WO2016170143A1 - Procédé de fabrication de matériaux composites à base de fibres thermoplastiques à base de copolymères de styrène - Google Patents

Procédé de fabrication de matériaux composites à base de fibres thermoplastiques à base de copolymères de styrène Download PDF

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Publication number
WO2016170143A1
WO2016170143A1 PCT/EP2016/059061 EP2016059061W WO2016170143A1 WO 2016170143 A1 WO2016170143 A1 WO 2016170143A1 EP 2016059061 W EP2016059061 W EP 2016059061W WO 2016170143 A1 WO2016170143 A1 WO 2016170143A1
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Prior art keywords
fibers
styrene copolymer
thermoplastic
fiber
styrene
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German (de)
English (en)
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Achim Bernhardt
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Ineos Styrolution Group GmbH
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Ineos Styrolution Group GmbH
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/047—Reinforcing macromolecular compounds with loose or coherent fibrous material with mixed fibrous material
    • C08J5/048—Macromolecular compound to be reinforced also in fibrous form
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/12—Copolymers of styrene with unsaturated nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/18—Homopolymers or copolymers of nitriles
    • C08L33/20—Homopolymers or copolymers of acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene
    • C08J2325/08—Copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2355/00—Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2323/00 - C08J2353/00
    • C08J2355/02—Acrylonitrile-Butadiene-Styrene [ABS] polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils

Definitions

  • thermoplastic fiber composite materials based on styrene copolymers
  • the present invention relates to a process for producing a thermoplastic fiber composite material V (also called organic sheet) comprising a thermoplastic styrene copolymer molding compound A and reinforcing fibers B, the process comprising the production of a textile structure G from the reinforcing fibers B and thermoplastic styrene Copolymer fibers F, which consist of the material of the thermoplastic styrene copolymer molding composition A.
  • V also called organic sheet
  • Fiber composite materials consist of reinforcing fibers embedded in a polymer matrix.
  • the fields of application of fiber composite materials are manifold.
  • fiber composite materials are used in the vehicle and aviation sectors.
  • fiber composite materials should prevent the tearing or other fragmentation of the matrix in order to reduce the risk of accidents caused by distributed component networks.
  • Many fiber composite materials are able to absorb relatively high forces under load before it comes to a total failure.
  • fiber composite materials are distinguished by high strength and rigidity, combined with low density and other advantageous properties, such as good aging and corrosion resistance, compared with conventional, non-reinforced materials.
  • the strength and rigidity of the fiber composite materials can be adapted to the loading direction and load type.
  • the fibers are primarily responsible for the strength and rigidity of the fiber composite material.
  • their arrangement determines the mechanical properties of the respective fiber composite material.
  • the matrix usually serves primarily to introduce the forces to be absorbed into the individual fibers and to maintain the spatial arrangement of the fibers in the desired orientation. Since both the fibers and the matrix materials are variable, numerous combinations of fibers and matrix materials come into consideration.
  • the connection of fibers and matrix to one another plays an essential role. For this purpose, it is necessary to achieve a complete and uniform penetration of the structure formed by the reinforcing fibers B with the matrix material.
  • the production of fiber composite materials from reinforcing fibers and synthetic resins is usually carried out in the form that textile structures, so-called fiber semi-finished products (eg fabrics, scrims or fiber mats) are impregnated with a synthetic resin, which is then brought to cure.
  • the synthetic resin consists of a pre-polymer and a hardener.
  • the pre-polymer here is a polymer or oligomer with a comparatively low molecular weight. Therefore, the synthetic resin initially has a low viscosity and can penetrate the semi-finished fiber quickly.
  • the hardener added shortly before impregnation initiates the polymerization of the pre-polymer.
  • thermosetting synthetic resins used are infusible after curing, the fiber composite materials must be produced in the form in which they are to be used later. A simple forming is not possible.
  • prepregs By producing preimpregnated fibers or semi-finished fiber products, so-called prepregs, it is possible to reduce the effort involved in the actual production of the final component.
  • semi-finished fiber products are impregnated with pre-polymer and then stored under a protected atmosphere (low temperature, low oxygen content). The curing can be done later at e.g. done by heating.
  • Thermoplastics have the advantage that they can be repeatedly reshaped by heating above the melting point of the polymer. This property is made use of in organic sheets which consist of reinforcing fibers which are embedded in a thermoplastic polymer matrix and can thereby be transformed under heating.
  • thermoplastics are high molecular weight. They therefore have a high viscosity even in the molten state. It is therefore very time-consuming to achieve complete penetration of the semi-finished fiber products.
  • US 2014/0232042 describes a method for the production of fasteners based on composite materials, which are produced from thermoplastic resin interspersed fiber flakes. These fiber flakes are made by first preimpregnating the fibers with thermoplastic resin and then cutting them into short sections. Such composites have the disadvantage that they are relatively less stable due to the short fiber lengths.
  • TW-B 235970 describes such yarns used as reinforcing fibers. These are obtained by twisting the reinforcing fibers together with thermoplastic fibers. The component is obtained by laying the fibers twisted together and then heating to a temperature sufficient to achieve penetration of the reinforcing fibers with the thermoplastic polymer.
  • Textile prepregs obtained in this way are characterized by good drapability, freedom from solvents and the use of efficient textile processing processes.
  • these advantages are offset by the high expense of producing the polymer filaments (see "Handbuch der Verbundtechnik, M. Neitzel, P. Mitschang, U. Breuer (ed.), Carl Hanser Verlag, Kunststoff, 2014, pages 182 to 183).
  • thermoplastic textile prepregs are described in the prior art.
  • DE 690 10 059 describes fabric structures in which fibers of non-thermoplastic reinforcing materials such as glass, aramid, carbon or silicon dioxide are woven or entangled together with fibers of thermoplastic materials such as polyetherimides, polyetheretherketones, polycarbonates, liquid-crystal polymers, polyphenylene sulfides or polyether sulfones.
  • This fabric is stacked together with other fabrics of the above materials to form multilayer laminates, which can be heat-formed and worked to obtain various rigid articles. No statement is made about the duration of the melting process.
  • PC polycarbonate
  • suitable additives such as hyperbranched polyesters, ethylene / (meth) acrylate copolymers or low molecular weight polyalkylene glycol esters.
  • An object of the invention is to provide a process for producing a thermoplastic fiber composite material (organic sheet), which ensures a thorough and rapid penetration of the reinforcing fibers with the thermoplastic polymer matrix.
  • the fiber composite material should be easy to produce. Furthermore, the method should be versatile and easily adaptable to the desired results.
  • thermoplastic fiber composite material V containing at least one thermoplastic styrene copolymer molding composition A as polymer matrix and at least one reinforcing fiber B, by first a textile structure G of the reinforcing fibers B and thermoplastic Styrene copolymer fibers F, prepared from the thermoplastic styrene copolymer molding compound A, which is then by heating the textile structure G to a temperature which is above the melting range of the thermoplastic styrene copolymer fibers F. and then cooling the obtained fiber composite material V, is obtained.
  • the resulting fiber composite material V is characterized in that the remaining after the melting of the thermoplastic styrene copolymer fibers F textile structure of the reinforcing fibers B is particularly uniformly penetrated by the thermoplastic styrene copolymer molding compound A.
  • a particularly advantageous feature of this process is that the time required to melt the styrene copolymer molding compound A and to penetrate the reinforcing fibers B with the styrene copolymer molding compound A can be significantly reduced, since the reinforcing fibers B and the thermoplastic styrene copolymer fibers F are already uniformly distributed in the textile structure G. Thus, the comparatively thin thermoplastic styrene copolymer fibers F can be rapidly melted.
  • the molten thermoplastic styrene copolymer molding compound A thus obtained does not have to penetrate far into the fabric of the reinforcement due to the uniform distribution. fibers B penetrate. After only a short time, a fiber composite material V uniformly interspersed with the styrene copolymer molding compound A is obtained. This is also possible with complicated molded parts such as, for example, shaped parts having different layer thicknesses in different regions of the molded part.
  • fiber composite materials V with regions of different thickness can be produced in this way, in particular, in an advantageous manner.
  • One aspect of the present invention thus relates to a process for producing a fiber composite material V comprising reinforcing fibers B and a thermoplastic styrene copolymer molding compound A comprising the steps: a. Production of a sheet-like or spatial textile structure G from the reinforcing fibers B and thermoplastic styrene copolymer fibers F, wherein the styrene copolymer fibers F are made of the material of the thermoplastic styrene
  • a fiber composite material V for the purposes of this invention is a material comprising a thermoplastic styrene copolymer molding compound A and at least one reinforcing fiber B, wherein the reinforcing fibers B are embedded in the thermoplastic styrene copolymer molding compound A.
  • Thermoplastic styrene copolymer molding compound A in this context means that it is a styrene copolymer molding compound A comprising at least one thermoplastic styrene-containing copolymer. Suitable co-monomers are, for example, a-methylstyrene, acrylonitrile, methacrylonitrile, and methyl methacrylate (MMA), conjugated dienes and / or acrylates.
