EP0981780A1 - Coated particles - Google Patents

Coated particles

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Withdrawn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)
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/en
Application filed by Agfa Gevaert AG filed Critical Agfa Gevaert AG
Publication of EP0981780A1 publication Critical patent/EP0981780A1/en
Withdrawn legal-status Critical Current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
    • 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
    • C09D183/00—Coating 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
    • C09D183/14—Coating 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/48—Macromolecular 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
    • C08G77/485—Macromolecular 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/48—Macromolecular 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
    • C08G77/50—Macromolecular 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/001—Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991—Coated
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31652—Of asbestos
    • Y10T428/31663—As 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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Abstract

PCT No. PCT/EP98/02728 Sec. 371 Date Nov. 8, 1999 Sec. 102(e) Date Nov. 8, 1999 PCT Filed May 11, 1998 PCT Pub. No. WO98/52992 PCT Pub. Date Nov. 26, 1998Oligomers soluble in organic solvents and obtainable by condensing identical or different monomers of the formula in which R1 means C1-C6 alkyl or C6-C14 aryl, R2 means hydrogen, alkyl or aryl, if b is 1, or alkyl or aryl, if b is 2 or 3, R3 means alkyl or aryl, m means 3 to 6, q means 2 to 10 and, b means 1, 2 or 3, are suitable for coating plastics, mineral and metallic substrates and glass.

Description

Beschichtete PartikelCoated particles
Die Erfindung betrifft beschichtete Partikel, insbesondere Partikel mit anorganischem Gehalt, vorzugsweise rein anorganische Partikel und besonders bevorzugt beschichtete magnetische Partikel, die als Carrier-Teilchen bei elektrostatografischen Entwicklern für die elektrostatografische Bilderzeugung verwendet werden.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.
Es ist eine Reihe von elektrostatografischen Druckmethoden bekannt, z.B. das direkte elektrostatische Drucken!, bei dem auf ein Empfangsmaterial, das kein latentes elektrostatisches Bild aufweist, Toner mittels eines elektronisch addressierbaren Druckkopfes aufgebracht wird.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.
In einer anderen Form des elektrostatischen Drückens werden Tonerbilder auf einem bilderzeugenden Element in Form einer rotierenden Trommel, die eine elektrostatischeIn another form of electrostatic printing, toner images are placed on an imaging element in the form of a rotating drum that is electrostatic
Schicht enthält, die aus einer Vielzahl kontrollierbarer Elektroden in und unter einer dielektrischen Schicht besteht, erzeugt. Es wird bildweise in den kontrollierbaren Elektroden elektrische Spannung erzeugt, die die Tonerteilchen aus einer Tonerquelle anzieht.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.
Weiterhin ist beim elektrografischen Drucken und elektrofotografischen Kopieren bekannt, ein latentes elektrostatisches Bild entweder für das zu kopierende Original oder für digitalisierte Daten, die ein elektronisch zugängliches Bild beschreiben, zu erzeugen.Furthermore, in electrographic printing and electrophotographic copying, it is known to generate a latent electrostatic image either for the original to be copied or for digitized data which describe an electronically accessible image.
In der Elektrofbtografie wird ein latentes elektrostatisches Bild durch die Schritte a) gleichförmiges Aufladen eines fotoleitfähigen Elementes und b) bildweises Entladen durch eine bildmäßig modulierte Belichtung erzeugt.In electrophotography, 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.
In der Elektrografie wird ein latentes elektrostatisches Bild durch bildweisen Niederschlag elektrisch geladener Teilchen erzeugt, z.B. durch einen Elektronenstrahl oder durch ionisiertes Gas auf ein dielektrisches Substrat. Die erhaltenen Latentbilder werden entwickelt, das heißt in sichtbare Bilder umgewandelt, indem man selektiv lichtabsorbierende Substanzen darauf niederschlägt, die Toner genannt werden und üblicherweise triboelektrisch geladen sind.In electrography, 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.
In der Tonerentwicklung latenter elektrostatischer Bilder werden zwei Techniken angewendet: Die Trockenpulver- und die Flüssigdispersionsentwicklung, wobei die Trockenpulverentwicklung die gebräuchlichere ist.Two techniques are used in toner development of latent electrostatic images: dry powder and liquid dispersion development, with dry powder development being the more common.
Die Trockenpulverentwicklung kann auf unterschiedliche Weise durchgeführt werden.The dry powder development can be carried out in different ways.
Eine Methode ist die Einkomponentenmethode, bei der der Toner selbst durch Reibung geladen, mit einer Walze transportiert und auf das Latentbild aufgetragen wird. Die Qualität ist begrenzt, insbesondere wenn Farbdrucke erzeugt werden sollen. Eine weitere Methode benutzt das Flüssigentwickeln, bei dem kolloidal geladene Toner- teilchen in einem flüssigen isolierenden Medium, z.B. einem Kohlenwasserstoff zumOne 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
Fotoleiter gebracht werden. Ein Nachteil dieser Methode ist die Emission von verdampften organischen Substanzen, insbesondere wenn es um große Druckgeschwindigkeiten geht. Eine dritte Methode benutzt einen Zweikomponentenentwickler. In diesem Fall bilden magnetisch aufziehbare, grobkörnige Carrier-Teilchen eine magne- tische Bürste auf der Oberfläche der Entwicklungswalze, indem sie die magnetischenBe brought photoconductor. 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
Haare der Bürste bilden. Auf der Oberfläche der Carrier-Teilchen sind triboelektrisch geladene Tonerteilchen anwesend. Diese werden gemäß der elektrischen Ladung des latenten elektrostatischen Bildes von den Carrier-Teilchen abgestreift, wodurch das Tonerbild erzeugt wird. In diesem Verfahren werden die Carrierteilchen vielfach wie- derverwendet; ihre mechanische Stabilität ist deswegen von besonderer Wichtigkeit.Form the hair of the brush. 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.
Als Alternative zur sogenannten magnetischen Bürste können auch nicht-magnetische elektrofotografische Entwickler aus zwei Komponenten verwendet werden. In einer speziellen Ausführungsform besteht der Entwickler aus Glaskügelchen, die gegebe- nenfalls beschichtet sind, und Tonerteilchen. Man läßt den Entwickler auf das das latente Bild tragende Element herabfallen und bewirkt auf diese Weise die Entwicklung, wie es in BE 828 210 beschrieben ist. Auch in diesem Fall werden die Carrierteilchen wiederverwendet.As an alternative to the so-called magnetic brush, non-magnetic electrophotographic developers made of two components can also be used. In a special embodiment, 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.
Im Falle oberflächenbeschichteter Carrierteilchen ist die Stabilität der Oberflächen- beschichtung von besonderer Wichtigkeit. Ungenügende mechanische Stabilität führt zu Qualitätseinbußen am Druckbild und der Entwickler muß ausgetauscht werden, was unnötige Stillstandzeiten und Kosten verursacht.In the case of surface-coated carrier particles, the stability of the surface coating is of particular importance. Insufficient mechanical stability leads to a loss of quality in the printed image and the developer must be replaced, which causes unnecessary downtimes and costs.
Für die Beschichtung der Carrier-Teilchen wird ein Material mit anti-haft Eigenschaften bevorzugt, um ein Verkleben des Toners auf der Carrieroberfläche zu vermeiden. In den meisten Fällen führt dies aber zu einer Verminderung der Haftung der Beschichtung auf dem Carrier, was zu einer Verkürzung der Standzeit führt, z.B. bei Verwendung von Silikonharzen als Carrierbeschichtungsmittel.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.
Aus US 4 977 054 sind Carrier, bestehend aus einem magnetischen Pulver und einer Silikonharzbeschichtung, bekannt. Das eingesetzte Silikonharz besteht aus D- und T- Baueinheiten (bei D-Einheiten ist das Siliciumatom über 2, bei T-Einheiten über 3 Sauerstoffatome mit weiteren Siliciumatomen verknüpft), wobei zusätzlich auch andere funktioneile Organosilane, wie di- und trialkoxyfunktionelle Organosilane und/oder di- und trialkoxyfunktionelle, stickstoffhaltige Organosilane, zugesetzt werden können. Die Auftragung erfolgt, wie den Beispielen zu entnehmen ist, in einem Wirbelbettreaktor; die Beschichtungen werden danach noch bei 190°C bis 296°C ausgehärtet.From US 4 977 054 carriers consisting of a magnetic powder and a silicone resin coating are known. 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.
