EP1163291A1 - Composites plastique contenant des oxydes metalliques - Google Patents

Composites plastique contenant des oxydes metalliques

Info

Publication number
EP1163291A1
EP1163291A1 EP00912473A EP00912473A EP1163291A1 EP 1163291 A1 EP1163291 A1 EP 1163291A1 EP 00912473 A EP00912473 A EP 00912473A EP 00912473 A EP00912473 A EP 00912473A EP 1163291 A1 EP1163291 A1 EP 1163291A1
Authority
EP
European Patent Office
Prior art keywords
plastic
component
plastic composites
less
oxidic compound
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Withdrawn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
EP00912473A
Other languages
German (de)
English (en)
Inventor
Juan Conzalez-Blanco
Jochen Mahrenholtz
Cliff Scherer
Stefanie KLINGELHÖFER
Werner Hoheisel
Jens Sicking
Lars KRÜGER
Ingo Steffens
Ulrike Pitzer
Gregor Kaschel
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.)
Bayer AG
Dow Produktions und Vertriebs GmbH and Co OHG
Original Assignee
Bayer AG
Wolff Walsrode 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 DE10004461A external-priority patent/DE10004461A1/de
Application filed by Bayer AG, Wolff Walsrode AG filed Critical Bayer AG
Publication of EP1163291A1 publication Critical patent/EP1163291A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals

Definitions

  • the invention relates to UV-absorbing plastic composites based on fine particulate fillers, which contain oxidic metal compounds, and to processes for their production.
  • Plastic foils made of polyamide and (thermoplastic) polyurethane are particularly preferred, which enable the products packaged therein, such as foodstuffs, to have improved UV protection and still retain their transparency.
  • the task was to produce plastic composites with particulate UV protection agents, which, in addition to the desired UV protection of the plastics and the packaging, have a speck-free plastic surface.
  • Fillers are used in plastics to improve mechanical properties (e.g. modulus of elasticity, impact strength, tensile strength), to increase heat stability, thermal and electrical conductivity, to improve UV stability or for coloring properties. They are usually added in a mass fraction of up to 60% by weight. Examples of such fillers are: talc, mica, kaolin, glass fibers, oxides, carbon black, starch.
  • a surface treatment is carried out, for example, with Polymers to achieve a good compatibility of the fillers in the plastic matrix.
  • Mass fractions in% of the kaolin to be ground should be added to cationic dispersing agents.
  • the ⁇ ass reduction range is defined down to 0.1 ⁇ m.
  • Widespread fine particulate fillers for plastics with primary particle sizes ⁇ 100 nm are, for example, silicon dioxide (Aerosil ® ) and carbon black: Aerosil ® (Degussa AG; Pigments series: Hydrophobic Aerosil ® , production, properties and applications) has primary particles from 5 to 50 nm in diameter; Carbon black (Degussa AG; Pigments series: Degussa carbon black pigments and pigment black preparations for plastics) with primary particle diameters from 10 to 100 nm.
  • Fine particulate powders with a primary particle diameter ⁇ 100 nm tend to agglomerate due to the high van der Waal forces; the stronger capillary forces also have an effect on pastes, so that it is not possible to take advantage of these powders (Nanostructured Materials 8 (4), 399 (1997)).
  • these fine particulate powders are aggregated, for example by sintering, partial melting or surface reactions, sinter bridges are formed which no longer allow redispersion (Nanostructured Materials, ibid.).
  • fine particulate fillers for plastics are, for example, colloidal SiO 2 suspensions with primary particle diameters between 5 - 150 nm (DD-A-
  • this method has the disadvantage that colloidal suspensions are usually precipitated in water. Furthermore, in this process the mostly aqueous phase has to be replaced by organic solvents and / or reactive monomers; this is associated with a high economic outlay. Another disadvantage of this process is that it can lead to agglomeration of the primary particles.
  • UV-absorbing plastic composites based on finely particulate fillers which contain oxidic metal compounds, can be produced by the process described below, the transparency of the moldings being retained.
  • Plastic foils made of polyamide and (thermoplastic) polyurethane are particularly preferred, in particular they should enable the products packaged therein, such as food, to have improved UV protection.
  • the primary particle size of the oxidic metal compounds used for spherical particles is between 0.5-50 nm. For needle-shaped (or ellipsoidal) particles, the longest axis has a value less than 300 nm. According to the invention, these particles, agglomerates or aggregates are wet comminuted.
  • finely particulate oxidic metal compounds by means of wet grinding could be used to produce concentrated suspensions with an average particle diameter of less than 100 nm.
  • the suspensions were prepared in the solvents or reactive monomers as they are required for the subsequent polymerization to give the corresponding plastic composites.
  • suspensions were then polymerized to a plastic composite, optionally after further dilution with monomers.
  • the suspensions produced in this way show a high stability in agglomeration and sedimentation.
  • the potential to absorb UV light can already be determined on the suspensions containing TiO 2 . It can be seen that acicular particles even have a higher absorption efficiency than spherical particles. This effect enables even more effective UV protection when installing needle-shaped particles in a plastic composite than when using the same mass of spherical particles.
  • the following table compares the absorption coefficient (as a function of the wavelength) of a suspension consisting of acicular primary particles with a length of approx. 80 nm and a thickness of approx. 10 nm that of spherical primary particles (diameter approx. 10 nm).
  • the mean particle diameter of the suspensions is defined as the d 0 value using the ultracentrifuge method (mass distribution).
  • d 50 means that 50% of the particles (based on the mass) are smaller than the specified size.
  • UV absorber is optically neutral.
  • the UV absorber should not make a significant contribution to light scattering and thus to clouding the composite. Since the efficiency for light scattering increases in proportion to the volume of a particle, breaking the needles into smaller units is advantageous in order to keep clouding of the plastic composite to a minimum.
  • Insulated primary particles of acicular morphology which are compared with the starting particle size by the process, are preferably incorporated into the plastic films. wet crushing to about half of the initial size of the longest axis of the primary particles. Due to the genuinely comminuted needle-shaped primary particles in the plastic films, it was possible to achieve a lower turbidity of the composite compared to the genuinely comminuted primary particles of acicular morphology.
  • Polymer composites based on polyamide and on (thermoplastic) polyurethane with titanium dioxide and cerium dioxide as fillers are preferred.
  • Polyamide films and (thermoplastic) polyurethane films with a plastic thickness of less than 200 ⁇ m are particularly preferred.
  • Plastic composites that contain magnetic oxides such as magnetite or maghemite as fillers show magnetic properties.
  • the application relates to the use of the plastic composites according to the invention for the production of moldings.
