DE3704686A1 - Dye diffusion process - Google Patents

Abstract

Coloured diffusion images can be produced by a rapid process in which a first sheet-form material which contains, on a layer base (support, carrier), at least one photosensitive silver halide emulsion layer and at least one non-diffusing dye-releasing agent and/or a second non-photosensitive sheet-form material which contains a binder layer containing a salt of a weak inorganic acid and a strong organic base, is/are moistened with an aqueous liquid, after which the two sheet-form materials are warmed to from 50 to 120@C in contact with one another on their coating sides and are subsequently separated from one another.

Description

The invention relates to a method for manufacturing colored images according to the color diffusion process, whereby development in the presence of a base releasing agent Connection is carried out.

It is known by means of suitable color photographic Recording materials colored images by heat treatment to manufacture. As coloring compounds are particularly suitable here those in non-diffusing form in the layer of a photographic Recording material can be stored can and as a result of the development of a diffusible Can release dye (color releaser).

The particular suitability of such paint releasers is based on the fact that the imagewise released dyes can be transferred to special image-receiving layers can form a brilliant color image that  not from annoying image silver or silver halide is superimposed and accordingly no post-treatment requirement. By combining heat development and color diffusion this results in an advantageous quick method for the production of colored pictures. One for this suitable recording material is, for example described in DE-A-32 15 485.

After this publication is a recording material with a layer that is a combination of Silver halide, silver benzotriazole, a color releaser and contains guanidine trichloroacetate (base donor), exposed imagewise and then in contact with subjecting an image-receiving sheet to heat treatment, wherein the imagewise released dye on the Image receiving sheet is transmitted. For the production multicolor images need several such combinations be present with the silver halide in each of these combinations for a different spectral range is sensitive to light and corresponding to it Spectral sensitivity assigned a color releaser who releases a dye of a different color, usually a color that is complementary to that Color of light for which the silver halide in question is predominantly sensitive. Such Mappings can be stacked in different layers be arranged.  

For the development and especially the diffusion of the released dyes are alkaline conditions conducive; these arise, for example, during decomposition of the base dispenser mentioned due to the heat treatment. On the other hand, if the alkaline conditions arise prematurely, e.g. B. with insufficient stability of the base donor, or if in the recording material a base is in free form, then leaves to desire the stability of the recording material left over and it's difficult, especially with longer ones Storage of the recording material before use, one sufficient density difference between areas less and get strong exposure.

There are already numerous chemical compounds as Base dispensers have been proposed, e.g. B. in DE-A- 35 29 930, DE-A-35 29 934, DE-A-35 30 053, DE-A- 35 30 063, DE-A-35 30 201, DE-A-35 30 213 and DE-A- 35 30 214; but overall these are not too complete satisfactory results.

It is also already known (e.g. from EP-A-0 121 765) that the color transfer of a pictorial distribution is more mobile Dyes from an originally photosensitive Layer into an image receiving layer through a Heat treatment carried out in the presence of water can be, for example a moistened with water Image receiving sheet in contact with one already developed, containing the mobile dyes Sheet is heated. The one for color diffusion  required base is in the original negotiate photosensitive sheet in which it at previous development through heat treatment in Absence of water from a base precursor compound has been released. This procedure too naturally has all the disadvantages of those methods in which the thermolabile base dispenser in close contact with the photosensitive layers and the Base from it during development by thermal treatment is released.

The invention has for its object a photographic To provide color diffusion processes, with the sharp by a simple heat treatment Diffusion images with high maximum color density and low veil can be made even if the recording material for a long time before use has been stored.

The present invention relates to a method for the production of colored pictures after the photographic Color diffusion process in which a first sheet Material that is on a substrate at least a photosensitive silver halide emulsion layer and at least one non-diffusing color Contains link that is capable of developing to be figuratively split and one to release diffusible dye, and / or a second non-photosensitive sheet material are moistened with an aqueous liquid, whereupon the two sheet-shaped materials in the coating side Contact heated to 50 to 120 ° C  and then separated from each other, characterized in that the second leaf-shaped Material at least one binder layer with a contained in it a weak inorganic salt Contains acid and a strong organic base.

In the method according to the invention, a premature Contact of the photosensitive material with base or Base precursors avoided. This will be achieved that the base in the form of a base precursor compound incorporated into a non-light sensitive material that is from the photosensitive material stored separately and with it only during development is brought into contact. The release continues the base not by thermal decomposition of the base precursor compound, but caused by their hydrolysis. This requires the presence of water. There the base is already needed for the development, this means that in the method according to the invention the presence of water during development essential feature is while in the known photothermographic process the actual development by heating in the absence of water ("in a substantially water-free condition ").

For carrying out the method according to the invention a non-photosensitive sheet material is required, that on a transparent or opaque substrate at least one binder layer with one  a weak inorganic salt dispersed therein Contains acid and a strong organic base. This Non-photosensitive sheet material serves as an auxiliary processing sheet and optionally also as Image receiving material. It is exposed with the image photosensitive sheet material on the coating side contacted after at least one of these two sheet materials with one aqueous liquid sufficiently moistened has been. The laminate thus formed is 50 to Heated to 120 ° C and then after a contact time, those for development and dye diffusion sufficient, e.g. B. separated again after 5 to 200 s.

