WO2016170129A1 - Utilisation de matériaux composites renforcés de fibres dans la fabrication de textiles techniques - Google Patents

Utilisation de matériaux composites renforcés de fibres dans la fabrication de textiles techniques Download PDF

Info

Publication number
WO2016170129A1
WO2016170129A1 PCT/EP2016/059038 EP2016059038W WO2016170129A1 WO 2016170129 A1 WO2016170129 A1 WO 2016170129A1 EP 2016059038 W EP2016059038 W EP 2016059038W WO 2016170129 A1 WO2016170129 A1 WO 2016170129A1
Authority
WO
WIPO (PCT)
Prior art keywords
fiber composite
composite material
thermoplastic
matrix
styrene
Prior art date
Application number
PCT/EP2016/059038
Other languages
German (de)
English (en)
Inventor
Philipp Deitmerg
Norbert Niessner
Eike Jahnke
Original Assignee
Ineos Styrolution Group Gmbh
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ineos Styrolution Group Gmbh filed Critical Ineos Styrolution Group Gmbh
Publication of WO2016170129A1 publication Critical patent/WO2016170129A1/fr

Links

Classifications

    • 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
    • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
    • C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
    • 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
    • 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
    • C08J2325/12—Copolymers of styrene with unsaturated nitriles

Definitions

  • the present invention relates to the use of a fiber composite material (also called organic sheet) for the production of technical textiles, the fiber composite material comprising a thermoplastic molding material A, which has elastomeric properties, and at least one layer of the reinforcing fibers B.
  • the at least one layer of the reinforcing fibers B is embedded in the matrix of the thermoplastic molding compound A, the thermoplastic molding compound A having at least one chemically reactive functionality during the production of the material.
  • Fiber composite materials or organic sheets usually consist of a multiplicity of reinforcing fibers which are 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 are to prevent the occurrence of total failure (such as tearing or other fragmentation) in order to reduce the risk of accidents through 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, for example, good aging and corrosion resistance, compared to conventional, non-reinforced materials.
  • Strength and rigidity are adaptable to the load 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 mostly serves primarily for introducing the forces to be absorbed into the individual fibers and for maintaining 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.
  • fiber-matrix adhesion The strength of the embedding of the fibers in the polymer matrix (fiber-matrix adhesion) can also have a considerable influence on the properties of the fiber composite material.
  • reinforcing fibers are regularly pretreated.
  • so-called sizing agents sizing agents
  • Such sizing is applied regularly to the fiber during manufacture in order to improve the further processibility of the fibers (such as weaving, laying, sewing).
  • the sizing is undesirable for subsequent processing, it must first be removed in an additional process step, such as by burning down.
  • glass fibers are also processed without sizing.
  • a further adhesion promoter is applied in an additional process step for the production of the fiber composite material.
  • Sizing and / or adhesion promoters form on the surface of the fibers a layer which can substantially determine the interaction of the fibers with the environment.
  • adhesion agents are available.
  • the matrix to be used and the fibers to be used the person skilled in the art can select a suitable adhesion promoter which is compatible with the matrix and with the fibers.
  • a technical challenge is that if the total failure occurs, the fiber composite material may suffer a brittle fracture. Consequently, for example, in the manufacture of technical textiles, which are regularly exposed to high stress, pose a significant risk of accident of torn fibers.
  • fiber composite materials with a wide load range where total failure is unlikely. Desirable are also good optical properties, as well as the ability to produce by means of fiber composite materials components with smooth surfaces.
  • WO 2008/058971 describes molding compositions which use two groups of reinforcing fibers.
  • the groups of reinforcing fibers are each provided with different adhesion promoter components which effect the different fiber matrix adhesions.
  • the second fiber-matrix adhesion is less than the first fiber-matrix adhesion, and the near-surface layers of reinforcing fibers of reinforcing fibers of the first group are formed with greater fiber matrix adhesion.
  • the matrix materials proposed are thermosetting plastics such as polyester and the thermoplastics polyamide and polypropylene.
  • WO 2008/1 19678 describes a glass-fiber-reinforced styrene-acrylonitrile copolymer (SAN) which is obtained by using maleic anhydride group-containing styrene Copolymer and cut glass fibers in its mechanical properties is improved. It is therefore taught the use of short fibers. It is therefore taught the use of short fibers. However, there is no indication of fiber composite materials.
  • SAN glass-fiber-reinforced styrene-acrylonitrile copolymer
  • CN 101555341 describes mixtures of acrylonitrile-butadiene-styrene (ABS), glass fibers, maleic anhydride-containing polymers and epoxy resins.
  • ABS acrylonitrile-butadiene-styrene
  • maleic anhydride-containing polymers acrylonitrile-butadiene-styrene
  • epoxy resins epoxy resins.
  • ABS and the maleic anhydride-containing polymer are initially charged to add the epoxy resin and then the glass fibers.
  • the fluidity of such a mixture containing a (thermoset) epoxy resin is very limited.
  • KR 100376049 teaches mixtures of SAN, maleic anhydride and N-phenyl maleimide-containing copolymer, chopped glass fibers and an aminosilane-based coupling agent.
  • the use of such a coupling agent leads to additional processing steps and thus increases the production costs.
  • PC polycarbonate
  • suitable additives such as hyperbranched polyesters, ethylene / (meth) acrylate copolymers or low molecular weight polyalkylene glycol esters.
  • EP-A 2 251 377 describes organo-sheets treated with an aminosilane size. It is not taught to use organic sheets for the production of technical textiles.
  • Glass fibers are often treated in the prior art 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 Water in water can be improved. Thus, it is possible to obtain uniform sheets by the wet laying method.
  • 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).
  • 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, in addition, can enhance affinity for synthetic resins, thus promoting the strength and integrity of a composite.
  • a lubricant gives the glass fibers and their products suppleness and reduces the mutual friction of the glass fibers, as well as 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.
  • organo-functional silanes such as aminopropyltriethoxysilane, methacryloxypropyltrimethoxysilane, glycidyloxypropyltrimethoxysilane and the like can 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.
  • PC polycarbonate
  • a technical object of the invention is to produce a fiber composite material (organogelc) which has suitable properties for the production of technical textiles.
  • the fiber composite material should be based on an easy-to-process, highly solvent-resistant, high stress-crack resistant, solid composite material and have a smooth surface. Ideally, the fiber composite material comes without adhesion promoter.
  • a fiber composite material comprising at least one thermoplastic molding composition A, which has elastomeric properties, as a matrix, at least one layers of reinforcing fibers B, and optionally at least one additive C, wherein the at least one layer of the reinforcing fibers B in the matrix is embedded, and the thermoplastic molding compound A has at least one chemically reactive functionality, which reacts with chemical groups of the surface of the reinforcing fibers B during the manufacturing process of the fiber composite material, is particularly suitable for the production of technical textiles.
  • the resulting fiber composite material has good strength and is tearing and solvent resistant.
  • thermoplastic fiber composite material comprising (or consisting of)
  • thermoplastic molding compound A as matrix