  • the thermoplastic styrene copolymer molding composition A is at least 50 wt .-% of a thermoplastic styrene copolymer, in particular at least 70 wt .-%, particularly preferably at least 90 wt .-%. In one embodiment, the styrene copolymer molding composition A is 100% by weight of a styrene copolymer.
  • thermoplastic fiber composite material V as described above, containing (or consisting of): a) 30 to 95 wt .-% of the thermoplastic styrene copolymer molding composition A, preferably 35 to 90 wt .-%, in particular 40 to 80 wt .-%
  • the invention relates to a process wherein the styrene copolymer of styrene copolymer molding material A is a styrene-butadiene block copolymer.
  • the styrene copolymer molding composition A may also contain polystyrene or (largely) consist of polystyrene.
  • the invention also relates to a process in which the thermoplastic styrene copolymer fibers F at least one copolymer from the group styrene / acrylonitrile copolymer (SAN), acrylonitrile / butadiene / styrene copolymers (ABS) and acrylonitrile / styrene / acrylic ester -Copolymers (ASA) included.
  • the invention relates to a process wherein the reinforcing fibers B are selected from the group consisting of carbon fibers, glass fibers and aramid fibers.
  • the invention also relates to a method in which the textile structure G is a woven fabric, scrim, knitted fabric, braid, knitted fabric, nonwoven fabric or felt, wherein in each case the thermoplastic styrene copolymer fibers F and the reinforcing fibers B are processed together.
  • the invention relates to a method in which the textile structure is a woven, knitted, laid or knitted fabric.
  • the textile structure G is particularly preferably a woven fabric, in particular a woven fabric which contains at least 5% by weight of reinforcing fibers B, more preferably at least 10% by weight of reinforcing fiber B.
  • the invention also relates to a thermoplastic fiber semi-finished product H containing thermoplastic styrene copolymer fibers F and reinforcing fibers B, wherein the thermoplastic styrene copolymer fibers F and the reinforcing fibers B by a textile manufacturing process to form a sheet-like or spatial textile entity G together were connected.
  • the invention relates to a semifinished fiber H in which the styrene copolymer of the styrene copolymer molding compound A is a styrene-butadiene block copolymer.
  • the invention also relates to a semi-finished fiber H, wherein the thermoplastic styrene copolymer fibers F at least one copolymer from the group styrene / acrylonitrile copolymer (SAN), acrylonitrile / butadiene / styrene copolymers (ABS) and acrylonitrile / styrene / Acrylic ester copolymers (ASA) included.
  • the invention relates to a semifinished fiber H in which the reinforcing fibers B are selected from the group consisting of carbon fibers, glass fibers and aramid fibers.
  • the invention also relates to a semi-finished fiber H, wherein the textile structure G is a woven, knitted, scrim, knitted, braided, knitted, nonwoven or felt, wherein each of the thermoplastic styrene copolymer fibers F and the reinforcing fibers B were processed together.
  • the semi-finished fiber H is a fabric, in particular a fabric containing at least 5 wt .-% of reinforcing fibers B, more preferably at least 10 wt .-% of reinforcing fibers B.
  • a molded article T is the subject of the invention, produced by a process comprising the following steps: a. Producing a semi-finished thermoplastic fiber H as described above; b. Shaping melting of the semi-finished fiber H to obtain the desired molding T;
  • the invention relates to a molding T, in which the semi-finished fiber H is provided on at least one side with a layer containing another thermoplastic material before the step of shaping.
  • the invention also relates to a molded part T, in which the shaping melting takes place by compression molding, hot pressing, diaphragm molding or hydroforming.
  • the fiber composite material V or the semi-finished fiber H contains at least 20 wt .-%, usually at least 30 wt .-%, based on the total weight of the fiber composite material V, the thermoplastic styrene copolymer molding material A.
  • the styrene Copolymer molding compound A preferably comprises from 30 to 95% by weight, more preferably from 35 to 90% by weight, often from 40 to 80% by weight and in particular from 45 to 75% by weight, based on the fiber composite material V, the semi-finished fiber H or the finished fiber composite material V from.
  • thermoplastic styrene copolymer molding compositions A are all thermoplastic see styrene copolymer molding compounds, which can be processed into fibers.
  • thermoplastic styrene copolymer molding compound A is preferably an amorphous molding compound, wherein amorphous state of the thermoplastic molding compound (thermoplastic) means that the macromolecules without regular arrangement and orientation, i. without constant distance, are arranged completely statistically.
  • the entire thermoplastic styrene copolymer molding compound A has amorphous, thermoplastic properties, is therefore fusible and (largely) non-crystalline.
  • the shrinkage of the thermoplastic styrene copolymer molding compound A, and therefore also of the entire fiber composite material V, is comparatively low. It can be obtained particularly smooth surfaces in the moldings.
  • the component A contains a partially crystalline fraction of less than 60 wt .-%, preferably less than 50 wt .-%, more preferably less than 40 wt .-%, based on the total weight of component A.
  • Semi-crystalline thermoplastics form both chemically regular, as well as geometric areas, d. H. There are areas where crystallites form. Crystallites are parallel bundles of molecular segments or folds of molecular chains. Individual chain molecules can partially pass through the crystalline or the amorphous region. Sometimes they can even belong to several crystallites at the same time.
  • the thermoplastic styrene copolymer molding compound A may be a blend of amorphous thermoplastic polymers and semi-crystalline polymers.
  • the thermoplastic styrene copolymer molding compound A can be, for example, a blend of a styrene copolymer with one or more polycarbonate (s) and / or one or more partially crystalline polymers (such as polyamide), the proportion of partially crystalline mixed components in the entire component A being less than 50 wt .-%, preferably less than 40 wt .-% should be.
  • the styrene copolymer molding compound A comprises at least styrene copolymer, in particular one suitable for the production of fiber composite materials V.
  • Amorphous thermoplastics are preferably used for the styrene copolymer molding compound A.
  • styrene copolymers such as styrene-acrylonitrile copolymers (SAN) or ⁇ -methylstyrene-acrylonitrile copolymers (AMSAN), impact-modified styrene-acrylonitrile copolymers, such as acrylonitrile-butadiene-styrene copolymers (ABS), styrene-methyl methacrylate Copolymers (SMMA), methacrylate-acrylonitrile-butadiene-styrene copolymers (MABS) or acrylic ester-styrene-acrylonitrile copolymers (ASA) used.
  • ABS styrene-acrylonitrile copolymers
  • AMSAN ⁇ -methylstyrene-acrylonitrile copolymers
  • ABS styrene-methyl methacrylate
  • Blends of the abovementioned copolymers with polycarbonate or semicrystalline polymers such as polyamide are also suitable, provided that the proportion of partially crystalline mixed components in component A is less than 50% by weight.
  • Acrylonitrile-butadiene-styrene copolymer according to the invention as thermoplastic styrene copolymer molding composition A can be prepared by known methods from styrene, acrylonitrile, butadiene and optionally a functional further monomer, such. Methyl methacrylate (MMA), maleic anhydride (MSA) or N-phenylmaleimide (N-PMI).
  • MMA Methyl methacrylate
  • MSA maleic anhydride
  • N-PMI N-phenylmaleimide
  • the ABS copolymer may, for. From 35 to 70% by weight of butadiene, from 20 to 50% by weight of styrene and from 9 to 38% by weight of acrylonitrile and from 0.1 to 5% by weight, preferably from 0.1 to 3% by weight. % of another functional monomer.
  • Component A can also be prepared from 35 to 70% by weight of at least one conjugated diene, 20 to 50% by weight of at least one vinylaromatic monomer and 9 to 38% by weight of acrylonitrile and 0.1 to 5% by weight, preferably 0.1 to 3 wt .-% of another functional monomer.
  • the component A of the invention is a styrene / butadiene copolymer such as e.g. Impact-resistant polystyrene, a styrene-butadiene block copolymer, e.g. Styrolux®, Styroflex® (both from Styrolution, Frankfurt), K-Resin®, Clearen®, Asaprene®.
  • styrene / butadiene copolymer such as e.g. Impact-resistant polystyrene, a styrene-butadiene block copolymer, e.g. Styrolux®, Styroflex® (both from Styrolution, Frankfurt), K-Resin®, Clearen®, Asaprene®.
  • the styrene copolymer molding compound A may consist of at least two mutually different thermoplastic styrene copolymer molding compositions.
  • these different molding material types may have a different melt volume flow rate (MVR) and / or different coalescing volume flow rate (MVR).
  • MVR melt volume flow rate
  • MVR coalescing volume flow rate
  • ABS molding compounds and SAN molding compounds can be combined.
  • the styrene copolymer molding composition A comprises, for example, 30 to 70% by weight of ABS molding composition and 70 to 30% by weight of SAN molding composition, in particular 50 to 70% by weight of ABS molding composition and 50 to 30% by weight. % SAN molding compound.
  • the component A has a MVR 240 ° C / 10 kg according to ISO 1 133 of at least 10 cm 3 / 10min, preferably at least 15 cm 3 / 10min, in particular at least 20 cm 3 / 10min.
