EP2824239A1 - Verstärkte Polymerplatten - Google Patents

Verstärkte Polymerplatten Download PDF

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Publication number
EP2824239A1
EP2824239A1 EP13176006.8A EP13176006A EP2824239A1 EP 2824239 A1 EP2824239 A1 EP 2824239A1 EP 13176006 A EP13176006 A EP 13176006A EP 2824239 A1 EP2824239 A1 EP 2824239A1
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EP
European Patent Office
Prior art keywords
polymeric
panel
monofilament
polymeric material
inner core
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Withdrawn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
EP13176006.8A
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English (en)
French (fr)
Inventor
Silvo Bolka
Gabriela Ambrozic
Branka Ramovs
Nusa Janzekovic
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.)
Akripol d o o
Center of Excellence for Polymer Materials and Technologies (PoliMaT)
Original Assignee
Akripol d o o
Center of Excellence for Polymer Materials and Technologies (PoliMaT)
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 Akripol d o o, Center of Excellence for Polymer Materials and Technologies (PoliMaT) filed Critical Akripol d o o
Priority to EP13176006.8A priority Critical patent/EP2824239A1/de
Publication of EP2824239A1 publication Critical patent/EP2824239A1/de
Withdrawn legal-status Critical Current

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    • E—FIXED CONSTRUCTIONS
    • E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
    • E01F—ADDITIONAL WORK, SUCH AS EQUIPPING ROADS OR THE CONSTRUCTION OF PLATFORMS, HELICOPTER LANDING STAGES, SIGNS, SNOW FENCES, OR THE LIKE
    • E01F8/00—Arrangements for absorbing or reflecting air-transmitted noise from road or railway traffic
    • E01F8/0005—Arrangements for absorbing or reflecting air-transmitted noise from road or railway traffic used in a wall type arrangement
    • E01F8/0017—Plate-like elements

Definitions

  • the present invention relates to reinforced polymeric panels, such as acrylic glass panels or polycarbonate panels, including embedded coated monofilaments.
  • the invention also relates to the production of polymeric panels including embedded coated monofilaments and having anti-noise and anti-fragmentation properties.
  • Polymeric panels such as acrylic glass panels are commonly used as anti-noise barriers installed, e.g., along motorways and railway lines, for the purpose of mitigating the resultant traffic noise.
  • EP1936035 entitled “Panels with anti-noise and anti-fragmentation properties on the basis of acrylic glass, process for their preparation and use thereof” discloses the manufacturing of panels on the basis of polymethylmethacrylate (PMMA, acrylic glass) with embedded reinforcing polymer monofilament fibers in the form of a three-dimensional fiber entanglement.
  • PMMA polymethylmethacrylate
  • EP1029984 entitled “Noise protection wall element” discloses a noise barrier segment for roads, highways and railways, and the like.
  • the segment comprising a transparent plate and fastening elements is characterized by the fact that in its installed state it is formed about a vertical axis in such a way that it protrudes from a plane defined by the noise protection wall.
  • the noise protection wall element consisting of one or more transparent plates, preferably of plastic material, and the transparent plates is fixing means.
  • Particularly preferred transparent plastics for the plate include poly(meth)acrylates, polycarbonates, polyvinyl chloride, and mixtures of these plastics.
  • For the acrylic plate a filament, grid or net made of polyamide, polypropylene, or other materials incompatible with the matrix plastic may be used.
  • WO2012/038961 entitled »Reinforced Acrylic Glass Panels discloses a transparent panel of acrylic glass having reinforcement elements (rigid cables and elastic cables) embedded in the panel and spaced apart in parallel longitudinally.
  • the rigid cables are made of a metal (steel, stainless steel, hardened steel, galvanized steel, iron, metal alloy, bimetal layers, and the like), while the elastic cables are formed of a metal (steel, stainless steel, galvanized steel, copper, brass, aluminum, bronze, iron, metal alloy, bimetal layers, and the like) having a percentage elongation (engineering strain at fracture) of at least 30%, and preferably between 40% and 80%.
  • the reinforcement elements may be separated and spaced apart from one other, or they may be intertwined with each other.
  • the reinforcement elements may be aligned horizontally, vertically, diagonally, or in the grid pattern.
  • EP1041212 entitled "Antifragmentation panel made of a thermoplastic polymer, particularly an acrylic polymer and use as a noisescreen” relates to anti-splitting plates of thermoplastic polymer material, particularly methacrylic polymer.
