pH value of the recording material or the image transfer

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unit with stabilization of the same or the same. Specific Examples of not suitable for the production of recording materials and image transfer units according to the invention diffusing color couplers and other details relating to this Types of photochemistry can be found, for example, in the United States patents 3,227,550 and 3,227,552.

According to a further advantageous embodiment of the invention are non-diffusing color couplers of the type described for the production of diffusing indophenols in combination with development inhibitors releasing couplers, for example of the type known from U.S. Patent 3,227,551. In this embodiment of the method of the invention, it is expedient to use image transmission units or film units, the photosensitive part of which has at least two color-forming units with layers which are opposite to different Zones of the visible spectrum are sensitive and which are separated from one another by separating layers, which consist of a hydrophilic Colloid and a water-insoluble reaction component are built up, which with mercaptans a water-insoluble Capable of forming salt. Such color-forming units can. thus, for example, be composed of:

1) a developable emulsion layer composed of a hydrophilic colloid and a water-insoluble metal salt, which ^ by a p ^ aminophenol color developing agent without with To be exposed to light developable to a perceptible density is, wherein the metal salt is in contact with a non-diffusing color coupler which is oxidized with the p-aminophenol color developing agent to form a able to react diffusing indophenol and

Density of at least 0.5, which is achieved when the emulsion layer is applied to a layer support in a thickness of 50 to 500 mg / 0.0929 m ^{2 support area} without being exposed for 5 minutes in a conventional developer (e.g. Kodak developer DK-50) is developed at 20 ⁰ C *

309 B 08/086 1

2) a photosensitive silver halide emulsion layer,

en "

the / silver halide with a non-diffusing, one Development inhibitor in release-setting color coupler is in contact, which with oxidized ρ-aminophenol color developer compound capable of reacting by releasing a diffusing mercaptan development inhibitor » which image-wise through the adjacent developable emulsion layer able to diffuse and inhibit development there.

As already stated, the developer connection exists at least predominantly from a customary known p-aminophenol developer compound, but preferably wholly or substantially wholly from a p-aminophenol developing agent.

Advantageously, the p-aminophenol developing agent thereby applied in the alkaline developing liquid or developing solution and the developable The emulsion layer is preferably composed of an emulsion of a hydrophilic colloid, silver thiocyanate and physical Development nuclei which can be developed to an easily recognizable density without being exposed to light. The developable Furthermore, the emulsion layer can also be produced using a metal salt, which can thereby be developed spontaneously physical development nuclei can be made to incorporate into the emulsion, for example as in the United States patent 3 227 551, column 6, lines 63 to 75 and column 7 »lines 1 to 10 are described in more detail. Another procedure What can be used to make the water-insoluble salts spontaneously developable is to pass the emulsion through Exposure to light or with the aid of chemical reducing agents, for example alkali metal borohydrides according to customary known methods pre-fogging photographic fogging processes.

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According to a further advantageous embodiment of the invention, non-diffusing couplers of the type described are common associated with physical development nuclei in each light-sensitive silver halide emulsion layer Seed layer used. In this embodiment of the method of the invention, an image transmission unit can advantageously be used which contains a silver halide solvent, preferably in a splittable container with the alkaline developing liquid. Each of the light-sensitive silver halide emulsion layers of such an image transfer unit contains an immobilizing coupler, i.e. for example a coupler with a ballast group which with a oxidized p-aminophen oil color developing agent to form an immobile reaction product is able to react. Each of the light-sensitive silver halide emulsion layers together with its "core layer is of a further silver halide emulsion layer and their germination in the film unit daxdi separated by a separating layer permeable to alkaline solutions. The task of the separating layers is to hold back silver complexes. After exposure to such a film unit penetrates the alkaline developing liquid separates the various layers, initiating the development of the latent ones produced Images in each of the light-sensitive silver halide emulsion layers. The p-aminophenol color developing agent present in the film unit develops each of the exposed silver halide emulsion layers, whereby the p-aminophenol color developing agent is oxidized imagewise. The oxidized developing agent then reacts with the immobilizing color coupler in each of the light-sensitive silver halide emulsion layers producing an immobile reaction product. That in everyone silver halide still present in the silver halide emulsion layers, i.e. the silver halide corresponding to the unexposed and consequently undeveloped areas then forms; with

3U ¹ JBOB / 0 8 6 T

the silver halide solvent present or through the developing liquid activated silver halide solvents a soluble silver ion complex, which in the adjacent The germ layer migrates. The transferred silver complex is then reduced or physically developed in the seed layer, whereby the developer compound is added. The oxidized developing agent then reacts with that in each Diffusing couplers present in the seed layer to produce imagewise distributions of diffusing cyan, magenta and yellow indophenols as a function of the imagewise exposure of each silver halide emulsion layer. At least some of the diffusible indophenols, which are present in an image-wise distribution, then diffuses into the image-receiving layer, in which a positive onium indophenoxide dye image is obtained when brought into contact with an onium compound.

If the image transfer unit has a layer which reduces the pH value, this decreases after it has been brought into contact with it alkaline developing liquid adjusts the pH of the transfer unit and stabilizes it in this way.

DiQphysical development seeds can be derived from the usual known physical development nuclei exist, e.g. metals present in colloidal form, for example colloidal Silver, gold, platinum, palladium or colloidal metal sulfides, for example colloidal silver sulfide or zinc sulfide. It is also possible to use substances which are able to form physical development nuclei, for example reducing agents and compounds having labile sulfur atoms. If necessary, the seed layer can also be split into two layers on each side of the photosensitive silver halide emulsion layer are arranged.

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The silver halide solvent can be any of the usual ones known silver halide solvents, for example an alkali metal or ammonium thiosulfate or a thiocyanate, e.g. sodium thiosulfate, ammonium thiosulfate, ammonium thiocyanate or potassium thiocyanate. Optionally, the silver halide solvent can be used be placed in a special shift.

Advantageously, between the seed layers and the silver halide emulsion layers or separating or barrier layers be arranged to avoid undesired mixing of the two layers in the coating process. The separating or barrier layers can optionally also Seeds and a non-diffusing coupler that reacts with oxidized color developing agent to form an immobile Reaction product is able to react, contained to the effectiveness to increase the transmission unit. For further details of such image transmission units, refer to British Patent 904,364, page 19, lines 1-41. .

