EP4263680A1

EP4263680A1 - Filler-containing thermoplastic polymer composite material reinforced with continuous fibers and having good surface smoothness

Info

Publication number: EP4263680A1
Application number: EP21836159.0A
Authority: EP
Inventors: Felix KLAUCK; Pierre JUAN; Norbert Niessner; Eike Jahnke; André LÜCK; Florian Piott; Dietmar Drummer; Leo Hoffmann
Original assignee: Ineos Styrolution Group GmbH
Current assignee: Ineos Styrolution Group GmbH
Priority date: 2020-12-16
Filing date: 2021-12-14
Publication date: 2023-10-25
Also published as: WO2022129016A1; US20240132679A1

Abstract

The invention relates to composite materials (organosheets) containing a thermoplastic molding compound, at least one continuous reinforcing fiber layer and at least one inorganic filler material. According to the invention, a sheet material consisting of continuous reinforcing fibers in a matrix composition comprising the molding compound is used, the thermoplastic molding compound containing at least one polyolefin, and optionally at least one further, polarity-functionalized polymer. The invention also relates to a process for producing the claimed composite material and to uses thereof.

Description

Filled continuous fiber reinforced thermoplastic polymer composites with low surface waviness

description

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. In particular, 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.

State of the art

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. At the same time, 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. In addition, 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. Furthermore, 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.

In the production of composite materials, the 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 (fiber-matrix adhesion) can also have a significant influence on the properties of the composite material. In addition, the process for producing the materials should be simple and inexpensive to carry out.

Since both the fibers and the matrix materials can be varied, there are numerous possible combinations of fibers and matrix materials. Due to the low chemical similarity between the fiber surface and the surrounding polymer matrix, there is often a low attraction and thus a low adhesion between fibers and matrix materials.

In order to optimize the fiber-matrix adhesion and to compensate for the low chemical similarity between the components, reinforcing fibers are regularly pre-treated with a so-called sizing (sizing agent). Such 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. In some cases, 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.

It is therefore desirable to provide composite materials with a low intrinsic weight and a wide load range in which the total failure does not manifest itself in the form of a material fracture. Composite materials with excellent optical properties, such as smooth and/or shiny surfaces, are also desirable. In order to obtain an aesthetically high-quality surface, especially in composites with a semi-crystalline thermoplastic matrix, it is crucial to reduce the shrinkage of the thermoplastic matrix, e.g. during cooling after the composite has been produced.

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.

WO 2008/119678 discloses 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.

The application WO 2016/170145 describes a method for producing 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. Optionally, 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.

DE 69831854 (T2) discloses a glass mat (GMT) material incorporating fillers which has improved properties over similar unfilled GMT composite materials. 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.

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.

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

(a) 10 to 85% by weight, based on the total weight of the fiber-reinforced polymer composition, of a polypropene (PP),

(b) 12.5 to 53% by weight, based on the total weight of the fiber-reinforced polymer composition, of the fibers (F),

(c) 2 to 12% by weight, based on the total weight of the fiber-reinforced polymer composition, of glass bubbles (GB) and

(d) 0.5 to 5% by weight, based on the total weight of the fiber-reinforced polymer composition, of a polar functionalized polypropene (PMP) as an adhesion promoter.

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-α-olefin copolymer, the matrix being composed of at least 90% by weight propylene and at most 10% by weight α-olefin based on the total weight of the propylene-based matrix, and ii) a dispersed ethylene-α-olefin copolymer comprising ethylene and at least one C3 to C10 α-olefin; - from 0 to 20% by weight, based on the weight of the composition, of an ethylene-α-olefin elastomer comprising ethylene and at least one C3 to C10 α-olefin; - optionally >5 to 15% by weight, based on the weight of the composition, of a high density polyethylene (HDPE); - from 1 to 30% by weight, based on the weight of the composition, of high talc aspect ratio as filler; - from 0 to 5% by weight, based on the weight of the composition, of another talc; - from 0.05 to 1% by weight, based on the weight of the composition, of a phenolic antioxidant additive; - from 0.05% to 1% by weight, based on the weight of the composition, of at least one amphiphilic protective additive comprising a hydrophilic part and a hydrophobic part; and - from 0 to 3% by weight, based on the weight of the composition, of one or more additional additives.

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. In addition, the composite material should be suitable for the production of moldings, films and coatings. Furthermore, the production of the composite material should be possible at low cost and in a common process with the shortest possible cycle times.