Die genannten Beschichtungen mit (polymeren) Siliconharzen haben jedoch den Nachteil, daß zur kompletten Aushärtung hohe Temperaturen notwendig sind (190 bis 296°C). Darüber hinaus zeigen viele Siliconharz-Beschichtungen zwar Antihaft-Ei- genschaften, notwendigerweise aber eine schlechte Haftung zum Untergrund. Gemäß US 4 4 977 054 müssen den Siliconharzen zur Verbesserung der Haftung daher z.B. di- und trialkoxyfunktionelle Organosilane zugesetzt werden. Aufgabe der vorliegenden Erfindung war daher die Bereitstellung von beschichteten Teilchen, insbesondere von Teilchen mit einem Gehalt an anorganischem Material und insbesondere von Carrier-Teilchen für elektrostatografische Prozesse, wobei die Teilchen einen magnetischen Kern und eine Beschichtung des Kernes aufweisen, dieHowever, the above-mentioned coatings with (polymeric) silicone resins have the disadvantage that high temperatures are necessary for complete curing (190 to 296 ° C.). In addition, many silicone resin coatings show non-stick properties, but necessarily poor adhesion to the substrate. According to US Pat. No. 4,977,054, 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) klebefrei ist, so daß freifließende, überwiegend agglomeratfreie Partikel erhalten werden.a) is tack-free, so that free-flowing, predominantly agglomerate-free particles are obtained.
b) auch bei erhöhter Temperatur nicht erweicht,b) does not soften even at elevated temperatures,
c) ein dauerhaftes Anhaften und Verkleben der farbgebenden Toner verhindert,c) prevents permanent adhesion and sticking of the coloring toners,
d) eine hohe Abriebfestigkeit aufweist,d) has a high abrasion resistance,
e) gut auf den Partikeln haftet, unde) adheres well to the particles, and
f) im Falle von Carrier-Teilchen für die Elektrofotografie für eine gute Auflad- barkeit sorgt, so daß genügend Toner aufgenommen und wieder abgegeben werden kann.f) in the case of carrier particles for electrophotography, ensures good chargeability so that sufficient toner can be taken up and released again.
Aufgabe der vorliegenden Erfindung war darüber hinaus, ein Verfahren zur Beschichtung von Teilchen, insbesondere von Teilchen mit einem Gehalt an anorganischem Material und insbesondere von magnetischen Partikeln bereitzustellen, das die obengenannten Nachteile nicht aufweist und z.B. dadurch gekennzeichnet ist, daß das Aufbringen der Beschichtung in möglichst einfachen Apparaten nach einem einfachenIt was also an object of the present invention to provide a process for coating particles, in particular particles with a content of inorganic material and in particular magnetic particles, which does not have the disadvantages mentioned above and e.g. characterized in that the application of the coating in the simplest possible apparatus after a simple
Verfahren und "die Aushärtung der Beschichtung bei niedrigeren Temperaturen erfolgt.Process and "the coating is cured at lower temperatures.
Überraschend wurde nun gefunden, daß beschichtete Partikel, insbesondere beschich- tete, anorganisches Material enthaltende Partikel erhalten werden, die die obengenannten Nachteile nicht aufweisen, wenn die Beschichtung aus monomeren polyfünk- tionellen Organosilanen und/oder deren Hydrolyseprodukten und/oder deren Reakti- onsprodukten mit heteroatomhaltigen Organosilanen und/oder Alkoxiden hergestellt wird.Surprisingly, it has now been found that 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.
Gegenstand der vorliegenden Erfindung sind daher Partikel (A), die mit einem Mate- rial (B) beschichtet sind, wobei die Partikel (A) vorzugsweise anorganisches Material enthalten, insbesondere anorganische Partikel sind und besonders bevorzugt magnetische Carrierteilchen für elektrostatografische Prozesse sind und wobei das Material (B) ein monomeres, polyfünktionelles Organosilan und/oder ein Hydrolyseprodukt daraus und/oder ein Reaktionsprodukt daraus mit einem heteroatomhaltigen Orga- nosilan und/oder einem Alkoxid ist.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.
Heteroatomhaltige Organosilane im Sinne der Erfindung bestehen aus mindestens einem Siliciumatom mit hydrolysierbaren und/oder kondensationsvernetzenden Gruppen wie -SiOR, wobei R insbesondere Alkyl, Cycloalkyl oder Aryl, bevorzugt Alkyl bedeutet, oder SiOH und mindestens einem über ein Kohlenstoffatom gebundenen heteroatomhaltigen organischen Rest, der ein Alkyl-, Cycloalkyl- oder Arylrest sein kann. Heteroatome der heteroatomhaltigen Organosilane sind bevorzugt N, P, S, F, Cl, Br O, B und AI.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.
Bevorzugte Heteroatome sind N und F, wobei Stickstoffatome besonders bevorzugt sind.Preferred heteroatoms are N and F, with nitrogen atoms being particularly preferred.
Bevorzugte stickstoffhaltige Organosilane entsprechen der Formel (I)Preferred nitrogen-containing organosilanes correspond to the formula (I)
(R2)2-N[(CH2)mNR2]n(CH2)mSi(OR3)3.0(R4)0 (I)(R 2 ) 2 -N [(CH 2 ) m NR 2 ] n (CH 2 ) m Si (OR 3 ) 3. 0 (R 4 ) 0 (I)
worinwherein
m 1 bis 10, bevorzugt 2 oder 3,m 1 to 10, preferably 2 or 3,
n 0 bis 2, bevorzugt 2, o 0 bis 2, bevorzugt 0n 0 to 2, preferably 2, o 0 to 2, preferably 0
R2 H, Alkyl oder Aryl, vorzugsweise HR 2 is H, alkyl or aryl, preferably H
R3, R4 Alkyl oder Aryl, vorzugsweise CH3 oder C2H5 bedeuten,R 3 , R 4 are alkyl or aryl, preferably CH 3 or C 2 H 5 ,
Bevorzugte Alkoxide entsprechen der Formel (II)Preferred alkoxides correspond to the formula (II)
MrfOROy (II)MrfOROy (II)
worinwherein
Mj Si, Sn, Ti, Zr, B oder AI Rj Alkyl oder Aryl, vorzugsweise C]-C4- Alkyl und y im Falle von Si, Sn, Ti, Zr 4 und im Falle von B oder AI 3 bedeuten.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.
Polyfünktionelle Organosilane im Sinne der Erfindung sind dadurch gekennzeichnet, daß sie mindestens 2, vorzugsweise mindestens 3 Siliciumatome mit jeweils 1 bis 3 hydrolysierbaren und/oder kondensationsvernetzenden Gruppen, insbesondere Alkoxy-, Acyloxy- oder Hydroxygruppen enthalten und die Siliciumatome mit jeweils einer Si, C-Bindung an eine die Siliciumatome verknüpfte Baueinheit gebunden sind.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.
Als verknüpfte Baueinheiten im Sinne der Erfindung seien im einfachsten Falle z.B. lineare oder verzweigte Cj- bis Cjo-Alkylenketten, C5- bis Cjo-Cycloalkylenreste, aromatische Reste, wie z.B. Phenyl, Naphthyl oder Biphenyl oder aber auch Kombinationen von aromatischen und aliphatischen Resten, genannt. Die aliphatischen und aromatischen Reste können auch Heteroatome, wie z.B. Si, N, O, S oder F enthalten.In the simplest case, 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. The aliphatic and aromatic radicals can also contain heteroatoms, such as Si, N, O, S or F.
Weiterhin seien als verknüpfte Baueinheiten auch ketten-, ring- oder käfigförmige Siloxane, wie Silsequioxane, genannt. Nachfolgend sind Beispiele für verknüpfende Baueinheiten aufgeführt, wobei mit X Si-Atome bezeichnet werden, die 1 bis 3 hydrolysierbare und/oder kondensationsver- netzende Gruppen aufweisen und mit Y entsprechende Si-Atome, die über eine Alk- ylenkette an die verknüpfende Baueinheit gebunden sind; n steht für eine Zahl 1 bis 10, m für eine Zahl 1 bis 6:Furthermore, chain-shaped, ring-shaped or cage-shaped siloxanes, such as silsequioxanes, may also be mentioned as linked structural units. Examples of 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:
Y Y Y YY Y Y Y
I I I II I I I
Y— si— Y ; Y— si— Y ; Y— Sn-Y Y— Sn-Y ;Y-si-Y; Y-si-Y; Y- Sn-Y Y- Sn-Y;
I II I
Y R RY R R
wobei R ein organischer Rest, z.B. Alkyl, Cycloalkyl, Aryl oder Alkenyl ist.where R is an organic residue, e.g. Is alkyl, cycloalkyl, aryl or alkenyl.