Strong organic bases for the invention Processes are suitable and in the form of their salts weak inorganic acids can be used are, for example, amidines and descendants of Guanidins and their vinylogous compounds. Many of these Compounds can be represented by the following formula (I) describe

in what mean

R¹, R², R³H or alkyl; R⁴H, alkyl, aryl, an amino group or a guanidino group

or R¹ together with R² represents an alkylene group 2, 3 or 4 carbon atoms and / or R³ together with R⁴ is an alkylene group with 3, 4 or 5 carbon atoms, one Vinylene group, a divinylene group (e.g. -CH = CH-CH = CH-) or a group of the formula

wherein

R¹ has the meaning given and p represents 2, 3 or 4; Veine vinylene group, especially -CH = CH-; n 0 or 1.

An aryl group represented by R⁴ is particular a phenyl group that is unsubstituted or substituted may be, preferably as such substituents with electron donor character (e.g. methyl, methoxy, Amino) come into question.

The optionally represented by R¹, R², R³ and R⁴ Alkyl groups can be the same or different, straight-chain or be branched and generally up to 12 carbon atoms contain; they preferably contain 1 to 3 carbon atoms.

Specific examples of suitable bases are given below. However, the invention is not limited to this.

The bases are used as weak acid salts. Carbonic acid is particularly suitable as an acid. For the incorporation into the layer structure come the usual dispersion methods in question. Usually the base salts are introduced into the casting batches in aqueous solution.  

The non-light-sensitive sheet material serves in primarily for the implementation of the invention Process the required alkali in the form of the Base released from the base precursor compound to To make available. In addition, there may be others Perform functions. For example, it can be a through diffusing dyes, dyeable dye stripping layer included if the dye pickling layer is not an integral part of the photosensitive Represents sheet material.

The dye pickling layer serves as an image receiving layer for the inclusion and definition of the development imagewise released dyes. It consists in essentially from a binder, the mordant for the definition of the non-diffusing paint separators released diffusible dyes contains. Serve as a mordant for anionic dyes preferably long-chain quaternary ammonium or phosphonium compounds, e.g. B. those as described are in US-A-32 71 147 and US-A-32 71 148.

Furthermore, certain metal salts and their hydroxides, the sparingly soluble with the acid dyes Form connections, be used. Furthermore are polymeric mordants should also be mentioned here, such as those described in DE-A-23 15 304, DE-A-26 31 521 or DE-A- 29 41 818 are described. Preferred stains are also Polyvinylimidazole stain that partially quaternizes are, for example with benzyl, hydroxyethyl,  Alkyl, epoxypropyl, propyl, methyl and ethyl halides, the degree of quaternization between 1 to Can be 50%. The dye mordants are in the Mordant layer in one of the usual hydrophilic Binder dispersed, e.g. B. in gelatin, polyvinyl alcohol, Polyvinyl pyrrolidone, fully or partially hydrolyzed Cellulose esters. Of course you can too some binders act as mordants, e.g. B. polymers of nitrogenous, possibly quaternary Bases, such as N-methyl-4-vinylpyridine, 4- Vinyl pyridine, 1-vinyl imidazole, such as described in US-A-24 84 430. Other useful stains Binding agents are, for example, guanylhydrazone derivatives of alkyl vinyl ketone polymers, such as described in US-A-28 82 156, or Guanylhydrazone derivatives of acylstyrene polymers, such as for example described in DE-A-20 09 498. In general however, the latter will be terminated Binders other binders, e.g. B. add gelatin.

The color photographic used in the method according to the invention Recording material contains on a dimensionally stable substrate at least one binder layer, which is a photosensitive silver halide, optionally in combination with an essentially non-photosensitive silver salt, and a non-diffusing coloring compound, which by Development to provide a diffusible dye can contains.  

An essential part of the invention used color photographic recording material is the silver halide made from silver chloride, Silver bromide, silver iodide or mixtures thereof and a particle size between 0.02 and 2.0 µm, can preferably have between 0.1 and 1.0 microns. The Silver halide grains can have a regular crystal structure, for example in the form of cubes or octahedra exhibit. But you can also use an irregular one Have crystal structure or in platelet form be. In the case of mixed crystals, the silver halides evenly over the entire crystal cross section be distributed. The silver halide composition can but also different in different areas be. So can also silver halide emulsions layered grain structure can be used in which at least two layers with a different one Silver halide composition are present. Usually become negative working silver halide emulsions used; but in other embodiments also directly positive working silver halide emulsions are used, such as those in DE-A- 23 32 802, DE-A-23 08 239 and DE-A-22 11 728 will. The photosensitive emulsion can be classified as unsensitized Silver halide are present or else through suitable additives chemically and / or spectrally be sensitized using the spectral sensitizer added before, during and after chemical ripening can be.  

The amount of the photosensitive silver halide can in the respective layer between 0.01 and 3.0 g per m², the actual amount used Silver halide as required the reactants used and the desired ones Effects.

In photographic developable by heat treatment It is known that recording materials can be used in many ways in addition to the photosensitive silver halide other substantially non-photosensitive or in any case, much less light-sensitive silver salts be used. Additions of are advantageous organic silver salts that are about the same or heavier are soluble as the photosensitive silver halide. Silver salts of organic, for example, are suitable cyclic imino compounds. In preferred examples include silver salts of benzotriazole and its Derivatives such as alkyl, hydroxy, sulfo or halogen-substituted benzotriazoles. The organic Silver salt compound that can be added in molar excess or deficit or equimolar to Silver halide compound can be added. It is that adapt to the respective requirements in the layer structure.  

Another essential part of the in the invention Process used photosensitive Recording material is a non-diffusing coloring compound. This can result in a the development of the redox reaction that is diffusible Release dye. It will be as follows referred to as paint splitter.