It was surprisingly found that 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.

In addition, a production process for such a thermoplastic, fiber-reinforced composite material was surprisingly found. If both the 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. By introducing the 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, preferably selected from glass fillers, mineral fillers, ceramic fillers and mixtures thereof, and d) > 0 to <10% by weight, preferably >0.01 to <10% by weight, more preferably >0.1 to <5% by weight, of at least one further additive D, preferably selected from processing aids, stabilizers, lubricants and mold release agents, flame retardants, dyes, pigments and plasticizers; wherein the at least one particulate, inorganic filler C has 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 (also measured according to ISO 11359-1 and ISO 11359-2), ie the relationship (I) applies:

Oc < OA (I); wherein the at least one particulate, inorganic filler C has a volume shrinkage that is 0.1 to 2 times as large as the volume shrinkage of the continuous reinforcing fiber B, the volume shrinkage resulting from the coefficient of thermal volume expansion ay in 1/K der respective component multiplied by the proportion by weight of the respective component in the composite material V in % by weight/100 and by the reciprocal density of the respective component in g/cm ³ , where the following relationship (II) applies: 0.1 to 2 (II) With

Ov,c = coefficient of thermal volume expansion of component C in 1/K,

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 = 3 * 0c; and civ.B = 3 * OB with

□A = average linear thermal expansion coefficient of component A; OB = average linear thermal expansion coefficient of component B; and

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. For the purposes of the present invention, 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. Typically, the linear thermal expansion coefficient a (in particular the average linear thermal expansion coefficient a) in 1/K results from the following relationship (III): With

AL = change in length of the test sample between two temperatures Ti and T2;

AT = temperature change (= T2-T1);

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. Typically, the coefficient of thermal expansion is determined in a temperature range ΔT in the range from -30 to 200°C, in particular 40 to 150°C, in particular 70 to 120°C.

Typically, the coefficient of thermal volumetric expansion Ov is obtained by replacing the terms “length” with “volume” in equation (III). It can be assumed that the coefficient of thermal volume expansion Ov corresponds to three times the linear thermal expansion coefficient a (av = 3 * a). A value averaged over two or three of the dimensions of the test sample is often used as the coefficient of linear thermal expansion, a.

For the purposes of the present invention, the volume shrinkage of the at least one filler C is as follows:

AVc=Ov,c * proportion by weight of component C in the entire composite material V in % by weight/100/density of component C in g/cm ³ ; where approximately Oy,c = 3 * Oc According to the present invention, the volume shrinkage of the at least one continuous reinforcing fiber B is as follows:

AVB=OV,B*weight proportion of component B in the entire composite material V in % by weight/100/density of component B in g/cm ³ ; where approximately OV,B = 3 * OB.

In embodiments in which the optional component D is present, 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.

In a preferred embodiment, 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-butyl (meth)acrylate, glycidyl (meth)acrylate and mixtures thereof, and the at least one repeating unit A2-II is selected from ethene, propene, butene, isobutene and mixtures thereof; 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 multiplicity number of filaments, preferably selected from inorganic or organic reinforcing fibers, in particular selected from glass fibers and/or carbon fibers, particularly preferably from glass fibers; c) > 1 to <60% by weight, preferably > 3 to <45% by weight, of at least one particulate, inorganic filler C, preferably selected from glass fillers, mineral fillers, ceramic fillers and mixtures thereof, and d) > 0 to <10% by weight, preferably >0.1 to <5% by weight, of at least one further additive D, where the following relationships (I) and (II) apply:

Oc < a _A (I) and 0.1 to 2 (II) With:

Ov,c = coefficient of thermal volume expansion of component C in 1/K,

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; and

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.

An alternative preferred embodiment of the invention relates to a fiber-reinforced, 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 >0.1 to <5% by weight, of at least one further additive D where the following applies: a _c <a _A and a _vc x proportion C x density B in q/ml

— - — — = 0.1 to 2 a _VB x proportion B x density C in g/ml with

C(v,c - coefficient of thermal volume expansion of component C in 1/K, 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 = 3 * 0c; and civ.B = 3 * OB with OA = mean linear thermal expansion coefficient of component A;

OB = average linear thermal expansion coefficient of component B; and 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.

