WO1990002779A1 - Use of fillers coated with trialkoxysilanes - Google Patents

Use of fillers coated with trialkoxysilanes Download PDF

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Publication number
WO1990002779A1
WO1990002779A1 PCT/AT1988/000071 AT8800071W WO9002779A1 WO 1990002779 A1 WO1990002779 A1 WO 1990002779A1 AT 8800071 W AT8800071 W AT 8800071W WO 9002779 A1 WO9002779 A1 WO 9002779A1
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Prior art keywords
fillers
coated
layered silicates
purpose mentioned
silicates coated
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Application number
PCT/AT1988/000071
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German (de)
French (fr)
Inventor
Norbert Wamser
Original Assignee
Naintsch Mineralwerke Gesellschaft M.B.H.
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Publication date
Priority to AT0014886A priority Critical patent/AT387970B/en
Application filed by Naintsch Mineralwerke Gesellschaft M.B.H. filed Critical Naintsch Mineralwerke Gesellschaft M.B.H.
Priority to PCT/AT1988/000071 priority patent/WO1990002779A1/en
Priority to JP88507316A priority patent/JPH03501134A/en
Priority to EP88907548A priority patent/EP0387251A1/en
Publication of WO1990002779A1 publication Critical patent/WO1990002779A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/40—Compounds of aluminium
    • C09C1/405—Compounds of aluminium containing combined silica, e.g. mica
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/10—Coating or impregnating
    • C04B20/1051—Organo-metallic compounds; Organo-silicon compounds, e.g. bentone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/12—Treatment with organosilicon compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
    • C09D5/084—Inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/48—Stabilisers against degradation by oxygen, light or heat
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds

Definitions

  • the present invention relates to modified fillers, in particular to silicate fillers from the group of the layers or phyllosilicates, which have been treated with silanes to modify their properties, cf. for example EPPlueddemann, Silane Coupling Agents, Plenum Press New York (1982), Chapter 7, pp. 167-205.
  • Silanes are generally used to improve the adhesion between filler and polymer. As an adhesion promoter, they result in improved mechanical strength and chemical resistance of the composite.
  • the filler surface interacts with the polymer via catalytic activity, orientation of molecular segments and other modifications of the polymer morphology at the phase interface, see AT-B-263973, GB-A-2038302, GB-A-2052458.
  • the surface modification of fillers also influences the rheological properties by changing the wetting, dispersion, viscosity, thixotropy and flow behavior in the binder.
  • the modification increases the binding forces in the boundary layer by reaction or better application of polymer segments and by removing any inhibitor effects of the filler the curing of the polymer.
  • an increased probability of breakage in brittle resins or fillers can eliminate or obscure recesses by modifying the surface of the surface. For example, soft fillers in hard polymers hardly bring any improvements despite modification.
  • Such brittle polymers include thermoplastic acrylic resins, methacrylate-styrene copolymers, various epoxies, polypheiryl sulfides, polystyrenes (hard), styrene-acrylonitrile copolymers (SAN) and others.
  • a silene modification of soft fillers is particularly advantageous for flexible resins and rubber. Harder fillers can be added to increase their strength.
  • thermoplastics for example in PE methacrylate silane systems.
  • Inhibitor effects with regard to the hardening of the composite occur primarily on metadl oxide surfaces, but also silicate surfaces (such as talc, mica etc.) can inhibit peroxide hardening. This reduction in the crosslinking exotherms can be prevented by silane modification (for example in the case of unsaturated polyesters).
  • the modification of the fillers also affects their dispersibility. Likewise, the viscosity of a medium containing the filler is changed by modifying the fillers with silanes, although a reduction in viscosity is generally to be expected, but acid-base properties play an important role. Neutral polymers require surface-active additives for a good dispersion, each polar additive lowers the viscosity. Acidic additives for basic fillers and basic additives for acidic fillers are used. Acidic fillers include silica gel, quartz, kaolin; basic fillers are, for example, talk (weak), calcite , Magnesite, aluminum hydroxide. The relative acidity of a filler is determined by its isoelectric point in the water.
  • Acidic fillers in basic polymers and basic fillers in acidic polymers result in good dispersibility without sap.
  • Lewis acids titaniumates are suitable for acidic fillers in basic polymers, but not for basic fillers in acidic polymers.
  • Acid fillers in acidic polymers and basic fillers in basic polymers require additives.
  • Cationic silanes or Lewis acids give the best results with acidic fillers in acidic polymers and some improvement with basic fillers in basic polymers.
  • Neutral silanes that have been modified with catalytic amounts of amines or titanates are generally more effective than pure silane.
  • Surface-active additives also increase the coupling power of neutral silanes.
  • the present invention thus relates to the use of trialkoxysilanes containing amino, epoxy, imidazoline, succinic anhydride, cyclohexyl, urea and / or vinyl groups, alone or in combination, of silicate fillers from the group of the layered or phyllosilicates , especially based on talc, chlorite and mica, in anti-corrosion varnishes, spray fillers and stoving stone fillers.
