DE102008000269A1 - Production of aqueous polymer dispersion for use e.g. as an adhesive bonding agent between metal and rubber, involves radical emulsion polymerisation of butadiene, styrene and vinylphosphonic acid - Google Patents

Abstract

A method (M1) for the production of aqueous polymer dispersions (I) by emulsion polymerisation of unsaturated monomers in presence of dispersants and radical initiators, in which the monomer mixture comprises (A) 19.9-90 wt.% conjugated aliphatic dienes, (B) 9.9-80 wt.% vinylaromatic compounds, (C) 0.1-10 wt.% unsaturated compounds with a phosphorus-containing functional group and (D) 0-20 wt.% other comonomers. Independent claims are included for (1) aqueous polymer dispersions (I) obtained by M1 (2) formed metal products coated with (I) (3) sulfur-vulcanised formed rubber products coated with (I) (4) a method (M2) for the production of formed products by coating a surface of a formed metal product with (I), drying the coated product, coating the dried surface with a sulfur-vulcanisable rubber mixture containing diene rubber(s) and then vulcanising the rubber (5) formed products obtained by M2 .

Description

The present invention is a process for the preparation of an aqueous polymer dispersion by free-radically initiated aqueous emulsion polymerization of ethylenically unsaturated compounds in the presence of dispersants and radical initiators, which is characterized in that for the emulsion 19.9 to 90% by weight conjugated aliphatic dienes (monomers A), 9.9 to 80% by weight vinylaromatic compounds (monomers B), 0.1 to 10% by weight ethylenically unsaturated compounds containing a phosphorus-containing functional group (monomers C), and 0 to 20% by weight copolymerizable ethylenically unsaturated compounds other than monomers A to C (monomers D) wherein the total amount of ethylenically unsaturated monomers A to D (total monomer amount) is 100 wt .-%.

object The present application is also the use of the after obtainable according to the invention aqueous polymer dispersions, in particular for coating of metal surfaces.

Modern pneumatic tires, in particular so-called radial tires, generally consist in their structure of a molded vulcanized rubber compound in which an inner metal structure (steel cord) is embedded. In order to improve the connection between steel cord and the rubber compound and thus the inner strength and thus the durability or the running properties of the tires, the steel cord is often provided with a coating of brass or zinc. Both brass and zinc can react with sulfur accelerator systems, allowing for adhesion to the rubber stock. Adhesion promoters used include metal oxides, organic cobalt compounds or zinc acrylates. As an alternative to sulfur adhesive systems, resorcinol-formaldehyde resins ( Röthemeyer / Summer; Rubber Technology; Pages 829 ff., Hanser-Verlag, 2001 ).

task The present invention was to provide a process for the preparation to provide novel aqueous polymer dispersions, which are suitable for coating metal surfaces and in particular adhesion-promoting properties between metal and rubber mixtures or vulcanized rubber mixtures.

The Task was by providing the according to the invention Method accessible aqueous polymer dispersions solved.

The implementation of free-radically initiated emulsion polymerizations of ethylenically unsaturated monomers in an aqueous medium has often been described above and is therefore sufficiently known to the person skilled in the art [cf. for this emulsion polymerization in Encyclopedia of Polymer Science and Engineering, Vol. 8, p. 659 et seq. (1987) ; DC Blackley, in High Polymer Latices, Vol. 1, pp. 35 ff. (1966) ; H. Warson, The Applications of Synthetic Resin Emulsions, Chapter 5, pages 246 ff. (1972) ; D. Diederich, Chemistry in our time 24, pages 135 to 142 (1990) ; Emulsion Polymerization, Interscience Publishers, New York (1965) ; DE-A 40 03 422 and Dispersions of Synthetic High Polymers, F. Hölscher, Springer-Verlag, Berlin (1969) ]. The free-radically initiated aqueous emulsion polymerization reactions are usually carried out by dispersing the ethylenically unsaturated monomers dispersively in aqueous medium in the form of monomer droplets and polymerizing them by means of a free-radical polymerization initiator. From this procedure, the present method differs only in the use of specific monomers.

Suitable monomers A are in particular aliphatic conjugated dienes having 4 to 9 carbon atoms. Frequently, 1,3-butadiene and substituted butadienes, such as 2-chloro or 2-methyl-1,3-butadiene used. Also suitable are conjugated, straight-chain and branched-chain pentadienes and hexadienes, and further straight-chain or branched-chain conjugated dienes having up to 9 carbon atoms. Of course, mixtures of various aliphatic dienes can be used. For reasons of economy and advantageous properties in copolymers, the 1,3-butadiene (Buta dien) as monomer A is particularly preferred.

Suitable monomers B are in particular aromatic monovinyl compounds of the general formula CH ₂ = CR ¹ R ² , where R ^{1 is} an aromatic nucleus having 6 to 10 carbon atoms, which may also contain other alkyl radicals and / or halogen substituents. R ² is hydrogen or an alkyl radical having 1 to 4 carbon atoms. Preferred monomers B are styrene, α-methylstyrene and vinyltoluene for reasons of economy and availability, with styrene being particularly preferred. Of course, mixtures of various vinyl aromatic compounds can be used.

suitable Monomers C are all ethylenically free-radically copolymerizable unsaturated compounds containing at least one phosphorus-containing functional group included. Examples are esters from Phosphoric acid and ethylenically unsaturated double bonds containing organic hydroxy compounds, such as the mono-, di- and Triesters of phosphoric acid with hydroxyalkyl acrylates or Hydroxyalkyl. Advantageous are the corresponding Monoesters of phosphoric acid and 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate or mixtures thereof. Also suitable are the mono-, Di- and triesters of phosphoric acid with alkoxylated hydroxyalkyl acrylates or hydroxyalkyl methacrylates. Advantageous are the corresponding ethoxylated or propoxylated derivatives having a degree of alkoxylation used from 1 to 10. Also according to the invention can be used, the vinyl-benzenephosphonic acid and their Derivatives and the vinylphosphonic acid and its mono-, Di- and Trieste. Of course it is possible Use mixtures of different monomers C. To be favoured Vinylphosphonic acid, monoester of phosphoric acid with hydroxyalkyl acrylates and hydroxyalkyl methacrylates and / or Monoester of phosphoric acid with alkoxylated hydroxyalkyl acrylates and hydroxyalkyl methacrylates used as monomer C. It understands it goes without saying that as monomers C also the corresponding, with bases, such as sodium hydroxide, potassium hydroxide or ammonia, in part or completely neutralized phosphoric acid compounds are.