  • the thermoplastic matrix also has a MVR 240 ° C / 10 kg according to ISO 1 133 of at least 10 cm 3 / 10min, preferably at least 15 cm 3 / 10min, in particular at least 20 cm 3 / 10min.
  • the term molecular weight (Mw) in the broadest sense can be understood as the mass of a molecule or a region of a molecule (eg a polymer strand, a block polymer or a small molecule) which is in g / mol (Da) and kg / mol (kDa) can be specified.
  • the molecular weight (Mw) is the weight average which can be determined by the methods known in the art.
  • thermoplastic molding compositions A preferably have a molecular weight Mw of from 60,000 to 400,000 g / mol, particularly preferably from 80,000 to 350,000 g / mol, it being possible to determine Mw by light scattering in tetrahydrofuran (GPC with UV detector).
  • the molecular weight Mw of the thermoplastic molding compositions A can vary within a range of +/- 20%.
  • Suitable preparation processes for the styrene copolymer molding compositions A are emulsion, solution, bulk or suspension polymerization, preference being given to solution polymerization (see GB 1472195).
  • the styrene copolymer molding compound A after the preparation is isolated by processes known to those skilled in the art and preferably processed into granules. Thereafter, the preparation of the thermoplastic styrene copolymer fibers F can be carried out by a method known to the person skilled in the art, in particular by melt extrusion.
  • Reinforcing fibers B component B
  • the thermoplastic fiber composite material V contains at least 5 wt .-% of the reinforcing fibers B (component B), based on the fiber composite material V.
  • the reinforcing fibers B are in the fiber composite material V vor- zugt of 5 to 70 wt .-%, particularly preferably from 10 to 65 wt .-%, often from 20 to 60 wt .-% and in particular from 25 to 55 wt .-%, based on the fiber composite material V, included .
  • As the material of the reinforcing fibers B all materials can be used which are processable into fiber and have a melting temperature which is greater than the melting temperature of the thermoplastic styrene copolymer molding composition A. Preferred are differences in the melting temperature of component A to B of at least 50 ° C, especially 70 ° C. In one embodiment, materials are used which have no thermoplastic behavior.
  • Suitable fibers are glass fibers, ceramic fibers, aramid fibers, carbon fibers, boron fibers, basalt fibers, steel fibers, and natural fibers such as flax, hemp, jute, kenaf ramie or sisal fibers. Particularly preferred are glass fibers, carbon fibers and aramid fibers.
  • the provision of the reinforcing fibers B can be effected by all methods known to the person skilled in the art and depends on the respective fiber type.
  • the reinforcing fibers B preferably have:
  • Glass fibers are preferably treated with a sizing, which protect each other especially the fibers. Mutual damage due to abrasion should be prevented. When mutual mechanical action should not come to the transverse fragmentation (fracture).
  • the cutting process of the fiber can be facilitated in order to obtain, above all, an identical staple length.
  • the size can be used to avoid agglomeration of the fibers.
  • the dispersibility of short fibers in water can be improved.
  • a sizing may help to produce improved cohesion between the glass fibers and the polymer matrix in which the glass fibers act as reinforcing fibers.
  • This principle is mainly used in glass fiber reinforced plastics (GRP). So far, the glass fiber sizes generally contain a large number of constituents, such as film formers, lubricants, wetting agents and adhesion promoters.
  • a film former protects the glass filaments from mutual friction and may additionally enhance affinity for synthetic resins, thus promoting the strength and cohesiveness of a composite material.
  • a lubricant gives the glass fibers and their products suppleness and reduces the mutual friction of the glass fibers, even during manufacture. Often, however, the adhesion between glass and resin is compromised by the use of lubricants. Fats, oils and polyalkyleneamines in an amount of 0.01 to 1 wt .-%, based on the total size, are mentioned.
  • a wetting agent causes a lowering of the surface tension and an improved wetting of the filaments with the size.
  • aqueous sizes for example, polyfatty acid amides in an amount of 0.1 to 1, 5 wt .-%, based on the total size to name.
  • organofunctional silanes such as, for example, aminopropyltriethoxysilane, methacryloxypropyltrimethoxysilane, glycidyloxypropyltrimethoxysilane and the like, may be mentioned.
  • Silanes which are added to an aqueous sizing are usually hydrolyzed to silanols. These silanols can then react with reactive (glass) fiber surfaces and thus form an adhesive layer (with a thickness of about 3 nm).
  • low molecular weight functional agents can react with silanol groups on the glass surface, with these low molecular weight agents subsequently reacting further (for example, in epoxy resins), thereby providing chemical bonding of the glass fiber to the polymer matrix.
  • such a preparation is time-consuming and lasts until complete curing of the polymers (for example the abovementioned epoxy resins) approximately between 30 minutes to more than one hour.
  • a functionalization by reaction with polymers is also known.
  • low molecular weight polycarbonate types it is possible to impregnate the glass fiber fabric or fabric well and to perform a "grafting" by reaction of functional groups on the glass fiber surface with the polycarbonate, which increases the compatibility with the polymer.
  • PC polycarbonate
  • the reinforcing fibers B are present in the fiber semifinished product H according to the invention together with the thermoplastic styrene copolymer fibers F as a woven, knitted, folded, knitted, braided, nonwoven or felt.
  • the textile structure G is a woven, knitted fabric, scrim or knit.
  • the textile structure G is a fabric, in particular one which contains at least 5 wt .-% of reinforcing fibers B.
  • a scrim is a sheet consisting of one or more layers of parallel, stretched threads. At the crossing points, the threads are usually fixed. The fixation is done either by material bond or mechanically by friction and / or positive locking.
  • the thread layers in multi-layered layers can all have different orientations, and can also consist of different thread densities and different thread counts.
  • a fabric is a textile fabric made up of at least two thread systems crossed at right angles or at right angles. Knitted fabric and knitwear are both among the knits, in which a thread loop is looped into another. Knitted fabrics (also called knits or hosiery) are made of thread systems by stitching on a knitting machine industrially produced fabrics. When knitting, however, one stitch is made next to the other (thread runs horizontally, along one course), while in effect the thread forms stitches on top of each other (thread runs vertically and forms a wale with the adjacent thread).
  • a braid is a textile structure, which is obtained by the regular interlacing of several strands of flexible material. The difference to weaving lies in the fact that when braiding the threads are not fed at right angles.
  • Nonwovens are structures of limited length fibers, filaments or cut yarns of any kind and of any origin which have been somehow joined together to form a nonwoven and joined together in some manner.
  • Felt is a textile fabric made of a disordered, difficult to separate fiber material and is produced by dry needling (needle felting) or by solidification with under high pressure emerging from a nozzle beam water jets.
  • the reinforcing fibers B in the form of a textile structure G ' which differs from the textile structure G of the semifinished fiber H that the textile structure G forming thermoplastic styrene copolymer fibers F by melting in the thermoplastic styrene Copolymer molding compound A have been transferred.
  • the textile structure G ' is thus formed only from the reinforcing fibers B and can thus differ in its structure from the structure G of the semifinished fiber product.
  • the textile structure G 'in the fiber composite material V is preferably a scrim, a woven fabric, a knitted fabric or a knitted fabric.
  • the textile structure G ' is a scrim or a fabric.
  • the reinforcing fibers B are preferably embedded in the fiber composite material V in a structurally defined and aligned form.
  • a laminate-like or laminar structure of the fiber composite material V is assumed.
  • Laminated laminates formed in this way comprise laminations of sheet-like reinforcing layers (of reinforcing fibers B) and layers of the styrene copolymer molding compound W moistening and holding them together.
  • the reinforcing fibers B are embedded in layers in the fiber composite material V. They can be obtained by arranging the textile structures G in several layers one above the other and optionally fixing them together. This fixation can be carried out by all methods familiar to the person skilled in the art, for example by knotting, linking, entangling, sewing or by the use of a suitable binder.
  • the textile structure G may be designed flat or spatially.
  • Flat in this context means that the structure G extends essentially in two dimensions and the third dimension only by the natural layer thickness a single-layer textile layer, which is given by the fiber thickness, is taken.
  • Spatially means in this context that the layer thickness of the structure G at least in some areas is greater than is predetermined by the natural layer thickness of a single-layer textile layer.
  • rib-like thickenings can be incorporated into the textile fabric by means of suitable textile processes.
  • the spatial textile structures G also include, for example, hollow bodies such as tubes or hoses.
  • a spatial configuration can be achieved by a method familiar to the person skilled in the art.
  • the reinforcing fibers B may additionally comprise auxiliaries which serve to produce and process the reinforcing fibers B, increase the durability of the reinforcing fibers B or improve the interaction of the reinforcing fibers B with the thermoplastic styrene copolymer molding material A. For this purpose, the so-called size regularly adhesion promoters are added.