  • thermoplastic molding composition A has elastomeric properties and at least one chemically reactive functionality during the manufacturing process of the thermoplastic fiber composite material, which in the manufacturing process of the fiber composite Material with chemical groups of the surface of reinforcing fibers B reacts for the production of technical textiles.
  • the present invention also relates, in other words, to a process for producing technical textiles comprising the following steps: (i) providing
  • thermoplastic molding compound A as matrix
  • thermoplastic molding compound A has at least one chemically reactive functionality which reacts with chemical groups of the surface of component B during the manufacturing process of the fiber composite material; (ii) contacting the components A and B, and optionally C, with each other, in particular by loading or coating the component B with a (preferably obtained by heating) viscous or liquid thermoplastic molding compound A, optionally further containing at least one additive C; and (iii) reacting the at least one chemically reactive functionality of component A with chemical groups of the surface of component B.
  • a received textile part (such as a fabric) can be sewn subsequently with one or more other textile parts according to the invention and / or one or more other textile parts according to the invention.
  • the fiber composite materials according to the invention can be designed so that they are printable and / or partially translucent.
  • the fiber composite materials according to the invention can be used to produce a variety of technical textiles which are particularly readily dyeable.
  • the invention particularly relates to the use of a thermoplastic fiber composite material as described above, containing (or consisting of) a) 30 to 95, in particular 45 to 80 wt .-%, particularly preferably 38 to 70 wt .-%, of the thermoplastic molding composition A. with elastomeric properties,
  • thermoplastic molding composition A comprises at least one (co) polymer having at least one chemically reactive functionality which reacts with chemical groups on the surface of the reinforcing fiber component B during the manufacturing process of the fiber composite material
  • a (co) polymer comprises at least one functional monomer A-1 whose functionality reacts with chemical groups on the surface of the reinforcing fiber component B during the production process of the fiber composite material.
  • the (co) polymer comprising monomer A-1 is also referred to herein as polymer component (A-a).
  • thermoplastic molding composition A may contain one or more (co) polymers which are optionally also free of such a chemically reactive functionality (therefore contain no functional monomer Al) and thus not with chemical groups on the surface during the manufacturing process of the fiber composite material the reinforcing fiber component B react.
  • a (co) polymer is also referred to herein as polymer component (A-b).
  • the invention particularly relates to the use of a thermoplastic fiber composite material as described above, wherein the thermoplastic molding material A is amorphous.
  • the invention relates to the use of a thermoplastic fiber composite material as described above, wherein the thermoplastic molding material A is amorphous and is based on an impact-modified styrene copolymer which has at least one chemically reactive functionality.
  • A is a SAN copolymer modified by monomers having a chemically reactive functionality.
  • Such a styrene copolymer when used as the polymer component (A-a), may be about a M-1-containing styrene copolymer (exemplified by a maleic anhydride-containing styrene copolymer). "Based thereon” is to be understood in the broadest sense as containing said component (s), preferably the said component (s) being greater than 50% by weight, more preferably greater than 75% by weight. even more preferably more than 90% by weight, even more preferably more than 95% by weight, or (largely) consisting of said component (s).
  • the invention particularly relates to the use of a thermoplastic fiber composite material as described above, wherein the matrix is based on a molding compound A which has at least one chemically reactive functionality, wherein the molding compound A is selected from the group consisting of: Styrene-based elastomers (S-TPE), hydrogenated or partially hydrogenated styrene-butadiene (block) copolymers, polyolefin-based thermoplastic elastomers, thermoplastic polyurethanes, and elastomeric polyether / esters (eg, polyester-based elastomer (e.g., of the HYTREL® type), if necessary; in mixture with polymers such as: polystyrene (transparent or impact-resistant), styrene-acrylonitrile polymers, acrylonitrile-butadiene-styrene copolymers, styrene-methyl methacrylate copolymers (SMMA), methacrylate-acryl
  • At least one of the (co) polymer components of the thermoplastic molding material A is a (co) polymer having at least one chemically reactive functionality as described herein (polymer component (A-a)).
  • polymer component (A-a) each of the copolymer components mentioned in the preceding paragraph can accordingly also have, in addition to the explicitly mentioned monomers, a reactive functionality which can react with the surface of the fibers B during the production of the fiber composite material.
  • each of the above-mentioned (co) polymers may also be a polymer component (A-a).
  • the above-mentioned polymer components in their use as polymer component (Aa) usually also at least one monomer Al, which mediates the chemically reactive functionality (hence the reaction with fibers B).
  • the polymer components mentioned above in their use as polymer component (Aa) may also additionally comprise a second monomer (or even a third monomer) which mediates the chemically reactive functionality.
  • any other (co) polymers without such functionality may be used in addition to the one or more polymer component (s) (A-a).
  • the abovementioned (co) polymers can be used, but then without the functionality (therefore without reactive monomer A-1).
  • the polymer component (A-a) of the thermoplastic molding composition A is based on a SAN copolymer.
  • the SAN copolymer then additionally comprises a monomer A-1 which reacts with the surface of the fibers B during the production process.
  • the invention relates to the use of a thermoplastic fiber composite material as described above, wherein the chemically reactive functionality of the thermoplastic molding composition A based on components selected from the group consisting of maleic anhydride, N-phenylmaleimide, tert-butyl (meth ) acrylate and glycidyl (meth) acrylate function, preferably selected from the group consisting of maleic anhydride, N-phenylmaleimide and glycidyl (meth) acrylate function.
  • the invention relates to the use of a thermoplastic fiber composite material as described above, wherein the thermoplastic molding material A 0.1 to 10 wt .-%, often 0.15 to 3 wt .-%, of monomers Al, based on contains the amount of component A, which have a chemically reactive functionality.
  • the invention relates to the use of a thermoplastic fiber composite material as described above, wherein the reinforcing fibers B consist of glass fibers which preferably contain as chemical-reactive functionality silane groups on the surface.
  • the invention relates to the use of a thermoplastic fiber composite material as described above, wherein the surface of the reinforcing fibers B contain one or more of the chemically reactive functionalities from the group: hydroxyl, ester and amino groups.
  • the invention relates to the use of a thermoplastic fiber composite material as described above, wherein the reinforcing fibers B consist of glass fibers which contain (preferably) as chemically reactive functionality silanol groups on the surface.
  • the invention relates to the use of a thermoplastic fiber composite material as described above, wherein the reinforcing fibers B are used in the form of a mat, a fabric, a mat, a nonwoven or a knitted fabric.
  • the invention relates to the use of a thermoplastic fiber composite material as described above, wherein the fiber composite material has a thickness of ⁇ 10 mm, preferably of ⁇ 2 mm, in particular of ⁇ 1 mm.
  • the invention relates to the use of a thermoplastic fiber composite material as described above, wherein the fiber composite material is layered and contains more than two layers.
  • the other layers may be the same or different in construction from those described above.
  • the invention particularly relates to the use of a thermoplastic fiber composite material as described above, for the production of surface materials for sports, leisure and safety shoes.
  • the invention relates to the use of a thermoplastic fiber composite material as described above, for the production of covers for high mechanical loads, in particular for sails.
