EP0093924B1 - Photographic registration material - Google Patents

Description

The invention relates to a photographic recording material which contains crosslinked polymer latices in photographic light-sensitive and non-light-sensitive layers.

Gelatin is generally used as a binder for photographic layers because of its advantageous properties as a protective colloid, as a dispersant and because of its chemical properties. Gelatin also has disadvantages as a photographic binder. So z. B. the insufficient dimensional stability under changing climatic conditions, d. H. at different temperatures and humidity levels that are inherent in the layers formed from it.

There has been no shortage of attempts to replace gelatin in whole or in part with other binders. From DE-A-2 442 165 z. B. known film-forming addition polymers or copolymers based on acrylamide, which can be hardened with gelatin hardening agents and which can be used as a gelatin substitute or gelatin modifier. US Pat. No. 3,026,293 describes acrylamide graft polymers which have the property of allowing only water vapor, but not water, to pass through as films. The polymers can be used as a gelatin substitute in photographic layers.

A disadvantage of these polymers is that they increase the viscosity of the coating solutions when mixed with gelatin, especially when the crosslinking agents required for layer hardening are added to the coating solutions. With the dwell times of the casting solutions that occur during the coating process, this leads to an increase in viscosity which makes a defined layer application per unit area impossible. Furthermore, linear high molecular weight polyacrylamides in aqueous solutions are so viscous that processing such solutions is associated with considerable difficulties.

DE-A-2 846 044 and US-A-4 234 671 disclose copolymer stains which are said to be particularly suitable for color diffusion transfer processes. These stains have an ammonium or a polymerized vinyl pyridine group.

The object of the invention is to provide crosslinked polymer latices which are not susceptible to hydrolysis, which do not impair the sensitometric properties of color photographic materials and which are compatible with the customary binders and which can be prepared in a simple manner.

entspricht, worin bedeuten :

• R' ein Wasserstoffatom oder eine Alkylgruppe mit 1 bis 6 Kohlenstoffatomen,
• R², R³ die gleich oder verschieden sein können, ein Wasserstoffatom, eine geradkettige oder verzweigte, gegebenenfalls substituierte Alkylgruppe mit 1 bis 6 Kohlenstoffatomen, einen Aralkylrest, wie Benzyl-, 2-Phenylethyl, einen gegebenenfalls substituierten Arylrest, wie Phenyl, Hydroxynaphthyl, 2-Hydroxy-3-carboxyphenyl, einen 5- oder 6-gliedrigen, gegebenenfalls substituierten heterocyclischen Ring, der als Heteroatome Sauerstoff oder Schwefel enthält,
• R⁴ ein Wasserstoffatom oder die Gruppe -COOR',
• L eine bivalente Gruppe, wie ein Alkylenrest mit 1 bis 6 Kohlenstoffatomen, einen Arylenrest mit 6 bis 10 Kohlenstoffatomen, z. B. Phenylen oder Naphthylen, einen Arylenalkylenrest mit 7 bis 11 Kohlenstoffatomen, z. B. Phenylenmethylen oder Phenylenethylen, oder eine Gruppe -COOR^S oder -CONHR^S, worin R⁵ eine der genannten bivalenten Gruppen sein kann,
• M den Rest aus polymerisierten Monomeren mit einer polymerisierbaren ethylenisch ungesättigten Gruppe,
• V einen aus einem polymerisierten Monomeren mit mindestens zwei ethylenisch ungesättigten Gruppen gebildeten Rest,
• m 0 oder 1, vorzugsweise 0,
• x mindestens 10 Gew.- %,
• y 89,5 bis 0 Gew.- %,
• z 10 bis 0,5 Gew.- %,

wobei die Summe der Gewichtsanteile x, y und z jeweils 100 % betragen soll und wobei unter die Formel fallende synthetische Bindemittel mit einem Rest, der die Funktion eines Farbkupplers, eines UV-Absorbers, eines Weißkupplers, eines Farbstoffs, eines Entwicklers, einer farbstoffabspaltenden oder - freisetzenden Verbindung, eines optischen Aufhellers, eines Metallionenspenders, eines Antischleiermittels, eines Toners, einer mit Formalin reaktiven Verbindung oder eines Beizmittels hat, nicht beansprucht werden.The invention relates to a photographic recording material composed of a layer support and at least one light-sensitive gelatin-containing silver halide emulsion layer applied thereon and optionally further non-light-sensitive gelatin-containing layers, at least one of the layers containing a synthetic binder which is formed from olefinically unsaturated carboxamide monomers and is introduced as a latex, characterized in that that the synthetic binder of the formula

corresponds, in which mean:

