EP1689810A1 - Thermoplastic, polymeric materials providing high ir absorption, method for the production thereof, and use thereof - Google Patents

Thermoplastic, polymeric materials providing high ir absorption, method for the production thereof, and use thereof

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Publication number
EP1689810A1
EP1689810A1 EP04798094A EP04798094A EP1689810A1 EP 1689810 A1 EP1689810 A1 EP 1689810A1 EP 04798094 A EP04798094 A EP 04798094A EP 04798094 A EP04798094 A EP 04798094A EP 1689810 A1 EP1689810 A1 EP 1689810A1
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EP
European Patent Office
Prior art keywords
thermoplastic
polymeric materials
inorganic metal
absorption
metal phosphate
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EP04798094A
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German (de)
French (fr)
Inventor
Bernd Hirthe
Kirsten Föhr
Thorsten Bier
Heike SÄNGER
Andrea Otremba
Michael Wedler
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Venator Germany GmbH
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Sachtleben Chemie GmbH
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds

Definitions

  • the invention relates to thermoplastic, polymeric materials with high IR absorption, a process for their production and their use.
  • thermoplastic polymeric materials
  • PET polyethylene terephthalate
  • PET compositions as packaging material in the form of foils, bottles and other container shapes may be mentioned as an example.
  • the polymer is usually fed to the process in the form of granules to form PET bottles.
  • the granules (“PET chips") are first melted in extruders and processed into so-called preforms using injection molding processes. In a further process step, these preforms are brought into the final bottle shape using the stretch blow molding process.
  • preforms are brought into the final bottle shape using the stretch blow molding process.
  • heating is typically to a temperature of 105 ° C. The heating can e.g.
  • preforms are irradiated with the light of a black radiator (radiator temperature 500 ° K to 3000 ° K, e.g. from commercially available quartz IR lamp radiators).
  • a black radiator radiation temperature 500 ° K to 3000 ° K, e.g. from commercially available quartz IR lamp radiators.
  • Polyester polymers only absorb for certain specific wavelength ranges of the IR spectrum and therefore only a low absorption of the energy made available.
  • US Pat. Nos. 4408004 and 4535118 cite graphite or carbon black as a suitable absorption additive with the additional requirement that the particle size as well as the maximum addition amount must be kept in a closely controlled range in order to maintain or maintain the optical clarity of the resulting bottles sufficiently not to cause an unacceptable gray color.
  • carbon black has a significantly higher absorption in the visible wavelength range than in the range 700 to 1500 nm, which is disadvantageous with regard to the maximum amount that can be used from the point of view of discoloration.
  • the object of the invention is to overcome the disadvantages of the prior art and in particular to provide thermoplastic, polymeric materials which can be heated in a simple and economical manner by irradiation with NIR and / or IR light to such an extent that further shaping processing is possible is.
  • thermoplastic, polymeric materials with high IR absorption which contain at least one inorganic metal phosphate of the general formula Me x (P0) y (OH) z , where Me consists of one or more elements from the group Cu, Fe, Mn, Sb, Zn, Ti, Ni, Co, V, Mg, Bi, Be, AI, Ce, Ba, Sr, Na, K, Ge, Ga, Ca, Cr, In or Sn, and where x, y and z are and x has values from 1 to 18, y values from 1 to 12 and z values from 0.2 to 10 and the inorganic metal phosphate can optionally also contain water of crystallization.
  • Me x (P0) y (OH) z where Me consists of one or more elements from the group Cu, Fe, Mn, Sb, Zn, Ti, Ni, Co, V, Mg, Bi, Be, AI, Ce, Ba, Sr, Na, K, Ge, Ga, Ca, Cr, In or Sn, and where x,
  • thermoplastic, polymeric materials have a high IR absorption without the addition of organic or organometallic substances to the polymers.
  • the purely inorganic compounds which are relatively easy to produce, or minerals of the general formula Me x (PO 4 ) y (OH) z which are easy to obtain, are able to bring about a high IR absorption in the polymers.
  • “High” IR absorption means that the transparency in the visible wavelength range 400 to 700 nm is not noticeably impaired and the absorption in the wavelength range 700 to 1500 nm is significantly higher than in the visible range; For example, the absorption of such a polymer at a wavelength of 1100 nm is at least twice as high as the absorption at 600 nm.
  • thermoplastic, polymeric materials polyester (such as polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN)), polyalkylenes (such as polyethylene (PE), polypropylene (PP)) , Vinyl polymers (such as polyvinyl chloride (PVC)), polyamides, polyacetals, polyacrylates (such as polymethyl methacrylate (PMMA)), polycarbonates, polystyrenes, polyurethanes, acrylonitrile-butadiene-styrene copolymers (ABS), halogen-containing polyalkylenes, polyarylene oxides or polyarylene sulfides.
  • PET polyethylene terephthalate
  • PTT polytrimethylene terephthalate
  • PBT polybutylene terephthalate
  • PEN polyethylene naphthalate
  • polyalkylenes such as polyethylene (PE), polyprop
  • Phosphate-containing compounds of the Dana classification VII - 41 and VII - 42 can be used as inorganic metal phosphates with the general formula Me x (P0) y (OH) z .
  • the Dana classification is described in: Dana's New Mineralogy, Eighth Edition, by Richard V. Gaines, H. Catherine Skinner, Eugene E. Foord, Brian Mason, and Abraham Rosenzweig, with sections by Vandall T. King, illustrations by Eric Dowty , (ISBN: 047119310-0) Copyright ⁇ 1997, John Wiley & Sons, Inc.
  • the inorganic metal phosphates preferably contain one or more of the elements Cu, Fe and Al.
  • inorganic metal phosphates with the general Formula Me x (P0 4 ) y (OH) z are preferably used: Cu 2 P0 4 OH, Cu 3 (P0 4 ) (OH) 3 Cu 3 (P0 4 ) (OH) 3 , Cu 5 (PO 4 ) 2 (OH) 4 , CuFe 2 (P0 4 ) 2 (OH) 2 (Cu, Zn) 2 ZnPO 4 (OH) 3 -2 (H 2 0), (Cu, Zn) 5 Zn (P0 4 ) 2 (OH ) 6 (H 2 0), Cu 3 AI 4 (P0 4 ) 3 (OH) 9 -4 (H 2 0),
  • the addition amount of the inorganic metal phosphates depends on the absorption of the polymer produced therefrom in the range from 400 to 700 nm (the transparency should be impaired as little as possible) and the absorption in the range from 700 to 1500 nm (the higher the absorption, the lower the addition amount) and is to be determined in preliminary tests if necessary.