  • H 2 C CHSi (OC 2 H 4 OCH 3 ) 3 and vinylbenzylaminoethylaminopropyltrimethoxysilane
  • CH 2 CHC 6 H 4 CH 2 NH (CH 2 ) 2 NH (CH 2 ) 3 Si (OCH 3 ) 3 , 4, 5-dihydro-1- [3- (triethoxysilyl)) propyl] imidazole (CH 2 ) 3 Si (OC 2 H 5 ) 3 ,
  • the amount of the silane applied according to the invention can expediently be up to about 2%, based on the dry weight of the filler.
  • the special silanes can be applied to the fillers by special methods, for example the slurry method in which the filler to be treated is treated with a suitable solvent, e.g. Ethanol, isopropanol or white spirit, mixed to a pulp and the coating agent (coating agent) dissolved in the solvent is added. After stirring in, the resulting slurry is carefully homogenized. Subsequent standing and drying results in the coated filler. Another manufacturing process involves stirring the coating agent in the diluted or undiluted state and homogenizing it in a high-performance stirrer. Finally, the dissolved silane can also be sprayed directly onto the filler moved in an air stream.
  • a suitable solvent e.g. Ethanol, isopropanol or white spirit
  • the fillers coated according to the invention have unexpectedly advantageous properties.
  • a silanization of talc or Plastorit ® (magnesium-potassium-aluminum-silicate), chlorite and mica with a trialkoxysilane having a substituent of the above-mentioned type results in a marked improvement in the resistance to corrosion, as measurements in the case of these coated fillers in corrosion protection lacquers based on aqueous epoxy resin systems Confirm salt spray test.
  • Coated talc fillers show an analogous behavior in alkyd resin systems.
  • Talc varieties coated according to the invention have also been found in spray fillers unsaturated polyester resins or PU resins compared to uncoated fillers have been shown to be significantly better in terms of flow properties and surface properties as well as in terms of mechanical properties such as impact resistance.
  • the following examples are intended to explain the invention in more detail.
  • the filler aftertreated according to the invention leads to a significant improvement in the paint properties of a stoving filler for motor vehicles based on a water-soluble polyurethane resin, such as the comparison of test formulations below (approach 1: with filler coated according to the invention; approach 2: uncoated filler according to the prior art ) and show the results obtained with it.
  • Top coat stand (with a commercially available automotive repair paint based on alkyd)
  • the filler aftertreated according to the invention also results in a significant improvement in the paint properties of a dispersion antirust paint based on a combination of a polyurethane dispersion and an acrylate copolymer dispersion, such as the one below
  • Part I is intensively predispersed, then completed with Part II and dispersed on the dissolver for 30 min.
  • Part III is pre-mixed using a cage stirrer (10 min), then the
  • Parts I + II are dispersed after dispersing with Part III using the cage stirrer.
  • the salt spray resistance is tested after one week of air drying in accordance with ASTM B 117/64.
  • the filler aftertreated according to the invention furthermore gives superior stone chip resistance in a stoving stone filler based on alkyd resin, as the following comparison of test formulations (approach 1: with filler coated according to the invention; approach 2: uncoated filler according to the prior art) and the results obtained thereby show.
  • the paint viscosity (according to DIN 53211, 23 ° C) is approx. 40s. After dilution with Shellsol A / Butanol 7/3, the spray viscosity (DIN 53211, 23 ° C) is approx. 23 s.
  • the stone chip filler is burned in at 150 ° C, 25 min.
  • the alkyd / melamine ratio is 85/15, the pigment / binder ratio is about 1/1.
  • the stone chip resistance determined according to a W test specification with a VW stone chip device, is as follows:

Abstract

Silicate fillers from the group of phyllosilicates coated with trialkoxysilanes having amino, epoxy, imidazoline, succinic acid anhydride, cyclohexyl, urea and/or vinyl groups are used in anticorrosive lacquers, spray fillers and stove stone-guard fillers, giving better results than uncoated fillers.

Description

VERWENDUNG VON MIT TRIALKOXYSILANEN  USE OF WITH TRIAL COXYSILANES
BESCHICHTETEN FÜLLSTOFFEN  COATED FILLERS
Die vorliegende Erfindung bezieht sich auf modifizierte Füllstoffe, insbesondere auf silikatische Füllstoffe aus der Gruppe der Schichtenoder Phyllosilikate, die zur Modifizierung ihrer Eigenschaften mit Silanen behandelt worden sind, vgl.hiezu etwa E.P.Plueddemann, Silane Coupling Agents, Plenum Press New York (1982), Kapitel 7, S. 167-205. The present invention relates to modified fillers, in particular to silicate fillers from the group of the layers or phyllosilicates, which have been treated with silanes to modify their properties, cf. for example EPPlueddemann, Silane Coupling Agents, Plenum Press New York (1982), Chapter 7, pp. 167-205.
