Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
  • B41M5/267—Marking of plastic artifacts, e.g. with laser
• • 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
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
• • 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
  • Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
  • Y10T156/10—Methods of surface bonding and/or assembly therefor
• • 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
  • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
  • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]

Definitions

• Nanoparticulate metal boride composition and its use for marking plastic parts
• the present invention relates to a nanoparticulate alkaline earth or rare earth boride composition, a polymer composition and an ink composition containing such a nanoparticulate composition, a method for marking (marking) plastic parts, and the further use of such a nanoparticulate composition.
• Nanoscale particles Preparations of particles with particle sizes in the nanometer range (nanoscale particles) have found application in many fields of technology.
• E P-A-1529632 describes a multilayer article, e.g. Example in the form of a heat protective film comprising a core layer and at least a first cover layer.
• the core layer contains a thermoplastic polymer and an IR absorber.
• the first cover layer comprises a thermoplastic polymer and an additive which is capable of absorbing electromagnetic radiation.
• Nanoparticulate metal borides can be used as IR-absorbing additives.
• the IR absorber layer is produced starting from a masterbatch which contains the metal boride in a solid polymeric carrier, for example by extrusion or coextrusion.
• US-A-2004/0028920 describes a masterbatch composition containing a thermoplastic polymer and a metal hexaboride as a thermal radiation shielding component.
• US 6,663,950 describes an optically active composite film containing a polymeric binder based coating containing nanoparticulate antimony tin oxide and nanoparticulate lanthanum hexaboride.
• No. 6,911,254 describes glass laminates with LaB 6 - and optionally additionally doped tin oxide nanoparticles as well as colorants and further additives containing polymeric intermediate layers.
• the LaB 6 is either dispersed in the interlayer polymer or applied thereto in another layer.
• a LaB 6 preparation as described in US 6,663,950 or a 6.3 wt .-% LaB 6 preparation in triethylene glycol bis (2-ethyl) hexanoate used.
• WO 2005/059013 has a disclosure content comparable to that of US Pat. No. 6,663,950 and US Pat. No. 6,911,254.
• US Pat. No. 6,737,159 describes a polyvinyl butyral film which contains at least one quaterylene-type NIR absorber and optionally additionally an inorganic IR absorber, such as LaB 6 .
• US Pat. No. 6,620,872 describes a polyvinyl butyral composition containing dispersed lanthanum hexaboride nanoparticles, optionally mixed with doped tin oxides.
• a 2.2% by weight preparation of lanthanum hexaboride nanoparticles in toluene or in triethylene glycol bis (2-ethyl) hexanoate is used.
• E P-A-1008564 describes liquid compositions for the production of heat-shielding films containing nanoparticulate metal hexaboride particles in combination with nanoparticulate tin-containing indium oxides (ITO) or antimony-containing tin oxides (ATO).
• Suitable solvents are generally water and organic solvents, such as alcohols, ethers, esters or ketones, concrete isobutyl alcohol and 4-hydroxy-4-methylpentan-2-one are used.
• EP-A-0905100 describes a coating dispersion for forming a selectively transmissive film containing nanoparticulate particles, including lanthanum boride.
• EP-A-943587 describes a liquid coating agent for forming a film for shielding heat rays containing nanoparticulate metal borides.
• Nd-Y AG lasers and excimer lasers are increasingly being used for the laser marking of plastics.
• Many plastics such.
• polyolefins and polystyrenes can be difficult or impossible to mark with lasers without additional modification.
• a CO 2 laser that emits light in the infrared range at 10.6 microns
• polyolefins and polystyrenes even at very high power only weak, barely legible marking.
• Nd-YAG lasers also show no interaction.
• the plastic must neither fully reflect the laser light nor let it through completely, because then there is no interaction.
• the absorption of energy is too strong, the plastic may evaporate in the irradiated area, resulting in engraving and no visible graphic marking.
• EP-A-684144 describes a composition for coloring plastic parts by laser irradiation, which contains a mixture of at least one opacifier and at least one chromogenic compound.
• the opacifiers are selected from mica, nanoscale TiO 2 and metal oxides based on antimony oxide.
• WO 01/00719 describes a polymer composition containing a polymer and an additive which enables laser marking.
• antimony trioxide with a particle size> 0.5 microns in a concentration of at least 0.1 wt .-% is used.
• WO 95/30546 describes laser-markable plastics, in particular thermoplastic polyurethanes, which contain pigments which are coated with doped tin dioxide.
• WO 02/055287 describes a method for producing laser-welded composite moldings.
• WO 2005/102672 describes a method for the weld-joining of plastic parts with the aid of laser radiation, in which one of the plastic parts to be joined has a material absorbing the laser radiation in the connection region, which may inter alia be a lanthanide or alkaline earth metal hexaboride.
• the hexaboride is used as a 1% strength by weight batch in polymethyl methacrylate.
• DE-A-102004051457 describes dye-colored laser-weldable plastic materials which contain nanoscale laser-sensitive particles, such as lanthanum hexaboride. To prepare these colorants, the nanoscale particles are incorporated under high shear into the plastic matrix or a liquid monomer-containing starting composition.
• DE-A-10 2004 0105 04 describes highly transparent plastic materials which are laser-markable and / or laser-weldable due to their content of nanoscale laser-sensitive metal oxides.
• the preparation is analogous to the method described in DE-A-10 2004 051 457.
• DE-U-20 2004 003 362 has a disclosure content comparable to DE 10 2004 010 504.
• the absorption of the dopant is not maximal at the laser wavelength used for labeling. Thus, a higher use amount of the dopant is required, which is often above 0.1%.
• antimony-containing dopants is undesirable because of the undesirable heavy metal loading of the doped plastics.
• Some of the pigments used hitherto as dopant, such as antimony-doped tin oxide, are electrically conductive. Their use increases the conductivity of the additized plastic and thus reduces its creep resistance, which is unfavorable for certain applications.
• WO 2006/029677 describes laser-markable and / or laser-weldable polymers which contain at least one boride compound as absorber, it being possible, for example, to obtain at least one boride compound.
• B. is lanthanum hexaboride.
• lanthanum hexaboride is micronized in a weakly acidic aqueous suspension.
• the liquid carrier medium is removed in each case.
• nanoparticulate preparations of metal borides with high solids contents which are preferably suitable for the addition of high molecular weight organic and inorganic materials, in particular polymers and printing inks.
• the nanoparticulate preparations are to be suitable in a special embodiment for use in a method for identifying plastic parts, which avoids as many of the aforementioned disadvantages.
• a first subject of the invention is therefore a dispersed, nanoparticulate preparation comprising a carrier medium which is liquid under standard conditions and at least one particulate phase of nanoscale particles dispersed therein, comprising at least one metal boride of the general formula MB 6 , where M is a metal component.
• Another object of the invention is a polymer composition containing at least one such nanoparticulate preparation.
• Another object of the invention is an ink composition containing at least one such nanoparticulate preparation.
• Another object of the invention is a method for modifying a plastic part with at least one metal boride, wherein
• the dispersed, nanoparticulate preparation incorporated into the plastic part or applied to the plastic part or used for the production of the plastic for the plastic part.
• Another object of the invention is a method for identifying a plastic part, in which one
• a plastic part which has at least in the region to be characterized at least one nanoparticulate metal boride absorbing the laser radiation of the general formula MB 6 , wherein M is a metal component, and
• the plastic part contains the metal boride in nanoparticulate form (in the form of nanoscale particles).
• a plastic part is provided which contains a dispersed-out, nanoparticulate preparation as defined above.
• a "dispersed-out” preparation is understood as meaning a preparation in which the dispersed nanoscale particles contained have substantially no molecular associates in the form of aggregates
• substantially no molecular associates in the form of aggregates means that in the dispersed preparation at most 1% by weight, preferably at most 0.1% by weight, of the nanoscale particles in the form of aggregates, based on the total content of nanoscale particles.
• a "dispersed-out” preparation according to the invention also has only a small proportion or substantially no molecular associates in the form of agglomerates. Agglomerates are understood to mean associates which can be redispersed to nanoscale particles.
• the proportion of nanoscale particles in the form of agglomerates in the dispersed preparation is preferably at most 10% by weight, preferably at most 1% by weight, based on the total content of nanoscale particles.
• a "dispersed-out" preparation can comprise molecular associates in the form of flocculates Flokkulates are particularly loose agglomerates, such as those formed, for example, by gravitational sedimentation, generally completely surrounded by the carrier medium and can be redispersed by simple stirring.
• “Nanoscale particles” in the sense of the present application are particles having a volume-average particle diameter of generally not more than 200 nm, preferably not more than 100 nm.
• a preferred particle size range is from 4 to 100 nm, in particular from 5 to 90 nm.
• Such particles are generally characterized
• the size of the particles can be determined, for example, by the UPA method (Ultrafine Particle Analyzer), for example by the laser scattered light method (laserlight back scattering).
• nanoparticulate preparation is understood to mean a preparation which contains nanoscale particles, ie reagglomeration or coalescence of the nanoscale particles does not take place or occurs only to a minor extent
• primary particles disperse and thus form extremely stable dispersions, and the "nanoparticulate preparation” according to the invention is therefore a “dispersed preparation”.
• liquid is understood to mean rheological properties which range from low-viscosity over pasty / ointment-like to gel-like.
• Flowable compounds typically have a higher viscosity than a liquid, but are not yet self-supporting, i. H. they do not maintain a form given to them without a shape-stabilizing covering.
• the term “liquid” should also include flowable components. The viscosity of such preparations is, for example, in a range of about 1 to 60,000 mPas.
• the metal boride MB6 is preferably selected from alkaline earth borides, rare earth borides and mixtures thereof.
• metal hexaborides MB6 are in particular yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, strontium or Called Calciumhexa- borid.
• a preferred metal boride MB6 is lanthanum hexaboride.
• the nanoparticulate preparations according to the invention are transparent in the visible range of the electromagnetic spectrum and essentially colorless.
• the considerable scattering observed in the visible spectral range in the case of microdispersed additives is avoided, so that it is also possible to label very well transparent plastics with the compositions according to the invention and according to the method according to the invention for identifying plastic parts.
• the nanoparticulate metal borides used according to the invention have a strong absorption.
• the disperse nanoparticulate preparations according to the invention are thus advantageously suitable for the addition of high molecular weight organic and inorganic compositions, in particular of plastics, paints and printing inks, for use in organic and inorganic composites and oxide layer systems. They are particularly suitable as an additive for the laser welding of plastics and in the processing of plastics under heating. For processing plastics under heating, radiation sources (eg heat lamps) are often used. These are usually characterized by a broad emission spectrum z.
• compositions for electrophotography as a component of security printing compositions, and as a component of compositions for controlling energy transfer properties. These include compositions, such as. B.
• the disperse nanoparticulate preparations according to the invention are also suitable in a particularly advantageous manner for the addition of plastics, the one Laser marking (eg with a Nd-Y AG laser at 1064 nm).
• the dispersed nanoparticulate preparations according to the invention have a thermal stability of generally at least 300 ° C. and can therefore also be incorporated directly into a polymer composition without decomposition in accordance with the customary, inexpensive and process-facilitating methods of mass addition. As they are advantageously neither degraded by thermal stress nor by irradiation, they allow for a precise adjustment of the polymer composition to a desired hue, which is also indicated by the subsequent labeling, except in the designated area, not changed.
