EP0981780A1 - Beschichtete partikel - Google Patents

Beschichtete partikel

Info

Publication number
EP0981780A1
EP0981780A1 EP98924296A EP98924296A EP0981780A1 EP 0981780 A1 EP0981780 A1 EP 0981780A1 EP 98924296 A EP98924296 A EP 98924296A EP 98924296 A EP98924296 A EP 98924296A EP 0981780 A1 EP0981780 A1 EP 0981780A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
aryl
particles
coated
particles according
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Withdrawn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
EP98924296A
Other languages
German (de)
English (en)
French (fr)
Inventor
Michael Mager
Johannes Eickmans
Rainer Bellinghausen
Serge Tavernier
Raf Voets
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.)
Xeikon Manufacturing NV
Original Assignee
Agfa Gevaert AG
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
Priority claimed from DE19807634A external-priority patent/DE19807634A1/de
Application filed by Agfa Gevaert AG filed Critical Agfa Gevaert AG
Publication of EP0981780A1 publication Critical patent/EP0981780A1/de
Withdrawn legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D183/00Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/14Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/48Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/485Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms containing less than 25 silicon atoms
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/48Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/50Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/001Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991Coated
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31652Of asbestos
    • Y10T428/31663As siloxane, silicone or silane

Definitions

  • the invention relates to coated particles, in particular particles with an inorganic content, preferably purely inorganic particles and particularly preferably coated magnetic particles, which are used as carrier particles in electrostatographic developers for electrostatographic imaging.
  • a number of electrostatographic printing methods are known, e.g. direct electrostatic printing !, in which toner is applied to a receiving material which has no latent electrostatic image by means of an electronically addressable print head.
  • toner images are placed on an imaging element in the form of a rotating drum that is electrostatic
  • Contains layer which consists of a plurality of controllable electrodes in and under a dielectric layer. Electrical voltage is generated in the controllable electrodes, which attracts the toner particles from a toner source.
  • a latent electrostatic image is generated by the steps a) uniformly charging a photoconductive element and b) imagewise discharging by means of an imagewise modulated exposure.
  • a latent electrostatic image is generated by imagewise precipitation of electrically charged particles, for example by an electron beam or by ionized gas on a dielectric substrate.
  • the latent images obtained are developed, that is to say converted into visible images, by selectively depositing light-absorbing substances thereon, which are called toners and are usually triboelectrically charged.
  • the dry powder development can be carried out in different ways.
  • One method is the one-component method, in which the toner itself is loaded by friction, transported with a roller and applied to the latent image. The quality is limited, especially when color prints are to be produced.
  • Another method uses liquid development, in which colloidally charged toner particles are in a liquid insulating medium, e.g. a hydrocarbon for
  • a disadvantage of this method is the emission of vaporized organic substances, especially when it comes to high printing speeds.
  • a third method uses a two-component developer. In this case, magnetically mountable, coarse-grained carrier particles form a magnetic brush on the surface of the development roller by the magnetic
  • Triboelectrically charged toner particles are present on the surface of the carrier particles. These are stripped from the carrier particles in accordance with the electrical charge of the latent electrostatic image, whereby the toner image is generated.
