EP4263680A1 - Matériau composite polymère thermoplastique contenant une charge renforcée par des fibres continues et ayant un bon lissé de surface - Google Patents

Matériau composite polymère thermoplastique contenant une charge renforcée par des fibres continues et ayant un bon lissé de surface

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Publication number
EP4263680A1
EP4263680A1 EP21836159.0A EP21836159A EP4263680A1 EP 4263680 A1 EP4263680 A1 EP 4263680A1 EP 21836159 A EP21836159 A EP 21836159A EP 4263680 A1 EP4263680 A1 EP 4263680A1
Authority
EP
European Patent Office
Prior art keywords
weight
composite material
fiber
thermoplastic
continuous reinforcing
Prior art date
Legal status (The legal status 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 status listed.)
Pending
Application number
EP21836159.0A
Other languages
German (de)
English (en)
Inventor
Felix KLAUCK
Pierre JUAN
Norbert Niessner
Eike Jahnke
André LÜCK
Florian Piott
Dietmar Drummer
Leo Hoffmann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ineos Styrolution Group GmbH
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 EP4263680A1 publication Critical patent/EP4263680A1/fr
Pending legal-status Critical Current

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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
    • 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
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
    • 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
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • 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
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/28—Glass
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/16—Ethene-propene or ethene-propene-diene copolymers
    • 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
    • C08J2400/00—Characterised by the use of unspecified polymers
    • C08J2400/22—Thermoplastic resins
    • 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/10—Homopolymers or copolymers of propene
    • C08J2423/12—Polypropene
    • 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/10—Homopolymers or copolymers of propene
    • C08J2423/14—Copolymers of propene
    • 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/16—Ethene-propene or ethene-propene-diene copolymers
    • 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
    • C08J2425/00—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
    • C08J2425/02—Homopolymers or copolymers of hydrocarbons
    • C08J2425/04—Homopolymers or copolymers of styrene
    • C08J2425/08—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
    • C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2469/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
    • 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
    • C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate

Definitions

  • the present invention relates to composite materials (organic sheets) containing a thermoplastic molding compound, at least one layer of continuous reinforcing fibers and at least one inorganic filler.
  • at least one fabric consisting of continuous reinforcing fibers is embedded in a matrix composition comprising the thermoplastic molding compound, the thermoplastic molding compound containing at least one polymer, in particular at least one polyolefin, and optionally at least one other polar-functionalized polymer.
  • the invention also relates to a method for producing the composite material according to the invention and its uses.
  • Composite materials or organic sheets often consist of a large number of reinforcing fibers embedded in a polymer matrix.
  • the areas of application of composite materials are diverse. For example, composite materials are used in the automotive and aviation sectors. The aim here is to prevent tearing or other fragmentation of the component through the use of composite materials, in order to reduce the risk of accidents caused by individual component fragments.
  • Many composite materials are able to absorb comparatively high forces under load before failure occurs.
  • a total failure of fibre-reinforced composite materials is expressed by the fact that components do not burst into many individual parts under bending stress when the maximum bending stress is exceeded, for example, but remain connected via the reinforcing fibers with individual fractures or biting points.
  • composite materials are distinguished from conventional, non-reinforced materials by their high strength and rigidity, which can be adjusted depending on the direction, while at the same time having a low density and other advantageous properties, e.g. good resistance to aging and corrosion.
  • the strength and stiffness of the composites can be adjusted to the direction and type of loading.
  • the fibers are primarily responsible for the strength and rigidity of the composite material.
  • their arrangement often determines the direction-dependent, mechanical properties of the respective composite material.
  • the primary purpose of the matrix is to introduce the forces to be absorbed into the individual fibers and to maintain the spatial arrangement of the fibers in the desired orientation.
  • the matrix protects the fiber from external influences and determines the long-term properties of the composite material. Above all, however, the choice of matrix material largely determines the external appearance of the composite material.
  • connection between fibers and polymer matrix and the critical fiber length play a particularly important role.
  • the strength of the embedding of the fibers in the polymer matrix can also have a significant influence on the properties of the composite material.
  • the process for producing the materials should be simple and inexpensive to carry out.
  • reinforcing fibers are regularly pre-treated with a so-called sizing (sizing agent).
  • a sizing (sizing agent) is often applied to the fiber during production in order to improve the further processing of the fibers (such as weaving, laying, sewing) at the same time.
  • reinforcing fibres such as glass fibres, are also processed without a size.
  • These glass fiber sizings often contain a large number of different components, such as film formers, lubricants, wetting agents and adhesion promoters.
  • the treatment of reinforcing fibers with a sizing serves, among other things, to prevent the fibers from being damaged by abrasion or to facilitate the cutting process of the fibers. Furthermore, the sizing can avoid agglomeration of the fibers and the dispersibility of fibers in water can be improved. However, a size can also contribute to the production of 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 composites. Typically, coupling agents in the size can increase the adhesion of polymers to the fiber surface by forming a bridging layer between both surfaces.
  • Organo-functional silane compounds such as aminopropyltriethoxysilane, methacryloxypropyltrimethoxysilane, glycidyloxypropyltrimethoxysilane and the like are often used.
  • a technical challenge is to avoid material breakage in the event of total failure of the fiber-reinforced composite materials, as this can result in a significant risk of accidents due to torn components. This is problematic, for example, in the case of components that are exposed to high loads.
  • WO 2008/058971 describes molding compositions which use different groups of reinforcing fibers.
  • the groups of reinforcing fibers are each provided with different adhesion promoter components, which are intended to bring about different fiber-matrix adhesions.
  • Thermosets such as polyester, and thermoplastics, such as polyamide and polypropene, are proposed as matrix materials. The aim of the application is to achieve improved fracture-mechanical behavior in the event of total failure.
  • the application WO 2010/074120 describes a fiber-reinforced polypropylene resin composition containing a reinforcing fiber, a largely unmodified polypropene resin and two other polypropene resins, comprising a carboxy-modified polypropene resin, the molecular weight of the various polypropylene resins is defined.
  • the aim here is to achieve the best possible fiber-matrix adhesion in order to optimize the mechanical properties of the composite material. In the application, this is achieved by adjusting the ratios of the two functional monomers.
  • the application WO 2019/086431 describes a fiber-reinforced composition characterized in that it contains a filler which remains in an outer region of the fiber bundles and thus reduces the shrinkage of the matrix.
  • the resin composition can be found both in the outer area with the fillers and in the inner area of the fiber bundles.
  • Glass fiber reinforced polypropylene resins are also described in CN-A 102 558685, CN-A 102 911433, CN 102924815, CN-A 103788470, CN-A 103819811, CN-A 104419058, CN-A 103772825, WO 2016/61, WO 2016/61 154791, CN-A 107 815013, CN-A 107 118437, WO 2019/010672 and CN-A 108164822.
  • thermoplastic molding compositions containing 5 to 95% of a copolymer A consisting of: 70-76% vinyl aromatic monomer A1, 24-30% vinyl cyanide monomer component A2 and 0-50% of one or more unsaturated, co- polymerizable monomers A3; 0-60% of a graft rubber B and 5-50% glass fibers C.
  • the molding compositions are produced by mixing the components and processed using the injection molding process.
  • thermoplastic fiber composite material consisting of a) 30 to 95% by weight of a thermoplastic matrix M, b) 5 to 70% by weight of a reinforcing fibers B, and c) 0 up to 40% by weight of an additive C.
  • the additives disclosed are particulate mineral fillers, processing aids, stabilizers, antioxidants, agents to prevent thermal decomposition and decomposition by ultraviolet light, lubricants and mold release agents, flame retardants, dyes and pigments and plasticizers.
  • WO 2016/170148 disclosed a method for producing a thermoplastic fiber composite material containing a) 30 to 95% by weight of a thermoplastic molding composition A as polymer matrix, b) 5 to 70% by weight of a fabric G made of reinforcing fibers B, and c) 0 to 40 wt.
  • WO 2016/170131 teaches a fiber composite material with a foam component as a strong, lightweight sandwich structure.
  • the fiber composite material contains a thermoplastic molding compound A and at least one layer of reinforcing fibers B.
  • the at least one layer of reinforcing fibers B is embedded in the matrix with the thermoplastic molding compound A, with the thermoplastic molding compound A having at least one chemically reactive functionality.
  • the fiber composite material has a further thermoplastic layer T and/or at least one foam layer S and is suitable for the production of molded parts.
  • Optional additives such as particulate mineral fillers, processing aids, stabilizers, antioxidants, heat and ultraviolet light degradation inhibitors, lubricants and mold release agents, flame retardants, dyes and pigments, and plasticizers may be included.
  • WO 2016/170098 discloses the use of a fiber composite material for producing transparent or translucent molded bodies, films and coatings.
  • the fiber composite material contains a thermoplastic molding compound A as a matrix and at least one layer of reinforcing fibers B, the at least one layer of reinforcing fibers B being embedded in the matrix with the thermoplastic molding compound A and the thermoplastic molding compound A having at least one chemically reactive functionality.
  • additives such as particulate mineral fillers, processing aids, stabilizers, antioxidants, thermal and ultraviolet light degradation inhibitors, lubricants and mold release agents, flame retardants, dyes and pigments, and plasticizers may be included.
  • WO 2016/170104 relates to the use of a fiber composite material in white goods.
  • the fiber composite material comprises a thermoplastic molding compound A and a reinforcing fiber B, with the layers of the reinforcing fiber B being embedded in a polymer matrix made from the thermoplastic molding compound A, and with the thermoplastic molding compound A having at least one chemically reactive functionality.
  • Disclosed as optional additives are particulate mineral fillers, processing aids, stabilizers, antioxidants, heat and ultraviolet light degradation inhibitors, lubricants and mold release agents, flame retardants, dyes and pigments, and plasticizers.
  • the filled glass mat thermoplastic (GMT) composite material comprises a polyolefin; glass fibers having a glass fiber length of at least about 6.4 mm (1/4 inch); and a mineral filler, the filler being selected from the group consisting of fiberglass, kaolin, mica, wollastonite, calcium carbonate, talc, precipitated calcium carbonate, barium sulfate, MOS2, ferrite, iron oxide, hollow spheres, aluminum trihydrate (ATH), Mg(OH)2 , TiÜ2, ZnO, barytes, satin white, iron oxide, metal powder, oxides, chromates, cadmium, fumed silicon dioxide, glass beads and basic lead silicate.