• R 'is a hydrogen atom or an alkyl group with 1 to 6 carbon atoms,
• R ² , R ³ which may be the same or different, a hydrogen atom, a straight-chain or branched, optionally substituted alkyl group having 1 to 6 carbon atoms, an aralkyl radical, such as benzyl-, 2-phenylethyl, an optionally substituted aryl radical, such as phenyl, hydroxynaphthyl, 2-hydroxy-3-carboxyphenyl, a 5- or 6-membered, optionally substituted heterocyclic ring which contains oxygen or sulfur as heteroatoms,
• R ^{4 is} a hydrogen atom or the group -COOR ',
• L is a divalent group, such as an alkylene radical having 1 to 6 carbon atoms, an arylene radical having 6 to 10 carbon atoms, e.g. B. phenylene or naphthylene, an arylene alkylene radical having 7 to 11 carbon atoms, e.g. B. phenylene methylene or phenylene ethylene, or a group -COOR ^S or -CONHR ^S , in which R ^{5 can be} one of the bivalent groups mentioned,
• M the remainder of polymerized monomers with a polymerizable ethylenically unsaturated group,
• V is a radical formed from a polymerized monomer with at least two ethylenically unsaturated groups,
• m 0 or 1, preferably 0,
• x at least 10% by weight,
• y 89.5 to 0% by weight,
• z 10 to 0.5% by weight,

where the sum of the proportions by weight x, y and z should each be 100% and wherein synthetic binders falling under the formula with a radical which functions as a color coupler, a UV absorber, a white coupler, a dye, a developer, a dye-releasing agent or - Releasing compound, an optical brightener, a metal ion donor, an antifoggant, a toner, a formalin-reactive compound or a mordant, are not claimed.

The crosslinked polymer latices of the invention, hereinafter referred to briefly as “latices”, can always be used in an advantageous manner when it is necessary to use a synthetic binder and to avoid the disadvantages of a strong increase in viscosity usually associated therewith.

The structural unit characterized by the general formula represents the polymerized form of a low molecular weight carboxylic acid amide. Suitable monomeric carboxylic acid derivatives are those which are copolymerizable with the monomers M and V described below, such as. B. methacrylic acid, acrylic acid, crotonic acid, maleic acid or (vinylphenyl) acetic acid derivatives.

in der bedeuten :

• n eine ganze Zahl größer als 1, vorzugsweise 2, 3 oder 4,
• R⁶ ein Wasserstoffatom oder einen Methylrest und
• R⁷ einen n-bindigen organischen Rest.
• R⁷ kann beispielsweise einen zwei- oder mehrbindigen organischen Rest bedeuten, der aus Alkylen-, Arylen-, Aralkylen-, Cycloalkylengruppen (bzw. bei mehrbindigen organischen Reste aus den entsprechenden mehrbindigen Analoga der genannten Gruppen), weiter Ester-, Sulfonylester-, Amid-, Sulfonamidgruppen, Ethersauerstoff- und Thioetherschwefelatom sowie Kombinationen der erwähnten Gruppen und Atome aufgebaut ist. R⁷ kann beispielsweise sein eine Methylen-, Ethylen-, Trimethylen-, Phenylen-, Phenylendioxycarbonyl-, 4,4'-Isopropylidenbisphenylenoxycarbonyl-, Methylenoxycarbonyl-, Ethylen-dioxycarbonyl-, 1,2,3-Propan-tri-yl-tris-(oxycarbonyl)-, Cyclohexylen-bis(methylenoxycarbonyl)-, Ethylenbis(oxyethylenoxycarbonyl-, Ethylidintrioxycarbonylgruppe. 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.