Generell werden Silane zur Haftungsverbesserung zwischen Füllstoff und Polymer eingesetzt. Als Adhäsionspromotor ergeben sie verbesserte mechanische Stärke und chemische Resistenz des Verbundstoffs. Die Füllstoffoberfläche tritt mit dem Polymer über katalytische Aktivität, Orientierung molekularer Segmente und andere Modifikationen der Polymer-Morphologie an der Phasengrenzfläche in Wechselwirkung siehe hiezu AT-B-263973, GB-A-2038302, GB-A-2052458. Silanes are generally used to improve the adhesion between filler and polymer. As an adhesion promoter, they result in improved mechanical strength and chemical resistance of the composite. The filler surface interacts with the polymer via catalytic activity, orientation of molecular segments and other modifications of the polymer morphology at the phase interface, see AT-B-263973, GB-A-2038302, GB-A-2052458.
Die Oberflächenmodifizierung führt bei Füllstoffen auch zur Beeinflussung der rheologischen Eigenschaften durch Äiderung der Benetzung, Dispersion, Viskosität, Thixotropie und des Fließverhaltens im Bindemittel.Die Modifizierung erhöht die Bindungskräfte in der Grenzschicht durch Reaktion oder besseres Anlegen von Polymersegmenten und durch Aufheben eventueller Inhibitoreffekte des Füllstoffs auf die Härtung des Polymers. Anderseits kann eine erhöhte Bruchwahrscheinlichkeit in spröden Harzen oder Füllstoffen Vertiesserungen durch eine Modifikation der Ctoerfläche aufheben bzw. verschleiern. So bringen weiche Füllstoffe in harten Polymeren trotz Modifizierung kaum Verbesserungen. Zu solchen spröden Polymeren zählen thermoplastische Acrylharze, Methacrylat-Styrol-Copolymere, verschiedene Epoxide, Polypheirylsulfide, Polystyrole (hart), Styrol-Acrylnitril-Copolymere (SAN) und andere. Eine Silenmodifizierung weicher Füllstoffe ist vor allem bei flexiblen Harzen und Gummi vorteilhaft. Zur Erhöhung ihrer Festigkeit sind Zusätze härterer Füllstoffe möglich. The surface modification of fillers also influences the rheological properties by changing the wetting, dispersion, viscosity, thixotropy and flow behavior in the binder. The modification increases the binding forces in the boundary layer by reaction or better application of polymer segments and by removing any inhibitor effects of the filler the curing of the polymer. On the other hand, an increased probability of breakage in brittle resins or fillers can eliminate or obscure recesses by modifying the surface of the surface. For example, soft fillers in hard polymers hardly bring any improvements despite modification. Such brittle polymers include thermoplastic acrylic resins, methacrylate-styrene copolymers, various epoxies, polypheiryl sulfides, polystyrenes (hard), styrene-acrylonitrile copolymers (SAN) and others. A silene modification of soft fillers is particularly advantageous for flexible resins and rubber. Harder fillers can be added to increase their strength.
Bei Thermoplasten spielen Homopolymerisationen und Nukleierungseffekte die entscheidende Rolle,beispielsweise bei PE-Methacrylatsilan-Systemen. Inhibitoreffekte bezüglich der Härtung des Verbundes treten vor allem bei Metadloxidoberflächen auf, aber auch silikatische Oberflächen (wie bei Talk, Glimmer etc.) können Peroxidhärtungen inhibieren. Durch eine Silanmodifizierung kann diese Erniedrigung der Vernetzungs- exothermen verhindert werden (z.B. bei ungesättigten Polyestern). Homopolymerizations and nucleation effects play a decisive role in thermoplastics, for example in PE methacrylate silane systems. Inhibitor effects with regard to the hardening of the composite occur primarily on metadl oxide surfaces, but also silicate surfaces (such as talc, mica etc.) can inhibit peroxide hardening. This reduction in the crosslinking exotherms can be prevented by silane modification (for example in the case of unsaturated polyesters).
Die Modifizierung der Füllstoffe beeinflußt auch ihre Dispergierbarkeit.Ebenso wird die Viskosität eines den Füllstoff enthaltenden Mediums durch eine Modifizierung der Füllstoffe mit Silanen verändert, wobei generell eine Erniedrigung der Viskosität zu erwarten ist,Säure- Basen-Eigenschaften aber eine wichtige Rolle spielen.Neutrale Polymere erfordern für eine gute Dispersion oberflächenaktive Additive, jeder polare Zusatz erniedrigt die Viskosität.Dabei werden saure Zusätze für basische Füllstoffe und basische Zusätze für saure Füller verwendet.Saure Füller sind u.a.Kieselgel,Quarz,Kaolin;basische Füllstoffe sind z.B.Talk (schwach), Calcit,Magnesit,Aluminiumhydroxid. Die relative Acidität eines Füllstoffes wird durch seinen isoelektrischen Punkt im Wasser bestimmt. The modification of the fillers also affects their dispersibility. Likewise, the viscosity of a medium containing the filler is changed by modifying the fillers with silanes, although a reduction in viscosity is generally to be expected, but acid-base properties play an important role. Neutral polymers require surface-active additives for a good dispersion, each polar additive lowers the viscosity. Acidic additives for basic fillers and basic additives for acidic fillers are used. Acidic fillers include silica gel, quartz, kaolin; basic fillers are, for example, talk (weak), calcite , Magnesite, aluminum hydroxide. The relative acidity of a filler is determined by its isoelectric point in the water.
