EP1910462A2

EP1910462A2 - Stabilised hdk suspensions for reinforcement of reactive resins

Info

Publication number: EP1910462A2
Application number: EP06764044A
Authority: EP
Inventors: Herbert Barthel; Michael Dreyer; Torsten Gottschalk-Gaudig
Original assignee: Wacker Chemie AG
Current assignee: Wacker Chemie AG
Priority date: 2005-07-28
Filing date: 2006-07-04
Publication date: 2008-04-16
Also published as: US20080207842A1; WO2007012547A2; CN101233182A; CN101233182B; JP5269592B2; KR20080039953A; JP2009503166A; KR101013929B1; DE102005035442A1; US8071666B2; WO2007012547A3

Abstract

Suspensions, containing at least 3 wt. % of particulate thickening agent, with an amount of at least 5 wt. % of a polymer, based on the pure particulate thickening agent without polymer, is bonded to said particulate thickening agent in the suspension, optionally at least one further polymer or several polymers are present free in the suspension, the relative viscosity ?/?o, where ? and ?o are measured at the same temperature and at 25 °C, is less than 100 and the relative viscosity ?/ ?o changes by less than a factor of 10 after storage for at least one week at a temperature of 40 °C and contains liquid phases, which, based on the total liquid phase, comprises 0 - 80 wt. % of a solvent or low molecular weight cross-linkable components with a viscosity of less than 100 mPas at 25 °C and, based on the total liquid phase, comprise 10-100 wt. % of polymer components or a mixture of two or more physically or chemically cross-linkable polymers.

Description

Stabilized HDK Suspensions for Reinforcement of

reactive resins

The invention relates to a suspension and products made therefrom.

The use of pyrogenic silica as thickener and rheological additive is known. Pyrogenic silica exhibits high space filling and strong interparticle interaction, and generates in liquid

Media stable gel states, especially at high solids content.

For use as reinforcing filler in reactive resins and polymer systems, however, high loadings with active fillers, which are also particulate thickeners, such as with fumed silica necessary. A high thickening effect and thus high viscosity and gel state, thus loss of flowability, in many cases represents a major problem in the processing of active, finely divided and colloidal fillers. It results in high viscosity, poor flowability, entrainment, non-pumpability, not Spreadability, non-sprayability, inadequate course of paints, varnishes and surface coatings, and insufficient processing properties.

It is known that the thickening effect of colloidal fillers in connection with OH groups are on their surface and on the other hand oxidic fillers with high specific surface area are subject to strong van der Waals interactions, and thus fluids such as polymers, reactive resins, paints, lacquers, Coating materials, adhesives, elastomers and plastomers thicken and constrict, ie increase their viscosity. A well-known way to suppress the thickening effect of metal oxides, which are also particulate thickener, is to treat them surface. Surface treatment, however, can in many cases also lead to a pronounced increase in viscosity and the formation of a flow limit, as described in EP-A-0686676.

The object of the invention is to improve the state of the art and in particular to provide flowable systems with at the same time a high proportion of conventional "thickening agents" which also serves as reinforcing filler.

The object is achieved by the invention.

Surprisingly, it has now been found that stable suspensions of finely divided and colloidal particles, which are at the same time particulate thickeners, are obtained by virtue of the fact that polymers are stable to the finely divided and colloidal particles which are at the same time particulate

Thickeners are bound in the suspension, in which case binding strong physical bonds and chemical bonds encloses, and so the use of finely divided particles, which are also particulate thickener, for reinforcing reactive resins such as adhesives,

Coating materials and printing inks by the use of stabilized suspensions according to the invention, such as dispersions, of particulate thickener is made possible.

Surprisingly, such large volume technically available and inexpensive to produce particulate thickeners, such as precipitated silica and fumed silica, fumed aluminas and titanium dioxides, as reinforcing fillers at a high degree of filling and thus high reinforcing effect and at the same low viscosity, and thus cost-effective handling and good and easy processing of the suspensions of the invention are used.

An object of the invention is a suspension, characterized in that it contains at least 3% by weight, preferably at least 6% by weight, more preferably at least 12% by weight, more preferably at least 15, most preferably at least 18% by weight, most preferably at least 24% by weight of particulate

Thickener containing at least one polymer of an amount of at least 5 weight percent, preferably at least 10 weight percent, more preferably at least 20 weight percent, most preferably at least 33 weight percent, more preferably at least 50 weight percent, based on the pure particulate thickener mass without polymer, to this particulate thickener is bound in the suspension, and that optionally at least one further polymer or more polymers is also present in the suspension freely, that the relative viscosity η _re i = η / η ₀ , where η and T | o at the same temperature and at a temperature of 25 ⁰ C are measured, less than 100, preferably less than 50, more preferably less than 10, most preferably less than 5, in particular preferably less than 3 and outstandingly preferably less than 2 and the relative viscosity η / ηo in storage for at least one week, preferably from at least 4 weeks, more preferably of at least 3 months, most preferably at least 6 months, particularly preferably of at least 12 months, at a temperature of 4O ⁰ C by less than a factor of 10, preferably by less than a factor of 10, preferably by less than a factor of 5, more preferably by less than a factor of 2.5, even more preferably by less than a factor of 1.5, and a liquid phase containing from 0 to 80% by weight, based on the total liquid phase, of preferably 0-50 weight percent, preferably 0-25 weight percent of one or more solvents, wherein the solvent may also be a crosslinkable component having a viscosity of less than 100 mPas, preferably less than 10 mPas, at 25 ⁰ C and based on the total liquid phase 10-100 weight percent, preferably 50-100 weight percent, more preferably 75-100 weight percent of a polymer component or a mixture of two or more physically or chemically crosslinkable polymers containing.

The determination of the amount of particulate thickener bound polymer in the suspension can be accomplished, for example, by filtration of the particulate thickener with fine filters, ultrafine filters with and without pressure, for example by pressure nutsche and submicron fine filters. The filtrate is preferably washed several times with a suitable solvent, preferably 3 times, more preferably 5 times. A suitable solvent is one such that the bound polymer would dissolve well in the unbound state. Preferably, the filter cake is washed until the wash liquor has less than 1 percent by weight polymer based on the particulate thickener used in the analysis run. Other preferred and suitable methods are medium gravitational centrifugation, such that particulate thickener sediments within the analysis time, but polymer does not sediment, and multiple solvent washing as described above. Suitable methods for determining polymer bound to inorganic particulate thickener are elemental analysis for carbon content, nitrogen content, silicon content, nuclear magnetic resonance methods such as ¹ H-NMR, ¹³ C-NMR, ¹⁵ N-NMR, ²⁹ Si-NMR, and infrared analysis in the different variants such as FTIR, DRIFT, ATIR.

The relative viscosity η / t | o is defined as the ratio of the viscosity η of the suspension according to the invention contains particulate thickener and the viscosity T | o liquid phase without particulate thickener, wherein η and T | o are measured at the same temperature and at a temperature of 25 ⁰ C.

The particulate thickeners according to the invention are preferably particulate thickeners which are solid at room temperature and under the pressure of the surrounding atmosphere, ie between 900 and 1100 hPa.

The particulate thickeners according to the invention are preferably insoluble or sparingly soluble in water or in other solvents which can be used to prepare the suspension according to the invention.

The particulate thickeners according to the invention preferably have a solubility, in water at pH 7.33 and an electrolyte background of 0.11 mol / l and a temperature of 37 ⁰ C, of less than 0.1 g / l, more preferably of less than 0, 05 g / l, at, at the pressure of the surrounding atmosphere, ie between 900 and 1100 hPa.

The particulate thickeners used according to the invention preferably have a molecular weight of greater than 10,000 g / mol, more preferably a molecular weight of from 50,000 to 100,000,000 g / mol, in particular from 100,000 to 10,000,000 g / mol, in each case preferably measured by means of static light scattering.

The particulate thickeners used according to the invention preferably have a carbon content of less than 50

% By weight, preferably less than 10% by weight, more preferably less than 5% by weight, most preferably less than 1% by weight, in particular preferably less than 0.1% by weight. The particulate thickeners according to the invention preferably have a Mohs hardness equal to or greater than 1. Particularly preferably, the particulate thickeners have a Mohs hardness greater than 4, very particularly preferably greater than 5, on.

Particulate thickeners may consist of preferably organosilicon resins such as silicone resins such as methyl silicone resins, for example consisting of units of the formula [(CH ₃₎ SiC> _3/2] or Phenylsilikonharzen, consisting for example of units of the formula [(CeH ₅ ) SiC> _3/2] or Methylphenylsilikonharzen, for example, consisting of units of the formula [(CH ₃₎ _x (CeH ₅₎ _y SiC> _3/2] with x + y = l, or from organic resins such as epoxy resins, such Acrylic resins, for example polymethylmethacrylates, and polymers such as polyolefins, for example polystyrene, and metal colloids, for example silver colloids, and metal oxides, such as oxides of III. Main group, such as aluminas, oxides of IV. Main group, such as silicas, germanium, and the main group, such as antimony oxides, or antimony tin oxides and, for example, oxides of the transition group metals, such as titanium (IV) dioxides, such as zirconium (IV) oxides, such as zinc oxides such as iron oxides, for example, such as ferrous oxides, ferric oxides such as magnetites, ferrites, and oxides of lanthanides such as cerium (IV) oxides; and any mixtures of these oxides, such as silica-alumina mixed oxides of arbitrary composition, preferably containing 20 to 100 weight percent of silica, such as silica-iron (III) oxide mixed oxides of arbitrary composition, preferably having a content of 20 to 100 Weight percent of silica, such as silica-titanium (IV) oxide mixed oxides of any composition, preferably containing 20 to 100 weight percent silica; and insoluble or sparingly soluble ionic and mineral compounds, for example calcium carbonates, barium sulphates, iron (II) sulphides, such as pyrites, calcium silicates, aluminum silicates, such as Aluminum layer silicates, eg clays, such as bentonites, montmorillonites, also those which are organically modified; and hectorites, even those that are organically modified; and micronized minerals and ground minerals; and sparingly soluble nonionic compounds such as boron nitrides, silicon nitrides or silicon carbides.

Preferred particulate thickeners according to the invention are metal oxides having BET specific surface areas of greater than 10 m ² / g, such as metal oxides prepared by precipitation processes, such as metal oxides produced in high-temperature processes, such as pyrogenic metal oxides produced in flame processes, such as metal oxides produced in plasma processes, as produced in hot-wall reactors Metal oxides and metal oxides produced by laser processes.

Silica particles, silica particles, aluminum oxide particles, titanium dioxide particles, zirconium dioxide particles, metal carbonates, and plastic particles are preferred as particulate thickeners.

Examples of metal carbonates are preferably precipitated barium carbonates or precipitated calcium carbonates, for example those modified with carboxylic acids and carboxylic acid salts, such as sodium or potassium stearates.

Particular preference is given as particulate thickeners to silicas having BET specific surface areas of greater than 10 m ² / g, more preferably synthetic silicas, such as wet-chemically prepared silicas, such as, for example

Silica sols and silica gels and precipitated silicas, such as pyrogenic silicas produced by flame processes, such as silicon dioxides produced in plasma processes, such as silicon dioxides prepared in hot wall reactors, such as silicon dioxides produced in laser processes Fumed silica is preferably prepared at preferred temperatures above 1000 ^° C.

Particulate thickening agents in the suspension may also be selected from any mixtures of the particulate thickeners listed above.

According to the invention, particulate thickening agents have an average diameter of less than 100 .mu.m. The particulate thickeners used according to the invention preferably have an average diameter of greater than 1 nm, preferably from 1 nm to 100 .mu.m, particularly preferably from 10 nm to 10 .mu.m, in particular from 10 nm to 1000 nm.

