DE10000281A1 - Production of an aqueous dispersion, useful as an adhesive, comprises emulsion polymerization of ethylenically unsaturated monomers in the presence of a dispersed fine particulate inorganic solid - Google Patents

Abstract

Production of an aqueous dispersion of particles comprising a polymer and a fine particulate inorganic solid (composite particles) comprises emulsion polymerization of a mixture of ethylenically unsaturated monomers in an aqueous medium by means of a radical polymerization inhibitor in the presence of a dispersed fine particulate inorganic solid and a dispersing agent. Production of an aqueous dispersion (I) of particles comprising a polymer and a fine particulate inorganic solid (composite particles) comprises emulsion polymerization of a mixture of ethylenically unsaturated monomers in an aqueous medium by means of a radical polymerization inhibitor in the presence of at least one dispersed fine particulate inorganic solid and a dispersing agent. The process is effected using (A) a stable aqueous dispersion of an inorganic solid having an initial solids concentration of at least 1 wt.% and whereby more than 90 wt.% of the original dispersed solid remains in dispersed form one hour after its preparation and having a weight average diameter of no greater than 100 nm. (B) the dispersed solid particles have an electrophoretic mobility that is different to the null point in an aqueous standard alkali chloride solution at a pH corresponding to the pH of the aqueous reaction medium at the start of the emulsion polymerzation and (C) the mixture of ethylenically unsaturated monomers comprises greater than 0 wt.% to no greater than 4 wt.% of a monomer (A) that either contains at least an acid group and/or corresponding anion if the dispersed solid inorganic particles have a positive electrophoretic mobility or contain an amino-, amido-, ureido- or N-heterocyclic group and/or an alkylated ammonium derivative protonated at the nitrogen group if the dispersed solid inorganic particles have a negative electrophoretic mobility. Independent claims are included for (i) the aqueous dispersion (I) of composite particles, and (ii) a composite particle powder prepared by drying of the aqueous dispersion (I).

Description

The present invention relates to a method for manufacturing an aqueous dispersion of polymer and finely divided inorganic solid particles (composite particles), in which a mixture of ethylenically unsaturated monomers in dispersed aqueous medium and by means of at least one ra radical polymerization initiator in the presence of at least one dispersed, finely divided inorganic solid and at least one dispersant using the radical method is polymerized aqueous emulsion polymerization. Further The present invention relates to the use of the aqueous Composite particle dispersion as well as the composite particle powder.

Aqueous dispersions of composite particles are generally known knows. These are fluid systems that function as a disperse phase in an aqueous dispersion medium consisting of several ver looped polymer chains existing polymer balls, the so-called polymer matrix, and fine-particle inorganic solid Particles built up in a disperse distribution hold. The diameter of the composite particles is often in the loading range from 50 nm to 5000 nm.

Just like polymer solutions when the solvent evaporates and aqueous polymer dispersions on evaporation of the aqueous Dispersing medium, have aqueous dispersions of composite parts the potential for the formation of modified, finely divided polymer films containing inorganic solids, which half them in particular as modified binders, e.g. B. for An line-colored or for masses for coating leather, paper or plastic films are of interest. The from aqueous dis Persions of composite particles in principle accessible compo Sit particle powders are also used as additives for Plastics, components for toner formulations or additives substances of interest in electrophotographic applications.

In the production of aqueous dispersions of composite particles The following state of the art can be assumed.

A process for the production of polymer-coated anorga African particles by means of aqueous emulsion polymerization in US-A 3,544,500. With this procedure the  inorganic particles before the actual aqueous emulsion polymerization coated with water-insoluble polymers. The Dispersion of those treated in a complex process Organic particles in an aqueous medium are made using special stabilizers.

EP-A 104 498 relates to a process for the production of poly mer-coated solids. The process is characterized by that finely divided solids, which have a minimal surface area dung, by means of a nonionic protective colloid in dispersed aqueous polymerization medium and the added ethylenically unsaturated monomers using nonionic poly polymerization initiators are polymerized.

US-A 4,421,660 discloses a process for the production of aqueous dispersions, the dispersed particles anor ganic particles completely surrounded by a polymer shell are given. The preparation of the aqueous dispersions is carried out by radically initiated aqueous emulsion polymers tion of hydrophobic ethylenically unsaturated monomers in property dispersed inorganic particles.

A process for the polymerization of ethylenically unsaturated Monomers in the presence of a charge-free inorganic solid particles that are mixed with nonionic dispersants aqueous reaction medium are stabilized in the US-A 4,608,401.

The radically initiated aqueous emulsion polymerization of Styrene in the presence of modified silica particles is described by Furusawa et al. in the Journal of Colloid and Interface Science 1986, 109, pages 69 to 76. The modification the spherical silica particles with a medium one Particle diameter of 190 nm takes place by means of hydroxypropylcel lulose.

Hergeth et al. (see Polymer, 1989, 30, pages 254 to 258) be write the radically initiated aqueous emulsion polymerisa tion of methyl methacrylate or vinyl acetate in the presence of aggregated fine-particle quartz powder. The particle sizes of the Aggregated quartz powder used are between 1 and 35 µm.

GB-A 2 227 739 relates to a special emulsion polymer tion process in which ethylenically unsaturated monomers in An presence of dispersed inorganic powders which are cationic Have charges polymerized using ultrasonic waves  become. The cationic charges of the dispersed solid Particle particles are treated by treating the particles with cat ionic agents, with aluminum salts being preferred. However, the document contains no information regarding particle sizes and stability of the aqueous solid dispersions.

EP-A 505 230 describes the free-radically aqueous emulsion poly merization of ethylenically unsaturated monomers in the presence of surface-modified silicon dioxide particles. They are functionalized using a special silanol group acrylic ester containing pen.

US-A 4,981,882 relates to the production of composite particles using a special emulsion polymerization process. Ver Essential to the driving are finely divided inorganic particles, which dispersed in an aqueous medium by means of basic dispersants are treating these inorganic particles with ethylenic unsaturated carboxylic acids and adding at least one am phiphile component for stabilizing the solid dispersion during emulsion polymerization. The finely divided inorganic Particles preferably have a particle size between 100 and 700 nm.

Haga et al. (see The Applied Macromolecular Chemistry 1991, 189, pages 23 to 34) describe the influence of type and con concentration of the monomers, type and concentration of the polymer tion initiators and the influence of pH on the polyme Renformation on titanium dioxide part dispersed in an aqueous medium chen. High yields when encapsulating the titanium dioxide particles are obtained when the polymer chains and the titanium dioxide part Chen have opposite charges. The publication contains however no information regarding the particle size and the stability activity of the titanium dioxide dispersions.

Long et al. describe in Tianjin Daxue Xuebao 1991, 4, pages 10 to 15 the dispersant-free polymerization of methyl methacrylate in the presence of finely divided silicon dioxide or Aluminum particles. Good yields when encapsulating the anor ganic particles are obtained when the end groups of the poly Merketten and the inorganic particles opposite La dung.

EP-A 572 128 relates to a manufacturing process of composite par particles in which the inorganic particles in an aqueous medium a certain pH with an organic polyacid or de salt are treated and then carried out radically initiated aqueous emulsion polymerization  ethylenically unsaturated monomers at a pH <9 follows.

Bourgeat-Lami et al. (see The Applied Macromolecular Chemistry 1996, 242, pages 105 to 122) describe the by radical aqueous emulsion polymerization of ethyl acrylate in the presence functionalized and non-functionalized silicon dioxide Particle accessible reaction products. In the polymerization experiments were generally anionically charged silicon dioxide particle, the nonionic nonylphenol ethoxylate NP30 and that Ionic sodium dodecyl sulfate (SDS) as emulsifiers and potassium Use peroxodisulfate as a radical polymerization initiator det. The authors describe the reaction products obtained as aggregates that contain more than one silicon dioxide particle or as a polymer cluster, which is based on the silicon dioxide form area.

Paulke et al. (see Synthesis Studies of Paramagnetic Polysty rene Latex Particles in Scientific and Clinical Applications of Magnetic Carriers, pages 69 to 76, Plenum Press, New York, 1997) describe three basic synthetic routes to the manufacture development of aqueous iron oxide-containing polymer dispersions. Because of insufficient stability of the aqueous solid dispersion the use of freshly felled for all synthesis routes Iron (II / III) oxide hydrate is an essential requirement. In app this freshly precipitated iron (II / III) oxide hydrate in the first synthesis route follows the radical one aqueous emulsion polymerization of styrene with SDS as emulsifier and potassium peroxodisulfate as a polymerization initiator. In the of The authors favored second synthesis route is styrene and Methacrylic acid in the presence of the freshly precipitated iron (II / III) oxide hydrate, the emulsifier N-cetyl-N, N, N-trimethylam monium bromide (CTAB) and special surface-active polymer tion initiators (PEGA 600) in methanolic / aqueous medium poly merized. In the third synthesis route, ethanol and meth oxyethanol as a polymerization medium, hydroxypropyl cellulose as Emulsifier, benzoyl peroxide as a polymerization initiator and a special iron (II / III) oxide / styrene mixture for the production of iron oxide-containing polymer dispersions used.

In Japanese laid-open patent publication JP 11-209622, a ver drive to the production of core / shell particles, which discloses a core of a silica particle and a polymer have shell. The production of the core / shell particles takes place in such a way that it is colloidal in aqueous medium silicon dioxide particles with a cationic vinyl mono or a cationic radical initiator  and then a radically initiated aqueous Emulsion polymerization with ethylenically unsaturated monomers he follows.

Armes et al. (see Advanced Materials 1999, 11, No. 5, pages 408 to 410) describe the production of silicon dioxide com positive particles, which are in an emulsifier-free, radical in itied aqueous emulsion polymerization at a pH of 10 with special olefinically unsaturated monomers in property of dispersed silicon dioxide particles are accessible. As a prerequisite for the formation of silicon dioxide-containing Polymer particles will have a strong acid / base interaction between the polymer formed and the acidic Si used silica particles postulated. Silicon containing poly Merisate particles were made with poly-4-vinylpyridine and copolymers obtained from styrene or methyl methacrylate with 4-vinylpyridine. As the lowest possible level of 4-vinylpyridine in methyl meth acrylate or styrene monomer mixtures, which are used for training are capable of composite particles containing silicon dioxide, were called 4 to 10 mol%.

In the unpublished German patent application with the file number 199 42 777.1 is a manufacturing process described by aqueous composite particle dispersions, in which the dispersed inorganic solid particles and those in the radically initiated aqueous emulsion polymerization set radical-generating and / or dispersing com components have opposite charges.

The object of the present invention was, given the first state of the art an improved method for Her position of an aqueous dispersion of composite particles after Radical initiated aqueous emulsion polymerisation method tion, which has the disadvantages of the process or only to a reduced extent and Composite particles with a balanced profile of good application delivers properties.

Accordingly, there is provided a process for the preparation of an aqueous dispersion of composite particles composed of polymer and finely divided inorganic solid material, in which a mixture of ethylenically unsaturated monomers is dispersed in aqueous medium and by means of at least one radical polymerization initiator in the presence of at least one dispers Distributed, finely divided inorganic solid and at least one dispersant is polymerized according to the free radical aqueous emulsion polymerization method, characterized in that

• a) a stable aqueous dispersion of the at least one anorga African solid is used, which characterizes it is terized that they at an initial solids concentration tion of ≧ 1 wt .-%, based on the aqueous dispersion of at least one solid, an hour after her Position more than 90 wt .-% of the originally dispersed Contains solid in dispersed form and their disper giert solid particles a weight average diameter ≦ have 100 nm,
• b) the dispersed solid particles of the at least one organic solid in a standard aqueous potassium chloride solution at a pH that corresponds to the pH of the aqueous reaction medium at the beginning of the emulsion polymerisa tion corresponds to a non-zero electrophoresis show mobility and
• c) the mixture of ethylenically unsaturated monomers <0 and ≦ 4 wt .-%, based on its total amount, contains at least one ethylenically unsaturated monomer A, which either
  • contains at least one acid group and / or its corresponding anion if the dispersed solid particles of the at least one inorganic solid have an electrophoretic mobility with a positive sign under the aforementioned conditions,
  or
  • - Contains at least one amino, amido, ureido or N-heterocyclic group and / or their protonated or alkylated ammonium derivatives when the dispersed solid particles of the at least one organic solid under the aforementioned conditions have an electrophoretic mobility with a negative sign Chen have.