Further preferred embodiments of the method of the invention employing non-diffusing color couplers Recording materials or image transfer units used, the intermediate layers between the various photosensitive Have color-forming units and which have the task of scavenging oxidized color developing agent or to bind, so as to prevent in other color-forming Units of unwanted dyes are generated. Such intermediate layers can be made from a hydrophilic polymer be constructed, for example from gelatin and an immobilizing Couplers of the type already described which are capable of reacting with oxidized ρ-aminophenol color developing agent to form an immobile reaction product,

3090Ü8 / Ö8 61

■ / ■

Such intermediate layers can also bind other substances, for example soluble silver ion complexes or mercaptans, whereby it is prevented that such compounds or complexes can get into other color-forming units. A developer scavenging interlayer can also be adjacent in the case of the described embodiment of the method of the invention to a light reflective layer of an image transfer unit to prevent excess color developing agent discolor or stain the image-receiving layer. Such a layer can, for example from a non-diffusing color coupler that reacts with an oxidized color developing agent to form an immobile Reaction product able to react and a silver halide emulsion, preferably one that is not exposed is developable, exist.

Preferably, in practicing the method of the invention, the p-aminophenol color developing agent is used in the alkaline Brought developing liquid applied. When using image transmission units, the one that can be developed in a camera Type is the p-aminophenol color developing agent preferably in the alkaline developing liquid housed in a splittable container. The p-aminophenol color developer compound however, it can also be in the negative part of an image transfer unit in a special layer or in the Silver halide emulsion layer itself. In this case, the developing agent is replaced by the alkaline Developing fluid activated. Although the developer association can be accommodated in any layer of a photographic light-sensitive material from which it can be made accessible for the development process by activation with the alkaline developing liquid, it has proven to be expedient to use the developer association

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formation of either the photosensitive silver halide emulsion layer or layers to add or to accommodate them in adjacent layers. .

To carry out the method of the invention are suitable common known p-aminophenol developing agents, which in oxidized form with common color couplers with the formation of Indophenol dyes are able to react »The p-aminophenol color developer compounds can therefore consist of the unsubstituted p-aminophenol or substituted p-aminophenols. In those cases where a high solubility of the developing agent or of the indophenol dye formed is desired is to produce diffusible indophenol dyes the ring of the p-aminophenol is advantageously substituted by water-solubilizing radicals, e.g. halogen atoms and / or halogen-containing radicals in the ortho and / or meta positions of the ring be.

Suitable p-aminophenol developer compounds for carrying out the process of the invention can be represented by the following structural formula:. -

H ₂ N-Ar-OH

where Ar is an arylene radical with 6 to 20 carbon atoms? ^! ₉ including a substituted arylene radical and one

condensed ring system. Ar is preferably a phenylene radical which optionally substituted in the ortho and / or meta position can, where the substituents are preferably composed of halogen atoms and / or radicals containing halogen atoms. If Ar stands for a condensed ring system, this can, for. B. a Be naphthalene or anthrylene ring system, d. H. a ring system built up from condensed benzene nuclei.

3G * juü-R70861

If the color developing agent used to carry out the method of the invention does not consist exclusively of a p-aminophenol developing agent, ie the p-aminophenol developing agent is used together with one or more other color developing agents, the latter can consist of conventionally known color developing agents which are oxidized in their Form able to react with color-forming couplers to form a dye. These compounds generally consist of aryl compounds which are _{substituted by an NH 2} radical.

Characteristic of the process of the invention is thus the production of indophenols in the presence of an onium compound, which together form onium indophenoxides or the production of indophenols and the subsequent treatment with a Onium compound with the production of onium indophenoxides. The onium compounds can either be soluble compounds which can be supplied in the form of a solution for the reaction with the indophenol (s). On the other hand you can the onium compounds, however, also consist of compounds of high Molecular weights exist which are relatively insoluble in water and consequently in at least one layer of the photographic Material or the image transfer unit can be arranged, for example the mordant layer or a mordant containing layer in which the indophenol or indophenols form onium indophenoxide dye images.

The use of onium compounds in the field of photography is known per se. For example, it is known from US Pat. No. 2,648,604 to be non-surface-active to use quaternary compounds as development accelerators. From U.S. Patents 2,271,623, 2,271,622 and 2 275 727 it is also known quaternary ammonium compounds, quaternary phosphonium compounds and tertiary sulfonium compounds as sensitizers for silver halide emulsions

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-f.

to use. From the US Patent 3 "146,102 and;.. $ ZTZ it is also known Oreiumverbindungen with common but Farfestöffentwicklern under Bildüfeertragungsverfahiren to use None servant patents is an indication of the availability of Öniumverbindungen to generate Ohiumindo- * ghenoxidfarbstöffen * Nium compounds which can be used according to the invention are described, for example _, in US Patents 3,146,102, 3,212,893-3,253,915 and J 266,894 and quaternary ammonium compounds.

It is known that organic compounds are used as quaternary ammonium compounds Compounds with a pentavalent nitrogen atom ^ denoted ;. Me- \ se compounds can be used as derivatives of ammonium compounds denote in which the four valences of nitrogen passing through Hydrogen atoms are saturated, are saturated by organic residues. The organic residues are generally bound directly to the pentavalent nitrogen atom, namely through a single carbon-nitrogen bond or a double carbon-nitrogen bond.

"Quaternary ammonium compounds" are to be understood here as meaning those compounds in which the pentavalent nitrogen atom is a Atom of the core atoms of a heterocyclic ring, or at to which four individual organic residues are bound to the nitrogen atom are, as is the case, for example, with quaternary tetraalkylammonium compounds the case is. So you can carry out the procedure Quaternary ammonium compounds suitable for the invention, for example can be represented by the following structural formulas:

R. f

R - N ⁺ -R

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/ -XX.

2238852

ι ι

ι \

where mean:

R is an organic radical;

Y is an anion, e.g. a hydroxyl, bromide, chloride or

Toluenesulfonate anion and

Z to complete a heterocyclic ring

required atoms.

As examples of compounds of structural formulas 1, 2 and 3 are called:

Tetraethylammonium bromide, N-ethylpyridinium bromide, N, N-diethylpiperidinium bromide, Ethylene-bis-pyridinium bromide, 1-ethylpyridinium bromide, T-phenethyl-3-picolinium bromide, tetraalkylammonium salts, Cetyltrimethylaminonium broraid, polyalkylene oxide bisquaternary Ammonium salts, e.g. polyethylene oxide-bis-pyridinium perchlorate, also the heterocyclic quaternary ammonium salts which form methylene bases, including 3-methyl-2-ethylisoquinolinium bromide, 3-methylisoquinolinium methyl p-toluenesulfonate, i-Ethyl-Z-methyl-S-phenäthylbenzimidazolium bromide, 5,6-

3 ü ^C JU ^f J i> / ü 8 6 1

Dichloro-1-ethyl-2-methyl-3- (3-sulfobutyl) benzimidazolium betaine and the pyridinium salts.