  • Such a sizing is applied regularly to the reinforcing fibers B during manufacture in order to improve the further processability of the reinforcing fibers B (such as weaving, laying, sewing). If the sizing is undesirable for subsequent processing, it must first be removed in an additional process step, such as by burning down. Then, for the production of the fiber composite material V, a further adhesion promoter is applied in an additional process step. Sizing and / or adhesion promoters form on the surface of the reinforcing fibers B a layer which can substantially determine the interaction of the reinforcing fibers B with the environment. Today, a variety of different adhesion agents are available.
  • the styrene copolymer molding composition A to be used and the reinforcing fibers B to be used the person skilled in the art can select a suitable adhesion promoter which is compatible with the styrene copolymer molding compound A and with the reinforcing fibers B.
  • the fiber composite material V optionally contains 0 to 40% by weight, preferably 0 to 30% by weight, particularly preferably 0.1 to 25% by weight, based on the sum of components A to C, one or more additive other than components A and B (auxiliaries and additives).
  • additives include particulate mineral fillers, processing aids, stabilizers, oxidation retarders, anti-heat and ultraviolet light decomposition agents, lubricants and mold release agents, flame retardants, dyes and pigments, and plasticizers. Even esters as low molecular compounds are mentioned. Also, according to the present invention, two or more of these compounds can be used. In general, the compounds are present with a molecular weight of less than 3000 g / mol, preferably less than 150 g / mol.
  • Particulate mineral fillers can be, for example, amorphous silica, carbonates such as magnesium carbonate, calcium carbonate (chalk), powdered quartz, mica, various silicates such as clays, muscovite, biotite, suzoite, tin malite, talc, chlorite, phlogopite, feldspar, calcium silicates such as wollastonite or kaolin, especially calcined kaolin.
  • carbonates such as magnesium carbonate, calcium carbonate (chalk), powdered quartz, mica, various silicates such as clays, muscovite, biotite, suzoite, tin malite, talc, chlorite, phlogopite, feldspar, calcium silicates such as wollastonite or kaolin, especially calcined kaolin.
  • UV stabilizers include, for example, various substituted resorcinols, salicylates, benzotriazoles and benzophenones, which can generally be used in amounts of up to 2% by weight.
  • oxidation inhibitors and heat stabilizers may be added to the thermoplastic molding compound.
  • lubricants and mold release agents which are usually added in amounts of up to 1 wt .-% of the thermoplastic composition.
  • these include stearic acid, stearyl alcohol, stearic acid alkyl esters and amides, preferably Irganox®, and esters of pentaerythritol with long-chain fatty acids. It is possible to use the calcium, zinc or aluminum salts of stearic acid and also dialkyl ketones, for example distearyl ketone.
  • ethylene oxide-propylene oxide copolymers can also be used as lubricants and mold release agents.
  • natural and synthetic waxes can be used. These include PP waxes, PE waxes, PA waxes, grafted PO waxes, HDPE waxes, PTFE waxes, EBS waxes, montan wax, carnauba and beeswaxes.
  • Flame retardants can be both halogen-containing and halogen-free compounds. Suitable halogen compounds, with brominated compounds being preferred over the chlorinated ones, remain stable in the preparation and processing of the molding composition of this invention so that no corrosive gases are released and efficacy is not thereby compromised. Preference is given to halogen-free compounds, such as phosphorus compounds, in particular phosphine oxides and Derivatives of acids of phosphorus and salts of acids and acid derivatives of phosphorus used. Phosphorus compounds particularly preferably contain ester, alkyl, cycloalkyl and / or aryl groups. Likewise suitable are oligomeric phosphorus compounds having a molecular weight of less than 2000 g / mol, as described, for example, in EP-A 0 363 608.
  • pigments and dyes may be included. These are generally in amounts of 0 to 15, preferably 0.1 to 10 and in particular 0.5 to 8 wt .-%, based on the buzzer of components A to C, included.
  • the pigments for coloring thermoplastics are generally known, see, for example, R. Gumbleter and H. Müller, Taschenbuch der Kunststoffadditive, Carl Hanser Verlag, 1983, pp. 494 to 510.
  • Suitable pigments are, for example, white pigments such as zinc oxide, zinc sulfide, lead white (2 PbC0 3 -Pb (OH) 2 ), lithopone, antimony white and titanium dioxide.
  • white pigments such as zinc oxide, zinc sulfide, lead white (2 PbC0 3 -Pb (OH) 2 ), lithopone, antimony white and titanium dioxide.
  • rutile and anatase-type of titanium dioxide, in particular the rutile form is used for the whitening of the molding compositions according to the invention.
  • Black color pigments which can be used according to the invention are iron oxide black (Fe 3 O 4 ), spinel black (Cu (Cr, Fe) 2 O 4 ), manganese black (mixture of manganese dioxide, silicon oxide and iron oxide), cobalt black and antimony black, and particularly preferred Carbon black, which is usually used in the form of furnace or gas black (see G. Benzing, Pigments for paints, Expert Verlag (1988), p. 78ff).
  • inorganic color pigments such as chromium oxide green or organic colored pigments such as azo pigments and phthalocyanines can be used according to the invention to adjust certain hues. Such pigments are generally available commercially.
  • thermoplastic fiber composite materials V Production of the thermoplastic fiber composite materials V
  • the process for producing a fiber composite material V comprising reinforcing fibers B and a thermoplastic styrene copolymer molding compound A comprises the steps: a. Producing a sheet-like or spatial textile structure G of the reinforcing fibers B and thermoplastic styrene copolymer fibers F, wherein the styrene copolymer fibers F are made of the material of the thermoplastic styrene copolymer molding compound A;
  • a sheet-like or spatial textile structure G comprising the reinforcing fibers B and thermoplastic styrene copolymer fibers F is provided in a first production step a.
  • the styrene copolymer fibers F consist of the thermoplastic styrene copolymer molding material A.
  • Suitable thermoplastic styrene copolymer molding compositions A are all thermoplastic styrene copolymer molding compositions which can be processed into fibers. Further, with respect to the styrene copolymer fibers F, all embodiments made regarding the styrene copolymer molding compound A are applicable.
  • the sheet-like or spatial textile structure G comprises any structure of textile fibers which can be produced by means of known textile production methods. Suitable textile structures G can be woven, knitted, laid, knitted, braided, nonwoven or felts. Preferably, the textile structure G is a woven, knitted fabric, scrim or knit. Particularly preferably, the textile structure G is a fabric.
  • the sheet-like or spatial textile structures G are characterized in that they are obtained by processing fibers of at least two materials with one another in the textile production process.
  • the fibers of at least two materials are at least one reinforcing fiber B and at least one styrene copolymer fiber F.
  • the joint processing can be carried out such that a part of the fibers in the textile manufacturing process for producing a textile structure G from the reinforcing fibers B by styrene Copolymer fibers F is replaced.
  • a single textile structure G is obtained, in which both fibers are incorporated.
  • the proportion of the at least one styrene copolymer fiber F can be kept constant or varied over the entire extent of the textile structure G. In areas with a higher proportion of styrene copolymer fibers F, a fiber composite material V with an egg is thus obtained after completion of the production process. property profile which to a higher degree corresponds to that of the styrene copolymer molding compound A (eg greater strength at room temperature), whereas areas with a smaller proportion of styrene copolymer fibers F are more similar in their property profile to the composite fiber fabric (eg greater flexibility at room temperature) ,
  • Examples are, in particular, co-weaving, in which a part of the warp threads and / or a part of the weft threads consists in each case of styrene copolymer fibers F.
  • the styrene copolymer fibers F are incorporated regularly into the fabric thus produced, e.g. in that every second warp and / or weft thread is a styrene copolymer fiber F.
  • the proportion of the styrene copolymer fibers F can be reduced by incorporating them at lower repetition rates, so that e.g. only every third or every fourth warp and / or weft yarn is a styrene copolymer fiber F.
  • the styrene copolymer fibers F can be used exclusively as a warp or weft. Both measures for varying the proportion of styrene copolymer fibers F can be combined or made independently.
  • the individual layers may have a different content of styrene copolymer fibers F.
  • co-knitting co-knitting
  • textile structures G are produced in that a knitted fabric of reinforcing fibers B and styrene copolymer fibers F is formed.
  • knitted fabrics, braids or nonwovens may also be produced in which part of the reinforcing fibers B has been replaced by thermoplastic styrene copolymer fibers F.
  • the proportion of styrene copolymer fibers F in the textile structure G is 30 to 95 wt .-% based on the textile structure, preferably 35 to 90 wt .-%, in particular 40 to 80 wt .-%.
  • the reinforcing fibers B make up 5 to 70 wt .-%, preferably 10 to 65 wt .-%, in particular 20 to 60 wt .-% of the textile structure G.
  • the textile structure may contain 0 to 40 wt .-% of one or more additives C, preferably 0 to 30 wt .-%, in particular 0.1 to 25 wt .-%.
  • the textile structure G is designed such that it has at least one rib-like thickening on at least one surface of the structure G.
  • a thickening represents a larger amount of material. In this way, a targeted stiffening of the finished fiber composite material V can be achieved.
  • the textile structure G is heated.
  • the temperature is chosen so that it is above the melting range of the thermoplastic styrene copolymer fibers F.
