EP1727660A1 - Method for producing plastic rods - Google Patents

Method for producing plastic rods

Info

Publication number
EP1727660A1
EP1727660A1 EP05700879A EP05700879A EP1727660A1 EP 1727660 A1 EP1727660 A1 EP 1727660A1 EP 05700879 A EP05700879 A EP 05700879A EP 05700879 A EP05700879 A EP 05700879A EP 1727660 A1 EP1727660 A1 EP 1727660A1
Authority
EP
European Patent Office
Prior art keywords
plastic
extruded
round
molding compound
tube
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP05700879A
Other languages
German (de)
French (fr)
Inventor
Bernfried Kalthof
Holger Lorenz
Satilmis Yilmaz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Roehm GmbH Darmstadt
Original Assignee
Roehm GmbH Darmstadt
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Roehm GmbH Darmstadt filed Critical Roehm GmbH Darmstadt
Publication of EP1727660A1 publication Critical patent/EP1727660A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04C—STRUCTURAL ELEMENTS; BUILDING MATERIALS
    • E04C3/00—Structural elongated elements designed for load-supporting
    • E04C3/02—Joists; Girders, trusses, or trusslike structures, e.g. prefabricated; Lintels; Transoms; Braces
    • E04C3/28—Joists; Girders, trusses, or trusslike structures, e.g. prefabricated; Lintels; Transoms; Braces of materials not covered by groups E04C3/04 - E04C3/20
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0013—Extrusion moulding in several steps, i.e. components merging outside the die
    • B29C48/0015—Extrusion moulding in several steps, i.e. components merging outside the die producing hollow articles having components brought in contact outside the extrusion die
    • B29C48/0016—Extrusion moulding in several steps, i.e. components merging outside the die producing hollow articles having components brought in contact outside the extrusion die using a plurality of extrusion dies
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/06—Rod-shaped
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/30—Extrusion nozzles or dies
    • B29C48/304—Extrusion nozzles or dies specially adapted for bringing together components, e.g. melts within the die
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2791/00—Shaping characteristics in general
    • B29C2791/004—Shaping under special conditions
    • B29C2791/006—Using vacuum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2791/00—Shaping characteristics in general
    • B29C2791/004—Shaping under special conditions
    • B29C2791/007—Using fluid under pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0022—Combinations of extrusion moulding with other shaping operations combined with cutting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
    • B29C48/10—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels flexible, e.g. blown foils
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/15—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor incorporating preformed parts or layers, e.g. extrusion moulding around inserts
    • B29C48/154—Coating solid articles, i.e. non-hollow articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/90—Thermal treatment of the stream of extruded material, e.g. cooling with calibration or sizing, i.e. combined with fixing or setting of the final dimensions of the extruded article
    • B29C48/904—Thermal treatment of the stream of extruded material, e.g. cooling with calibration or sizing, i.e. combined with fixing or setting of the final dimensions of the extruded article using dry calibration, i.e. no quenching tank, e.g. with water spray for cooling or lubrication
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/90—Thermal treatment of the stream of extruded material, e.g. cooling with calibration or sizing, i.e. combined with fixing or setting of the final dimensions of the extruded article
    • B29C48/905—Thermal treatment of the stream of extruded material, e.g. cooling with calibration or sizing, i.e. combined with fixing or setting of the final dimensions of the extruded article using wet calibration, i.e. in a quenching tank
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/911—Cooling
    • B29C48/9115—Cooling of hollow articles
    • B29C48/912—Cooling of hollow articles of tubular films
    • B29C48/913—Cooling of hollow articles of tubular films externally
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2033/00—Use of polymers of unsaturated acids or derivatives thereof as moulding material
    • B29K2033/04—Polymers of esters
    • B29K2033/12—Polymers of methacrylic acid esters, e.g. PMMA, i.e. polymethylmethacrylate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2069/00—Use of PC, i.e. polycarbonates or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0018—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular optical properties, e.g. fluorescent or phosphorescent
    • B29K2995/0026—Transparent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2023/00—Tubular articles
    • B29L2023/22—Tubes or pipes, i.e. rigid

Definitions

  • the invention relates to a method for extruding round bars from transparent plastics such as, for example, polymethyl methacrylate (PMMA), polycarbonate (PC) or (PET) polyethylene.
  • transparent plastics such as, for example, polymethyl methacrylate (PMMA), polycarbonate (PC) or (PET) polyethylene.
  • Round bars with smaller diameters can be obtained in good quality by extrusion of a PMMA molding compound, such as Plexiglas ® 7H.
  • EP 1 291 160 (Fiberstars) describes the continuous coextrusion of polymeric optical fibers by first extruding a thin coating and then extruding the core of the polymeric optical fiber from a crosslinkable polymer.