Onium compounds suitable for carrying out the process of the invention are also tertiary sulfonium and quaternary phosphonium compounds, in particular those of the following structural formulas:

4) (R), S® Χ ^θ "and

5) (R), P® X ⁰

where mean:

R is an organic radical, e.g. an alkyl, aralkyl or

Aryl radical and

X is an anion, e.g. a hydroxyl-bromide, chloride or

Toluenesulfonate anion. -

Examples of tertiary sulfonium and quaternary phosphonium compounds, which are suitable for carrying out the method of the invention are, for example:

Lauryl dimethyl sulfonium p-toluene sulfonate, nonyl dimethyl sulfonium p-toluene sulfonate and octyldimethylsulfonium p-toluenesulfonate, Butyldimethylsulfoniumbromid, Triäthylsulfoniumbromid, Tetraäthylphosphoniumbroaid, Dimethyl sulfonium p-toluenesulfonate, dodecyldimethylsulfonium p-toluenesulfonate, Decyldimethylsulfonium ptoluenesulfonate and ethylene-bis-oxymethyltriethylphosphonium bromide.

The onium compounds can be used as hydroxide or in salt form be used. If the onium compounds are used in the form of salts, the anion can be derived from any acid. It is only to be noted that "in the case in which the anion from

3 0 ' ¹ Ji- "I) H / 0861

an iodide anion, the iodide may have certain disadvantageous May have effects on the emulsion and that in these cases precautionary measures should occasionally be taken, provided the onium compound with an emulsion layer before its complete Development is brought into contact.

Particularly advantageous results are obtained when the Onium compounds can be used in the form of their bromides.

Particularly advantageous heterocyclic quaternary ammonium compounds, which form suitable methylene bases in alkaline solutions are, for example:

1-Y-phenylpropyl-2-picolinium bromide,

2,4-Dimethy1-1-phenethylpyridinium bromide, 2,6-dimethyl-i-phenethylpyridinium bromide, 5-ethyl-2-methyl-1-phenethylpyridinium bromide, 2-Athy1-1-phenethylpyridinium bromide,

1- / ~ 3- (N-pyridinium bromide) propyl_7-2-picolinium-p-toluenesulfonate

p-toluenesulfonate

Anhydro-1- C4-sulfobutyl) -2-picolinium hydroxide

C ₄ H ₆ SO ₃

a- P i colin-ß-naphthoylme thyIb romi d

86 1

ir

i-ß-Phenylcarbamoyloxyäthyl ^ -picoliniumbromid

CH ₃ . Br

C ₂ H ₄ OCONHC ₆ H

1-methyl-2-picolinium-p-toluenesulfonate, i-phenethyl-S ^ o-trimethylpyridinium bromide, i-phenethyl-4-n-propylpyridinium bromide, 4 - '\ - hydroxypropyl-1-phenethylpyridinium bromide and 1-η-heptyl-2-picQlinium bromide.

According to a particularly advantageous embodiment of the invention the dye images are made using a polymer with onium residues or pickled onium groups.

Typical mordants this type are Viny pyridinium compounds, such as the well-known from the US Patent 2,484,430 type polymers with quaternary ammonium groups, such as the writing ent from ^ _n U.S. Pat en 3625694 and 3639357 and Belgian Patent Specification 729! 202 known type;

$ 09008/0061

and also polymers with quaternary ammonium residues from U.S. Patents 3,488,706 and 3,557,006.

According to a further particularly advantageous embodiment of the invention, so-called onium coacervate dressings are used as dressings are used, for example those of the type known from U.S. Patent 3,271,147.

The alkaline developing or working solutions suitable for practicing the method of the invention consist of conventional ones aqueous solutions of at least one alkaline compound, e.g. sodium hydroxide, sodium carbonate or an amine, e.g. diethylamine, and preferably have a pH value above 12. They preferably contain a developer compound of the type already described. Preferably such Uses solutions that contain a viscosity-increasing substance, for example a high molecular weight polymer, for example an ether which is inert and water-soluble towards alkaline solutions, e.g. hydroxyethyl cellulose or an alkali metal salt the carboxymethyl cellulose, e.g., sodium carboxymethyl cellulose. The substance increasing the viscosity can be more advantageous Manner in concentrations of about 1 to about 5 percent by weight, based on the weight of the developing liquid, and preferably imparts a viscosity of from about 100 ops to about 200,000 cps to the developing liquid.

Preferably the alkaline developing or working liquid is applied in a splittable container. However, it is also possible to introduce the developing liquid into the image transfer unit or film unit, for example between the transparent cover sheet and light-sensitive ink, in another way, for example by spraying or injecting or injecting the developing liquid or developing solution with the aid of communicating glitdtrs, similar to hypodtratsch

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Injection syringes, which can be arranged on or in the camera or a camera cartridge.

The method of the invention is useful for producing transfer images from a wide variety of onium indophenoxides Formats.

In the photographic image transfer units suitable for carrying out the process of the invention, the image-receiving layer can be arranged on a special support in such a way that the image-receiving layer with its support can be applied to the light-sensitive photographic element after the latter has been exposed to light. Photographic image transfer units of this type are known, for example, from U.S. Patent No. 3,362,819. Such image transmission units furthermore have at least one splittable container which is arranged in the image transmission unit in such a way that, when pressure forces are exerted, it can be exposed to pressure by means of pressure-exerting members, for example such as are present in cameras in which a photographic material is not only exposed but can also be developed at the same time, can pour its contents between the image-receiving layer or the image-receiving element and the outermost layer of the light-sensitive element. After the photosensitive element has been developed, the image-receiving element can then be separated from the photosensitive element.

However, the image receiving layer can also be an integral part the image transfer unit and between the support of the photosensitive element and the lowest photosensitive element Be arranged silver halide emulsion layer. Such negative photosensitive element image transfer units and integrated image receiving layer are described in more detail in DOvS 2 052 130, for example. These image transmission units exhibit a photosensitive element, with a transparent one

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Layer carrier on. On top of this are applied: an image receiving layer, an opaque light-reflecting layer, for example a titanium dioxide layer and at least one silver halide emulsion layer. After exposure of the photosensitive element, a splittable container with an alkaline Working fluid and an opaque worksheet placed on the exposed photosensitive element. By the action of pressure exerters Members, for example the members arranged in a camera, the splittable container is split open, wherein it its contents pours over the photosensitive element of the image transfer unit when the unit is withdrawn from the camera will. The developing liquid then underdevelops the exposed or exposed silver halide emulsion layers Generation of dye images as a function of development, which then diffuse into the image receiving layer to produce a positive, right-side readable image that passes through the transparent substrate on the opaque reflective background can be viewed. For further details, reference is made to DOS 2,052,130.