The particulate thickeners preferably have an average primary particle particle size d _PP of 0.5 to 1000 nm, preferably 5 to 100 nm, more preferably 5 to 50 nm. Suitable measuring methods for this purpose are, for example, the determination of the BET surface areas and the material density : d _PP = 6 / (BET * material density) or for example the transmission electron microscopy or high-resolution

Scanning electron microscopy, e.g. in field emission mode, or, for example, ultrasound spectroscopy in the measurement range 1 to 100 MHz. Further examples of primary particle size measurement methods are small angle X-ray scattering (SAXS), small angle neutron scattering (SANS) and small angle light scattering (SALS), where the primary particle size is obtained as the transition from surface scattering to Particle-particle scattering, this can be evaluated as the transition of the Porod regime to the Guinier regime.

Particular preference is given to using particulate thickeners which have a broad primary particle distribution. The total distribution width of all primary particles over all aggregates is preferably greater than 2, more preferably greater than 3, very particularly preferably greater than 5, based on the mean Primary particle diameter of all primary particles. Preferably, the internal distribution width of the primary particles in an aggregate is less than 5, preferably less than 3, more preferably less than 2, most preferably less than 1.5, wherein the internal distribution width represents the ratio between the largest and smallest primary particle diameter in an aggregate.

The particulate thickeners preferably have an average secondary structure or aggregate particle size d _Ag gr of 50 to 5000 nm, preferably 100 to 500 nm, measured as the hydrodynamic diameter. Suitable measurement methods for this purpose are, for example, dynamic light scattering or photocorrelation spectroscopy or quasi-elastic light scattering. For measurement of concentrations greater than 0.01% by weight of particulate thickener, this measurement can be corrected for multiple scatter by measuring in backscatter, for example at 170 ° to 175 °, or by cross-correlation. Further examples of aggregate particle size measurement methods are small-angle X-ray scattering

(SAXS), Small Angle Neutron Scattering (SANS) and Small Angle Light Scattering (SALS).

Particular preference is given to using particulate thickeners which have a broad aggregate size distribution. Preferably, the total width of all aggregates distribution is greater than 2, more preferably greater than 3, most preferably greater than 5, based on the average aggregate diameter of all aggregates. The quotient of the 97.5% total transit value to the 2.5% total pass value of the total distribution width of all aggregate diameters of all aggregates is preferably greater than 2, particularly preferably greater than 3, very particularly preferably greater than 5, very particularly preferably greater than 10. The particulate thickening agents preferably have an average tertiary or agglomerate particle size d _Ag gi of greater than 100 nm, measured as a geometric diameter. Suitable measurement methods for this purpose are, for example, laser light diffraction or sieving methods.

The particulate thickeners preferably have a specific surface area of from 1 to 1000 m.sup.2 / g, preferably from 10 to 500 ^m.sup.2 / g, very particularly preferably from 25 to 350 ^m.sup.2 / g. The BET surface is measured by known methods, preferably in accordance with German industrial standard DIN 66131 and DIN 66132.

In a preferred embodiment, the BET specific surface area of the particulate thickeners is 10-150 m ² / g, more preferably 30-80 m ² / g.

Preferably, the particulate thickening agents have a fractal dimension of the surface D _s of preferably less than or equal to 2.3, preferably less than or equal to 2.1, more preferably from 1.95 to 2.05, the fractal dimension of the surface D _s here defined as: Particle surface is proportional to the particle radius R high D _s .

The particulate thickening agents preferably have a fractal dimension of the mass D _m of preferably less than or equal to 2.8, preferably equal to or less than 2.5, particularly preferably 1.9 to 2.2. The fractal dimension of the mass D _m is defined as: Particle mass is proportional to the particle radius R high D _m .

Preference is given to using hydrophilic pyrogenic silicas which are freshly prepared and, for example, come directly from the flame, those which have cooled, those which deacidify and are cleaned, those that are stored intermediately or already packaged commercially. It is also possible to use hydrophobized or silylated silicas, for example commercial ones.

Mixtures of different silicas may be used, e.g. Mixtures of silicic acids of different BET surface area, or mixtures of silicas with different degree of hydrophobing or Silyliergrad.

In a preferred embodiment, the particulate thickeners are hydrophobic particulate thickeners.

In another preferred embodiment, the particulate thickeners are preferably surface-modified

Metal oxides, wherein the surface-modified metal oxides are preferably silylated organosilicon-modified metal oxides, very particularly preferably surface-modified, preferably silylated, organosilicon-compound-modified, fumed silica.

Particular preference is given to particulate thickeners which are surface-modified organofunctionally. Particular preference is given to particulate thickeners which are organofunctionally surface-modified with organosilicon compounds

Particular preference is given to using particulate thickeners which have been prepared according to EP-A-896 029, EP-A-1302444, EP-A-1304332 and EP-A-1473296.

In the preparation of the hydrophobic particulate thickener, additional densification processes may be used during the silylation or hydrophobization process be used as compression by suction of the air or gas content by suitable vacuum methods, such as compaction by mechanical methods, such as press rolls, ball mills, edge mills, screw compressors and briquetting.

In the preparation of the hydrophobic particulate thickener, deagglomeration processes may additionally be employed during the silylation or hydrophobization process, such as pin mills or refining devices.

It can be uncompressed, with tap density less than 60 g / l, but also compacted, with tap densities greater than 60 g / l, silicas are used. The tap density can be determined according to DIN EN ISO 787-11. Particular preference is given to particulate thickeners having tamping densities according to DIN EN ISO 787-11 of tapped densities greater than 60 g / l, particularly preferably greater than 120 g / l, very particularly preferably greater than 250 g / l, in particular greater than 500 g / l.

Preferably, particulate thickening agents form the aggregates of a porosity> 0.5, especially> 0.8, in particular> 0.9, in particular> 0.95. The porosity ε of a pile material is defined as ε = 1 - _M ateriai volume / volume _eld entire volume with _Ma teriai = volume of particulate thickeners and volume body _Kθ = volume of the pile material. Can ε the porosity by mercury porosimetry or using inert gases such as helium or argon can be determined by measuring the void volume Volumeni _EER of the pile material, with ε = Volumenieer / volume _eld

In a particular preferred embodiment, particulate thickeners are nanoparticles. According to the invention, the particulate thickener and particle-bound polymer in the liquid preferably form a colloidal suspension. Colloidal suspension of particulate thickeners means in this case that the transparency of the suspension, measured as a continuous light, ie unabsorbed light, is not less than 50%, preferably less than 25%, more preferably less than 10% than that of the particle-free liquid or crosslinked mass ,

According to the invention, the particulate thickening agents are preferably distributed colloidally in the suspension. The colloidal distribution of the particulate thickening agents in the suspension is indicated by a high transparency of the suspension. The transparency is preferably greater than 50%, preferably greater than 75%, particularly preferably greater than 90%, based on the suspension or liquid not containing particulate thickener or crosslinked mass prepared therefrom.

The preparation of the suspension or dispersion according to the invention is carried out as described below. According to the invention particulate thickener is mixed in the monomer, oligomer, polymer or resin and dispersed and thereby dispersed and suspended, preferably under the action of shear energy, such as mechanical or ultrasonic shear, for example, are used for predispersion and also for main dispersion dissolver. The dispersing effect of the dissolver is determined by the differential speed between the disk surface and

Grinded material achieved. In normal Lackmahlgütern with viscosities of between 10 to 50 Pa * s fine tooth discs are used at 25 ⁰ C, for high-viscosity fluids up to 100 Pa * s at 25 ⁰ C coarse toothed discs. The peripheral speeds are preferably 10-25 m / s and the dispersion times are preferred in the range 15-40 min. Manufacturers of dissolvers are for example W. Niemann GmbH & CoKg, VMA-Getzmann GmbH or also the company Netsch GmbH. An alternative to predispersion and main dispersion together with dust-free powder feed form machines which form a suction vacuum in the liquid stream and disperse according to the ROTOR-STATOR principle. The settings of the slots in the stator can be adapted to the task. Manufacturer is for example the company Y-ray. For the dispersion, for example: 3 rolls, in particular for the production of pasty, printing inks; Ball mills, which are used with steel and ceramic balls (20 -30mm diameter) in certain proportions to the material to be ground and agitator ball mills. Description of a stirred ball mill: In a grinding pot, which is filled with sand or grinding beads, a stirring shaft rotates with grinding discs. The ground material is pumped from below or even in horizontal mills from the end face through the grinding pot, for example. The grinding media used are generally sand, hard glass balls and preferably ceramic grinding beads of 0.1 to 3.0 mm.

The millbase viscosity is these aggregates typically at a viscosity of 0.5 to 4 Pa * s at 25 ⁰ C. Preferably, for example, ultrasound-based dispersing, for example, ultrasonic tips, sonolators, ultrasound cells with one or more ultrasonic transducers or one or more Sonotrodes or one or more ultrasonic horns, which can be operated discontinuously or continuously in flow, used. Particularly preferred dispersing aggregates such as HIGH PRESSURE HOMOGENIZER and WET JET MILLS offer the possibility of an increased

Energy density entry of up to> 10 ¹⁰ J / m ³ to achieve optimum dispersing performance and particularly suspension according to the invention. Further preferred examples are dispersing aggregates which are introduced into the dispersant by vigorous shaking, such as Red Devil or Speedmixer Engerie, or Planetary mixers or planetary dissolvers, or for example for systems with high viscosity, for example over 10 Pa * s at 25 ⁰ C, roll mills, kneaders, internal mixers, extruders, such as single extruder, twin screw extruder, preferably according to the invention is a combination of one or more methods , and thereby the particulate thickener is dispersed and suspended.

In accordance with the invention, the dispersion, oligomer, polymer or resin described above, preferably "in situ", chemisorptively binds to particulate thickener, ie achieves a chemical reaction between oligomer, polymer or resin and particulate thickener, or physico-reactive oligomer, polymer or resin bonded to particulate thickener.

According to the invention, the suspension of the particulate thickener in the liquid is stable. In this case, stable means that, after a time greater than 100 hours, sedimentation of the particulate thickening agents of less than 10%, preferably less than 5%, particularly preferably less than 1%, of the total mass of particulate thickener occurs.

Stable means, according to another method of measurement, that no gelling, no stability or no strain occurs.

No gelling can be determined by fluidity, even at rest and without external shear.

No stability, ie flowability, means that even at low shear stress, the viscous fraction, the loss modulus G "of the viscoelastic suspension, is greater than the elastic fraction, the storage modulus G 'of the Viscoelastic suspension is preferably measured at a shear stress less than 1 Pa or at a deformation less than 1 percent.

No Verstrammung means that the relative viscosity η _re i = η / r | o, less than 100, preferably less than 50, more preferably less than 10, most preferably 5, more preferably less than 3, outstanding preferably less than 2 and the relative viscosity η _re i = η / ηo with a storage of at least one week, preferably of at least 4 weeks, more preferably of at least 3 months, most preferably of at least 6 months, more preferably of at least 12 months, at a temperature of 4O ⁰ C by less than a factor of 10, preferably by less than a factor of 10, preferably by less than a factor of 5, more preferably by less than a factor of 2.5, even more preferably by less than a factor of 1.5.

According to the invention, the liquid phase is a flowable material having a viscosity of 0.1 to 100,000 Pas

Temperatures of -12O ⁰ C to 500 ⁰ C and a shear rate of 0.001 s ^"1 to 1,000,000 s ^{" 1} .

According to the invention, the liquid phase may preferably contain solvents, such as inert and reactive, nonpolar and polar, protic and non-protic solvents. Solvents may in pure form have a viscosity of less than 100 mPas at 25 ⁰ C, preferably less than 10 mPas, more preferably less than 2 mPas.