  • ATH aluminum trihydrate
  • DE 202017004083 U1 describes a fiber matrix semi-finished product which has a core of semi-finished fiber layers impregnated with at least one matrix component, preferably comprising polyamide or polypropylene, and at least one cover layer of a highly viscous, tough film which is used during the shaping of the Component such as a deep-drawing film is used, described, with which pores that can occur during the forming of conventional fiber matrix semi-finished products can be avoided or closed.
  • matrix component preferably comprising polyamide or polypropylene
  • the matrix component can optionally contain fillers and/or reinforcing materials selected from the group consisting of mica, silicate, quartz, wollastonite, kaolin, amorphous silicic acids, nanoscale minerals, in particular montmorillonite or nano-boehmite, magnesium carbonate, chalk, feldspar, barium sulfate, glass beads, Ground glass and/or fibrous fillers and/or reinforcing materials based on carbon fibers and/or glass fibers comprise.
  • EP-A 0945253 describes a filled thermoplastic glass mat composite (GMT) with a polyolefin, glass fibers and a filler.
  • the filled GMT composite has mechanical properties similar to unfilled GMT composites.
  • the preferred polyolefins include polypropylene, polyethylene, polymethylpentene, and copolymer blends thereof.
  • the glass fibers are longer than 6.4 mm (1/4 inch) and preferably at least 12.7 mm (1/2 inch) long.
  • the glass fibers can be continuous glass mats, such as unidirectional or random mats and woven or non-woven mats or chopped fibers.
  • the filler is selected from mineral, synthetic or vegetable sources and is preferably selected from mica, talc, calcium carbonate and barium sulphate.
  • EP-A 3394171 describes a fiber reinforced polypropylene composition with reduced weight and retained mechanical properties and articles formed therefrom.
  • the fiber reinforced polymer composition comprises
  • Cut glass fibers also known as short fibers or cut strands, are preferably used as fibers F.
  • the polymer composition can be processed into shaped articles, preferably injection molded articles or foamed articles.
  • DE 10 2017125438 describes a fiber-reinforced composite material comprising a fiber material which has a plurality of continuous fibers each formed from filaments, a plastic matrix material which fills an inner space between the filaments of a respective continuous fiber and surrounds the continuous fibers in an outer space, and a quantity of particles.
  • the particles preferably comprise glass particles, in particular hollow glass bodies, and/or carbon particles and/or mineral particles and/or ceramic particles and/or temperature- and/or pressure-expanded particles.
  • WO 2019/086431 discloses a fiber-reinforced composite material comprising a fiber material which has a plurality of continuous fibers each formed from filaments, a plastic matrix material which fills an inner space between the filaments of a respective continuous fiber and surrounds the continuous fibers in an outer space, and a lot of particles.
  • the particles are preferably selected from or consist of glass particles, in particular hollow glass bodies, and/or carbon particles and/or mineral particles and/or ceramic particles.
  • a first volume concentration of the particles in relation to the matrix material in the inner spatial area is lower than a second volume concentration of the particles in relation to the matrix material in the outer spatial area, the second volume concentration being homogeneous, and the second volume concentration in the outer spatial area being related to a volume concentration related to the matrix material of the filaments in the inner spatial area is adapted so that temperature-dependent material properties of the composite material in the outer spatial area and in the inner spatial area are adjusted.
  • the first volume concentration and the second volume concentration are preferably chosen such that a temperature-specific expansion coefficient of the composite material in the inner spatial area deviates by at most 15% from a temperature-specific expansion coefficient of the composite material in the outer spatial area.
  • WO 2018/114979 teaches an automotive interior part made from a thermoplastic composition comprising from 48 to 95% by weight based on the weight of the composition of at least one heterophasic propylene copolymer; wherein the heterophasic propylene copolymer consists of i) a propylene-based matrix consisting of a propylene homopolymer and/or a propylene- ⁇ -olefin copolymer, the matrix being composed of at least 90% by weight propylene and at most 10% by weight ⁇ -olefin based on the total weight of the propylene-based matrix, and ii) a dispersed ethylene- ⁇ -olefin copolymer comprising ethylene and at least one C3 to C10 ⁇ -olefin; - from 0 to 20% by weight, based on the weight of the composition, of an ethylene- ⁇ -olefin elastomer comprising ethylene and at least one C3 to C10 ⁇ -olefin;
  • An object of the invention is to provide an improved fiber reinforced composite material based on a thermoplastic (co)polymer which has good strength and high surface quality (i.e. low surface waviness), as well as resistance to stress cracking and solvents.
  • the composite material should be suitable for the production of moldings, films and coatings.
  • the production of the composite material should be possible at low cost and in a common process with the shortest possible cycle times.
  • a fiber-reinforced composite material with the above properties can be obtained by introducing a filler into a thermoplastic matrix polymer and impregnating the textile fibers to compensate for shrinkage and significantly reduce the measured surface waviness of the resulting fiber-reinforced composite material can.
  • thermoplastic molding composition and the filler are added in the form of powder, then in conventional manufacturing processes buildup forms on the pressing tool, which can affect the service life of the pressing tool.
  • thermoplastic molding composition and the filler in the form of a thermoplastic film or, alternatively, by introducing the thermoplastic molding composition as a thermoplastic film and the filler in the form of a powder, which is fed in below the thermoplastic film, adhesions on the pressing tool can be completely avoided .
  • the present invention relates to a fiber-reinforced, thermoplastic composite material V, comprising (or consisting of): a) >5 to ⁇ 20% by weight, preferably >7 to ⁇ 18% by weight, of a thermoplastic molding composition A, the thermoplastic molding composition A comprises at least one thermoplastic polymer A1, preferably at least one polyolefin, and optionally at least one polar functionalized polymer A2, comprising repeating units of at least one functional monomer A2-I; b) >20 to ⁇ 80% by weight, preferably >50 to ⁇ 80% by weight, of at least one continuous reinforcing fiber B in the form of filament bundles, comprising a large number of filaments, preferably selected from inorganic or organic reinforcing fibers, particularly preferably selected made of glass fibers and/or carbon fibers, particularly preferably made of glass fibers; c) > 1 to ⁇ 60% by weight, preferably > 3 to ⁇ 45% by weight, of at least one particulate, inorganic filler C,
  • Proportion C proportion by weight of component C in the entire composite material V in % by weight /100
  • OV,B coefficient of thermal volume expansion of component B in 1/K
  • ⁇ A average linear thermal expansion coefficient of component A
  • OB average linear thermal expansion coefficient of component B
  • the linear thermal expansion coefficient a (CLTE, Coefficient of Linear Thermal Expansion) is determined according to ISO 11359-2 (in particular ISO 11359-2:1999), with ISO 11359-1 (in particular ISO 11359-2: 2015) describes the general principles of thermomechanical test methods.
  • the linear thermal expansion coefficient a (in particular the average linear thermal expansion coefficient a) in 1/K results from the following relationship (III):
  • Lo reference length of the sample at room temperature in the direction of measurement.
  • the size and location of the temperature range AT is typically selected in accordance with the ISO 11359-1, 2 standards.
  • the coefficient of thermal expansion is determined in a temperature range ⁇ T in the range from -30 to 200°C, in particular 40 to 150°C, in particular 70 to 120°C.
  • the volume shrinkage of the at least one filler C is as follows:
  • the volume shrinkage of the at least one continuous reinforcing fiber B is as follows:
  • thermoplastic molding composition A in particular the proportion of the thermoplastic molding composition A can be adjusted accordingly, so that the sum of components A, B, C and D is 100% by weight and is not exceeded.
  • the proportions of components A, B, C and optionally D add up to 100% by weight.
  • a preferred embodiment of the invention relates to a fiber-reinforced, thermoplastic composite material V, comprising (preferably consisting of): a)> 5 to ⁇ 20 wt .-%, preferably> 7 to ⁇ 18 wt .-%, a thermoplastic molding composition A, wherein the thermoplastic molding composition A contains at least one thermoplastic polymer A1, preferably at least one polyolefin, and optionally at least one polar functionalized polymer A2, comprising repeating units of at least one functional monomer A2-I; and wherein the at least one polyolefin is selected from homo- or copolymers of ethene, propene, butene and/or isobutene, and wherein the polar functionalized polymer A2 is a copolymer of at least one repeating unit A2-I and at least one repeating unit A2-II is, wherein the at least one repeating unit A2-I is selected from maleic anhydride, N-phenylmaleimide, tert-
  • Proportion C proportion by weight of component C in the entire composite material V in % by weight /100
  • OV,B coefficient of thermal volume expansion of component B in 1/K
  • Proportion B proportion by weight of component B in the entire composite material V in % by weight/100; and where the following relationships hold: av,c and civ.B With:
  • ⁇ A average linear thermal expansion coefficient of component A
  • OB average linear thermal expansion coefficient of component B
  • Oc average linear thermal expansion coefficient of component C; and where the percentages by weight are in each case based on the entire fiber-reinforced, thermoplastic composite material V and the sum of components A, B, C and D is 100% by weight.