  • addition quantities of 0.0002 to 2% by weight of inorganic metal phosphate, based on the finished thermoplastic, polymeric material have proven to be suitable.
  • a preferred addition amount is in the range of 0.001 to 0.1% by weight.
  • the inorganic metal phosphates are to be used in the form of naturally occurring minerals, these must first be ground up.
  • the inorganic metal phosphate preferably has crystallite sizes (measured according to Scherrer) from 0.005 to 5 ⁇ m, particularly preferably from 0.001 to 2 ⁇ m.
  • solutions of the metal ion (s) and a solution of the respective P0 component are precipitated in an aqueous medium.
  • the pH value, temperature, rate of addition, addition concentrations and order of addition must be set in a known manner.
  • Corresponding solutions of the sulfates, chlorides, nitrates, hydroxides or oxides can be used, for example, as metal ion solutions.
  • Suitable solutions for the P0 4 component are, for example Phosphoric acid or its soluble salts (such as alkali or alkaline earth phosphates).
  • the products can be treated hydrothermally (heating the aqueous precipitation suspension to temperatures> 100 ° C. at elevated pressure) and / or thermally treated in the dried state.
  • the inorganic metal phosphate can be added to the polymer at various times during the production of the thermoplastic, namely before, during and after the polymerization reaction.
  • the inorganic metal phosphate is preferably added in the form of a suspension (e.g. in an inert solvent or a reactant).
  • a suspension of the inorganic metal phosphate in monoethylene glycol (or in propanediol or butanediol) can be added at different times in the reaction.
  • thermoplastic polymer materials containing one or more inorganic metal phosphates are used wherever thermoplastic polymer materials are softened by heating by means of IR radiation and then subjected to shaping processing.
  • the materials according to the invention are used in particular in the production of preforms, their heating with IR radiation and subsequent processing into articles for use (eg packaging).
  • heating is typically carried out by means of IR radiation to a temperature of 90 to 120 ° C., preferably 100 to 110 ° C.
  • thermoplastic polymers depending on the glass transition temperature and melting temperature, such heating temperatures are to be selected at which the subsequent shaping further processing of these polymers can be technically realized.
  • the product obtained was filtered off and washed to a filtrate conductivity ⁇ 100 ⁇ S / cm.
  • the filter cake was then dispersed in water using a dissolver and dried in a laboratory spray tower.
  • the dry product had a well-developed crystal structure (see Figure 3).
  • Example 3 Absorption spectrum of Cu 2 P0 4 OH
  • Example 1 1.0 g of the copper phosphate Cu 2 P0 4 OH prepared in Example 1 was mixed with 1.0 I of an alkyd resin binder (DSM AD-9). An absorption spectrum in the wavelength range from 400 to 2000 nm was recorded from this mixture (see FIG. 1). The spectrum shows that the metal phosphate according to the invention has a significantly increased absorption with a maximum at 1150 nm in the range from 700 to 1600 nm relevant for IR radiation heating.
  • Example 4 Energy consumption of Cu 2 P0 4 OH in PET when irradiated with an IR radiator compared to pure PET and PET with carbon black.
  • Example 1 The copper phosphate produced in Example 1 was incorporated in a concentration of 0.01%, based on the plastic, in polyethylene terephthalate by means of an extruder. The melt was injection molded into platelets 9 mm thick. Transmission spectra of the platelets were recorded with a spectrometer in the range from 400 to 1600 nm.
  • FIG. 2 shows on the one hand the energy emitted by an IR lamp at a radiation temperature of 2450 K (curve 1) and on the other hand the corresponding wavelength-dependent energy consumption of various test plates (curves 2 to 4) when irradiated with this radiation source.
  • the formulation according to the invention (curve 4) has a significantly lower absorption in the visible range (400 to 700 nm) and thus a lower clouding or coloring potential than the comparative sample corresponding to the prior art (curve 3).
  • the NIR range 800 to 1600 nm
  • the clearly increased radiation absorption of the formulation according to the invention and thus better energy yield in the heating process in comparison to pure PET (curve 2) and to the comparison sample (curve 3) can be seen.

Abstract

Disclosed are thermoplastic, polymeric materials that provide high IR absorption and contain at least one inorganic metal phosphate of general formula Mex(PO4)y(OH)z, wherein Me represents one or several elements from the group comprising Cu, Fe, Mn, Sb, Zn, Ti, Ni, Co, V, Mg, Bi, Be, Al, Ce, Ba, Sr, Na, K, Ge, Ga, Ca, Cr, In, or Sn while x and y are integers and x = (1 ... 18), y = (1 ... 12), and z = (0.2 ... 10), the inorganic metal phosphate optionally also containing water of crystallization.

Description

Thermoplastische, polymere Werkstoffe mit hoher IR-Absorption, Verfahren zu deren Herstellung und deren VerwendungThermoplastic, polymeric materials with high IR absorption, process for their production and their use
Die Erfindung betrifft thermoplastische, polymere Werkstoffe mit hoher IR- Absorption, ein Verfahren zu deren Herstellung und deren Verwendung.The invention relates to thermoplastic, polymeric materials with high IR absorption, a process for their production and their use.
Um thermoplastische, polymere Werkstoffe (z.B. Polyester, wie Polyethylen- terephthalat (PET)) in ihre bestimmungsgemäße Form zu bringen, werden die Werkstoffe oftmals erhitzt, wobei diese erweichen und damit formbar werden.In order to bring thermoplastic, polymeric materials (e.g. polyester, such as polyethylene terephthalate (PET)) into their intended shape, the materials are often heated, whereby they soften and thus become malleable.
