EP0027231B1 - Photographic material comprising a mordant layer - Google Patents

Description

The invention relates to a photographic material comprising a layer support and at least one layer applied thereon, which contains a mordant for acid dyes consisting of a polymer.

The use of polymeric mordants for acidic dyes in photographic layers is a known measure. In this way, either diffusing acidic dyes can be defined (image-receiving layer) or it can further increase the diffusion resistance in the case of acidic dyes or other photographically active compounds which have a low tendency to diffuse be improved. In general, photographic layers can include photosensitive layers, e.g. Silver halide emulsion layers, or non-light sensitive layers, e.g. Adhesive layers, intermediate layers, filter layers, antihalation layers and cover layers can be understood.

To carry out the color diffusion transfer process, a light-sensitive material is usually used, which contains coloring compounds in or adjacent to at least one silver halide emulsion layer, and an image-receiving material, consisting essentially of an image-receiving layer arranged on a layer support, in which the desired color image is generated by image-transferring diffusing dyes . This requires that there be firm contact between the photosensitive material and the image-receiving layer for at least a finite period within the development time, so that the imagewise distribution of diffusing dyes produced in the photosensitive material as a result of development can be transferred to the image-receiving layer. The contact can be made after development has started or it can have been made before development begins. The latter is the case, for example, if an integral recording material is used in which the light-sensitive material and the image-receiving material form an integral unit. Embodiments of the color diffusion transfer method are known in which such an integral unit continues to exist even after the development process has ended; i.e., the photosensitive material is not separated from the image-receiving material even after the color transfer has taken place. Such an embodiment is described, for example, in DE-A-2 019 430. However, according to another embodiment, the image-receiving material which carries the finished image after the color transfer can also be separated from the light-sensitive material, e.g. be separated by means of a stripping layer arranged between the two. With regard to such an embodiment, reference is made, for example, to DE-A-2 049 688.

From US-A-3709690, suitable polymers are known as mordants for the production of image-receiving layers, which are obtained by quaternizing a polymer having tertiary nitrogen atoms with an alkylating agent or aralkylating agent.

DE-A-2445782 describes water-insoluble polymers as mordants which are prepared by reacting polymers containing chloromethyl groups with tertiary amines and which can be crosslinked by the method described in US Pat. No. 3,859,096. A disadvantage of the use of such mordants in instant photography is that when they are used there is a tendency for the mordant image dyes to migrate from the image areas to non-image areas. This migration of dyes, which is based on the fact that the mordant does not hold the dyes firmly enough, leads to color fringing and, in particular, to reduced color densities during storage.

From DE-A-2551 786 it is also known to use water-insoluble polymers in dispersion form for pickling dyes. These latex stains have the advantage that they can be prepared in a simple manner with the known binders, ready to cast, stable solutions. However, it is disadvantageous that the mordant layers produced from the casting solutions do not bind the dyes sufficiently. Sufficient color densities are achieved directly after the transfer of the dyes into the mordant layer, but after storage of the colored mordant layers there is a diffusion of the dyes from the mordant layer into the rest of the layer structure, particularly in the case of a multilayer structure. This back diffusion leads to a reduction in the color densities during storage and thus to an undesired fading of the image.

The object of the invention is to find suitable diffusion-resistant polymers as mordants for the production of image-receiving layers, which are able to hold the image dyes transferred to the image-receiving layer in such a way that the image dyes can no longer migrate, so that dye images of increased density can be obtained even when stored over longer periods of time .

It has been found that the polymeric mordants described below can be used advantageously wherever acidic dyes have to be mordanted. They are particularly suitable as pickling agents for image-receiving layers.

worin bedeuten :

• Q ein Stickstoff- oder Phosphoratom ;
• R¹, R² und R³ jeweils einen carbocyclischen Rest oder einen Alkylrest wobei R¹, R² und R³ die gleiche oder eine voneinander verschiedene Bedeutung haben können, oder zwei der genannten Reste vervollständigen zusammen einen 5- oder 6-gliedrigen heterocyclischen Ring,
• R⁴ Wasserstoff oder Alkyl,
• X^⊖ ein Anion.

The invention relates to a photographic material comprising a layer support and at least one layer arranged thereon, which contains a mordant for acidic dyes consisting of a polymer, characterized in that it contains as a mordant a polymer with at least 10 mol% of repeating units with the following formula I contains:

in which mean:

• Q is a nitrogen or phosphorus atom;
• R ¹ , R ² and R ³ each represent a carbocyclic radical or an alkyl radical, where R ¹ , R ² and R ^{3 can have} the same or a different meaning, or two of the radicals together complete a 5- or 6-membered heterocyclic ring ,
• R ^{4 is} hydrogen or alkyl,
• X ^⊖ an anion.

The recurring units of the above formula I are to be represented in the following by the symbol A.

Alkyl radicals represented by R ¹ , R ² and R ³ in formula I are straight-chain or branched and normally have 1 to 12 carbon atoms. Examples include methyl, ethyl, propyl, isobutyl, pentyl, hexyl, heptyl, dodecyl.