Another alternative preferred embodiment of the invention relates to a fiber-reinforced, thermoplastic composite material V comprising (preferably consisting of): a)> 5 to <20 wt .-%, preferably> 10 to <20 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 >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 D, where the following relationships (I) and (II) apply:

Oc < a _A (I) and 0.1 to 2 (II) With:

Ov,c = coefficient of thermal volume expansion of component C in 1/K,

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,

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 where OA = average linear thermal expansion coefficient of component A; OB = average linear thermal expansion coefficient of component B; and 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.

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.

Thermoplastic molding compound A

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.

The 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.

The 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. In a particularly preferred embodiment of the invention, 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.

In addition to the thermoplastic polymer A1, the 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. In addition, the thermoplastic molding composition A can comprise further polymers A3 which are different from the polymers A1 and A2.

In one embodiment, the 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.

The 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.

In a preferred embodiment, 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.

In a preferred embodiment of the invention, the thermoplastic molding composition A comprises the polymers A1 and A2 and comprises no further polymers A3. In an alternative embodiment, the thermoplastic molding composition A contains the polymers A1 and A2 and optionally at least one further polymer A3. Typically, the at least one optional polymer A3 can be selected from any thermoplastic polymer other than A1 and A2. For example, 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. 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.

In particular, the 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.

More preferably, 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. 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 preferably consists of components A1, A2 and A3.

Thermoplastic Polymer A1

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. Preferably contains 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. 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 .

The 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.

Polar Functionalized Polymer A2

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.

In a preferred embodiment, 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.

According to a preferred embodiment, 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).

In addition to the repeating units A2-I, 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. More preferably, 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. They are known, for example, under the product names PRIEX® 20093 (BYK), Orevac® CA100 (Arkema) and Scona® TPPP 9021 (BYK) and are commercially available. 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.

In particular, 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.

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.

In a particularly preferred embodiment, 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.

Continuous reinforcement fiber B

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.

Typically, the density of the continuous reinforcing fiber B ranges from 1.4 g/cm ³ to 2.8 g/cm ³ . Preferably, 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 . Preferably, 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.

Typically, the continuous reinforcing fiber B comprises a large number of individual filaments, the mean filament diameter being in a range from 2 to 35 μm, preferably from 5 to 25 μm. The filaments of the continuous reinforcing fiber B are often bundled into rovings, fabrics and/or yarns.

In a further preferred embodiment, 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.

Thus, in one embodiment of the invention, 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. In addition, 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. For example, 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.

Often there is no suitable affinity between the polymer matrix and the reinforcing fibers. This can be overcome by using adhesives that increase the adhesion of polymers to the fiber surface. Typically, organofunctionalized silanes such as aminopropyltriethoxysilane, methacryloxypropyltrimethoxysilane, glycidyloxypropyltrimethoxysilane, and the like are used.

In an alternative, preferred embodiment of the invention, 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).

In one embodiment, 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.

Typically, the known qualities of glass fibers are used, depending on the requirements and area of application, e.g. glass fibers of the E-Glass type (E=Electric; Aluminum nium borosilicate glass with less than 2% alkali oxides), S glass (S=Strength; aluminum silicate glass with additions of magnesium oxide), R glass (R=Resistance, aluminum silicate glass with additions of calcium and magnesium oxide ), M-glass (M=modulus, glass containing berrylium), C-glass (C=chemical, fiber with increased chemical resistance), ECR-glass (E-glass corrosion-resistant), D-glass (D = dielectric, fiber with low dissipation factor), AR glass (AR=Alkaline Resistant, fiber developed for use in concrete, enriched with zirconium (IV) oxide), Q glass (Q=quartz, fiber made of quartz glass SiO2) and hollow glass fibers.

E-glass fiber is often used as the standard fiber for general plastic reinforcement and electrical applications. In a preferred embodiment of the invention, glass fibers with a filament diameter of 5 to 25 μm 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.

In addition, it is also possible to use carbon fibers (also called carbon fibers or carbon fibers) as the continuous reinforcing fiber B. Typically, 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. Typically, 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 such. g. scrims, woven fabrics, mats, nonwovens, knitted fabrics, braids or multiaxial fabrics, 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. According to a preferred embodiment, 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.

In a fabric, 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.

In a further embodiment, 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.

In a further embodiment, 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. For example, all of the layers can be of the same type or some of the layers can have a different structure. 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.