Als Beispiel sei die bekannte Verwendung von PET-Zusammensetzungen als Verpackungsmaterial in Form von Folien, Flaschen und anderen Behälterformen angeführt. Zur Ausformung von PET-Flaschen wird das Polymer üblicherweise in Granulatform dem Prozess zugeführt. Das Granulat ("PET-Chips") wird zunächst in Extrudern aufgeschmolzen und über Spritzgussverfahren zu sogenannten Vorformlingen (Preforms) verarbeitet. In einem weiteren Verfahrensschritt werden diese Vorformlinge über das Streckblasverfahren in die endgültige Flaschenform gebracht. Um die plastische Umformung der Vorform zu einer gebrauchsfähigen Flasche durchführen zu können, ist es erforderlich, die Vorform auf eine Temperatur oberhalb des Glaspunkts und unterhalb des Schmelzpunktes des Polyesters zu erwärmen. Für PET erfolgt die Erwärmung typischerweise auf eine Temperatur von 105 °C. Die Erwärmung kann z.B. dadurch erfolgen, dass die Vorformlinge mit dem Licht eines schwarzen Strahlers (Strahlertemperatur 500 °K bis 3000 °K, z.B. aus kommerziell verfügbaren Quartz-IR-Lampenstrahlern) bestrahlt werden. Allerdings weisen z.B. Polyester-Polymere nur für einige bestimmte Wellenlängenbereiche des IR-Spektrums eine Absorption und deswegen nur eine geringe Aufnahme der zur Verfügung gestellten Energie auf.The well-known use of PET compositions as packaging material in the form of foils, bottles and other container shapes may be mentioned as an example. The polymer is usually fed to the process in the form of granules to form PET bottles. The granules ("PET chips") are first melted in extruders and processed into so-called preforms using injection molding processes. In a further process step, these preforms are brought into the final bottle shape using the stretch blow molding process. In order to be able to carry out the plastic shaping of the preform into a usable bottle, it is necessary to heat the preform to a temperature above the glass point and below the melting point of the polyester. For PET, heating is typically to a temperature of 105 ° C. The heating can e.g. in that the preforms are irradiated with the light of a black radiator (radiator temperature 500 ° K to 3000 ° K, e.g. from commercially available quartz IR lamp radiators). However, e.g. Polyester polymers only absorb for certain specific wavelength ranges of the IR spectrum and therefore only a low absorption of the energy made available.
In der US Patentschrift 6197851 wird vorgeschlagen, einem Polymer für die Herstellung von Flaschen nach dem Streckblasverfahren mindestens eine organische oder Organometall- Verbindung zuzusetzen, die Licht im Wellenlängenbereich 700 bis 1200 nm mindestens doppelt so stark absorbiert wie im Wellenlängenbereich 400 bis 700 nm. Damit soll das Absorptionsvermögen und somit die Energieaufnahme des Polymers für NIR- und IR-Strahlung erhöht werden. Von Nachteil der angegebenen organischen Verbindungen ist, dass diese nur relativ aufwändig hergestellt werden können und dementsprechend teuer sind.In US Pat. No. 6,197,851 it is proposed to add at least one organic or organometallic compound to a polymer for the manufacture of bottles by the stretch blow molding process, which absorbs light in the wavelength range 700 to 1200 nm at least twice as strongly as in Wavelength range 400 to 700 nm. This is intended to increase the absorption capacity and thus the energy consumption of the polymer for NIR and IR radiation. The disadvantage of the specified organic compounds is that they can only be produced with relatively great effort and are accordingly expensive.
Die US-Patentschriften 4408004 und 4535118 nennen als geeigneten absorptionswirksamen Zusatzstoff Graphit oder Carbon Black mit der zusätzlichen Anforderung, dass die Partikelgröße wie auch die maximale Zusatzmenge in einem eng kontrollierten Bereich gehalten werden müssen, um die optische Klarheit der resultierenden Flaschen hinreichend aufrecht zu erhalten bzw. keine inakzeptable Graufärbung zu bewirken. Allerdings hat Carbon Black eine deutlich höhere Absorption im sichtbaren Wellenlängenbereich als im Bereich 700 bis 1500 nm, was von Nachteil hinsichtlich der unter Verfärbungsgesichtspunkten maximal einsetzbaren Zugabemenge ist.US Pat. Nos. 4408004 and 4535118 cite graphite or carbon black as a suitable absorption additive with the additional requirement that the particle size as well as the maximum addition amount must be kept in a closely controlled range in order to maintain or maintain the optical clarity of the resulting bottles sufficiently not to cause an unacceptable gray color. However, carbon black has a significantly higher absorption in the visible wavelength range than in the range 700 to 1500 nm, which is disadvantageous with regard to the maximum amount that can be used from the point of view of discoloration.
Aufgabe der Erfindung ist es, die Nachteile des Standes der Technik zu überwinden und insbesondere thermoplastische, polymere Werkstoffe bereitzustellen, die sich durch Bestrahlung mit NIR- und/oder IR-Licht auf einfache und wirtschaftliche Weise soweit erwärmen lassen, dass eine weitere formgebende Verarbeitung möglich ist.The object of the invention is to overcome the disadvantages of the prior art and in particular to provide thermoplastic, polymeric materials which can be heated in a simple and economical manner by irradiation with NIR and / or IR light to such an extent that further shaping processing is possible is.
Gelöst wird die Aufgabe durch thermoplastische, polymere Werkstoffe mit hoher IR-Absorption, die mindestens ein anorganisches Metallphosphat der allgemeinen Formel Mex(P0 )y(OH)z enthalten, wobei Me aus einem oder mehreren Elementen der Gruppe Cu, Fe, Mn, Sb, Zn, Ti, Ni, Co, V, Mg, Bi, Be, AI, Ce, Ba, Sr, Na, K, Ge, Ga, Ca, Cr, In oder Sn besteht, und wobei x, y und z sind und x Werte von 1 bis 18, y Werte von 1 bis 12 und z Werte von 0,2 bis 10 einnimmt und das anorganische Metallphosphat gegebenenfalls noch Kristallwasser enthalten kann. Es wurde gefunden, dass derartige thermoplastische, polymere Werkstoffe eine hohe IR-Absorption aufweisen, ohne dass den Polymeren organische oder metallorganische Stoffe zugegeben wurden. Überraschend sind die rein anorganischen und relativ leicht herzustellenden Verbindungen, bzw. leicht zu gewinnenden Minerale der angegebenen allgemeinen Formel Mex(P04)y(OH)z in der Lage, in den Polymeren eine hohe IR-Absorption zu bewirken. Unter "hoher" IR-Absorption ist dabei zu verstehen, dass die Transparenz im sichtbaren Wellenlängenbereich 400 bis 700 nm nicht merklich beeinträchtigt wird und die Absorption im Wellenlängenbereich 700 bis 1500 nm deutlich höher als im sicht- baren Bereich liegt; z.B. ist die Absorption eines solchen Polymers bei einer Wellenlänge von 1100 nm mindestens doppelt so hoch ist wie die Absorption bei 600 nm.The object is achieved by thermoplastic, polymeric materials with high IR absorption which contain at least one inorganic metal phosphate of the general formula Me x (P0) y (OH) z , where Me consists of one or more elements from the group Cu, Fe, Mn, Sb, Zn, Ti, Ni, Co, V, Mg, Bi, Be, AI, Ce, Ba, Sr, Na, K, Ge, Ga, Ca, Cr, In or Sn, and where x, y and z are and x has values from 1 to 18, y values from 1 to 12 and z values from 0.2 to 10 and the inorganic metal phosphate can optionally also contain water of crystallization. It has been found that such thermoplastic, polymeric materials have a high IR absorption without the addition of organic or organometallic substances to the polymers. Surprisingly, the purely inorganic compounds which are relatively easy to produce, or minerals of the general formula Me x (PO 4 ) y (OH) z which are easy to obtain, are able to bring about a high IR absorption in the polymers. “High” IR absorption means that the transparency in the visible wavelength range 400 to 700 nm is not noticeably impaired and the absorption in the wavelength range 700 to 1500 nm is significantly higher than in the visible range; For example, the absorption of such a polymer at a wavelength of 1100 nm is at least twice as high as the absorption at 600 nm.