• the stability of the nanoparticulate metal borides used according to the invention also permits their use in applications in which the formation of undefined degradation products must be ruled out, such as applications in the medical and food packaging sectors.
• nanoparticulate metal borides according to the invention are largely stable to migration in all common matrix polymers, which is also a prerequisite for use in the medical and food packaging sectors.
• Methods for producing nanoscale particles are known in principle. They are based, for example, on a precipitate of aqueous solutions of metal salts by raising or lowering the pH with a suitable base or acid.
• a metal boride MB 6 which is already in the form of nanoscale particles, can be brought into intimate contact with the carrier medium.
• the bringing into contact is preferably carried out under the entry of shear energy in known devices These include, for example, stirred tank, ultrasonic homogenizers, high pressure homogenizers, dynamic mixing, such as Zahnkranzdispergiermaschinen and Ultra-Thurrax devices, and static mixers, eg. B. systems with mixing nozzles.
• the preparation of the nanoparticulate preparation according to the invention is preferably carried out by incorporating at least one metal boride MB 6 in the carrier medium with simultaneous comminution, preferably with grinding.
• a metal boride MB 6 can be used, which is already present in the form of nanoscale particles.
• the comminution is carried out in equipment suitable for this purpose, preferably in mills such as, for example, ball mills, stirred ball mills, circulation mills (stirred ball mill with pin grinding system), disk mills, annular chamber mills, twin-cone mills, three-roll mills and batch mills.
• the grinding chambers are equipped with cooling devices for removing the heat energy introduced during the grinding process.
• the ball mill Drais Superflow DCP SF 12 the circulation mill system ZETA Fa.
• the comminution preferably takes place with the addition of the main amount, in particular at least 80% to 100% of the carrier medium.
• the time required for comminution depends in a manner known per se on the desired degree of fineness or the particle size of the active ingredient particles and can be determined by the person skilled in the art in routine experiments. For example, grinding times in the range of ⁇ A to 72 hours have proven useful, although a longer period of time is also conceivable.
• Pressure and temperature conditions during comminution are generally not critical, for example, normal pressure has proven to be suitable.
• temperatures for example, temperatures in the range of 10 ° C to 100 ° C have proven to be suitable.
• the particles used can be surface-modified or surface-coated.
• the compounds having surface-active groups are preferably selected from the salts of strong inorganic acids, eg.
• Nitrates and perchlorates saturated and unsaturated fatty acids such as palmitic acid, margaric acid, stearic acid, isostearic acid, nonadecanoic acid, lignoceric acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid and elaosteric acid, quaternary ammonium compounds such as tetraalkylammonium hydroxides, e.g. Tetramethylammonium hydroxide, silanes, such as alkyltrialkoxysilanes, and mixtures thereof.
• the nanoscale particles used according to the invention have no surface modifiers.
• the dispersed-out, nanoparticulate preparation is preferably produced by in situ comminution, in particular in situ milling, in the liquid carrier medium in which it is subsequently used (for example by incorporation in or application to a polymer composition).
• the carrier medium from the nanoparticulate preparation is no longer removed and its proportion is reduced at most to the extent that the dispersed state is maintained.
• Any partial or complete replacement of the carrier medium is carried out by liquid-liquid reaction in which the dispersed state is maintained.
• the carrier medium is no longer replaced after preparation of the dispersed, nanoparticulate preparation.
• the Addition of one or more other components may be carried out before, during or after preparation of the dispersed preparation.
• the preparation obtained by in situ comminution is subjected to further processing immediately after its preparation.
• the solids content of the nanoscale composition according to the invention is preferably at least 10% by weight, more preferably at least 20% by weight, based on the total weight of the preparation.
• the content of metal boride MB 6 of the nanoscale composition according to the invention is preferably at least 50% by weight, particularly preferably at least 70% by weight, based on the total solids content of the preparation.
• the carrier medium (the coherent phase) of the nanoparticulate preparations according to the invention is liquid under standard conditions.
• the boiling point of the carrier medium (or of the carrier medium mixture) is preferably at least 40 ° C., particularly preferably at least 65 ° C.
• the carrier medium is preferably selected from esters of alkyl and arylcarboxylic acids, hydrogenated esters of arylcarboxylic acids, polyhydric alcohols, ether alcohols, polyether polyols, ethers, saturated acyclic and cyclic hydrocarbons, mineral oils, mineral oil derivatives, silicone oils, aprotic polar solvents and mixtures thereof.
• suitable liquid esters of alkylcarboxylic acids are preferably based on a dC 2 o-alkanecarboxylic acid. These are preferably selected from formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid and arachic acid.
• the esters are preferably based on the following alkanols, polyhydric alcohols, ether alcohols and polyether polyols.
• Suitable carrier medium esters of arylcarboxylic acids are preferably esters of phthalic acid with alkanols, in particular the esters with dC 3 o-alkanols, especially Ci-C 2 o-alkanols and very especially d-Ci 2 -alkanols.
• esters of phthalic acid with alkanols in particular the esters with dC 3 o-alkanols, especially Ci-C 2 o-alkanols and very especially d-Ci 2 -alkanols.
• Such compounds are commercially z. B. available as a plasticizer.
• alkanols are in particular methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, 2-pentanol, 2-methylbutanol, 3-methylbutanol, 1, 2-dimethylpropanol , 1, 1-dimethylpropanol, 2,2-dimethylpropanol, 1-ethyl-propanol, n-hexanol, 2-hexanol, 2-methylpentanol, 3-methylpentanol, 4-methylpentanol, 1, 2-dimethylbutanol, 1, 3-dimethylbutanol, 2,3-dimethylbutanol, 1, 1-dimethylbutanol, 2,2-dimethylbutanol, 3,3-dimethylbutanol, 1, 1, 2-trimethylpropanol, 1, 2,2-trimethylpropanol, 1-
• Suitable carrier medium suitable polyhydric alcohols are, for. As ethylene glycol, glycerol, 1, 2-propanediol, 1, 4-butanediol, etc.
• Suitable ether alcohols are, for. B. compounds having two terminal hydroxyl groups joined by an alkylene group which may have 1, 2 or 3 non-adjacent oxygen atoms. These include z.
• ethylene glycol monomethyl ether ethylene glycol dimethyl ether, ethylene glycol, etc. are suitable, even under standard conditions, liquid polyether polyols, eg. B. polyalkylene glycols.
• hydroxyl-terminated compounds and repeat units which are preferably selected from (CH 2 CH 2 O) x I , (CH (CH 3 ) CH 2 O) X 2 and ((CH 2 ) 4 O) x 3 where x 1, x 2 and x3 independently represent an integer of 4 to 2500, preferably 5 to 2000, stand.
• the sum of x1, x2 and x3 stands for an integer from 4 to 2500, in particular 5 to 2000.
• polyoxyalkylenes which have two or three different repeating units, the order is arbitrary, ie it can be randomly distributed, alternating or block repeating units.
• Suitable ethers are acyclic and cyclic ethers, preferably cyclic ethers, more preferably tetrahydrofuran.
• Suitable carrier medium saturated acyclic and cyclic hydrocarbons are, for. As tetradecane, hexadecane, octadecane, xylene and decahydronaphthalene.
• Paraffin and paraffin oils high-boiling mineral oil derivatives, such as decalin and white oil, and liquid polyolefins are also suitable as the carrier medium.
• Suitable carrier medium aprotic polar solvents are, for.
• amides such as formamide or dimethylformamide, dimethyl sulfoxide, acetonitrile, dimethyl sulfone, sulfolane, and in particular nitrogen heterocycles, such as N-methylpyrrolidone, quinoline, quinaldine, etc.
• no water is used as the carrier medium.
• a carrier medium that consumes small amounts Contains water, generally at most 5 wt .-%, preferably at most 1 wt .-%, based on the total weight of the carrier medium.
• Clearly defined small amounts of water can contribute to a stabilization of the dispersed, nanoparticulate preparation according to the invention. This also applies to the use of only slightly water-miscible carrier media.
• the dispersed-out, nanoparticulate preparation according to the invention contains a carrier medium which is suitable as a component for the preparation of a polymer.
• carrier media which are suitable as starting material (monomer) for a polymerization reaction.
• the polymerization reaction may be a polycondensation, polyaddition, free-radical polymerization, cationic polymerization, anionic polymerization or coordinate polymerization. It is preferably a polycondensation or polyaddition.
• the carrier medium is used to prepare a polymer selected from polyethers, polyesters, polycarbonates, polyurethanes, and mixtures thereof.
• the carrier medium is used to prepare a polyether which is selected from homopolymers and copolymers of cyclic ethers, such as the polyalkylene glycols defined below.
• the carrier medium is used for producing a polyether polyurethane, in particular based on at least one polytetrahydrofuran.
• the statements relating to these polymers are referred to below.
• the carrier medium used to prepare a polymer is selected from polyhydric alcohols, ether alcohols, polyether polyols, ethers, and mixtures thereof.
• the carrier medium used to prepare a polymer is particularly preferably selected from ethylene glycol, glycerol, 1,3-propanediol, 1,4-butanediol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, acyclic and cyclic ethers, polyether polyols and mixtures thereof.
• a specific carrier medium for making a polymer is hydroxyl terminated polytetrahydrofuran.
• the molecular weight of the polytetrahydrofuran is preferably in a range of 200 to 10,000, more preferably 500 to 2,500.
• the carrier media used according to the invention may contain at least one further component which is compatible with the carrier medium.
• these include z. As natural and synthetic fats and waxes. Suitable z. As the esters of saturated and mono- or polyunsaturated, straight-chain or branched Ce-C 3 o fatty acids with Ci-C 3 o-alkanols. Preference is given to the esters of saturated C 2 -C 24 -fatty acids with C 8 -C 24 -alkanols and mixtures thereof. This includes z. Stearyl stearate.
• Another object of the invention is a method for modifying a plastic part with at least one metal boride, wherein
• the dispersed, nanoparticulate preparation incorporated into the plastic part or applied to the plastic part or used for the production of the plastic for the plastic part.
• the nanoparticulate preparations of the invention may be incorporated into a polymer component or applied to at least a portion of such a composition via a lamination or coating process. Preference is given to the production of plastic compositions by a mass addition process. Extrusion, coextrusion (in this case the thickness of the additized coextrusion layer is generally at least 25 ⁇ m, typically 50 ⁇ m), injection molding, blow molding and kneading, may be mentioned as suitable mass addition methods.
• the nanoparticulate preparations according to the invention are, as mentioned, particularly advantageous for use in polymer compositions and printing ink compositions.
• the boiling temperature and / or the flame temperature of the nanoparticulate preparations are then preferably above the processing temperature used for producing the polymer composition or printing ink composition.
• the nanoparticulate preparations according to the invention are furthermore, as mentioned, particularly advantageous for use in a method for identifying a plastic part.
• the plastic part used for labeling then contains the metal boride in an amount of at most 0.05 wt .-%, more preferably of at most 0.02 wt .-%, based on the total weight of the plastic part.
• the required amounts are thus significantly lower than in other known from the prior art additives for laser marking.
• the metal borides used according to the invention thus avoid an undesired one Heavy metal load of the doped plastic parts and also have a good tracking resistance.
• the plastic part has the nanoparticulate metal boride absorbing the laser radiation in the region to be marked. Due to the small amounts required, however, it is often feasible to additize the entire plastic part with the metal boride.
• a removal of the carrier medium used according to the invention after incorporation into a plastic part is generally not required.