Integral image transmission units from the DOS are also suitable for carrying out the method of the invention 2,052,145 known type. Such image transfer units also have a photosensitive element with a transparent Layer carrier on. In the case of these image transfer units, the following are applied to the transparent substrate: an image-receiving layer, an opaque light-reflecting layer and at least one light-sensitive silver halide emulsion

another ji layer. The image transmission unit has the / a transparent Cover sheet and a splittable container with alkaline developing liquid and an opacifier between the top layer of the photosensitive element and the trans-

3 O ¹ J '■ · ■'.! I! / 086 1

parent cover sheet. Such an image transmission unit can in a camera of the type known for the exposure and processing of photographic recording materials by the transparent cover sheet are exposed through, whereupon the unit is formed by a pair of pressing members The gap can be removed from the camera. In doing so, the splittable container is split open and its contents pour out together with opacifiers via the negative part of the film unit, this being made insensitive to light. The developing liquid develops the silver halide emulsion layer or silver halide emulsion layers to produce image dyes as a result of the development which then enters the image receiving layer producing a positive right-hand side legible image that passes through the transparent support can be viewed on the opaque reflective background, diffuse for more details of this type of photographic For image transmission units, reference is made to DOS 2,052,145.

The usual Compounds are used as long as they are only suitable for staining the onium indophenoxide dye images or otherwise Way to fix. The cheapest build-up in individual cases an image-receiving layer depends of course on the dye or dyes to be pickled. It is preferably used as Mordants or fixatives that use an onium compound is able to react with the transferred indophenols to form one or more onium indophenoxides. Are acidic To pickle or fix dyestuffs, the image-receiving layer can have hishy mordants, in particular polymeric basic ones Have mordants, for example polymers of aminoguanidine derivatives of vinyl methyl ketone, as for example in the

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US Pat. No. 2,882,156, or basic polymeric mordants from the Belgian patent 729 202 known type.

Other suitable mordants which are suitable for the preparation of image-receiving layers for image transfer units according to the invention are, for example, poly-4-vinylpyridines and the like. Particularly effective pickling agents for the production of Image transfer units according to the invention are, for example, those known from U.S. Patents 3,271,148 and 3,271,147 Pickling agents.

If necessary, the image-receiving layer does not need any special ones To contain mordant, but can have a self-pickling effect, for example when the image-receiving layers made of polymers permeable to alkaline solutions, such as N-methoxymethylpolyhexylmethylene adipamide, are partially hydrolyzed Polyvinyl acetate, polyvinyl alcohol with and without plasticizers, cellulose acetate and / or gelatin or other substances are of a similar nature. Particularly advantageous results are often obtained when the image receiving layer, the is preferably permeable to alkaline solutions, is transparent and has a thickness of about 0.0063 to 0.010 mm. Of course, the thickness of the image receiving layers can also be outside the specified range.

Advantageously, the image-receiving layer can also contain compounds which absorb ultraviolet rays in order to improve the to protect stained dye images from fading due to the action of ultraviolet light. Finally, in the Image receiving layer may also contain optical brighteners, for example based on stilbene, coumarin-ι triazine or oxazole, and also dye stabilizers, e.g. chromanols and / or alkyl phenols.

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By using a pH reducing substance in the image receiving element of an image transfer unit according to the invention the stability of the transmitted image can usually be further increased. Suitable for reducing the pH value Substances are those which reduce the pH value of the image receiving layer from about 13 or 14 to at least 11, preferably 5 to 8, within a short period of time after transfer of the dye image. Appropriate to the pH reducing substances are made up of polymers. Acids such as those described in U.S. Patent 3,362,819 as well as solid acids and metal salts in the normal state, for example zinc acetate, zinc sulfate, magnesium acetate and the like, as described, for example, in U.S. Patent 2,584,030. Such substances, which reduce the pH value reduce the pH of the image transfer unit after development to terminate development and inhibit one further dye transfer with stabilization of the dye image obtained. '

Optionally, a photographic image transfer unit according to the invention can further comprise an inert delay or Have a separating layer over the pH reducing layer, which delays or controls the pH reduction, namely as a function of the speed with which the alkali diffuses through the inert retardation or separation layer. Such Retardation or separation layers can, for example, consist of gelatin or polyvinyl alcohol or other substances from the U.S. Patent 3,455,686 of the known type. Such a layer can also compensate for the various Reaction rates are effective within a wide temperature range. For example, a too early Prevent pH decrease with the help of such layers,

■ ■■■: / 088 1

when the transfer process is carried out at a temperature above room temperature, for example at a temperature of 35 to 38 ^° C. Such retardation or separating layers preferably have a thickness of approximately 0.00254 to 0.0178 mm. Particularly advantageous results are obtained when the retardation layer is constructed using a hydrolyzable polymer or a mixture of such polymers which are slowly hydrolyzed by the developing liquid. Examples of such hydrolyzable polymers are polyvinyl acetate, polyamides and cellulose esters.

The following examples are intended to illustrate the invention in more detail.

Example 1 (comparative example)

A) On a cellulose acetate layer support with a gelatin adhesive layer to improve the adhesion of emulsion layers to be applied
a gelatin-silver halide emulsion was applied in such a way that the following amounts to a support area of 0.0929 m: 150 mg silver, 500 mg gelatin, 114 mg α-pivalyl-α- (3-pentadecyl-4-nitrophenoxy) -4-sulfamylacetanilide (coupler I) and 114 mg of diethyl lauramide.

The obtained recording material was then passed through a test object exposed with graduated density levels and by means of a viscous developer solution of the composition given below developed, in contact with an image-receiving sheet, consisting of a support and a coated thereon Gelatin layer with a quaternary mordant, consisting of copoly / styrene-N, N-dimethyl-N-benzyl-N-3-maleiimidopropyl) ammonium chloride_7. The contact time was 2 minutes.

⁺ Mixed polymer of styrene and Ν, Ν-dimethyl-N-benzyl-N-3-maleimidopropyl) ammonium chloride

3 IUIi: Il M / 086 1

After separating the photosensitive element from the image receiving element In the latter, a negative yellow dye image of the test object used was left behind.

Composition of the developer solution

KOH 35.9 g

4-Amino-N-ethyl-N-ß-hydroxyethylaniline 40.0 g

Piperidinohexose reductone 0.2 g

5-methylbenzotriazole 0.2 g

Hydroxyethyl cellulose 30 g made up to 1 liter with water.

In Figure 1, curve Y represents the spectrophotometric data obtained on this transferred yellow dye image.