Als thermoplastische, polymere Werkstoffe können eingesetzt werden: Polyester (wie Polyethylenterephthalat (PET), Polytrimethylenterephthalat (PTT), Poly- butylenterephthalat (PBT), Polyethylennaphthalat (PEN)), Polyalkylene (wie Poly- ethylen (PE), Polypropylen (PP)), Vinylpolymere (wie Polyvinylchlorid (PVC)), Polyamide, Polyacetale, Polyacrylate (wie Polymethylmethacrylat (PMMA)), Polycarbonate, Polystyrole, Polyurethane, Acrylnitril-Butadien-Styrol-Copolymere (ABS), Halogenhaltige Polyalkylene, Polyarylenoxide oder Polyarylensulfide.The following can be used as thermoplastic, polymeric materials: polyester (such as polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN)), polyalkylenes (such as polyethylene (PE), polypropylene (PP)) , Vinyl polymers (such as polyvinyl chloride (PVC)), polyamides, polyacetals, polyacrylates (such as polymethyl methacrylate (PMMA)), polycarbonates, polystyrenes, polyurethanes, acrylonitrile-butadiene-styrene copolymers (ABS), halogen-containing polyalkylenes, polyarylene oxides or polyarylene sulfides.
Bevorzugt weisen in obiger Formel x, y und z folgende Werte auf: x = (1 ... 5), y = (1 ... 4) und z = (0,2 ... 5). Als anorganische Metallphosphate mit der allgemeinen Formel Mex(P0 )y(OH)z können phosphathaltige Verbindungen der Dana-Classification VII - 41 und VII - 42 eingesetzt werden. Die Dana- Classification ist beschrieben in: Dana's New Mineralogy, Eighth Edition, by Richard V. Gaines, H. Catherine Skinner, Eugene E. Foord, Brian Mason, and Abraham Rosenzweig, with sections by Vandall T. King, lllustrations by Eric Dowty, (ISBN: 047119310-0) Copyright © 1997, John Wiley & Sons, Inc.In the above formula, x, y and z preferably have the following values: x = (1 ... 5), y = (1 ... 4) and z = (0.2 ... 5). Phosphate-containing compounds of the Dana classification VII - 41 and VII - 42 can be used as inorganic metal phosphates with the general formula Me x (P0) y (OH) z . The Dana classification is described in: Dana's New Mineralogy, Eighth Edition, by Richard V. Gaines, H. Catherine Skinner, Eugene E. Foord, Brian Mason, and Abraham Rosenzweig, with sections by Vandall T. King, illustrations by Eric Dowty , (ISBN: 047119310-0) Copyright © 1997, John Wiley & Sons, Inc.
Bevorzugt enthalten die anorganischen Metallphosphate eines oder mehrere der Elemente Cu, Fe und AI. Als anorganische Metallphosphate mit der allgemeinen Formel Mex(P04)y(OH)z werden bevorzugt eingesetzt: Cu2P04OH, Cu3(P04)(OH)3 Cu3(P04)(OH)3, Cu5(PO4)2(OH)4, CuFe2(P04)2(OH)2 (Cu,Zn)2ZnPO4(OH)3-2(H20), (Cu,Zn)5Zn(P04)2(OH)6 (H20), Cu3AI4(P04)3(OH)9-4(H20),The inorganic metal phosphates preferably contain one or more of the elements Cu, Fe and Al. As inorganic metal phosphates with the general Formula Me x (P0 4 ) y (OH) z are preferably used: Cu 2 P0 4 OH, Cu 3 (P0 4 ) (OH) 3 Cu 3 (P0 4 ) (OH) 3 , Cu 5 (PO 4 ) 2 (OH) 4 , CuFe 2 (P0 4 ) 2 (OH) 2 (Cu, Zn) 2 ZnPO 4 (OH) 3 -2 (H 2 0), (Cu, Zn) 5 Zn (P0 4 ) 2 (OH ) 6 (H 2 0), Cu 3 AI 4 (P0 4 ) 3 (OH) 9 -4 (H 2 0),
CuAI3(P04)4(OH)3-4(H20), (Zn,Cu)AI6(P04)4(OH)8-4(H20), CuFe6(P04)4(OH)8-4(H2O), CaCu6[(P04)2(P03OH)(OH)6]-3(H20) oderCuAI 3 (P0 4 ) 4 (OH) 3 -4 (H 2 0), (Zn, Cu) AI 6 (P0 4 ) 4 (OH) 8 -4 (H 2 0), CuFe 6 (P0 4 ) 4 (OH) 8 -4 (H 2 O), CaCu 6 [(P0 4 ) 2 (P0 3 OH) (OH) 6 ] -3 (H 2 0) or
Cu2Mg2(P04)2(OH)2-5(H20).Cu 2 Mg 2 (P0 4 ) 2 (OH) 2 -5 (H 2 0).