In the paint releasers used according to the invention there are a variety of connection types, all of which differ in their bond strength distinguish redox-dependent link, which one Dye residue with a ballast residue Carrier remainder linked.

In this context is also a summary Representation of the subject area in Angew. Chem. Int. Ed. Engl. 22 (1983), 191-209, in which the most important of the known systems are described.

Redox-active have proven to be particularly advantageous Color releaser of the formula

BALLAST - REDOX - DYE,

in what mean

A ballast remnant  REDOX a redox active group, i. H. a group, the under the conditions of alkaline Development can be oxidized or reduced and depending on whether they are oxidized or in the reduced state, in different extent of an elimination reaction, a nucleophilic displacement reaction, a hydrolysis or is subject to another cleavage reaction with the result that the rest of DYE is split off, and DYE the rest of a diffusible dye, e.g. B. a yellow, purple or Cyan dye, or the rest of one Dye precursor.

Ballast residues are residues that make it possible to the color releasers according to the invention in the commonly used in photographic materials store hydrophilic colloids in a diffusion-resistant manner. For this are preferably suitable organic radicals, in general straight chain or branched aliphatic groups with generally 8 to 20 carbon atoms and optionally also carbocyclic or heterocyclic if appropriate contain aromatic groups. With the rest These residues are part of the molecule either directly or indirectly, e.g. B. connected via one of the following groups: -NHCO-, NHSO₂-, -NR-, where R is hydrogen or alkyl means -O- or -S-. In addition, the ballast residue  also contain water-solubilizing groups, such as. B. Sulfo groups or carboxyl groups, also in anionic Form can exist. Because the diffusion properties on the molecular size of the total compound used depend, in certain cases it is sufficient e.g. B. if the total molecule used is large enough, use short-chain residues as ballast residues.

Redox-active carrier residues of the structure BALLAST-REDOX- and corresponding color releasers are in a wide variety Embodiments known. For a detailed description can be dispensed with at this point to the overview article in the app. Chem. Int. Ed. Engl. 22 (1983) 191-209.

For the sake of explanation only, a few examples of redox-active carrier residues are listed below, from which a dye residue is split off in accordance with an image-related oxidation or reduction:

The groups enclosed in brackets are functional Groups of the dye residue and become together with this from the remaining part of the carrier rest separated. The functional group can to act as a substituent that is immediate Influence on the absorption and possibly complex formation properties of the released dye can. The functional group, on the other hand, can but also from the chromophore of the dye through a Intermediate link or link be separated. The functional group can also eventually together with the pontic the diffusion and pickling behavior of the released Dye. Suitable links are, for example Alkylene or aryl groups.

The residues of are basically as dye residues Dyes of all dye classes are suitable, insofar as they are sufficiently diffusible to leave the photosensitive Layer of photosensitive material in one Diffuse image receiving layer. To this Purpose can dye residues with one or more alkali-solubilizing groups. As an alkali solubilizer Groups are suitable among others Carboxyl groups, sulfo groups, sulfonamide groups as well aromatic hydroxyl groups. Such alkali solubilizing Groups can be used in the invention Color splitters already pre-formed or only from the cleavage of the dye residue from that with ballast groups contaminated carrier residue result. Of dyes, those particularly for the method according to the invention  suitable are to be mentioned: azo dyes, Azomethine dyes, anthraquinone dyes, phthalocyanine dyes, indigoid dyes, triphenylmethane dyes, including such dyes with Metal ions are complexed or can be complexed.

Among the residues of dye precursors are the residues to understand such connections that take place in the course of photographic Processing, especially under the conditions the development of heat, be it through oxidation, be it through coupling, through complex formation or through Exposure of an auxochrome group in a chromophore System, for example by saponification, in dyes be transferred. Dye precursors in this Leuco dyes, couplers or can also be useful Dyes that are processed in others Dyes are converted. Unless a distinction between dye residues and the residues of Dye precursors is essential the latter should also be called the following Dye residues can be understood.

Suitable color releasing agents are described, for example, in:
US-A-32 27 550, US-A-34 43 939, US-A-34 43 940,
DE-A-19 30 215, DE-A-22 42 762, DE-A-24 02 900,
DE-A-24 06 664, DE-A-25 05 248, DE-A-25 43 902,
DE-A-26 13 005, DE-A-26 45 656, DE-A-28 09 716,
DE-A-28 23 159, BE-A-8 61 241, EP-A-00 04 399,
EP-A-00 04 400, DE-A-30 08 588, DE-A-30 14 669,
GB-A-80 12 242.

The paint releasers can in some embodiments of the heat development process according to the invention as oxidizable or couplable paint releasers, in other than reducible color releasers. Each according to whether the dye is from the oxidized or from the reduced form of the paint release is released, is obtained using conventional negative working Silver halide emulsions from the original one negative or positive exposure. One can, therefore, as desired by choosing suitable color releasing systems positive or create negative pictures.

Oxidizable paint releasers are particularly suitable described for example in DE-A-26 45 656.

If the paint releaser is oxidizable, then it provides itself represents a reducing agent which is immediately or indirectly with the participation of electron transfer agents (electron transfer agent, ETA) through the image exposed silver halide is oxidized. Here there is a pictorial differentiation with regard to the ability to release the diffusible dye. If, on the other hand, the paint release is reducible then you should use it in combination with a reducing agent present in a limited amount, a so-called electron donor compound or an electron donor precursor compound found in this Case next to the paint splitter and the photosensitive  Silver halide contained in the same binder layer is. Even in the case of using reducible Color release in combination with electron donor compounds the participation of electron transfer agents turn out to be cheap.