  • the thin coating made of a fluorine-containing polymer.
  • the task was therefore to provide a process for the production of round bars with larger diameters.
  • the object was achieved by a process for the production of rods from transparent plastics by extrusion of a plastic molding compound, characterized in that an extruded plastic molding compound is separated and a plastic tube is extruded from the plastic molding compound 1 and, after entry into a vacuum tank calibrator, the freshly extruded after about 20 cm Fill the pipe parallel with the previously separated molten plastic molding compound 2 and process the newly formed plastic body as in the usual pipe extrusion.
  • the method is characterized in that the plastic tube, produced with the plastic molding compound 1, enables the plastic molding compound 2 to be taken up by means of supporting air and negative pressure during calibration.
  • round rods with large diameters can be produced with excellent optical quality and a particularly uniform cross-section using the method according to the invention. Time-consuming post-processing steps are not necessary.
  • round bars with diameters of any size can be produced. Round bars with diameters up to 200 mm are preferred, especially preferably up to 80 mm. Depending on the capacity of the extruder, however, all diameter sizes are conceivable.
  • Round bars of larger diameter produced using conventional processes usually have a matt surface. It has been found that the round bars produced by the process according to the invention have particularly good optical properties. Surprisingly, it was found that the round bars according to the invention are highly transparent. The process according to the invention produces streak-free round rods which have a greater degree of light transmission than the conventionally produced round rods. The round rod produced according to the invention transports visible light better than conventionally produced round rods. It has surprisingly been found that the round bars according to the invention have particularly uniform cross sections. The measurement of the roundness of the round bars according to the invention shows excellent values. With the method according to the invention, round bars can be produced from a wide variety of plastics. Polymethyl methacrylate, polycarbonate or polyethylene are preferred, polymethyl methacrylate is particularly preferably used.
  • Another object of the invention is a device for producing the round bars according to the invention.
  • the device is characterized in that an extruded round rod of smaller diameter in an internal extrusion tool parallel to an extruded tube of larger diameter in an extrusion tool is introduced into a calibrator without contact after leaving the extruder and fuses with each other there after about 20 cm, the extruded Tube preferably undergoes a form-stabilizing cooling before it merges with the round rod.
  • the diameter ratio of the plastic rod, made of the plastic mass 2, to the plastic tube, made of the plastic mass 1, is arbitrary.
  • a rod to tube ratio of 1: 2 is preferred.
  • the rod to tube ratio is ideally between 6:20 to 45:50, very particularly preferably 9:20, 20:40 or 22:50.
  • the ratio of the length of the path of the plastic mass 1 (the plastic tube) to the filling with the plastic mass 2 (the rod) to the diameter of the plastic tube is variable and is dependent on throughput and surface quality.
  • extruders are used, which are selected according to the processing temperature, type of plastic or throughput.
  • extruders are available to the person skilled in the art, for example: single-screw extruders, degassing extruders, cascade or tandem extruders, high-speed extruders, planetary roller extruders, twin-screw extruders, piston extruders or ram extruders.
  • the downstream vacuum tank calibrator is used as an annealing section (full water bath and / or blown air).
  • FIG. 1 shows the device according to the invention with which the tube and rod are extruded.
  • the melt is extruded through the gap into a tube. With the internal nozzle, the melt is formed into a rod, which fills the extruded tube after approx. 20 cm after entering the vacuum tank calibrator.
  • the plastic tube and the delayed extruded solid rod are tempered in the vacuum tank calibrator so that sufficient dimensional stability is achieved.
  • the rod according to the invention is then slowly cooled. It can be expanded / developed using conventional processing methods.
  • Round rods can also be produced, the plastic mass 1 of which is colored, while the Plastic mass 2 is not colored or colored differently, or the plastic mass 1 is not colored while the plastic mass 2 is colored.
  • the rods produced according to the invention are used in trade fair and shop construction (e.g. as decorative elements), in construction (e.g. banisters or stair supports), in the lighting industry (e.g. as a lighting object), in the furniture industry (e.g. table or chair legs) or in advertising technology ,
  • Non-colored polymethyl methacrylate granules are melted in a single-screw extruder.
  • a tube with a diameter of 50 mm is extruded over the device according to the invention. After entering a vacuum tank calibrator, after 20 cm the freshly extruded tube is filled in parallel with the plastic mass of the rod. The rod is slowly cooled. Cylindrical test specimens with a length of 180 mm are cut from it. The end faces perpendicular to the cylinder axis are polished by hand on a polishing belt.