  • thermoplastic composite material V comprising (preferably consisting of): a)> 5 to ⁇ 20 wt .-%, preferably> 10 to ⁇ 18 wt .-%, a thermoplastic molding composition A, wherein the thermoplastic molding composition A contains at least one thermoplastic polymer A1, preferably at least one polyolefin, and optionally at least one polar functionalized polymer A2, comprising at least one functional monomer A2-I; b) >50 to ⁇ 80% by weight, preferably >50 to ⁇ 60% by weight, of at least one continuous reinforcing fiber B in the form of filament bundles, comprising a multiplicity of filaments; c) > 20 to ⁇ 45% by weight, preferably > 30 to ⁇ 40% by weight, of at least one inorganic, mineral filler C, preferably selected from inorganic carbonates, particularly preferably calcium carbonate, and d) > 0 to ⁇ 10% by weight %, preferably >
  • OV,B coefficient of thermal volume expansion of component B in 1/K
  • thermoplastic molding composition A contains at least one thermoplastic polymer A1, preferably at least one polyolefin, and optionally at least one polar functionalized polymer A2, comprising at least one functional monomer A2-I; b) >50 to ⁇ 80% by weight, preferably >70 to ⁇ 80% by weight, of at least one continuous reinforcing fiber B in the form of filament bundles, comprising a multiplicity of filaments; c) >1 to ⁇ 20% by weight, preferably >3 to ⁇ 10% by weight, of at least one inorganic glass filler C, in particular hollow glass bodies, and d) >0 to ⁇ 10% by weight, preferably >0.1 to ⁇ 5% by weight, of at least one further additive
  • Proportion C proportion by weight of component C in the entire composite material V in % by weight Z100
  • OV,B coefficient of thermal volume expansion of component B in 1/K
  • the composite material V is preferably characterized in that the thermoplastic molding compound A is inserted into the filament bundles of the continuous reinforcing fibers B penetrates, but the fillers C only penetrate up to a maximum of 10% into the filament bundles of the continuous reinforcing fibers B, based on surface areas of a cross section of the filament bundles. This is ensured by a suitable selection of the fillers and leads to an accumulation of the fillers C in the areas of the molding compound A that lie between the continuous reinforcing fibers B. In return, only small amounts of filler e are found within the continuous reinforcing fibers B, ie between the individual filaments of a filament bundle.
  • the filler C is also found almost exclusively in the outer area of the filament bundles, i.e. in an area up to 10% of the diameter of a single filament bundle. Suitable analysis methods for this are, in particular, electron microscopy or reflected light microscopy of the cross-sectional areas of the continuous reinforcing fibers B in the composite material V.
  • the composite material V contains at least 5% by weight, usually at least 7% by weight, based on the total weight of the composite material V, of the thermoplastic molding composition A.
  • the composite material V contains ⁇ 20% by weight, usually at most 18 % by weight, based on the total weight of the composite material V, of the thermoplastic molding composition A.
  • thermoplastic molding composition A is contained in the composite material V from 5 to ⁇ 20% by weight, preferably from 7 to 18% by weight, in particular 10 to 18% by weight, based on the composite material V.
  • thermoplastic molding composition A is preferably contained in the composite material V from 5 to 50% by volume, preferably from 10 to 40% by volume and particularly preferably from 15 to 35% by volume, based on the composite material V.
  • the thermoplastic molding composition A contains at least one thermoplastic polymer A1.
  • the thermoplastic polymer A1 is preferably an amorphous or partially crystalline polymer.
  • the thermoplastic polymer A1 is preferably an amorphous or semi-crystalline polymer selected from polystyrenes (PS), styrene/Ac- rylnitrile copolymers (PSAN), acrylonitrile/butadiene/styrene copolymers (ABS), acrylate/styrene/acrylonitrile copolymers (ASA), polycarbonates such as polycarbonates based on bisphenol A, polyesters, polyamides such as polyamide 6 and polyamide 6.6, polyolefins, and mixtures of the aforementioned polymers.
  • PS polystyrenes
  • PSAN styrene/Ac- rylnitrile copolymers
  • ABS acrylonitrile/butadiene/styrene copolymers
  • ASA acrylate
  • the thermoplastic polymer A1 comprises at least one polyolefin or consists of at least one polyolefin, it being possible for the polyolefin to be a polyolefin homopolymer and/or a polyolefin copolymer.
  • thermoplastic molding composition A can optionally comprise at least one polar functionalized polymer A2, which comprises repeating units of at least one functional monomer A2-I.
  • thermoplastic molding composition A can comprise further polymers A3 which are different from the polymers A1 and A2.
  • thermoplastic molding composition A1 contains up to 100% by weight of the at least one thermoplastic polymer A1 selected from homo- or copolymers of polyamide, polypropylene and polyethene.
  • thermoplastic molding composition A can also contain from 0 to 99% by weight of the at least one polymer A2 and/or the polymers A3, based in each case on the total weight of the thermoplastic molding composition A.
  • the thermoplastic molding composition A contains 60 to 99.9% by weight, more preferably 70 to 99.9% by weight, particularly preferably 75 to 99.9% by weight, particularly preferably 90 to 99% by weight. -%, more preferably 94 to 97% by weight, of the at least one thermoplastic polymer A1, in particular a thermoplastic polyolefin homopolymer or polyolefin copolymer A1, and 0.1 to 40% by weight, preferably 0.1 to 30% by weight %, particularly preferably 0.1 to 20% by weight, particularly preferably 1 to 10% by weight, more preferably 3 to 6% by weight of the at least one polar functionalized polymer A2, the figures in weight -% in each case based on the total weight of the thermoplastic molding composition A.
  • the thermoplastic molding composition A comprises the polymers A1 and A2 and comprises no further polymers A3.
  • the thermoplastic molding composition A contains the polymers A1 and A2 and optionally at least one further polymer A3.
  • the at least one optional polymer A3 can be selected from any thermoplastic polymer other than A1 and A2.
  • the at least one optional polymer A3 can be selected from polystyrenes (PS), styrene/acrylonitrile copolymers (PSAN), acrylonitrile/butadiene/styrene copolymers (ABS), acrylate/styrene/acrylonitrile copolymers (ASA), polycarbonates, polyesters , polyamides, polyolefins and mixtures thereof.
  • PS polystyrenes
  • PSAN styrene/acrylonitrile copolymers
  • ABS acrylonitrile/butadiene/styrene copolymers
  • ASA acrylate/styrene/acrylonitrile copolymers
  • polycarbonates polyesters , polyamides, polyolefins and mixtures thereof.
  • the at least one optional polymer A3 is particularly preferably selected from polyethene, ethene/propene copolymers, styrene polymers and styrene/acrylonitrile copolymers, with the proviso that the at least one polymer A3 is different from the polymers A1 and A2.
  • the polymer A3 can preferably be at least one amorphous polymer.
  • thermoplastic molding composition A has a proportion by weight of less than 50% by weight of polymers A3, more preferably less than 30% by weight.
  • the thermoplastic molding composition A preferably contains (or consists of): a-1) 50 to 99.9% by weight, preferably 70 to 99.9% by weight, particularly preferably 79 to 98% by weight, particularly preferably 90 up to 97% by weight of a thermoplastic polymer A1; a-2) 0.1 to 20% by weight, preferably 0.1 to 10% by weight, particularly preferably 1 to 8% by weight, particularly preferably 3 to 7% by weight, of the at least one polar functionalized polymer A2; a-3) 0 to 49.9% by weight, preferably 0 to 29.9% by weight, more preferably 1 to 20% by weight, of at least one further polymer A3; where the polymers A1, A2 and A3 are different from one another, and where the percentages by weight are in each case based on the total weight of the thermoplastic molding composition A and the sum of the components A1, A2 and A3 is 100% by weight.
  • the thermoplastic molding composition A preferably comprises the components A1, A2 and A3 or consists of these.
  • the thermoplastic molding composition A contains (or consists of): a-1) 60 to 99% by weight of at least one polymer A1 selected from the group consisting of propene homopolymers, propene copolymers, styrene copolymers, polyamides and polycarbonates; a-2) 1 to 40% by weight of a polar functionalized polymer A2; and a-3) 0 to 10% by weight of at least one further polymer A3, the polymer A3 being different from the polymers A1 and A2.
  • thermoplastic molding composition preferably consists of components A1, A2 and A3.
  • the thermoplastic molding composition A preferably contains at least 50% by weight, preferably at least 60% by weight, in particular at least 80% by weight, of at least one thermoplastic polymer A1, preferably at least one polyolefin, based on the total weight of the thermoplastic molding composition A.
  • the thermoplastic molding composition A contains the at least one polymer A1 in a range from 70 to 99.9% by weight, more preferably 90 to 99% by weight, particularly preferably 92 to 97% by weight, based on the total weight of the thermoplastic molding composition A
  • the thermoplastic polymer A1 is preferably an amorphous or partially crystalline homopolymer or copolymer of ethene, propene, butene and/or isobutene.
  • the polymer A1 particularly preferably comprises at least one propene homopolymer and/or propene-ethene copolymer (also referred to as polypropene impact copolymer).
  • the polymer A1 particularly preferably comprises (or is) a propene-ethene copolymer.
  • the polymer A1 is preferably at least one propene-ethene copolymer, the propene-ethene copolymer preferably having a melt mass flow rate MFR (determined according to DIN EN ISO 1133 at 230° C./2.16 kg ) in the range 40g/10min to 120g/10min, preferably 80g/10min to 120g/10min, more preferably 90g/10min to 110g/10min, and often about 100g/10min , having.
  • MFR melt mass flow rate
  • the polymer A1 is preferably at least one propene-ethene copolymer with a Density (according to DIN EN ISO 1183-1:2019-09) ⁇ 0.95 g/cm 3 , in particular in the range from 0.89 g/cm 3 to 0.93 g/cm 3 , preferably from 0.895 g/cm 3 to 0.915 g/ cm3 .
  • the thermoplastic polymer A1 is preferably at least one propene-ethene copolymer with a modulus of elasticity (measured according to DIN EN ISO 178) in the range from 1400 MPa to 2100 MPa, often around 1550 MPa.
  • the thermoplastic polymer A1 preferably has a thermal expansion coefficient OAI according to ISO 11359-1 and ISO 11359-2 in a range from 50* 10'6 K'1 to 100* 10 -6 K'1 , in particular in a range of 60* 1 O' 6 K' 1 to 90*1 O' 6 K' 1 .
  • thermoplastic polymer A1 preferably has a coefficient of thermal volume expansion OV,AI, determined according to the formula described above, in a range from 150*10 -6 K' 1 to 300*10' 6 K -1 , in particular in a range of 180*10 -6 K' 1 to 270*1 O' 6 K' 1 .
  • the thermoplastic A1 preferably has a melting point (DSC, measured according to DIN EN ISO 11357-3) in a range from 100 to 200.degree. C., in particular in a range from 135 to 160.degree.
  • Suitable polyolefins are available, for example, under the trade name Rigidex 380-H100 from INEOS Olefins & Polymers Europe.
  • the optional polar functionalized polymer A2 is different from polymer A1 and comprises repeating units of at least one functional monomer A2-I.