For creating positive color images of positive ones Templates (original) when using negative working Silver halide emulsions are suitable, for example recording material according to the invention, the reducible Paint releaser with a carrier residue of the following Formula contains:

in what mean

R1 alkyl or aryl; R²alkyl, aryl or a group together with R³ completed an encoded ring; R³hydrogen, alkyl, aryl, hydroxyl, halogen such as Chlorine or bromine, amino, alkylamino, dialkylamino including cyclic amino groups (such as piperidino, Morpholino) acylamino, alkylthio, alkoxy, Aroxy, Sulfo, or a grouping together with R² completed a condensed ring;  R⁴alkyl; R⁵alkyl or preferably hydrogen,

and wherein at least one of R¹ to R⁴ is one Contains ballast residue.

That in combination with a reducible paint splitter electron donor compound used serves equally as a reducing agent for the silver halide, and Paint splitter. The fact that the silver halide and Color releasing in the oxidation of the electron donor compound sort of compete with each other, the former is superior to the latter the existing silver halide according to a previous one figurative exposure determining for the Image areas within which the paint splitter passes through the electron donor compound in its reduced form is transferred.

The electron donor compound present in a limited amount is under the conditions of development, e.g. B. when warming the imagewise exposed color photographic Recording material, depending on the extent of the exposure oxidizes and consequently no longer stands for a reaction with the paint splitter. This creates a visual distribution, as it were on unused electron donor compound.  

As an electron donor compound, for example, are not or only slightly diffusing derivatives of hydroquinone, of benzisoxazolone, p-aminophenol or ascorbic acid (e.g. ascorbyl palminate) (DE-A-28 09 716).

Other examples of electron donor compounds are from DE-A-29 47 425, DE-A-30 06 268, DE-A-31 30 842, DE-A-31 44 037, DE-A-32 17 877 and EP-A-01 24 915 and Research Disclosure 24,305 (July 1984). It has It has been shown that the electron donor compounds mentioned even under the conditions of heat development meet the requirements for them and therefore also as electron donor compounds in the context of the present Invention are suitable. Particularly suitable are those electron donor compounds that are only under the conditions of heat development in the layer corresponding electron donor precursor compounds be formed, d. H. Electron donor compounds that in the recording material before development only in in a masked form, in which it is practical are ineffective. Under the conditions of heat development then the electron donor compounds, which are initially ineffective converted into its effective form by for example, certain protective groups hydrolytically be split off. In the present case, the mentioned electron donor precursor compounds as electron donor compound Roger that.  

In a further embodiment, couplable ones can also be used Paint releasers are used as a result a coupling reaction a diffusible dye can release. There are two options. In the first case, the dye is only through chromogenic coupling formed, with a diffusion-inhibiting Split the ballast group from the coupling position becomes. In the other case there are no diffuses Coupler in the coupling point one pre-formed dye residue as an escape group included, which split off by coupling and thus becomes diffusible. Such systems are, for example in US-A-32 27 550. With the paint splitter it can also be a polymer Couplers of the dye-releasing type act like they are described for example in DE-A-34 22 455.

The essential components of color photography mentioned Recording material, namely the silver halide emulsion and the paint releasing agent, if necessary in combination with an electron donor compound, are next to each other dispersed in a binder in front. This can equally be hydrophobic act like hydrophilic binders, but the latter are prefers. As a binder for the photosensitive Layer preferably gelatin is used. This can however in whole or in part by other natural or synthetic binders to be replaced. Natural Binders are e.g. B. alginic acid and its derivatives such as Salts, esters or amides, cellulose derivatives such as Carboxymethyl cellulose, alkyl cellulose such as hydroxyethyl cellulose, Starch and its derivatives as well  Caragenate suitable. On synthetic binders mentions polyvinyl alcohol, partially saponified polyvinyl acetate and polyvinyl pyrrolidone.

Examples of hydrophobic binders are polymers made from polymerizable ethylenically unsaturated monomers such as alkyl acrylates, alkyl methacrylates, styrene, vinyl chloride, Vinyl acetate, acrylonitrile and acrylamides. Furthermore, polyester, polyurethane compounds and waxes are used. Such polymers can be used for example in latex form.

The photosensitive binder layer contains for the Generation of monochrome color images associated with the photosensitive silver halide one or more Color releasers, from which dyes of a certain Color to be released. The total resulting Color can change by mixing several dyes surrender. In this way it is also possible to go through exactly coordinated mixing of several color releasers of different Color black and white images. To The production of multicolored color images includes color photography Recording material of the present invention several, d. H. usually three, assignments of Color releasers and different spectrally sensitized Silver halide, preferably each the absorption area of the released from the paint splitter Dye with the range of spectral Sensitivity of the associated silver halide dis essentially coincides. The different assignments from color releaser and assigned silver halide  can be in different binder layers of color photographic Recording material housed be, preferably between these different Binder layers separating layers from a water-permeable Binders, e.g. B. gelatin, are the for example a scavenger for developer oxidation products included, which is essentially the function have different assignments from each other separate and also to counteract a color falsification. In such a case, it contains color photography Recording material of the present Invention, for example, a light-sensitive binder layer, in which the silver halide contained therein mainly sensitive to red due to spectral sensitization and in which there is a teal color splitter contains a further light-sensitive binder layer, in which the silver halide contained therein mainly sensitive to green due to spectral sensitization and in which there is a purple dye releaser and a third photosensitive binder layer, in which the silver halide contained therein due to self sensitivity or through spectral sensitization predominantly blue sensitive and contains a yellow dye releaser is.