  • the temperature is at least 10 ° C above the melting temperature of the thermoplastic styrene copolymer fibers F, more preferably at least 25 ° C, especially at least 50 ° C.
  • Step b is carried out at a temperature of at least 200 ° C, preferably at least 250 ° C, more preferably at least 300 ° C, especially at 300 ° C to 400 ° C. In this case, it should preferably be ensured that as far as possible no pyrolysis occurs and the components used are not thermally decomposed.
  • the residence time at temperatures of> 200 ° C. is not more than 10 min, preferably not more than 5 min, more preferably not more than 2 min, in particular not more than 1 min. Often 10 to 60 seconds are sufficient for the thermal treatment.
  • the process in particular the steps b, can in principle be carried out at any pressure (preferably atmospheric pressure or overpressure), with and without pressing of the components.
  • any pressure preferably atmospheric pressure or overpressure
  • the properties of the fiber composite material V can be improved.
  • the step b at a pressure of 5-50 bar and a pressing time of 10-60 s, preferably at a pressure of 10-30 bar and a pressing time of 15-40 s performed.
  • the step of heating softens the thermoplastic styrene copolymer fibers F incorporated in the fabric G until the styrene copolymer fibers F finally melt and form the styrene copolymer molding compound A.
  • the molten styrene copolymer molding compound A can now penetrate the cavities of the remaining textile structure G 'formed by the reinforcing fibers B and uniformly impregnate this. Since the styrene copolymer molding compound A in the form of the styrene copolymer fibers F is already present uniformly in the textile structure G 'formed by the reinforcing fibers B, a uniform and complete impregnation of the textile structure G' can take place within a shorter time and / or at lower temperatures are achieved.
  • the elevated temperature of the step b is maintained until the styrene copolymer fibers F have had time to melt and uniformly fill the voids in the remaining textile fabric G 'of reinforcing fibers B.
  • the structure G is preferably heated for at least 10 seconds, in particular for at least 20 seconds. The duration is dependent on the set temperature, so that a higher Temperaturn requires a shorter heating time, while at a temperature which is closer to the melting temperature of the styrene copolymer fibers F, a longer time is necessary to the styrene copolymer molding compound A, which has uniformly impregnated the textile structure G 'of reinforcing fibers B.
  • a third production step c the fiber composite material V obtained in step b is cooled. This can be done by suspending the ambient temperature or by actively cooling the fiber composite material V or the device by means of which the heating is carried out.
  • the cooling is preferably carried out in such a way that the fiber composite material V obtained from step B is made of reinforcing fibers B and still softened or melted styrene copolymer molding compound A without changing the shape of the fiber composite material V.
  • fiber composite material V of reinforcing fibers B and still softened or molten styrene copolymer molding compound A is preferably cooled in the mold used for heating until the fiber composite material V has a temperature below the melting range of styrene Copolymer molding compound A is located.
  • the Fiber composite material V of the device removed only when sufficient strength of the styrene copolymer molding compound A has been established.
  • the fiber composite material V of the device is removed only when the fiber composite material V on the surface has a temperature which is at least 5 ° C below the melting temperature of the styrene copolymer molding compound A, more preferably at least 10 ° C.
  • the fiber composite material V produced by the method described above is characterized in that it comprises at least one sheet-like or spatial textile structure G 'of reinforcing fibers B, which is embedded in the thermoplastic styrene copolymer molding compound A, wherein the styrene copolymer Formmasse A, the cavities between the reinforcing fibers B substantially fills.
  • "Substantially fills in” in this context means that the cavities to at least 80 vol .-%, preferably 90 vol .-%, in particular 95 vol .-% are filled with the styrene copolymer molding composition A.
  • first textile structures G can be prepared, which can be consolidated in a further step to a composite material as fiber composite material V.
  • the invention also relates to a semifinished fiber product H.
  • This corresponds to the planar or spatial textile structure G provided in step a comprising reinforcing fibers B and styrene copolymer fibers F. It can be obtained by using at least one reinforcing fiber B and at least one styrene copolymer.
  • Fibers F are processed together in a textile processing process to a holding textile composite.
  • the styrene copolymer fibers F consist of the thermoplastic styrene copolymer molding compound A.
  • Suitable thermoplastic styrene copolymer molding compositions A are all thermoplastic styrene copolymer molding compositions which can be processed into fibers.
  • all designs that were made regarding the styrene copolymer molding compound A are made from the material from which the styrene copolymer fibers F are made, all designs that were made regarding the styrene copolymer molding compound A
  • thermoplastic styrene copolymer fibers F can be effected by all methods known to the person skilled in the art, in particular by melt extrusion.
  • the thermoplastic styrene copolymer fibers F preferably have a filament number of more than 500, in particular more than 1000, and a yarn count of from 10 to 5000 tex, in particular from 50 to 4000 tex.
  • the reinforcing fibers B reference is made to the statements made above.
  • the reinforcing fibers B are processed into fabrics together with the styrene copolymer fibers F by a textile-technical process familiar to the person skilled in the art. Common methods are weaving, knitting, knitting, laying, braiding, felting and knotting.
  • the sheet-like textile structures G in the context of this invention are preferably fabrics, scrims, knits, braids, knitted fabrics, nonwovens or felts according to the abovementioned definitions. Preference is given to tissue. Possible weave types of weave include canvas weave, twill weave and satin weave.
  • the semi-finished fiber H according to the invention is characterized in particular by the fact that the fibers are dimensionally stable connected to each other in order to fix them. This is achieved either by achieving a mechanical fixation, such as by knotting, linking, entangling, sewing or by the friction of the fiber surfaces together.
  • the semi-finished fiber H can also be bound to each other by the BeSchichtung by means of a suitable binder. Suitable binders are known to the person skilled in the art. Preference is given to a mechanical fixation of the fibers with one another, so as to achieve a sufficient dimensional stability, so that the semi-finished fiber H is storable and transportable.
  • the fiber semifinished product H thus obtained can be stored and transported in a space-saving manner in rolled-up form and subsequently brought into the fiber composite material V of the desired shape by the method described above according to steps b and c.
  • the fiber composite material V can also be reinforced by the fact that in the manufacturing step b in addition to at least one side of the semifinished fiber H a layer of a thermoplastic molding material A 'is applied.
  • the molding compound can be the same or different from the styrene copolymer molding composition A.
  • the molding composition may be, for example, a styrene-containing polymer, a polycarbonate, a polyolefin, or another thermoplastic polymer known to the person skilled in the art.
  • A is a styrene copolymer or a polycarbonate.
  • styrene copolymers such as styrene-acrylonitrile copolymers (SAN) or ⁇ -methylstyrene-acrylonitrile copolymers (AMSAN), impact-modified styrene-acrylonitrile copolymers, such as acrylonitrile-butadiene-styrene copolymers (ABS ), Styrene-methyl methacrylate copolymers (SMMA), methacrylate-acrylonitrile-butadiene-styrene copolymers (MABS) or acrylic ester-styrene-acrylonitrile copolymers (ASA).
  • ABS acrylonitrile-butadiene-styrene copolymers
  • SMMA Styrene-methyl methacrylate copolymers
  • MABS methacrylate-acrylonitrile-butadiene-styrene copolymers
  • ASA acrylic ester-styrene-acrylonit
  • the molding compound A ' can be applied in the form of a film, a melt, a granulate of a powder or another form familiar to the person skilled in the art on at least one side of the semifinished fiber H.
  • the molding material A ' is applied in the form of a film or granules on at least one side of the semi-finished fiber H.
  • the molding compound is distributed uniformly over at least part of the entire surface of the semifinished fiber H.
  • the molding compound A is applied to at least part of the surface of both sides of the semi-finished fiber H.
  • the molding compound A is applied, this is done in an amount of at least 0.1 g / cm 2 , preferably at least 1 g / cm 2 , more preferably at least 3 g / cm 2 on at least one surface of the semifinished fiber H.
  • the invention also relates to a molded part T which can be obtained or obtained from the semifinished fiber H described by deformation. This can be done in any desired manner, for example by mechanical shaping by means of a shaping body, which can also be a roller with embossing.
  • the still moldable fiber composite material V in which the thermoplastic styrene copolymer molding compound A and optionally the molding compound A 'still present (partially) molten, ie, during the implementation of step b or subsequently formed thereon.
  • a cured fiber composite material V can be cold-formed or re-formed with reheating.
  • the molded part T is obtained by a method in which the semi-finished fiber H described above is provided in a first step a.
  • the semi-finished fiber H is brought into the desired shape under shaping melting.
  • any method familiar and suitable to the person skilled in the art can be used.
  • the semi-finished fiber H is brought into the desired shape of the molded part T by compression molding, hot pressing, diaphragm molding or hydroforming.
  • compression molding the textile semifinished product is led into an open mold, heated and pressed under pressure.
  • hot pressing the molds are heated.
  • diaphragm molding a semifinished product is placed between two elastic membranes, the so-called diaphragms, the space of which is evacuated.
  • the semi-finished product is heated to softening and then placed together with the diaphragm in a forming tool. This preferably consists only of a mold half, which has a temperature below the softening temperature of the material.