Further ethylenically unsaturated, copolymerizable monomers D, which differ from the monomers A to C, for example, C ₁ - to C ₁₂ -alkyl esters of ethylenically unsaturated C ₃ - to C ₅ monocarboxylic and C ₄ - to C ₈ -dicarboxylic acids , such as methyl methacrylate or n-butyl acrylate, ethylenically unsaturated C ₃ - to C ₅ -mono- and C ₄ - to C ₈ -dicarboxylic acids and their water-soluble salts, such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid and their alkali metal and ammonium salts corresponding nitrile or amide compounds, such as acrylonitrile, methacrylonitrile, acrylamide or methacrylamide or so-called crosslinking monomers, for example the di-esters of dihydric alcohols, such as alkylene glycol diacrylates and dimethacrylates, and divinylbenzene, vinyl methacrylate, vinyl acrylate, allyl methacrylate, allyl acrylate, diallymaleate, diallyl fumarate or cyclopentadienyl acrylate and the methacrylic acid and acrylic acid C ₁ -C ₈ hydroxides yalkyl esters are used.

According to the invention the monomers A to D in the free-radically initiated aqueous Emulsion polymerization separately or together as a homogeneous Mixture be used.

Preference is given to the preparation of the aqueous polymer dispersion according to the invention 19.9 to 80% by weight Monomers A, 19.9 to 80% by weight Monomers B, 0.1 to 10% by weight Monomers C, and 0 to 20% by weight Monomers D, and especially preferred 34.9 to 65% by weight Monomers A, 34.9 to 65% by weight Monomers B, 0.1 to 5% by weight Monomers C, and 0 to 10% by weight Monomers D, used.

According to the invention, the total amount of monomers A to D can be initially charged in the aqueous reaction medium prior to initiation of the polymerization reaction. However, it is also possible, if appropriate, to initially introduce only a partial amount of the monomers A to D in the aqueous reaction medium before initiation of the polymerization reaction and then to select the polymerization under polymerization conditions during the free-radical emulsion polymerization according to the invention, the total amount or the residual amount remaining, if appropriate, is added continuously or discontinuously in accordance with the consumption. In this case, the metering of the monomers A to D can be carried out as separate individual streams, as inhomogeneous or homogeneous (part) mixtures or as a monomer emulsion. Advantageously, the monomers A and B are metered in the form of a monomer mixture and the monomers C and D in the form of an aqueous monomer emulsion or monomer solution. With particular advantage, the individual components are mixed and homogenized only immediately prior to entry into the polymerization reactor via static and / or dynamic mixing devices.

According to the invention co-dispersants used in the present process, the both the monomer droplets, as well as the formed Polymerisatteilchen dispersed in the aqueous medium hold and so the stability of the produced aqueous Ensuring polymer dispersion. As a dispersant Both come to carry out radical aqueous Emulsion polymerizations commonly used protective colloids as well as emulsifiers.

Suitable protective colloids are, for example, polyvinyl alcohols, polyalkylene glycols, alkali metal salts of polyacrylic acids and polymethacrylic acids, gelatin derivatives or acrylic acid, methacrylic acid, maleic anhydride, 2-acrylamido-2-methylpropanesulfonic acid and / or 4-styrenesulfonic acid-containing copolymers and their alkali metal salts but also N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylcarbazole, 1-vinylimidazole, 2-vinylimidazole, 2-vinylpyridine, 4-vinylpyridine, acrylamide, methacrylamide, amines group-bearing acrylates, methacrylates, acrylamides and / or methacrylamides containing homo- and copolymers. A detailed description of other suitable protective colloids can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular Materials, Georg-Thieme-Verlag, Stuttgart, 1961, pages 411-420 ,

Of course, mixtures of protective colloids and / or emulsifiers can be used. Frequently, dispersants used are exclusively emulsifiers whose relative molecular weights, in contrast to the protective colloids, are usually below 1000. They may be anionic, cationic or nonionic in nature. Of course, in the case of the use of mixtures of surfactants, the individual components must be compatible with each other, which can be checked in case of doubt by hand on fewer preliminary tests. In general, anionic emulsifiers are compatible with each other and with nonionic emulsifiers. The same applies to cationic emulsifiers, while anionic and cationic emulsifiers are usually incompatible with each other. An overview of suitable emulsifiers can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular Materials, Georg-Thieme-Verlag, Stuttgart, 1961, pages 192 to 208 ,

According to the invention however, especially emulsifiers are used as dispersants.

Common nonionic emulsifiers are z. B. ethoxylated mono-, di- and tri-alkylphenols (EO degree: 3 to 50, alkyl radical: C ₄ to C ₁₂ ) and ethoxylated fatty alcohols (EO degree: 3 to 80, alkyl radical: C ₈ to C ₃₆ ). Examples are the Lutensol ^® A grades (C ₁₂ C ₁₄ fatty alcohol ethoxylates, EO units: 3 to 8) Lutensol ^® AO-marks, (C ₁₃ O ₁₅ -Oxoalkoholethoxylate, EO units: 3 to 30), Lutensol ^® AT-marks (C ₁₆ C ₁₅ fatty alcohol EO 11 to 80), Lutensol ^® ON brands (C ₁₀ -Oxoalkoholethoxylate, EO units: 3 to 11) and the Lutensol ^® tO brands (C ₁₃ - Oxoalkoholethoxylate, EO degree: 3 to 20) of Fa. BASF AG.

Usual anionic emulsifiers are z. B. Alkali metal and ammonium salts of alkyl sulfates (alkyl: C ₈ to C ₁₂ ), of sulfuric monoesters of ethoxylated alkanols (EO degree: 4 to 30, alkyl: C ₁₂ to C ₁₈ ) and ethoxylated alkylphenols (EO degree: 3 to 50 , Alkyl radical: C ₄ to C ₁₂ ), of alkylsulfonic acids (alkyl radical: C ₁₂ to C ₁₈ ) and of alkylarylsulfonic acids (alkyl radical: C ₉ to C ₁₈ ).