• Another object of the invention is a polymer composition containing at least one nanoparticulate preparation, as defined above.
• the polymer compositions according to the invention or the plastic parts used according to the invention contain a thermoplastic polymer component or consist of a thermoplastic polymer component.
• Thermoplastics are characterized by their good processability and can in the softened state z. B. be processed by molding, extrusion, injection molding or other molding processes to form parts.
• the polymer composition according to the invention is obtainable by polymerization of a reaction mixture containing a dispersed nanoparticulate preparation which contains a liquid carrier medium which is at least partially incorporated into the polymer.
• a reaction mixture containing a dispersed nanoparticulate preparation which contains a liquid carrier medium which is at least partially incorporated into the polymer.
• the polymer compositions according to the invention or the plastic parts used according to the invention contain a polymer component or consist of a polymer component which is preferably selected from the group of polyolefins, polyolefin copolymers, polytetrafluoroethylenes, ethylene-tetrafluoroethylene copolymers, polyvinyl chlorides, polyvinylidene chlorides, polyvinyl alcohols, polyvinyl esters, Polyvinylalkanal, polyvinyl ketals, polyamides, polyimides, polycarbonates, polycarbonate blends, polyesters, polyester blends, poly (meth) acrylates, poly (meth) acrylate-styrene copolymer blends, poly (meth) acrylate-polyvinylidene difluoride blends, polyurethanes, Polystyrenes, styrene copolymers, polyethers, polyether ketones and polysulfones and mixtures thereof.
• polymers from the group of polyolefins, polyolefin copolymers, polyvinylalkanals, polyamides, polycarbonates, polycarbonate-polyester blends, polycarboxylic carbonate-styrene copolymer blends, polyesters, polyester blends, poly (meth) acrylates, poly (meth) acrylate-styrene copolymer blends, poly (meth) acrylate-polyvinylidene difluoride blends, styrene copolymers and polysulfones and mixtures thereof.
• the polymer composition according to the invention comprises at least one polyurethane or consists of at least one polyurethane.
• the polyurethane is preferably at least one polyether polyurethane, more preferably at least one polytetrahydrofuran polyether urethane. Preference is given to thermoplastic polyetherpolyurethanes.
• Particularly preferred polymers for use as plastic parts to be marked are transparent or at least translucent. Examples which may be mentioned are: polypropylene, polyvinyl butyral, polyamide [6], polyamide [6,6], polycarbonate, polycarbonate-polyethylene terephthalate blends, polycarbonate-polybutylene terephthalate blends, polycarbonate-acrylonitrile / styrene / acrylonitrile copolymer blends , Polycarbonate
• Acrylonitrile / butadiene / styrene copolymer blends polymethyl methacrylate-acrylonitrile / butadiene / styrene copolymer blends (MABS), polyethylene terephthalate, polybutylene terephthalate, polymethyl methacrylate, impact-modified polymethyl methacrylate, polybutyl acrylate, polymethyl methacrylate-polyvinylidene difluoride blends, acrylonitrile / buta- diene / styrene copolymers (ABS), styrene / acrylonitrile copolymers (SAN) and polyphenylene sulfone and mixtures thereof.
• MABS polymethyl methacrylate-acrylonitrile / butadiene / styrene copolymer blends
• ABS acrylonitrile / buta- diene / styrene copolymers
• Suitable and preferred polymers are specified below.
• a preferred embodiment of the present invention relates to a polymer composition wherein the polymer is selected from polyolefins, polyolefin copolymers and polymer blends containing at least one polyolefin homo- or copolymer.
• Preferred polyolefins contain at least one copolymerized monomer selected from among ethylene, propylene, but-1-ene, isobutylene, 4-methyl-1-pentene, butadiene, isoprene and mixtures thereof. Suitable homopolymers, copolymers of said olefin monomers and copolymers of at least one of said olefins as the main monomer and other monomers (such as vinyl aromatic) as comonomers.
• Preferred polyolefins are also low density polyethylene homopolymers (PE-LD) and polypropylene homopolymers and polypropylene copolymers.
• Preferred polypropylenes are, for example, biaxially oriented polypropylene (BOPP) and crystallized polypropylene.
• Preferred mixtures of the abovementioned polyolefins are, for example, mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP / HDPE, PP / LDPE) and mixtures of various types of polyethylenes (for example LDPE / HDPE) ,
• PE polyethylene
• VPL very low density
• PE-LD low density
• LD low density
• ICI high pressure process
• LLDPE linear low density
• PE-MD middle-density
• the density is between 0.93 and 0.94 g / cm 3 ;
• PE-HD High Density
• HD High Density
• polyethylene produced in a gas phase fluidized bed process using catalysts (usually supported), e.g. B. Lupolene® (Basell).
• catalysts usually supported
• B. Lupolene® Basell
• polyethylene produced using metallocene catalysts.
• polyethylene is z. B. as Luflexen® (Basell) commercially available.
• ethylene copolymers all commercially available ethylene copolymers are suitable, for example Luflexen® types (Basell), Nordel® and Engage® (Dow, DuPont).
• comonomers z. B ⁇ -olefins having 3 to 10 carbon atoms, in particular propylene len, 1-butene, 1-hexene and oct-1-ene, also alkyl acrylates and methacrylates having 1 to 20 carbon atoms in the Alkyl radical, especially butyl acrylate.
• Further suitable comonomers are dienes such. Butadiene, isoprene and octadiene.
• Further suitable comonomers are cycloolefins, such as cyclopentene, norbornene and dicyclopentadiene.
• the ethylene copolymers are usually random copolymers or block or impact copolymers.
• Suitable block or impact copolymers of ethylene and comonomers are, for. B. polymers in which in the first stage, a homopolymer of the comonomer or a random copolymer of the comonomer, for example, with up to 15 wt .-% ethylene produces and then in the second stage, a comonomer-ethylene copolymer having ethylene contents of 15 to 80% by weight polymerized. In general, as much of the comonomer-ethylene copolymer is copolymerized to the extent that the copolymer produced in the second stage has a content of from 3 to 60% by weight in the end product.
• the polymerization for the preparation of the ethylene-comonomer copolymers can be carried out by means of a Ziegler-Natta catalyst system.
• catalyst systems based on metallocene compounds or on the basis of polymerization-active metal complexes can be used.
• HDPE mainly manufactures toys, household items, technical hardware and beer crates. Some HDPE grades are used in disposable and mass daily necessities.
• the field of application of LDPE extends from films over paper coating to thick and thin-walled molded parts. LLDPE exhibits advantages over LDPE in mechanical properties and in stress cracking resistance. Application of LLDPE is mainly found in pipes and films.
• polypropylene is to be understood below as meaning both homopolymers and copolymers of propylene.
• Copolymers of propylene contain minor amounts of monomers copolymerizable with propylene, for example
• C 2 -C 8 -Alk-1 -ene such as ethylene, but-1-ene, pent-1-ene or hex-1-ene.
• Two or more different comonomers can also be used.
• Suitable polypropylenes are u. a. Homopolymers of propylene or copolymers of propylene with up to 50 wt .-% of copolymerized other alk-1-enes having up to 8 C-atoms.
• the copolymers of propylene are random copolymers or block or impact copolymers. If the copolymers of propylene have a random structure, they generally contain up to 15% by weight, preferably up to 6% by weight, of other alk-1-enes having up to 8 carbon atoms, in particular ethylene, but-1 -en or a mixture of ethylene and but-1-ene.
• Suitable block or impact copolymers of propylene are, for. B. Polymers in which in the first stage, a propylene homopolymer or a random copolymer of propylene with up to 15 wt .-%, preferably up to 6 wt .-%, of other alk-1-ene with up to 8 C And then in the second stage a propylene
• Ethylene copolymer having ethylene contents of 15 to 80 wt .-%, wherein the propylene-ethylene copolymer may additionally contain further C 4 -C 8 -Alk-I -ene, addresse- lymerinstrument.
• the propylene-ethylene copolymer may additionally contain further C 4 -C 8 -Alk-I -ene, addresse- lymerinstrument.
• the polymerization for the production of polypropylene can be carried out by means of a Ziegler-Natta catalyst system. Particular preference is given to using those catalyst systems which, in addition to a titanium-containing solid component a), also comprise cocatalysts in the form of organic aluminum compounds b) and electron donor compounds c).
• catalyst systems based on metallocene compounds or on the basis of polymerization-active metal complexes are usually carried out by polymerization in at least one, often in two or more successive reaction zones (reactor cascade), in the gas phase, in a suspension or in a liquid phase (bulk phase).
• reactor cascade The usual reactors used for the polymerization of C 2 -C ⁇ -alk-1-enes can be used. Suitable reactors include continuously operated stirred tanks, loop reactors, powder bed reactors or fluidized bed reactors.
• the polymerization for the preparation of the polypropylene used is carried out under conventional reaction conditions at temperatures of 40 to 120 ° C, in particular from 50 to 100 ° C and pressures of 10 to 100 bar, in particular from 20 to 50 bar.
• Suitable polypropylenes generally have a melt flow rate (MFR), according to ISO 1 133, of 0.1 to 200 g / 10 min., In particular from 0.2 to 100 g / 10 min., At 230 ° C and under a weight of 2.16 kg, up.
• MFR melt flow rate
• Another embodiment of the present invention relates to a polymer composition wherein the polymer is selected from copolymers of mono- or diolefins with vinyl monomers and mixtures thereof. These include ethylene /
• Propylene copolymers linear low density polyethylene (LLDPE) and blends thereof with low density polyethylene (LDPE), propylene / but-1-ene copolymers, propylene / isobutylene copolymers, ethylene / but-1-ene copolymers, ethylene / hexene Copolymers, ethylene / methylpentene copolymers, ethylene / heptene copolymers, ethylene / octene copolymers, propylene / butadiene copolymers, isobutylene / isoprene copolymers, ethylene / alkyl acrylate copolymers, ethylene / alkyl methacrylate copolymers, ethylene / vinyl acetate, Copolymers and their copolymers with carbon monoxide or ethylene / acrylic acid copolymers and their salts (ionomers) and terpolymers of ethylene with propylene and a die
• LDPE / ethylene-propylene copolymers As polypropylene / ethylene-propylene copolymers, LDPE / ethylene-vinyl acetate copolymers (EVA), LDPE / ethylene-acrylic acid copolymers (EAA), LLDPE / EVA, LLDPE / EAA and alternating or random polyalkylene / carbon monoxide copolymers and mixtures thereof with other polymers, e.g. B. polyamides.
• EVA LDPE / ethylene-vinyl acetate copolymers
• EAA LDPE / ethylene-acrylic acid copolymers
• LLDPE / EVA LLDPE / EVA
• LLDPE / EAA alternating or random polyalkylene / carbon monoxide copolymers and mixtures thereof with other polymers, e.g. B. polyamides.
• halogen-containing polymers include polytetrafluoroethylene homopolymers and copolymers, polychloroprene, chlorinated and fluorinated rubbers, chlorinated and brominated copolymer of isobutylene-isoprene (halogenated rubber), chlorinated and sulfochlorinated polyols. lyethylenes, copolymers of ethylene and chlorinated ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, in particular polymers of halogen-containing vinyl compounds, for.