All those are fine for the method according to the invention lige inorganic solids suitable, which stable aqueous Form dispersions at an initial solids concentration tion of ≧ 1 wt .-%, based on the aqueous dispersion of we at least one solid, one hour after it was made  more than 90% by weight of the originally dispersed solid fes contained in dispersed form and their dispersed solid particles have a weight-average diameter ≦ 100 nm point and also at a pH that corresponds to the pH of the aqueous reaction medium at the beginning of the emulsion polymerization corresponds to a non-zero electrophoretic mobili act.

The quantitative determination of the initial solids concentration and the solids concentration after one hour and the determination the weight average particle diameter can, for example using the analytical ultracentrifuge method (cf. see S.E. 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 an eight-cell AUC multiplexer: high resolution Particle Size Distribution and Density Gradient Techniques, W. Mächtle, pages 147 to 175).

Metals, metal compounds, such as metal oxides and metal salts, but also semimetal and non-metal compounds are suitable as finely divided inorganic solid materials which can be used according to the invention. Precious metal colloids, such as, for example, palladium, silver, ruthenium, platinum, gold and rhodium, and alloys containing these can be used as finely divided metal powder. Examples of finely divided metal oxides are titanium dioxide (for example commercially available as Hombitec® brands from Sachtleben Chemie GmbH), zirconium (IV) oxide, tin (II) oxide, tin (IV) oxide (for example commercially available as Nyacol® SN brands from Akzo-Nobel), aluminum oxide (for example commercially available as Nyacol® AL brands from Akzo-Nobel), barium oxide, magnesium oxide, various iron oxides, such as iron (II) oxide (wuestite), iron (III) oxide (hematite) and iron (II / III) oxide (magnetite), chromium (III) oxide, anti mon (III) oxide, bismuth ( III) oxide, zinc oxide (for example, commercially available as Sachtotec® brands from Sachtleben Chemical GmbH), nickel (II) oxide, nickel (III) oxide, cobalt (II) oxide, Cobalt (III) oxide, copper (II) oxide, yttrium (III) oxide (for example commercially available as Nyacol® YTTRIA brands from Akzo-Nobel), cerium (IV) oxide ( for example commercially available as Nyacol® CEO2 brands from Akzo-No bel) amorphous and / or in their different crystal modifications and their hydroxy oxides, such as, for example, hydroxytitane (IV) oxide, hydroxyzirconium (IV) oxide, hydroxyaluminium oxide (for example commercially available as Disperal® brands from Condea-Chemie GmbH ) and hydroxy iron (III) oxide amorphous and / or in their different crystal modifications. The following amorphous and / or in their different crystal structures present metal salts can in principle be used in the process according to the invention: sulfides, such as iron (II) sulfide, iron (III) sulfide, iron (II) disulfide (pyrite), tin - (II) sulfide, tin (IV) sulfide, mercury (II) sulfide, cadmium (II) sulfide, zinc sulfide, copper (II) sulfide, silver sulfide, nickel (II) sulfide , Cobalt (II) sulfide, cobalt (III) sulfide, manganese (II) sulfide, chromium (III) sulfide, titanium (II) sulfide, titanium (III) sulfide, titanium - (IV) sulfide, zirconium (IV) sulfide, antimony (III) sulfide, bismuth (III) sulfide, hydroxides such as tin (II) hydroxide, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, Barium hydroxide, zinc hydroxide, iron (II) hydroxide, iron (III) hydroxide, sulfates such as calcium sulfate, strontium sulfate, barium sulfate, lead (IV) sulfate, carbonates such as lithium carbonate, magnesium carbonate, calcium carbonate, zinc carbonate, Zirconium (IV) carbonate, iron (II) carbonate, iron (III) carbonate, orthophosphates , such as lithium orthophosphate, calcium orthophosphate, zinc orthophosphate, magnesium orthophosphate, aluminum orthophosphate, tin (III) orthophosphate, iron (II) orthophosphate, iron (III) orthophosphate, metaphosphates, such as lithium metaphosphate, calcium metaphosphate, aluminum metaphosphate, pyrophosphate such as magnesium pyrophosphate, calcium pyrophosphate, zinc pyrophosphate, iron (III) pyrophosphate, tin (II) pyrophosphate, ammonium phosphates, such as magnesium ammonium phosphate, zinc ammonium phosphate, hydroxylapatite [Ca ₅ {(PO ₄ ) ₃ OH}], orthosilicates, such as Li thiumorthosilicate, calcium / magnesium orthosilicate, aluminum orthosilicate, iron (II) orthosilicate, iron (III) orthosilicate, magnesium orthosilicate, zinc orthosilicate, zirconium (III) orthosilicate, zirconium (IV) orthosilicate, metasilicates, such as Lithium metasilicate, calcium / magnesium metasilicate, calcium metasilicate, magnesium metasilicate, zinc metasilicate, layered silicates such as sodium aluminum silicate and sodium magnesium silicate, especially in sponta n delaminating form, such as Optigel® SH (brand of Südchemie AG), Saponit® SKS-20 and Hektorit® SKS 21 (brands of Hoechst AG) as well as Laponite® RD and Laponite® GS (brands of Laporte Industries Ltd.), Aluminates, such as lithium aluminate, calcium aluminate, zinc aluminate, borates, such as magnesium metaborate, magnesium orthoborate, oxalates, such as calcium oxalate, zirconium (IV) oxalate, magnesium oxalate, zinc oxalate, aluminum oxalate, tatrates, such as calcium tatate, acetylacetonates, such as aluminum acetylacetonate, III) acetylacetonate, salicylates, such as aluminum salicylate, citrates, such as calcium citrate, iron (II) citrate, zinc calcium, palmitates, such as aluminum palmitate, calcium palmitate, magnesium palmitate, stearates, such as aluminum stearate, calcium stearate, magnesium stearate, zinc stearate, laurate, such as calcium laurate, lino leate, such as calcium linoleate, oleates, such as calcium oleate, iron (II) oleate or zinc oleate.

As an essential semimetal compound that can be used according to the invention be amorphous and / or in different crystal structures present silicon dioxide called. Suitable according to the invention Silicon dioxide is commercially available and can, for example as Aerosil® (brand of Degussa AG), Levasil® (brand of Bayer AG), Ludox® (brand of DuPont), Nyacol® and Bind zil® (trademarks from Akzo-Nobel) and Snowtex® (trademark from Ni san Chemical Industries, Ltd.). According to the invention suitable non-metal compounds are, for example, colloidal Present graphite or diamond.

Leave as at least one finely divided inorganic solid further use all the aforementioned connections, their waiters surfaces with polymeric compounds or inorganic materials were modified.

As fine-particle inorganic solids, such are particularly ge suitable, whose solubility in water at 20 ° C and 1 bar (absolute) ≦ 1 g / l, preferably ≦ 0.1 g / l and in particular ≦ 0.01 g / l. Be compounds selected from the group around are particularly preferred including silicon dioxide, aluminum oxide, tin (IV) oxide, yttri um (III) oxide, cerium (IV) oxide, hydroxy aluminum oxide, calcium carbo nat, magnesium carbonate, calcium orthophosphate, magnesium ortho phosphate, calcium metaphosphate, magnesium metaphosphate, calcium pyro phosphate, magnesium pyrophosphate, iron (II) oxide, Iron (III) oxide, iron (II / III) oxide, titanium dioxide, hydroxylapa tit, zinc oxide and zinc sulfide. Sili are particularly preferred cium dioxide, aluminum oxide, hydroxy aluminum oxide, calcium carbonate, Magnesium carbonate, calcium orthophosphate, hydroxyapatite and Ti tandioxid.

The commercially available compounds can also be advantageous of the Aerosil®, Levasil®, Ludox®, Nyacol® and Bindzil® brands (Silicon dioxide), Disperal® brands (hydroxy aluminum oxide), Nya col® AL brands (aluminum oxide), Hombitec® brands (titanium dioxide), Nyacol® SN brands (tin (IV) oxide), Nyacol® YTTRIA brands (Ytt rium (III) oxide), Nyacol® CEO2 brands (cerium (IV) oxide) and Sach totec® brands (zinc oxide) in the process according to the invention be set.

The fine particles which can be used in the process according to the invention organic solids are such that those in aqueous The reaction medium dispersed solid particles by weight have an average particle diameter of ≦ 100 nm. Successful if such fine-particle inorganic solids are used, their dispersed particles a weight average particle diameter <0 nm but ≦ 90 nm, ≦ 80 nm, ≦ 70 nm, ≦ 60 nm, ≦ 50 nm,  ≦ 40 nm, ≦ 30 nm, ≦ 20 nm or ≦ 10 nm and all values in between show. The determination of the weight-average particles diameter can be, for example, using the analytical method Ultracentrifuge take place (see S.E. Harding et al., Analy tical ultracentrifugation in Biochemistry and Polymer Science, Royal Society of Chemistry, Cambridge, Great Britain 1992, Chap ter 10, Analysis of Polymer Dispersions with an Eight-Cell-AUC- Multiplexer: High Resolution Particle Size Distribution and Den sity Gradient Techniques, W. Mächtle, pages 147 to 175).

The accessibility of finely divided solids is prin to the expert Known partially and is done, for example, by felling freak ions or chemical reactions in the gas phase (cf. E. Matijevic, Chem. Mater. 1993, 5, pages 412 to 426; Ullmann's Encyclopedia of Industrial Chemistry, Vol. A 23, pages 583 to 660, Verlag Chemie, Weinheim, 1992; D. F. Evans, H. Wennerström in The Colloidal Domain, pages 363 to 405, Verlag Chemie, Wein Heim, 1994 and R. J. Hunter in Foundations of Colloid Science, Vol. I, pages 10 to 17, Clarendon Press, Oxford, 1991).

The stable solid dispersion is produced by Disperse the finely divided inorganic solid into the aqueous medium. Depending on the manufacturing process of the finely divided anorga African solids either succeed directly, for example for precipitated or pyrogenic silicon dioxide, aluminum oxide etc. or by adding suitable auxiliaries, such as, for example, dis perfuming agent.

According to the invention, Dis pergiermittel used that both the finely divided inorganic solid particles as well as the monomer droplets and the formed composite particles in the aqueous phase dispers ver divides hold and so the stability of the aqueous compo generated Ensure sit particle dispersion. Come as a dispersant both to carry out radical aqueous emulsion polymerizations commonly used as protective colloids emulsifiers are also considered.

Suitable protective colloids are, for example, polyvinyl alcohols, Polyalkylene glycols, alkali metal salts of polyacrylic acids and Po lymethacrylic acids, cellulose, starch and gelatin derivatives or Acrylic acid, methacrylic acid, maleic anhydride, 2-acrylic amido-2-methylpropanesulfonic acid and / or 4-styrenesulfonic acid ent holding copolymers and their alkali metal salts as well N-vinyl pyrrolidone, N-vinyl caprolactam, N-vinyl carbazole, 1-vinyl imidazole, 2-vinylimidazole, 2-vinylpyridine, 4-vinylpyridine, acrylic amide, methacrylamide, amine group-bearing acrylates, methacrylates,  Homo- and copoly containing acrylamides and / or methacrylamides merisate. A detailed description of other suitable ones Protective colloids can be found in Houben-Weyl, Methods of Organi chemistry, Volume XIV / 1, Macromolecular Substances, Georg-Thieme- Verlag, Stuttgart, 1961, pages 411 to 420.