  • the thermoplastic molding composition A preferably contains at least 0.1% by weight, more preferably at least 1% by weight, particularly preferably at least 3% by weight, and in particular at least 3% by weight, of the at least one polar functionalized polymer A2, based on the total weight of the thermoplastic molding composition A.
  • the thermoplastic molding composition A preferably contains at most 30% by weight, more preferably at most 20% by weight, particularly preferably at most 15% by weight and in particular at most 10% by weight, of the at least one polar functionalized polymer A2, based on the total weight of the thermoplastic molding compound A.
  • the thermoplastic molding composition A preferably contains the at least one polar functionalized polymer A2 in the range from 0.1 to 30% by weight, preferably 0.1 to 20% by weight, particularly preferably 1 to 15% by weight, in particular preferably 3 to 10% by weight, based on the total weight of the thermoplastic molding composition A.
  • the polar functionalized polymer A2 serves as a compatibilizer between the thermoplastic molding composition A and the continuous reinforcing fiber B.
  • the polar functionalized polymer A2 has at least one polar, preferably chemically reactive, functionality (typically provided by the repeating units of the at least one functional monomer A2-I), which can react with chemical groups on the surface of the continuous reinforcing fiber B during the manufacturing process of the composite material V and bonds (covalent bonds, ionic bonds, van der Waals bonds) can form, resulting in a composite material V with good strength, in particular a good fiber-matrix adhesion is obtained.
  • the polar-functionalized polymer A2 often increases the polarity of the thermoplastic molding composition A, which increases the compatibility with polar surfaces of the reinforcing fibers, in particular the polar surfaces of glass fibers or surfaces of reinforcing fibers that are polar-functionalized by sizing agents.
  • the polar functionalized polymer A2 comprises at least 0.1% by weight, preferably 0.1 to 5% by weight, particularly preferably 0.1 to 3% by weight, particularly preferably 0.1 to 1 5% by weight, more preferably 0.1 to 0.5% by weight, based on the total weight of the polymer A2, of repeating units of the at least one functional monomer A2-I.
  • the at least one functional monomer A2-I is selected from the group consisting of maleic anhydride (MA), N-phenylmaleimide (PM), tert-butyl (meth)acrylate and glycidyl (meth)acrylate (GM), in particular selected from the group consisting of maleic anhydride (MA), N-phenylmaleimide (PM) and glycidyl (meth)acrylate (GM).
  • the polar-functionalized polymer A2 preferably comprises at least repeating units of a further monomer A2-II, which differs from the monomer A2-I.
  • the proportion of repeating units of the monomer A2-II is up to 99.9% by weight, preferably in a range from 95 to 99.9% by weight, particularly preferably 97 to 99.9% by weight, particularly preferably 98.5 to 99.9% by weight, more preferably 99.5 to 99.9% by weight, based on the total weight of the polymer A2, of repeating units of the at least one monomer A2-II.
  • the monomer A2-II is preferably selected from ethene, propene, butene and/or isobutene.
  • the polar functionalized polymer A2 is preferably a copolymer of repeating units of at least one monomer A2-II selected from ethene, propene, butene and/or isobutene, and repeating units of at least one functional monomer A2-I selected from maleic anhydride, N-phenylmaleimide , tert-butyl (meth)acrylate and glycidyl (meth)acrylate.
  • the polar functionalized polymer A2 is a copolymer of propene repeating units and repeating units of at least one functional monomer A2-I selected from maleic anhydride, N-phenylmaleimide, tert-butyl (meth)acrylate and glycidyl (meth) acrylate.
  • the polar functionalized polymer A2 is particularly preferably a propene graft copolymer, repeating units of the abovementioned functional monomers A2-I being grafted onto a polypropene.
  • the polar functionalized polymer A2 is preferably a propene-maleic anhydride graft copolymer, the graft core consisting predominantly of propene repeating units and the graft shell consisting predominantly of maleic anhydride repeating units.
  • Such polar functionalized polymers A2 and their preparation are described, for example, in US Pat. No. 10/189933 B2.
  • the polar functionalized polymer A2 is particularly preferably one or more propene-maleic anhydride graft copolymers which have a proportion of maleic anhydride as monomer A2-I in the range from 0.01 to 5% by weight, preferably 0.1 to 0 4% by weight, particularly preferably from 0.15 to 0.25% by weight, based on the total weight of the polar functionalized polymer A2.
  • the polar functionalized polymer A2 is a polymer which has a density (according to DIN EN ISO 1183-1:2019-09) in a range from 0.8 to 1.0 g/cm 3 , preferably in a range from 0.85 g/cm 3 to 0.95 g/cm 3 , in particular from 0.895 g/cm 3 to 0.915 g/cm 3 , often from about 0.9 g/cm 3 .
  • the polar functionalized polymer A2 preferably has a melt mass flow rate (MFR) (determined according to DIN EN ISO 1133, at 190° C./0.325 kg) in the range from 8 g/10 min to 15 g/10 min, in particular 9 g /10 min to 13 g/10 min.
  • MFR melt mass flow rate
  • the polar functionalized polymer A2 is preferably a polymer which has a melting point (measured according to DIN EN ISO 11357-3) in the range from 160 to 165° C. and/or a viscosity (measured according to DIN EN ISO 1628-1) in the range of 0.07 to 0.08 l/g.
  • the polymer A1 is a propene-ethylene copolymer, preferably with a density of 0.898 g/cm 3 to 0.900 g/cm 3 ; and the functionalized polymer A2 is a propene graft copolymer such as PRIEX® 20093 from BYK-Chemie.
  • the composite material V contains at least 20% by weight, preferably at least 40% by weight, particularly preferably at least 45% by weight, particularly preferably at least 50% by weight, based on the total weight of the composite material V, of the continuous reinforcing fibers B. In a preferred embodiment, the composite material V contains >50% by weight, based on the total weight of the composite material V, of the continuous reinforcing fibers B. The composite material V generally contains at most 80% by weight, based on the total weight of the composite material V, of the continuous reinforcing fibers B.
  • the at least one continuous reinforcing fiber B is contained in the composite material V from 20 to 80% by weight, preferably from 40 to 80% by weight, particularly preferably from 50 to 80% by weight, based on the composite material V. In a preferred embodiment, the at least one continuous reinforcing fiber B is contained in the composite material V in an amount of 51 to 80% by weight, based on the composite material V.
  • the continuous reinforcing fiber B is preferably contained in the composite material V from 20 to 80% by volume, preferably from 30 to 70% by volume and particularly preferably from 40 to 55% by volume, based on the composite material V.
  • the continuous reinforcement fibers B are preferably selected from glass fibers, carbon fibers, aramid fibers and natural fibers and/or mixed forms of the continuous reinforcement fibers B mentioned.
  • the continuous reinforcement fibers B are more preferably selected from glass fibers and/or carbon fibers, in particular glass fibers.
  • the density of the continuous reinforcing fiber B ranges from 1.4 g/cm 3 to 2.8 g/cm 3 .
  • the density of the continuous reinforcing fiber B selected from glass fibers is in the range from 1.8 g/cm 3 to 2.8 g/cm 3 .
  • the density of the continuous reinforcing fiber B selected from carbon fibers is in the range of 1.4 g/cm 3 to 1.9 g/cm 3 . Suitable methods for density determination are known to those skilled in the art.
  • the density of the continuous reinforcing fiber B is typically determined according to test standard ASTM C693.
  • the continuous reinforcing fiber B is typically a bundle of a multiplicity of filaments. Such bundles of filaments (also referred to as multifilaments) are formed during the manufacture of fibers.
  • the continuous reinforcing fiber B according to the invention therefore corresponds to a filament bundle made up of a large number of individual filaments.
  • the continuous reinforcing fiber B comprises a large number of individual filaments, the mean filament diameter being in a range from 2 to 35 ⁇ m, preferably from 5 to 25 ⁇ m.
  • the filaments of the continuous reinforcing fiber B are often bundled into rovings, fabrics and/or yarns.
  • the continuous reinforcing fibers B have one or more functional groups, preferably polar functional groups, particularly preferably functional groups selected from hydroxyl, ester, amino and silanol groups, on at least part of their surface.
  • the polar functional groups arranged on the surface of the continuous reinforcing fibers B can be formed directly by the fiber material itself (especially in the case of glass fibers) or by applying at least one sizing agent to the surface of the continuous reinforcing fibers B.
  • the continuous reinforcing fiber B may comprise a sizing agent applied to at least a portion of the surface of the continuous reinforcing fiber B.
  • Fibers for fibrous reinforcing materials are often treated with a sizing agent, particularly to protect the reinforcing fibers. Mutual damage caused by abrasion can thus be prevented. If a mechanical impact occurs, there must be no cross-fragmentation (breakage) of the reinforcing fibers.
  • the sizing agent can prevent agglomeration of the reinforcing fibers.
  • a sizing agent can also contribute to improved cohesion between the reinforcing fibers and the polymer matrix in the composite material V.
  • Suitable sizing agents generally include a large number of different ingredients such as film formers, lubricants, wetting agents and adhesives.
  • Film formers protect the fibers from rubbing against each other and can also increase affinity for polymers, thereby promoting composite strength and adhesion. Mention may be made of starch derivatives, polymers and copolymers of vinyl acetate and acrylic esters, epoxy resin emulsions, polyurethane resins and polyamides in a proportion of 0.5 to 12% by weight, based on the total weight of the sizing agent.
  • Lubricants give the fibers and their products flexibility and reduce the friction between the reinforcing fibers. Often, however, the liability between Reinforcement fiber and polymer affected by the use of lubricants. Mention should be made of fats, oils and polyalkyleneamines in an amount of 0.01 to 1% by weight, based on the total weight of the sizing agent.
  • wetting agents cause a reduction in surface tension and improved wetting of the filaments with the sizing agent.
  • polyfatty acid amides in an amount of 0.1 to 5% by weight, based on the total weight of the sizing agent, should be mentioned for aqueous finishing.
  • organofunctionalized silanes such as aminopropyltriethoxysilane, methacryloxypropyltrimethoxysilane, glycidyloxypropyltrimethoxysilane, and the like are used.
  • the continuous reinforcing fibers B of the present invention are (essentially) free of a sizing agent, i.e. they comprise less than 3% by weight, preferably less than 1% by weight, and in particular less than 0 1 wt of use according to the present invention. This can be achieved, for example, by thermal desizing processes (e.g. incineration of the sizing agent).