  • Two cylindrical test specimens with a length of 180 mm are produced from square bars made of non-colored polymethyl methacrylate. It becomes a cylindrical test specimen with a diameter of 60 mm and a test specimen with 80 mm
  • V2 Diameter (V2) manufactured. The end faces perpendicular to the cylinder axis are polished as described in Example 1.
  • a transmission spectrum in the wavelength range 380 nm to 780 nm is measured according to DIN 5036 with an integration sphere. The measurements are carried out in both directions. Average values from 4 spectra, 2 in each of the two transmission directions, are given. The fluctuation range within the 4 measurements was +/- 0.3%. The results are summarized in the following table:
  • Example 4 The samples are irradiated along the cylinder axis by a HeNe laser. A photo is taken perpendicular to this. The more inhomogeneous the material, e.g. due to impurities or density fluctuations, the brighter it shines in this arrangement, in the sense of light scattering. Sample E1 shows the least light scatter. In addition, the roundness of the round rod produced according to the invention (sample E1) was examined. To do this, the diameter is measured at 5 different points of the cross-section. The results are summarized in the following table.
  • Example 5 Roundness of a round bar with a nominal diameter of 50 mm
  • a tube with a diameter of 40 mm is extruded. After entering a vacuum tank calibrator, after 20 cm the freshly extruded tube is filled in parallel with the plastic mass of the rod. The rod is slowly cooled. Cylindrical test specimens with a length of 180 mm are cut from it. The end faces perpendicular to the cylinder axis are polished by hand on a polishing belt. Sample E2
  • Table 2 Roundness of a round bar with a nominal diameter of 40 mm

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Architecture (AREA)
  • Manufacturing & Machinery (AREA)
  • Civil Engineering (AREA)
  • Structural Engineering (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Shaping Of Tube Ends By Bending Or Straightening (AREA)

Abstract

The invention relates to a method for extruding round rods from transparent plastics such as for example polymethylmethacrylate (PMMA), polycarbonate (PC) or polyethylene (PET) and to a method for producing said round rods.

Description

Verfahren zur Herstellung von Kunststoffstäben Process for the production of plastic rods
Die Erfindung betrifft ein Verfahren zur Extrusion von Rundstäben aus transparenten Kunststoffen wie beispielsweise Polymethylmethacrylat (PMMA), Polycarbonat (PC) oder (PET) Polyethylen.The invention relates to a method for extruding round bars from transparent plastics such as, for example, polymethyl methacrylate (PMMA), polycarbonate (PC) or (PET) polyethylene.
Runde Stäbe aus Plexiglas® sind bekannt und werden von der Röhm GmbH & Co. KG vermarktet.Round rods made of Plexiglas ® are known and are marketed by Röhm GmbH & Co. KG.
Je nach Anforderung kann die Herstellung dieser Stäbe als aufwendig gelten. Zuerst wird nach bekannten Methoden eine ebene Platte aus PMMA hergestellt, die in Vierkantstäbe zerteilt wird. Die Vierkantstäbe werden anschließend mechanisch bearbeitet (überdreht und poliert). Dieses Verfahren ist arbeitsaufwendig und somit wirtschaftlich nicht sehr interessant, zumal auch mit entsprechendem Abfall verbunden. Ein relativ hohes Preisniveau für Rundstäbe dieser Art ist gegeben. Ein weiteres Verfahren ist das Gießen von Stäben, jedoch ebenfalls aufwendig und wirtschaftlich eher untergeordnet.Depending on the requirements, the production of these rods can be considered complex. First, a flat plate made of PMMA is manufactured according to known methods, which is divided into square bars. The square bars are then machined (turned and polished). This process is labor-intensive and therefore not very interesting economically, especially since it also involves corresponding waste. A relatively high price level for round rods of this type is given. Another method is the casting of bars, but also complex and economically subordinate.
Rundstäbe mit kleineren Durchmessern kann man in guter Qualität durch Extrusion einer PMMA-Formmasse, wie beispielsweise Plexiglas® 7H erhalten.Round bars with smaller diameters can be obtained in good quality by extrusion of a PMMA molding compound, such as Plexiglas ® 7H.
Dieses Verfahren gestaltet sich jedoch bei Stäben ab ca. D=25 mm verfahrensbedingt schwierig, da infolge einer hohen Wärmeenergie, die von dem extrudierten Stab durch Kühlung abzuführen ist, eine ausreichende Formstabilität erst nach einiger Zeit erzielt werden kann, was sich nachteilig dahingehend auswirkt, dass es zu Durchbiegungen kommen kann. Diesem Effekt kann dahingehend entgegen gewirkt werden, indem geeignete Kühlstrecken, z.B. Kühlluft, aufgebracht wird, in Verbindung mit Stützrollen.However, this process is difficult for bars from approx. D = 25 mm, because due to a high thermal energy that has to be dissipated from the extruded bar by cooling, sufficient dimensional stability can only be achieved after some time, which has a disadvantageous effect. that there may be deflections. This effect can be counteracted by using suitable cooling sections, e.g. Cooling air is applied in connection with support rollers.