• PVC polyvinyl chloride
• PVDC polyvinylidene chloride
• PVF polyvinylidene fluoride
• copolymers thereof such as vinyl chloride / - vinylidene chloride, vinyl chloride / vinyl acetate or vinylidene chloride / vinyl acetate
• Polyvinyl chloride is used with a different content of plasticizers, with a content of plasticizers from 0 to 12% as hard PVC, more than 12% as soft PVC or with a very high content of plasticizers as PVC paste.
• Usual plasticizers are z. Phthalates, epoxides, adipic acid esters.
• Polyvinyl chloride is prepared by radical polymerization of vinyl chloride in bulk, suspension, microsuspension and emulsion polymerization. The polymerization is often initiated by peroxides.
• PVC is widely used, for example as foamed artificial leather, insulated wallpaper, household items, shoe soles, furniture profiles, floor coverings or pipes.
• Polyvinylidene chloride is prepared by radical polymerization of vinylidene chloride. Vinylidene chloride can also be copolymerized with (meth) acrylates, vinyl chloride or acrylonitrile. Polyvinylidene chloride and the vinylidene copolymers are processed into films, for example, but also into profiles, tubes and fibers. One important application relates to multilayer films; the good barrier properties of the polyvinylidene chloride are also used for coatings.
• polymer compositions wherein the polymer is selected from homopolymers and copolymers of cyclic ethers such as polyalkylene glycols, e.g. For example, polyethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.
• Polyalkylene glycols are formed by polyaddition of a cyclic ether such as ethylene oxide, propylene oxide or tetrahydrofuran with an OH compound as a starter molecule, such as water. Starter molecules for the polyaddition may also be dihydric or polyhydric alcohols.
• Low molecular weight polyalkylene glycols are used as synthetic lubricants.
• polyalkylene glycols are used as solubilizers for surfactant combinations, as binders in soaps, as constituents in inks and stamping inks, as plasticizers and as release agents.
• a further preferred embodiment of the present invention relates to a polymer composition in which the polymer is selected from polyacetals, copolymers of polyacetals with cyclic ethers and polyacetals, with thermoplastic polyurethanes, acrylates or methyl acrylate / butadiene / styrene copolymers are modified.
• Polyacetals are formed by polymerization of aldehydes or cyclic acetals.
• a technically important polyacetal is polyoxymethylene (POM), which is obtainable by cationic or anionic polymerization of formaldehyde or trioxane.
• Modified POM is obtained, for example, by copolymerization with cyclic ethers, such as ethylene oxide or 1,3-dioxolane.
• cyclic ethers such as ethylene oxide or 1,3-dioxolane.
• thermoplastic polyurethane elastomers gives POM-based polymer blends.
• Unreinforced POM is characterized by very high stiffness, strength and toughness. POM is preferably used for household appliance and apparatus construction, vehicle construction, mechanical engineering, sanitary engineering and installation technology.
• polyaryl ethers are polyphenylene oxides whose main chain is made up of phenylene units linked via oxygen atoms, which are optionally substituted by alkyl groups.
• a technically significant polyphenylene oxide is poly-2,6-dimethylphenyl ether.
• polyaryl sulfides are polyphenylene sulfides obtainable by polycondensation of 1, 4-dichlorobenzene with sodium sulfide. They are characterized by high strength, stiffness and hardness. They are suitable as a substitute for metals in the construction of pump housings and other elements of mechanical and apparatus engineering. Further fields of application for polyphenylene sulfides are electrical engineering and electronics.
• polyurethanes are, for example, cellular polyurethanes, for.
• TPU thermoplastic polyurethanes
• thermosetting or elastic polyurethanes or polyisocyanurates are well known and their preparation is described many times. It is usually carried out by reacting dihydric and higher isocyanates or corresponding isocyanate analogues with isocyanate-reactive compounds. The preparation is carried out by customary processes, for example in the one-shot process or by the prepolymer process, for. B.
• Polyurethanes are generally composed of at least one polyisocyanate and at least one compound having at least two isocyanate-reactive groups per molecule. Suitable polyisocyanates preferably have 2 to 5 NCO groups. The isocyanate-reactive groups are preferably selected from hydroxyl, mercapto, primary and secondary amino groups. These preferably include di- or higher polyols.
• Suitable polyisocyanates are aliphatic, cycloaliphatic, araliphatic and aromatic isocyanates.
• Suitable aromatic diisocyanates are, for example, 2,2'-, 2,4'- and / or 4,4'-diphenylmethane diisocyanate (MDI), 1, 5-naphthylene diisocyanate (NDI), 2,4- and / or 2,6-tolylene diisocyanate (TDI), diphenylmethane diisocyanate, 3,3'-dimethyl-diphenyl-diisocyanate, 1, 2-diphenylethane diisocyanate and / or phenylene diisocyanate.
• MDI 2,2'-, 2,4'- and / or 4,4'-diphenylmethane diisocyanate
• NDI 1,5-naphthylene diisocyanate
• TDI 2,6-tolylene diisocyanate
• Aliphatic and cycloaliphatic diisocyanates include, for example, tri-, tetra-, penta-, hexa-, hepta- and / or octamethylene diisocyanate, 2-methyl-pentamethylene-1,5-diisocyanate, 2-ethylbutylene-1,4-diisocyanate, 1-isocyanato 3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 1, 4- and / or 1, 3-bis (isocyanatomethyl) cyclohexane (HXDI), cyclohexane-1,4-diisocyanate, 1-methyl-2,4- and / or 2,6-cyclohexanediisocyanato and / or 4,4'-, 2,4'- and / or 2,2'-dicyclohexylmethane diisocyanate ,.
• the preferred diisocyanates include hexamethylene diisocyanate (HMDI) and isophorone diisocyanate.
• HMDI hexamethylene diisocyanate
• isophorone diisocyanate examples of higher-functional isocyanates are triisocyanates, eg. B. Triphenylmethane-4,4 ', 4 "-triisocyant, furthermore the cyanurates of the aforementioned diisocyanates, as well as the oligomers obtainable by partial reaction of diisocyanates with water, for example the biurets of the aforementioned diisocyanates, furthermore oligomers obtained by targeted reaction of semiblocked diisocyanates with polyols which have on average more than 2 and preferably 3 or more hydroxyl groups.
• High-functional polyols in particular polyether polyols based on highly functional alcohols, sugar alcohols and / or saccharides as starter molecules, are used as polyol components for rigid polyurethane foams, which may optionally have isocyanurate structures.
• polyether polyols based on highly functional alcohols, sugar alcohols and / or saccharides as starter molecules
• polyol components for rigid polyurethane foams, which may optionally have isocyanurate structures.
• flexible polyisocyanate polyaddition products eg.
• polyurethane foams or RIM materials are 2- and / or 3-functional polyether polyols based on glycerol and / or trimethylolpropane and / or glycols as starter molecules as polyols and 2- and / or 3-functional polyether-based on glycerol and / or trimethylolpropane and / or glycols as alcohols to be esterified as polyols.
• Thermoplastic polyurethanes are usually based on predominantly difunctional polyester polyalcohols and / or polyether polyalcohols, which preferably have an average functionality of from 1.8 to 2.5, particularly preferably from 1.9 to 2.1.
• the polyurethane is preferably at least one polyether polyurethane, more preferably at least one polytetrahydrofuran polyether urethane.
• a specific embodiment is thermoplastic polyurethanes based on predominantly difunctional polyether polyalcohols.
• the preparation of the polyether polyols is carried out according to a known technology.
• Suitable alkylene oxides for the preparation of the polyols are, for example, 1,3-propylene oxide, 1,2- or 2,3-butylene oxide, styrene oxide and preferably ethylene oxide and 1,2-propylene oxide.
• the alkylene oxides can be used individually, alternately in succession or as mixtures.
• alkylene oxides are used which lead to primary hydroxyl groups in the polyol.
• Particularly preferred polyols used are those which have been alkoxylated with ethylene oxide to complete the alkoxylation and thus have primary hydroxyl groups.
• Further suitable polyetherols are polytetrahydrofurans and polyoxymethylenes.
• the polyether polyols have a functionality of preferably 2 to 6 and in particular 2 to 4 and molecular weights of 200 to 10,000, preferably 200 to 8,000.
• Suitable polytetrahydrofurans are compounds of the general formula
• polytetrahydrofurans preferably have a number average molecular weight in the range from 200 to 100,000, preferably 250 to 8,000.
• Suitable polytetrahydrofurans can be prepared by cationic polymerization of tetrahydrofuran in the presence of acidic catalysts, such as. For example, sulfuric acid or fluorosulfuric acid, are produced. Such production processes are known to the person skilled in the art.
• Suitable polyester polyols may be prepared, for example, from organic dicarboxylic acids having 2 to 12 carbon atoms, preferably aliphatic dicarboxylic acids having 4 to 6 carbon atoms, and polyhydric alcohols, preferably diols having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms.
• the polyester polyols preferably have a functionality of 2 to 4, in particular 2 to 3, and a molecular weight of 480 to 3000, preferably 600 to 2000 and in particular 600 to 1500.
• the polyol component may also include diols or higher alcohols.
• Suitable diols are glycols preferably having 2 to 25 carbon atoms. These include 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1, 6-hexanediol, 1, 10-decanediol, diethylene glycol, 2,2,4-trimethylpentanediol-1, 5, 2,2-dimethylpropanediol 1, 3, 1, 4-dimethylolcyclohexane, 1, 6-dimethylolcyclohexane, 2, 2-bis (4-hydroxyphenyl) propane (bisphenol A), 2,2-bis (4-hydroxyphenyl) butane (bisphenol B) or 1, 1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane ( Bisphenol C).
• Suitable higher alcohols are for.
• pentavalent alcohols pentoles. They usually have 3 to 25, preferably 3 to 18 carbon atoms. These include glycerol, trimethylolethane, trimethylolpropane, erythritol, pentaerythritol, sorbitol and their alkoxylates.
• chain extenders e.g., a molecular weight of 40 to 300. Suitable examples include aliphatic, cycloaliphatic and / or araliphatic diols having 2 to 14, preferably 2 to 10 carbon atoms, such as.
• ethylene glycol 1, 3-propanediol, 1, 2-propanediol, 1, 10-decanediol, 1, 2, 1, 3, 1, 4-dihydroxycyclohexane, diethylene glycol, dipropylene glycol and preferably ethylene glycol, 1, 4- Butanediol, 1, 6-hexanediol and bis (2-hydroxyethyl) hydroquinone, triols such as 1, 2,4-, 1, 3,5-trihydroxycyclohexane, glycerol, trimethylolpropane, triethanolamine and low molecular weight hydroxyl-containing polyalkylene oxides based on ethylene and / or 1, 2-propylene oxide and the aforementioned diols and / or triols as starter molecules.
• Suitable stoppers include, for example, monofunctional alcohols or secondary amines.
• a further preferred embodiment of the present invention relates to a polymer composition in which the polymer is selected from polyureas, polyimides, polyamideimides, polyetherimides, polyesterimides, polyhydantoins and polybenzimidazoles.
• Polyureas are known to be formed by polyaddition of diamines and diisocyanates.
• Polyimides whose essential structural element is the imide group in the main chain, are formed by reaction of aromatic tetracarboxylic dianhydrides with aliphatic or aromatic diamines.
• Polyimides are used, inter alia, as adhesives in composites, as well as for coatings, thin films, for example as insulating material in microelectronics, for high-modulus fibers, for semi-permeable membranes and as liquid-crystalline polymers.
• polyesters preferably at least one linear polyester.