  • the invention relates to a method for producing a thermoplastic fiber composite material as described above, comprising the steps: (i) providing:
  • thermoplastic molding material A having elastomeric properties, comprising a copolymer A-1 containing monomers A-1 having a chemically reactive functionality
  • step (iii) reacting the monomers A-1 of the copolymer A-1 with the chemically reactive functionality B-1 of the reinforcing fibers B from step (ii) to form covalent bonds.
  • the invention relates to technical textiles, produced from a fiber composite material as described above, which was produced as described above after the steps (i) to (iii).
  • the invention relates to textiles produced from a thermoplastic fiber composite material as described above containing (or consisting of) the components A to C.
  • the fiber composite material contains at least 20 wt .-%, usually at least 30 wt .-%, based on the total weight of the fiber composite material, the thermoplastic matrix M or the thermoplastic molding composition A, which has elastomeric properties (molding material A).
  • the thermoplastic molding compound A can also be referred to as a thermoplastic or (partially) crosslinked elastomer molding compound A.
  • the thermoplastic matrix (M) containing the molding compound A is in the fiber composite material preferably from 30 to 95 wt .-%, particularly preferably from 35 to 90 wt .-%, often from 35 to 75 wt .-% and in particular from 38 to 70% by weight, based on the fiber composite material, available.
  • the thermoplastic matrix M preferably corresponds to the thermoplastic molding compound A.
  • the molding material A consists mainly (more than 50%, in particular more than 90%) of a copolymer (A-1).
  • the molding material A is at least 75 wt .-%, preferably at least 90 wt .-% of the copolymer A-1.
  • the thermoplastic molding compound A can also consist only of copolymer A-1.
  • thermoplastics having elastomeric properties are suitable as molding material A, in particular styrene-based elastomers (S-TPE), hydrogenated or partially hydrogenated styrene-butadiene (block) copolymers, thermoplastic elastomers on polyols fin-base, thermoplastic polyurethanes and elastomeric polyether / esters of HYTREL® type used, if appropriate mixed with non-impact modified or impact-modified styrene copolymers, preferably acrylonitrile-butadiene-styrene copolymers (ABS), Methacrylate-acrylonitrile-butadiene-styrene copolymers (MABS) and acrylic ester-styrene-acrylonitrile copolymers (ASA).
  • ABS acrylonitrile-butadiene-styrene copolymers
  • MABS Methacrylate-acrylonitrile-butadiene-styren
  • At least one of the (co) polymer components of the thermoplastic molding composition A is a (co) polymer having at least one chemically reactive functionality as described herein (polymer component (Aa)) , Accordingly, it is preferred that at least one of the abovementioned polymer components (therefore at least one (optionally modified) polystyrene and / or at least one copolymer A-1 comprises at least one monomer A-1.
  • the polystyrene may therefore be a polystyrene-maleic anhydride copolymer.
  • one or more further optional (co) polymers without such functionality can be used. It will be understood that this may optionally also be polystyrene and / or a copolymer A-1 (each comprising no monomer A-1).
  • thermoplastic molding compound A (component 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 component A has amorphous, thermoplastic properties, is therefore fusible and (largely) non-crystalline.
  • the shrinkage of the component A, and therefore also of the entire fiber composite material is comparatively low.
  • the component A contains a partially crystalline fraction of less than 50 wt .-%, 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, ie there are areas, in which 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.
  • the thermoplastic molding compound A can also be a blend of amorphous thermoplastic polymers and semicrystalline polymers.
  • Component A may be, for example, a blend of an impact-modified styrene-acrylonitrile 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% by weight .-%, preferably less than 40 wt .-%, often less than 25 wt .-% should be.
  • the component A used comprises at least one copolymer A-1 which comprises monomers A-1 which form covalent or non-covalent bonds with the functional groups B-1 of the embedded reinforcing fibers B.
  • the proportion of monomers Al in the component A can be chosen variable. The higher the proportion of monomers Al and the functional groups (B1), the stronger the bond between the molding compound A and the reinforcing fibers B can be.
  • Monomers Al may still be present as monomers in copolymer A-1 or may be incorporated into copolymer A-1. Preferably, the monomers Al are incorporated in the copolymer A-1.
  • the copolymer A-1 is constructed with a proportion of monomers A1 of at least 0.1% by weight, for example from 0.1 to 10% by weight, preferably of at least 0.5% by weight, in particular of at least 1 wt .-%, z. B. from 1 to 3 wt .-%, based on A-1.
  • monomers Al which can form covalent bonds with the functional groups Bl of the fibers B, all monomers are suitable which have such properties.
  • monomers A1 preference is given to those which can form covalent bonds by reaction with hydroxyl or amino groups.
  • the monomers Al have:
  • copolymer A-1 or other (co) polymer contained in component A may contain one or more other monomers capable of covalent or noncovalent bonding with fibers B.
  • the monomers A-I are selected from the group consisting of:
  • Glycidyl (meth) acrylate (GM).
  • the monomers A-1 are selected from the group consisting of maleic anhydride (MA), N-phenylmaleimide (PM) and glycidyl (meth) acrylate (GM).
  • two of these monomers A-1 may be contained in the copolymer A-1.
  • the copolymer A-1 of the molding compound A may optionally contain further functional monomers A-II.
  • the matrix component M contains at least one thermoplastic molding compound A, in particular one suitable for the production of fiber composite materials.
  • amorphous thermoplastics having elastomeric properties are preferably used.
  • 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), wherein the impact-modified styrene-acrylonitrile copolymers with monomers (Al) are modified.
  • ABS acrylonitrile-butadiene-styrene copolymers
  • SMMA styrene-methyl methacrylate copolymers
  • MABS methacrylate-acrylonitrile-butadiene-
  • thermoplastic molding composition A at least one of the polymer components in the thermoplastic molding composition A is modified with monomer A-1 (polymer component (A-a)), preferably one or more of the abovementioned styrene copolymers is modified with monomer A-1.
  • Any other polymer components for example styrene copolymers, preferably those as mentioned above may optionally be additionally present in the thermoplastic molding composition A, which are not optionally modified with monomer A-1 (polymer component (A-b)).
  • Blends of the abovementioned copolymers (one or more polymer components (Aa) and optionally (Ab)) with polycarbonate or partially crystalline 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 .%.
  • SAN (M-1) copolymers (with modification by monomers A-1) as component of the thermoplastic molding composition A (optionally also as sole polymeric constituent).
  • Blends of the abovementioned styrene copolymers with polycarbonate or partially crystalline 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.
  • An inventive (a-methyl) styrene-methyl methacrylate copolymer (as polymer component (Aa)) as molding compound A is prepared from, based on the (o-methyl) styrene-methyl methacrylate copolymer, at least 50 wt .-%, preferably 55 to 95 wt .-%, particularly preferably 60 to 85 wt .-%, (a-methyl) styrene, and 4.9 to 45 wt .-%, preferably 14.9 to 40 wt%, methyl methacrylate and 0.1 to 5% by weight, preferably 0.1 to 3% by weight, of a monomer Al, such as maleic anhydride.
  • a monomer Al such as maleic anhydride
  • the (a-methyl) styrene-methyl methacrylate copolymer may be random or a block polymer.
  • Component A can also be prepared from, based on component A, at least 50% by weight, preferably 55 to 95% by weight, particularly preferably 60 to 85% by weight, of vinylaromatic monomer, 4.9 to 45% by weight. %, preferably 14.9 to 40% by weight, methyl methacrylate and 0.1 to 5 wt .-%, preferably 0.1 to 3 wt .-%, of a monomer Al, such as maleic anhydride.
  • An inventive acrylonitrile-butadiene-styrene copolymer as component A is prepared by known methods from styrene, acrylonitrile, butadiene and a functional further monomer Al, such as. For example, methyl methacrylate.