  • the carrier particles are reused many times in this process; their mechanical stability is therefore of particular importance.
  • non-magnetic electrophotographic developers made of two components can also be used.
  • the developer consists of glass beads, which are optionally coated, and toner particles. The developer is allowed to fall onto the element carrying the latent image and in this way the development is carried out as described in BE 828 210. In this case too, the carrier particles are reused.
  • a material with non-stick properties is preferred for the coating of the carrier particles in order to avoid sticking of the toner to the carrier surface. In most cases, however, this leads to a reduction in the adhesion of the coating to the carrier, which leads to a shortening of the service life, e.g. when using silicone resins as carrier coating agents.
  • the silicone resin used consists of D and T units (in the case of D units the silicon atom is linked via 2 oxygen atoms, in the case of T units via 3 oxygen atoms it is linked to other silicon atoms), with other functional organosilanes, such as di- and trialkoxy-functional organosilanes and / or di- and trialkoxy-functional, nitrogen-containing organosilanes can be added.
  • the application takes place, as can be seen from the examples, in a fluidized bed reactor; the coatings are then cured at 190 ° C to 296 ° C.
  • the above-mentioned coatings with (polymeric) silicone resins have the disadvantage that high temperatures are necessary for complete curing (190 to 296 ° C.).
  • many silicone resin coatings show non-stick properties, but necessarily poor adhesion to the substrate.
  • di- and trialkoxy-functional organosilanes for example, must therefore be added to the silicone resins in order to improve the adhesion.
  • the object of the present invention was therefore to provide coated particles, in particular particles with a content of inorganic material and in particular carrier particles for electrostatographic processes, the particles having a magnetic core and a coating of the core, which
  • a) is tack-free, so that free-flowing, predominantly agglomerate-free particles are obtained.
  • coated particles in particular coated particles containing inorganic material, are obtained which do not have the disadvantages mentioned above if the coating consists of monomeric polyfunctional organosilanes and / or their hydrolysis products and / or their reactants. onproducts with heteroatom-containing organosilanes and / or alkoxides is produced.
  • the present invention therefore relates to particles (A) which are coated with a material (B), the particles (A) preferably containing inorganic material, in particular being inorganic particles and particularly preferably being magnetic carrier particles for electrostatographic processes, and the Material (B) is a monomeric, polyfunctional organosilane and / or a hydrolysis product thereof and / or a reaction product thereof with a heteroatom-containing organosilane and / or an alkoxide.
  • Heteroatom-containing organosilanes for the purposes of the invention consist of at least one silicon atom with hydrolyzable and / or condensation-crosslinking groups such as -SiOR, where R in particular denotes alkyl, cycloalkyl or aryl, preferably alkyl, or SiOH and at least one heteroatom-containing organic radical bonded via a carbon atom, which is a May be alkyl, cycloalkyl or aryl.
  • Heteroatoms of the heteroatom-containing organosilanes are preferably N, P, S, F, Cl, Br O, B and Al.
  • Preferred heteroatoms are N and F, with nitrogen atoms being particularly preferred.
  • Preferred nitrogen-containing organosilanes correspond to the formula (I)
  • n 1 to 10, preferably 2 or 3
  • n 0 to 2 preferably 2, o 0 to 2, preferably 0
  • R 2 is H, alkyl or aryl, preferably H
  • R 3 , R 4 are alkyl or aryl, preferably CH 3 or C 2 H 5 ,
  • Preferred alkoxides correspond to the formula (II)
  • M j is Si, Sn, Ti, Zr, B or Al
  • R j is alkyl or aryl, preferably C ] -C 4 -alkyl and y in the case of Si, Sn, Ti, Zr 4 and in the case of B or Al 3.
  • Polyfunctional organosilanes in the sense of the invention are characterized in that they contain at least 2, preferably at least 3 silicon atoms, each with 1 to 3 hydrolyzable and / or condensation-crosslinking groups, in particular alkoxy, acyloxy or hydroxy groups, and the silicon atoms each with an Si, C- Binding to a structural unit linked to the silicon atoms.