worin R¹ und R² H-Atome oder C₄- bis C₂₄-Alkyl bedeuten und nicht gleichzeitig H-Atome sind, und M¹ und M² Alkalimetallionen und/oder Ammoniumionen sein können, als geeignet erwiesen. In der allgemeinen Formel (I) bedeuten R¹ und R² bevorzugt lineare oder verzweigte Alkylreste mit 6 bis 18 C-Atomen, insbesondere mit 6, 12 und 16 C-Atomen oder Wasserstoff, wobei R¹ und R² nicht beide gleichzeitig H-Atome sind. M¹ und M² sind bevorzugt Natrium, Kalium oder Ammonium, wobei Natrium besonders bevorzugt ist. Besonders vorteilhaft sind Verbindungen (I), in denen M¹ und M² Natrium, R¹ ein verzweigter Alkylrest mit 12 C-Atomen und R² ein H-Atom oder R¹ ist. Häufig werden technische Gemische verwendet, die einen Anteil von 50 bis 90 Gew.-% des monoalkylierten Produktes aufweisen, wie beispielsweise Dowfax^® 2A1 (Marke der Dow Chemical Company). Die Verbindungen (I) sind allgemein bekannt, z. B. aus US-A 4269749 , und im Handel erhältlich.Other anionic emulsifiers further compounds of the general Formula (I)

in which R ¹ and R ^{2 are} H atoms or C ₄ - to C ₂₄ -alkyl and are not simultaneously H atoms, and M ¹ and M ^{2 may be} alkali metal ions and / or ammonium ions have been found suitable. In the general formula (I), R ¹ and R ^{2 are} preferably linear or branched alkyl radicals having 6 to 18 C atoms, in particular having 6, 12 and 16 C atoms or hydrogen, where R ¹ and R ^{2 are} not both simultaneously H and Atoms are. M ¹ and M ² are preferably sodium, potassium or ammonium, with sodium being particularly preferred. Particularly advantageous compounds (I) are those in which M ¹ and M ^{2 are} sodium, R ^{1 is} a branched alkyl radical having 12 C atoms and R ^{2 is} an H atom or R ¹ . Frequently, technical mixtures are used which have a proportion of 50 to 90 wt .-% of the monoalkylated product, such as Dowfax ^® 2A1 (trademark of the Dow Chemical Company). The compounds (I) are well known, for. B. off US-A 4269749 , and commercially available.

Suitable cationic emulsifiers are usually a C ₆ - to C ₁₈ alkyl, alkylaryl or heterocyclyl-containing primary, secondary, tertiary or quaternary ammonium salts, alkanolammonium salts, pyridinium salts, imidazolinium salts, oxazolinium salts, morpholinium salts, thiazolinium salts and also salts of amine oxides, Quinolinium salts, isoquinolinium salts, tropylium salts, sulfonium salts and phosphonium salts. Examples include dodecylammonium acetate or the corresponding sulfate, the sulfates or acetates of the various 2- (N, N, N-trimethylammonium) ethylparaffinsäureester, N-Cetylpyridiniumsulfat, N-Laurylpyridiniumsulfat and N-cetyl-N, N, N-trimethylammonium sulfate, N- Dodecyl-N, N, N-trimethylammonium sulfate, N-octyl-N, N, N-trimethylammonium sulfate, N, N-distearyl-N, N-dimethylammonium sulfate; and Gemini surfactant N, N '- (lauryldimethyl) ethylenediamine disulfate, ethoxylated tallow fatty alkyl -N-methyl ammonium sulfate and ethoxylated oleylamine (for example Uniperol.RTM ^® AC from. BASF AG, about 12 ethylene oxide). Numerous other examples can be found in H. Stache, Tensid-Taschenbuch, Carl-Hauser-Verlag, Munich, Vienna, 1981 and in McCutcheon's, Emulsifiers & Detergents, MC Publishing Company, Glen Rock, 1989 , It is favorable if the anionic counter groups are as low as possible nucleophilic, such as perchlorate, sulfate, phosphate, nitrate and carboxylates, such as acetate, trifluoroacetate, trichloroacetate, propionate, oxalate, citrate, benzoate, as well as conjugated anions of organosulfonic acids, such as methyl sulfonate , Trifluoromethylsulfonate and para-toluenesulfonate, furthermore tetrafluoroborate, tetraphenylborate, tetrakis (pentafluorophenyl) borate, tetrakis [bis (3,5-trifluoromethylphenyl) borate, hexafluorophosphate, hexafluoroarsenate or hexafluoroantimonate.

The Emulsifiers preferably used as dispersants are advantageous in a total amount ≥ 0.005 and ≤ 10 wt%, preferably ≥ 0.01 and ≤ 5 wt .-%, in particular ≥ 0.1 and ≦ 3% by weight, based in each case on the total monomer amount, used.

The Total amount of as a dispersant in addition or instead Of the emulsifiers used protective colloids is often ≥ 0.1 and ≦ 10% by weight and often ≥ 0.2 and ≦ 7 % By weight, in each case based on the total monomers.

Prefers However, anionic and / or nonionic emulsifiers are as Dispersants used.

According to the invention the total amount of the dispersant in the aqueous reaction medium be submitted before initiation of the polymerization reaction. It but is also possible, possibly only a subset of the dispersant in the aqueous reaction medium Initiate the polymerization reaction and then under Polymerization conditions during the inventive radical emulsion polymerization the total amount or optionally Remaining residual amount of the dispersant continuously or to add discontinuously. The addition of the dispersants preferably takes place in the form of an aqueous monomer emulsion.

The release of the free-radically initiated aqueous emulsion polymerization takes place by means of a free-radical polymerization initiator (free-radical initiator). It may in principle both to peroxides as also act on azo compounds. Of course, redox initiator systems come into consideration. As peroxides may in principle inorganic peroxides, such as hydrogen peroxide or peroxodisulfates, such as the mono- or di-alkali metal or ammonium salts of peroxodisulfuric, such as their mono- and di-sodium, potassium or ammonium salts or organic peroxides, such as alkyl hydroperoxides, for example tert-butyl, p-menthyl or cumyl hydroperoxide, as well as dialkyl or diarylperoxides, such as di-tert-butyl or di-cumyl peroxide are used. The azo compounds are essentially 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile) and 2,2'-azobis (amidinopropyl) dihydrochloride (AIBA, corresponding to V-50 from Wako Chemicals). Use. Suitable oxidizing agents for redox initiator systems are essentially the abovementioned peroxides. Suitable reducing agents may be sulfur compounds having a low oxidation state, such as alkali metal sulfites, for example potassium and / or sodium sulfite, alkali hydrogen sulfites, for example potassium and / or sodium hydrogen sulfite, alkali metal metabisulfites, for example potassium and / or sodium metabisulfite, formaldehyde sulfoxylates, for example potassium and / or sodium formaldehyde sulfoxylate, Alkali salts, especially potassium and / or sodium salts, aliphatic sulfinic acids and alkali metal hydrogen sulfides, such as, for example, potassium and / or sodium hydrosulfide, salts of polyvalent metals, such as iron (II) sulfate, iron (II) ammonium sulfate, iron (II) -phosphate, endiols such as dihydroxymaleic acid, benzoin and / or ascorbic acid, and reducing saccharides such as sorbose, glucose, fructose and / or dihydroxyacetone. In general, the amount of the radical initiator used, based on the total amount of monomers, 0.01 to 5 wt .-%, preferably 0.1 to 3 wt .-% and particularly preferably 0.2 to 1.5 wt .-%.