Assign the dispersed inorganic solid particles electrophoretic mobility with a negative sign neutral protective colloids according to the invention, such as poly vinyl alcohols, polyalkylene glycols, cellulose, starch and gela tin derivatives and anionic protective colloids, d. H. Protective col loide whose dispersing component has at least one has negative electrical charge, such as alkali metal salts of Polyacrylic and polymethacrylic acids, acrylic acid, methacrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, 4-styrene sulfone copolymers containing acid and / or maleic anhydride and their alkali metal salts and alkali metal salts of sulfonic acids high molecular weight compounds such as polystyrene, good suitable. Assign the dispersed inorganic solid part However, electrophoretic mobility with a positive approach characters, are also neutral protective col loids, such as the aforementioned polyvinyl alcohol hole, polyalkylene glycols, cellulose, starch and gelatin leather vate, but also cationic protective colloids, d. H. Protective colloids, whose dispersing component has at least one positive has electrical charge, such as that on nitrogen protonated and / or alkylated derivatives of N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylcarbazole, 1-vinylimidazole, 2-vinylimi dazol, 2-vinylpyridine, 4-vinylpyridine, acrylamide, methacrylamide, amine group-bearing acrylates, methacrylates, acrylamides and / or Homo- and copolymers containing methacrylamides, well suited gnet. In principle, with dispersed solid particles electrophoretic mobility with a negative sign Mixtures of non-interfering neutral and anionic protection colloids are used. Accordingly, at Fest particles of matter with an electrophoretic mobility with positi The sign also includes mixtures of neutral and non-interfering use cationic protective colloids.

Of course, mixtures of emulsifiers and / or Protective colloids are used. Often used as a disperser only emulsifiers whose relative mo in contrast to the protective colloids, molecular weights are more common less than 1500. They can be both anionic, cationi shear or non-ionic in nature. Needless to say in the case of using mixtures of surfactant sub punch the individual components to be compatible with what  in case of doubt be checked on the basis of a few preliminary tests can. In general, anionic emulsifiers are among themselves and compatible with nonionic emulsifiers. The same applies also for cationic emulsifiers, while anionic and cationi emulsifiers are usually not compatible with one another. An overview of suitable emulsifiers can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular Fabrics, Georg-Thieme-Verlag, Stuttgart, 1961, pages 192 to 208.

Common nonionic emulsifiers are e.g. 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 include the Lutensol® A grades (C ₁₂ C ₁₄ fatty alcohol ethoxylates, EO grade: 3 to 8), Luten sol® AO grades (C ₁₃ C ₁₅ oxo alcohol ethoxylates, EO grade: 3 to 30), Lutensol ® AT grades (C ₁₆ C ₁₈ fatty alcohol ethoxylates, EO grade: 11 to 80), Lutensol® ON grades (C ₁₀ oxo alcohol ethoxylates, EO grade: 3 to 11) and the Lutensol® TO grades (C ₁₃ -Oxoalko holethoxilate, EO grade: 3 to 20) from BASF AG.

Common anionic emulsifiers are e.g. B. alkali metal and ammonium salts of alkyl sulfates (alkyl radical: C ₈ to C ₁₂ ), of sulfuric acid half-esters of ethoxylated alkanols (EO degree: 4 to 30, alkyl radical: C ₁₂ to C ₁₈ ) and ethoxylated alkyl phenols (EO degree: 3 to 50, alkyl radical: C ₄ to C ₁₂ ), of alkyl sulfonic acids (alkyl radical: C ₁₂ to C ₁₈ ) and of alkylarylsulfonic acids (alkyl radical: C ₉ to C ₁₈ ).

Compounds of the general formula I have also proved to be further anionic emulsifiers

wherein R ¹ and R ^{2 are} H atoms or C ₄ - to C ₂₄ -alkyl and are not simultaneously H atoms, and A and B can be alkali metal ions and / or ammonium ions. In the general formula I, R ¹ and R ^{2 are} preferably linear or branched alkyl radicals having 6 to 18 carbon atoms, in particular having 6, 12 and 16 carbon atoms or -H, where R ¹ and R ^{2 are} not both H atoms at the same time are. A and B are preferably sodium, potassium or ammonium, with sodium being particularly preferred. Connections I in which A and B are sodium, R ^{1 is} a branched alkyl radical having 12 C atoms and R ^{2 is} an H atom or R ¹ are particularly advantageous. Technical mixtures are frequently used which have a proportion of 50 to 90% by weight of the monoalkylated product, such as Dow fax® 2A1 (trademark of the Dow Chemical Company). The compounds I are generally known, e.g. B. from US-A 4,269,749, and commercially available.

Suitable cationic emulsifiers are generally a C ₆ - to C ₁₈ -alkyl or aralkyl group or a heterocyclic radical having primary, secondary, tertiary or quaternary ammonium salts, alkanolammonium salts, pyridinium salts, imidazolnium salts, oxazolinium salts, morpholinium salts and thiazolinium salts, as well as thiazolinium salts, and thiazolinium salts, as well as thiazolinium salts, and thiazolinium salts of amine oxides, quinolinium salts, isoquinolinium salts, tropylium salts, sulfonium salts and phosphonium salts. Examples include dodecylammonium acetate or the corresponding hydrochloride, the chlorides or acetates of the various 2- (N, N, N-trimethylammonium) ethyl paraffinic acid esters, N-cetylpyridinium chloride, N-laurylpyridinium sulfate and N-cetyl-N, N, N-tri methylammonium bromide, N-dodecyl-N, N, N-trimethylammonium bromide, N-octyl-N, N, N-trimethlyammonium bromide, N, N-distearyl-N, N-dime thylammonium chloride and the gemini surfactant N, N '- (lauryldime thyl) ethylenediamine dibromide. Numerous other examples can be found in H. Stache, Tensid-Taschenbuch, Carl-Hanser-Verlag, Munich, Vienna, 1981 and in Mc Cutcheon's, Emulsifiers & Detergents, MC Publishing Company, Glen Rock, 1989.

Because non-ionic emulsifiers both with dispersed solid Particles can be used that have an electrophoretic mobility with a positive or negative sign, they are according to the invention particularly well suited. With dispersed solid particles of matter with an electrophoretic mobility with positi In addition, cationic emulsifiers are also used or mixtures of non-interfering nonionic and katio African emulsifiers can be used. Suitable in a corresponding way opt for the dispersed solid particles with an electro phoretic mobility with negative sign anionic emul gators or mixtures of non-interfering nonionic and anionic emulsifiers.

As a rule, 0.05 to 20% by weight, frequently 0.1 to 5% by weight, often 0.2 to 3% by weight of dispersant, based in each case on the Total amount of the at least one finely divided inorganic solid substance and the mixture of ethy used for the polymerization lenically unsaturated monomers. The Ge total amount of at least one dispersant used in the process  be presented in the aqueous solid dispersion. However, it is also possible, possibly only a part amount of at least one dispersant in the aqueous Submit solid dispersion and the total amount or the counter any remaining amount of the at least one disperser by means of continuous during the radical emulsion polymerization admit nuously or discontinuously.

According to the invention, however, only such finely divided inorganic Solids suitable, the aqueous solid dispersion at a Initial solids concentration of ≧ 1 wt .-%, based on the aqueous dispersion of the finely divided inorganic solid, one hour after their production more than 90 wt .-% of ent originally dispersed solid in dispersed form holds and their dispersed solid particles a weight have average diameter ≦ 100 nm. The beginning is common solids concentrations ≦ 60% by weight. Can be advantageous, however also initial solids concentrations ≦ 55% by weight, ≦ 50% by weight, ≦ 45% by weight, ≦ 40% by weight, ≦ 35% by weight, ≦ 30% by weight, ≦ 25% by weight, ≦ 20% by weight, ≦ 15% by weight, ≦ 10% by weight and ≧ 2% by weight, ≧ 3% by weight, ≧ 4% by weight or ≧ 5% by weight and all values in between, each based on the aqueous dispersion of the finely divided anor ganic solid.

It is essential to the invention that the dispersed solid particles in a standard potassium chloride aqueous solution at pH, the pH of the aqueous reaction medium at the beginning of the emul ion polymerization corresponds to a non-zero elec Show tropheretic mobility. Under aqueous reaction medium at the beginning of the emulsion polymerization in this document understood aqueous reaction medium, the immediately before addition of the at least one radical polymerization initiator lies. The pH value is determined at 20 ° C and 1 bar (absolute) with commercially available pH meters. Depending on the performed The pH measurement is therefore carried out on an aqueous disperser sion, which only the at least one finely divided anorga African solid or additionally the at least one dispersant medium and / or additionally used for emulsion polymerization set monomers and optionally further auxiliaries holds.

The method for determining electrophoretic mobility is known to the person skilled in the art (see, for example, R. J. Hunter, Introduction to mo colloid science, chapter 8.4, pages 241 to 248, Oxford University Press, Oxford, 1993 and K. Oka and K. Furusawa, in Electrical Phenomena at Interfaces, Surfactant Science Series, Vol. 76, Chapter 8, pages 151 to 232, Marcel Dekker, New York,  1998). The electrophoretic mobility of the aqueous reak tion medium dispersed solid particles is by means of a commercial electrophoresis device, such as the Ze tasizer 3000 from Malvern Instruments Ltd., at 20 ° C and 1 bar (absolutely) determined. For this, the aqueous solid particle dis persion with a pH neutral 10 millimolar (mM) aqueous Ka lium chloride solution (standard potassium chloride solution) as far as ver thins that the solid particle concentration about 50 to 100 mg / l is. The adjustment of the measurement sample to the pH value the aqueous reaction medium at the beginning of the emulsion polymerization has, takes place by means of the common inorganic acids; how for example dilute hydrochloric acid or nitric acid or bases, such as dilute sodium hydroxide solution or potassium hydroxide solution. The wan change of the dispersed solid particles in the electric field is by means of the so-called electrophoretic light scattering detected (see e.g. B. R. Ware and W. H. Flygare, Chem. Phys. Lett. 1971, 12, pages 81 to 85). The sign of the electrophoretic mobility through the migration direction of the dispersed solid particles, i. H. hike the dis solidified particles to the cathode, is their electrophoric positive mobility, on the other hand they migrate to the anode, it is negative.

Are surface-modified solid particles, as in are described for example in the prior art, so will determine electrophoretic mobility with these surface-modified particles carried out. Is against finely divided inorganic solid only with the help of Disper yaw dispersible, the determination of the electropho retic mobility with suitable non-ionic dispersants means take place, regardless of whether in the invention Process actually cationic or anionic dispersant means are used. This is necessary because the ionic dispersant on the dispersed solid adsorb material particles and thus their electrophoretic mobili change or reverse activity.

A suitable parameter for the electrophoretic mobility of dispersed solid particles to a certain extent influence or adjust, is the pH of the aqueous reak medium. By protonation or deprotonation of the disper solid particles becomes the electrophoretic mobility in the acidic pH range (pH <7) in positive and in alkali range (pH <7) changed in the negative direction. On suitable pH range for the process according to the invention is the within which there is a radically initiated aqueous emul sion polymerization can be carried out. This pH range is in  usually at pH 1 to 12, often at pH 1.5 to 11 and often at pH 2 to 10.

The pH of the aqueous reaction medium can be obtained using commercially available acids, such as dilute hydrochloric acid or bases, such as dilute sodium hydroxide solution. It is often advantageous if a part or all of the the amount of acid or base used to adjust the pH aqueous reaction medium before the at least one finely divided inorganic solid is added.

