WO2013030385A1 - Corps composite - Google Patents

Corps composite Download PDF

Info

Publication number
WO2013030385A1
WO2013030385A1 PCT/EP2012/067039 EP2012067039W WO2013030385A1 WO 2013030385 A1 WO2013030385 A1 WO 2013030385A1 EP 2012067039 W EP2012067039 W EP 2012067039W WO 2013030385 A1 WO2013030385 A1 WO 2013030385A1
Authority
WO
WIPO (PCT)
Prior art keywords
pmma
composite body
layer
abs
colorants
Prior art date
Application number
PCT/EP2012/067039
Other languages
German (de)
English (en)
Inventor
Johann Kappacher
Thomas Peis
Anton HÖLLER
Original Assignee
Senoplast Klepsch & 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 & Co. Gmbh filed Critical Senoplast Klepsch & Co. Gmbh
Publication of WO2013030385A1 publication Critical patent/WO2013030385A1/fr

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
    • B32B1/00—Layered products having a non-planar shape
    • 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
    • B32B27/30—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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • 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
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B32B3/30—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer formed with recesses or projections, e.g. hollows, grooves, protuberances, ribs
    • 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
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • 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
    • B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
    • B29C51/02—Combined thermoforming and manufacture of the preform
    • 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
    • B32B2250/04—4 layers
    • 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
    • B32B2250/05—5 or more layers
    • 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
    • B32B2250/246—All polymers belonging to those covered by groups B32B27/32 and B32B27/30
    • 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
    • B32B2272/00—Resin or rubber layer comprising scrap, waste or recycling material
    • 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
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/402—Coloured
    • B32B2307/4026—Coloured within the layer by addition of a colorant, e.g. pigments, dyes
    • 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
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/408—Matt, dull surface
    • 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
    • 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
    • B32B2307/70—Other properties
    • B32B2307/71—Resistive to light or to UV
    • 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
    • B32B2307/70—Other properties
    • B32B2307/712—Weather resistant
    • 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
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • 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
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/734—Dimensional stability
    • 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
    • B32B2307/70—Other properties
    • B32B2307/738—Thermoformability
    • 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
    • B32B2605/00—Vehicles
    • B32B2605/08—Cars