  • the continuous reinforcing fiber B is one or more glass fibers.
  • the at least one continuous reinforcing fiber B is particularly preferably one or more glass fibers whose surface comprises functional groups selected from hydroxyl, ester, amino and silanol groups, preferably silanol groups.
  • E Electric; Aluminum nium borosilicate glass with less than 2% alkali oxides)
  • S glass Strength; aluminum silicate glass with additions of magnesium oxide
  • E-glass fiber is often used as the standard fiber for general plastic reinforcement and electrical applications.
  • glass fibers with a filament diameter of 5 to 25 ⁇ m are used, which are usually combined with multifilament yarn (roving).
  • Such a multifilament yarn (roving) preferably has a fineness of 1200 tex. These are preferably used both as warp threads and as weft threads in a fabric G.
  • carbon fibers also called carbon fibers or carbon fibers
  • carbon fibers are industrially manufactured fibers made from carbon-containing starting materials, which are converted into graphite-like carbon by chemical reactions adapted to the raw material. Common isotropic and anisotropic types can be used, with anisotropic fibers typically having high strength and rigidity combined with low elongation at break in the axial direction.
  • Carbon fibers are often used as a stiffening component for lightweight construction.
  • carbon fibers have a diameter of about 5 to 9 microns, with 1,000 to 24,000 filaments usually being combined to form a multifilament yarn (roving).
  • the continuous reinforcing fiber B is preferably used as the fabric G.
  • the flat structure G is preferably a scrim, a woven fabric, a mat, a fleece, a knitted fabric, a mesh or a multiaxial scrim, which is formed at least partially from filament bundles of the continuous reinforcing fibers B.
  • the con- continuous reinforcing fiber B embedded in the composite material V as a fabric G preferably selected from wovens, mats, nonwovens, scrims and knitted fabrics, in particular wovens and scrims.
  • the further processing of continuous reinforcing fiber B to fabrics G in the form of semi-finished textile products is usually carried out on weaving machines, braiding machines or multiaxial knitting machines or, in the area of the production of fiber-reinforced plastics, directly on prepreg systems, pultrusion systems (pultrusion systems) or winding machines.
  • the continuous reinforcing fibers B can be embedded in the composite material V as a flat structure G in any orientation and arrangement.
  • the continuous reinforcing fibers B are often not statistically evenly distributed in the composite material V, but rather as a flat structure G, i.e. in levels with a higher and those with a lower proportion (therefore as more or less separate layers).
  • a laminate-like or laminar structure of the composite material V is preferably assumed, the composite material V comprising a multiplicity of flat structures G, comprising the continuous reinforcing fibers B.
  • Flat laminates formed in this way typically contain composites built up in layers from flat reinforcement layers (surface structure G comprising continuous reinforcement fibers B) and layers of a wetting and cohesive matrix composition (also referred to herein as matrix composition M), which comprises at least the thermoplastic molding composition A.
  • matrix composition M also referred to herein as matrix composition M
  • the continuous reinforcing fibers B are embedded in the composite material V in layers.
  • the continuous reinforcing fibers B are preferably present as a flat structure G.
  • the fibers are typically ideally parallel and stretched. Endless fibers are mostly used.
  • Fabrics are typically created by weaving endless fibers, such as rovings. The weaving of fibers is inevitably accompanied by a deflection (undulation) of the fibers. In particular, the undulation causes a reduction in the compressive strength parallel to the fibers.
  • mats best hen mostly made of long fibers that are loosely connected to each other with a binding agent. Due to the use of long fibers, the mechanical properties of components made of mats are inferior to those of fabrics.
  • Nonwovens are typically structures made of fibers of limited length, continuous fibers (filaments) and/or chopped yarns which have been joined together in any known manner to form a nonwoven and usually connected via a binder. Knitted fabrics typically refer to thread systems that are created and connected by stitch formation.
  • the invention relates to a composite material V which has a ribbing or a sandwich structure and is built up in layers.
  • the method steps for ribbing are known to those skilled in the art.
  • the invention relates to a composite material V described herein, the composite material V having a layered structure and containing more than two, often more than three, layers.
  • a layer comprises at least one sheet G made of continuous reinforcing fibers B, which is embedded in at least one matrix composition (herein also referred to as matrix composition M), which comprises at least the thermoplastic molding composition A.
  • the composite material V contains at least 1% by weight, preferably at least 3% by weight, particularly preferably at least 4% by weight, based on the total weight of the composite material V, of at least one particulate inorganic filler e.
  • the composite material V contains at most 60% by weight, preferably at most 45% by weight, particularly preferably at most 40% by weight, based on the total weight of the composite material V, of at least one particulate, inorganic filler C.
  • the at least one particulate, inorganic filler C is contained in the composite material V from 1 to 60% by weight, preferably 3 to 45% by weight, particularly preferably 5 to 40% by weight, based on the composite material V as a whole.
  • the composite material according to the invention contains
  • V at least 5 to 60% by volume, preferably 15 to 50% by volume and particularly preferably 25 to 40% by volume, based on the composite material V, of at least one particulate, inorganic filler C.
  • the particulate, inorganic filler C is preferably selected from glass fillers, mineral fillers, ceramic fillers and mixtures thereof.
  • Suitable glass fillers include, in particular, glass powder and hollow glass bodies, particularly preferably hollow glass bodies. Glass hollow bodies are characterized by a particularly low density and thus enable the production of fiber-reinforced composites
  • V with a low density are advantageous as light but mechanically stable materials.
  • Suitable mineral fillers include in particular silicates, phosphates, sulfates, carbonates, hydroxides and borates, particularly preferably carbonates.
  • Carbonates, in particular calcium carbonate, are advantageously characterized by worldwide availability at a low price and are also commercially available in many different size distributions.
  • Suitable ceramic fillers include, in particular, boron nitrite (BN - borazon), aluminum oxide (AI2O3), silicates, silicon dioxide, zirconium(IV) oxide, titanium(IV) oxide, aluminum miniumtitanate, barium titanate and silicon carbide (SiC) and boron carbide (B4C ). Ceramic fillers contribute in particular to improving the hardness and scratch resistance of the composite material V.
  • the at least one particulate, inorganic filler C is preferably selected from mineral fillers, which can be present both in crystalline form and in amorphous form (in particular as glass fillers).
  • the at least one particulate, inorganic filler C is preferably selected from glass powder, hollow glass bodies, amorphous silica; carbonates (e.g. magnesium carbonate, calcium carbonate (chalk)); powdered quartz; Mica; silicates such as clays, muscovite, biotite, suzoite, tin maletite, talc, chlorite, phlogopite, feldspar; kaolin and calcium silicates (such as wollastonite).
  • the composite material V according to the invention contains 3 to 45% by weight of at least one particulate, inorganic filler C in crystalline and/or amorphous form, selected from silicates, phosphates, sulfates, carbonates and borates.
  • the composite material V according to the invention comprises >20 to ⁇ 45% by weight, more preferably >30 to ⁇ 40% by weight, of at least one particulate, inorganic filler C selected from inorganic carbonates, preferably calcium carbonate. It was able to be shown that, despite this high amount of filler e, it is possible to provide a composite material V which has good mechanical properties and at the same time has surfaces with particularly low surface waviness, i.e. with a particularly smooth surface.
  • the composite material V according to the invention comprises >1 to ⁇ 20% by weight, preferably 3 to ⁇ 10% by weight, of at least one particulate, inorganic filler C selected from hollow glass bodies. It was possible to show that this quantity of hollow glass bodies is suitable for providing a low-density composite material V which has surfaces with particularly low surface waviness, i.e. with a particularly smooth surface.
  • inorganic fillers C which have a linear thermal expansion coefficient Oc (CLTE, Coefficient of Linear Thermal Expansion, measured according to ISO 11359-1 and ISO 11359-2) which is lower than the linear thermal expansion coefficient OA of the thermoplastic molding composition A, ie Oc ⁇ QA.
  • Oc linear thermal expansion coefficient
  • OA linear thermal expansion coefficient
  • the at least one particulate, inorganic filler C also preferably has a coefficient of thermal expansion Oc (CLTE, Coefficient of Linear Thermal Expansion, measured according to ISO 11359-1 and ISO 11359-2) that is 0.2 to 5 times greater as the coefficient of thermal expansion OB of the continuous reinforcing fiber B, more preferably 0.3 to 1 times, ie, 0.2 OBS OC S 5 OB, particularly 0.3 OBS OC ST OB.
  • CLTE coefficient of thermal expansion
  • Oc Coefficient of Linear Thermal Expansion
  • the particulate, inorganic filler C preferably has a coefficient of linear thermal expansion Oc (CLTE, Coefficient of Linear Thermal Expansion, measured according to ISO 11359-1 and ISO 11359-2) in the range from 2*10' 6 K' 1 to 20*1 O ' 6 K' 1 , preferably 5*1 O' 6 K' 1 to 15*10 -6 K' 1 , particularly preferably 7*1 O' 6 K' 1 to 12*10 -6 K' 1 .
  • CLTE coefficient of linear thermal expansion
  • inorganic fillers C are used for which the following relationship (II) applies: 0.1 to 2 (II) With:
  • Proportion C proportion by weight of component C in the entire composite material V in % by weight Z100
  • OV,B coefficient of thermal volume expansion of component B in 1/K
  • ⁇ A average linear thermal expansion coefficient of component A
  • OB average linear thermal expansion coefficient of component B
  • Oc mean linear thermal expansion coefficient of component C. Details for determining the linear thermal expansion coefficient a and the coefficient of thermal volume expansion Ov are described above.
  • V a vr x Antell C x Density B in q/ml
  • the density of the inorganic fillers C is preferably in a range of 0.1 to 5 g/ml, more preferably in particular 0.2 to 4 g/ml, especially 0.2 to 2.8 g/ml. Suitable methods for determining the density are known to those skilled in the art.
  • the density of inorganic fillers C is typically determined according to the test standard DIN-ISO 787/10.
  • the density of hollow glass spheres, which can preferably be used according to the invention as particulate, inorganic filler e, is preferably in a range from 0.1 to 1.0 g/ml, more preferably in a range from 0.2 to 0.6 g/ml. ml.