V is preferably the radical formed from a monomer which can be polymerized by addition polymerization and has at least two ethylenically unsaturated groups, the monomer corresponding to the following formula

in which mean:

• n is an integer greater than 1, preferably 2, 3 or 4,
• R ^{6 is} a hydrogen atom or a methyl radical and
• R ^{7 is} an n-bonded organic radical.
• R ⁷ can mean, for example, a divalent or polyvalent organic radical which consists of alkylene, arylene, aralkylene, cycloalkylene groups (or in the case of polyvalent organic radicals from the corresponding polyvalent analogues of the groups mentioned), further ester, sulfonyl ester or amide -, Sulfonamide groups, ether oxygen and thioether sulfur atom as well as combinations of the groups and atoms mentioned. R ⁷ can be, for example, methylene, ethylene, trimethylene, phenylene, phenylenedioxycarbonyl, 4,4'-isopropylidenebisphenyleneoxycarbonyl, methyleneoxycarbonyl, ethylene-dioxycarbonyl, 1,2,3-propanetri-tris - (oxycarbonyl) -, cyclohexylene-bis (methyleneoxycarbonyl) -, ethylene bis (oxyethyleneoxycarbonyl, ethylidintrioxycarbonyl 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-Cyclohexylendimethylendimethacryl at; Di-ethylenglykoldimethacrylat, Di-isopropylenglykoldimethacrylat ; Ethylendiacrylat: Ethylendimethacrylat, Ethylidendiacrylat, 1,6-Diacrylamidohexan ; 1,6-Hexamethylendiacrylat ; 1,6-Hexamethylendimethacrylat ; N,N'-Methylenbisarylamid ; Neopentylglykoldimetharylat ; 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; Di-ethylene glycol dimethacrylate, di-isopropylene glycol dimethacrylate; Ethylene diacrylate: ethylene dimethacrylate, ethylidene diacrylate, 1,6-diacrylamidohexane; 1,6-hexamethylene diacrylate; 1,6-hexamethylene dimethacrylate; N, N'-methylenebisarylamide; Neopentyl glycol dimetharylate; 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 formation of the units V are trivinylcyclohexane, divinylbenzene, tetraallyloxyethane, 1,4-butylene dimethacrylate. Two or more of the monomers mentioned can also be used side by side to form units V of the polymers according to the invention.

A wide variety of monoethylenically unsaturated monomers copolymerizable with the customary monomers can be used for the units M. Monomers with conjugated ethylenically unsaturated bonds are also suitable for this purpose. Typical suitable monomers N are: ethylene, propylene, 1-butene, 4-methylpentene-1, styrene, a-methylstyrene, monoethylenically unsaturated esters of aliphatic acids, e.g. B. vinyl acetate, isopropenylacetate, allyl acetate and the like; Esters of ethylenically unsaturated mono- and dicarboxylic acids, e.g. B. methyl methacrylate, ethyl acrylate, glycidyl acrylate. Glycidyl methacrylate, butyl acrylate, cyanomethyl (meth) acrylate, nitrophenyl (meth) acrylate, carbomethoxymethyl (meth) acrylate, carboethoxymethyl (meth) acrylate, furthermore other monoethylenically unsaturated compounds such as acrylonitrile, allyl cyanide and also certain conjugated dienes, e.g. B. butadiene, isoprene and 2,3-dimethylbutadiene.

Water-soluble monomers such as, for. As acrylic acid, methacrylic acid, itaconic acid re. Maleic acid, acrylamido-2-methylpropanesulfonic acid, sulfoethyl methacrylate, N-vinylpyrrolidone.

The grouping M can be formed not only from a single monomer, but also from various of the monomers mentioned.

The latices according to the invention can be produced in various ways. According to a preferred production process, crosslinked polymer latices are used, which are converted into the polymeric amides in polymer-analogous reactions. Suitable starting compounds are e.g. B. crosslinked (meth) acrylic ester latexes, which react with amines to the polymeric amides according to the invention.