Examples of reactive solvents are preferably reactive diluents, such as monostyrene; such as monoacrylates, such as alkyl acrylates, for example methyl acrylate, such as alkyl alkyl acrylates, such as methyl methacrylate, or Hexyl methacrylate, or oligoalkyl alkyl acrylates, or glycidyl ethers, such as allyl glycidyl ether.

Examples of inert and non-polar solvents are preferably aliphatic hydrocarbons, such as cyclic, linear and branched saturated hydrocarbons, such as hexanes, such as n-hexane, or cyclohexane, or deans, such as n-decane, and cyclic, linear and branched unsaturated hydrocarbons, such as hexene, and are aromatic hydrocarbons such as benzene, toluene or xylene, and mixtures of hydrocarbons such as gasoline, such as mineral spirits, such as higher boiling hydrocarbons.

An example of protic solvents is water.

Further examples of protic solvents are preferably alcohols, such as alkyl alcohols, such as methanol, such as ethanol, such as propanols, such as n-propanol and isopropanol, such as butanols.

Examples of polar and non-protic solvents are preferably ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, ethers, such as diethyl ether, tetrahydrofuran, dioxane, and amides, such as dimethylformamide.

According to the invention, the liquid phase may preferably contain polymers, oligomers, and resins, individually or as any mixtures. According to the invention, the liquid phase may contain a plurality of polymers, a plurality of oligomers, and a plurality of resins, individually or as any mixtures.

Polymer is a compound made up of greater than 3 subunits of a monomer.

Polymers, oligomers, and resins preferably have a molecular weight of 100 to 10,000,000 mol / g, especially preferably 500-50,000 mol / g, most preferably 500-5,000 mol / g.

Polymers, oligomers, and resins may preferably be linear, cyclic, or branched, or mixtures of polymers.

Examples of polymers are preferably organosilicon compounds, such as organo (poly) silanes, organo (poly) siloxanes, such as dialkylpolysiloxanes, for example polydimethylsiloxanes, and copolymers thereof, such as polydimethylsiloxane-polyurethane copolymers, obtainable as reaction products of α, G0-amino-terminated polydimethylsiloxanes and Alkylisocyanaten (available from Wacker-Chemie GmbH under the name Geniomer ^® ), such as

Organo (poly) silazanes and organo (poly) silicarbanes; Polyolefins such as polyethylenes and polypropylenes, for example, substituted polylefins such as silyl-terminated polyisobutylenes; Polyurethanes, polyols, such as hydroxyl-containing polyesters, hydroxy-containing polyether, methyldimethoxysilylpropyl-terminated

Polypropylene glycols (available, for example, as "MS polymers" from the company Kaneka Corp. Japan), hydroxy-containing polyacrylates, polyisocyanates such as aliphatic and aromatic polyisocyanates, isocyanate-terminated polyurethane prepolymers prepared by reacting polyols with polyisocyanates in excess and their silyated derivatives (eg available under the name DESMOSEAL® from Bayer AG, Germany); (poly) epoxy compounds such as bisphenol A and bisphenol F based epoxides, compounds containing monomeric, oligomeric and polymeric glycidoxy functions, such as diglycidyl ethers based on Bisphenol A and bisphenol F, epoxy novolac precursors and resins, epoxyalkyd resins, epoxy acrylates, aliphatic epoxides such as linear alkylene bisglycidyl ethers and cycloaliphatic glycidyl ethers, such as 3,4-epoxycyclohexyl-3,4-epoxycyclohexane carboxylates and aromatic epoxides such as triglycidyl ethers of p-aminophenol and triglycidyl ethers of methylenedianiline; (Poly) amines, such as cyclic and linear amines, such as hexamethylenediamine, aromatic amines, such as 4, 4 'methylenebis (2,6-diethylaniline), bis (2-aminoalkyl) -polyalkylene oxide, such as bis (2-aminopropyl ) - Polypropylene glycol and Jeffamine (amino-functional polypropylene oxides), (poly) amidoamines, (poly) mercaptans, (poly) carboxylic acids, (poly) carboxylic acid anhydrides; Acrylates and their esters, such as glycidyl acrylates, alkyl acrylates and their esters, methacrylates and their esters, polysulphide-forming polymers and polysulfides, such as thioplasts (available, for example, under the trademark Thiokol from Toray Thiokol Co. Ltd.).

Further examples of polymers are preferably film-forming polymers. Preferred examples of film-forming polymers are physical drying paint binders, such as e.g. Polyvinyl chloride and its copolymers, polyacrylates and their copolymers, polyvinyl acetates and polyvinyl butyrals and their copolymers, bitumen, hydrocarbon resins; Chlorinated rubbers, cyclic rubber, polyurethanes, epoxy resins, epoxy resins-polyester.

Preferred according to the invention are reactive polymers, reactive oligomers, and reactive resins.

Preferred examples are reactive polymers, prepolymers, reactive precursors, polymers which can be used as binders, for example for paints and varnishes, adhesives and sealants, or for elastomers and plastic plastics, and which interact with themselves or with the particulate thickeners , react or network. Preferred reactive polymers are resin and hardener systems, such as those used for the preparation of resins and elastomers, such as for epoxy resins and elastomers, for polyurethane resins and elastomers, for silicone resins and elastomers, and for acrylates, such as for polyolefins. as for

Polycarbonates, as for polysulfones, as for polysulfides, and as for polyamides.

Preference according to the invention is given to reactive polymers, oligomers, and resins for the preparation of crosslinking systems from US Pat

Range of coating materials and adhesives and sealants.

Examples of polymers and reactive polymers are preferably organic polymers, such as polymers, such as poly (meth) acrylates, such as polyvinyl esters, such as polyvinyl alcohols, such as

Polyvinyl acetals, such as polyvinyl chloride, such as polyfluorinated polyethylenes, with monomeric starting components such as methyl methacrylate, butyl acrylate, ethylhexyl acrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, acrylic acid, styrene.

Examples of polymers and reactive polymers are preferably organic polymers, such as polycondensation resins, such as oil-free saturated polyesters and oil-modified polyester resins, such as fatty oils, short-, medium- and long-oil alkyd resins,

Oil-based cooks, and combinations thereof, as well as modified alkyd resins such as styrene-modified alkyd resins, acrylic acid ester-modified alkyd resins, silicone-modified alkyd resins, urethane-modified alkyd resins, epoxy resin-modified alkyd resins such as oxidatively drying

Paint binders, such as short. Medium and long oil alkyd resins, oil cakes, and combinations thereof, and polyesters.

Examples of polymers and reactive polymers are preferably organic polymers such as chemically or reactively drying Paint binders, such as polyurethanes, such as 1-component and 2-component polyurethanes, such as epoxy resin system, such as 2-component epoxy resin systems, such as epoxies, which are crosslinked with amines, and those which are crosslinked with isocyanates.

Examples of polymers and reactive polymers are preferably silicon-containing polymers, such as polysiloxanes, such as polyorganosiloxanes, such as linear or cyclic dialkylsiloxanes having an average number of dialkylsiloxy units greater than 3. The dialkylsiloxanes are preferably dimethylsiloxanes. Preference is given to linear polydimethylsiloxanes having the following end groups: trimethylsiloxy-, dimethylhydroxysiloxy-, dimethylchlorosiloxy-, methyldichlorosiloxy-, dimethylmethoxysiloxy-, methyldimethoxysiloxy-, dimethylethoxysiloxy-, methyldiethoxysiloxy-,

Dimethylacethoxysiloxy, methyldiacethoxysiloxy and dimethylhydroxysiloxy groups, especially with trimethylsiloxy or dimethylhydroxysiloxy end groups.

The abovementioned polydimethylsiloxanes preferably have a viscosity at 25 ^° C. of from 20 to 10,000,000 mPas, more preferably from 100,000 mPas to 10,000,000 mPas, very particularly preferably from 1,000,000 to 10,000,000 mPas.

Further examples of organosiloxanes are preferred

Silicone resins, in particular those which contain, as the alkyl group R are methyl groups (CH ₃₎ which is particularly preferred are those which contain the R3SiOχ / 2 and SiO _4/2 ~ units or those RSiC> 3/2 and optionally R2SiC> Contain 2/2 ~ units, wherein R is hydrogen or saturated or unsaturated optionally substituted hydrocarbon radical having 1 to 12 carbon atoms.

The organosiloxanes may each be a single species as well as a mixture of at least two species act such substances.

Examples of polymers are preferably silicone oils, such as organofunctional silicone oils, particularly preferably aminoalkyl-functional polysiloxanes, polymethylsiloxanes and

Polydimethylsiloxanes. Examples of polymers are silicone resins, particularly preferably organofunctional silicone resins, particularly preferably aminoalkyl-functional silicone resins.

Preferred examples are silicone copolymers, and hybrid systems containing organopolysiloxanes and silicon atom-free polymers. Preferred examples of the present invention are thermoplastic silicone elastomers characterized by .alpha.,. Omega.-terminal termination with 3-aminoalkyldialkylsiloxy radicals such as 3-aminopropyldimethylsiloxy radicals and a degree of

Final termination greater than 90%, preferably greater than 95%, particularly preferably greater than 99% based on the initial OH end groups of a linear alpha-omega terminal OH polydimethylsiloxane, and subsequent reaction of the terminal OC, G0-terminated aminoalkylsiloxanes with

Alkyl diisocyanates were prepared. The thermoplastic silicone elastomers preferably have a siloxane content of greater than 80 percent by weight, preferably greater than 90 percent by weight, and are preferably solid at 25 ^° C. and have a viscosity of from 10,000 to 100,000 Pas at a temperature of HO ⁰ C.

Further examples of polydimethylsiloxanes are preferably polymers for the preparation of silicone rubbers, such as polymers for the preparation of 1-component or 2-component

Silicone elastomers which are storage-stable with the exclusion of moisture but which cure and harden under the action of water or moisture; or of 1-component or 2-component silicone elastomers which are peroxidic, for example at elevated temperature, such as 80 to 200 ^° C., for example Linkage of saturated and / or unsaturated alkyl groups, are crosslinkable, or by addition reaction of olefinic C = C double bonds and silane groups Si-H, preferably under the action of a catalyst such as platinum, palladium or ruthenium, at room temperature or temperatures of 10 to 15O ⁰ C are networkable.

Examples of condensable groups siloxane is organopolysiloxane, preferably containing units of the formulas SiO _4/2 , R3SiO _1/2 , R2SiO _2/2 and RSiO ₃₇₂ , wherein R is hydrogen or saturated or unsaturated optionally substituted hydrocarbon radical having 1 to 12 carbon atoms is.

Example of silicone resins are preferably those which consist of RSiC> _3/2, RsSiOi _/ 2 and SiC> _{a 4/2} units wherein R is hydrogen or saturated or unsaturated optionally substituted hydrocarbon radical having 1 to 12 carbon atoms, in any combination preferably with molecular weights of 100 to 20,000 grams per mole, and a viscosity of 50 to

50000 mPas at a temperature of 25 ^° C. or, if the silicone resins are solids, at a viscosity of the 0.1 to 50% strength by weight solution of the silicone resins in an inert solvent, such as toluene, tetrahydrofuran, methyl ethyl ketone or isobutylene glycol. Propanol of 50 to 50,000 mPas at a temperature of 25 ⁰ C. Preferred examples are methyl silicone resins and phenyl silicone resins and methyl phenyl silicone resins. Preference is given to silicone resins having primary, secondary and tertiary aminoalkyl functions and having an amine number of 0.5 to 10 and a molecular weight of 250 to 20 000 mol / g.