Particulate, inorganic filler e

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. In a preferred embodiment, 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. These 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). Hollow glass bodies and carbonates, in particular calcium carbonate (chalk), are very particularly preferred. In a preferred embodiment, 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.

In a further preferred embodiment, 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.

In a further alternative preferred embodiment, 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.

In a preferred embodiment, fillers C with an average particle size D50 in the range of up to 300 μm, more preferably of up to 100 μm, particularly preferably of up to 70 μm, in particular in a range of 1 μm to 50 μm, as particulate, inorganic filler e used.

According to the invention, inorganic fillers C are used 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. Preferably, the relationship Oc < 0.3 OA applies. 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.

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 .

According to the invention, inorganic fillers C are used for which the following relationship (II) applies: 0.1 to 2 (II) With:

Ov,c = coefficient of thermal volume expansion of component C in 1/K,

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: av,c = 3 * 0c; and civ.B = 3 * OB with:

□A = average linear thermal expansion coefficient of component A;

OB = average linear thermal expansion coefficient of component B; and

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.

The relationship (IV) preferably applies: a _v rX proportion Cx density B in q/ml ,,

- — — = 0.44 to 1.5 (IV) a _{v B} x proportion B x density C in g/ml

It was observed that with a value of >0.44 in relation (IV), a 50% reduction in the surface waviness of the composite material V obtained could be achieved.

More preferably, the relationship (V) applies: a _vr x Antell C x Density B in q/ml

- — — = 0.50 to 1.2 (V) a _{v B} x proportion B x density C in g/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.

In one embodiment of the production of the composite material V according to the invention, 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. In another embodiment, 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.

Other additives D

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. Typically, 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.

In the production of the composite material V according to the invention, the additives D are typically added to the thermoplastic molding composition A.

For example, 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. As 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.

Examples of suitable 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.

In a preferred embodiment, 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. Examples of 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. For example, the calcium, zinc or aluminum salts of stearic acid and dialkyl ketones, for example distearyl ketone, can be used.

Furthermore, 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.

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.

Furthermore, 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. Gächter 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 Anstrichmittel, Expert-Verlag (1988), p. 78ff).

In addition, inorganic colored pigments, such as chrome oxide green, or organic colored pigments, such as azo pigments and phthalocyanines, can be used according to the invention to set specific shades. Such pigments are generally commercially available. Furthermore, it can be advantageous to use the pigments or dyes mentioned in a mixture, for example carbon black with copper phthalocyanines.

In addition to the additives mentioned, which are usually added to the thermoplastic molding composition A, the continuous reinforcing fibers B can also comprise additives, in particular in the form of a surface coating, a so-called size (size). Typically, 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. Process for the production of the fiber-reinforced composite material V

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.

The preferred embodiments with regard to the 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.

According to process step (i), 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. Preferably, 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.

According to the invention, 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. In addition, 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.

In a preferred embodiment, 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. In one embodiment, 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. In one embodiment, 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.

In one embodiment, 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. In this embodiment, 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 μm to 500 μm, preferably 50 to 400 μm, particularly preferably 65 to 200 μm. The film can include the filler C or be (essentially) free of filler C.

The components A and optionally D or the 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.

In one embodiment of the invention, 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.

In an alternative embodiment of the invention, 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.

In a particularly preferred embodiment, 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 μm to 500 μm, preferably 50 to 400 μm, particularly preferably 65 to 200 μm.

In a preferred embodiment, 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. As a rule, 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. This means that it 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. In a preferred embodiment of the invention, 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.

In a further embodiment of the invention, 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. Optionally, 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. In order to achieve the effect of improved surface quality according to the invention, it is necessary for at least the layers that form the surface of the layered structure L (and thus also of the subsequent composite material V) to have a particularly high surface quality, at least the 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 (ie without the filler C) 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.

According to the invention, 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. For example, 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. Alternatively, 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. It is also possible according to the invention to first provide a mixture of 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.

In a preferred embodiment of the invention, 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.

In a further preferred embodiment of the invention, 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.

In a further preferred embodiment of the invention, 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. Such 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. As a rule, 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).

According to process 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. For this purpose, 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.

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.

As a rule, a time interval of 0.1 to 30 minutes, more preferably 0.2 to 10 minutes, is sufficient to achieve complete impregnation of the continuous reinforcing fibers B with the thermoplastic molding composition A. The 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.