The starting latices can in a known manner by emulsion copolymerization of monomeric polymerizable esters with polyfunctional monomers, such as. B. described in DE-A-26 52 464, are produced. Those monomeric esters are expediently used which have sufficient reactivity for the aminolysis to be carried out in the following stage. Examples of monomeric esters which are suitable for the preparation of the crosslinked starting latices are (meth) acrylic acid methyl ester, cyanomethyl (meth) acrylate, nitrophenyl (meth) acrylate, carbomethoxy methyi (meth) acrylate, carboethoxymethyl (meth) acrylate or chloromethyl (meth -) acrylate.

The production of reactive esters is known from peptide chemistry (Houben-Weyl, Vol. 15/1 (1974), p. 28). The synthesis of reactive (meth) acrylic acid esters is in Makromol. Chem. 181, 2485 (1980) and European Polymer Journal 15, 167 (1979).

Other reactive derivatives of polymerizable acids are also suitable for the preparation of the starting latices. Examples include N-hydroxyphthalimide esters (European Polymer Journal 15, 603 (1979)); Acrylic acid benzotriazolides (J. Polym. Sci. Chem. Ed. 16, 1435 (1978)); Methacryloylimidazole (J. Polym. Sci. Chem. Ed. 12, 2453 (1974)).

Another production possibility is to start from crosslinked (meth) acrylic acid latices, as described in DE-A-26 52 464. In this case it is necessary to activate the carboxylic acid groups before the reaction with the amines. Ways to activate the carboxylic acid groups are known and z. B. described in Houben-Weyl, Volume 15/1 (1974), p. 28. The acid groups can also be activated by conversion into the acid halide or anhydride form. For this purpose, the reagents known from low-molecular chemistry are suitable, such as. B. thionyl chloride, phosphorus pentachloride, phosphorus trichloride or acetic anhydride.

The crosslinked reactive starting latices are then reacted with amines to form the polymer latices according to the invention. The latices used as starting compounds can be present as aqueous dispersions. In those cases where the reactive starting latices can react with water, the starting latices are used as dispersions which contain organic, preferably polar, organic solvents as dispersants. It is often also expedient to use mixtures of water and organic solvent as dispersants.

The reaction conditions such as reaction time, temperature and the use of catalysts depend on the starting latex used. In general, the reaction conditions can be chosen as they are known from the analogous reactions of linear uncrosslinked polymers or from low molecular weight chemistry. Descriptions of these possibilities can be found in Houben-Weyl, Volume 14/2 (1963), p. 738, Makromol. Chem., Rapid Connun. 1, 655 (1980), European Polymer Journal 15, 167 (1979), J. Polym. Sci. Chem. Ed. 12, 2453 (1974), J. Polym. Sci. Chem. Ed. 16, 1435 (1978), J. Polym. Sci. Chem. Ed. 12,553 (1974), Makromol. Chem. 175: 391 (1974), Makromol. Chem. 178, 2159 (1977) and Makromol. Chem. 181, 2495 (1980).

worin bedeuten

• R² ein Wasserstoffatom, eine geradkettige oder verzweigte, gegebenenfalls substituierte Alkylgruppe mit 1 bis 6 Kohlenstoffatomen, einen Aralkylrest, wie Benzyl-, 2-Phenylethyl, einen gegebenenfalls substituierten Arylrest, wie Phenyl, Hydroxynaphthyl, 2-Hydroxy-3-carboxyphenyl, einen 5- oder 6- gliedrigen, gegebenenfalls substituierten heterocyclischen Ring, der als Heteroatome Sauerstoff oder Schwefel enthält,
• R³ hat die Bedeutung von R², wobei R² und R³ gleich oder verschieden sein können.

Amines which are suitable for the preparation of the latices according to the invention have the structure

in what mean

• R ^{2 is} a hydrogen atom, a straight-chain or branched, optionally substituted alkyl group having 1 to 6 carbon atoms, an aralkyl radical such as benzyl, 2-phenylethyl, an optionally substituted aryl radical such as phenyl, hydroxynaphthyl, 2-hydroxy-3-carboxyphenyl, a 5 - or 6-membered, optionally substituted heterocyclic ring which contains oxygen or sulfur as heteroatoms,
• R ³ has the meaning of R ² , where R ² and R ^{3 can be the} same or different.