If in formula IR ¹ , R ² , R ³ the meaning of carbocyclic radicals, then these are optionally substituted cycloalkyl, aralkyl or aryl radicals with preferably 5 to 12 carbon atoms; Possible substituents are, for example: halogen, nitro, cyano, alkyl, alkoxy, alkylthio or alkoxycarbonyl, where in the case of the last-mentioned substituents the alkyl group preferably has 1 to 4 carbon atoms. Examples of such optionally substituted cycloalkyl, aralkyl or aryl radicals are, for example, cyclopentyl, cyclohexyl, benzyl, p-methylbenzyl, chlorobenzyl, nitrobenzyl, cyanobenzyl, methoxybenzyl, methoxycarbonylbenzyl, ethylthiobenzyl, phenyl, tolyl.

Examples of 5- or 6-membered heterocyclic rings completed by two of the radicals R ¹ , R ² and R ³ are, for example, the pyrrolidine, the piperidine and the morpholine ring.

R ¹ and R ² are particularly advantageously methyl and R ^{3 is} a benzyl radical. An alkyl group represented by R ⁴ is preferably a methyl group.

X ^⊖ is a conventional photographically acceptable anion, for example a halide ion, for example bromide or chloride, or a sulfate, alkyl sulfate, alkyl or aryl sulfonate, for example a p-toluenesulfonate, acetate, phosphonate or dialkyl phosphate ion.

worin A die angegebene Bedeutung hat und worin bedeuten

• M den Rest eines polymerisierten Monomeren mit einem polymerisierbaren ethylenisch ungesättigten Rest ;
• V den Rest eines polymerisierten Monomeren mit mindestens zwei polymerisierbaren ethylenisch ungesättigten Resten, z.B. Vinylresten ;
• x, y, z, die den Anteil der einzelnen Comonomeren am Polymer kennzeichnenden Zahlwerte und zwar derart, daß
• x für 10 bis 99 Mol-%
• y für 0 bis 90 Mol-%
• z für 0 bis 5 Mol-% steht.

The polymer according to the invention preferably contains recurring units of the formula II below.

where A has the meaning given and where mean

• M is the residue of a polymerized monomer with a polymerizable ethylenically unsaturated residue;
• V is the residue of a polymerized monomer with at least two polymerizable ethylenically unsaturated residues, for example vinyl residues;
• x, y, z, the numerical values characterizing the proportion of the individual comonomers in the polymer, in such a way that
• x for 10 to 99 mol%
• y for 0 to 90 mol%
• z represents 0 to 5 mol%.

worin bedeuten :

• n eine ganze Zahl größer als 1, vorzugsweise 2, 3 oder 4;
• R⁵ einen n-bindigen organischen Rest ; und
• R⁶ ein Wasserstoffatom oder einen Methylrest.
• R⁵ kann beispielsweise einen 2- oder mehrbindigen organischen Rest bedeuten, der aus Alkylen-, Arylen-, Aralkylen-, Cycloalkylengruppen (bzw. bei mehrbindigen organischen Resten aus den entsprechenden mehrbindigen Analoga der genannten Gruppen), weiter Ester-, Sulfonylester-, Amid-, Sulfonamidgruppen, Ethersauerstoff- und Thioetherschwefelatomen sowie Kombinationen der erwähnten Gruppen und Atome aufgebaut ist. R⁵ kann beispielsweise sein eine Methylen-, Ethylen-, Trimethylen-, Phenylen-, Phenylendioxycarbonyl-, 4,4'-Isopropyliden-bisphenylenoxycarbonyl-, Methylenoxycarbonyl-, Ethylen-dioxycarbonyl-, 1,2,3-Propantri-yl-tris-(oxycarbonyl)-, Cyclohexylen-bis(methylenoxycarbonyl)-, Ethylenbis(oxyethylenoxycarbonyl)-, Ethylidyn-trioxycarbonylgruppe. Vorzugsweise werden dabei solche Monomeren ausgewählt, die in Gegenwart von starkem Alkali stabil sind und nicht besonders reaktiv sind, so daß keine Hydrolyse während der Copolymerisation erfolgt.

Particularly advantageous polymers for producing the mordant layers are those of the formula II, where V is the residue of a monomer polymerizable by addition polymerization with at least two ethylenically unsaturated residues, for example vinyl residues of the following formula III:

in which mean:

• n is an integer greater than 1, preferably 2, 3 or 4;
• R ^{5 is} an n-bonded organic radical; and
• R ^{6 is} a hydrogen atom or a methyl radical.
• R ⁵ can mean, for example, a 2- or multi-bonded organic radical which consists of alkylene, arylene, aralkylene, cycloalkylene groups (or in the case of multi-bonded organic radicals from the ent speaking multivalent analogues of the groups mentioned), further ester, sulfonyl ester, amide, sulfonamide groups, ether oxygen and thioether sulfur atoms and combinations of the groups and atoms mentioned. R ⁵ can be, for example, methylene, ethylene, trimethylene, phenylene, phenylenedioxycarbonyl, 4,4'-isopropylidene bisphenyleneoxycarbonyl, methyleneoxycarbonyl, ethylene dioxycarbonyl, 1,2,3-propanetri-tris - (oxycarbonyl) -, cyclohexylene-bis (methyleneoxycarbonyl) -, ethylene bis (oxyethyleneoxycarbonyl) -, ethylidyn-trioxycarbonyl group. Monomers are preferably selected which are stable in the presence of strong alkali and are not particularly reactive, so that no hydrolysis takes place during the copolymerization.