  • the invention also relates to moldings produced from plastic composites according to the invention and the processes described in the claims.
  • the application also relates to plastic composites according to the invention, characterized in that the oxidic compound is present as primary particles, agglomerate, aggregate and / or as a mixture thereof, the agglomerates and aggregates having an average particle size of less than 100 nm.
  • the application relates to plastic composites containing at least one finely dispersed oxidic compound (component a) with an average particle size of less than 100 nm, which is an oxide of the elements Ti, Zn, Sn, W, Mo, Ni, Wi, Ce , In, Hf, Fe, whereby of these oxides individual or mixtures of oxides from this group can be used and / or
  • plastic composites according to the invention characterized in that the plastic matrix made of polyamide films with a thickness of less than
  • the titanium dioxide particles in the composite have an ellipsoidal morphology and the longest axis is less than 50 nm, preferably less than 40 nm.
  • the application also relates to plastic composites according to the invention, characterized in that the plastic matrix consists of polyamide foils with a thickness of less than 200 ⁇ m, wherein the polyamide foil can also be part of a composite foil.
  • the invention relates to plastic composites containing at least one oxide
  • PSE such as, for example, BaTiO 3 , CaTiO 3 , SrTiO 3 , BaZrO 3 , CaZrO 3 , SrZrO 3 , with a spherical morphology and an average primary particle size of less than 50 nm, preferably less than 30 nm and particularly preferably less than 15 nm and / or an acicular or ellipsoidal morphology, the longest axis being less than 100 nm.
  • the invention further relates to the production of these plastic composites based on suspensions obtained by wet grinding and containing compounds of component a).
  • auxiliaries which are customary per se, such as, for example, surfactants and polymers, preferably surfactants.
  • the suspensions according to the invention - if appropriate a further proportion - of component (d) and any polymerization initiators which may be required are added.
  • the polymerization is then carried out in a manner known per se to the person skilled in the art, e.g. through an increase in temperature.
  • the compounds of component a) include at least one oxide of the elements Ti, Zn, Sn, W, Mo, Ni, Wi, Ce, In, Hf, Fe, with individual but also mixtures of oxides from this group being used can and / or reaction products of oxides of metals of the fourth, fifth and sixth subgroup (IVb, Vb, VIb) of the Periodic Table (PSE) with hydroxides and / or
  • Carbonates of the metals of the first and second main groups (I, II) of the PSE preferably BaTiO 3 , CaTiO 3 , SrTiO 3 , BaZrO 3 , CaZrO 3 , SrZrO 3 , with a spherical morphology and an average primary particle size of less than 50 nm, are preferred less than 30 nm and particularly preferably less than 15 nm and / or a needle-shaped or ellipsoidal morphology, the longest axis being less than
  • 300 nm preferably less than 200 nm, particularly preferably less than 100 nm. is.
  • the oxides to be used according to the invention can be produced, for example, using the following processes: flame hydrolysis, flame pyrolysis, plasma processes, sol-gel processes, controlled nucleation and growth processes and
  • Emulsion and microemulsion processes The morphology and average particle size of the primary particles of the powders and pastes of the oxides can be determined with the aid of electron micrographs.
  • the primary particles of the oxides can have a spherical shape. They can also be in the form of their agglomerates or aggregates, these having an average particle size of less than 100 nm.
  • the primary articles can also be acicular or ellipsoidal morphology.
  • the longest axis should be less than 300 nm, preferably less than 200 nm and particularly preferably less than 100 nm.
  • Particularly preferred compounds of component a) are titanium dioxide and cerium dioxide.
  • Another particularly preferred component (a) is also BaTiO 3 .
  • Iron oxides are also preferred.
  • the preferred oxides also include oxides with a finite magnetization, for example ferrites, in particular maghemite and magnetite.
  • the compounds of component (a) contained in the plastic composites according to the invention can be present either in the form of their primary particles, agglomerates or aggregates of primary particles or mixtures of the two.
  • Agglomerates or aggregates are understood to be particles in which several primary particles interact with one another via van der Waals forces, or in which the Primä ⁇ modifier are connected by surface reaction or "sintering" during the manufacturing process.
  • the primary particles can optionally additionally have a coating with at least one further inorganic oxide, preference being given to silicon dioxide, zirconium dioxide and aluminum oxide.
  • Component (a) is preferably used in an amount of 5 to 30% by weight, in particular 10 to 30% by weight, particularly preferably 15 to 30% by weight, based on the total preparation, the amounts given on the
  • pH regulators are to be understood. These include inorganic mineral acids such as sulfuric acid, hydrochloric acid, nitric acid, perchloric acid and organic acids such as benzenesulfonic acid, 1-naphthalenesulfonic acid, chloroacetic acid, terephthalic acid, trichloroacetic acid. Benzene sulfonic acid is particularly preferred.
  • Component (b) is preferably used in an amount of 0.001 to 5% by weight, based on the total preparation, the amounts given being based on the suspension.
  • Suitable solvents (c) are, for example: water, aliphatic C 1 -C alcohols, such as methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol or tert-butanol, aliphatic ketones, such as acetone, methyl ethyl ketone, Methyl isobutyl ketone or diacetone alcohol, polyols, such as ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, trimethylolpropane, polyethylene glycol with an average molecular weight of 100 to 4000, preferably 400 to 1500 g / mol or