Examples of suitable amines are ammonia or alkylamines, e.g. B. methylamine, dimethylamine, ethylamine, propylamine, or butylamine, arylamines, e.g. B. aniline, 4-methylaniline or optionally substituted aminophenols, aralkylamines, e.g. B. optionally substituted butylamines, aminocarboxylic acids, for. B. lysine or glycine, alkylenediamines, e.g. B. diaminoethane, diaminohexane or hydroxyalkylamines, e.g. B. aminoethanol, alkoxyalkylamines, e.g. B. methoxyethylamine, amino ureas z. B. aminoethyl urea, secondary cyclic amines in which R ² and R ^{3 represent} a common radical, for. B. morpholine or piperdin.

The particles of the latices of the invention generally have diameters from 20 nm to 1 µm and preferably 30 to 300 nm. The latices are coated with the binders customary in photographic materials, such as, for. B. gelatin, polyvinyl alcohol, carboxymethyl cellulose or hydroxyethyl cellulose compatible and form transparent layers in the mixture.

The cleaning of the latices can be carried out by methods known to those skilled in the art, e.g. B. by flakes or redispersion, by dialysis, by ultrafiltration or by mixing with gelatin, pasta and water.

The latices can be stabilized by wetting agents. Often, however, stabilization by adding wetting agents is not necessary, especially if the latices contain ionic groups such as carboxyl or sulfonyl groups or quaternary ammonium groups.

The latices are generally used as aqueous dispersions. If the preparation is carried out in a non-aqueous medium, the solvent is removed by known methods, such as. B. by distillation, dialysis, ultrafiltration or by flaking and redispersing.

To use the latices in photographic layers, the latices are generally mixed with natural or synthetic binders such as gelatin or other hydrophilic macromolecular substances. The amount of latex added is usually 20 to 85% by weight, preferably 50 to 85% by weight, based on the total amount of the binder used. The latices according to the invention are preferably used in a mixture with gelatin as a binder.

The latices of the invention can advantageously be used in a wide variety of photographic materials, both in photosensitive and non-photosensitive layers of such materials. Examples of non-light-sensitive layers include receiving layers as used in diffusion transfer materials, further photographic auxiliary layers used in connection with light-sensitive layers. In such layers, the latices can be used as a binder or for modifying the binder.

The following examples serve to illustrate the invention.

Base latex A

A mixture of 200 g of water, 2.5 g of a 30% by weight aqueous solution of an anionic wetting agent of the formula was added under nitrogen

29.4 g of carbomethoxymethyl acrylate and 1.2 g of divinylbenzene were heated to 75 ° C. under nitrogen. After stirring for 10 minutes, a solution of 0.3 g of potassium peroxodisulfate in 10 g of water and a solution of 0.3 g of sodium metabisulfite in 10 g of water were simultaneously added dropwise within one hour. After stirring for a further 3 hours at 75 ° C., the latex obtained was filtered. The solids content was 11.5% by weight.

Base latex B

The preparation was carried out as described for latex A, with the difference that 2.4 g of divinylbenzene were used.

Base latex C

The preparation was carried out as described for latex A, with the difference that 3.6 g of divinylbenzene were used.

Base latex D

The preparation was carried out as described for latex A, with the difference that 1.5 g of 1,2,4-trivinylcyclohexane were used instead of divinylbenzene.

Latex 1

100 g of starting latex A were mixed with 5.6 g of propylamine and stirred at 95 ° C. for 8 hours. The low molecular weight components were then removed by dialysis in running water. The degree of conversion was determined by elemental analytical measurement of the nitrogen value:

More latices

As described under Latex 1, the starting latices A to D were reacted with various amines. The reaction conditions and the degree of conversion are given in Table 1 below.

The latices 1 to 5 can be used as binder additives.

example 1

100 ml of a 10 wt .-% aqueous binder solution consisting of a mixture of gelatin and linear high molecular weight polyacrylamide in a weight ratio of 10: 1 and 100 ml of a 0.2 wt .-% solution of the below. Hardening agent A in water was poured onto a cellulose triacetate base provided with an adhesive layer using a conventional cascade casting machine and dried.