  • the modified ABS copolymer may, for. For example, up to 70% by weight (about 35 to 70% by weight) of butadiene, up to 99.9% by weight (about 20 to 50% by weight) of styrene and up to 38% by weight.
  • Component A can also be prepared from 3 up to 70% by weight (about 35 to 70% by weight) of at least one conjugated diene, up to 99.9% by weight (about 20 to 50% by weight) of at least one vinyl aromatic monomer and up to 38 wt .-% (about 9 to 38 wt .-%) of acrylonitrile and 0.1 to 20 wt .-%, preferably
  • a monomer A-l such as maleic anhydride.
  • the modified ABS copolymer may contain: 35 to 70% by weight of butadiene, 20 to 50% by weight of styrene and 9.9 to 38% by weight of acrylonitrile, and 0.1 to 5 wt .-%, preferably 0.1 to 3 wt .-%, of a monomer Al, such as maleic anhydride.
  • 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 9.9 to 38% by weight of acrylonitrile and 0.1 to 5% by weight.
  • % preferably 0.1 to 3 wt .-%, of a monomer A-
  • the inventive component A is a styrene / butadiene copolymer such as impact polystyrene, a styrene-butadiene block copolymer such as Styrolux®, Styroflex®, K-Resin, Clearen, Asaprene, a polycarbonate, an amorphous polyester or an amorphous polyamide.
  • styrene / butadiene copolymer such as impact polystyrene, a styrene-butadiene block copolymer such as Styrolux®, Styroflex®, K-Resin, Clearen, Asaprene, a polycarbonate, an amorphous polyester or an amorphous polyamide.
  • This may also be a polymer component as described above, which contains at least one functional monomer A1 in said molding composition.
  • one or more other (co) polymers without such functionality can be used.
  • Further preferred matrix materials as component A are styrene-based elastomers ("S-TPE”), which are known, inter alia, as Kraton® or Asaflex, which are preferably materials comprising linear, branched or star-shaped styrene-butadiene Hydrogenated or partially hydrogenated styrene-butadiene (block) copolymers may also be used, as are polyolefin-based thermoplastic elastomers, so-called TPOs, which may include polyethylene and / or polypropylene (block) copolymers, Likewise, thermoplastic polyurethanes (“U-TPE”) are among the possible matrix materials as component A, as well as technical elastomers (such as, for example, polyether / ester),
  • thermoplastic molding composition A is modified with monomer A-1 (polymer component (A-a)), preferably one or more of the abovementioned styrene-based elastomers is modified with monomer A-1.
  • polymer component (A-b) one or more other (co) polymers without such functionality
  • the matrix M can consist of at least two mutually different molding compositions A.
  • these various molding compound types may have a different melt flow index (MFI), and / or other co-monomers or additives.
  • 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.
  • the molding compositions A preferably have a molecular weight Mw of from 60,000 to 400,000 g / mol, often from 80,000 to 350,000 g / mol, where Mw can be determined by light scattering in tetrahydrofuran (GPC with UV detector).
  • Mw can be determined by light scattering in tetrahydrofuran (GPC with UV detector).
  • the molecular weight Mw of component A can vary within a range of +/- 20%.
  • Component A preferably contains a styrene copolymer modified by a chemically reactive functionality, which, apart from the addition of the monomers A1, is composed essentially of the same monomers as the "normal styrene copolymer".
  • Copolymer ", wherein the monomer content +/- 5%, the molecular weight +/- 20% and the melt flow index (determined at a temperature of 220 ° C and a load of 10 kg according to the ISO method 1 133) +/- 20% ISO Method 1 133 will preferably be understood as meaning DIN EN ISO 1 133-1: 2012-03.
  • melt flow rate (melt volume rate MVR), the thermoplastic polymer composition used as the polymer matrix A 10 to 70 cm 3/10 min, preferably 12 to 70 cm 3/10 min, particularly 15 to 55 cm 3/10 min at 220 ° C / 10kg (measured according to IS01 133).
  • the melt flow rate is (Melt Volume rate, MVR) of the thermoplastic polymer composition used as the polymer matrix A 10 to 35 cm 3/10 min, preferably 12 to 30 cm 3/10 min, particularly 15 to 25 cm 3/10 min at 220 ° C / 10kg (measured according to IS01 133).
  • melt flow rate (melt volume rate MVR) of the thermoplastic polymer composition used as the polymer matrix A 35 to 70 cm 3/10 min, preferably 40 to 60 cm 3/10 min, in particular 45 to 55 cm 3/10 min at 220 ° C / 10kg (measured according to IS01 133).
  • the viscosity number is 60 to 90 ml / g, preferably 65 to 85 ml / g, in particular 75 to 85 ml / g.
  • Suitable preparation methods for component A are emulsion, solution, bulk or suspension polymerization, preference being given to solution polymerization (see GB 1472195).
  • component A is isolated after the preparation by processes known to those skilled in the art, and preferably processed into granules. Thereafter, the production of the fiber composite materials can take place.
  • the fiber composite material contains at least 5 wt .-%, based on the fiber composite material, the reinforcing fiber B (component B).
  • the reinforcing fiber B in the fiber composite material is preferably from 5 to 70% by weight, particularly preferably from 10 to 65% by weight, often from 25 to 65% by weight and in particular from 29.9 to 61, 9 wt .-%, based on the fiber composite material included.
  • the reinforcing fiber B is preferably used as the sheet F.
  • the reinforcing fiber B can be any fiber whose surface has functional groups which can form a covalent bond with the monomers A-1 of the component A, which have a chemically reactive functionality.
  • continuous fibers including fibers which are the product of a single fiber twist
  • the reinforcing fibers B are therefore preferably not short fibers ("chopped fibers") and the fiber composite material is preferably not a short glass fiber reinforced material
  • At least 50% of the reinforcing fibers B preferably have a length of at least 5 mm, more preferably at least 10 mm or more than 100 The length of the reinforcing fibers B also depends on the size of the fabric made from the fiber composite material.
  • a fabric, fabric or knitted fabric differs from short fibers, since in the former, coherent, larger fabrics F are produced, which as a rule will be longer than 5 mm.
  • the fabrics, scrims, knitted fabrics, etc. are preferably present in such a way that they pass (largely) through the fiber composite material. Therefore, the fabrics or scrims are preferably such that they (substantially) pull through the existing of the fiber composite material textile. Pull through extensively here means that the fabric or scrim or continuous fibers pull through more than 50%, preferably at least 70%, in particular at least 90%, of the length of the textile.
  • the length of the textile is the largest extent of this in one of the three spatial directions.
  • the fabrics or scrims or continuous fibers pass through more than 50%, preferably at least 70%, in particular at least 90%, of the surface of the textile.
  • the area of the textile here is the area of the largest extent of the textile in two of the three spatial directions.
  • the textile is preferably (largely) flat.
  • the functional groups Bl on the surface of the reinforcing fiber B are selected from hydroxy, ester and amino groups. Particularly preferred are hydroxy groups.
  • the reinforcing fibers B are glass fibers which have hydroxyl groups in the form of silanol groups as chemically reactive functionality Bl on the surface.
  • the reinforcing fibers B may be embedded in the fiber composite material in any orientation and arrangement.
  • the reinforcing fibers B are present in the fiber composite material is not statistically uniformly distributed, but in levels with higher and those with lower proportion (therefore as more or less separate layers).
  • the reinforcing fibers B may be present, for example, as fabrics, mats, nonwovens, scrims or knitted fabrics. Laminated laminates formed in this way contain laminations of sheet-like reinforcing layers (of reinforcing fibers B) and layers of the polymer matrix wetting and holding them, containing at least one component A. According to a preferred embodiment, the reinforcing fibers B are embedded in layers in the fiber composite material , Preferably, the reinforcing fibers B are present as a flat structure F.
  • the fibers are ideally parallel and stretched.
  • endless fibers Tissues are created by the interweaving of continuous fibers, such as rovings.
  • the interweaving of fibers inevitably involves an ondulation of the fibers.