Definitions

  • the invention relates to a multilayer thermoplastic coextruded composite body for producing self-supporting three-dimensional components, preferably for automotive body panels, agricultural utility vehicle trim or boat covers, comprising layers comprising polymethylmethacrylate (PMMA) and acrylonitrile-butadiene-styrene terpolymers (ABS). Furthermore, the invention relates to a method for producing such composite bodies and the use of the composite body.
  • PMMA polymethylmethacrylate
  • ABS acrylonitrile-butadiene-styrene terpolymers
  • thermoformable, multilayer, coextruded composites in outdoor applications places high demands on the properties of this composite.
  • the most important properties include high heat resistance, high UV and weathering stability, high scratch resistance, good mechanical properties and high resistance to chemicals.
  • the multilayer coextruded composites should be colored according to customer requirements.
  • Multilayer coextruded composite bodies of the type mentioned for outdoor use are known in the literature.
  • H. Kappacher describes in Plastics 86 (1996), pp 388 to 392 coextruded PMMA / ABS composite panels. This article also mentions abutments comprising a support made of ABS / PC blend (acrylonitrile / butadiene / styrene copolymer / polycarbonate blend).
  • EP 0 361 823 Bl describes multilayer, coextruded composites based on fluorine-containing polymers and also containing acrylonitrile / butadiene / styrene copolymers (ABS).
  • Composite bodies of the above type are converted by means of thermoforming in the desired component geometry, trimmed and used in a variety of applications: body parts for electric vehicles and small cars s, paneling for agricultural vehicles (eg tractor roofs or bonnet covers), boat covers, roof boxes, spare wheel covers, etc.
  • thermoforming An alternative manufacturing method of roof modules, the twin-sheet process also called the "2-plate-forming" called: It is a further development of thermoforming and represents an economical and resource-saving process for the production of precise, rigid hollow bodies of almost any geometry. While thermoforming involves heating and then reshaping a composite, this is done in the twin-sheet process with two mold halves either sequentially (American twin-sheet version) or simultaneously (European twin-sheet version or simultaneous twin-sheet molding) Usually hollow bodies are formed, which are either tank-like (by means of two negative tools) or also designed as panel / housing-like products, in which one mold half is formed negative, the second mold half is shaped positively, ie in the direction of the first mold half Stable semi-finished for the outer shell and a it optically and haptic appealing semi-finished for indoor use, you get composite body with the desired property profile. Although the method appears to be inexpensive due to the small number of sub-steps, but has the disadvantage that both for the outer shell and for the interior different semifinished products must be provided with the
  • the starting position underlying the invention is based on meeting the requirements for both the visible outside and the visible inside of a body part such.
  • the multilayer, coextruded composite body as a whole must additionally have good mechanical properties, thermoformability (thermal ductility), adequate heat resistance and good thermoforming behavior.
  • a multilayer, thermoplastic, co-extruded composite body for producing a self-supporting three-dimensional component, preferably a body part for motor vehicles, fairing part for agricultural utility vehicles or a boat cover, comprising in order (i) optionally a cover layer (1) comprising polymethylmethacrylate (PMMA), toughened polymethyl methacrylate (HI-PMMA) or a mixture thereof, and optionally UV additives, (ii) a first intermediate layer (2) disposed below the optional cover layer (1) comprising polymethyl methacrylate (PMMA), impact modified polymethylmethacrylate (HI-PMMA) or a mixture thereof, and colorants and optionally UV additives.
  • a cover layer (1) comprising polymethylmethacrylate (PMMA), toughened polymethyl methacrylate (HI-PMMA) or a mixture thereof, and optionally UV additives
  • a second intermediate layer (3) comprising acrylonitrile-butadiene-styrene terpolymers (ABS) and additionally containing colorants and optionally UV additives,
  • a substrate layer (4) comprising acrylonitrile-butadiene-styrene terpolymers (ABS) and colorants and
  • a backsheet (5) comprising acrylonitrile-butadiene-styrene terpolymers (ABS), thermoplastic polyurethanes, polymethyl methacrylate (PMMA), impact modified polymethylmethacrylate (HI-PMMA), or a mixture of PMMA and HI-PMMA; Colorants and optional additives to improve the scratch resistance, to reduce the gloss or combinations thereof.
  • ABS acrylonitrile-butadiene-styrene terpolymers
  • PVM polymethyl methacrylate
  • HI-PMMA impact modified polymethylmethacrylate
  • Colorants and optional additives to improve the scratch resistance, to reduce the gloss or combinations thereof.
  • the invention is based on the recognition that such a multilayer, coextruded composite body does not require additional reinforcement and has optimal properties as a self-supporting three-dimensional component.
  • the cover layer (1) and the intermediate layer (2) meet the requirements, which are also placed on the paint layers of motor vehicle bodies, the back cover layer (5) meets the requirement of interior trim.
  • the inventors have discovered that such multilayer, coextruded composites meet the needs of customers.
  • Such multilayer, coextruded composites can be formed in a single step, with both the front and the back in succession having the desired optical, mechanical and haptic properties.
  • the upper side and / or the lower side of the multilayer, coextruded composite body is provided with a grain or are provided with graining.
  • Figures 1 and 2 show the structure of multilayer coextruded composites of the invention.
  • 1 shows a layer structure with a cover layer (1), a first intermediate layer (2), a second intermediate layer (3), a substrate layer (4) and a back-side cover layer (5).