  • Diphragma and softened semi-finished products are pressed into the tool half by means of compressed air and the semifinished product cools down under forced pressure and isostatic pressure.
  • hydroforming an assembly consisting of upper and lower tools is used, the lower tool forming the counter-mold into or onto which the laminate is to be imaged.
  • the upper tool consists of a closed down by means of a flexible membrane chamber, which can be subjected to the deformation with hydraulic pressure.
  • the thermoplastic molding compound Before forming, the thermoplastic molding compound must be softened by heating, e.g. by convection ovens or contact heating.
  • the stability of the molded part T can be increased by the addition of additional amounts of thermoplastic material.
  • the semifinished fiber H can be provided on at least one side with an additional amount of a thermoplastic molding material A 'before the step of shaping melting.
  • the molding material may be the same or different from the styrene copolymer molding compound A, which forms the basis for the styrene copolymer fibers F. With regard to the selection of the styrene copolymer molding compound A, the statements made above apply.
  • the molding compound A ' can be applied in the form of a film, a melt, a granulate of a powder or another form familiar to the person skilled in the art on at least one side of the semifinished fiber H.
  • the molding material A ' is applied in the form of a film or granules on at least one side of the semi-finished fiber H.
  • the molding material is uniformly applied to at least part of the distributed throughout the entire surface.
  • the molding compound A ' is applied to at least part of the surface of both sides of the semifinished fiber H.
  • the molding compound A ' is applied, this is done in an amount of at least 0.1 g / cm 2 , preferably at least 1 g / cm 2 , more preferably at least 3 g / cm 2 on at least one surface of the semi-finished fiber H.
  • step b the semi-finished fiber H and possibly applied to one or more sides thereof molding compound A 'is heated.
  • a temperature is used which is above the temperature of the melting range of the styrene copolymer fibers F and possibly the molding compound A '.
  • a temperature of at least 200 ° C, preferably at least 250 ° C, more preferably at least 300 ° C, in particular at 300 ° C to 400 ° C is applied. In this case, it should preferably be ensured that as far as possible no pyrolysis occurs and the components used are not thermally decomposed.
  • the pressing process can basically be carried out at any pressure (preferably atmospheric pressure or overpressure), with and without pressing on the components.
  • the step b at a pressure of 5-50 bar and a pressing time of 10- 60 s, preferably at a compression pressure of 10-30 bar and a pressing time of 15-40 s, performed.
  • the pressing operation is continued until the thermoplastic styrene copolymer fibers F are melted to an extent sufficient to penetrate the textile fabric G 'as a styrene copolymer molding material A.
  • the pressing operation is held until all the voids of the textile structure G 'formed by the reinforcing fibers B are completely filled with the molten styrene copolymer molding compound A.
  • the pressing process at temperatures of> 200 ° C is not more than 10 minutes, preferably not more than 5 minutes, more preferably not more than 2 minutes, in particular not more than 1 min. Often, 10 to 60 seconds are sufficient to avoid pyrolysis of the polymer. As hot pressing all the skilled person for this purpose devices can be used.
  • step b at least one sub-step of step b at a temperature of 300 to 340 ° C, in particular from 300 to 320 ° C, for 10 s up to 1 min (for example, from (about) 15 s, 20 s, 25 s, 30 s, 40 s, 50 s or 60 s). This can then improve the connection of the reinforcing fibers with the matrix.
  • a last step c the obtained fiber composite material V is cooled below the melting point of the styrene copolymer molding compound A.
  • the styrene copolymer molding compound A solid and the fiber composite material V can be removed from the mold used.
  • This step can also be called solidification.
  • the solidification which generally takes place with removal of heat, can then lead to a ready-to-use molded part T.
  • the molding T may be further finished (e.g., deburred, polished, colored, etc.).
  • the process can be carried out continuously, semicontinuously or discontinuously. According to a preferred embodiment, the process is carried out as a continuous process, in particular as a continuous process for producing smooth or three-dimensionally embossed films. Alternatively, it is also possible to produce shaped parts T semi-discontinuously or discontinuously.
  • the organic sheets are therefore preferably provided with a ribbing or laminated on a foamed thermoplastic core or on a honeycomb core as outer layers (welded).
  • a ribbing formation of a ribbed structure
  • optimal rib dimensions include production, aesthetic and constructive aspects.
  • the ribbing can take place by means of an injection molding material, which ensures a cohesive connection to the organic sheet and thus gives rise to a high moment of resistance.
  • the ribbing is achieved by already designing the textile structure G by textile production methods in such a way that the structure G has thickenings on at least one surface.
  • fiber composite materials V are obtained, which contain a ribbing due to this local surplus of material. This can be supported by correspondingly shaped dies.
  • the foam core can be glued to the cover layers or it is caused by an additional thermoplastic layer on the organic sheet, a claw in the foam structure.
  • the achieved weight reduction is advantageous for all moving components, since energy saving can be achieved by reducing the weight of the moving masses.
  • thermoplastic molding compositions described here are non-polar surface, which enables direct coating, pasting and printing.
  • a further advantage of the molded parts T produced according to the invention is the high rigidity and strength which can be achieved within the shortest residence time in the production process.
  • the stiffness and strength can be achieved by a sandwich composite or z. B. be further increased by a ribbing.
  • the core material in the sandwich composite both a foam core (e.g., Rohacell from Evonik) and a honeycomb core (e.g., Honeycomps from EconCore) can be used.
  • the core consists of a chemically compatible thermoplastic in order to heat-weld and to facilitate lamination in the production process.
  • thermoplastic molding composition in particular one of the abovementioned styrene copolymers, should be used.
  • a suitable thermoplastic molding composition in particular one of the abovementioned styrene copolymers, should be used.
  • a SAN, ABS or ASA-based thermoplastic molding composition is used.
  • a grain can be shaped by means of the tool wall, whereby the surface additionally can be functionalized (scratch resistance, concealment of sink marks).
  • the additional layer of thermoplastic can be colored opaque, so that optically no organic sheet can be assumed, or one can specifically induce a "fiber look" through the use of a transparent layer It is possible to reduce costs and at the same time to reduce the weight, which can facilitate the assembly of the component and of the device.With the use of organ sheets in addition to a cost and weight advantage but also an aesthetic advantage of an amorphous, transparent styrene copolymer molding compound A, a so-called "fiber-look" can be achieved. Even with the use of glass fiber, which is naturally transparent, can be made visible by painting the fibers.
  • the organic sheets according to the invention have the advantage that they can be used unpainted, wherein the coating step can be saved in comparison to the steel sheet.
  • the weight of mobile devices can be reduced.
  • the wall thickness is oversized, often due to inadequate flowability of the injection molding compound or too low a flow path / wall thickness ratio.
  • the use of organic sheets can therefore substantially reduce the wall thickness since the organic sheet only has to be reshaped and thus can be made with a small thickness even for very large components.
  • the organic sheets according to the invention can be produced, for example, with a thickness of ⁇ 1 mm, preferably ⁇ 0.7 mm, particularly preferred ⁇ 0.5 mm.
  • these thin sheets of organ made with a ribbing and Umklamung are very rigid components, since the organo sheet is located in the edge of the shell component, which has an increase in the resistance moment result. Due to the amorphous styrene copolymer molding compound A and thus low shrinkage, the moldings have a very smooth surface, which can still be painted or laminated as needed.
  • the organosurfaces can also achieve a large weight advantage. Again, the stiffening of the components can be supported by means of a ribbing. In addition, functional integration can save subsequent assembly steps and addi- tional components, thus providing a cost advantage in addition to weight.
  • FIG. 1 shows the fiber composite materials, the test no. 1 were obtained.
  • FIG. 1A shows the visual documentation.
  • FIG. 1B shows the microscopic view of a section through the laminar fiber composite material arranged in a horizontal orientation (left: 25-fold magnification, right: 50-fold magnification), the fibers clearly being shown as horizontally extending dark layer between the bright layers of thermoplastic molding material can be seen.
  • Figure 1 C shows the 200-fold magnification, it can be seen that the impregnation is not completed in some places.
  • FIG. 2 shows the fiber composite materials, which according to test no. 2 were obtained.
  • FIG. 2A shows the visual documentation.
  • FIG. 2B shows the microscopic view of a section through the laminar fiber composite material arranged in a horizontal orientation (left: 25-fold magnification, right: 50-fold magnification), the fibers clearly being in the form of a running dark layer can be seen between the light layers of thermoplastic molding material.
  • FIG. 2C shows a magnification of 200 times, whereby it can be seen that the impregnation is partly not completed.
  • FIG. 3 shows the fiber composite materials which have been tested according to test no. 3 were obtained.
  • FIG. 3A shows the visual documentation.
  • FIG. 3B shows the microscopic view of a section through the laminar fiber composite material arranged in a horizontal orientation (left: 25-fold magnification, right: 50-fold magnification), with no layer of fibers being recognizable is.
  • Figure 3C shows the 200-fold magnification, it can be seen that the impregnation is largely completed.
  • FIG. 4 shows the fiber composite materials which have been tested according to test no. 4 were obtained.