  • the linked structural units in the sense of the invention are, for example, linear or branched C j to C j o-alkylene chains, C 5 to C j o-cycloalkylene radicals, aromatic radicals, such as phenyl, naphthyl or biphenyl, or combinations of aromatic and aliphatic radicals.
  • aromatic radicals such as phenyl, naphthyl or biphenyl, or combinations of aromatic and aliphatic radicals.
  • the aliphatic and aromatic radicals can also contain heteroatoms, such as Si, N, O, S or F.
  • chain-shaped, ring-shaped or cage-shaped siloxanes such as silsequioxanes
  • linking structural units are listed below, with X denoting Si atoms which have 1 to 3 hydrolyzable and / or condensation-crosslinking groups and with Y corresponding Si atoms which are bonded to the linking structural unit via an alkylene chain ; n stands for a number 1 to 10, m for a number 1 to 6:
  • R is an organic residue, e.g. Is alkyl, cycloalkyl, aryl or alkenyl.
  • polyfunctional organosilanes are compounds of the general formulas (IV), (V) and (VI): (R 5 ) 4 . i Si [(CH 2 ) p Si (OR 6 ) a (R 7 ) 3 . a ] i (IV)
  • R 5 alkyl or aryl
  • -Rg is hydrogen, alkyl or aryl if a is 1 and alkyl or aryl if a 2 or
  • R 7 is alkyl or aryl, preferably methyl and a is 1 to 3;
  • R 10 is alkyl or aryl, preferably methyl
  • r 1 to 10 preferably 2 to 4, c 1 to 3, k 2 to 4, preferably 4 R alkyl or aryl, preferably methyl,
  • R 13 is alkyl or aryl, preferably methyl and
  • R 14 is alkyl or aryl.
  • polyfunctional organosilanes examples are:
  • Nitrogen-containing alkoxysilanes are, for example
  • fluorine-containing alkoxysilanes examples are:
  • x is 1 to 3 and R, R 'alkyl, cycloalkyl or aryl, preferably ethyl or methyl are.
  • alkoxides which can be used to prepare the reaction products according to the invention, e.g. To improve the abrasion resistance or the tribological properties are:
  • reaction products according to the invention can also be finely divided
  • Conductivity-inducing agents for example carbon and charge-regulating agents, for example nigrosine, can also be added to the coating.
  • Material B preferably contains 0.1 to 100% by weight of polyfunctional organosilane, 0 to 20% by weight of heteroatom-containing organosilane (I), 0 to 70% by weight of nanoparticles and 0 to 99.9% by weight Alkoxide (II).
  • the material particularly preferably contains B.
  • Magnetic inorganic particles are preferred as particles.
  • the magnetic particles are preferably iron oxide pigments of the formula (III) (M 2 O) x (Fe 2 O 3 ) z (III)
  • M 2 Li Mg, Sr, Ba, Mn, Fe (II), Co, Ni, Cu, Zn, Cd and
  • the molar ratio of x to z is between 0 and 1, preferably between 0.3 and 1.
  • composite particles consisting of 20 to 85% by weight of magnetic microparticles and an organic or inorganic binder, e.g. an organic polymer or a ceramic material. It is also possible to use non-magnetic cores such as glass beads.
  • reaction products B) according to the invention are generally applied as a coating to the particles A).
  • the polyfunctional organosilanes can be applied to the particles A in bulk or in a solvent, if appropriate in the presence of a catalyst.
  • Coating B) is obtained after evaporation of the solvent and curing at a suitable temperature.
  • the polyfunctional organosilanes are first mixed with alkoxides and, for example, heteroatom-containing organosilanes and / or nanoparticles, and, if appropriate in the presence of a catalyst, are applied to the particles A and cured.
  • volatile starting materials such as tetraethyl orthosilicate
  • this coating solution is applied to the iron oxide-containing materials using suitable methods, for example in a fluidized bed, the volatile constituents are evaporated and the coating thus obtained is optionally post-cured thermally.
  • Suitable catalysts are organic and inorganic acids or bases, for example HCO 2 H, CH 3 COOH, HCl, NH 4 OH and alkali metal hydroxides, and F-containing salts such as NaF or NH 4 F.
  • the added metal alkoxides themselves, such as Ti (OC H 5 ) 4 and Ti (Oi-C 3 H 7 ) 4 can be catalytically active.
  • Metal soaps such as zinc octoate or dibutyltin laurate can also be used.