• Divinylbenzol ; Allylacrylat ; Allylmethacrylat ; N-Allylmethacrylamid ; 4,4'-Isopropylidendiphenyldiacrylat ; 1,3-Butylendiacrylat ; 1,3-Butylendimethacrylat; 1,4-Cyclohexylendimethylendimethacrylat ; Diethylenglykol-dimethacrylat ; Diisopropylenglykoldimethacrylat ; Ethylendiacrylat ; Ethylendimethacrylat ; Ethylidendiacrylat; 1,6-Diacrylamidohexan ; 1,6-Hexamethylendiacrylat ; 1,6-Hexamethylendimethacrylat ; N,N'-Methylenbisacrylamid ; Neopentylglykoldimethacrylat ; Tetraethylenglykoldimethacrylat Tetramethylendiacrylat ; Tetramethylendimethacrylat ; 2,2,2-Trichlorethylidendimethacrylat ; Triethylenglykoldiacrylat ; Triethylenglykoldimethacrylat ; Ethylidyntrimethacrylat ; 1,2,3-Propantriyltriacrylat ; Vinylmethacrylat ; 1,2,4-Trivinylcyclohexan, Tetraallyloxyethan.

Examples of monomers from which the units (V) can be formed are:

• Divinylbenzene; Allyl acrylate; Allyl methacrylate; N-allyl methacrylamide; 4,4'-isopropylidenediphenyl diacrylate; 1,3-butylene diacrylate; 1,3-butylene dimethacrylate; 1,4-cyclohexylene dimethylene dimethacrylate; Diethylene glycol dimethacrylate; Diisopropylene glycol dimethacrylate; Ethylene diacrylate; Ethylene dimethacrylate; Ethylidene diacrylate; 1,6-diacrylamidohexane; 1,6-hexamethylene diacrylate; 1,6-hexamethylene dimethacrylate; N, N'-methylenebisacrylamide; Neopentyl glycol dimethacrylate; Tetraethylene glycol dimethacrylate tetramethylene diacrylate; Tetramethylene dimethacrylate; 2,2,2-trichloroethylidene dimethacrylate; Triethylene glycol diacrylate; Triethylene glycol dimethacrylate; Ethylidyntrimethacrylate; 1,2,3-propane triyl triacrylate; Vinyl methacrylate; 1,2,4-trivinylcyclohexane, tetraallyloxyethane.

Particularly advantageous monomers for the generation of units (V) are trivinylcyclohexane, divinylbenzene, tetraallyloxyethane, 1,4-butylenedl methacrylate. Two or more of the monomers mentioned can also be used next to one another for the production of units (V) of the polymers according to the invention.

A wide variety of monoethylenically unsaturated monomers copolymerizable with the other monomers can be used to produce the units (M). Monomers with conjugated ethylenically unsaturated bonds can also be used here.

• Ethylen ; Propylen ; 1-Buten ; 4-Methylpenten-1 ; Styrol ; α-Methylstyrol ; monoethylenisch ungesättigte Ester von aliphatischen Säuren z.B. Vinylacetate, Isopropenyl-acetat, Allylacetat und dergleichen; Ester von ethylenisch ungesättigten Mono- und Dicarbonsäuren, z.B. Methylmethacrylat, Ethylacrylat, Glycidylacrylat, Glycidylmethacrylat, Butylacrylat, ferner sonstige monoethylenisch ungesättigte Verbindungen wie beispielsweise Acrylnitril, Allylcyanid sowie ferner bestimmte konjugierte Diene, z.B. Butadien, Isopren und 2,3-Dimethylbutadien.

Typical suitable monomers are:

• Ethylene; Propylene; 1-butene; 4-methylpentene-1; Styrene; α-methylstyrene; monoethylenically unsaturated esters of aliphatic acids, for example vinyl acetates, isopropenyl acetate, allyl acetate and the like; Esters of ethylenically unsaturated mono- and dicarboxylic acids, for example methyl methacrylate, ethyl acrylate, glycidyl acrylate, glycidyl methacrylate, butyl acrylate, furthermore other monoethylenically unsaturated compounds such as, for example, acrylonitrile, allyl cyanide and also certain conjugated dienes, for example butadiene, isoprene and 2,3-dimethyl.

The units (V) are preferably present at 1.0 to 5.0 mol%, the units (M) at 0 to 45 mol% and the units with the ω-substituted buten-2-yl- (meth) according to the invention 40 to 99 mol% of acrylate residue (A).