• Suitable polyesters and copolyesters are described in EP-A-0678376, EP-A-0 595 413 and US Pat. No. 6,096,854, which are hereby incorporated by reference Reference is made.
• Polyesters are known to be condensation products of one or more polyols and one or more polycarboxylic acids.
• the polyol is a diol and the polycarboxylic acid is a dicarboxylic acid.
• the diol component can be selected from ethylene glycol, 1,4-cyclohexanedimethanol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 1, 2-cyclohexanediol, 1, 4-cyclohexanediol, 1, 2-cyclohexanedimethanol and 1, 3-cyclohexanedimethanol.
• diols whose alkylene chain is interrupted one or more times by non-adjacent oxygen atoms.
• diethylene glycol triethylene glycol, dipropylene glycol, tripropylene glycol and the like.
• the diol contains 2 to 18 carbon atoms, preferably 2 to 8 carbon atoms.
• Cycloaliphatic diols can be used in the form of their cis or trans isomer or as a mixture of isomers.
• the acid component may be an aliphatic, alicyclic or aromatic dicarboxylic acid.
• the acid component of linear polyesters is usually selected from terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, 1,12-dodecanedioic acid, 2,6-naphthalenedicarboxylic acid and mixtures thereof ,
• the functional derivatives of the acid component such as esters, for example the methyl ester, anhydrides or halides, preferably chlorides.
• Preferred polyesters are polyalkylene terephthalates, and polyalkylene naphthalates, which are obtainable by condensation of terephthalic acid or naphthalenedicarboxylic acid with an aliphatic diol.
• Preferred polyalkylene terephthalates are polyethylene terephthalates (PET) which are obtained by condensation of terephthalic acid with diethylene glycol. PET is also available by transesterification of dimethyl terephthalate with ethylene glycol with elimination of methanol to bis (2-hydroxyethyl) terephthalate and its polycondensation to release ethylene glycol.
• PET polyethylene terephthalates
• polyesters are polybutylene terephthalates (PBT) obtainable by condensation of terephthalic acid with 1,4-butanediol, polyalkylene naphthalates (PAN) such as polyethylene-2,6-naphthalate (PEN), poly-1,4-cyclohexanedimethylene terephthalate (PCT ), as well as copolyesters of polyethylene terephthalate with cyclohexanedimethanol (PDCT), copolyesters of polybutylene terephthalate with cyclohexanedimethanol.
• PBT polybutylene terephthalates
• PAN polyalkylene naphthalates
• PEN polyethylene-2,6-naphthalate
• PCT poly-1,4-cyclohexanedimethylene terephthalate
• PDCT cyclohexanedimethanol
• Particularly suitable polymers are selected from poly- or copolycondensates of terephthalic acid, such as polyethylene or copolyethylene terephthalate (PET or CoPET or PETG), poly (ethylene 2,6-naphthalate) s (PEN) or PEN / PET copolymers and PEN / PET blends.
• PET and PBT are widely used in the production of fibers and also have high resistance as thermoplastic materials for engineering parts such as bearings, gears, cams, rollers, switch housings, connectors, handles, control buttons.
• PET is widely used as a material for beverage bottles.
• polystyrene resin is selected from polycarbonates, polyestercarbonates and mixtures thereof.
• Polycarbonates are formed z.
• Suitable dihydroxy compounds are aliphatic or aromatic dihydroxy compounds.
• suitable aromatic dihydroxy compounds are bisphenols, such as 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), tetraalkyl bisphenol A, 4,4- (meta-phenylene diisopropyl) diphenol (bisphenol M), 4,4- ( para-phenylenediisopropyl) diphenol, 1, 1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (BP-TMC), 2,2-bis (4-hydroxyphenyl) -2-phenylethane, 1 , 1-bis (4-hydroxyphenyl) cyclohexane (bisphenol-Z) and optionally mixtures thereof.
• the polycarbonates can be branched by using small amounts of branching agents.
• Suitable branching agents include phloroglucinol, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptene-2, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) - heptane; 1, 3,5-tri (4-hydroxyphenyl) benzene; 1,1,1-tri (4-hydroxyphenyl) heptane; 1, 3,5-tri- (4-hydroxyphenyl) benzene; 1,1,1-tri- (4-hydroxyphenyl) -ethane; Tri- (4-hydroxyphenyl) -phenyl-methane, 2,2-bis [4,4-bis (4-hydroxyphenyl) -cyclohexyl] -propane; 2,4-bis- (4-hydroxyphenyl-isopropyl) -phenol; 2,6-bis (2-hydroxy-5'-methyl-benzyl) -4-methyl phenol; 2- (4-hydroxyphenyl) -2- (2,4-dihydroxypheny
• chain termination are, for example, phenols such as phenol, alkylphenols such as cresol and 4-tert-butylphenol, chlorophenol, bromophenol, cumylphenol or mixtures thereof.
• the proportion of chain terminators is usually 1 to 20 mol%, per mole of dihydroxy compound.
• a further preferred embodiment of the present invention relates to a polymer composition in which the polymer is selected from polysulfones, polyisocyanates and polysulfones. ether sulfones, polyether ketones and mixtures thereof. Polyether ketones are used, for example, in the electrical industry and in vehicle construction.
• the present invention relates to a polymer composition wherein the polymer is selected from synthetic resins.
• the synthetic resins include crosslinked polymers derived from aldehydes on the one hand and phenols, ureas and melamines on the other hand, such as phenol / formaldehyde resins, urea / formaldehyde resins and melamine / formaldehyde resins.
• the synthetic resins include drying and non-drying alkyd resins and unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents, and halogen-containing modifications thereof having low flammability.
• the synthetic resins include crosslinkable acrylic resins which are derived from substituted acrylates, such as epoxy acrylates, urethane acrylates or polyester acrylates.
• the synthetic resins include alkyd resins, polyester resins and acrylate resins, crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins and crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds.
• epoxy resins are formed by ring-opening crosslinking reaction of polybasic epoxides. Examples of epoxy resins include diglycidyl ethers of bisphenol-A or bisphenol F.
• the synthetic resins can be crosslinked with acid anhydrides or amines, with or without accelerators.
• the synthetic resins also include hydrocarbon resins, which usually have a molecular weight below 2000.
• the hydrocarbon resins can be divided into three groups, petroleum resins, terpene resins and coal tar resins.
• the hydrocarbon resins in the context of this invention, the hydrogenated modifications thereof and polyalkylenes are calculated.
• polymer composition wherein the polymer is selected from natural polymers such as cellulose, rubber, gelatin and chemically modified derivatives thereof, for example cellulose acetates, cellulose propionates and cellulose butyrates, or the cellulose ethers such as methylcellulose; as well as rosin and its derivatives.
• natural polymers such as cellulose, rubber, gelatin and chemically modified derivatives thereof, for example cellulose acetates, cellulose propionates and cellulose butyrates, or the cellulose ethers such as methylcellulose; as well as rosin and its derivatives.
• Cellulose is mainly used in blends with PET fibers in the clothing sector; also as artificial silk, linings, curtain fabrics, tire cord, cotton wool, dressings and sanitary articles.
• cellulose esters are screwdriver handles, eyeglass frames, brushes, combs, ball-point pens, technical parts such as motor vehicle steering wheels, lamp and device covers, typewriter keys, electrical insulation films, photographic films, and heat- and heat-resistant thermoplastics Binder processed for paints.
• Cellulose ethers serve as binders for clearcoat for textiles, paper, films and metals. Natural rubber (1, 4-cis-polyisoprene) is indispensable for many applications, for example radial tires.
• polymer composition wherein the polymer is selected from naturally occurring and synthetic organic materials which are pure monomeric compounds or mixtures of such compounds, e.g. As mineral oils, animal and vegetable fats, oil and waxes, or oils, fats and waxes based on synthetic esters, such as phthalates, adipates, phosphates or trimellitates, and also mixtures of synthetic esters with mineral oils in any weight ratios, generally those which are used as spin agents, as well as aqueous emulsions of such materials.
• Another preferred embodiment of the present invention relates to a polymer composition wherein the polymer is selected from aqueous emulsions of natural or synthetic rubber.
• the aqueous emulsions of natural or synthetic rubber include natural latex or latices of carboxylated styrene / butadiene copolymers.
• polymer composition wherein the polymer is selected from polymers derived from unsaturated alcohols and amines or from their acyl derivatives or acetals such as polyvinyl acetate (PVAC) and polyvinyl alcohol (PVAL).
• PVAC polyvinyl acetate
• PVAL polyvinyl alcohol
• polyvinyl acetals are formed, for example, when reacted with formaldehyde polyvinylformale (PVFM) or with butyraldehyde, the Polyvinylbu- tyrale (PVB).
• PVFM formaldehyde polyvinylformale
• PVB Polyvinylbu- tyrale
• Polyvinyl compounds are not thermoplastic materials because of their low glass transition temperature, but polymer resins.
• coating compounds for example for carpet backings, cheese coatings, paper coating slips, paint and pigment binders, lacquer raw materials, glues, adhesives, protective colloids, chewing gum, concrete admixture, films for the production of laminated glass for windshields of motor vehicles and many other purposes.
• a further preferred embodiment of the invention relates to a polymer composition in which the polymer is selected from polyamides (abbreviation PA) or copolyamides which have as essential structural elements amide groups in the polymer main chain.
• Polyamides can be prepared, for example, by polycondensation from diamines and dicarboxylic acids or derivatives thereof.
• Suitable diamines are, for example, alkyldiamines such as C 2 -C 2 o-alkyldiamines, eg. Hexamethy lendiamin, or aromatic diamines, such as Ce- to C 2 0 aromatic diamines, z.
• m-, o- the p-phenylenediamine or m-xylenediamine are examples of the polymer.
• Suitable dicarboxylic acids include aliphatic dicarboxylic acids or their derivatives, for example chlorides, such as C 2 - to C 2 o-aliphatic dicarboxylic acids, eg. As sebacic acid, decanedicarboxylic acid or adipic acid or aromatic dicarboxylic acids, for example Ce- to C 2 0 aromatic dicarboxylic acids or their derivatives, for example chlorides, such as 2,6-naphthalenedicarboxylic acid, isophthalic acid or terephthalic acid.
• chlorides such as C 2 - to C 2 o-aliphatic dicarboxylic acids, eg. As sebacic acid, decanedicarboxylic acid or adipic acid or aromatic dicarboxylic acids, for example Ce- to C 2 0 aromatic dicarboxylic acids or their derivatives, for example chlorides, such as 2,6-naphthalenedicarboxylic acid, isophthalic acid or terephthalic acid
• polyamides examples include poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide, PA 6,6 (polyhexamethylene adipamide), PA 4,6 (polytetramethylene lenadipamide), PA 6,10 (polyhexamethylene sebacamide), PA 6 / 9, PA 6/12, PA 4/6, PA 12/12, wherein the first number always indicates the number of carbon atoms of the diamine and the second number indicates the number of carbon atoms of the dicarboxylic acid.
• Polyamides are also by polycondensation of amino acid, for example C 2 -C 2 o-amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid or by ring-opening polymerization of lactams, eg. B. caprolactam available.
• examples of such polyamides are PA 4 (composed of 4-aminobutyric acid), PA 6 (composed of 6-aminohexanoic acid).
• PA 11 is a polyundecanolactam
• PA 12 is a polydodecanolactam.
• PA indicates the number of carbon atoms of the monomer.