  • the filaments may be formed by any material which can form tangles such as braided rope.
  • they may be formed of polymeric material thread such as polyamide, polyesters such as polyethylene terephthalate, and it may also be of metal thread (thread of copper for example) or natural textile fibers like cotton.
  • the reinforcing of the matrix material was heretofore achieved by embedding more or less untreated polymer monofilaments into the matrix.
  • Such monofilaments are often incompatible with the matrix polymer, in particular, when the matrix material is non-polar and the monofilaments comprise polyamide or polypropylene.
  • the weak adhesion between the monofilament and the matrix polymer can cause the complete debonding of the monofilament from the matrix, consequently, an ineffective retention of fragments of the plate formed after a collision of an object with the acrylic glass.
  • the monofilament often breaks at impact, leading to poor retention of fragments upon collision.
  • the matrix material e.g., acrylic glass
  • the inventors now found that it was advantageous to assure a proper adhesion of the matrix material to the monofilament so that under the impact of shock, the monofilament will slide inside the plate without de-bonding completely. This improves the effect of retention of plate fragments upon impact.
  • EP1111136 describes surface treatment of the monofilament polyamide and/or polypropylene threads with dissolved phenol formaldehyde resin in the presence of p-toluene sulfonic acid as catalyst. Primer layer is applied only partially or over the whole surface of the reinforcing monofilament thread.
  • the phenol-formaldehyde can create a brittle joint with the polyamide, which may cause in the case of mechanical deformation of the whole acrylic plate, de-bonding of the monofilaments and the matrix.
  • the present inventions addresses the above shortcomings of the prior art.
  • the invention relates to a polymeric panel comprising a matrix of a first polymeric material and at least one polymeric monofilament embedded therein, wherein said at least one monofilament includes an inner core of a second polymeric material and an outer layer of a third polymeric material adjacent said inner core.
  • the first polymeric material is selected from the group consisting of poly(methyl methacrylate), polycarbonate and polyvinyl chloride.
  • the second polymeric material is a hydrophilic polymer.
  • Said third polymeric material comprises a co-polymer formed from polar and non-polar monomers.
  • said first polymeric material is poly(methyl methacrylate) (PMMA).
  • the second polymeric material is polyamide (PA), polypropylene (PP), or polyethylene terephthalate (PET), preferably polyamide (PA).
  • the third material comprising a co-polymer formed from polar and non-polar monomers may be in form of (or comprise) a co-extruded blend of said co-polymer formed from polar and non-polar monomers and said second material, i.e., the material forming the inner core (e.g., PA).
  • the co-polymer formed from polar and non-polar monomers is preferably styrene maleic anhydride (SMA).
  • the third polymeric material i.e., the material of the outer layer of the filaments
  • the third polymeric material preferably includes from 0.1 to 20%, or 0.5 to 10%, or 1 to 8% or 3 to 6%, or from 4.5 to 5.5% of SMA (by weight).
  • the inner core of the monofilament is pre-stretched prior to co-extruding the third polymeric material on its surface. This provides for improved mechanical properties of the monofilament.
  • the panel includes multiple polymeric monofilaments arranged in parallel. This provides for an advantageous and even distribution of the reinforcement over the entire panel.
  • the panel may be from 5 mm to 50 mm thick.
  • the at least one monofilament may be from 0.5 to 5 mm, or from 1 to 3 mm, or from 2 to 3 mm in diameter.
  • the thickness of the outer layer of the third material is from 0.001 to 2 mm, or from 0.01 to 0.5 mm or from 0.02 to 0.1 mm thick.
  • the inner core and the outer layer of the at least one monofilament may be produced by co-extrusion of the third material on the pre-fabricated, and optionally pre-stretched, polymeric core.
  • the polymeric panel may be from 0.4 m to 5 m in length and from 0.4 to 5 m in width.
  • the panel is preferably rectangular. It may be substantially flat.
  • the present invention also resides in a method of making a polymeric panel, said method comprising (i) providing a first polymeric material; (ii) providing at least one monofilament, said at least one monofilament having an inner core of a second polymeric material and an outer layer of a third polymeric material, and (iii) embedding said at least one monofilament in said first polymeric material, wherein said first polymeric material is selected from the group consisting of poly(methyl methacrylate), polycarbonate and polyvinyl chloride; said second polymeric material is a polar polymer; and said third polymeric material comprises a co-polymer formed from polar and non-polar monomers.