  • FIG. 2 shows a layer structure with a first intermediate layer (2), a second intermediate layer (3), a substrate layer (4) and a back-side cover layer (5).
  • a grain may be present on the cover layer (1), on the back cover layer (5) on both layers (1, 5) or not at all. For an advantageous feel, this may be present on the back cover layer (5).
  • the optional cover layer (1) comprises PMMA (polymethyl methacrylate) or HI-PMMA (impact-modified polymethyl methacrylate) or a blend thereof.
  • the topcoat (1) may include UV additives to provide higher UV resistance of the surface and the composite. The most important properties of PMMA are summarized in Hans Domininghaus, "The Plastics and Their Properties", Edition 1998, S 455 - 481.
  • PMMA is suitable as outer layer material particularly for outdoor applications, as it is already very UV
  • UV additives UV absorbers and UV stabilizers
  • UV absorbers and UV stabilizers in the amount of 0.01 to 5 wt.%, in the intermediate layer (2) and., Is stable and scratch resistant, shows a very good chemical resistance and is transparent
  • the second intermediate layer (3) used materials and colorants are additionally protected from UV radiation, which significantly improves both the mechanical behavior and the color stability over the period of use when exposed to UV light.
  • the intermediate layer (2) comprises PMMA (polymethyl methacrylate) or HI-PMMA (impact-modified polymethyl methacrylate) or a blend thereof and colorant.
  • the intermediate layer (2) may optionally be additionally added UV additives.
  • the second intermediate layer (3) comprises acrylonitrile-butadiene-styrene terpolymers (ABS) and additionally colorants and optionally UV additives.
  • ABS belongs to the amorphous thermoplastics and is characterized by a good impact strength, a high mechanical strength and rigidity, a high impact resistance in the cold, a high Dimensional stability in heat and high thermal shock resistance. Due to the low weather resistance, ABS is coextruded with one or more layers of PMMA (cover layer (1) and first intermediate layer (2)).
  • the proportions of the monomer proportions can vary from 15-35% acrylonitrile, 5-30% butadiene and 40-60% styrene.
  • ABS acrylonitrile-butadiene-styrene terpolymers
  • Thermoplastics of this type generally also exhibit very good mechanical properties, such as high toughness and stiffness, and these materials are also coextruded with one or more layers of PMMA (covering layer (1) and first intermediate layer (2)) in order to improve the weathering resistance.
  • PMMA covering layer (1) and first intermediate layer (2)
  • ABS blends and their properties are in Hans Domininghaus, "The plastics and their properties", output 1998, p 749-750.
  • the substrate layer (4) preferably represents the largest percentage of the total layer thickness of the multilayer coextruded composite body and comprises acrylonitrile-butadiene-styrene terpolymers (ABS) and additionally colorants and optionally mixed regrind or in-line recyclate.
  • ABS acrylonitrile-butadiene-styrene terpolymers
  • Other materials which can also be used according to the invention for producing the substrate layer (4) are blends of polycarbonate (PC) and ABS or of PA and ABS or blends of ABS in general with thermoplastic materials which have an elevated heat resistance compared to ABS. For cost reasons, the addition of mixed millbase is preferred.
  • the back cover layer (5) is coextruded with the overlying layers and fulfills decorative purposes.
  • it should have the following characteristics: dyed, matt, scratch-resistant, optionally grained and with a pleasant feel.
  • ABS acrylonitrile-butadiene-styrene terpolymers
  • TPU thermoplastic polyurethane elastomers
  • PMMA, HI-PMMA or mixtures of PMMA and HI-PMMA are used as materials.
  • ABS, PMMA, HI-PMMA and TPU are preferably matt or matt or both. This can be achieved by matting agents and / or the use of matt materials.
  • Further materials which can also be used according to the invention for the production of the rear-side cover layer (5) are blends of polycarbonate (PC) and ABS or of polyamide (PA) and ABS or generally blends of ABS with thermoplastic materials, which increased compared to ABS Have heat resistance and which result in coextrusion adhesion with PMMA.
  • Thermoplastic polyurethane elastomers are polyadducts of polyisocyanate and polyols which exhibit rubber-like behavior. They are further characterized by a high degree of flexibility, high damping capacity, which makes them particularly suitable as interior material for motor vehicles, favorable friction and wear behavior and pleasant leather-like feel.
  • thermoplastic polyurethane elastomers TPU
  • the materials of the back cover layer (5) are additionally colorants, as well as additives to reduce the gloss, so-called matting agents or additives added to improve the scratch resistance.
  • Matting agents are generally additives which influence the surface of a coating in such a way that its gloss level is lowered. Also glass beads of different sizes can cause the desired mattness in invention s proper composites. Matting agents usually cause a specific roughness of the coating surface, whereby a diffuse light scattering arises. The amount added is preferably between 0.1% by weight and 15% by weight. A distinction is usually made between inorganic and organic matting agents, which can be added equally (also as a mixture) to the layer. The inorganic matting agents include silicas, silicates as well as other inorganic fillers and mixtures of the above. In the structure according to the invention, pearlescent and metallic effect pigments can also be mentioned as matting agents in addition to their property of producing special visual effects.
  • Polymer beads preferably acrylate beads, polyethylene, polypropylene or copolymers, may, for example, be used as organic additives to improve mattness.
  • Scratch resistance in the sense of the invention is understood to be the sensitivity of a surface to the introduction of superficial visually perceptible defects with pointed objects.