Other preferred examples of reactive polymers according to the invention are preferably silane-terminated, silane-functional and organosilane-modified polymers, such as Polymers containing mono-, di- and tri-alkoxysilane radicals, terminal, or linked in the chain. Examples thereof are silane-terminated polymers prepared via the reaction of aminoalkylalkoxysilane and mono-, di- and / or polyisocyanates, or by copolymerization of

Methacryloxyalkylsilanes and acrylates or alkylacrylates, also with mixed copolymerization with other olefins, such as styrenes, such as monostyrene, alkoxysilane-functional polyols prepared by hand, or by reaction of alkoxysilanes with polyols, such as polyacrylate polyols,

Polyester polyols or polyether polyols, as used for the production of polyurethanes. The silane termination of polyacrylate polyols can be carried out by copolymerization with methacryloxy-functional alkoxysilanes, such as 3-methacryloxypropyltrimethoxysilane or preferably with 1-methacryloxymethyltrimethoxysilane.

The silane termination of polyisocyanates can be carried out by reaction with amino-functional alkoxysilanes, such as 3-aminopropyltrimethoxysilane or preferably with 1-piperazinomethyltrimethoxysilane.

Further examples of reactive polymers which are preferred according to the invention are preferably epoxy-functional or glycidoxy-functional monomers, oligomers or polymers, such as epoxide resins, such as diglycidyl ether of bisphenol A, cycloaliphatic epoxides, as used, for example, for producing epoxy adhesives, composites, glass-fiber-reinforced epoxides. Plastics and epoxy surface coatings are used.

Examples of epoxides are preferably epoxy resins, such as liquid, semi-solid, solid epoxy resins, epoxy resins consisting for example of binders, bisphenol A and / or bisphenol F and phenol novolak glycidyl ether, cresol novolak glycidyl ether, cycloaliphatic glycidyl compounds and epoxidized cycloolefins and hardeners based on aliphatic amines, such as polyfunctional amines based on

Polyetherpolyamines, alkylenediamines, such as propylenediamines, or cycloaliphatic amines, polyaminoamides, Mannich bases, epoxide adducts, mercaptans, acid anhydrides.

Further examples of epoxy compounds are preferably cycloaliphatic epoxides, and alkylene bisglycidyl ethers, such as

-O-CH ₂ -CH-CH ₂

Bisphenol A based di-glycidyl ethers, such as

with n preferably from 0 to 10, particularly preferably 0 to 5

Examples of epoxy novolac resins, such as those of the formula

bifunctional epoxy compounds, such as cycloaliphatic epoxy compounds,

trifunctional epoxy compounds, such as

tetrafunctional epoxy compounds, such as

Further examples of reactive polymers which are preferred according to the invention are preferably amino-functional polymers, oligomers or monomers, such as polyalkylene oxides, which are amino-functional, such as Jeffamine, as used, for example, for producing elastic and semi-elastic epoxy adhesives, composites, glass-fiber-reinforced epoxy resins. Plastics and epoxy surface coatings used as a hardener.

Another preferred example of reactive polymers are preferably amino group-containing monomers, oligomers, polymers and resins, such as hardeners for epoxy systems or hardeners for polyurethane systems, or hardeners for moisture-curing 1-component silicone adhesives and sealants, or leveling and flow aids, For example, be used as additives in coating systems, or mixtures thereof. Another preferred example of polymers are preferably unsaturated polyester resins derived from di-, tri-, and mono- or polyfunctional carboxylic acids and their anhydrides, such as phthalic anhydride, isophthalic acid, terephthalic acid, hexahydrophthalic anhydride, tetrahydroxophthalic anhydride, hexahydroxoterephthalic acid, adipic acid, maleic acid, fumaric acid, azelaic acid, sebacic acid , Decanedicarboxylic acid, dimerized fatty acids, trimellitic anhydride, pyromellitic anhydride, 1,4-cyclohexanedicarboxylic acid, dimethylolpropionic acid and mono- or polyhydric alcohols, such as polyols, such as ethylene glycol, 1,2-propanediol, 1,5-pentanediol, diethylene glycol, 1, 4- Butanediol, 1, 6-hexanediol, neopentyl glycol, trimethylpentanediol, 1, 4-cyclohexanedimethanol, tricyclodecanedimethanol, trimethylolpropane, glycerol, pentaerythritol, hydrogenated bisphenol A, bisphenol A bis hydroxyethyl ether are formed, and their modifications with monomers of the type Acrylic monomers, alkoxysiloxanes and alkoxypolysiloxanes. Examples are amino-formaldehyde resins, such as urea formaldehyde resins, melamine-formaldehyde resins and

Benzoguanamine consist of amino compounds such as aromatic amines, carboxylic acid amides, cyanamides, guanamines, guanediamines, ureas, sulfonamines, Sulfurylamiden, thioureas, triazines (melamine resins),

Urethanes and carbonyl compounds such as, acetaldehyde, acetone,

Butyraldehyde, formaldehyde, glyoxal, propionaldehyde,

Trichloracetalaldehyd.

Further examples are phenol-formaldehyde resins.

Another preferred example of polymers and reactive polymers according to the invention are preferably polyaddition resins such as polyurethanes, such as, for example, 2-component polyurethanes, 1-component polyurethanes, 1-component moisture-curing polyurethanes obtained from prepolymers such as polyisocyanates, prepared from base products such as aromatic diisocyanates such as toluene diisocyanate, methylene diphenyl diisocyanate, xylene diisocyanate, aliphatic diisocyanates such as hexamethylene diisocyanate or hexyl diisocyanate, cycloaliphatic diisocyanates, and the isomeric mixtures of the respective diisocyanates listed, blocked or protected polyisocyanates based on typical blocking agents such as malonic esters and acetoacetic esters, secondary amines, Butanone oximes, phenols, caprolactams, alcohols.

In one embodiment of the invention, the suspension preferably contains at least one polymer which is physisorptively bound to one or more particulate thickening agents.

On the surface of the particulate thickener, the polymers may be physisorptive via preferably van der Waals forces, such as London's fluctuating dipoles or dispersion energy, Debye dipoles, Keesoms-induced dipoles, hydrogen bonds, or hydrogen bonds, especially between -OH, -NH, - SH, -CO, -F, -Cl groups on the one hand, and -OH, -NH, -SH groups on the other, as well as coordinative, ionic, and ionic Lewis acid-base bonds, Brönsted acid-base bonds, and interactions between electrophilic and nucleophilic groups bound.

More preferably, polymers attached to particulate thickener preferably contain carboxyl groups which may be end-capped and / or pendant in the polymer, preferred examples being polyesters preferably containing such carboxyl groups conjugated to unsaturated olefinic groups, further preferred examples Polymers containing oxygen ether atoms that exhibit nucleophilicity or weak basicity. In a preferred embodiment according to the invention, the suspension preferably contains basic oxygen atoms bound to particulate thickener. Examples of polymers for this are polyalkylene oxides, polyols, polyesters. Preferred examples are polyesters, for example those which can be crosslinked with melamine. Further preferred examples of polymers are polyols, such as polyester polyols, polyacrylate polyols, polyalkylene oxide polyols, as are used, for example, for the preparation of 1- and 2-component polyurethanes.

Particularly preferred examples of physisorptively bound to particulate thickener polymers are coating additives and flow control agents, for example, polyalkylene oxide-modified polydialkylsiloxanes, particularly preferred

Polydimethylsiloxanes. Preferred examples are α, G0 terminal, or chain, or linear or branched, or copolymers, or block or block copolymers, propylene group bonded, polyethylene oxide and polypropylene oxide modified polydimethylsiloxanes, wherein one C atom of the propylene group on Si atom of the siloxane and another C atom of the propylene group is bonded to an O atom of the polyalkylene oxide. Preferably, the polyalkylene oxide-modified polydialkylsiloxanes have a viscosity at 25 ⁰ C of 100 to 100,000 mPas, particularly preferably from 500 to 5,000 mPas, and are used in amounts based on the particulate thickeners of preferably 0.1 to 10 weight percent, more preferably from 0 , 5 to 2.5 weight percent used.

The suspension preferably contains greater than 3% by weight, preferably greater than 12% by weight, more preferably greater than 15% by weight and most preferably greater than 18% by weight of particulate thickener, preferably fumed silica with a BET specific surface area greater than 150 m ² / g. If the particulate thickener contains a fumed silica having a BET specific surface area of less than 150 m ² / g, then the suspension contains greater than 20 percent by weight, more preferably greater than 30

Weight percent, most preferably greater than 40 weight percent of fumed silica. The relative viscosity η _re i is less than 100, preferably less than 50, particularly preferably less than 10, very particularly preferably less than 5, in particular preferably less than 3 and outstandingly preferably less than 2.

In a further embodiment of the invention, the suspension preferably contains at least one polymer chemisorptively bound to one or more particulate thickening agents.

Preferably, the suspension contains at least one polymer which is chemisorptively bound to said particulate thickener, said particulate thickener being provided by partial or total surface modification with surface groups which chemically react with the polymer.

Preferably, the suspension contains at least one polymer which is chemisorptively bound to this particulate thickener, this particulate thickener being provided with organofunctional siloxy groups by partial or complete silylation, prepared for example according to EP-A-896 029, EP-A-1302444, EP-A-1304332, and EP-A-1473296, and which chemically react with the polymer. On the surface of the particulate thickener, the polymers may be bound chemisorptively via at least one bond per polymer molecule, preferably bound over several bonds per polymer molecule.

In another embodiment of the invention, the suspension contains various polymers which are preferably bound to one or more particulate thickening agents chemisorptive and physisorptive, or else as a mixture of these types of binding.

Polymer bound to particulate thickener can be prepared by surface modification of particulate thickener with polymer.

In accordance with the invention, the polymer bound to the particulate thickener may preferably be prepared by "in situ" surface modification of a particulate thickener with a polymer.

"In situ" surface modification of particulate thickener with polymer means that particulate thickener is dispersed in polymer, or polymer mixture or in polymer solvent mixture and thereby or during dispersion or after dispersion, the polymer is bound to particulate thickener, chemically or physically The chemical or physical distinction is given by the binding energy of a single molecular binding site: below 70 kcal per mole there is a physical bond, above 70 kcal per mole there is chemical bonding.

According to the invention, the polymer is preferably bound in the suspension to particulate thickener by high shear energy dispersing according to the invention, as described above Preparation of the suspension according to the invention under the action of high shear energy, of optionally reactive particulate thickeners which may contain, for example, reactive organofunctional siloxy or alkylsiloxy groups, for example prepared according to EP-A-896 029, EP-A-1302444, EP-A- 1304332, and EP-A-1473296 in optionally reactive polymers, for example as described above under reactive polymers.

According to the invention are preferably particulate to 100 parts

Thickener greater than 10 parts of polymer, preferably greater than 20 parts, more preferably greater than 50 parts, most preferably greater than 100 parts of polymer bound.

According to the invention, the suspension preferably contains at least one polymer chemisorptively bound to these particulate thickeners, this particulate thickener preferably epoxy groups, amino groups, mercapto groups, acrylate groups, isocyanate groups, protected isocyanate group, carboxylic anhydride groups or Carbinol groups which react chemically with the polymer. Here, the respective chemical groups may be present alone or in any mixtures with each other.

Another preferred example of suspension according to the invention is preferably epoxy-functionalized particulate thickener, preferably silica, more preferably fumed silica, in amino-containing monomers, oligomers, polymers and resins, such as hardeners for epoxy systems, or hardeners for polyurethane systems , or harder for moisture-crosslinking 1-component silicone adhesives and sealants, or leveling and flow aids in coating systems, for example as additives, or mixtures thereof, is suspended, as above and, according to the invention, a chemical reaction, preferably "in situ", of the primary (-NH ₂ ) or secondary (-NH) amino group of the polymer with the surface-bound epoxy groups of the particulate thickener takes place.