The implementation of a radically initiated aqueous emulsion polymerization of ethylenically unsaturated monomers has been described many times and is therefore sufficiently known to the person skilled in the art [cf. e.g. B. Encyclopedia of Polymer Science and Engineering, Vol. 8, pages 659 to 677, John Wiley & Sons, Inc., 1987; DC Blackley, Emulsion Polymerization, pages 155 to 465, Applied Science Publishers, Ltd., Essex, 1975; DC Blackley, Polymer La tices, 2 ^nd Edition, Vol 1, pages 33 to 415, Chapman & Hall., 1997; H. Warson, The Applications of Synthetic Resin Emulsions, pages 49 to 244, Ernest Benn, Ltd., London, 1972; D. Diederich, Chemistry in our time 1990, 24, pages 135 to 142, Verlag Chemie, Weinheim; J. Piirma, Emulsion Polymerization, pages 1 to 287, Academic Press, 1982; F. Hölscher, dispersions of synthetic high polymers, pages 1 to 160, Springer-Verlag, Berlin, 1969 and the patent DE-A 40 03 422]. It is usually carried out in such a way that the ethylenically unsaturated monomers, frequently with the use of dispersants, are dispersed in aqueous medium and polymerized by means of at least one radical polymerization initiator. The method according to the invention differs from this procedure only in the additional presence of at least one finely divided inorganic solid which has an electrophoretic mobility which differs from zero and at least one monomer A.

Suitable ethylenically unsaturated monomers for the process according to the invention include in particular in a simple manner radically polymerizable nonionic monomers, such as ethylene, vinyl aromatic monomers such as styrene, α-methylstyrene, o-chlorostyrene or vinyl toluenes, esters of vinyl alcohol and 1 to Monocarboxylic acids containing 18 carbon atoms, such as vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl laurate and vinyl stearate, esters of α, β-monoethylenically unsaturated mono- and dicarboxylic acids preferably having 3 to 6 carbon atoms, such as in particular acrylic acid, methacrylic acid, Maleic acid, fumaric acid and itaconic acid, with alkanols which generally have 1 to 12, preferably 1 to 8 and in particular 1 to 4, carbon atoms, such as, in particular, methyl, ethyl, n-butyl, isobutyl acrylic acid and methacrylic acid and -2-ethylhexyl ester, maleic acid dimethyl ester or maleic acid di-n-butyl ester, nitriles α, β-mono ethylenically unsaturated carbons acids such as acrylonitrile and C _4-8 conjugated dienes such as 1,3-butadiene and isoprene. The named monomers generally form the main monomers which, based on the total amount of the monomers to be polymerized by the process according to the invention, normally comprise a proportion of more than 86% by weight. As a rule, these monomers have only moderate to low solubility in water under normal conditions [20 ° C, 1 bar (absolute)].

Monomers which usually increase the internal strength of the films of the polymer matrix normally have at least one epoxy, hydroxyl, N-methylol or carbonyl group, or we have at least two non-conjugated ethylenically unsaturated double bonds. Examples of these are two monomers having vinyl residues, two monomers having vinylidene residues and two monomers having al kenyl residues. The di-esters of dihydric alcohols with α, β-monoethylenically unsaturated monocarboxylic acids are particularly advantageous, among which acrylic and methacrylic acid are preferred. Examples of such monomers having two non-conjugated ethylenically unsaturated double bonds are alkylene glycol diacrylates and dimethacrylates, such as ethylene glycol diacrylate, 1,2-propylene glycol diacrylate, 1,3-propylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1-butylene glycol and 1-butylene glycol ethylene glycol 1 2-propylene glycol dimethacrylate, 1,3-propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate as well as divinyl benzene, vinyl methacrylate, vinyl acrylate, allyl methacrylate, allyl acrylate, diallyl maleate, diallyl fumarate, methylenebisacrylate, tricyclylate acrylate, tryl acrylate Of particular importance in this context are the methacrylic acid and acrylic acid-C ₁ -C ₈ -hydroxyalkyl esters such as n-hydroxyethyl-, n-hydroxypropyl- or n-hydroxybutyl acrylate and - methacrylate as well as compounds such as diacetone acrylamide and acetylacetoxyethyl acrylate or - methacrylate. According to the invention, the aforementioned monomers, based on the total amount of the monomers to be polymerized, are often polymerized in amounts of up to 10% by weight.

According to the invention, such ethylenically unsaturated monomers A are used termed monomers used, either at least one acid group and / or their corresponding anion or at least one Amino, amido, ureido or N-heterocyclic group and / or  their ammonium deri protonated or alkylated on nitrogen vate included.

Assign the dispersed solid particles of the at least one inorganic solid with an electrophoretic mobility with a positive sign, the monomers A become ethylenically unsound saturated monomers with at least one acid group are used, whose acid group is selected from the group comprising the Carboxylic, sulfonic, sulfuric, phosphoric and Phosphonic acid group. Examples include acrylic acid, meth acrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, 4-styrene sulfonic acid, 2-methacryloxyethyl sulfonic acid, vinyl sulfone acid and vinylphosphonic acid and phosphoric acid monoesters of n-hydroxyalkyl acrylates and n-hydroxyalkyl methacrylates, as in for example phosphoric acid monoesters of 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate and 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate or 4-hydroxybutyl meth acrylate. According to the invention, however, the ammonium and Alkali metal salts of the aforementioned at least one acid group using ethylenically unsaturated monomers. As Alkali metal is particularly preferred sodium and potassium. At the ammonium, sodium and potassium salts of Acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, Crotonic acid, 4-styrenesulfonic acid, 2-methacryloxyethylsulfonic acid, Vinylsulfonic acid and vinylphosphonic acid as well as the mono- and di- Ammonium, sodium and potassium salts of phosphoric acid monoesters of 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxy butyl acrylate and 2-hydroxyethyl methacrylate, 3-hydroxypropyl meth acrylate or 4-hydroxybutyl methacrylate. Anhy dride of ethylenically unsaturated acids, such as that Maleic anhydride and ethylenically unsaturated monomers with at least one CH-acidic function, such as 2- (acety Use lacetoxy) ethyl methacrylate as monomer A.

Acrylic acid, methacrylic acid, maleic acid, fumarate are preferred acid, itaconic acid, crotonic acid, 4-styrenesulfonic acid, 2-meth acryloxyethyl sulfonic acid, vinyl sulfonic acid and vinyl phosphonic acid used.

Assign the dispersed inorganic solid particles of the we at least one inorganic solid but one electrophoric tables with a negative sign are called mono mere A ethylenically unsaturated monomers used that little least one amino, amido, ureido or N-heterocyclic group and / or their Ammo protonated or alkylated on nitrogen contain sodium derivatives.  

Examples of monomers A which contain at least one amino group ten are 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 3-amino propyl acrylate, 3-aminopropyl methacrylate, 4-amino-n-butyl acrylate, 4-amino-n-butyl methacrylate, 2- (N-methylamino) ethyl acrylate, 2- (N-methylamino) ethyl methacrylate, 2- (N-ethylamino) ethyl acrylate, 2- (N-ethylamino) ethyl methacrylate, 2- (N-n-propylamino) ethyl acrylate lat, 2- (N-n-propylamino) ethyl methacrylate, 2- (N-iso-propyl amino) ethyl acrylate, 2- (N-iso-propylamino) ethyl methacrylate, 2- (N-tert-butylamino) ethyl acrylate, 2- (N-tert-butylamino) ethyl methacrylate (for example commercially available as Norsocryl® TBAEMA from Elf Atochem), 2- (N, N-dimethylamino) ethyl acrylate (For example, commercially available as Norsocryl® ADAME the Elf Atochem), 2- (N, N-Dimethylamino) ethyl methacrylate (at for example commercially available as Norsocryl® MADAME der Elf Atochem), 2- (N, N-diethylamino) ethyl acrylate, 2- (N, N-Di ethylamino) ethyl methacrylate, 2- (N, N-di-n-propylamino) ethyl acryl lat, 2- (N, N-di-n-propylamino) ethyl methacrylate, 2- (N, N-di-iso-pro pylamino) ethyl acrylate, 2- (N, N-di-iso-propylamino) ethyl methacrylic lat, 3- (N-methylamino) propyl acrylate, 3- (N-methylamino) propyl methacrylate, 3- (N-ethylamino) propyl acrylate, 3- (N-ethylamino) pro pyl methacrylate, 3- (N-n-propylamino) propyl acrylate, 3- (N-n-propyl amino) propyl methacrylate, 3- (N-iso-propylamino) propyl acrylate, 3- (N-iso-propylamino) propyl methacrylate, 3- (N-tert-butyl amino) propyl acrylate, 3- (N-tert-butylamino) propyl methacrylate, 3- (N, N-dimethylamino) propyl acrylate, 3- (N, N-dimethylamino) propyl methacrylate, 3- (N, N-diethylamino) propyl acrylate, 3- (N, N-diethyl amino) propyl methacrylate, 3- (N, N-di-n-propylamino) propyl acrylate, 3- (N, N-di-n-propylamino) propyl methacrylate, 3- (N, N-di-iso-propyl amino) propyl acrylate and 3- (N, N-di-iso-propylamino) propylmethacry lat.

Examples of monomers A which contain at least one amido group ten are acrylamide, methacrylamide, N-methyl acrylamide, N-methyl methacrylamide, N-ethyl acrylamide, N-ethyl methacrylamide, N-n-Pro pylacrylamide, N-n-propyl methacrylamide, N-iso-propylacrylamide, N-iso-propyl methacrylamide, N-tert-butylacrylamide, N-tert-butyl methacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N, N-diethyl acrylamide, N, N-diethyl methacrylamide, N, N-di-n-propyl acrylamide, N, N-di-n-propyl methacrylamide, N, N-di-iso-propylacryl amide, N, N-di-iso-propyl methacrylamide, N, N-di-n-butylacrylamide, N, N-di-n-butyl methacrylamide, N- (3-N ', N'-dimethylaminopropyl) me thacrylamide, diacetone acrylamide, N, N'-methylenebisacrylamide, N- (Di phenylmethyl) acrylamide, N-cyclohexylacrylamide, but also N-vinyl pyrrolidone and N-vinylcaprolactam.  

Examples of monomers A which contain at least one ureido group hold are N, N'-divinylethylene urea and 2- (1-imidazo lin-2-onyl) ethyl methacrylate (e.g. commercially available as Norsocryl® 100 from Elf Atochem).

Examples of monomers A which are at least one N-heterocyclic Group contains 2-vinylpyridine, 4-vinylpyridine, 1-vinylimi dazol, 2-vinylimidazole and N-vinylcarbazole.

The following compounds are preferably used: 2-vinylpyri din, 4-vinylpyridine, 2-vinylimidazole, 2- (N, N-dimethylamino) ethyl acrylate, 2- (N, N-dimethylamino) ethyl methacrylate, 2- (N, N-diethyl amino) ethyl acrylate, 2- (N, N-diethylamino) ethyl methacrylate, 2- (N-tert-butylamino) ethyl methacrylate, N- (3-N ', N'-dimethylamino propyl) methacrylamide and 2- (1-imidazolin-2-onyl) ethyl methacrylate. Depending on the pH of the aqueous reaction medium, some or the total amount of the aforementioned nitrogen-containing monomers A in the quaternary ammonium form protonated on nitrogen lie.