  • the measurement method used is the testing of the micro-hardness according to ISO 4586-2.14.
  • additives for improving scratch resistance both inorganic and organic substances are used. Examples include: alumina, silica, siloxanes, polyamides, fatty acids, etc. As will be seen from the examples below, also effect pigments or matting agents can increase the scratch resistance.
  • thermoplastic polyurethane elastomers which are suitable for the use according to the invention, can only be done in very thin layers, as they usually show a low intrinsic stiffness and heat resistance. If one were to use materials of this kind as a substrate, there would be no component which shows neither the room nor the elevated temperatures required for the application as a vehicle roof rigidity and dimensional stability. In this case, coextrusion offers the possibility of applying a thin, functional layer with the desired optical and haptic properties, without substantially changing the mechanical properties.
  • Matt polymethyl methacrylate (PMMA) or matte impact-modified polymethylmethacrylate (HI-PMMA) are brittle materials. They can be used only in very thin layers, since at too high layer thicknesses, a significant embrittlement of the multilayer, coextruded composite body would occur. This is also illustrated in Table 1, in which Example 4 described has the lowest values in the instrumented puncture when observing the total energy. However, they show good scratch resistance and deep mattness.
  • Gloss is the property of a surface to reflect light in whole or in part, it only arises when both the lighting is bundled, and reflects the surface mirroring. Surface structures smaller than 0.01 mm influence the gloss of a surface. It can be quantitatively determined with gloss meters. The exact one Definition as well as the physical connections are described in ⁇ NORM EN ISO 2813; Edition 1999-06-01: "Coating Determination of the reflectometer value of coatings below 20 °, 60 ° and 85 °" The equipment used for the tests is the device: Haze Gloss, serial number: 868941 (manufacturer: Byk Gardner GmbH , 82538 Geretsried, Germany) The reflectometry value at 60 ° is used as the measurement geometry.
  • the micro-scratch hardness is determined according to ISO 4586-2.14. Three specimens of 100 x 100 mm are cut from the body to be tested. At the intersection of the diagonals, a 6.5 mm diameter hole is drilled. The surfaces to be tested are tested with a non-attacking agent, z. As spirit, and a soft cloth and stored for 24 h under normal conditions.
  • the principle of the scratch test is that a weighted tip of a diamond (angle 90 °, tip radius 90 ⁇ ) is pulled over the layer. The measurement is made with a Universal Scratch Tester (Model 413). To adjust the weight arm one of the weights and the counterweight with integrated dragonfly are needed.
  • the weight is placed on the scale arm in such a way that the knurled screw points to the front for locking the weight. Then it is pushed on the scale arm so far to the right (to the fulcrum) until the left side (with marking) is flush with the scale value "0.” The counterweight is then placed to the right of the fulcrum (and the load weight) and moved as far until the arm is in free-floating position in horizontal position (check by the level) By tightening the knurled screw the counterweight is locked in this position
  • the balance arm with the test tool and the weight to be used is now in equilibrium Place the sample in the center of a sample tray.Turn the knurled nut clockwise to secure the sample plate firmly in place.
  • the scale arm can be adjusted in height by the knurled nut to ensure that the top of the arm is always level is pushed on the scale arm to the value 0.1, so that the clamped Pr above is slightly charged.
  • the horizontal position of the scale arm can be determined exactly with the counterweight and can be corrected by raising or lowering the axle with the aid of the knurled nut. Depending on the choice of weight, a maximum force of 1 N or 10 N may be effective.
  • Each scale on the scale arm corresponds to a weight of 0.01 N or 0.1 N. Die prescribed load is achieved by shifting the weight. The sample tray is rotated once around its axis at a speed of 5 rpm. As a measure of the scratch hardness of the tested material applies the lowest weight, which leaves a self-contained mark on the specimen, ie if the first load already strong traces to see the load must be gradually reduced. If no traces are visible, the load must be increased gradually.
  • test panels are tested.
  • the stressed surface is cleaned with a non-attacking solvent (eg ethanol) and a soft cloth.
  • the specimen is then covered with the observation template, mounted on the rotatable table of the viewing device and examined with the naked eye at a viewing distance of 400 mm for permanent markings. These must be continuously visible in all segments of the observation template.
  • the template can additionally be moved on the test specimen.
  • a marking is considered to be permanent if it is still recognizable 24 hours after the test (storage in normal climate).
  • it is necessary to pivot the specimen in the observation device on the rotatable table so that it can be judged under all angles of incidence of the light.
  • As a measure of the behavior under scratch stress applies the lowest weight, which has still caused a self-contained marking on all 3 specimens.
  • UV additives can be added. Depending on the mode of action of these additives, a distinction is made in UV absorbers and UV stabilizers. UV absorbers lead to absorption of the UV radiation which passes through the polymer and convert it into heat energy. As an example of very effective UV absorbers, benzophenones can be mentioned.
  • UV stabilizers inhibit the free radicals caused by UV rays and stop further decomposition.
  • HALS hindered amine light stabilizers
  • PC polycarbonate
  • PA polyamide