  • polyfunctional organosilanes optionally in the presence of alkoxides
  • the polyfunctional organosilanes are combined with the alkoxides, a solvent, water and a catalyst with stirring and reacted for a certain time before films can be obtained from these solutions or, after complete reaction (gelation), moldings can also be obtained.
  • the film-forming properties of the reaction product (B) are a useful indicator that the solutions are suitable for coating the particles. If you coat e.g. a glass plate, a transparent, largely crack-free film wetting the entire area should be obtained after the volatile constituents have evaporated. However, the tendency to crack formation increases with the layer thickness of the film.
  • the nitrogen-containing alkoxysilanes are only added after the polyfunctional organosilanes and optionally alkoxides have been reacted, as indicated above, and this precondensate has been diluted with further solvent.
  • nitrogen-containing silanes such as H 2 N- (CH 2 ) 3 Si (OMe) 3 , catalyze the hydrolysis and condensation of alkoxysilanes. This can lead to the most reactive component, eg H 2 N- (CH 2 ) 3 Si (OCH 3 ) 3 , being hydrolyzed rapidly and condensed to an insoluble solid. This can prevent it by adding the nitrogen-containing alkoxysilanes to the diluted coating solution.
  • solvents examples include Alcohols, such as methanol, ethanol, n-propanol, n-butanol, iso-propanol, sec-butanol or ethylene glycol, ketones, such as acetone or methyl ethyl ketone, amides, such as N-methylpyrrolidone or water. Because of their good miscibility with the precondensate, alcohols, in particular isopropanol, are particularly preferred. Mixtures of different solvents can also be used.
  • Alcohols such as methanol, ethanol, n-propanol, n-butanol, iso-propanol, sec-butanol or ethylene glycol
  • ketones such as acetone or methyl ethyl ketone
  • amides such as N-methylpyrrolidone or water. Because of their good miscibility with the precondensate, alcohols, in particular isopropanol, are particularly preferred. Mixtures of different solvents
  • the solvents can be applied after application of the coating solution, e.g. recovered by condensation and used again, if necessary after cleaning, in the process.
  • the coating is preferably cured at temperatures from 25 to 220 ° C., particularly preferably from 80 to 180 ° C., very particularly preferably from 100 to 140 ° C.
  • the amount of the coating applied, based on the core is between 0.1 and 10% by weight, preferably between 0.5 and 5% by weight and particularly preferably between 0.5 and 2% by weight.
  • the coated inorganic particles in particular the carrier particles for electrophotography containing a magnetic core, are in particular spherical and have an average particle diameter of 20 to 200 ⁇ m, preferably 40 to 120 ⁇ m. It is also possible to apply two or more layers to the particles (A), for example first an electrically insulating layer and then a layer which improves the stability of the coated particles under mechanical stress.
  • Suitable organic solvents for the oligomers are, for example, mono- and polyfunctional alcohols, such as methanol, ethanol, n-butanol, ethylene glycol.
  • the oligomers can be prepared directly from the monomers of the formula (V) or from the starting products for the preparation of the monomers of the formula (V), those starting compounds being those of the formula (V) which have a halogen atom instead of the OR 9 group , for example a chlorine, bromine or
  • oligomers are an example of the hydrolysis products used as material B.
  • these oligomers are suitable for coating particles, in particular particles with an inorganic content, preferably purely inorganic particles.
  • Alkoxides for example those of the formula II, and / or nanoparticles.
  • the flowability is determined using an outlet cup and 500 g of the coated particles.
  • the specific resistance ( ⁇ spec ) of the carrier was determined in a cylindrical measuring cell with an inner diameter of 22.5 mm, which was filled with carrier 4 mm high, on which a stamp was placed, which was loaded with 1 kg. At a voltage of 200 V, the current was read on the measuring device and ⁇ specifically calculated as follows:
  • the charge acceptance (-Q / m) was determined by development. For this purpose, 100 parts by weight of carrier and 5 parts by weight of toner were used in the developer unit. mixes. The developer mixture was activated in a commercial copier for 10 minutes. After development, both the amount of toner discharged (m) and its charge (Q) were measured.
  • the amount of coating given in the examples is given from the sum of the amount of polyfunctional organosilane and tetraethylorthosilicate used in% by weight compared to the amount of carrier.
  • the proportion of the nitrogen-containing aminosilane (b-1) or (b-8) is given in% by weight compared to the coating material.
  • Carrier mixed with 50 ceramic beads with a diameter of 10 mm in a bottle of 120 ml, so that the filling level of the bottle is about 50%.
  • the bottle is rotated for 16 hours on a roller table at a speed of 25 m / min. This process partially rubs off the coating and determines the amount of coating material rubbed off as follows:
  • the amount rubbed off is so small that it cannot be determined gravimetrically. But it can be very well homogeneously on a sheet of paper of a known optical
  • the particles can be coated using various methods, e.g. in an industrial fluidized bed reactor or in a 2 1 three-necked flask with stirrer, injection system for the solution containing the coating material and a cooler for the recovery of the evaporated solvent.
  • a coating temperature of 80 to 100 ° C at a slight negative pressure of 950 to 1,000 mbar absolute with a coating time of 15 to 60 minutes has proven to be expedient. Curing takes place in the same vessel at 120 to 190 ° C for 20 minutes to 4 hours. "X" in Tables 1 to 3 means that the substance was not used.
  • Bontron N-O 2 is a nigrosine compound used for charge control; Spilon black TRH a Cr-azo complex that is used for charge control; Carbon black is a conductive soot.
  • the coating was carried out at 70 ° C and 50 mbar.
  • the product was dried at 90 ° C for 30 minutes and cured at 140 ° C for 16 hours.
  • the results are shown in Table 5.
  • the particles were sticky and therefore formed a lot of agglomerates or stuck to the kettle. A large amount of dust accumulated when drying.
  • Coatings were applied in a fluidized bed reactor under the following conditions to 2 kg of the ferrite particles with solutions 22 to 27:
  • the mixture was then cured for about 90 minutes at a bed temperature of 150 ° C. and finally cooled to room temperature.
  • ⁇ spec was 4 x 10 5 ⁇ cm; -Q / m was 9.3 ⁇ C / g.
  • Example 6 7.5 kg of a ferrite carrier as in Example 6 were coated with solution 30 at 85 ° C. and 980 mbar, dried and cured at 160 ° C. for 2 hours.
  • the coating amount was 2.1% by weight, the content of b-7 1.0% by weight.
  • ⁇ spec was 2.2 x 10 9 ⁇ cm; -Q / m was 16.1 ⁇ C / g; Abrasion: 0.12; Coarse fraction> 125 ⁇ m 0.9% by weight.
  • Example 6 7.5 kg of ferrite camer as in Example 6 were coated with solution 32 at 85 ° C. and 980 mbar, dried and cured at 140 ° C. for 2 hours.
  • the coating amount was 1.0% by weight, the proportion of b-7 2.0% by weight.
  • s sp pe e z z was 1.5 x 10 8 ; -Q / m was 18 ⁇ C / g; abrasion: 0.12; coarse fraction> 125 ⁇ m 0.% by weight.
  • Mn-Mg ferrite particles from Powdertech Co. Ltd. were used as particles containing iron oxide for the coating experiments.
  • Tetraethyl orthosilicate, 8.25 g water and 0.16 g para-toluenesulfonic acid were combined with stirring in this order and stirred for another hour.
  • the mixture was then diluted with 204.9 g of isopropanol and, in the case of solution 37, 0.2 g (b-7) were added.
  • Ammonia was introduced through a gas inlet tube until saturation and the mixture was stirred for 4 hours. Excess ammonia was then removed and ammonium chloride was filtered off. The filtrate was neutralized with Na 2 CO 3 , mixed with filter aid (diatomaceous earth) and heated to 130 ° C. at a pressure of 10 mbar.
  • the product was obtained as a clear liquid with a viscosity of 80 mPa.s, a density of 1.00 g / ml and a residual amount of hydrolyzable chlorine of 7 ppm.
  • the condensation product of 1,3,5,7-tetramethyl-1,3,5,7-tetra- (2- (diethoxymethylsilyl) ethylene) cyclotetrasiloxane was a continuous molar mass distribution with an average number average (M j of 1 350 g / mol and an average weight average of