In another embodiment of the present Invention, each of the aforementioned associations is made from photosensitive Silver halide and color releaser in the form a so-called complex coacervate.  

Under a complex coacervate is a dispersion form understood in which a mixture of the essentials Ingredients in a common casing from a hardened Binder is included. Such dispersions are also known as packet emulsions. they are obtained through complex coacervation.

Methods of making a packet emulsion in which a color-forming substance through complex coacervation is incorporated, for example, are described in US-A-32 76 869 and US-A-33 96 026. The use of Package emulsions in heat-developable recording materials is described for example in DE-A-35 10 685.

The use of packet emulsions enables according to the invention the combination of several emulsion parts finally the relevant paint splitter in one Binder layer without the spectral assignment lost and thereby a color falsification occurs. This is possible because of the extent of the Exposure of a specific silver halide particle is almost exclusively decisive for the extent of Dye release from the dye releaser that is in the same coacervate particle (package) like the silver halide. The use of packet emulsions thus enables the accommodation of one blue-sensitive, one sensitive to green and one sensitive to red Silver halide emulsion and each spectral assigned paint releasers in the same binder layer, without serious color falsification must be feared.  

In addition to the components already mentioned, this can Color photographic recording material used according to the invention contain other ingredients and auxiliary substances. These other ingredients or auxiliaries can be in a photosensitive layer or in a not contain sensitive layer.

Such auxiliaries are, for example, auxiliary developers. These auxiliary developers generally have developing ones Properties for exposed silver halide; in the present In the first place, they have a beneficial effect on the between the exposed silver halide and the reactions occurring in the reducing agent, the reducing agent being oxidizable in the case of use Color releasers to be identical to the latter can, or in the case of the use of reducible paint releasers in turn reacted with the paint splitter. Since this reaction is mainly in a carry over Electrons exist, the auxiliary developers are also called Electron transfer agent; ETA).

Examples of suitable auxiliary developers include hydroquinone, Catechol, pyrogallol, hydroxylamine, ascorbic acid, 1-phenyl-3-pyrazolidone and their derivatives, e.g. B. 4-methyl-1-phenyl-3-pyrazolidone, 4,4-dimethyl-1- phenyl-3-pyrazolidone, 4-hydroxymethyl-4-methyl-1-phenyl- 3-pyrazolidone, 4-hydroxymethyl-4-methyl-1-tolyl-3-pyrazolidone and 4,4-dihydroxymethyl-1-phenyl-3-pyrazolidone. In certain cases it is advantageous to mask this Form with an alkaline removable protective group  to use. Because the auxiliary developers, as it were perform a catalytic function, it is not necessary that they are present in stoichiometric amounts are. In general, it is sufficient if they are in quantities up to 1/2 mole per mole of paint releasing agent in the layer available. The incorporation into the shift can for example from solutions in water-soluble solvents or in the form of aqueous dispersions which were obtained using oil formers.

Color developers are required for coupling color systems. Please refer to the usual p-phenylenediamine developers, furthermore on aminophenols. For reasons of stability it is advantageous to add the developer use in masked form, with the protecting group is then split off under the process conditions.

In some configurations, the photosensitive element can of the method according to the invention also an image receiving layer included, especially if not already the non-photosensitive base precursor containing sheet-like material such Contains image receiving layer. Those in such image receiving layers Pickling agents used have already been used mentioned. The image receiving layer can in this case arranged above the photosensitive layers be below or between the photosensitive Layers and the layer support. In both cases the substrate is transparent and it is continue between the image receiving layer and the  photosensitive layers an alkali-permeable pigment-containing light-reflecting binder layer, that of the optical separation between negative and positive and as an aesthetically pleasing background for the transferred positive color image.

For integral layer units made of light-sensitive Element and image receiving element can also be stripping layers with a separation of the enable two layer elements.

The supports for the photosensitive element and if necessary for the image receiving element at the process temperature remains dimensionally stable. Come into question usual film or paper documents. Prefers polyester materials are used.

As a curing agent for both the photosensitive Element as well as for the image receiving element can conventional photographic materials Hardening agents as well as quick and instant hardeners are used will. Suitable curing agents are, for example described in DE-A-24 39 551.

The photosensitive element (= first leaf-shaped Material) is exposed imagewise, if necessary through the substrate if it is transparent. For processing becomes either the photosensitive element or the non-photosensitive sheet (= second sheet-shaped Material) or both with sufficient  Amount of water or one consisting mainly of water Liquid moistened, whereupon the two materials be folded and heated on the coating side. The aqueous liquid can optionally be a wetting agent and / or contain limescale. After development and transferring the color image into the image receiving layer become the two leaf-shaped materials separated from each other; the color image transferred is then depending on the design, as a supervisory picture or slide visible.

Example 1

A photosensitive element of a color photographic Recording material for the color diffusion process was by plotting the one described below Layers on a transparent substrate Polyethylene terephthalate manufactured. The quantities each refer to 1 m².

Layer 1

A layer with a green sensitized, with sulfur matured silver halide emulsion from 0.5 g of NgNO₃ (20 mol% AgCl, 80 mol% AgBr; average grain diameter 0.4 µm), with 0.001 g of 1-phenyl-5-mercaptotetrazole, 0.05 g 5-methylbenzotriazole, 0.05 g potassium bromide, 0.3 g color releaser M-1 (emulsified in 0.15 g diethyl lauramide), 0.06 g of compound SC and 1 g of gelatin.