  • Colorant is according to DIN 55943 the collective name for all coloring substances. Colorants are classified according to their chemical structure in inorganic and organic colorants. In both groups, the origin can be divided into natural and synthetic, or according to the color quality into white, colored and black colorants, as well as into effect and luminous colorants.
  • Inorganic colorants are almost always pigments.
  • the organic colorants are classified according to their solubility in the respective application medium into insoluble pigments or soluble dyes. Pigments are insoluble colorants in the application medium while dyes are soluble in the application medium.
  • Effect pigments which can be used in the first intermediate layer (2) can be divided into two large classes, the pearlescent and the metallic effect pigments, according to the literature, Gunter Buxbaum, "Industrial Inorganic Pigments", Issue 1993, pages 207-224 Species can be used to achieve special visual effects, they can also be used in combination with normal pigments and / or dyes.
  • the multilayer coextruded composites of this invention can be prepared in a one-step process by means of adapter or die coextrusion.
  • the materials of the layers (1), (2), (3), (4) and (5) are made flowable in each case by thermal action in an extruder and combined in an adapter system or a multi-channel nozzle to said composite body, calibrated via a smoothing calender , passed over a cooling section and as a result longitudinal and transverse hemmed.
  • the embossing of the grain at the top is done preferably by rolling rollers are mounted in Glättkalander: If the thermoplastic composite body from the nozzle, it is smoothed immediately after exiting between two rollers.
  • the roller which is wrapped by the upper side of the thermoplastic multilayer co-extruded composite, with a grain, so that it imprints into the not yet cooled and therefore soft thermoplastic surface of the cover layer.
  • the roller which comes into contact with the back of the thermoplastic multilayer coextruded composite body after exiting the thermoplastic multilayer coextruded composite body may also be grained, thereby also embossing the surface of the backside cover layer of the thermoplastic multilayer composite. In each case, however, it is necessary that the thermoplastic to be embossed is above the melting temperature, so that The embossing can also transfer well into the thermoplastic matrix.
  • thermoplastics When using different embossing, it may also be necessary to set different melt temperatures of the thermoplastics: If deep imprints are used, ie graining with a high depth, higher temperatures are recommended since at higher temperatures the thermoplastic is less viscous and thus more easily fills the deeper imprinting images.
  • Embossing is understood in the art as a process of pressure forming in which grain is pressed into a surface. Graining is the structuring of a surface that is essentially responsible for the haptic and visual properties. The term was originally used for the surface structure of leather, but was then transferred to industrially produced graining. These are ubiquitous on plastic injection molded parts or synthetic leather. Graining can affect the feel or feel of a surface, as well as produce a characteristic optical scattering behavior and visual appearance of a surface.
  • Multilayered coextruded composite members as defined above and also in the appended claims can be formed from the sheet multilayer co-extruded composites by thermoforming (thermoforming).
  • the multi-layer composites are heated in a thermoforming machine over the softening point and immediately afterwards pulled over a tempered form.
  • a vacuum in the air space which is located between thermoplastic multilayer coextruded composite body and the tempered form, the semi-finished product is pressed to the mold, cooled and then removed from the mold. Afterwards, the blank is trimmed to the correct size, which gives a three-dimensional component with a defined, very well reproducible geometry.
  • multilayer coextruded composite bodies according to the invention were produced by means of coextrusion processes.
  • a plant consisting of five extruders was used.
  • the melts of the individual extruders were combined in an adapter system, discharged through a nozzle with a discharge width of 1600 mm and in the Smoothed up-stack calendering process, passed over a circa 15-meter-long cooling path and consequently lined longitudinal and transverse.
  • Second interlayer 3 0,365 mm 100% ABS + coloring
  • Substrate layer 4 2.817 mm 80% ABS + coloring + 20% mixed
  • Example 1 represents a comparative example in which the back is made of standard ABS without any additives.
  • Second interlayer 3 0.360 mm 100% ABS + coloring
  • Substrate layer 4 2.815 mm 80% ABS + coloring + 20% mixed
  • Second interlayer 3 0.370 mm 100% ABS + coloring
  • Substrate layer 4 2,797 mm 80% ABS + coloring + 20% mixed grist
  • Second interlayer 3 0.375 mm 100% ABS + coloring
  • Substrate layer 4 2.817 mm 80% ABS + coloring + 20% mixed
  • Back side layer 5 0.187 mm 100% PMMA matt + coloring
  • Second interlayer 3 0.375 mm 100% PC / ABS + coloring
  • Substrate layer 4 2.817 mm 80% PC / ABS + staining + 20% mixed
  • Example 5 was provided on the back with a technical grain.
  • Tab. 1 Compilation of characteristic values of the materials used in Examples 1 - 5.
  • MFR melt mass flow rate
  • MVR melt volume flow rate
  • MFR analog > Measuring conditions: temperature at 230 ° C, load at 3.8 kg MFR analogue; Measuring conditions: temperature at 220 ° C, load at 10 kg
  • Example 1-5 The layer thicknesses of Examples 1-5 were measured on a thin section using a Nikon Eclipse ME600 microscope, the data are in millimeters.
  • Examples 1 and 2 also illustrate that e.g. Mica as an effect pigment also significantly increases the scratch resistance of the ABS layer (by a factor of 4).
  • a further finding from the tests is that the scratch sensitivity of an interior surface can be drastically reduced with a back embossing, also in combination with additives to improve the scratch resistance (in this case mica).