  • the ondulation causes in particular a reduction of the fiber-parallel compressive strength.
  • Mats are usually made of short and long fibers, which are loosely connected by a binder. Through the use of short and long fibers, the mechanical properties of components made of mats are inferior to those of fabrics.
  • 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. Knitted fabrics are thread systems through machine formation.
  • the fabric F is preferably a scrim, a fabric, a mat, a nonwoven or a knitted fabric. Particularly preferred as a fabric F is a scrim or a fabric.
  • the fiber composite material used optionally contains 0 to 40% by weight, preferably 0 to 30% by weight, particularly preferably 0.1 to 10% by weight, based on the buffers of components A to C, at least one of the components A and B different additive (auxiliaries and additives).
  • Particulate mineral fillers processing aids, stabilizers, oxidation retarders, agents against heat decomposition and decomposition by ultraviolet light, lubricants and mold release agents, flame retardants, dyes and pigments and plasticizers are to be mentioned.
  • esters as low molecular weight compounds are mentioned.
  • 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 may 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 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 using halogen-free compounds, for example phosphorus compounds, in particular phosphine oxides and derivatives of acids of phosphorus and salts of acids and acid derivatives of phosphorus. 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.
  • white pigments such as zinc oxide, Zinc sulfide, lead white (2 PbC03.Pb (OH) 2), lithopone, antimony white and titanium dioxide.
  • 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 (Fe304), spinel black (Cu (Cr, Fe) 204), manganese black (mixture of manganese dioxide, silicon oxide and iron oxide), cobalt black and antimony black, and particularly preferably carbon black, which is usually present in Form of Furnace- or gas black is used (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.
  • pigments or dyes in a mixture, for example, carbon black with Kupferphtha- locyaninen, since in general the color dispersion in the thermoplastics is facilitated.
  • Production and Use of the Fiber Composite Materials (Organo Sheet) Organic sheets are preferably processed by injection molding or pressing.
  • a further cost advantage can be generated by a functional integration, for example by the injection-molding or pressing of functional elements, since further assembly steps, for example the welding of functional elements, can be dispensed with.
  • the process for producing a fiber composite material includes the steps:
  • thermoplastic molding composition A having elastomeric properties, comprising a copolymer A-1 containing monomers Al, which have a chemically reactive functionality (and optionally one or more further (co) polymers (Aa) and / or (From));
  • thermoplastic molding compound A Melting the thermoplastic molding compound A and displacing (or bringing into contact) this molding compound A with the reinforcing fiber B from step (i);
  • the manufacturing process may include the phases of impregnation, consolidation and solidification (consolidation) common in the manufacture of composites, which process may be influenced by the choice of temperature, pressure and times employed.
  • the fiber composite material contains (or consists of) the fiber composite material: a) 30 to 95 wt .-% of at least one thermoplastic molding composition A with elastomeric properties,
  • Step (ii) of the process the melting of the component A and the placing (contacting) of this melt with the reinforcing fibers B, can be carried out in any suitable manner.
  • the matrix M can be converted into a flowable state and the reinforcing fibers B are wetted to form a boundary layer.
  • steps (ii) and (iii) may be performed simultaneously.
  • a chemical reaction takes place in which the monomers A-1 form a covalent bond with the surface of the reinforcing fibers B (usually via a bond to the functional groups B-1).
  • esterification e.g., esterification of maleic anhydride monomers with silanol groups of a glass fiber.
  • the formation of a covalent bond may also be initiated in a separate step (e.g., by temperature elevation, radical starter, and / or photo-initiation). This can be done at any suitable temperature.
  • the steps (ii) and / or (iii) are 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-340 ° C.
  • a temperature of at least 200 ° C preferably at least 250 ° C, more preferably at least 300 ° C, especially at 300 ° C-340 ° C.
  • An exception may be: a composition which releases reactive groups by thermal cleavage, such as tert-butyl (meth) acrylate, isobutene is released by thermal elimination at temperatures of about 200 ° C and the remaining functional group (essentially an acid function) can then react with the fiber surface.
  • the residence time 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 for the thermal treatment.
  • the process, in particular the steps (ii) and (iii), can in principle be carried out at any pressure (preferably atmospheric pressure or overpressure), with and without pressing of the components. When pressed with overpressure, the properties of the fiber composite material can be improved.
  • the surface quality can be substantially increased compared to the semicrystalline thermoplastics for such textiles, since the lower shrinkage of the amorphous thermoplastics, the surface topology, due to the fiber-rich (intersection point in tissues) and fiber-poor regions, essential is improved.
  • first layers of reinforcing fibers B can be prepared with differently prepared reinforcing fibers B, wherein an impregnation of the reinforcing fibers B takes place with the matrix of component A.
  • impregnated layers with reinforcing fibers B with different fiber-matrix adhesion can be present, which can be consolidated in a further working step to form a composite material as fiber composite material.
  • the reinforcing fibers B Before the layers of reinforcing fibers B are laminated with the matrix of component A, at least a part of the reinforcing fibers B can be subjected to a pretreatment in the course of which the subsequent fiber-matrix adhesion is influenced.
  • the pretreatment may include, for example, a coating step, an etching step, a heat treatment step or a mechanical surface treatment step.
  • a coating step for example, by heating a part of Reinforcing fibers B an already applied adhesion promoter are partially removed.
  • thermoplastic fiber composite material according to the invention for producing coverings for high mechanical loads
  • the reinforcing fibers B are used in the form of a mat, a fabric, a mat, a fleece or a knitted fabric, the fiber composite material is layered and contains more than two layers.
  • thermoplastic fiber composite material for producing coverings for high mechanical loads
  • reinforcing fibers B in the form of a gel, a fabric, a mat, a nonwoven or a knitted fabric are used and
  • the fiber composite material has a thickness of ⁇ 2 mm, preferably ⁇ 1 mm.
  • Such a thickness of ⁇ 2 mm may provide a (partially) elastic / flexible fiber composite material.
  • thermoplastic fiber composite material according to the invention for the production of covers for high mechanical loads
  • the reinforcing fibers B are used in the form of a mat, a fabric, a mat, a fleece or a knitted fabric, the fiber composite material is layered and contains more than two layers,
  • no adhesion promoter in particular no adhesion promoter from the group consisting of aminosilanes and epoxy compounds, is used in the production of the fiber composite material.
  • the present invention relates to the use of a thermoplastic fiber composite material having a thickness of ⁇ 10 mm, comprising:
  • thermoplastic, amorphous molding material A having elastomeric properties, which is based on an impact-modified styrene copolymer, comprising 0.1 to 10 wt .-% of monomers Al, based to the amount of component A, which have a chemically reactive functionality.
  • the reinforcing fibers B are preferably used in the form of a gel, a fabric, a mat, a nonwoven or a knitted fabric, and c) 0 to 40, in particular 0.1 to 10 wt .-%, of at least one additive C, wherein the at least one layer of the reinforcing fibers B is embedded in the matrix and wherein the thermoplastic molding composition A has elastomeric properties and in the manufacturing process of the thermoplastic fiber composite material having at least one chemically reactive functionality, which in the manufacturing process of the fiber composite material with chemical groups of Surface of the reinforcing fibers B reacts, for the production of technical textiles, in particular for the production of covers for high mechanical loads