According to the invention the total amount of radical initiator in the aqueous reaction medium be submitted before initiation of the polymerization reaction. It but is also possible, possibly only a subset of the radical initiator in the aqueous reaction medium Initiate the polymerization reaction and then under Polymerization conditions during the inventive radical emulsion polymerization the total amount or optionally Remaining residual amount according to consumption continuously or discontinuously.

Under Initiation of the polymerization reaction becomes the start of the polymerization reaction the present in the polymerization vessel monomers understood after radical formation of the radical initiator. It can the Initiation of the polymerization reaction by addition of radical initiator to the aqueous polymerization mixture in the polymerization under Polymerization carried out. But it is also possible that a partial or the total amount of the radical initiator that the submitted monomer containing aqueous polymerization mixture in the polymerization vessel under conditions which are not suitable to trigger a polymerization reaction, for example, at low temperature, are added and after in the aqueous polymerization mixture polymerization conditions be set. Under polymerization conditions are included to generally understand those temperatures and pressures including the free-radically initiated aqueous emulsion polymerization proceeds with sufficient polymerization rate. she are particularly dependent on the radical initiator used. The type and amount of the radical initiator, the polymerization temperature, are advantageous and the polymerization pressure is selected so that the radical initiator a half-life ≤ 3 hours, especially advantageously ≤ 1 Hour and most advantageously ≤ 30 minutes and always enough starting radicals available to initiate or maintain the polymerization reaction.

When Reaction temperature for the inventive radical aqueous emulsion polymerization comes the entire range from 0 to 170 ° C into consideration. It will be usually temperatures of 50 to 120 ° C, often 60 to 110 ° C and often 70 to 100 ° C applied. The inventive radical aqueous emulsion polymerization can be smaller, equal or greater at one pressure 1 atm [1.013 bar (absolute), atmospheric pressure] so that the polymerization temperature exceeds 100 ° C and may be up to 170 ° C. In the presence of 1,3-butadiene as monomer a) in the process according to the invention preferably polymerized under elevated pressure. there The pressure can be 1,2, 1,5, 2, 5, 10, 15 bar or even higher Take values. Are emulsion polymerizations in negative pressure are performed, pressures of 950 mbar, often of 900 mbar and often 850 mbar (absolute). Advantageous is the inventive radical aqueous Emulsion polymerization at 1 atm or in overpressure until to 20 bar with exclusion of oxygen, in particular under an inert gas atmosphere, such as under nitrogen or argon.

The aqueous reaction medium can in principle also in subordinate Amounts (≤ 5% by weight) of water-soluble organic Solvents such as methanol, ethanol, isopropanol, Butanols, pentanols, but also include acetone, etc. It is preferred the inventive method, however, in the absence of such Solvent carried out.

In addition to the abovementioned components, it is also possible optionally to use free radical-transferring compounds in the process according to the invention in order to reduce or control the molecular weight of the polymers obtainable by the polymerization. These are essentially aliphatic and / or araliphatic halogen compounds, such as n-butyl chloride, n-butyl bromide, n-butyl iodide, methylene chloride, ethylene dichloride, chloroform, bromoform, bromotrichloromethane, Dibromdichlormethan, carbon tetrachloride, carbon tetrabromide, benzyl chloride, benzyl bromide, organic thio compounds such as primary , secondary or tertiary aliphatic thiols such as ethanethiol, n-propanethiol, 2-propanethiol, n-butanethiol, 2-butanethiol, 2-methyl-2-propanethiol, n-pentanethiol, 2-pentanethiol, 3-pentanethiol, 2-methyl -2-butanethiol, 3-methyl-2-butanethiol, n-hexanethiol, 2-hexanethiol, 3-hexanethiol, 2-methyl-2-pentanethiol, 3-methyl-2-pentanethiol, 4-methyl-2-pentanethiol, 2 Methyl-3-pentanethiol, 3-methyl-3-pentanethiol, 2-ethylbutanethiol, 2-ethyl-2-butanethiol, n-heptanethiol and its isomeric compounds, n-octanethiol and its isomeric compounds, n-nonanethiol and its isomeric compounds , n-Dexanthiol and its isomeric Verbindu n-undecanethiol and its isomeric compounds, n-dodecanethiol and its isomeric compounds, n-tridecanethiol and its isomeric compounds, substituted thiols, such as, for example, 2-hydroxyethanethiol, aromatic thiols, such as benzenethiol, ortho, meta, or para Methylbenzenethiol, as well as all others in Polymer Handbook 3 rd edtition, 1989, J. Brandrup and EH Immergut, John Wiley & Sons, Section II, pp. 133-141 Sulfur compounds described, but also aliphatic and / or aromatic aldehydes, such as Acetaldeyhd, propionaldehyde and / or benzaldehyde, unsaturated fatty acids such as oleic acid, dienes with non-conjugated double bonds, such as divinylmethane or vinylcyclohexane or hydrocarbons with readily abstractable hydrogen atoms, such as toluene, for Commitment. However, it is also possible to use mixtures of non-interfering radical-chain-transferring compounds mentioned above.

The optionally used in the process according to the invention Total amount of radical chain transferring compounds, based on the total monomer, is usually ≤ 5 Wt .-%, often ≤ 3 wt .-% and often ≤ 1 Wt .-%.

Cheap it is when a partial or the total amount of optionally used radical chain transferring compound to the reaction medium fed prior to the initiation of free-radical polymerization becomes. In addition, a partial or the total amount the radical chain transferring compound to the aqueous Reaction medium advantageously also together with the monomers A to D are fed during the polymerization.

