WO2013030385A1 - Corps composite - Google Patents
Corps composite Download PDFInfo
- 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
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 67
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 82
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 82
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims abstract description 66
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims abstract description 52
- 239000000203 mixture Substances 0.000 claims abstract description 32
- 239000003086 colorant Substances 0.000 claims abstract description 31
- 239000000654 additive Substances 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 26
- 239000000758 substrate Substances 0.000 claims abstract description 21
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 21
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 21
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims abstract description 12
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims description 19
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 239000000049 pigment Substances 0.000 claims description 12
- 239000004952 Polyamide Substances 0.000 claims description 11
- 230000000694 effects Effects 0.000 claims description 11
- 229920002647 polyamide Polymers 0.000 claims description 11
- 239000004417 polycarbonate Substances 0.000 claims description 11
- 229920000515 polycarbonate Polymers 0.000 claims description 11
- 239000006224 matting agent Substances 0.000 claims description 9
- 238000004049 embossing Methods 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- -1 siloxanes Chemical class 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- 230000009969 flowable effect Effects 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 241000594011 Leuciscus leuciscus Species 0.000 claims 1
- 238000003825 pressing Methods 0.000 claims 1
- 230000001681 protective effect Effects 0.000 claims 1
- 239000010410 layer Substances 0.000 description 98
- 238000004040 coloring Methods 0.000 description 19
- 238000012360 testing method Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- 229920003023 plastic Polymers 0.000 description 8
- 239000004033 plastic Substances 0.000 description 8
- 238000003856 thermoforming Methods 0.000 description 8
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 229920001971 elastomer Polymers 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000000806 elastomer Substances 0.000 description 5
- 239000011229 interlayer Substances 0.000 description 5
- 239000011265 semifinished product Substances 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
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- 239000011324 bead Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000010445 mica Substances 0.000 description 4
- 229910052618 mica group Inorganic materials 0.000 description 4
- 230000000007 visual effect Effects 0.000 description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- 239000012963 UV stabilizer Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
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- 230000006750 UV protection Effects 0.000 description 2
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- 239000002699 waste material Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 241000238633 Odonata Species 0.000 description 1
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- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
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- 230000002349 favourable effect Effects 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
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- 239000007924 injection Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
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- 239000005056 polyisocyanate Substances 0.000 description 1
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- 150000003077 polyols Chemical class 0.000 description 1
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- 150000004760 silicates Chemical class 0.000 description 1
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- 238000003860 storage Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
Classifications
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- 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
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- B32B1/00—Layered products having a non-planar shape
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- 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
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- 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
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- 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
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- B32B27/00—Layered products comprising a layer of synthetic resin
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
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- B32B2307/00—Properties of the layers or laminate
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- B32B2307/71—Resistive to light or to UV
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- B32B2307/712—Weather resistant
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B2307/00—Properties of the layers or laminate
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- B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
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- B32B2307/00—Properties of the layers or laminate
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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.
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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 |
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
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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 |
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