  • the fiber composite material has other properties as described herein.
  • the reinforcement layers can be completely interconnected during the manufacturing process (laminating).
  • Such fiber composite material mats offer optimized strength and rigidity in the fiber direction and can be processed particularly advantageously.
  • the method can also include the production of a molded part T.
  • the method comprises, as a further step (iv), a three-dimensional shaping into a molded part T.
  • a three-dimensional shaping into a molded part T.
  • a cured fiber composite material can also be cold formed.
  • a (substantially) solid molding T is obtained at the end of the process.
  • the process comprises curing the product obtained from one of the steps (iii) or (iv).
  • 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 molded part T can still be finished (eg deburred, polished, dyed, etc.).
  • the process can be carried out continuously, semicontinuously or discontinuously.
  • the process is carried out as a continuous process, in particular as a continuous process for the production of smooth or three-dimensionally embossed films.
  • the reinforcing fibers B may be layer-wise impregnated and consolidated as layers of (or as sheets of F) reinforcing fibers B in a single processing step with the matrix M containing component A.
  • the production of the fiber composite material can be carried out in this way in a particularly efficient manner.
  • the behavior of the fiber composite material can be specifically and highly individually influenced. In each case different types of fibers or the same types of fibers can be used.
  • groups of reinforcing fibers B may each be provided with different adhesion promoter compositions effecting the different fiber matrix adhesions.
  • the different compositions may differ only in the concentrations or have other compositions. It is essential that significantly different fiber-matrix adhesions are set by the different adhesion promoter compositions.
  • the reinforcing fibers of the primer can be applied as part of the size. However, it can also be an additional process of thermal desizing or other desizing can be provided which destroys or removes the already applied sizing. Subsequently, the reinforcing fiber can then be coated with a finish containing the coupling agent and adapted to the particular matrix and the desired fiber-matrix adhesion.
  • the organic sheets can simultaneously take on functional properties through the use of different fibers (e.g., metal or aramid fibers).
  • leather-like technical textiles can also be produced.
  • the use as a transparent material is conceivable. This can be used to visualize underlying layers, thus creating a depth effect. Even in safety shoes, this material can have advantages due to the high strength.
  • the upper material can be fitted so that it is puncture- and cut-resistant, so that the foot is protected by the upper material. Textiles for covers
  • Sails are made of woven polyester threads.
  • the disadvantage of the polyester fiber is the lower strength compared to the glass fiber in the organic sheet, so that with the same load capacity a smaller weight of the glass fabric can be selected in the organic sheet.
  • thinner material can be used, which can lead to a cost and weight reduction.
  • the permeability through the complete impregnation of the fabric with, for example, Styroflex® much lower, which can be further increased the efficiency of the sail.
  • FIG. 1 shows the fiber composite materials which have been tested according to test no. 1 were obtained.
  • FIG. 1A shows the visual documentation.
  • FIG. 1B shows the microscopic appearance of a section through the laminar fiber composite material arranged in a horizontal orientation (left: 25-fold magnification, right: 50-fold magnification), wherein the fibers clearly show horizontally extending dark layer between the light 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. 3 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.
  • 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. 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.
  • FIG. 4C shows a magnification of 200 times, whereby it can be seen that the impregnation at individual points is not completely completed.
  • FIG. 5 shows the fiber composite materials which are determined according to test no. 5 were obtained.
  • FIG. 5A shows the visual documentation.
  • FIG. 5B 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 4C shows the 200-fold magnification, it can be seen that the impregnation is not completely completed in a few places.
  • FIG. 6 shows the production of the fiber composite materials (here: glass fiber fabric) in the press inlet V25-V28. It is clearly recognizable that such a production method allows continuous production. In addition, it can be seen from the imprinting of the pattern that the fiber composite material can also be shaped in three dimensions.
  • 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
  • the described fiber composite materials (organic sheets), in particular with amorphous, thermoplastic matrix are particularly suitable for the production of technical textiles see. Some examples are shown below.
  • Fiber composite material 1 is made by injection molding.
  • a component A consisting of
  • Example B Sails
  • Example C Seat Cover With the organic sheets according to the invention both a flexible (eg sail) and firm textile (for example shoe) are produced.
  • the crack resistance of the end products is compared to conventional textiles, without the fiber composite material according to the invention, significantly optimized.
  • 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
  • Impregnation Weft threads Central unimpregnated areas, all-round lightly impregnated
  • 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
  • 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
  • the fibrous composite materials according to the invention can be used to produce a wide variety of technical textiles which are particularly readily dyeable.
  • Example of multilayer organic sheets 40 wt .-%, based on the fiber composite material, of an acrylonitrile-styrene-maleic anhydride copolymer as thermoplastic molding material A (prepared from: 75 wt .-% of styrene, 24 wt .-% acrylonitrile and 1 wt .-% maleic anhydride) is compounded with 60 wt .-%, based on the fiber composite material, a glass-based reinforcing fiber with chemically reactive functionality (silane groups) on the surface [GW 123-580K2 of PD Glasseiden GmbH]. Further investigation of multilayer fiber composite materials
  • 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 twill weave (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 °, basis weight 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)
  • All produced composite fiber materials could each be produced as (large) flat textile materials in a continuous process, which could be cut to size (in laminatable, transportable 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.
  • a thin glass fiber fleece (GV50, see above) applied on both sides. This had no noticeable influence on the mechanical properties.
  • the mean wave depth (MW Wt) and the spatial ration value (Ra) were determined for numerous fiber composite materials. It was found that the MW Wt for all fiber composite materials in which the matrix contains a functional component that can react with the fibers is clearly ⁇ 10 ⁇ m, whereas in composite fiber 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 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 puncture behavior (dart test according to ISO 6603) was determined for the fiber composite materials.
  • the fiber composite materials showed a high stability of Fm> 3000 N.
  • the resulting fiber composite materials could be formed in good three-dimensional form, for example into half shell-shaped materials, such as shoe caps. It was also found that the resulting fiber composite materials could be printed and laminated.
  • 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 can be produced reproducibly. These can be produced colorless or colored and optionally subsequently dyed and / or laminated.
  • the fiber composite materials showed good to very good optical, haptic tables and mechanical properties (such as their puncture resistance). Mechanically, the tissues showed slightly greater strength 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 (organic sheets) according to the invention can be well converted into three-dimensional shapes, for example for shoe caps.