  • said first polymeric material is poly(methyl methacrylate).
  • the second polymeric material is polyamide (PA), polypropylene (PP), or polyethylene terephthalate (PET), but preferably polyamide.
  • said third material comprises a co-extruded blend of said co-polymer formed from polar and non-polar monomers and said second material.
  • the co-polymer formed from polar and non-polar monomers is preferably styrene maleic anhydride (SMA).
  • SMA styrene maleic anhydride
  • the third polymeric material may include, e.g., from 0.1 to 20%, or 0.5 to 10%, or 1 to 8%, or 3 to 6%, or from 4.5 to 5.5% by weight of SMA, based on the total weight of the third material.
  • said inner core of said monofilament is pre-stretched prior to co-extrusion of the third polymeric material onto the surface of the inner core.
  • the method may include embedding multiple monofilaments in said first material, said multiple monofilaments being arranged in parallel fashion.
  • the multiple monofilaments may form a mesh.
  • the polymeric panel is produced to be from 5 mm to 50 mm thick.
  • the at least one monofilament may be from 0.5 to 5 mm, or from 1 to 3 mm, or from 2 to 3 mm in diameter.
  • the outer layer of a third material has preferably a radial thickness of from 0.001 to 2 mm, or from 0.01 to 0.5 mm or from 0.02 to 0.1 mm.
  • the panels produced are from 0.4 m to 5 m long, and have a width of from 0.4 to 5 m. Other dimensions are of course possible.
  • the panel is preferably a rectangular panel.
  • the panel is preferably a substantially flat panel.
  • the panel may be formed by extrusion of the first material and embedding said at least one monofilament in the extruded first material.
  • Panels according to the invention can also be formed by casting or molding.
  • said at least one monofilament is produced by co-extrusion of said third material on said inner core to form an outer layer.
  • said second material forms said inner core and said third material forms said outer layer.
  • said core is coated (preferably fully coated) by said third material.
  • the polycarbonate is a polymer made from bisphenol A according to the structural formula:
  • Acrylic glass or “PMMA”, according to the invention, shall be understood as being a poly(methyl methacrylate) polymer, also referred to under the IUPAC name poly(methyl 2-methylpropenoate)), and having the structural formula:
  • SMA Styrene maleic anhydride
  • SMA is a polymer having the elemental formula (C 8 H 8 ) n (C 4 H 2 O 3 ) m .
  • SMA may alternatively be defined as comprising multiple units of the following structural elements:
  • a “matrix”, according to the invention, shall be understood as being a three-dimensional structure or material, in which other structures or materials are embedded.
  • a preferred matrix of the invention is a hardened polymeric resin, e.g., PMMA resin, in which at least one monofilament is embedded.
  • the present invention relates to reinforcing monofilament fibers and their use in polymer panels (e.g. acrylic glass panels, polycarbonate panels, PVC panels) with improved thermal and mechanical properties.
  • the reinforcing monofilaments are embedded in a matrix in such a manner that they are preferably oriented parallel to each other, and the fibers are preferably distributed essentially uniformly throughout the entire cross-section.
  • the present invention assures good adhesion of the monofilaments to the polymeric matrix by providing monofilaments with an additional layer (a coating layer) of a polymeric material.
  • the additional layer of a polymeric material may be coextruded onto the core of the monofilament fibers, to form a surface layer on the inner core.
  • the coextruded surface layer is preferably compatible with both the material of the inner core, and with the matrix material.
  • the adhesive connection of the surface layer to the inner core and to the matrix material is preferably stable in the wide temperature range (from -40°C to +135°C), at which temperatures preferably no de-bonding between the surface layer, the inner core and the matrix material should occur.
  • Good adhesion between monofilament fibers and the matrix ensures better mechanical properties of the polymeric panels, especially in terms of the Young's modulus (E-modulus) and mechanical strength.
  • Suitable reinforcing monofilament fibers according to the invention have an inner core consisting of or at least comprising polyamide (PA), polypropylene (PP), polyethylene terephthalate (PET), or mixtures thereof.
  • PA polyamide
  • PP polypropylene
  • PET polyethylene terephthalate
  • the monofilament fibers are polyamide fibers.
  • Preferred matrix materials are plastics, preferably transparent plastics, such as poly(meth)acrylates (PMMA), polycarbonates, polyvinyl chloride, and mixtures thereof.