• Polyamides may optionally be prepared with an elastomer as a modifier.
• Suitable copolyamides are, for example, block copolymers of the above-mentioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, for example with polyethylene glycol, polypropylene glycol or polytetramethylene glycol; and polyamides or copolyamides modified with EPDM or ABS; and polyamides condensed during processing (RIM polyamide systems).
• Polyamide is used in injection molded parts with high demands on toughness, abrasion resistance and thermal stability (dimensional stability), such as for plastic components in the engine compartment of automobiles, gears, etc.
• polyamide is used in synthetic fibers (eg nylon, nylon).
• polymer composition wherein the polymer is selected from polymers derived from ⁇ , ⁇ -unsaturated acids and their derivatives, such as polyacrylates and polymethacrylates; Polymethyl methacrylates (PMMA), polyacrylamides (PAA) and polyacrylonitriles (PAC), impact-modified with butyl acetate.
• PMMA Polymethyl methacrylates
• PAA polyacrylamides
• PAC polyacrylonitriles
• the polymerization can be carried out as a solution polymerization in water, as a precipitation polymerization, for example in benzene, or as a suspension polymerization.
• Polyacrylic acid is used in the form of its salts as a thickener and in aqueous media for coatings.
• Acrylic acid and its copolymers with acrylamide are used as suspension aids for pigments, as flocculants in water treatment, as drilling aids in mining, as paper auxiliaries, as adhesives for metal / plastic compounds and for many other purposes.
• Polyacrylate esters are mainly used as binders for paints and varnishes, in the paper industry in coating slips and as binders and sizing agents, for the finishing of textiles, in adhesives and sealants, as leather auxiliaries, as elastomers and for many other purposes.
• a large field of application for PMMA is the use as a hardening component in binders of coating resins.
• PAA is mainly used as a flocculant in water treatment, as a paper aid and as a flotation aid in mining.
• it is still used as a clarifier for fruit juices, textile auxiliaries, as crosslinkers in coatings, eg.
• As in the leather industry used as a thickener in paint dispersions, in adhesives and many other applications.
• Fields of application of PAC are knitwear, home textiles (eg blankets, curtains, upholstery fabrics) and carpets.
• a further preferred embodiment of the present invention relates to a polymer composition in which the polymer is selected from copolymers of the monomers mentioned in the above paragraph with each other or with other unsaturated monomers such as acrylonitrile / butadiene copolymers, acrylonitrile / alkyl acrylate copolymers, acrylonitrile / alkoxyalkyl acrylate or acrylonitrile / vinyl halide Copolymers or acrylonitrile / alkyl methacrylate / butadiene terpolymers.
• unsaturated monomers such as acrylonitrile / butadiene copolymers, acrylonitrile / alkyl acrylate copolymers, acrylonitrile / alkoxyalkyl acrylate or acrylonitrile / vinyl halide Copolymers or acrylonitrile / alkyl methacrylate / butadiene terpolymers.
• polystyrene poly (p-methylstyrene), poly ( ⁇ -methylstyrene), copolymers of styrene or ⁇ -methylstyrene with dienes or acrylic derivatives or graft copolymers of styrene or ⁇ methyl styrene.
• Unmodified styrenic polymers can be processed into foams that are used in construction and packaging.
• Copolymers of styrene or ⁇ -methylstyrene with dienes or acrylic derivatives include styrene / butadiene, styrene / acrylonitrile, styrene / alkyl methacrylate, styrene / butadiene / alkyl acrylate, styrene / butadiene / alkyl methacrylate, styrene / maleic anhydride, styrene / acrylonitrile / methyl acrylate; High impact strength blends of styrene copolymers and other polymer, e.g.
• styrene such as styrene / butadiene / styrene, styrene / isoprene / styrene, styrene / ethylene / butylene / styrene or styrene / ethylene / propylene / styrene.
• Graft copolymers of styrene or ⁇ -methylstyrene e.g. Styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers; Styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; Styrene, acrylonitrile and methyl methacrylate on polybutadiene; Styrene and maleic anhydride on polybutadiene; Styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; Styrene and maleimide on polybutadiene; Styrene and alkyl acrylates or methacrylates on polybutadiene; Styrene and acrylonitrile on ethylene / propylene / diene terpolymers; Styrene and acrylonitrile on polyalkyl acrylates or poly
• ABS acrylonitrile butadiene styrene foam
• housing for electrical and electronic equipment (telephones) e.g. B. Housing for electrical and electronic equipment (telephones), automotive parts.
• polymer blend is understood to mean a mixture of two or more polymers or copolymers, and polymer blends serve to improve the properties of the base component.
• polymer blends include PP / EPDM, polyamide / EPDM or ABS, PVC / EVA, PVC / ABS, PVC / MBS, PC / ABS, PBTP / ABS, PC / ASA, PC / PBT, PVC / CPE, PVC / acrylates, POM / Thermoplastic PUR, PC / Thermoplastic PUR, POM / Acrylates, POM / MBS, PPO / HIPS, PPO / PA 6.6 and Copolymers, PA / HDPE, PA / PP, PA / PPO, PBT / PC / ABS or PBT / PET / PC.
• ABS Acrylonitrile-butadiene-styrene copolymers
• the polymer composition of the present invention may contain at least one additive which is preferably selected from colorants, antioxidants, light stabilizers, metal deactivators, antistatic agents, reinforcing and filling agents, anti-fogging agents, biocides, antistatic agents and other additives.
• colorant in the context of the invention comprises both dyes and pigments.
• the pigment may be an inorganic or organic pigment.
• colorants are organic compounds which have fluorescence in the visible part of the electromagnetic spectrum, such as fluorescent dyes. In principle, all colorants which permit laser marking of plastic parts additivated with them are suitable.
• Suitable inorganic color pigments are white pigments such as titanium dioxide in its three modifications rutile, anatase or brookite, lead white, zinc white, zinc sulfide or lithopone; Black pigments such as carbon black, iron oxide black, iron manganese black or spinel black; Colored pigments such as chromium oxide, chromium oxide hydrate green, cobalt green or ultramarine green, cobalt blue, iron blue, milori blue, ultramarine blue or manganese blue, ultramarine violet or cobalt and manganese violet, iron oxide red, cadmium sulfoselenide, molybdate red or ultramarine red; Iron oxide brown, mixed brown, spinel and corundum phases or chrome orange; Iron oxide yellow, nickel titanium yellow, chrome titanium yellow, cadmium sulfide, cadmium zinc sulfide, chrome yellow, zinc yellow, alkaline earth chromate, Naples yellow; Bismuth vanadate, interference pigments, luster pigments
• Suitable inorganic pigments include: Pigment White 6, Pigment White 7, Pigment Black 7, Pigment Black 11, Pigment Black 22, Pigment Black 27/30, Pigment Yellow 34, Pigment Yellow 35/37, Pigment Yellow 42, Pigment Yellow 53 Pigment Brown 24, Pigment Yellow 18, Pigment Yellow 184, Pigment Orange 20, Pigment Orange 75, Pigment Brown 6, Pigment Brown 29, Pigment Brown 31, Pigment Yellow 164, Pigment Red 101, Pigment Red 104, Pigment Red 108, Pigment Red 265, Pigment Violet 15, Pigment Blue 28/36, Pigment Blue 29, Pigment Green 17, Pigment Green 26/50
• the colorant is an organic pigment or an organic dye, in particular a transparent colorant.
• suitable organic pigments are aniline black, anthrpyrimidine pigments, azomethine pigments, anthraquinone pigments, monoazo pigments, bisazopigments, benzimidazolone pigments, quinacridone pigments, quinophthalone pigments, dicarboxylic pigments, topyrrolopyrrole pigments, dioxazine pigments, flavanthrone pigments, indanthrone pigments, indolinone pigments, isoindoline pigments, isoindolinone pigments, thioindigo pigments, metal complex pigments, perinone pigments, perylene pigments, pyranthrone pigments, phthalocyanine pigments, thioindigo pigments, triarylcarbonium pigments or metal complex pigments.
• Suitable organic pigments include: Examples of organic pigments are: Cl. (Color Index) Pigment Yellow 93, Cl. Pigment Yellow 95, Cl. Pigment Yellow 138, Cl. Pigment Yellow 139, Cl. Pigment Yellow 155, Cl. Pigment Yellow 162, Cl. Pigment Yellow 168, Cl. Pigment Yellow 180, Cl. Pigment Yellow 183, Cl. Pigment Red 44, Cl. Pigment Red 170, Cl. Pigment Red 202, Cl. Pigment Red 214, Cl. Pigment Red 254, Cl. Pigment Red 264, Cl. Pigment Red 272, Cl. Pigment Red 48: 2, Cl. Pigment Red 48: 3, Cl. Pigment Red 53: 1, Cl. Pigment Red 57: 1, Cl. Pigment Green 7, Cl. Pigment Blue 15: 1, Cl. Pigment Blue 15: 3, Cl. Pigment Violet 19.
• pigments mentioned can also function as fillers or reinforcing agents and / or as nucleating agents.
• Another possible additive group also represents the visual impression, the mechanical properties or the haptic modifying additives, for.
• matting agents such as titanium dioxide, chalk, barium sulfate, zinc sulfide, fillers such as nanoparticulate silica, aluminum hydroxide, clay and other phyllosilicates, glass fibers and glass beads.
• the stabilizer component can be added in solid or liquid form before, during and after the preparation of the polymer.
• the pigment component and the stabilizer component may also be incorporated together or sequentially before, during or after the preparation of the polymer.
• the polymer composition according to the invention usually contains at least one UV stabilizer in an amount of 0.01 to 5 wt.%, Preferably 0.02 to 2.5 wt.% And especially preferably 0.01 to 1.0 wt.%. , based on the total weight of the composition.
• composition of the present invention may further contain at least one additive selected from antioxidants, metal deactivators, antistatic agents, reinforcing and filling agents, antifogging agents, biocides and antistatic agents.
• the optionally used antioxidants, light stabilizers, Metal Ideseptatoren have a high migration fastness and temperature resistance.
• Suitable antioxidants, light stabilizers, metal deactivators are selected, for example, from groups a) to s):
• the group a) of the 4,4-diarylbutadienes include, for example, compounds of the formula
• the compounds are known from EP-A-916 335.
• the substituents R 10 and / or Rn are preferably d-C ⁇ -alkyl and Cs-C ⁇ -cycloalkyl.
• the group b) of the cinnamic acid esters includes, for example, isoamyl 4-methoxycinnamate, 2-ethylhexyl 4-methoxycinnamate, methyl- ⁇ -methoxycarbonyl- cinnamate, methyl ⁇ -cyano- ⁇ -methyl-p-methoxycinnamate, butyl ⁇ -cyano- ⁇ -methyl-p-methoxy-cinnamate and methyl ⁇ -methoxycarbonyl-p-methoxycinnamate.
