EP1763435A1 - Procede de production d'un corps composite - Google Patents

Procede de production d'un corps composite

Info

Publication number
EP1763435A1
EP1763435A1 EP05758971A EP05758971A EP1763435A1 EP 1763435 A1 EP1763435 A1 EP 1763435A1 EP 05758971 A EP05758971 A EP 05758971A EP 05758971 A EP05758971 A EP 05758971A EP 1763435 A1 EP1763435 A1 EP 1763435A1
Authority
EP
European Patent Office
Prior art keywords
pmma
abs
organometallic compound
composite body
group
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Withdrawn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
EP05758971A
Other languages
German (de)
English (en)
Inventor
Johann Kappacher
Thomas Sitka
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.)
Senoplast Klepsch and Co GmbH
Original Assignee
Senoplast Klepsch and Co GmbH
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 Senoplast Klepsch and Co GmbH filed Critical Senoplast Klepsch and Co GmbH
Publication of EP1763435A1 publication Critical patent/EP1763435A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/283—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysiloxanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/14—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by a layer differing constitutionally or physically in different parts, e.g. denser near its faces
    • B32B5/145—Variation across the thickness of the layer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/584—Scratch resistance
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes

Definitions

  • the present invention relates to a method for producing a composite body.
  • Such composites often consist of a support layer of acrylonitrile-butadiene-styrene copolymers (ABS) on which a top layer of polymethyl methacrylate (PMMA) is disposed to improve the weathering properties, surface hardness, gloss and chemical resistance of the composite.
  • ABS acrylonitrile-butadiene-styrene copolymers
  • PMMA polymethyl methacrylate
  • the composite bodies are usually produced by coextrusion of all layers or lamination, to which the thermoforming or hot edge of the composite board produced in this way can be added to form a shaped body.
  • Generic composites can be used anywhere where the replacement of painted surfaces by co-extruded or laminated surfaces is desired, for example in the sanitary sector, motor vehicles, commercial vehicles, furniture, refrigerators and in the advertising industry.
  • Composite bodies with a cover layer of PMMA have the problem that they need to be improved in terms of abrasion and scratch resistance, dirt repellence and chemical resistance to painted surfaces.
  • the object of the invention is to provide a generic composite body in which the surface properties of the PMMA cover layer are improved by a permanent, resistant to external influences enrichment of polyorganosiloxanes in the outer region of the PMMA cover layer.
  • the extruded or laminated composite is deep-drawn or hot-edged into a molded article.
  • the invention is based on the surprising discovery that the molecules of the organometallic compound compounded into the PMMA mass by heating the mass, for example by the process of coextrusion or lamination, due to the surface activity of the long-chain organic compounds with the organometallic part, which oriented in air, can migrate to the surface of the PMMA mass and so form a molecular film, which causes the desired physicochemical properties.
  • the organic moiety of the macromolecule is physically entangled in the PMMA matrix, making wiping the layer physically and chemically impossible. This shows that the concentration of the organometallic compound in the PMMA mass is greatest in the region of its surface.
  • the migration of the organometallic molecules to the surface takes place optimally when the layer formed from the PMMA and the organometallic compound has a temperature above the glass transition temperature of the PMMA, which is exceeded anyway during coextrusion or lamination, since the polyorganosiloxanes are not yet firmly in the Inside the layer formed from the PMMA and the organometallic compound are incorporated. If necessary, can also be heated externally, for example, in a deep drawing process.
  • a lamination film must first be produced by (co) extrusion.
  • the PMMA and the organometallic compound can either be homogenized in situ or a precompound is prepared. Subsequently, in both cases, the lamination.
  • the preparation of the polymer compound can be carried out, for example, by mixing the PMMA and the organometallic compound in the screw of an extruder. This eliminates an additionally required process step, since the PMMA must be extruded anyway. It is also possible to re-granulate the polymer compound of PMMA and the organometallic compound after its formation and before coextrusion or lamination.
  • the invention also relates to a composite body having at least one cover layer and a further layer, as produced, for example, by the method described wherein at least one of the further layers comprises at least one of the following polymers: PS, ABS, PMMA, HI-PMMA, ASA, PC, PC-PET (G), PC-PBT, ABS-PC, ASA-PC, ABS PA or mixtures thereof, and the at least one cover layer of - preferably impact-modified - PMMA and an organometallic compound - preferably polyorganosiloxane - exists.
  • a composite body can be produced from the composite body by deep drawing or hot edges.
  • the composite has at least two, preferably three or five, layers, wherein at least one cover layer consists of PMMA and the organometallic compound and at least one of the further layers consists of one of the following polymers or mixtures thereof : PS, ABS, PMMA, HI-PMMA, ASA, PC, PC-PET (G), PC-PBT, ABS-PC, ASA-PC, ABS-PA.
  • both cover layers of the composite body consist of PMMA and the organometallic compound. This is especially advantageous when the layers arranged between the cover layers consist of PMMA.