The polymers used according to the invention can be prepared by customary emulsion polymerization processes, for example by emulsion polymerization of a 4-halobutenyl methacrylate with a polyunsaturated monomer (V) and a mono-ethylenically unsaturated monomer (M), expediently in the presence of an anionic surface-active compound, for example sodium lauryl sulfate or in the presence the sodium salt of a sulfonated condensate of an alkylphenol-ethylene oxide condensate (e.g. Alipal (trade name), manufacturer General Dyestuff Corp., USA) and the like, and expediently in the presence of a radical generator or radical initiator, for example in the presence of a free-radical initiator of the redox type, for example in the presence of potassium persulfate Sodium bisulfite; Potassium persulfate Fe ²⁺ ; H ₂ O ₂ -Fe ²⁺ and the like. For example, methods such as those described in US-A-3,072,588 can be used.

worin R¹, R², R³ und Q die angegebene Bedeutung haben, umgesetzt werden, zweckmäßig bei Temperaturen von etwa -20 °C bis etwa 150 °C. Dabei wird ein polymerer Microgel-Latex erhalten.The polymer 4-halogenobutenyl methacrylate latex obtained in this process can be treated with a tertiary amine or tertiary phosphine of the following formula

wherein R ¹ , R ² , R ³ and Q have the meaning given, are implemented, expediently at temperatures from about -20 ° C to about 150 ° C. A polymeric microgel latex is obtained.

The 4-halobutyl (meth) acrylates required as the starting compound are known, for example from US Pat. No. 3,255,163. They can be obtained, for example, by transesterification of methyl (meth) acrylate with 4-halo-2-buten-1-ol . A further production process for the monomers mentioned is described in DE-A-2 827 323. The monomers obtained in this way are either subjected directly to the polymerization to give the poly-4-halogenobutyl (meth) acrylate, which is then quaternized, or they are first quaternized and the monomeric quaternary salts thus obtained are then polymerized with the monomers (M) and (V) in the presence of a radical generator. In the latter case, the use of a surface-active compound in the polymerization is possible, but not necessary, since the monomeric ammonium salt has surface-active properties. The resulting polymer latex contains, without further reaction, a sufficient number of cationic units which are necessary for the pickling action. It is also possible to polymerize the 4-chlorobutenyl monomer together with a monomeric quaternization product obtained therefrom and that To quaternize polymer with a tertiary amine or phosphine, which may be different from that which was used for the quaternization of the monomer, to form a polymer according to the invention.

In the preparation of the polymers in the manner described, some repeating units of the following formula can be formed by hydrolysis of the reactive halobutyl methacrylate residues with the release of HCl

Furthermore, cross-reactions within a latex particle can occur through the reaction of two reactive halogenobutenyl methacrylate residues in the presence of water, so that the effect of the polyfunctional monomer (V) is enhanced. In some cases, it may also be sufficient to dispense with the use of a polyfunctional monomer (V) and to bring about the crosslinking of the latex particle exclusively via the reaction of the halobutenyl groups. However, the polymers used according to the invention preferably consist of at most up to 5 mol% of recurring units which have arisen in the manner indicated by modifying the halobutyl radical.

The water-dispersible polymers used according to the invention can have a particle size of 20-500 nm. As a rule, they have a particle size of approximately 50 nm to approximately 200 nm, preferably a particle size of 60-100 nm.

The polymers used according to the invention are comparatively easy to produce, since the polymers can be produced in a vessel. The need to use larger amounts of solvents is eliminated. The polymers which can be prepared in the manner described are typically not completely quaternized. In general, the degree of quaternization is from about 80 to about 100 mol%.

Polymers which can be used according to the invention can thus be composed, for example, of:

The polymers prepared by the described method are generally sufficiently pure and only contain non-disruptive amounts of impurities. In some cases, however, cleaning of the polymer dispersions may be required. The methods of dialysis or ultrafiltration known to the person skilled in the art are suitable for this. Mixed bed ion exchangers can also be used successfully to remove ionic impurities, which enable complete desalination of the polymers. The polymer dispersions according to the invention can be cleaned particularly effectively by a flock / redispersion process. By acidifying the dispersion, the polymer can be flocculated and separated as a solid and washed with dilute acids and solvents. The subsequent redispersion of the polymer takes place e.g. by simply stirring it into water in the neutral to weakly alkaline pH range.

The cleaning process described also offers the possibility of drying the polymer after the flocking and washing process and isolating and storing it as a powdery solid. A bacterial attack frequently observed in the storage of aqueous dispersions can thus be excluded.