Beispiele für polyfunktionelle Organosilane sind Verbindungen der allgemeinen Formel (IV), (V) und (VI): (R5)4.iSi[(CH2)pSi(OR6)a(R7)3.a]i (IV)Examples of 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)
woπnwoπn
i 2 bis 4, bevorzugt 4, p 1 bis 4, bevorzugt 2 bis 4,i 2 to 4, preferably 4, p 1 to 4, preferably 2 to 4,
R5 Alkyl oder Aryl,R 5 alkyl or aryl,
-Rg Wasserstoff, Alkyl oder Aryl, wenn a 1 ist und Alkyl oder Aryl, wenn a 2 oder-Rg is hydrogen, alkyl or aryl if a is 1 and alkyl or aryl if a 2 or
3 ist,3 is
R7 Alkyl oder Aryl, vorzugsweise Methyl und a 1 bis 3 bedeuten;R 7 is alkyl or aryl, preferably methyl and a is 1 to 3;
woπnwoπn
m 3 bis 6, vorzugsweise 3, q 2 bis 10, vorzugsweise 2, b 1 bis 3,m 3 to 6, preferably 3, q 2 to 10, preferably 2, b 1 to 3,
Cj-Cg- Alkyl oder C6-Ci4-Aryl, vorzugsweise Methyl oder Ethyl, RQ Wasserstoff, Alkyl oder Aryl, wenn b 1 ist, oder Alkyl oder Aryl, wenn b 2 oder 3 ist, undC j -Cg alkyl or C 6 -Ci4 aryl, preferably methyl or ethyl, RQ hydrogen, alkyl or aryl if b is 1, or alkyl or aryl if b is 2 or 3, and
R 10 Alkyl oder Aryl, vorzugsweise Methyl bedeuten;R 10 is alkyl or aryl, preferably methyl;
(Rl4)4-kSi[OSi(R11)2(CH2)rSi(OR12)c(R13)3.c]k (VI)(Rl4) 4 -kSi [OSi (R 11 ) 2 (CH 2 ) r Si (OR 12 ) c (R 13 ) 3 . c ] k (VI)
worin r 1 bis 10, bevorzugt 2 bis 4, c 1 bis 3, k 2 bis 4, bevorzugt 4 R Alkyl oder Aryl, vorzugsweise Methyl,wherein 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^2 H, Alkyl oder Aryl, bevorzugt H, CH3, C2H5, C3H7, wenn c 1 und Alkyl oder Aryl, bevorzugt CH3, C H5, C3H7, wenn c 2 oder 3 ist,R ^ 2 H, alkyl or aryl, preferably H, CH 3 , C 2 H 5 , C 3 H 7 if c 1 and alkyl or aryl, preferably CH 3 , C H5, C 3 H 7 if c 2 or 3 is
R13 Alkyl oder Aryl, bevorzugt Methyl undR 13 is alkyl or aryl, preferably methyl and
R14 Alkyl oder Aryl bedeuten.R 14 is alkyl or aryl.
Beispiele für polyfünktionelle Organosilane sind:Examples of polyfunctional organosilanes are:
(a-1 Si[(CH2)2Si(OH)(CH3)2]4,(a-1 Si [(CH 2 ) 2 Si (OH) (CH 3 ) 2 ] 4 ,
(a-2 H3C-Si[(CH2)2Si(OH)(CH3)2]2 (a-2 H 3 C-Si [(CH 2 ) 2 Si (OH) (CH 3 ) 2 ] 2
(a-3 C6H5-Si[(CH2)2Si(OH)(CH3)2]3,(a-3 C 6 H 5 -Si [(CH 2 ) 2 Si (OH) (CH 3 ) 2 ] 3 ,
(a-4 Si[(CH2)3Si(OH)(CH3)2]4,(a-4 Si [(CH 2 ) 3 Si (OH) (CH 3 ) 2 ] 4 ,
(a-5 cyclo-{OSiCH3[(CH2)2Si(OH)(CH3)2]}4,(a-5 cyclo- {OSiCH 3 [(CH 2 ) 2 Si (OH) (CH 3 ) 2 ]} 4 ,
(a-6 cyclo-{OSiCH3[(CH2)2Si(OCH3)(CH3)2]}4.(a-6 cyclo- {OSiCH 3 [(CH 2 ) 2 Si (OCH 3 ) (CH 3 ) 2 ]} 4 .
(a-7 cyclo-{OSiCH3[(CH2)2Si(OCH3)2CH3]}4,(a-7 cyclo- {OSiCH 3 [(CH 2 ) 2 Si (OCH 3 ) 2 CH 3 ]} 4 ,
(a- cyclo-{OSiCH3[(CH2)2Si(OC2H5)2CH3]}4,(a- cyclo- {OSiCH 3 [(CH 2 ) 2 Si (OC 2 H 5 ) 2 CH 3 ]} 4 ,
(a-9 cyclo-{OSiCH3[(CH2)2Si(OC2H5)3]}4, Stickstoffhaltige Alkoxysilane sind z.B.(a-9 cyclo- {OSiCH 3 [(CH 2 ) 2 Si (OC 2 H 5 ) 3 ]} 4 , Nitrogen-containing alkoxysilanes are, for example
(b-1) H2N-(CH2)3Si(OCH3)3 (b-1) H 2 N- (CH 2 ) 3 Si (OCH 3 ) 3
(b-2) H2N-(CH2)3Si(OC2H5)3 (b-2) H 2 N- (CH 2 ) 3 Si (OC 2 H 5 ) 3
(b-3) H2N-(CH2)2-HN-(CH2)3Si(OCH3)3 (b-3) H 2 N- (CH 2 ) 2 -HN- (CH 2 ) 3 Si (OCH 3 ) 3
(b-4) H2N-(CH2)2-HN-(CH2)3Si(OCH3)2(CH3)(b-4) H 2 N- (CH 2 ) 2 -HN- (CH 2 ) 3 Si (OCH 3 ) 2 (CH 3 )
(b-5) C6H5-HN-(CH2)3Si(OCH3)3 (b-5) C 6 H 5 -HN- (CH 2 ) 3 Si (OCH 3 ) 3
(b-6) C6H5-HN-(CH2)3Si(OC2H5)3 (b-6) C 6 H 5 -HN- (CH 2 ) 3 Si (OC 2 H 5 ) 3
(b-7) H2N-(CH2)2-HN-(CH2)2-HN-(CH2)3Si(OCH3)3 (b-7) H 2 N- (CH 2 ) 2 -HN- (CH 2 ) 2 -HN- (CH 2 ) 3 Si (OCH 3 ) 3
(b-8) H2N-(CH2)2-HN-(CH2)2-HN-(CH2)3Si(OC2H5)3.(b-8) H 2 N- (CH 2 ) 2 -HN- (CH 2 ) 2 -HN- (CH 2 ) 3 Si (OC 2 H 5 ) 3 .
Fluorhaltige Alkoxysilane sind z.B.:Examples of fluorine-containing alkoxysilanes are:
(d-1) F3C-(CH2)2-SiR'3.x(OR)x (d-1) F 3 C- (CH 2 ) 2 -SiR ' 3 . x (OR) x
(d-2) F3C-(CF2)7-(CH2)2-SiR'3.x(OR)x (d-2) F 3 C- (CF 2 ) 7 - (CH 2 ) 2 -SiR ' 3 . x (OR) x
(d-3) (F3C)2CF-O-(CH2)3-SiR'3.x(OR)x (d-3) (F 3 C) 2 CF-O- (CH 2 ) 3 -SiR ' 3 . x (OR) x
(d-4) (3-F3C-C6H4)-SiR' 3.x(OR)x (d-4) (3-F 3 CC 6 H 4 ) -SiR ' 3 . x (OR) x
(d-5) (3-F3C-C6H4)2Si(OR)2 (d-5) (3-F 3 CC 6 H 4 ) 2 Si (OR) 2
wobei x 1 bis 3 und R, R' Alkyl, Cyloalkyl oder Aryl, bevorzugt Ethyl oder Methyl sind.where x is 1 to 3 and R, R 'alkyl, cycloalkyl or aryl, preferably ethyl or methyl are.
Beispiele für Alkoxide, die zur Herstellung der erfindungsgemäßen Reaktionsprodukte eingesetzt werden können, um z.B. eine Verbesserung der Abriebfestigkeit oder der tribologischen Eigenschaften zu erreichen, sind:Examples of 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:
(c-1) Si(OC2H5)4 (c-1) Si (OC 2 H 5 ) 4
(c-2) B(OC2H5)3 (c-2) B (OC 2 H 5 ) 3
(o-3) Al(O-i-C3H7)3 (o-3) Al (OiC 3 H 7 ) 3
(c-4) Zr(O-i-C3H7)4.(c-4) Zr (OiC 3 H 7 ) 4 .