As monomers A, which is a quaternary alkyl ammonium on nitrogen have structure, are mentioned as examples 2- (N, N, N-trime thylammonium) ethyl acrylate chloride (e.g. commercially ver can be added as Norsocryl® ADAMQUAT MC 80 from Elf Atochem), 2- (N, N, N-trimethylammonium) ethyl methacrylate chloride (e.g. commercially available as Norsocryl® MADQUAT MC 75 der Elf Atochem), 2- (N-methyl-N, N-diethylammonium) ethyl acrylate chloride, 2- (N-methyl-N, N-diethylammonium) ethyl methacrylate chloride, 2- (N-methyl-N, N-di-n-propylammonium) ethyl acrylate chloride, 2- (N-Me ethyl-N, N-di-n-propylammonium) ethyl methacrylate, 2- (N-Ben zyl-N, N-dimethylammonium) ethyl acrylate chloride (e.g. com commercially available as Norsocryl® ADAMQUAT BZ 80 from Elf Ato chem), 2- (N-benzyl-N, N-dimethylammonium) ethyl methacrylate chloride (For example, commercially available as Norsocryl® MADQUAT BZ 75 from Elf Atochem), 2- (N-benzyl-N, N-diethylammonium) ethyl acrylate chloride, 2- (N-benzyl-N, N-diethylammonium) ethyl methacrylic latchloride, 2- (N-benzyl-N, N-di-n-propylammonium) ethyl acrylate lo rid, 2- (N-benzyl-N, N-di-n-propylammonium) ethyl methacrylate chloride, 3- (N, N, N-trimethylammonium) propyl acrylate chloride, 3- (N, N, N-trime thylammonium) propyl methacrylate chloride, 3- (N-methyl-N, N-diethyl ammonium) propyl acrylate chloride, 3- (N-methyl-N, N-diethylammo nium) propyl methacrylate chloride, 3- (N-methyl-N, N-di-n-propylam monium) propyl acrylate chloride, 3- (N-methyl-N, N-di-n-propylammo nium) propyl methacrylate chloride, 3- (N-benzyl-N, N-dimethylammo nium) propylacrylate chloride, 3- (N-benzyl-N, N-dimethylammonium) pro pyl methacrylate chloride, 3- (N-benzyl-N, N-diethylammonium) propyl acrylate chloride, 3- (N-benzyl-N, N-diethylammonium) propyl methacrylate chloride,  3- (N-Benzyl-N, N-di-n-propylammonium) propyl acrylate chloride and 3- (N-benzyl-N, N-di-n-propylammonium) propylmethacry latchlorid. Of course, instead of the above Chlorides also used the corresponding bromides and sulfates become.

2- (N, N, N-Trimethylammonium) ethyl acrylate chloride are preferred, 2- (N, N, N-trimethylammonium) ethyl methacrylate chloride, 2- (N-Ben zyl-N, N-dimethylammonium) ethyl acrylate chloride and 2- (N-Ben zyl-N, N-dimethylammonium) ethyl methacrylate chloride used.

In the process according to the invention, mixtures of ethylenic unsaturated monomers used, based on their total amount, <0 and <4 wt .-%, usually 0.05 to 3.0 wt .-%, hu fig 0.1 to 2.5 wt .-% and often 0.2 to 2.0 wt .-% of the least contain a monomer A.

The proportion by weight of the mixture of ethylenically unsaturated Monomers based on the total amount of at least one fine Partial inorganic solid and the mixture of ethyl nisch unsaturated monomers, is usually between 10 and 99 wt .-%, often between 25 and 90 wt .-% and often between between 40 and 80% by weight. According to the invention, the total amount of Monomer mixture together with the at least one fine part ligen inorganic solid in the reaction medium who submitted the. But it is also possible, possibly only one Partial amount of the monomer mixture in the aqueous solid disper sion and then during the radical emulsion poly merisation the total amount or the remaining amount, if any Remaining amount of the monomer mixture according to consumption con add continuously or discontinuously.

Coming as at least one radical polymerization initiator for the radical aqueous emulsion polymer according to the invention tion all those who are able to get a ra dical aqueous emulsion polymerization in the presence of the little trigger a finely divided inorganic solid. It can in principle be both peroxides and azo trade connections. Of course, redoxinitia also come door systems into consideration. In principle, peroxides can be inorganic cal peroxides, such as hydrogen peroxide or peroxodisulfates, such as the mono- or di-alkali metal or ammonium salts of Peroxodi sulfuric acid, such as its mono- and disodium, Potassium or ammonium salts or organic peroxides, such as alkyl hydroperoxides, for example tert-butyl, p-mentyl or cumyl hydroperoxide, as well as dialkyl or diaryl peroxides, such as di-tert. Butyl or di-cumyl peroxide can be used. As an azo compound  find essentially 2,2'-azobis (isobutyronitrile), 2,2'-azo bis (2,4-dimethylvaleronitrile) and 2,2'-azobis (amidinopropyl) dihy drochloride (AIBA, corresponds to V-50 from Wako Chemicals) use. Essentially come as oxidizing agents for redox initiator systems the peroxides mentioned above. As a corresponding Reducing agents can sulfur compounds with low oxi dation stage, such as alkali sulfites, for example potassium and / or Sodium sulfite, alkali hydrogen sulfites, for example potassium and / or sodium bisulfite, alkali metabisulfites, for example Potassium and / or sodium metabisulfite, formaldehyde sulfoxylates, for example potassium and / or sodium formaldehyde sulfoxylate, Al potash salts, especially potassium and / or sodium salts aliphatic Sulfinic acids and alkali metal hydrogen sulfides, such as Potassium and / or sodium hydrogen sulfide, salts of polyvalent Me talle, such as iron (II) sulfate, iron (II) ammonium sulfate, egg sen- (II) phosphate, endiols, such as dihydroxymaleic acid, benzoin and / or ascorbic acid and reducing saccharides, such as Sor bose, glucose, fructose and / or dihydroxyacetone who used the. As a rule, the amount of radicals used is 's polymerization initiator, based on the total amount of Monomer mixture, 0.1 to 3 wt .-%.

Assign the dispersed solid particles of the at least one inorganic solid with an electrophoretic mobility negative sign, are considered at least one radical Polymerization initiator, preferably peroxodisulfates, such as the Mono- or di-alkali metal or ammonium salts of the Peroxodischwe rock acid, such as the mono- and disodium, potassium or ammonium salts of peroxodisulfuric acid and hydrogen peroxide used in an alkaline medium.

Assign the dispersed solid particles of the at least one inorganic solid with an electrophoretic mobility positive sign, is considered at least one radical Polymerization initiator preferably used AIBA.

According to the invention, the total amount of at least one radika lischen polymerization initiator together with the at least a finely divided inorganic solid in the reaction medium be presented. But it is also possible, possibly single Lich a subset of the at least one radical polymer risationsinitiators in the aqueous solid dispersion place and then during the radical emul invention sionpolymerisation the total amount or the ver remaining quantity according to consumption continuously or admit discontinuously.  

As a reaction temperature for the radical according to the invention aqueous emulsion polymerization in the presence of at least one the entire area comes from finely divided inorganic solids from 0 to 170 ° C. As a rule, temperatu ren from 50 to 120 ° C, often 60 to 110 ° C and often ≧ 70 to 100 ° C applied. The radical aqueous emulsion according to the invention Polymerization can be at a pressure less than, equal to or greater than 1 bar (absolute) are carried out so that the polymerization temperature can exceed 100 ° C and can be up to 170 ° C. Before volatile monomers such as ethylene and butadiene are also preferred or polymerized vinyl chloride under increased pressure. It can the pressure is 1.2, 1.5, 2.5, 10, 15 bar or even higher values to take. Are emulsion polymerizations carried out in negative pressure leads to pressures of 950 mbar, often 900 mbar and often Set at 850 mbar (absolute). The invention is advantageous Adequate radical aqueous emulsion polymerization at 1 bar (absolutely) under an inert gas atmosphere, such as under Nitrogen or argon.

In principle, the aqueous reaction medium can also be water-soluble organic solvents, such as methanol, ethanol, Isopropanol, butanols, pentanols, but also include acetone etc. However, the method according to the invention is preferred in the absence carried out such solvents.

It is essential to the invention that the dispersed solid particles of the at least one inorganic solid among the above be conditions written a non-zero electrophoresis table mobility. Is the sign of the electro phoretic mobility positive, such as monomers A are ethylenically unsaturated monomers used, at least contain an acid group and / or its corresponding anion. In contrast, the sign of electrophoretic mobility is ne gativ, such monomers A are such ethylenically unsaturated Mo nomers used which have at least one amino, amido, ureido or N-heterocyclic group and / or the derivable Am contain monium derivatives.

The method according to the invention can be carried out in this way, for example be that a stable aqueous dispersion of at least a finely divided inorganic solid containing either a partial or the total amount of water required, we at least one dispersant, the at least one polymer risk initiators and / or the monomer mixture and the ge if necessary, further conventional auxiliaries and additives in one Reaction container presented and the contents of the reaction container heated to reaction temperature. At this temperature  the remaining amounts of what, if any, with stirring sers, the at least one dispersant, the monomer mixture cal and any other usual auxiliary and Additives added continuously or discontinuously and then optionally further to the reaction temperature held.

The method according to the invention can also be carried out in this way be that a stable aqueous dispersion of at least a finely divided inorganic solid containing either a partial or the total amount of water required, we at least one dispersant and / or optionally white teren usual auxiliaries and additives and possibly single Lich a subset of the monomer mixture and / or the little least a polymerization initiator in a reaction vessel submits and the contents of the reaction vessel to the reaction temperature heating up. At this temperature, the Ge velvet or any remaining amount of the monomer rengemisches and / or the at least one polymerization initia tors and any remaining amounts of what sers, the at least one dispersant and / or the given if necessary, other conventional auxiliaries and additives continuously or added batchwise and then optionally kept at the reaction temperature.

The composite particles accessible according to the invention have in the Rule particle diameter of ≦ 5000 nm, often ≦ 1000 nm and often ≦ 400 nm. The particle diameters are usually determined usually by transmission electron microscopy (see e.g. L. Reimer, Transmission Electron Microscopy, Springer-Verlag, Berlin, Heidelberg, 1989; D. C. Joy, The Basic Principles of EELS in Principles of Analytical Electron Micro skopy, edited by D.C. Joy, A.D. Romig, Jr. and J.I. Gold stein, Plenum Press, New York, 1986; L. C. Sawyer and D. T. Grupp, Polymer Microscopy, Chapman and Hall, London, 1987).

The composites obtainable by the process according to the invention particles can have different structures. Frequently composite particles with a raspberry-shaped structure are obtained. The Composite particles according to the invention can one or more of the contain finely divided solid particles. The finely divided feast Particle particles can be completely enveloped by the polymer matrix his. However, it is also possible for some of the fine particles Solid particles are enveloped by the polymer matrix while a another part is arranged on the surface of the polymer matrix. Of course, it is also possible that a large part of the finely divided solid particles on the surface of the polymer matrix  is bound. ≧ 50% by weight or ≧ 60% by weight are preferred, often ≧ 70% by weight or ≧ 80% by weight and often ≧ 85% by weight or ≧ 90% by weight of the finely divided solid particles, in each case related on the total amount contained in the composite particles finely divided solid particles, on the surface of the polymer matrix bound. It should be noted that in individual cases, it depends gig of the solids concentration of the dispersed composite par particles, also to a small partial agglomeration of the composite par article can come.

Of course, after completion of the main polymer tion reaction in the aqueous dispersion of the composite particles remaining amounts of monomer by steam and / or inert gas stripping and / or chemical deodorization, as in for example in the documents DE-A 44 19 518, EP-A 767 180 or DE-A 38 34 734 are described, can be removed without the properties of the aqueous composite particle dispersion change in part.

Aqueous dispersions of composite particles, which after the be described inventive methods are produced, eigen NEN as raw materials for the production of adhesives, such as for example, pressure sensitive adhesives, construction adhesives or industrial adhesives substances, binders, such as for paper strips niche, emulsion paints or for printing inks and varnishes for Printing on plastic films, for the production of nonwovens as well as for the production of protective layers and water vapor barriers, like for example with the primer. Furthermore, the composite particle disks accessible by the process according to the invention persions also for modifying cement and mortar form Use lations. The according to the inventive method common composite particles can in principle also in the medical diagnostics and other medical applications gene (see e.g. K. Mosbach and L. Andersson, Nature, 1977, 270, pages 259 to 261; P. L. Kronick, Science 1978, 200, Pages 1074 to 1076; US-A 4,157,323). Beyond that the composite particles also as catalysts in various use aqueous dispersion systems.