  • the density of carbonates which can preferably be used according to the invention as particulate, inorganic filler C, is preferably in a range from 1.0 to 4.0 g/ml, more preferably in a range from 2.0 to 2.8 g/ml. ml.
  • the particulate, inorganic filler C is typically added to the thermoplastic molding composition A before the components are contacted with the continuous reinforcing fiber B.
  • all three components data are combined in one process step. Further details on the production of the composite material V according to the invention can be found in the section on the production process contained herein.
  • the composite material V according to the invention can optionally contain 0 to 10% by weight, preferably 0 to 5% by weight, particularly preferably 0.01 to 10% by weight, particularly preferably 0.1 to 5% by weight, based on the total Composite material V, one or more additives D included.
  • the optional additive D is customary auxiliaries and additives that are different from components A to C.
  • Typical plastic additives are described, for example, in H. Zweifel et al., Plastics Additives Handbook, Hanser Verlag, 6th edition, 2009.
  • the additives D are typically added to the thermoplastic molding composition A.
  • the at least one further additive D can be selected from processing aids, stabilizers, lubricants and mold release agents, flame retardants, dyes, pigments and plasticizers.
  • stabilizers for example, antioxidants (oxidation retardants) and agents against heat decomposition (heat stabilizers) and decomposition by ultraviolet light (UV stabilizers) are used.
  • Suitable UV stabilizers include various substituted resorcinols, salicylates, benzotriazoles and benzophenones. UV stabilizers are typically used in amounts of up to 2% by weight, preferably from 0.01 to 2% by weight, based on the composite material V as a whole. Common UV stabilizers are described, for example, in H. Zweifel et al., Plastics Additives Handbook, Hanser Verlag, 6th edition, 2009, pp. 246-329.
  • antioxidants and heat stabilizers are sterically hindered phenols, hydroquinones, substituted representatives of this group, secondary aromatic amines, optionally in combination with phosphorus-containing acids or their salts, and mixtures of these compounds.
  • Common antioxidants are, for example, in H. Zweifel et al., Plastics Additives Handbook, Hanser Verlag, 6th edition, 2009, pp. 40 to 64.
  • Antioxidants of the Irganox® (BASF) type are preferably used.
  • Antioxidants and heat stabilizers are typically used in amounts of up to 1% by weight, preferably from 0.01 to 1% by weight, based on the composite material V as a whole.
  • the composite material according to the invention contains
  • V one or more lubricants and mold release agents as additives D.
  • Common lubricants and mold release agents are described, for example, in H. Zweifel et al., Plastics Additives Handbook, Hanser Verlag, 6th edition, 2009, pp. 563-580.
  • suitable lubricants and mold release agents are stearic acid, stearyl alcohol, stearic acid esters and amides, and esters of pentaerythritol with long-chain fatty acids.
  • the calcium, zinc or aluminum salts of stearic acid and dialkyl ketones, for example distearyl ketone can be used.
  • ethene oxide-propene oxide copolymers can also be used as lubricants and mold release agents.
  • Natural and/or synthetic waxes can also be used. Examples include PP wax, PE wax, PA wax, grafted PO wax, HDPE wax, PTFE wax, EBS wax, montan wax, carnauba wax and beeswax.
  • Lubricants and mold release agents are typically used in amounts of up to 1% by weight, preferably from 0.01 to 1% by weight, based on the composite material V as a whole.
  • the composite material according to the invention contains
  • V 0.01 to 1 wt. %, preferably 0.1 to 0.9 wt 1-glycerol monostearate.
  • Suitable flame retardants can be halogen-containing or halogen-free compounds.
  • Suitable halogen compounds are chlorinated and/or brominated compounds, with brominated compounds being preferable to chlorinated ones.
  • Halogen-free compounds such as, for example, phosphorus compounds, in particular phosphine oxides and derivatives of phosphorus acids and salts of acids and acid derivatives of phosphorus, are preferably used.
  • Phosphorus compounds particularly preferably contain ester, alkyl, cycloalkyl and/or aryl groups. are also suitable Oligomeric phosphorus compounds with a molecular weight of less than 2000 g/mol, as described in EP-A 0 363 608, for example.
  • pigments and dyes can be present as additives D in the composite materials V according to the invention. These are typically present in amounts of from 0 to 10% by weight, preferably from 0.1 to 10% by weight and in particular from 0.5 to 8% by weight, based on the composite material V as a whole.
  • Typical pigments for coloring thermoplastics are well known, see e.g. H. Zweifel et al., Plastics Additives Handbook, Hanser Verlag, 6th edition, 2009, pp. 855-868 and 883-889 as well as R. Gumbleter and H. Müller, Taschenbuch der Kunststoffadditive, Carl Hanser Verlag, 1983, pp. 494 to 510.
  • the first preferred group of pigments are white pigments, such as zinc oxide, zinc sulfide, white lead (2 PbCOs ⁇ Pb(OH)2), lithopone, antimony white and titanium dioxide. Of the two most common crystal modifications (rutile and anatase type) of titanium dioxide, the rutile form in particular is used to whiten the molding compositions according to the invention.
  • Another preferred group of pigments are black color pigments, such as iron oxide black (FesO ⁇ , spinel black (Cu(Cr,Fe)2O4), manganese black (mixture of manganese dioxide, silicon oxide and iron oxide), cobalt black and antimony black, and particularly preferably carbon black is usually used in the form of furnace or gas black (see G. Benzing, Pigmente für Anstrichstoff, Expert-Verlag (1988), p. 78ff).
  • inorganic colored pigments such as chrome oxide green
  • organic colored pigments such as azo pigments and phthalocyanines
  • Such pigments are generally commercially available.
  • the continuous reinforcing fibers B can also comprise additives, in particular in the form of a surface coating, a so-called size (size).
  • size size
  • sizing agents generally contain a large number of different ingredients such as film formers, lubricants, wetting agents and adhesives. These are described in more detail in the description of continuous reinforcing fibers B section herein.
  • Another subject of the invention is a process for producing the composite materials V according to the invention, the process comprising at least the following process steps: i) providing at least one continuous reinforcing fiber B, at least one thermoplastic molding composition A, at least one particulate inorganic filler C, and optionally at least an additive D; ii) combining the at least one thermoplastic molding composition A, the at least one particulate inorganic filler C, and optionally the at least one additive D, with the at least one continuous reinforcing fiber B; iii) impregnation of the continuous reinforcing fiber B with the at least one thermoplastic molding compound A, the at least one particulate, inorganic filler C, and optionally the at least one additive D, in order to obtain a composite material V; iv) consolidation of the composite V obtained; v) optional solidification of the composite material V obtained and/or optional further process steps.
  • composition of the composite material V and the components A, B, C and D, as described above in connection with the composite material V also apply in a corresponding manner to the method according to the invention.
  • the continuous reinforcing fiber B is preferably provided in the form of a flat structure, in particular a flat structure G.
  • This is preferably provided flat, in its full surface area.
  • the surface filaments F described herein, such as woven fabrics, mats, fleeces, scrims or knitted fabrics, comprising the continuous reinforcing fibers B are used. More preferably, woven fabrics or scrims, in particular woven fabrics, which comprise the continuous reinforcing fibers B or consist of them, are used.
  • the sheet G has a first and a second surface.
  • Components A and optionally D can be provided as a powder, as granules, as a melt or as a film, alone or in combination with the filler e. To this end, it is generally advantageous first to produce a thermoplastic matrix composition M which comprises at least components A and optionally D.
  • the thermoplastic matrix composition M contains at least the thermoplastic molding composition A described herein, which comprises at least one thermoplastic polymer A1, and optionally at least one polar functionalized polymer A2, comprising at least one repeating unit of a functional monomer A2-I, and optionally further polymers A3 and/or optional Additive D, contains.
  • the at least one particulate, inorganic filler e described herein, in particular hollow glass bodies and/or carbonates, can be introduced into the thermoplastic matrix composition M.
  • the thermoplastic matrix composition M comprises at least one thermoplastic molding composition A and optionally the additives D or consists of these components A and D.
  • the particulate, inorganic filler C is introduced into the thermoplastic matrix composition M to form a mixture To obtain matrix composition M and filler C.
  • the thermoplastic matrix composition M is provided by mixing the molding composition A and optionally the additives D, with the filler C also being able to be introduced into the matrix composition in the same process step.
  • the thermoplastic matrix composition M comprises the thermoplastic molding composition A and optionally the additives D, and is (essentially) free of the particulate inorganic filler C.
  • the inorganic filler is independent of the thermoplastic matrix composition M during the production of the Composite material V introduced into this. The different manufacturing processes are described in more detail below.
  • the thermoplastic matrix composition M can be provided by means of known methods, in particular by jointly extruding, kneading and/or rolling the polymers A1 and optionally A2 and/or A3 with the optional additives D. If the filler C is to be used together with the thermoplastic matrix composition M in the production of the composite material V, the filler C can advantageously also be combined with the polymers A1 and, if appropriate, A2 and/or A3 with the optional additives D by joint extrusion, kneading and/or or rollers can be incorporated into the thermoplastic matrix composition M.
  • the thermoplastic matrix composition M can be provided as a powder, as granules, as a melt or as a film.
  • the thermoplastic matrix composition M is preferably provided as a film, in particular as a film with a thickness of 25 ⁇ m to 500 ⁇ m, preferably 50 to 400 ⁇ m, particularly preferably 65 to 200 ⁇ m.
  • the film can include the filler C or be (essentially) free of filler C.
  • thermoplastic matrix composition M can thus be brought together in process step (ii) as a powder, as granules, as a melt or as a film, alone or in combination with the filler C with the fabric G made of continuous reinforcing fibers B.
  • components A and optionally D are combined with continuous reinforcing fiber B, preferably as a film, i.e. a film of matrix composition M, and component C as a powder.
  • components A, C and optionally D are combined with continuous reinforcing fiber B as a film, i.e. a film of matrix composition M and filler C.
  • components A and optionally D are brought together as a film with the continuous reinforcing fiber B, where the film can optionally comprise the filler C.
  • the film preferably has a thickness of 25 ⁇ m to 500 ⁇ m, preferably 50 to 400 ⁇ m, particularly preferably 65 to 200 ⁇ m.