Die erfindungsgemäßen Reaktionsprodukte können darüber hinaus auch feinteiligeThe reaction products according to the invention can also be finely divided
Metalloxide oder Metalloxidhydroxide der Elemente Si, Sn, In, Ti, Zr, B oder AI enthalten, z.B. Kieselsole, die insbesondere organische Lösungsmittel enthalten. Deren bevorzugte Primärteilchengröße liegt im Bereich von 1 bis 50 nm; sie werden nachfolgend als „Nanopartikel" bezeichnet. Auch Leitfähigkeit induzierende Mittel, z.B. Kohlenstoff und ladungsregulierende Mittel, z.B. Nigrosin, können der Beschichtung zugegeben werden.Contain metal oxides or metal oxide hydroxides of the elements Si, Sn, In, Ti, Zr, B or Al, e.g. Silica sols, which contain organic solvents in particular. Their preferred primary particle size is in the range from 1 to 50 nm; they are referred to below as "nanoparticles". Conductivity-inducing agents, for example carbon and charge-regulating agents, for example nigrosine, can also be added to the coating.
Vorzugsweise enthält das Material B 0,1 bis 100 Gew.-% polyfünktionelles Organosilan, 0 bis 20 Gew.-% heteroatomhaltiges Organosilan (I), 0 bis 70 Gew.-% Nanopar- tikel und 0 bis 99,9 Gew.-% Alkoxid (II). Besonders bevorzugt enthält das Material BMaterial 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.
20 bis 80 Gew7-% polyfünktionelles Organosilan, 20 bis 80 Gew.-% Alkoxid (II), 0 bis 10 Gew.-% heteroatomhaltiges Organosilan (I) und 0 bis 50 Gew.-% Nanopartikel.20 to 80% by weight of polyfunctional organosilane, 20 to 80% by weight of alkoxide (II), 0 to 10% by weight of heteroatom-containing organosilane (I) and 0 to 50% by weight of nanoparticles.
Als Partikel sind magnetische anorganische Teilchen bevorzugt.Magnetic inorganic particles are preferred as particles.
Die magnetischen Teilchen sind bevorzugt Eisenoxidpigmente der Formel (III) (M2O)x (Fe2O3)z (III)The magnetic particles are preferably iron oxide pigments of the formula (III) (M 2 O) x (Fe 2 O 3 ) z (III)
woπnwoπn
M2 Li, Mg, Sr, Ba, Mn, Fe(II), Co, Ni, Cu, Zn, Cd undM 2 Li, Mg, Sr, Ba, Mn, Fe (II), Co, Ni, Cu, Zn, Cd and
das molare Verhältnis von x zu z zwischen 0 und 1, bevorzugt zwischen 0,3 und 1 liegt.the molar ratio of x to z is between 0 and 1, preferably between 0.3 and 1.
Es ist weiterhin möglich, zusammengesetzte Partikel zu verwenden, die aus 20 bis 85 Gew.-% magnetischer Mikropartikel und einem organischen oder anorganischen Bindemittel bestehen, z.B. einem organischen Polymer oder einem keramischen Material. Weiterhin ist die Verwendung nicht-magnetischer Kerne wie Glasperlen möglich.It is also possible to use 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.
Die erfindungsgemäßen Reaktionsprodukte B) werden im allgemein als Beschichtung auf die Partikel A) aufgetragen. Die polyfunktionellen Organosilane können in Substanz oder in einem Lösungsmittel gelöst, gegebenenfalls in Gegenwart eines Katalysators, auf die Partikel A aufgebracht werden. Nach dem Verdampfen des Lösemittels und Aushärtung bei einer geeigneten Temperatur erhält man die Beschichtung B).The 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.
In einer bevorzugten Ausfuhrungsform werden die polyfunktionellen Organosilane, gegebenenfalls in einem Lösemittel, zunächst mit Alkoxiden und z.B. heteroatomhaltigen Organosilanen und/oder Nanopartikeln vermischt, und, gegebenenfalls in Ge- genwart eines Katalysators, auf die Partikel A aufgebracht und gehärtet. Zur Erhöhung der Reaktivität und zur Verminderung des Austrags niedrigsiedender, leichtflüchtiger Ausgangsmaterialien, wie Tetraethylorthosilikat, ist es besonders günstig, die Ausgangsmaterialien zunächst mit Wasser zur Reaktion zu bringen, gegebenenfalls in Gegenwart eines Katalysators. Dabei bilden sich reaktive, weniger flüchtige Oligo- und/oder Polymere. Nach einer bestimmten Reaktionszeit wird diese Beschichtungslösung mit geeigneten Verfahren, z.B. im Wirbelbett, auf die eisenoxidhaltigen Materialien aufgebracht, die flüchtigen Bestandteile verdampft und die so erhaltene Beschichtung gegebenenfalls thermisch nachgehärtet.In a preferred embodiment, the polyfunctional organosilanes, if appropriate in a solvent, 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. In order to increase the reactivity and to reduce the discharge of low-boiling, volatile starting materials, such as tetraethyl orthosilicate, it is particularly advantageous to first react the starting materials with water, if appropriate in the presence of a catalyst. This forms reactive, less volatile oligomers and / or polymers. After a certain reaction time, 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.
Geeignete Katalysatoren sind organische und anorganische Säuren oder Basen, z.B. HCO2H, CH3COOH, HCl, NH4OH und Alkalihydroxide sowie F-haltige Salze wie NaF oder NH4F. Ebenso können die zugesetzten Metallalkoxide selbst, wie Ti(OC H5)4 und Ti(Oi-C3H7)4 katalytisch wirksam sein. Auch Metallseifen wie Zink- octoat oder Dibutylzinnlaureat können eingesetzt werden.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. Likewise, 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.
Angaben zur Hydrolyse und Kondensation von polyfunktionellen Organosilanen, gegebenenfalls in Gegenwart von Alkoxiden, finden sich z.B. in DE-OS 196 03 242 und WO 94/06897. Z.B. werden die polyfunktionellen Organosilane mit den Alkoxiden, einem Lösungsmittel, Wasser und einem Katalysator unter Rühren zusammengegeben und eine bestimmte Zeit zur Reaktion gebracht, ehe aus diesen Lösungen Filme oder, nach vollständiger Reaktion (Gelierung), auch Formkörper erhalten werden können. Die Filmbildungseigenschaften des Reaktionsproduktes (B) sind ein brauchbarer Hinweis dafür, daß die Lösungen zur Beschichtung der Partikel geeignet sind. Beschich- tet man z.B. eine Glasplatte, so sollte nach dem Verdampfen der flüchtigen Bestandteile ein transparenter, den gesamten Bereich benetzender, weitgehend rißfreier Film erhalten werden. Allerdings steigt die Rißbildungstendenz mit der Schichtdicke des Films.Information on the hydrolysis and condensation of polyfunctional organosilanes, optionally in the presence of alkoxides, can be found e.g. in DE-OS 196 03 242 and WO 94/06897. For example, 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.
In einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens, werden die stickstoffhaltigen Alkoxysilane erst zugesetzt, nachdem die polyfunktionellen Organosilane und gegebenenfalls Alkoxide, wie oben angegeben, zur Reaktion gebracht worden sind und dieses Vorkondensat mit weiterem Lösungsmittel verdünnt worden ist. Wie aus der Literatur bekannt, katalysieren stickstoffhaltige Silane, wie H2N- (CH2)3Si(OMe)3 die Hydrolyse und Kondensation von Alkoxysilanen. Dies kann dazu führen, daß die reaktivste Komponente, z.B. H2N-(CH2)3Si(OCH3)3, rasch hy- drolysiert wird und zu einem unlöslichen Feststoff kondensiert. Dies kann verhindert werden, indem die stickstoffhaltigen Alkoxysilane in die verdünnte Beschichtungslösung gegeben werden.In a preferred embodiment of the process according to the invention, 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. As is known from the literature, 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.
Um eine homogene Verteilung der Beschichtungslösung auf allen eisenoxidhaltigen Partikeln zu erreichen, ist es günstig, das Vorkondensat noch mit weiterem Lösungsmittel zu verdünnen. Darüber hinaus verläuft in verdünnten Lösungen die Weiterreaktion der eingesetzten polyfunktionellen Organosilane und Alkoxide wesentlich langsamer, was zu einer verbesserten Lagerstabilität der Beschichtungslösungen führt.In order to achieve a homogeneous distribution of the coating solution on all particles containing iron oxide, it is advantageous to dilute the precondensate with a further solvent. In addition, the further reaction of the polyfunctional organosilanes and alkoxides used in dilute solutions is considerably slower, which leads to an improved storage stability of the coating solutions.
Als Lösungsmittel, die zum Verdünnen des Vorkondensats eingesetzt werden können, seien z.B. Alkohole, wie Methanol, Ethanol, n-Propanol, n-Butanol, iso-Propanol, sec-Butanol oder Ethylenglycol, Ketone, wie Aceton oder Methylethylketon, Amide, wie N-Methylpyrrolidon oder auch Wasser genannt. Wegen ihrer guten Mischbarkeit mit dem Vorkondensat sind Alkohole, insbesondere iso-Propanol besonders bevor- zugt. Auch Mischungen verschiedener Lösungsmittel können eingesetzt werden.Examples of solvents that can be used to dilute the precondensate 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.