It should also be noted that those obtainable according to the invention aqueous dispersions of composite particles in a simple manner redispersible composite particle powders can be dried (e.g. Freeze drying or spray drying). This is especially true then when the glass transition temperature of the polymer matrix he Composite particles accessible according to the invention ≧ 50 ° C, preferably ≧ 60 ° C, particularly preferably ≧ 70 ° C, very particularly preferably ≧ 80 ° C and particularly preferably ≧ 90 ° C or ≧ 100 ° C. The composite particle powder  are suitable as u. a. as additives for art substances, components for toner formulations or additives in electrophotographic applications.

Examples

For the following examples it was considered to be a finely divided inorganic Solid silicon dioxide, yttrium (III) oxide and cerium (IV) oxide used. The commercially available sili were exemplary ziumdioxidsole Nyacol® 2040 (20 nm) and Nyacol® 830 (10 nm) der Akzo-Nobel and Ludox® HS30 (12 nm) from Dupont set. Nyacol® YTTRIA [yttrium- (III) oxide] (10 nm) and Nyacol® CEO2 {ACT} [cerium (IV) oxide] (10 up to 20 nm). The values given in parentheses correspond the diameters of the respective inorganic solid particles according to the manufacturer's instructions.

The solid dispersions used in the examples met all demands made on them, namely that they should Initial solids concentration of ≧ 1 wt .-%, based on the aqueous dispersion of the solid, one hour after it Production more than 90 wt .-% of the originally dispersed Contained solids in dispersed form and their disper giert solid particles a weight average diameter ≦ 100 nm and also the dispersed inorganic solid particles in a standard aqueous potassium chloride Solution at a pH equal to the pH of the aqueous reaction mediums at the beginning of the emulsion polymerization corresponded to one of Showed zero different electrophoretic mobility.

1st example

In a 500 ml four-necked flask equipped with a reflux cooler, a thermometer, a mechanical stirrer and one Dosing device, were under nitrogen atmosphere at 20 ° C and 1 bar (absolute) 80 g deionized and oxygen-free water as well as 0.04 g of 1 M sodium hydroxide solution and stirring (250 um rotations per minute) 20 g Nyacol® 2040 added. Then heated up the reaction mixture to a reaction temperature of 75 ° C. on. The pH of this aqueous phase, measured at room temperature tur, was 10.

In parallel, an aqueous emulsion consisting of 10 g of styrene, 10 g of n-butyl acrylate, 0.19 g of 1 M sodium hydroxide solution, 80 g of deionized and oxygen-free water, 1 g of a 20% strength by weight aqueous solution of the nonionic emulsifier lutensol ® AT18 (trademark of BASF AG, C ₁₆ C ₁₈ fatty alcohol ethoxylate with 18 ethylene oxide units) and 0.25 g Norsocryl® ADAMQUAT MC 80 (80% strength by weight aqueous solution of 2- (N, N, N-trimethylammonium ) ethyl acrylate chloride) (feed 1). An initiator solution was prepared from 0.23 g of ammonium peroxodisulfate and 45 g of deionized and oxygen-free water (feed 2).

At the reaction temperature, 5 g of the stirred reaction medium from feed 2 added. After 5 minutes and at the same time starting, the stirred reaction medium was metered in at Reakti temperature the inlet 1 over 2 hours and the rest of the inlet 2 over 2.5 hours too. The reaction mixture was then stirred mix for a further 1 hour at the reaction temperature and then cool down Room temperature.

The aqueous composite particle dispersion thus obtained had one Solids content of 11.4% by weight, based on the total weight the aqueous composite particle dispersion.

Transmission electron microscopic investigations using deionized water to a solids content of about 0.01% by weight of dilute aqueous composite particle dispersion, with a Zeiss 902 device from Zeiss showed a raspberry-shaped compo sit particles with a diameter of about 250 nm. Free Si silicon dioxide particles were practically undetectable.

By centrifuging the composite particle dispersion (3000 rev per minute, duration 20 minutes) was complete sediment tion of the dispersed particles. In the supernatant water-clear solution could be by transmission electron mi microscopic investigations did not detect any silicon dioxide particles sen.

The sign determination of the electrophoretic mobility he followed generally for the fine-particle inorganic solids using the Zetasizer 3000 from Malvern Instruments Ltd., Great Britain. For this purpose, the finely divided inorganic was diluted Solid dispersion with aqueous pH-neutral 10 mM potassium chloride rid solution (standard potassium chloride solution) so far that its solid particle concentration was between 50 and 100 mg per liter. Using dilute hydrochloric acid or dilute sodium hydroxide solution one the pH, which the aqueous reaction medium immediately had before adding the polymerization initiator.

Using 1 M sodium hydroxide solution, the mixture was adjusted to 60 mg / l silicon of the Nyacol® 2040 dispersion pH of 10 a. The electrophoretic mobility of the silica particles  in Nyacol® 2040 there was a negative sign che on.

The solids content was generally determined by about 1 g of the Composite particle dispersion in an open aluminum pan with an inside diameter of approx. 3 cm in a drying cabinet Was dried at 150 ° C for 2 hours. To determine the festival content, two separate measurements were carried out and the corresponding mean is formed.

1. Comparative example

Example 1 was repeated with the exception that instead of 0.25 g Norsocryl® ADAMQUAT MC 80 0.25 g deionized and acidic substance-free water was used.

The particle dispersion formed had a solids content of 11.1% by weight, based on the total weight of the aqueous particles dispersion, on. The cloudy reaction mixture obtained was mixed with by means of transmission electron microscopic measurements. Raspberry-shaped composite particles were not detectable.

By centrifuging the cloudy dispersion (3000 revolutions per Minute, duration 20 minutes) no sedimentation of the disper gated particles can be achieved.

2. Comparative example

Example 1 was repeated with the exception that instead of 0.25 g Norsocryl® ADAMQUAT MC 80 0.2 g of the sodium salt of 4-styrene sulfonic acid was used.

The particle dispersion formed had a solids content of 11.4% by weight, based on the total weight of the aqueous particles dispersion, on. The cloudy reaction mixture obtained was mixed with by means of transmission electron microscopic measurements. Raspberry-shaped composite particles were not detectable.

By centrifuging the cloudy dispersion (3000 revolutions per Minute, duration 20 minutes) no sedimentation of the disper gated particles can be achieved.

2nd example

In a 500 ml four-necked flask were placed under a nitrogen atmosphere at 20 ° C and 1 bar (absolute) 60 g deionized and oxygen free water and 1.5 g of 1 M hydrochloric acid are introduced and with stirring  (250 revolutions per minute) 20 g Nyacol® 2040 added. On finally, the aqueous phase was made up with 1.62 g of 1 M hydrochloric acid to a pH of 2.5 and filled it with water containing 1 M hydrochloric acid had been adjusted to a pH of 2.5, to 100 g. The reaction mixture was then heated to a Reaction temperature of 75 ° C. The pH of this aqueous Phase, measured at room temperature, was 2.5.

An aqueous emulsion consisting of 10 g was prepared in parallel Styrene, 10 g n-butyl acrylate, 80 g deionized and oxygen free water, 0.44 g of a 45% by weight aqueous solution of Dowfax® 2A1 and 0.2 g of 4-vinylpyridine (feed 1). A Initiator solution was made up of 0.23 g ammonium peroxodisulfate and 45 g deionized and oxygen-free water (Zu run 2).

At the reaction temperature, 5 g of the stirred reaction medium from feed 2 added. After 5 minutes and at the same time starting, the stirred reaction medium was metered in at Reakti temperature of feed 1 over 2 hours and the rest of feed 2 over 2.5 hours too. The reaction mixture was then stirred mix for another hour at reaction temperature and then cool down Room temperature.

The composite particle dispersion thus obtained had a solid content of 11.5 wt .-%, based on the total weight of the aqueous composite particle dispersion. The presence of him beer-shaped composite particles with a diameter of about 200 to 300 nm was determined by means of transmission electron microscopy proven studies. Free silica particles could not be demonstrated practically.

The silica particles from Nyacol® 2040 showed one pH 2.5 an electrophoretic mobility with negative Sign on.

By centrifuging the composite particle dispersion (3000 rev per minute, duration 20 minutes) was complete sediment tion of the dispersed particles. In the supernatant water-clear solution could be by transmission electron mi microscopic examinations practically no silicon dioxide part evidence.  

3. Comparative example

Example 2 was repeated with the exception that instead of 0.2 g 4-vinyl pyridine 0.2 g deionized and oxygen-free Water were used.

The particle dispersion formed had a solids content of 11.6% by weight, based on the total weight of the aqueous particles dispersion, on. The cloudy reaction mixture obtained was mixed with by means of transmission electron microscopic measurements. Raspberry-shaped composite particles were not detectable.

By centrifuging the cloudy dispersion (3000 revolutions per Minute, duration 20 minutes) no sedimentation of the disper gated particles can be achieved.

4. Comparative example

Example 2 was repeated with the exception that instead of 0.2 g of 4-vinyl pyridine 0.2 g of the sodium salt of 4-styrene sulfone acid was used.

The particle dispersion formed had a solids content of 11.5% by weight, based on the total weight of the aqueous particles dispersion, on. The cloudy reaction mixture obtained was mixed with by means of transmission electron microscopic measurements. Raspberry-shaped composite particles were not detectable.

By centrifuging the cloudy dispersion (3000 revolutions per Minute, duration 20 minutes) no sedimentation of the disper gated particles can be achieved.

3rd example

In a 500 ml four-necked flask were placed under a nitrogen atmosphere at 20 ° C and 1 bar (absolute) 60 g deionized and oxygen free water and 1.5 g of 1 M hydrochloric acid are introduced and stirred 20 g Nyacol® 2040 added (250 revolutions per minute). On finally, the aqueous phase was made up with 1.62 g of 1 M hydrochloric acid to a pH of 2.5 and filled it with water containing 1 M hydrochloric acid had been adjusted to a pH of 2.5, to 100 g. The reaction mixture was then heated to a Reaction temperature of 75 ° C. The pH of this aqueous Phase, measured at room temperature, was 2.5.  

An aqueous emulsion consisting of 10 g was prepared in parallel Styrene, 10 g n-butyl acrylate, 80 g deionized and oxygen free water, 1 g of a 20 wt .-% aqueous solution of the ionic emulsifier Lutensol® AT18 and 0.05 g 4-vinylpyridine forth (inlet 1). An initiator solution was made from 0.23 g of ammonium peroxodisulfate and 45 g deionized and oxygen-free water water produced (inlet 2).

At the reaction temperature, 5 g of the stirred reaction medium from feed 2 added. After 5 minutes and at the same time starting, the stirred reaction medium was metered in at Reakti temperature the inlet 1 over 2 hours and the rest of the inlet 2 over 2.5 hours too. The reaction mixture was then stirred mix for a further 1 hour at the reaction temperature and then cool down Room temperature.

The composite particle dispersion thus obtained had a solid content of 11.1 wt .-%, based on the total weight of the aqueous composite particle dispersion. The presence of him beer-shaped composite particles with a diameter of about 220 nm was measured using transmission electron microscope Un tests demonstrated. Free silicon dioxide particles practically no evidence.

4th example

In a 500 ml four-necked flask were placed under a nitrogen atmosphere at 20 ° C and 1 bar (absolute) 60 g deionized and oxygen free water and 1.5 g of 1 M hydrochloric acid are introduced and stirred 20 g Nyacol® 2040 added (250 revolutions per minute). On finally, the aqueous phase was made up with 0.5 g of 1 M hydrochloric acid to a pH of 7 and filled it with deionized and oxygen-free water to 100 g. Then you heated the Re action mixture to a reaction temperature of 85 ° C. The pH of this aqueous phase, measured at room temperature, be wore 7.