For the production of the image-receiving layers according to the invention, the polymers obtained are generally cast as latex, and they can be used in the same way as in the production or, if appropriate, in a subsequent cleaning operation. accrued, or in the form of a redispergate, if a drying process was upstream. Redispersion in an aqueous medium is remarkably easy to do, which is believed to be due to the large number of polar groups in the polymer. If appropriate, further substances, in particular hydrophilic colloidal binders, can be added to the polymers according to the invention in the production of image-receiving layers. As such, the usual known hydrophilic colloids come into question which are used quite generally for the production of photographic layers, for example gelatin, colloidal albumin, polysaccharides, cellulose derivatives, synthetic resins, e.g. Polyvinyl compounds, for example polyvinyl alcohol and polyvinyl alcohol derivatives, acrylamide polymers, polyurethanes and the like.

The polymers used according to the invention are used in customary concentrations, the optimum amount of mordant in each case depending on the type and amount of the dye to be mordanted, the mordant itself and the manner in which the image is produced. The necessary or cheapest concentration of mordant can be easily determined in individual cases. The amount of mordant in the image-receiving layer is expediently at least 10% by weight, based on the total solids content, preferably up to 50% by weight and more.

The most common known additives can be incorporated into the mordant layer, for example UV absorbers, e.g. substituted 2-hydroxyphenylbenzotriazoles (Tinuvin, Aandelsname) and hydroxybenzophenones and the like, and antioxidants, e.g. tert. Butylated hydroxyanisole, butylated hydroxytoluene, substituted chromanoie and the like. Insofar as such additives are substances which are soluble in organic solvents, they are expediently used in the form of an emulsifier in an aqueous medium.

The mordants used according to the invention can be used to produce a wide variety of photographic materials which have a mordant layer with the aid of which acidic dyes are to be stained.

One or more of the mordants used according to the invention can also be used, namely in one layer or in two or more different layers of a photographic material. The pickling agents used according to the invention can also be used together with other known pickling agents in the same layer or in different layers of the same material.

According to the present invention, the said polymers are mainly used as mordants for diffusing image dyes, i.e. they represent an essential component of image-receiving layers for the color diffusion transfer process. Such image-receiving layers are usually arranged on a transparent or non-transparent layer support and together with them form the image-receiving material. This is either non-photosensitive as a separate image-receiving sheet which can form an integral part of a photosensitive recording material if the image-receiving layer is in firm contact with the photosensitive silver halide emulsion layers.

Suitable supports are, for example, paper, optionally coated with a plastic, glass, metal foils or films made from organic film formers of materials such as cellulose esters, polyethylene terephthalate, polycarbonate or other polymers. By storing opacifying agents such as pigments, opaque carrier layers can also be produced from the materials mentioned last.

In its simplest form, the photographic material according to the invention consists of a support and an image-receiving layer arranged thereon, which contains the polymer of the formula I, optionally together with a colloidal binder. In order to improve the adhesion of the image-receiving layer to the layer support, the latter can be provided with a conventional adhesive layer. Such a material is suitable as an image-receiving material for any type of photographic color diffusion transfer process in which acid diffusing image dyes or acid diffusing color formers (image dye precursors) are used or imagewise released and can be transferred to an image receiving layer. After the transfer has taken place, such a material in the image-receiving layer has an image-wise distribution of one or more acid dyes.

According to an advantageous embodiment of the invention, the photographic material has, in addition to an image-receiving layer with the polymers according to the invention, at least one layer with an acid dye or a precursor compound for an acid dye, and at least one light-sensitive layer, in particular a light-sensitive silver halide emulsion layer. The acid dyes or precursor compounds for acid dyes mentioned are collectively referred to below as coloring compounds. Advantageously, the photographic material according to the invention can also contain a plurality of light-sensitive silver halide emulsion layers of different spectral sensitivity, as well as further non-light-sensitive layers such as intermediate layers, cover layers and other layers of the most varied functions, as are customary in multi-layer color photographic recording materials.

The photographic materials of the invention, i.e. the image-receiving materials, and in particular the color-photographic recording materials, which contain such an image-receiving material as an integral part, can also contain acidic layers and so-called braking or deceleration layers, which together form a so-called neutralization system. Such a neutralization system can be arranged in a known manner between the layer support and the image receiving layer arranged thereon or at another location in the layer structure, e.g. above the photosensitive layers, i.e. beyond these photosensitive layers viewed from the bit reception layer. The neutralization system is usually oriented so that the braking or retarding layer is between the acid layer and the location where the alkaline developing liquid or paste is exposed. Such acid layers, brake layers or neutralization layers consisting of both are known, for example, from US Pat. No. 2,584,030, US Pat. No. 2,983,606, US Pat. No. 3,362,819, US Pat. No. 3,362,821, DE-A- 2,455,762, DE-A-2 601 653, DE-A-2 716 505, DE-A-2 601 653, DE-A-2 716 505, DE-A-2 816 878. Such a neutralization system can be known in the art Way also contain two or more brake layers.