  • the thermoplastic matrix composition M comprises 20 to 80% by volume, preferably 20 to 70% by volume, in particular 30 to 60% by volume, based on the total volume of the matrix composition M, of the at least a particulate, inorganic filler C, preferably selected from particulate mineral or amorphous (glass-like) spherical fillers, preferably selected from hollow glass spheres or carbonates.
  • the remainder of the thermoplastic matrix composition M consists of the thermoplastic molding composition A described herein, which preferably consists of the polymers A1 and A2, and optionally the additives D.
  • the at least one thermoplastic molding composition A, the at least one particulate, inorganic filler C, and optionally the at least one further additive D, are combined with the at least one continuous reinforcing fiber B, preferably at elevated temperature.
  • the components A, B, C and optionally D are particularly preferably heated to a temperature of more than 130°C, in particular of at least 160°C.
  • Process step (ii) is preferably carried out at least temporarily at a temperature in a range from 160°C to 350°C, particularly preferably at a temperature in a range from 190°C to 290°C. This achieves a fixation of the structure obtained.
  • a time interval of 0.1 to 30 minutes, more preferably 0.2 to 10 minutes, is sufficient to achieve adequate fixation of the continuous reinforcing fibers B and the thermoplastic molding composition A.
  • Suitable methods and devices are known to those skilled in the art. For example, interval hot presses can be used to advantage.
  • Method step (ii) is preferably carried out in such a way that at least one layer structure L is obtained from at least two layers, the layer structure L being at least one layer made of reinforcing fibers B, in particular one layer of a fabric G made of reinforcing fibers B, at least one layer which contains at least the comprises thermoplastic molding composition A, and at least one layer which comprises at least the filler C.
  • the at least one layer, which comprises at least the thermoplastic molding composition A, and the at least one layer, which comprises at least the filler e can be the same as or different from one another.
  • thermoplastic molding composition A can be at least one layer, which comprises at least the thermoplastic molding composition A, and at least one separate layer, which comprises at least the filler C, or at least one layer, which comprises at least the thermoplastic molding composition A and at least the Filler e includes.
  • a layered structure L is provided from at least one layer of reinforcement fibers B, in particular one layer of a fabric G from reinforcement fibers B, and at least two layers, which comprise at least the thermoplastic molding composition A and the filler C, the at least two layers, which comprise at least the thermoplastic molding composition A and the filler C, are arranged on each of the first and second surfaces of the at least one layer of reinforcing fibers B, in particular a layer of a fabric G made of reinforcing fibers B, so that the at least one layer of reinforcing fibers B, in particular a layer of a fabric G made of reinforcing fibers B, is arranged between at least one layer which comprises at least the thermoplastic molding composition A and the filler e.
  • a layer structure L is provided from a large number (i.e. at least 4) layers, the layer structure L having at least n layers of reinforcing fibers B, in particular one layer of a fabric G made of reinforcing fibers B, and at least m layers, which at least thermoplastic molding compound A and the filler C comprise, where n>1, in particular>2, and m>1, preferably>2.
  • Adjacent layers can be identical to or different from one another.
  • the layer structure L can also include further layers, which include the at least one thermoplastic molding composition A, but (substantially) contain no filler C.
  • thermoplastic molding composition A and the filler include C.
  • Such a layer is also referred to herein as a surface layer O.
  • Layers of reinforcing fibers B are provided in particular in the form of layers of a fabric G made of reinforcing fibers B.
  • Layers of thermoplastic molding composition A are provided, in particular in the form of powders, granules, melts or films, which comprise the molding composition A and optional additives D. These are preferably directly on at least one surface of an adjacent layer, in particular a layer of reinforcing fibers B, for example a layer of a fabric G applied. This can be done by sprinkling (in the case of powders or granules), pouring and/or raking (in the case of melts) or laying on (in the case of films). Layers of thermoplastic molding composition A are preferably applied in the form of powders or films.
  • layers of thermoplastic molding compound A and filler C are provided in the form of powders, granules, melts or films which comprise the molding compound A, the filler C and optional additives D. These are preferably applied directly to at least one surface of an adjacent layer, in particular a layer of reinforcing fibers B, e.g. This can be done by sprinkling (in the case of powders or granules), pouring and/or raking (in the case of melts) or laying on (in the case of films).
  • the molding compound A and the filler C can be applied separately or together.
  • the filler C in the form of a powder can be scattered on at least one surface of an adjacent layer, in particular a layer of reinforcing fibers B, e.g , is covered.
  • the filler C in the form of a powder and the molding composition A in the form of a powder or granules can be applied essentially simultaneously to at least one surface of an adjacent layer, in particular a layer of reinforcing fibers B, e.g. a layer of a fabric G.
  • thermoplastic molding composition A and filler C in the form of a powder, granules, a melt or a film, which is then applied together to at least one surface of an adjacent layer, in particular a layer of reinforcing fibers B, e.g. a layer of a fabric G, is applied.
  • the layer structure L comprises at least one surface layer O, which is formed from a film which comprises at least one thermoplastic molding compound A and optional additives D.
  • the layer structure L comprises at least one surface layer O, which is obtained by initially depositing at least one filler C in the form of a powder on at least one surface of an adjacent layer, in particular a layer of reinforcing fibers B, eg a layer a sheet G, is scattered and then covered with at least one film, which comprises at least one thermoplastic molding composition A and optional additives D.
  • Such a layer structure L is particularly suitable for significantly reducing the occurrence of adhesions of the filler on the pressing tool during production.
  • the layer structure L comprises at least one surface layer O, which is obtained in that a film comprising at least one thermoplastic molding composition A, at least one filler C and optional additives D, on at least one surface of an adjacent layer, in particular a layer of reinforcing fibers B, is placed.
  • a layer structure L is particularly suitable for significantly reducing the occurrence of adhesions of the filler on the pressing tool during production and also facilitates the use of fillers C with a particularly low density and / or particularly small average particle size, without them being undesirable during the production process Distributed in a wrong way and thus e.g. contaminate the production facilities.
  • the layer structure L thus obtained is preferably fixed by heating in process step (ii).
  • the layer structure L is particularly preferably heated to a temperature of more than 130.degree. C., in particular of at least 160.degree.
  • Process step (ii) is preferably carried out at least temporarily at a temperature in a range from 160°C to 350°C, particularly preferably at a temperature in a range from 190°C to 290°C.
  • a fixation of the resulting layer structure L is achieved in this way.
  • a time interval of 0.1 to 30 minutes, more preferably 0.2 to 10 minutes is sufficient to achieve adequate fixation of the layer structure L. Suitable methods and devices are known to those skilled in the art. For example, interval hot presses can be used to advantage.
  • the layer structure L is then fed to method step (iii).
  • the continuous reinforcing fiber B is impregnated with the at least one thermoplastic molding compound A, the at least one particulate, inorganic filler C, and optionally the at least one further additive D, or with the matrix composition M.
  • the The prefixed structure obtained in step (ii), in particular the layered structure L is heated to a temperature of at least 180° C., particularly preferably at a temperature in the range from 200 to 290° C., in order to melt the thermoplastic molding composition A and thus complete the impregnation enable.
  • thermoplastic molding composition A Due to the comparatively low viscosity of the thermoplastic molding composition A, preferably complete impregnation of the continuous reinforcing fibers B with the molding composition A is possible with sufficient speed.
  • thermoplastic molding compound A penetrates into the interstices of individual continuous reinforcing fibers B and also partly into interstices between the individual filaments (i.e. in the filament bundles) from which the continuous reinforcing fibers B are formed.
  • the optional additives D generally penetrate together with the thermoplastic molding composition A into the interstices mentioned in the filament bundles.
  • the inorganic fillers C only penetrate to a maximum of 10% into the filament bundles of the continuous reinforcing fibers B. This increases the local concentration of filler C outside the filament bundles. This has a positive effect on the surface quality of the composite materials V, which have particularly low surface waviness. The waviness present due to the continuous reinforcing fibers B is thus compensated for by the filler C. This effect can be achieved through the properties described herein of the particulate, inorganic filler C, the continuous reinforcing fibers B and the thermoplastic molding composition A, in particular through their relationships with regard to the thermal expansion coefficients and the volumetric shrinkage.
  • the method for producing the composite material V according to the invention preferably comprises the steps: i-1) providing at least one continuous reinforcing fiber B, the surface of the continuous reinforcing fibers B having one or more functional groups selected from hydroxyl, ester, amino and silanol groups comprises, preferably in the form of at least one fabric G; i-2) providing at least one thermoplastic molding composition A, wherein the thermoplastic molding composition A comprises at least one thermoplastic polymer A1 and optionally at least one polar functionalized polymer A2, comprising at least repeating units of at least one functional monomer A2-I; i-3) providing at least one particulate, inorganic filler C, and i-4) optionally providing at least one further additive D; ii) Combining the at least one thermoplastic molding compound A, the at least one particulate inorganic filler C, and optionally the at least one further additive D, with the at least one continuous reinforcing fiber B, the components being combined at a temperature of at least 160° C , preferably at
  • thermoplastic molding composition A the continuous reinforcing fibers B (in particular when the continuous reinforcing fibers B are embedded in layers).
  • the continuous reinforcing fibers B can be impregnated with the thermoplastic matrix composition M and consolidated as a sheet G in a single processing step.
  • the composite material V can thus be produced particularly efficiently.
  • the steps mentioned can be carried out in a separate sequence.
  • layers of reinforcing fibers with differently prepared continuous reinforcing fibers B can first be produced, with partial impregnation of the continuous reinforcing fibers B with the matrix composition M taking place. Thereafter, partially impregnated layers with continuous reinforcement fibers B with different fiber-matrix adhesion can be present, which can be completely impregnated and consolidated as a composite material V in a further work step to form a material composite.
  • the continuous reinforcing fibers B Before the layers of continuous reinforcing fibers B are laminated with the thermoplastic matrix composition M, at least some of the continuous reinforcing fibers B can be subjected to a pretreatment, during which the subsequent fiber-matrix adhesion is influenced.
  • the pretreatment can contain, for example, a coating step, an etching step, a heat treatment step or a mechanical surface treatment step.
  • an adhesion promoter that has already been applied can be at least partially removed, for example by heating part of the continuous reinforcing fibers B.