  • FIG. 4A shows the visual documentation.
  • FIG. 4 shows the visual documentation.
  • FIG. 4B shows the microscopic view of a section through the laminar fiber composite material arranged in a horizontal orientation (left: 25-fold magnification, right: 50-fold magnification), with no layer of fibers being recognizable.
  • Figure 4C shows the 200-fold magnification, it can be seen that the impregnation is not completely completed at individual points.
  • FIG. 5 shows the fiber composite materials W which have been tested according to test no. 5 were obtained.
  • FIG. 5A shows the visual documentation.
  • FIG. 5B shows a microscopic view of a section through the laminar fiber composite material arranged in a horizontal orientation (left: 25x magnification, right: 50x magnification), whereby no layer of fibers is discernible.
  • FIG. 4C shows a magnification of 200 times, whereby it can be seen that the impregnation is not completely completed in a few places.
  • Laminate thickness 0.5 mm
  • Laminate tolerances max. ⁇ 0.1 mm according to semi-finished product
  • Sandwich panel thickness max. 30 mm
  • Tool pressure Press unit 5-25 bar, infinitely variable for minimum and maximum tool size (optional)
  • Mold temperature control 3 heating and 2 cooling zones
  • Opening travel press 0.5 to 200 mm Production direction: right to left
  • the described fiber composite materials V are particularly suitable for the production of components for the automotive industry, household goods, electrical appliances, sports equipment, construction and construction materials and medical technology.
  • Acrylonitrile-butadiene-styrene copolymer continuous fiber obtained from a thermoplastic ABS molding composition prepared from 45% by weight of butadiene, 30% by weight of styrene, and 25% by weight of acrylonitrile (styrene copolymer fibers F) ,
  • Both fiber types are woven together in such a way that every second weft and warp thread is formed from a carbon fiber or an ABS fiber.
  • the semi-finished fiber H obtained by the process described above is introduced into the interval hot press and pressed at 250 ° C for 30 seconds at a pressure of 15 bar.
  • the fiber composite material V is cooled and removed from the interval hot press.
  • Styrene copolymers as thermoplastic styrene copolymer molding compound A and
  • thermoplastic semi-finished fiber products and fiber composite materials V and molded parts thereof which contain the thermoplastic styrene copolymer molding compound A, layers of reinforcing fibers B and optionally an additive C.
  • the process simplifies the production, in particular by virtue of the fact that the styrene copolymer molding compound A is already penetrated uniformly with the reinforcing fibers B by the preceding step of producing a semi-finished fiber product H in the form of a textile structure G. So textile structures G, which do not have a uniform thickness, can be converted into fiber composite materials V and moldings without the impregnation of thicker areas is incomplete or can be guaranteed only with great expenditure of time.
  • Laminate thickness 0.2 to 9.0 mm
  • Laminate tolerances max. ⁇ 0.1 mm according to semi-finished product
  • Sandwich panel thickness max. 30 mm
  • Tool pressure Press unit 5-25 bar, infinitely variable for minimum and maximum tool size (optional)
  • Mold temperature control 3 heating and 2 cooling zones
  • Opening travel press 0.5 to 200 mm
  • A1 (comparison): S / AN with 75% styrene (S) and 25% acrylonitrile (AN), viscosity number
  • A2 S / AN / maleic anhydride copolymer having the composition (wt%): 74/25/1, Mw of 250,000 g / mol (measured via gel permeation chromatography on standard columns with monodisperse polystyrene calibration standards)
  • B1 Bidirectional glass fiber substrate 0/90 ° (GF-GE) with basis weight
  • Matrix layer in top layer not visible on the roving
  • Impregnation Warp threads Central unimpregnated areas, all around slightly impregnated Impregnation Weft threads: in the middle clearly unimpregnated areas, all around slightly impregnated
  • Air inclusions little, only in roving
  • Matrix layer in middle position recognizable
  • Matrix layer in top layer little recognizable by the roving
  • Impregnation Warp threads Central unimpregnated areas visible, partially impregnated all around, partially unimpregnated
  • Matrix layer in middle position not recognizable
  • Matrix layer in top layer easily recognizable
  • Impregnation Warp threads hardly any unimpregnated areas visible, all-round well impregnated
  • Impregnation Weft threads hardly any unimpregnated areas visible, all-round well impregnated
  • Micro-impregnation mostly completed Microscopic evaluation in semi-finished products:
  • Matrix layer in middle position hardly recognizable
  • Matrix layer in cover layer recognizable
  • Impregnation Warp threads Slightly unimpregnated areas visible, all-round well impregnated
  • Impregnation Weft threads unimpregnated areas visible, but impregnated all around
  • Matrix layer in middle position not recognizable
  • Matrix layer in cover layer recognizable
  • Impregnation warp threads little unimpregnated areas visible, all-round well impregnated
  • Impregnation Weft threads little unimpregnated areas recognizable, all-round well impregnated
  • Table 5 shows the fiber composite materials obtained in a series of experiments.
  • pure SAN (A1) and an S / AN / maleic anhydride copolymer (A2) were combined and tested with a commercially available scrim and fabric reinforcement in an identical process.
  • the fiber volume content of the composites was 42%.
  • the improved quality of the impregnation and connection between fiber and matrix is not reflected in the bending stiffness, but clearly in the flexural strength (fracture stress) of the samples investigated.
  • SAN SAN-MA terpolymer, weight composition (% by weight): 73/25/2, Mw:
  • PC OD easy flowing, amorphous optical grade polycarbonate for optical
  • PA6 semi-crystalline, easy-flowing polyamide 6
  • Fibers (B3): glass fiber fabric twill 2/2 (GF-KG) with basis weight 300 g / m 2 ,
  • the described fiber composite materials are particularly suitable for the production of moldings, films and coatings. Some examples are shown below. Unless otherwise stated, the moldings are made by injection molding.
  • thermoplastic molding composition A 40% by weight, based on the fiber composite material, of an acrylonitrile-styrene-maleic anhydride copolymer as thermoplastic molding composition A (prepared from: 75% by weight of styrene, 24% by weight of acrylonitrile and 1% by weight of maleic anhydride) is compounded with 60% by weight, based on the fiber composite material, of a glass-based reinforcing fiber with chemically reactive functionality (silane groups) on the surface [GW 123-580K2 of PD Glasseiden GmbH].
  • ABS acrylonitrile-butadiene-styrene copolymer
  • thermoplastic molding material A ABS produced from: 45% by weight butadiene, 30% by weight Styrene, 24% by weight of acrylonitrile and 1% by weight of maleic anhydride
  • Example B Lens covers
  • the components are as defined above.
  • the bending stress and the flexural modulus were determined according to DIN 14125: 201 1 -05.
  • Table 7 shows the conditions of the experiments carried out.
  • the pressing pressure was approximately 20 bar in all test series.
  • Table 8 Average values of the maximum bending stress of the warp and weft directions of the produced organic sheets according to the mixtures Cf. 2, V5, V7, V9, Vgl. 10, V12 to V14 and Cgl. 15, wherein the production temperature was at least 300 ° C.
  • Table 8 shows the average of nine measurements each.
  • Table 8 shows that the organic sheets V5, V7, V9, V12, V13 and V14 according to the invention have a higher average maximum bending stress than the organo sheets comprising a matrix containing 75% by weight of styrene (S) and 25% by weight of acrylonitrile ( AN) (See Figures 10 and 15).
  • S styrene
  • AN acrylonitrile
  • Laminate thickness 0.2 to 9.0 mm
  • Laminate tolerances max. ⁇ 0.1 mm according to semi-finished product
  • Sandwich panel thickness max. 30 mm
  • Tool pressure Press unit 5-25 bar, infinitely variable for minimum and maximum tool size (optional)
  • Mold temperature control 3 heating and 2 cooling zones
  • Opening travel press 0.5 to 200 mm
  • T [° C] temperature of the temperature zones * ( * The press has 3 heating zones and 2 cooling zones.
  • Construction / lamination 6-layer structure with melt middle layer; Production process: melt direct (SD)
  • M1 (SAN type): styrene-acrylonitrile-maleic anhydride (SAN-MA) terpolymer (S / AN / MA: 74/25/1) with an MA content of 1% by weight and an MVR of 22 cm 3 / 10 min at 220 ° C / 10kg (measured to IS01 133);
  • M1 b corresponds to the abovementioned component M1, the matrix additionally being admixed with 2% by weight of carbon black.
  • M2 (SAN type): styrene-acrylonitrile-maleic anhydride (SAN-MA) terpolymer (S / AN / MA: 73/25 / 2.1) with an MA content of 2.1% by weight and an MVR of 22 cm 3/10 min at 220 ° C / 10kg (measured according to IS01 133);
  • M2b corresponds to the abovementioned component M2, the matrix additionally being admixed with 2% by weight of carbon black.
  • M3 (SAN type): blend of 33% by weight of M1 and 67% by weight of the SAN copolymer Luuran VLN, therefore 0.33% by weight of maleic anhydrideMA) in the entire blend;
  • M3b corresponds to the abovementioned component M3, the matrix additionally being admixed with 2% by weight of carbon black.