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)

Abstract

L'invention concerne un corps composite thermoplastique coextrudé multicouche destiné à être utilisé comme élément structural autoporteur en trois dimensions, de préférence pour des pièces de carrosserie de véhicules automobiles, des pièces d'habillage de véhicules utilitaires agricoles ou d'éléments de couverture de bateaux, comprenant (i) le cas échéant une couche de recouvrement (1), comprenant du polyméthacrylate de méthyle (PMMA), du polyméthacrylate de méthyle résistant au choc (HI-PMMA) ou un mélange de ces composés, ainsi que des additifs anti-UV facultatifs; (ii) une première couche intermédiaire (2), disposée sous la couche de recouvrement (1) facultative et comprenant du polyméthacrylate de méthyle (PMMA), du polyméthacrylate de méthyle résistant au choc (HI-PMMA) ou un mélange de ces composés, ainsi que des colorants et le cas échéant des additifs anti-UV; (iii) une deuxième couche intermédiaire (3), comprenant un terpolymère d'acrylonitrile-butadiène-styrène (ABS) et contenant en plus des colorants et le cas échéant des additifs anti-UV; (iv) une couche substrat (4), comprenant un terpolymère d'acrylonitrile-butadiène-styrène (ABS) et des colorants; et (v) une couche de recouvrement arrière (5), comprenant un terpolymère d'acrylonitrile-butadiène-styrène (ABS), des matériaux à base de polyuréthanes thermoplastiques, de polyméthacrylate de méthyle (PMMA), de polyméthacrylate de méthyle résistant au choc (HI-PMMA) ou d'un mélange de PMMA et HI-PMMA, ainsi que des colorants et le cas échéant des additifs pour améliorer la résistance aux rayures, pour réduire la brillance, ou des combinaisons de ces éléments.
PCT/EP2012/067039 2011-09-01 2012-08-31 Corps composite WO2013030385A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP11179774 2011-09-01
EP11179774.2 2011-09-01