Die Zugabemenge der anorganischen Metallphosphate richtet sich nach der Absorption des daraus hergestellten Polymers im Bereich 400 bis 700 nm (die Transparenz soll möglichst wenig beeinträchtigt werden) und der Absorption im Bereich von 700 bis 1500 nm (je höher die Absorption, desto geringer die Zugabemenge) und ist gegebenenfalls in Vorversuchen zu ermitteln. Im allgemeinen haben sich abhängig von der Werkstoffdicke und von zulässigen Farbveränderungen (diese hängen von dem jeweiligen Einsatzgebiet ab) Zugabemengen von 0,0002 bis 2 Gew.-% anorganisches Metallphosphat, bezogen auf den fertigen thermoplastischen, polymeren Werkstoff, als geeignet erwiesen. Eine bevorzugte Zugabemenge liegt im Bereich von 0,001 bis 0,1 Gew.-%.The addition amount of the inorganic metal phosphates depends on the absorption of the polymer produced therefrom in the range from 400 to 700 nm (the transparency should be impaired as little as possible) and the absorption in the range from 700 to 1500 nm (the higher the absorption, the lower the addition amount) and is to be determined in preliminary tests if necessary. In general, depending on the material thickness and permissible color changes (these depend on the respective field of application), addition quantities of 0.0002 to 2% by weight of inorganic metal phosphate, based on the finished thermoplastic, polymeric material, have proven to be suitable. A preferred addition amount is in the range of 0.001 to 0.1% by weight.
Sollen die anorganischen Metallphosphate in Form von natürlich vorkommenden Mineralien eingesetzt werden, müssen diese erst aufgemahlen werden. Das anorganische Metallphosphat hat bevorzugt Kristallitgrößen (gemessen nach Scherrer) von 0,005 bis 5 μm, besonders bevorzugt von 0,001 bis 2 μm.If the inorganic metal phosphates are to be used in the form of naturally occurring minerals, these must first be ground up. The inorganic metal phosphate preferably has crystallite sizes (measured according to Scherrer) from 0.005 to 5 μm, particularly preferably from 0.001 to 2 μm.
Zur Herstellung der anorganischen Metallphosphate Mex(P0 )y(OH)z werden Lösungen des oder der jeweiligen Metallionen und eine Lösung der jeweiligen P0 -Komponente in wässrigem Medium zur Ausfällung gebracht. Hierbei sind abhängig von der herzustellenden Verbindung in bekannter Weise pH-Wert, Temperatur, Zugabegeschwindigkeit, Zugabekonzentrationen und Zugabereihenfolge einzustellen. Als Metallionlösungen können z.B. entsprechende Lösungen der Sulfate, Chloride, Nitrate, Hydroxide oder Oxide eingesetzt werden. Geeignete Lösungen für die P04-Komponente sind z.B. die Phosphorsäure oder deren lösliche Salze (wie Alkali- oder Erdalkaliphosphate). Weiterhin können zur Ausbildung der gewünschten Verbindung die Produkte hydrothermal (Erhitzen der wässrigen Fällsuspension auf Temperaturen > 100°C bei erhöhtem Druck) behandelt und/oder in getrocknetem Zustand thermisch behandelt werden.To produce the inorganic metal phosphates Me x (P0) y (OH) z , solutions of the metal ion (s) and a solution of the respective P0 component are precipitated in an aqueous medium. Depending on the compound to be produced, the pH value, temperature, rate of addition, addition concentrations and order of addition must be set in a known manner. Corresponding solutions of the sulfates, chlorides, nitrates, hydroxides or oxides can be used, for example, as metal ion solutions. Suitable solutions for the P0 4 component are, for example Phosphoric acid or its soluble salts (such as alkali or alkaline earth phosphates). Furthermore, to form the desired compound, the products can be treated hydrothermally (heating the aqueous precipitation suspension to temperatures> 100 ° C. at elevated pressure) and / or thermally treated in the dried state.
Die Zugabe des anorganischen Metallphosphates zum Polymer kann zu verschiedenen Zeitpunkten der Thermoplast-Herstellung erfolgen, nämlich vor, während und nach der Polymerisationsreaktion. Bei der Polyesterherstellung wird das anorganische Metallphosphat bevorzugt in Form einer Suspension (z.B. in einem inerten Lösungsmittel oder einem Reaktionspartner) zugegeben. Beispielsweise kann bei der Polyalkylenterephthalat-Synthese eine Suspension des anorganischen Metallphosphats in Monoethylenglykol (bzw. in Propandiol oder Butandiol) zu verschiedenen Zeitpunkten der Reaktion zugegeben werden. Insbesondere bei der Polyalkylenherstellung ist es auch möglich, das anorganische Metallphosphat in Form eines (separat gefertigten) hochkonzentrierten Compounds während der Schmelzecompoundierung (z.B. vor der Extrusion zu Granulat oder Vorformlingen) zuzugeben.The inorganic metal phosphate can be added to the polymer at various times during the production of the thermoplastic, namely before, during and after the polymerization reaction. In polyester production, the inorganic metal phosphate is preferably added in the form of a suspension (e.g. in an inert solvent or a reactant). For example, in the polyalkylene terephthalate synthesis, a suspension of the inorganic metal phosphate in monoethylene glycol (or in propanediol or butanediol) can be added at different times in the reaction. In polyalkylene production in particular, it is also possible to add the inorganic metal phosphate in the form of a (separately manufactured) highly concentrated compound during melt compounding (e.g. before extrusion into granules or preforms).
