EP0387251A1 - Utilisation de charges enrobees de trialkoxysilanes - Google Patents

Utilisation de charges enrobees de trialkoxysilanes

Info

Publication number
EP0387251A1
EP0387251A1 EP88907548A EP88907548A EP0387251A1 EP 0387251 A1 EP0387251 A1 EP 0387251A1 EP 88907548 A EP88907548 A EP 88907548A EP 88907548 A EP88907548 A EP 88907548A EP 0387251 A1 EP0387251 A1 EP 0387251A1
Authority
EP
European Patent Office
Prior art keywords
fillers
coated
layered silicates
purpose mentioned
silicates coated
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP88907548A
Other languages
German (de)
English (en)
Inventor
Norbert Wamser
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Naintsch Mineralwerke GmbH
Original Assignee
Naintsch Mineralwerke GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Naintsch Mineralwerke GmbH filed Critical Naintsch Mineralwerke GmbH
Publication of EP0387251A1 publication Critical patent/EP0387251A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Ceramic Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Structural Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Paints Or Removers (AREA)

Abstract

On utilise des charges au silicate appartenant au groupe des phyllosilicates dans des laques anticorrosives, des charges de pistolage et des charges thermodurcissables pour antigravillonnage. Ces charges au silicate sont enrobées de trialkoxysilanes qui contiennent des groupes amine, époxyde, imidazoline, anhydride succinique, cyclohexyle, urée et/ou vinyle, et permettent d'obtenir de meilleurs résultats que des charges non enrobées.
EP88907548A 1988-09-12 1988-09-12 Utilisation de charges enrobees de trialkoxysilanes Withdrawn EP0387251A1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/AT1988/000071 WO1990002779A1 (fr) 1988-09-12 1988-09-12 Utilisation de charges enrobees de trialkoxysilanes

Publications (1)

Publication Number Publication Date
EP0387251A1 true EP0387251A1 (fr) 1990-09-19

Family

ID=3682657

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88907548A Withdrawn EP0387251A1 (fr) 1988-09-12 1988-09-12 Utilisation de charges enrobees de trialkoxysilanes

Country Status (3)

Country Link
EP (1) EP0387251A1 (fr)
JP (1) JPH03501134A (fr)
WO (1) WO1990002779A1 (fr)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4015703A1 (de) * 1990-05-16 1991-11-21 Basf Lacke & Farben Verfahren zum beschichten elektrisch leitfaehiger substrate und kathodisch abscheidbarer waessriger elektrotauchlack
DE4041663A1 (de) * 1990-12-22 1992-06-25 Merck Patent Gmbh Silanisierte pigmente und deren verwendung zu vergilbungsinhibierung von pigmentierten kunststoffen
JP2624027B2 (ja) * 1991-05-14 1997-06-25 富士ゼロックス株式会社 表面処理無機微粉末を用いた電子写真現像剤
DE4124579A1 (de) * 1991-07-24 1993-01-28 Metzeler Gimetall Ag Elektrorheologische fluessigkeit
DE4233396A1 (de) * 1992-10-05 1994-04-07 Merck Patent Gmbh Oberflächenmodifizierte Oxidpartikel und ihre Anwendung als Füll- und Modifizierungsmittel in Polymermaterialien
US5698309A (en) * 1992-10-05 1997-12-16 Hoechst Aktiengesellschaft Molded bodies made of polyester containing covalent-bonded oxide particles
DE19818924A1 (de) 1998-04-28 1999-11-04 Degussa Oberflächenmodifizierte Füllstoffe, Verfahren zu deren Herstellung sowie deren Verwendung
EP1199335B1 (fr) * 2000-10-21 2010-12-22 Evonik Degussa GmbH Silice fonctionalisée
EP1199336B1 (fr) * 2000-10-21 2014-01-15 Evonik Degussa GmbH Silice fonctionalisée et à structure modifiée
US20120288649A1 (en) * 2009-12-30 2012-11-15 William Blackwood Friction reducing coatings
WO2011115755A1 (fr) * 2010-03-17 2011-09-22 Imerys Kaolin, Inc. Peinture comprenant des minéraux rendus hydrophobes et procédés associés
JP6030344B2 (ja) * 2012-05-28 2016-11-24 Ｊｆｅスチール株式会社 塗装鋼板およびその製造方法、ならびに加工品および薄型テレビ用パネル

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3834924A (en) * 1972-06-08 1974-09-10 Huber Corp J M Process for manufacturing surface modified inorganic pigments

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9002779A1 *

Also Published As

Publication number Publication date
WO1990002779A1 (fr) 1990-03-22
JPH03501134A (ja) 1991-03-14

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