Publications (1)

Publication Number Publication Date
WO2013030385A1 true WO2013030385A1 (fr) 2013-03-07

Family

ID=46755034

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2012/067039 WO2013030385A1 (fr) 2011-09-01 2012-08-31 Corps composite

Country Status (1)

Country Link
WO (1) WO2013030385A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103879033A (zh) * 2014-04-16 2014-06-25 昆山市耐光包装材料有限公司 高强度塑料包装盒
CN105904815A (zh) * 2016-04-15 2016-08-31 上海福助工业有限公司 一种亚光pe复合膜包装材料及其制备方法
EP3074227B1 (fr) 2013-11-29 2019-12-25 REHAU AG + Co Corps composite multicouches
CN111662529A (zh) * 2020-07-06 2020-09-15 苏州润佳工程塑料股份有限公司 一种消光abs复合材料
EP3074226B1 (fr) 2013-11-29 2020-09-23 REHAU AG + Co Corps composite multicouches
DE202022101371U1 (de) 2022-03-15 2023-03-30 REHAU Industries SE & Co. KG Mehrschichtiger Verbundkörper

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0361823B1 (fr) 1988-09-26 1995-02-15 E.I. Du Pont De Nemours And Company Procédé pour la fabrication d'une structure composite en matière thermoplastique et des nattes de fibres (SMC)
WO2002090109A1 (fr) * 2001-05-10 2002-11-14 Senoplast Klepsch & Co. Gmbh & Co. Kg Feuille composite multicouche pour mobilier, sensiblement exempte de polychlorure de vinyle et de polyolefine
EP1561575A1 (fr) 2004-02-03 2005-08-10 Bayer MaterialScience AG Eléments composites de polyuréthane avec une couche de surface de métal ou de thermoplastique et procédé pour leur préparation
WO2005102697A1 (fr) 2004-04-20 2005-11-03 Webasto Ag Piece composite pour une carrosserie de vehicule, notamment pour un toit de vehicule, et son procede de production

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0361823B1 (fr) 1988-09-26 1995-02-15 E.I. Du Pont De Nemours And Company Procédé pour la fabrication d'une structure composite en matière thermoplastique et des nattes de fibres (SMC)
WO2002090109A1 (fr) * 2001-05-10 2002-11-14 Senoplast Klepsch & Co. Gmbh & Co. Kg Feuille composite multicouche pour mobilier, sensiblement exempte de polychlorure de vinyle et de polyolefine
EP1561575A1 (fr) 2004-02-03 2005-08-10 Bayer MaterialScience AG Eléments composites de polyuréthane avec une couche de surface de métal ou de thermoplastique et procédé pour leur préparation
WO2005102697A1 (fr) 2004-04-20 2005-11-03 Webasto Ag Piece composite pour une carrosserie de vehicule, notamment pour un toit de vehicule, et son procede de production