  • PMMA poly(meth)acrylates
  • Pcarbonates polycarbonates
  • polyvinyl chloride polyvinyl chloride
  • Polymeric panels of the invention have improved thermal and mechanical properties, which are based on a matrix material, such as polymethylmethacrylate or polycarbonate, with embedded reinforcing polymeric monofilament fibers, where in the polymeric monofilament fibers are coated with a compatible surface material.
  • a matrix material such as polymethylmethacrylate or polycarbonate
  • embedded reinforcing polymeric monofilament fibers where in the polymeric monofilament fibers are coated with a compatible surface material.
  • Figure 1 A polymeric panel with embedded monofilaments, according to the invention, is shown in Figure 1 .
  • a schematic presentation of the co-extruded monofilament is shown in the Figure 2 .
  • a process for co-extruding the outer layer onto an inner core is depicted in Figure 3 .
  • a prefabricated inner core 4 of the monofilament 2 is advanced through extrusion tool 5, while a melted blend 6 of a polymer formed from polar and nonpolar monomers (e.g., SMA) and the polymer of the inner core (e.g., PA) is forced through the extrusion nozzle in tool 5.
  • a continuous outer layer 3 is thereby formed on the inner core 4 of monofilament 2.
  • the embedding of a monofilament having an outer layer of a polymeric material assures good adhesion of the monofilament to the matrix.
  • a surface layer of a polymeric material comprising both polar and non-polar monomers, a strong adhesive connection between the thermoplastic core of the monofilament and the polymeric matrix can be achieved.
  • the adhesion of the monofilaments to the acrylate matrix can be adjusted by the relative amount of the co-polymer formed from polar and non-polar monomers in the outer layer, as well as by the co-extrusion parameters (see Example 1).
  • the panels according to the present invention have improved anti-braking and anti-fragmentation properties, so that in the case of vehicle crashing into a polymeric panel of the invention e.g. along the road, the co-extruded monofilament will prevent the falling-off of any, even small broken particles from the polymeric panel onto the roadway or elsewhere, so that under the effect of shock the monofilament slide into the plate without extract completely while exerting the effect of retention of plate fragments.
  • the embedded reinforcing monofilament threads provide good adhesion on acrylic glass matrix assuring that in the case of mechanical deformation of the whole acrylic plate, de-bonding between filaments and acrylic matrix does not occur, and the monofilaments do not break under the impact.
  • the new co-extrusion structure according to the invention assures that the impact energy is directed toward the interface between the co-extruded layer and monofilament thus preventing the monofilament from cracking.
  • the outer layer formed on the inner core of the monofilaments comprises a polymer comprising both polar and nonpolar monomers (e.g., a block co-polymer or a random copolymer), such as poly(styrene maleic anhydride) (SMA).
  • SMA poly(styrene maleic anhydride)
  • the outer layer formed on the inner core of the monofilaments may in particular comprise a co-extruded blend of a polymer comprising polar and nonpolar monomers (e.g., block copolymer or random copolymer), such as SMA, and the polymeric material of the inner core (e.g. PA).
  • An outer layer formed from such a material confers good compatibility with both the material of the inner core (e.g.
  • the presence of polar and nonpolar monomers in the one component of a co-extruded blend of the outer layer is particularly advantageous to confer good adhesive properties to core and matrix material.
  • Technical difficulties encountered when using only the co-polymer comprising polar and non-polar monomers e.g., pure SMA as the coating material tends to dissolve in the pre-polymer during polymerization process) can be circumvented by using a co-extruded mixture of the co-polymer comprising polar and non-polar monomers and the material which forms the inner core, to form the outer layer.
  • the co-extruded outer layer is stable in the wide temperature range (e.g., from -40°C to +135°C), at which temperatures preferably no delamination and de-bonding occurs between the outer layer, the core material and the acrylic matrix.
  • the invention provides for a monofilament which: (a) provides good adhesion between the monofilament and acrylic glass is effective in a broad temperature range, and (b) in the case of vehicle crashing into the acrylic glass, the monofilament slides into the plate without extract completely thus efficiently exerting the retention of plate fragments.
  • the novel methods of producing polymeric panels according to the invention prevent other deformation which may occur in the process of the production of acrylic plates with embedded polyamide monofilaments.