  • PA6 semi-crystalline, easy-flowing polyamide Durethan B30S
  • Glass filament cooper fabric (short names: GF-KG (LR) or LR), twill weave 2/2, basis weight 290 g / m 2 , roving EC9 68tex, finish TF-970, delivery width 1000 mm (type: 01 102 0800-1240; Manufacturer: Hexcel, obtained from: Lange + Ritter)
  • Glass filament cooper fabric short designations: GF-KG (PD) or PD
  • twill weave 2/2 basis weight 320 g / m 2
  • roving 320tex finish 350
  • delivery width 635 mm type: EC14-320-350, manufacturer and supplier : PD Glasseide GmbH Oschatz
  • Glass filament scrim (short name: GF-GE (Sae) or Sae) 0 45 90 -45 °, weight per unit area 313 g / m 2 , main roving 300tex, finish PA size, delivery width
  • Sae ns glass filament scrim 300 g / m 2 , manufacturer's name: Saertex new sizing, + 457-457 + 457-45 °
  • Glass fiber fleece (short name: GV50), basis weight 50 g / m 2 , fiber diameter 10 ⁇ , delivery width 640 mm (Type: Evalith S5030, manufacturer and supplier: Johns Manville Europe) Visual assessment
  • All produced composite fiber materials could be produced in each case as (large) sheetlike Orga- nobleche in a continuous process, which could be cut to size (in laminatable, customary transport dimensions such as 1 m x 0.6 m).
  • the embedded fiber material was just recognizable when examined in detail against the light.
  • the embedded fiber material was not / hardly recognizable even under closer light in the backlight.
  • LSM confocal laser scanning microscopy
  • Fiber-composite materials with four embedded layers of the respective fabric of fibers (here GF-KG (PD) (4) or Sae (4)) were produced in the respective matrix.
  • PD GF-KG
  • Sae (4) GF-KG
  • GV50 thin fiberglass mat
  • the mean wave depth (MW Wt) and the spatial ration value (Ra) were determined for numerous fiber composite materials. It was shown that the MW Wt is clearly ⁇ 10 ⁇ m for all fiber composite materials in which the matrix contains a functional component that can react with the fibers, whereas in fiber composite materials with comparable PA6 and PD (OD) matrices is clearly ⁇ 10 ⁇ .
  • the determined spatial values were also significantly lower for composite fiber materials according to the invention. By way of example, these are the measured values below.
  • the strength in the warp and weft directions was examined separately. It could be shown that the fiber composite materials are very stable in both warp and weft directions. In the warp direction, the fiber composite materials are usually even more stable than in the weft direction.
  • the matrix components A are as described above.
  • Fiber components B (unless described above)
  • FG290 glass filament fabric 290g / m 2 , manufacturer's name: Hexcel HexForce® 01202 1000 TF970
  • FG320 glass filament fabric 320g / m 2 , manufacturer's name: PD Glasseide GmbH Oschatz EC 14-320-350
  • Sae MuAx313, glass filament scrim 300g / m 2 , manufacturer's name: Saertex XE-PA-313-655
  • Sae ns glass filament scrim 300g / m 2 , manufacturer's name: Saertex new sizing, + 457-457 + 457-45 °
  • the following transparent fiber composite materials were produced, into each of which two-dimensional fiber material was introduced.
  • the fiber composite materials produced each had a thickness of about 1, 1 mm.
  • a thin fiberglass mat (GV50, see above) was applied to the produced fiber composite materials on both sides. This one has none noticeable influence on the mechanical or optical properties.
  • the following bending strengths according to DIN EN ISO 14125 were determined for the samples:
  • the following black-colored fiber composite materials were produced, in which 2% by weight of carbon black was added to the matrix and introduced into the respective flat fiber material.
  • the fiber composite materials produced each had a thickness of about 1, 1 mm.
  • a thin fiberglass mat (GV50, see above) was applied to the produced fiber composite materials on both sides. This has no noticeable influence on the mechanical or optical properties.
  • the following bending strengths according to DIN EN ISO 14125 were determined for the samples: Table. Intransparent fiber composite materials - bending strength
  • the fabrics used can be processed into fiber composites with particularly high flexural strength.
  • the fiber composite materials according to the invention in which the matrix contains a component which reacts with the fibers (here: maleic anhydride (MA)), have a significantly higher flexural strength than the comparative molding compositions without such a component, such as PC (OD) or PA6.
  • a bending strength of 150 MPa was found for the fiberglass material Luran 378P G7, which is not according to the invention and reinforced with short glass fibers, and therefore has a significantly lower flexural strength.
  • the impact resistance and puncture behavior (Dart Test to ISO 6603) was determined for the fiber composite materials. Again, the fiber composite materials showed a high stability of Fm> 3000 N.
  • the evaluation of different textile systems based on glass fibers with different matrix systems to a fiber composite material has shown that good fiber composite materials (as organic sheets and semi-finished products made from them) can be produced reproducibly. These can be made colorless or colored.
  • the fiber composite materials showed good to very good optical, haptic and mechanical properties (such as with regard to their flexural strength and puncture resistance). Mechanically, the tissues showed somewhat greater strength and rigidity than scrim.
  • the styrene copolymer-based matrices (SAN matrices) tended to result in better fiber composite materials in terms of mechanical properties than the alternative matrices such as PC and PA6.
  • the fiber composite materials according to the invention could be produced semi-automatically or fully automatically by means of a continuous process.
  • the fiber composite materials (organo-nobleche) according to the invention can be easily transformed into three-dimensional semi-finished products.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

L'invention concerne un procédé de fabrication d'un matériau composite à base de fibres (V), contenant des fibres de renforcement (B) et une masse de moulage en copolymère de styrène (A) thermoplastique, comprenant les étapes suivantes : a) fabrication d'un produit (G) textile planiforme ou tridimensionnel à partir des fibres de renforcement (B) et de fibres en copolymère de styrène (F) thermoplastiques, les fibres en copolymère de styrène (F) étant composées de la matière de la masse de moulage en copolymère de styrène (A) thermoplastique ; b) chauffage du produit textile (G) à une température qui est supérieure à la plage de fusion des fibres en copolymère de styrène (F) thermoplastiques ; c) refroidissement du matériau composite à base de fibres (V) obtenu à l'étape b).
PCT/EP2016/059061 2015-04-22 2016-04-22 Procédé de fabrication de matériaux composites à base de fibres thermoplastiques à base de copolymères de styrène Ceased WO2016170143A1 (fr)

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Cited By (1)

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CN118620345A (zh) * 2024-06-05 2024-09-10 揭阳市万生实业有限公司 一种abs复合材料及其制备方法

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GB1472195A (en) 1973-08-31 1977-05-04 Basf Ag Manufacture of
DE3614533A1 (de) * 1986-04-29 1987-11-05 Walter Isphording Verfahren zum herstellen von kompakten, eine verstaerkungseinlage aus fasern enthaltenden formkoerpern aus thermoplastischem kunststoff
EP0363608A1 (fr) 1988-09-22 1990-04-18 General Electric Company Mélange de polymères comprenant un polycarbonate aromatique, un copolymère et/ou polymère greffé contenant du styrène et un ignifugeant à base de phosphate, articles formés à partir de ce mélange
DE69010059T2 (de) 1989-04-14 1994-10-27 Hexcel S A Thermoplastische Gewebe.
TW235970B (en) 1993-06-23 1994-12-11 Prince Sports Group Inc Process for making fabrics, unidirectional tapes, and tubular structures
DE69218920T2 (de) * 1991-01-24 1997-07-17 Prince Sports Group Inc Borden Langfaseriger verstärkte thermoplastischer rahmen, insbesondere für einen tennisschläger
US20110020572A1 (en) 2009-07-25 2011-01-27 Lanxess Deutschland Gmbh Structural organosheet-component
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GB1472195A (en) 1973-08-31 1977-05-04 Basf Ag Manufacture of
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EP0363608A1 (fr) 1988-09-22 1990-04-18 General Electric Company Mélange de polymères comprenant un polycarbonate aromatique, un copolymère et/ou polymère greffé contenant du styrène et un ignifugeant à base de phosphate, articles formés à partir de ce mélange
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DE69218920T2 (de) * 1991-01-24 1997-07-17 Prince Sports Group Inc Borden Langfaseriger verstärkte thermoplastischer rahmen, insbesondere für einen tennisschläger
TW235970B (en) 1993-06-23 1994-12-11 Prince Sports Group Inc Process for making fabrics, unidirectional tapes, and tubular structures
US20110020572A1 (en) 2009-07-25 2011-01-27 Lanxess Deutschland Gmbh Structural organosheet-component
DE102010028433A1 (de) * 2010-04-30 2011-11-03 Deutsche Institute Für Textil- Und Faserforschung Denkendorf Hybridgarn zur Herstellung von Formteilen
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118620345A (zh) * 2024-06-05 2024-09-10 揭阳市万生实业有限公司 一种abs复合材料及其制备方法

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