B) The procedure described in section A) was repeated, but this time a recording material with a silver halide emulsion layer the coupler 1-phenyl-3- (3,5-dicarboxyanilino) -octadecylcarbamylphenylthio) -5-pyrazolone was used as a yellow dye-forming coupler (Coupler II)

2 at a concentration of 88 mg per 0.0929 m of support surface in

2 contained 44 mg of Nn-butyl acetanilide as a coupler solvent per 0.0928 m of support area. .

In Figure 1, the curve M represents that in this transmission image spectrophotometric data obtained.

C) The procedure described under Section A) was repeated, but this time a recording material with a silver halide emulsion layer whose yellow dye-forming coupler was used from 1-hydroxy-4 - ^ "a- (3'-pentadecylphenoxy) -butyramido_7phenoxy-N-ethyl- (2", 5 "-dicarboxy) -2-naphthanilide (Coupler III) at a concentration of 100 mg per 0.0929 m 2 support area in 101 mg of diethyl lauramide as a coupler solvent existed per 0.0929m support surface.

3 0 9808/0861

In Figure 1, curve C represents the spectrometric data, obtained in this transfer image.

The procedure described was repeated, but this time the recording materials described in Sections A, B and C were used were developed by means of a developer of the composition given below:

Na ₂ CO ₃ .H ₂ O 22 g

KBr 1.0 g

Na ₂ SO ₃ 2.0 g

2,6-dibromo-4-aminophenol 7.4 g pH adjusted to 12 with NaOH
made up to 1100 ml with water.

The spectrophotometric data of the transfer images obtained in this case are shown in FIG. 1 in curves Y ', M ¹ and C.

A comparison of the two sets of curves in Figure 1 shows that the spectrophotometric qualities of the image dyes produced by the process of the invention are just as good as the qualities of the image dyes obtained by the conventionally known process used with a p-phenylenediamine developing agent moreover more favorable, in particular with regard to the narrower bandwidth and the lower undesired blue absorption of the magenta dye, represented by the curve M ¹ .

Example 2

A) First , a photosensitive recording material was produced by placing it on a cellulose acetate support with a gelatin adhesive layer

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a silver halide emulsion layer was applied in such a way that on a support area of 0.0929 m ^{2 there were} 108 mg of silver, 400 mg of Glatin and 152 mg of coupler III. A second silver halide emulsion layer was then applied to this layer in such a way that the following amounts to a support area of 0.0929 m: 100 mg gelatin, 25 mg di-n-butyl phthalate and 25 mg 1-hydroxy-2- / ~ A- (2.4 -di-tert-amylphenoxy) -n-butyl_7naphthamide and 25 mg 5- / α- (2,4-di-tert-amylphenoxy) hexanamido_7-2-heptafluorobutyramidophenol, ie color couplers containing ballast groups for binding excess oxidized p-aminophenol .

The recording material was then sensitometrically through a Test object exposed to graduated density levels and then exposed to an image receiving sheet for 60 seconds at room temperature brought into contact in the presence of a viscous developing liquid of the following composition:

NaOH '10 g

2-chloro-4-aminophenol 13.2 g

Hydroxyethyl cellulose 20 g

made up to 1 liter with water.

The image-receiving layer of the image-receiving element contained as Mordant copoly / styrene-NjN-dimethyl-N-benzyl-N ^ -maleiimidopropyl) ammonium chloride_ /.

After separation of the image-receiving element from the recording material, the image-receiving element remained in the image-receiving layer a negative blue-green reproduction of the photographed test object. The image-receiving element was washed for 3 minutes and dried. The obtained maximum and minimum image densities of the transfer image (read by a status M red filter) are listed in Table I below.

-X-

B) The procedure described in section A) was repeated. However, this time, a developing liquid was used which contained a common p-phenylenediamine color developing agent, namely 4-amino-N-ethyl-N-ß-hydroxyethylaniline, instead of 2-chloro-4-aminophenol, in such a concentration

2 tion that 90 mg of 4-amino-N-äthy1-N-ß-hydroxyäthyIanilin accounted for a support area of 0.0929 m.

The maximum and minimum densities of the transmission image, which are shown in in the same way as when the other developer was used are shown in Table I below.

Table I. Max Procedure typ ^D min 1.69
1.57 A.
B. 0.16
0.26

From the data compiled in the table it follows that when using a p-aminophenol color developing agent according to the invention a dye transfer image is obtained which has more favorable sensitometric properties than the transfer image, that using a common p-phenylenediamine color developing agent was obtained.

Example 3

A) For comparison purposes, a recording material was initially used produced by being coated on a cellulose acetate substrate with a gelatin adhesive layer

3 I) M H -.1 H / U β 6 1

a gelatin-silver halide emulsion was applied in such a way that

2 that on a substrate area of 0.0929 m there was a total of 150 mg Silver, 500 mg gelatin, 110 mg of the blue-green dye image forming coupler N-ethyl-N- (3,5-disulfamoylphenyl) -1hhydroxy-4- {4- / ~ 2- (3-pentadecylphenoxy) butyramido 7phenoxy} -2-naphthamide (Coupler IV) and 110 mg of the coupler solvent, diethyl lauramide.

The recording material was then exposed to a test object with graduated density levels and then to a developer solution of the composition given below in contact with an image-receiving element having an image-receiving layer comprising copoly- _/ / "" styrene-N, N-dimethyl-N-benzyl-N-3 -maleiimidopropyl) ammonium chloride7 developed as a pickling agent. The contact time was 5 minutes. The transfer took place at room temperature. After separation of the image-receiving element from the recording material, a well-defined negative blue-green-colored reproduction of the test object remained in the image-receiving layer of the image-receiving element.

The obtained transfer image became the H and D curves recorded.

Development fluid

Na ₂ CO ₃ .H ₂ O 22 g

Ascorbic acid 0.385 g

KBr 0.625 g

NaOH 4 g

4-Amino «-N-ethyl-N-ß-hydroxyethylaniline 11 g

A second sample of the recording material was exposed and developed in the same manner as the image-receiving element with the transferred dye image, a 24 hour fade test was subjected to a xenon lamp.

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In the case of this sample, the loss of dye density in an image area with an original density of 1.0 determined. The results obtained are shown in Table II below.

A third portion of the recording material prepared was exposed in a corresponding manner, and developed, after which the image-receiving element containing the transferred dye image was stored one week at a temperature of 6O ⁰ C and a relative humidity 7OV-strength long. The change in dye density was determined. The data obtained are summarized in Table III below.

B) The procedures described in section A) were repeated, but this time a developing liquid was used, which instead of the p-phenylenediamine color developing agent, namely 4-amino-N-ethyl-N-ß-hydroxyethylaniline this time one p-aminophenol color developing agent, namely 2,6-dibromo-4-aminophenol contained according to the invention. The results obtained in these experiments, which are also shown in Tables II and III show the improved dye stability achieved by practicing the method of the invention.