  • the composite body then consists entirely of acrylic, with its surfaces having the desired properties.
  • particularly advantageous mechanical properties and surface properties result if the total thickness of the composite body is 0.05 to 13 mm and the thickness of the further layers is 0.01 to 9 mm in each case.
  • the main extruder layer (the thickest layer) may be 4 to 9 mm thick.
  • Example 1 relates to a coextruded composite panel.
  • Example 2 relates to a laminated composite panel,
  • Example 3 relates to further coextruded composite panels:
  • Example 1 :
  • a sanitary panel produced by the method according to the invention consisting of an ABS / PMMA composite, having a 5% coextruded PMMA top layer (relating to total thickness, for example a PMMA top layer of 200 ⁇ m at 4 mm total plate thickness, was tested ): In this top layer, 2.5 percent by weight of polyorganosiloxane were incorporated.
  • the incorporation on the extruder can be done by various methods.
  • Tests were carried out on the extruded plate and on the deep-drawn part.
  • the deep-drawn part was deep-drawn by default with a PE protective film. Checked was on
  • Used Scratch Resistance Tester Universal Scratch Tester Model 413 from Ericsson.
  • the test device consists of a frame with a movable support surface. This support surface can be moved from the horizontal at a constant tilting speed (via an electric motor) to the vertical. It measures the angle at which a arranged on the support surface support weight begins to slip.
  • the bearing surface sliding surface
  • the contact surface is 63 x 63 mm.
  • As a support weight a steel weight was used with a net weight of 504 grams.
  • the sample to be tested (plate) is placed on the support surface, which is in the 0 ° position, with the surface to be tested upwards (about DIN A4, thickness between about 1 - 6 mm).
  • the steel weight is placed with the felt covering.
  • the support surface driven by an electric motor, moves uniformly around the fulcrum. In the range of 0 ° to 50 °, a uniform lifting speed of about 37 sec. respected.
  • a protractor is attached to the inclination of the support surface can always be checked.
  • the test person moves the support surface by pressing a button around the fulcrum, constantly monitoring the weight.
  • the button for the lifting drive is released, whereby the support surface is stopped in the upward movement ung.
  • the contact angle and surface tension were determined on ABS / PMMA sheets of the type described above with addition of 2.5% and 5% polyorganosiloxane, respectively.
  • the surface energy and the contact angle of composite bodies according to the invention were determined before and after deep-drawing.
  • test fluids water, glycerol, ethylene glycol, 1-octanol and n-dodecane.
  • the measurement is carried out with a contact angle measuring device from Krüss (G2).
  • the advancing angle of the sample drop on the test plate is measured in the range between 8-12 ⁇ l drop volume.
  • the evaluation method used is the method according to Owens-Wendt-Rable & Kaelbe. This method is mainly used for low energy surfaces (polymers). With the contact angle measurements of the liquid drops on the surface of the solid polymers, both the total surface tension of the solid and the polar and dispersive fractions can be determined.
  • concentrations of polyorganosiloxanes were incorporated into PMMA.
  • concentrations were used: 0.5 percent by weight, 1 percent by weight, 1, 5 percent by weight, 2.5 percent by weight.
  • the polymer compounds were prepared by means of a compounding unit and the granules were pressed on a press into films having a thickness of about 400 ⁇ m. These laminates were laminated in the calender on ABS plates. From the specimens obtained, the sliding friction (Slip property) was measured, as in Example 1. As support surface, a 63 x 63 mm sliding surface made of felt was used. The weight was 504 g. The sliding friction on deep-drawn parts was measured to simulate the deep-drawing process.
  • Scratch resistance makes the surface of the composite more resistant.
  • the specimens used were ABS-PMMA composites with a total thickness of 4 mm with a 5% coextruded HI-PMMA top layer (plate 2) with the stated additions of polyorganosiloxane.
  • the composite bodies were deep-drawn with or without PE protective film (about 1: 1, 5).
  • polyorganosiloxanes of the following mean average formula are provided:
  • A represents an alkyl group having 1 to 8 carbon atoms
  • Z represents an aliphatic group having 1 to 14 carbon atoms
  • A is methyl
  • Z is alkylene ether, namely - (CH 2 ) 3 -O- (CH 2 ) 2 -,
  • Q is -O-CO-NH- (CH 2 ) 17 -CH 3 and m is 21.8, n and o are each 1.
  • [-O-CO- (CH 2 ) 5 -] is 22
  • 9 is 22,9-O-CO- groups in an aliphatic polyester having a molecular weight of about 2660.
  • Z is selected from the group consisting of an alkylene group having 1 to 14 carbon atoms, an alkylene ether, alkylene thioether or alkyleneamide group having 2 to 14 carbon atoms and an alkylene-amide group having 2 to 14 carbon atoms.
  • A represents a linear alkyl group having 1 to 4 carbon atoms.
  • the mass ratio of polydimethylsiloxane block to polyester block is 1: 1 to 1: 3.
  • FIG. 2 shows schematically the layer structure of an embodiment of a composite body according to the invention, which consists of five layers
  • FIG. 3 shows in tabular form various possibilities of the compositions of the five layers of the exemplary embodiment according to FIG. 2.
  • the carrier layer S 3 made of ABS, on which a middle layer S 2 of PMMA is arranged, can be seen.
  • a cover layer S 1 a layer of a polymer compound of impact-modified PMMA and polyorganosiloxane.
  • FIG. 2 shows an exemplary embodiment of a composite body 1 according to the invention, which consists of five layers S 1 , S 2 , S 3 , S 4 and S 5 .
  • Various possibilities of the compositions of the individual layers are shown in FIG.