  • the layers of continuous reinforcing fibers B can be fully bonded to one another during the manufacturing process (laminating).
  • Such composite material mats offer optimized strength and rigidity in the fiber direction and can be further processed in a particularly advantageous manner.
  • the method comprises a three-dimensional shaping to form a molded part T as a further method step (v).
  • thermoplastic molding composition A is still (partially) melted, shaped.
  • a cured composite material V can also be cold-formed or reheated before forming, so that the thermoplastic molding composition A is (partially) molten.
  • a (largely) solid molded part T or composite material V is preferably obtained at the end of the process.
  • the method therefore preferably comprises, as a further step (v), curing of the molded part T or of the product obtained from step (iv). This step is often referred to as solidification.
  • the solidification which usually takes place with the withdrawal of heat, usually leads to a ready-to-use molded part T.
  • the molded part T or the composite material V can also be post-processed, for example by the steps of milling, cutting, burring, polishing and/or coloring.
  • the process according to the invention for producing the composite material V can be carried out continuously, semi-continuously or discontinuously.
  • the process is carried out as a continuous process, in particular as a continuous process, e.g., for the production of smooth or three-dimensionally embossed films.
  • the method according to the invention for producing the composite material V can be carried out semi-continuously or discontinuously.
  • the process for producing the composite material V according to the invention can preferably be carried out using an interval hot press.
  • the method comprises a ribbing step.
  • the improvement in component rigidity through ribbing is based on the increase in area moment of inertia.
  • the optimal dimensioning of the ribs includes aspects of production technology, aesthetics and design. The method steps for ribbing are known to those skilled in the art.
  • a further aspect of the invention relates to the use of the composite material V according to the invention for the production of molded parts T, for example by conventional deformation processes such as compression molding, rolling, hot pressing, stamping.
  • Another aspect of the invention relates to the thermoplastic matrix composition M according to the invention described herein, containing the thermoplastic molding composition A, and optionally one or more further additives D, and the mixture of the thermoplastic matrix composition M and the at least one particulate, inorganic filler C.
  • the thermoplastic according to the invention Matrix composition M can preferably be provided together with the at least one continuous reinforcing fiber B, preferably in the form of a fabric G, preferably selected from woven fabrics, mats, fleeces, scrims and knitted fabrics.
  • thermoplastic matrix composition M If the mixture of the thermoplastic matrix composition M and the at least one particulate, inorganic filler e is used, composite materials V with a particularly high surface quality (low surface waviness, high gloss) can be obtained.
  • the density of the composite materials V was determined according to DIN EN ISO 1183-1:2019-09 on test specimens using the immersion method.
  • the density of the molding compounds A was determined in accordance with DIN EN ISO 1183-1:2019-09.
  • the density of the reinforcing fibers B was determined according to ASTM C693.
  • the density of the filler C is typically determined according to DIN-ISO 787/10.
  • the melt mass flow rate MFR (melt flow rate) was determined according to DIN EN ISO 1133 at 230° C./2.16 kg for the polymer A1 and at 190° C./0.325 kg for the polar functionalized polymer A2.
  • the melting point Tm was determined by means of differential scanning calorimetry (DSC) in accordance with DIN EN ISO 11357-3.
  • the mean linear thermal expansion coefficients a (CLTE, Coefficient of Linear Thermal Expansion) were determined as the arithmetic mean of the values in the longitudinal and transverse directions in accordance with ISO 11359-1 and ISO 11359-2.
  • Chemically modified propene graft copolymer (white granules) with grafted maleic anhydride (0.15 to 0.25% by weight) having a density of about 0.9 g/cm 3 .
  • melt mass flow rate MFR (190°C/0.325 kg) 9 g/10 min to 13 g/10 min; Melting point (DSC) 160°C to 165°C.
  • thermoplastic molding composition A (comprising the polymers A1 and A2) and the additive D with the following composition was used as the matrix composition M:
  • the matrix composition M is obtained by intensively mixing components A1, A2 and D in an extruder.
  • the matrix composition M was obtained as powder P(M) and provided as Film F(M) of thickness 67 ⁇ m and 135 ⁇ m.
  • a composition of matter containing filler (M+C) was prepared as film F(M+C) by mixing components A1, A2, D and C and forming into a film having a thickness of 135 ⁇ m and 270 ⁇ m.
  • the composite materials V described in Table 1 with a proportion of 40 to 48% by volume of reinforcing fibers B and two layers of the glass fiber twill fabric were produced from the components described above by means of a described hot-pressing process.
  • the process for producing the composite materials V comprises the following process steps, which are explained in more detail below: i) providing at least one fabric G made from continuous reinforcing fibers B; the continuous reinforcing fiber is used as roll goods, and unwound within the process; ii) combining the thermoplastic matrix composition M containing the thermoplastic molding composition A and the at least one particulate inorganic filler C with the sheet G of continuous reinforcing fibers B: the matrix composition M and the continuous reinforcing fiber B are in the manners described below at 160-220 °C merged; iii) Impregnation of the continuous reinforcing fiber B with the thermoplastic matrix composition M: the assembled layer structure is pressed in an interval hot press, the structure containing the thermoplastic matrix A, the continuous rein
  • the pressing tool is lowered onto the pressing species and raised again, and the species is pulled a little further in the lifting cycle.
  • the pressing tool has a temperature of 200-280°C.
  • the composite is pressed at 1-3 MPa for 5-40 seconds per stroke;
  • Consolidation of the composite V after the hot-pressing zone, the composite with the separating plates is transferred to a colder zone of the pressing tool.
  • the temperature is 80-180 °C.
  • the composite is pressed at 1-3 MPa for 5-40 seconds per stroke.
  • the matrix material is solidified and a finished composite material V is obtained; v) optional cooling and optional further process steps.
  • Process step i) includes the provision of the glass fiber body fabric used by laying it out flat.
  • Process step ii) was carried out in three alternative embodiments, which are described below as process steps ii-a), ii-b) and ii-c).
  • the sheet G of continuous reinforcing fibers B was provided flat in its full areal extent.
  • the matrix composition M and optionally the filler C were applied to the fabric G in one step, each in the form of powder P(M) or P(C).
  • the composite was heated using a hot press so that the matrix composition M was bonded to the fabric G and optionally the filler C.
  • Composite V was not fully consolidated at this step.
  • the sheet G of continuous reinforcing fibers B was provided flat in its full areal extent.
  • the filler C was applied to the fabric G in the form of powder P(C).
  • the matrix composition M was applied in the form of a film F(M) to the surface of the fabric G provided with the powdered filler C, so that the filler C was enclosed on one or both sides.
  • the composite was heated using a hot press, so that the matrix composition M was bonded to the fabric G and the filler C.
  • Composite V was not fully consolidated at this step.
  • Process step ii-c) The sheet G of continuous reinforcing fibers B was provided flat in its full areal extent. Films F(M+C) made from matrix composition M and filler C were used. Layer structures L from the fabric G and the films were produced and pressed directly into the fully consolidated composite material V in a hot press.
  • Process step ii) represents the merging of the various components. In each case, an assessment was made of the extent to which adhesions occurred on the pressing tool during the manufacturing process:
  • the flexural modulus E r and the maximum flexural stress o max according to the 3-point flexural test according to DIN 14125 were determined on the composite materials produced. The values were measured in the directions °0° (in the direction of the grain) and 90° (perpendicular to the direction of the grain), respectively. The results are shown in Tables 2 to 5.
  • the geometric surface shape of the composite materials V produced was determined by determining the maximum heights Sz according to the geometric product specification DIN EN ISO 25178. Due to the unequal shrinkage behavior of thermoplastic molding compound A and continuous reinforcing fiber B in fabric G, without filler C the textile fiber architecture is visible on the composite surface, the so-called fiber topography. In order to improve the surface quality, ie to reduce the appearance of the textile fiber architecture and thus to minimize the geometric product specification in the form of the maximum height Sz, the fillers C described were added to the thermoplastic molding composition A.
  • Composite materials V with different compositions were produced and characterized in the manner described.
  • the filler contents were chosen such that the volume content of filler C in the entire matrix composition M (based on the total volume of components M and C) corresponded to a content of about 50% by volume.
  • Table 2 Production and testing of composite materials with different layer structures L and process step ii-a), examples 1, 2 and comparative example C1.
  • Examples 1 to 6 are according to the invention, C1 represents a comparative example. Examples 1 to 6 show that the introduction of filler C into the composite material V according to the invention reduces the surface waviness in comparison to the comparative example
  • the matrix composition M in the form of films (F(M), cf. Examples 3 to 6) instead of powder (P(M), cf. Examples 1, 2), the occurrence of adhesions of the filler on the Significantly reduce pressing tools during manufacture.
  • Examples 7 to 10 show how a reduction in surface waviness can be achieved by successively increasing the total amount of filler C. In order to halve the surface waviness, values of > 0.44 had to be achieved for the ratio of volume shrinkage C/volume shrinkage B.
  • Table 5 Production of thermoplastic fiber-reinforced plastics with different filler contents, Examples 7 to 10.
  • the mechanical properties of the composite materials V according to the invention remain sufficiently good even with comparatively low proportions of thermoplastic molding composition A.

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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)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne des matériaux composites (feuilles organiques) contenant un composé de moulage thermoplastique, au moins une couche de fibres de renforcement continue et au moins un matériau de charge inorganique. Selon l'invention, un matériau en feuille constitué de fibres de renforcement continues dans une composition de matrice comprenant le composé de moulage est utilisé, le composé de moulage thermoplastique contenant au moins une polyoléfine, et éventuellement au moins un autre polymère à polarité fonctionnalisée. L'invention se rapporte également à un procédé pour la production d'un matériau composite demandé et les utilisations associées.
EP21836159.0A 2020-12-16 2021-12-14 Matériau composite polymère thermoplastique contenant une charge renforcée par des fibres continues et ayant un bon lissé de surface Pending EP4263680A1 (fr)

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EP20214722 2020-12-16
PCT/EP2021/085643 WO2022129016A1 (fr) 2020-12-16 2021-12-14 Matériau composite polymère thermoplastique contenant une charge renforcée par des fibres continues et ayant un bon lissé de surface

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