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Silicon Polymers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Developing Agents For Electrophotography (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Glanulating (AREA)
  • Manufacturing Of Micro-Capsules (AREA)
  • Medicinal Preparation (AREA)
EP98924296A 1997-05-23 1998-05-11 Beschichtete partikel Withdrawn EP0981780A1 (de)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE19721626 1997-05-23
DE19721626 1997-05-23
DE19807634 1998-02-23
DE19807634A DE19807634A1 (de) 1997-05-23 1998-02-23 Beschichtete Partikel
PCT/EP1998/002727 WO1998053372A1 (de) 1997-05-23 1998-05-11 Beschichtete partikel

Publications (1)

Publication Number Publication Date
EP0981780A1 true EP0981780A1 (de) 2000-03-01

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EP19980924297 Expired - Lifetime EP0981570B1 (de) 1997-05-23 1998-05-11 Organosilan-oligomere
EP98924296A Withdrawn EP0981780A1 (de) 1997-05-23 1998-05-11 Beschichtete partikel

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EP19980924297 Expired - Lifetime EP0981570B1 (de) 1997-05-23 1998-05-11 Organosilan-oligomere

Country Status (9)

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US (2) US6136939A (pt)
EP (2) EP0981570B1 (pt)
JP (2) JP2002502447A (pt)
AT (1) ATE226226T1 (pt)
AU (2) AU7653698A (pt)
CA (1) CA2290455C (pt)
ES (1) ES2184268T3 (pt)
PT (1) PT981570E (pt)
WO (2) WO1998053372A1 (pt)

Families Citing this family (44)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7559494B1 (en) 1996-09-03 2009-07-14 Ppg Industries Ohio, Inc. Method of forming non-stoichiometric nanoscale powder comprising temperature-processing of a stoichiometric metal compound
US6344271B1 (en) * 1998-11-06 2002-02-05 Nanoenergy Corporation Materials and products using nanostructured non-stoichiometric substances
US6933331B2 (en) * 1998-05-22 2005-08-23 Nanoproducts Corporation Nanotechnology for drug delivery, contrast agents and biomedical implants
US6569397B1 (en) * 2000-02-15 2003-05-27 Tapesh Yadav Very high purity fine powders and methods to produce such powders
US6360562B1 (en) * 1998-02-24 2002-03-26 Superior Micropowders Llc Methods for producing glass powders
DE19814060A1 (de) * 1998-03-30 1999-10-07 Bayer Ag Borhaltige Mischungen, Hybridmaterialien und Beschichtungen
DE19824188A1 (de) * 1998-05-29 1999-12-02 Bayer Ag Wäßrige Zubereitung zur Behandlung mineralischer Baustoffe
DE19828256A1 (de) * 1998-06-25 1999-12-30 Bayer Ag Antifoulingmittel, ein Verfahren zur Herstellung und deren Verwendung sowie daraus hergestellte Antifoulingbeschichtungen
CZ297008B6 (cs) * 1998-11-24 2006-08-16 Bayer Aktiengesellschaft Vodné prípravky pro osetrení minerálních stavebních hmot, zpusob jejich výroby a jejich pouzití
US6420029B1 (en) 1998-11-26 2002-07-16 Xeikon International Hybrid carrier coating containing a silane network and a polymeric compound not containing silicon atoms
DE19925926A1 (de) * 1999-06-08 2000-12-14 Bayer Ag Katalysatoren auf Basis Titan-haltiger, organisch-anorganischer Hybridmaterialien zur selektiven Oxidation von Kohlenwasserstoffen
DE19927409A1 (de) 1999-06-16 2000-12-21 Bayer Ag Verwendung stickstofffreier Verbindungen als Haftvermittler für siliciumbasierte Kratzfestbeschichtungen auf Kunststoffen
DE50008772D1 (de) 1999-08-20 2004-12-30 Bayer Materialscience Ag Anorganische beschichtungszusammensetzung, ein verfahren zu deren herstellung sowie deren verwendung