Die Verwendung finden die thermoplastischen, eine oder mehrere anorganische Metallphosphate enthaltenden polymeren Werkstoffe überall dort, wo thermo- plastische, polymere Werkstoffe durch Erwärmung mittels IR-Strahlung erweicht und anschließend einer formgebenden Weiterverarbeitung unterzogen werden. Insbesondere bei der Herstellung von Vorformlingen, deren Erwärmung mit IR- Strahlung und anschließender Verarbeitung zu Gebrauchsgegenständen (z.B. Verpackungsmittel) werden die erfindungsgemäßen Werkstoffe verwendet. Bei PET erfolgt die Erwärmung mittels IR-Strahlung typischerweise auf eine Temperatur von 90 bis 120 °C, bevorzugt von 100 bis 110 °C. Für andere thermoplastische Polymere sind je nach Glastemperatur und Schmelztemperatur entsprechend solche Erwärmungstemperaturen zu wählen, bei denen die anschließende formgebende Weiterverarbeitung dieser Polymere technisch realisiert werden kann. Der Gegenstand der Erfindung wird anhand der folgenden Beispiele näher erläutert:The thermoplastic polymer materials containing one or more inorganic metal phosphates are used wherever thermoplastic polymer materials are softened by heating by means of IR radiation and then subjected to shaping processing. The materials according to the invention are used in particular in the production of preforms, their heating with IR radiation and subsequent processing into articles for use (eg packaging). In PET, heating is typically carried out by means of IR radiation to a temperature of 90 to 120 ° C., preferably 100 to 110 ° C. For other thermoplastic polymers, depending on the glass transition temperature and melting temperature, such heating temperatures are to be selected at which the subsequent shaping further processing of these polymers can be technically realized. The subject matter of the invention is explained in more detail with the aid of the following examples:
Beispiel 1 : Herstellung der Verbindung Cu2P04OHExample 1: Preparation of the compound Cu 2 P0 4 OH
100 g CuS04 x 5 H20 wurden in ca. 400 ml heißem Wasser (T = 80 ± 5 °C) und 105 g Na3P04 x 12 H2O in ca. 600 ml heißem Wasser (T = 80 ± 5 °C) gelöst. Anschließend wurde die Na-Phosphat-Lösung unter kräftigem Rühren langsam und kontinuierlich zur Cu-Sulfat-Lösung gegeben. Es wurde 120 Minuten bei 80 °C nachgerührt.100 g CuS0 4 x 5 H 2 0 were in approx. 400 ml hot water (T = 80 ± 5 ° C) and 105 g Na 3 P0 4 x 12 H 2 O in approx. 600 ml hot water (T = 80 ± 5 ° C). The Na phosphate solution was then slowly and continuously added to the Cu sulfate solution with vigorous stirring. The mixture was stirred at 80 ° C for 120 minutes.
Das erhaltene Produkt wurde abfiltriert und bis zu einer Filtratleitfähigkeit < 100 μS/cm gewaschen. Danach wurde der Filterkuchen mit einem Dissolver in Wasser eindispergiert und in einem Laborsprühturm getrocknet. Das trockene Produkt hatte eine gut ausgebildete Kristallstruktur (siehe Figur 3).The product obtained was filtered off and washed to a filtrate conductivity <100 μS / cm. The filter cake was then dispersed in water using a dissolver and dried in a laboratory spray tower. The dry product had a well-developed crystal structure (see Figure 3).
Beispiel 2: Herstellung der Verbindung Cu2PO4OH (hydrothermal)Example 2: Preparation of the compound Cu 2 PO 4 OH (hydrothermal)
100 g CuS0 x 5 H20 wurden in ca. 400 ml heißem Wasser (T = 80 ± 5 °C) und 105 g Na3P04 x 12 H2O in ca. 600 ml heißem Wasser (T = 80 ± 5 °C) gelöst. Anschließend wurde die Na-Phosphat-Lösung unter kräftigem Rühren langsam und kontinuierlich zur Cu-Sulfat-Lösung gegeben. Es wurde 120 Minuten bei 80 °C nachgerührt.100 g CuS0 x 5 H 2 0 were in approx. 400 ml hot water (T = 80 ± 5 ° C) and 105 g Na 3 P0 4 x 12 H 2 O in approx. 600 ml hot water (T = 80 ± 5 ° C) solved. The Na phosphate solution was then slowly and continuously added to the Cu sulfate solution with vigorous stirring. The mixture was stirred at 80 ° C for 120 minutes.
Die erhaltene Fällsuspension wurde anschließend im Autoklaven für 2 Stunden auf eine Temperatur von 180 °C erhitzt, wobei sich ein Druck von 10 bar einstellte. Danach wurde das Produkt abfiltriert, bis zu einer Filtratleitfähigkeit < 100 μS/cm gewaschen, mit einem Dissolver in Wasser eindispergiert und in einem Laborsprühturm getrocknet. Das Produkt hat eine gut ausgebildete Kristallstruktur (siehe Figur 4). Beispiel 3: Absorptionspektrum von Cu2P04OHThe precipitate suspension obtained was then heated in an autoclave for 2 hours to a temperature of 180 ° C., a pressure of 10 bar being established. The product was then filtered off, washed to a filtrate conductivity <100 μS / cm, dispersed in water using a dissolver and dried in a laboratory spray tower. The product has a well-developed crystal structure (see Figure 4). Example 3: Absorption spectrum of Cu 2 P0 4 OH
Es wurde 1 ,0 g des in Beispiel 1 hergestellten Kupferphosphates Cu2P04OH mit 1 ,0 I eines Alkydharzbindemittels (DSM AD-9) gemischt. Von dieser Mischung wurde ein Absorptionspektrum im Wellenlängenbereich von 400 bis 2000 nm aufgenommen (siehe Figur 1 ). Aus dem Spektrum ist ersichtlich, dass das erfindungsgemäße Metallphosphat im für die IR-Strahlungserwärmung relevanten Bereich von 700 bis 1600 nm eine deutlich erhöhte Absorption mit einem Maximum bei 1150 nm aufweist.1.0 g of the copper phosphate Cu 2 P0 4 OH prepared in Example 1 was mixed with 1.0 I of an alkyd resin binder (DSM AD-9). An absorption spectrum in the wavelength range from 400 to 2000 nm was recorded from this mixture (see FIG. 1). The spectrum shows that the metal phosphate according to the invention has a significantly increased absorption with a maximum at 1150 nm in the range from 700 to 1600 nm relevant for IR radiation heating.
Beispiel 4: Energieaufnahme von Cu2P04OH in PET bei Bestrahlung mit einem IR-Strahler im Vergleich zu reinem PET und PET mit Carbon Black.Example 4: Energy consumption of Cu 2 P0 4 OH in PET when irradiated with an IR radiator compared to pure PET and PET with carbon black.
Das in Beispiel 1 hergestellte Kupferphosphat wurde in einer Konzentration von 0.01 %, bezogen auf den Kunststoff, in Polyethylenterephthalat mittels eines Extruders eingearbeitet. Die Schmelze wurde zu Plättchen von 9 mm Schichtdicke spritzgegossen. Von den Plättchen wurden Transmissionsspektren mit einem Spektrometer im Bereich von 400 bis 1600 nm aufgenommen.The copper phosphate produced in Example 1 was incorporated in a concentration of 0.01%, based on the plastic, in polyethylene terephthalate by means of an extruder. The melt was injection molded into platelets 9 mm thick. Transmission spectra of the platelets were recorded with a spectrometer in the range from 400 to 1600 nm.