Die Lösungsmittel können nach dem Aufbringen der Beschichtungslösung, z.B. durch Kondensation, zurückgewonnen und erneut, gegebenenfalls nach Reinigung, in den Prozeß eingesetzt werden.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.
Die Aushärtung der Beschichtung erfolgt bevorzugt bei Temperaturen von 25 bis 220°C, besonders bevorzugt von 80 bis 180°C, ganz besonders bevorzugt von 100 bis 140°C.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.
Die Menge der aufgebrachten Beschichtung liegt, bezogen auf den Kern, zwischen 0, 1 und 10 Gew.-%, bevorzugt zwischen 0,5 und 5 Gew.-% und besonders bevorzugt zwischen 0,5 und 2 Gew.-%.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.
Die beschichteten anorganischen Teilchen, insbesondere die einen magnetischen Kern enthaltenden Carrier-Teilchen für die Elektrofotografie sind insbesondere kugelförmig und besitzen einen mittleren Teilchendurchmesser von 20 bis 200 μm, vorzugsweise 40 bis 120 μm. Es ist auch möglich, zwei oder mehr Schichten auf die Partikel (A) aufzubringen, z.B. zunächst eine elektrisch isolierende Schicht und darüber eine Schicht, die die Stabilität der beschichteten Teilchen bei mechanischer Beanspruchung verbessert.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 μm, preferably 40 to 120 μm. 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.
Anstelle der polyfunktionellen Organosilane können auch daraus erhaltene Oligomere verwendet werden, insbesondere Oligomere aus den Organosilanen der Formel (V).Instead of the polyfunctional organosilanes, it is also possible to use oligomers obtained therefrom, in particular oligomers from the organosilanes of the formula (V).
Geeigente organische Lösungsmittel für die Oligomeren sind beispielsweise mono- und polyf nktionelle Alkohole, wie Methanol, Ethanol, n-Butanol, Ethylenglykol.Suitable organic solvents for the oligomers are, for example, mono- and polyfunctional alcohols, such as methanol, ethanol, n-butanol, ethylene glycol.
Die Oligomeren lassen sich aus den Monomeren der Formel (V) oder aus den Ausgangsprodukten zur Herstellung der Monomeren der Formel (V) direkt herstellen, wobei als Ausgangsprodukte solche Verbindungen der Formel (V) in Betracht kommen, die anstelle der Gruppe OR9 ein Halogenatom, z.B. ein Chlor-, Brom- oderThe 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
Iodatom enthalten.Contain iodine atom.
Diese Oligomere sind ein Beispiel für die Hydrolyseprodukte, die als Material B eingesetzt werden.These oligomers are an example of the hydrolysis products used as material B.
Diese Oligomere eignen sich, wie vorstehend dargestellt, zur Beschichtung von Partikeln, insbesondere Partikeln mit anorganischem Gehalt, vorzugsweise rein anorganischen Partikeln.As described above, these oligomers are suitable for coating particles, in particular particles with an inorganic content, preferably purely inorganic particles.
Die Anwendung dieser Oligomere erfolgt gegebenenfalls unter (Co)-Kondensation mitThese oligomers are optionally used with (co) condensation
Alkoxiden, beispielsweise denen der Formel II, und/oder Nanopartikeln. BeispieleAlkoxides, for example those of the formula II, and / or nanoparticles. Examples
Vorbemerkungen:Preliminary remarks:
Als eisenoxidhaltige Partikel für die Beschichtungsversuche wurden Cu-Zn-Ferrit-As iron oxide-containing particles for the coating tests, Cu-Zn-ferrite
Teilchen der Firma Powdertech Co. Ltd. 217 Toyofuta, Kashiwa-Shi, Chiba (Japan) eingesetzt, die wie folgt charakterisiert werden:Particles from Powdertech Co. Ltd. 217 Toyofuta, Kashiwa-Shi, Chiba (Japan), which are characterized as follows:
d50: 50 μm Dichte: 2,68 g/cm3 d 50 : 50 μm density: 2.68 g / cm 3
Sättigungsmagnetisierung: 60-70 emu/gSaturation magnetization: 60-70 emu / g
Widerstand: 2 • 107 Ohm • cmResistance: 2 • 10 7 ohms • cm
Die Bestimmung der Fließfähigkeit erfolgt mit einem Auslaufbecher und 500 g der beschichteten Teilchen.The flowability is determined using an outlet cup and 500 g of the coated particles.
Der spezifische Widerstand (Ωspez) des Carriers wurde in einer zylindrischen Meßzelle mit einem Innendurchmesser von 22,5 mm, die 4 mm hoch mit Carrier gefüllt war, auf den ein Stempel gesetzt wurde, der mit 1 kg belastet wurde, bestimmt. Bei einer Spannung von 200 V wurde die Stromstärke am Meßgerät abgelesen und Ωspez wie folgt berechnet:The specific resistance (Ω 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 Ω specifically calculated as follows:
Ωspez = (U/1) x (S/d) [Ω cm]Ω spec = (U / 1) x (S / d) [Ω cm]
U = angelegt Spannung (200 V)U = applied voltage (200 V)
I = gemessene StromstärkeI = measured current
S = innere Oberfläche der Meßzelle (4 cm2) d = Höhe des eingefüllten Carriers (0,4 cm)S = inner surface of the measuring cell (4 cm 2 ) d = height of the filled carrier (0.4 cm)
Die Ladungsaufnahme (-Q/m) wurde durch Entwicklung bestimmt. Dazu wurden 100 Gewichtsteile Carrier und 5 Gewichtsteile Toner in der Entwicklereinheit ge- mischt. Die Entwicklermischung wurde in einem kommerziellen Kopiergerät 10 Minuten aktiviert. Nach der Entwicklung wurde sowohl die abgegebene Menge Toner (m) als auch dessen Aufladung (Q) gemessen.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.
Die Ladungsaufnahme ergab sich also aus:The charge absorption therefore resulted from:
Q(in 10 C)Q (in 10 C)
-Q/m = [μC / g] m (in g)-Q / m = [μC / g] m (in g)
Die in den Beispielen angegebene Beschichtungsmenge wird aus der Summe der ein- gesetzten Menge des polyfunktionellen Organosilans und des Tetraethylorthosilikats wiedergegeben in Gew.-% gegenüber die Menge des Carriers. Der Anteil des stickstoffhaltigen Aminosilans (b-1) bzw. (b-8) wird in Gew.-% gegenüber Beschichtungs- material angegeben.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.
Um eine gleichmäßige Benetzung der Partikel mit der Beschichtungslösung zu gewährleisten, wurden die in den Tabellen 1 bis 3 beschriebenen Mischungen nach 60 Minuten Rühren mit Isopropanol verdünnt. Dabei wurde soviel Isopropanol zugegeben, daß pro kg Carrier 50 ml Lösung eingesetzt werden konnte.In order to ensure uniform wetting of the particles with the coating solution, the mixtures described in Tables 1 to 3 were diluted with isopropanol after 60 minutes of stirring. So much isopropanol was added that 50 ml of solution could be used per kg of carrier.
Zur Bestimmung der Abriebfestigkeit der Beschichtung werden 80 g beschichteterTo determine the abrasion resistance of the coating, 80 g are coated
Carrier mit 50 keramischen Perlen mit einem Durchmesser von 10 mm in einer Flasche von 120 ml gemischt, so daß der Füllgrad der Flasche ca. 50 % ist. Die Flasche wird 16 Stunden auf einem Rollentisch mit einer Geschwindigkeit von" 25 m/min gedreht. Durch diesen Prozeß wird die Beschichtung teilweise abgerieben und die Menge an abgeriebenem Beschichtungsmaterial wie folgt bestimmt: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:
Die abgeriebene Menge ist so gering, daß sie gravimetrisch nicht bestimmbar ist. Sie läßt sich aber sehr gut homogen auf einem Blatt Papier einer bekannten optischenThe 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
Dichte (bestimmt mit einem Macbeth-Densitometer) verteilen. Es wird dann wiederum die optische Dichte gemessen. Die in den Tabellen angegebenen Werte sind dann Dichtedifferenzen, die sehr gut reproduziert werden können. Je kleiner der Wert, desto geringer der Abrieb.Spread density (determined using a Macbeth densitometer). The optical density is then measured again. The values given in the tables are then density differences that can be reproduced very well. The smaller the value, the less abrasion.
Die Beschichtung der Partikel kann nach unterschiedlichen Methoden vorgenommen werden, z.B. in einem industriellen Fließbettreaktor oder in einem 2 1-Dreihalskolben mit Rührer, Einspritzsystem für die das Beschichtungsmaterial enthaltende Lösung und einem Kühler zur Rückgewinnung des verdampften Lösungsmittels.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.