EP1227781B9 (en) * 1999-10-28 2006-03-08 3M Innovative Properties Company Dental materials with nano-sized silica particles
US6551754B2 (en) 2000-04-11 2003-04-22 Xeikon, N.V. Method for coating carrier particles
DE10102739A1 (de) * 2001-01-23 2002-07-25 Bayer Ag Verfahren zur Herstellung von Sol-Gel-Kondensaten auf Basis polyfunktioneller Organosilane sowie deren Verwendung
US6593392B2 (en) * 2001-06-22 2003-07-15 Corning Incorporated Curable halogenated compositions
ES2235076T3 (es) * 2001-09-11 2005-07-01 3M Innovative Properties Company Recubrimientos duros de nanocomposiciones resistentes a las manchas y metodos para fabricacion de los mismos.
DE10162443A1 (de) * 2001-12-19 2003-07-03 Bayer Ag Verfahren zur Herstellung von dielektrischen Schichten unter Verwendung multifunktioneller Carbosilane
DE10217202A1 (de) * 2002-04-18 2003-11-06 Bayer Ag Anti-Haft-Beschichtungen für Reaktoren
DE10225825A1 (de) * 2002-06-11 2004-01-08 Bayer Ag Multifunktionelle Carbosiloxane mit linearen und cyclischen Strukturelementen
US6797380B2 (en) * 2002-07-31 2004-09-28 General Electric Company Nanoparticle having an inorganic core
DE10244212A1 (de) 2002-09-23 2004-03-25 Bayer Aktiengesellschaft Zinkoxiddispersionen in halogen- und wasserfreien Dispersionsmedien
DE10245725A1 (de) * 2002-10-01 2004-04-15 Bayer Ag Schichtsystem und Verfahren zu dessen Herstellung
KR100488347B1 (ko) * 2002-10-31 2005-05-10 삼성전자주식회사 실록산계 수지 및 이를 이용한 반도체 층간 절연막의형성방법
JP2004168846A (ja) * 2002-11-19 2004-06-17 Asahi Glass Co Ltd 複合微粒子およびその製造方法
US7708974B2 (en) 2002-12-10 2010-05-04 Ppg Industries Ohio, Inc. Tungsten comprising nanomaterials and related nanotechnology
US6866711B2 (en) 2003-01-17 2005-03-15 Fitzgerald Alphanso Sinclair Composite pigment composition containing silica
US6838495B2 (en) 2003-01-17 2005-01-04 Louis Frank Gatti Rubber composition comprising composite pigment
US7419527B2 (en) * 2003-05-08 2008-09-02 Particle Sciences, Inc. Increased density particle molding
KR100506695B1 (ko) * 2003-06-02 2005-08-08 삼성전자주식회사 실록산계 수지 및 이를 이용한 반도체 층간 절연막
KR100507967B1 (ko) * 2003-07-01 2005-08-10 삼성전자주식회사 실록산계 수지 및 이를 이용한 반도체 층간 절연막
DE102004003675A1 (de) * 2004-01-24 2005-08-11 Degussa Ag Dispersion und Beschichtungszubereitung enthaltend nanoskaliges Zinkoxid
DE102004008056A1 (de) * 2004-02-19 2005-09-08 Bayer Materialscience Ag Sol-Gel-Beschichtungen aus wasserlöslichen Oxalamiden
EP1582270A1 (en) * 2004-03-31 2005-10-05 Vlaamse Instelling voor Technologisch Onderzoek Method and apparatus for coating a substrate using dielectric barrier discharge
JP4706411B2 (ja) * 2005-09-21 2011-06-22 住友電気工業株式会社 軟磁性材料、圧粉磁心、軟磁性材料の製造方法、および圧粉磁心の製造方法
FR2911494B1 (fr) * 2007-01-19 2009-04-10 Rech S Tech Dentaires R T D Sa Element prothetique dentaire radio-opaque
DE102008054329A1 (de) 2008-11-03 2010-05-06 Bayer Materialscience Ag Erzeugnisse mit verbesserter Flammwidrigkeit
DE102010013865B4 (de) * 2010-04-01 2015-12-31 Alanod Gmbh & Co. Kg Reflektor mit hoher Resistenz gegen Witterungs- und Korrosionseinflüsse und Verfahren zu seiner Herstellung
JP2011241291A (ja) * 2010-05-18 2011-12-01 Tosoh Corp ポリ環状シロキサン、その製造方法、およびその用途
KR101860710B1 (ko) * 2011-07-27 2018-05-25 삼성전자주식회사 내지문성 코팅 조성물 및 이를 이용한 피막
AU2012292554B2 (en) * 2011-08-10 2014-10-30 Magforce Ag Agglomerating magnetic alkoxysilane-coated nanoparticles
EP2871646A1 (en) * 2013-11-06 2015-05-13 Basf Se Temperature-stable soft-magnetic powder
WO2021152136A1 (en) * 2020-01-31 2021-08-05 Magforce Ag Paste comprising magnetic alkoxysilane-coated metal containing nanoparticles