Gute Dispergierbarkeit ohne Sasätze ergeben saure Füllstoffe in basischen Polymeren und basische Füllstoffe in sauren Polymeren. Lewis-Säuren (Titanate) sind für saure Füller in basischen Polymeren geeignet, nicht aber für basische Füller in sauren Polymeren. Acidic fillers in basic polymers and basic fillers in acidic polymers result in good dispersibility without sap. Lewis acids (titanates) are suitable for acidic fillers in basic polymers, but not for basic fillers in acidic polymers.
Saure Füller in sauren Polymeren und basische Füller in basischen Polymeren benötigen Zusatze. Kationische Silane oder Lewis-Säuren ergeben die besten Resultate bei sauren Füllstoffen in sauren Polymeren und manche Verbesserung bei basischen Füllstoffen in basischen Polymeren. Acid fillers in acidic polymers and basic fillers in basic polymers require additives. Cationic silanes or Lewis acids give the best results with acidic fillers in acidic polymers and some improvement with basic fillers in basic polymers.
Neutrale Silane,welche mit katalytischen Mengen an Aminen oder Titanaten modifiziert worden sind,sind generell effektiver als das reine Silan.Oberflächenaktive Zusätze erhöhen auch die Kupplurιgskraft neutrale Silane. Neutral silanes that have been modified with catalytic amounts of amines or titanates are generally more effective than pure silane. Surface-active additives also increase the coupling power of neutral silanes.
Trotz dieser bekannten,eingehend untersuchten Zusammenhänge und der Vielzahl von verschiedensten, mit unterschiedlichen Silanen modifizierten Füllstoffen besteht nach wie vor ein Bedarf nach Füllstoffen,insbesondere silikatischer Natur,mit gegenüber den bekannten Produkten noch weiter verbesserten Eigenschaften. Despite these known, thoroughly investigated relationships and the large number of different fillers modified with different silanes, there is still a need for Fillers, in particular silicate in nature, with properties which are even better than those of known products.
Überraschenderweise wurde nunmehr gefunden, daß eine Nachbehandlung von Schichtsilikaten, insbesondere Talk, Chlorit und Glimmer, mit speziellen Silanen zu modifizierten Füllstoffen mit überlegenen Eigenschaften in Korrosionsschutzlacken, Spritzfüllern und Einbrennsteinschlagfüllern führt. Surprisingly, it has now been found that aftertreatment of layered silicates, in particular talc, chlorite and mica, with special silanes leads to modified fillers with superior properties in anti-corrosion lacquers, spray fillers and stoving stone fillers.
Gegenstand der vorliegenden Erfindung ist somit die Verwendung von mit Amino-, Epoxy-, Imidazolin-, Bernsteinsäureanhydrid-,Cyclohexyl-, Harnstoff- und/oder Vinylgruppen aufweisenden Trialkoxysilanen,allein oder in Kombination,beschichteten silikatischen Füllstoffen aus der Gruppe der Schichten- oder Phyllosilikate, insbesondere auf der Basis von Talk,Chlorit und Glimmer, in Korrosionsschutzlacken, Spritzfüllern und Einbrennsteinschlagfüllern. Beispiele für erfindungsgemäß als Modifizierungsmittel bevorzugte Silane sind Aminopropyltrimethoxysilan H2N (CH2)3Si(OCΗ3)3,Aminopropyltriethoxysilan H2N ((CH2)3Si(OC2H5)3,Aminoethylaminopropyltrimethoxysilan H2N(CH2)2NH (CH2)3Si(OCH3)3,Glycidyl-oxypropyl-trimethoxysilan
Figure imgf000005_0001
H2C CH-C H2O(CH2)3Si(OCH3)3,Vinyltrimethoxysilan H2C = CHSi(OCH3)3,Vinyltriethoxysilan H2C = CHSi(OC2H5)3, Vinyl-tris(ß-methoxyethoxy)-silanThe present invention thus relates to the use of trialkoxysilanes containing amino, epoxy, imidazoline, succinic anhydride, cyclohexyl, urea and / or vinyl groups, alone or in combination, of silicate fillers from the group of the layered or phyllosilicates , especially based on talc, chlorite and mica, in anti-corrosion varnishes, spray fillers and stoving stone fillers. Examples of silanes preferred as modifiers according to the invention are aminopropyltrimethoxysilane H 2 N (CH 2 ) 3 Si (OCΗ 3 ) 3 , aminopropyltriethoxysilane H 2 N ((CH 2 ) 3 Si (OC 2 H 5 ) 3 , aminoethylaminopropyltrimethoxysilane H 2 N (CH 2 ) 2 NH (CH 2 ) 3 Si (OCH 3 ) 3 , glycidyl oxypropyl trimethoxysilane
Figure imgf000005_0001
H 2 C CH-C H 2 O (CH 2 ) 3 Si (OCH 3 ) 3 , vinyl trimethoxysilane H 2 C = CHSi (OCH 3 ) 3 , vinyl triethoxysilane H 2 C = CHSi (OC 2 H 5 ) 3 , vinyl tris (ß-methoxyethoxy) silane
H2C = CHSi(OC2H4OCH3)3 und Vinylbenzylaminoethylaminopropyl-trimethoxy- silan CH2=CHC6H4CH2NH(CH2)2NH(CH2)3Si (OCH3) 3 , 4,5-Dihydro-1-[3-(triethoxysilyl))- propyl]-imidazol (CH2)3Si(OC2H5)3,
Figure imgf000005_0002
H 2 C = CHSi (OC 2 H 4 OCH 3 ) 3 and vinylbenzylaminoethylaminopropyltrimethoxysilane CH 2 = CHC 6 H 4 CH 2 NH (CH 2 ) 2 NH (CH 2 ) 3 Si (OCH 3 ) 3 , 4, 5-dihydro-1- [3- (triethoxysilyl)) propyl] imidazole (CH 2 ) 3 Si (OC 2 H 5 ) 3 ,