Preferably, the particulate thickener, preferably fumed silica, contains from 0.1 to 50, more preferably 1 to 20, most preferably 5 to 15 weight percent of surface-bound epoxy groups, preferably glycidylalkylsiloxy groups or glycidoxylalkylsiloxy groups.

The particulate thickener is preferably epoxy-functional surface-functionalized metal oxide or silica, preferably pyrogenic silica prepared, for example, in EP-A-896,029, EP-A-1302444, EP-A-1304332 and EP-A-1473296.

The suspension according to the invention preferably comprises particulate thickening agents, such as preferably metal oxides, preferably silica, particularly preferably fumed silica, which are fully or partially surface-functionalized with epoxy groups, ie only 10-90%, preferably 25-75% of the surface and surface silanol groups with epoxy groups. Silane are implemented.

The suspension according to the invention preferably contains at least 3% by weight, preferably from 3 to 50, particularly preferably from 3 to 25, in particular preferably from 10 to 20% by weight of particulate thickener, preferably pyrogenic silica. The dispersing of the particulate thickener, preferably fumed silica, can be carried out in the presence of a solvent, in a ratio of 0.1 to 10 to the system polymer and particulate thickener; The dispersion can also be carried out without solvent, for sealing and adhesive systems preferred without solvent, for coating systems preferably with solvent.

The suspension according to the invention preferably contains greater than 5, preferably greater than 10, particularly preferably greater than 15 and very preferably greater than 18 percent by weight of particulate thickener, preferably metal oxide, more preferably silica, most preferably fumed silica which functionalises epoxy groups and has a BET specific surface area greater than 150 m ² / g.

Preferably, the suspension according to the invention contains, based on amino-containing polymers, greater than 10, preferably greater than 15, particularly preferably greater than 25 and very particularly preferably greater than 35 percent by weight of a particulate thickener, preferably metal oxide, particularly preferably silica, very particularly preferably fumed silica which surface-functionalizes epoxy groups and has a BET specific surface area smaller than 150 m ² / g.

The relative viscosity η _re i = η / η o of the suspension according to the invention is preferably less than 100, preferably less than 50, particularly preferably less than 10, very particularly preferably less than 5, in particular preferably less than 3 and outstandingly preferably less than 2.

The particulate thickeners which can be isolated from the suspension according to the invention, preferably fumed silica, preferably have a carbon content of greater than 2, preferably from 3 to 50 and more preferably from 5 to 50 percent by weight.

The isolatable from the suspension of the invention particulate thickener, preferably fumed silica, have a content of preferably extractable by means of tetrahydrofuran components of greater than 5, preferably 5 to 100 and particularly preferably from 10 to 50 weight percent.

According to the invention, the suspension preferably contains at least one polymer which contains epoxy groups and preferably the particulate thickener contains amino groups, mercapto groups, carboxylic anhydride groups and carbinol groups, where the respective group may be present alone or in any desired mixtures which chemisorptively bind the polymer.

According to the invention, the suspensions preferably contain particulate thickening agent, preferably with

Amino groups, preferably aminoalkyl groups, is functionalized and to this particulate thickener, partially or completely, preferably in "in-situ" processes, epoxy-functional or glycidoxy-functional monomers, oligomers or polymers, such as epoxy resins, are reacted Example according to the invention by reacting silica-functionalized, preferably fumed silica functionalized with amino groups, in an epoxy-functional monomer, oligomer, polymer or resin and dispersed as described above to prepare the suspension according to the invention, preferably under the action of high shear energy such described above, or by combination of one or more of the methods described above, and thereby dispersed and suspended, and according to the invention, preferably "in situ", a chemical reaction of the epoxy groups of the epoxy monomer as described above, Oligomer, polymer or resin with the amino groups of the particulate thickener, preferably fumed silica, so for example one of the typical epoxy-amine crosslinking reactions.

The particulate thickeners, preferably fumed silica, preferably contain from 1 to 50% by weight, particularly preferably from 1 to 20% by weight, particularly preferably from 5 to 15% by weight surface-bound amino groups, such as aminoalkylsiloxy groups, such as primary, -NH 2, and secondary, -NH, amino groups. Particular preference is given to particulate thickeners, preferably metal oxides, particularly preferably pyrogenic silica, which are partially surface-functionalized with amino groups, ie only 10-90%, preferably 25-75% of the surfaces, preferably surface silanol groups, are reacted with aminosilane. The suspension contains greater than 3 percent by weight, preferably from 3 to

50, more preferably 3 to 25 weight percent, more preferably 10 to 20 weight percent particulate thickener, preferably fumed silica. The dispersing of the particulate thickener, preferably fumed silica. This can be done in the presence of a solvent, in a ratio of 0.1 to 10 to the bulk polymers and particulate thickeners; The dispersion can also be carried out without solvent, for sealing and adhesive systems preferably without solvent, for coating systems preferably with solvent.

Preferred is a suspension of the invention containing at least one polymer having carbinol, or isocyanate groups and containing the particulate thickener having silanol groups and siloxane groups, wherein the respective group may be present alone or in any mixtures with each other, the Physiologically bind the polymer. According to the invention, suspensions preferably contain particulate thickener which has silanol groups and siloxane groups and to which monomers, oligomers or polymers, such as polyols, such as acrylate polyols, such as polyester polyols, such as polyether polyols, can be bound physisorptively. This can be done, for example, according to the invention by mixing and dispersing particulate thickener comprising silanol groups and siloxane groups, such as fumed silica, into one or more polyols, preferably under the action of high shear energy, as described above, or a combination of one or more the methods described above, and thereby dispersed and suspended. The suspension contains greater than 3 percent by weight, preferably from 3 to 50, particularly preferably from 3 to 25 percent by weight, in particular preferably from 10 to 20

Weight percent particulate thickener, preferably fumed silica.

The dispersing of the particulate thickener, preferably fumed silica, can be carried out in the presence of a

Solvent, in the ratio 0.1 to 10 to the mass of polymers and particulate thickeners; The dispersion can also be carried out without solvent, for sealing and adhesive systems preferably without solvent, for coating systems preferably with solvent.

According to the invention, the suspension preferably contains at least one polymer containing isocyanate groups and wherein the particulate thickener silanol, siloxane, amino, and carbinol groups, wherein the respective group may be present alone or in any mixtures with each other, chemisorptive with the polymer tie.

According to the invention, suspensions preferably contain particulate thickener which is preferred with amino groups Aminoalkylgruppen is functionalized and to this particulate thickener, partially or completely, preferably in "in-situ" processes, isocyanate-functional or protected isocyanate-functional monomers, oligomers or polymers, such as isocyanate-functional polymers, the

Preparation of 1- and 2-component polyurethanes are reacted. This can be done, for example, according to the invention by mixing and dispersing silica-functionalized silicic acid, preferably fumed silica functionalized with aminoalkyl groups, into an isocyanate-functional monomer, oligomer, polymer or resin, preferably under the action of high shear energy as described above, or a combination by one or more of the methods described above, and thereby dispersed and suspended, and according to the invention, preferably "in situ", a chemical reaction of the isocyanate groups of the isocyanate monomer, oligomer, polymer or resin as described above with the Amino groups of the particulate thickener, preferably fumed silica prepared according to EP-A-1304332 takes place, that is, for example, a typical isocyanate-amine or urethane crosslinking reactions.

The particulate thickeners, preferably fumed silica, preferably contain from 1 to 50% by weight, particularly preferably from 1 to 20% by weight, more preferably from 5 to 15% by weight surface-bound amino groups, such as aminoalkylsiloxy groups, such as primary -NH 2, and secondary, -NH, amino groups , Particular preference is given to particulate thickeners, preferably metal oxides, particularly preferably pyrogenic silica, which are partially surface-functionalized with amino groups, ie only 10-90%, preferably 25-75% of the surfaces, preferably surface silanol groups, are reacted with aminosilane. Preferably, the suspension contains from 3 to 50 percent by weight particularly preferably from 3 to 25% by weight, in particular preferably from 10 to 20% by weight, of particulate thickening agents, preferably pyrogenic silica. The dispersing of the particulate thickener, preferably fumed silica, can be carried out in the presence of a

According to the invention, the suspension preferably contains at least one polymer which preferably contains amino groups and a particulate thickener which has silanol groups, carbinol groups and carboxylic acid groups, it being possible for the respective groups to be present alone or in any mixtures which bind the polymer in a physisorptive manner.

Preferred according to the invention is a suspension which contains particulate thickening agents, which preferably carries acidic groups, such as acidic metal, metalloid and

Non-metal hydroxide groups, such as -OH groups, such as B-OH, P-OH, Al-OH, Si-OH, Ge-OH, Zr-OH groups, particularly preferably silanol groups (Si-OH) of the silica surface, particularly preferably silanol groups of the fumed silica surface , and containing on the surface of particulate thickener polymers having basic groups, such as amines, such as primary, secondary and tertiary amines, such as polymers bearing amino groups, such as primary, secondary or tertiary amines, such as alkylene di-, tri- and Polyamines, such as amino group-containing polyalkylene oxides, such as Jeffamine, or aliphatic or arylaliphatic polyamines and polyamidiamines, aminosiloxanes, such as linear and branched aminosiloxanes, such as liquid and solid aminosiloxanes, such as aminosiloxane polymers or resins, for example polydimethylsiloxanes with or in the chain bonded to a Si atom alkylamino groups, such as 2-amino-ethyl-3-amino-propyl groups, 3-amino-propyl or 1-amino-methyl groups, having a viscosity at 25 ⁰ C. from 500 to 5000 mPas and an amine number of 0.5 to 10.

Particularly preferred according to the invention are primary, secondary and tertiary amino alcohols and their esters with mono-, di- and polycarboxylic acids. Preferred examples of amino alcohols are cyclic amino alcohols such as piperidine alcohols such as 4-piperidine alcohols. Preferred examples of carboxylic acids are dicarboxylic acid having 2 to 24 carbon atoms, more preferably 4 to 12 carbon atoms. Very particular preference is given to piperidinyl sebacates, such as, for example, piperdinylesterified O, G0-dicarboxylic acids, particularly preferably bis-1,2,2,6,6-pentamethyl-4-piperidinyl-sebacate or methyl-1,2,2,6,6 Pentamethyl-4-piperidinyl-sebacate), and mixtures thereof, which are used as liquid light stabilizers (HALS: hindered-amine light stabilizer)).

According to the invention, preference is given to a suspension which contains particulate thickening agents, particularly preferably fumed silica, preferably those containing SiOH groups, and basic polymer containing basic particulate thickeners, such as aminopolysiloxane, such as polydimethylsiloxanes having terminal or in the chain bonded to an Si atom

Alkylamino groups, such as 2-amino-ethyl-3-amino-propyl groups, 3-amino-propyl or 1-amino-methyl groups, having a viscosity at 25 ⁰ C of 500-5000 mPas and an amine value of 0.5 to 10.

According to the invention preferably contains the suspension, at least one polymer containing carboxylic acid groups and particulate thickener having the amino groups, wherein the respective group alone or in any mixtures be present together, which bind the polymer physisorptive.

According to the invention, the suspension preferably contains particulate thickeners which contain basic groups and polymers which are bonded to particulate thickeners and contain acidic groups.

An inventively particularly preferred example of particulate thickeners containing basic groups are here preferably metal oxides, preferably silicic acids, particularly preferably fumed silica which are partially surface-functionalized with aminoalkylsiloxy groups, ie those in which 10 to 90%, preferably 25-75% of the total surface are silylated , preferably those in which 10 to 90%, preferably 25-75%, of the surface silanol groups of the untreated silica are substituted with aminoalkylsiloxy groups.