The polymers obtainable by the process according to the invention may in principle have glass transition temperatures in the range from -70 to + 150 ° C, often -70 to + 100 ° C and often -50 to + 50 ° C. If the aqueous polymer dispersions are to be used for coating metals, then the monomers A to D are chosen such that the resulting polymer has a glass transition temperature T _g ≥ -70 and ≦ + 50 ° C. Frequently, the monomers A to D are chosen so that the glass transition temperatures of the resulting polymers between -50 and + 20 ° C. By glass transition temperature is meant here the midpoint temperature according to ASTM D 3418-82, determined by differential thermal analysis (DSC) [cf. also Ullmann's Encyclopedia of Industrial Chemistry, page 169 . Verlag Chemie, Weinheim, 1992 and Zosel in paint and varnish, 82, pages 125 to 134, 1976 ].

After Fox ( TG Fox, Bull. Phys. Soc. 1956 [Ser. II] 1, page 123 and according to Ullmann's Encyclopedia of Industrial Chemistry, Vol. 19, page 18, 4th edition, Verlag Chemie, Weinheim, 1980 ) applies to the glass transition temperature of at most weakly crosslinked copolymers in a good approximation: 1 / T G = x 1 / T G 1 + x 2 / T G 2 + .... x n / T G n . where x ¹ , x ² , .... x ^{n are} the mass fractions of the monomers 1, 2, .... n and T _g ¹ , T _g ² , .... T _g ⁿ the glass transition temperatures of each of only one of Monomers 1, 2, .... n constructed polymers in degrees Kelvin. The glass transition temperatures of these homopolymers of most ethylenically unsaturated monomers are known (or can be determined experimentally in a simple manner known per se) and, for example, in US Pat J. Brandrup, EH Immergut, Polymer Handbook 1 st Ed. J. Wiley, New York, 1966, 2 nd Ed. J. Wiley, New York, 1975 and 3 rd Ed. J. Wiley, New York, 1989 , as in Ullmann's Cncyclopedia of Industrial Chemistry, page 169, Verlag Chemie, Weinheim, 1992 listed.

Advantageous can the inventive free-radically initiated aqueous emulsion polymerization also in the presence of a Polymer seed, for example in the presence of 0.01 to 3 wt .-%, often from 0.02 to 2% by weight and often from 0.04 to 1.5% by weight a polymer seed, in each case based on the total monomer amount, respectively.

A polymer seed is used in particular if the particle size of the polymer particles to be produced by means of a free-radically aqueous emulsion polymerization is to be adjusted in a targeted manner (see, for example, for this US-A 2520959 and US-A 3397165 ).

In particular, a polymer seed is used whose polymer seed particles have a narrow particle size distribution and weight-average diameters D _w ≦ 100 nm, frequently ≥ 5 nm to ≦ 50 nm and often ≥ 15 nm to ≦ 35 nm. The determination of the weight-average particle diameter is known to the person skilled in the art and is carried out, for example, by the method of the analytical ultracentrifuge. Weight-average particle diameter in this document is understood to mean the weight-average D _W50 value determined by the method of the analytical ultracentrifuge (cf. SE Harding et al., Analytical Ultracentrifugation in Biochemistry and Polymer Science, Royal Society of Chemistry, Cambridge, Great Britain 1992 . Chapter 10, Analysis of Polymer Dispersions with Eight-Cell AUC Multiplexers: High Resolution Particle Size Distribution and Density Gradient Techniques, W. Mächtle, pp. 147-175 ).

Within the context of this document, a narrow particle size distribution is to be understood as _meaning the ratio of the weight-average particle diameter D _w50 and the number-average particle diameter D _N50 [D _w50 / D _N50 ] _≦ 2.0, preferably ≦ 1.5 and in particular determined by the method of the analytical ultracentrifuge preferably ≦ 1.2 or ≦ 1.1.

Usually the polymer seed is in the form of an aqueous polymer dispersion used. The aforementioned quantities are based on the polymer solids content of the aqueous polymer seed dispersion; they are therefore as parts by weight of polymer seed solids, based on the total monomer amount, indicated.

Becomes a polymer seed used, so is advantageously a Fremdpolymersaat used. In contrast to a so-called in situ polymer seed, which prepared before the start of the actual emulsion polymerization in the reaction vessel and which has the same monomeric composition as that by the subsequent radically initiated aqueous Emulsion polymerization prepared polymer is under a Fremdpolymersaat a polymer seed understood in a separate Reaction step was prepared and their monomeric composition from that by the free-radically initiated aqueous emulsion polymerization produced polymer is different, but nothing else means than that for the production of Fremdpolymersaat and zur Preparation of the aqueous polymer dispersion different Monomers or monomer mixtures of different composition be used. The production of a foreign polymer seed is the Skilled in the art and usually takes place in such a way, that a relatively small amount of monomers as well as a relatively large Amount of emulsifiers presented in a reaction vessel and at reaction temperature, a sufficient amount of polymerization initiator is added.

According to the invention preferred becomes a polymer foreign seed with a glass transition temperature ≥ 50 ° C, often ≥ 60 ° C. or ≥ 70 ° C and often ≥ 80 ° C or ≥ 90 ° C used. Particularly preferred is a polystyrene or a Polymethyl methacrylate polymer.

The Total amount of Fremdpolymersaat can be submitted in the polymerization become. But it is also possible, only a subset to submit the foreign polymer seed in the polymerization vessel and the remaining amount during the polymerization add together with the monomers A to D. If necessary, but also the Gesamtpolymersaatmenge in the course of the polymerization be added. Preferably, the total amount of Fremdpolymersaat presented before initiation of the polymerization in the polymerization.

The According to the invention accessible aqueous Polymerisate dispersions usually have a polymer solids content of ≥ 10 and ≤ 70 wt%, often ≥ 20 and ≦ 65% by weight and often ≥ 25 and ≦ 60% by weight, in each case based on the aqueous polymer dispersion, on. The quasi-elastic light scattering (ISO standard 13 321) determined number-average particle diameter (cumulant z-average) is usually between 10 and 2000 nm, often between 20 and 1000 nm and often between 100 and 700 nm and 100 to 400 nm.

Frequently in the resulting aqueous polymer dispersions, the residual contents of unreacted monomers and other low-boiling compounds by the skilled person also known chemical and / or physical methods [see, for example EP-A 771328 . DE-A 19624299 . DE-A 19621027 . DE-A 19741184 . DE-A 19741187 . DE-A 19805122 . DE-A 19828183 . DE-A 19839199 . DE-A 19840586 and 19847115 ] lowered.

The accessible by the method according to the invention aqueous polymer dispersions can in particular as a binder in the production of adhesives, sealants, Plastic cleaning, paper coating compounds, non-woven fabrics, paints and organic substrate coating agents, such as For example, leather or textile fabrics, as well as for modification be used by mineral binders.