Eine Beschichtungstemperatur von 80 bis 100°C bei einem leichten Unterdruck von 950 bis 1 000 mbar absolut bei einer Beschichtungszeit von 15 bis 60 Minuten hat sich als zweckmäßig erwiesen. Die Härtung erfolgt im gleichen Gefäß bei 120 bis 190°C während 20 Minuten bis 4 Stunden. „X" in den Tabellen 1 bis 3 bedeutet, daß die Substanz nicht eingesetzt wurde.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.
Tabelle 1Table 1
Tabelle 1 (Fortsetzung Table 1 (continued
IPA = IsopropanolIPA = isopropanol
Tabelle 2Table 2
Tabelle 3 Table 3
Bontron N-O 2 ist eine Nigrosinverbindung, die zur Ladungskontrolle dient; Spilon black TRH ein Cr-azokomplex, der zur Ladungskontrolle dient; Carbon black ist ein leifähiger Ruß.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.
Beschichtungsbeispiel 1Coating Example 1
7,5 kg der Ferritpartikel wurden mit den Lösungen 1 und 2 bei 85°C und 980 mbar beschichtet, getrocknet und durch 3 -stündiges Erhitzen auf 140°C gehärtet. Die Ergebnisse stehen in Tabelle 4.7.5 kg of the ferrite particles were coated with solutions 1 and 2 at 85 ° C. and 980 mbar, dried and hardened by heating at 140 ° C. for 3 hours. The results are shown in Table 4.
Tabelle 4Table 4
Vergleichsbeispiel 1Comparative Example 1
Eine Lösung von 3,6 g eines Silikonharzes mit 95 Gew.-% T-Einheiten und 5 Gew.-%A solution of 3.6 g of a silicone resin with 95% by weight T units and 5% by weight
M-Einheiten (Verknüpfung des Si-Atoms über ein Sauerstoffatom mit einem weiteren Si-Atom), 2,1 g eines Silikonharzes mit 100 Gew.-% T-Einheiten, 300 ml Methyl- ethylketon und 0,84 g (b-1) wurde unter Rühren in dieser Reihenfolge zusammengegeben. Man erhielt eine verarbeitungsfertige Beschichtungslösung die auf 1 kg Ferritpartikel eine 0,5 gew.-%ige Beschichtung ergab.M units (linkage of the Si atom via one oxygen atom to another Si atom), 2.1 g of a silicone resin with 100% by weight T units, 300 ml of methyl ethyl ketone and 0.84 g (b-1) were combined in this order with stirring. A ready-to-use coating solution was obtained which gave a 0.5% by weight coating on 1 kg of ferrite particles.
Die Beschichtung erfolgte bei 70°C und 50 mbar. Das Produkt wurde 30 Minuten bei 90°C getrocknet und 16 Stunden bei 140°C gehärtet. In der Tabelle 5 sind die Ergebnisse dargestellt.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.
Tabelle 5Table 5
Die Teilchen waren klebrig und bildeten daher eine Menge Agglomerate oder klebten am Kessel fest. Beim Trocknen fiel eine größere Menge Staub an.The particles were sticky and therefore formed a lot of agglomerates or stuck to the kettle. A large amount of dust accumulated when drying.
Beschichtungsbeispiel 2Coating Example 2
7,5 kg der Ferritpartikel wurden mit den Lösungen 3 bis 13 bei 95°C und 980 mbar beschichtet, bei 90°C 30 Minuten getrocknet und 4 Stunden bei 140° gehärtet. Die Ergebnisse sind in Tabelle 6 aufgelistet. Tabelle 67.5 kg of the ferrite particles were coated with solutions 3 to 13 at 95 ° C. and 980 mbar, dried at 90 ° C. for 30 minutes and cured at 140 ° for 4 hours. The results are listed in Table 6. Table 6
Beschichtungsbeispiel 3Coating Example 3
1 kg der Ferritpartikel wurde mit den Lösungen 14 bis 21 bei 70°C und 200 mbar beschichtet, bei 90°C und 50 mbar 30 Minuten getrocknet 4 Stunden bei 140°C gehärtet. Die Ergebnisse sind in Tabelle 7 aufgeführt. 1 kg of the ferrite particles was coated with solutions 14 to 21 at 70 ° C. and 200 mbar, cured at 90 ° C. and 50 mbar for 30 minutes, dried at 140 ° C. for 4 hours. The results are shown in Table 7.
Tabelle 7Table 7
Beschichtungsbeispiel 4Coating Example 4
Beschichtungen wurden in einem Wirbelbett-Reaktor unter folgenden Bedingungen auf 2 kg der Ferrit-Partikel mit den Lösungen 22 bis 27 aufgebracht:Coatings were applied in a fluidized bed reactor under the following conditions to 2 kg of the ferrite particles with solutions 22 to 27:
Bettemperatur: 100°CBed temperature: 100 ° C
Gastemperatur: 135°CGas temperature: 135 ° C
Sprührate: 90 kg/hSpray rate: 90 kg / h
Sprührichtung: von untenSpray direction: from below
Sprühdauer: 40 minSpray duration: 40 min
Danach wurde ca. 90 min bei 150°C Bettemperatur nachgehärtet und schließlich auf Raumtemperatur abgekühlt.The mixture was then cured for about 90 minutes at a bed temperature of 150 ° C. and finally cooled to room temperature.
Die Ergebnisse sind in Tabelle 8 aufgeführt. Tabelle 8The results are shown in Table 8. Table 8
Beschichtungsbeispiel 5Coating Example 5
7,5 kg der Ferritpartikel wurden mit Lösung 5 wie in Beschichtungsbeispiel 1 beschichtet und bei unterschiedlichen Bedingungen gehärtet. Die Ergbnisse sind in Tabelle 9 festgehalten.7.5 kg of the ferrite particles were coated with solution 5 as in coating example 1 and cured under different conditions. The results are shown in Table 9.
Tabelle 9Table 9
Beschichtungsbeispiel 6 Coating Example 6
1 kg Magnetit-Carrier CM 40-75 SH der Fa. Hoganas AB, S 26383 Hoganas (Schweden) mit einem mittleren Teilchendurchmesser von 65 μm und einer Sätti- gungsmagnetisierung von 90 emu/g wurde mit Lösung 28 und einer Beschichtungsmenge von 1,0 Gew.-% und einem Gehalt an b-1 von 4,0 Gew.-% beschichtet.1 kg of magnetite carrier CM 40-75 SH from Hoganas AB, S 26383 Hoganas (Sweden) with an average particle diameter of 65 μm and a saturation magnetization of 90 emu / g was mixed with solution 28 and a coating amount of 1.0 % By weight and a content of b-1 of 4.0% by weight.
Ωspez betrug 4 x 105 Ω cm; -Q/m betrug 9,3 μC/g.Ω spec was 4 x 10 5 Ω cm; -Q / m was 9.3 μC / g.
Beschichtungsbeispiel 7Coating Example 7
3,5 kg Glasperlen mit einem mittleren Durchmesser von 360 μm wurden mit Lösung 29 beschichtet. Die Beschichtungsmenge betrug 0,4 Gew.-%. Eine gut haftende Beschichtung wurde erhalten. Die beschichteten Glasperlen eignen sich als elektrofoto- grafische Cascaden-Entwickler nach Beimischung von Toner.3.5 kg of glass beads with an average diameter of 360 μm were coated with solution 29. The coating amount was 0.4% by weight. A well adhering coating was obtained. The coated glass beads are suitable as electrophotographic Cascaden developers after adding toner.
Beschichtungsbeispiel 8Coating Example 8
7,5 kg eines Ferrit-Carriers wie in Beispiel 6 wurden mit Lösung 30 bei 85°C und 980 mbar beschichtet, getrocknet und 2 Stunden bei 160°C gehärtet. Die Beschichtungsmenge betrug 2,1 Gew.-%, der Gehalt an b-7 1,0 Gew.-%.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.
Ωspez betrug 2,2 x 109 Ω cm; -Q/m betrug 16,1 μC/g; Abrieb: 0,12; Grobanteil >125 μm 0,9 Gew.-%.Ω spec was 2.2 x 10 9 Ω cm; -Q / m was 16.1 µC / g; Abrasion: 0.12; Coarse fraction> 125 μm 0.9% by weight.
