WO2013030385A1

WO2013030385A1 - Composite body

Info

Publication number: WO2013030385A1
Application number: PCT/EP2012/067039
Authority: WO
Inventors: Johann Kappacher; Thomas Peis; Anton HÖLLER
Original assignee: Senoplast Klepsch & Co. Gmbh
Priority date: 2011-09-01
Filing date: 2012-08-31
Publication date: 2013-03-07

Abstract

Multi-layer thermoplastic, co-extruded composite body for use as a self-supporting three-dimensional component, preferably for bodywork parts for vehicles, panelling parts for agricultural vehicles or boat covers, consisting of (i) optionally a covering layer (1), consisting of polymethylmethacrylate (PMMA), impact-resistance modified polymethylmethacrylate (HI-PMMA) or a mixture thereof, and optionally UV additives, (ii) a first intermediate layer (2) arranged below the optional covering layer, said intermediate layer consisting of polymethylmethacrylate (PMMA), impact-resistance modified polymethylmethacrylate (HI-PMMA) or a mixture thereof, and colorants and optionally UV additives. (iii) a second intermediate layer (3), consisting of acrylonitrile butadiene styrene terpolymers (ABS), and additionally containing colorants and optionally UV additives, (iv) a substrate layer (4), consisting of acrylonitrile butadiene styrene terpolymers (ABS), and colorants and (v) a rear covering layer (5), consisting of acrylonitrile butadiene styrene terpolymers (ABS), materials based on thermoplastic polyurethanes, polymethylmethacrylate (PMMA), impact-resistance modified polymethylmethacrylate (HI-PMMA) or a mixture of PMMA and HI-PMMA, and colorants and optionally additives for improving scratch-resistance, reducing gloss or combinations thereof.

Description

composite body

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.

The use of 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. In addition, 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.

For the production of roof modules for small cars s or steep cladding for agricultural vehicles, composite bodies of this type according to the Reinforced thermoforming on the back and optionally with interior trim. Methods for the production of components of this type are described inter alia in EP 1 561 575 AI and WO 2005/102697 A. The method described is quite suitable roof modules represent, but it is due to the many juxtaposed method steps and the amount of materials very expensive.

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) Mostly 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 result different properties, which in turn provide a costly result.

In both production methods, the back side of the thermoplastic semi-finished product used, which forms the surface, is not visible, since it is covered either by the reinforcement or by the second semifinished product. Both manufacturing methods therefore have the disadvantage that they lead to higher costs for the product due to the multi-stage process control or the high amount of material used.

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. B. a roof module to unite in a thermoplastic semi-finished, and process this in the least possible number of steps to process the body part. It was therefore an object of the present invention to provide a multilayer, coextruded composite body without having to operate the effort with the twin-sheet process or additional amplification steps. At the same time, however, certain properties must be ensured on the overall composite, as well as on the front side and on the back side of the multilayer, coextruded composite body.

At the front, the following characteristics must be ensured:

1. Coloring in uni and / or effect coloring to avoid varnishing

2. good chemical resistance and scratch resistance of the surface,

3. high surface quality,

4. excellent UV resistance.

The following properties are required on the back:

1. languor

2. Scratch resistance

3. if necessary graining

4. Pleasant grip feel.

The multilayer, coextruded composite body as a whole must additionally have good mechanical properties, thermoformability (thermal ductility), adequate heat resistance and good thermoforming behavior.

The prior art does not provide multi-layer composites in which all of these properties are sufficiently met.

The object is achieved by 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.

(iii) a second intermediate layer (3) comprising acrylonitrile-butadiene-styrene terpolymers (ABS) and additionally containing colorants and optionally UV additives,

(iv) a substrate layer (4) comprising acrylonitrile-butadiene-styrene terpolymers (ABS) and colorants and

(v) 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.

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. Thus, 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.

In a preferred embodiment, it is provided that the upper side and / or the lower side of the multilayer, coextruded composite body is provided with a grain or are provided with graining.

Preferred embodiments will be described below.

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). On the presentation of a grain was omitted. 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).

Cover layer (1)

The optional cover layer (1) comprises PMMA (polymethyl methacrylate) or HI-PMMA (impact-modified polymethyl methacrylate) or a blend thereof. Optionally, 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. Due to the properties described, PMMA is suitable as outer layer material particularly for outdoor applications, as it is already very UV The use of UV additives (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.