Especially advantageous, however, is the use of an inventive aqueous polymer dispersion for coating surfaces metallic shaped body (metal surfaces) and / or of surfaces of moldings consisting of with sulfur vulcanizable rubber mixtures. Especially advantageous the aqueous compositions of the invention are suitable Polymerisate dispersions therefore as adhesion promoters between metal surfaces and surfaces of sulfur vulcanizable rubbery mixtures, as they are, for example, in the manufacture of car tires.

The Auftagsmengen of aqueous polymer dispersions in so doing, that per square meter of metal surface or rubber mixture 1 to 1000 g, preferably 10 to 750 g and particularly advantageously 100 to 600 g of inventive Polymer were applied.

When suitable metals are in particular the metals of the 4th to 8th Subgroup of the Periodic Table of the Elements into consideration. Examples titanium, zirconium, vanadium, chromium, iron, Cobalt or nickel. Of course, the term includes Metal also metal alloys, like the most different types of steel, Brass or bronze. The metals or their Shaped bodies in the form of sheets, wires, tapes or profiles and three-dimensional structures produced therefrom be used.

The Sulfur vulcanizable rubber mixture can be used to rubber known to those skilled in the art for use in tires but at least one of the group of diene rubbers must be selected. To include diene rubbers all rubbers with an unsaturated carbon chain, at least partially derived from conjugated dienes. Especially preferred is when the diene rubber or the diene rubbers selected is or are from the group consisting of natural rubber (NR), synthetic polyisoprene (IR), polybutadiene (BR) and styrene-butadiene copolymer (SBR, E-SBR, S-SBR). These diene rubbers blend well with rubber mixtures process and show good tire properties. Preferred are Rubber mixtures whose diene rubber content ≥ 95 phr (parts per hundred rubber).

The Production of the shaped bodies according to the invention is advantageously such that at least a partial area, Advantageously, the total area of the metallic molding, for example, a steel cord, with the invention aqueous polymer dispersion is coated on it then the coated metallic shaped body is subjected to a drying step. Especially advantageous this drying step takes place at a temperature higher is, as the minimum film-forming temperature (MFT) of the aqueous used Polymer dispersion. The determination of the MFT is carried out according to DIN 53787. After the drying step, the coated area of the metallic shaped body with a vulcanizable with sulfur A rubber blend containing at least one diene rubber coated and then this raw rubber / metal composite in a heated press or vulcanized in a drying oven.

In addition, the rubber-vulcanizable rubbery mixture used in the manufacture of car tires may contain conventional additives in conventional parts by weight. These additives include, for. As plasticizers, aging inhibitors such. B. N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine (6PPD), N-isopropyl-N'-phenyl-p-phenylenediamine (IPPD), 2,2,4-trimethyl-1, 2-dihydroquinoline (TMQ) and other substances, such as those from J. Schnetger, Encyclopedia of Rubber Technology, 2nd edition, Hüthig book publishing house, Heidelberg, 1991, pages 42 to 48 are known, coupling agents, processing aids such as zinc oxide and fatty acids such as stearic acid, waxes, masticating aids such as 2,2'-Dibenzamidodiphenyldisulfid (DBD), vulcanization aids and fillers.

The vulcanization is carried out in the presence of sulfur or sulfur donors, with some sulfur donors can also act as a vulcanization accelerator. As sulfur donors, for example, thiuram derivatives such as tetramethylthiuram disulfide and dipentamethylenethiuram tetrasulfide, morpholine derivatives such as dimorpholyl disulfide, dimorpholyl tetrasulfide and 2-morpholinodithiobenzothiazole and caprolactam disulfide can be used. Sulfur or sulfur donors are used in the last mixing step in the amounts customary by the expert from 0.4 to 10 parts by weight of sulfur, preferably in amounts of 1.5 to 6 parts by weight of sulfur, based on 100 parts by weight of diene rubber added to the gum stock.

Of Furthermore, the rubber mixture can Vulkanisationsbeeinflussende Substances, such as vulcanization accelerators, vulcanization retarders and vulcanization activators, contained in conventional amounts the required time and / or the required temperature of the To control vulcanization and the vulcanizate properties too improve. The vulcanization accelerators can do this for example, be selected from the following accelerator groups: Thiazole accelerators such as 2-mercaptobenzothiazole, sulfenamide accelerator such as benzothiazyl-2-cyclohexylsulfenamide, guanidine accelerators such as Diphenylguanidine, thiuram accelerators such as tetrabenzylthiuram disulfide, Dithiocarbamate accelerators such as zinc dibenzyldithiocarbamate, amine accelerator such as cyclohexylethylamine, thioureas such as ethylene thiourea, Xanthate accelerators, disulfides. The accelerators can also be used in combination with each other, being synergistic Effects can result.

When Fillers are both substances that the physical Improve properties of the vulcanized rubber blend (e.g. As carbon blacks or bright, active fillers and reinforcing synthetic resins) as well as substances that vulcanized the bulk cost of the Lower rubbery gum mixture (eg inert extenders, colored pigments and white pigments, as well as fillers on the Vulcanization are influential and also called activators such as zinc oxide, magnesium oxide, magnesium carbonate, litharge, Mennige, calcium hydroxide).

When using light active fillers, silane coupling agents can be added to the rubber-iron mixture in customary quantities known to the person skilled in the art. As silane coupling reagents, it is possible to use all silane coupling reagents known to the person skilled in the art for use in rubber mixtures. Examples of suitable coupling reagents are bifunctional organosilanes which have at least one alkoxy, cycloalkoxy or phenoxy group as leaving group on the silicon atom and which, as other functionality, have a group which, if appropriate, can undergo a chemical reaction with the double bonds of the polymer after cleavage. The latter group may be the following chemical groups: -SCN, SH, NH ₂ , or -S _x - (where x = 2-8). Thus, as silane coupling agents, for example, 3-chloropropyltriethoxysilane, 3-thiocyanatopropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, and vinyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-thiocyanatopropyltrimethoxysilane or 3,3'-bis (triethoxysilylpropyl) polysulfides having 2 to 8 sulfur atoms, such as bis (triethoxysilylpropyl) disulfide and 3,3'-bis (triethoxysilylpropyl) tetrasulfide (TESPT), or mixtures of the sulfides having 1 to 8 sulfur atoms with different held on the different sulfides are used. Also blocked mercaptosilanes, as they are known from the WO 99/09036 are known, can be used as a silane coupling agent.