Family Cites Families (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3576033A (en) * 1967-05-22 1971-04-20 Stevens & Co Inc J P 1-methyl-phenylene-2,4-bis(triethoxysilyl propylene-3'-ureylene)
BE786221A (fr) * 1971-07-15 1973-01-15 Dow Corning Ltd Copolymeres sequences organiques de siloxane et leur procede d'obtention
CA1039552A (en) * 1973-02-26 1978-10-03 Myron J. Lenhard Developer mixtures
US4600677A (en) 1982-03-15 1986-07-15 Xerox Corporation Organoalkoxysilane carrier coatings
US4461867A (en) * 1982-09-27 1984-07-24 General Electric Company Composition for promoting adhesion of curable silicones to substrates
JPH0719079B2 (ja) * 1983-06-03 1995-03-06 富士ゼロックス株式会社 静電荷像現像用キャリヤ粒子
JPS61127733A (ja) * 1984-11-27 1986-06-16 Toray Silicone Co Ltd 新規なオルガノポリシロキサン化合物
US4689085A (en) * 1986-06-30 1987-08-25 Dow Corning Corporation Coupling agent compositions
JPS6385759A (ja) * 1986-09-30 1988-04-16 Fujitsu Ltd 電子写真用キヤリア
JP2560085B2 (ja) * 1988-07-22 1996-12-04 花王株式会社 静電荷像現像用現像剤
JPH0686574B2 (ja) * 1989-02-03 1994-11-02 信越化学工業株式会社 室温硬化性オルガノポリシロキサン組成物
JPH054995A (ja) * 1991-01-17 1993-01-14 Shin Etsu Chem Co Ltd 有機けい素化合物およびその製造方法
US5378790A (en) * 1992-09-16 1995-01-03 E. I. Du Pont De Nemours & Co. Single component inorganic/organic network materials and precursors thereof
JP2801492B2 (ja) * 1993-01-22 1998-09-21 信越化学工業株式会社 電子写真キャリア用コーティング剤及びそれを用いたキャリア
JPH06350866A (ja) * 1993-06-04 1994-12-22 Sony Corp ダイナミックフォーカス回路
JPH07118279A (ja) * 1993-10-19 1995-05-09 Shin Etsu Chem Co Ltd 有機けい素化合物
JPH07181743A (ja) 1993-12-24 1995-07-21 Kao Corp 電子写真用キャリア及びその製造方法
US5677410A (en) * 1995-05-16 1997-10-14 Bayer Ag Carbosilane-dendrimers, carbosilane-hybrid materials, methods for manufacturing them and a method for manufacturing coatings from the carbosilane-dendrimers
US5798430A (en) * 1995-06-28 1998-08-25 E. I. Du Pont De Nemours And Compnay Molecular and oligomeric silane precursors to network materials
US5707783A (en) * 1995-12-04 1998-01-13 Complex Fluid Systems, Inc. Mixtures of mono- and DI- or polyfunctional silanes as silylating agents for top surface imaging
DE19603241C1 (de) * 1996-01-30 1997-07-10 Bayer Ag Multifunktionelle, cyclische Organosiloxane, Verfahren zu deren Herstellung und deren Verwendung
US5709975A (en) * 1996-07-23 1998-01-20 Eastman Kodak Company Coated hard ferrite carrier particles
DE19632700C1 (de) * 1996-08-14 1998-02-26 Bayer Ag Carbosilan-Dendrimere mit Si-O-Metall-Bindungen, ein Verfahren zu deren Herstellung und deren Verwendung
DE19650147A1 (de) * 1996-12-04 1998-06-10 Bayer Ag Leitfähige, organisch-anorganische Hybridmaterialien
JP4291415B2 (ja) * 1997-02-25 2009-07-08 バイエル・アクチエンゲゼルシヤフト 有機−無機ハイブリッド材料
DE69811442T2 (de) * 1997-08-20 2003-12-24 Xeikon Int Nv Methode zur Beschichtung von Trägerteilchen in elektrostatischen Entwicklern
WO1999036356A2 (en) * 1998-01-15 1999-07-22 Cabot Corporation Polyfunctional organosilane treatment of silica
DE19814060A1 (de) * 1998-03-30 1999-10-07 Bayer Ag Borhaltige Mischungen, Hybridmaterialien und Beschichtungen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9853372A1 *

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US6136939A (en) 2000-10-24
WO1998052992A1 (de) 1998-11-26
AU7653698A (en) 1998-12-11
EP0981570B1 (de) 2002-10-16
WO1998053372A1 (de) 1998-11-26
EP0981570A1 (de) 2000-03-01
PT981570E (pt) 2003-01-31
ATE226226T1 (de) 2002-11-15
US6413638B1 (en) 2002-07-02
ES2184268T3 (es) 2003-04-01
AU7653598A (en) 1998-12-11
CA2290455C (en) 2007-04-10
CA2290455A1 (en) 1998-11-26
JP2001525833A (ja) 2001-12-11
JP2002502447A (ja) 2002-01-22

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