Figure imgf000005_0002
(3-Triethoxysilylpropyl)-bernsteinsäureanhydrid  (3-Triethoxysilylpropyl) succinic anhydride
O 2HO 2 H
Figure imgf000005_0003
Figure imgf000005_0003
Cyclohexylethyl-tri met hoxysilan Cyclohexylethyl-tri met hoxysilane
C-(CH2)2 -Si(OCH3)3,
Figure imgf000005_0004
β-(3 ,4-Epoxy-cyclohexyl)-ethyl-trimethoxysilan C-(CH2)2-Si(OCH3) 3 und Bis-trimethyl-
Figure imgf000006_0001
C- (CH 2 ) 2 -Si (OCH 3 ) 3 ,
Figure imgf000005_0004
β- (3,4-epoxy-cyclohexyl) -ethyl-trimethoxysilane C- (CH 2 ) 2 -Si (OCH 3 ) 3 and bis-trimethyl-
Figure imgf000006_0001
silylharnstoff C
Figure imgf000006_0002
-[NH-Si(CH3) 3 ] 2. silylurea C
Figure imgf000006_0002
- [NH-Si (CH 3 ) 3 ] 2 .
Vorteilhafte Ergebnisse wurden bei Einsatz kationischer Silane erzielt, beispielsweise bei Verwendung von Aminopropyltriethoxysilan. Die Menge des erfindungsgemäß aufgebrachten Silans kann zweckmäßig bis zu etwa 2%, bezogen auf das Trockengewicht des Füllstoffes, betragen. Advantageous results have been achieved when using cationic silanes, for example when using aminopropyltriethoxysilane. The amount of the silane applied according to the invention can expediently be up to about 2%, based on the dry weight of the filler.
Das Aufbringen der speziellen Silane auf die Füllstoffe kann nach speziellen Methoden erfolgen, beispielsweise nach der Slurry-Methode, in welcher der zu behandelnde Füllstoff mit einem geeigneten Lösungsmittel, z.B. Ethanol, Isopropanol oder Testbenzin, zu einem Brei angerührt und das im Lösungsmittel gelöste Beschichtungsmittel (Coatingmittel) zugegeben wird. Nach dem Unterrühren wird die resultierende Aufschlämmung sorgfältig homogenisiert. Ein anschließendes Stehenlassen und Trocknen ergibt den gecoateten Füllstoff. Ein weiteres Herstellungsverfahren sieht das Einrühren des Coatingsmiittels in verdünntem oder unverdünntem Zustand und ein Homogenisieren in einem Hochleistungsrührer vor. Schließlich kann auch das gelöste Silan direkt auf den in einem Luftstrom bewegten Füllstoff aufgesprüht werden. The special silanes can be applied to the fillers by special methods, for example the slurry method in which the filler to be treated is treated with a suitable solvent, e.g. Ethanol, isopropanol or white spirit, mixed to a pulp and the coating agent (coating agent) dissolved in the solvent is added. After stirring in, the resulting slurry is carefully homogenized. Subsequent standing and drying results in the coated filler. Another manufacturing process involves stirring the coating agent in the diluted or undiluted state and homogenizing it in a high-performance stirrer. Finally, the dissolved silane can also be sprayed directly onto the filler moved in an air stream.
Die erfindungsgemäß gecoateten Füllstoffe weisen unerwartet vorteilhafte Eigenschaften auf. So ergibt eine Silanisierung von Talk oder Plastorit® (Magnesium-Kalium-Aluminiumsilikat), Chlorit und Glimmer mit einem Substituenten der vorstehend genannten Art aufweisenden Trialkoxysilan bei Anwendung dieser gecoateten Füllstoffe in Korrosionsschutzlacken auf der Basis wässeriger Epoxidharzsysteme eine ausgeprägte Verbesserung der Korrosionsbestärdigkeit, wie Messungen im Salzsprühtest belegen. Ein analoges Verhalten zeigen gecoatete Talk-Fullstoffe in Alkydharzsystemen. Erfindungsgemäß gecoatete Talksorten haben sich auch in Spritzfüllern auf der Basis ungesättigter Polyesterharze oder PU-Harze gegenüber ungecoateten Füllstoffen als deutlich besser hinsichtlich Verlaufeigenschaften und Oberflächeneigenschaften sowie hinsichtlich mechanischer Eigenschaften wie z.B.Steinschlagbeständigkeit erwiesen. Die nachfolgenden Beispiele sollen die Erfindung näher erläutern. The fillers coated according to the invention have unexpectedly advantageous properties. Thus, a silanization of talc or Plastorit ® (magnesium-potassium-aluminum-silicate), chlorite and mica with a trialkoxysilane having a substituent of the above-mentioned type results in a marked improvement in the resistance to corrosion, as measurements in the case of these coated fillers in corrosion protection lacquers based on aqueous epoxy resin systems Confirm salt spray test. Coated talc fillers show an analogous behavior in alkyd resin systems. Talc varieties coated according to the invention have also been found in spray fillers unsaturated polyester resins or PU resins compared to uncoated fillers have been shown to be significantly better in terms of flow properties and surface properties as well as in terms of mechanical properties such as impact resistance. The following examples are intended to explain the invention in more detail.