An aqueous emulsion consisting of 20 g was prepared in parallel Styrene, 80 g deionized and oxygen-free water, 1 g egg ner 20 wt .-% aqueous solution of the nonionic emulsifier Lutensol® AT18 and 0.2 g of 4-vinylpyridine (feed 1). A Initiator solution was made up of 0.45 g sodium peroxodisulfate and 45 g deionized and oxygen-free water (Zu run 2).  

At the reaction temperature, 5 g of the stirred reaction medium from feed 2 added. After 5 minutes and at the same time starting, the stirred reaction medium was metered in at Reakti temperature the inlet 1 over 2 hours and the rest of the inlet 2 over 2.5 hours too. The reaction mixture was then stirred mix for a further 1 hour at the reaction temperature and then cool down Room temperature.

The composite particle dispersion thus obtained had a solid content of 11.6 wt .-%, based on the total weight of the aqueous composite particle dispersion. The presence of him beer-shaped composite particles with a diameter of about 140 to 220 nm was measured using transmission electron microscopy proven studies. Free silica particles could not be demonstrated practically.

The silica particles from Nyacol® 2040 showed one pH of 7 an electrophoretic mobility with negative Sign on.

5th example

Example 4 was repeated with the exception that the aqueous Re Action medium was adjusted to a pH of 5.

For the preparation of the template were under a nitrogen atmosphere at 20 ° C and 1 bar (absolute) 60 g deionized and oxygen free water and 1.5 g of 1 M hydrochloric acid are introduced and stirred 20 g Nyacol® 2040 added (250 revolutions per minute). On finally, the aqueous phase was made up with 1.0 g of 1 M hydrochloric acid to a pH of 5 and fill it with water containing 1 M hydrochloric acid had been adjusted to a pH of 5 100 g. The reaction mixture was then heated to a reak tion temperature of 85 ° C. The pH of this aqueous phase, measured at room temperature was 5.

The composite particle dispersion thus obtained had a solid content of 11.6 wt .-%, based on the total weight of the aqueous composite particle dispersion. The presence of him beer-shaped composite particles with a diameter of about 170 nm was measured using transmission electron microscope Un tests demonstrated. Free silicon dioxide particles practically no evidence.  

The silica particles from Nyacol® 2040 showed one pH of 5 is an electrophoretic mobility with negative Sign on.

6th example

In a 500 ml four-necked flask were placed under a nitrogen atmosphere at 20 ° C and 1 bar (absolute) 60 g deionized and oxygen free water and 1.5 g of 1 M hydrochloric acid are introduced and stirred 20 g Nyacol® 2040 added (250 revolutions per minute). On finally, the aqueous phase was made up with 1.62 g of 1 M hydrochloric acid to a pH of 2.5 and filled them with deionized and oxygen-free water mixed with 1 M hydrochloric acid pH of 2.5 had been adjusted to 100 g. After that the reaction mixture was heated to a reaction temperature of 85 ° C. The pH of this aqueous phase, measured at room temperature temperature, was 2.5.

An aqueous emulsion consisting of 20 g was prepared in parallel Styrene, 80 g deionized and oxygen-free water, 2 g egg ner 20 wt .-% aqueous solution of the nonionic emulsifier Lutensol® AT18 and 0.2 g 2-vinylpyridine (feed 1). A Initiator solution was made up of 0.45 g sodium peroxodisulfate and 45 g deionized and oxygen-free water (Zu run 2).

At the reaction temperature, 5 g of the stirred reaction medium from feed 2 added. After 5 minutes and at the same time starting, the stirred reaction medium was metered in at reak tion temperature the inlet 1 over 2 hours and the rest of Zu run 2 over 2.5 hours. The reaction was then stirred mixture for 1 hour at the reaction temperature and then cooled to room temperature.

The composite particle dispersion thus obtained had a solid content of 10.5 wt .-%, based on the total weight of the aqueous composite particle dispersion. The presence of him beer-shaped composite particles with a diameter of about 140 to 180 nm was measured using transmission electron microscopy proven studies. Free silica particles could not be demonstrated practically.  

7th example

Example 6 was repeated except that for the preparation of feed 1 instead of 0.2 g of 2-vinylpyridine 0.2 g of Norsocryl® MADAME [2- (N, N- (Dimethylamino) ethyl methacrylate)] was used the.

The composite particle dispersion thus obtained had a solid content of 11.8 wt .-%, based on the total weight of the aqueous composite particle dispersion. The presence of him beer-shaped composite particles with a diameter of about 170 nm was measured using transmission electron microscope Un tests demonstrated. Free silicon dioxide particles practically no evidence.

8. Example

In a 500 ml four-necked flask were placed under a nitrogen atmosphere at 20 ° C and 1 bar (absolute) 60 g deionized and oxygen free water and 1.5 g of 1 M hydrochloric acid are introduced and stirred 20 g Nyacol® 2040 added (250 revolutions per minute). On finally, the aqueous phase was made up with 1.62 g of 1 M hydrochloric acid to a pH of 2.5 and filled them with deionized and oxygen-free water mixed with 1 M hydrochloric acid pH of 2.5 had been adjusted to 100 g. After that the reaction mixture was heated to a reaction temperature of 85 ° C. The pH of this aqueous phase, measured at room temperature temperature, was 2.5.

An aqueous emulsion consisting of 10 g was prepared in parallel Styrene, 10 g 2-ethylhexyl acrylate, 80 g deionized and acidic substance-free water, 1 g of a 20 wt .-% aqueous solution of non-ionic emulsifier Lutensol® AT18 and 0.05 g 4-vinylpy ridin forth (inlet 1). An initiator solution was made from 0.45 g Na triumperoxodisulfate and 45 g deionized and oxygen-free Water produced (inlet 2).

At the reaction temperature, 5 g of the stirred reaction medium from feed 2 added. After 5 minutes and at the same time starting, the stirred reaction medium was metered in at Reakti temperature of feed 1 over 2 hours and the rest of feed 2 over 2.5 hours too. The reaction mixture was then stirred mix for another hour at reaction temperature and then cool down Room temperature.  

The composite particle dispersion thus obtained had a solid content of 11.5 wt .-%, based on the total weight of the aqueous composite particle dispersion. The presence of him beer-shaped composite particles with a diameter of about 300 nm was determined by means of transmission electron microscope Un tests demonstrated. Free silicon dioxide particles practically no evidence.

Example 9

Example 8 was repeated except that for the preparation of feed 1 instead of 10 g of styrene 10 g of methyl methacrylate ver were applied.

The composite particle dispersion thus obtained had a solid content of 11.1 wt .-%, based on the total weight of the aqueous composite particle dispersion. The presence of him beer-shaped composite particles with a diameter of about 220 nm was measured using transmission electron microscope Un tests demonstrated. Free silicon dioxide particles practically no evidence.

10. Example

Example 9 was repeated except that for the preparation of feed 1 instead of 10 g of 2-ethylhexyl acrylate 10 g of n-butyl acrylate were used.

The composite particle dispersion thus obtained had a solid content of 11.4 wt .-%, based on the total weight of the aqueous composite particle dispersion. The presence of him beer-shaped composite particles with a diameter of about 220 nm was measured using transmission electron microscope Un tests demonstrated. Free silicon dioxide particles practically no evidence.

Example 11

In a 500 ml four-necked flask were placed under a nitrogen atmosphere at 20 ° C and 1 bar (absolute) 40 g deionized and oxygen free water and 1.5 g of 1 M hydrochloric acid are introduced and stirred 40 g Nyacol® 2040 added (250 revolutions per minute). On finally, the aqueous phase was made up with 3.99 g of 1 M hydrochloric acid to a pH of 2.5 and filled them with deionized and oxygen-free water mixed with 1 M hydrochloric acid pH of 2.5 had been adjusted to 100 g. After that the reaction mixture was heated to a reaction temperature of  85 ° C. The pH of this aqueous phase, measured at room temperature temperature, was 2.5.

An aqueous emulsion consisting of 20 g was prepared in parallel Styrene, 20 g n-butyl acrylate, 60 g deionized and oxygen free water, 2 g of a 20 wt .-% aqueous solution of the ionic emulsifier Lutensol® AT18 and 0.1 g 4-vinylpyridine forth (inlet 1). An initiator solution was made from 0.9 g sodium per oxodisulfate and 45 g deionized and oxygen-free water manufactured (inlet 2).

At the reaction temperature, 5 g of the stirred reaction medium from feed 2 added. After 5 minutes and at the same time starting, the stirred reaction medium was metered in at Reakti temperature of feed 1 over 2 hours and the rest of feed 2 over 2.5 hours too. The reaction mixture was then stirred mix for another hour at reaction temperature and then cool down Room temperature.

The composite particle dispersion thus obtained had a solid content of 22.9 wt .-%, based on the total weight of the aqueous composite particle dispersion. The presence of him beer-shaped composite particles with a diameter of about 120 to 300 nm was determined by means of transmission electron microscopy proven studies. Free silica particles could not be demonstrated practically.

Example 12

In a 500 ml four-necked flask were placed under a nitrogen atmosphere at 20 ° C and 1 bar (absolute) 15 g deionized and oxygen free water and 1.5 g of 1 M hydrochloric acid are introduced and stirred ren (250 revolutions per minute) 73.5 g Nyacol® 2040 added. The aqueous phase was then made up with 8.24 g of 1 M salt acid to a pH of 2.5 and filled it with entioni treated and oxygen-free water with 1 M hydrochloric acid pH 2.5 had been set to 100 g. Then you heated up the reaction mixture to a reaction temperature of 85 ° C. The pH of this aqueous phase, measured at room temperature, was 2.5.

An aqueous emulsion consisting of 34.3 g was prepared in parallel Styrene, 34.3 g n-butyl acrylate, 31.4 g deionized and acidic substance-free water, 3.43 g of a 20 wt .-% aqueous solution of the non-ionic emulsifier Lutensol® AT18 and 0.1 g 4-vinyl pyridine forth (feed 1). An initiator solution was made from 1.54 g sodium peroxodisulfate  and 45 g deionized and oxygen free Water produced (inlet 2).

At the reaction temperature, 5 g of the stirred reaction medium from feed 2 added. After 5 minutes and at the same time starting, the stirred reaction medium was metered in at Reakti temperature of feed 1 over 2 hours and the rest of feed 2 over 2.5 hours too. The reaction mixture was then stirred mix for another hour at reaction temperature and then cool down 1 room temperature.

The composite particle dispersion thus obtained had a solid content of 37.5 wt .-%, based on the total weight of the aqueous composite particle dispersion. The presence of him beer-shaped composite particles with a diameter of about 120 to 240 nm was determined by means of transmission electron microscopy proven studies. Free silica particles could not be demonstrated practically.

13. Example

In a 500 ml four-necked flask were placed under a nitrogen atmosphere at 20 ° C and 1 bar (absolute) 50 g deionized and oxygen free water and 1.5 g of 1 M hydrochloric acid are introduced and stirred ren (250 revolutions per minute) 26.7 g Nyacol® 830 (with a Silicon dioxide solids content of 30 wt .-%) added. Then The aqueous phase was placed on with 4.06 g of 1 M hydrochloric acid a pH of 2.5 and filled it with deionized and oxygen-free water, which is brought to pH with 1 M hydrochloric acid had been set from 2.5 to 100 g. Subsequently the reaction mixture was heated to a reaction temperature of 85 ° C. The p 08446 00070 552 001000280000000200012000285910833500040 0002010000281 00004 08327H value of this aqueous phase, measured at room temperature, was 2.5.

An aqueous emulsion consisting of 20 g was prepared in parallel Styrene, 80 g deionized and oxygen-free water, 2 g egg ner 20 wt .-% aqueous solution of the nonionic emulsifier Lutensol® AT18 and 0.2 g Norsocryl® MADAME (inlet 1). A Initiator solution was made up of 0.45 g sodium peroxodisulfate and 45 g deionized and oxygen-free water (Zu run 2).