Beschichtungsbeispiel 9Coating Example 9
7,5 kg Feπit-Carrier wie in Beispiel 6 wurden mit Lösung 31 bei 85°C und 980 mbar beschichtet, getrocknet und 4 Stunden bei 160°C gehärtet. Die Beschichtungsmenge betrug 1,6 Gew.-%, der Anteil an b-7 0,9 Gew.-%. Ω "ssppeezz betrug 1,5 x 108; -Q/m betrug 18,7 μC/g; Abrieb 0,14; Grobanteil >125 μm 0,1 Gew.-%.7.5 kg of Feπit carrier as in Example 6 were coated with solution 31 at 85 ° C. and 980 mbar, dried and cured at 160 ° C. for 4 hours. The coating amount was 1.6% by weight, the proportion of b-7 0.9% by weight. Ω " s sp pe e z z was 1.5 x 10 8 ; -Q / m was 18.7 μC / g; abrasion 0.14; coarse fraction> 125 μm 0.1% by weight.
Beschichtungsbeispiel 10Coating example 10
7,5 kg Ferrit-Camer wie in Beispiel 6 wurden mit Lösung 32 bei 85°C und 980 mbar beschichtet, getrocknet und 2 Stunden bei 140°C gehärtet. Die Beschichtungsmenge betrug 1,0 Gew.-%, der Anteil an b-7 2,0 Gew.-%.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.
Ω "ssppeezz betrug 1,5 x 108; -Q/m betrug 18 μC/g.; Abrieb: 0,12; Grobanteil >125 μm 0, Gew.-%.Ω " s sp pe e z z was 1.5 x 10 8 ; -Q / m was 18 μC / g; abrasion: 0.12; coarse fraction> 125 μm 0.% by weight.
Beschichtungsbeispiel 11Coating Example 11
7,5 kg Ferrit-Carrier wie in Beispiel 6 wurden mit Lösungen 33 bis 35 bei 85°C und7.5 kg ferrite carrier as in Example 6 were with solutions 33 to 35 at 85 ° C and
980 mbar beschichtet, getrocknet und 2 Stunden bei 140°C gehärtet. Die Ergebnisse sind in Tabelle 10 dargestellt:Coated 980 mbar, dried and cured at 140 ° C for 2 hours. The results are shown in Table 10:
Tabelle 10Table 10
Beispiel 12Example 12
Mit den nach den Beschichtungsbeispielen 2, Probe 2.3 und 9 hergestellten Carrier wurden Entwickler hergestellt und durch Beimischung von Toner im Dauerdrucktest in einem digitalen Fabdrucker (Chromapress® der Fa. Agfa-Gevaert AG) geprüft. Es wurden über 400 000 Kopien des Formates DIN A4 mit gleichbeibend guter Qualität hergestellt.Developers were produced with the carriers produced according to coating examples 2, samples 2.3 and 9 and by adding toner in the continuous pressure test tested in a digital color printer (Chromapress ® from Agfa-Gevaert AG). Over 400,000 copies of the DIN A4 format were produced with consistently good quality.
Beispiel 13Example 13
Als eisenoxidhaltige Partikel für die Beschichtungsversuche wurden Mn-Mg-Ferrit- Teilchen der Firma Powdertech Co. Ltd. 217 Toyofuta, Kashiwa-Shi, Chiba (Japan) eingesetzt, die wie folgt charakterisiert werden:Mn-Mg ferrite particles from Powdertech Co. Ltd. were used as particles containing iron oxide for the coating experiments. 217 Toyofuta, Kashiwa-Shi, Chiba (Japan), which are characterized as follows:
d50: 51 μmd50 : 51 μm
Dichte: 2,34 g/cm3 Density: 2.34 g / cm 3
S ättigungsmagnetisierung : 60-70 emu/gSaturation magnetization: 60-70 emu / g
Widerstand: 4 • 108 Ohm • cmResistance: 4 • 10 8 ohms • cm
7,5 kg der Ferritpartikel wurden mit den Lösungen 36 und 37 bei 85°C und 980 mbar beschichtet, getrocknet und durch 2-stündiges Erhitzen auf 140°C gehärtet. Die Ergebnisse stehen in Tabelle 11.7.5 kg of the ferrite particles were coated with solutions 36 and 37 at 85 ° C. and 980 mbar, dried and hardened by heating at 140 ° C. for 2 hours. The results are shown in Table 11.
Tabelle 11Table 11
Die Lösungen 36 und 37 wurden wie folgt hergestellt:Solutions 36 and 37 were made as follows:
39,7 g des nach Beispiel 15 (s.u.) hergestellten Oligomers, 15,0 g Isopropanol, 37,7 g39.7 g of the oligomer prepared according to Example 15 (see below), 15.0 g of isopropanol, 37.7 g
Tetraethylorthosilikat, 8,25 g Wasser und 0, 16 g para-Toluolsulfonsäure wurden unter Rühren in dieser Reihenfolge zusammengegeben und für eine weitere Stunde gerührt. Danach wurde mit 204,9 g Isopropanol verdünnt und, im Fall der Lösung 37, 0,2 g (b-7) zugegeben.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.
Beispiel 14: Herstellung von l,3,5,7-Tetramethyl-l,3,5,7-tetra-(2-(dichlormethyl- silyl)ethylen)-cyclotetrasiloxanExample 14: Preparation of 1,3,5,7-tetramethyl-1,3,5,7-tetra- (2- (dichloromethylsilyl) ethylene) -cyclotetrasiloxane
229,3 g (0,667 mol) l,3,5,7-Tetramethyl-l,3,5,7-tetravinyl-cyclotetrasiloxan, 125 g Xylol und 36 mg Platin-Katalysator wurden unter Rühren auf 60°C erwärmt. An- schließend wurden 252,1 g (2,668 mol) Methyldichlorsilan zugetropft. Es fand eine exotherme Reaktion statt. Nach Beendigung des Zutropfens wurde noch 2 Stunden unter Rückfluß gerührt. Nach Abkühlen auf Raumtemperatur wurde mit N2 belüftet, Filterhilfsmittel (Kieselgur) zugesetzt und filtriert. Das Produkt wurde ohne weitere Untersuchung für weitere Synthesen eingesetzt.229.3 g (0.667 mol) l, 3,5,7-tetramethyl-l, 3,5,7-tetravinyl-cyclotetrasiloxane, 125 g xylene and 36 mg platinum catalyst were heated to 60 ° C. with stirring. 252.1 g (2.668 mol) of methyldichlorosilane were then added dropwise. An exothermic reaction took place. After the dropping had ended, the mixture was stirred under reflux for 2 hours. After cooling to room temperature, the mixture was aerated with N 2 , filter aids (diatomaceous earth) were added and the mixture was filtered. The product was used for further syntheses without further investigation.
Beispiel 15: Herstellung des Kondensationsproduktes von 1,3,5,7-Tetramethyl- 1,3,5, 7-tetra-(2-(diethoxymethylsilyl)ethylen)-cyclotetrasiloxanExample 15: Preparation of the condensation product of 1,3,5,7-tetramethyl-1,3,5,7-tetra- (2- (diethoxymethylsilyl) ethylene) cyclotetrasiloxane
600 g der gemäß Beispiel 14 hergestellten Lösung von 1,3,5,7-Tetramethyl-1,3,5,7- tetra-(2-(dichlormethylsilyl)ethylen)-cyclotetrasiloxan wurden vorgelegt. Hierzu wurden bei einem Druck von ca. 500 mbar 500 g Ethanol unter die Flüssigkeitsoberfläche eingeleitet. Anschließend wurde bis zu einem Druck von .10 mbar und einer Temperatur von 60°C destilliert und mit N2 belüftet. Dann wurden weitere 250 g Ethanol zugegeben und bis zu einem Druck von 10 mbar und einer Temperatur. von 100°C destilliert und dann mit N2 belüftet. Über ein Gaseinleitungsrohr wurde bis zur Sättigung Ammoniak eingeleitet und 4 Stunden gerührt. Anschließend wurde überschüssiges Ammoniak entfernt und Ammoniumchlorid abfiltriert. Das Filtrat wurde mit Na2CO3 neutralisiert, mit Filterhilfsmittel (Kieselgur) versetzt und bis 130°C bei einem Druck von 10 mbar ausgeheizt.600 g of the solution of 1,3,5,7-tetramethyl-1,3,5,7-tetra- (2- (dichloromethylsilyl) ethylene) -cyclotetrasiloxane prepared according to Example 14 were presented. For this purpose, 500 g of ethanol were introduced under the liquid surface at a pressure of approximately 500 mbar. The mixture was then distilled to a pressure of .10 mbar and a temperature of 60 ° C. and aerated with N 2 . Then a further 250 g of ethanol were added and up to a pressure of 10 mbar and a temperature. distilled from 100 ° C and then aerated with N 2 . 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.