Preferred examples are particulate thickeners, such as, preferably, metal oxides, such as silicic acids, preferably pyrogenic silicas functionalized with aminoalkyl groups, prepared as described in EP-A-896 029, EP-A-1302444, EP-A-1304332, and EP-A- 1473296 described.

A preferred example of acidic group-containing polymer according to the invention are preferably polymers which contain acidic carboxyl groups (-COOH) terminally and laterally or only laterally or only terminally, such as polyacrylates, such as polyalkylalkylacrylates, such as polyesters, or weakly acidic hydroxyl groups (-OH). such as carbinol (-C-OH) groups in alcohols and polyols, such as polyesters, especially those with measurable amounts of free carboxylic acid groups (-COOH) groups, such as those polymers such as for the preparation of 1-component and 2-component polyurethanes for Surfaces- Coatings, adhesives and sealants, glass fiber reinforced plastics are used, in particular those having an acid number according to DIN 53402 or ISO 3682 greater than 1 ml / g, preferably greater than 5 ml / g, more preferably greater than 10 ml / g, most preferably greater than 20 ml / g, more preferably greater than 50 ml / g.

According to the invention, preferably suspensions contain greater than 1 percent by weight of carboxyl-containing polymer having an acid number greater than 1 ml / g and greater than 5 weight percent, preferably greater than 10 weight percent, more preferably greater than 15 weight percent and most preferably greater than 18 weight percent of a particulate thickener surface-functionalized with aminoalkylsiloxy groups , such as preferably metal oxides, preferably silica, particularly preferably fumed silica, for example prepared according to EP-A-1304332, with a specific surface area of greater than 150 m ² / g according to BET. The suspension according to the invention particularly preferably contains 25% by weight and very particularly preferably more than 35% by weight of a fumed silica having a specific surface area of less than 150 m ² / g according to BET.

Preferred are suspensions containing at least one polymer containing silanol groups and siloxane groups and containing the particulate thickener having silanol groups, siloxane groups and alkylsiloxy groups, which groups may be present alone or in any mixtures with each other, which chemisoptically bind the polymer.

A preferred example of a suspension according to the invention is preferably polysiloxane, preferably polyalkylsiloxane, more preferably polydimethylsiloxane containing particulate thickener, preferably fumed silica, with polysiloxane, preferably polyalkylsiloxane, especially preferably polydimethylsiloxane grafted. This is preferably done by Aufpolykondensieren or grafting of polydimethylsiloxane on pyrogenic KIESELSÄURE, this can be done by basic, for example with amines or ammonia, catalysis. This can be done, for example, by thermally driven

Reaction happen, here are temperatures of greater than 15O ⁰ C, preferably greater than 200 ⁰ C, required at reaction times greater than 5 hours or preferably at temperatures greater than 25O ⁰ C, more preferably greater than 300 ⁰ C at reaction times of less than 1 hour. A minimum reaction time of reaction time of less than 15 minutes should not fall below and a maximum temperature of greater than 400 ⁰ C, preferably not greater than 35O ⁰ C should not be exceeded. Another preferred chemical reaction can be achieved oxidatively at temperatures greater than 100 ⁰ C and oxygen content of greater than 1 percent by volume; a favorable for process reasons preferred variant is the mechano-chemically induced reaction at temperatures greater than -4O ⁰ C and average shear rates greater than 1000 s ^"1 and local shear rates greater than 10000 s ^{" 1} . This can be done by suspending and dispersing the silicic acid with high shear aggregates which introduce globally and locally very high shear energies into the suspension, such as mixing turbines, such as high speed kneaders or rolls such as 2 rolls, preferably with a friction greater than 1.01 or so 3-roll. The invention thus obtained

Suspensions exhibiting a fluidity and a soft mass, at a degree of filling of the suspension of up to 50 weight percent of particulate thickener.

Preferably, the particulate thickener, preferably fumed silica, a content of polydimethylsiloxane of greater than 10, preferably greater than 25, more preferably greater than 33, more preferably greater than 50 weight percent, measured over the carbon content of greater than 3.3, preferably greater than 8, more preferably greater 11, more preferably larger 50 weight percent. This can preferably be determined for the purpose of analysis by extraction / dissolution and sedimentation with decanting or dissolving and separating centrifuging, and then measuring the isolated particulate thickener, preferably pyrogenic silica on carbon content, for example by elemental analysis.

Coating material, adhesive and sealant may preferably be produced, at least using the suspension according to the invention.

Preferably, synthetic or natural rubber or rubber, at least using the suspension according to the invention can be prepared.

Suspensions according to the invention can be used for the preparation of preferably coating materials, preferably for scratch-resistant coating materials and coating materials with improved surface mechanics, for the production of adhesives and sealants, preferably for high-strength and impact-resistant adhesives and sealants.

Surprisingly, such large volume technically available and inexpensive to produce particulate thickeners, such as precipitated silica and fumed silica, pyrogenic

Aluminum oxides and titanium dioxides, as reinforcing fillers at a high degree of filling and thus high reinforcing effect and low viscosity at the same time, and thus cost-effective handling and good and easy processing of the suspensions of the invention are used.

Suspensions according to the invention can be used preferably for the preparation of coating materials, adhesives and sealants with a high loading of particulate matter Thickener at the same time low viscosity and thus excellent processability can be used.

The suspensions according to the invention can preferably be used for the preparation of peroxide crosslinked or addition-crosslinked silicone rubbers of high degree of filling with pyrogenic silica and high strength, high modulus, high notch strength and high elasticity of the crosslinked compositions while excellent processing properties such as flowability of the uncrosslinked compositions.

The suspensions according to the invention can preferably be used to produce high-strength and / or elastic coatings, epoxy-based adhesives and sealants, with high strength, high modulus, high energy fracture and high impact strength, using epoxies as binders and using Jeffamines, polymeric amines, aliphatic Amines and aromatic amines as a hardener, are used.

The suspensions according to the invention can preferably be used for producing high-hardness and / or elastic surface coatings from 2-component POLYURETHANES, using polyols as binders and isocyanates as hardeners, wherein surface coatings with high gloss, low surface abrasion and high transparency coupled with excellent scratch resistance with gloss losses less than 50% and high chemical resistance. example 1

Preparation of a transparent 2-component polyurethane topcoat with 9.5 percent by weight fumed silica

Solid: 92.5 g of a hydroxyl-containing acrylate resin having an acid number of 9-12 mg / g, an OH number of 4.2% (based on the solids of the binder), a glass transition temperature Tg = 34 ⁰ C, an average molecular weight of 1900 g / mol are adjusted with solvent to a solids content of 52.5 weight percent, by adding 47.5 weight percent of a solvent mixture of aromatic hydrocarbons, glycol ether, butyl acetate and having a viscosity at T = 25 ⁰ C of 450 mPas added. Subsequently, 7.5 g of hydrophilic fumed silica having a BET specific surface area of 50 m ² / g, obtainable from Wacker-Chemie GmbH, D, under the name ^HDK® D05 are added in portions while stirring with a dissolver. Subsequently, this approach is pulped by a bead mill to a grindometer value at the resolution limit of the grindometer test of about 0 to 5 microns. The content of fumed silica is 13.4 percent by weight based on the solids. 100 parts of this mixture are then mixed with 6.8 parts of the hydroxyl-containing acrylate resin described above and 2 parts of 98 percent butyl acetate and 0.6 parts of 1 percent dibutyltin dilaurate solution in 98 percent butyl acetate and then this total approach, here the component binder , with a polyisocyanate of the type HDI trimer (trimer of hexymethylene diisocyanate) as a hardener, with a

Molecular weight of 505 g / mol, an isocyanate (NCO) content of 22 percent by weight based on solids, a solids content of 100 percent by weight and a viscosity at T = 25 ⁰ C of 2000 mPas, mixed in a mixing ratio binder to hardener of 100 to 23 , This final mixture of binder and hardener has the following characteristics: STOCHIOMETRIC IMPLEMENTATION of - OH and -NCO is 1 to 1, SOLID-BODY FORMULATION is 64% by weight and PYROGENIC SILICA is 9.5% by weight in the solid state.

Obtained is a very flowable system with very low absolute viscosity, low relative viscosity, low intrinsic viscosity, low thixotropy, near Newton's flow behavior and thus excellent paint body as a basis for good formulability and thus processability as a topcoat.

The rheological data of the formulation, measured with a cone plate rheometer from the company Physica, D, type UDS 200 are given in Tables 1 and 2.

Example 2

The procedure is as in Example 1, but instead of hydrophilic fumed silica with a specific

Surface according to BET of 50 m ² / g, available from Wacker-Chemie GmbH, D under the name HDK ^® D05 is hydrophilic fumed silica having a BET specific surface area of 125 m ² / g, available from Wacker chemistry GmbH, under the name HDK ^® S13 used.

We obtain a highly flowable system with very low absolute viscosity, low relative viscosity, low intrinsic viscosity, low thixotropy, near Newton's flow behavior and thus excellent paint body as a basis for good formulability and thus processability as a topcoat. The rheological data of the formulation, measured with a cone plate rheometer from the company Physica, D, type UDS 200 are given in Tables 1 and 2.

Example 3

The procedure is as in Example 1, but instead of hydrophilic fumed silica having a BET specific surface area of 50 m ² / g, available from Wacker-Chemie GmbH, D under the name HDK ^® D05 is hydrophilic fumed silica with a BET specific surface area of 150 m ² / g, available from Wacker-Chemie GmbH, D, under the name ^HDK® V15.

Example 4

The procedure is as in Example 1, but instead of hydrophilic fumed silica having a BET specific surface area of 50 m ² / g, available from Wacker-Chemie GmbH, D under the name HDK ^® D05 is hydrophilic fumed silica with a BET specific surface area of 200 m ² / g, available from Wacker-Chemie GmbH, D, under the name ^HDK® N20. We obtain a highly flowable system with very low absolute viscosity, low relative viscosity, low intrinsic viscosity, low thixotropy, near Newton's flow behavior and thus excellent paint body as a basis for good formulability and thus processability as a topcoat.

Example 5

Surface according to BET of 50 m ² / g, available from the company Wacker-Chemie GmbH, D, under the name HDK ^® D05 is hydrophilic fumed silica having a BET specific surface area of 300 m ² / g, available from the Fa. Wacker-Chemie GmbH, D under the name HDK ^® T30, used.

We obtain a highly flowable system with very low absolute viscosity, low relative viscosity, low intrinsic viscosity, low thixotropy, near Newton's flow behavior and thus excellent paint body as a basis for good formulability and thus processability as a topcoat.

Table 1: Examples 1 to 5 absolute viscosity [mPas].

Visk: absolute viscosity at 25 ⁰ CD: shear rate in [l / s] Without HDK: without fumed silica

Table 2: Examples 1 to 5 relative viscosity η _re i = η / η ₀ . Rel. Visk: relative viscosity at 25 ⁰ CD: shear rate in [l / s]

Example 6

Lifts with dry layer thicknesses of 40 .mu.m to glass with subsequent drying during storage for 30 minutes at room temperature and subsequent storage and curing for 30 minutes at a temperature of 13O ⁰ C in a convection oven are prepared from the respective batches according to Examples 1 to 5 with the doctor. After a further 24 hours' storage at room temperature, these coating films prepared in this way are measured in accordance with ASTM D1003 in transparency, transparency and clarity. Except with Example 1, HDK ^® D05, become high obtained transparent clearcoats. HDK D05 has primary particles larger than 50 nm, therefore, even with homogeneous colloidal distribution, only low transparency is to be expected. The high clarity of the coating body indicates the good and homogeneous colloidal distribution of fumed silica. It will measure an excellent glossy lacquer surface that confirms the excellent low viscosity and leveling properties of the clearcoat. The high smoothness of the paint films proves the very good

Processing properties of the topcoat due to its low viscosity, as described in Examples 1 to 5.