Landscapes

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

Abstract

L'utilisation d'un matériau composite thermoplastique renforcé de fibres, qui contient a) au moins une matière à mouler thermoplastique A servant de matrice, b) au moins une couche de fibres de renfort B, et c) éventuellement au moins un additif C, ladite au moins une couche constituée des fibres de renfort B étant insérée dans la matrice et la matière à mouler thermoplastique A possédant des propriétés élastomères et au moins une fonctionnalité chimiquement réactive qui, pendant le processus de fabrication du matériau composite renforcé de fibres, réagit avec des groupes chimiques de la surface des fibres de renfort B, est particulièrement adaptée à la fabrication de textiles techniques.
PCT/EP2016/059038 2015-04-22 2016-04-22 Utilisation de matériaux composites renforcés de fibres dans la fabrication de textiles techniques WO2016170129A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102015207366.1 2015-04-22
DE102015207366 2015-04-22

Publications (1)

Publication Number Publication Date
WO2016170129A1 true WO2016170129A1 (fr) 2016-10-27

Family

ID=55913600

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2016/059038 WO2016170129A1 (fr) 2015-04-22 2016-04-22 Utilisation de matériaux composites renforcés de fibres dans la fabrication de textiles techniques

Country Status (1)

Country Link
WO (1) WO2016170129A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022129045A1 (fr) * 2020-12-16 2022-06-23 Ineos Styrolution Group Gmbh Procédé de production d'un matériau composite renforcé par des fibres contenant un polymère thermoplastique