Examples 4 A and 4 B

The procedures described in Sections A and B of Example 3 were repeated, but this time an image-receiving sheet with an image-receiving layer with a coacervate of Nn-hexadecyl-N-morpholinium ethosulfate and methyl tri-ndodecylammoniura-p-toluenesulfonate, as in the USA Patent 3,271,147 was (coacervate I) may be used. Equally favorable results were obtained when the development as a color developing agent, a p-aminophenol, was in fact used 2,6-dibromo-4-aminophenol. The results obtained are summarized in the following tables later 11 and III.

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- 3ϊ

Examples 5 A and 5 B

The procedures described in Sections A) and B) of Example 3 were repeated, but this time using recording materials with silver halide emulsion layers containing Coupler III in place of Image Transfer Coupler IV. In this case too, results similar to those described in Example 3 were obtained when used as the color developing agent 2,6-dibromo-4-aminophenol was used according to the invention. The results obtained are as follows Tables II and III compiled.

Examples 6 A and 6 B

The procedures described in Sections A) and B) of Example 3 were repeated with recording materials whose Silver halide emulsion layers contained yellow dye providing transfer coupler I in place of Coupler IV. In terms of heat stability, favorable results as described in Example 3 were again obtained when development was carried out using 2,6-dibromo-4-aminophenol as the color developing agent. The results obtained are compiled in Tables II and III.

Examples 7A and 7B

Equally favorable results in terms of thermal stability of the transfer images were then obtained when image-receiving elements were obtained by the process described in Examples 6A and 6B were used whose image receiving layer contains a coacervate mordant, namely the coacervate I contained. The results of these tests are also summarized in Table III below.

j ίί / ö 8 6 1 ^r

to-

Examples 8 A and 8 B

further

Equally favorable results in terms of thermal stability were / then achieved when the procedures described in Examples 6 were repeated, but using the one yellow dye delivering transmission coupler ot- / 4-N-methyl-N-octadecylsulfamy1) phenoxy _? - α-pivalyl-4-sulfoacetanilide, Potassium salt (coupler V). The results obtained are as follows later Table III compiled.

Examples 9 A and 9 B

Correspondingly favorable results in terms of the heat stability achieved were obtained using the method described in Example 8 with an image receiving element having a das The image-receiving layer containing Coacervat I was repeated. The results obtained are shown in Table III below.

Cup Tabel II Xenon lamp exposure £ 0.16 at ler Pickling agent 24 hours Color developer- color developer
connection I ⁺ connection H ⁺ 0.11 game IV reception bFatt (a) 0.39 0.12 3 IV quaternary pickling
medium connection (b) 0.16 4th III quaternary pickling
medium coacervate (a) 0.22 5 quaternary pickling
medium connection

3 U y b 'ι H / 0 8 6 1

Table III

Example- Kupp- pickling agent- picture- one-week treatment in the oven play ler___ receiving sheet color developer- color developer-

connection I connection II ⁺⁺

IV quaternary pickling 0.11 +0.07

medium connection
(a)

IV quaternary pickling 0.09 0.02

medium coacervate
(b)

III quaternary pickling- 0.01 +0.04

. medium connection
(a)

I quaternary pickling 0, S1 +0.05

medium connection
(a)

I quaternary pickling 0.30 0.11

medium coacervate
Cb)

V quaternary pickling 0.24 +0.06

medium connection
Ca)

V quaternary pickling 0.18 0.08

medium coacervate
(b)

(a) Copoly / styrene- (N, N-dimethyl-N-benzyl-N-3-maleiimidopropyl) ammonium chloride_7

(b) Coacervate I = coacervate from N-n-hexadecyl-N-morpholinium ethosul-

fat and methyl tri-n-dodecylammonium p-toluenesulfonate

+ = 4-amino-N-ethyl-N-ß-hydroxyethylaniline ++ - 2,6-dibromo-4-aminophenol

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/ »Ft.

Example 10

A) First, a photosensitive recording material was produced by placing a gelatin adhesive layer on a layer support made of cellulose acetate
were applied:

1. a silver halide emulsion layer per 0.0929 m

Carrier surface 108 mg silver, 500 mg silver, 152 mg of the color coupler III and 90 mg 2-chloro-4-aminophenol. HCl

2. a gelatin layer with 100 mg per 0.0929 m of support area

Gelatin, 25 mg di-n-butyl phthalate and the two ballast groups containing capture couplers: 1-hydroxy-2- ^ Δ- (2,4-di-tert-amylphenoxy) -n-butyl_7naphthamide and 5- ^ a- (2,4-di-tert-amylphenoxy) hexanamido_7-2-heptafluorobutyramidophenol in concentrations of 25 and -76 mg.

A strip of the recording material produced was sensitometrically a test object with graduated density levels exposed and then for 60 seconds at room temperature with an image receiving layer with an image receiving layer Copoly ^ styrene CN.N-dimethyl-N-benzyl-N-S-malelmidopropyljammonium chloride_7 as a mordant in the presence of a viscous developing liquid of the composition given below brought into contact:

NaOH 10 g

Hydroxyethyl cellulose 20 g
made up to 1 liter with water.

The image-receiving sheet was as described in Example 1 Construction.

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Similarly, a second penalty was imposed on the image recording material exposed and then to a second section of the same image receiving element for 90 seconds brought into contact under otherwise identical development conditions.

After the image-receiving elements were separated, well-defined ones remained in the image-receiving layers of these elements in both cases bluish-green reproductions of the photographed Test object. The image-receiving members were washed for 3 minutes and dried. The determined minimum and maximum densities of the transfer images are given in Table IV below compiled.

B) The procedure described in section A) was used of a light-sensitive recording material

2
fetches, which contained 90 mg of the usual p-phenylenediamine developer compound 4-amino-N-ethyl-N-ß-hydroxyethylaniline per 0.09 m 2 carrier surface. In this case, dye densities of 0.25 and 0.42, respectively, were obtained in the image-receiving layers of the image-receiving elements with no discernible image details. The densities are also listed in Table 4 below.

Table 4

2,6-dibromo-4-aminophenol

4-amino-N-ethyl-N-ß-hydroxyethylaniline

Contact time in seconds

mm

Max

0.06 0.80

0.08 1.04

0.25 0.25

0.42 0.42

The data compiled in Table 4 clearly show the Recognize the advantages of using a recording material with incorporated p-aminophenol color developing agent compared to the use of a conventional p-phenylenediamine color

3 Γ «π ν ο :: / ü 8 β 1

-f-

developer connection can be obtained.
Example 11

This example illustrates the use of a p-aminophenol color developing agent in the context of a color diffusion transfer process with the combined use of colorless and colored Image transfer couplers in the photosensitive element.