In a particular embodiment, the photographic material according to the invention may further contain one or more pigment-containing opaque layers which are permeable to aqueous liquids. These can perform two functions. On the one hand, the undesired access of light to light-sensitive layers can be prevented, and on the other hand, such a pigment layer can form an aesthetically pleasing background, in particular if a light or white pigment, for example Ti0 _{2, has been} used. Integral color photographic recording materials with such a pigment layer are known, for example from US-A-2 543 181 and DE-B-1 924 430. Instead of a pre-formed opaque layer, means can also be provided in order to produce such a layer only in the course of the development process . In accordance with the two functions mentioned, such pigment layers can be constructed from two or more partial layers, one of which, for example, is a white pigment and the other is, for example, a dark one. Contains light-absorbing pigment, such as carbon black.

• 1. einen transparenten Schichtträger,
• 2. eine Bildempfangsschicht,
• 3. eine lichtundurchlässige Schicht (Pigment-schicht)
• 4. ein lichtempfindliches Element mit mindestens einer lichtempfindlichen Silberhalogenidemulsionsschicht und mindestens einer dieser zugeordneten farbgebenden Verbindung,
• 5. eine Bremsschicht,
• 6. eine saure Polymerschicht,
• 7. einen transparenten Schichtträger.

In a particularly preferred embodiment of the invention, the photographic material is an integral color photographic recording material for carrying out the color diffusion transfer process and has, for example, the following layer elements:

• 1. a transparent layer support,
• 2. an image receiving layer,
• 3. an opaque layer (pigment layer)
• 4. a light-sensitive element with at least one light-sensitive silver halide emulsion layer and at least one coloring compound assigned to it,
• 5. a brake layer,
• 6. an acidic polymer layer,
• 7. a transparent substrate.

This material can be composed in such a way that two different parts are produced separately from one another, namely the light-sensitive part (layer elements 1-4) and the cover sheet (layer elements 5-7), which are then placed on one another on the layer side and connected to one another, if appropriate using spacer strips so that a space for receiving a precisely measured amount of a developing liquid is formed between the two parts. The layer elements 5 and 6, which together form the neutralization system, can also be arranged, however in the opposite order, between the layer support and the image-receiving layer of the light-sensitive part.

Means may be provided to introduce a developing liquid between two adjacent layers of the integral recording material, e.g. in the form of a laterally arranged, splitable container which, when subjected to mechanical forces, pours its contents between two adjacent layers of the recording material, in the present case between the photosensitive part and the cover sheet.

The photosensitive element which, in the case of an integral recording material, is an essential component of the photographic material according to the invention or, if the photographic material according to the invention is itself not photosensitive but essentially consists only of the support and the image-receiving layer, must be brought into contact with it during the development process. contains a light-sensitive silver halide emulsion layer in the case of a single-dye transfer process and associated with this a coloring compound. The coloring compound can be in a layer adjacent to the silver halide emulsion layer or in the silver halide emulsion layer itself, in the latter case the color of the image dye is preferably selected so that the predominant absorption range of the coloring compound does not match the predominant sensitivity range of the silver halide emulsion layer. For the production of multicolored transfer images in true-to-life colors, however, the light-sensitive element contains three such assignments of color-providing compound and light-sensitive silver halide emulsion layer, the absorption range of the image dye resulting from the color-providing compound generally matching the range of spectral sensitivity of the assigned silver halide emulsion layer. However, it is beneficial for achieving the highest possible sensitivity if the color-providing compound is arranged in a separate binder layer (viewed in the direction of the light incident during the exposure) behind the silver halide emulsion layer or has an absorption which is different from that of the image dye ("Shifted image dyes" US-A-3 854 945).

The developer oxidation products created during the development of a silver halide emulsion may of course only have an effect on the assigned coloring compound. Separating layers are therefore generally present in the light-sensitive element, which effectively prevent the diffusion of the developer oxidation products into other, unassigned layers. These separating layers can e.g. contain suitable substances which react with the developer oxidation products, for example non-diffusing hydroquinone derivatives or, if the developer compound is a color developer compound, non-diffusing color couplers.

The coloring compounds can be colored compounds which are themselves diffusible and which begin to diffuse when the layers are treated with an alkaline working liquid and are only determined by the development at the exposed areas. However, the coloring compounds can also be diffusion-resistant and release a diffusing dye in the course of development.

Coloring compounds which are a priori diffusible are known, for example, from German patents 1,036,640, 1,111,936 and 1,196,075. The so-called dye developers described therein contain a dye residue and a grouping which is capable of exposing the same molecule Developing silver halide.

• US-A-3 227 550, US-A-3 443 939, US-A-3 443 940, DE-A-1 930 215, DE-A-2 242 762, DE-A-2 402 900, DE-A-2 406 664, DE-A-2 505 248, DE-A-2 543 902, DE-A-2 613 005, DE-A-2 645 656, DE-A-2 809 716, BE-A-861 241.

Of the processes known to date for the production of color photographic images by the color diffusion transfer process, those based on the use of diffusion-resistant, color-imparting compounds from which diffusing dyes or dye precursor products are cleaved during development and transferred to an image-receiving layer have recently become increasingly important . Such non-diffusing coloring compounds are described, for example, in the following publications:

• US-A-3 227 550, US-A-3 443 939, US-A-3 443 940, DE-A-1 930 215, DE-A-2 242 762, DE-A-2 402 900, DE- A-2 406 664, DE-A-2 505 248, DE-A-2 543 902, DE-A-2 613 005, DE-A-2 645 656, DE-A-2 809 716, BE-A- 861 241.