The Production of the rubber-iron mixture used according to the invention takes place in a conventional manner in one or more Mixing stages. For this purpose, the Gummirohmischung in a kneader or mixed on a rolling mill. Subsequently, the Gummirohmischung further processed, for example by an extrusion process, and brought into the appropriate form. A blank produced in this way is used in the manufacture of the green tire, in particular pneumatic vehicle tire blank, arranged as known.

The accessible by the method according to the invention Dispersion polymers have in particular advantageous adhesion-promoting Properties between metals and vulcanizable or vulcanized Rubber mixtures on and are therefore advantageous for the production of radial tires, conveyor belts hoses, V-belts, compensators or roll rubbers.

The following non-limiting example is intended to illustrate the invention

I) Preparation of the aqueous polymer

Polymer dispersion D1

In a 6 l pressure reactor equipped with a MIG stirrer and 3 metering devices at 20 to 25 ° C (room temperature) and under nitrogen atmosphere, 620 g of deionized water, 4 g of the emulsifier Dowfax ^® 2A1 from Dow Chemicals (aqueous solution with a solids content of 45 wt .-%) and 77 g of a 33 wt .-% aqueous solution of polystyrene seed (particle size 30 nm, with 16 parts by weight emulsifier Disponil ^® LDPS 20 from. Cognis), and 5 wt .-% of the feeds 1A and 1B submitted. Subsequently, the reactor contents were heated with stirring (180 rpm) to 90 ° C, and on reaching 85 ° C, 52 g of Feed 2 added. After reaching 90 ° C. (about 10 minutes), the remaining amounts of feed 1A and feed 1B were metered in at the same time continuously over a period of 360 minutes and at feed 2 within 390 minutes at constant flow rates. Over the entire metering time, the flow rates of feed 1A and feed 1B were homogenized shortly before entering the reactor. Subsequently, the reactor contents were allowed to react for a further 2 hours at 90.degree. Thereafter, the reactor contents were cooled to room temperature, adjusted with a 15 wt .-% aqueous ammonia solution to a pH of 7.5 and the pressure vessel was relaxed to atmospheric pressure. Subsequently, the resulting aqueous polymer dispersion was filtered through a sieve with a mesh size of 100 microns. Inlet 1A 1350 g deionized water 230 g a 3 wt .-% aqueous tetrasodium pyrophosphate solution 38 g a 15 wt .-% aqueous sodium dodecyl sulfate solution 28 g of Dowfax ^® 2A1 77 g a 15 wt .-% aqueous methacrylamide solution 6 g acrylic acid 46 g vinylphosphonic Feed 1B 1265 g styrene 34 g tert-dodecyl 943 g butadiene Inlet 2 236 g a 4 wt .-% aqueous sodium persulfate solution

The obtained aqueous polymer dispersion D1 had a Solids content of 45.8 wt .-%, based on the total weight of aqueous dispersion, on. The glass transition temperature became -1 ° C and the particle size determined to 156 nm.

Comparative dispersion VD

The Preparation of the aqueous comparative dispersion VD took place analogous to the preparation of the polymer dispersion D1 with the difference that no vinyl sulfonic acid used and for it the amount of styrene increased to 1288 g and the amount of butadiene to 966 g has been.

The Comparative aqueous dispersion VD obtained had a solids content of 45.9 wt .-%, based on the total weight of the aqueous Dispersion, on. The glass transition temperature became -2 ° C and the particle size determined to be 151 nm.

The Solids contents were generally determined by a defined Quantity of the respective aqueous polymer dispersion (ca. 5 g) at 140 ° C in a drying oven to constant weight was dried. Two separate measurements were carried out in each case. The values given in the examples represent the mean value of these two measurement results.

The Determination of the glass transition temperature was carried out according to DIN 53765 by means of a DSC820 device, series TA8000 the Fa. Mettler-Toledo Int. Inc ..

The average particle diameter of the polymer particles was determined by dynamic Light scattering on a 0.005 to 0.01 wt .-% aqueous Polymerisatdispersion at 23 ° C by means of an autosizer IIC from Malvern Instruments, England. It is stated the mean diameter of the cumulant analysis (cumulant z-average) the measured autocorrelation function (ISO standard 13321).

II) Carrying out the bonding tests

steel sheets (Material S235JR + AR according to DIN EN 10025) in the Dimensions 150 × 40 × 8 mm (length / width / thickness) were treated with steel gravel up to purity SA 2½ (according to DIN ISO 12944 Part 4) blasted and then in a drying oven stored at 40 ° C until use.

• ¹⁾ N'-Isopropyl-N'-phenyl-p-phenylen-diamin (z. B. Vulkanox^® 4010NA der Fa. Lanxess GmbH)
• ²⁾ styrolisiertes Diphenylamin (z. B. Rhenofit^® DDA der Fa. Rhein Chemie Rheinau GmbH)
• ³⁾ N-Cyclohexyl-2-benzothiazyl-sulfenamid (z. B. Vulkacit^® CZ der Fa. Lanxess GmbH)

As the diene rubber-containing rubber ingot mixture, a natural rubber-based compound was used which was modeled on a practical steel cord adhesive mixture except that any adhesion promoters were omitted in this mixture. This compound had the following composition: component Parts by weight natural rubber 100 stearic acid 1.0 Carbon black (N 330) 50.0 zinc oxide 8.0 Anti-aging agent IPPD ¹⁾ 0.75 Anti-aging agent SDPA ²⁾ 1.0 Insoluble sulfur 4.0 Accelerator CBS ^{3 )} 0.65

• ¹⁾ N'-isopropyl-N'-phenyl-p-phenylene-diamine (z. B. Vulkanox ^® 4010NA of Fa. Lanxess GmbH)
• ²⁾ styrenated diphenylamine (z. B. Rhenofit ^® DDA Fa. Rhein Chemie Rheinau GmbH)
• ³⁾ N-cyclohexyl-2-benzothiazyl-sulfenamide (z. B. Vulkacit ^® CZ Fa. Lanxess GmbH)

The Gummirohmischung according to the above composition was in a laboratory kneader (W & P GK 2UK) and then on a laboratory roll mill rolled to a roll skin with about 6 mm thickness. For this roller skin were strips in the dimensions 250 × 40 mm (length / width) cut out.