First there was an eight layer resolving multicolor reversal transfer material of the structure specified below:

The following were applied to a cellulose acetate layer support: (The concentration data given below relate to

2 each on a substrate surface of 0.0929 m.)

1. a layer of red-sensitive reverse silver chlorobromide iodide emulsion of the type known from US Pat. No. 3,227,552 with 220 mg of gelatin, 125 mg of silver and 125 mg of the color coupler III (cf. layer 1 in Example 8, column 17, of the USA patent);

2. a layer with 100 mg of a mixture of secondary alkyl hydroquinones of the type known from Belgian patent 763 752 and 150 mg of gelatin;

3. a layer of 80 mg 4- {4- {ct- / ~ 4- (8-acetamido-1-hydroxy-3,8-disulfo-2-naphthylazo) phenoxy_7acetamido} phenoxy} -N- / ~ 4- ( 2,4-di-p-amylphenoxy) butyl_7-1-hydroxy-2-naphthamide, Disodium salt (Coupler VI) and 100 mg gelatin;

4. a layer of a green-sensitive reverse silver halide emulsion of the type known from US Pat. No. 3,227,552 with 125 mg of silver and 93 mg of gelatin;

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Hi

5. a layer of 15 mg Carey Lea silver, 100 mg of a mixture from secondary alkylhydroquinones from the deT Belgian patent 763,752 known type and 150 mg gelatin;

6. a layer of 80 mg of N- ^ ~ 4 ~ (2,4 ~ di-t.-amylphenoxy) butyl_7-4 - / "4- {a- ^" 4- {4 - / "N-ethyl-N - (2-sulfoethyl) amino_7-2-tolylazo} -phenoxy_7acetamido} phenoxy_7-l-hydroxy-2-naphthamide (Coupler VII) and 100 mg gelatin;

7 »a layer of a blue-sensitive reverse silver chlorobromide iodide emulsion of the type known from US Pat. No. 3,227,552 with 125 mg of silver and 93 mg of gelatin (cf. layer 5 in Example 8 in column 18 of the USA patent) and

8. a gelatin top layer of 80 mg gelatin.

The recording material was then passed through a multicolor test object exposed with graduated density levels and then in the presence of the viscous developing liquid indicated below developed in contact with an image-receiving element having an image-receiving layer with the coacervate I according to Example 4. The contact duration was 6 minutes at room temperature.

Developing fluid

2,6-dibromo-4-aminophenol 25 g

4-aminophenol. HCl Ig

NaOH '20 g

Piperidinohexose reductone 0.8 g

Hydroxyethyl cellulose 28 g made up to 1 liter with water.

After separating the photosensitive element from the image receiving element the latter was washed in water for 5 minutes and then dried.

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Ht

In this way, a positive multicolor image of excellent quality was obtained in the image-receiving layer. The image areas were very dense. Furthermore, the yellow, purple, and blue-green separation images exhibited well-balanced hues and, in addition, favorable minimum density values were obtained. The transferred dyes had favorable hues and were of high color purity.

Example 12

First, what is known as an integral multilayer photosensitive recording material was developed from the Belgian patent 757 959 known type produced in that in the order given below the following layers on one transparent cellulose acetate film base:

1) a coacervate image-receiving layer according to Example 4;

2) an opaque, light reflective layer of TiC ^ dispersed in gelatin;

3) a layer of gelatin with carbon black dispersed therein;

4) layers 1 to 8 according to Example 11;

5) with a transparent cover sheet made of polyethylene terephthalate a layer of polyacrylic acid and a retardation layer.

After imagewise exposure of the recording material according to Example 11 was converted into alkaline developing liquid from a splittable container with carbon black as an opacifying agent between the actual photosensitive material and the transparent cover sheet introduced and distributed. After development had taken place, there was a color image in the image-receiving layer of the laminate Excellent quality visible on a white background, provided the image was viewed through the transparent substrate.

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Claims (20)