The curing agent A used has the formula

The material was stored for 7 days at 30 ° C and 50% relative humidity. The wet scratch resistance (NKF) and the swelling factor (QF) were then measured.

To determine the wet scratch resistance, a metal tip of a defined size is passed over the wet layer and loaded with increasing weight. The wet scratch resistance is indicated by the weight at which the tip leaves a visible scratch mark on the layer. A high weight corresponds to a high wet scratch resistance.

The swelling is measured gravimetrically after treatment of a test strip in distilled water at 22 ° C. for 10 minutes. It is characterized by the swelling factor:

The example was repeated, the latex 5 according to the invention being used instead of polyacrylamide. The changes (in%) of swelling factor (AQF) and wet scratch resistance (ANKF) were determined using the following formulas:

Wie die Ergebnisse zeigen, werden die Schichteigenschaften durch die erfindungsgemäßen Verbindungen im Vergleich zu linearen Polymeren deutlich verbessert.The results of this comparison are summarized in the following table:

As the results show, the layer properties are significantly improved by the compounds according to the invention compared to linear polymers.

Example 2

• Auslaufzeit vor Wärmebehandlung : 45 s
• Auslaufzeit nach Wärmebehandlung : 44 s

200 ml of latex 4 were adjusted to pH 13.5 with sodium hydroxide solution. The viscosity was then determined in a DIN cup with a 2 mm nozzle (run-out time in s). The latex was then heated to 50 ° C. for 24 hours and the run-out time was finally determined again:

• Run-out time before heat treatment: 45 s
• Flow time after heat treatment: 44 s

The result confirms that the crosslinking points are not dissolved by the heat treatment in the alkaline medium, that the latex is therefore stable under the specified conditions.

Claims (3)

1. Photographic recording material consisting of a layer support and, applied thereto, at least one light-sensitive gelatine-containing silver halide emulsion layer and optionally other light-insensitive, gelatine-containing layers, at least one of the layers containing a synthetic binder formed from olefinically unsaturated carboxylic acid amide monomers and introduced in the form of a latex, characterised in that the synthetic binder corresponds to the formula

wherein

R¹ denotes a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,

R² and R³ are identical or different and denote a hydrogen atom, an unsubstituted or substituted alkyl group having 1 to 6 carbon atoms, an aralkyl group, an unsubstituted or substituted aryl group, a 5- membered or 6-membered unsubstituted or substituted heterocyclic ring containing oxygen or sulphur,

R⁴ denotes a hydrogen atom or the group --COOR',

L denotes a bivalent group,

M denotes a radical of polymerised monomers containing an ethylenically unsaturated group,

V denotes a radical formed from a polymerised monomer containing at least two ethylenically unsaturated groups,

m denotes 0 or 1,

x denotes at least 10 % by weight,

y denotes 89.5 to 0 % by weight,

z denotes 10 to 0.5 % by weight,

wherein the sum of the proportions by weight of x, y and z should in each case be 100 % and wherein synthetic binders falling under the formula and containing a radical which has the function of a colour coupler, a UV absorber, a white coupler, a dyestuff, a developer, a dyestuff-cleaving or -liberating compound, an optical brightener, a metal-ion donor, an anti-fogging agent, a toner, a compound which is reactive with formalin or a mordant, are not claimed.

2. Photographic recording material according to Claim 1, characterised in that M is a water-soluble monomer from the group comprising acrylic acid, methacrylic acid, itaconic acid, maleic acid, acrylamido-2-methylpropane-sulphonic acid, sulphoethyl methacrylate or N-vinylpyrrolidone, and V is a polymerised monomer which corresponds to the formula

wherein

R⁶ denotes a hydrogen atom or a methyl radical,

R⁷ denotes an n-valent organic radical and

n denotes an integer greater than 1.

3. Photographic recording material according to Claim 1, characterised in that the particle size of the synthetic binder is between 20 nm and 1 micrometre.