Beide Maßnahmen wirken sich jedoch ebenfalls als nachteilig aus, da der Stab infolge seines Eigengewichts in sich zusammensinkt, was deutlich spürbareHowever, both measures also have a disadvantage, since the rod collapses due to its own weight, which is clearly noticeable
Durchmesserdifferenzen zur Folge hat - der Stab ist unrund. Darüber hinaus kann die Oberflächentransparenz negativ beeinflusst werden, die Staboberfläche erscheint trüb. BESTATIGUNGSKOPIE Ein Herabsetzen der Extrusionsgeschwindigkeit um für den Stab verbesserte Abkühlbedingungen zu schaffen, verringert die Fertigungskosten auf wirtschaftlich nicht mehr tragbare Werte.Differences in diameter result - the rod is out of round. In addition, the surface transparency can be negatively affected, the rod surface appears cloudy. BESTATIGUNGSKOPIE Lowering the extrusion speed in order to create improved cooling conditions for the rod reduces the production costs to economically unsustainable values.
EP 1 291 160 (Fiberstars) beschreibt die kontinuierliche Coextrusion von polymeren optischen Fasern, indem zuerst eine dünne Beschichtung extrudiert und dann den Kern der polymeren optischen Faser aus einem vernetzbaren Polymer extrudiert. Die dünne Beschichtung aus einem fluorhaltigen Polymer.EP 1 291 160 (Fiberstars) describes the continuous coextrusion of polymeric optical fibers by first extruding a thin coating and then extruding the core of the polymeric optical fiber from a crosslinkable polymer. The thin coating made of a fluorine-containing polymer.
Bei herkömmlichen Extrusions-Verfahren kommt es zu Verformungen der Stäbe durch das Eigengewicht, sobald Stäbe mit größeren Durchmessern hergestellt werden.In conventional extrusion processes, the bars are deformed by their own weight as soon as bars with larger diameters are produced.
Aufgabe war es daher, ein Verfahren zur Herstellung von Rundstäben mit größeren Durchmessern zur Verfügung zu stellen.The task was therefore to provide a process for the production of round bars with larger diameters.
Die Aufgabe wurde gelöst durch ein Verfahren zur Herstellung von Stäben aus transparenten Kunststoffen durch Extrusion einer Kunststoffformmasse, dadurch gekennzeichnet, dass man eine extrudierte Kunststoffformmasse auftrennt und aus der Kunststoffformmasse 1 ein Kunststoffrohr extrudiert und nach Eintritt in einen Vakuumtankkalibrator nach ca.20 cm das frisch extrudierte Rohr parallel mit der zuvor abgetrennten geschmolzenen Kunststoffform masse 2 füllt und den neu gebildeten Kunststoffformkörper wie bei der üblichen Rohrextrusion weiter verarbeitet. Das Verfahren zeichnet sich dadurch aus, dass das Kunststoffrohr, hergestellt mit der Kunststoffformmasse 1 , mittels Stützluft und Unterdruck während der Kalibrierung, die Aufnahme der Kunststoffformmasse 2 ermöglicht.The object was achieved by a process for the production of rods from transparent plastics by extrusion of a plastic molding compound, characterized in that an extruded plastic molding compound is separated and a plastic tube is extruded from the plastic molding compound 1 and, after entry into a vacuum tank calibrator, the freshly extruded after about 20 cm Fill the pipe parallel with the previously separated molten plastic molding compound 2 and process the newly formed plastic body as in the usual pipe extrusion. The method is characterized in that the plastic tube, produced with the plastic molding compound 1, enables the plastic molding compound 2 to be taken up by means of supporting air and negative pressure during calibration.
Überraschend wurde gefunden, dass mit dem erfindungsgemäßen Verfahren Rundstäbe mit großen Durchmessern in einer hervorragenden optischen Qualität und besonders gleichmäßigen Querschnitt hergestellt werden können. Aufwendige Nachbearbeitungsschritte sind nicht erforderlich. Mit dem erfindungsgemäßen Verfahren können Rundstäbe mit Durchmessern beliebiger Größe hergestellt werden. Bevorzugt werden Rundstäbe mit Durchmessern bis zu 200 mm, besonders bevorzugt bis zu 80 mm, hergestellt. In Abhängigkeit von der Kapazität des Extruders sind jedoch alle Durchmesser-Größen denkbar.Surprisingly, it was found that round rods with large diameters can be produced with excellent optical quality and a particularly uniform cross-section using the method according to the invention. Time-consuming post-processing steps are not necessary. With the method according to the invention, round bars with diameters of any size can be produced. Round bars with diameters up to 200 mm are preferred, especially preferably up to 80 mm. Depending on the capacity of the extruder, however, all diameter sizes are conceivable.