In the cited documents both those non-diffusing coloring compounds are described which produce negative color images when conventional negative silver halide emulsions are used, and those which produce positive color images when negative silver halide emulsions are used. In the former case, if positive color images are desired, either the use of directly positive silver halide emulsions or, if negative emulsions are used, one of the known reversal methods, e.g. by the silver salt diffusion process (US-A-2 763 800) or by using compounds which release development inhibitors as a result of development.

example 1 Preparation of polymer A

400 ml of water and 5 g of Triton 770 wetting agent (30% strength) - (trade name and commercial product from Röhm and Haas) were heated to 60 ° C. while passing nitrogen through.

6 g of a mixture of 38.5 g of 4-chloro-2-butenyl methacrylate (monomer 1), 22.1 g of ethyl acrylate (monomer 2) and 1.45 g of 1,2,4-trivinylcyclohexane (monomer 3 ). After stirring for 10 minutes at 60 ° C., 0.6 g of potassium peroxydisulfate and 0.6 g of sodium metabisulfite were added, the rest of the monomer mixture was added dropwise in 30 minutes and the mixture was stirred for a further 2 hours. The latex obtained (polymer A) had a solids content of 12% and was free from sedimented parts. The polymers B, C, D, E and F were also prepared in an analogous manner, with a variation of the monomers 1, 2 and 3 in terms of type and amount, as can be seen from the table below.

Preparation of the polymer 1

₂₀₀ g of polymer A with a solids content of 12% were mixed with 40 ml of isopropanol and mixed in 15 minutes with a solution of 10.7 g of N, N-dimethylbenzylamine in 20 ml of isopropanol and stirred at 60 ° C. for 6 hours. The latex obtained was filtered through a paper filter and had a solids content of 8.5%. In an analogous manner, the polymers 2-15 were also prepared as latices from the polymers AF and corresponding amines, as can be seen from Table 2 below.

(See the tables, page 10).

Example 2

• 1. Eine Beizschicht aus 2,7 g eines Mischpolymerisats bestehend aus Styrol, N, N, N-Trimethyl-N-(4-vinyl-benzyl-) ammoniumchlorid und Divinylbenzol gemäß Beispiel 2 der DE-A-2 551 786 und 2,7 g Gelatine.
• 2. Eine Reflektionsschicht mit 18 g Ti0₂ und 2,6 g Gelatine.
• 3. Eine Rußabdeckschicht mit 1,87 g Ruß und 2,0 g Gelatine.
• 4. Eine einen blaugrünen Farbstoff freisetzende Schichtbestehend aus 0,53 g der Verbindung L und 1,06 g Gelatine.
• 5. Eine rotempfindliche direktpositiv arbeitende Emulsionsschicht mit 1,46 g Silber, 0,23 g 2-Octadecylhydrochinonsulfosäure-5, 1,9 g Gelatine und 0,028 mg der Verbindung 0 (Verschleierungsmittel).
• 6. Eine Sperrschicht mit 0,4 g 2-Acetyl-5-octadecylhydrochinon und 1 g Gelatine.
• 7. Eine einen purpurnen Farbstoff freisetzende Schicht bestehend aus 0,89 g der Verbindung M und 1,1 g Gelatine.
• 8. Eine grünempfindliche direktpositiv arbeitende Emulsionsschicht mit 1,33 g Silber, 0,21 g 2-Octadecylhydrochinonsulfosäure-5, 1,75 g Gelatine, 0,07 mg der Verbindung O und 1,96 mg der Verbindung P (Verschleierungsmittel).
• 9. Eine Sperrschicht aus 0,8 g 2-Acetyl-5-octadecylhydrochinon und 1 g Gelatine.
• 10. Eine einen gelben Farbstoff freisetzende Schicht bestehend aus 0,85 g der Verbindung N und 1,28 g Gelatine.
• 11. Eine blauempfindliche direktpositiv arbeitende Emulsionsschicht bestehend aus 1,27 g Silber, 0,2 g Octadecylhydrochinonsulfosäure-5, 1,67 g Gelatine und 0,04 mg der Verbindung O.
• 12. Eine Deckschicht mit 0,04 g 2-Acetyl-5-octadecylhydrochinon und 1,0 g Gelatine.
• 13. Eine Härteschicht mit 0,3 g der Verbindung Q and 0,3 g Gelatine.

An integral color photographic recording material was produced in that the following layers were applied in succession to a transparent support made of polyester film. The quantities given relate to 1m ² . For the formulas of the compounds L, M, N, O, P, Q, reference is made to the formula appendix.