  • one of the undesirable side-effects affecting the quality of reinforced acrylic plates is the retention of water droplets originating from hygroscopic polyamide monofilament, which causes local deformations on the monofilament-acrylic glass surface.
  • the co-extrusion conditions and the obtained composition of the pre-formed monofilament used according to this invention prevent such a defect to occur.
  • the obtained uniform surface area between a co-extruded monofilament and an acrylic plate assures that the optical uniformity is achieved as a consequence of the compatibility between the acrylic plate and the co-extruded monofilament.
  • the outer layer can be applied partially or over the entire surface of the inner core of the monofilaments.
  • the material of the outer layer can be easily recycled, because only thermoplastic materials are used for the production.
  • the co-extrusion of an outer layer according to the invention allows also higher temperature during the production of acrylic plates, which ensures better mechanical properties of the acrylic plates, shorter production time and less energy consumption during the production process.
  • the monofilaments can be in any chosen color; a transparent monofilament is also possible. In a preferred embodiment, however, the monofilaments are black. This provides good visibility of the filaments in the polymeric panels, and is useful for preventing birds from flying into the panel.
  • Acrylic panels of the invention may be produced by casting or by extrusion.
  • a conventional casting process for a transparent acrylate glass plates is described in EP1936035 . It comprises three steps: prepolymerization of methylmethacrylate and additives in the reactor, prepolymer casting at temperature 30 - 80°C for 10 to 16 hours and the final consolidation of acrylic plates in an air oven at temperature 100 - 135°C for at least 1 hour.
  • the mold is composed of two glass plates, and a PVC seal.
  • pre-prepared monofilaments can be inserted into the mold during the assembly process of the casting mold, namely by tightening and fixing the monofilaments with a diameter of from, e.g., 1.5 to 3 mm in parallel alignment onto the seal, which is introduced along the edge of the lower glass so that the monofilament threads are subsequently incorporated inside the glass plate after the completion of the polymerization process.
  • the adhesion of the monofilaments to the acrylate matrix can be adjusted by the percentage of e.g. SMA in the the co-extruded outer layer of the monofilaments.
  • SMA e.g. SMA in the co-extruded outer layer of the monofilaments.
  • the outer layer of the monofilament is formed from a co-extruded mixture of polyamide and SMA, wherein the SMA is present in the coextruded mixture at a concentration of 0.1 to 20%, or 0.5 to 10%, or 1 to 8%, or 3 to 6%, or from 4.5 to 5.5% by weight.
  • the polymeric panels of the invention show a significant improvement in E-modulus behavior.
  • Figure 4 shows the percent improvement of the E-modulus of acrylic glass with embedded PA monofilaments coated with a co-extruded polymeric mixture according to the invention (in this case, 4.8%wt SMA in PA) relative to acrylic glass with conventional (non-coated) PA monofilaments.
  • Significantly improved E-modulus is demonstrated over the entire temperature range of from -50°C to 90°C.
  • Monofilaments were prepared by co-extrusion of a polymeric material comprising PA and SMA to form an outer layer on a pre-formed polymeric core of the monofilament.
  • a conventional screw-extruder was used with a nozzle similar to the one shown in Figure 3 .
  • a prefabricated inner core 4 of the monofilament 2 was advanced through extrusion tool 5, while a melted blend 6 of a polymer formed from polar and nonpolar monomers (SMA) and the polymer of the inner core (PA) was forced through the extrusion nozzle in tool 5.
  • a continuous outer layer 3 was thereby formed on the inner core 4 of monofilament 2.
  • the polymeric core is formed from PA.
  • the relative amount of SMA in the co-extruded material of the outer layer was 4.8% by weight.
  • the outer layer was co-extruded from a mixture of pellets containing polyamide (PA) pellets and poly (styrene maleic anhydride, SMA) pellets.
  • PA polyamide
  • SMA poly (styrene maleic anhydride
  • black Masterbatch (Cabot Corp, Boston, MA, USA) was added to the polymeric material to be co-extruded.
  • Black Masterbatch was added in form of pellets.
  • a minimum of 1.5 wt% of Masterbatch was used (relative to the weight of PA in the coextruded polymeric material).
  • the resulting coated monofilaments were water cooled and automatically wound on the spooler.
  • Minimal thickness of the outer layer was 0.05 mm.
  • Zone 1 is the feed zone and Zones 2-5 are the consecutive zones of the screw-extruder from feed to nozzle.