The aqueous polymer dispersions were prepared by hand with a A brush on both the sheets and the strips of rubber mixture applied and allowed to dry (23 ° C, relative humidity 50%, 1 hour). The order quantity was calculated so that They are about 500 g of polymer per square meter sheet / rubber mixture amounted to. Subsequently, the strips of rubber blend were placed on the sheets and by means of a corrugated steel roll Rolled around enclosed between sheet metal and rubber mixture To remove air. In parallel, a control experiment was carried out, in which, however, the sheet and the rubber blend strip not were coated with aqueous polymer dispersion.

to Vulcanization of the rubber compound became the composites thus produced stored in a drying oven at 160 ° C for 30 minutes, wherein the composite body weighted by a 0.5 kg weight were to prevent a bounce.

III) Conducting the adhesion tests

The Test specimens were placed on a tensile testing machine (Zwick 1475) a peel test correspond to DIN 53531 at a Test speed: subjected to 50 mm / minute.

The determined peel strengths and the evaluation of the respective crack images are recorded in Table 1 below: Table 1: Evaluation of the peel tests D1 VD1 control experiment Maximum force [N] 47.6 40.5 <2 Peel strength [N / mm] 11.9 10.1 <2 cracking Demolition in the bond one-sided demolition of the metal no attachment evaluation Note 1 Grade 4 Grade 5

• Note 1: flächendeckende (auf > 95% der Fläche) Anhaftung von Verklebungsmaterial auf dem Substrat
• Note 2: weitgehend flächendeckende (auf > 80% der Fläche) Anhaftung von Verklebungsmaterial auf dem Substrat
• Note 3: großflächige (auf > 50% der Fläche) Anhaftung von Verklebungsmaterial auf dem Substrat
• Note 4: teilweise (auf < 50% der Fläche) Anhaftung von Verklebungsmaterial auf dem Substrat
• Note 5: keine/kaum (auf < 10% der Fläche) Anhaftung von Verklebungsmaterial auf dem Substrat

The following assessment criteria were applied:

• Grade 1: area-covering (on> 95% of the area) adhesion of bonding material on the substrate
• Grade 2: largely covering (to> 80% of the surface) adhesion of bonding material on the substrate
• Grade 3: large area (> 50% of the area) adhesion of bonding material on the substrate
• Grade 4: partial (to <50% of the area) adhesion of bonding material to the substrate
• Grade 5: no / hardly (to <10% of the surface) adhesion of adhesive material to the substrate

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• - DE 4003422 A [0006]
• - US 4269749A [0020]
• - US 2520959 A [0037]
• - US 3397165 A [0037]
• EP 771328A [0045]
• - DE 19624299A [0045]
• - DE 19621027 A [0045]
• DE 19741184A [0045]
• - DE 19741187 A [0045]
• - DE 19805122 A [0045]
• - DE 19828183 A [0045]
• - DE 19839199 A [0045]
• - DE 19840586 A [0045]
• - DE 19847115 [0045]
• WO 99/09036 [0056]

Cited non-patent literature

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• - Encyclopedia of Polymer Science and Engineering, Vol. 8, p. 659 et seq. (1987) [0006]
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• - D. Diederich, Chemistry in Our Time 24, pages 135 to 142 (1990) [0006]
• Emulsion Polymerization, Interscience Publishers, New York (1965) [0006]
• Dispersions of synthetic high polymers, F. Hölscher, Springer-Verlag, Berlin (1969) [0006]
• - Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular Materials, Georg-Thieme-Verlag, Stuttgart, 1961, pages 411-420 [0015]
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• - H. Stache, Tensid-Taschenbuch, Carl Hauser Verlag, Munich, Vienna, 1981 [0021]
• McCutcheon's, Emulsifiers & Detergents, MC Publishing Company, Glen Rock, 1989 [0021]
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Claims (15)

Process for the preparation of an aqueous polymer dispersion by free-radically initiated aqueous emulsion polymerization of ethylenically unsaturated compounds in the presence of dispersants and free-radical initiators, characterized in that for the emulsion polymerization 19.9 to 90% by weight conjugated aliphatic dienes (monomers A), 9.9 to 80% by weight vinylaromatic compounds (monomers B), 0.1 to 10% by weight ethylenically unsaturated compounds containing a phosphorus-containing functional group (monomers C), and 0 to 20% by weight copolymerizable ethylenically unsaturated compounds other than monomers A to C (monomers D) wherein the total amount of ethylenically unsaturated monomers A to D (total monomer amount) is 100 wt .-%. Method according to claim 1, characterized in that that the monomers A and B are used as monomer mixtures. Method according to one of claims 1 and 2, characterized in that as monomer A 1,3-butadiene and as Monomer B styrene is used. Method according to one of claims 1 to 3, characterized in that as monomers C vinylphosphonic acid, Monoester of phosphoric acid with hydroxyalkyl acrylates and Hydroxyalkylmethacrylaten and / or monoesters of phosphoric acid with alkoxylated hydroxyalkyl acrylates and hydroxyalkyl methacrylates be used. Method according to one of claims 1 to 4, characterized in that the radically initiated aqueous Emulsion polymerization carried out in the presence of a polymer seed becomes. Aqueous polymer dispersion available according to a method according to one of the claims 1 to 5. Use of an aqueous polymer dispersion according to claim 6 as a binder in the production of adhesives, sealants, plastic plasters, paper coatings, Nonwoven fabrics, paints and coating compositions for organic substrates and for the modification of mineral binders. Use of an aqueous polymer dispersion according to claim 6 for coating metal surfaces. Metallic molded body coated with an aqueous polymer dispersion according to claim 6th Use of an aqueous polymer dispersion according to claim 6 for the coating of surfaces of sulfur vulcanizable rubbery mixtures. Moldings of sulfur vulcanizable Rubber mixtures coated with an aqueous polymer dispersion according to claim 6. Use of an aqueous polymer dispersion according to claim 6 as adhesion promoter between metal surfaces and surfaces of sulfur vulcanizable rubbery mixtures. Process for the production of moldings, characterized in that at least a partial surface of a metallic shaped body with an aqueous polymer dispersion coated according to claim 6, thereafter the coated molded article was subjected to a drying step and then the coated surface the metallic molded body with a sulfur vulcanizable rubbery mixture, containing at least one diene rubber is coated and thereto then this Gummirohmischung is vulcanized. A method according to claim 13, characterized in that the drying step at a tempera is performed, which is higher than the minimum film-forming temperature of the aqueous polymer dispersion used according to claim 6. Moldings available after one Method according to one of the claims 13 or 14.