Teil der Erfindung sind somit auch die Rundstäbe, die mit dem erfindungsgemäßen Verfahren hergestellt werden können.The round bars which can be produced by the method according to the invention are therefore also part of the invention.
Mit herkömmlichen Verfahren hergestellte Rundstäbe größeren Durchmessers weisen zumeist eine matte Oberfläche auf. Es wurde gefunden, dass die nach dem erfindungsgemäßen Verfahren hergestellten Rundstäbe besonders gute optische Eigenschaften aufweisen. Überraschend wurde gefunden, dass die erfindungsgemäßen Rundstäbe hochtransparent sind. Durch das erfindungsgemäße Verfahren werden streifenfreie Rundstäbe hergestellt, die gegenüber den herkömmlich angefertigten Rundstäben einen größerer Lichttransmissionsgrad aufweisen. Der erfindungsgemäß hergestellte Rundstab transportiert sichtbares Licht besser als herkömmlich erzeugte Rundstäbe. Überraschend wurde gefunden, dass die erfindungsgemäßen Rundstäbe besonders gleichmäßige Querschnitte aufweisen. Die Messung der Rundheit der erfindungsgemäßen Rundstäbe zeigt hervorragende Werte. Mit dem erfindungsgemäßen Verfahren können Rundstäbe aus verschiedensten Kunststoffen hergestellt werden. Bevorzugt werden Polymethylmethacrylat, Polycarbonat oder Polyethylen, besonders bevorzugt wird Polymethylmethacrylat verwendet.Round bars of larger diameter produced using conventional processes usually have a matt surface. It has been found that the round bars produced by the process according to the invention have particularly good optical properties. Surprisingly, it was found that the round bars according to the invention are highly transparent. The process according to the invention produces streak-free round rods which have a greater degree of light transmission than the conventionally produced round rods. The round rod produced according to the invention transports visible light better than conventionally produced round rods. It has surprisingly been found that the round bars according to the invention have particularly uniform cross sections. The measurement of the roundness of the round bars according to the invention shows excellent values. With the method according to the invention, round bars can be produced from a wide variety of plastics. Polymethyl methacrylate, polycarbonate or polyethylene are preferred, polymethyl methacrylate is particularly preferably used.
Überraschend wurde gefunden, dass mit dem erfindungsgemäßen Verfahren Kunststoffstäbe aus nicht eingefärbtem Polymethylmethacrylat mit einem Transmissionsgrad von über TD65 85% hergestellt werden können.Surprisingly, it was found that 6 5 85% can be produced with the inventive process plastic bars of uncolored polymethylmethacrylate having a transmittance of about T D.
Ein weiterer Gegenstand der Erfindung ist eine Vorrichtung zur Herstellung der erfindungsgemäßen Rundstäbe.Another object of the invention is a device for producing the round bars according to the invention.
Die Vorrichtung ist dadurch gekennzeichnet, dass ein extrudierter Rundstab kleineren Durchmessers in einem innenliegenden Extrusionswerkzeug parallel mit einem extrudierten Rohr größeren Durchmessers in einem Extrusionswerkzeug berührungslos nach dem Verlassen des Extruders in einen Kalibrator eingeführt werden und dort nach ca. 20 cm miteinander verschmelzen, wobei das extrudierte Rohr bevorzugt vor der Verschmelzung mit dem Rundstab eine formstabilisierende Abgkühlung erfährt. Das Durchmesserverhältnis des Kunststoffstabes, hergestellt aus der Kunststoff masse 2, zum Kunststoffrohr, hergestellt aus der Kunststoffmasse 1 , ist beliebig. Bevorzugt wird ein Verhältnis Stab zu Rohr von 1 :2. Das Verhältnis Stab zu Rohr liegt idealerweise zwischen 6: 20 bis 45:50, ganz besonders bevorzugt bei 9:20, 20:40 oder 22:50.The device is characterized in that an extruded round rod of smaller diameter in an internal extrusion tool parallel to an extruded tube of larger diameter in an extrusion tool is introduced into a calibrator without contact after leaving the extruder and fuses with each other there after about 20 cm, the extruded Tube preferably undergoes a form-stabilizing cooling before it merges with the round rod. The diameter ratio of the plastic rod, made of the plastic mass 2, to the plastic tube, made of the plastic mass 1, is arbitrary. A rod to tube ratio of 1: 2 is preferred. The rod to tube ratio is ideally between 6:20 to 45:50, very particularly preferably 9:20, 20:40 or 22:50.