Figur 2 zeigt zum einen die von einer IR-Lampe bei einer Strahlungstemperatur von 2450 K abgegebene Energie (Kurvenzug 1 ) und zum anderen die entsprechenden wellenlängenabhängigen Energieaufnahmen verschiedener Prüfplättchen (Kurven 2 bis 4) bei Bestrahlung mit dieser Strahlungsquelle. Die erfindungsgemäße Formulierung (Kurve 4) weist im sichtbaren Bereich (400 bis 700 nm) eine deutlich geringere Absorption und somit geringeres Trübungs- bzw. Färbungspotential auf als die dem Stand der Technik entsprechende Vergleichsprobe (Kurve 3). Im NIR-Bereich (800 bis 1600 nm) hingegen ist die deutlich erhöhte Strahlungsaufnahme der erfindungsgemäßen Formulierung und somit bessere Energieausbeute im Erwärmungsprozess im Vergleich zu reinem PET (Kurve 2) und zur Vergleichsprobe (Kurve 3) erkennbar. FIG. 2 shows on the one hand the energy emitted by an IR lamp at a radiation temperature of 2450 K (curve 1) and on the other hand the corresponding wavelength-dependent energy consumption of various test plates (curves 2 to 4) when irradiated with this radiation source. The formulation according to the invention (curve 4) has a significantly lower absorption in the visible range (400 to 700 nm) and thus a lower clouding or coloring potential than the comparative sample corresponding to the prior art (curve 3). In the NIR range (800 to 1600 nm), on the other hand, the clearly increased radiation absorption of the formulation according to the invention and thus better energy yield in the heating process in comparison to pure PET (curve 2) and to the comparison sample (curve 3) can be seen.

Claims

Patentansprüche claims
1. Thermoplastische, polymere Werkstoffe mit hoher IR-Absorption, enthaltend mindestens ein anorganisches Metallphosphat der allgemeinen Formel Mex(P04)y(OH)z , wobei Me aus einem oder mehreren Elementen der Gruppe Cu, Fe, Mn, Sb, Zn, Ti, Ni, Co, V, Mg, Bi, Be, AI, Ce, Ba, Sr, Na, K, Ge, Ga, Ca, Cr, In oder Sn besteht, und wobei x und y ganze Zahlen sind und x = (1 ... 18), y = (1 ... 12) und z = (0,2 ... 10) und das anorganische Metallphosphat gegebenenfalls noch Kristallwasser enthalten kann.1. Thermoplastic, polymeric materials with high IR absorption, containing at least one inorganic metal phosphate of the general formula Me x (P0 4 ) y (OH) z , where Me consists of one or more elements from the group Cu, Fe, Mn, Sb, Zn , Ti, Ni, Co, V, Mg, Bi, Be, AI, Ce, Ba, Sr, Na, K, Ge, Ga, Ca, Cr, In or Sn, and where x and y are integers and x = (1 ... 18), y = (1 ... 12) and z = (0.2 ... 10) and the inorganic metal phosphate may also contain water of crystallization.
2. Thermoplastische, polymere Werkstoffe nach Anspruch 1 , dadurch gekenn- zeichnet, dass diese einen oder mehrere der Kunststoffe Polyester, Polyalkylene, Vinylpolymere, Polyamide, Polyacetale, Polyacrylate, Polycarbonate, Polystyrole, Polyurethane, Acrylnitril-Butadien-Styrol- Copolymere (ABS), Halogenhaltige Polyalkylene, Polyarylenoxide oder Polyarylensulfide enthalten.2. Thermoplastic, polymeric materials according to claim 1, characterized in that these one or more of the plastics polyester, polyalkylene, vinyl polymers, polyamides, polyacetals, polyacrylates, polycarbonates, polystyrenes, polyurethanes, acrylonitrile-butadiene-styrene copolymers (ABS) Contain halogen-containing polyalkylenes, polyarylene oxides or polyarylene sulfides.
3. Thermoplastische, polymere Werkstoffe nach Anspruch 2, dadurch gekennzeichnet, dass diese einen oder mehrere der Kunststoffe Polyethylen- terephthalat (PET), Polytrimethylenterephthalat (PTT), Polybutylen- terephthalat (PBT), Polyethylennaphthalat (PEN), Polyethylen (PE), Polypropylen (PP), Polyvinylchlorid (PVC) oder Polymethylmethacrylat (PMMA) enthalten.3. Thermoplastic, polymeric materials according to claim 2, characterized in that these one or more of the plastics polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC) or polymethyl methacrylate (PMMA).
4. Thermoplastische, polymere Werkstoffe nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass für die allgemeine Formel Mex(P04)y(OH)z gilt: x = (1 ... 5), y = (1 ... 4) und z = (0,2 ... 5).4. Thermoplastic, polymeric materials according to one of claims 1 to 3, characterized in that for the general formula Me x (P0 4 ) y (OH) z applies: x = (1 ... 5), y = (1. .. 4) and z = (0.2 ... 5).
5. Thermoplastische, polymere Werkstoffe nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass als anorganische Metallphosphate mit der allgemeinen Formel Mex(P04)y(OH)z eingesetzt werden: Cu2P04OH, Cu3(P04)(OH)3 Cu3(P04)(OH)3, Cu5(P04)2(OH)4, CuFe2(P04)2(OH)2 (Cu,Zn)2ZnP04(OH)3-2(H20), (Cu,Zn)5Zn(P04)2(OH)6-(H20), Cu3AI4(P04)3(OH)9-4(H20), CuAI3(P04)4(OH)3-4(H20), (Zn,Cu)AI6(P04)4(OH)8-4(H2O), CuFe6(P04)4(OH)8-4(H20), CaCu6[(PO4)2(P03OH)(OH)6]-3(H20) oder Cu2Mg2(P04)2(OH)2-5(H20).5. Thermoplastic, polymeric materials according to one of claims 1 to 4, characterized in that are used as inorganic metal phosphates with the general formula Me x (P0 4 ) y (OH) z : Cu 2 P0 4 OH, Cu 3 (P0 4th ) (OH) 3 Cu 3 (P0 4 ) (OH) 3 , Cu 5 (P0 4 ) 2 (OH) 4 , CuFe 2 (P0 4 ) 2 (OH) 2 (Cu, Zn) 2 ZnP0 4 (OH) 3 -2 (H 2 0), (Cu, Zn) 5 Zn (P0 4 ) 2 (OH) 6 - (H 2 0), Cu 3 AI 4 (P0 4 ) 3 (OH) 9 -4 (H 2 0), CuAI 3 (P0 4 ) 4 (OH) 3 -4 (H 2 0), (Zn, Cu) AI 6 (P0 4 ) 4 (OH) 8 - 4 (H 2 O), CuFe 6 (P0 4 ) 4 (OH) 8 -4 (H 2 0), CaCu 6 [(PO 4 ) 2 (P0 3 OH) (OH) 6 ] -3 (H 2 0 ) or Cu 2 Mg 2 (P0 4 ) 2 (OH) 2 -5 (H 2 0).