Beispiel 1: Example 1:
Der erfindungsgemäß nachbehandelte Füllstoff führt zu einer deutlichen Verbesserung der lacktechnischen Eigerischaften eines Einbrenn-Füllers für Kraftfahrzeuge auf der Basis eines wasserlöslichen Polyurethanharzes, wie die nachstehende Gegenüberstellung von Versuchsrezepturen (Ansatz 1: mit erfindungsgemäß gecoatetem Füllstoff; Ansatz 2: ungecoateter Füllstoff nach dem Stand der Technik) und die damit erhaltenen Ergebnisse zeigen.  The filler aftertreated according to the invention leads to a significant improvement in the paint properties of a stoving filler for motor vehicles based on a water-soluble polyurethane resin, such as the comparison of test formulations below (approach 1: with filler coated according to the invention; approach 2: uncoated filler according to the prior art ) and show the results obtained with it.
Figure imgf000007_0001
Figure imgf000007_0001
Nach dem L ackauftrag mittels Spritzautomat auf Fe-Blech ST-30 und 30 min Trocknung bei 120°C wurden die folgenden Prüfungen vorgenommen: 1) Korrosionsschutz nach ASTM-B/117-64 After the lacquer application by means of an automatic spray gun on Fe-ST-30 sheet and 30 min drying at 120 ° C, the following tests were carried out: 1) Corrosion protection according to ASTM-B / 117-64
2) Steinschlagtest  2) Stone chip test
3) Hahnerpik-Test  3) Hahnerpik test
4) Erichsentiefung  4) Erichsen deepening
5) Glanz  5) shine
6) Decklackstand (mit einem handelsüblichen Kfz-Reparaturlack auf Alkyd- Basis)  6) Top coat stand (with a commercially available automotive repair paint based on alkyd)
Figure imgf000008_0001
Figure imgf000008_0001
Beispiel 2:  Example 2:
Der e rfindungsgemäß nachbehandelte Füllstoff ergibt auch eine deutliche Verbesserung der lacktechnischen Eigenschaften einer Dispersions-Rostschutzfarbe auf der Basis einer Kombination einer Polyurethan-Dispersion mit einer Acrylat-Copoylmerisat-Dispersion, wie die nachstehende The filler aftertreated according to the invention also results in a significant improvement in the paint properties of a dispersion antirust paint based on a combination of a polyurethane dispersion and an acrylate copolymer dispersion, such as the one below
Gegenüberstellung von Versuchsrezepturen (Ansatz 1: mit erfindungsgemäß gecoatetem Füllstoff; Ansatz 2: ungecoateter Füllstoff nach dem Stand der Technik) und die damit erhaltenen Ergebnisse zeigen.
Figure imgf000009_0001
Comparison of test formulations (batch 1: with filler coated according to the invention; batch 2: uncoated filler according to the prior art) and show the results obtained therewith.
Figure imgf000009_0001
Zur Herstellung der Rostschutzfarbe wird Teil I intensiv vordispergiert, dann mit Teil II komplettiert und 30 min am Dissolver dispergiert.  To produce the anti-rust paint, Part I is intensively predispersed, then completed with Part II and dispersed on the dissolver for 30 min.
Teil III wird mittels eines Käfigrührers vorgemischt (10 min), worauf die Part III is pre-mixed using a cage stirrer (10 min), then the
Teile I + II nach dem Dispergieren mit Teil III unter Verwendung des Käfigrührers aufgelackt werden.  Parts I + II are dispersed after dispersing with Part III using the cage stirrer.
Nach dem Lackauftrag mittels Spritzautomat auf Fe-Blech ST-30 (30μm Trockenfilm) erfolgt die Prüfung der Salzsprühbeständigkeit nach einer Woche Lufttrocknung gemäß ASTM B 117/64. After applying the varnish using an automatic spray gun on Fe-ST-30 sheet (30μm dry film), the salt spray resistance is tested after one week of air drying in accordance with ASTM B 117/64.