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
"senosan(R) automotiv - Kunststoff-Platten und -Folien zum Thermoformen", INTERNET CITATION, 1 June 2010 (2010-06-01), pages 1 - 7, XP002664698, Retrieved from the Internet <URL:<www.senoplast.com/fileadmin/user_upload/deutsch/pdf/Prospekte_aktuell_2010/Sparte_1_Prospekt_D.pdf> [retrieved on 20111130] *
H. KAPPACHER, KUNSTSTOFFE, vol. 86, 1996, pages 388 - 392
HANS DOMININGHAUS: "Die Kunststoffe und ihre Eigenschaften", 1998, pages: 1161 - 1171
HANS DOMININGHAUS: "Die Kunststoffe und ihre Eigenschaften", 1998, pages: 393 - 404
HANS DOMININGHAUS: "Die Kunststoffe und ihre Eigenschaften", 1998, pages: 455 - 481
HANS DOMININGHAUS: "Die Kunststoffe und ihre Eigenschaften", 1998, pages: 749 - 750
KAPPACHER H: "KAROSSERIETEILE AUS PMMA/ABS. ÖCAR BODIES MADE OF PMMA/ABS", KUNSTOFFE INTERNATIONAL, CARL HANSER VERLAG, MUNCHEN, DE, vol. 86, no. 3, 1 March 1996 (1996-03-01), pages 388,390 - 392, XP000587710, ISSN: 0023-5563 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3074227B1 (fr) 2013-11-29 2019-12-25 REHAU AG + Co Corps composite multicouches
EP3074226B1 (fr) 2013-11-29 2020-09-23 REHAU AG + Co Corps composite multicouches
CN103879033A (zh) * 2014-04-16 2014-06-25 昆山市耐光包装材料有限公司 高强度塑料包装盒
CN105904815A (zh) * 2016-04-15 2016-08-31 上海福助工业有限公司 一种亚光pe复合膜包装材料及其制备方法
CN111662529A (zh) * 2020-07-06 2020-09-15 苏州润佳工程塑料股份有限公司 一种消光abs复合材料
DE202022101371U1 (de) 2022-03-15 2023-03-30 REHAU Industries SE & Co. KG Mehrschichtiger Verbundkörper

Similar Documents

Publication Publication Date Title
WO2013030385A1 (fr) Corps composite
DE69329655T2 (de) Geprägte mehrschichtfolie
DE69935500T2 (de) Harzzusammensetzung und daraus hergestellte folie
EP2357276B2 (fr) Structure plate multicouche et son procédé de fabrication
EP1060209B1 (fr) Procede pour produire des films de pmma durcis en surface, extremement brillants sur les deux faces, exempts de corps gelifiants, et manipulables selon le procede de &#34;surmoulage du film&#34;
EP2990195B1 (fr) Film composite multicouches gaufré et contrecollé par fusion
WO2000037237A1 (fr) Procede de production de films dotes d&#39;une couche contenant des melanges de fluoropolymeres et de polyacrylates
EP3210772B1 (fr) Lamine decoratif contrecolle par fusion
EP1787802A1 (fr) Film en polyamide comprenant une couche recouvrante
DE102005063237A1 (de) Bespannkomponente und Verfahren zur Herstellung derselben
EP2709843B1 (fr) Composites multicouches à propriétés physiques améliorées
EP2565033B1 (fr) Corps composite
EP3533601A1 (fr) Structure composite pour volet de recouvrement de coussin gonflable de sécurité et article à coudre de la structure composite
DE102015203964A1 (de) Prallkörper für Fahrzeuge und Verfahren zum Fertigen desselben
WO2013030090A1 (fr) Pièce d&#39;équipement, en particulier pour l&#39;habitacle d&#39;un véhicule, et procédé de fabrication
EP1412179B1 (fr) Feuille composite multicouche pour mobilier, sensiblement exempte de polychlorure de vinyle et de polyolefine
DE102009049122B4 (de) Kratzfeste Polypropylenfolie
DE202016008503U1 (de) Schmelzekaschiertes Dekorlaminat
EP0759351A1 (fr) Méthode et appareil pour la production de feuilles de tableau de bord avec deux ou plusieurs couleurs ou tableau de bord fabriqué à partir de telles feuilles
EP3533600B1 (fr) Structure composite pour volet de recouvrement de coussin gonflable de sécurité et article de couture de la structure composite
DE69918673T2 (de) Lage zur foliendekoration, verfahren zu ihrer herstellung und foliendekorierter gegenstand
DE8220682U1 (de) Folienbahn, insbesondere tiefziehfaehige folienbahn, fuer kraftfahrzeuginnenraeume
DE112018000812T5 (de) Laminat, dekorative Folie, Verfahren zur Herstellung von Laminat, Verfahren zur Herstellung eines Formkörpers und Formkörper
EP3233483B1 (fr) Film composite apte à l&#39;emboutissage et au gaufrage et procédé de fabrication et utilisation dudit film
EP1593488B1 (fr) Film laminé et procédé de sa fabrication

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12751553

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12751553

Country of ref document: EP

Kind code of ref document: A1