6. Thermoplastische, polymere Werkstoffe nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass die Zugabemenge der anorganischen Metallphosphate 0,0002 bis 2 Gew.-%, bezogen auf den fertigen thermoplastischen, polymeren Werkstoff, beträgt.6. Thermoplastic, polymeric materials according to one of claims 1 to 4, characterized in that the amount added of the inorganic metal phosphates is 0.0002 to 2 wt .-%, based on the finished thermoplastic, polymeric material.
7. Thermoplastische, polymere Werkstoffe nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass die Zugabemenge der anorganischen Metallphosphate 0,001 bis 0,1 Gew.-%, bezogen auf den fertigen thermoplastischen, polymeren Werkstoff, beträgt.7. Thermoplastic, polymeric materials according to one of claims 1 to 6, characterized in that the amount added of the inorganic metal phosphates is 0.001 to 0.1 wt .-%, based on the finished thermoplastic, polymeric material.
8. Thermoplastische, polymere Werkstoffe nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass das anorganische Metallphosphat nach Scherrer gemessene Kristallitgrößen von 0,005 bis 5 μm aufweist.8. Thermoplastic, polymeric materials according to one of claims 1 to 7, characterized in that the inorganic metal phosphate according to Scherrer has measured crystallite sizes of 0.005 to 5 microns.
9. Thermoplastische, polymere Werkstoffe nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass das anorganische Metallphosphat nach Scherrer gemessene Kristallitgrößen von 0,001 bis 2 μm aufweist.9. Thermoplastic, polymeric materials according to one of claims 1 to 8, characterized in that the inorganic metal phosphate according to Scherrer has measured crystallite sizes of 0.001 to 2 microns.
10. Verfahren zur Herstellung von thermoplastischen, polymeren Werkstoffen mit hoher IR-Absorption, enthaltend mindestens ein anorganisches Metallphosphat der allgemeinen Formel Mex(P04)y(OH)z, dadurch gekennzeichnet, dass Lösungen des jeweiligen Metallions, bzw. der jeweiligen Metallionen, und eine Lösung der jeweiligen P04-Komponente in wässrigem Medium zur Ausfällung gebracht werden, das erhaltene Produkt getrocknet und in einen thermoplastischen, polymeren Kunststoff eingearbeitet wird. 10. A process for the preparation of thermoplastic, polymeric materials with high IR absorption, containing at least one inorganic metal phosphate of the general formula Me x (P0 4 ) y (OH) z , characterized in that solutions of the respective metal ion or the respective metal ions , and a solution of the respective P0 4 component is precipitated in an aqueous medium, the product obtained is dried and incorporated into a thermoplastic, polymeric plastic.
11. Verfahren nach Anspruch 10, dadurch gekennzeichnet, dass als Metallionlösung entsprechende Lösungen der Sulfate, Chloride, Nitrate, Hydroxide oder Oxide eingesetzt werden.11. The method according to claim 10, characterized in that corresponding solutions of the sulfates, chlorides, nitrates, hydroxides or oxides are used as the metal ion solution.
12. Verfahren nach Anspruch 10 oder 11 , dadurch gekennzeichnet, dass als Lösung für die P0 -Komponente Phosphorsäure oder Lösungen deren löslicher Salze, wie Alkali- oder Erdalkaliphosphate, eingesetzt werden.12. The method according to claim 10 or 11, characterized in that the solution for the P0 component phosphoric acid or solutions of their soluble salts, such as alkali or alkaline earth metal phosphates, are used.
13. Verfahren nach einem der Ansprüche 10 bis 12, dadurch gekennzeichnet, dass zur Ausbildung des gewünschten Metallphosphates die Fällungsprodukte hydrothermal behandelt und/oder in getrocknetem Zustand thermisch behandelt werden.13. The method according to any one of claims 10 to 12, characterized in that the precipitation products are treated hydrothermally and / or thermally treated in the dried state to form the desired metal phosphate.
14. Verwendung der in den Ansprüchen 1 bis 9 beschriebenen thermoplastischen, polymeren Werkstoffe in Verfahren, bei denen thermoplastische, polymere Werkstoffe durch Erwärmung mittels IR-Strahlung erweicht und anschließend einer formgebenden Weiterverarbeitung unterzogen werden.14. Use of the thermoplastic, polymeric materials described in claims 1 to 9 in processes in which thermoplastic, polymeric materials are softened by heating by means of IR radiation and then subjected to a shaping further processing.
15. Verwendung der in den Ansprüchen 1 bis 9 beschriebenen thermoplastischen, polymeren Werkstoffe bei der Herstellung von Vorformlingen, die mittels IR-Strahlung erwärmt und anschließend zu Gebrauchsgegenständen und Verpackungsmitteln verarbeitet werden. 15. Use of the thermoplastic, polymeric materials described in claims 1 to 9 in the manufacture of preforms which are heated by means of IR radiation and then processed to articles of use and packaging.
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DE10356334A1 (en) 2005-06-23
CN1886450B (en) 2010-10-06
DE10356334B4 (en) 2016-02-11
US20070155881A1 (en) 2007-07-05
US8410207B2 (en) 2013-04-02
TWI449738B (en) 2014-08-21
WO2005052049A1 (en) 2005-06-09
CN1886450A (en) 2006-12-27
JP2007512401A (en) 2007-05-17
BRPI0417010A (en) 2007-02-21
KR20070009540A (en) 2007-01-18
TW200530312A (en) 2005-09-16

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