Ergebnisse:  Results:
(Durchschnittswerte aus je 3 Prüfplatten)  (Average values from 3 test plates each)
Salzsprühtest nach ASTM B117/64 - Endbeurteilung nach 250 Stunden: Blasengrad Salt spray test according to ASTM B117 / 64 - final assessment after 250 hours: Degree of bladder
Ansatz 1 Ansatz 2 Approach 1 Approach 2
Figure imgf000010_0002
Figure imgf000010_0001
Figure imgf000010_0002
Figure imgf000010_0001
x→ m3/gl-3  x → m3 / gl-3
Fläche → in Ordnung m3-4/gl-5  Area → ok m3-4 / gl-5
Beispiel 3: teilweise  Example 3: partially
Unterwanderung  Infiltration
Der erfindungsgemäß nachbehandelte Füllstoff ergibt wei terhin eine überlegene Steinschlagbeständigkeit in einem Einbrennsteinschlagfülier auf Alkydharzbasis , wie die nachfolgende Gegenüberstellung von Versuchsrezepturen (Ansatz 1 : mit erfindungsgemäß gecoatetem Füllstoff; Ansatz 2 : ungecoateter Füllstoff nach dem Stand der Technik) und die damit erhaltenen Ergebnisse zeigen .  The filler aftertreated according to the invention furthermore gives superior stone chip resistance in a stoving stone filler based on alkyd resin, as the following comparison of test formulations (approach 1: with filler coated according to the invention; approach 2: uncoated filler according to the prior art) and the results obtained thereby show.
Figure imgf000010_0003
Die Lackviskosität (nach DIN 53211, 23°C) beträgt ca. 40s. Nach Verdünnung mit Shellsol A/Butanol 7/3 beläuft sich die Spritzviskosität (DIN 53211, 23°C) auf ca. 23 s. Das Einbrennen des Steinschlagfüllers erfolgt bei 150°C,25 min. Das Alkyd/Melamin-Verhältnis beträgt 85/15, das Verhältnis Pigment/Bindemittel etwa 1/1.
Figure imgf000010_0003
The paint viscosity (according to DIN 53211, 23 ° C) is approx. 40s. After dilution with Shellsol A / Butanol 7/3, the spray viscosity (DIN 53211, 23 ° C) is approx. 23 s. The stone chip filler is burned in at 150 ° C, 25 min. The alkyd / melamine ratio is 85/15, the pigment / binder ratio is about 1/1.
Die Steinschlagbeständigkeit, ermittelt nach einer W-Prüfvorschrift mit einem VW-Steinschlaggerät, ist wie folgt: The stone chip resistance, determined according to a W test specification with a VW stone chip device, is as follows:
Ansatz 1 Ansatz 2 Approach 1 Approach 2
Bewertung 1 (sehr gut) 6 (sehr schlecht)  Rating 1 (very good) 6 (very bad)

Claims

PATENTANSPRÜCHE : PATENT CLAIMS:
1. Verwendung von mit Amino-, Epoxy-, Imidazolin-, Bernsteinsaureanhydrid-,1. Use of with amino, epoxy, imidazoline, succinic anhydride,
Cyclohexyl-,Harnstoff- und/oder Vinylgruppen aufweisenden Trialkoxysilanen, allein oder in Kombination, beschichteten silikatischen Füllstoffen aus der Gruppe der Schichten- oder Phyllosilikate, insbesondere auf der Basis von Talk,Chlorit und Glimmer,in Korrosionsschutzlacken, Spritzfüllem und Einbrennsteinschlagfüllern.Trialkoxysilanes containing cyclohexyl, urea and / or vinyl groups, alone or in combination, coated silicate fillers from the group of layered or phyllosilicates, in particular based on talc, chlorite and mica, in corrosion protection lacquers, spray fillers and stoving stone fillers.
2. Verwendung von mit Aminopropyltrimethoxysilan beschichteten Schichtensilikaten für den in Anspruch 1 genannten Zweck. 2. Use of layered silicates coated with aminopropyltrimethoxysilane for the purpose mentioned in claim 1.
3. Verwendung von mit Aminopropyl-triethoxysilan beschichteten Schichtensilikaten für den inAnspruch 1 genannten Zweck.  3. Use of layered silicates coated with aminopropyl-triethoxysilane for the purpose stated in claim 1.
4. Verwendung von mit Aminoethyl-aminopropyl-trimethoxysilan beschichteten Schichtensilikaten für den in Anspruch 1 genannten Zweck.  4. Use of layered silicates coated with aminoethyl-aminopropyl-trimethoxysilane for the purpose mentioned in claim 1.
5. Verwendung von mit Glycidyl-oxyproryl-trimethoxysilan beschichteten Schichtensilikaten für den in Anspruch 1 genannten Zweck.  5. Use of layered silicates coated with glycidyl-oxyproryl-trimethoxysilane for the purpose mentioned in claim 1.
6. Verwendung von mit Vinyltrimethoxysilan beschichteten Schichtensilikaten für den in Anspruch 1 genannten Zweck. 6. Use of layered silicates coated with vinyltrimethoxysilane for the purpose mentioned in claim 1.
7. Verwendung von mit Vinyltriethoxysilan beschichteten Schichtensilikaten für den in Anspruch 1 genannten Zweck.  7. Use of layered silicates coated with vinyltriethoxysilane for the purpose mentioned in claim 1.