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2160778A1 (de) * 1971-12-08 1973-06-14 Basf Ag Glasfaserverstaerkte styrolpolymerisate
GB1472195A (en) 1973-08-31 1977-05-04 Basf Ag Manufacture of
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
US5008145A (en) * 1987-10-23 1991-04-16 The B. F. Goodrich Company Glass fiber reinforced poly(vinyl chloride) blend with improved heat distortion and tensile strength
KR100376049B1 (ko) 2000-12-28 2003-03-15 제일모직주식회사 유리섬유 강화 스티렌계 열가소성 복합재료
EP1923420A1 (fr) * 2006-11-14 2008-05-21 Bond Laminates Gmbh Materiau composite renforce par des fibres et procede de production de celui-ci
WO2008110539A1 (fr) * 2007-03-13 2008-09-18 Basf Se Matériau composite renforcé par fibres
WO2008119678A1 (fr) 2007-03-29 2008-10-09 Basf Se Compositions d'abs renforcé par de la fibre de verre, présentant des rigidité et ténacité améliorées
CN101555341A (zh) 2009-05-25 2009-10-14 国家复合改性聚合物材料工程技术研究中心 一种高强玻纤增强abs复合材料及其制备方法
EP2251377A1 (fr) 2009-05-11 2010-11-17 Basf Se Styrocopolymères renforcés
US20110020572A1 (en) 2009-07-25 2011-01-27 Lanxess Deutschland Gmbh Structural organosheet-component
WO2011023541A1 (fr) * 2009-08-31 2011-03-03 Basf Se Procédé de fabrication de copolymères san renforcés par des fibres de verre présentant une résistance aux impacts améliorée et une usinabilité simplifiée
CN102924857A (zh) 2012-08-23 2013-02-13 上海金发科技发展有限公司 一种玻纤增强苯乙烯/马来酸酐复合材料及其制备方法

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2160778A1 (de) * 1971-12-08 1973-06-14 Basf Ag Glasfaserverstaerkte styrolpolymerisate
GB1472195A (en) 1973-08-31 1977-05-04 Basf Ag Manufacture of
US5008145A (en) * 1987-10-23 1991-04-16 The B. F. Goodrich Company Glass fiber reinforced poly(vinyl chloride) blend with improved heat distortion and tensile strength
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
KR100376049B1 (ko) 2000-12-28 2003-03-15 제일모직주식회사 유리섬유 강화 스티렌계 열가소성 복합재료
WO2008058971A1 (fr) 2006-11-14 2008-05-22 Bond-Laminates Gmbh Matériau composite à fibres et procédé pour sa production
EP1923420A1 (fr) * 2006-11-14 2008-05-21 Bond Laminates Gmbh Materiau composite renforce par des fibres et procede de production de celui-ci
WO2008110539A1 (fr) * 2007-03-13 2008-09-18 Basf Se Matériau composite renforcé par fibres
WO2008119678A1 (fr) 2007-03-29 2008-10-09 Basf Se Compositions d'abs renforcé par de la fibre de verre, présentant des rigidité et ténacité améliorées
EP2251377A1 (fr) 2009-05-11 2010-11-17 Basf Se Styrocopolymères renforcés
CN101555341A (zh) 2009-05-25 2009-10-14 国家复合改性聚合物材料工程技术研究中心 一种高强玻纤增强abs复合材料及其制备方法
US20110020572A1 (en) 2009-07-25 2011-01-27 Lanxess Deutschland Gmbh Structural organosheet-component
WO2011023541A1 (fr) * 2009-08-31 2011-03-03 Basf Se Procédé de fabrication de copolymères san renforcés par des fibres de verre présentant une résistance aux impacts améliorée et une usinabilité simplifiée
CN102924857A (zh) 2012-08-23 2013-02-13 上海金发科技发展有限公司 一种玻纤增强苯乙烯/马来酸酐复合材料及其制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
R. GÄCHTER; H. MÜLLER: "Taschenbuch der Kunststoffadditive", 1983, CARL HANSER VERLAG, pages: 494 - 510

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022129045A1 (fr) * 2020-12-16 2022-06-23 Ineos Styrolution Group Gmbh Procédé de production d'un matériau composite renforcé par des fibres contenant un polymère thermoplastique

Similar Documents

Publication Publication Date Title
EP3286258B1 (fr) Procédé pour la fabrication d'un matériau composite fibreux constitué de polymères amorphes chimiquement modifiés avec des fibres de renforcement
EP3286256B1 (fr) Matériau composite translucide à base de fibres en polymères modifiés chimiquement
EP3286000A1 (fr) "organosheets" (plaques de composite thermoplastique renforcé de fibres) à base de polymère de styrène pour produits blancs
EP3286257B1 (fr) Procédé de fabrication de matériaux composites renforcés par des fibres à partir de polymères amorphes modifiés chimiquement
EP3285999A1 (fr) Utilisation d'un matériau composite fibreux ayant une structure en sandwich et un composant en matière alvéolaire
DE2423809A1 (de) Verfahren zur herstellung von kuenstlichem holz
EP3285998B1 (fr) Utilisation de materiaux composites fibreux pour produire des corps moulés transparents ou translucides
DE3117280A1 (de) Gegenstaende aus thermoplastischen polymeren, welche mit glasfasern verstaerkt sind
WO2016170129A1 (fr) Utilisation de matériaux composites renforcés de fibres dans la fabrication de textiles techniques
US20200231767A1 (en) Fibre-reinforced composite with reduced surface waviness
WO2015185573A1 (fr) Élément composite renforcé par fibres et procédé pour le produire
WO2016170143A1 (fr) Procédé de fabrication de matériaux composites à base de fibres thermoplastiques à base de copolymères de styrène
WO2016170127A1 (fr) Matériaux composites thermoplastiques renforcés de fibres à base de copolymères de styrène, et procédé de production desdits matériaux
DE102006010231A1 (de) Kunststoffhaltiges System
WO2022180018A1 (fr) Matériau composite renforcé par des fibres comprenant un (co)polymère de styrène et des fibres naturelles
WO2022129016A1 (fr) Matériau composite polymère thermoplastique contenant une charge renforcée par des fibres continues et ayant un bon lissé de surface
WO2022129045A1 (fr) Procédé de production d'un matériau composite renforcé par des fibres contenant un polymère thermoplastique
EP3147120A1 (fr) Materiau composite pour la fabrication d'objets moules, objet moule et procede de fabrication de l'objet moule
JANETZKO et al. Toughness Improvement in Hybrid Composites Made of Carbon Fibre Reinforced Polypropylene and Self-Reinforced Polypropylene B. FABICHab*, I. TAKETAª, L. GORBATIKHa, SV LOMOVa
EP3213903A1 (fr) Procede de fabrication d'un composant a partir d'une matiere plastique renforcee de fibres comprenant une surface fonctionnelle ou une surface decorative
EP2918407A1 (fr) Composite en fibres synthétiques, ainsi que procédé et structure stratifiée destinés à sa fabrication
EP2599624A1 (fr) Corps composite

Legal Events

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

Ref document number: 16720767

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16720767

Country of ref document: EP

Kind code of ref document: A1