According to the invention, 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 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 in order to obtain a prefixed structure, in particular a layer structure L; iii) impregnation of the continuous reinforcing fiber B with 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, in order to obtain a composite material V, the impregnation being carried out at a temperature of at least 180° C takes place, particularly preferably at a temperature in a range from 200 to 290°C; iv) consolidation of the composite V obtained; v) optional solidification and/or optional further process steps.

In process step (iv), during the consolidation, air inclusions in the composite material V are reduced and a good bond is produced between the thermoplastic molding composition A and the continuous reinforcing fibers B (in particular when the continuous reinforcing fibers B are embedded in layers). After impregnation and consolidation, it is preferable to obtain a (as far as possible) pore-free composite material. 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.

Alternatively, the steps mentioned can be carried out in a separate sequence. For example, 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.

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. In particular, 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 (fabric G) 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.

According to a preferred embodiment, the method comprises a three-dimensional shaping to form a molded part T as a further method step (v).

This can be done in any way, such as mechanical shaping by a shaping body, which can also be a roller with embossing. Preference is given to the still malleable composite material V, in which the thermoplastic molding composition A is still (partially) melted, shaped. Alternatively or additionally, 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.

Optionally, 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.

According to a preferred embodiment, 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.

Alternatively, 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.

In a preferred embodiment, the method comprises a ribbing step. The improvement in component rigidity through ribbing (creation of a ribbed structure) is based on the increase in area moment of inertia. In general, 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.

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 present invention is further illustrated by the following examples and claims.

examples

Various fiber-reinforced composite materials V were produced from components A1, A2, B, C1 or C2 and D. The components and methods for their characterization are described below.

characterization methods

Unless otherwise stated, the components used were characterized according to the methods described below.

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.

The average coefficient of thermal volume expansion Ov was determined according to the equation Ov = 3 * a.

Components A, B, C and D used

Polymer A1 polyolefin

propene-ethene copolymer having a density of 0.898 g/cm ³ to 0.900 g/cm ³ ; a melt mass flow rate MFR (230°C/2.16 kg) of 90 to 110 ml/10 min, mostly 100 ml/10 min; a melting point (DSC) of 135 °C to 159 °C, a thermal expansion coefficient OAI = 60*1 O' ⁶ K' ¹ to 90*1 O' ⁶ K' ¹ , coefficient of thermal volume expansion OV,AI = 3 * OAI = 180*10' ⁶ K' ¹ to 270*1 O' ⁶ K' ¹

Polar Functionalized Polymer A2 Propene Graft Copolymer

(PRIEX® 20093 from BYK-Chemie)

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.

Continuous reinforcement fiber B glass fiber

(E-glass fibers from Lange + Ritter GmbH)

A glass fiber twill fabric 2/2 with the following properties was used as continuous reinforcement fiber B: size PP-compatible, basis weight 600 g/m ² , 1200 tex roving yarn in warp and weft, 25 threads/10 cm in warp and weft direction, coefficient of thermal expansion QB = 5*1 O' ⁶ K' ¹ to 6*1 O' ⁶ K' ¹ , coefficient of thermal volume expansion OV,B = 3 * OB = 15*10' ⁶ K' ¹ to 18*10' ⁶ K' ¹ (16.5*1 O' ⁶ K' ¹ ), density B = 2.55 g/ml to 2.58 g/ml (2.57 g/ml).

Particulate, inorganic filler e

The following fillers C were used:

C1 CaCOs with a mean particle size of 35 pm

(Omyacarb® 30-AV from OMYA)

Coefficient of thermal expansion aci = 10*10 ^-6 K' ¹ , coefficient of thermal volume expansion av,ci = 3 * aci = 30*10' ⁶ K' ¹ , density C1 = 2.3-2.8 g/ml (2, 65g/ml)

C2 Hollow glass spheres with an average particle size of 20 μm

(Glass Bubbles iM16K by 3M™)

Thermal expansion coefficients Oc2 = 8*1 O' ⁶ K' ¹ to 9*1 O' ⁶ K' ¹ , coefficient of thermal volume expansion av,c2 = 3 * Oc2 = 24*10' ⁶ K' ¹ 27*10' ⁶ K ' ¹ (25.5*10 ^-6 K' ¹ ), density C2 = 0.46 g/ml

Additive D Distilled monoglyceride (1-glycerol monostearate, white powder).