• the group c) of the benzotriazoles includes, for example, 2- (2'-hydroxyphenyl) benzotriazoles, such as 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3 ', 5'-di-tert-butyl- 2'-hydroxyphenyl) benzotriazole, 2- (5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5 '- (1, 1, 3,3-tetramethylbutyl) phenyl) benzotriazole , 2- (3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl) -5 chloro-benzotriazole, 2- (3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl) -benzotriazole, 2- (2'-hydroxy
• group d) of the hydroxybenzophenones include
• 2-hydroxybenzophenones such as 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone,
• the group e) of the diphenylcyanoacrylates includes, for example, ethyl-2-cyano-3,3-diphenylacrylate, which is obtainable, for example, commercially under the name Uvinul® 3035 from BASF AG, Ludwigshafen, 2-ethylhexyl-2-cyano-3, 3-diphenylacrylate, which is commercially available, for example, as Uvinul® 3039 from BASF AG, Ludwigshafen, and 1, 3-bis - [(2'-cyano-3 ', 3'-diphenylacryloyl) oxy] -2,2 -bis ⁇ [2'-cyano-3 ', 3'-diphenyl acryloyl) oxy] methyl ⁇ propane, which is commercially available, for example, under the name Uvinul® 3030 from BASF AG, Ludwigshafen.
• the group f) of the oxamides include, for example, 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butyloxanilide, 2,2'-didodecyloxy-5,5 'di-tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide, N, N'-bis (3-dimethylaminopropyl) oxamide, 2-ethoxy-5-tert-butyl-2'-ethyloxanilide and its mixture with Ethoxy-2'-ethyl-5,4'-di-tert-butyloxanilide and mixtures of ortho-, para-methoxy-disubstituted Oxani- liden and mixtures of ortho- and para-ethoxy disubstituted Oxaniliden.
• Group g) of 2-phenyl-1,3,5-triazines includes, for example, 2- (2-hydroxyphenyl) -1,3,5-triazines such as 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1, 3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazine, 2- (2,4-dihydroxyphenyl ) -4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1, 3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl
• the group h) of the antioxidants includes, for example:
• Alkylated monophenols such as, for example, 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di- tert -butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2- ( ⁇ -methylcyclohexyl) -4,6-dimethylphenol, 2, 6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, unbranched or branched in the side chain nonylphenols such as 2,6-di-nonyl-4-methyl phenol, 2,4-dimethyl-6- (1-methylundec-1-yl) -phenol,
• Alkylthiomethylphenols such as 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol.
• Hydroquinones and alkylated hydroquinones such as 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol , 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4 hydroxyphenyl stearate, bis- (3,5-di-tert-butyl-4-hydroxyphenyl) adipate.
• Tocopherols such as ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol and mixtures thereof (vitamin E).
• Hydroxylated thiodiphenyl ethers such as 2,2'-thio-bis (6-tert-butyl-4-methyl-phenol), 2,2'-thio-bis (4-octylphenol), 4,4'-thio-bis ( 6-tert-butyl-3-methylphenol), 4,4'-thio-bis (6-tert-butyl-2-methylphenol), 4,4'-thio-bis (3,6-di-sec-amylphenol ), 4,4'-bis (2,6-dimethyl-4-hydroxyphenyl) disulfide.
• Alkylidene bisphenols such as 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 2,2'-methylenebis (6-tert-butyl-4-ethylphenol), 2,2 ' -Methylene-bis [4-methyl-6- ( ⁇ -methylcyclohexyl) phenol], 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-methylenebis (6 -nonyl-4-methylphenol), 2,2'-methylenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (4,6-di-tert-butylphenol), 2, 2'-ethylidene-bis (6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis [6- ( ⁇ -methylbenzyl) -4-nonylphenol], 2,2'-methylene-bis [6 - ( ⁇ , ⁇ -dimethylbenzyl) -4-
• Benzyl compounds such as 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl-4-hydroxy-3,5 di-tert-butylbenzylmercaptoacetate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) amine,
• Hydroxybenzylated malonates such as dioctadecyl-2,2-bis (3,5-di-tert-butyl-2-hydroxybenzyl) malonate, di-octadecyl-2- (3-tert-butyl-4-hydroxy-5-methylbenzyl ) malonate, di-dodecylmercaptoethyl 2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate, bis [4- (1,1,3,3-tetramethylbutyl) phenyl] -2 , 2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate.
• Hydroxybenzyl aromatics such as 1, 3,5-T ⁇ s- (3, 5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1, 4-bis (3,5- di-tert-butyl-4-hydroxybenzyl) -2,3,5,6-tetra- methylbenzene, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) phenol.
• Triazine compounds such as 2,4-bis (octylmercapto) -6- (3,5-di-tert-butyl-4-hydroxyanilino) -1, 3,5-triazine, 2-octylmercapto-4,6-bis (3 , 5-di-tert-butyl-4-hydroxyanilino) -1, 3,5-triazine, 2-octylmercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyphenoxy) - 1 , 3,5-triazine, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenoxy) -1, 3,5-triazine, 1, 3,5-tris (3,5 di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-tris (3 , 5-d
• Benzyl phosphonates such as dimethyl 2,5-di-tert-butyl-4-hydroxybenzyl phosphonate, diethyl 3,5-di-tert-butyl-4-hydroxybenzyl phosphonate
• Acylaminophenols such as 4-hydroxy-lauric acid anilide, 4-hydroxystearic acid anilide, 2,4-bis-octylmercapto-6- (3,5-di-tert-butyl-4-hydroxyanilino) -s-triazine and octyl-N- (3,5-di-tert-butyl-4-hydroxyphenyl) -carbamate.
• Esters of ß- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with mono- or polyhydric alcohols such.
• Esters of ß- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid with monohydric or polyhydric alcohols such.
• Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with mono- or polyhydric alcohols such as.
• Amides of .beta .- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid such as. N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylenediamine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -trimethylenediamine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -hydrazine, N, N'-bis [2- (3- [3,5-di-tert-butyl-4 -hydroxyphenyl] -propionyloxy) -ethyl] -oxamide (eg Naugard® XL-1 from Uniroyal).
• vitamin C Ascorbic acid (vitamin C)
• Amine antioxidants such as N, N'-di-isopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N, N'-bis (1, 4-dimethylpentyl) -p- phenylenediamine, N, N'-bis (1-ethyl-3-methylpentyl) -p-phenylenediamine, N, N'-bis (1-methylheptyl) -p-phenylenediamine, N, N'-dicyclohexyl-p-phenylenediamine, N , N'-diphenyl-p-phenylenediamine, N, N'-bis (2-naphthyl) -p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylene diamine, N- (1, 3-dimethylbutyl) -N'-phenyl-p-pheny
• nickel compounds include, for example, nickel complexes of 2,2'-thio-bis [4- (1,1,3,3-tetramethylbutyl) phenol], such as the 1: 1 or 1: 2 complex, optionally with additional ligands such as n-butylamine, triethanolamine or N-cyclohexyl-diethanolamine, nickel dibutyldithiocarbamate, nickel salts of 4-hydroxy-3,5-di-tert-butylbenzylphosphonklamonoalkylester such.
• nickel complexes of ketoximes such.
• Example of 2-hydroxy-4-methylphenylundecyl ketoxime nickel complex of 1-phenyl-4-lauroyl-5-hydroxypyrazole, optionally with additional ligands.
• the group j) of the hindered amines include, for example, bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis (2,2,6,6-tetramethylpiperidin-4-yl) succinate, bis (1 , 2,2,6,6-pentamethylpiperidin-4-yl) sebacate, bis (1-octyloxy-2,2,6,6- tetramethylpiperidin-4-yl) sebacate, bis (1, 2,2,6,6-pentamethylpiperidin-4-yl) -n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensation product of 1-one (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, the condensation product of N, N'-bis (2, 2,6,6-tetramethylpiperidin-4-yl) hexamethylenediamine and 4-tert-octylamin
• Uvinul® 5050 H (BASF Aktiengesellschaft, Ludwigshafen), and corresponding polymer-analogous reaction products with 4-amino-1, 2,2,6,6-pentamethylpiperidine (eg "methylated Uvinul® 5050 H"), Condensation products of tetramethylolacetylenediurea and 4-amino-2,2,6,6-tetramethylpiperidine, e.g. B.
• Uvinul® 4049 H (BASF Aktiengesellschaft, Ludwigshafen), and corresponding condensation products with 4-amino-1, 2,2,6, 6-pentamethylpiperidine (eg "methylated Uvinul® 4049 H"), poly [[6 - [(1,1,3,3-tetramethylbutyl) amino] -1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidinyl) imino] 1, 6-hexanediyl [(2,2,6,6-tetramethyl-4-piperidinyl) imino]]) [CAS No.
• the group k) of the metal deactivators includes, for example, N, N'-diphenyloxalic diamide, N-salicylal-N'-salicyloyl-hydrazine, N, N'-bis (salicyloyl) hydrazine, N, N'-bis (3,5 di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1, 2,4-triazole, bis (benzylidene) oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenyl hydrazide, N, N'-diacetyl adipic dihydrazide, N, N Bis (salicyloyl) oxalic acid dihydrazide, N, N'-bis (salicyloyl) thiopropionyl dihydrazi
• the group I) of the phosphites and phosphonites includes, for example, triphenyl phosphite, diphenylalkyl phosphites, phenyl dialkyl phosphites, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, diisodecylpentaerythritol
• the group m) of the hydroxylamines include, for example, N, N-dibenzylhydroxylamine, N, N-diethylhydroxylamine, N, N-dioctylhydroxylamine, N, N-dilaurylhydroxylamine, N, N-ditetradecylhydroxylamine, N, N-dihexadecylhydroxylamine, N, N-dioctadecyl Hydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, N-methyl-N-octadecylhydroxylamine and N, N-dialkylhydroxylamine from hydrogenated tallow fatty amines.
• the group n) of the nitron include, for example, N-benzyl- ⁇ -phenylnitrone, N-ethyl- ⁇ -methylnitrone, N-octyl- ⁇ -heptylnitrone, N-lauryl- ⁇ -undecylnitrone, N-tetradecyl- ⁇ -tridecylnitrone, N Hexadecyl- ⁇ -pentadecyl nitrone, N-octadecyl- ⁇ -heptadecyl nitrone, N-hexadecyl- ⁇ -heptadecyl nitrone, N-octadecyl- ⁇ -pentadecylnitrone, N-heptadecyl- ⁇ -heptadecyl nitrone, N-octadecyl- ⁇ -hexadecylnitrone, N-methyl - ⁇ -heptade
• the group o) of the amine oxides includes, for example, amine oxide derivatives as described in US Patent Nos. 5,844,029 and 5,880,191, didecylmethylamine oxide, tridecylamine oxide, tridodecylamine oxide and trihexadecylamine oxide.
• the group p) of the benzofuranones and indolinones includes, for example, those described in U.S. Patents 4,325,863; 4,338,244; 5,175,312; 5,216,052; 5,252,643; in DE-A-431661 1; in DE-A-4316622; in DE-A-4316876; or 3- [4- (2-acetoxyethoxy) phenyl] -5,7-di-tert-butylbenzofuran-2 (3H) -one, 5.7, described in EP-A-0589839 or EP-A-0591102 -Di-tert-butyl-3- [4- (2-stearoyloxyethoxy) phenyl] -benzofuran-2 (3H) -one, 3,3'-bis [5,7-di-tert-butyl-3- (4 - [2-hydroxyethoxy] phenyl) benzofuran-2 (3H) -one], 5,7-di
• the group q) of thiosynergists includes, for example, dilauryl thiodipropionate or distearyl thiodipropionate.
• the group r) of the peroxide-destroying compounds include, for example, esters of ⁇ -thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl ester, mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zinc dibutyl dithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis ( ⁇ dodecylmercapto) propionate.