  • a casting chamber is formed from two prefabricated acrylic glass panels (2000 mm x 1220 mm x 8 mm) and a peripheral seal of 4 mm thickness. Monofilaments produced according to Example 1, having a diameter of 0.9 mm, are clamped in the chamber at intervals of 30 mm and parallel to one another. A low viscosity cold setting methacrylate resin containing a redox initiator system is then poured into the chamber. After hardening of the resin, a polymeric panel according to the invention was obtained.
  • a polymeric panel is casted in three steps: (1) pre-polymerization of methylmethacrylate and additives in the reactor, (2) pre-polymer casting at temperature 30 - 80°C for 10 to 16 hours and (3) the final consolidation of acrylic plates in an air oven at temperature 100 - 135°C for at least 1 hour.
  • the mold is composed of two glass plates, and a PVC seal. Pre-prepared monofilaments are inserted into the mold during the assembly process of the casting mold, namely by tightening and fixing the monofilaments with a diameter of from, 1.5 in parallel alignment onto the seal, which is introduced along the edge of the lower glass so that the monofilament threads are subsequently incorporated inside the glass plate after the completion of the polymerization process.
  • Impact strength was measured for a polymeric panel comprising coated monofilaments (4.8%wt SMA in PA) according to the invention and compared to a polymeric panel comprising conventional (non-coated) monofilaments of same diameter. Impact strength was measured according to EN ISO 179.
  • the panels had similar overall geometry and matrix composition.
  • the panel comprising monofilaments coated according to the invention exhibited an impact strength determined according to EN ISO 179 of 30.3 kJ/m 2 .
  • the panel comprising conventional PA monofilaments exhibited an impact strength of only 28.2 kJ/m 2 .
  • the panel according to the invention showed hence greater impact strength.
EP13176006.8A 2013-07-10 2013-07-10 Verstärkte Polymerplatten Withdrawn EP2824239A1 (de)

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EP13176006.8A EP2824239A1 (de) 2013-07-10 2013-07-10 Verstärkte Polymerplatten

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0769595A1 (de) * 1995-10-21 1997-04-23 Degussa Aktiengesellschaft Brandsicheres, transparentes Scheibenelement und dessen Verwendung
EP1029984A1 (de) 1999-02-19 2000-08-23 Röhm Gesellschaft mit beschränkter Haftung Lärmschutzwandsegment
EP1041212A1 (de) 1999-03-30 2000-10-04 Atofina Splitterschutzscheibe aus einem thermoplastischem Polymer, insbesondere einem polymerem Acryl und Verwendung als Lärmschutzwand
EP1041213A1 (de) * 1999-03-30 2000-10-04 Atofina Splitterschutzscheibe aus thermoplastischem Polymer und Verwendung als Lärmschutzwand
EP1936035A1 (de) 2006-12-22 2008-06-25 Akripol proizvodnja in predelava polimerov, d.d. Tafel mit Lärm- und Splitterschutzeigenschaften auf der Basis von Kunstglas, Verfahren zu ihrer Herstellung und Verwendung dafür
WO2012038961A1 (en) 2010-09-21 2012-03-29 Plazit Iberica Plastic Solutions, S.A. Reinforced acrylic glass panels

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0769595A1 (de) * 1995-10-21 1997-04-23 Degussa Aktiengesellschaft Brandsicheres, transparentes Scheibenelement und dessen Verwendung
EP1029984A1 (de) 1999-02-19 2000-08-23 Röhm Gesellschaft mit beschränkter Haftung Lärmschutzwandsegment
EP1041212A1 (de) 1999-03-30 2000-10-04 Atofina Splitterschutzscheibe aus einem thermoplastischem Polymer, insbesondere einem polymerem Acryl und Verwendung als Lärmschutzwand
EP1041213A1 (de) * 1999-03-30 2000-10-04 Atofina Splitterschutzscheibe aus thermoplastischem Polymer und Verwendung als Lärmschutzwand
EP1936035A1 (de) 2006-12-22 2008-06-25 Akripol proizvodnja in predelava polimerov, d.d. Tafel mit Lärm- und Splitterschutzeigenschaften auf der Basis von Kunstglas, Verfahren zu ihrer Herstellung und Verwendung dafür
WO2012038961A1 (en) 2010-09-21 2012-03-29 Plazit Iberica Plastic Solutions, S.A. Reinforced acrylic glass panels

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