  • Glycerol monohydroxyether, preferably monohydroxyalkylether, particularly vorzugt mono-C ⁇ -C -alkylglykolether as Ethylenglykolmonoalkyl-, -monomethyl-, -diethylenglykolmonomethylether or diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monoethyl ether, thiodiglycol, triethylene glycol monomethyl ether or monoethyl ether, also 2-pyrrolidone, N-methyl-2-pyrrolidone, N -Ethyl-pyrrolidone, N-vinyl-pyrrolidone, 1,3-dimethyl-imidazolidone, dimethylacetamide and dimethylformamide.
  • mono-C ⁇ -C -alkylglykolether as Ethylenglykolmonoalkyl-, -monomethyl-, -diethylenglykolmonomethylether
  • Component (c) is preferably used in an amount of 19 to 12% by weight, in particular 18 to 12.5% by weight, particularly preferably 16.9 to 12.5% by weight, based on the total preparation , is used, the amounts given being based on the suspension.
  • Suitable monomers d) are, for example:
  • Caprolactams in particular ⁇ -caprolactam; Dicarboxylic acids, especially adipic acid; Diamines, especially hexamethylenediamine; Polyols-polyethers; Polyols-polyester; Diisocyanates, especially toluene diisocyanate, hexamethylene diisocyanate, 4,4 'methylene di (phenyl isocyanate), 4,4' methylene di (cyclohexyl isocyanate).
  • Component (d) is preferably used in an amount of 75.9 to 48% by weight, in particular 71.9 to 50% by weight, particularly preferably 68 to 50% by weight, based on the total preparation , the quantities being based on the suspension.
  • Suitable auxiliaries such as surfactants or polymers are to be regarded as component e).
  • Component (e) is preferably used in an amount of 0.05 to 5% by weight, in particular 0.05 to 2.5% by weight, based on the total preparation, the amounts given being based on the suspension .
  • the plastic composites according to the invention are produced from suspensions of components (a), (b), (c), (d) and optionally (e).
  • component (a) is generally in powder form or in the form of the water-moist presscake together with part of the pH regulator b) optionally the solvent (c) and with the monomers d) to give a homogeneous grinding suspension, for example by means of an agitator chute, Dissolvers and similar aggregates, if necessary after pre-shredding, struck (ie introduced and homogenized).
  • the wet comminution of component (a) includes both the pre-comminution and the fine grinding.
  • the solids concentration of component (a) of the suspension is preferably above the desired concentration of the finished suspension.
  • the desired final concentration is preferably set after the pre-comminution. After the pre-crushing, grinding is carried out to the desired particle size distribution. Come for this grind
  • Units such as kneaders, roller mills, kneading screws, ball mills, rotor-stator mills, dissolvers, corundum disc mills, vibrating mills and in particular high-speed, continuously or discontinuously charged agitator ball mills with grinding media with a diameter of 0J to 5 mm are possible.
  • the grinding media can be made of glass, ceramic or metal, e.g. Be steel.
  • Grinding temperature is preferably in the range of 0 to 250 ° C, but usually at room temperature, especially below the cloud point of the surfactant used (component e).
  • the grinding can be carried out partially or completely in a high-pressure homogenizer or in a so-called jet disperser (known from DE-A-19 536 845), as a result of which the grinding body abrasion content in the suspension or Release of soluble substances from the grinding media, can be reduced to a minimum or completely avoided.
  • a so-called jet disperser known from DE-A-19 536 845
  • the wet comminution of ellipsoidal or needle-shaped primary particles in an agitator ball mill at agitator speeds of at least 3000 revolutions per minute and comminution bodies made of zirconium dioxide with a grain size between 0.3 and 0.4 mm leads to real comminution, i.e. for breaking the ellipsoidal primary particles into smaller units.
  • an agitator ball mill with an inner lining made of silicon carbide and with a ceramic disk stirrer made of silicon carbide is used.
  • the suspension obtained is mixed in the desired monomers of component (d) and possibly with further pH regulators of component b) and homogenized, and adjusted to the desired final concentration.
  • these are optionally finely filtered, for example using 0.5 to 5 ⁇ m membrane or glass filters.
  • the plastic composites according to the invention are produced on the basis of the suspensions of components (a), (b), (c), (d) and optionally (e).
  • the suspensions produced according to the invention are polymerized.
  • the necessary polymerization initiators must also be added.
  • the suspensions prepared according to the invention can also be dried after being dispersed in a stirred ball mill. Drying temperatures of 20 to 150.degree. C., in particular 50 to 120.degree. C., are preferably used, with the application of a vacuum also being advantageous.
  • Drying is generally carried out using the usual drying apparatus such as paddle dryers, drying cupboards, spray dryers, fluidized bed dryers, freeze drying etc.
  • the residual water content after drying is preferably less than 2% by weight, based on the solids content.
  • the thus dried and modified oxidic compound (or additive) can be incorporated (compounded) with granules of thermoplastic materials, for example in an extruder, into the plastic matrix.
  • the plastic composites thus produced according to the invention preferably consist of
  • Polyamide or (thermoplastic) polyurethane are polyamide or (thermoplastic) polyurethane.
  • the plastic composites thus produced according to the invention particularly preferably consist of polyamide and / or (thermoplastic) polyurethane.
  • Component (a) is preferably present in an amount of 5 to 30% by weight, in particular 10 to 30% by weight, particularly preferably 15 to 30% by weight, based on the total preparation used, the quantities being based on the suspension.
  • Component (b) is preferably used in an amount of 0.001 to 5% by weight, based on the total preparation, the amounts given being based on the suspension.
  • Component (c) is preferably used in an amount of 19 to 12% by weight, in particular 18 to 12.5% by weight, particularly preferably 16.9 to 12.5% by weight, based on the total preparation , is used, the amounts given being based on the suspension.