Abstract

L'invention concerne un procédé permettant de produire un corps composite, selon lequel il est prévu de coextruder ou de laminer en un corps composite (1) comportant au moins une couche de recouvrement (S<sub
EP05758971A 2004-07-08 2005-07-01 Procede de production d'un corps composite Withdrawn EP1763435A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AT11552004 2004-07-08
PCT/AT2005/000248 WO2006005090A1 (fr) 2004-07-08 2005-07-01 Procede de production d'un corps composite

Publications (1)

Publication Number Publication Date
EP1763435A1 true EP1763435A1 (fr) 2007-03-21

Family

ID=34972240

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05758971A Withdrawn EP1763435A1 (fr) 2004-07-08 2005-07-01 Procede de production d'un corps composite

Country Status (2)

Country Link
EP (1) EP1763435A1 (fr)
WO (1) WO2006005090A1 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102006060163A1 (de) * 2006-12-18 2008-06-19 Evonik Röhm Gmbh Folienverbund
DE102009020937A1 (de) * 2009-05-12 2010-11-18 Bayer Materialscience Ag Kälte schlagzähe Coextrusionsfolien
AT508460A1 (de) 2009-06-26 2011-01-15 Senoplast Klepsch & Co Gmbh Verfahren zur erhöhung der ritzhärte eines körpers
KR20130055311A (ko) * 2011-11-18 2013-05-28 삼성디스플레이 주식회사 표시장치용 윈도우 패널 및 이를 포함하는 표시 장치
EP3167003B1 (fr) 2014-07-11 2019-09-04 SABIC Global Technologies B.V. Compositions thermoplastiques à faible brillance, procédé de fabrication de ces dernières et articles les comprenant
US10000654B2 (en) * 2015-03-05 2018-06-19 Flex-N-Gate Corporation Automotive plastic panel
PL3558674T6 (pl) 2016-12-21 2022-10-03 Athlone Extrusions Limited Termoformowalny wytłaczany arkusz z efektem granitowym
CN110157025B (zh) * 2018-02-12 2021-06-18 比亚迪股份有限公司 一种复合板材
JP7193402B2 (ja) * 2019-03-29 2022-12-20 住友化学株式会社 自動車ルーフ用部材及び自動車ルーフ用部材の製造方法

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AT388705B (de) * 1987-08-24 1989-08-25 Intec Plastic Prod Verbundplatte
GB9322810D0 (en) * 1993-11-05 1993-12-22 Ici Plc Moulded composites
IT1316160B1 (it) * 2000-01-07 2003-04-03 Telma Guzzini S R L Articoli stampati ad alto contenuto di filler e relativo processo dipreparazione
DE10214436A1 (de) * 2002-03-27 2003-10-23 Blanco Gmbh & Co Kg Giessmasse und daraus hergestellte Kunststoffformkörper
DE10349144A1 (de) * 2003-10-17 2005-05-12 Roehm Gmbh Polymermischung für mattierte Spritzgußteile
AT500082B1 (de) * 2003-10-31 2007-08-15 Senoplast Klepsch & Co Gmbh Mehrschichtiger verbundkörper und dessen herstellung

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Also Published As

Publication number Publication date
WO2006005090A1 (fr) 2006-01-19

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