Dimodan® HP from DuPont Danisco

Matrix composition M

A mixture of the 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:

Table 1. Composition of 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 µm and 135 µm. 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 µm and 270 µm.

production method

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 reinforcing fiber B and the filler C is processed between two steel dividers. 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; iv) 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. Here the temperature is 80-180 °C. The composite is pressed at 1-3 MPa for 5-40 seconds per stroke. Here, the matrix material is solidified and a finished composite material V is obtained; v) optional cooling and optional further process steps. Process steps i) and ii)

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).

Process step ii-a)

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.

Process step ii-b)

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 steps iii) + iv)

The following tests were carried out on an interval hot press (manufacturer: Teubert Maschinenbau GmbH, type HP007), which is able to produce a composite material from polymer film, melt or powder, for the quasi-continuous production of fiber-reinforced thermoplastic semi-finished products, laminates and sandwich panels .

Characterization of process step ii):

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:

1 no buildup on the pressing tool

2 small adhesions on the pressing tool

3 medium adhesions on the pressing tool

4 strong adhesions on the pressing tool

Mechanical characterization of the composites

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.

Characterization of the geometric surface shape of the composite material

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.

In order to measure the resulting surface quality, samples measuring 95×70 mm ² were repeatedly measured and evaluated using the optical white light method (phase stepped deflectometry=PSD). The results are shown in Tables 2, 3, 4 and 5.

Results

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.

^[1] Layer structure legend: P(M) = matrix composition M in the form of powder; G = fabric G; P(C1) powdered filler C1; P(C2) powder filler C2. " ₇ . 0.1 to 2

^[3] Bending stress Omax.

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

1 can be reduced by a factor of four to five. The surface appearance of the composite materials V is thus significantly improved. The lowest surface waviness was achieved with a content of 33% by weight of filler C1 or 8% by weight of filler 02, based on the total weight of the composite material V (cf. Examples 3 and 6). Table 3: Production and testing of composite materials with different

Layer structures L and process steps ii-b) or ii-c), examples 3 to 6 ^[1] Layer structure legend: P(M) = matrix composition M in the form of powder; F(M) = matrix composition M in the form of a film; G = fabric G; P(C1) powdered filler C1; P(C2) powdered filler C2; F(M+C2) = film comprising matrix composition M and filler C2; behind the film the respective thickness of the film is listed in μm (67 μm or 135 μm for the films F(M); 135 μm or 270 μm for the films F(M+C2) " 0.1 to 2

^[3] Bending stress Omax.

By using 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.

Table 4: Production of thermoplastic fiber-reinforced plastics with different filler contents, comparative examples C2 to C4. ^[1] Layer structure legend: F(M) = matrix composition M in the form of a film; G = fabric G; F(M+C2) = film comprising matrix composition M and filler C2; behind the film the respective thickness of the film is listed in μm (67 μm or 135 μm for the films F(M); 135 μm or 270 μm for the films F(M+C2) „ ₇ . 0.1 to 2

^[3] Bending stress Omax.

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.

^[1] Layer structure legend: F(M) = matrix composition M in the form of a film; G = fabric G; F(M+C2) = film comprising matrix composition M and filler C2; behind the film the respective thickness of the film is listed in μm (67 μm or 135 μm for the films F(M); 135 μm or 270 μm for the films F(M+C2). r

¹ ₉₁ J Volume shrinkage C „ ₇ . - Volume shrinkage B 0.1 to 2

^[3] Bending stress O

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.

Claims

62

patent claims

1. Fiber-reinforced, thermoplastic composite material V, comprising: a)> 5 to <20 wt .-% of a thermoplastic molding composition A, wherein the thermoplastic molding composition A comprises at least one polymer A1 and optionally at least one polar functionalized polymer A2, comprising at least repeating units of at least one functional Monomers A2-I; b) >20 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 <60% by weight of at least one particulate, particulate, inorganic filler C, and d) >0 to <10% by weight of at least one further additive D; wherein the at least one particulate, inorganic filler C has 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 (also measured according to ISO 11359-1 and ISO 11359- 2), wherein the at least one particulate, inorganic filler C has a volume shrinkage which is 0.1 to 2 times as large as the volume shrinkage of the continuous reinforcing fiber B, wherein the volume shrinkage results from the coefficient of thermal volume expansion ay in 1/K of the respective component multiplied by the proportion by weight of the respective component in the composite material V in % by weight/100 and by the reciprocal density of the respective component in g/cm ³ , where the relationship (II) applies: 0.1 to 2 (II) With:

Ov,c = coefficient of thermal volume expansion of component C in 1/K,

Proportion C = proportion by weight of component C in the entire composite material V in % by weight /100, 63

QV,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:

Ov,c = 3 * 0c; and civ.B = 3 * OB with:

2. Fiber-reinforced, thermoplastic composite material V according to claim 1, wherein the at least one particulate, inorganic filler C has a thermal expansion coefficient Oc which is 0.2 to 5 times as large as the thermal expansion coefficient OB of the continuous reinforcing fiber B.