Table 3 ASTM D1003 Measurement in transmission for transparency, haze and clarity

Transp: Transparency

Haze: haze

Clarity: clarity

Without HDK: without fumed silica

Example 7

Preparation of a transparent 2-component polyurethane topcoat with 15 weight percent fumed silica on solid: 61.1 g of a hydroxyl-containing acrylate resin having an acid number of 9-12 mg / g, an OH number of 4.2% (based on solid binder) one

Glass transition temperature Tg = 34 ⁰ C, a molecular weight of 1900 g / mol, adjusted to a solids content of 52.5 weight percent, by adding 47.5 weight percent solvent consisting of aromatic hydrocarbons, glycol ether esters and butyl acetate with a viscosity at T = 25 ⁰ C of 450mPas. This approach is presented in a batch tank together with 24.8 g of a solvent mixture of SolvessolOO to 98 percent butyl acetate = 70 to 30. To this approach, 10.9 g of fumed silica having a BET specific surface area of 300 m ² / g, available from Wacker-Chemie GmbH under the name HDK ^® T30, added in portions with stirring to a dissolver and then the Approach via a bead mill to a

Grindometer value at the resolution limit of the test from 0 to 5 μm digested. This total formulation thus prepared is then treated with 0.5 g of piperidinyl sebacate (a mixture of 75% by weight of bis-1,2,2,6,6-pentamethyl-4-piperidinyl sebacate and 25% by weight of methyl 1,2,3,6,6 pentamethyl-4-

Piperidinyl sebacate), available from Ciba Specialty Chemicals, CH under the trade name Tinuvin ^® 292 (a liquid universal light stabilizer (HALS: hindered amine light stabilizer)), mixed, and 1.0 g of a 1 percent Dizinndibutyldilaurat solution -percentage-98 in butyl acetate, and 0.7 g of a nonionic surfactant based on polyethylene oxide-modified polydimethylsiloxane having a density of 1.04 kg / 1, available under the trade name BYK ^® 331 available from Byk-Chemie, D, as 10% solution in 98% butyl acetate, and 10.1 g of the hydroxyl-containing acrylate resin described above and with 3.0 g of a solvent mixture of SolvessolOO to 98 percent butyl acetate = 70 to 30 completed. This entire batch is mixed at a mixing ratio of 100 to 18.5 with a polyisocyanate of the type HDI trimer, having a molecular weight of 505 g / mol, an NCO content of 22% on solids, a solids content of 100% by weight and a viscosity at T = 25 ⁰ C of 2000 mPas, mixed. The overall system is characterized by the following parameters: STOCHIOMETRIC IMPLEMENTATION OH to NCO = 1 to 1, SOLID BODY FORMULATION 54% by weight, PYROGENIC SILICA HDK ^® T30 15% solids by weight.

Obtained is an excellent flowable system with very low absolute viscosity, low relative viscosity, very low intrinsic viscosity, very low thixotropy, near Newton's flow behavior and thus excellent paint body as a basis for good formulability and thus processability as a topcoat.

The rheological data for Example 7, measured with a cone plate Rheometer Fa. Physica, D, type UDS 200, are given in Table 3.

Table 3: Example 7 absolute viscosity [mPas] Visc: absolute viscosity at 25 ⁰ CD: shear rate in [l / s]

example

From the batch of Example 7 elevators at dry film thicknesses of 35 .mu.m mounted on glass with the doctor, after storage and drying for 30 minutes at room temperature and cured by storage and curing for 30 minutes at a temperature of 130 ⁰ C in a convection oven. After subsequent storage for 24 hours at room temperature, these films are measured according to ASTM D1003 in transmission. The high clarity of the paint body shows the good and homogeneous colloidal distribution of fumed silica. It will measure an excellent glossy lacquer surface that confirms the excellent low viscosity and leveling properties of the clearcoat.

Table 4: Measurement Example 8 according to ASTM D1003 in Transmission Transp: Transparency Haze: Turbidity Clarity: Clarity Without HDK: without pyrogenic silica

Example 9

The scratch resistance of the paint surface of the cured paint film according to Example 8 is determined using a Scheuer test device according to Peter-Dahn. For this purpose a scouring fleece Scotch ^Brite® 2297 / scouring agent 3M Scotch-Brite CF-HP S-SFN (soft) with an area of 45 x 45 mm with a weight of 1000 g is weighted. With this, the paint samples are scratched with a total of 40 strokes. Both before and after completion of the scratching tests, the gloss of the coating is measured with a gloss meter Microgloss 20 ° from Byk. As a measure of the scratch resistance of the coating, the loss of gloss compared to the initial value is determined

Table 5: Luster loss of example

Example 10

Preparation of a transparent 2-component polyurethane topcoat with 15 weight percent fumed silica on solids: 62.1 g of a hydroxyl group-containing acrylate resin having an acid number 9-12 mg / g, an OH number of 4.2% on solid binder, a glass transition temperature Tg = 34 ⁰ C, a molecular weight of 1900 g / mol, a solids adjusted to 52.5 weight percent, by addition of 47.5 weight percent solvent containing aromatic hydrocarbons, glycol ether, butyl acetate and a viscosity at 25 ⁰ C of 450 mPas are in one Batch tank along with 24.8 g of a solvent mixture consisting of SolvessolOO to 98 percent butyl acetate = 70 presented to 30 and this 10.9 g of an aminoalkyl-modified fumed silica, available under the trade name HDK® H30RA at the company Wacker-Chemie GmbH , D, which has a content of Aminopropyldimethylsiloxy groups of 0.09 mol / g and for example according to EP-A-1304332 hergeste and a carbon content of 5 weight percent and a nitrogen content of 1 weight percent, both determined by elemental analysis, (based on a hydrophilic fumed silica having a specific surface area of 300 m ² / g HDK available from Wacker-Chemie GmbH , D, under the trade name HDK® T30), added in portions to a dissolver with stirring, and then the batch digested via a bead mill to a grindometer value at the resolution limit of the grindometer test from 0 to 5 microns. This total mixture was then treated with 0.5 g of piperidinyl sebacates (a mixture of 75% by weight of bis-1,2,3,6,6 Pentamethyl-4-piperidinyl sebacate and 25 weight percent methyl-1,2,2, 6, 6-pentamethyl-4-piperidinyl sebacate), available from Ciba Specialty Chemicals, CH under the trade name Tinuvin ^® 292 (a liquid universal light stabilizer (HALS: hindered amine light stabilizer)), and 1.0 g of 1 percent

Dizinndibutyldilaurat solution in 98 percent butyl acetate, and 0.7 g of a nonionic surfactant based on polyethylene oxide-modified polydimethylsiloxane with a density of 1.04 kg / 1, available under the trade name BYK ^® 331 available from Byk-Chemie, D, as a 10 percent solution in 98 percent butyl acetate, and with 10.1 g of the hydroxyl group-containing acrylate resin described above and with 3.0 g of a solvent mixture of SolvessolOO to 98 percent butyl acetate = 70 to 30 completed. This total batch of the binder component is 100 to 18.5 with a polyisocyanate of the type HDI trimer as a hardener, with a molecular weight of 505 g / mol, an NCO content of 22% based on solids, with a solids content of 100 percent by weight and a viscosity of 2000 mPas mixed. The overall system is characterized by the following parameters: STÖCHIOMETRISCHE IMPLEMENTATION -OH to -NCO = 1 to 1; SOLID-BODY FORMULATION 54% by weight; PYROGENIC SILICONE HDK ^® is 15% by weight in the solid state.

Obtained is an excellent flowable system with very low absolute viscosity, low relative viscosity, very low intrinsic viscosity, low thixotropy, near Newton's flow behavior and thus excellent paint body as a basis for good formulability and thus processability as a topcoat.

The rheological data for Example 10, measured with a cone-plate Rheometer Fa. Physica, D, type UDS 200, are given in Table 5. Table 5: Example 10 absolute viscosity [mPas] viscous: absolute viscosity at 25 ⁰ CD: shear rate in [l / s]

The measurements were done with a cone plate rheometer

Example 11

For this approach storage during 30 minutes at room temperature and then further storage for 30 minutes at 13O ⁰ C are prepared in a convection oven with a doctor blade elevators with a dry film thickness of 35μm on glass subsequently. Subsequently, after further storage for 24 hours at room temperature, these films are measured in accordance with ASTM D1003 in transmission. The high clarity of the coating body indicates the good and homogeneous colloidal distribution of fumed silica. It will measure an excellent glossy lacquer surface that confirms the excellent low viscosity and leveling properties of the clearcoat.

Table 6: Measurement Example 11 according to ASTM D1003 in Transmission Transp: Transparency Haze: Turbidity Clarity: Clarity Without HDK: without fumed silica

Example 12

The scratch resistance of the paint surface of the cured paint film according to Example 11 is determined using a Scheuer test device according to Peter-Dahn. For this purpose a scouring fleece Scotch ^Brite® 2297 / scouring agent 3M Scotch-Brite CF-HP S-SFN (soft) with an area of 45 x 45 mm with a weight of 1000 g is weighted. With this, the paint samples are scratched with a total of 40 strokes. Both before and after completion of the scratching tests, the gloss of the coating is measured with a gloss meter Microgloss 20 ° from Byk. As a measure of the scratch resistance of the coating, the loss of gloss compared to the initial value is determined

Table 7: Loss on loss Example 11

Example 13

:

Chemicals under the name Dow DER 330, or from the company Shell under the name of Epikote 828, having a polymerization index of n = 0.15 and a molecular weight of Mn = 340 + 284. n = 382.6 g / mol, that is preheated to liquefy for 2 hours at a temperature of 5O ⁰ C, 25 g of an aminoalkyl-modified fumed silica, obtainable under the trade name of HDK ^® H30RA in Fa. Wacker-Chemie GmbH, D, which has a content of aminopropyldimethylsiloxy groups of 0.09 mol / g and for example, in accordance to EP-a-1304332 can be prepared, and has a carbon content of 5 weight percent and a nitrogen content of 1 weight percent, both determined by elemental analysis, (based on a hydrophilic fumed silica having a specific surface area of 300 m ² / g HDK available from Wacker-Chemie GmbH D, under the trade name ^HDK® T30), incorporated, incorporated and dispersed with a dissolver Turbotest 33 / 300P, Rayneri. The silica is metered into the liquid phase gradually, first with a number of revolutions of the mixer of 500 revolutions per minute, then for a few minutes at a higher number of revolutions of 3300 per minute, ie about a peripheral

Circulation speed of the disc of 11 m / s dispersed before further silica is added. When all the silica is incorporated and dispersed, it is dispersed at one revolution to 3300 per minute for 1 hour. By dispersing the fumed silica of the composition may come to 60 and 8O ⁰ C to heating up. The dispersing quality is monitored with a grindometer to a value close to 0 μm, with optical microscopy, and with viscosity measurements. The mixture is then finally degassed in a vacuum reactor, for 30 minutes and at one hour at a temperature of 8O ⁰ C, with slow stirring.

Example 14

The procedure is as in Example 13, but instead of 475 g DGEBA Dow DER330 uses 450 g of DGEBA Dow DER330, and instead of HDK ^® H30RA pyrogenic silica (25 g), 50 g of HDK ^® H30RA fumed silica are used

Example 15

The procedure is as in Example 13, but instead of 475 g DGEBA Dow DER330 425 g DGEBA Dow DER330 are used, and instead of 25 g of fumed silica HDK ^® H30RA 75 g of fumed silica HDK ^® H30RA used.