Das Verhältnis der Länge des Weges der Kunststoff masse 1 (des Kunststoffrohres) bis zur Auffüllung mit der Kunststoffmasse 2 (des Stabes) zum Durchmesser des Kunststoffrohres ist variabel und steht im Abhängigkeit zu Durchsatz und Oberflächenqualität.The ratio of the length of the path of the plastic mass 1 (the plastic tube) to the filling with the plastic mass 2 (the rod) to the diameter of the plastic tube is variable and is dependent on throughput and surface quality.
Zur Bereitstellung der Kunststoffschmelze werden Extruder verwendet, die je nach Verarbeitungstemperatur, Kunststoffart oder Durchsatz entsprechend ausgewählt werden. Dem Fachmann steht eine Vielzahl von Extrudern zur Verfügung, z.B.: Einschnecken-Extruder, Entgasungs-Extruder, Kaskaden- oder Tandem-Extruder, Schnellläufer-Extruder, Planetwalzen-Extruder, Doppelschnecken-Extruder, Kolben- Extruder oder Ram-Extruder.To provide the plastic melt, extruders are used, which are selected according to the processing temperature, type of plastic or throughput. A large number of extruders are available to the person skilled in the art, for example: single-screw extruders, degassing extruders, cascade or tandem extruders, high-speed extruders, planetary roller extruders, twin-screw extruders, piston extruders or ram extruders.
Der nachgeschaltete Vakuumtankkalibrator wird als Temperstrecke (Wasservollbad und/oder Gebläseluft) eingesetzt.The downstream vacuum tank calibrator is used as an annealing section (full water bath and / or blown air).
In Figur 1 ist die erfindungsgemäße Vorrichtung dargestellt, mit der Rohr und Stab extrudiert werden.FIG. 1 shows the device according to the invention with which the tube and rod are extruded.
Die Schmelze wird durch den Spalt zu einem Rohr extrudiert. Mit der innenliegenden Düse, wird die Schmelze zu einem Stab geformt, der nach Eintritt in den Vakuumtankkalibrator nach ca. 20 cm das extrudierte Rohr füllt. Das Kunststoffrohr, sowie zeitverzögert der extrudierte Vollstab werden im Vakuumtankkalibrator so temperiert, dass eine ausreichend Formstabilität erreicht wird. Anschließend wird der erfindungsgemäße Stab langsam abgekühlt. Er kann mit herkömmlichen Verarbeitungsmethoden weiten/erarbeitet werden.The melt is extruded through the gap into a tube. With the internal nozzle, the melt is formed into a rod, which fills the extruded tube after approx. 20 cm after entering the vacuum tank calibrator. The plastic tube and the delayed extruded solid rod are tempered in the vacuum tank calibrator so that sufficient dimensional stability is achieved. The rod according to the invention is then slowly cooled. It can be expanded / developed using conventional processing methods.
Es können klare farblose oder eingefärbte Stäbe hergestellt werden. Ebenso können Rundstäbe hergestellt werden, deren Kunststoffmasse 1 eingefärbt ist, während die Kunststoff masse 2 nicht oder andersfarbig eingefärbt wird, bzw. die Kunststoffmasse 1 nicht eingefärbt wird, während die Kunststoffmasse 2 eingefärbt wird.Clear, colorless or colored rods can be produced. Round rods can also be produced, the plastic mass 1 of which is colored, while the Plastic mass 2 is not colored or colored differently, or the plastic mass 1 is not colored while the plastic mass 2 is colored.
Die erfindungsgemäß hergestellten Stäbe werden im Messe- und Ladenbau (z.B. als dekorative Elemente), im Bau (z.B. Treppengeländer oder Treppenstützen), in der Leuchtenindustrie (z.B. als Leuchtobjekt), in der Möbelindustrie (z.B. Tisch- oder Stuhlbeine) oder in der Werbetechnik verwendet.The rods produced according to the invention are used in trade fair and shop construction (e.g. as decorative elements), in construction (e.g. banisters or stair supports), in the lighting industry (e.g. as a lighting object), in the furniture industry (e.g. table or chair legs) or in advertising technology ,
Die im Folgenden gegebenen Beispiele werden zur besseren Veranschaulichung der vorliegenden Erfindung gegeben, sind jedoch nicht dazu geeignet, die Erfindung auf die hierin offenbarten Merkmale zu beschränken. The examples given below are given to better illustrate the present invention, but are not intended to limit the invention to the features disclosed herein.