First intermediate layer (2)

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.

Second intermediate layer (3)

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. Detailed information on the properties of acrylonitrile-butadiene-styrene terpolymers (ABS) can be found in Hans Domininghaus, "The plastics and their properties", 1998 Edition, S 393-404. Other materials which fiction, according to the preparation of the second intermediate layer ( 3), blends of polycarbonate (PC) and ABS or of polyamide (PA) and ABS or generally blends of ABS with thermoplastic materials which have an increased heat resistance compared to ABS and which give adhesion in the coextrusion with PMMA. 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. ABS blends and their properties are in Hans Domininghaus, "The plastics and their properties", output 1998, p 749-750.

Substrate layer (4)

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. 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.

Back cover layer (5)

The back cover layer (5) is coextruded with the overlying layers and fulfills decorative purposes. Thus, according to the invention, it should have the following characteristics: dyed, matt, scratch-resistant, optionally grained and with a pleasant feel. On the one hand acrylonitrile-butadiene-styrene terpolymers (ABS) or thermoplastic polyurethane elastomers (TPU), 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.

Detailed information on the properties of thermoplastic polyurethane elastomers (TPU) can be found in Hans Domininghaus, "The plastics and their properties", Edition 1998, pp. 1161-1171.

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.

Crosslinked polymers in bead form ("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. In order to be able to characterize this parameter, the measurement method used is the testing of the micro-hardness according to ISO 4586-2.14. As 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.

Due to the necessity to make the back side of a multi-layer composite visible in the sense of the invention as well, the requirement to find solutions to various problems arose in both a technical and a commercial perspective:

If one did not coextrude a thin backside topcoat (5), the following problems would arise:

1. More costly colorants must be used. The visualized back makes it necessary to use higher colorants in terms of degree of dispersion and light fastness than would normally be used in the substrate layer (4), if this is not visible on the back. By incorporating a thin backside topcoat (5), the use of the higher quality colorants can be limited to the thin backside topcoat (5), thus resulting in no significant commercial disadvantage. Their concentration is very low in relation to the total thickness of the co-extruded composite body, since the volume of the back-side cover layer (5) is substantially lower than that of the substrate layer (4).

2. The addition of additives to improve the mattness and scratch resistance usually leads to a reduction of the mechanical values. If the additive treatment is carried out only in the rear-side cover layer (5), the influence on the mechanical properties of the overall composite compared to an additive coating in the entire substrate layer (5) is negligible.

3. The use of thermoplastic polyurethane elastomers (TPU), 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.

4. 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.

Measurement methods used to characterize the backside topcoat (5) Gloss:

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 ÖNORM 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.

Micro hardness:

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 μιη) 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. In order to obtain a statistical statement, three test panels are tested. First, 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. In case of doubt, 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). For this purpose, 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

The ultraviolet portion of sunlight destroys the chemical bonds in certain polymers in a process called photodegradation. This causes changes in the chemical and physical behavior due to the chemical changes in the polymer. Breakage, discoloration, color changes are z. B. consequences of these reactions. In order to prevent or delay effects of this kind, 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. As an example of very effective stabilizers, HALS (hindered amine light stabilizers) can be mentioned. When using polycarbonate (PC) or polyamide (PA) as a blend component, it should be ensured that the light stabilizers used do not contain basic amines as functional groups, since these lead to the depolymerization of PC or PA and thereby may worsen the mechanical properties of the overall composite.

colorants

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.

Mixed Grist

When driving in and adjusting the coextrusion system, different parameters such as the total thickness, the predetermined thicknesses of the individual layers, the width, the homogeneous thickness of the individual layers across the width and the color of the front and back specified by the customer must be adapted and adjusted in that they correspond to the given structure or requirements. The same process must be selected if the overall thickness, width or color changes according to the customer's request. Also, the cut to the specified format (length and width) inline, which means that the supernatants are cut off and incurred as waste. During these Ein- or Umstellvorgänge material is made, which is the It contains PMMA and / or HI-PMMA of the optional cover layer (1) and intermediate layer (2) and also the polymers of the other layers of the inventive construction and is therefore called mixed ground material. If this is not added to the process, this has a negative impact on the commercial success of the product: The mixed regrind must be factored in, since the raw material consumption de facto occurs, so the customer must pay the entire material use, but receives only a part of the material (the part of the semi-finished products to which the order was made). The rest, namely the mixed regrind, is useless for him.