Table 8 Mixing ratios of the suspensions according to Examples 13, 14 and 15: Silica HDK® H30RA suspensions in epoxy DGEBA DER330

Weight% appearance

^HDK® Mass ^HDK® of mass

H30RA H30RA [g] Mass DGEBA [g] at 5O ⁰ C

5 25 475 Example 13 flowable

10 50 450 Example 13 Flowable

15 75 425 Example 13 Flowable

The reaction of an epoxy functionality unit with e = 1 and a primary amine functionality with a = 2 leads to the formation of a chemisorptive and chemical bonding of the epoxy resin DGEBA and the aminoalkyl-silica HDK ^® H30RA. The functional stoichiometric ratio is defined by the amino hydrogen atom to epoxy function ratio r = a / e

The silicic acid contained in the suspension is dissolved by dissolving 2.5 g of the epoxy resin-and-silica suspension according to Example 13, 14 and 15 in 50 ml of tetrahydrofuran and then centrifuging in a laboratory centrifuge at 5000 Separated revolutions per minute and the sediment was washed by taking up five times in tetrahydrofuran and centrifuging free, unbound epoxy resin, cleaned and separated from the unbound epoxy resin, dried and analyzed. This so isolated from the suspension silica has a carbon content of 41 weight percent, as well as a mass loss in the thermogravimetry to 55O ⁰ C under air of 42 weight percent. This corresponds to an average conversion of 1.7 moles of the amino hydrogen groups of the silica HDK® H30RA with one mole of the epoxy groups of the epoxy resin. I-NMR, 13 C-NMR and infrared spectroscopy confirm the surface reaction of the aminoalkyl-functional silica HDK® H30RA with the epoxy resin DGEBA. This elemental analysis gives for examples 13, 14 and 15 ratios of r = a / e = of about 0.85, which under in-situ conditions of

Mixture was carried out chemisorptive binding of the epoxy resin DGEBA on the aminoalkyl-functional silica HDK ^® H30RA occupied.

Example 16

To 450 g of a H ₂ N-CH-CH ₂ - (- O-CH ₂ -CH-) _n -NH 2 liquid bis- (2-aminopropyl) - ^ QJ_ |

Polypropylene glycol, available under the name Jeffamine D2000 ^®, Fa. Huntsman, having the formula and chain length n = 33.1, molecular weight Mn = 2000 g / mol, 50 g of a fumed with hydrophilic silica, available from the Fa. Wacker-Chemie GmbH under the name HDK ^® T30 added, incorporated and dispersed with a dissolver Turbotest 33 / 300P, Rayneri, or with a Dispermat with a toothed disc of 65 mm diameter. The silica is gradually added to the liquid phase, first with a number of revolutions of the mixer of 500 revolutions per minute, then for a few minutes at a higher number of revolutions of 3300 per minute, ie about a peripheral peripheral speed of the disc of 11 m / s dispersed before adding more silica. When all the silica is incorporated and dispersed, at a

RPM dispersed at 3300 per minute for 1 hour. By dispersing the fumed silica of the composition may come to 60 and 8O ⁰ C to heating up. The dispersing quality is monitored with a grindometer to a value close to 0 μm, with optical microscopy, and with viscosity measurements. The mixture is then finally degassed in a vacuum reactor, for 30 minutes and at one hour at a temperature of 8O ⁰ C, with slow stirring.

Example 17

The procedure is as in Example 16, but instead of 450 g Jeffamin D2000 ^® 400 g Jeffamin D2000 ^® are used, and instead of 50 g of fumed silica HDK ^® T30 100 g of fumed silica HDK ^® T30 are used

Table 9: mixing ratios of the dispersions: silicic acid HDK ^® T30 in Jeffamine ^® D2000

Wt% mass HDK ^® mass Jeffamin D2000 ^®

HDK ^® T30T30 [g] [g]

10 50 450 Example 16

20 100 400 Example 17 The silicic acid contained in the suspension is separated by dissolving 2.5 g of the epoxy resin and silica suspension according to Example 16 and 17 in 50 ml of tetrahydrofuran and subsequent centrifuging in a laboratory centrifuge at 5000 revolutions per minute and the sediment by five times

Washed in tetrahydrofuran and centrifuged from free, unbound epoxy resin, cleaned and separated from the unbound epoxy resin, dried and analyzed. The elemental analysis gives a carbon content for the on hydrophilic silica HDK ^® T30 physisorptively bound Jeffamine from about 20 weight percent for the examples. 16 and 17

Example 18

The masses of Examples 13, 14 and 15 are mixed with a solid amino hardener, 4, 4 ^f methylene-bis-2, 6-

Diethylaniline, MDEA, molecular weight Mn = 310 g / mol, for example available from the Fa. Lonza, cross-linked. For this MDEA is heated to 90 ⁰ C, liquefied and mixed into the masses of Example 13, 14 and 15 and the mixture into a Brought form. The ratio of DGEBA to MDEA is 71.17 to 28.83. The crosslinking is implemented in a programmable oven: 4 hours at 135 ⁰ C, followed by aftercrosslinking for 4 hours at 19O ⁰ C.

The crosslinked masses with fumed silica HDK ^® H30RA show a significantly increased strength and impact resistance compared to compositions without fumed silica.

Example 19

The mass of Example 16, 17 are crosslinked with DGEBA Dow DER330. For this purpose, DGEBA is heated to 50 ⁰ C, then liquefied and mixed in the compositions from examples 16 and 17, and the mixture placed into a mold. The ratio of DGEBA Dow DER330 to Jeffamine D2000 ^® is hereby 27.67 to 72.33. The crosslinking is implemented in a programmable oven: 4 hours at 120 ⁰ C, followed by a post-crosslinking for 4 hours at 15O ⁰ C.

The crosslinked masses with fumed silica HDK ^® T30 show a significantly increased strength and elasticity compared to compositions without fumed silica.

Example 20

1 kg Wacker one aminoalkyl-modified fumed silica, available under the trade name HDK ^® H30RA from Wacker-Chemie GmbH, D, which has a content of aminopropyldimethylsiloxy groups of 0.09

Mol / g and can be prepared, for example, according to EP-A-1304332, having a carbon content of 5% by weight and a nitrogen content of 1% by weight, both determined by elemental analysis (based on a hydrophilic fumed silica having a specific gravity)

Surface of 300 m ² / g HDK available from Wacker-Chemie GmbH, D, under the trade name HDK ^® T30), is 45 minutes to 9 kg liquid epoxy resin bisphenol A diglycidyl ether, (DGEBA: diglycidyl ether of bisphenol A) such as available N from the company. Dow Chemicals under the trade seeds Dow DER ^® 330, or from the Fa. Shell under the name Epikote ^® 828, having a polymerization index of n = 0.15 and a molecular weight of Mn = 340 + 284 = 382.6 g / mol, incorporated with a planetary dissolver; the temperature is limited to 60 ⁰ C; it results in a mass with a relative Viscosity of 3.2.

The silicic acid contained in the suspension is separated by dissolving 2.5 g of the epoxy resin-and-silica suspension in 50 ml of tetrahydrofuran and then centrifuging in a laboratory centrifuge at 5000 revolutions per minute and the sediment by taking up in tetrahydrofuran five times and centrifuging free , unbound epoxy resin, cleaned and separated from the unbound epoxy resin, dried and analyzed. This so isolated from the suspension silica has a carbon content of 41 weight percent, as well as a mass loss in the thermogravimetry to 55O ⁰ C under air of 42 weight percent. This corresponds to an average reaction of 1.7 moles of amino-hydrogen groups of the Silica HDK ^® H30RA with one mole of the epoxy groups of the epoxy resin.

Claims

claims

A suspension, characterized in that it contains at least 3% by weight of particulate thickener, wherein at least one polymer has an amount of at least 5% by weight, based on the pure particulate thickener mass without polymer, bound to these particulate thickening agents in the suspension, and optionally at least one further polymer or several polymers is also present free in the suspension, that the relative viscosity η / ηo _r where η and T | o are measured at the same temperature and at a temperature of 25 ⁰ C, is less than 100, and the relative viscosity η / ηo when stored for a period of at least one week at a temperature of 4O ⁰ C changes by less than a factor of 10, and liquid phase, based on the total liquid phase 0 - 80 weight percent of a solvent or low molecular crosslinkable component with a viscosity of less than 100 mPas at 25 ⁰ C and based on the entire liquid phase contains 10-100 weight percent of a polymer component or a mixture of two or more physically or chemically crosslinkable polymers.

2. Suspension according to claim 1, that particulate

Thickening agents are metal oxides, metal carbonates, and plastic particles

3. Suspension according to claim 2, that metal oxides are silicon dioxide particles, silica particles, aluminum oxide particles, titanium dioxide particles, zirconium dioxide particles.

4. Suspension according to claim 3, that the silica particle is fumed silica.

5. Suspension according to claim 1-4, characterized in that at least one polymer is bound physisorptiv to this particulate thickener.

6. Suspension, according to claim 1-5, characterized in that at least one polymer is chemisorptively bound to this particulate thickener.

7. Suspension, according to claim 6, characterized in that at least one polymer is chemisorptively bound to this particulate thickener, and this particulate thickener is equipped by partial or complete surface modification with surface groups that react chemically with the polymer.

8. A suspension according to claim 7, characterized in that the partial or complete surface modification of the surface-active particulate thickener is a silylation with organofunctional siloxy groups.

9. Suspension, according to claim 7 and 8, characterized in that at least one polymer is chemisorptively bound to this particulate thickener, and this particulate thickener organofunctional epoxy, amino, mercapto, acrylate, isocyanate, carbinol groups and carboxylic anhydride Having groups which react chemically with the polymer.

10. Suspension, according to one or more of the preceding

Claims, characterized in that at least one polymer contains epoxy groups and that the particulate thickener amino, mercapto, carboxylic anhydride, and carbinol groups, wherein the respective group alone or in any Mixtures may be present together which bind chemisorptively with the polymer.

11. A suspension according to one or more of the preceding claims, characterized in that at least one polymer contains isocyanate groups and that the particulate thickener silanol, amino, and carbinol groups, wherein the respective group may be present alone or in any mixtures can chemisorptively bind with the polymer.

12. A suspension according to one or more of the preceding claims, characterized in that at least one polymer contains amino groups and that the particulate thickener silanol groups, carbinol, carboxylic acid groups, wherein the respective group may be present alone or in any mixtures with each other, which bind physisorptively with the polymer.

13. Suspension, according to one or more of the preceding

Claims, characterized in that at least one polymer contains carboxylic acid groups and that the particulate thickener has amino groups, wherein the respective group may be present alone or in any mixtures which bind physisorptive with the polymer.

14. Suspension according to one or more of the preceding claims, characterized in that at least one polymer contains carbinol or isocyanate groups and that the particulate thickener silanol groups and siloxane

Groups, wherein the respective group may be present alone or in any mixtures with each other, which bind physisorptively with the polymer.

15. Suspension according to claim 1 to 4, and 6, characterized in that at least one polymer contains silanol groups or siloxane groups, wherein the respective group may be present alone or in any mixtures with each other, and that the particulate thickener silanol groups , Siloxane groups and alkylsiloxy groups, wherein the respective group may be present alone or in any mixtures which chemisoptically bind with the polymer.

16. Coating material, adhesive and sealant, which are at least produced using a suspension according to one or more of the preceding claims.

17. Synthetic or natural rubber or gum, which is produced at least using a suspension according to claim 15.