• 1. a pickling layer of 2.7 g of a copolymer consisting of styrene, N, N, N-trimethyl-N- (4-vinyl-benzyl) ammonium chloride and divinylbenzene according to Example 2 of DE-A-2 551 786 and 2, 7 g gelatin.
• 2. A reflection layer with 18 g Ti0 ₂ and 2.6 g gelatin.
• 3. A soot cover layer with 1.87 g of soot and 2.0 g of gelatin.
• 4. A cyan dye-releasing layer consisting of 0.53 g of Compound L and 1.06 g of gelatin.
• 5. A red-sensitive, direct-positive emulsion layer with 1.46 g of silver, 0.23 g of 2-octadecylhydroquinone sulfonic acid 5, 1.9 g of gelatin and 0.028 mg of compound 0 (fogging agent).
• 6. A barrier layer with 0.4 g of 2-acetyl-5-octadecyl hydroquinone and 1 g of gelatin.
• 7. A purple dye-releasing layer consisting of 0.89 g of compound M and 1.1 g of gelatin.
• 8. A green sensitive direct positive emulsion layer with 1.33 g of silver, 0.21 g of 2-octadecylhydroquinone sulfonic acid 5, 1.75 g of gelatin, 0.07 mg of compound O and 1.96 mg of compound P (fogging agent).
• 9. A barrier layer consisting of 0.8 g of 2-acetyl-5-octadecylhydroquinone and 1 g of gelatin.
• 10. A yellow dye-releasing layer consisting of 0.85 g of compound N and 1.28 g of gelatin.
• 11. A blue-sensitive, directly positive emulsion layer consisting of 1.27 g of silver, 0.2 g of octadecylhydroquinone sulfonic acid-5, 1.67 g of gelatin and 0.04 mg of compound O.
• 12. A top layer with 0.04 g of 2-acetyl-5-octadecyl hydroquinone and 1.0 g of gelatin.
• 13. A hardening layer with 0.3 g of compound Q and 0.3 g of gelatin.

A neutralization layer and timing layers were applied to a second transparent support.

Both sheets were combined into a set on the layer side and glued to the edges. After exposure through the second support, a developer paste was distributed between the two films with an application of 100 _V -m, which was determined by spacers between the sheets.

• 1,5 ml Benzylalkohol
• 6 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidon
• 0,2 g Hydrochinon
• 70 g KOH
• 1 g Na₂S0₃
• 3 g Methylbenztriazol
• 155 g Ruß
• 34 g Natrosol HHR 250 (Handelsname)
• 726 g Wasser

The composition of the paste was:

• 1.5 ml benzyl alcohol
• 6 g of 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone
• 0.2 g hydroquinone
• 70 g KOH
• 1 g Na ₂ S0 ₃
• 3 g methylbenztriazole
• 155 g of carbon black
• 34 g Natrosol HHR 250 (trade name)
• 726 g water

Integral recording materials 1-15 according to the invention were produced and processed analogously, the polymers 1-15 according to the invention being used in the pickling layer instead of the known pickling agent.

The color densities measured behind the blue (B), green (G) and red filters (R) were measured after 1 hour of contact time and are summarized in Table 3.

Table 4 contains examples of improved image stability during the drying phase with regard to redissusion, especially of the yellow dyes.

(See the tables, page 12).

Formula appendix to example 2

Claims (6)

1. A photographic material consisting of a substrate and at least one layer coated thereon wich contains a polymeric mordant for acidic dyes, characterised in that it contains as a mordant a polymer having at least 10 mol % of recurring units of the following formula I

in which

Q represents a nitrogen or phosphorus atom,

R¹, R² and R³ each represent a carbocyclic or alkyl radical, or two of the radicals R¹, R² and R³ may together complete a 5- or 6- membered heterocyclic ring

R⁴ represents hydrogen or alkyl, and

X⁸ represents an anion.

2. A material according to claim 1, characterised in that the mordant contains recurring units of the following formula II

in which

Q represents a nitrogen or phosphorus atom,

R¹, R² and R³ each represent a carbocyclic radial or an alkyl radical or two of the radicals R¹, R² and R³ together complete a 5- or 6- membered heterocyclic ring,

R⁴ represents hydrogen of alkyl

X° represents an anion

V represents the residue of a polymerised monomer having at least two polymerisable ethylenically unsaturated radials,

M represents the radical of a polymerised monomer having one polymerisable ethylenically unsaturated radical, und

x, y, z represent the figures indicating the proportions of the individual comonomers in the polymer, such that

x represents from 10 to 99 mol %,

y represents from 0 to 90 mol %, and

z represents from 0 to 5 mol %

3. A material according to one of the claims 1 and 2, characterised in that the layer containing the polymeric mordant contains one or more acidic dyes in an imagewise distribution.

4. A material according to claim 1, characterised in that R¹, R² and R³ are the same or different and represent methyl, ethyl or benzyl.

5. A material according to claim 1, characterised in that R⁴ represents methyl.

6. A material according to one of the claims 1, and 2, characterised in that it contains at least one light-sensitive silver halide emulsion layer in contact with the layer containing the polymeric mordant, and a colour-providing compound is associated with the silver halide emulsion layer in uniform distribution.