  • Component (d) is preferably used in an amount of 75.9 to 48% by weight, in particular 71.9 to 50% by weight, particularly preferably 68 to 50% by weight, based on the total preparation , the quantities being based on the suspension.
  • Component (e) is preferably used in an amount of 0.05 to 5% by weight, in particular 0.05 to 2.5% by weight, based on the total preparation, the amounts given being based on the suspension .
  • suspensions according to the invention if appropriate a further portion, component (d) and any required poly- merization initiators too.
  • the polymerization is then carried out in a manner known per se to the person skilled in the art, for example by increasing the temperature.
  • Plastic composites according to the invention are preferably characterized in that the plastic matrix consists of polyamide films with a thickness of less than 200 ⁇ m, the polyamide film also possibly being part of a composite film.
  • the finished polymer composite according to the invention contains 0.01-30% by weight of component a), preferably 0.05-10% by weight, particularly preferably 0.5-5% by weight.
  • This suspension is wet-crushed in a stirred ball mill, Drais-PML-V / H, using grinding balls made of zirconium oxide with a size of 0.3 to 0.4 mm, crushing body filling degree 70%, stirrer speed 4000 rpm over a period of 360 minutes.
  • the agitator and the inner material consist of silicon carbide.
  • the particle characterization was carried out using the ultracentrifuge (mass distribution) method. The following values were determined for the mass distribution:
  • dio means that 10% of all particles are not larger than 44 nm
  • d50 means that 50% of all particles are not larger than 65 nm
  • d90 means that 90% of all particles are not larger than 102 nm.
  • particles are to be understood as primary particles as well as aggregates or agglomerates.
  • dio means that 10% of all particles are not larger than 21 nm
  • d50 means that 50% of all particles are not larger than 33 nm
  • d ⁇ 0 means that 90% of all particles are not larger than 51 nm.
  • particles are to be understood as primary particles as well as aggregates or agglomerates.
  • 60 g of the wet-crushed suspension are added to 940 g of a ⁇ -caprolactam melt at 90 ° C. in a cylindrical, double-walled glass apparatus with a heated drain, a filling volume of approx. 1 liter and a metal spiral stirrer. After triple N compensation, the mixture is heated to 200 ° C. with stirring. After one hour at 200 ° C, the temperature is raised to 270 ° C and held for 4 hours. The melt is then spun off and the strand obtained is granulated. After 10 hours of extraction with water in the Soxhlet apparatus, the granules are dried in a water jet vacuum for 48 hours.
  • the dry material is used on a conventional flat film line
  • Nozzle 300 mm, flexible lip
  • Casting roller, chrome-plated The film has a thickness of 50 ⁇ m and contains 1% by weight of TiO. It appears transparent and has no specks on the surface. Their UV protection properties are shown in the following table, in which the light transmission values are plotted in comparison to a pure, unfilled polyamide film.
  • the dry material is processed on a conventional flat film line with a single screw extruder to a mono flat film with a width of 300mm and a thickness of 50 ⁇ m at a melt temperature of 270 ° C and a chill roll temperature of 90 ° C.
  • the system (type Riehne) consists of the following units:
  • Nozzle 300 mm, flexible lip
  • the film has a thickness of 50 ⁇ m and contains 1% by weight of TiO. It appears transparent and has specks on the surface. It also has a higher one
  • hematite (Sicotrans L2816 ® BASF, primary article size: length approx. 100 nm, width approx. 10 nm with agglomerate sizes of up to several ⁇ m, determined by means of transmission electron microscopy) are dissolved in 2000 g of a solution of ⁇ -caprolactam in deionized water (80 wt .Tln. ⁇ -caprolactam and 20 parts by weight of water) with intensive mixing with a laboratory stirrer and the pH is adjusted to pH 2.5 with a benzenesulfonic acid solution.
  • This suspension is in a stirred ball mill, Drais-PML-V / H, using grinding balls made of zirconium oxide with a size of 0.3 to 0.4 mm, crushing fill level 70%, stirrer speed 4000 rpm for 30 minutes at a pH - Value of 2.5 to 3 wet crushed.
  • the agitator and the inner material of the mill are made of silicon carbide.
  • the particle characterization was carried out using the ultracentrifuge (mass distribution) method. The following values were determined for the mass distribution:
  • dio means that 10% of all particles are not larger than 19 nm
  • dso means that 50% of all particles are not larger than 29 nm
  • d90 means that 90% of all particles are not larger than 46 nm.
  • particles are to be understood as primary particles as well as aggregates or agglomerates.
  • maghemite press cake (Bayer AG, primary particle diameter 10 nm with agglomerate sizes of up to several ⁇ m, determined by means of transmission electron microscopy, solids content is 45% by weight) are dissolved in 1610 g of a solution of ⁇ -caprolactam in water (80 parts by weight ⁇ -Caprolactam and 20 parts by weight of water) with intensive mixing with an Ultraturrax and the pH is adjusted to pH 2.5 with a benzenesulfonic acid solution.
  • This suspension is in a stirred ball mill, Drais-PML-V / H, using grinding balls made of zirconium oxide with a size of 0.3 to 0.4 mm, crushing degree of filling 70%, stirrer speed 4000 rpm over a period of 60 minutes wet crushed at a pH of 2.5 to 3.
  • the agitator and the inner material of the mill are made of silicon carbide.
  • the suspension is then filtered under pressure through a filter sieve with a mesh size of 5 ⁇ m.
  • the particle characterization was carried out using the ultracentrifuge (mass distribution) method. The following values were determined for the mass distribution:
  • dio means that 10% of all particles are not larger than 23 nm
  • dso means that 50% of all particles are not larger than 40 nm
  • d90 means that 90% of all particles are not larger than 107 nm.
  • particles are to be understood as primary particles as well as aggregates or agglomerates.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