The obvious solution would be to shred the resulting waste in order to produce ground material which is added back to the multi-layer composite, for example in the substrate layer. In the context of the invention, mixed ground material can be added to the production process in the substrate layer (4).

Production of the composite body

The multilayer coextruded composites of this invention can be prepared in a one-step process by means of adapter or die coextrusion. In this case, 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. It is possible to provide 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. Alternatively or additionally, 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. 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.

Processing of multilayer coextruded composites

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. By applying 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.

applications

The invention will be explained below by way of examples. For this purpose, multilayer coextruded composite bodies according to the invention were produced by means of coextrusion processes. For the production, 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.

The following examples illustrate properties and advantages of the invention. All data are% by weight.

Example 1 :

Total thickness: 3.51 mm

Layer thickness composition

Cover layer 1 0.044 mm 100% HI-PMMA

First intermediate layer 2 0.106 mm 100% HI-PMMA + coloring

Second interlayer 3 0,365 mm 100% ABS + coloring

Substrate layer 4 2.817 mm 80% ABS + coloring + 20% mixed

grist

Back cover 5 0,178 mm 100% ABS

Example 1 represents a comparative example in which the back is made of standard ABS without any additives.

Example 2:

Total thickness: 3.50 mm

Layer thickness composition

Top coat 1 0.043 mm 100% HI-PMMA

First intermediate layer 2 0.107 mm 100% HI-PMMA + coloring

Second interlayer 3 0.360 mm 100% ABS + coloring

Substrate layer 4 2.815 mm 80% ABS + coloring + 20% mixed

grist

Back cover 5 0,175 mm 98% ABS matte + 2% mica

Example 3:

Total thickness: 3.51 mm

Layer thickness composition

Cover layer 1 0.045 mm 100% HI-PMMA

First intermediate layer 2 0.108 mm 100% HI-PMMA + coloring

Second interlayer 3 0.370 mm 100% ABS + coloring

Substrate layer 4 2,797 mm 80% ABS + coloring + 20% mixed grist

Back cover layer 5 0,190 mm 100% TPU matt + color

Example 4:

Total thickness: 3.53 mm

Layer thickness composition

Top coat 1 0.042 mm 100% HI-PMMA

First intermediate layer 2 0.109 mm 100% HI-PMMA + coloring

Second interlayer 3 0.375 mm 100% ABS + coloring

Substrate layer 4 2.817 mm 80% ABS + coloring + 20% mixed

grist

Back side layer 5 0.187 mm 100% PMMA matt + coloring

Example 5:

Total thickness: 3.52 mm

Layer thickness composition

Top coat 1 0.042 mm 100% HI-PMMA

First intermediate layer 2 0.109 mm 100% HI-PMMA + coloring

Second interlayer 3 0.375 mm 100% PC / ABS + coloring

Substrate layer 4 2.817 mm 80% PC / ABS + staining + 20% mixed

grist

Back cover 5 0.187 mm 100% PC / ABS + 2% mica + coloring

Example 5 was provided on the back with a technical grain.

Information on the raw materials used:

Tab. 1: Compilation of characteristic values of the materials used in Examples 1 - 5.

MFR measured according to ISO 1133: 2005 06 01; "Determination of the melt mass flow rate (MFR) and the melt volume flow rate (MVR) of thermoplastics"; [] = gl 10 min;

Elongation at break measured acc. ISO 527-2, "Determination of tensile properties", July 1996 issue), [] =%, measurement at RT

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

⁵⁾ MFR analog ^I) ; Measuring conditions: temperature at 190 ° C, load at 5 kg

⁶⁾ Elongation at break measured according to DIN 53504: 2009 10; "Testing of rubber and elastomers determination of tear strength; Tensile strength, elongation at break and tensile stress values "

The layer thicknesses of Examples 1-5 were measured on a thin section using a Nikon Eclipse ME600 microscope, the data are in millimeters.