8. Verwendung von mit Vinylbenzylaminoethylaminopropyltrimethoxysilan beschichteten Schichtensilikaten für den in Anspruch 1 genannten Zweck.  8. Use of layered silicates coated with vinylbenzylaminoethylaminopropyltrimethoxysilane for the purpose mentioned in claim 1.
9. Verwendung von mit 4,5-Dihydro-1-[3-(triethoxysilyl)propyl]-imidazol beschichteten Schichtensilikaten für den in Anspruch 1 genannten Zweck.  9. Use of layered silicates coated with 4,5-dihydro-1- [3- (triethoxysilyl) propyl] imidazole for the purpose mentioned in claim 1.
10.Verwendung von mit (3-Triethoxysilylpropyl)-bernsteinsäureanhydrid beschichteten Schichtensilikaten für den in Anspruch 1 genannten Zweck. 10.Use of layered silicates coated with (3-triethoxysilylpropyl) succinic anhydride for the purpose mentioned in claim 1.
11.Verwendung von mit Cyclohexylethyl-trimethoxysilan beschichteten Schichtensilikaten für den in Anspruch 1 genannten Zweck.  11. Use of layered silicates coated with cyclohexylethyl-trimethoxysilane for the purpose mentioned in claim 1.
12.Verwendung von mit β-(3,4-Epoxy-cyclohexyl)-ethyl-trimethoxysilan beschichteten Schichtensilikaten für den in Anspruch 1 genannten Zweck. 12.Use of layered silicates coated with β- (3,4-epoxy-cyclohexyl) ethyl trimethoxysilane for the purpose mentioned in claim 1.
13. Verwendung von mit Bis-trimethylsilylharnstoff beschichteten Schichtensilikaten für den in Anspruch 1 genannten Zweck. 13. Use of layered silicates coated with bis-trimethylsilylurea for the purpose mentioned in claim 1.
14. Verwendung der silanmodifizierten Füllstoffe nach den Ansprüchen 1 bis 13, mit der Maßgabe, daß sie mit bis zu 2% des Silans, bezogen auf das Trockengewicht des Füllstoffes, beschichtet sind.  14. Use of the silane-modified fillers according to claims 1 to 13, with the proviso that they are coated with up to 2% of the silane, based on the dry weight of the filler.
PCT/AT1988/000071 1986-01-22 1988-09-12 Use of fillers coated with trialkoxysilanes WO1990002779A1 (en)

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AT0014886A AT387970B (en) 1986-01-22 1986-01-22 Use of silicatic fillers coated with trialkoxysilanes
PCT/AT1988/000071 WO1990002779A1 (en) 1988-09-12 1988-09-12 Use of fillers coated with trialkoxysilanes
JP88507316A JPH03501134A (en) 1988-09-12 1988-09-12 Use of fillers coated with trialkoxysilane
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US5338434A (en) * 1990-05-16 1994-08-16 Basf Lacke & Farben Aktiengesellschaft Process for the coating of electrically conductive substrates and a cathodically depositable aqueous electrocoating paint
EP0492223A3 (en) * 1990-12-22 1992-08-12 Merck Patent Gesellschaft Mit Beschraenkter Haftung Silanised pigments and their use in inhibiting yellowing of pigmented plastics
EP0492223A2 (en) * 1990-12-22 1992-07-01 MERCK PATENT GmbH Silanised pigments and their use in inhibiting yellowing of pigmented plastics
US5665511A (en) * 1991-05-14 1997-09-09 Fuji Xerox Co., Ltd. Surface-treated inorganic fine particle and electrophotographic developer using the same
EP0524528A1 (en) * 1991-07-24 1993-01-27 Metzeler Gimetall Ag Electrorheological fluid
US5494949A (en) * 1992-01-05 1996-02-27 Merck Patent Gesellschaft Mit Beschrankter Haftung Surface-modified oxide particles and their use as fillers and modifying agents in polymer materials
WO1994007948A1 (en) * 1992-10-05 1994-04-14 MERCK Patent Gesellschaft mit beschränkter Haftung Surface-modified oxide particles and their use as fillers and modifiers in polymer materials
WO1994007945A1 (en) * 1992-10-05 1994-04-14 Hoechst Aktiengesellschaft Molded bodies made of polyester cotaining covalent-bonded oxide particles
US6239194B1 (en) 1998-04-28 2001-05-29 Huels Aktiengesellschaft Surface-modified fillers, process for their preparation and their use
EP1199335A1 (en) * 2000-10-21 2002-04-24 Degussa AG Functionalized silicic acids
EP1199336A1 (en) * 2000-10-21 2002-04-24 Degussa AG Functionalized, structure modified silicic acids
US7144930B2 (en) 2000-10-21 2006-12-05 Degussa Ag Functionalized, structurally modified silicas
WO2011082137A1 (en) * 2009-12-30 2011-07-07 Dow Corning Corporation Friction reducing coatings
EP2547734A4 (en) * 2010-03-17 2013-07-24 Imerys Kaolin Inc Paint comprising hydrophobized minerals and related methods
US9346964B2 (en) 2010-03-17 2016-05-24 Imerys Kaolin, Inc. Paint comprising hydrophobized minerals and related methods

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