At the reaction temperature, 5 g of the stirred reaction medium from feed 2 added. After 5 minutes and at the same time starting, the stirred reaction medium was metered in at Reakti temperature of feed 1 over 2 hours and the rest of feed 2 over 2.5 hours too. The reaction mixture was then stirred  another 1 hour at reaction temperature and then cooled Room temperature.

The composite particle dispersion thus obtained had a solid content of 12.0 wt .-%, based on the total weight of the aqueous composite particle dispersion. The presence of him beer-shaped composite particles with a diameter of about 160 to 200 nm was measured using transmission electron microscopy proven studies. Free silica particles could not be demonstrated practically.

The silica particles from Nyacol® 830 showed one pH 2.5 an electrophoretic mobility with negative Sign on.

14. Example

In a 500 ml four-necked flask were placed under a nitrogen atmosphere at 20 ° C and 1 bar (absolute) 50 g deionized and oxygen free water and 1.5 g of 1 M hydrochloric acid are introduced and stirred ren (250 revolutions per minute) 26.7 g Ludox® HS30 (with a Silicon dioxide solids content of 30 wt .-%) added. Then The aqueous phase was set up with 1.88 g of 1 M hydrochloric acid a pH of 2.5 and filled it with deionized and oxygen-free water, which is brought to pH with 1 M hydrochloric acid had been set from 2.5 to 100 g. Subsequently the reaction mixture was heated to a reaction temperature of 85 ° C. The pH of this aqueous phase, measured at room temperature temperature, was 2.5.

An aqueous emulsion consisting of 10 g was prepared in parallel Styrene, 10 g n-butyl acrylate, 80 g deionized and oxygen free water, 1 g of a 20 wt .-% aqueous solution of the ionic emulsifier Lutensol® AT18 and 0.05 g 4-vinylpyridine forth (inlet 1). An initiator solution was made from 0.45 g sodium per oxodisulfate and 45 g deionized and oxygen-free water manufactured (inlet 2).

At the reaction temperature, 5 g of the stirred reaction medium from feed 2 added. After 5 minutes and at the same time starting, the stirred reaction medium was metered in at Reakti temperature of feed 1 over 2 hours and the rest of feed 2 over 2.5 hours too. The reaction mixture was then stirred mix for another hour at reaction temperature and then cool down Room temperature.  

The composite particle dispersion thus obtained had a solid content of 9.7 wt .-%, based on the total weight of the aqueous Composite particle dispersion, on. The presence of raspberry-shaped gene composite particles with a diameter of about 200 nm by means of transmission electron microscopic examinations proven. Free silica particles could be practically do not prove.

The silica particles from Ludox® HS30 showed one pH value of 2.5 is an electrurophoretic mobility with negative Sign on.

15. Example

In a 500 ml four-necked flask were placed under a nitrogen atmosphere at 20 ° C and 1 bar (absolute) 60 g deionized and oxygen free water and 0.01 g of 1 M hydrochloric acid are introduced and stirred ren (250 revolutions per minute) 40 g Nyacol® CEO2 {ACT} (with a nem cer (IV) oxide solids content of 20 wt .-%) added. On then heated to a reaction temperature of 85 ° C. The pH of this aqueous phase, measured at room temperature, was 3.

An aqueous emulsion consisting of 20 g was prepared in parallel Styrene, 80 g deionized and oxygen-free water, 1 g egg ner 20 wt .-% aqueous solution of the nonionic emulsifier Lutensol® AT18 and 0.2 g of the sodium salt of 4-styrene sulfone acid (feed 1). An initiator solution was made from 0.45 g AIBA and 45 g of deionized and oxygen-free water (Inlet 2).

At the reaction temperature, 5 g of the stirred reaction medium from feed 2 added. After 5 minutes and at the same time starting, the stirred reaction medium was metered in at reak tion temperature the inlet 1 over 2 hours and the rest of Zu run 2 over 2.5 hours. The reaction was then stirred mixture for 1 hour at the reaction temperature and then cooled to room temperature.

A solids content of 11.2 wt .-%, based on the total Ge important of the aqueous composite particle dispersion, the so pointed lengthy composite particle dispersion. By transmission elec Tron microscopic measurements were raspberry-shaped composite detected particles with a diameter of about 200 to 400 nm. Free cerium (IV) oxide particles could practically not be detected become.  

The cerium (IV) oxide particles from Nyacol® CEO2 {ACT} showed in one pH 3 an electrophoretic mobility with positive Sign on.

By centrifuging the composite particle dispersion (3000 rev per minute, duration 20 minutes) was complete sediment tion of the dispersed particles.

5. Comparative example

Example 15 was repeated with the exception that the Her position of feed 1 instead of 0.2 g of the sodium salt of 4-styrenesulfonic acid 0.25 g Norsocryl® ADAMQUAT MC 80 was used has been.

The particle dispersion formed had a solids content of 11.4% by weight, based on the total weight of the aqueous particles dispersion, on. The cloudy reaction mixture obtained was mixed with by means of transmission electron microscopic measurements. Raspberry-shaped composite particles were not detectable.

By centrifuging the cloudy dispersion (3000 revolutions per Minute, duration 20 minutes) no sedimentation of the disper gated particles can be achieved.

16. Example

In a 500 ml four-necked flask were placed under a nitrogen atmosphere at 20 ° C and 1 bar (absolute) 42.9 g deionized and oxygen free water and stirring (250 revolutions per mi 57.1 g Nyacol® YTTRIA (with a yttrium (III) oxide solid substance content of 14 wt .-%) added. Then you heated it Reaction mixture to a reaction temperature of 85 ° C. The pH of this aqueous phase, measured at room temperature, be wore 7.2.

An aqueous emulsion consisting of 20 g was prepared in parallel Styrene, 80 g deionized and oxygen-free water, 1 g egg ner 20 wt .-% aqueous solution of the nonionic emulsifier Lutensol® AT18 and 0.2 g methyl acrylic acid (feed 1). A Initiator solution was made from 0.45 g AIBA and 45 g deionized and oxygen-free water produced (inlet 2).

At the reaction temperature, 5 g of the stirred reaction medium from feed 2 added. After 5 minutes and at the same time starting, the stirred reaction medium was metered in at Reakti temperature of feed 1 over 2 hours and the rest of feed  2 over 2.5 hours too. The reaction mixture was then stirred mix for another hour at reaction temperature and then cool down Room temperature.

The composite particle dispersion formed had a solid matter hold of 13.7 wt .-%, based on the total weight of the aqueous Composite particle dispersion, on. By transmission electron mi Microscopic measurements were made using raspberry-shaped composite particles demonstrated a diameter of about 90 nm. Free ytt rium (III) oxide particles could practically not be detected the.

The yttrium (III) oxide particles from Nyacol® YTTRIA showed at ei nem pH 7.2 an electrophoretic mobility with positi the sign.

Claims (13)

1. A process for the preparation of an aqueous dispersion of particles built up from polymer and finely divided inorganic solid (composite particles), in which a mixture of ethylenically unsaturated monomers is dispersed in an aqueous medium and is dispersed by means of at least one radical polymerisation initiator in the presence of at least one disperse, finely divided inorganic solid and at least one dispersant is polymerized according to the method of radically aqueous emulsion polymerization, characterized in that

• a) a stable aqueous dispersion of the at least one organic solid is used, which is characterized in that it has an initial solid concentration of ≧ 1% by weight, based on the aqueous dispersion of the at least one solid, one hour after its preparation contains more than 90% by weight of the originally dispersed solid in dispersed form and the dispersed solid particles have a weight-average diameter ≦ 100 nm,
• b) the dispersed solid particles of the at least one inorganic solid in an aqueous standard potassium chloride solution at a pH which corresponds to the pH of the aqueous reaction medium at the beginning of the emulsion polymerization, show a non-zero electrophoretic mobility and
• c) the mixture of ethylenically unsaturated monomers <0 and ≦ 4 wt .-%, based on its total amount, contains at least one ethylenically unsaturated monomer A, which ent

• - Contains at least one acid group and / or its corresponding anion if the dispersed solid particles of the at least one inorganic solid under the aforementioned conditions have an electrophoretic mobility with a positive sign, or
• - Contains at least one amino, amido, ureido or N-heterocyclic group and / or their ammonium derivatives protonated or alkylated on nitrogen if the dispersed solid particles of the at least one inorganic solid under the aforementioned conditions have an electrophoretic mobility with a negative sign Chen have.

2. The method according to claim 1, characterized in that the at least one inorganic solid is selected from the Group comprising silicon dioxide, aluminum oxide, Tin (IV) oxide, yttrium (III) oxide, cerium (IV) oxide, hydroxy aluminum oxide, calcium carbonate, magnesium carbonate, calcium orthophosphate, magnesium orthophosphate, calcium metaphosphate, Magnesium metaphosphate, calcium pyrophosphate, magnesium pyro phosphate, iron (II) oxide, iron (III) oxide, iron (II / III) oxide, titanium dioxide, hydroxylapatite, zinc oxide and zinc sul fid. 3. The method according to any one of claims 1 or 2, characterized records that the at least one inorganic solid in Water at 20 ° C and 1 bar (absolute) a solubility ≦ 1 g / l Has water. 4. The method according to any one of claims 1 to 3, characterized records that the at least one dispersant is an emul gator is. 5. The method according to any one of claims 1 to 4, characterized records that the at least one monomer A at least one Contains acid group and / or their corresponding anion, wel che from the group comprising the carboxylic acid, sulfonic acid, Sulfuric acid, phosphoric acid and phosphonic acid group out chooses. 6. The method according to any one of claims 1 to 5, characterized records that the at least one monomer A is selected from the group comprising acrylic acid, methacrylic acid, malein acid, fumaric acid, itaconic acid, crotonic acid, 4-styrene sulfone acid, 2-methacryloxyethyl sulfonic acid, vinyl sulfonic acid and Vinylphosphonic acid. 7. The method according to any one of claims 1 to 4, characterized records that the at least one monomer A is selected from the group comprising 2-vinylpyridine, 4-vinylpyridine,  2-vinylimidazole, 2- (N, N-dimethylamino) ethyl acrylate, 2- (N, N-dimethylamino) ethyl methacrylate, 2- (N, N-diethyl amino) ethyl acrylate, 2- (N, N-diethylamino) ethyl methacrylate, 2- (N-tert-butylamino) ethyl methacrylate, N- (3-N ', N'-dimethyl aminopropyl) methacrylamide and 2- (1-imidazolin-2-onyl) ethyl methacrylate and 2- (N, N, N-trimethylammonium) ethyl acrylate chloride, 2- (N, N, N-trimethylammonium) ethyl methacrylate chloride, 2- (N-benzyl-N, N-dimethylammonium) ethyl acrylate chloride and 2- (N-benzyl-N, N-dimethylammonium) ethyl methacrylate chloride. 8. The method according to any one of claims 1 to 6, characterized records that the at least one radical polymer on initiator is 2,2'-azobis (amidinopropyl) dihydrochloride. 9. The method according to claim 7, characterized in that the at least one radical polymerization initiator from the Group comprising sodium peroxodisulfate, potassium peroxodisulfate, Ammonium peroxodisulfate is selected. 10. Aqueous dispersion of composite particles, available after a method according to any one of claims 1 to 9. 11. Aqueous dispersion according to claim 10, characterized in that bezogen 50 wt .-% of the finely divided solid particles, based on the total amount contained in the composite particles finely divided solid particles, on the surface of the Polymer matrix are bound. 12. Use of an aqueous dispersion of composite particles according to claim 10 or 11, as an adhesive, as a binder, for the production of a protective layer, for the modification of Cement and mortar formulations or in medical Diagnosis. 13. Composite particle powder, obtainable by drying one aqueous dispersion of composite particles according to claim 10 or 11.