Layer 2

A layer with 0.035 g of 4-methyl-4-hydroxymethyl-1- phenyl-3-pyrazolidone, 0.008 g sodium sulfite, 0.3 g der Compound SC, 0.03 g of compound WA and 0.8 g of gelatin. With this layer, that too became Hardener applied.  

Paint splitter M-1

Connection SC

WA connection

An image receiving member for the recording material was produced by on a substrate from paper coated with polyethylene following Layers were applied one after the other. The quantities also refer to 1 m² each.

Layer 1

A layer with 2 g guanidinium carbonate, 0.007 g of Compound WA and 1 g gelatin.  

Layer 2

A stain layer with 2 g polyurethane stain (from 4,4′- Diphenylmethane diisocyanate and N-ethyldiethanolamine, quaternized with epichlorohydrin according to DE-A-26 31 521, Example 1), 0.035 g of compound WA and 2 g of gelatin.

Layer 3

An intermediate layer with 1 g gelatin.

Layer 4

A hardening layer with 0.25 g formalin and 0.85 g gelatin.

The processing was done in such a way that a step wedge exposed exposure material 3 s dipped in water and then in the layer Contact with the image receiving element heated to 90 ° C for 30 s has been. After that, both elements were separated from each other Cut. One was on the image receiving element purple negative image of the exposure original receive. When measured behind the green filter, the minimum density was at 0.16 and the maximum density at 2.15.

Example 2

A photosensitive element was made with following layers.  

Layer 1

A layer with a blue-sensitized, with sulfur matured silver halide emulsion from 0.5 g of AgNO₃ (20 mol% AgCl, 80 mol% AgBr; average grain diameter 0.8 µm), with 0.004 g of 1-phenyl-5-mercaptotetrazole, 0.05 g 5-methylbenzotriazole, 0.05 g potassium bromide, 0.4 g color releasing compound Y-1 (emulsified in 0.2 g diethyl lauramide), 0.06 g of compound SC and 1 g of gelatin.

Layer 2

A layer with 0.035 g of 4-methyl-4-hydroxymethyl-1- phenyl-3-pyrazolidone, 0.008 g sodium sulfite, 0.3 g der Compound SC and 0.8 g gelatin.

Layer 3

A protective layer with 0.5 g gelatin. With this The hardener was applied simultaneously to the layer.

Paint splitter Y-1

Processing was carried out as described in Example 1. The contact time in this case was 15 s. It was received a yellow negative image of the exposure original. The minimum density was 0.17 and the maximum density 2.12. Measurement behind blue filter.  

Example 3

A photosensitive element was made with following layers.

Layer 1

A layer with a red sensitized, with gold / - Sulfur-ripened silver halide emulsion from 0.5 g AgNO₃ (4 mol% AgCl, 89 mol% AgBr, 7 mol% AgI; medium Grain diameter 0.3 µm), with 0.5 mg 1-phenyl-5- mercaptotetrazole, 0.05 g 5-methylbenzotriazole, 0.05 g Potassium bromide, 0.2 g color releasing agent C-1 (emulsified in 0.1 g of diethyl lauramide), 0.06 g of the compound SC and 1 g Gelatin.

Layers 2 and 3 correspond to layers 2 and 3 in Example 2.

Paint releaser C-1

The same image receiving element was used for the development as used in Example 1, but with the Difference that in layer 3 0.1 g of 5-methylbenzotriazole were stored.  

Processing was carried out as described in Example 1. In this case, a blue-green negative image of the Get exposure template. The minimum density was 0.14, the maximum density 1.70 (measurement behind red filter).

Example 4

A photosensitive element was made with following layers.

Layer 1

 A layer with a green sensitized, with sulfur matured silver halide emulsion from 0.5 g of AgNO₃ (20 mol% AgCl, 80 mol% AgBr; average grain diameter 0.4 µm), with 0.5 mg of 1-phenyl-5-mercaptotetrazole, 0.05 g 5-methylbenzene triazole, 0.05 g potassium bromide, 0.3 g color releaser M-2 (emulsified in 0.3 g tricresyl phosphate), 0.06 g of compound SC and 1.3 g of gelatin.

Layers 2 and 3 corresponded to layers 2 and 3 in Example 2.

Paint splitter M-2

The processing corresponded to example 1. It was a Obtained purple negative image of the original. The The minimum density was 0.27 and the maximum density was 1.98.

Example 5

Layer structure and processing corresponded to example 4, but with the difference that in layer 1 instead of M-2 0.3 g of the paint releasing agent M-3 were used. At After a processing time of 60 s at 90 ° C the minimum density was at 0.29 and the maximum density at 2.19.

Paint splitter M-3

Example 6

Visual structure and processing corresponded to example 4, but with the difference that in layer 1 0.4 g of Color releaser M-4 were used. With a process time of 5 s at 90 ° C was a minimum density of 0.26 and get a maximum density of 1.36.  

Paint splitter M-4

Example 7

Example 4 was repeated, but with 0.35 g of the Paint splitter M-5. The process time was 60 s. The Minimum / maximum densities were 0.19 / 1.02.

Paint splitter M-5

Example 8

An image receiving element was manufactured by on a layer support made of polyethylene Apply the following layers of paper one after the other were. The quantities given relate to 1 m².

Layer 1 corresponded to Layer 2 from Example 1.  

Layer 2

A layer with 2.8 g of compound BD, 0.007 g of Compound WA and 1 g gelatin.

Layer 3

A hardening layer with 0.25 g formalin and 0.85 g Gelatin.