BeispieleExamples
Beispiel 1example 1
In einem Einschnecken-Extruder wird nicht eingefärbtes Polymethylmethacrylat- Granulat geschmolzen. Über die erfindungsgemäße Vorrichtung wird ein Rohr mit einem Durchmesser von 50 mm extrudiert. Nach Eintritt in einen Vakuumtankkalibrator wird nach 20 cm das frisch extrudierte Rohr parallel mit der Kunststoffmasse des Stabes gefüllt. Der Stab wird langsam abgekühlt. Es werden daraus zylindrische Probekörper mit 180 mm Länge zugeschnitten. Die zur Zylinderachse senkrecht stehenden Stirnflächen werden auf einem Polierband per Hand poliert.Non-colored polymethyl methacrylate granules are melted in a single-screw extruder. A tube with a diameter of 50 mm is extruded over the device according to the invention. After entering a vacuum tank calibrator, after 20 cm the freshly extruded tube is filled in parallel with the plastic mass of the rod. The rod is slowly cooled. Cylindrical test specimens with a length of 180 mm are cut from it. The end faces perpendicular to the cylinder axis are polished by hand on a polishing belt.
Probe E1Sample E1
Vergleichsbeispiel 1Comparative Example 1
Aus Vierkantstäben aus nicht eingefärbtem Polymethylmethacrylat werden 2 zylindrische Probekörper mit 180 mm Länge hergestellt. Es wird ein zylindrischer Probekörper mit 60 mm Durchm " "" und ein Probekörper mit 80 mmTwo cylindrical test specimens with a length of 180 mm are produced from square bars made of non-colored polymethyl methacrylate. It becomes a cylindrical test specimen with a diameter of 60 mm and a test specimen with 80 mm
Durchmesser (V2) hergestellt. Die zur Zylinderachse senkrecht stehenden Stirnflächen werden wie in Beispiel 1 beschrieben poliert.Diameter (V2) manufactured. The end faces perpendicular to the cylinder axis are polished as described in Example 1.
Proben V1 und V2Samples V1 and V2
Beispiel 3Example 3
Ein Transmissionsspektrum im Wellenbereich 380 nm bis 780 nm wird nach DIN 5036 mit Integrationskugel gemessen. Die Messungen werden jeweils in beiden Durchstrahlrichtungen durchgeführt. Es werden Mittelwerte aus 4 Spektren, je 2 in beiden Durchstrahl richtungen, angegeben. Die Schwankungsbreite innerhalb der 4 Messungen betrug +/- 0,3%. Die Ergebnisse sind in der folgenden Tabelle zusammengestellt:A transmission spectrum in the wavelength range 380 nm to 780 nm is measured according to DIN 5036 with an integration sphere. The measurements are carried out in both directions. Average values from 4 spectra, 2 in each of the two transmission directions, are given. The fluctuation range within the 4 measurements was +/- 0.3%. The results are summarized in the following table:
Tabelle 1 : Lichttransmissionsgrade für Normlicht D65 Table 1: Light transmittance for standard light D65
Beispiel 4 Die Proben werden entlang der Zylinderachse von einem HeNe-Laser durchstrahlt. Senkrecht dazu wird eine Fotoaufnahme gemacht. Je inhomogener das Material ist, z.B. durch Verunreinigungen oder Dichtefluktuationen, desto heller leuchtet es in dieser Anordnung, im Sinne von Lichtstreuung. Die Probe E1 zeigt die geringste Lichtstreuung. Zusätzlich wurde die Rundheit des erfindungsgemäß hergestellten Rundstabes (Probe E1 ) untersucht. Dazu wird der Durchmesser an 5 verschiedenen Punkten des Querschnittes gemessen. Die Ergebnisse sind in der folgenden Tabelle zusammengestellt.Example 4 The samples are irradiated along the cylinder axis by a HeNe laser. A photo is taken perpendicular to this. The more inhomogeneous the material, e.g. due to impurities or density fluctuations, the brighter it shines in this arrangement, in the sense of light scattering. Sample E1 shows the least light scatter. In addition, the roundness of the round rod produced according to the invention (sample E1) was examined. To do this, the diameter is measured at 5 different points of the cross-section. The results are summarized in the following table.