Table 2: Compilation of the measurement results of Examples 1 - 5.

Micro-hardness of surface according to: ISO 4586-2. 14; [] = N, measured at the back of the multilayer, coextruded composite.

²⁾ gloss in GLE (gloss units) according to ÖNORM EN ISO 2813; Edition 1999-06-01: "Paints and varnishes - Determination of the reflectometer value of coatings below 20 °, 60 ° and 85 °", measured on the back of the plate, measuring instrument: Haze Gloss from Byk Gardner, viewing angle: 60 °

³⁾ Measured according to ÖNORM EN ISO 6603-2, Ausgabe 2002-04-01: Plastics - Determination of puncture behavior of solid plastics, Part 2: Instrumented impact test (ISO 6603-2: 2000), [] = Joule, measured at RT, Test specimen tested with impact on the cover layer (1).

⁴⁾ n. D .: Not definable, because grained

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).

Claims

claims

1. Multilayer thermoplastic coextruded composite body, for the production of self-supporting three-dimensional components, preferably body parts for motor vehicles, covering parts for agricultural vehicles or boat covers, comprising

(i) optionally a cover layer (1) comprising polymethyl methacrylate (PMMA), impact-modified polymethylmethacrylate (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 optional UV additives.

(v) a backing layer (5) comprising acrylonitrile-butadiene-styrene terpolymers (ABS), thermoplastic polyurethanes, polymethylmethacrylate (PMMA), impact-modified polymethyl methacrylate (HI-PMMA), or a mixture of PMMA and HI-PMMA, and Colorants and optional additives to improve the scratch resistance, to reduce the gloss or combinations thereof.

2. The composite body according to claim 1, characterized in that the top and / or the bottom of the multilayer, coextruded composite body is provided with a grain or are provided with grainings.

3. Composite body according to claim 1 or claim 2, characterized in that at least one of the layers selected from the group second intermediate layer (3), substrate layer (4) and back cover layer (5) comprises a blend of ABS and a thermoplastic, which has a higher heat resistance than the pure ABS has.

4. Composite body according to one of claims 1 to 3, characterized in that at least one of the layers selected from the group second intermediate layer (3), substrate layer (4) and back cover layer (5) comprises a blend of polycarbonate and ABS or polyamide and ABS ,

5. A composite body according to one of claims 1 to 4, characterized in that the back-side cover layer (5) is matt, is frosted and / or matting has smittel.

6. The composite body according to claim 5, characterized in that the back-side covering layer (5) consists of 0.1% by weight to 15% by weight of matting agent.

7. A composite body according to any one of claims 1 to 6, characterized in that the back-side covering layer (5) contains as an additive for improving the scratch resistance alumina, silica, siloxanes, polyamides, fatty acids, effect pigments or mixtures thereof.

8. Composite body according to one of claims 1 to 7, characterized in that the colorants of the first intermediate layer (2), the second intermediate layer (3) un / or the back cover layer (5) include effect pigments.

9. Composite body according to one of claims 1 to 8, characterized in that the colorants of the first and second intermediate layer (2, 3) comprise effect pigments.

9. Composite body according to one of claims 1 to 8, characterized in that the composite body has on at least one side a peelable protective film.

10. A method for producing a composite body according to one of claims 1 to 9, characterized in that the materials of the layers (1), (2), (3), (4) and (5) in each case an extruder by thermal action flowable be made and merged in an adapter system or a multi-channel nozzle, where appropriate, the top and / or back is provided with a grain by applying pressure.

11. The method according to claim 10, characterized in that the materials merged into layers are smoothed by calender rolls.

12. The method according to claim 10 or claim 11, characterized in that the grain by embossing, preferably by means of graining, which has a calender roll, is generated.

13. Use of a composite body according to one of claims 1 to 10 for the production of a body part for motor vehicles, trim parts for agricultural vehicles, boat covers, roof boxes, spare wheel covers and the like.

14. A three-dimensional member comprising a thermoformed composite body according to any one of claims 1 to 9.

15. Bodywork part for motor vehicles, trim part for agricultural vehicles, boat cover, roof box or spare wheel cover comprising a composite body according to one of claims 1 to 9 or a component according to claim 14.