• esters of ⁇ -thiodipropionic acid for example the lauryl, stearyl, myristyl or tridecyl ester
• mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole zinc dibutyl dithiocarbamate
• dioctadecyl disulfide pentaerythritol tetrakis ( ⁇ dodecylmer
• the group s) of the basic costabilizers include, for example, melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, higher fatty acid alkali and alkaline earth salts, for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony catecholate or zinc catechinate.
• Diphenylcyanoacrylates such as ethyl-2-cyano-3,3-diphenylacrylate, are particularly suitable as further light-stabilizing agents.
• a further preferred embodiment of the present invention therefore relates to a composition wherein the compound of formula (I) is N, N'-bis (formyl) -N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl ) -1,6-hexanediamine and the further light stabilizer is 2-cyano-3,3-diphenylacrylic acid ethyl ester.
• the compound of formula (I) is N, N'-bis (formyl) -N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl ) -1,6-hexanediamine
• the further light stabilizer is 2-cyano-3,3-diphenylacrylic acid ethyl ester.
• As a further antioxidant in particular sterically hindered amines come into consideration.
• a further preferred embodiment of the present invention therefore relates to a composition wherein the compound of formula (I) is N, N'-bis (formyl) -N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl ) -1,6-hexanediamine and, as another light stabilizer, the polymer-analogous reaction products of 4-amino-2,2,6,6-tetramethylpiperidine and maleic acid / C 2 oC 24 - ⁇ -olefin copolymers, or the corresponding product methylated at the piperidine nitrogen atom.
• the additives of group t) are used in the usual amounts. Usually, they are used in an amount of 0 to 60 wt .-%, based on the total weight of the composition.
• the composition may also contain anti-statistic agents.
• antistatic agents are, for example, amine derivatives such as N, N-bis (hydroxyalkyl) alkylamines or -alkyleneamines, polyethylene glycol esters and ethers, ethoxylated carboxylic acid esters and amides and glycerol mono- and distearates, and mixtures thereof.
• Suitable fillers or reinforcing agents include, for example, the above-mentioned pigments such as carbon black, graphite, calcium carbonate, silicates, talc, mica, kaolin, mica, barium sulfate, metal oxides and hydroxides, wood flour and flours or fibers of other natural products, synthetic fibers .
• fibrous or pulverulent fillers are also carbon or glass fibers in the form of short glass fibers, long glass fibers, ground glass fibers, glass fabrics, glass mats or glass silk rovings, chopped glass, glass beads and wollstonite.
• composition according to the invention may also comprise nucleating agents.
• Suitable nucleating agents include, for example, inorganic ones
• Substances for example talc, metal oxides such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of preferably alkaline earth metals; organic compounds such as mono- or polycarboxylic acids and their salts such.
• metal oxides such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of preferably alkaline earth metals
• organic compounds such as mono- or polycarboxylic acids and their salts such.
• polymeric compounds such as ionic copolymers ("ionomers").
• the subject matter of the present invention is an ink composition containing at least one printing ink and at least one nanoparticulate preparation according to the invention.
• Printing inks are solid, pasty or liquid colorant preparations that are used in printing presses. Suitable inks depend on the particular printing process in which they are used and the material being printed.
• the material to be printed can be both absorbent and non-absorbent and in its dimension one-dimensional, z.
• Flat materials are z.
• Cylindrical or conical materials are z.
• Preferred materials are paper and plastic films. Suitable plastics are the polymers mentioned in the inventive polymer composition.
• the printing ink composition according to the invention can be used in all common printing processes, such.
• the printing ink composition according to the invention is preferably used in offset printing.
• Suitable colorants are both pigments and dyes. Suitable pigments and dyes are all customary colorants in the respective printing process.
• the printing ink composition according to the invention generally contains a colorant composition customary for the respective printing process and a nanoparticulate preparation according to the invention.
• Usual colorant compositions contain in addition to the colorant in general binders, which are usually referred to as Druckfirnisse, and additives such as driers, diluents, wax dispersions and optionally catalysts or initiators for radiation drying.
• the composition is determined by the printing process, the substrate to be printed and by the printing process. sought quality in terms of appearance, such as gloss, opacity, hue and transparency, and physical properties, such as water, grease, solvent resistance, rub resistance and laminating ability, selected individually.
• varnishes for pasty offset, book and screen inks z.
• Suitable varnishes for flexo, gravure and screen inks are z.
• the equipment of the colorant composition with the nanoparticulate preparation for example, by intimately mixing these components.
• all individual components of the colorant composition can be mixed together with the polyisobutenephosphonic to the ink composition of the invention.
• individual components of the colorant composition it is also possible for individual components of the colorant composition to be mixed first with the polyisobutenephosphonic acid and then this mixture to be mixed with the remaining components.
• Another object of the invention is the use of a nanoparticulate preparation as defined hereinbefore as an additive for a polymer composition or ink compositions.
• Another object of the invention is a method for identifying a plastic part, as described above.
• the inscription with the laser takes place, for example, in such a way that the specimen is brought into the beam path of a laser, preferably a pulsed laser.
• a laser preferably a pulsed laser.
• Nd-YAG laser is preferred.
• the power of the laser used depends on the particular application and can be determined in individual cases by the skilled person readily.
• the use of the pigmented plastic according to the invention can be carried out in all areas where previously customary printing process for labeling of plastics be used.
• moldings of the plastic according to the invention can be used in the electrical, electronics and automotive industries.
• the marking and labeling of z As cables, wires, trim or functional parts in the heating, ventilation and cooling area or switch, plug, lever and handles, which consist of the plastic according to the invention can be marked even in hard to reach places with the help of laser light.
• the plastic system according to the invention can be used in packaging in the food sector or in the toy sector due to its low heavy metal content.
• the markings on the packaging are characterized by the fact that they are wipe and scratch resistant, stable in subsequent sterilization processes, and hygienically pure in the marking process can be applied.
• Complete label images can be permanently applied to the packaging for a reusable system.
• Another important field of application for laser marking are plastic brands for the individual marking of animals, so-called cattle tags or ear tags.
• a barcode system stores the information that is specific to the animal. These can then be recalled when needed using a scanner.
• the lettering must be very durable, as the marks sometimes remain on the animals for several years.
• lanthanum hexaboride (HC Starck, Glossary) was 20.4% (1 kg LaB 6 and 3.9 kg carrier medium of THF and stearyl stearate) by means of 3 mm ZrO 2 -Mahl- bodies for 14 h in a Drais mill dispersed , Subsequently, the suspension was spray-dried. The resulting primary particle size was about 80 nm.
• nanoparticulate (example 1, 2) or non-nanoparticulate (comparative example 1, 2) lanthanum hexaboride, polyamide 6 (standard polyamide (Ultramid B3UG4 LS gray, BASF Aktiengesellschaft)) , Glass fibers and melamine cyanurate were extruded in a twin-screw extruder to a polyamide mixture and then further processed in an injection molding machine.
• polyamide 6 standard polyamide (Ultramid B3UG4 LS gray, BASF Aktiengesellschaft)
• Glass fibers and melamine cyanurate were extruded in a twin-screw extruder to a polyamide mixture and then further processed in an injection molding machine.
• Example 1 69.985% polyamide 6 20% glass fibers 10% melamine cyanurate
• lanthanum hexaboride nanodispersed, dispersed in THF, stearyl stearate was additionally added during the milling
• Example 2 69.985% polyamide 6 20% glass fibers 10% melamine cyanurate
• lanthanum hexaboride nanodispersed, dispersed in THF, in addition stearyl stearate was added during the milling
• the laser source used was a 50 W multimode Nd: YAG solid-state laser with a wavelength of 1064 nm.
• the beam diameter in focus was 100 ⁇ m. Contrast determination was visual, ranging from 1 (very good) to 6 (very poor).
• the laser inscribability was measured visually, the CTI (Comparative Tracking Index) was determined according to IEC112, the elongation at break (in%) according to ISO 527-2 and the Charpy impact strength at 23 ° C (in kJ / m 2 ) according to ISO 179/1 eil ,
• the polyamide 6 additized according to the invention with nanoparticulate lanthanum hexaboride has a better contrast of the label with a significantly lower proportion of additive and thus advantages in the mechanical properties and the CTI.
• the laser contrast agent LaB 6 in polytetrahydrofuran (M n 1000) is ground to nanoparticles, a 10% strength by weight dispersed dispersion being obtained.
• This 10% suspension is diluted with pure polytetrahydrofuran (M n 1000) to such an extent that test specimens with 10 to 1000 ppm LaB 6 based on the total weight TPU can be prepared.
• Important for a sharp laser marking is a very good distribution of the contrast agent in the polyurethane matrix. This is achieved by dispersing the LaB 6 in the liquid precursor of the TPU by dispersing.
• the incorporation of a dry LaB 6 nanopowder into a (TPU) polymer melt led to a poorer distribution and also to a dust load during incorporation.
• the second incorporation method is the preparation of a concentrate (eg a 2% concentrate) according to the above-mentioned method (grinding of LaB 6 in polytetrahydrofuran and preparation of a TPU from this polytetrahydrofuran) and adding a corresponding amount of the concentrate to one Standard TPU directly before processing into injection molded or extruded products.
• This method offers the advantage of being able to vary the concentration of the LaB 6 in the polymer matrix more easily.
• the carrier medium with the dispersed LaB 6 nanoparticles is used as starting material for the preparation of the polyether-polyurethanes.
• Injection molded articles were prepared from a thermoplastic polyether polyurethane of Shore hardness 85A based on 1000 parts of polytetrahydrofuran having an average molecular weight of 1000, 600 parts of MDI and 126 parts of 1,4-butanediol. which contained 100 ppm of LaB 6 previously ground to nanoparticles in polytetrahydrofuran (M n 1000).
• Injection molded articles were prepared from a thermoplastic polyether polyurethane Shore hardness 85A based on 1000 parts of polytetrahydrofuran having an average molecular weight of 1000, 600 parts of MDI and 126 parts of 1,4-butanediol, the 1000 ppm LaB 6 , previously in polytetrahydrofuran (M n 1000) were milled to nanoparticles.
• Injection molded bodies were produced from a thermoplastic polyurethane of Shore hardness 9OA.
• To prepare the thermoplastic polytetrahydrofuran urethane 1000 parts of butylhexyl adipate having a molecular weight of 2000, 580 parts of MDI, 162 parts of 1,4-butanediol and 90 parts of TPU concentrate 3 were subjected to a polyaddition.
• the TPU1 injection-molded sheets were transparent, the TPU2 and TPU4 injection-molded sheets were dark green / black and partially transparent.
• TPU1 after labeling with a Nd: YAG laser at 1064nm, showed a dark writing on a transparent background, with the writing "inside" the test panel and with no surface defects. After glazing, TPU2 and TPU4 showed a very fine white writing on a dark background.

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• 2007
  • 2007-02-06 CN CNA2007800099674A patent/CN101405146A/zh active Pending
  • 2007-02-06 EP EP07704393A patent/EP1998962A1/de not_active Withdrawn
  • 2007-02-06 US US12/282,578 patent/US20090029121A1/en not_active Abandoned
  • 2007-02-06 WO PCT/EP2007/051135 patent/WO2007107407A1/de active Application Filing
  • 2007-02-06 KR KR1020087025549A patent/KR20090006832A/ko not_active Application Discontinuation
  • 2007-02-06 AU AU2007228912A patent/AU2007228912A1/en not_active Abandoned
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