PATENT CLAIMS A photographic image transfer method in which (A) a photographic recording material consisting of a Layer support and at least one silicon halide emulsion layer applied thereon, which contains an immobile color coupler or with one containing an immobile color coupler Layer is in contact, exposed imagewise, developed with a color developing agent, and this in image-wise Diffusible dye occurring during distribution is transferred to an image-receiving layer or in which (B) a photographic Recording material, consisting of a layer support and at least one silicon / halide emulsion layer applied to it, that contains a mobile color coupler or with one that contains a mobile color coupler Layer is in contact, exposed imagewise, with a color developing solution with imagewise immobilization of the color coupler developed and part of the mobile color coupler diffused into an image receiving layer and oxidized with color developing agent is implemented, characterized in that one 1.) as a color developer compound alone or at least predominantly a p-aminophenol is used and that 2.) the oxidation product by reaction of color couplers with p-aminophenol obtained indoplienol dye by reaction with an onium compound into an onium indophenoxide dye convicted. 2. A photographic image transfer method according to claim 1, characterized in that the onium compound is a quaternary Ammonium compound used. 3. A photographic image transfer method according to claim 2, characterized in that the onium compound is a poly- 3 (Y a B 0 B / ü 8 6 1 BATH ORiGIMAL. mere quaternary Animonimiiverbinduiig used and this in the The image receiving layer. 4. Photographisclies image transfer method according to claim 1, characterized in that one uses a photographic recording material which contains a p-amino phenol color developing agent in at least one layer. 5. A photographic image transfer method according to claim 1, characterized in that one uses a photographic recording material used that as a non-diffusing color coupler contains at least one pyrazolone, pyrazolthioazole, phenolic or non-chain ketomethylene color coupler. 6. A photographic image transfer method according to claim 1, characterized in that a photographic recording material is used which acts as a non-diffusing color coupler contains at least one color coupler of the following structure Ballast group - connecting link ( coupling residue - solubilizing remainder) _n where mean: the ballast group: an organic, photographically inert residue of such molecular size and configuration that the color coupler cannot diffuse during alkaline development; the link: an azo, mercury, oxy, alkylidene, thio, dithio, azoxy, aminoalkyl, sulfonyloxy, acyloxy or imido radical; the coupler radical: a 5-pyrazolone, pyrazolotriazole, phenolic or open-chain ketone-ethylene coupler radical, which in 3 Π 9 J «H H / U 8 B 1 BATH ORIGINAL Coupling position is substituted by the link; the solubilizing group: a hydrogen atom or an acidic solubilizing group, if the color tivic compound contains an acidic solubilizing residue, or an acidic solubilizing residue if the color developer is used is free from an acidic, solubilizing residue, and η = 1 or 2 if the link is an alkylidene radical, and = 1 if the link is an azo, mercury, oxy, thio, dithio or azoxy radical. 7. A photographic image transfer method according to claim 1, characterized characterized in that the imagewise exposed recording material by developing a) an image-receiving layer on the layer furthest away from the support or applies an image receiving element; b) between the image receiving layer or the image receiving element and the exposed recording medium has at least one splittable container with an alkaline developing liquid introduces and c) exerts pressure on the sandwich formed, splitting up the container or containers, so that the contents of the container or containers Pour container between the outermost layer of the exposed recording material and the image receiving layer able. 8. A photographic image transfer method according to claim 1, comprising a) a photographic recording material composed of a layer support and a blue-sensitive layer applied to it Silver halide emulsion layer containing a diffusing yellow dye forming, non-diffusing 309B08 / 0861 BAD ORIQINAt contains the color coupler or with such a color coupler containing layer is in contact, a green sensitive Silver halide emulsion layer which have a providing a diffusing, purple-red dye, Contains non-diffusing color couplers or with a puts such a color coupler-containing layer in contact and a red-sensitive silver halide emulsion layer., the one, diffusing blue-green dye supplying, non-diffusing color coupler or with a layer containing such a color coupler is in contact, exposed to the correct image, b) the exposed photographic recording material with an alkaline developing solution, and in which one c) allows the dyes formed and produced in imagewise distribution to diffuse into an image-receiving layer, characterized in that a p-amino phenol is used as the color developer compound alone or at least for the most part and that the diffusing indophenol dyes produced are converted into onium indophenoxide dyes. 9. Photographic image transfer process according to Claims 1 and 8, characterized in that a recording material is used whose color couplers all correspond to the following structure: Ballast group - connecting link - (coupler residue - solubilizing residue) _n where the ballast group, the link, the coupler radical, the solubilizing radical and η have the meaning already given own. 3098ÜÖV0861 BATH ORIGINAL 10. Photo graphic image transmission unit for performing the method according to claims 1 to 9 _S which can be developed by passing through a gap formed by two pressure-exerting members and consists of: a) a photosensitive photographic element composed of a Layer support with at least one silver halide emulsion layer applied thereon, which layer is non-diffusing Contains color coupler or is in contact with such a color coupler-containing layer with capable of forming a diffusing dye from the oxidation product of a developing agent; b) an image receiving layer; c) at least one splittable container with an alkaline Developing liquid that is used when the Film unit to pour its contents into the film unit through the gap formed by two pressure-exerting members able, and d) a silver halide developing agent in at least a layer of the unit associated with the silver halide emulsion layer is in contact and / or one of the rupturable containers, characterized in that the color developing agent alone or at least predominantly consists of a p-aminophenol exists and that an onium salt is also present in the image receiving layer or in a layer which makes contact therewith is. 11. A photographic image transfer unit according to claim 10, characterized in that the photosensitive photographic An element consisting of a support and at least one red-sensitive silver halide emulsion coated thereon, some have a diffusing blue-green dye 3 0 ¹ J: j ■ JH / 0 8 6 1 BATH ORIGINAL containing non-diffusing color coupler generating or is in contact with a layer containing such a color coupler, a green-sensitive silver halide emulsion layer containing a diffusing magenta image dye contains generating, non-diffusing color coupler or is in contact with a layer containing such a color coupler, and a blue-sensitive silver halide emulsion layer, which contains a non-diffusing color coupler providing a diffusing yellow image dye or is in contact with a layer containing such a color coupler. 12. Photographic image transfer unit according to claims 10 and 11, characterized in that the image receiving layer in the light-sensitive element between the support and the outermost light-sensitive silver halide emulsion layer is arranged. 13. Photographic image transfer unit according to claims 10 to 12, characterized in that it is a transparent one Layer support and a transparent cover sheet over the dated transparent support of the photosensitive element has furthest layer and that further at least one the splittable container contains an opacifier and is arranged transversely to a leading edge of the photosensitive element is, so that when a pressure is applied to the container it is split and its contents between the potted transparent cover sheet and the outermost layer of the photographic element. 14. Photographic image transfer unit according to claims 10 to 12, characterized in that it is 1.) a transparent one Layer support has that 2.) the image transfer unit also includes a worksheet that is based on the The most distant layer is applied to the transparent substrate 309808/0861 can be, and that 3.) the splittable container arranged in such a way is that when developing the image transfer unit by applying pressure, its contents between the worksheet and the outermost layer of the photosensitive photographic Able to pour element. 15. Photographic image transfer unit according to claims 10 to 14, characterized in that it additionally has a contains a pH-reducing substance » 16. A photographic image transfer unit for carrying out the method according to claims 1 to 9, which is carried out by passing through developed by the gap formed by two pressure-exerting members and consists of: I. A photographic photosensitive element comprising a support coated thereon in the following order are: a) a direct-positive red-sensitive silver halide ^ emulsion layer with a non-diffusing color coupler, which reacts with an oxidized color devi disgusting compound a diffusing blue-green dye able to form; b) a direct positive green sensitive silver halide emulsion layer with a non-diffusing color coupler that reacts with an oxidized color developer compound a diffusing purple Able to form dye, and c) a direct positive blue sensitive silver halide emulsion layer with a non-diffusing color coupler that reacts with an oxidized color developing agent capable of forming a diffusing yellow dye; 309808/0861 II. An image receiving element made of a non-carrier and a thereon applied image receiving layer, which after exposure of the photographic element on the blue-sensitive Silver halide emulsion layer can be applied, and III. at least one splittable container with an alkaline developing fluid used to develop the Image transfer unit can be brought into such a position that it will print its contents when split exerting members between the image-receiving layer and the blue-sensitive silver halide emulsion layer of the able to pour light-sensitive elements, characterized in that the image transfer unit is used alone or at least predominantly as a color developing agent Part contains a p-aminophenol developing agent and that the image-receiving layer contains an onium salt or is in contact with a layer containing an onium salt. 17. Photographic image transfer unit according to claims 10 to 16, characterized in that the onium salt of a polymeric quaternary ammonium salt and is arranged in the image-receiving layer. 18. Photographic image transfer unit according to claim 16, characterized in that the color developing agent in at least one layer of the photographic photosensitive element is disposed. 19. Photographic image transfer unit according to claim 16, characterized in that the color developing agent in at least one of the splittable containers is arranged. 20. A photographic image transfer unit according to claims 10 to 19, characterized in that all of the color developing agent consists of a p-aminophenol. 309808/0861