Tabelle 2: Rundheit eines Rundstabes mit einem Soll-Durchmesser von 50 mm Beispiel 5 Gemäß dem Beispiel 1 wird ein Rohr mit einem Durchmesser von 40 mm extrudiert. Nach Eintritt in einen Vakuumtankkalibrator wird nach 20 cm das frisch extrudierte Rohr parallel mit der Kunststoffmasse des Stabes gefüllt. Der Stab wird langsam abgekühlt. Es werden daraus zylindrische Probekörper mit 180 mm Länge zugeschnitten. Die zur Zylinderachse senkrecht stehenden Stirnflächen werden auf einem Polierband per Hand poliert. Probe E2 Table 2: Roundness of a round bar with a nominal diameter of 50 mm Example 5 According to Example 1, a tube with a diameter of 40 mm is extruded. After entering a vacuum tank calibrator, after 20 cm the freshly extruded tube is filled in parallel with the plastic mass of the rod. The rod is slowly cooled. Cylindrical test specimens with a length of 180 mm are cut from it. The end faces perpendicular to the cylinder axis are polished by hand on a polishing belt. Sample E2
Es wurde die Rundheit des erfindungsgemäß hergestellten Rundstabes (Probe E2) untersucht. Dazu wird der Durchmesser an 5 verschiedenen Punkten des Querschnittes gemessen. Die Ergebnisse sind in der folgenden Tabelle zusammengestellt.The roundness of the round rod produced according to the invention (sample E2) was examined. To do this, the diameter is measured at 5 different points of the cross-section. The results are summarized in the following table.
Tabelle 2: Rundheit eines Rundstabes mit einem Soll-Durchmesser von 40 mm Table 2: Roundness of a round bar with a nominal diameter of 40 mm

Claims

Patentansprüche claims
1. Verfahren zur Herstellung von Stäben aus transparenten Kunststoffen durch Extrusion einer Kunststoffformmasse, dadurch gekennzeichnet, dass man eine extrudierte Kunststoffformmasse auftrennt und aus der Kunststoffformmasse 1 ein Kunststoffrohr extrudiert und nach Eintritt in einen Vakuumtankkalibrator nach ca.20 cm das frisch extrudierte Rohr parallel mit der zuvor abgetrennten geschmolzenen Kunststoffformmasse 2 füllt und den neu gebildeten Kunststoffformkörper wie bei der üblichen Rohrextrusion weiter verarbeitet.1. A process for the production of rods from transparent plastics by extrusion of a plastic molding compound, characterized in that an extruded plastic molding compound is separated and a plastic pipe is extruded from the plastic molding compound 1 and, after entering a vacuum tank calibrator, the freshly extruded pipe is parallel to the after about 20 cm previously separated molten plastic molding compound 2 fills and processed the newly formed plastic body as in the usual pipe extrusion.
2. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass Kunststoffstäbe aus nicht eingefärbtem Polymethylmethacrylat mit einem Transmissionsgrad von mindestens XD65 85% hergestellt werden.2. The method according to claim 1, characterized in that plastic rods are made from non-colored polymethyl methacrylate with a transmittance of at least XD 6 5 85%.
3. Verfahren nach Anspruch 1 - 2, dadurch gekennzeichnet, dass die Kunststoffmasse eingefärbt ist.3. The method according to claim 1-2, characterized in that the plastic mass is colored.
4. Rundstab, hergestellt nach einem Verfahren gemäß der Ansprüche 1-3.4. round rod, produced by a method according to claims 1-3.
5. Vorrichtung zur Herstellung von Rundstäben, dadurch gekennzeichnet, dass ein extrudierter Rundstab kleineren Durchmessers in einem innenliegenden Extrusionswerkzeug parallel mit einem extrudierten Rohr größeren Durchmessers mit einem außenliegenden Extrusionswerkzeug berührungslos nach dem Verlassen des Extruders in einem Kalibrator eingeführt werden und dort nach ca. 20 cm miteinander verschmelzen. 5. Apparatus for the production of round bars, characterized in that an extruded round rod of smaller diameter in an internal extrusion tool is introduced in parallel with an extruded tube of larger diameter with an external extrusion tool without contact after leaving the extruder in a calibrator and there after about 20 cm merge with each other.
6. Vorrichtung zur Herstellung von Rundstäben gemäß Anspruch 5, dadurch gekennzeichnet, dass das Rohr vor der Verschmelzung mit dem Rundstab formstabilisierend abgekühlt wird.6. Device for the production of round bars according to claim 5, characterized in that the tube is cooled to stabilize the shape before the fusion with the round bar.
7. Verwendung von Rundstäben im Messe- und Ladenbau, im Bau, in der Leuchtenindustrie, in der Möbelindustrie und in der Werbetechnik. 7. Use of round bars in trade fair and shop construction, in construction, in the lighting industry, in the furniture industry and in advertising technology.
EP05700879A 2004-03-25 2005-01-13 Method for producing plastic rods Withdrawn EP1727660A1 (en)

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CN104441554A (en) * 2014-07-23 2015-03-25 河南盛世塑业有限公司 Coextrusion mold of plastic cylindrical bar and plastic cylindrical bar

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