L'invention concerne des composites plastique à base de matières de charge à fines particules ou de matières de charge contenant des composés métalliques oxydiques, et leur procédé de production.
EP00912473A 1999-02-23 2000-02-17 Composites plastique contenant des oxydes metalliques Withdrawn EP1163291A1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE19907702 1999-02-23
DE19907702 1999-02-23
DE10004461A DE10004461A1 (de) 1999-02-23 2000-02-02 Metalloxide enthaltende Kunststoffkomponente
DE10004461 2000-02-02
PCT/EP2000/001289 WO2000050504A1 (fr) 1999-02-23 2000-02-17 Composites plastique contenant des oxydes metalliques

Publications (1)

Publication Number Publication Date
EP1163291A1 true EP1163291A1 (fr) 2001-12-19

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP00912473A Withdrawn EP1163291A1 (fr) 1999-02-23 2000-02-17 Composites plastique contenant des oxydes metalliques

Country Status (4)

Country Link
EP (1) EP1163291A1 (fr)
JP (1) JP2002537463A (fr)
AU (1) AU3423100A (fr)
WO (1) WO2000050504A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002072154A1 (fr) 2001-03-08 2002-09-19 Nanosolutions Gmbh Nanoparticules paramagnetiques
DE102017004563A1 (de) 2017-03-05 2018-09-06 Entex Rust & Mitschke Gmbh Entgasen beim Extrudieren von Polymeren
DE102018001412A1 (de) 2017-12-11 2019-06-13 Entex Rust & Mitschke Gmbh Entgasen beim Extrudieren von Stoffen, vorzugsweise von Kunststoffen

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Publication number Priority date Publication date Assignee Title
KR950023662A (ko) * 1994-01-20 1995-08-18 박홍기 권취성이 우수한 고투명성 폴리에스터 필름의 제조방법
DE4402873A1 (de) * 1994-02-01 1995-08-03 Basf Ag Zusammensetzungen, enthaltend Metallpartikel im Nanometergrößenbereich
DE69535370T2 (de) * 1994-06-06 2007-10-18 Catalysts & Chemicals Industries Co. Ltd., Kawasaki Thermoplastische harzfolie und verfahren zu ihrer herstellung
DE4433018C1 (de) * 1994-09-16 1996-04-25 Schulman A Plastics Polymere Zusammensetzung, Verfahren zu ihrer Herstellung und eine Verwendung

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Title
See references of WO0050504A1 *

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JP2002537463A (ja) 2002-11-05
WO2000050504A1 (fr) 2000-08-31
AU3423100A (en) 2000-09-14

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