Connection BD

As a photosensitive element for processing with a layer structure served the above image receiving element, which corresponded to that in Example 4, but with the difference that layer 1 contained 0.3 g of the paint releasing agent M-1. The processing corresponded to example 1. As the minimum density was a value of 0.13 as the maximum density Get value of 2.04.

Example 9

For the production of a light-sensitive element was a polyethylene terephthalate with the following layers.  

Layer 1

A layer with a blue sensitive, with sulfur matured silver halide emulsion from 0.5 g of AgNO₃ (20 mol% AgCl, 80 mol% AgBr; average grain diameter 0.86 µm), with 0.005 g of 2-mercaptobenzimidazole-5-sulfonic acid, 0.25 g of 1-phenyl-5-cyanoethylthiotetrazole, 0.02 g Potassium bromide, 0.4 g of the color releasing agent Y-1 (emulsified in 0.2 g diethyl lauramide) and 1 g gelatin.

Layer 2

An intermediate layer of 1 g gelatin, with 0.5 g of the Compound SC, 0.36 g of 4-methyl-4-hydroxymethyl-1-phenyl 3-pyrazolidone, 0.008 g sodium sulfite and 0.03 g of the compound WA.

Layer 3

A layer with a green sensitive, with sulfur matured silver halide emulsion from 0.5 g of AgNO₃ (20 mol% AgCl, 80 mol% AgBr; average grain diameter 0.41 µm), with 0.005 g of 2-mercaptobenzimidazole-5-sulfonic acid, 0.25 g of 1-phenyl-5-cyanoethylthiotetrazole, 0.05 g Potassium bromide, 0.32 g of the paint releasing agent M-1 (emulsified in 0.16 g of diethyl lauramide), 0.025 g of compound SC and 1.55 g gelatin.  

Layer 4

An intermediate layer of 1 g gelatin, with 0.5 g of the Compound SC, 0.36 g of 4-methyl-4-hydroxymethyl-1-phenyl 3-pyrazolidone, 0.008 g sodium sulfite and 0.03 g of the compound WA.

Layer 5

A layer with a red sensitive, with sulfur matured silver halide emulsion from 0.5 g of AgNO₃ (20 mol% AgCl, 80 mol% AgBr; average grain diameter 0.48 µm), with 0.005 g of 2-mercaptobenzimidazole-5-sulfonic acid, 0.25 g of 1-phenyl-5-cyanoethylthiotetrazole, 0.02 g Potassium bromide, 0.23 g of the color releasing agent C-2 (emulsified in 0.12 g diethyl lauramide) and 0.9 g gelatin.

Paint releaser C-2

Layer 6

A top layer of 2.0 g gelatin, 0.05 g of the compound SC and 0.3 g of carbon black.  

Layer 7

A hardening layer with 0.5 g gelatin, which is an instant hardener was added.

A basic image-receiving element on one with polyethylene coated paper was with the following layer arrangement manufactured;

Layer 1

A base dispenser layer consisting of 3 g gelatin, 4 g Guanidinium carbonate and 0.003 g of compound WA.

Layer 2

A pickling layer with 2 g of gelatin and 2 g of that in Example 1 dye stain described.

Layer 3

An intermediate layer with 1 g gelatin.

Layer 4

A hardening layer with 0.85 g gelatin and 0.25 g Formalin.

The photosensitive element was covered by the pad exposed and processed as described in Example 1. In the image receiving section were made for negative reproduction measured the following color densities with the exposure original:  

Example 10

A photosensitive member was manufactured by the following layers on a polyethylene terephthalate support were applied.

Layer 1

A green sensitive silver halide emulsion as in Example 1 from 0.38 g of AgNO₃, with 0.19 g of 5-methylbenzotrialzole, 0.002 g of potassium bromide, 0.24 g of the paint releasing agent M-6, 0.17 g of the electron donor ED (M-6 and DE emulsified in an oil former mixture of 0.1 g diethyl lauramide and 0.31 g of a hydrophilic oil former OF) and 0.64 g gelatin.

Paint splitter M-6

Layer 2

An auxiliary layer consisting of 1.5 g gelatin and 0.12 g of 4-methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone and 0.03 g sodium sulfite.

Layer 3

A hardening layer consisting of 0.5 g gelatin and an emergency hardener.

This recording material was processed with the basic image receiving sheet described in Example 9 under the conditions given in Example 1. in the Image-receiving element resulted in a purple-colored positive reproduction the exposure template. The behind Green filter measured minimum density was 0.10 and the Maximum density at 1.85.

Example 11

It became a photosensitive member as in Example 10 made, the layer 1 in the following manner was changed:

Layer 1

A green sensitive silver halide emulsion as in Example 1 from 0.38 g AgNO₃, with 0.07 g 5-methylbenzotriazole, 0.24 g of the paint releasing agent M-6 (emulsified in 0.24 g of diethyl lauramide) and 0.12 g of compound SC.  

Processed under the same conditions as in Example 10, 0.27 results for D _min and 1.77 for D _max .

Example 12

It became a positive working, multi-colored recording material created in the on a polyethylene terephthalate support following layers applied were:

Layer 1

A layer with a red sensitive, with sulfur matured silver halide emulsion from 0.38 g of AgNO₃ (20 mol% AgCl, 80 mol% AgBr; average grain diameter 0.48 µm), with 0.075 g of 5-mercaptobenzotriazole, 0.24 g of the Color releaser C-1, 0.13 g of the electron donor ED (emulsifies in 0.17 g diethyl lauramide and 0.2 g des hydrophilic oil former OF) and 0.93 g gelatin.