Das Produkt fiel als klare Flüssigkeit mit einer Viskosität von 80 mPa.s, einer Dichte von 1,00 g/ml und einer Restmenge an hydrolysierbarem Chlor von 7 ppm an. Mittels schneller Gelpermeationschromatographie (SGPC) mit Dichlormethan als Lösungsmittel und IR- und RI-Detektor wurde die Molmassenverteilung ermittelt. Das Kondensationsprodukt von 1,3,5, 7-Tetramethyl- 1,3,5, 7-tetra-(2-(diethoxy-methylsilyl)- ethylen)-cyclotetrasiloxan lag als kontinuierliche Molmassenverteilung mit einem mitt- leren Zahlenmittel (Mj von 1 350 g/mol und einem mittleren Gewichtsmittel vonThe 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. Means Rapid gel permeation chromatography (SGPC) with dichloromethane as solvent and IR and RI detector, the molecular weight distribution was determined. 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
3 355 g/mol vor. 3,355 g / mol.

Claims

Patentansprüche claims
1. Partikel (A), die mit einem Material (B) beschichtet sind, wobei das Material (B) ein monomeres, polyfünktionelles Organosilan und/oder ein Hydrolyse- produkt daraus und/oder ein Reaktionsprodukt daraus mit einem heteroatomhaltigen Organosilan und/oder einem Alkoxid ist.1. Particles (A) which are coated with a material (B), the material (B) being a monomeric, polyfunctional organosilane and / or a hydrolysis product thereof and / or a reaction product thereof with a heteroatom-containing organosilane and / or Is alkoxide.
2. Beschichtete Partikel nach Anspruch 1, dadurch gekennzeichnet, daß die Partikel (A) anorganisches Material enthalten.2. Coated particles according to claim 1, characterized in that the particles (A) contain inorganic material.
3. Beschichtete Partikel nach Anspruch 1, dadurch gekennzeichnet, daß die Partikel (A) anorganische Partikel sind.3. Coated particles according to claim 1, characterized in that the particles (A) are inorganic particles.
4. Beschichtete Partikel nach Anspruch 1, dadurch gekennzeichnet, daß die Par- tikel (A) magnetische Carrier-Teilchen für elektrostatografische Prozesse sind.4. Coated particles according to claim 1, characterized in that the particles (A) are magnetic carrier particles for electrostatographic processes.
5. Beschichtete Partikel nach Anspruch 1, dadurch gekennzeichnet, daß das he- teroatomhaltige Organosilan ein stickstoffhaltiges Organosilan oder ein fluor- haltiges Organosilan ist.5. Coated particles according to claim 1, characterized in that the heteroatom-containing organosilane is a nitrogenous organosilane or a fluorine-containing organosilane.
6. Beschichtete Partikel nach Anspruch 5, dadurch gekennzeichnet, daß das stickstoffhaltige Alkoxysilan der allgemeinen Formel (I)6. Coated particles according to claim 5, characterized in that the nitrogen-containing alkoxysilane of the general formula (I)
(R2)2-N[(CH2)mNR2]n(CH2)mSi(OR3)3.0(R4)0 (I)(R 2 ) 2 -N [(CH 2 ) m NR 2 ] n (CH 2 ) m Si (OR 3 ) 3 . 0 (R 4 ) 0 (I)
entspricht,corresponds to
worinwherein
m 1 bis 10, n 0 bis 2, o 0 bis 2, R2 H, Alkyl oder Aryl,m 1 to 10, n 0 to 2, o 0 to 2, R 2 H, alkyl or aryl,
R3, R4 Alkyl oder Aryl, bedeuten.R 3 , R4 are alkyl or aryl.
7. Beschichtete Partikel nach Anspruch 1, dadurch gekennzeichnet, daß die Alkoxide der allgemeinen Formel (II)7. Coated particles according to claim 1, characterized in that the alkoxides of the general formula (II)
M^OR^y (II)M ^ OR ^ y (II)
entsprechen, worincorrespond to what
Mj Si, Sn, Ti, Zr, B oder AIM j Si, Sn, Ti, Zr, B or AI
Rj Alkyl oder Aryl und y im Falle von Si, Sn, Ti, Zr 4 und im Falle von B oder AI 3 bedeuten.R j is alkyl or aryl and y in the case of Si, Sn, Ti, Zr 4 and in the case of B or Al 3.
8. Beschichtete Partikel nach Anspruch 4, dadurch gekennzeichnet, daß die magnetischen Caπierteilchen magnetische Eisenoxidpigmente der Formel (III)8. Coated particles according to claim 4, characterized in that the magnetic Caπierpartchen magnetic iron oxide pigments of the formula (III)
(M2O)x (Fe2O3)z (III)(M 2 O) x (Fe 2 O 3 ) z (III)
worinwherein
M2 Li, Mg, Sr, Ba, Mn, Fe (II), CO, Ni, Cu, Zn, Cd bedeuten undM 2 is Li, Mg, Sr, Ba, Mn, Fe (II), CO, Ni, Cu, Zn, Cd and
das molare Verhältnis von x zu z zwischen 0 und 1 liegt.the molar ratio of x to z is between 0 and 1.
9. Beschichtete anorganische Partikel nach Anspruch 1, dadurch gekennzeichnet, daß die polyfunktionellen Organosilane mindestens 2 Siliciumatome mit jeweils 1 bis 3 hydrolysierbaren und/oder kondensationsvernetzenden Gruppen enthalten und die Siliciumatome mit jeweils einer Si, C-Bindung an eine die Siliciumatome verknüpfende Baueinheit gebunden sind. 9. Coated inorganic particles according to claim 1, characterized in that the polyfunctional organosilanes contain at least 2 silicon atoms, each with 1 to 3 hydrolyzable and / or condensation-crosslinking groups, and the silicon atoms are bonded with a Si, C bond to a unit linking the silicon atoms .
10. Beschichtete anorganische Partikel nach Anspruch 1, dadurch gekennzeichnet, daß die polyfunktionellen Organosilane Verbindungen der allgemeinen Formeln (IV), (V) und(VI) sind:10. Coated inorganic particles according to claim 1, characterized in that the polyfunctional organosilanes are compounds of the general formulas (IV), (V) and (VI):
(R5)4.iSi[(CH2)pSi(OR6)a(R7)3.a]i (IV)(R 5 ) 4 . i Si [(CH 2 ) p Si (OR 6 ) a (R 7 ) 3 . a ] i (IV)
Ru^SitOSiCR! ι) (CH2)rSi(OR12)c(R13)3.c]k (VI)Ru ^ SitOSiCR! ι) (CH 2 ) r Si (OR 12 ) c (R 13 ) 3 . c ] k (VI)
woπnwoπn
i 2 bis 4,i 2 to 4,
P 1 bis 4,P 1 to 4,
R5 Alkyl oder Aryl,R 5 alkyl or aryl,
R Wasserstoff, Alkyl oder Aryl, wenn a 1 ist und Alkyl oder Aryl, wenn a 2 oder 3 ist,R is hydrogen, alkyl or aryl if a is 1 and alkyl or aryl if a is 2 or 3,
R7 Alkyl oder Aryl, a 1 bis 3 m 3 bis 6, q 2 bis 10,R 7 alkyl or aryl, a 1 to 3 m 3 to 6, q 2 to 10,
R8 CrC6-Alkyl oder C6-C14-Aryl,R 8 C r C 6 alkyl or C 6 -C 14 aryl,
R9 Wasserstoff, Alkyl oder Aryl, wenn b 1 ist, oder Alkyl oder Aryl, wenn b 2 oder 3 ist,R 9 is hydrogen, alkyl or aryl if b is 1 or alkyl or aryl if b is 2 or 3,
R10 Alkyl oder Aryl, r 1 bis 10, c 1 bis 3, k 2 bis 4, R 10 alkyl or aryl, r 1 to 10, c 1 to 3, k 2 to 4,
Rπ Alkyl oder Aryl,R π alkyl or aryl,
R12 H, Alkyl oder Aryl, wenn c 1 und Alkyl oder Aryl, wenn c 2 oder 3 ist,R 12 is H, alkyl or aryl when c is 1 and alkyl or aryl when c is 2 or 3,
R13 Alkyl oder Aryl undR 13 is alkyl or aryl and
R14 Alkyl oder Aryl bedeuten.R14 is alkyl or aryl.
11. Beschichtete anorganische Partikel nach Anspruch 1, dadurch gekennzeichnet, daß sie kugelförmig sind, einen mittleren Teilchendurchmesser von 20 bis 200 μm aufweisen und die Menge der aufgebrachten Beschichtung 0, 1 bis 10 Gew.-%, bezogen auf anorganischen Kern, beträgt. 11. Coated inorganic particles according to claim 1, characterized in that they are spherical, have an average particle diameter of 20 to 200 microns and the amount of coating applied is 0.1 to 10 wt .-%, based on the inorganic core.
EP98924296A 1997-05-23 1998-05-11 Coated particles Withdrawn EP0981780A1 (en)

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

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