3. Fiber-reinforced, thermoplastic composite material V according to claim 1 or 2, wherein the thermoplastic molding composition A penetrates into the filament bundles of the continuous reinforcing fibers B, but the fillers C only penetrate to a maximum of 10% into the filament bundles of the continuous reinforcing fibers B, based on surface proportions of a cross section of the filament bundles, penetrate.

4. Fiber-reinforced, thermoplastic composite material V according to at least one of claims 1 to 3, wherein the thermoplastic molding composition A comprises (and preferably consists of) the following components: 64 a-1) 60 to 99% by weight of at least one component A1 of a polymer selected from the group consisting of propene homopolymers, propene copolymers, styrene copolymers, polyamides and polycarbonates, a-2) 1 to 40% by weight of one component a polar functionalized polymer A2; and a-3) 0 to 10% 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. Fibre-reinforced, thermoplastic composite material V according to at least one of Claims 1 to 4, where components A1 are selected from a polymer based on polypropylene. Fiber-reinforced, thermoplastic composite material V according to at least one of claims 1 to 5, wherein the components A1 are a propene-ethene copolymer with a melt mass flow rate (MFR) determined according to DIN EN ISO 1133 (230 ° C / 2.16 kg) in one range from 40 g/10 min to 120 g/10 min. Fiber-reinforced, thermoplastic composite material V according to at least one of claims 1 to 6, wherein the polar-functionalized polar-functionalized polymer A2 has at least one repeating unit derived from a monomer selected from the group consisting of maleic anhydride, acrylic acid, N-phenylmaleimide, tert-butyl methacrylate, glycidyl methacrylate , includes. Fiber-reinforced, thermoplastic composite material V according to at least one of claims 1 to 7, wherein the polar functionalized polymer A2 is a graft copolymer of propene and maleic anhydride with a maleic anhydride content of 0.1 to 5% by weight, based on the total weight of the polar functionalized polymer A2, is. Fibre-reinforced, thermoplastic composite material V according to at least one of claims 1 to 8, wherein the filler C has an average particle diameter of 1 to 300 μm. 65

10. Fiber-reinforced, thermoplastic composite material V according to at least one of claims 1 to 9, wherein the filler C is selected from the group of glass fillers, mineral fillers and/or ceramic fillers.

11 . Fibre-reinforced, thermoplastic composite material V according to at least one of claims 1 to 10, wherein the filler C is selected from hollow glass bodies and/or calcium carbonate.

12. Fiber-reinforced, thermoplastic composite material V according to at least one of claims 1 to 11, wherein the continuous reinforcing fibers B are selected from the group comprising glass, carbon, aramid, natural fibers and/or mixed forms of the reinforcing fibers mentioned.

13. Fiber-reinforced, thermoplastic composite material V according to at least one of claims 1 to 12, wherein the continuous reinforcing fibers B are selected from glass fibers and/or carbon fibers.

14. A method for producing a fiber-reinforced, thermoplastic composite material V according to at least one of claims 1 to 13, wherein the method comprises at least the following method 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 one further 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 further 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 composition A, the at least one inorganic filler C, and optionally the at least one further additive D, in order to obtain a composite material V; iv) consolidation of the composite V obtained; v) optional solidification and/or optional further process steps. 66 Method for producing a fiber-reinforced, thermoplastic composite material V according to claim 14, wherein the method comprises at least the following method steps: i-1) providing at least one continuous reinforcing fiber B, wherein the surface of the continuous reinforcing fibers B has one or more functional groups selected from hydroxy, ester, amino and silanol groups; 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 composition 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 to obtain a pre-fixed structure; 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 further additive D, in order to obtain a composite material V, the impregnation being carried out at a temperature of at least 180° C occurs; iv) consolidation of the composite V obtained; v) Solidification and/or optional further process steps.