Paint releaser C-3

Layer 2

An intermediate layer of 0.9 g gelatin, with 0.52 g of the Compound SC, 0.12 g of 4,4-dimethyl-1-phenyl-3-pyrazolidone, 0.03 g sodium sulfite and 0.028 g of the compound WA.

Layer 3

A layer with a green sensitive, with sulfur matured silver halide emulsion from 0.38 g of AgNO₃ (20 mol% AgCl, 80 mol% AgBr; average grain diameter 0.41 µm), with 0.004 g of 2-mercaptobenzimidazole-5-sulfonic acid, 0.002 g potassium bromide, 0.188 g 5-methylbenzotriazole, 0.242 g of the color releasing agent M-6, 0.17 g of the electron donor ED (M-6 and ED emulsified in an oil former mixture from 0.1 g of diethyl lauramide and 0.31 g of the hydrophilic oil former OF) and 0.97 g gelatin.

Layer 4

An intermediate layer of 1.6 g of gelatin, with 0.52 g of the Compound SC, 0.8 g of colanyl yellow HR dispersant (from Hoechst) and 0.02 g of compound WA.

Layer 5

A layer with a blue sensitive, with sulfur matured silver halide emulsion from 0.5 g of AgNO₃ (20 mol% AgCl, 80 mol% AgBr; average grain diameter 0.40 µm), with 0.25 g 5-methylbenzotriazole, 0.005 g 2- Mercatobenzimidazole-5-sulfonic acid,  0.264 g of the paint release Y-2 and 0.226 g of compound ED (emulsified in 0.15 g of diethyl lauramide) and 0.22 g of the hydrophilic Oil former OF) and 0.92 g gelatin.

Paint splitter Y-2

Layer 6

A top layer of 2.1 g gelatin, 0.02 g of the compound WA and an emergency hardener.

Exposure and processing was carried out as described in Example 1 with the basic explained in Example 9 Image receiving sheet.

For the positive reproduction of the exposure template the following densities were measured:

Example 13

An image receiving element according to Example 9 was produced, by layer 1 2 g of guanidinium carbonate were added.

Example 14

An image receiving element as in Example 13 but in Layer 1 with 3.0 g of potassium carbonate instead of guanidinium carbonate.

Example 15

As in Example 14, but with 1.5 g of potassium carbonate.

The image receiving elements were compared from the Examples 9, 13, 14 and 15 with that described in Example 10 photosensitive element combined and after a diving time in water of 2 s at room temperature, Contacted for 30 s at 96 ° C. In the respective reception element were behind the green filter in the Table values determined:

The result shows that guanidinium carbonate is one for this method represents a particularly suitable base.

Claims (8)

1. A process for producing colored images by the photographic color diffusion process, in which a first sheet-like material which contains at least one photosensitive silver halide emulsion layer and at least one non-diffusing coloring compound which is capable of being imagewise split during development and thereby releasing a diffusible dye, and / or a second non-light-sensitive sheet material is / is moistened with an aqueous liquid, the two sheet materials in contact on the coating side are heated to 50 to 120 ° C and then separated from one another, characterized in that the second sheet material contains at least one binder layer with a salt of a weak inorganic acid and a strong organic base contained therein. 2. The method according to claim 1, characterized in that that processing takes place at 70 to 105 ° C. 3. The method according to claim 1, characterized in that the second non-photosensitive sheet Material can be dyed by diffusing dyes Contains layer.   4. The method according to any one of claims 1 to 3, characterized characterized in that in the second non-photosensitive sheet-like material included Salt a carbonate of a strong organic base is. 5. The method according to claim 4, characterized in that the strong organic base guanidine or a Is amidine. 6. The method according to claim 4, characterized in that the strong organic base is a compound of the following formula (I) wherein R¹, R², R³H or alkyl; R⁴H, alkyl, aryl, an amino group or a guanidino group or R¹ together with R² denotes an alkylene group with 2, 3 or 4 C atoms and / or R³ together with R⁴ denotes an alkylene group with 3, 4 or 5 C atoms, a vinylene group, a divinylene group or a group of the formula wherein R1 has the meaning given and p is 2, 3 or 4; Veine vinylene group; n 0 or 1. 7. The method according to any one of claims 1 to 6, characterized in that the coloring compound used in the first sheet material is a redox-active color releaser of the following formula BALLAST - REDOX - FARBSTOFF,
in which BALLAST is a ballast residue REDOX a redix-active group, that is to say a group which can be oxidized or reduced under the conditions of alkaline development and, depending on whether it is in the oxidized or in the reduced state, to different degrees of an elimination reaction, a nucleophilic displacement reaction, a hydrolysis or another Cleavage reaction is subject to the result that the remainder of DYE is cleaved off, and DYE the remainder of a diffusible dye, e.g. B. a yellow, purple or teal dye, or the rest of a dye precursor, 8. The method according to claim 7, characterized in that a reducible color splitter with a carrier residue of the following formula is used wherein R¹ is alkyl or aryl; R² alkyl, aryl or a group which together with R³ completes a fused ring; R³hydrogen, alkyl, aryl, hydroxyl, halogen such as chlorine or bromine, amino, alkylamino, dialkylamino including cyclic amino groups (such as piperidino, morpholino), acylamino, alkylthio, alkoxy, aroxy, sulfo, or a group which together with R² completes a fused ring ; R⁴alkyl; R⁵alkyl or preferably hydrogen, and wherein at least one of the radicals R¹ to R⁴ contains a ballast radical.